(SANITIZED)SOVIET BLOC PAPERS ON MACROMOLECULAR CHEMISTRY(SANITIZED)

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80T00246A010900180001-1
• Release Decision: RIPPUB
• Original Classification: C
• Document Page Count: 871
• Document Creation Date: December 22, 2016
• Document Release Date: August 27, 2009
• Sequence Number: 1
• Publication Date: July 21, 1960
• Content Type: REPORT

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INTEIiDEPENDANCE ENTRE CERTAINES PROPRIETES
PHYSICO-MECANIQUES ET LES CONDITIONS
DE SYNTHESE DU POLYPROPYLENE
Dans le cadre des recherches pour 1'obtention et la transforma-
tion du polypropylene, on a constate certaines influences des-
condilions de synthese sur les caracteristiqu.es physico-meca-
niques de ce polymere.
La polymerisation du propylene a ete executee d'apres les
methodes habituelles: comme matiere premiere, on a utilise soft
la fraction C3 soit le propylene concentre et un sol-
vant hydrocarbure; comme catalyseur, on a utilise les alcoyles~
d'aluminium et le trichlorure de thane daps un rapport
molaire variant entre 1 et 9. On travaillait a des pressions entre
8 et 40 atm. et des temperatures entre 50 et 80? C.
? Par modification des conditions de synthese (rapport molaire
entre catalyseur et cocatalyseur, pression et temperature de tra-
vail), on obtient a volonte des polymeres de poids moleculaires~
divers, variant entre 30 000 et 45 000 (determines par viscosi-
metrie), mais qui peuvent differer entre eux par la dispersion
du degr,~ de polymerisation et leur teneur en cendres.
En meme temps qu'une variation du degre de polymerisation,
on enregistre aussi tine modification relative du degre d'isotacti-
cite.
L'etude des proprietes physico-mecaniques a montre-
que celles-ci dependent eu premier lieu du poids moleculaire.
lin augmentant le poids moleculaire on constate une elevation
de la resistance a la traction, une elevation de 1'indice de flui-
dite et de la temperature de ramollissement d'apres Vicat. Les-
proprietes dielectriques dependent de fa~on sensible de la teneur
en cendres du polymere.
Bien que les accroissements des proprietes physico-mecaniques-
presentent une variation a peu pres lineaire; on constate. que ces-
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variations sont accentuees de maniere differente dans les divers
intervalles du poids moleculaire. L'augmentation de la resistan-
ce a latraction estplus accentuee pour M = 30 000-100 000 tandis
que les indices de fluidite presentent une variation plus accentuee
dans 1'intervalle M = 120 000 - 250 000. Bien que les poids
moleculaires eleves correspondent a des caracteristiques physico-
mecaniques superieures, cependant la technologie de la transfor-
mation usuelle limite 1'intervalle dans lequel ces polymeres
peuvent titre utilises a des fins industrielles.. En examinant
1'interdependance entre les conditions de transformation et le
poids moleculaire, on a etabli que 1'intervalle le plus interessant
du point de vue pratique se situe entre 100 000 et 220 000, even-
tuellement meme 250 000..
La connaissance de la variation des proprietes physico-meta-.
niques .permet de trier les polymeres .en vue de leurs utilisations
diverses.
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ycTaxoBxexo, uTO 3TI3 xaMexexHx BbIpaxceHbi pas.ni3uHO B paa~Ix~I-
xblx nHTepsa~Iax Moxexyaslpaoro Beca. PocT conpoTHBaleaxti paa-
pbrBy BbtpaxseH xp*~e R~LSi M = 30 000-100 000, B To BpeMR xax
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Summary
It has been established that in the processing of propylene
the conditions of its synthesis have a certain influence on the
physico-mechanical properties of the polymer.
The raw materials in the polymerization of propylene are
ether propylene-propane fractions or concentrated propylene in
a hydrocarbon solvent, alkylaluminum and titanium trichloride
in molar ratios within the limits 1=9 serving as catalysts.
'The reaction is carried out at pressures 8-40 atm. and tempera-
tures 50-80?.
By changing the conditions of synthesis (molar ratio of cata-
ilyst: cocatalyst, pressure and temperature) one may obtain at
will polymers with molecular weights varying from 30000 to
450 000 (determinations made with the aid of the viscometric
:method). The polymers may differ in polydispersity and ash
content.
The degree of isotacticity changes with change in the extent
bf polymerization.
A study of the physico-mechanical 'properties showed that
they depend predominately upon the molecular weight. It has
been found that with growth in molecular weight there is an increase
in tensile strength, in the fluidity and in the Vikat softening
point. The dielectric properties are greatly dependent upon the
-ash .content.
Although the changes in physico-mechanical properties are
almost a linear function of the molecular weight they have been.
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found to be manifested differently in different molecular weight
ranges. The growth in tensile strength is more clearly expressed for-
M = 30 000-100 000, whereas the index of fluidity shows change
in the range M = 120 000-250 000.
Although higher molecular weights correspond to higher-
physico-mechanical characteristics ordinary processing limits-
the use of polymers with such weights for industrial purposes.
In a study of the relation between the processing conditions
and the molecular weight it was found that the range of practical
interest is between 100 000 and 220 000, and possibly even 250 000..
Depending upon their physico-mechanical properties variou~-
fields of application of the polymers inay be recommended.
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9. J. N a t t a, P. C o r r a d i n"i, Angew. ChenL, 68, 393, 1956.
2: N. E. H o r n e, J. P. K i e h e, Industr. Engng. Chem., 48, 784, 1956.
3. B. Z[. Ba6nijxnr~, B.. A.. ,i[onron.nocx, B. A. Ifporlb,
Xnrvil3~f. aayxa x npoai., 2, 392, 1957.
-4.I~I.I4.BonAblpeaa, B. A.Roni,onrrocx, B.A.Kponl,,
TaM xce, 2, 391, 1957.
5. E. 1!I. Txxrrxosa, 1?. A. ,I~orlronnocx, A. Id. Mapeii,
M. 3. A n b 2 m y n e p, ,T~oxn: AH CCCP, 124, 595, 1959.
6. E.1'I.TnrrrrxoBa, B. A.Z(ozrronnocx, P.H.I~oBanes-
c x a sr, T. r. }IC y p a rr n e B a, J~oxn. AH CCCP, X29, 1306, 1959.
7. E.I~I.Txrltrxosa, B. A.~I,onronnocx, T. I'.}KypaB.rre-
Ba, P. H. I{oBa~IeBCxan,'T. FI. ICypeabrxxa, ,t[oxn.
AH CCCP, 129, 1068, 1959.
_ Summary
Crystalline 1=4 trans-polymers of butadiene and isoprene of
regular structure are formed in by polymerization of dimes
on a chromic catalyst (chromium oxide on alumosilicate).
1-4 trans-Polybutadiene with a specific, weight of 1,015 has
crystalline modifications melting at 75 and 135? C. They 1-4
trans-polyisop'rene resembles natural gutta-percha.
13
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~tihen a-butylene undergoes polymerization do the same cata~
]yst, a crystalline polymer is formed of specific weight 0,96 and
melting point ca. .140? C.
Impairment of the 1-4 trans structure by copolymerization
of butadiene or isoprene with other compounds leads to a loss
of capacity for crystallization and to transition to the high j ela=
stic state.
The butadiene -isoprene copolymer contains about 55
butadiene links while preserving the 1-4 trans structure of th'e
chain and has a glass temperature of ca. -90? C, coinciding
with the value calculated on the basis of a linear relation between
the copolymer composition and the glass temperature. ` '
By copolymerization ethylene units could be incorporated in
the trans-polyisoprene chain to the extent of ca. 40 mole%. The
polymer formed has a glass temperature of -76? C as compared
with -71? C for 1-4 polyisoprene. ?
Polymerization of butadiene induced by the cobalt,oxide-die-
thylaluminumhalides proceeds at a high rate already at 0? C.
.The polybutadiene formed has predominately 1-4 links ?of cis
configuration (about 85%) and only a small quantity (5-r8%')
of 1-2 links. Owing to the high content of 1=4 links the polymer
has a glass temperature as low as -115? C.
Unlike organometallic -titanium tetrachloride systems,
interaction. between cobalt oxides and organoaluminum compounds
in the temperature range 0 to 80? C is not accompanied by
formation of gaseous hydrocarbon products. .
Resume
Au tours de polymerisation des dienes sur le catalyseur,-
1'oxyde de chrome sur 1'alumosilicate, -~ se forwent 1,4-trans-
polymeres cristallins a structure reguliere de butadiene et ~d'iso-
prene. 1,4-trans-Polybutadiene a poids specifique 1,015 a deux
modifications cristallines a temperature de fusion 75 et 135?. Le
1,4-trans-polyisoprene.est analogique a la gutta-percha naturel~le.
Par suite de, polymerisation de butylene sur le meane ?cataly-
seur on obtient le polymere cristallin a poids specifique '0,96~et a
temperature de fusion 140? environ.
La violation de la structure de 1,4-trans-chaine par .moyen ode
copolymerization de butadiene et isoprene avec d'aut~res compo-
ses aboutit a la perte de capacite .du polymere a la cTistallisation
et a son transfert en etat de haute elasticite.
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Le copolymere de butadiene avec 1'isoprene contenant envi-
ron 55% des motifs butadieniques en gardant 1,4-trans-structure
de chaine a une temperature de vitrification .pres de 90?, qui
coincide a la valour calculee, en partant de 1'existance de depen-
dance lineaire entre la composition de copolymere et son tempera-
ture de vitrification.
Solon la methode de copolymerisation on a introduit daps la
chaine de trans-polyisoprene vers 40% mol. des motifs ethyleni-
ques. Le polymere obtenu a la temperature de, vitrification -76?
contre -71? pour 1,4-polyisoprene.
La polymerisation de butadiene sous 1'influence du systeme
qui est compose de cobalte et de halogenures de diethylaluminium
se deroule a une vitesse considerable memo a 0?. Le polybutadiene
obtenu a essentiellement 1,4-cis-configuration des motifs (a peu
pres .85%) et seulement un petit nombre (5-8%) de 1,2-motifs.
A cause de haute teneur en 1,4-motifs le polymere a une basso
temperature de vitrification (vers - 115?).
Contrairement aux . systemes, qui component les composes
metalloorgani,ques et le tetrachlorure de thane, 1'interaction
entre les oxydes de cobalt et les organo-aluminiens dans les in-
tervallesdes temperatures de 0 a 80? nest pas suivie par la forma-
tion des hydrocarbures gazeux.
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pocTx o6pbisa ueIIx [5-9] IIo Nlepe aaTpyRHeIIHSI AHC~c~yaliII cso-
6oAxbix paRllxasos B oTBepxrRaiox~ei~cx peaxuxoxxoH cllcTerie.
OAxaxo,ecnx B c~Iy~ae ~IIIIIel~xoi~ IIo~IIIMepxsauIIx McTK~iMeTaxpII,aa-
Ta Ha6~IioRaeTCSI ~ixIItb IIpII a~25-30%, To B e.iry-
~Iae Tpexriepxoi~ IIonIIMepxaauIIx IIOJIx3C~IIpaI(pII7IaTOB BFI3iCOCTb
II3MexFIeTCFI HaCTOJIbiCO ~bICTpO, TiTO aBTOycxopeHxe CTaHOBIITCFI
IIpal{TYI?IOCI{x 3aM0THbIM B CaMOM HatlaJle IIpeBpaH~eIIIIFI (pIIC. 1,CL) 1.
TaxIIM O6pa3OM, IIl]OI~eCC C CaMOI'O HaiIaJla pa3BIIBaeTCFI xe-
crai;xoxapxo, TaIC icax B XOJ~e IIOJIxMepII3al~xII IIpOxCXOJ~xT Ha-
ICOIIJIexIIe paJ[IIHaJIOB - HOCYITeJIeYI I7exei3. KOHB;eHTpaI~xFI IIO-
CJIeJ[HIIX B 3OIIe peal{I(xx Ha r~Iy6oxxx cTaAIIxx IIonxMepxsaullli
paBHa 1016-1018 IIapaMarHIITxbix xacTxu xa 1 c.,u3 (IISMepexo
McTORoM OIIP Ha o6pasuaX TpIISTx~Iexr~Ixxo~IbAxMeTaxpirnaTa,
oTBepalcRaBIIixxcx IIpx 20-25? B IIpIICyTCZBIIII ---1 % IIepexllcx
6eH3ox~Ia II ---1 % RIIMeTx~iaHxsKxa). ~opnia cxrxana ~IIP A.nx
HaxaIIalxBaioII~erocsl paRIIxa~Ia HpaxTIIxecicx xe oT.ax~IaeTCSI oT
Taxosol~ Rnx IIo~IxMeTII~iMeTaicpx.rlaTxoro paRIIxaaia.
Paa6aB~IeaHe peaxz~HOHxo~I cgcTeMbl HeBSIaxI3nl pacTBOpIITe-
JIeM yMexbIIIaeT CICOpOCTb IIOJIIIMepx3aI~xII He TOJIbHO BCJieJ~CTBIIe
BJIIISIIIIIfi paCTBOpxTeJISI Ha CICOpOCTb OTj(eJIbHbIX 3JIeM0HTapIIbIx
aI{TOB~ 3T0 yMOHbIIIeIIxe O6yCJIOBJIeHO, B 3HatIxTeJIbIIOx CTEIIOHx,
cHIIxcexxeNl IIcxoAxox BuaxocTx pealcuHOxxoyi cxcTenlbl, a Taxaxe
cxIIaxeHxenl exoco6xocTH excTeMbl is cTpyicTypoo6paaoBaxIIio,
o ~Ienl csxAeTe~IbcTByeT yA~IHHeHxe HepxoRa xxRyxuIIII (pxc. 2,6}.
c ytilexbxiexxeM, xoHi;ellTpaRIIII o~iIIroMepa B pacTBOpe. PTO o60-
axa~aeT, IITO ~enl nleHbHle cxoco6xocTb xo~IxMepxsauHOxxO~I cx-
CTOMbI IC o6pasoBaxIIlo cTpyxTypbi, CTa6xJIII3IIpyI0II~eI3 CBO6OJ[Hble
pa~xlCaJIbI, T0M 6OJIee J;JIxTeJIbHOe BpeMx Tpe6yeTCx J~JIFI J~OCTII}xe-
HHSI yc.noBHi3, B xoTOpbix cxopocTb .o6pblBa ueIIII ,nxMHTllpyeTCSI
RIIC~c~yaxe~i. I{ax BHAxo II3 pxc. 2, e, c yse~IHUexxehi BslaxocTII pac-
TBOpxTeJlfl CICO1lOCTb IIOJIIIMepH3ai~xx IIpI3 IIpOiIxX paBHbIx yCJIO-
BIISIX pe3K0 BO3paCTaeT.
I Ha scex pgcyaxax r/rMBKC oTaoiuexlle Texyu~e~ rny6~lar~ npe-
Hpangeagx x Nlaxcxnlanaao~.
P~3c. 1; a, 6. IIonHMepl3aaisxx uonx3c~Bpaxpll~aTOS rlpx 25? /'
a- s 6Jloxe;xox>;exTpaljllH HxIIgIIaTOpa: 0,25 % nepexIICFI 6exaoIIJla H 0,25?/? JjIIMETHJI-
aHIIJIIIHa; 1 - j[HMETaHpIIJIaTTpIIOTIIJIEHPHHHOHb; 2 - Mj[ci~ I-I; 3 - Mjjcl~-2 ;: 6 -
Il paCTBOpe 8 6eHaoJIE; 1 - xoxueHTpagIIH MZ[~-1 32 ?/p, HCpCIiI3CH 6exaoH.na i "/o ,~ pHMC-
TIiHflHNHIIHa I%; 2 -xOHI[EHTPa~H MZ[$'2 32%,. IIepexIICII 6eH30IIJIa 1%, jl.TitMCTHJI-
aHIIHAAa I ~/p; 3 - xOHI[CHTpa$7H Mz[~-L 49 %,HepexxcH 6exaoH,na 0,5%,TiHMCTH711HHJIHHa
0,5%; 4-xOHIjEHTpaIpIH MZ[~-2 43%i HepexIICII 6eHaoIIHa 0,5%, AIIMCTHJIBHNJIIIb~~ 0,5%~
5 - xOHIjEHTpaL[IIA Mz[4>'2 25"/p; IIepexIICII 6eHaoHJIa ~,5~/p; J[FiMCTSISIaFIISJIHH~~ 0,5~/a;
G - xOHIIEHTpaI~I1H JjIIMETBIipIIJIBTTpIIBTIIJIeHCJIIIxOJIH 35?/p, HCpOKHCH 6CH30H7Ia, Q,5%,
J[IIMeTHJIaxHJIIlxa 0,5%.
%~
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
100 170 140
BPPMA, M11H
ZO 40 60 BO BpeMA, MuN
6
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
Qg
0,8
QB
0,5
?ua d
~Q3
?QP
160 /$D
BpeMn, ,irun
U
PflC. 2,'a, 6, a. lio.rr~3Mepxaauxx A~Me~raxph.nam~~pn3Ti~nearnAiconx IIpx 20?.
a - a 6noi~e; .H 'HpilcyTC~rsiz~i -'>ar336HTOpa- 6exaoxxaoaa; aoauexTpagHti aHagHaropa
2% HepeHHCli 6eHaoHaia, 1% jjHMe~'a~zaxH~iHaa; 1 - 0,00385, 2 - 0,0074, 3 - 0,0138.
4 -.0,032, 5 - 0,064% HarH6HTOpa 6eltaoxalloaa; 6 -- H pacTSOpe a 6eaaone; xoagexTpa-
[jHH HHI7IjISaTOpa: 2%IIepCF{HCIf OCA:301ISIa, 1 % JjHMCTI3JIaHHJIHHa; HOHIIeHTpaljHa GeH 80Jta;
/ - 0, 2-20, 3 - 40, 4 - 60,':5 - 80%;
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
f/~MCKC
,,o r
16 YO If
Bpe,vA, MuH ,
a
Pnc.l, a - a pacTxope; 1 - t;ongercTpaAnn s nonxAli3Tn.nexnnxkoIIb~TanaTe omtro;ae=
pa 2,5%, nepexxcx 6exaoxaca 0,24%, AxMeTxnaxxainxa 0,12%; 2 -xoxgexTparxxRs rpx-
aTnnex rn;ixoneonxromepa 2,5%, nepexncii 6exaox,na.0,5%,.PfnMeTxnaflxnxi[a; 0,i?fo
BJIlIFIH13e MdJILI~ J~OC)aBO1C 3I~1(~el{THBHbIX HIIi'I36HTOpOB (X~II~Of3') ,
Ha no~IHMepllaai~Illo HonIIac~xpaxpH,naTOS Tare oT~ix~aeTCSI~ oT
11a6.nloRaeMOro B c~Iyxae ~1gHe~Ixo~I 1io~Ignzepxaal~IIH. IIoxa~aao
1111,iITO B xoAe HaRyxuHOHHOro ueplloRa IIpx'iaHrH6ilponaHi#o~
rlo.n>MepHaai~xH cpeRHSlsi R.aHHa xIIHeTxxecxoii ~euII' Ro'cTxraeT
10 sBexbeB. IIpH ~Ilixel~xol~ Ho~lxMepHSai~Hr3 Taxtie iipesp~liteHxe
HO 11pHB0~(YIT K .yB0JII3LI0HHI0 BSI3HOCTH, a rlpg Tpexalepxb~i - ,3.a~,
MOTHO yBeJIH~IIIBaeT BA3xOCTb, BCJIeRCTBHe ilerO' 3J~e]V~IeII'Pai)13af1
peal{I~iIFI B3aHMOJ~e~ICTBI3FI CBO6OZ[HOI'O paJ~YIxaJIa C MOJieI{yJIOII
IIHP11OlITOpa IIepeXOZ(HT B J~H(~(~y3I3OHHyIO O6JIaCTb, 3(~1C~el{THBHOCTb
lIHr11611TOpa 3aMOTIIO CHH?xaeTCH II BM0CT0 OTileT7IHB0 BbIpa?xeHIIOTO
HepIIOJ~a HHJ.~yxI~HH Ha6JII0I~aeTCSi JIJ!IIIIb HepI3OJ~ 3aTOpMO?KeH-
Horo rlpellpau>;eHHSI (pHC. 2, a). IIocxonbxy ac~c~exTIIBHOCTb xHrH-
61ITOpa Ho Mepe xpespari;eHlls HaAaeT lace cH~lbaee,`x c~nixee,
HecnloTpx Ha ero upxcyTCTBge, Ha~gHaeTCSi aBTOycxopesHe 11
ReHCTBIIe HHrH6HTOpa, TaxgM o6paaoM, ge Ho~IepHblBaeTCa aaxa~lb-
HbIbI neprioRonl, a Ao~I~xao yiIHTbII3aTbcfi g Ha r~iy6oxgx cTaAaxX.
I~poMe Toro, upA o6cyx{ReHHH B~IgslHxsl HHrx6gTOpoB Heo6xoAi3Mo
IIpHH13AIaTb BO BHI3MaH1%Ie; iITO B HpYICYTCTBIII3 I3HrH6gTOpOB: yXyR-
H1aeTCSI CHOCOG$OCTb CI3CT0MbI 1{ cTpyxTypoo6pasosaHAlo. .
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
Ha pxc. 1,a HpeucTaBJlexbi IcHxeTx~Iecxxe xpxBble uJISI xoJlx-
niepxaauHx xoJlxa~iHpaxpxJlamoB B 6Jloxe B cpaBxxMbEx ycJlosxxx.
}'aaJlx*IUe B xx peaxuxoxxol~ crroco6xocTH, Ho-BxRxMOpIy, B sHa-
~IIITeJlbxox czexexH o6ycJIOBJIexo yBeJlx~EexxeM xcxoRxoK Bslaxo-
cTr~ H cnoco6HOCTx IC cTpylcTypoo6paaoBaxHlo Hpx yRJlHxexxH oJIII-
roMepxoH ueux, Tenl 6oJlee, ~ITO npH HoJIHnlepHSauxH Tex xce rIO-
JIRa~IxpaxpuJlaTOB B Hesslsxllx pacTBOpxTeJlxx, pasJIII~IIIe B IIx
peaxi;xoxxor~ cuoco6xocTH xxseJlHpyeTCx (pxc. 1,6).
TpexMepxblH npoRyxT HoJlxMepxsauliH xoJIII3(~IlpaxpllJlaTOB
xepacTBOpHnI, xe HJIaBxTCSI, RocTaTO~HO TepMOCTOex (Ao TeMxepa-
Typ 200-250?). Mexaxxxecxne csoHCTBa ero aasxcxT oT J;JIxHbI
uexx oaiHroMepa: B cJlyuae xopoTxxx ueueK o6paayloTCSI xpyxlcHe
TBepAble czexJla, B cJlynae onexb AJlxxxbEx (n~4) - aJIacTH~Ixble,
B cJlynae n = 2 xpo~Ixile TBepAble czexJla.
IIoaluac~HpaxpxalaTbl c n = 8 Hpx ozaepxcRexHx HpespaigalOTCx
B pesHxoxoAo6xbIl`I MaTepxaal, a IIOJIII3C~Hp c n = 20 HOJIxMepx-
syezcx TOJIbKO Ro cTy~xeo6paaHOro IlpoAyxTa. IIpeRcTaBJISIeT
axa*II3TeJIbxbII3 i~xTepec cuoco6HOCTb HoJIKac~HpaxpHJlaTOB c 6oJIb-
~III3M paaMeponl cJloxcHOac~xpxoro 6Jloxa (n~ 2) npespax~aTbcfl
Ilpx KOMHaTHOI3 TeMxepaType B OTCyTCTBHe xHHI~xHpyIOx[IIX CII-
CTeM B paCTBOpIIMbIYI B OpraHHileCKxX paCTBOpHTeJIHX, coRepxca-
I7~$I3 JjBOI3Hble CBSI3x, pa3B0TBJIeHHbII3 HOpOIIIKOOrOpa3xbII3 6eJIbII3
HOJIHMep. B ollpeAeJlexxblx yc.nosxslx x xxxuHxposaxxasl noJlxnze-
pxaauxx HoJIHac~xpaxpllJlaTOB NloaxeT 6bITb xaxpaBJlexa B cTOpoxy
o6pa3osaxHa aTOro pa3BeTBJlexxoro, xe HMeIOIi~ero Hoxepe~Hblx
csxae~ HoJIHMepHOro HpoRyltTa.
lIoJII3a~ixpaxpxJlaTbl B HpIlcyTCTBxx paRllxaJlbxo-I~exxblx xxx-
I[HaTOpOB COHOJIIdMepx3yIOTCII CO CTHpOJIOHI (40-50 ~~ ), MOTIIJIMOT-
aILpHJIaTOM H RpyrxMx BI4H.HJIOBLIDII2 MOHOD1epaMI3 C 06pa30Ba-
Ht~IeM HeuJlaBxxx II xepacTBOpxMblx xoJlHnlepxblx HpoRyxTOB.
YIcHblTaxgsl noJlxMepoB x coxoalxnlepoB xa oclloBe Hosblx TH-
nos. xoJlHac~xpaxpxJlaTOB HoxaaaJlx, PTO rlocJleAxxe nloryT xai3Tx
IIII3poxoe npxMexexxe B pa3Jlx~xbix o6JlacTSlx TexxxxH.
JIHTepaTypa
1. A. A. B e p p u fi, 1'. JI. 1T O II O B a, l3. ~. Y1 c a e B a, BbicoxoMo-
nex., coeR., 1, 951, 195,9.
2. A. A: Bepnliu, I'. JI. IIonosa, E. ~. 1~IcaeBa, J~ox.n.
Ali CCCP, 126, 83, 1959.
3. A. A. BepJtxu, T. A.lf ec~e.nu, 10. N1. ~xnnuiioacxatl,
IO. N1. C x B e p r yi x, BbicoxoMOnexyJl. coeA.,, 2, 411, 1960..
4. 1 . B. 1# o'p'o n e B, B. B. II a B Jr o ~, A. A. B e p ~ ii x, Bbicoxo-
n~onexyJl. coed., 1, 1396, 1959.
5. C. C.'M e A n e lI e B n gyp., ?I{. c~ua. ai+Mtix, 17, 391, 1943.
G. E. T r o m m s d o r f u. a., Makromolek. Cliem., 1, 169, 1.947.
7. R. N o r r i c 1~, R. S m i t li. Nature? 150, 336, 1942.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
8. TLans. Faraday Soc., 45, 323, 1949.
9. J. Amer. Chem. Soc., 73, 1700, 1951.
10. X. C. B a r A a c a p v sr ii. Teopxrr paRxxanbxoii nonxnrepxaagxx,
Mocxrsa, 1959, cTp. 14L.
Summary
The method of telomerization has been employed in the syn-
thesis of the telomer homologs of polyacrylateesters with succes-
sively increasing degrees of polymerization (n) and of telomers
.differing in the nature of the polyester chain.
Compounds have been synthesized of the general formula
CH3 CH3
CH2 = G - COORO - [- OCR1000R0 -]n - OC - C = CH2
where R and Rr are alkyl or aryl radicals and n=2, 4, 8 and 20.
tiVith change in (n) from 2 to 20 the structural viscosity of the
polyacrylateesters increased from 150 to 8000 centistokes (20?),
,the specific gravity from 1.213 to 1.308 'and n~ from' 1.515 to
1.5479.
The presence of double bonds in the molecules. of the poly-
acrylateesters synthesized made it possible to carry out their
polymerization (hardening) in the presence of radical chain ini-
tiators with the formation of glassy or elastic, insoluble, non-
melting polymers of sufficient thermal stability and endowed with
a number of valuable properties so as to be of considerable practi-
cal potentiality.
The changes in physical properties of the reaction system (gela-
tion, gradual increase in density and finally the formation of a
glass structure) in the course of the polymerization beginning
from the very early stages (the gelation point is reached at 5-
10% conversion) are responsible for a number of specificities
in the kinetics of the hardening of polyacrylate esters. Owing
to this we undertook a detailed investigation of the polymerization
kinetics under widely varying conditions. Polymerization in bulk.
takes place autocatalytically since with increasing degree of
structuration in the course of polymerization the rate of diffu-
sion of free radicals diminished, leading to a decrease in rate of
chain termination. The rate of reaction begins to diminish mar-
kedly only at large extents of polymerization.
A study has been made of the effect of diluting Che reaction
mixture with an inert solvent, of the initiation rate, nature of
the initiating agent, temperature, chemical structure of 1;he ini-
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tial polyacrylate ester, .as well as of the addit,iou of inhibi-
ting agents on the polymerization l~inetics. The results obtained
have been discussed from-the standpoint of the capacity of
the system for structuration under, the various conditions of
reaction.
The heats of hardening of the polyacrylate esters with succes-
sively increasing distance between the terminal double bonds
have been measured and their values have been discussed with
respect to the reaction mechanism. '
Dans le. travail une methode de la telomerisaCion de
a ete utilisee pour la synthese des telomeres -homologues
des acrylates polyesteriques avec la croissance successive du
degre de polymerisation (n) ainsi que des telomeres differencies
selon la nature de chaine polyesterique.
On a obtenu des composes ayarrt une formule generale:
CHs CHs
C[3z = C - COORO [OCft1000R0]n OC - C = CHZ
toil R et Ri sont des radicaux alcoyliques et aryliques avec
n - 2, 4, 8 et 20).
Si n varie de 2 a 20 la viscosite structurelle des acrylates
polyesteriques s'accroit de 150 a 8000 centistocks (a 20?), le
poids moleculaire, de 1.213 a 1.308, nD de 1,515 a 1.5479.
L'existance de doubles liaisons daps les molecules d'acrylates
polyesteriques synthetises . a permis de les polymeriser (durcis-
ser) en presence des initiateurs radicalaires en formant des
polymerisats vitreux et elastiques, insolubles, infusibles, asset
thermostables et possedant un complexe des proprietes physico-
mecaniques precieuses ce qui donne la perspective pour leur
utilisation industrielle.
Le changement des proprietes physiques du systeme reaction-
nel (formation du gel, 1'accroissement successif de . sa . densite
'Pt, enfin, formation de structure vitreuse) au tours de polymeri-
sation commendant daps les premiers stages de reaction (le point
de formation du gel a lieu au degre de conversion de 5-10%)
cause toute une serie de particularites cinetiques de durcisse-
ment des acrylates polyesteriques, aussi .aeons-nous entrepris
une etude detaillee de la cinetique de polymerisation. dans des
conditions largement variees.
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La polymerisation en bloc s'effectue autocatalytiquement car
au fur et a mesure d'elevation du degre de formation de structure
au cours de polymerisation la vitesse de diffusion des radicaux
libres diminue ce qui cause une.diminution de la vitesse de ruptu-
re de chaine.
Le ralentissement de la reaction ne devient sensible que pour
de tres hauts degres de conversion.
On a etudie 1'influence de la dilution du 'systeme reactiorrnel
par un solvant inerte, I'influence de la vitesse d'amorgage, de
la nature de 1'initiateur, de la temperature, de la structure chi-
mique de 1'acrylate polyesterique initial ainsi que 1'influence
des additions d'inhibiteurs sur le caractere de la cirietique de~
polymerisation. Des resultats obterius ont ete discutes du point
de vue de 1'aptitude du systeme reactiorrnel a la formation de
structure daps de diverses conditions d'execution du processus.
On'a mesure les chaleurs de durcissement des acrylates poly-
esterique avec une augmentation successive de la distance entre
doubles liaisons termineuses et on a discute leur valeur du point.
de vue du mecanisme de durcissement.
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STRUCTURE D):S POLYESTERS DURCIS
1K. Bohtla~+,eckJ, J. MGeziva, A. Sterrrschuss,
V. Zvo~e.ar
Parmi les substances macromoleculaires reticulees, ce sont les
produits de la copolymerisation des polyesters non-satures
~et du styrene lesquels semblent etre specialement propres aux
etudes de structure. Sous 1'influence des agents hydrolysants,
ils sont transformer en copolymeres solubles dont on peut de-
terminer la quantite et la composition. Pour raccourcir la me-
thode habituelle, on a essays de determiner, a 1'electrode de goutte
de mercure, les acides fumarique et maleiiiique rendus libres
pendant I'hydrolyse. Les resultats, publies dans une communi-
cation preliminaire, etaient superieurs de ceux de Hayes, et des
..resultats dune grande etude publiee par Funke. Afin de trouver
lies raisons de ces differences, on a effectue des analyses compara-
tives a 1'aide dune methode independente. C'est pourquoi qu'on
a modifie la methode de Funke: la solution de KOH dans
1'alcool benzylique est; remplacee par une solution glycolique ce
qui permet d'effectuer 1'hydrolyse a une temperature plus ele-
vee. L'hydrolyse achevee, la solution est.acidifiee et le copoly-
inere isole sous forme d'acide biers filtrable. On determine. la
composition de ce dernier par 1'analyse volumetrique des grou-
per COOH, sous controle conductimetrique. Les avantages des
:modifications sont comme suit: 1. Les produits d'hydrolyse sont
solubles dans le milieu glycolique, 2. la duree de 1'hydrolyse
est 4-6 heures, 3. 1'analyse volumetrique est plus vite que Celle
elementaire. En titrant 1'exces de KOH sous controle conducti-
metrique, on obtient. des points d'equivalence distincts, ce qu'on
ne peut constater pour les titratio,ns. potentiometriques ou visu-
elles.
Apres avoir separe le copolymere, on a estime les acides lib-
res fumarique et maleinique dans la solution filtree. Dans le
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bilan total (tab. 1) de ces'acides, on en marque 40-50%. Dans
le cas de glycolyse, ce n'est pas surprenant parce que 1'addition
vite des anions alcoyles a la liaison double fumarique est connue
?depuis longtemps. Les resultats de 1'hydrolyse peuvent titre
interpretes grace a 1'etude cinetique de 1'addit.ion d'eau lagnelle
a ete pu.bliee recemment par Erickson.
Determination des asides libres fumarique et maleinique
11,38
6,98
5,34
3,92
3,32
2,95
6,7L
4,75
5,34
2,92
1,53
1,21
4,G9
~i,06
2,75
2,76
1,40
1,06
En appliquant, a nos conditions, les constances de vitesse pu-
bliees, on obtient un degre d'addition de 50%, ce qui est en bon
.accord avec les resultats experimentaux. C'est par cette reaction
laterale que les quantites d'acides libres reductibles a 1'electrode
?de mercure sort rendues moires elevees, et par consequence,les
valeurs de conversion de copolymerisation semblent titre plus
?elevees. Voila pourquoi le controle polarographique etait mis a
part, et 1'analyse gravimetrique et conductimetrique appliquee
.aux recherches suivantes.
1. Tout d'abord, on a etudie le sours de la copolymerisation.
Suppose que les memes parametres gouvernent la copolymerisa-
Lion du styrene avec les diesters et polyesters fumariques, on a
?calcule la composition moyenne des copolymeres. Au debut de
la reaction, on a trouve un accord satisfaisant des resultats cal-
cules et ceux experimentaux (fig. 1). On se rend compte de ce que
?cette concordance ne demontre pas 1'identite exacte des paramet-
res des deux couples, mais on peut~supposer, pour raison structu-
relles, que les parametres reels ne soient pas trop eloignes. Cette
supposition permet d'interpreter les donnees experimentales
?d'une maniere qualitative. Aux stades avances de .reaction, la
composition des copolymeres trouvee' differe de la composition
?calculee. Les copolymeres sort plus riches en styrene. Voila
pourquoi la conversion finale des groupes fumariques ne s'ap-
proche .de 100% qu'aux cas exceptionnels dont 1'importance pra-
~tique est minimale.
2. Si le melange du styrene et du polyester est dilue par un
solvant, par un ester phtalique par exemple, les conversions
.augmentent, passent un maximum, et puffs reviennent aux valeurs
voisines ;de celles des melanges non - dilues. Cependant I'effet
du solvant n'excede pas 10% du maximum (fig. 2).
59
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
0.5 - K 1,0
rig. l . Copolymerisation du .styrene
avec un polyester Composition du co-
polymere en fonction de ]a conk=ersion
de monomeres
5,..... fraction molaire du styrene initial
5.... fraction molaire du styrene dins le
copolymere
K..... conversion des monomeres
0,5 Fo
Fig: 3. Gonversion des groupes funra-
~'iques (e) en fonction de la composi-
tion du, melange initial
r~,? .... traction molaire des fumarates ini-
tiale
Q.:.. mtslange dilu8 par DBF 20%,
-}-...... m8lange non-dilue
l0 20 ` 30
_. % DBF
Fig. 2. Conversiori des groupes
fumariques (e) en fonction
de dilution
DBF... phtalate de butyle
P'ig. 4 Gonversion des groupes fuma-~
riques (e) en fonction de composition
et de structure des polyesters
1-Courbe experimentale, 2, Courbe de
Funke, 3-Courbe calculee des maleates purs
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
3. Pour estimer 1'influence du composant polyfonctionnel, on
a polymerise un polyester avec le styrene, en proportions diffe-
rentes, dans un melange contenant 20% de phtalate de butyle.
La figure 3 represente la fonction reliant la conversion des grou-
ppesfumariques avec le contenu de ces derrieres dans. le melange
initial. On observe un point d'inflexion situe pies de F?= 0,43,
~ce qui correspond a la composition azeotropique du systeme
styrene - fumarate d'ethyle. Moins , elevees les conversions,
plus grande est la fraction molaire de polyester.
Si la fraction F? excede Celle du melange azeotropique, la
polymerisation des groupes fumariques doit se derouler exclu-
sivement au stade final. Cette reaction etant extremement
lente, la polymerisation est stoppee sans atteindre une con-
version complete. Si les groupes fumariques sort, au surplus,
fixees au reseau de polymere, leur mobilite, et par'consequen-
~ce, 1'a reactivite et la conversion finale sort reduites.
Si la fractionFo est plus petite que Celle azeotropique, les grou-
pes fumariques s'epuisent plus vite que le styrene.VSila pourquoi
an pourrait compter sur une conversion complete, si d'autres
facteurs n'intervenaient, en limitant par exemple la mobilite
des groupes et des radicaux. 'La mobility depend de la, densite
du reseau, laquelle est determine par la proportion styrene /po-
lyester et par la,structure de la chaine de polyester. Pour estimer
1'importance de ces facteurs, on a analyse ley polyesters contenant
des glycols et des asides divers modifiants en proportions diffe-
rentes. Les resultats en sort reuni dans la figure 4. Le role decisif
de la proportion styrene/polyester s'y. manifeste dune maniere
univoque tandis que la structure de la chaine de polyester n'exerce
aucune influence signifiante. .
4. La figure montre un accord avec des donnees de Hayes et
un desaccord considerable avec celles.de Funke. Afin d'expliquer
ce desaccord, on a d'abord compare la methode modifiee avec
~celle de Funke. Les resultats fournis par la seconds etaient un
peu plus bas: Comme ley resultats?de la methods modifiee etai-
~ent constatns independemment de la duree de glycolyse, la pe-
tite difference observes a ete attribuee aux pertes pendant 1'iso-
lation du copolymers d'apres Funke (tab. 2).
Cependant, cette difference est trop insignifiante pour qu'elle
puisse se manifester dans la conversion d,'une maniere remar-
~quable. Voila pourquoi it a fallu chercher une autre explication:
Les experiences de noire collegue Klaban ont demontre que.le
regime de polyesterification, specialement la temperature, exerce
une influence penetrants a 1'isomerisation cis-trans des polyesters;
plus elevee est la temperature, plus elevee est 1'isomerisation.
1)ans le travail present, ley polyesters ont ete prepares a une
temperature .de 230? C, et ils possedent une haute fraction de
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forme fumarique, 89% en moyenne. Au contraire, les produits~
de Funke ont ete~prepares a 100-130? C, et ils contiennent pro-
bablement une quantite considerable de liaisoz.is cis, c'est-a-
dire, des groupes maleiniques.
Les parametres du couple styrene -esters maleiniques favori-
sent 1'addition styrene -styrene de telle maniere que le styrene
soil epuise, quand la conversion des maleates n'atteint que 50`%,
comme le clemontre la courbe calculee pour le couple styrene -
maleate d'ethyle.
La courbe de Funke est situee entre celles des maleates purs et
Celle des polyesters preponderamment fumariques. On arrive a.
une conclusion vraisemblable que c'est 1'isomerisation incomple-
to qui reduit la conversion des polyesters.dans le travail de Fun-
ke.et qu'il faut respecter cette isomerisation daps toutes les etudes:.
Tomes resultats de present travail peuvent titre resumes en conclu
lions suivantes:
1: La glycolyse des polyesters, sous controles gravimetrique~
et conductimetrique, tilt plus vile et plus satisfaisante que_ le~
proces de la degradation au milieu d'eau ou d'alcool benzyliquo.
Elle peut titre appliquee pour les etudes cinetiques de' oopoly-
merisation.
2. La conversion finale, de copolymerisation des polyesters
depend de la proportion styrene/groupes . fumariques, de la di-
lution et du degre d'isomerisation cis-trans.
3. La structure du polyester n'exerce aucune influence signi-
fiante a la conversion..
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AsTOpec~iepaT
1'IccJieRoBaHHe cocTOIIT B. IIsyileIIIIII couoJilrniepxaauIIx cTIIpoJIa~
c xexacblII[exxblMll IIoJIII3(~IIpaMII nteTORonI, oIIllcaxxbl~I paxee.
1'Isy~IaJlocb BJinxHlle nioRHC~iiuHpyioBjHx, xenoJlHMepHSyIOH~IIXCSI
xxcJioT (c~TaJlesoii, xIITapxo~I; axAonieTxJiex -. TeTparIIRpoc~TaJle-
BoI~) xa nioJIOI{yJISIpxbie BOCa noJlIISC~xpoB. 1'IccJleRosaJiocb Taxalce
BJIIIxxxe ocJIa6Jlexxx c~yniaposblx cBSiaeii, o6ycJIOBJIexxoro xo-.
JIx*IecTBOM MoRIIC~III~I3pyI0ii[IIx xxcJloT, cTI3poJIa rI nJlacTxc~IIxaTO-
pa, H RJIIIxoi~ rJli3xoJleso~I z;eIIx.
YcTaxoBJlexo, ~ITO xoxuexTpaRIIx c~yalapoBbix rpyIIII COIIOJIII-
niepOB 6bIJIa BCOTJ~a niexbIIIe, HOM IIpeJ~Cxa3axHasl, IICXOJ~FI x3 COCTa?
Ba IICXOJ~HOx CMOCx. CocTaB COIIOJIgMepOB 3aBIICIIT OT HOHI[OIITpa-
I[IrII MOI~II(~IIL[HpyIOII~eiI IfI3CJIOTbI, OT ,L~JIIIHbI rJIIIKOJIOB013 I~eIII3 H
oT nloJlexyJlslpxoro Beca IIoJlxac~IIpa. Pa3JIIiuIISI npxIIxcaxbl cTe-
pllueexIIM ac~c~exTaM.
Pe3yJIbTc`1TbI IIpeRbIRyIl~xx pa6oT 06Cy?ESj{aIOTCH C 3TOIi TOiIKI[
spexgsl.
Summary
The copolymerization of styrene with unsaturated polyesters
has been investigated with the aid of a procedure described ear-
lier. The effect of non-polymerizing modifier acids (phthalic,
succinic, endomethylene - tetrahydrophthalic) on the molecu-
lar weights of the polyesters has been elucidated. A study vas
also made of the effect of weakening the fumaric links with respect
to the amounts of modifying acids, styrene _and plasticizer and
to the length of the glycol chain.
The concentration of fumaric groups was always found to be
less than that predicted from the initial mixture composition.
The copolymer composition depends upon the concentration of
the modifier acid, upon the length of the glycol chain and upon
the molecular weight of th'e polyester. The differences are ascribed
to steric effects.
The results of previous investigations are discussed from this
standpoint.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
HUBbI1~I CIIOCOS IIOJIYLIEHI~Ifi CJIO?KHbIX IIOJII~I3cI~I~IP06
H IIIX OJII~IrOM:EPOB
E. H. 3ure~6'eparc.ax, A. E. ~I#y/~uxoea,
S. M. Ten/~sixoe
(CCCP) ,
Ilpx BaaxMOuei~cTBxx xa xo~IORy xliTpx~IOB c. HCl x cllxpTanlx
06pa3yIOTCFI XJIOprI3J~paTbI I3MI3FI03(~I3pOB, rFIJ~pOJII330M K01'OpbIX,
I{aH x3B0CTH0, IIOJIyBaIOT CJIO?I{Hble 3(~xpbI:
IIpHBeRexxax peaxuilsl xcxo~Ibaosalia R~Ix xo~Iyuellrzsl c~IOx{-
xl~Ix xo~Ix3c~xpoB x xx o~IxroMepoB ria RxxxTpi~sloB, .r~Ir3xoneil 13
HCI. HaAo nonaraTb, ~ITO o6pasosaxxe co~Iel~ 13Mxx03(~xpOB, xa-
~Hxalonge~cx c BaaxMOReHCTBxx HxTpx~IOB x $Cl, xpoTexaeT B.
COOTBOTCTBYIII C OJ~xOI3 YI3 CJIeJ~ylOx~xX CXOM:
RCN -I-- HCI ~ RCN ? HCI ~ [ RC - NH H RC = NH] CI~ ~H [RC=N H ]+Cl--~
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
1VIbI HpeRHOJIOaI{IIJiII, iITO B CJIy~Iae HIITpIIJIOB, OOJIaJ~aIOII);HX B '
peaxz~IIxx, IIOZ[O~HbIX CI~iHTe3y raJIOHJ~rHJ;paTOB IIMIIH03(~IIpOB, BbI=
COROII peaxI[HOHHOII CII0006HOCTbIO (T: e., IIpH CIIJibH03JIexTpOOT-,
pHl~aTeJIbHOM OCTaTxe R), IICTIIHHbIYI MOXaHII3M B3aIIMOJ~eI3CTBIIA?
nreaxRy IICXORHbIMI3 I{OMIIOH0HT8MH OTpa}I{aeTCTI rJIaBHbIM 06pa30M
cxenlom (-2). B cJlygae axe HIImpHJIOB~ co cpeAHei3 peaxr~IIOaaoB'cno-
COCHOCTbIO H B ~IaCTHOCTII, aJIII(~aTIItIeCxIIX j{IIHIITpIIJIOB, XJIOpIIRbi
]IMOHIIIIXJIOpIII~OB I (cxeMa 3) SIBJIHIOTCH Ba1xHbIMII IIpOMeaxyTOtI-
?IbIMII IIpoAyxTaiilll peaxz~IIII. PasrpaxH~exlle Bo BpeiieHII npo~ec-
coB o6pasoBaHIISI xalopIIRoB IIMOHIII3xJIOpIIJ[os II HX. BsaIIMOAeI~cT-
BHSI CO CIIIIpTaMII II03BOJIHJIO HaM pa3pa60TaTb MOTOJ~bI IIOJIyiieHIIH
sJloprHRpaTOB IIoJIYIlIMIIHO3(~HpoB H i~x oJIllrorlepoil [2].
CIiHTea cJloaxablx IIoJIHac~HpoB IIposORIIJIII cJleRylozgxM o6pa-
aonl. PacTBOp RgHHTpx.na B ac~Hpe, RIIOxcaae HJIII RpyroM bpraHH-
iIECI{OM paCTBOpIITeJie IIpH ~-rJ~ HaCbIII~aJIII XJIOpHCTbIM BOJ~OpO-
~oM. IIocJle IIepeMeHIIIBaHIISI B Te~IeHIIe 1-2 xac. Ao6asJIxJI~I 3xBII-
MOJIHpHOe xOJIII~IeCTBO rJIIII{OJIFI II upoAoJlal{aJlx IIepeMeIIIIIBaHIIe
ewe xeci{oJlbxo xacos. 06pasoBaBIIlliecsl coJIII IIoJIHIiMIIIIOac~HpoB
HbIIIaAaJIH B ocaAox B BIIAe TBepAblx IIpoRyxTOB HJIH oTCJIaIIBaJIIICb
B BIIRe rycTbix axII~xoeTeil. IIo IIcTe~IeHIIII cyrox B IIpIlcyTCTBIHI
Hares B oTCyTCTBHe oeliosaxIIg IIpoBOAIIJIH rxApoJlHa:
4HC1
? NCRCN [?HO (CHz),,,~ OCI(CHZ)~ CO (CI-IZ)n, OH, 2C1- H2O
0 0
II II
HO (CHz),,i OC(CH2)n CO (CHZ)i20H.
YIa aAIIHOHxTpII,na, BBHRy IIs6xpaTe~Ibxol~ peaxuHOHHOCnoco6-
HOCTII IIpHCyTCTByIOII~I3X B H0M HHTpIIJIbHbIX rpyIIII IIpII rII~pOXJ10-
pxposaHIIx ,MOxcHO IIOJIyLIi3Tb C xOJlgileCTBel3HbiM'BbIXOJ~OM XJIOpgR
S-r;IIa$sa~IepHMOHHI~x~IOpIIRa. IIoc~IeAHHI~ oxasa~ICSI xcx~Ilo~-
TeJibHO yJ~06HbIM B xaiIOCTBe IIpOMeaxyTOiIHOrO IIpOJ~yxTa B pslRe
cI3HTeaoB. Paaee' H3 Hero 6bIJjII IIoJIyileHbl 8-i;xaIIBa~IepaMHA ~
a~IxII~IOBble 3(~Hpbl 8-ullaxsa~Iepgaaosol~ xxc~IOTbi [1]. B Roxna-
j~blBaeMOII pa60Te C 3xBIIMOJIHpHbIM B IIOJIOBIIHHbIM MOJIHpHbIM KO-
JIIItIeCTBOM a, w-r~Il3xo~Ie~I xepe3 COJII3 IIbIyIH03c~IIpOB IIoaly*Ieabi
cooTBeTCTBeHHO ' w-oxc~Ia~Ixx~IOSble 3(~JI3pbI b-uHassanepxaxoso~
xIIC~IOTbI g RII-(S-t;Haasa~IepaTbl) a,w-r~IHxo~Ieg:
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a
NC(CFI2)gC0(CHa)mOC(CH2),,CNI++ 2CI-
II II J
NI-I~ NHS
Hz0 ~ H80
~NC(CH~)4C0"(CH~);mOH' ~ ~ NC(CH2)4G0(CH2)mOG(CH2)9CN
~NC(CI-I ~)4C0(CH2),,~~OH ~+ CI-
II
U
XapaxTepHCTHxa HO~Iy*Ielillblx coeAHxexx~I ? HpxBeReaa B
Ta6aI. 2. Bice, yxas,aIIHble o~Illroi~epbl cHxTe3r~posaHbl HanIEI
Ta6nrcua 2'
XaparrepHCrnxn aonyve~Ifiwx.onFiro~cepoe
I YlaMepeii0 ng~i? 25?
,;;; TaxH'M .OGpa'30M; B .3aBI3GIIDIOCTII OT COOTHOIIIeHIIH MexcRy JjH-
)IIfiTpIIJIOM, : FJIYIE{OJIOM I3 ~IC.l, peaISI~HH Me?ICj{y HHnIII MO?KeTObITb
,HBIIpaBJIeHa B' CTOpOHy CI3HTe3a HH3IfOMOJIOI{yJIFIpHbIX CJIO?I{HbIX
IIOJII43.(~ILpOB. ILJIH. ~pOTBETCTRyIOII(ILX OJIIIPOble.pOB. .'.'
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
;.Jix~.mepaTypa ,iil:~~.~.j~.? ... ~.'
1. L. H. 3 n~ b 6 e p hi a a; A L. if y"n ii x o u a. 'iii o6ii~. Yr~nnx,l~;'
T694, 3039, 1959; ~. ' ; j i .; ~ ~ ,,
2. ~.. H. 3 it n b 6 e p az: a u, : H. ' M. T o~n; a~; n ir.o u:! , BracPxorzan.r
coeA., 1, 93~, 1959. ,:; ~~.. ~ ~ ~ .
3. A. P i n n e ~~, r. Klein. Ber. 10, 1889, 1877.
Until recently the salts of iminoesters were prepared 'iir gene-
ral only from monofunctional nitriles:and alcohols`::In the papers
published by us in.1959 we. brave shown that chlorides of imonium~;
_ chlorides, produced by interaction between nitrites and . hyd~rogerl
chloride in.1 : 2 molar ratios,will on reaction inthe cold~with equi-
valentamounts of primary.alcoholsgive; ahigh yield'af iniino esters
chlorides. that in the presence,.of .water will hydrolyze .to ahe.:esters'. i
Summary
rtc- N-I-aIIC~~II~ C1,~J.CI= rz_?H "L`~co~~~~ C1~1~, ? ,,...
-~ RC -~- NI34C1
I
o r~~
Air investigation into the. mechanism of reaction between nit-
rites, hydrogen chloride and alcohols led to the synthesis of imino-
esters using bifunctional reactants and thus to polyiminoester
halohydrides and to the products of their hydrolysis, polyesters.
The method developed differs from the conventional synthe-
sis of polyesters in its .being based on a reaction. heretofore not
used f.or the synthesis of polymers. Moreover the reaction is car
ried out in the cold, whereas, ordinarily, elevated~temperatures~
are used for obtaining polyesters.
Depending upon the reactant ratio, from. dinitriles; glycols
and hydrogen chloride new low molecular. polyesters (M 1000-~
1900) have been obtained with nitrile and alcohol terminal groups.
First o# all in the series of dinitriles and glycols ~ containing ali->
phatic and .aromatic radicals ui,w'-dioxyalky esters of dicarboxy-'
tic acids have been synthesized. Owing the selective reactivity
of the nitrile groups. from adipodinitrile besides thedoles' bhe
heretofore unknown w-oxyest;ers of S-cyanovalerie acid and glycol
di (S-dicyanovalerates) have been obtained.
_ v
=rr o
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The molecular weight of the, polyesters was determined visco-
metrically and, was calculated from the results of analysis of the
terminal groups. The results obtained in both cases coincided,
what, in particular, indicates the practical absence of ring sys-
tems in the products.
Resume
~? 'Jusqu'~ present des sels d'imino-esters etaient obtenus
d'habitude seulement en partant de nitriles monofonctionels
et alcohols:.
- : Dans ~ nos articles; publiees en 1959; noun aeons montre que
les produits d'interaction des nitriles .avec HCl en rapport 1 : 2
(les chlorures d'immoniumchlorides), en reagissant a froid avec
des quantites equimoleculaires des alcohols primaires, donnent un
grand rendement d'imino-esters hydrochloriques qui 'en pre-
sence d'eau se hydrolysent en formant les esters:
NH2- +
// -R'On
RCRC = N.~- 2HC1 ~_' RC Cl .,
C1
NHS + ~ 0
// ~ -xYo
RC I Cl- .-. RC -}- NH4CI
L'examen du mecanismo de la reaction entre nitriles, HCl et
alcohols permet synthetister des sels d'imino=ester en utili-
sant les produits de depart bifonctionnels et d'obtenir ainsi les
hydrates des halogenures de polyiminoesters et. produits de leur
hydrolyse,- les polyesters.
La methode de preparation des polyesters differe des methodes
habituelles a cause de ce qu'elle se base. suT la reaction non-utili-
see jusqu'a present pour 1'obtention des composes polymeri-
ques. En outre, la synthese s'effectue a froid, tandis qu'habituel-
lement on obtient les,polyesters a temperature eleyee.
A partir de dinitriles; glycols et HCI, nous aeons obtenu, se-
lon ies rapports des composants, les nouveaux esters a poids
moleculaires relativement bas (1000-1900), avec groupes nit-
riles et alcoholiques termineux.
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En premier lieu, a partir de la serie de nitriles et glycols,
contenants les radicaux aliphatiques et aromatiques, on ete
abtenus w,w'-esters dioxyalcoyles des acides dibasiques.
A cause de r~activite selective des groupes nitriles, a partir
de dinitrile adipique, outre des dioles, nous avons obtenu avec
un grand rendement des w - oxyesters de - 1'acide S-cyanovale-
rianique et di-esters S-cyan-valerianiques des glycols-a, w,
inconnus jusqu'a present.
Le poids mol~culaire des polyesters etait dStermine par voie
viscosimetrique et calcule a 1'aide des resultats d'analyse des
groupements termineux. Dans les deux cas nous avons re~u les
resultats coincidants, ce qui indique a 1'absence. pratique des
systemes cycliques daps les produits obtenus.
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L''ANALYSE DES POLYESTERS RETICULES
M. Bohilanecky, ~. Stex~aschicss
Les produits de copolymerisation des polyesters non-satures
avec Te styrene ont ete degrades par le 1~OH, et les acides fuma-
rique et maleinique, rendus libres, ont ete determines a 1'elec-
trode de goutte de rrlercure. Les resultats de ~cette methode indi-
quant un degre de reaction plus eleve que celui trouve par d'aut-
res auteurs, on a fait des analyses comparatives, utilisant la
m^thode de Funke modifies. On effectue la degradation au milieu
glycolique pendant.4-6 heures. Apres avoir determine le poids
du copolymers gravimetriquement, on en estime la composition
en titrant des groupes carboxyliques. Les resultats correspon-
dent avec ceux de Hunter et, avec certaines limitations, avec
ceux de Funke. Toutefois, ils sont plus bas que les resultats de
1'analyse polarographique. La difference en est attribuee a
]'addition d'alcool a la liaison double fumarique.Cette explication
est fondee sur les mesures cinetiques.
La methode decrite est plus vite que celles utilisees jusqu'a
present; ells peat etre appliques aux etudes de structure des po-
lyesters reticules et des processils pendant la reticulation.
Aszopec~epaz
IIpoRyxzbl cono~Ixhleprlsanxll xexacbiu~exxblx uoalnac~xpos co
CTIIpOJIOM Reczpyxzypxposa~Ill eRxxM xa~Ix, x ocBO6oxcRalolttllecx
c~yMaposylo II rza~IexxoBylo xIlc~IOZI~I onpeReasI~III nonxporpac~x-
uecxx. Pesy~Ibzazbl noxasa~Ix, uzo czenexb npespau~exxx 6o.aee
~3blcoxa, ueM Hal~Rexxau RpyrHMII aszoparlx, iipxueM 6blalx cAe-
~Iaxbl cpaBxxze~Ibxble axa~Ixsbl MezoAonl ~yxxe (sxAoxaMexex-
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
xblM). J~ecTpyKi;IIlo ocylgecTB~Ix.nH B r.aIIxoaleBOi3 cpeue B Te-
=IeHIIe 4-6 uacoB. IIoc~Ie onpeRe,neHIIH Beca cono.aHNlepa, co-
cTaB oi;eaIIBa~Ig TKTposaHllenl Kap6oxcll~Ibxblx rpyuH. Pesynb=
TaT?bI COOTBETCTByIOT HaI3J~eHHI~iM X,aHTepOM, II, C HOKOTOphIMI~
OrpaHIIUeHIIxMII,- pe3yJIbTaTaM ~yHKe., QI;HaKO OHII HII]I{e, =ieD~
pe3yJibTBTbI IIOJIFIpOrpaf~II=IeCKOPO aHaJIII3a. Pa3HIII~a OTHOCEHa
3a C=IeT IIpIICOeRIIHOHIIFI CIIIIpTa K J~BOI3HO73 CBH3II C~lyMapoBOII KIIC=
.IIOTbI. e~TO o6~HCHeHxe OCHOBaHO Ha K~IHOTII=IeCKIIX II3MepeHIIHX:
OIIIICaHHhII3. McTOA'61>ICTpee, ueM IIpIIhIeHFiBIIIIIecSI Ro cgx IIop
OH BIO}IfeT IIpIIMOHFITbCH K II3yHeHIIIO CTpyKTypbI CII[IITbIX IIOJIII3C~)II~
pos H K IIpoi~eccy,.upoxcxoRslu~enly Bo Bperlx cHrxBaHIIx.
Summary
Products of the copolymerization . of unsaturated polyester
and styrene were decomposed by potassium hydroxide and the
liberated fumaric and malefic acids were determined polarogra-
phically. The results showed that the extent of conversion is higher
than that found by other authors,. comparative analyses being made
with the aid of a modified Funke method. Decomposition was
carried out in a glycol medium for 4-6 hours. After the gravimet-:
ric determination of the polymer weight the composition was
evaluated by titration of the carboxyl groups. The results are
in agreement with those obtained by Hunter and with some'
restrictions with those by Funke. However they are lower than
the results obtained by polarography. The difference is ascribed
to the addition of alcohol to the? double bonds of fumaric acid.
This interpretation is based on kinetic measurements.
The method described is faster than those employed heretofore.
[t may be applied in studies of cross-linked polymers: and of
the cross-linking process.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
O CYIHTE3E H CBOI%ICTBAX IfPIICTAJIJII~IiIECICI~IX
IIOJII%IMEPOB TI~IIIA IIOJII~I-n-KCI~IJII~IJIEHA
H IlOJII~IcI~EHI~IJIEHMETI~IJIA
A. A. Baxuceicam, E. II. Me/c~~tuxoea,
D7. P. I# paxoescx,
Jl. B. liyxapeecc, I'. A. I'.2a8xoecxuu
(CCCP)
C ue.nblo IIoaly*IeHIIx HonftMepxblx yr~IesoRopoRos c IIoBbIIIteH-
HOI3 TOIIJIOCTOI3ICOCTbIO 6bIJIH IIpOBej[eHbI OIIbITbI IIO CHHTe3y JIH-
$eHHbIX IIOdIIIMepOB peryJISipAOrO CTpOeHIISi TI3IIa IIOJIIIKCgJIIIJIeHa
I x Ho~IHC~eHxnellMeTllna II,
(- CH~ArCf-I2-),1 I- ArCH2 ] ,~ CHZ = ~ ~ -CHZ
~ -~
I II III
coAepsxali;IIx apoMaTIIxecxIIe ullx.nbl B ocaosxou 1;eIIg. IIo~IIIMepbl
IIepBOro TftIIa, coAepxcaII~IIe CHz-rpyIIIIbl B n-IIOJIOHfeHIII3, 6bt~Ix
HeRaBao IIo~IyeeIIbl IIIBapueM [1] II RpyrIIMft aBTOpaMII IIpII Bblcoxo-
TeMIIepaTypxoM IIIIpo~III3e n-xcH~IO~Ia II Hexozopblx ero IIpoII3BOR-
HbIX B pe3yJibTaTe IIOJIYIMepII3aI;HI3 JIeTyzIIIX IIpOMe?ICyTOiIHbIX
xgHOIIAIIbIx yralesoRopoRoB TIIna n-xcII~III~Ieaa (III). 3TH IIo~III-
Mepbl oTnftxaall~cb 6onbIIlog TeHReH~fte~I x xpxcTa.n~III3auIIII, BbI-
COKOI3 TeMIIepaTypOi3 IIJIaBJieHIIFI (f[aIIpIIMep, OKOJIO 40~~ B . CJiy-
llae IIOJIYI-n-IfCIIJIIIJIeHa) YI He paCTBOpfIJIIICb B HI33KOHIIIIFIII~IIX
pacTBOpftTe~Ixx. ORxaxo IIOJIy~IIITb 3TI3M IIyTOM IIOJIIIMepbI I ft3
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THJIHa(~TaJIIIHa He yJ;aJIOCb [2] OtIeBIIj(HO BCJIeJ;CTBIIe H0B03M05IC-
IIOCTII o6pa3osaHftsl IIpoMexcyTO~Ixblx xxHOIIRHbtx nloxoMepoB ftBII
IIX HOCTOI3ICOCTII B yCJIOBHFIX IIIIpOJIII3a. TaxIIM 06pa30M, paCCMaT-
pIIBaeMbIYI MOTOJ~, IIO-BIIJ;IIMOMy, IIpIIMeHI3M rJIaBHbIDI O~pa30M ]~JIfi
CIIHTe3a IIOJIIIMepOB I, COj{ep7lfaIglIX B ueIIII 3B0HbH n-xcx~III~Iexa
CHz~_ jCHz - II~Ix ero HpoIISBORxbIx, 3aMeBgeHIIblx B xApe.
Ffax IIoxa3a~IH BpayH FI ~apTIIHr [3], xacTftuHO pacTSOpi3Mbli~,
I:pIICTa.a~Illxecxlll~ IIonH-n-xcII~III~IeH, cxoRHbII~ IIo cTpoeIIIIlo H
CBOI3CTBaM C IIOJII3MepOM, O~pa3yI0II[HMCFI IIpH III3pOJIII3e, MOHCeT
6bITb IIo~IyxeH Taxxce no crloco6y Blopua, a ftMexao IIpII B3axMO-
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ReiICTBHII MOTaJIJIHilecxOPO IIaTpIISI c XJIOpIICTbIM n-KCIIJIIIJIEI3O\I
B xI3IISIII;eM xGI3JIOJiO HJII3 J~HOxcaHe
nC1CH~-~_~- CH2CI N~ [- CHL-~_~-CHz,n
ORHaxo sTa peaxul~sl, xoTOpaSI, IIo xaiIIIIM RaxHbIM [4], nerxo
IIReT B RHOxcaae yxce IIpH xorlIIaTHOI~ TeMIIepaType c o6paaosa-
xxeni ~Ierxo pacTBOpIIMOro B BbICOxOxHIIHII~IIX pacTBOpHTe~Ixx
IIo~IH-n-xcx~Ix~Iexa, Ro cxx IIop xe ~bIJIa IIcnoalbaollaIIa ANSI, cHH-
Tesa Rpyrxx IIo,aHMepoB THIIa I, xoTx Morna SIBIITbcx 6oSlee o6-
II~IIM MOTOJ~OM CHHTe3a TaxIIX IIOJIHMepOB. MbI pacnpocTpaIIx,nH
ee Ha J[HXJIOpDIeTIIJIbHble IIpoHaBORHble xexoTOpblx Rpyrllx apo-
MaTHUecxxx yr~IeBOAopoRoB, a IInleaxo n- H .~c-xcHnoSloB, RH~eIIII-
~Ia, AHC~eHH,naIeTaHa H Hac~Ta~Ixxa, paxee oIIHCagxble B nIITepaType
x IIMeBIIIHe cTpoexxe IV-VIII, rl~e
X = CHzCI
CH3 X X
_~ ~% ~~
X-~-~ -X (1V); ~ ~~ (V).
/\/ ~ H
CII~ CH3
X - ~-~-~ ~ - X (Vl);
~_~ ~~~
X -~_~- CHI -~~- X (VII); .
X -~`~- X X -/
Peaxi~Hlo uposoAIIaIH IIpII 20-25? B cpeRe RIIOxcaaa B IIpgcyT-
cTBIIH 1,5-xpaTxoro IIa6blTxa HazpHx IIpH xoH~eHTpa>~HH.AHxno-
pHRa, pasaol~ 0,7 Mo~Ix B 1 rc pacTBOpIITe~Ix. IIo~IIIMepbl BbIAe~Ix-
JIIICb H3 paCTBOpa IIo Mepe O6pa3OBflHIISi g, IIOCJIe raIIIeHIISI H3-
6blTxa HaTpIISI MOTaHOJIOM II yJ~aJIeHIISI HH3xOMOJIexyJlSipHbIX IIpfl-
MOCeII aljeTOHOM, IIpeJ~CTaBJISIJIII IIOTITH 6eCI;BOTHble IIOpOIIIxII yrJle-
BoRopoAHOro cocTaBa, IIIIOrAa coAepaxaBIIrIIe ranoHR. IIo.ayxexable
IIOJIIIMepbl o6xapy;xH~III IIpH peIITrexorpac~HxecxoM Hcc~IeAosaHIIH
HaJIHLIIIe xpHCTaJIJIH*rHOCTH ~CM. pIIC. 1 II 2~, CT8II0Hb xOTOpOH Ba-
pIIIIpOBaJIa B 3aBIICHMOCTH OT HX CTpOOHHSi. I{ax BHJ~HO II3 Ta6JI. 1,
OHH CIIJIbHO pa3JIII~IaJII3cb TaK9ICe IIO paCTBOpIIDIOCTH II IIO T. IIJI.
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cBixzble .TpexMepxble IIo~IIIMepbl, xe pacTBOpx~IIICb Aaxce. B xx~IISr-
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pexoRsl B xcIIAxoe cocTOxxxe, TorRa xax IIpoII3soAxble Rpyrxx
yr.aesoRopoAos pacTBOpsI~Ixcb B 6poMxac~Taxxxe. x IInaBII.aIICb,
IIepexoRx s IIoAsIIaxxylo xcxRxocTb. IIpx 3TOM IIpox3soRxoe-
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OL
6
l0 14
1R 27. 26 30 34 3B 42
T. IIJI. (130-135?), ~Ierxo pacTSOpx~nocb Raxce s xo~IORxoM xalopo-
c~opMe. IIpox3soAxoe Rxc~exx~IMeTaxa, e 6o~Iee xcxo sblpaxcexxoR
xpHCTaTIJIxiIHOCTbx), IIJIaBxJIOCb IIpx 250-255? x xaxxxa~IO pac-
TBOpFITbCFI B 6pOMxa(~TaJlxxe JIII]IIb IIpx 130?; IIpox3BORIIOe xce
n-xcxno.aa, o6.aaRax IIOJ~OCHO IIo.ax-n-xcII.aII.aexy 6o.ablIIOU Tex-
,I{exI~I3eI3 K xpHCTaJIJIg3aI~xx, IIJIaBxJIOCb OxOJIO 350?, T. e. xeCIfOJIb-
xo xxxce xoc~IeRxero, xo xa~xIIa~IO pacTBOpxTbcx. B 6poMxac~Ta.nII-
-xe To.abxo IIpx 235?, T. e, xa 25? BblzIIe, ~ieM IIo~Ix-n-xcx.aII.aeII.
LITO xacaeTCSI Mo~Iexynslpxoro seta pacTSOpxMblx xo~Ixnle-
'pOB; TO xaM IIOKa y~{aJIOCb OIIpeJ;eJII~Tb er0 (IIO PaCTy) JIFIIIIb B cJiy-
-xae ~nerxo pacTBOpIIMOro IIpox3BORxoro rw-xcxnona, IIpx~IeM B 3a-
?sxcgMOCTx oT yc~IOSxH o6pa3osaxxx IIo~IxMepa.ox Bapxxposa~I oT
1850 uo 4000:
LITO xacaezcsl IIo~IxMepoB TIIIIa IIo~Ixc~exx,nexMeTxna [-CsHq-
CH$-].~, To Taxoe cTpoeIIge paaee IIpHRasa~IOCb pacTBOpIIMbIH~
alerxoII~IasxxM IIpoRyxzaM IIo~IxxoARexcauxx x~IOpxcroro 6ex-
.3xala B IIpACyTCTBxI3 xaTaJlx3aTOjlOB tI~pKAe~Ix - I{pac~TCa. OR-
xaxo IIO. FIOBbIM RaxxblM 3Tx aMOpc~xble IIpoRyxTbl IIpeAcTas.nslloT
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~co6or~ IIOJIHMepbl, CxJIbHO pa3BeTB,neHHl~e BcneRcTExe MHOrOIfpaT-
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~ Rpyroi~ cTOpoxr~I AaBxo HsBecTxo, xTO apoMaTHSecxxe yr~feBORo-
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z~xH c c~opala.abRerxRoaf c o6paaol;axxeM RHapx,nMeTaxOB, a Taxaxe
10 74 7B 2Z 26 30 34 38 4P
PIIC. 2. IIonxhlep II3 AllhnopMeTxn-.n~-xcllnona
(ciieTO a - npii 20?; 6 - ^pa 100?)
C1fOJIOO6pa3xbIX .nerxo paCTBOpI311fbIX Hx3KOxnaBKHX, JIHOO He-
II.aafsxHx xepacTBOpHnfl~Ix HpoRyfcTOB, xoTOpble xacTO coRepxcaT
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~rIH~Iecfcylo HpHpoAy aTxx cMO.n ellje xeafbax cxHTaTb Bblsfcxexxoi,
xo IIx csoi~czBa x, B ~IaczxocTH, Hx Hecxoco6xocTb I{ xpxcTa.n~fHaa-
I[Hrf yxaal~IBaIOT xa xa.nHxHe cMecei~ HosfHMepoB Hepery.nxpxoro
cTpoexxfl.
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xHSI aBTOpaafx RaxxoH cTaTbx 6f~IJIx xocTaB~IexI~ oxblTbi xoxRex-
cauxx Hapac~opala c aponlaTHxecxHazH yr~felloAopoRanfH B cpeRe
lcxxxfr~eH neAflxoH yxcycxo~I xHCnoTf~I, coAepxcafueH xoxuexTpH-
poBaxxyfo cepxylo xlic~foTy. I~Ia .n~-xcH.nona, xceBRolcyMO.na Ii xac~-
Ta~fHxa 6f~IJIH Ho.ay~Iexvl Iuaaxox.aallxHe aMOpc~xlae, a H3 RHC~exx.n-
nfeTaxa H_RHC~exllafaTaxa - ~ICHRxHe cMO.nvI, pacTBOpHMble B .apo-
nfaTH~Iecxllx yr,neBOAopouax.OAxaxo xa n-ICCx.nona H Aypona s TeX
:1;e yc.noBllslx yRa~focb flo.nyxHTh Bbfcoxox,naBxxe xpxcTan7lx~fecxlle
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CsoiicTea nonn~repoa Tnna noun-n-xcnnnnena, pony
PacTxopxmocTb s a-6poMaacpTasinxe (B13)
CTpoexxe ssexa no,nxn~epxoi3 Bean
Ten~xepaTypa (?C)
nepexoAa no.nnMepa
~
xoxgexrpagnx
xac~a~exc~x
x pacTeop n xonn
~ecTSe
npx z. xnn.
2.5% ~ fo%
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230-
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j CHZ--
235
255
34
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JIerxopacTSOpxri
npx 20?
H3C~~~~CFI3
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~_~ ~-/
130
155
30
CHZ-~ ~-~ ~-CHZ-
\-/ \_/
Hepac~~xopnmi
-CHZ-~~-CHZ- ~
A. [IepacTxopnni
+
I
\-~
-~ ~
-CHZ-
~_/
I
~_ j -CHZ -
B. PacTSOp~ini
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T. nJL, ?C
TeMnepaTypa
TemnepaTypa HTOpo~l
HpxcTa.nJna~l-
IIpHMexaxxe
nepHOil
xpO3paYxOCT4I
npospavxocTU
(nOCJIC HOMyTHCHHfi~
HOCTb
420-435
405-420
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~o n nocne nepexpit-
CTaJIJIH3aIInli N3 a-I~~FI
345-350
350-355
-~-{--~-
To xce
130-135
-
~-
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J],eHiiH n3 XJIOpO(~lOpMa MC-
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250-255
250-255
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-}-
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310-315
305-310
liocJie 4-5 ~Iac. xnust-
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;ao~IxMepbl, pacTBOpxMSIe nxmb s Bblcoxoxxxsllgxx pacTSO-
pxTenxx I3 xalaBxBxlxecsl xpx 265 i3 350? (cM. Ta6n. 2 x pllc. 3
~I 4), PTO yxaablBaeT xa perynxpxocTb xx cTpoex>asl, T. e: xa
Rl 14 18 2?. 26 30 34 38
Pxc. 3. lIonIlNlep xs Aypona PI rlapac~opMa
20
6 1D l4 18 22 26 30 34 38
Pgc. 4. IIo~Ilcmlep xa Aypona H ~xx~IOpnleTxnRypona
IIOIITOpxenlocTV B xx ueHxx asexbe~I - Ar - CHz-, rRe Ar = A
n~III B:
cH3 cHs
. ~
/
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HNC CH3 CH9
IIo~IxMepbi Toro xce Tuxa, xpaxTx~ecxx ~,xRexTx~xble xo cBOii-
cTBaivl x pexTrexorpanlMaM c BbIHIeoHHCaxlibinlx, yRaaiocb uoaly-
~IxTb TaKHfe `IIyTOM IIOnIIIiOHZI,exCBI[HI3 B aHaJIOrx9xbIX yCJIOBHAX
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CBOFICTBa nonnniepos Tuna nonnnieTnnenc~iennna,
z~a n-xcnnona zi Rypona .
-A-CHz-
265
-A-CHz-
265
-A-CH2-
255
-A-CHz-13-
255
-C (-Iz-
PacTIIOp;I-
MOCTb II
aIIHa071e
3,6
4,6
4,2
8,2
AHz-}-CFIzO
AHZ-~A(CH2Cl)z
AH2-~A(CH2OCOCH3)z
AH2-~-B(CH2CI)2
BHz-}-CFIzO
AHz-~B(CH2CI)z
A H2-{-B(CH2OCOCH3)z
AHz-{-A(CH2C1)z '
AHz-~CsH4(CH2C1)z
-B-CHz-
-B-CHz-
-B-C H2-
=B-C H2-A-'
-CH2-
- B-CHz-C6H9-
-CH2
350
315
325
340
7,3
8;1
7,0
6,9 ,
n-KCx~io~ia x Aypona c xx Axx~iopMeTx~ibxblNlx x Axa~eTOxcriaie-
TxJIbHbIMx IIpOx3BOJ~IIbI111x IIO CXeMaM:
C Rpyrog CTOpOHbI 3Ty peaKuxio OKa3aJIOCb B03MOHCxbIM pac-
IIpOCTpaHIiTb xa ciiecx apoMaTx~lecxxx yr~IesoRopoRos c Axx.aop-
McTxJIbIIbiMI3 IIpoxsBOAxbinix yr.neBOAopoRoB Apyroro cocTasa x
IIO.nyuxTb TaISx11I xyTeni reTepoxonliniepbl Txxa [- Ar - CHz-
Ar' - CH2l,,, coRepxcax>;xe sBeHbsl RByx paaxbix yr~ieBORopoRoB,
xaxpxniep n-KCx.no.na x Rypo~Ia. IIo cBOHM c11oI~cTBani aTx xo.nx-
Mepbl oT.nx~a.nllcb aHauxTe.nbxbini cxoAcTBOni c ronioxo~IxniepaMx.
B tipoAyKTax coBMecTxo~I IIonxxoHRexcauxx yr~IesoRopoRoB
C J~xXJIOpMeTxJIbxblMx IIpOx3BOJ[HbIMI3 o6Hapyxcex x~IOp, cBxaaH-
xbIil ~OLIeBxZ(IIO B B13J~e ICOHI[eBbIX rpynx - CH2C1) B ICOJIIILIeCTBe
OT 4 J~O $ aT01VIOB Ha Ka?Kjl;ble 100 ap0!\IaTxLIeCKxX xRep I[eIII3.
B xonliniepax xce,xo~IyueHxblx IIa yr~ieBOAopoRoB x xapac~opnia x.all
J[IlaljeTOKCxxpOH3BOJ~HbIx yrJIOBOJ~OpOj);OB, IIO-BFI~{I311IOMy, x111eJII3Cb
KOHI~eBble rpyIIIIbI CH3000CHz-, IIORBepraBIIIIIECFI 011ibIJIeHIIIO
npx xarpesaHlill xo.nxnlepoB co cxxpTOiloi~ x~e.aoubio H coRepxcaB-
mxecsl, cyRx i~o ~xe~IaM onibineHxsl, B Iconr3~IecTSe oT 4 Ro 7: xa
~ ]1fe}xpyeapcAawil cl;Mnosnyn;, cexq;;R 1 97
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xaxsRble 100 apoMaTx~Iecxllx xRep uexx. 8TO aoRTBepxcRaeTCSI TeM,
uTO upx xoxRexcauxg Rypo.na c x36bITxoM xapac~opMa, xapxRy c
xo~IxMepoM yAa~IOCb BbIAe~Ixzb Axal;eTOxcxMeTx~IRypo~I x Roxa-
3aTb, TITO CIIxpTOBbII3 paCTBOp, IIOJIyiIaeMbIYI xOCJie OnIbIJlexxlI, CO-
AepxcxT COJIb JIeTy~Ie13 C IIapOM OpraxxileCxOx xxCJIOTbI B xOJIIITie-
CTBe, 6JIx3xOni x paCCTIxTaHIIOMy x3 TIxCJia OMbIJIexIISI.
Mo~Iexyalslpxbli3 Bec xoJly~Iexxblx xonxMepos xoxa eII~e ollpe-
J~eJIxTb He yZ(aJIOCb BcneRcTBIIe xx IIJIO:Y013 paCTBOpxMOCTx, IIO,
Cy]~FI IIO COJ~epSxaxxl0 XJIOpa B xOJIxMepaX x IIO KX iII3CJIaM OnIbIJIe-
HxH, Ox He IIpeBbIIIIaeT 2000-3000, scJlx cgxTazb, IITO xaxcRasl
Maxponlo~Iexy~Ia coAepxcllT To.abxo oAxy ~yxxurloxaalbxylo rpy~Iny.
JIsTepaTgpa
l.. int. S z w a r c, J. Polymer Sci., 6, 31,9, 1951; Nature, 403, 1947.
2. L. E r r e d e, B. L a n d r u m, J. Amer. Chem. Soc., 79, 4952, 1957.
3. C. J. B r o w n, A. S. Farthing, J. Chem. Soc., 1953, 3270.
4. A. A. BaxmeiiAT, E. II. Menbxnxona, JI. B. I~yxape-
s a, M. I'. 1~ p a rc o s sr x, ?itypn. nprrxJ~. xrrNrnx, 31, ].898, 1958.
5. H. C. Haas, ll. J. Livingston, M. Saunders, J. Poly-
. mer Sci., 15, 503, 1955.
6. R?. W e g 1 e r, Angew. Chem., A60, 88, 198.
Summary
With the aim of obtaining polymeric hydrocarbons of enhanced
thermostability the synthesis has been carried out of linear. po-
lymers of regular structure of the type (- CHsArCH~-)n and
(ArCHa-)n with aromatic units in the chain.
Polymers of the first type were obtained by reaction of metal-
lic sodium with the dichloromethylderivatives of benzene, m-
and p-xylenes, diphenylmethane, diphenyl and naphthalene in
dioxane medium at 20-25?. The rrz-xylene derivative lead
a CHzCI group in m-position and the others, dichlorides in the
~p- or p; p-'positions. The polymers were precipitated from the
solutions on forming and after disposal of excess sodium with
the aid of methanol and elimination of the low molecular impu-
ritis they appeared as colorless powders of the composition of
hydrocarbons; at times containing chlorine.
X-ray analysis of the polymers revealed the presence of a
crystalline structure the degree of which varied, depending upon
the structure. The .polymers differed greatly in solubility and
melting points. Thus naphthalene and diphenyl derivatives, evi-
dently being cross -linked, three -dimensional polymers,
did not dissolve even in boiling a-bromonaphthaYene and decom-
98
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
posed above 300? and 550? without passing to the liquid state,
whereas derivatives of other hydrocarbons dissolved in bromonaph-
thalene, melted, passing over to a mobile liquid, and probably
were linear polymers of low molecular weighs.. The meta - xy-
lease derivative was distinguished by low crystallinity, low met-
ling point (130-135?) and easily dissolved in chloroform even
in the cold. Diphenylmethane derivatives with amore clearly
expressed crystallinity melted at 250-255? and began to dis-
solve in a-bromonaphthaline only at 130?. p-Xylene derivati-
ves, in turn, like polyparaxylylene possessing a strong tendency
for crystallization, melted at 350?, i. e, a little below the latter,
I~ut began to dissolve in bromonaphthalene only at 235?, or 25?
higher. As for the molecular weight of the soluble polymers, it
could be determined (according to Rust's method) only in the
case of the ,insoluble meta-xylene derivative; which, depending
upon the conditions of formation, varied from 1850 to 4000.
Polymers of the second type were obtained by polyconden-
sation of aromatic hydrocarbons with paraform and also with the
dichloro-, dioxy-, and diacetoxy -methyl derivatives ~ of ara-
matic hydrocarbons in boiling glacial acetic aid containing sul-
L'uric acid. In this way starting from p -xylene and dureno]
one could obtain high melting crystalline polymers with mel-
ting points above 250 and 320?, dissolving only in high boiling
solvents. Condensation of durenol with dichloromethyl deri-
vatives of p- and m-xylene, as well as with para-xylylene
chloride led to the formation of high melting polymers of the
type (- ArCHzAr'CH2-)n containing two different aromatic
units in the chain.
Resume
Dans le but d'obtenir les hydrocarbures polymeriques a une
stabilite thermique elevee on a effectue la synthese des polyme-
res lineaires de structure ordonnee de deux types (- CH2AaCHz-)?
et (- ArCHz-)n ayant des motifs aromatiques dans la chaine.
Les polymeres du premier type oast ete obtenus a la suite de
t'interaction de sonde metallique au sein du dioxane avec les
derives dichloromethyles de benzene, de meta- et paraxylenes,
de diphenylmethane, de diphenyl et de naphtalene a 20-25?
parmi lesquels le derive dii metaxylene composait les groupes
CHzCI en meta-positions et d'autres dichlorides en p- ou
p, p'-positions. Au fur et a mesure de la formation les polyme-
res etaient separes de solution, et apres la suppression de 1'~xces
7 ~~~
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
de sonde par le methanole et 1'elimination des impuretes a?bas
poids moleculaire ils presentaient les poudres incolores de com-
position hydrocarbonee qui comprenait parfois le haloide.
Les polymeres obtenus a la suite de 1'etude. radiographique
ont manifeste la presence de cristallinite, .dont le degre variait
en fonction de leur structure et differaient fortement? suivant
leer solubilite et le point de fusion. Ainsi les derives de naphta-
lene et diphenyl en representant evidemment .les polymeres
tridimensionnels reticules, ne dissolvaient pas meme daps 1.'a-.
bromonaplrtalene bouillant et se decomposaient a une tempera-
ture.superieure a 300 et 550? sans passer en etat liquide tandis
que les derives des autres hydrocarbures se dissolvaient en bromo-
'naphtalene, fondaient passant en liquide mobile e.t representai-
ent evidement des polymeres lineaires e bas poids moleculaire.
Le derive de metaxylene se distinguait par une faible cristal-
linite, un bas point de fusion (130-135?) et se .dissolvait faci-
lement meme en chloroforme froid. Le derive de diphenylmetha=
ne, a une cristallinite plus nette, fondait a 250-255? et commen-
-~ait a se dissoudre dans le bromonaphtalene seirlement a 130?.
Et le derive de p -xylene, ayant aussi 'que le polypara-xylilene
une graride tendence a la cristallisation, fondait a une tempera-
ture d'environ 350? c'est-a-dire un pen inferieure a Celle du
derriier, mais it ne commengai t a se .dissoudre dans le. bromo-
naphtalene qu' a 235? soit depassant de-25? la temperature de
dissolution du poly-p-xylilene. En ce :qui: concerne le poids
moleculaire des polymeres solubles; on .a r.eussi a le determiner
{selon 'Bast) seulement dans le cas du derive metaxylene,.suivant
les conditions de la formation de celui-ci .il ,variait-de:,1850
~ 4000.
Les polymeres du deuxieme type etaient obtenus par voie de
polycondensation des hydrocarbures aromatiques avec le para-
formaldehyde ainsi que les derives de dichlore-, dioxy- et dia-
cetoxy-methyles des hydrocarbures aromatiques .dans? 1'acide
acetique glace bouillant qui, contient 1'acide sulfurique. Par
"cette` voie, en. partant de p-xylene et durene on a reussi ~
'gbtenir des polymeres cristallins a une haute temperature de fusion.
~~Ils, fondaient au-dessus de 250 et 320? et se dissolvaient seule-
mert dans les solvants a point d'ebullition eleve; ici la conden-
~sation du du.rene avec les derives dichloromeihyles de para-
et meta-xylene aussi qu'avec le Para-xylilene chloreux~a abou-
~tit a la formation des polymeres avec point de fusion haut du
4type'(= Ai'CHzAr'CHs-)n, comportant dans la chaine les. motifs
aromatiques de deux hydrocarbures clifferents.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
IlI~IKJIIILIECKAFi lIOJII~IMEPH3AIjI~IFI
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Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
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Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
j.~xBxxxJiaueTaJiH xax coeRxHexHx c RBynISI x3oJlrsposaxxblMx RBOi~-
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
paTypa 6~na pasxa 80?, a xox~exTpauiix R~xxTpxna aaoxaoMac-
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Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
I~ax BxRxo xa Ta6aI. 2, cTexexb aueTa~IxpoBaxxsl n xonr~AxBi3-
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Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
~I~aH, IIpH COBMBCTHOII IIOJIIIMepII3aL[HI3 ~~.~ CO CTI3pOJIOM B IIpII-
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pOJIa B IIOJIyileHHbIX COIIOJIIIMepaX IIOZ[TBepSlij(aeTCR TaICXCe 3JIe-
MOHTapHbIM aHaJIH30M (Ta6JI. 3)
'Pa6nxga 3
COOOJINMepN38l(HA ABG CO CTNpOJIOM
MonHpnoe cooTHOme-
MoJIHpIIOe
cooTxome,
T. I3JI. conoJlHMepa
Hue jjBB n cTnpona B
HcxouHO~i cmecn
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cTHpoJla B_
a z[BB .IS
cono.numepe
,
o0
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: 87, G8
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- 14,49
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56-58
KHTepeCHO OTMBTIITb, iITO IIpH COIIOJII3MepH3aI~HH ~,B~i C BH-
HHJIaB;eTaTObi B IIpIICyTCTBHYI D,rJ-1 MOJI.% Z[HHHTpHJIa a30H30-
biaCJIRHOYI HHCJIOTbI 06pa3yeTCR COIIOTIHDIep, B I{OTOpOM MoJiapxoe
cooTHOIIreHIIe 3Bexbes, IIo orlpeReJlexlllo 6yTHpaJlbHbix H aueTaT-
HbIX rpyIIII, IIpaKTHtIeCIfII COOTBOTCTByeT MOJIRpHOMy 000THOIIIe-
HHIO hiOHOMepOB B IICXOJ~HOH CMOCH (Ta671. ~I)
MoJlnpaoe cooTHOme-
MonHpl3oe coo,HOme-
MoJlnpHOe coorxome-
MoJlapnoe cooTHO-
HHC Z[BB 1I BHHHJI-
Hne 3BCHbCB ~j(BB H
I3He j[BIi H BI3HI3JI-
meHHC 3HCH heB
aHCTBTa B HCXO,gH013
B33HHJ1alICTBTa B COIIO-
a1[eTflTa B nCxOjIHOf3
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40:60
38 , 32:61, 68
90:9 0.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
BO3MOHfIIOCTb I{FIxJIO-I~IIxJIi3LIeCx0I3 COIIOJIYIMepII3aLjI3A IIOKit-
~aaaa FIa IIpllniepe cosniecTxor~ IIOJIIIMepII3aT~IIII ZjBci~ II uB~, a
Taxxce J~BB i3 ABB. .
CH2 CH2 CHI CHZ
? CH ICH ICH ICH
. --> .
! 0 0 -~ 0 0
\CH / \CH/ .
... - CHZCHCHzCHCH~ CHCH2CH -
I I I I
0 0 0 0
-> \ / \ /
CH CH
I I
R R'
IIoJiyueIIIIbie conoJlIIMepbl soporIIO pacTBOpxlozcx B 6eilaone,
snopoc~opnie, auezoxe II o6JIaRaIOT BbicoxFlnlH aRre3lloxxbinlII cBOi~-
-cTBanIII.
HanIFI FI3yiIaJIIICb TaxHCe XIIniFItIeCxIIe CBOI3CTBa IIOJIIIJ{FIBIIFIIIJI-
a1;eTaJIeYI C IjeJlbx) oupeReJleFliix IIX CTpyIiTypbI. IIoJIIIRIIBIIxxJr-
aueTaJIII ae cnoco6x>;i x pealcl~Fianl ?rFIJ~pFiposaIIIIa II x IIpFicoeAi~I-
HeIIIIIO 6pOMa, tITO yxa3bIBaeT FIa OTCyTCTBIIe i(BOIIIIbix CBH3eFI B
IIOJIFiMepe.
CTpOeFIIIe IIpOJ~yKTOB I~IIxJIIIileCF{OIi IIOJIIIDIepII3aI~FIII J~13BIIIIIIJI-
al~eTaJle~i OxOIIiIaTeJIbFIO 6bIJI0 J~Oxa3aII0 rIIApOJIII3ONI IIpI3 IIOn1O=
ngFl BoRxo-cIIIlpTOSOro pacTBOpa coJlslIIOxFICJIOro rIIApoxcllJlanlIIIIa.
_- CHzCHCH2CH - ? ? - CH2CHCH~CI-i -
i I I I
0 0 xZo OH OH -}-RCHO
~ /
CH
I
~.I
I{ax II cJleRosaJlo oxcFlAaTb, 3Ta peaxuFlsl IIpI3BOZ[IIT I{ o6paaosa-
IIIIIO IIOJIIIBIIIIIIJIOSOro cIIIIpTa. IIoJlyuexIIbli~ 6eJIbII~ IIopoIItox xo-
porIIO .pacTBOpsleTCri BBone II IIo aJlenieIITapxoniy cocTasy cooTBeT-
CTByeT IIOJIIIBIIIIIiJIOBOMy CIIFIpTy. HaJII3iII3e IIIBCTIITIJI2IIIILIX I~FIx-
noB B IIoJIxRxBxxHJraueTaJlxx IIoRTBepaxRaeTCa ~-rJIIIxoJlenou
CTpyxTypOi3 IIOJIyileHHOPO IIOJIIIBIIHIIJIOBOrO. CIII3pTa, iITO B CBO [O.
?oxepeRb IIOKa3aII0 OxIICJIEHIIOM er0 IIO II3B0CTIIOYI nieTOJ~I3xe B i>aa-
BeJlesyx) xIICJIOTy.
TaxIInl o6pa3onl, ~Be BFIHIIJIbIIble rpyIIIIbI j(IiBI3FI.I3JIaI~eTaJIOI-I
;IIpII aiexcnioJlexyJlHpao-BIIyTpIIMOJIexyJlxpxoil IIoJlIIniepFlaaI~IIFI
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
pearHpyloT. IIo TgIIy uro.aosa.x xsocTy> c o6paaoBaHHert HIecTII-
xnellxt~Ix uHx~IH~ecxHx Ho~IHnrepoB IIo~IHRHBHHH~IaueTa.nea, T, e..
aI{eTaJIbHbIx IIIlOH3BOJ~HbIX .IIOJIHBHHHJIOBOrO CIIHpTa.
'JIgTepaTypa
1. Cs. B. B u t I e r, R. J. A n g e 1 0, J. Amer. Chem. Soc., 79, 3128?
1957. '
2. C. S. 1VI' a r v e 1, R. D: V e s t, J. Amer. Chem. Soc., 79, 5771, 9.957.
C. S. M a r v e 1, J. K. S t i 1 1 e. J. Amer. Chem. Soc., 80, 1740,
1958.
3. C. r. M a u o x a, M. r. A s e z n a. Asz. cnxA. CCCP, 126264, 1959;.
C. I'. M a R o a n, NI. I'. A s e z n a, ?K. o6B~e~I xnMnll, 30, 697, 1960;
C.1'.Ma>Zonx, M.I'.Anezxa, IVi.r. Bocxaanx, Bblcoxo-
Monex. coeA., 2, 314, 1960.
Summary
In the course of the last two years reports have been appearing
on a .new type of polymerization, called cyclic polymerization.
This constitutes an intramolecular closure of isolated dienes~
into five or six membered. rings with concurrent intermolecular
growth of the chain.
We have synthesized for the first time divinyl acetals and have
investigated their capacity for cyclic polymerization.
A method has been developed for the synthesis of divinylace-
tals tllrough ,interaction of aldehydes with ethylene chlorohydrin~
and the subsequent dehydrochlorination of ~, p'-dichlorodiethyl-.
acetals.The structure of the divinylacetal. monomers was proved,.
in particular, by hydrolysis and hydrogenation. '
It has been shown that in the presence of initiators. of radical
polymerization divinylacetals polymerize only by means of the
cyclic mechanism with the formation of acetal derivative o~
polyvinyl alcohol, i. e. polyvinylacetals.l
OCH = CHz ... - CH,-CHCH2CH- .. .
RCH ~ 0' O
~ ~ /
OCH = CH2 CH
I
R
where R=H, CH3i C3H,, iso-C3H,, iso-C4H? and CsHb, Poly~~
vinylacetals have .been obtained with the extent of acetylation
reaching 100 %.
1 The name upolivinylacetalN based on the name of the monomer should
be` changed `to upolydivinylacetal>.
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Up to the present time the possibility of cyclic copolymeriza-
~tion was not known. ~~e have investigated this reaction on the
examples of the copolymerization of divinylacetals with vinyl
and dime monomers.
OCH =CHs ? ? ? CH2CHCHZCHCH2
RCH< ?-{-CH2 = CHJ~ -. 0 0 CH:{ -
OCH =CH2 ~ ~
CH
~~
where R=H, CH3 and C3H,; X=OCOCH3, CN and C~Hb.
The possibility of cyclic cyclo-copolymerization has been
demonstrated by copolymerization of divinylformal and divinyl-
~ethanal.
All polymers obtained by us are white powders or rubber-
like thermoplasts, easily soluble in most organic solvents and
possessing high adhesive properties. They do not add hydrogen
or bromine, indicating the absence of double bonds.
The structure of the polyvinylacetals obtained on cyclopoly-
merization of divinylacetals was demonstrated by means of hyd-
rolysis. As was to be expected polyvinyl alcohol was formed, of
which in turn the glycol structure was proved by its oxidation
to oxalic acid:
Hence two vinyl groups of the divinylacetals during intra-
inter molecular polymerization react by the mecha-
nism to form polyvinylacetals with six-membered cyclic
structures.
R~sum~
Pendant deux dernieres annees on a decrit une nouvelle espece
de polymerisation, qui est consistee a cyclisation intramolecu-
laire par cinq ou six membres, des dimes isoles, avec la croissan-
ce intermoleculaire simultanee de chaine.
C'est pour la premiere fois que nous avons synthetise des
acetals divinyliques et etudie leur aptitude a la polymerisation
cyclique.
La methode de preparation des acetals divinyliques par in-
teraction des aldehydes avec chlorhydrine ethylenique, avec de-
hydr'ochloruration posterieure de ~, ~'-dicliloroacetals diethyli-
~ques a ete developpee. La structure des monomeres obtenus (ace-
tals divinyliques) a ete prouvee, en particulier, par reactions de
l'hydrolyse et de 1'hydrogenation.
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Nous aeons montre; que la polymerisation des acetals divin.y-
ligries en presence des amorceurs de polymerisation radicalaire est
dirigee exclusivement a la polymerisation cyclique suivie par
la formation des derives d'acetals de 1'alcool polyvinylique,
soft des acetals polydivinylique
OCH - CI-I,
RC'H~
ocFl - cH.,
ou R = H, CH3i C3H,, iso-C3H,, iso-C~H, et CsH~.
Nous aeons obtenu des acetals polydivinylique dont le degre?
d.'acetalation atteint 100%.
La possibilte de copolymerisation cyclique n'etait pas etudiee
jusqu'a present. Nous aeons. examine cette reaction prenant a.
titre d'exemple les acetals divinyliques avec les monomeres de
vinyle et de diene.
OCIi = CH2 ? ~ ?CI32CHCH2-CHCH2CL-I\--
ItCFI~ -{- CHI = CHX> O 0
OCH = CIi~ \ /
CH
I
I I
ou H = H, CH3 et C3H,; X = OCOCH3, CN et Ce.Hb.~
La possibilte de copolymerisation cyclo-cyclique est mon-
tree par.la copolymerisation des aldehydes formique et acetique~
divinyliques.
Tous les polymeres et copolymeres obtenus etaient ies poudres
blanches ou matieres thermoplastiques, semblables a caoutchouc;:
ils sont solubles daps la plupart des solvants organiques et ont
une tres forte adhesion. On ne peut pas les hydrogener 'et ils_
n'additionnent pas le brome, ce qui indique a 1'absence de doub-
les liaisons daps les polymeres.
La structure des produits de la polymerisation cyclique des_
acetals divinyliques etait prouvee a 1'aide de 1'hydrolyse des
acetals polydivinyliques. Dans ce cas, comme it fallait attendee,
se forme 1'alcool polyvinylique dont la structure R-glycoligne~
etait a son tour prouvee par oxydation. en acide oxalique.
Ainsi deux groupes vinyliques des acetals divinyliques, au~
cours de la polymerisation intra -inter - moleculaire, rea-
gissent selon le type en formant 'des .poly-
meres cycliques a 6 membres,- acetals polydivinyliques. '
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Next 6 Page(s) In Document Denied
Q
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
~- ..CI~IHTE3 I{PI~ICTAJIJII~ILIECI{OI'0
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
Ta6niri;a 1
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
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xxem s nonxpxaagxoaxom mxxpocxone. llpx sppas>;xoxnposaxnn c geT~rpeaxJropxcTarm yrnepoAOm npx xxnexun x xa xonoAy 6btnx nonyvexr~
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
-pHTeJIb, CICOpOCTb IIOJIIIi1IepH3aI;HH J~OTISIiHa ObIJIa 6bI paCTx YIJIII
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"?ISeHIISI,' iITO CaMbIM IIORXOZ(SIII~YIM . J{JIFI 06'bliCHeHHfI IIOJIyileHHbIX
pQ3y7IbTaTOB IIpg II07IIIMe.pH3aI;I3H B HeIIOJIfipHbIx pacTSOpHTe~ISIx,
:xB.aHeTCx ~ aHIIOHHbIFi ~ xoopRKHauHOHxbiH MexaHH3M, npeA~IOxceH-
HbI~I HaTTa. ,
JIxTepaTypa
1..G. N a t t a,
F. D a n u s s o, .
D. S i a n e's i,
iVlarkomolek. Chem.,
28,. 253, 1958.
2. ,G. N a t t a,
F. ll a n u s s o,
D. S i a n e s i,
Makromolek. Chem.,
.30,.
238, 1959.
-3. O.
F. Solomon, NI. D i m o n i e, Cerere
de patent RPR,
` 11. XII: 59.
4. C. H. Y m a x o B, A. ~. H n x o n a e B, I>Ias. AH CCCP, OTR. xAM.
a., 1956, 83.
.5. C. H. Y m a x o B; , A. di, H x x.o n a e s, YIaa. AH CCCP, OTC. xRM.
IL, 1956,-226.
Symmary
The polymerization of large ring vinyl compounds is of consi-
derable interest in the interpretation of the mechanism of action
?of complex organometallic catalysts.
Numerous vinyl compounds have been investigated up to now
:but no study has been made of compounds containing large rings.
,Studies on the isotactic polymerization of vinylcarbazol have
.brought to light very important facts permitting of a number of
inferences as to the mechanism of isotactic polymerization.
Despite the large molecular volume of vinylcarbazol and the
-steric hinderances that should be expected due to this a
atudy of the polymerization kinetics has revealed reaction rates
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
similar 'to 'those observed in the polymerization of other mono-
mers.
The study of the polymerization of vinylcarbazol and of other
monomers showed that the butyllithium -~- titanium chloride
catalyst. belongs to the organometallic complex type that act
.either by a stepwise or ionic mechanism.
" The specific features of complex organometallic catalysts iri
.the polymerization of "vinylcarbazol are evidently associated
with preliminary activation of the active centers during which
:activation of the monomer also takes place.
Tlie formation of polymers with an isotactic microstructure
"is due to one of the possible mechanisms of the catalysis, namely,
to non-stepwise" action.
In the polymerization of vinylcarbazol in the presence of
~organolithium compounds and titanium 'tet'rachloride' the micro-
structure of the resultant polymer and the rate of polymerization
depend upon the formation of other than primary complex com-
pounds: "
The "microstructure of isotactic polyvinylcarbazol has a par-
ticular shape of spherulites, depending upon the nature of the
catalyst. ~ .
Resume
La polymerisation des vinyles a Brands cycles presence un
brand interet a 1'occasion de 1'explication du mecanisme d'action
~cles catalyseurs organometalliques complexes.
Parmi de nombreux composes vinyliques studies jusqu'a
present du point de vue cinetique les composes a Brands cycles
Rn'ont pas ete encore examines.
L'etude de la cinetique de polymerisation isotactique de
vinylcarbasol ont revels des faits particulierement interessarlts
qui ont permis de faire quelques conclusions a propos le meca-
nisme isotactique de polymerisation. Malgre que le vinylcarba-
sol ait un grand volume moleculaire et it faille s'attendre a
1'existance des encombrements au tours de sa polymerisation
1'etude de la cinetique de polymerisation a montre de telles vi-
~esses de reaction qui sont observees'a la polymerisation d'autres
monomeres.
En se basant sur 1'etude de polymerisation de vinylcarbazol
~t d'autres monomeres on a montre que le catalyseur, butyl-
lithium - tetrachlorure de titans, se rapporte a la classe de cata-
dyseurs du type des complexes organometalliques qui peuvent
agir soft selon le type du mecanisme graduel soit selon le type des
Bons.
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Des proprietes particulieres des catalyseurs organometalli--
ques complexes a la polymerisation de vinylcarbazol soot evidem-
ment Bees a .une activation preliminaire des centres actifs au
cours de laquelle se produise aussi 1'activation de monomere.
La formation des polymeres ayant une microstructure isotac-
tique est conditionnee par une des possibilites d'action du cata-
lyseur, a savoir, par le caractere non-graduel d'action.
Si polymerises le vinylcarbazol avec des organo-lithiens et
le tetrachlorure de titane la. microstructure du polymere obtenu.
et la vi~esse de reaction de polymerisation dependent aussi de la
formation de plusieurs autres composes complexes outre les pri-
forme specifique des spherolithes suivant la nature de catalyseur.
La microstructure du polyvinylcarbazol isotactque a une
maires.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
O IIOJIYLIEI3I~II~I I30BbIX ~'I%irI0I3 JII~IHEI%lIIb1X
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
rRe R' - Tpez. 6yzoxci3~Ibxbie II McTII~Ibxbie paRIIxa~Ibt, o6paaylo-
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
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mepIIMCHTa7IbHBA ItpABaH
C Rpyrou cTOpoasl, cor~Iacllo xpxxslTOaly Rorryx~exxlo; xoac~,
c~xi~xexT xonxnrepx3auxx n = 2~~+1. OTCIORa xo~Iy*~aeM c.aeAylo-.
rRylo aasxcxMOCTb nrexcRy ~Ixc~IOM Mo.aeil cBO6oRxlix paRxxa.rloB II
Icoac~c~xuxex'ronl n:
NR=2- n
YIs pxc. 2 sllRxo, *ITO axcxepxnlellTa~Ibxo IIa6~IIOAaeMax xpxsasl
2 xnleeT Toxxo Taxol~ ~ICe xapaxTep, xTO x TeopeTxxecxasl xpxsasi
1 1'I Roso.abxo 6slxal:o c xe~I cosxaRaeT, *ITO xoRTBepacRaeT cRe.nax-
xoe Roxyxlexxe o xapaxTepe pocTa uexx.
I~Ia sTOro c~IeRyeT Aa.nee, ~ITO xepelcxcb TpeT. 6yTx.na ii ycslor3x-
srx axcxepxMexTa pa3.aaraeTCSI Taxxnl o6pasoM, xTO xs oRxoro Monsl
Iiepexxcr3 snlecTO Rsyx Mo~Ier~ axTxBxblx xo oTxoxrexxlo x pacT-
>3opxTesllo paRxxa~IOS [8, 9] o6paayeTCSI 1 aro.ab Taxxx paRxxanor3
rI cooTSe~eTBexxo aTOnly NlaxcxNlynl alo~Ielsy~ISlpxoro Iteca AocT[I-
raeTCFI IIpx paGXOJ~e IIepeI{xCx, 6JIx$KOnI K RByM MOJIFIM xa MOJIb yr-
,neBOJ[O1lOJ[a. c~TO i~I05rCeT CI~ITb 06~HCxeHO,TOM,. TiTO xOJIORxxa IIepr30-
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
xaxa~Ibxn BoaHIIxIII c~paxuxrl).
~oRepxcaxxe azaKZx~IecxoH uaczx B ?eoxb~IxMepe xnleeT upx6~IxaH-
Te~Ibxo IIoczoxxxoe sxaxexxe,' pasxoe -~-52%. IIo~IxMepbl, no~Iy-
xexxble IIpx y Be~Ix*Iexxx . Mo~Ixpxoro ~coozxoIIlexxx McHtRy Rxa~t-
JIIIJIIIpOx3BOJ~HbIDIx KpeMHHx x rlpoxII:nexa OT 0,04 Ro 0,15, xMenH
xecxo~nbxo 6o~Iee Bblcoxylo zeMIIepazypy II:nassteHxa H B Hesila*III-
Te~Iiixoli czeuexH zepx.al~ ~IIO~IHyIO pacTSOpxnlocTb B Aexa~Ixxe.
CpaBxexxe MexaxH~ecKHx csoi~cmB coIIO~iIIMepoB McTHJi(~eHHJi-
~xa.a~Ix~ICII~Iaxa H RxMeTx~IRxa~I~Ix~ICx~Iaxa c IIpoIIg~IeaoM IIoxasa-
~IO, ~IZO IIoc~IeRHxe o6~IaRaIOT IIpxMepxo B ABa paaa MexbIIlel~ IIpo~-
xocTblo xa pa3pblB, xeM Biie.pBble. CorIO~IHMepbl MezH.ac~exi3~IRHa~I-
.TIxJICIIJIaHa C HpOIIxJIeHOM 06JIaj(aIOT BbICOKHM OTxOCHTeJIbHbIM yR-
.alxxeHxeM (600=700%).. YBe~Ix~exIIe oTxocHTe~Ibxoro coAepxcaxIIx
Mezx~IC~eHx~Rxa~I~Ix,rrcx~naxa B coxo~IIIMepax c IIpoIIx~nexoM saMeT-
Iio y,nyxIIlaez Hx zepnloMexaxHUecKHe csol~cTBa IIo cpasxexHlo c
~epMOMexaxH~ecKxMx , cBOHCZBanIH 'cono~nHMepos RHMezx~IAxa~I-
~Ix~ICIr 2 (CZHS)3 Sn00CC (CI{3) = CH.~ -}- Cr-IgoC:r{y
CBOgCTBa IIOJIyTieIIHbIX COOJ.~IIIIOHHII 3TOT aBTOp He HCCJIej~OBaJI
H He HCIIOJib30BaJI gX J{JIH IIOJIyLIeHIIH BbiCOxOMOJIexyJIHpHLIX Ma-
TepgaJloB. AHAepcoH IIpeRIIOJIaraJl, xTO McTaxpIIJlosaH xIICJIOTa
6yReT IIOJIIIMepIl3osaTbcH B ycJloBIIxx IIposeAeHIIH peax~IIll c relc-
Ca3TIIJICTaHHOxCIIJ{OM CJIHIIIKOM 6bICTpO H OTxa3aJICH OT OIIbITOB
C xIICJIOTOI3.
MbI HaIIIJIII BIIepBble B 1958 r. [4], xTO nteTaxpIIJloBasl xIICJIOTa
pearIIpyeT C TpIIaJIHIIJI(apIIJI)CTaHHOJIaMII I'.?:II rexcaaJIxIIJI(apHJI)-
CTaHHOKCIIJ.[aMII C06pa30BaHIIOM COOTBOTCTByIOIIjIIx TpIIaJIxIIJI(apHJI)-
CTaHHIIJIMOTaxpIIJIaTOB, c~TO ~bIJIO IIOJ~TBep}KReHO H IIOCJIOJ~yIO-
II~II-ffi pa60TaMII [5, 6]. PeaxuIISl IIpOBO]jIITCH B BOJ~HOM paCTBOpe
HJIH B cpeRe o6blxHblx opraxIIxecxIIx pacTBOpIITe.nel~:
ReSnOH-~-CH2 == C. (CH3) COOH -~ H3Sn00CC (CH3) _ CH2 -}- FIzO
1r3SnOSnR3 -~- 2CH = C (CH3)-COOH -~ 2R3Sn00CC (CHe)= CH2 -E- HZO
AHaJIOrIIiIHbIM o6pa3onl pearllpyloT c McTaxpIIJlosoII xIICJloroii Ii
JjIIaJIHIIJi(apIIJI)CTaHHORCIIJ;bI:
RzSnO-{-2CH2=C(CH3)COOH~R2Sn(OOCC(CH3)=CHa)a,
OCpa3yx IIpII 3TONI J{IIaJIxIIJi(apIIJI)CTaHHIIJIOHJ~IIMOTaxpIIJlaTbI. Peax-
I;IISI IIpoTexaeT Jlerxo c BblxoRoM oJIOBOOpraxHgecxllx nleTaxpx-
dIaTOB AO 8O %. 1VIbI IIOJIy*IIIJIII IIO yxa3aHHbIM peaxi;IIHM pa3JIIIYHble
11 Dtert:AyxapoAxbiki cumno3nyai, cexgxR 1
1Gr
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
zpxa~Ixll.a (apII~I) czaHiix~Ihsezaxpx.aazbl II AIla~xx~I (aplr~I)czalulll-
~IeaAIlMezaxpll,nazbl, B xozopblx paRt~xa~Ianlx xsalulozcx
CHs, CzHs, CsHv, CaH9, CbFiu, CsHls~ C;Hls, C8H17 g CsHs.
Tpga~xx~I(apII~I)czanall~IMezaxpg~Iazbl upeRczaB~I$IOZ co6oll
zl3epAble xpxcza.a~Ixxecxxe Berr;eczBa, paczBOpr3M>;Ie s ac~Ilpe,
6easo~Ie x Rpyrnx opranllxecxnx paczBOpKZe~Ixx; aepaczBOpxMble
B soAe. Hexozopr~Ie csol~czsa noalygexa>;Ix nlezaxpx~Iazos npe~-
czas,neabl s za6nnue.
~N3nK0-xnntnvecsne~ csoac~rsa ~rpnanxnn(apnn)cTaxnnnn181'axpunaTOs
ReSn000C (CHs) = CHz u Ananccnn (apna)t:Taiu~n~leaAnmeTaxpNnaTmi
R25n [OOCC (CHs) = CHz]z
(CHs)s Snb1As
(CaHs)sSnNIA
(N-C3H7)3SRMA1
(x-C4H s)sSnb1A4
(uao-C4Hs)sSnMAI
(uao-CsHu)aSnMAI
(tc-Cs H ls)sSnMAI
(r~-C~H15)3SnRIA1
(Cs~Is)sSnMAs
(CHs)z Sn (MA)z
(CzHs)z Sn (MA)C
(~i-CsH7)z Sn(N1A)2
(rc-C4Hs)z Sn (MA)2
(uao-CgHs)z Sn (MA)Z
(uao-CsHll)zSn(MA)2
(}i-CvHls)zSn(MA)z
(rc-CsHls)z Sn(MA)Z
(Cc11s)zSnMA~ .
110
75,0
48,5
17,0.
10,0
15,0
19,0
23,0
86,0
141,0
137,0
61,0
50,0
36;0
75,0
21,0
Bl,~vxc-
nexo
1,4805
1,5651
92,87
92,23
1,4804
1,5649
92,87
92,20
1,4790
1,0999
101,1
107,5
1,4820
1,0688
120,2
120,2
1,4844*
1,0599*
134,9
134,4
npx z4?.
7Ionyvexza xnepni,~e. ~
e no uxrepaTypxranl Aaxxxtii, 2~, nn 140-144? [i1 J.
? no nxTepaTypx~mi naxlllinr, z. nn. 122? [2].
IIo nxTepaTypxstm Aaxxtam, T. nal.'20-22? [2].
s no nxTepaTypxraar Aaxx1~M, z. xn. 91-92? [27? .
72,1
81,0.
83, 0?~
78,0
80,0
78,5
79,0
77,0
65,6
70,6
79,9
81,0
85.E
s2,o
83,0
76,7
79,7
73,t!
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
~JIOBOOpraxII~ICCHxe MOTaf{pxJIaTbI xOJII3Mepx3yIOTCSi B IIpIICyT-
CTBIIII HaTaJIII3aTOpOB xJIII ~e3 xIIX, o6paayH xpoapaxxble cTeHJIO-
o6paaHbie BeH~ecTBa.
BbICIIIIIe TpIIa~IHx~I(apH~I)cTaxxIInMeTaxpII~IaTbI II AIIa~IxII~i-
apH~I)cTaxHx~IeHRHMeTaxpH~IaTbI - Bslaxxe, x{IIRHIIe coeRxxe-
IIIIx, cxoco6xbie IIOJIxMepx3pBaTbCfi Rax{e IIpII HOMIIaTHOB TeEiIIe-
paType c o6paaosaxxehl xpospauxbix re~Ieo6paaxbix MaTepxa-
noB.
Bbicoxorio~Iexy,nxpxbie coeRHxexxx, xo~Iy*Iexxbfe xaMII IIo~III-
Dfepx3alT,Hei3 OJIOBOOpraHlIileCICHX MOTaHpIIJIaTOB, IIpeJ~CTaBJifIIOT
CO6OH BHHx7Ibxble xOJIN-IepbI H BbleH)T c~IeRyloB~ee cTpoexIIe:
ft= ~I, ast:itn, a R' = CH3, C2H5, .. C~Hf, ff Co HS
O~IOBOOpraxII~ecHIIe nfeTaxpll,naTbl x RIrnleTal{pxalaTbl coxo~IIIDIe-
pH3yIOTCSI C pa3JIxiIHbIbix DIOHOMepaPIII TaHHMII, HaI{ MOTxJIMOTa-
KpHJIaT, CTIfpOJI, aHpHJIOHIITpxJI, I~YIHJIOIIexTaJ~IIex. YI T. ~{. C 06pa-
30BaIIxeM IIpO3paiIxbIX TBepJ.[bIX xJIH AIfIPHHX MaTepHaJIOB B 3aBx-
CIIMOCTx OT xCXOJ~HbIX rfoHOnlepoB.
~OdIIIllfepII3aI;IIIO H COIIOJIx111epH3aI~xIO &IO?HHO IIpOBOj;IITb HaI{
6JIOiIHbIbf, TaK II BOJ~xO-3.1fyJIbCHOIIHbI11f IIYTOM HJIH B CpeRe paCTBO-
pxTe.nsl.
COBMeCTxaA IIOJiIlniepII3aB;IIf1 TpYIaJIKIIJI(apIIJI)CTaHHII1IM0Ta-
HpxJIaTOB x J~xaJIHxJI(apH.n)CTaxHIIJIeHJ;xMOTaI{pxJIaTOB C BYIHxJIO-
BbI14fH 11fOHOMepaDfII YI3yiIaJlaCb Ha14fIi Ha IIpxbiepaX TpI33TH7ICTaHHHJI-
-IOTaKpxJlaTa H CTxpOJIa, a TaHH{e J[I33TIIJICTaxxIIJIeHJ~xMOTaI{pIIJiaTa
H J~H6yTII7ICTaHxxJIeHJ~II11ieTaHpHJIaTa CO CTHpOJIOM. KOHeLIHble IIp0-
j~yHTbI COIIOJIHMepII3aI~IIII HepaCTBOpHMbI B 6ex3OJie, B TO BpeDIA
HaK IIOJIHblepbI TIFICTbIX Tpxa~IHII~ICTaxHII?naieTaxpII~IazoB ~IaCTxLIHO
pacTBOpxMbl B ~eH3OJIe.
IIpII oxpeRe~IexxII coxpoTxs~Iexxx yuapy cono~IxMepa Tpx3Tg~-
c'raHxll~InlezaxpH,naza c McTH~InfeTaxpll~Iazoal, Iio. J~IillczaTy, 6bIJIH
xo~Iy*Iexbl c~IeRyIOII~IIe axaxexHSl: 8,33; 7,36 KI'/cn~2; TsepAoczb IIo
Spxxe~Ilo (xpll xarpyaxe 25 ~z) cocTaBH~Ia-26,5; 26,5; 31,8 xI'/.~.~a:
YIcxblTaxllsl Rxs~Iel{Tpx*IecxIIx CBOI3CTB ero Ra~III c~IeRyIOIgIIe,
pe3yJIbTaTbI.
yJ~eJIbHOe IIOBepXHOCTHOe COIIpOTHBJIeHIIe 1,4.1015 o.?u,.yRe~Ib-
xoe o6?be~fxoe coxpoTIIBSexxe 3,0 ?1015 0.~ ? c.~c, tg yr.~Ia Rxa~IexTpII--,
TICCHHX IIOTepb IIpII 106 2L~ 0,027, IIpII 50 2l~ 0,037, ,j~H3JIeHTpIITie-
cxax xpoxHi~aeNlocTb xpx 106 z~ 4,3, xpx 50 zip 5,0, cpeRHee xpo6IIB-
Igoe xaxpslx{exlie 13,5 xe/.~c.~c.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
IIpI~ HayueHllH Bouonor,aoll~eHli$ o6paaua ~1bIJI0 ycTaxoB.nello,
iITO' HHISaKHX BHJ~YIMbIR H3MeHQHY1i3 He HpOH30III~TO HOCJIe Hpe6bIBa-
HHSI 06pa3I[a B TeileHHe 13 MecHi;eB B I~HCTIIJIJiIIpOBaHH0I3 BO]~e,
IfpOMe BbIBIeyIIOMSIHYTbIX OJIOBOOpraHIIileCKHX McTaxpHJta-
TOB HaMI3 ~blJi$ IIOJIyLIeHbI CDIOJIbI IIpII B3aHM0AeI3CTBI3H P6KCa3TIIT7-
CTaHHOi{CHJ{a (C2I36)3SnOSn(C2Hb)3 H RH3TIIJICTaHHOHa (C2Hb)2SI1O
C rJIHI~HJ;HbI11I CIIIipTO-I, a TaISSHe HpH B3aH-IOReY1CTBIIH 3(~IIpOB
-Ha(~TOJIa HJIH pe30pljHHa H TpH3TIIJICTaHHOJIa C C~OpMaJIbRerH]~ODI,
I'I3yLIeHHe CBOi3CTB 3TYIX CMOJI npoRonxcaeTCa;
JluTepaTypa
2: IE. A. A u A p n a u o n, Ycnexrr xrrNtrrrr, 27; 1257, 1958.
2. M. M. I{OTOrI, T. M. I.rrce.aersa, B. A. f]aprruo~c, uor:n.
AH CCCP, 125, 1263, 1959.
3. J.Monterrnoso, J. Anrews, L. Dlarinelli, J. Polymel?
Sci., 32, 523, 1958.
4. M. ~. IIIocTaxoBCxrrii, B. I[. I{oTperrea, ,I~. A. I~o~c-
x x x x gyp. ?I~.. npxxn. xrrMrrlr, 21, 1434, 1958.
S.,I);.A.I{o*rxrza, B. II.ICozpenes, M.cP.IJIoczaxoiicxnii
x Ap. Brrcoxoazo~rex. coeR., 1, 482, 1959
6.,i~.A.I{o=rxr3rr, B.FI.IfoTpe.nev, C.li.lia.rr~rrrrrra rr~p.
BbrcoxoMO~rex. coeR., 1, 1507, 1959.
7. T. H a r a d a, Scient. Papers. Inst. Phys. Chem. ResearcL, To-
kyo, 35, 290, 1939.
8. G. K e r k, aazerrz APP, 7V~ 946447. P?It Xrrnr., 1~'0 1, pec~epal?
2205, 1958.
-9. A. C. Smith, r. G. R o c h o w, .f. Amer. Chem. Soc., 75, 4103,
1'953.
10. H. A "n d e r s o n, J. prgan. Chem., 22, 147, 1957.
11. A.Saitow, 1'J. G. Ilochov, D. Seyterth, J. Org. l:liew.,
23, 116, 1958.
summary
Organotin monomers and polymers are becoming of increasing
importance. They are suggested for use as insectifullgicides, sta-
bilizers of polyvinylcllloride resins and paints, as special purpose
rubbers, anti-mould chemicals for wood and textiles, antihel-
minthics, etc.
" Of considerable theoretical and practical interest are organo-
-tin polymeric materials.
In the report the results are described of studies carried out in
the Laboratory of Vinyl Compounds of the Institute of Organic
Chemistry of. the Academy of Sciences, USSR and in the Plastics
Institute of the State Committee on Chemistry of the Council of
Ministers, USSR. The syntheses of a number of organotin poly-
964
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mers have been developed, in particular, of the organotin polymeth-
ylmethacrylates from trialkyl/aryl stannylmethacrylates R3Sn-
OCO(CH3)=CHz and dialkyl/aryl stannylenedimethacrylates
RzSn[OCOC(CH3).=CHz]z and of copolymers on their basis:
The high molecular compounds obtained by polymerization of
the organotin esters are a new class of vinyl polymers with the
structure:
-~ - Q I Jn
Organotin esters copolymerize with various unsaturated mono-
mers such as methylmethacrylate, styrene, acrylonitrile, cyclo-
pentadiene, etc. The copolymers are mechanically strong, trans-
parent materials. They represent considerable barriers to the pas-
sage of x-rays.
The organotin esters R3SnOCOC(CH3)=CHz and R2Sn[OCOC
(CHI)=CHz]z containing the alkyl radicals R-amyl, hexyl
and higher groups polymerize already at room temperature
in the absence of catalysts to form soft and elastic polymeric ma-
terials.
In the report a number of properties are discussed of another
class of organotin polymers, namely, dialkyl/arylstannanes
(RzSnO)o. It is suggested that they are high molecular compounds.
Their X-ray diagrams and the results of other physico-che-
mical analyses are examined. A study of their Debye crystallo-
grams showed that they have a regularly oriented structure. They
are highly reactive and are sources for the preparation of new or-
ganotin compounds and of a number of organotinPlement com-
pounds, such as organotinsilicon, organotinlead and other deriva-
tives. Some of their physicochemical properties are described.
Resume
Dans le rapport sont exposes les resultats des etudes, effectu-
ees au laboratoire des vinyles de 1'Institut de Chimie Organi-
que de 1'A. S. de 1'URSS eta 1'Institut des Plastiques du ComitC
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d'Etat du Conseil des Ministres de Chimie. On a elabore les synthe-
ses ~ de certains composes detain organique monomeres
et polymeriques, notamrrment, les polymethylmethacrylates
detain organique a partir trialcoyl (aryl)-stannilmethacrylates
R3SnOCOC(CH3)=CHz et dialcoyl(aryl)-stannilenedimethac-
rylates, aussi qu'on a obtenu sur leur base les copolymeres. Les
produits a haut poids moleculaire obtenus par polymerisation
des esters organostanniques- presentent ~ une nouvelle classe de
polymeres vinyliques et ont la structure: ,
Les esters se copolymerisent avec de divers monomeres insa-
tures: methylmethacrylate,styrolene, acrylonitrile, cycloperitadie-
ne et quelques autres. Les copolymeres presentent des materiaux
transparents, mecaniquemerit solides. Les esters organostanniques
R3SnOCOC(CH3)=CHz et RaSn[OCOC(CH )=CHz)z contenant
les radicaux alcoyles R-amyle, hexyle et superieurs se
polymerisent deja 'a temperature ordinaire sans catalyseurs.
Dans le rapport on a eclairci quelques proprietes d'autre
Classe des polymeres organostanniques -dialcoyl (aryl) stanna-
nes RzSnO.
. On suppose qu'ils presentent des composes a haut poids mole-
culaire. Leurs radiogrammes et les resultats d'autres recherches
physico-chimiques ont ete envisages. L'etude de leur Debaygram-
mes temoigne de leur structure correcte orientee. Its ont une
tres haute reactivite et composent une source pour 1'obtention de
nouveaux composes organostanniques et plusieurs composes
etain-elementoorganiques, par exemple, silicoetainorganiques,
germanium-etainorganiques et d'au.tres derives. Leurs certaines
proprietes physico-chimiques sont- decrites.
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BJII~IFIHI~IE XI~IMI~iLIECI{OI'O CTPOEHI~IH
HA CIIOCOFHOCTb K HOJII~IMEPI~I3AI~I~IYI
HEHPEJ~EJIbHbIX
METAJIJIOOPI'AHI~IiIECIfI~IX COEJ~I~IHEiII~II%i
lI. M. IComo~, T. M. IC~~~ae.~caa, ~. C. ~r~opu-ICC~.{c~ic
(CCCP)
~0 HaCTOHII~erO BpeA10HII.II0nIIMepII3aI~HH HOIIpeAenbHbIX Me-
TannOOpraHII~IeCKIIX COe~(HHeHIIg H3yiieHa IIej{OCTaTO~IHO, HOCMOTpH
Ha T0, iITO IIOnytIeHHe MOTannCOJ{ep}KaII~HX IIOnIIMepOB IIMeeT ~OJib-
IIIOI3 T80peTIItIeCKHi3 H IIpaxTII*ieCKIIi3 IIHTepeC (onosoopraHII*iecxlse
xayxyxH H Ap.). .lIIIIIIb HeRasxo oIIHCaIIO IIonyileHHe HexoTOpbIx
onosoopraHIIgecxIIx IIonIIMepoB [1-4] II coIIOnIIniepos TpHbleTIIn-
annIInrep~Iaaa c0 cTIIponoM IIoR BbicoxHM AaBneHIIeM [5]. YIs IIe-
MHOrIIx nIITepaTypabtx AaHHbix [6, 7] HasecTHO o cyII;ecTBOSaHIIII
pTyTbcoRepxcaII~IIx IIonIIniepoB.
HarIII IICCJIeJ{OBaHa CII0006HOCTb K IIOnHMepH3aI;HH H COIIOJIH-
MepII3aI~IIII pa3nIIiIHbIX annIInbHI,IX H BIIHIInbHbIX IIp0II3BOZ[HbIX
onosa II cBHHI;a, McTaxpHnaTOB II.axpIInaTOB opraHIIxecxIIx coe-
RHxeHIIII onoBa, cBIIHua, pTyTII II pHR McTanncoRepxcaigIIx
cTIIponos. '
jIOnIIMepH3aljIIfl BIIHIInbHbIx II annIInb-
HbIR IIp0II3B0 J;HbIX OnOBa H CBHHija. B O~bi~I-
HbTX yCJIOBHHx annHnbHble COeJ~HHeHHFI OJIOBa H CBIIHL~a I3
BIIHIInbHbie COeZ[IIHBHIIfi OJIOBa IIe IIOnIIMepII3yIOTCFI H OKa-
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xeHIIH. AnnHnbabie coeAIIHeHIIH onosa HBnHIOZCH 6onee sc~c~ex-
TIIBHbIMII HHrII6IITOpaMII IIOnHhiepH3al(HII, TieM COOTBOTCTByx)IIjIIe
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xarx613pyioII[eMy J[eI3CTBIIIO Ha IIoJIiIMepII3auxio BI3I3IIJIbHbIX MOHO-
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TeTpaa~I~Ix~IO.noBO~TeTpaBIIIIx,no.aoBO >an.nII,nTpRMeTII~IOnoso>aai-
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IIo.nsipxoH rpyIIIIbi IIIIII xepe3 6eII3o~Ibaoe xo,nbz~o, MbI xa6~IioRaeni
Apyrxe 3axoxoMepHOCTII B IIpoTexaIIIIil IIpoueccoB IIo~IAMepI33ai~iiil
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HOJIIINie piI3 al~IIfi IvieTaJIJICO J[E p}x aIIjIIX
axpIIJIaTOB II McTaKpI3JIaT0B. HaniII BIIepBbie~
IIo~Iy~et3bl IIo,nANlepx3ylolgIIecsl rleTaxpx~IaTbI (axpII.aaTbi) TpII-
a~IxII~I(apII~I)IIporI3BOAxbix o~IOSa [2), nieTaxpxalaTbl (axpx~IaTbI}
TpIIC~eaII~ICBIIIIZ;a II c~eIIx~ipTyTH. CHIITe3 McTan.acoRep}i{aII;IIX
axpIInazoB II McTaxpII~IazoB ocylz;ecTB.asI~III s3a~iMOAeI~cTBHeM co-
oTBeTCTByioII;IIx AIeTa~i,aoopraIIII~Iecxxx rr3Rpooxxce~I o6~el~ c~op-
iry,nbi Rn_iMenOH II hleTaxpII,noBOK . (axpII~IOBOH) I{HC,aOTbI B at;e-
Torie ii7ii~ cuiipTe no o6II~enly ypasaeIIIIx):
Rn_IMe"`OH -{- CII2 = Cf1~C00H -~ CH2 -~GR~COOMe"Rn_I -{- Ii~O>
r,qe ..R -- C6H~; CHa; C2Hb; CgH9i R' - H; CHa; ble -- Hg, Pb, Sn.
McTa,n~ICORepx{aII~xe axpII~IaTbI g McTaxpx,aaTbl IIpeAcTaB~ISIioT
co6oi~ 6ec~seTabie xpxcTa~I.aII*IecxIIe Be~ecTBa, pacTBOpi3Mble B
opraIIII~ecxxx pacTBOpIITe~Ixx.
GRONCTBa axpllnaTOB Ii AI0T8I{pnAaTOB
MezaxpHnaT ~ieHII~IpTyTx ,
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McTaxpHnaT TpHCpeHlrno~IOBa .
AxpH.rlaT TpH~iealr~IO~IOBa .
McTaxpx.naT TpH(FG-6yTHn)onosa
AI{paraaT TpII (>t-6yTi~,a) o~oBa
48-50
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201-~03
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II MBTgJIMe1'axpFidiaTObl C 06pa30.B8HII8M TBepi~bIX IIp03paTIIIbIX, .COz
IIOJIi3MepOB.
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,~JISI xccJleRosaxxsl cxoco6xocTx K no~Ixnlepxaauxx McTa.nJI-
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3al[gI3 0,3 M paCTBOpOB B TOJIyOJIe B IIpIICyTCTBIIII 0,25 % ~[IIHgT-
pPIJIa aaOg30MaCJIIIHOFi ItIICJIOTbI J~xJIaTOMOTpIILIECI{xbi MOTOJ.jOM IIpI3
65, 80 I3 105?. IIoxasaxo, xTO McTaJiJlcoAepaltaiztHe rleTaxpxJlaTl~
aoJ1IlMepxsyloTCSI sxauxTeJlbxo JIer~Ie,uerl McTxJrMeTaxpxJlaT(pxc.1).
B aasxcxMOCTII OT xpllpoRbl NIeTaJIJIa, BxoRxiuero B coczaB McTa-
KpxJIaTa, Ha6JIIO~aIOTCft 3aMOTxble pa3J[IIiI13SI B CIiOpOCTAx IIOJIIIMe-
pz3sauxx.
!0 10 30 40 50 60 70 90
BpBMR, M(LH
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AIeTaJIJICO~epxcaBzlfx AleTaxpll,na~ros Ale~~aJl,nco~epxcaBzlfs cTZlponos
npI-I 80?. npll 80?.
- ~IeTHJiMeTaxpHJlaT, 2 - AleTafipllafa?r l - cTlipon, 2 - TpHC~eHxnHnIOM6Hn-
TpII(S]CfIHJICDIiHI[8. 3- A1CT8 HIlHJ11T TI1H(~CHH.~1- CTIIPOJ[, 3 - Tn3I(~1C1i117ICTDHHIIJICTNIIO?f .\
'~ OJIODT. 4 - MCT.T IijIIIJIftT QICHHJIpT}TIf.
Hayuexxr~e nleTaJlJlcoRepx:ax~He 1I6TaYipIIJIdTbI xo cxopocT--~
IIOJIYIMepII3aI~IIx 06pa3yIOT CJIEJ~yIOx[xII pslA: 11IOTc`lltpIlJIaT (~eHIIJI-
pTyTx,:~IeTaxpxJlaT Tpxc~exllJloJlolla; nleTaltpllJlaT Tpllc~exxJlcBxxua~
McTx,nMeTaxpllJlaT. I~IxTepecxo oTnleTxTb, ~ITO yRJlxxexlle aJ1ItxJ1b-
xoro paRxxaJla B oJloBOCORepxtax~xx McTaItpIIJlaTax oxaablBaeT
BJrxxxxe xa cBOilcTSa xo.nyxaeMblx xoJI~Inlepos. Tax, ecJlx nleTa-
It.pxJlaTbl TpIrnIeTxJI(aTnJI)oJ1oBa xpeRcTaBJISIIOT co6oil TBepAr~Ie cTex-
Jloo6paaxl~Ie xoJllrnlepbl, To NleTaxpllJlaT Tpx6yTliJloJloBa xoJlyuaeTCSI
B BxRe xpoapa~Ixoro 6ecr~BeTxoro sJlacTxxxoro reJisl.
IIoJlxalepbl McTaJrJlcoRepxtalt~IIx pacc~IIITaHbI 3IIaueHxH 3HeprIIIl axTIIBai;IIII McTa,n~ICORepxcaII;IIx
?CTIIpOJIOB. ~HII OKa3aJIIICb paBHbI J~JIFI TpII~eHIIJICTaHHIIJICTIIpOJia
43,4 -~- 0,5 xxCLJG/.hLO/Gb, J~JiH Tpx~eHI3nIIJIIOMGIIJICTIIpOaa 15,0-1-
0,8 K~carc/.~to~cb, R~ISI cTIIpo~Ia 20~-0,5 ~~carc/.~torcb.
J~aHHble xIIHeTIIxII IIOJIIIDIepII3al(III3 I3 paccgHTaxHble 3xaxexlill
aaeprIIII axTIIBauIIII IIoxa3blBaloT, ~ITO McTa~I~ICOAepxcaII;IIe cTII-
poJIbl IIOJIIIMepI33yIOTCf! 3HaiIIITeJIbHO TIer~Ie, LIeM HesaMeII;eHHblg
~cTIIpon (pxc. 2).
IIo cxopocTII IIOJIIIMepII3al[IIII IIsy4easble saMeigeaxble cTIIpo.nbI
06pa3yIOT CJIOJ;yI0II;I3I3 pSIJ~: Tpg(~eHHJICTaHHI3JICTI3pOJI ~ TpI3(~eHI3Ji-
IIJIIOM6YIJICTIIpOJI ~ CTIIpOJt.
MOTaJIJICOJ~ep}KaIgIIe CTI3pOJIbI HBJISIIOTCH TepMIIileCKg CTa(1IIdIb-
HbIMII COej~I3H0HIIAMII. Hax6o~IbIIreg TepMIIxecxoll CTa~IIJIbHOCTbIO
?06JIaJ(aeT OJIOBOCOZ(ep}KaII[I3I3. 3aMeIt;OHHbIII CTIIpOJI, HaHAIOHb-
IIIei3 - pTyTHOOpI'aIIII~IeCKIII3 CTI3pOJI. TaxIIM OGpasOM, IIO CB00I3
TepMgtIeCKOI3 CTa6xJIbHOCTII OHI3 06pa3yI0T cneRyloII~IIi~ pslR: TpH-
?c~eHA.neTaHHH~ICTIIpo~I ~ -TpII(~eHI3JiIIJIIOM6IIJICTIIpoJi > c)IeHiia-n-
BIIHFIJIC~eHIIJi pTyTb .
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,(I) 6bIJi0 o6Hapyxcexo HBJIeHIIe RIICIIponopr;IIOxxpoBaHgsl I
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c o6pa3osaxxenl
~oprax~I~Iecxoro
AIIC~exli,npTyTx II xosoro ileIIpeAe.abxoro pTyTiiu-
coeRxxexllx - 6uc-(n-sxxll.ac~exII~I)pTyTn - ([ i;
2CFIL = CH CnHy I-Ig C~HS -~
I
-~ (CeHS)z Hg' -; CIIz = CH CaH4?Hg CaH,, CI[ = CFI.
II
CoeRIIHexxe II , ouexb nerxo IIonllniepII3yezcsl c o6pa3osaxlleni
~repacTBOpIInloro II xeII.r;osa, .dI. B. JIaulre, JI. B. LIepnoaa, A.I..
B o p Ir c o n a, B. B. B o p x c e n x o, Bl~rcoxonlonex. coeA., 1,.
9507, 1959. .
S. B. B. Ifoplllax, A. M. Ilo~ISlxona, B. cp. Mnpoxo>3,.
A. R. IT e ?r p o li, ' Man. All CCCP; oTzs. xIIrI. u., 9959, 178.
6. K. B r o d e r s o n. J. K u u k e 1, Chem. Ber., 91, 2698, 9958.
7. 'I'. 'Cray 1 o r, J.' Polymer Sci., 32, 541, 9959.
8. L e e b t i c k, II. R a m s d e n, J..Org. Cbem., 23, 935, 9958.
9. M. iVI. I~oTOa, T. M. I{r3cenesa, ~. C: ~.ropxacxlll,
Man. AH CCCP, OTC. slrM. x., ~I959.
Summary ,
The synthesis of metal-containing polymers is of considerable
theoretical and practical interest (organotin rubbers, etc.). We
liave investigated the polymerization and copolymerization ca-
pacities of various alkyl and vinyl derivatives of tin and lead,.
of tin, lead and mercury methacrylates and of a number of me-
tal-containing styrenes. It has been shown that the a11yT
derivatives of tin and lead and'the vinyl derivatives of tin do
not polymerize under conditions of radical polymerization
and have an inhibiting effect on the polymerization of vinyl
monomers (styrene, methyl methacrylate). The inhibiting effect
increases with the number of alkyl and vinyl groups in the orga-
nometal molecule, the allyl compounds of tin being more effective
than the corresponding vinyl derivatives. In respect of their
inhibiting action on the polymerization of vinyl monomers the
compounds form the following series: tetraa11y1tili ~ tetravi-
nyltin > allyltrimethyltin > diallyldiphenyltin > al.lyltri-
phenyltin > vinyltriphenyltin > vinyltrimethyltin. Another re-
lation is found in the case of. organo-metallic compounds where
the vinyl group is bound to the metal atom through a polar group
O
I =- C~~ ~ or benzene ring.
~0 -
We have shown that the acrylates and methacrylates of aryl
and alkyl derivatives of tin, lead and mercilr}~ easily polymerize
and copolymerize with vinyl monomers. ?
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New compounds also are the metal-containing styrenes. tiVe have
synthesized for the first time, under the conditions of a Leeb-
tick-Ramsden reaction, mercury- and lead-containing styrenes.
Pb >
> Hg.
In studies on the polymerization of p-vinylphenylmercury
disproportionation tivas fOlllld t0 take place, leading to the for-
mation 'of the symmetric divinyl derivative of diphenylmercury
(I) and of diphenylmercury (II). Specially synthesized Bis-p-.
vinyldiphenylmercury (I) was found to polymerize easily with
the formation of an insoluble three-dimensional polymer, not
melting up to 250? and decomposing above this temperature
with the liberation of metallic. mercury. The polymer of (I) evi-
dently has the structure
- C l I2 -- C I-I -
C
~'j b
r \1
~%
- CEf - Lf'j2 -
As aresult of the investigation it has been shown that there
is a considerable difference in the polymerization capacity of
unsaturated organometal compounds and in the properties, of
the polymers and copolymers formed, depending upon the na-
ture of the bond between the vinyl group and the metal atom.
Resume
L'obtention des polymeres metallorg?aniques presence un grand
interet theorique et pratique (caoutchoucs organostanniques,
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etc.). Nous avons etudie 1'aptitude a la polymerisation et copo-
lymerisation de divers derives allyliques et= vinyliques d'etair~
et, de plomb, des methacrylates detain, de plomb, de mercure
et de plusieurs styrolenes contenants des metaux. Ici, on a mon-
tre,? que, dans' les conditions de polymerisation radicalique les
allyliques d' etain et de plomb aussi que les vinyliques d' etain
ne se polymerise pas et produit_une action inhibitrice sur la poly-
merisation des monomeres vinyliques (styrolene, methacrylate
de methyle). L'effet d'inhibition augmente avec le Hombre
des groupes allyliques et vinyliques dans une molecule des orga-
nometalliques, les composes allyliques d' etain etant des inhi-
biteurs de polymerisation plus intensifs que les composes viny-
liques correspondants. D'apres leur action inhibitrice sur la
polymerisation des monomeres vinyliques les composes exami-
nes forme la serie: tetraallyletain ~ tetravinyletain > allyl=
trimethyletain > diallyldiphenyletain > allyltriphenyletain > vi-
nyltriphenyletain > vinyltrimethyletain. Pour les 'organo-
metalliques insatures ou des groupes de vinyle sont lies avec un
0
atome de metal par 1'intermediaire de groupe.polaire (- ~~'
~0-
ou de noyau de benzene, nous oliservons d'autres r,egularites.
Nous avons montre que les acrylates et methacrylates des
derives aryles et alcoyles detain, de _plomb et de mercure se
polymerisaient et se copolymerisaient facilement avec-des mo-
nomeres vinyliques.
De nouveaux composes son.t aussi presences par les styrole-
nes contenants des metaux.
Pour la premiere fois nous avons synthetise dans les condi-
tions de reaction de Leebtick et Ramsden les styrolenes contenant
le mercure et le plomb. Pour la premiere fois nous avons etudie
la susceptibilite a la polymerisation et copolymerisation, et quel-
ques proprietes des styrolenes metalliques suivants:
p-phenylmercurstyrolene
p-styriltriphenylplomb ,
p-styryltriphenyletain
Ces styrolenes metalliques sont facilement polymerises avec
les monomeres vinyliques dans les conditions de polymerisation
radicalique.
L'etude de la cinetique de polymerisation montre que les
styrolenes metalliques se polymerisent a une vitesse plus grande
que le styrolene insubscitue. Selon la stabilite thermique les
styrolenes forme la serie: Sn>Pb>Hg. En etudiant le processus
de polymerisation. de.,p-vinylphenylmercure qui presente un
organomercure asymetrique on a revele un phenomene de dis=
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proportionation aboutissant a la formation de derive divinylique?
symetrique du diphenylmercure (I) et du diphenylmercure (II).
Le bis-p-vinyldiphenylmercure (I) specialement synthetise se
polymerise facilement en donnant un polymere reticule insoluble
qui est infusible jusqu'a 250? C et se decompose a temperature,.
superieure a 250? C, ce qui est suivie par la separation de mercure?
metallique. Le polymere I aurait la structure:
-CHI-CH-
I
~~
I
-CH-CIIa-
Au moyen de 1'etude executee on a montre que daps les orga-
nometalliques insatures, on observe selon le caraclere de liaison
de groupe vinylique avec 1'atome de metal une difference consi-
derable en aptitude a la polymerisation et en proprietes dew
polvmeres et copolymeres obtenus.
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KOOtIEPATI~IBHbIE HPOI~ECCbI
HP[~I~ IIOJII~IKOHJ~EHCAI)~YII~I BIIOHOJII~IMEPOB
~I. B. Bore?vxexucm,eux
06pasosaxlle .ocxosxblx .6xoxo~Ixnlepos = 6e~IxoB n xyx~Iex-
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_202
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c~iaTa (~~) x N - M -. L nlo~Iexy~I BoRbI. Pes orpaxxxexxx o6x~-
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xapbl xyx~IeoTxRoB, EI. I~ooxepaTxaxocTb xpot~ecca oxxcblBaeTCx
uoTexi;xa~IOM
rRe j - sonlep ssexa, x. xoTopoMy xpKCOeRxxxeTCx HT~, a~ _
=0, ec~Ix xpxcoeRxxx~ICx xyxneoTxA, a~ = 1, ec~Ix
npxcoeRxxx~ICx x a~ _ = 1, ec~Ix aBexo ocTa-
~IOCb cso6oAxbIM. IIpx xo~IxxoxRexcauxx napbl HT~ B pacTBOp
BbIRe~IxeTCSI oAxa Mo.nexyna ~~ [12]. BI>I*Ixc~Iexxe cTaTxcTr:ue-
cxol3 cyMMbi (c. c.) cxcTeMbl J~HI~ - pacTBOp c y*IeTOM (1), a Tax-
xce BO3M0?ICxOCTx xpxcoeRxxexxx Mo.nexy~I HzO, a xe xyx~IeoTx-
AoB, xpxsoRxTCx xo NIeTOAy YIallxra, paspa6oTaxxoaly xpxrlexx-
TeJlbxo x Teopxx c~eppoMarxeTxaMa [13]. Pac=IeT RaeT IIpx
n~MIL>N
K - ~N-M-L)N[4 (N M -L) ~M /nr-M-L\r.X .
X ~ N-bf-LgiMq ~Lq,2N p 2e1 (N -1) -~- Nee )
ex ~ T ,
D = 2E1 + ez 21n (94 M.
RT + \ gF 4L I
3Recb qo' - c. c. cso6oAxoK H2O, q' - cso6opxoro HT~, q" -
cBO6oAxoro ~~, q - xpxcoe~xxexxoro xylc~IeoaxRa, ~maxo - Malccx-
Ma~IbxblA xopexb ypasxexxx
(3)
203
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llpx eB > 1 I xopxx ypasxexxx (3) xnzeroT sxR
L - xapaxTepxsyeT rx6xocTb n~exx.
Txxa s: pacTSOpe pasxo "4 qo - c. c. cssraaxxor~ Monexyxs~ H2O,
`4 kT + In (4q'/ 4L) + In 3 - In C1 ~ 90' N N - L exp RT)-1nG
B RT; C=-A~~-2]n3-RT
M~ npepxonaraeM, xTO xxcxo Mo~exyn xyx.aeoTxRos xaxcRdra
xpxueM B-~C-}-A xyx.aeoTxRos pasxo
OAxospeMexxo
8.1n Q
r - a?D
PaccMOTpxM Asa cnyxarr.
1) B -}- C = A < 0, n~M3KC = ~2, l = z. Ecnx D < 0, To T = 0,
ec~x D > 0, To r - N. PeRyxnxxa~xx npoxcxoRxT xpx xepexo-
Ae D uepes xynb, yc,nosxe peRyx.nxx/a~xx
~2e1 -}- e2 > 2RT In 1 M ~ 44"/ (6)
2) B -}- C - A > 0, AMaxc = A3, Z = 0. Ecnx B -{- C - A -}- D < 0,
To r = 0 - Rso~xax cxxpaxb . coxpaxxeTCA, a ec~x ?B -~- C -
- A -}- D > 0, To -r = N, T. e. xpoxcxoRxT RexaTypagxx, paap;e-
xexHe Rsogxog cnxpaxx xa use conbsaTxposaxx~x Rexx. Yc.aosxe
RexaTypa~xx
O6a xepexoRa TeM 6oxee peaxx, ~eM 6oxbuie N [9]. I~Ia ypasxexxs~
(6) eneRyeT, xTO peRyx.nxxauxx AHI# xoRasxReTCx xpx yse.nx-
~exxx coRepxcaxxx ~~ s pacTSOpe. rpy6ax ouexxa RaeT . gq"
q' ~-10-2: IIpxaxMax E1= 4 K~a.~/.~worcb, E2=7 ?x~arc/.~uorcb; xa-
xoRxM, xTO peAyxnxxan~xx npexpax~aeTCn xpx L/M > 7-?102.
I{opx6epr RosoRxx.. L/NI Ro 102_ IIpx aTOnz peRyx.nxxauxfl
RHI~ ex~e xixa, xo c ynieHbxiexxoH cxopocTbio [12, 14].
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
~Ipx xocxeRosaTenbxo~ peRyx.axxauxx AHK B pacTBOpe pacTeT
coRepxcaxxe ~~ x yMexbxiaeTCx , coAepaxaxxe HTcI~. Ocyx~ecTB-
nxeTCa csoero poRa - xpo~ecc B xoxue xox-'
uoB xpexpaII~aeTCx. ~oxycTxM, xTO xa xexoTOpo~ cTaAxx xpo-
~eGCa xMe,aocb S RBOi~xbix cxxpane~ RHI#, M Mo~exyx HTcI~
x L Mo~exyn ~~. MaxcHManbxoe uxcno xoxyxarox~xxcx RBO~-
xbix cxxpa~ei~ S .-~- t xaxoRKTCS xa yc.nosxx MxxxMyMa? cso6oR-
aog axeprxx..IIo.ay~aeM
1 M 49 ( ZEi - Es
[ 4 ? 9, - I, exp \- 2RT )
t 2NIex _ 2Ei - Ez .~ 99~~ '
L p ( 2RT ) 4q'
BbrxoR J_[HI~ Ao~xcex saBHCeTb oT oTxocxzexbxoro coRep>icaxxa
T -[- Lj x A -{- T, Tax xax I' -}- I.~ o6paayFOT Tpx, a A ~-- .T - RBe
BoRopoRxbie cBxsx. PacueT RaeT
[r+ul
yIa xs.aoxcexxoro cxeRyeT, xTO peRyxxxxauxx RHI~ xpx MxTOSe
1xxBbIX xJIeTOx MOHCeT 6bITb OIII3caxa TepMOJ~xxaMxtIeCKx x xe
xpeRCTaBJIHeT CO6Ox 6xo.norxxecxo~ aaraRxx. IIpxBeRexxbie pac-
*~eTbi Ro.axcxbi 6bITb Roxonxexbi yxeTOM poxx xeopraxx~ecxxx
xoxoB, ReHCZSxe xoTOpbix, no-BxRxMOMy, cBORxTCx x xsMexexxio
,3c~c~exTxsxbix sxauexx~. TepMORxxaMxsecxxr~ pacxeT xoxasbrBaeT,
PTO Bepos~TxocTb HxexpaBx~bxoro> xpxcoeRxxexxx HT4~, xe
coxposoaxAaiox~erocx xoxRexoauxe~i, xxxTOxcxo nMana.
xax c~epMexTaTxsxbiH xpouecc, cocTO~T B xccxeRoBaxxx ero xx-
xeTxxx. HecoMxexxo, PTO xxxeTxxa xoxxxoxRexca~xx 6xoxo.nx-
MepoB xBnxeTCx xooxepaTxBxoK x cooTBezcTByiou~xe ypaBxexxR
xe.axxegxbi. B xacTORx~ee BpeMa xa~zx xauaTa paspa6oTxa xxxe-
Txxecxo~ Teopxx.
BxocxxTea 6enxa MoaxeT 6biTb nioAexxposax xa TOE xre ocxose.
HeRocTaTOx axcxepxMexTa~bxblx Aaxxbix xe xoaso.nxeT xoxa
cosRaTb MoAenb; RBnRiox~yiocx Bxoxxe peaxxcTxeecxoH. ORxaxo,
MO?xxO? BbIpa3xTb ysepexxocTb B ToM, xTO ocxoBxoe xo.noxcexxe
Teopxx - xooxepaTxsxbiH cxxTea xa MaTpxue - xpaBxxbxo i~ B
aTOM c.aygae.
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YueT xooxepaTxBxocTx rroxceT oxasaTbcA npeasr~nar~xo Baax-
xbiM xpx xccneRosaxxx xpoueccos reTeporexxoro icaTa.nxsa a
xxMxx xo.nxMepoB ~ x xxsxonio.aexy~xpx~x coeRxxexxH.
JIRTepaTypa
1. M. B. B o n b x e n m T e 13 n, IConc~Ilrypar;nonxax cTaTIICTIIxa nonx-
Mepablx i;enet3, YIaA. AH CCCP, M. - JL,. -1959.
2. M. B. B onbxenmTeilx, 0. P. IITx>;bIn, ?I{. Texx. c~ICa., 25,.
649, 1955; ~Ilanxa TsepAoro Te~Ia (c6opxxx), 1959.
3. M. B. B o .n b x e n m T e i3 a, J. Polymer Sci., 29, 441, 1958.
4. 0. S. lI T x R bI n, I0. A. III a p o II o s, 7Ii. Texx. c~xa., 27, 2744,.
1957. _
5. T. M. 1?nplnTelin, IO. FI. I'oT~In6, 0. B. IITx~bix; J~o-
x.naR as CxMnoallyMe, cexqux II.
6. P. D 'o t y, Coll. Czehoslov., Chem. Commun. Special ussue 22, 5, 1957;:
Rev. Mod. Phys., 31, 107, 1959.
7. J. H. G i b b s, E. A. 0. M a r z i o., J. Chem. Phys., 30, 271, 1959..
8. B. H. Z i m m, J. K: B r a g g, J. Cliem: Phys., 31, 525, 1959.
9. M. B. B o n b x e n ~ T e ~ a, J_[oxn. AH CCCP (s ne~aTx).
10. M. B. Bo~Ibx?exlnTeiiti, A. M. E.nbxulesx~I, J~ox.n. AH
CCCP (a IIe*IaTx). '
11. M. B. BoabxeaIIITeI3u,A. M. Enbnlnesll~, J~oxn.AHCCCP?
(a nexaTn).
12. A. K o r n b e r g, Rev. Mod. Phys., 31, 200 (1959).
13. C. N e w e 1 I , E. ,M o n t r o 1 1, ~ Rev. Mod. Phys., 25, 353 (1953) _
14 M. J. Bessman, J. R. Lehman, E. S. Simms. A. Korn-
b e r g J. Biol. Chem., 233, 171, 1958:
Summary
The main features of polycondensation of biopolymers -
nucleic acids and proteins-can be summarized in the follow-
ing. The reactions are accomplished with the participation of
enzymes and take place on some kind of template. Many facts
show .that the template for desoxyribonucleic acid (DNA) is
a nucleoproteinic complex containing DNA and for protein, a
complex conytaining DNA and RNA (ribonucleic acid). The
polycondensation process on a template is a cooperative pheno-
menon essentially determined by the near neighbor interactions
of monomers linked by hydrogen bonds 'to the polymer chains.
acting as the template. From this and a simple model a statis-
tical theory for the reduplication synthesis of DNA has been. de-
veloped. The reaction has been shown to start at a certain cri-
tical concentration of the monomers in solution, the ,process
being characterized by a specific thermodynamic phase transi-
tion.
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The following factors have been taken into account: the hydrogen.
bond energy, the energy of nucleotide polycondensation liberated
in a sequence of coupled reactions, the influence of the solvent
(water) and the flexibility of the free polymer chain. The cal-
culations are based on the Icing method used in the theory of
ferromagnetism. The transition during the reduplication synthesis
is the sharper the longer the length of the template chain.
The same treatment can be applied to the statistical-tliermo-
dynamics analysis of. protein. biosynthesis in the form of a-heli-
ces (after Pauling and Cori). Polycondensation of amino acids?
also proceeds by a cooperative mechanism. In this case not only
the hydrogen bonds between the amino acids and the template
have to be taken into account, but also the intramolecular hyd-
rogen bonds of the resultant a-helix: Also in the case of amino
acid polycondensation on a template a sharp transition takes
place at a definite monomer concentration (or at a definite tem-
perature).
The kinetics of polycondensation of biopolymers can be trea-
ted analogously if we take into account the cooperative character
of the process. The corresponding differential equations are non-
linear, but their approximate solution makes it possible to cha-
racterize the. main features of the process.
The above simple models can be generalized to include the
successive biosynthesis of nucleic acids and proteins as a united
process.
The same conceptions may be employed in the theory of he-
terogeneous catalysis.
Resume
Les particularites essentielles de la polycondensation des
biopolymeres (acides nucleiques et proteines) consistent a ce,
que ces processus s'effectuent avec la participation des ferments
ont lieu cur une matrice. A ce qu'il parait c'est un complexe
nucleoproteique qui sort de matrice pour 1'acide desoxyribonuc-
leique (ADRN), ce complexe contient le meme ADRN; pour
la proteine le role de matrice est joue par le complexe, contenant
(ADRN) et ARN (acide ribonucleique). La polycondensation
cur la matrice est un processus cooperatif determ-ine essentiel-
lement par une action reciproque des monomeres voisins qui
sont adsorbes moyennant des liaisons hydrogeniques cur une
chaine polymerique en taut que la matrice. Ces representations
sont placees a la base dune theorie statistique approximee de
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la synthese de reduplication de 1'ADRN. I1 a ete montre que
la .formation de 1'ADRN se passe a partir dune certaine concen-
tration critique des monomeres en solution comme une sorte
de transition de phase thermodynamique. Ici, on a pris en con-
sideration les facteurs suivants: 1'energie de liaison hydrogeni-
~que, 1'energie emise pendant 1a polycondensation duns les chai-
nes des reactions conjuguees, 1'influence de solvant, 1a specifi-
cite chimique, des monomeres (nucleotides) et la flexibilite
des ~chaines polymeriques fibres. Les calculs sont bases sur la
methods d'Izingue, appliques daps la theorie du ferromagne=
tisme. La transition pendant la synthese de reduplication est
d'autant plus brusque que la chains po`lymerique .sur la matrice
est plus longue.. Des idees. pareilles ont tits prises pour base de
1'analyse statistique-thermodynamique de la biosynthese de
proteins .sous forme d'a-spirals de Pawling et Kori. La poly-
condensation des amino=acides s'accomplit egalement suivant
le mecanisme cooperatif; daps ce cas it est necessaire de prendre
en consideration non seulement des liasons hydrogeniques entre
-des amino-acides et la matrice, mais aussi des liaisons hydro-
geniques :intramoleculaires daps un a-spiral apparaissant.
Dans le cas la polycondensation des amino-acides sur la ma-
trice de meme a lieu une. transition brusque a~une certaine con-
~centration .des monomeres.
La cinetique de la polycondensation des biopolymeres peut
titre realises en partant du compte de ~ccooperativite> du proces-
sus. Des equations appropriees sont nonlineaires; leur solution
approximee permet de caracteriser des particularites d'execii-
tion. du processus.
Des representations approximees qui sont donnees ci-dessus
peuvent titre generalisees daps le but d'examiner la biosynthese
successive des acides nucleiques et des proteines. Les memes
representations analogues peuvent titre utilisees pour la theorie
de catalyse heterogene.
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HOJII~ItiOHJ~EHCAI~IAFI 3cI~I~IPOB a-AN~I1[HOKI~ICJ~IOT
B HPI~ICYTCTBHII~I J~BYOKI~ICIII YI'JIEPOj~A
I#. T. IZopoutizc~c, 70. l7. Xgp2uat, T. ,Z{. F#osapeuxo,
H. 8. IZpoxopoea, H. Ti. Hocxoaa
(CCCP)
OTxpbITYIe CaMOII1lOx3BOJIbHOI~ IIOJII3KOHJ~exCaL~YIx 3(~IIpOB
a-aMI3HOxxCJIOT 6bITi0 IIO CyII~eCTBy IIepBbIM CJIyiIaeM, xor~a xIIrsIIxy
yj~aJIOCb Ha~JIIOJ~aTb CyIxTe3 IIOIITxRHOYI CBSI3I3 BHe OpraxYIaMa.
HOCMOTpFI xa . TO, iITO IIOJIxxOxJ~eHCaI;xIO. 3[~xpOB a-aMIIIIOxYICJIOT,
ycxueHxo xayuaux eII~e I{yp~xyc [1 ] x ~g~ep [2], a IIoaAxee
~pexxeub II Ka~anbcxg~ [3], xaTauIITxuecxoe Ae~cTBHe pxRa xxc-
~brx BeII;ecTB, Taxxx xax x,nopxcTbig BoRopoR, yxcycxax x IIpo-
IIxoHOSax xxc,noTbi, RByoxxcb yruepoRa II Ap., 6bixo cpasxxTe~b-
Ho xeRasxo oTxpbiTO B IIaIIrer~ ua6opaTOpxx [4]. Haute BxxMaaxe
B IIepsyFO o~epeAb upxBUexno xxx~xxposaxxe IIonxxoxAexca~xx
ac~xpoB a-aMxxoxxc.aoT (r~naBxbinz o6pasoM ruHuxxa x d, l-auaxx-
xa) RByoxxcbio yr.nepoRa. Bo-IIepBbix, Rsyoxgcb yruepoAa - aTo
aopMa.abxaR cocTaBHaA ~acTb aTMOCC~epbr II oxa, BepoxTxo, xBUx-
a~acb gxxuxaTOpoM IIonxxoIIRexca~IIg ac~xpoB . a-aMIIxoxxc.noT,
onxcaxxbix RpyrIIMx aBTOpaMx [1-3]. Bo-BTOpbix, ac~xpbr a-arsx-
HOKIICJIOT 06pa3yIOT Tax Ha3bIBaeMble xap6aMaTbI Pt1VHg ? OOCIVHR,
pORCTBexHble xap6aMaTaM, xOTOpble 6bi~x IIOCTyJIIIpOBaHbI B
xaHeCTBe IIpOMeHCyTOiIHbIx coeRxxexxg IIpx IIonxxoxRexcauxH
axrxRpxRoB N-xap6oxcx-a-aMgxoxgcuoT [5] - IIpouecca, xax-
6oxee ~acTO xcIIO~bayeMOro R~ts~ exxTeaa BbrcoxoMOUexy~xpxbix
IIOJIxIIOIITII].~OB .
Bbi~a IIoRpo6xo xayuexa IIo~nxxoxRexcan~xx aTx~osoro ac~IIpa
ruxn~IIxa, Tax xax B aTOM cuyuae peax~xx xReT c yAo6xo~ Aus~ xc-
'.c~neRosaxxx cxopocTbio, a BbtxoA AxxeTOIIHIIepaaxxa cpaBxxTe~b-
xo xeseuIIx.
IIpg pa3xbIX xaLIaJlbxbIX OTHOCFITeJIbxbIX (MOJlxpxbiX) xOHI~eH-
Tpal~xfIXFixxI~xaTOpa xMOHOMepa(a(~)~Ipa aMIIHOKFiCJIOTbI) [CO2]~[8]
oT 0,005 Ro 0,16 6bixa gay*~exa xHxeTxxa xsMexexgx cocTasa.
IIouxxoxAexcaTa (pacxoR MoxoMepa, BbixoR AxxeTOIIHIIepaaxxa,
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
xoxuexzpauxsl aMxIIlloro a3oza) x paECxxzaxa cpeRxslx czOIIeIIb
xo~txMepx3ai~xx xexzxAxoii c~paxztxx (ne). Bo BpeMx peaxl~xx
aloxonlep pacxoAyeTCSI B cooTBezczsxx c peaxuxex xepsoro xo-
pxRxa, a xoxczaxza cxopocTl pacxoRa noxoMepa Moxozoxxo pac-
TeT c yse~IxxexxeM [COzI/[Ol L61. CpeAxxsl czexexb xo~Ixnlepx3a-
uxx ?nxxei~xo yse~IxxxBaezcsl c pacxoRoM MoxoMepa [7]. 8zo yxa-
sblsaez, PTO yA.axxexxe z~exel~ xexzxRoB xpoxcxoRxT Bc~IeAcTBi~e
czyxex~azoro xpxcoeRxxexxx oRxoro aMxxoxxc~IOTxoro oczazxa.
I{oxr;exzpauxx aMxxxoro a3oza B xpoAyxzax peaxr~xx (xoc~Ie y~a-
~Iexxsl MoxoMepa x cxxpza) xpx Raxxol~ Be~Ixxxxe [C021/[O] oc-
Taezcx xoczoxxxol~. Tax xax xoxi~exzpar~xx RxxeTOxxxepaaxxa
[2] B xpoRyxzax peaxuxx xpx xxxuHxposaxxx IIpx IIOMOx(x COz
xaRaez, To xaNlexexxe xoxuexzpauxx aMxxxoro aaoza, a Tenl
6o~Iee MoxoMepa, xpoxcxoRxT 6onbn behaviour, extraordinary cir-
cumstances must be provided for these reactions. With other
words, the rule of functionality is valid only under the general
circumstances of the present phenoplast-industry, where some
of the possible ways of a simultaneous reaction-group are favo-
ured. Other circumstances produce other types of reactions, with
different intermediates and special cured resins [6-10], diffe-
ring from the common phenol-formaldehyde resit.
Furfural as condensing agent has like formaldehyde two
aldehyde-functional possiblities, yet the way in which this he-
terocyclic aldehyde acts is highly different in the curing stage:
there is a possibility of splitting one C = C double bond and star-
ting anew Bifunctional cross linking reaction, or splitting two
C = C double bonds, thus starting a further tetrafunctional
reaction; which greatly help the formation of three-dimensional
networks. On the other hand the mechanical strength of the very
dense network, is lowered, the product becomming a brittle mass
without any elasticity. For this reason the industrial application
of fi2rfural condensates is limited.
Phenolhomologue-furfural resins
Theoretically the disadvantages of phenolhomologue conden-
sates and for furfural-resins might compensate each other. By mi-
xing the two types of products, or by preparing them simultane-
ously, excellent products have been expected, concerning both the-
ir mechanical strength, thermostability and elasticity. Yet the
experimental facts did not fulfill these hopes.
A phenol-furfural resin containing s/b parts of furfural,
showed all the disadvantages of furfural resins. Adding less fur-
fural to the reaction mixture, the cross-linking reaction is incom-
plete. Condensing phenols with afurfural-formaldehyde mixture,
unhomogeneous products are obtained, because of the difference
of the rates of afurfural-condensation and that of a formalde-
hyde reaction: formaldehyde is occupying the more reactive places.
When the slower-reacting furfural is first condensed, the reac-
tion mixture, to accomplish the formaldehyde-reaction, is to
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~ 2a
~ /0
40
30
ZO
JO
.~ ZO
~` /0
30
.c 20
~ 10
40
~ 30
~ 20
/0
Lr /r Lr c .~ /r / f~
A/f A Bf-0e CL( /f D/( EN~ ~(
GK N/f "/f
K /K
1
H
L
L
L
L
L
L
fL
L
F
L
~
L L
nL
AL
BL
B L
C
D
E
FL
6L
HL
JL
N D N N Fc N GP NN,I N
0
0
0
0
0
0
0 '0
0
0
DO
/
BO
H
/0
JO
II
f0
FO
f ~
HO
J
AO
A B
CO
C
E
GO
Fig. 1 Curing time of formaldehyde- and furfural-phenoplast resins and
of their 1 : 1 mixtures.
Formaldehyde resins: A -phenolic novolac; B- phenolic resole; C-m-p-cresolic novolac:.
D-m-p-cresolic resole; E-o-cresolic hovolac; F-o-cresolic resole; G-p-cresolic novolac;
H-p-cresolic resole; I - xylenolic novolac; J - xylenolic resole. Furfural resins;
S -phenolic condensate; L - m - p-cresolic condensate (DAB IV); M - o-
cresolic condensate; N- p -cresolic condensate; O - xylenolic condensate '(natural
mixture of homologues).
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be heated for such a long time, that crosslinking of furfural might:
occur. '
In our experiments we prepared mixed furfural-formalde-
lryde type phenoplasts, condensing different phenolhomologues
tivith different aldehydes. The resins were cured, mechanical, ele-
-ctrical and thermical data were measured, both with pure cured
20 ~ 40 60
BO 60 40
17/N Standard ' -
Fig. ?. Impact strength values of mouldings; mixtures of phenolic
formaldehyde ;~ and furfural condensates. F : Furfural-phenol resin,
N :phenolic novolac resin.
resins and with moulding powder compositions, the resin compo-
nents of which were single condensates and mixtures of such ma-
terials.
We succeeded in preparing mixed products, with fair mechani-
cal, elastic, and thermical data, the resins having a ho
mogeneous and optimal network, by condensing first a formal-
dehyde-type phenoplast to its uA> stage, at the same time pre-
paring aphenol-furfural -stage resin, mixing the two in-
termediates and curing the mixture together, after having com-
pounded them with fillers, dyestuffs, and other auxiliaries.
From the point of view of the moulding industry, the physical
data of a phenoplast present only a part of its qualification, the
moulding characteristics, first of all the moulding time are not
less important. To evaluate the rate of cure, formaldehyde and
furfural condensates of different phenols were prepared in the
A-stage, and time the necessary for the resin becoming brittle
was measured in a bath of 160?. Theresults of individual conden-
sates were compared with similar data of the corresponding re-
sin-mixtures. Only three out of the 50 investigated mixtures ne-
eded longer curing times than the component resins, whereas
twenty tests cured faster than any of the component resins. Fig. 1
shotivs the results of the curing tests. The first value in every
;grou.p of three represents the curing time of the furfural resin,
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
the third that of the formaldehyde resin, while the one in betwe=
' en stands for the. time needed for the curing of a mixture (1 : 1)
of the former two.
i ~ ~ ~
0 20 40 60 80 100 % F
100 80 60 40 20 0 % R
Fig. 3. Impact strength values of mouldings:mixtures of o-cresol-form-
aldehyde and phenol-furfural resins. F: Furfural-phenol resin, R:
o-cresolic resole component.
Moulding powders were prepared by mixing the formaldehyde-
type and the furfural-type A-stage resins with wood-flour and
other moulding-powder components, so, that the resin-content of
~ ~ ~ ~ ~
20 40 60 80 100 % F
Fig. 4 Electrical strength of phenoplastic mouldings
1. Mixtures corresponding to those in Fig. 2;
2. Mixtures corresponding to those in Fig. 3.
F: Phenol-furfural resin.
the product was 47,5 %.The mechanical data when plotted against
the forma)dehyde/furfural ratio showed a maximum, while the
electrical strength changes linearly with the composition.
Figs. 2 and 3 represent changes of impact strength of phenol-fur-
fural and phenol-formaldehyde, as well as phenol-furfural., and.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
ortho-cresol formaldehyde resin mixtures, respectively. Fig. 4
shows the change of electrical strength data of the-same mouldings.
The measurements were carried out according to the DIN speci-
fications.
A special advantage of the investigated moulding powders was
the good flow during the first seconds after the mould had been
closed, which enables the moulder to produce precise complica-
ted forms. The powder passes rapidly through .the B-stage~ancl
becomes cured.
The above-mentioned process and the results obtained can be
summerized as follows:
1. Homogeneous formaldehyde-furfural mixed phenoplasts
were obtained by mixing A-stage formaldehyde phenoplasts with
A-stage furfural phenoplasts and curing the mixture in a separate
step t11 ].
2. Phenol homologues, which are known as poor resinforming
components, were incorporated in phenoplast compositions accor-
ding to our method. The slow cure, as well as the bad mechanical
and electrical data of these homologues were eliminated as a
result of the modifying effect of the furfural-formaldehyde resins.
3. With the above-mentioned method a new effect was obser-
ved consisting in a high rate of cure of phenoplast mixtures, com-
pared with that of the component resins.
4. Higher impact strength values might be obtained with these
mixtures, than are usual with the component materials.
. 5. The method allows the partial replacement of o formaldehyde
by furfural, which offers a possibility of englarging. the raw mate-
rial sources of phenoplasts.
In order to give a possible explanation of these effects we
suggest the following consideration:
The furfural-parts of the condensed macromolecule form so-
mething like a skeleton for the formaldehyde-parts, or in the con-
trary: the formaldehyde-parts act as intramolecular softeners
for the furfural-parts. This gives the possibility of using homolo-
gues with poor resin-forming properties.
The good mechanical data might be explained by the balanced
periodical occurance of highly crosslinked and linear sections in
the macromolecule, the former producing resistance against pres-
sure and flexure, the latter giving elasticity to the product. The
utmost homogeneity of the product is however the chief requi-
rement for good results.
The short curing time may be based upon the different reac-
tion-rates and the reaction-heat. In the mould a quick condensation
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
occurs with formaldehyde, accelerated by hexamethylenetetra-
.mine. The evolved heat initiates the polymerization of the fu-
-ran-rings, producing more heat, thus promoting curing of the who-
le mass. In some cases accelerators could be helpful for initiating
the furan-reaction [12], but. generally this was unnecessary. As
ultimate reason of the effect we might assume an interaction bet-
~veen the two different types of reactions, each of which improve
l;he rate and the result of the other one.
References
1. F. J. W a 1 k e r, Formaldehyde, N. Y. Reinhold, 165-166, 1944.
2. V. B 5 r, Magy. Szab. 142, 178, 39/c., 1952.
3. E. G u n d e r m a n n, Chem. Technik, 5, 40, 1953.
4. F. S. G r a ri g e r, Industr. Engng. Chem., 24, 442, 1932.
S. R. W e g l e r, E. R e g e I, Makromolek. Chem., 9, 1, 1952.
6. N. J. L. M e g s o n, J. Soc. Chem. Ind., 52, 422T, 1933.
7. W. G. Musty, S. R. Finn, J. Appl. Chem., 1, 182, 1951.
8. F. LI l l m a n n, K. B r i t t g n e r, Ber., 42, 2539, 1909.
9. N. J. L. M e g s o n, A. A. D r u m m o n d, J. Soc. Chem. 'Ind., 49,
251T, 1930; M. K o e b n e r, Angew. Chem., 46, 251, 1933.
1.U. K. H u 1 t s c h, Ber., 74, 898, 1533, 1539, 1941; 75, 106,
363, 1942.
11. J. A. M i k e s et al. Hung. Pat., 145647, 1953.
9.2. C. H. B r o w n, Industr. Engng. Chem., 44, 2673, 1952.
AsTOpec~epaT
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TaIOT, *ITO Taxxe peaxz;xoxxocxoco6xble aTOMbI BoAopoAa xaxoAslTCx
B opmo- x napa-xo~IOaI{exxxx.
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Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
ileCxIIMg CBOI3CTBaMI3 CO~IeTaHIIEM (~)ypaHOBbIX CMOJI, KOTOpbIM CBOS3-
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
Resume
Le durcissement des resines phenoliques depend de la presen-
ce''dans le noyau de phenol des atomes reactionnels d'hydrogene.
D'habitude on croft que les atomes actifs pareils de 1'hydrogene
se trouvent en ortho- et Para-positions.
Les phenoplastes, composes d'unites structurelles uniformes,
aussi bien.que mixtes, comportant deux, pas plus;. atomes d'hyd-
rogene par molecule de monomers, forwent en general seulement
les chaines lineaires sans reticulations transversales quelconques.
Dares la condensation du phenol avec le furfurol a lieu la ten-
dence a la reticulation, de ces homologues lineaires car outre la
presence du groups aldehydique , bifonctionnel daps .le noyau
furanique it y a 2'-4 points reactionnels (conformement au ca-
ractere de la reaction).
Par suite du processus de reticulation transversals, suivi par
la formation des produits cassants, les difficultes daps 1'utili-
sation industrielle des resines furfurol-phenoliques apparaissent.
On a faitune tentative d'obtenir des phenolplastes ayant de
bonries proprietes techniques par la combinaison des resines fu-
raniques auquels est propre 1'effet de reticulation transversals
avec des resines a mauvais durcissement et a faible reactivite
a base des homologues de phenol.
En condensant le furfurol avec le cresol-ortho on a obtenii
de mauvais resultats, ainsi que pour diverses resines xylenol-
furfuroliques.
Une tentative d'effectuer la condensation en utilisant le mP-
lange du furfurol avec ]e formaldehyde s'est trouve egalement
maleureux puisque le constituant le plus actif a bloque les cent-
res plus actifs ce .qui genait 1'engagement daps la reaction du con-
stituant rests.
Le produit obtenu etait heterogene et' contenait les insertions
aussi.bien des condensats a un constituant que des produits non-
coiiderises. ,
La methods efficace de solution du problems trouvee par
1'auteur consists en ce que la resins furfurol-cresolique au stade
A est melange avec la resins formaldehydique au mews stade. ,
La condensation ulterieure et le durcissement dont effectues,
avec le melange homogene obtenu.
On a determine, les indices suivants des resines durcies, ou
fusibles: stabilite, thermique, resistance a choc, tension de rup-
ture' et temps, de durcissement, temps necessaire pour la tran-
sformation"du melange en masse cassante (lors 'du chauffage,
daps le bain a 160?C).
L'appreciation effectues pour 50 melange a montre que dares
23 cas le temps de durcissement du melange etait plus court que
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
pour toute resine composante; dans 13 cas on a trouve une depen-
dance Presque lineaire de la composition du melange; et seule-
ment dans 1 cas it necessitait plus de temps que pour les. consti-
tuants, separes. Le changement .des proprietes dielectriques se
produit en dependance lineaire ,envers la composition, la courbe
de resistance mecanique a le maximum.
Comme la couleur foncee, la structure reticulee et 1'insolubi-
lite des produits obtenus ne permettent pas d'etudier exactement
le changement de structure, le changement est caracterise par
les reactions mutuelles simultanees de plusieurs types auquelles
sont entraines les monomeres, les intermediaires et le milieu re-
actionnel. A cette occasion est exclue la possibilite des experien-
ces-models executees dans les conditions simples et biers etudi--
ees. Les produits obtenus sur la base du travail donne soot .uti-~~
lises par 1'industrie depuis une annee pour remedier des difficul--
tes temporaires relatives aux matieres premieres.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
O I'ETEPOrEHHOM METOJ~E HOJII~II{OHAEHCAI~I~II~I
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
IIongaM~iAos Aei~cTBHe pacTSOpHTeneg cxaabiBaeTCR B oc$oBHOM Ha
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
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3aDI0CTIITeJIFI B aMIIxOrpyxIIe j[xaJIKxJIaxxJixxa II BJIxHHxe 3aM0CTII-
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rc-IIpoIIll.naxII~IIIx, N,N-Rx-rc-6yTxnaxx~iIIx, N,N-RII-h-oxTII~I-
axx~ixx,
6) N,N-RIIa~I.ax~Iaxx.nxx,
a) N,N-RxnleTx~i-n-6poazaxx~txx,
z) N,N-RIIMeTII~I-n-TO~IyxRIIx.
u~Ix cpasxexIIx B~IIISIxxsl pa3~ix~xbix Rxa~IKx~IaxII~IIIxoB xa
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oTxocIITe.abxo xxxuxxpylox~eH cxcTenlbl x KoxcTaxTa cxopocTli RBIs
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pe3yJlbTaTbI, IIOJ(CileT RaxxbIX IIpOBOJ~I37ICfi R.nsl axcTpaxo~IHposax-
xoro AxaMeTpa xlapxxa, paBxoro 0,6 c.~c.
SbIJIO xai~Rexo, xTO IIo~IxMepII3auIISI n-x~IOpoTxpo~Ia, xxxi;xIIpo-
Baxxax cxcTenlo~I IIepexrlcb 6ex3ox~Ia -{-' RIIa~iKII~Iaxx~Ixx, IIpoTe-
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 Approved For Release 2009/08/28: CIA-RDP80T00246A010900180001-1
KaeT B HatlaJlbHOII CTai~HII IIpII IIOCTOSIHHOI3 xOHI~eHTpaI;I3II MOHO-
Mepa cor~Iacao c~IeAyloII~eMy ypasaeHHlo:
/dM1
- I ~t Jo = R~ = k [(Bz202)0 ' (uIIanxHJlaHxalxH)0]n,
IIpH*IeM 3HaxeHHSI n II ' k ]~JIH pa3JIH~HbIX ]~IIaJixI3JIafIIIJIIIHOB H
TeMIIepaTyp IIpxseReHI,I s Ta6~I. 1.
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Temnepa-
TYPar ?C
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25
0,42
1,62
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25
0,37
9,15
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25
0,34
0,95
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25
0,34
.1,00
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25'
0,33
1,00
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25
0,36
0,87
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25
0,33
2,17
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. 25
0,33
0,36
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15
.0,43
0,59
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35
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HasReilbl 6~Ixsxge IIo Be~Ig*IgHe aHaxeHHH IIoxasaTeSlx n. Hexo-
Topax IIoc~IeRosaTe~IbaocTr; ~bIJIa oTMe~Ieaa E ToM c~Iyxae, xorAa
c yse~IIIxeHHeM AngHbl a.ngc~aTIIxecxo~I t;eIIII yMexbrIIaeTCx IIoxaaa-
Te~Ib n. I~IaMegeaKe TeMIIepaTypbi s RaHHOM gHTepBa~Ie IIpaxTx*Iecxg
He oxasblBaeT s~IxxHIISS Ha IIoxasaze.nb IIo~IgMepxaaz~HII:
ORHOSpeMeHHO c IIopslAxoM peaxugII IIonxMepIISauIIx 6bIJIa
oupeRe~IeHa xoacTaHTa cxopocTH I~, aHaxeHxsl xoTOpo~I Taxxce
IIpxseReabl s Ta6~I. 1.
~ibIJIO HagAe$o, xTO c yse~IgxHSax)II;egcx R~IgHOiI a~Ixc~aTgge-
cxol~ ueIIg y TpeTHxHOro aTOMa asoTa yMeHblIIaezcx (sa Hcx~Iloxe-
AHOM N, N-Z[g-FG-IIpOIIgJIaHxJIxHa') xOHCTaHTa CIfOpOCTII IIOJIHMe-
pHSar~xx. Taxxce AsyxpaTHOe aaMeir;eHBe a~IJIIIJIbabIM paAgxaSloM
(N,N-Axa~ISlII.naHxnHH) cHgxcaeT Ha*IaSlbaylo cxopocTb, ~ibIJIO IIoR-
TBepHCJ~eHO, TiTO 3aM0CTI3TeJIb Ha 6eH30JIbHOM HJ~pe, HaxOAHII[HgCH
s napa-no~IOxceHIIII, xoTOpbtH IIpxTHrxsaeT a~IexTpoabl (-Br), sbI-
ablsaeT xe6oSlbIIroe aaMeR~IeHHe IIo~IgMepH3ai;HII, B To speMx xax aa-
M0CTI3TeJIb, OTTaJIxIIBax)IIjgg 3JIeKTpOHbI (-CH3), sIBSIxeTCSI IIpI3eg-
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 Approved For Release 2009/08/28: CIA-RDP80T00246A010900180001-1
Hog aBxoro ycxopeHHH IIonHMepHaa~HH IIo cpasaexHio c N,N-AI.z-
McTHaaHHnHHOM [8-141. .
Bbtaa onpeReaeaa o6II~aA aHeprHA axTHBan~HH HoHHMepHSauHH
n-xnopcTHpoaa, xHH~HHposaaaoro cgcTeMOg IIepeKIICb 6easoHna -{-
-I- RHaaxHaaaHaHH. HagAeHHbie aaa~eHIIS_IIpHBeAeabi s Ta6a. 2j
Ta6nx~a2
3aaveuxn o6~eii aaeprAS airr8saggR Rna nonAMepxaaq>g
n-xnopczApona, gaxuAgposaxHOH c~czeMOi~ neper:gcb
6enaorfna -{- Anamc~naHRriRu
N,N-ABMezxnaBxnna
N,N-~(nsz8nannnxa
N,N-Z(n-ra-nponn.naaAngg .
N,N-J-[n-x.-6yzxnaaxnma
~N,N-Rx-K-oxz8naaannH
n-BpoM-N,N-RnMe~gna$gnHx. .
N,N-ABMeTBn-n-TOJIyI3J~I3H
N,N-J~aanuanaan.nna
11,9 t 1,5
.11,9 ~ 1,4
12,2 ~ 1,1
11,8 ~ 1,5
12,4 ~ 0,7
11,9 ~ 0,3
8,6 ~ 0,5
11,5 ~ 1,0
I{aK BHAHO II3 Ta6.a. 2, o6II;aH aHeprHH axzHBa~HH Rnx AHCIIep-
CHOHHOg IIOJIHMepI33aI[HH yMBHbIIIaeTCH C `Z3 76KaJG/.hLOJGb - IIpH'
HHH~HHpoBaHHH TOIIJIOBbIM pasaoxcexHeM IIepeKHCH 6eaaogna -B:
cpeRHeM Ro 11, 9 K~ca.~/.n~or~b IIpH HHHI~HIIpoBaHHH egczeMOg IIepeKHCb?
6eaaoHaa = AHa.aKH~aHHaHx as HcKaio~eHgeM N,N,-RHMeTIIn-n-
zo~yHAHHa, xorRa oxa cocTaBaReT 8,6 xxarc/.~orcb.
3aKaioaeHIIe
Pe3yxbTaTbi pa6OTbI IIOKa3bIBaIOT, tITd MOTOJ{ HccneAosaHHR~
KHHeTHKH IIoaHMepHaa~IIH B cTOa6HKe pacTBOpa agaegaoro rpa-~
J;HOHTa IIJIOTHOCTH J~aeT TOiIHble H BOCIIpOH3BOJ~IIMble pe3yJIbTaTbI,.
SIBJIFIeTCH BbICOKOIIpOH3BORHTeJIbHbIM, Tpe6yeT He6OJIbIII0r0 KOJIH-
ileCTBa DIOHOMepa H HHHI~HaTOpa H, KpOMe TOTO, J~eJIaeT BO3MOHCHbI11i~
Ha6.nioRaTb BnHRHHe cpeAbt Ha xgHezIIxy AHCnepcgoHHOg IIoaIIMe-
pHaa~IIH. .
JlgTepaTypa
1 K. L i n d e r s t r o m-L a n g, H. Lan z, Jr., Compt, rend. tray, lab..
Carlsberg, Ser. chim., 21, 315, 1938.
2. S. Tessler, N. T. W o o d b e r r y, H. M a r k, J. Polymer Sci.,
1, 437, 1946.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
3. R. F. Boyer, R. S. Spencer, R. M. Wiley, J. Polymer
Sci., 1, 249, 1946.
4. 0. W i c h t e r l e, J. Z e l i n g e r- AoxnaR na aay~xoi3 xonc~e-
pea~urt IIpaxccxoro XI3MfIxo-Texxonori~xecxoro xacTxTyTa - 1 nionn
1956 r.
,5. J. M. M i 1 1 s, J. Polymer Sci., 19, 585, 1956.
6. 0. W i c h t e r l e, J. Z e l i n g e r, Chem. prom. 7, 265, 1957.
7. F. H r a b a k- AnccepTagxx - c~onR. Mocx: nncTnTyTa Toxxoir xnaz.
Texnonornx M. B. JloMOxocosa.
8. L. H o r n? e r, K. S c h e r f, Ann. Chimie, 573, 35; 1951.
9. M..I m o t o, K. T a k e m o t o, J. Polymer Sci., 19, 579, 1956.
10. J. L a 1, R. C r e e n, J. Polymer Sci., 17, 403, 1955.
11. E. R e t h y, I. G e s z y; Makromolek. Chem., 25, 176, 1958.
~12. T. H. M e l t z e r, A. V. T o l o l s k y, J. Amer. Chem. Soc., ?6, 5178,
1954.
13. M. I m o t o, T. 0 t s u, T. 0 t a. Makromolek. Chem., 16, 1.0, 1955.
14. I. G e s z y, E. R e t h y, Malcro~nolek. Chem., L5, 186, 1955.
Summary
A new micromethod is described for investigating dispersion
polymerization. The method is based on the changes in density
of a drop of the polymerizing monomer in a column of solution
with a constant density gradient. The benzoyl peroxide-dialkyl-
aniline induced polymerization of p-chlorostyrene in sodium chlo-
ride solution has been investigated.
With the aid of the method the effect of the medium
. (aqueous solution) on the polymerization reaction has been stu-
died. The dependence of the dispersion polymerization upon the
medium is the resultant of a decrease in the initial polymeriza-
tion rate, by the water and a retardation of the polymerization
by sorbed oxygen. The effect of the medium depends upon
the specific surface area of the monomer-polymer drops.
In polymerization in the presence of N-alkylanilines it has
been found that the polymerization rate decreases with increasing
size of the alphatic substituent at the nitrogen atom. The incorpora-
tion of bromine in the para position of aniline slows down the
polymerization, whereas a methyl group accelerates it.
The rate of polymerization is expressed by the equation: R~=
= k(/BzzOz/ : /dialkylaniline/o)n, the value of n approaching 0,3~.
The over-all activation energy has been foun equal to
11,9kcallrr~ole for all dialkylanilines accepting N,N-dimethyl-p-
toluidine for which. the value was 8,G kcal/mole.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
Resume
Une nouvelle methode pour 1'etude de polymerisation en
dispersion est decrite daps le travail. La methode est .basee
sur' la variation de la densite de goutte de monomere polymerise
dans la colonne de solution a gradient constant de densite. On
etudiait la polymerisation de p-chlorure de styrolene amorcee
par le systeme peroxyde de benzoyle-dialcoylaniline en solution
du sel de cuisine.
Par la methode decrite on etudiat 1'influence du milieu (solu-
tion aqueuse) sur le cours du processus de polymerisation.
Le deroulement de polymerisation en dispersion depend du
milieu. de fagon que 1'eau augmente la vitesse initiale de polyme-
risation tandis que 1'oxygene absorbe ralentit la polymerisation.
L'influence du milieu depend de la surface specifique des gouttes
monomere-polymeriques.
Lors de polymerisation en presence de N-alcoylaniline on a
trouve que la vitesse de polymerisation chute au fur et a mesure
de la croissance de substituant aliphatique chez 1'azote. L'introdu-
ction du brome dans 1'aniline (en p-position) ralentit la polyme-
risation, 1'introduction du groupe methylique 1'accelere.
La vitesse de polymerisation est determinee par 1'equation.
Rp = k(/BzzOz/:/dialcoylaniline/~)n,
la valeur n est proche. de 0,35.
On a trouve que 1'energie d'activation est egale a 11,9
kcal/mol pour tons les dialcoylanilines sauf N, N-dimethyl-p-to-
luidine pour laquelle la valeur d'energie d'activation est trouvee
8,6 kcal/mol.
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Q
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
TEPMI~ILIECKOE CTAPEHI~IE IIOJIIIXJIOPOIIPEHA.
M. ICecc.2ep, B. Mama,ecxa, Sl. II o.~a,uex
(Liexocnosaxxa)
CTapeIIHlo IIo~Ir3x~IOpoupexa, couposoxsRaloII~eMycsl BbIRe~Ie-
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
McTpe I~eHCCa UR-10. B HexoTOpblx c~Iy*Iaxx cIIIIMa~III AIIC~c~epeII-
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TOCFI IIpH J~IIOBHORi CBOTe B IIpxCYTCTBIIII B03J~yXa IIpH KOMHaT-
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dW/dM
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secant no~Il3xnoporlpexa cse:xero. (Z), coczapBBBIe-
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2 *Iaca ITpII 80? (3)
.My cTapexIIlo IIpII 80? B Texexxe Rsyx ~IacoB xa Bo3Ryxe, npeA-
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Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
o~IeHb 6bicTpo riaRa~Ia Bo BpeMx HsAiepexlisl II uocne 48 _~racciB 6i~I~Ia
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xy~Ixpxoro Beca BTOpoI~ c~paxuxH HporlcxoRx~IO McR~Iexaee, Ho Bce~
xce xaMxoro 6bicTpee, ueM B c~iy~ae Bcex ocTa~Ibxbix c~paxr~ill~,
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B Hxc~paxpacxoi~ o6~IacTx xepeocaxcRexxoro Ho~Ixniepa, xe HoAsep-
raBBlerocu c~~paxul3oxllposaHHlo, Haxecexxoro B Bx~e n~rexxx xa
H.aacTHxxy . opoMxcTOro xa~iHx,. Hpx xarpeBaxlaH B Teilexxe pas-.
Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
nx~xbix xepxoRos BpeMexn xpx 80?. I~poMe 3TOro oxpeAenx~x co-
Aepxcaxxe rpyxx C=0 B pacTBOpax pasnxuxbzx ~ipaxRxH cocTapgB=
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xe xoRseprasixerocs ~ipaxuxoxxposaxxFO, o6pas~a x c~paxuxH
o6pas~a IIoc~e ero czapexxR B Te~exxe 2 ~acbB xpg?80?., xoxasax
xa pxc. 2. ~ '
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CTExx BosAyxa, 02, Nz xpx pasxxxxoH TeMxepaType xa o6pasr~ax,
~pxxcRi~ xepeocaixAeHxi>zx. I~poMe Toro xsyga~nx Bnxuxxe cxoco6a
xpxrozoB~exxR o6pas~oB Ha cxopocTb BbiRenexxx xnopxczoro
BoAopoAa: Oxasanocb, uTO B oAxxaxosbix yc~oBxxx BbiReBexxe
x~opxczoro BoRopoAa IIpoTexaeT B *~xcTOM xxcnopoRe McAnexxee,
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pacTBOpe B xpxcyTCTBxx axx~xxa, g 3TO saMeR~exxe TeM 6o~bxte,
ileM J~OJIbIIIe ' IIpOBOJ;xTCx xarpesaxxe.
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nx~xbix xepxoRoB BpeMexII xpx 65?: ,`
I~oxexxi~e eTexexx xpncTan~xsauIIg x xoayxepxoRbi . (oTxo-
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Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
06cyxtRexxe pesySlbTaTOs
? IlepBbinl aTanoM oxpeAe.neHHU MexaxxaMa cTapexHx HoSlxx.ao-
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axa,nHS BbIReSIxIOluHxcH HpoRyxTOB. CTpyxTypHble HaMexeHHSI B
axaxHTeSlbxoi~ czenexH cs$aaxbl c cocTaBOnI Ho.nHMepa. Ha ocxo-
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BbIHIeHIioi~ TenlnepaType coAepx{aHxe BblcoxoMOJlexyaSlpxblx c~paK-
unil B6apacTaeT. 061uax Ao~Ix Hxaxonlo~IexySISIpHbIx c~paKuni3 npH
' aTOnI xe xaMexxeTCx, xecnloTpx Ha To, ~ITO yse~IH~IHBaeTCx RoSISI
6oalee HHaxoMOSlexy~ISlpxblx HpoAyxTOS. C BoapacTaloluei3 TenlHe-
paTypOH' 3T0 yMexbIIIOHHe ORHOpOJ~HOCTH CxJIbHO yBeJIHtIHBaeTCFI
(xpHBaSI 3, pxc. 1). IloaTOMy xcxo, nTO npH oxilcSlexxH HonH-
xnopoxpexa II1lOI3CXOZ[I3T oRxospeMeHHO H cTpyxTypllposaxHe x
coxpaH~exIIe noSlHMepHblx uenei3. 3HanHTe.abxblii pocT Ro~IH Bblco-
xonlo~IexySISIpHbIx c~paKugi3 HpH HosblHlexxoiI TenrriepaType Ho-
KaablBaeT, ~ITO peaxuHH cTpyxTypnposaxHx B npouecce cTapexHa
xa BosRyxe npeo6,naRaloT H&I~ peaxuHSIMH RecTpyKuHH.
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caMOnpoHSBOSIbxoI3 RecTpyxuHH pacTBOpoB uepsblx RByx c~paxulli3
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npH noBbllHexxoii TenlHepaType Ha BoaRyxe, 6oSlbme cxopocTx
J~eCTpyKijxn OCTaJIbHbIX (~paKuHI3, CBHJ~eTeJIbCTByeT O TOM, LITO
s peaxullx cTpyxTypxpoBaHHx HpnxHMaloT ynacTHe r~IaBxbinl 06-
pasoM cBSISH 6oSlee c.aa6ble, nenl cBSlsb C - C HJIH C - O: YBe.aII-
~exlle cxopocTll ynbTpaaByxosoH RecTpyxuHH,B 4,5 pasa RSIa co-
cTapHBHlerocH no~IHMepa noRTBepx{RaeT sTOT BbIBOR. HaH6oSlee
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rHfi KOTOpOI3 IIpHOJIH3IITeJIbHO B 2,5 pa3a MexbDIe 3HeprHH CBH3H
C - C HJIH C - 0. CoRepx{aHHe Hepexncxoi~ cBxaH, BepoxTxo, sxa-
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uHH Ao oHpeRe.nexxoiI npeAenbxoH j[JIIIHbI uenH, npHxehl
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yx{e xe oTMe~a~IOCb (pxc. 2). IIpH RecTpyKuHH o6paaua,
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
Pxc. 3. B.axxxge BpeMexx aBaxyxpoBatcxx as
~?cxopoczb oTn;erinexxR xnopxczoro xoAopoAa as
~ xoaAyxe npx 80?; t --~ spensx axaxyxponaxiix.
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apensexetK Anx o6pa3gos, xarpeBasxrxxcx s zeuexiie
paaa~iuat~ix xepxoAos BpeMeaR npn'65? xa soaAy xe: '
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Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
xe xoRBeprasuierocx c~paxuxoxxposaxulo, BcneRcTBxe paapblBa cBSI-
sel~ b6pasyloTCSI alonexynbl xonllaiepa c ToH >Ite npeRenbxol~ Anxxoii
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xxxte xpxTxxecxoH. IIepriax c~paxr~ux uonuMepa,~;xarpesasmerocsi
xa, BoaRyxe xpx 80?. x yxte B, xauaale oxblTa xacTllxxo caMOxpo-
x3BOJIbxO xoRBeprxierocsl RecTpyxuuu, upoAonSltaeT xpeTepxe-
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TOH xte J~nxxbI I~exeg,' xax x xe pa3J~enexxbIl3 xa C]lpaxljxx CBe?xHi3
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CBx3x x O6pa3OBanxCb MOnexyJIbI C TOi3 xte J~JIxHOI3 uexx-, xaxIle
o6paayloTCSI B cny~ae o6paaua, xe paaRenexxoro xa c~paxul~Il.
IIpeAenbxax Rnxlla ueuu Aonxtxa 6bina 6bI Tenl 6oalbxie xpu6nm-
xtaTbcsl x Benu~xxe, AocTUrxyTOr~ y c~paxux~ 2-4, xeM.6onbu~ee
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saxxrl.
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6b~no Aoxa3axo Bblcoxoe coRepxtaxue C=0 rpyxx B uepBOK c~pax-
uxx. B cBx3u cTeM, xTO xapaxTep oltucnuTenbxbix peaxuug AB-
nslezcx paRuxanbxblM, xaAo uonaraTb, PTO xapannenbxo coRep-
xtaxxlo C=0 rpyxx xaMexxeTCx x coRepxcaxxe ocTanbxb~X
rpyxx, co~epxtarl~xx xucnopoR, a axa~uT x coAepaxaxxe uepc-
xuceH, PTO xaxoRuTCx B.cornacxx c Bblme xpxaeRexxbinlx peaynl.-
TaTarlx xayxexxx AecTpyxuxu uoR ReHCTBUeM yni,TpaaByxa. II~:ri
I-ISy~Iexxx cxexTpoB xornox~exxR B xxc~paxpacxol~ o6nacTx, cxslTblx
B Te~exxe cTapexllx uonxnlepa, 6bino xal~Rexo, xTO cxauana yMeI1I,-
IBaeTCx coRepxtaxxe rpyuxbl OH (3310 c.roc-i). OAxoBpeMenlio
xaxxxaeT yse~Ix~IUSaTbcsi coRepxtaxue rpyuxbl C=0 ~ (1730-
1800 c.nc-i, Itap6oxcxnbxo~I x xap6oxx~IbxoK). IIocne xeaxa~xTenti-
xoro yse.axxexxx coRepxtaxxx aTOH rpyrlxvl Moxtxo aaMeTI~~~I,
xoxIIxtexxe coRepxtaxxx rpyxx CCl (602-607 cnti-I), CCl = CH -
(826 c.mc-i), CRIRz = CHR~ (3025 c.ac-1) x CHz (1315; 2840-C0
u 2920-50 cnc-I). I~Iariexellxx coRepxtaxxs~ rpyxxbl C = CIT2.
(91Oc.n~-I)xpxsTOM ycTaxosxTb ile yAaalocb,xo xo xonoce 3080 cac-'
rlOrxxo xpeRuonaraTb, xTO coRepSltaxxe Bi3xx.rrbxblx rpyxu yae-
nx~xBaeTCx. Xopoulo BxRxo ysenxuexue coRepxtaxux coxpilslcel_-
xbix RBOI3xbix csslaeii (1602 c.tic-I). IIonoca xornou~exxsl, cooT>3eT-
cTBylox~ax aTxM cBSIasIM, pacxlxpxeTCx B cTOpoxy 6onee Bbicoxlix
~acTOT, PTO Morno 6bI 6bITb csaaaxo c xoxBnexxeM rpyxu C = C
x -CO - C. B 6onee xosRxxx c~asax cxosa ysenxuxsaeTCn
xixpoxali xonoca nornou~exxx xpx 3420 c.~-I, cooTBerczsylou~asi
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xaeT x ~xnbR [6].
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cTapexxu, Moxtxo cy~xTb x xo xaoTepMaM xpucTa.anuaal~xx (pxe. 4),
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
xoTOpble Moxcxo 6biJro Rnsl eBexcero .x RJix cocTapHBHlerocsl noJrH-
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PTO cTexexb cTpyxTypxp.osaxHS IIoJrHxJiopoxpexa, xarpesaBnierocs
42 xaca Ro 100?, 6o.nbIIle cTeuexx cTpyxTypxposaxxa o6paaua
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peaxuxx, BblabrBalox~eH HoxHxcexxe xpxcTaJrnHaauxx, HpaxTll-
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npx BblReJrexxx xJlopxcTOro BoAopoAa (9,5 xxar~?.n~orcb-1). IIpli
cTapexHx npx TeAlIIepaType, IIpeBblIIlaloII~e~i c~aaosblH IIepexoA
IIepBOro poAa, BbIReJreHxe HCl oxasblBaeT peIIlalol~ee BJIIIfl-
xlle xa BeJiHtlxxy RoJ1H, cxoco6xox xpxcTaJrJrxaosaTbcx noc.ne
oxJraxrRexxsl. IIpII BbIAeJrexHx xJropxczoro BoAopoRa o6paayx3TCs
C0rM0HTbI, HOCII0006Hble ICpxCTaJIJIx30BaTbCFi, HO He CHII?xax)H~He
IIOj~BxHfxOCTII I~eIIx, Tall iITO CICOpOCTb II1]OI~eCCa ICpHCTaJIJIx3ar~xx
B CyII[xOCTI3 He II3M0HSIeTCH.
I~Iay~lexxe cxopocTx BblReJrexl?ISS HCl II BJrIIxxxe aBaxyllpo-
Baxxsl IIoRTBepAIIJro, B cor.nacHx c pa6oTOii I~yab~IHllcxoro [71,
Baxcxylo poJ1b cBO6oRHOro H csxaaxxoro xxcJropoRa B 3TOli pe-
axuHH. CpaBxelixe cxopocTx BbIReJrexxsl HCl RJrx o6paauoB,
xpailHB~xxcx xa BoaRyxe x B BaxyyMe,. IIolcasblBaeT, PTO B oT-
cyTCTBxe xxcJropoAa B sHauxTeJrbxoH Alepe IIpoxBJraloTCx pe-
axul~x, BeRyx~He x xoxHxcexxlo coRepxcaxxsl peaxuHOxxocxoco6-
xblx rpyxH B IIoJrxAlepe x x o6pasosaxxlo ycTOHUxBblx cBxaei3.
B IIpxcyTCTBxx xxcJropoRa, xao6opoT; y13eJrHLIIIBaeTCx gxcJro i~exT-
pos xxi~uxxposaxllx.
O~bILIxble HHrII6xTOpbI paJ~xxaJIbxbIX peaxl[I3I3 (6eH30XHHOH,
(~exOTHaBIIx LI T. II.)' B 3xa9xTeJlbxOx Mepe TOpM03FIT IIpouecc.
OIIbITbl IIo xarpesaxxlo IIoJrHMepa c axxJlxxoM IIoxa3blIIaIOT,
xTO yxacTxx c aJi.nz3JrbxoH cTpyxzypoH oxasblsaloT pexlalomee
BJrHxxHe IIpu IIxxuxxposaxxII IIpouecca oxxcJleHHx.
B rasoo6paaxblx IIpoRyxTax AecTpyxuxx, IIpoBORxArola HpI~
~oJZee Bblcoxxx TeAlHepaTypax B BaxyyAle, 6blJlo Roxaaaxo McTO-
RoM Macc-cnexTpoAleTpx~lecxoro axaJrxaa xaJixxxe: HCI, CSz,
COS, SO2, aAIIIHOB H BEII[eCTB C MaccaMx OT 85 J~0 105. HeJrbasl
xcxJrlo~xTb IIpxcyTCTBxx xxcJropo~coRepxcam~xx IIpoRyxTOS. B
HpoRyxTax pasJroxcexIIx oRxoro Toribxo TeTpa3TnJrTxypaMRxcyJib-
~Hua 6bI7I0 o61lapyxceHO IIaJix~xe CSz, COS, SOz H aAlxlloB.
22* 335
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
B ilpxcyrcisxx' aTOro coeAxHe$xsi nenv~sr IIoaTOnly xoalyxxTb' Iia=
Ae'xcxblx peaynbTaTOB axanl~sa IIpoRyxTOB.
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npx CTapeIlI3Ii, xHxt~xxpyIOTCSI O'KxCJIKTeJIbxbIMx p(?~1I{LjI3fIMN, CO-
IIpoBOxcAalongxMxcx o6pa3oBaxAeM xepexi3cxblx rpynil. Ha xoR
'aTxx peaxi;xl3 B~IxsieT, TaxxM o6paaoM; rlpxcyTCTSxe xxcnopoRa B
.alo6ol3 c~aae IIpxroTOB~Iexxn Iionxrlepa. Ozx~eIInellxe uepexxcx
BbI3bIBaeT peaxz;xx c pasBr3TOiI BblpoxcRexxoH "uexblo .A axcnoxex-
Y~i3a~IbxblK pocT xxc,na paRxxa.noli. Cza6xJIbxbIMli IIpoRyxTaMrl
paasxTxsl ueIIx xs.nxloTCx rpyliIIbl C = 0, C = OH`~'x 'C - O,
iIO x caMx xepexxcx coxpaxxloTCx B IIo~IxMepe :e" Teuexxe Ronroro
BpeMexl~.IIOCaIe oxoli~axxsl xarpesa. BblAe.nexllro HCl IIpeAxiecT-
syeT peaxuxu xepeRaxx MexcAy Mo~Iexy.aoli~ no.allMepa x .nIO61~InI
paAxxa.nonl. PaAxxa,n Re~IaeT C-CI-cBx3b aTOnla x.nopa IieycTOI~~I-I-
so~I, x xoc.ne oTii~eII~Ielilsx x.aopxeTOro - BoRopoAa xpoxcxoAxT
xeper;axa paAxxana c uocneRylou~xrl oc~Ia6.aexxenl cBSlax cneRylo-
iuero aTOMa x.aopa. ?HoAo6xbIII i~IexaxHSM IIpeAxoalaraeT ApJIb-
blailll ]8] A~Ix no~IxBxxx.nxnopxAa. BblRenexxe HCl coxposox~HSI IIpxcoeRxxexxx xo.nxMepxoro paAHxa~Ia x IIHTporpyIIIIe
[20l Mexee BeposlTxa. YIsBecTHO, uTO peaxi~HOxxocuoco6Hbli~ c~e-
xyIJIbHbII3 paAxxan He pearHpyeT c xxTporpyIIHOH apoalaTllxecxHx
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((2) IIpOTexaIOT JierICO BCJIeZ(CTBHe 60JIbIII0i3 IIOJ~BHSxHOCTx aTODIa BO-
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1131.
B Ta6~I. 4 coxocTaB.aexbl xoxcTaxTbl kx ANSI npeAcTaBHTe~Iei-i
'TpeX xJIaCCOB THIIIIzIHbIX xxrHCHTOpOB.
Ta6~II~ga 4
KOHCTaIITbI kxAnn ~aaax~~xb~x paANlcaalos
Bennvt?na kx (n/.MOnb?cer) A.nn nonnn2epati~x
paAxna,noa ,
BA ~ MA ~ AH ~ -IM ~
36000
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B Ta~Ji. 4 IIOJItiIDlepxble paJ~xxaJlbI IIOMeH~exbi B IIOpSIRICe y6bI-
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yxaaaxxo%I 3axoxoniepxocTx. Tax, c a.nelcTpoxoalcl;exTOpxo%I nlo~Ie-
xy~IO~I 6exaoxHHOxa c IIaI16o~IbiIIeH cxopocTblo pearHpyeT IIoaIIIMe-
Tx~IMeTaxpx~IaTHbI~I paAHxa~I, o6~IaRalolt~HH xaHMeHbIIteil 3~IexTpo-
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C Rpyrol~ cTOpoHbl, RHHxTpo6eHSO.a He pearHpyeT c xo~IHaxpx~IO-
HIITpxJIbHbIDI pai[xxaJIOM, iITO MO?xIIO OG'bSICHHTb CH7IbxOI3 3JIeKTpO-
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poxoRoxopxol3 Monexy~IOi~ axTpauexa a~IexTpoxoaxi~exTOpHbII~
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
IIOJInaKpnJiH~iTpI3JIbHbIYi paAYIHaJr peari3pyeT C 6oJlbruex CIfOpOCTbIO,.
~renl aTO cJleRyeT na peaxz~HOHHOCnoco6HOCTrr 3TOro paRrr--
xaJla.
J1irTepaT~?pa
1. S. F o o r d, J. Chem. Soc., 48, 1940.
2. G. S c h u 1 z, Makromolek. Chem., 1, 94, 1947.
3. J. B r e i t e n b a c h, L. Elektrochem., 60, 286, 1956.
4. P. Bart 1 e t, H. K w a r t, J. Amer. Chem. Soc., 72, 1051, 1950..
5. J. K i c e, J. Amer. Chem. Soc., 76, 6274, 1954.
6. J. K i c e, J. Polymer Sci., 19, 123, 1956.
7. B. A. RonroIIJloc?x, J~. C. I{opoTxrrna, P. A. Tiap-
c~exoBa, B. JI. Epyca.nllMCxIIx, E. B. N1nJ~oBCxasl..
Bonpoc~r xIIMIIxecxoi~ xnxeTnxx; xaTaJrnsa x pearsrirroaxoK cnoco6-
xocTrl: I~IaA-BO AH CCCP, MOCHBa, 1955, 303.
8. 3. A. CIIIIxu>;rxa, X. C. BarAacapbxx, }Ii. r~na. XxMxx,_
32, 1958, 2663.
9. 3. A. Cnxxubrxa, X. C. Bar,gacapasrx, N{. errs. xrraruII:,.
(s xe~raTx). ?
10. 3. A. CIIrrrrubrna, X. C. Ear~acapbxx, }If. ~irrs. xxMxx,.
(B IIe*raTII).
11. X. C. B a r A. a c a p b sr u, AxccepTauxB. ~xaxxo-xxNrxaecxrrzc rrx-
cTIITyT IrM. JI. I3. I#apnosa, Nlocxsa. 1950.
12. X. C. B a r A a.c a p b x rr, ;3~. (~IIIS. xxMIIII, 32, 2614, 1958.
13. X. C. B' a r A a c a p b a x, }I~. ~ixs. xxMxx, 22, 1181, 1948.
14'. X. C. B a r A a c a p b sr x, Teoprrx paRxxanbxoir no~rxMeprraauxrr,
I/IsA-BO AH CCCP, 14Iocxna, 1959.
15. W. Behgoudh, S. Melntosh, R. Thomson, Nature,
184, 266, 1959.
16. P. ICI. MxsrroTIIxcxax, X. C. BarAacapr~srx, E. A. yIa-
p a x n e B x u, }If. c~xs. xuarxx, 31, 1019, 1957.
17. X. C. BarRacapbsin, P. ICI. 11xJIIOTI3xCxax, }Ii. c~xs.
XYIMIIII, (B IIe4aTI3).
18. M. S z w a r e, J. Polymer Sci., 16, 367, 1955.
19. X. C. B a r R a c a p b x x, }iC. c~xs. xxMxrr ~B xezraTn).
20. P. B a.r t 1 e t t, G. Ii a m rn o n d, ?i. Polymer Sci., 6, 617, 1951..
Summary
A quantitative study of chain transfer and inhibition reactions
makes it possible to ' determine - the ratios kx/Icp where kp and
kx are the chain growth and transfer constants. Since the absolute?
values of the constants kp are known for a number.of monomers it
is possible to determine the absolute values. of the constants kx..
We have investigated the inhibiting action of some types of
aromatic .compounds in the polymerization of vinyl acetate,
methyl acrylate, acrylonitrile and methyl methacrylate.
In the polymerization of vinyl acetate the inhibiting effect
of the aromatic hydrocarbons increases in the order: toluene,.
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~diphenyl, naphthalene, phenanthrene, anthracene. The logarithm
~of kX is linearly related to the logarithm of the methyl affinity.
The inhibiting effect increases on incorporating substituents,
both electrodonating and electron accepting, in the benzene ring.
'There is no relation, however, between the value of kx and Ham-
met's 6-constant. An outstanding position is assumed by nitro-
benzene of which the IcX constant is by 3-4 magnitudes higher
than that of the other substituted benzenes.
The incorporation of substituents in the meta and Para posi-
tions of the benzene ring follows ?the Hammet rule, the electron
donating substituents causing a decrease in the kX. values.
Similar relations are observed in the polymerization of methyl-
methacrylate, but the absolute values of kX are by 3-4 mag-
nitudes lower than in the polymerization of vinyl acetate. Because
-of this under the experimental conditions (kx < 0.21lmole. sec.
.at 50?) the interaction of the polymethylacrylate radical with mo-
lecules of the addition agent was not revealed in the case of many
?of the substances investigated, for instance of all monosubsti-
tuted benzenes, excepting nitrobenzene.
A comparison of the lcX values for polyvinylacetate, polyme-
thylacrylate, polymethylmethacrylate and acrylonitrile radicals
permits a number of conclusions to be made concerning the influ-
ence of the polar factor on radical reactions.
The data obtained lead to definite conclusions as to the inhi-
biting mechanism of aromatic compounds. The primary act is the
.addition of the polymer radical to the aromatic ring with the for-
mation of anon-reactive radical, In the case of nitro compounds,
the polymer radical reacts with the nitro group, probably, by
transferring to pit a ,~-hydrogen atom.
It has been found that in the polymerization of vinyl acetate
-irr the presence ~o'f the inhibitors in question each molecule of the
latter terminates two kinetic chains; regeneration of the chains
does not take place and the polymer molecules form as the result
~of disproportionation between the polymer radical and the radi-
cal formed during interaction. oi' the former with t:$e inhibitor
molecule.
Resume
L'etude :quarititatv.e ~iles reactions de transition de chaine et
~d'inhibition permet de definir les valeure kX/Ic~? hP et kX, constan-
~te de vitesse de croissance et de transition de chaine. ~.omme les
waleurs absoluts ~da la constant,e kr, sont connues pour certains
monomeres it devient aussi possible de definir ]es valeurs abso-
]ues de la canstante .k.X..
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i1'ulis avoiis studio faction inhibitrice 'de certaines classes
flee aromatiques sur la polymerisation de 1'acetate de vinyle, de
1'acrylate de methyle, de 1'acrylonitrile et du methacrylate de-
methyle.
Dane la cas de polymerisation de 1'acetate de vinyle 1'action~.
inhibitiice des aromatiques s'accroit suivant. I'ordre toluene,.
diphsnyle, naphtalene, phenantrene, anthracene. Log kX est lie .
linsairement a log de 1'apparente methylique.
Par suite d'insertion daps le noyau de benzene des substituants~
aussi electronodonneurs qu'?lectronoaccepteurs faction inhibi-
trice s'accroit. lci, on observe 1'absence de quelque relation entre
la valour kX et lee constantes a Hammet. Une position exclusive
est occupee par le nitrobenzene pour lequel la constants kx est
de 3-4 ordres plus grande quo pour d'autres derives de benzene.
Si 1'introduire' dans une molecule de nitrobenzene lee substi--
tuants en. meta- et para-position faction inhibitrice change sui--
want. la regle Hammet, lee substituants sleci;rodonneurs diminu-
ent kX.
Si polymeriser 1'acrylate de methyle on pout observer lee rela--
tions'analogiques cependant lee valeurs absolues des constantes
lcX est de 3-4 ordres moindres quo dans le cas de polymerisation
d'acetate de vinyle. C'est pourquoi pour plusieurs composes
studies par exemple pour tous les substituants de benzene sauf~
le nitrobenzene 1'interaction du radical de.polymsthylacrylate avec-
les molecules 'des additions n'a pas ets trouvee dans lee conditi-
ons de nos effete.
(kXC0,2 1/mol sec. a 50?)
La comparaison de valour lcX pour des radicaux polymeriques
d' acetate de vinyle, de methylacrylate, de methacrylate de methy--
le et d'acrylonitrile permet ~de faire quelques conclusions rela~i--
ves a 1'influence du facteur polaire sur lee reactions radicaliques.
Les donnees obtenues aboutissent a certaines conclusions con--
cernant le mecanisme d'inhibition par lee aromatiques. L'acte
primaire d'inhibition consists ~i 1'addition de. radical polymeri-
que au noyau aromatique suivie par la formation de radical non -
reactionnel. Dans le cas des composes nitriques le radical polyme-
rique reagit avec le nitro -groups probablement par transfert
a ells de ~-atoms d'hydrogene.
On constate quo pendant la polymerisation de 1'acstate de vi-
nyle avec lee inhibiteurs quo nous aeons studies chaque mole-
cule de 1'inhibiteur rompt deux chaines cinstiques,.la regenera-
tion des chaines ne s'effectue pas, les molecules polymeriques se~~
forment par suite de reaction de disproportionation d'un radical;.
polymerique et d'un radical qu.i s'est forme grace a 1'interactionh
du.radical polymsrique avec la molecule d;'inhi:biteur.
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I~I%IHETI~II{A
I~IHI'IITHIPOBAI3I~IfI HOJII~IMEPI~l3AI~I~IIA CTI~IPOJIA
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
xpxBORIInI xoRpo6xble Raxxble R~Ix ocxosxoro coeAllxexxx - TpII-
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0,850
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0,163
.
-
3
1,55
1,29
166
213
0,819
0,201
-
4
2,25
1,89
269
326
0,701
0,277
64,4
5
2,30
'2,79
418
483
0,734
0,314
64,1 .
6
4,02
3,42.
508
575
0>683
0,319
-
. B aTOi~ Ta6~Ixue xo g zo - xa~Ia~Ibxbie xoxi;exTpauxx xxxuxa-
Topa x xxrx6xTOpa, x - cpeRxxx xoxi;exTpauxx xxxuxaTOpa Bo
BpeNla xepxoRa xxrx6xposaxgx, w -cxopocTb xoxgMepxaaz;xx
6es xxrx6xTOpa,, woT -cxopocTb xo~IxMepxaaz~xx xoc~Ie xepxoRa
Ilxrx6xposaxxx, cp'o - xapaMeTp saMeR~Iexxx, ka - xoxczaxTa
cxopocTx pocTa ztexx.
Ha pxc. 2 itoxasaxbl aaBxcxMOCTx tti = F (~) x t' = F (~ ~.
Ffax BxRxo xa pxcygx~, xaaxyx~axcx R~IxTe~IbxocTb xepxoRa xx-
rx6xpo$axxsl xe -xB~ISlezc'x ,~Ii3xe~Ixoi~ c~yxxi;xeg oTxo~exxx zo/x,
a B To xce BpeMx axauexxsl t2, xoaly~Iexxble pac*IeTxbIM xyzeM, oxexb
xopoIIto yxnaRblBaloTCx xa IIpslMyio.
IIocxo~Ibxy, xoHCTaxTa cxopocTx xxguxxposaxxx xaBeczxa
[16-181, TO MO}xx0 OIIpeZ(eJlxTb 3xagexxe,~: J~~Ix TpxHYITp06ex30Jia
NIbI xo~Iyxx~Ix ~, = 2,98 -~ 0,1. '
YIa Raxxblx Rx~IaTOMeTpx~ecxxx xariepexxg 6bino oxpeRenexo
axaeexxe k6/k2. Hecxo7lbxo Taxxx TIIIIxTixbIX xpABblx xoxaaaxo
xa pxc. 3.
. Haxoxeu, s Ta6~I. 2 co6paxbl Bce ocxoBxble xxxeTx~ecxxe xapa-
McTpbl xcc~IeRosaxxblx gxrx6xTOpoB; aRecb ~ - xoxcTaxza aa-
McR7~I,~exxsl.
Y1.3BeCTHb, iITO IIOJIRpxble (~IaKTOpbI MOryT Oxa3bIBaTb Cyx[eCT-
sexxoe B~Igxxxe xa cxopocTb paRxxa~Ibxblx peaxi~xK [19]. IIpx
xcc~IeRosaxxx xxxeTgxx gxrx6xposaxxog xo~IxMepxsaz~xx aleTx~I-
axpg~IaTa, Cxxxi;bl$og g BarRacapbxxoM [10l ~bIJIO xai~Rexo, qTo
B. c~Iy~ae nseTa- s xapa-aaMex~exxblx xxTpocoeRxxexl3~i xoxcTax-
TbI CAOpoCTx xHrg6BpoBaFlxsl IIOJ~~IxHFIIOTCH IIpaBxTiy raM11I0Ta,
Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28: CIA-RDP80T00246A010900180001-1
Asexcl[y noa~y~ef:$~rsx sxa~exxxaix k6/kz c ,xoxcTaxTahrx I'aMMeTa.
Ta6axga 2
Ki+xerx~ecxxe xapaxTepxcTxxx paAa xxrx6xropos
-NH2
11,8
3,780,2
-'OH
211
2,68 ~ 0,1
- OCH3
20,3
2,96 ~ 0,2
-CH3
14,6
3,13 ~ 0,2
- H
64,L
2,98 ~ 0,1
- C1
58,5
2,73 t 0,1
C02C2H5
42; 5
4, 04 ~ 0,1
10
20
17
26
37
49
48
0,12
1,94
.1,08
0,77
1,04
1,74
0
xpx~ent xoxcTaxTa p, xapaxTepHSy~ox~aR peaxuirio,xn7eeT sxa~exxe
x-0,8.
HaMx 6~~a cRe~axa axa~orx~xaa uoxxxxo o6HapyaxIITb c~ieAylovgylo TexJ;exI~IIIO -
3JIexTTIOHOJ~OIIOpxble 3aM0CTIITeJIII yBeJII3iIIIBax)T CTOXIIOMOTpiitIe-
~xxx x03(~l(~1HI~IIeIIT.
nOCKOJIbxy pL ~ 1~ TO HHPIICHTOp MO?XeT y~IaCTBOBaTb TOJIbX0
18 HBCXOJI:bICxX IIOCJIej1,OBaT0JIb13bIX peaXuIIxx. B csx3ll C 3TI3Ai
CJieJ[yeT OCTaHOBxTbCFI Ha MOXaHII3Me?IIHrII6xpOBaHHH. IIO HeJ.~aB-,
'HIIM xcc~IeRosaxHxM [4, 5] IIepsasl peaxz~gx - HpIICOeJ;I3Heilxe,
alaitpopaAHxa~Ia x xxTporpyHIIe xo ypasxeHHlo:
0'
'' R' ~- ArN02 ~ Ar-N (kb) (1)
? 0 _ R..
IcoxczaxT cxopocTII Ilxrr36xposaxIIx o- x n-HxTpoaHH~IIIHOB pasxo
Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
OTxocxTeJlbxo AaJlbxeHxleH cyAb6b1 aTOro npoMexcyTOxHOro pa~x~
xaJla HMeloTCx RBa paaJrr3uHbrx HpeRHOJroaxexllsl: YIxaMOTO H CHnIa-
nlypa [4] xoJlaraloT, PTO ylcaaaxxblH paRxxaJl pacxaRaeTea IIo Mo-
xoMOJlexyJlxpxoH peax~HH c o6paaosaxHenl xHTpoaocoeAHxexIlsl x
paAHxaJIa RO'; XaNrnroxR H r7apTJIeTT [22] cxHTaloT BeposlT-
xbinc HpoTexaxxe cJIeAylox~eH peaxz~xll:
0'
R'-{-Ar-N/ -.Ar-NO-[-ROR(k~+) (2)+
0-R
IIo-sHRHNIOrIy, cJleRyeT y~ieczb rI peaxulllo rlpHCOeRxxexllx paRx-
Haxoxeu; xo RaHxbIM [4] H [5] IIs peaxuxoxxoH crlecH rloxcHO BbI-
ReJIHTb aaMeH{eHHble rHRpoxcHJlaMxxbl. ' IIocxOJlbxy IIOCJIeRHII6
HIOryT 06pa30BI,IBaTbCFI TOJIbICO H3 HHTp03000eJ{HHBHHYI, TO CJlej~yOT
IIpeJ~IIOJIO1xHTb eu[e H peaxuHx):
x
/~
2R'-}-Ar-NO -? Ar-N
CooTBeTCTBexxo NlexaxHSMy, HpeAcTaBJIeliHOnly ypaBllexHxnlYn
(1-4) Moxcxo oxpeAeJIHTb cTexi~oMeTpHxecxHil xoac~c~HuxeHT..
~CIIOJIb3yII yCJIOBHe CTaT~IIOHapHOCTH (OTHOCHTeJIbHO xOHi[eHTpa-
? uxH Bcex npoarexcyTO~Ixbrx xpoRyxTOB), MbI xoJly~laenl
^+
k~ l
b 6 1
CTOXHOMOTpxTIOCxxLi x03C~(~YII[xeHT, COOTBBTCTByIOH~HYI 3TOH1y Me-
X8Hx3My, DIO?xeT IIJIaBHO MBHFITbCFI B IIpeReJIBX OT 2 Ro 4 B aaBx-
CxMOCTH OT OTHOBIeHYISr CxOpOCTeI3 peal{H,IIII (2) H (3), tITO H Ha~JIIO-
J~aeTCFI Ha OIIbITe. C IIONIOII[bx) BbIpalxeHIIH (5) MO1xx0 paCCiIHTaTb
k5/k52+. IIO-BIrZ(HMOMy, 3T0 OTHOIIIeHHe, HoAo6xo kblks, Toxce RoJrxc=
HO 3aBxCeTb OT 3xaileHYIS 6, IIpHileN1 T00peTHireCxH O?xxJ~aeTCFI, 'ITO
~+ - p2T~0. PHC. 5, Ha xoTOpoM Hao6paxcexa 3Ta aaBHCHnloczb,
IIOJ.(TBep?xi~aeT BCe BbIIIIeCHa3aHxble IIpei~IIOJiO?xexI3TI.
}3 pe3yJlbTaTe H3 rpa(~Hxa IIOJIyTIaeM Q+ - P2+ = 1,05. e~TO
03xaTiaeT, iITO xpH BBeAeHHH 3JIexTpOH0A0IiOpHOrO 3aMECTHTeJIA
Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
~'AIeI1bxI8eTCfl xOJIOxcxTeJIbxbIYt 3apHJ~ Ha . yrJIepOJjHOM
g1TODIe~. N.' T0M CaMbIM OCIIa6eBaeT CBSI3b N - 0, I3 Oj~xOBpeN1eHB0
Z"CKOrH@TCS peaKl(IIA (~), ~ITO COOTBOTCTBeHHO xORbIIIIaeT CTEXY.p-
~ICTpxBeCxQ19 x03(~(~xljxeHT.
-NH? -DH?DCN3 CHi -H ?Cl
Pric. 5. 3asricirnrocTb ks/k5+ oT xoxcTaHT 1'abiMeTa.
? 3xauexxsl h;5+/k52+ xe xoR~xxxlozcx npaBllny 1 aalMeTa B c.ny-
~Iae aaMecTxTe~IeH -OH II -C02C2H5. Z[aIx rpyxxbi -0H axa*Ie-
Hgx /cs+/k52+ BblrIIe . IIoaTOhly nloxcxo xpeRno~IaraTb,
?~ITO BoRopoRxblH nlocTxx cyII~ecTByeT Rare B nporlexcy'ro~Ixonl pa-
:RRxa~Ie. Hao6opoT, y -COaCaHS MbI xonyxxnx axaxexxe ~, _
=4,04 x-0,1, *ITO, xo-BxAxnloNly, o6~bxcxReTCSI xo~IxbINI oTCyTCTBxerl
~peaxuxx (3). Ec.nx rrpxxxTb Bo BxxMaxxe xMelox~xecsl y-COzC2H5
~o.nbrIIHe cTepxgeciclle rlpexslTCTI~xsI, aTOT pesyalb'raT xe xB~ISIeTCx
xeoxcx~axxblM.
JIHTeparypa
1. I. I. Ostromyslinsky, M. Y. Shipard, USA Pat.
1550323, 1925.
2. S.. Y. F o o r d, J. Chem.. Soc., 1940, 48. -
3. C. C. P r i c e , P. A. D u r h a m, J, Amer. Chern. Soc., 65, 757, 1943.
4. N: I n a m o t o, .O. S i m a m u r a, J. Org. Chem., 23,.408, 1959.
5. W. P. Norris, J. Amer. Cheni. Soc., 81, 4239, 1959."
6: ~P. D. Bart 1 e t t, H. K ~~ a r t, J. Amer. Chem.. Soc.; 72,' 1051, 1950.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
7. P. D. B a r t l e t t, H. K w a r t, J. Amer.- Chem. Soc., 74, 3969,
1952.
8. I. L. K i u, J. Amer. Chem. Soc., 76, 6274, 1954:
9. 3. A. C x x x u bt n a, X. C. B a.r R a c a p b n x, }Ii. c~ua. xxbin~c,
32, 2614, 1958.
10. 3. A..C u x x R r~ x a, X. C. B as A a c a p b x ii, )I{. c~na. xxMnx,
32, 2663, 1958.
11. F. T u d o s, V. T.ii r s t, Acta Chimi Hung., 15, 389, 1959.
12. C. H. Bamford, W. Y. Barb, A. D. Jenkins, P. F.
0 n y o n. The kinetics of vinyl polymerization by radical mechanisms.
London Butterworths Sci. Publ., .1958.
13. IIe Rix I'~5.; -
YBe~Ix~exxe aKTxBxocTli? x,nopoxpexa xo cpasaexxlo c 6yTa-
AHexoM o6~bslcxxeTCx xo~Ixpxsaz~xel~ Mo~Iexy~Ibl x~IOpoxpexa xoR
B.nxxaxeM aTOMa x~IOpa; B pesy~IbTaTe cMe~exxx a~IeKTpoxxoil
xdIOTI30CTx:
1' -\ 8 ? .
CHz= f -CH=CHI - - -~+-CHI=C-CH=CH2
-'~~ c~
B peay~ibTaTe cx~ibHO sblpaxcexxoi~ xo~IxpxocTx (Rgxo~IbxblK Mo-
MexT = 1,42 D) Mo~elcy~iii 'X,nopoxpexa B $o~Ibxleg cTexexx opx-
exTl3posaxbl oRxa K Rpyrog B' IIo~IOxcexxx 1,4 x o6naRaloT 6o~IbxleH
aKTFt&xOCTbIO B xpouecce IIOJIxMepx3aI~xx.. ~TOjIOIIpeH yCTyIIBGT
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
('TbIO . axxy.ar~pyeT ero. B peay~IbTaTe aTOro 1~~B npn6.nnxcaeTCx
no pacizpeRealexxlo s~IexTpoxxblx n.aoTxocTeH x clrcTenle IIa RByx
II30JInpOBaxxbIx J~BOnxbIX CBSI3ex, aICTIIBHOCTb ICOTOpbIX B peax-
r BbIRep?KaH-
HbIX IIOpO3xb B IIpIICyTCTBIIII aHaJIOrxiIxbIX KOJIHileCTB IIHIIIjxaTOpa
II IIpII Toi~ xce TeMIIepaType. I'x6pxR~IbIH IIo~Ixniep c~IIKCxponanll
IIO H36bITOtIxOMy (OTHOCIITe7IbH0 iSOHTpOJIH) IIOPJIOII~eHIiIO Ha BOJI-
HaX 262 II 269 .M1G(~, XapaKTepxOniy J~JIFi IIOJIHCTIIpOJIa. ~Ia prIC. 1
IIpliseRexbl YcI~-cxeKTpbl pslRa Hccne~osaxHbix IIo.nxnlepoB. CxcTe-
DibI IIOJ~O6HOI'O THIIa HCKJIIOtIHTeJIbHO iIyBCTBHTeJIbIIbI K HpHMOCSID[
u xxc~IOpoRy. ~' CJiII oIIbiT IIponoRH~III 6e3 IIpe~BapHTe~Ibxoro yRa-
.nexHx Kxc~IOpoRa, To B oxTaxosoM 3xcTpaKTe yAaeTCx ooxapy~ICHTb
JIIIIIIb? CJIeRbI IIOJIIICTHpOJIa. IiOJII1ileCTBO IIOJIIICTYIpOJia, CBFI3bIBaIO-
II~erOCSI C IIOJIiIII3O~OyTIIJIeHOni B NIOJ[eJIbHbIX CIICTeDIax 3TOr0 BII~[a,
cocTaB,nxeT B cpeAHetil 7-10 Bec. % oT o61l~ero Beca IIo~IHnlepa,
3KCTparxposaxxoro oKTaxoM. I~I3 cIICTenI, IIpeAcTaB~ISIIOII~xx co-
6o~I pacTBOp IIo~Ixnlepa B cMecll pacTBOpIITe~ISI H Rpyroro nloxoMepa,
xaMII H3y*iexbl: 1) pacTBOp IIo.aHHSO6yTII~IeHa B cMecll To.nyo~Ia II
cTHpo~Ia (1 : 1 IIo o6~eMy) KoxuexTpauHIl 1x/100 .ntrc B IIpilCyzcT-
BIIiI ---10 % McI~T (oT Beca IIo~Ixnlepa) H 2) pacTBOp IIo~IIIH3o6yTx-
neHa B cnlecx 3TII~16eH3o~Ia Ii cTllpo~Ia (1 : 1 IIo o6~eMy) KoxuellTpa-
I[HH 3 a/100.ntirc B IIpxcyzcTBHH IIP, MST H Rpyrxx HHIIr~HaTOpos.
IIpx --100? IIpoxcxoRx~Ia xo~IxMepx3auxx cTxpo~Ia H 3a c~IeT MLjP
aa6nioRa~iocb o6pa3osaxxe rII6pxRxbix no~iIIMepoB, KoTOpoe (~IIK-
cxpolla~iocb Taxxce IIo YcI~-IIOr~IOU~exIIlo oxTaxoBbix aKCTpaxTOB
Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
H~uyTeM Hec~e~IOMeTpH~ecxoro TIITposaxHx; BbixoR coczaB~Ixn-~-5 % .
I'1cc~IeRosaxa 6bIJIa Taxxce cHCZeMa, IIpeRcTaBnsIloII~asl co6oll
~5%-HbIH (IIO Becy) paCTBOp IIOJII36yTaAHOHa B CTHpOJte B IIpHCyTCTBHII
"~,1 2~1~~ .hL/b J;HHHTpHJIa a3OH3OMaCJIHHOyI ICHCJIOTbI, B ICOTOpOI3 IIpH
^-1QU~ IIpOH3BOJ;HJIH IIOJiHMepH3aI~HIO CTHpOJIa: $ c~Iyuae aTO>3
~CLICTOMbi C IIOJIIICTHpOJIOM.3a C~TeT MuP CBH3bIBaJIOCb J~O 5~0~ pa-
3TOM CJlyiiae rHbpIIJ~HOrO IIOJIHMepa HMe=
CIO cTpyxTypy re~Ix. Ha 'pllc. 2 IIoxa-
3axa xpllBax aec~e~IOMeTpHxecxoro THT-
paxTOS H3 upoRylcTa pealcr~HH . B Taxoi~
cllcTeMe. 0 TOM, ,xaxoro THIIa rH6pHR-
Hble IIOJIHMepbI 6bIJIH HOJlyiieHbl B Toi~
0,6 ~-- I HJIII HHOYI cHCTeMe, C yBepeHHOCTbIO CRa-
"~? I I '~,Z JIaraTb, HTO BO BCOX CJIyTIaFIX; 3a HCH-
0,4 r ~~ ~ o6pasosaHlle 6~IOx-corIO~IHnIepoB I3JIH
IIpIIBHTbIx coIIOJiHMepoB, Ho c Ma~IbIM
xo.aIIUecTBOM pa3BeTB~IexIIi~, *ITO c~alc-
Oz ~- Il ~ / "3 TH~Iec B 3ICSHBa~IeHTHO ~JIOIf-cos ~ IIDIe-
noro ao McTOAy , rH pIIZ[Hble IIOJTIIMepbI B BbICIIIeH CTe-
3 - oxTaaosoro axcTpaxTa .xa IIOHH IIOJIIIJ~IICIIepCHbI, xax IIO pa3Me-
cxcTeM~ no~xao6yTx,nea -F no- paiK, TaIC'H. IIO COCTaBy, tITO He II03B0-
~xcTnpon -{- i % IIB IIOCJIe .IIpO- 7IHJI0 IIT1OH4BP,CTII T(1LITTT,TP, llA(:ifP.TT,T Tf(1H-
pane. IIoc~IeRHenl c~Iyuae ( o-xblH
pacTBOp rIO~IH6yTaAHexa B cTIIpo~Ie)
HMe.ao MecTO IIplicoeRHxeHIIe AHMeTII~I-
l ~/ ~ I~HaHMOTHJIbHbIX paJ~HISaJIOB IS ABOFT-
300 tea. 260 HbIDI CBSI3FIM B IIOJIO?HeHIIO 1,2 (yMeHb-
x.M~ IueHHe ullc~Ia ABOi3xblx cBS3eiI 6bI~Io
PxC. 3. y~-CIIeTfTpbI IIOPJTO- 3a(~III{CIIpOBaIIO IIO ~K-CIIeKTpaM), IIO-
ruexTTx: 3TOMy B 3TOM C~Iyxae IIOJIyiIaJIH rJIaB-
1 - no,nxcTUpona, .2 - 6nox-no- HbIM O6pa3OM IIpHBHTble , COIIOJIIIMepbI.
~Nmepa cTxpona x xaonpeaa (co- HOJIyTIaIOII~IIeCSI B MOJ{eJIbHbIX CIICTOMaX
-cTana i : i ao secy), uonyeex- 6
nepeocarxAexx~. (I{oageaTpa~a l;'I'aHT CIiOpOCTII IVII~J'. Il~IUCTiIH UI~eHI{a
nonnMepos 0,05 z/100 .un CHCI,). BbIXOJ~OB IIO3BOJISIeT, O~[HaKO, 3aKJIIO-
H13Tb, iITO McHCIjeIIHOI3 OGMOH HJIH MaK-
ponlo~Iexy~Ixpliax pexoM6i3xauIIx IIpo-
TekaeT C McHbIIIe~I BepOfITIIOCTbIO, ileM pOCT ~OICOBbIY B0T-
13eYI Ha IIOJIH]~IIOHOBbIX ' I;eIIHX . 3a CTieT , B3aHDIOReYICTBHFi , CBO-
6oRHbIx paRHxa~IOB c J(BOYIHbIMII csasxniII. Me>xueuxoH, o6MeH
? T0M 6OJIee BepOHTOH, ileM 6OJibIIIe CIIOCO6HOCTb `COOTBOTCTByIOIIjerO
MaxpopaRIIica~Ia cTa6II~III3IIposaTbcsl pexoM6IIHauHeH (3TO 6bino
Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
-~~ ~ i i ~
0 ' 10 20 30 60 50 60
Qo6aBneno ocadumenp, %
6 e
Yxc. 2. Hec~e.aoMerpxYecxoe rxrposaxxe
a : 1 - oxraxoaoro axcrpaxra ,-xa cxcreM~ xonx6yTaAxex ~- xonxcTxpox+AxxxTpxn
a301730M3CJix HOI3 ESISCSIOr6I, 2-xOJIiICTxp OJIa, 3 - xOJISi6yTaj[xexa (C - 0,005 2/1~~ .Mn,
paCTBOpNTe7Ib - TORyOx, OCaJ{xre7lb - 8Tx7I0Bb[i3 CIIxpT), 6: 1 - 6xox-coxonxMepa
crxpo.na x xaoxpexa (xoxyvexxoro xo McTOAy nxcxxs~x uexeH>), 2 - xoxTponbxoro
xonxerxpona, 3 - xoxrpo:[bxoro xo~[xx aoxpexa, 4 - xx Mexaxxeecxo~i cMecx (c =
=0,005 z/100 .nan, cxcreMa ro~cyo;i-arxnoas[K cxxpr). e: 1 - npxsxroro coxom3Mepa
crxpona xa xonxMerxnMeraxpxrcare c 6oxbmxM 4xCSI0M 6oxoxbcx seraeK xonxcrxpona
(xoxygexxoro xpx xoMO.ux 6yrxxm3rxx); 2 - xoxrponbxoro xoxxcrxpona, 3 - xoxr-
pon6xoro xoxccMercixxeraxpK nara, ~ - xx Mexaxxvecxo~r cMecx (c = 0,005 a/100 ten,
ciicrexa ro:cyo~t - arxnou~a cxxpr).
Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
xaMII IIoxa3axo Taxxce IIyTeM AecTpyxuHH IIo~IIICTIIpo~Ia B 6ex3o.ne`
IIoR Rei~cTBIIelil McI~T IIpII 120-140? B aTrlocc~epe aproxa,, AecTpyx-
uxxl xoxTpo,axposa~III Bxcxo3HMeTpIIgecxII. IIpx IIxzexcHBxoM pac-
Halle MST Ha6nloRa~IOCb IIaRexxe Bx3xocTH xa ---30%, a xoc~Ie ero~
II3pacxoRosaxIISl olla BoapacTana Ho~ITII Ao HcxoAxoro 3xagexIISl)..
? HOBble MOTOJ~bI IIJ~eHTII(~IIxa--
I~IIII II aHaJIII3a rII6pIIJ~HbIx IIOJIII-
MepoB 6bIJIII axpo6IIpoBaxbl xa.
6.nox-coxonIIMepax:
H HpHBIITbIx coxo,nIIMepax g3-
BecTxoH cTpyxTypbl, Ho~Iyxexxblx
J McTOAoM :
yIIOMIIHaBIIIaxCFI Bbliile Y~-
CIIexTpOCIfOIIIIfi IIO3BOJIHeT C60JIb-
? HIOI3 TO~IxOCTbIO OIIpeJ~eJIFiTb xO-'
' JIIILIeCTBO CBH3aHHOrO XIIMIIileCHI3:
Ho~IIICTIIpo.na, Ra~xe ec~III oxo~
2 cocTaB~IxeT Bcero 0,1-0,01 % oT~ .
o6B~ero Beca xexor~IOII~alox~era~
Ho~IIIMepa.
IIo~peRcTBOM xec~e~IOMeTpII-
xecxoro TIITpoBaxIIx 6bino IIoxa-
~ 3aIIO, ~ITO xpIIBble ocaxcRexIIx
~JIOx-coxo~IIIMepoB II c~Ia6o pa3-
+ BeTBJIeHHbIX IIpIIBIITbIX COIIOJiIIMe-
poB yx~IaAbIBalozcsl MexcAy xpII-;
HyBe~rc qNa MBHUCK HNaemc BbIMII oca~ICRexIIx R~ISI cooTBeTCT-'
ByIOII~IIx ronloxo~IIIMepoB, Torp;a
Pxc. 3 - CeAxMexTauxoxllble AIIa- ~ xax B c~Iyuae Ho~IIIMepoB c 6o.nb-
rpaMMbl 6:nox-conoxxMepa czxpona ILT73bI iIIICJIOM IIpgBIITbix BeTBeir
x II3Oxpexa E CACTeMe XJIOpxCTbl~i OHH H2OTJIIIiiIIMbI OT xpIIBbIXOCa?IC-
6yTil.n - Axx,nopaTax
(1 :~ 1 IIo o6~eMy). AexIIx cII~Ibxo pa3BeTB.aexxoro II
1- 120 Mxx.; 2-240 MHx.; 3-750 MhH. BblcoxoMO~Iexy.axpxoro POMOIIO-~
JIxMepa IIpIIBIITOPO MOHOMepa..
y~[O6HbIM ~bICTpbIM xaileCTBOIII3bIM MOTOJ{OM I3CIIbITaHIISI HBJiFi-
eTCFi IIpIIrOTOBJIexIIe IIJIeHOx II3 rII6pIIJ~xOPO IIOJIIIMepa TaxIIM 06-
pa30M, IITO6bI TOIIJIOBOO J~BII?xeHIIe I~eIIOTIeK OJ~xOrO II3 J~ByX TIIIIOB:
ObIJIO IIOJIHOCTbIO IIOAaBJIeHO. HaIIpIIMep, II3 ~JIOx-COIIOJIIIMepa CTII-
pOJIa H II3OIIpeHa MOSICHO IIOJIyzIIITb TIIIIIITIHble CTexJIOO6pa3Hble?
IIJIeFIICII BbIIIapIIBaHIIOM pacTBOpa B MOTIIJI9TIIJIxeTOxe II xayxyxo-
IIoRo6xble - BbIHapIIBaxIIeM pacTBOpa B oxTalle. B Taxxx II~Iex-
xax xepacTBOpIIMbII~ xoMHOxexT IIrpaeT po,nb IIpocTOro xaxo~IxII-
Te~Ix.
R~Ix xo~IIIUecTBexxoro axaaII3a xaMII 6bIJI IIpIIMeIlex McTOA, oc-
xosaxxbll~ xa y~IbTpa~exTpIIC~yrxposaxIIII B rpa>~IIeI3Te II:noTxo-
cTII. (]~.nx 6IIO~IOrIIxecxgx cgcTeM Taxol~ McTOu 6bl,n paxee HpeR~IO-
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
'?ICOH MPCeJIbCOHOM.~ CMecb rOM0II0JIIIMepOB II IIX TIIOpHZ{HbIII HO-
.JIIIMep IIOJ~BepraIOT BO3J~eHCTBIIIO MOII7;IIbIX I);eHTpO6e13CHbIX HOJIOH
B CMOCII paCTBOpIITeJIeI3, HOJ{OOpaHIIbIX TaIfIIM O~pa3OM, ~iTO IIJIOT-
HOCTH HX HpIIMepHO COBIIa]~aIOT C IIJIOTHOCTHMII rOM0II0JIIIMepOB.
IIO IICTetIeHIIII HOCICOJIbICIIX iIaCOB yCTaHaBJIIIBaeTCH paBHOB0CII0e
paCIIpeZ{eJIEHIIe HJIOTHOCTIi BJ~OJIb CeZ(HMEHTaI~IIOIiHOII ICIOBOTbI H
I I I ~ 1
64 65 66 67
I I~ I 1 I
6B 69 70 7J 72
I ~ Xm I .
Pnc. 4r YlnTerpa.nbnasl xpllBasi pasnosecaoro pacnpeAenenBSl 6nox-
cononllMepa a uonoce.
~rII6pIIRH3~IK IIoJIIIMep co6IIpaeTCH B ysxylo IIoJlocy B cepez~IIlie'xIO-
:B2TbI~ rOMOIIOJIIIMepbI, eCJIII OIIII HpIICyTCTByIOT, CO6IIpaIOTCf3 y Me-
HIICIfa II Ha RHe, O6pa8yII TaM IIpII6JIII3IITeJIbHO 6apOMATpIIiIECKIIO
paCIIpeZ{eJIOHIIA. e~TO IIO3BOJIFIeT B IIpIIHI~IIIIe OIIpeJ~eJIIITb xaIC 'OT-
_HOCIITeJIbHhIe .ICOJIII?IeCTBa ICOMHOHeHTOB 'TpOIIHOH CIICTOMfiI, TaIC II
_IIx cpeAHIIe nioJiexyJlsipxbie Beca. BeposiTHO, J[JIH rII6pIIRIIOro
_IIOJIIIMepa yI{aCTCH TaIC}ICe OIIpe]~eJIHTb j~BO3IFIyIO .HOJIIIJ~IICHepC-
,HOCTb.
OIIbITbI aTOro pop;a HpOJ~eMOHCTpIIpOBaHbI Ha. pIIC. ~3 H 4.
HaICOHOI[, `~bIJIO IICCJIej(OBaHO "paCCEHHIIe peHTTOHOBCICIIX JIyLIe3i
_IIOJ~ 11IaJibIMII yr.JIaMH pacTBOpaMII rII6pIIAHbIX IIoJrIIMepoB. IIo IIpeu-
_BapIITeJIbHbIM:Z[aHHbIM'OTOT MOTOJ~ HO3BOJIHOT yCTaHOBIITb'.i1aIi' pas-
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
MepbI Mo~Iexynxpablx HJIy61iOB B I~eJIOM, Tax H pa3MepbI OTj[eJIb-
xblx 6.aoxos. Ha pgc. 5 npgBeAexa xpgBasl yr~IOBOro pacnpeAe.ne~
HIIfI IIHTOHCISBHOCTH paCCeHHgH, Z[eMOHCTpgpyK)II~aH 3Ty B03M0?K-
HOCTb,
Pic. 5 - 38BYICAMOCTb lg I =
= f (~~) Rnx Toro xce 6~rox-corlo-
~xMepa.
I~ - NHTexcxsflocTb paccexaHOro
Cu Ka-gsnyeenxR noA yr~oM cp.
I -yeacTOx, xapaxTep~syxnzH~ pas-~
uep aced 'xonexynbr, 2- yyacTOx,
sapaxTepxsyioa~HU paaa+ep 6noxa.
Summary
Interchain exchange reactions with the formation of
polymers take place in mixed solutions of two polymers or in so-
lutions of polymers dissolved in monomers, in the pre-
Bence of free radical initiators.
A number of methods, namely, nephelometric titration, UV
spectroscopy, refractometry and pycnometry were used to iden-
tify and analyze the hybrid polymers.
A qualitative method for determining the ehybridity> of poly-
mers was developed. This consisted in determing the optical and
mechanical (relaxation) properties of polymer films obtained from
various solvents (poor solvents for some and good solvents for the
other blocks or branches of the hybrid polymer).
For the quantitative investigation of systems containing the
Hybrid polymers a new method employing an.ultracentrifuge has_
been .developed. This is a modification of Mesel'sons method
(equilibrium centrifugation in a concentration gradient) and con-
sists in centrifuging a mixture of two (homo) polymers and their
hybrid polymer in a mixture of two solvents of which the density
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
has been so chosen that the homopolymers give the }3oltzmann di-
stribution at the bottom and at the meniscus of the cell and the
hybrib polymer accumulates in a band in the central,part. Theo-
retically the method allows one to determine simultaneously the
molecular weight distribution of all three polymers and the compo-
sition of the polymer.
The present experiments are important in throwing light on
the secondary reactions taking place in radical homopolymeriza-
tion and leading to unusual multimodal or strained distributions..
Resume
Des reactions d'echange interchaines passant en solutions mix-
tes de deux polymeres ou en solutions des polymeres dans les mo-
nomeres en presence des initiateurs (sources des radi-
caux libres) en aboutissant a la formation des polymeres hybri-
des.
Pour identifier et analyser les polymeres hybrides on a appli-
que plusieurs methodes, a savoir: le titrage nephelometrique,
UV - spectroscopie ainsi que les determinations refractometri-
que et picnometrique de composition.
Une methode qualitative a ate elaboree pour 1'etablissement.
de 1'hybridite des polymeres; cette methode consiste a 1'obtention
des films a partir de differents solvants (bons pour des uns et mau-
vais pour d'autres blocs ou chainons lateraux du polymere hybri-
de) suivie par 1'etude des proprietes optiques et mecaniques de ces
films.
Pour une_ etude quantitative des systemes qui contiennent des
polymeres on a trouve une nouvelle methode necessi-
taut 1'utilisation dune ultracentrifugeuse qui est une modifica-
tion de la methode de Messelson (centrifugation equilibree dans
un gradient de densite) et consiste a ce qu'un melange de deux ho-
mopolymeres et de leur polymere est centrifugue dans un
melange de deux solvants les densit~s desquels sont choisis de fa-
~on q.ue de les homopolymeres donnent des repartitions de
Holzman pies du fond et pres du menisque, tandis que le polyme-
re s'accumule sous forme dune bande en partie moyenne
dune cirvette. La methode en principe permet de ~ determiner
simultanement les repartitions des poids moleculaires des trois
polymeres et la composition du polymere .
Ces experiments ont une grande importance pour comprendre
les reactions secondaires, qui s'ecoulent a 1'homopolymerisation
radicale et aboutissant a la naissanee des repartitions multimoda-
les et aigues.
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Next 22 Page(s) In Document Denied
Q
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
KINETIC INVESTIGATIONS
?N TI-iE RADICAL POLYMERISATIONT OF VINYL MONOMERS
IN PRESENCE OF SiC14
G. ~Iccrrl~, I~. Nitrai, G. Kovii-cs, V. P. Li
(II ungar~)
The investigations of the radical polymerisation processes
yaking place in presence of alien substances is very promising not
manly from the point of view of elucidating regularities of the po-
lymerisation processes but also of obtaining good possibilites
for the qualitative and quantitative evaluation of the comport-
ment of different compounds in radical reactions.
The comportment of compounds containing Si atoms in
Tree-radical reactions has been scarcely investigated. The
papers published in connection with telomerisation syntheses (1,
2] contain data mainly of qualitative character in connection
with the radical addition of compounds containing Si atom to
.unsaturated compounds.
The kinetics of the radical polymerisation of styrene and met-
hyl metacrylate initiated with azobisizobutyronitrile taking pla-
ce in presence of 5iCla was dilatometrically investigated at 50,
X60, and 70? (tables 1 and 2). In presence of SiCla, the total velo-
city of polymerisation of the above-mentioned monomers
remains unchanged. The chain-transfer constant concerning
SiCla (figs. 1-6) are summarized in table 3.
In presence of SiC14, the vinyl acetate does .not polymerise
when initiated with azobisizobutyronitrile.
From our experimental data the conclusion can be drawn that
the absolute value of the chain -transfer constant diminishes
with increase of the temperature. In case of mercaptans, the abso-
lute value of the chain -transfer constant similarly decreases
with increase of the temperature. In case of CCIa, the chain-
. transfer constant relating to CC14 increases with the temperature.
The absolute value of the chain -transfer constants concerning
.SiCla has about the same order of magnitude as the corresponding
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
P 10'~
Fig. 1 Change of the values of 1/P with the
SiC14 concentration when polymerizing sty-
' rene at 50?.
0,15 0,20 0,25
SiCly/St
0, 20 0,25
SiCly/St
Fig. 2. Change of the values of 1/P, with
the SiC14 concentration when polymerizing
styrene at 60?.
0.70 0,15
SiCly/St
Fig. 3. Change o$ the values of 1/P with
the SiCh; concentration when polymerizing
r styrene at 20?.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
als o.20
SiCl,,/MN,~t
Fig. 4. Change of the values of 1/P -with
the SiCl4 concentration when polymerizing
methyl methacrylate at 50?.
0,20 0,25
SiCly/MMA
Fig. 5. Change of the values of 1/P with
Lhe SiC14 concentration when polymerizing
methyl methacrylate at 60?.
0,15 0,20 0,25
SiClq/MMA
Fig. 6. Change of the values of 1/P with
the SiCl4 concentration when polymerizing
methyl methacrylate at 70?.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
~'ig. 7. Velocity of irradiation polymerization of styrene as a function oi'
the SiCl4 concentration at 50?, in case of an intensity of 38 000 r~hour.
10 20 30 u0 50 60 70 80 SiCl4y?Df VOL
rig. 8. Velocity of irradiation polymerization of methyl methacrylate , s
a function of the SiCI.~ concentration at 50?, in case of an intensity
of 38 000 r/hour.
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 Approved For Release 2009/08/28: CIA-RDP80T00246A010900180001-1
50
50
50
50
50
80
' so
~60
so
?60
60
70
70
70
70
.70
8,462
.8,303
8,117
7,618
6,945
8,377
7,940
7,660
7,680
6,120
5,120
8,292
8,056
7,883
7,291
6,801
ABIN?10-Z
mole?1-s
4,661
4,574
4,471
4,196
3,826
5,344
5,218
4,730
4,497
4,436
4,125
0,953
0,926
0,906
0,838
0,783
Si CI.
mole?1-1
0,1567
0,3415
0,8383
1,5068
0,1930
0,4735
1,1380
1,5221
1,8990
.0,3221
0,4045
0,9898
1,4731
0,390
0,360
0,290
0,270
0,190
0,332
0,306.
0,296
0,254
0,242
0,236
0,310
0,305
0,295
0,280
0,255
1,42
1,G4
2,19
2,42
3,88
1,85
2,03
2,09
2,55
2,82
2,90
1,96
2,11
2,17
2,31
2,64
'Tempe-
sa;?Ce,
1liethyl meths-
crylate, mole. 1-'
CABIN) f0~
mole. 1-1
(SiCI~, mole.
1-'
! ?10-'
P
50
9,081
2,477
1,42
2,835
:50
8,915
2,432
0,1496
1,.38
2,856
50
8,752
2,387
0,3210
1,33
3,092
.50
8,457
2,307
0,5924
1,27
3,286
50
8,127
2,229
0,8829
1,20
3,541
~60
8,8896
0,585
2,13
1,438
~~60
8,203
0,527
0,8184
1,70
2,240
=60
7,301
0,483
1,5030
1,52
2,597
:60
6,927
0,455
1,8390
1,18
3,973
70
8,888
0,154
1,55
2,526
70
8>557
0,148
0,3048
1,50
2,638
70
8,015
0,139
4,8050
1,42
2,835
70
7,268
0,126
1,4940
1,31
3,154
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
28
26
24
22
20
10 20 30 40 50 60 70' ,,. 80 SiCly%DE YOI.
'Fig. 9. Velocity of irradiation polymerization of vinylacetate as a functiorr~
of the SiC14 concentration at 50?, in case of an intensity of ;38000 r/hour.
values measured in case of CC14 although the Binding energy of
the Si - Cl bond amounts to 85,8 kcal mole-r while that of the?
C -'Cl bond amounts to 66,5 kcal mole-I [5]'.
Temperature
?C
50
60
70
113, 6~
41;2'
32,4
methyl met- 50 I' 8,12
hacrylate 60 4,92
70 3,05
The velocity of irradiation polymerisation of styrene, metliyY`
met:acrylate, and vinyl acetate initiated by X -rays was mea-
sured as a function of the concentration of SiC14 by the aforemen-
lioned dilatometric method. In figs. 7 and 8 it can be seen that
in case of styrene and methyl metacrylate the total velocity of
polymerisation increases with the concentration of SiCla until
about 25-30% by volume of SiCl4 concentration, na-
melt' in case of styrene the increase is ab?ut threeftstd while irn
Chain transfer
conatant? 10-6
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
ISe npH-
cnoco6~Iexxll (noc.ne He6o~IbmoH 11ioZ[n(~HICaI[HII) nioal;xo IlsniepaTb?
3IHT0HCiIBHOCTb C~JIyOpeCI~eHI(IIn, '
c~TIINI AreTOJ~OM 6biJI II3yileH XOJ[ IIOJIHMepI33aI[IIII nIl'TIIJIDIOTa-
xprl~IaTa II 6yTn~InieTaicpn~IaTa. BbIJIO xaiiRexo,? =ITO cicopocTb?
peaicuiln nocTOxxxa xexoTOpoe Bpenisi, a aaTeni peaxo BospacTaeT.
Ycxopexne n HsMexexxe xoxcTanT cxopocTn iroRTBeparcRexo pe-
ay~IbTaTanix Apyrnx aBTOpoB.
Summary
The investigation of polymerisation processes to high degrees??
of conversion is not only technological important,. but is interes-
ting for knowledge of free radical processes occuring in nonfluid.
media.
A method was developel for polymerization studies at high:.
degrees of conversion. This method is based on measurement
of 1.he change in rate of the polarization of a monomer solution.
containing a small quantity of fluorescent substance (if the mono-
mer does not fluoresce).
As fluorescent substance a compound should be. employed that
does not affect the polymerisation kinetics. The concentration{.
of fluorescent substance is of the order 10`~ g/cm3. The fluores=
cence should be excited with light of such wavelength, which does-
not initiate polymerisation.
The apparatus consists of a thermostated polymerisation.
vessel and a sensitive device to measurement of i,he rate of'~
polarisation of. light. By the same device (with ~a little mod{--
fication) it is possible to measure the intensity of fluorescence.,
By use of this method the entire course of the polymerisation+
of methyl methacrylate and buthyl mathacrylate was examined_
The rate of reaction was found to be constant for some time and
then to rise sharply. The acceleration and the change of the rate- .
constani;s was confirmed by the reaul.ts of. other. authors:.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
yICCJIEROBAFII~IE 3AI{OHOMEPHOGTEI%I 3MYJIbCI~I0HII01h~
I I 0 J I I ~I M E P I ~I 3 A I~ I~ I I ~I
T. I#p~2c2ccax, M. Map2apacnaoaa.
(CCCP)
B paOOTaX McJ[BOJ~(eBa C COTpyj~I3iIICaAIli [1-3], HOCBf1II~0IIHbiX'
IICCJIeJ~OBaxIIIO 3niyJIbCIIOHHOI3 IIOJIx111epii3al~Illl CTI3pOJIa II I130IIpG-
xa, 6bI7I0 IIOICa3aH0, `iT0 COPJIaCIIe C HaIiJ~eHIIbI111I 3ICCIIepIlblexTaJlb-
iIbI111x pe3yJlbTaTan[1[ DIOSICeT 6bITb J~OCTIIrHyTO, eCJIrI paCCl\1aTpIIBaTb-
311iyJlbraTOp KaK OO'benl, B ICOTOpOni BO3HIIICaeT Ii pa3BHBaeTCFI 06-
I}jxii IIpOI~eCC IIOdIIID[epII3aI~IIiI. c~TO RaeT II1Jr}xr~IIIIYIaJIbHyIO B03-
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7IIrDiepII3aI~IIII rI IiCII0JIb3OBaTb Z(Jiii OHxCaIIrIfi HaI7J~eHHbIX 3aICOI10-
nlepxocTeii B IIepBOnl IIpx6~IIIxcexliil o6brxxylo a~IeniexTapxyio
cllcTeniy peaxulri~ ronioreIIxoir IIo~xnlepII3az~IIH. ,i~~x Aaxbxei~i--
IIrero IiayLlexllsi 3alcoxonlepxocTei~ aniy.nbcxoxxoii Ho~IIIrlepx3auHx
II IIx paccrloTpexlisl xan1II 6bIJI0 npeAHpxxxTO IIccseRosaHHe Ho~II1--
~Iepli3aulix mleTrisinleTaxpH~IaTa (MMA), xsiopoxpexa (XII) II Bx--
Hx,nIIRexx~iopIIRa (BX) B IIpllcyzcTSxx pa3~ill=iHblx 3r1y~IbraTOpoB-
II IIHHI~xaTOrIOB B IIIxpOICOM IIHTepBaJIe rll' HOHr~eIITpai[iii3 31 IIpll
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Bxxnlaxxe 6bI~I0 o6paH~exo xa o~rHCTxy xcxoRxblx Bex~ecTB Ii Tn~a--
Tenbxoe IIpoBeRexxe oIIbITOB. J~~Ix rcxxeTli=ie.ciClix IIcc~ieAo}IaHI?ii-~
rloalili~IepH3ai[IiII 6bI~Ia HpIIi`Iexexa ycTaxoBlca, axa~IOrli=Ixasi Toni,.
icoTOpasl oxxcaxa R pa6oTe BepTO~IOnIe [4]. B xaxecTBe 3nly~Ibra--
TOpOB 6bIJ[H IICHOJIb3OBaxLI ~IaypaT xaTpilsl (JIH) II xaTplieBbie
co,nll cy,abc~oxxc.aoT yr~IesoRopoRoB xcllpxoro ps1Ra (NIK), B ica-
~IOCTBe HIIriI~iiaTOpOB - IIepeICIICb 6eII3OI}JIa (1117) 13 HepCyJIb(~aT'
ICaJlxfi (III). I{a>KjJ;bIi3 OxbIT HpOBOZ(IIJIII OJ[HOIIpeDI0Iix0 B J~By.I'
J{HJIaTO1~ieTpaX. IZOBTOpeHIIe OIIbITOB, IIOCTaI3JIeIIIIbI~X B OJ~IIIia1C0-
Bbix yc~ioBxax, IIoica3asio Ho~ixyio xlrxeTx~ieci;yio Bocxpori3BORr1-
nlocTb IIosiyxexllbix pesy~IbTaTOB. I~IccneRosaxlle IIposoRHalli Ho
RByni ocxoBxbinl IcxxeTHneclcIIni IIaparleTpani - 3aBxcxriocTII cico-
pocTx Hosilinie?plraaullx oT icoxueHTpaulur sniy~IbraTOpoB (C;,~,)
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
YI xolluexTpauHIl IiIlHuxaTOpa (Cnx). CKOpocTb IIoJ1IIMepHaauHH v
BesAe Bblpaxfexa B rpanlMax xoJiHNlepa xa 100 /urc BoRxoK ~iaabl,
B xac. Z[Jrx HJiJ1IOCTpaullx xaKReHxblx aaxoxonlepxocTei3 IIpHBeRex
pllc. 1, xa KoTOponl Ilao6paxfexa aaBHCxMOCTb cxopocTII xoJIHMe-
pIl3ai~xx XJIOIIOIIpeHa OT Cah,. e~TI3 3aBHCHrIOCTII XapaKTepH3yIOTCfl
TpeMx TIIIIanIx KpIIBbIX. KpHBaF1 2 IIOKa3bIBaeT, iITO B xpHCyTCTBI3Ii
PHC. 1 - 3aBHCHMOCTb cxopocTH HonHMepxaauHB
xnoponpexa B 3MyJISCHII OT. xOHI[G HTpa1~HI1 3MyJIb-
raTOpa.
1 -MH; CIII{ = 0,0125, 2 -JIH; CHB = O,U25, 3 - MK;
CHB = 0,025:.1, 2 x 3 - sucnepnmexTa.nbx~e Aaxx~e;
'/:
4 - no ypasxexxio v=[K?Cnx] CooTxomexne opraxxvec-
Hoi3 n soAxoi3 c~as = 1 : 2: 1 X30?, 2 x 3 - 4D?. Bce xoxuexT-
paunn etilpax~.
jIIb v IIpoxopuIIOxaJlbxa Cam RJrx JIH ~0 3xaxexllx CamC 2. IIpI1
?C3m> 2 xacTyxaeT pesKOe xsMexexxe xapalfzepa KpxsoH H v cTa-
kiOBxTCH He3aBHCHMOYI OT Cam. c~TO II3M0HOHHe, KaK 6yReT IIOKa3a-
HO RaJ1ee, o6~bxcxxeTCx o6paaosaxxei,I IIOJIIIMOJIeKyJIlIpxbIX CJIOOB
nlbI.na xa xOBepXHOCTiI IIOJIIIMepHbIX TiaCTHI~. B IIpHCyTCTBHx II~C,
?IfOPJ~a J~eI3CTByeT 3aKOH Z/-~ Cnxl/2 (pIIC. 1, KpxBax .7, IIpepbIBHCTaA
~KpxBasl 4), xepexoA K xeaaBHCxnIOCTH cxopocTH coBeplHaeTCSI 60-
..nee.IIJlasxo. B cJiyxae sMyJlbraTOpa MIf x IIxxuxazopa IIB npo-
?xOpI~HOxaJIbHaFI 3aBHCHMOCTb J OT C3M paCIIpOCTpaHFIeTCfI Ha BCe
:IIHTepBaJlbI IICCJIeJ[OBaHHbIX Cam, iITO CBIIJ~eTeJIbCTByeT O 3aBIICI1-
niOCTH CKJIOHHOCTH 3MyJIbraTOpOB K OrOpa3OBaHI3I0 IIOJIHMOJIeKy-
-JIApHbI% CJIOOB Ha IIOJIHMepxbIX iIaCTxI~aX He TOJIbKO OT BeJIxLIHHbI
,IIX o6vgei~ xOBepXHOCTH, HO H OT IIpIIpoAbl 3MyJlbraTOpa. AxaJro-
'rxilHble 3aKOHODIepHOCTIi Ha6JIIOJ~aKITCA II xpH IIOJIHMepH3aI7III3
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
BX, xo c' HexoTOpbIMH oT~IxuHxlvill, o6yc.aoB~Iexxbinix c~xsll~e-
cxoi~ HpxpoRoH aTOro xo~IllMepa (cTex~IOO6pasHOe cocTOaxxe,
HepacTBOpxMOCTb nioxOMepa B HonHMepe, oco6ble cBoHCTBa aRcop6-
I),xx MbIJIa II Rp.). c~Tx OCOCeHHOCTx He blOryT '6bITb paCCMOTpexbI
B 3TODI J~OxJiaJ);e B CBfI3x C OrpaHxTIeHHOCTbIO er0 06'beMa. B J~aJIb-
HeIIIIIe11I 6yAyT x3JI0?ICexbI TOJIbxO pe3yJlbTaTbI xCCJIeJJ;OBaHx~I IIO-
~Ixliepxsauxll MMA. B sTOai csygae xcc,ne~osaxlle xxxeTlluecxxx
YIIC. 2. 3aBIICI3MOCTb cxopocTx no.nxMeplrsagnsa
McTII~nMeTaxpllnaTa B aHlynbclsl3 oT xollueltTpas~rtlt
aMy.nbraTOpa (50?).
1 - bix; CIIg = 0,013 5; 2 - JIH; CxB = 0,0125; 3 - Mx;
CIIx = 0.0125. 2 tt 3 - oxcnepbmexTa,nc,xwe uattttwe;
~_- no ypasxextsto_v = IfC~~~z? xpalixRx .nesa>3 opatsxaTa
~atx xpttsoi3 1.
saxoxonlepxocTeii coxposoxcRa~IOCb onpeRe~Iexlleni paal\Iepa H
LIIICJIa IIOJIxMepxbIX iIaCTxi~ B IIOCJIeJ~OBaTeJIbHbIX CTaJ~xSIX IIOJIxDie-
px3ai[IIH HpH pa3HbIX yCJIOBxHX C II011-IOH7;bI0 11ieTOJ~a ' DibIJlbxOrO
TIIT~JOBaHxFI x? YI3MepeHxfl 3JIexTpOIIpOBORxOCTx IIOJIytIeHHbIX JIa-
TexCOB. '~aHHble O 3aBHCHMOCTI3 CIfOpOCTII IIOJIHMepH3aI1,xII MMA
oT xoxuexTpauxx aiviy~IbraTOpoB xpxseAexbl xa pxc. 2. 3Recb Bxu-
xo, *ITO xapaxzep aaxoxoMepxocTeH axa~IOrliuex pacci`IOTpexxbinl
aasxcxMOCZHivi XII xa pxc. 1. 3aBxcHMOCTb cxopocTli Ho~IIIMe-
prlaauHH MMA oT xoxueHTpauHH xxxullaTOpoB, HpeRcTaB~Iexxasl
xa pxc. 3, sIB~IxeTCSI o6II~eiI R.aa 6o~IbIIreil ~IacTli IIpoueccoB sl`iy~Ib-
clloxxo~i xo~IxMepxaar~HH. Oxa paxee xa6.aloRa~Iacb? IIpr3 a1,iy~Ib-
cxoxxo>!i Ho~IxivlepHSauHH xaoxpexa [4] II cTllpo~Ia [3] II 6bl.na .
HaMx xoxcTaTllposaxa ' IIpri IIo~Ixaiepllsai>;IIIi XB x XII. IIpx
9 MerxpyxapoAxwit cttmnoahyM, cexgtrfi 2
129
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~Ma~Iblx xoH>;eHTpauHxx v ,~ CgH '/_, apH COnbIIIHX - IIoxa3aTeJIb
cTeueHx McHbIIIe 1/2; B IIpeAe~Ie v.~ C?aa.
0TH oTx~IOxeHHx oT aaxoHa xsa~paTHOro xopHx, xax 6bI~IO yxa-
3aH0 B pa60TaX [1-3~, 06'bFICHFIIOTCSI TOM, *ITO B peaxuHH o6pblBa
IIo~IIIMepHblx paRgxa~IOB IIyTeM Hx BaaHMHOro coeRgaeaHA Bx~IIO-
xaloTCII peax>;HII MexcAy IIo~IHalepablhlH g IIepBI3iIHbIMH pa~Hxa-
~IaMx. IIpx IIpeo6~IaRaaIIH peaxi~Hl~ o6pblBa IIocneRaero THIIa
Ql 0,2 03 0,4 c
Pxc. 3. 3aBACAMOCTb cxopocTx nonxMepxaauxiFl
hieTIITIMOTaxpI3dlaTa B 3MyJIbCIII3 OT ~ xOHIjeHTpaI;III3
IIHIIIjI3aTOpa.
1.- IIB; CMK = 1;2 - HB; CJIH = i; ~ - Hx; CMI{ = i.
I, 2 x 3 - axeneIlxMexTa7lbable Aaaa6ie; 4, 6 a 8 - no ypas-
'~=. Coorxomeane ~aa = i : 2. Hpaiiasrx
xexHto v = KC
na
~nexax opAnaaTa Ann Kpasoih 8 a 6.
CICOpOCTb IIOJIIIMepII3aI~IIH He 3aBHCIIT OT KOHI[OHTpaI~IIH IIHHI[IIa-
TOpa. OZ(HHM H3 IiHTepOCHbIX Ha~JIIOj.~eHIIYI, CReJIaHHbIX IIpII BbI-
IIOJIIIOHHH HCCJIeJ~OBaHHH, FiBJIHeTCFI TO, iITO HaJIHTIHe IIpeJ~eJIbHbIX
3HaTi@HIIYI IIO 3DIyJibraTOpy ~He3aBHCHMOCTb CxOpOCTH OT xOH-
I~eHTpaI~IIH 3MyJIbraTOpa~ IIpeJ~CTaBIISPeT COCO~I He IICxJIIO~IeHIIe,
xax 3T0 MO}xH0 6bIJI0 C~IHTaTb paHeO, a J~OBOJIbHO 06IIZee HBJIeHHO.
].~JIH BbIHCHOHIIH IIpIIpOAbI 3TOr0 HBJIeHHH 6bIJIII B3HTbI JIaTexCbi
IIonHMeTr~~IMeTaxpII~IaTa, izo~Iy~eHHble B yc~IOBxHx, IIoxasaxxblx
CTpeJIxaMII Ha ApHBOI3 Y pIIC. 2, H IIOABeprHyTbl H3y~IOHHIO MOTOJ~OM
MbIJIbHOrO THTpOBaFIIISI H 3JIexTpOIIpOBOJ~HOCTH. e~THMII II3MepeHHH-
MH 6bIJi0 IIOxa3aH0, ~ITO B 06JIaCTII IIpOIIOpIT,HOHaJIbHOI3 3aBHCHAIO-
CTH. CxOpOCTH OT KOHI~eHTpaI~HII 3MyJIbraTOpa ~CL~ IIOBepXHOCTb
IIOJIHMepHbIX ?IaCTHlj He HaCbIII[eHa MbIJIOM, B TO*ixe IlepeXOZ[a ~6~ -
IIOJIHOCTbIO IIOKpbITa MOJIexyJIaMH MbIJIa, a B 30He IIOCTOffHHOI3
~IIpeJjeJIbHOYI~ CKOpOCTII ~B~ HMeOTCH H36bITOx MbIJIa. e~TOT H36bITOIi
'.130
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H0 HBJIIIeTCA xCTOLIHItI{OM B03HYIIfHOBeHHA MxI~eJIJI, ~ITO Hex36eH;-
x0 HpHB0Ji0 6bI x yBBJIxTIeHHx) CxOpOCTx IIOJIxMepI33a]~HII, .a o6pa- .
3yeT IIOJIxMOJIexyJIflpHble CJIOH x3 MOJIexyJI 3MyJIbraTOpa Ha IIO-
BepXHOCTx IIOJIIIMepxblX iIaCTxI~. HBCTyIIJIeHIIe npeRe~Ia cxopocTx~
xOJITIMepII3al~Hx IIO xoxuexTpauxx sMy~IbraTOpa 3a$HCTIT OT paa-
Mepa II gIIC~Ia xacTHi~, T. e. oT o6x~eia xosepxxocTx IIoJIxAiepxbix.
xacTllu. C ysenxuexHeM xoHuexTpa~gxx xIIH1~Hazopa, Hpli oAxoH~
TT TOI3 x;e PJiy(xxe nO7IHMepHSaII;HH, OGpa3yeTCSI 60JIbxIOe gxCna
? Pxc.4.3asxcxAlocTS cxopocTx xonllAlcpllaauxil
McTBnaleTaxpxnaTa oT xoxuexTpauxil aMynbraTOpa
MI{.xpx pasxiax xoxuexzpauxxx xxxuxaTOpa.
1 ri 2 - Cxg = 0,0125 x 0,025, coorsercTaexxo. CooTxomeac~e
has = f : 2; 50? ?
6o~Iee Menxxx xacTxu. 06x~asl IIOBepXHOCTb xplI 3TOAi yse~III*I1~I-
BaeTCa,.x, c~IeRosaze~Ibxo, xacblx;exlle xosepxxocTx H o6pasosaHIIe
IIo~IxAlonexy~Ixpxbix c~IOeB aAly~IbraTOpa xacTyxaeT IIpx 6o~ib-
xie1=l xoxz>;exTpal>;xx AIbI~Ia, xax sTO BHAxo xa pxc. 4; rRe xpeR-
cTaB~Iexa cxopocTb xo~IIIAIepxaai~xx MMA xax c~yxxuHx xox-
1{exTpai~xx aAly~IbraTOpa MI{ RSA RByx xoxuexzpai~xil xxxuxaTO-
pa IIB. COOTBeTCTByIOx;ee 3TOMy rpac~xxy xaMexexxe paaMepa
(RnaAleTpa d) 13 ~xc~Ia IIo.nxAlepxbix xacTHZ; N xpll bAxoii x Toi~ xce
r~Iy6xxe xo~IHMepxsauHll xoxaaaxo xa pxc. 5. B~Ixxxxe xoII-
uexTpat>;Hx IIIIx>~xaTOpa xa paaMep ~IacTxu cl~~Ibllee IIposlB~IaeTCSI
xpx oTxocgTe~Ibxo Ma~tbix axa~eHHSIx Ca,,, s.nHaxxe xa 4xc~IO *Ia-
CTxI~, HaOCOpOT, IIpx 60~Ibxlxx CaM. PHC. 5 xoxaabisaeT TaxHCe
CIIJIbHyIO 3aBIICHMOCTb IIapaMOTpOB CLI H N xOnxAlepHbiX *IaCTHI1
OT xOHI~eIITpal~xII 3My7IbraTOpa. ~OJ~pO~Hbie AaHHble 06 I33MexeHIIFIX
pa3Mepa II iIxCJIa IIOJIHMepHbIX xaCTIII[ B pa3JIx~SHbIX CTaJ~IISIx IIO-
JlxMepH3aI~xH MMA xpx pa3JlxtIxbIX xoxuexTpauxslx aAly~Ibra-
Topa MI{ x xxH>~xaTOpa IIB 6yRyT paccAlOTpexbi B ApyroAl Mecze.
B 3TOAI J{OxJIaJ;e cneRyeT TOJIbxO OTAIeTIITb OjJxH pe3ynbTaT,
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o N d
-~ 500} 250
'o
_ KonuvecmBa 3Mynb2amopo MK, 2/100Mn
~ BodHOU ma36~
~T'xc. 5. YIsMeH~tii[e AxaMeTpa (d) x xxcna (N)., xacTxu xo-
alxMeTx,aMeTaxpx~TaTa B aasxcxMOCTII oT xoxrjenTpauIIr3
~My.nbraTOpa \1I# npx paaxoH xoxuexTpagITIT nepexnct3
6exaoxsa. CooTxoxlerixe c~aa=1 : 4; 50?. 1,~Iy6xxa noel-I-
Mepllaagxx 9,44 z IIo.axMepa /100 .mwc BoAxo~T ~iasr~.
IIepel;ucb 6exson~Ia: X. - 0,0125 x o - 0,025 z ;100 .non
BoArroH .c~asbl; Y IT 2 - N; 3 x 4 - cl
d 0 2 4 6 8
'o e
a 100 E 50
C C>
U
O
'~ 1 0 6 12 18 2~4 30- 36
KonuvecmBo nonunaepa,z/~OOnmBoBNOrip~a3ei
PKC. 6. I~I3Mexexxe AnaMeTpa (cl) n xricxa (N)'
-~IflCTxlj II07InMETxJIMETaxpx.IIaTa B 3aBIICITMOCTII OT
xoxuexTpal;xn no~rnhTepa IIpx pasxbTx eoozxoBle-
xllxs r~Iaa. Cns = 0,0125; Chsx= 2. CooTllorxern3e
opralr~ixecxoH n~BOAxo~i c~aa: X -1 : 4; 0=1 : 2.
50?.Tx2-LV;3x4-d"-?
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
xoTOpbli'I HMeeT cyH~ecTBexlioe axanelllie AXIS paccnroTpelulH Bonpoca
o rlexaxl'isnle srly~Ibcltoxxoi3 xo~Illnlepxaauxil. 9TO xoRTBepaicRexxe
c~axTa o coxpaxexxH xocTOxxcTBa Be~II'IUxxbl o6n~ei-i nosepxllOCTII
xo~IilMepxbix ~acTliu B Teuexxe Bcero _.xpouecca xo~il'Inleplaaauux.
McRBeReB c coTpyRxxxaalH [1, 6], Bxepsble oTrleTxBxlne aTOT c~axT,
o6~xclnlnx ero npoxcxoxcRealle xax pesyalbzaT xB~IeHn%I Bsaxnio-
c~IxxaxllH (xoa~Iecuexuxll) xo~IllnlepHbix nacTHu..3Tx xB~IexHx
B3aIIMOCJIxIIc`1HI3R. Hex3~e5I4H0 ~(OJISI{HbI ~bIJIH xpIIBeCTx K yDieHb-
IIIeIIItIO iIIICJIa lIOJIxDIepHbIX iIaCTIIi~ B XOJ~e xO7IIIblepx3aljI'IiI. He-
IiOTOpble 3ICCnepHDieIITaJIbHble J~OHa3aTeJIbCTBa 6bIJII'i IINx npll-
Beuexbl Ha OCHOBe xCHOJIb3OBaHxFi bieTOJ[a csezopacceslxxsi. Ha-
xIxn1II IICCJIeJ~OBaHIIHbrII 6bIJI0. OTileTJIxBO x0Ifa3aH0, xax 3T0 BIiJ[HO
IIa pllc. 6, ~ITO Hpx pocTe RuanieTpa xo~iHnlepHbix nacTHl~ Hpoxop-
ulloxa.nbllo xo~Ix~IecTBy o6pasoliaBxlerocx nonxnlepa, Iix nllc~io
peaxo xaAaeT c rny6xxoil xo~IHnlepxaaunx. IIo~IyueHlibie peay.ab-
TBTbi HBXOZ(iITCfr B xpOTHBOpeiIIIH C TOOpxAhIII, OCHOBaHHbrDiII
Ha ROxyII~eHxII J~IiCiCpeTHOCTx nOJlxbiepHbIX iIaCTHr( II H8II3nI0HAe-
rlocTll IIx nxc~Ia B xoRe xo~iliniepxaauxl'i rI xao6opoT, xopomo
cor~IacyeTCSI. c xpe~cTaBsieHxxnrll 06 anry.nbcxoxxoil xonxrrepxaa-
I~IIx xax ICBa3xrO-ioreHHO1~I IIpOI~eCCe, B ICOTOpOD4 3(~C~IeKTIIBHbIYI
o6~eri HexocpeRcTSexxo cBSlaax c o6~enloni xnlelox~erocsl B cncTerle
amiynbraTOpa. ?
. JIaT'ep,aTypa
1. C. C., M e A s e R e n, Simposio internazionale di chimica macromoleco-
lara, Milano -Torino, 1956. Ricerca Sci. Suppl. 25, 1955.
2. C. C. 111 e A s e A e B, Simposium on Macromoleculare Chemistry, Praha,
1957.
3. C. C. McAseAes, 17. 111. Xomlllxoscxliii, A. I1. Illeiix-
xep, E. B. 3a6onoTCxax, r. R. Bepexciloii. C6.
, nr~m. 1, 1958, cTp. 1.
4. E. B a r t h o l o m e, H. G e r r e n s,leitschrift fiir Electrochemie,
3, 334, 1956. '
5. A. IL ll[ e i3 ri x e p, C. C. M e A n e R e s, ?K. ~nsnu. xnrnur, 29,
250, 1955.
6. E. B. 3a6o~IOTCxax, ICI. r. Co6osena, Ff. B. Alaxse-
u o B a, C. C. M c A a e A e B, I~o~I~IOrIAiI. x;., 28, 420, 1956.
Summary
A kinetic study of the polymerization of methylmethacrylate,
vinylidene chloride and chloroprene in aqueous emulsion has
been studied over a wide range of concentrations of emulsifier
and initiator. '
Potassium persulfate, hydrogen peroxide, sodium perborate,
benzoyl peroxide and azodiisobutyrodinitril were used ?as ini-
tiators and the sodium salts of the sulfo acids of aliphatic hydro-
carbons (MK emulsifier) and sodium laurate as emulsifiers.
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The . esoap titration> method coupled with conductimetric
titration were. employed to determine the number and size of the
polymer particles formed at various stages of the polymerization
..process with respect to the concentration of the substances parti-
cipating in .the- latter.
- The kinetic relations and the. data on the particle number
and size were discussed from the standpoint of existing views
on the mechanism of emulsion polymerization. This led to the
conclusion that the discretive principle can not be applied to poly-
mer particles, i. e. they can not be considered as micro -spaces
where polymerization takes place independently of each other.
The experimental findings indicate that the relations are
determined by the over-all volume of the emulsifier, independe-
ntly of whether it is in the form of micelles or is on the surface
of - -the polymer particles. .
Resume
On a fait 1'.etude de la cinetique. de polymerisation en emul-
~sions aqueuses du methacrylate de methyle, du chlorure de
vinylidene et du chloroprene en de larges intervalles de concentra-
tion de 1'agent .emulsionnant et de 1'initiateur.
A titre des initiateurs etaient employes le ,persulfate de po-
t,asse, 1'eau oxygenee, le perborate de soude, le peroxyde de ben-
zoyle et 1'azodinitrile d'acide isobutirique. En qualite des emul-
sionnants etaient utilises les sels de soude des alcoylsulfates
(emulsionnant MK); le laurate de soude.
Dares le but de determiner la quantite et la dimension des
particules polymerisees formees durant de differents stades de
polymerisation aux diverses concentrations des substances. uti-
lisees au processus on a applique le procede du en combinaison avec la methode conductometrique.
Les regularites cinetiques trouvees et les resultats -des me-
sures du nombre et des dimensions des. particules polymerisees
ont ete discutees du point de vue des idees existantes sur le me-
chanisme de polymerisation en emulsion. Cette discussion aper-
mis de faire la conclusion, que le principe de discretion ne peut
pas titre applique envers les particules polymerisees, c'est-a-dire
que celles ne peuvent titre considerees comme microvolume, daps
lequel s'effectue la polymerisation independamment d'autres
particules.
Les resultats des essais nous montrent que les regularites
trouvees sont dues au volume total. de 1'agent emulsionnant,
sort. qu'il se trouve sous forme,de micelles, soft qu'il -se trouve
sur la surface des particules polymerisees.
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EIiOPOCTb HOJIgMEPI~I3AIjI~III j~Jlfi Oj~HOI~I iIACTI~IL~bI
HP1I 3MyJIbCI~IOHHUI~I IIOJII~IMEPI~I3AI~I~II~I
'
.2oycuex
A. Pacucaacex, M. I
(T3exocacosaxxR)
ORxH H3 aszopoB_aTOro RoxnaRa [1] BbtpasH~I cxopocTb RnR
~OJ~HOi3 ~IaCTHI(bI IIpH 3MyJIbCIIOHHOI3 IIOJIH11IepH3aIjHH B O~JIaCTII
IIOCTOFIHHOI3 CI(OpOCTH IIOJIHMepH3auHH c~opMy~IOH, xoTOpylo aa-
'4'eM MOJ~H(~JHI[HpOBaJI H IIOJIy~iHJi OTHOIIIeHIIe
1 _ 2 n ka (x)
v - K + K '
pol(l) vi
sRe
vpol(fy- CxOpOCTb IIOJII3MepH3aI~HH ~JISI OJ{HOII TiaCTHII,bI
72 - xOHI~eHTpaI~HA BCOX iIaCTHI( B 3MyJIbCHH (.hLOJGb ?.2-1);
v'i -cxopocTb sxeRpeHHU paAgxa~IOs xHxuxaTOpa B ua-
cTHub1;
(x) - axTHBHasI xoHueHTpauHH. aaMeR~IHTe~Ix Boxpyr pa-
cTyluero pa~Bxana (,~co.2b?ra-1);
ka - xxHeTHxecxasl IIoczoslHHas o6pbisa ueIIH IIpH HoMOII~H
aaMeAngTenx (rc?.,worcb-Ice~-1);
,k2 - xgHeTHUecxax IIoczoxHHasl pocza ueHH (~c?.?orcb-1
(M) = axTHBxax xoaueHTpauHx MoaoMepa Boxpyr pacTy-
Hzero paRHxa~Ia (.~co.~t ? r~-I);
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HOFI iIaCTHubI 3aBYIC~IT TOJIbKOOT BeJIIIiIHHbI COOTHOIIIeHHSI MexcRy
Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
xxc~IOM xacTxu x cxopocTblo BxeRpexllx paAxxa~ioB xxxuxaTOpa
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x0 x pa36aBIITeJIeM Ojlraxx~IeCx0I3 (~a3bi, B p03yJIbTaTO iIOrO o6~Ier-
~IxTCx Axc~~iysxx MoxoMepa x cepbl x paAxxanaM, Bosxxxxlxal
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~exxblil xocne o6pa6oTxx ~IaTexca T9TA, pacTBOpx~ICx B 6exaone
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
cTBOSana 0,43 II IIpII6nII>xanacb x axcuepHnleIITanbxblM Aaxal~nl
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
B 3Tgx oIIbIZax cpasxxsanx xHx~gIIpyiou~ge csogcTSa ' IIepe-
xxcg 6eaaoxna (IIP), aepcyxbc~aza: xa~xx g 'aaoxao6yTgpo-
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cones 278 hLO.M1b/!c; 3 - Ha4aJIbHaH ISOHI[eHTpaIIHR' MO-
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nee 6bicTpbinl, eeM peaxuxe BoaHxxxosexxe cso6oRxblx paRHxanos.
I~Is aTOro cneAyeT, eTO cTexellb Hpespaluellxe aasllcllT oT cxopocTil
Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
BoaxHxxoBexHSI cBO6oRxbix paRlixa~IOB, a Taxxce oT IcoxuexTpauxx
noxoMepa.
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~IHMepHaauHx) nfoaxxo 6bIJI0 6br HpxxaTb xoxuexTpauxlo ~Nfoxonfepa
(ICpoNie xoHueBOro aTaxa Hpouecca) sa IIOCTOAHHyx), To IcpHBasf
xanfexexxi~ noTexuxa~Ia, oxpeRe~ixloH~au cxopocTb Boaxxxxolfexnx
nE.MB
0
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-40
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Pxc. 4. ~IaMefleage uoTexf~mana s cllcTeMe, ffe coRepaxair;efa
MolfoMepa.
1 - xavanaxaR xosAexrpauxR C, = 0,00427 .?onb/n; 2 - xa9anaxaR
xoxgexTpagxx Cz = 0,0128.MOne/n.
CBOC~OJ~HbIX paRHxa~IOS, J;OJiaxxa 6bIJIa 6bI OHpeJ[eJIHTb $ CTeHexb
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1~0HTpaI[HfIX xOMIIOHexTa (OxHCJIHTeJIbxO-BOCCTaHOBHTeJIbHOI3 CH-
cTeNibl), xo HpH pasllbix xoxuexTpai~xxx afoxoNfepa peaxl~HSI
npaxTHxecxH HpepbiBaeTCx xa .pasxoH cTexexx HpeBpaH~exxx.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
~:.H.a" ocxosaxnH" HonyueaHbrx peay.abTaTOB H xHxezH?iecxHx
o6cyxcReHHir MO1IfH0 BbI~IHCJIHTb 3Ty xoHeLIHyIO czeIIeHb IIpespa-
?II~eHHR.:: ~ ,. ..
IIonHax ,TeopeTH*recxas xHTepHpeTauHx aTHx srB~reHxg Tpe6yeT
~pac~HpexHx:axcHepHMeHTanbHbrx MaTepna~roB ,H xBrrxeTCx npeR-
:nteTOM .. AarrbxeirmHx. HccneRoBaHHi3.
JIgTepazypa
1. W. Kern, Angew. Chem., A59, 168, 1947; Makromolek. Chem., 1,
209, 249, 1947;. Makromolek. Chem., 2, 48, 1948; Angew. Chem., 61,
471, 1949.
2. J. H. B a x e n d a l e g cozp., Trans. Faraday Soc., 42, 155, 668, 675,
1946.
3. R. G. K. Bacon, Trans. Faraday Soc., 42, 140, 1946: , ,
4. J. M. K o l t h o f f, A. J. M e d a l i a, J. Amer. Chem. Soc., 71,
3784, 3789, 1949.
5. C. D. J o s e f o w i t z, H. "Mark, Polym. Bull., 1; 140, 1945.
investigated.
Summary
The change in potential during emulsion polymerization in
a system in which the oxidizing agent is soluble in the disperse
phase and the reducing agent in the aqueous medium, has been
tion method .; ;, ~ _ 1
The time potential curve was found to be linearly related
to the'`'cu~rve''depicting the change in'~nionomer concentration.
The results of the measurements were subjected to mathemati-
cal treatriierit' to determine"the correlaton'coefficient and to de-
rive the direct regression 'equation.
Moreover other systems containing reducing and oxidizing
agents and' the 'monomer in a single 'phase have been studied.
The change in potential in the process of polymerization for va-
'rying initial corrcentratioiis'of th'e monomer has been determined.
A gelation ha's' been established' between the results obtained and
? .. ...
the -polymerization process.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
On a fait 1'.etude de. la variation de potentiel pendant la po-
lymerisation en emulsion Bans le~ systems; ,oii 1'oxydant est so-
luble en phase disperses tandis que;.le reducteur est en phase
aqueuse. '
Le controls du tours de processus et.ait effectue par la methods
absorptionometrique daps la. region ultraviolette.
On a etabli que la courbe de variation de potentiel dans le
temps se trouve en correlation lineaire aver la courbe. de ._v.ariation
de concentration du monomers.
Dans le but d'etablir la valeur du coefficient de correlation
et' de deduire une equation de regression directs les resultats des
mesures ont ete soumis a 1'analyse mathematique.
Sur la base des donnees obtenues on a determine , la depen-
dance entre la variation de potentiel et la variation de concen-
tration du monomers.
En plus` on a etudie quelques autres systemes qui" renferment
le reducteur, 1'oxydant et le' monomers en phase aqueuse. Une
variation de potentiel au tours du procede de polymerisatigri
pour de diverses .concentrations initialer du monomers pent
etre calculee. '
On a etabli la liaison entre les resultats obtenus et~"le tours
du procede. de polymerisation. .. ~ '
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
fl3yLIEHI~IE MEXAHI~I3MA 3MYJIbCI~I0HH0I%I
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
uxH xy~Iesoro, IIepBOro x BTOporo IIopslAxoB II xaIIlnII cooTBeT-
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
X~IOpoxpex 6br~I o~IHrgeH HO McTORy BKerpexa [3l x 3axac ero
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TepMOIIapOI3 C IIOJ~XOAfiII;xM yCxJIHTeJIeM IIOCTOHxHOI'O TOKa H Ca-
MOxHIIIyIl[II11I MHJIJIxBOJIbTMOTpOM [4].
KIIHCTHKa 3MyJIbCIIOHHOI3 IIOJIIIMCpI33aI(I3I3 CTIIpOJIa
J~~ISI xa~Ix6posonHblx x3nlepexHK IIpoBORx~Ix 3My~bcxoxxylo
HOJIxMepx3al);HIO XOpOIIIO x3yLIeHHOrO MOHOMepa CTH])OJIa.
Ha pxc.. 1 IIpeAcTaB~IeH THIIH~IHbIYI cJlyiIaYI 3aBHCHMOCTH ~T
xpH IIOJIxMepx3al;Hx CTxpOJia B 3MyJIbCxOHH013 CIICTOMe OT Bpe-
11I0HH. rOpH30HTaJIbFIaFI iIaCTb KpHBOi3' COOTBETCTByeT IIepHOi~y
peaxl>;~iH xy~Ielloro IIopxRKa xpx o6x~ei~ cxopocTll IIonxa3epH3a-
3~HH vs = 8,01 ?10_8 .~eorcv ?e.~ti_3 ?ee~-1; yeTaxoB~IeHxoH Ha ocxolla-
Hxx pe3yJlbTaTOB ]~ByX x3MepeHI3I3, IIp0I33BeJ(exxbIX C TO~IHOCTbIO
1-2%. 3a 3TxnI xepxoRoM c~IeRyeT xepxoR cxopocTH peaxl~xx
xepBOro IIopHAKa, Bblxxcnexxbli~ H3 ypallxexxx (3). Ha pxc. 1
IIpeRcTaB~Iexbl Toxce 3xaxexHx cxopocTx peaKuHH xy~Ielloro no-
paAxa, Bb3xHC~IexHble H3 ypallxexxx (2) c MoMexTa ox~3axcRexxsl
cxcTeMbl Ao ~Tp = 0 npH6aB~IexHeM pacTBOpa IIxIII~HaTOpa xpx
xOBTOj)HObi OIIbITe.
B TOTIKe IIeperH~a, B KOTOp0I3 MCX8Hx3M peaKI~HH II3MeHHeTCH,
x xCile3a30T xOCJIe][HHe KaIIJIH MOHODIepa, BOCb DIOHOMep HaXO~xTCR
B ~iacTxl~ax ~IaTeicca II xpx x3BecTxoH ?r~Iy6xxe xpespax~exxx(npll
xaxlxx H3nlepexHxx'B IIpeRenaX 41-43%)MOxcxo BbluHC.TxTb xoH-
3~eHTpa3~illo r3oxoMepa B ~acTxlzax ~IaTexca [5l.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
Z 3 4 s s ~ a
P11C. 1. 3HCII2~1IIM0I1TaJIbIIxH 3aBfiCIiMOCTb ~7' _-- f ~'C~ j~JIR 9MYJIbCIi0BII0S1 IIOJIIIMep33aal[i3II CT1i~JOJIa.
OTIIOIIICIffiC (~a3 1:3,31 ~68 225; TCMIICPaTyPa TOPMOCTBTa ~IO~.
1 - cocrae eoAxor~ ~aa~: amynbrarop 5,8 z/n,K:S:O, 1,052 a/n; 2 - npx6aenexbi K=S=O, 2,104 a/n -F KHSOe 0,819 a/n.
Bb~9xcnexo xa ypaaxexxx (2); nb~vxcnexo xa ypanxexxx (3).
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
3xaxexxx' r.ny6xx xpespax~e~ixa sbi~ixe~iexxbi~ x~ o~xome-
xxi~ [4] R~ixK = 0,118 ~cKar~ ?apaa-i ?.rotutc'1 xC = 0,3 xKarc ? ZpaB-1
xopoxio cosxaAaioT c peay~ibTazaMx oxbiTOS.
x
1 x
0,4. 0,6 O.B 10
Crc2 ~2 ~8
i PHC. 2. Y - 3aBHCHMOCTb CxopOCTH 3MyJIbCHOHHOii 'IIOJIHMe-
pH3aI~HH CTHpOdia 1JS OT xOHI[eHTpai~HH K2S2Og~ 2 - aasxcx-
Moczb xo.nHxecTSa aacTHu ~aTexca N oT xoxuexTpar~Hx KzS20g.
Ha ocxosaxxx xoRa xpxsoK aasxcxniocTx DT oT speMexx
~ioxcxo aaMeTxTb ac~c~exT resieo6paaosaxxsi s xpeResiax 65-
75 %-xoi~ r.ny6xxbi xpespax~exxsi [6]. J~axbxei~xixrz Ro6as~texxeM
~ixxi~xazopa so speMSi xepxoAa peaxuxx xy~iesoro xopxAxa,
xorRa yx;e xe xpxcyTCTByioT cso6oRxbie rsxue~x~ sNiy~ibra-
Topa x xe MoryT soaxxxaTb xosbie ~iacTxuii, cxopocTb xo~ixMe-
pxaauxx xosbicxTb xe~ibsx. ORxaxo ycxopexxe peaxuxx s o6na-
?cTx re~ieo6pasosaxxx (xpeRcTas~iexxoH xa pxc. 1 xyxxzxpHOi~
xpxsoK 2) rioxceT 6biTb sbissaxo xosbixiexxeNi icoxz;exTpauxx
cBO6oRxbix paRxxa~ios B gacTxuax ~iaTexca.
J~~ix cxygau 3My~ibciioxxo%i xo~ixMepxaauxx rsoxoMepa cTx-
po.aa, oxexb Maio pacTSOpxnioro s soRe, s cxcTeMe, s xoTOpoi~
cso6oAxbie paAxxa~ibi o6pasyiozcsi s soRxoii c~aae x y~iasnxsaioTCx
uacTKuaMx uo~ixMepa, nixorxe aszopbi Roxa3a~ix xoponiee cor~ia-
cxe c sr~soAanix xReaaibxoi~ xxxeTxxx CiMI3Ta x OsapTa [7]. 3Ta
Teopxx x xpx orpaxxuiisaioir~xx xpeRxo~ioaicexxxx, o6cyxcAaeMbix
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
McRBeResblM [8], y~oBSeTBOpHTe.nbxo oxxcbisaeT RazIIlblii caryllaii
xxxuxxposaxxsl.
Ha ocxose Raxxbix, xo~Iygexxbix xpx i13n1epexxll o61uei~. cxo-
pocTx peaxuxx, xaMx Talfxfe ~bIJiO ycTaxoB~IeIIO cor~Iacxe c 3TOiI
?Te' pIIe~I. Hla pxc. 2 xpeRcTaB~Iexa B cxcTenie ~BOilHbix norapxc~-
ni xeclfxx xoopRllxaT 3asxcxMOCTb xiic~ia ~IacTxu oT xoxuexTpauxH
II xuxaTOpa xpx xoczoxxuoH xoxuexTpauxx 3n1y~IbraTOpa. YrdIO-
BDIII ICO3(~1(~1xuIlexT O6OxX I~yxKIjHOHaJIbxbIX 3aBHCHMOCTeI3 COOT-
IIe~CTByeT, xo TeopHx, 0,4-~i CT0II0HH KoxueHTpauxH xxHuxaTO~Ia.
B nxxxxa xacTHu 6bIJIa oxpeAe~Iexa nieTOAoM cseTOpaccexxxH xo
al~agexxxM AxcxDinleTpiill.
BbI~IHC~IexxaH xa ocxosaxHli xsniepexxbix .sxaxexllH o61uHx
~ciCopocTei~ peaxulill, xHC~ia uacTHu x IfoxueHTpauHH Moxoniepa
(5,,7 ?10-3 ,VLOJEb -C.hG-3) B xacTxuax ~iaTexca IfIIHeTHgeCxasl xox-
cTaxTa pocTa uexli cTxpo~Ia xpx 40? oTBe*IaeT 3Haxexxlo
1C~2 .~ ?.ntio.nb-I ?ce~-I Ii xaxoRxTCx B xopoxieni cor~IacxH c pe3y~Ib-
Tay~Tanila Rpyrxx aB~ropoB [5, 9], xonyxexxblMx H3 HxxeTH~ecHxx
II~MepexxYI B 3MyJIbCHOHxOii CIICTOMe.
f KI3HCTii1{a 3MyJIbCIlOIIHOI3 xOJlxniepx3al~Itl1 xJiopoxpexa
XOJ~ OTj~eJIbxbIX yLIaCTHOB IfpxB013 3aBHCHMOCTII TOMHepaTypbI
~OT BpeMexx xpx 3n1y~IbclloxxoH Ho~iHMepx3auHII x~IOpoxpexa
(pgc. 3) Moxfxo cpasxxTb c Taxosbini xpH 3nly~IbcHOxxol~ xo.nxnie-
pl33auFIH cTxpo~Ia. IIoc~Ie xepxoRa pealfuxH Hy.nesoro xopslRxa,
?cyAx xo 3Ha~exxslnl, Bbl~xc~Iexxbini x3 ypasxellxH (3), yxfe xpH
37, %-xOi~ r~Iy6Hxe xpespax~exxH xacTyxaeT xopoTlfxx xepxoR
p~alfuHH HepBOro xoptlRxa.
~TO~bI OHpej{eJlxTb, x3nieHSIeTCFi JIH CIfOpOCTb IIOJIxniepx3ai(HII
'Ha OJ~Hy iiaCTHuy, B xepxoAe HyJIeBOPO IIOpFIJ~Ha J[OIIOJiHHTeJIbHO
'IIpH6aB7IHJIII HIIxI~xaTOp. KaIf BHJ~HO x3 pxC. 3, B 3TOrI xepxoRe
o6u~ax cxopoczb peaxuxx He xoBbicii.nacb. Taxlle pe3yJIbTaTbl
HpOTIiBOpeiIaT yKa3axIISIni MOpTOHa x COTpyJ~HiiICOB [10], I(OTOpble
ycTaxoBx~II3 Ilpx xpxBxTOK Ho~Ixnlepx3auilll x~IOpoxpexa 3aBII-
?cxnlocTb cxopocTil peaxuxx B oAxoyi uacTHue oT IfoxuexTpauxx
Ilxxullaxopa. ORxaxo 3Tx aBTOpbI Be~Ix oxblTbl c Apyro%t xo~Ixnle-
pll3auxoxxo~i cxcTenioil x pacxoaxAexxe pe3ynbTaTOB, xonlllnlo
OCTaJIbHbIX C~aKTOpOB, 111O1IfeT 6bITb BbI3BaH0 IIpxC3TTCTBHOM 3anieJ[-
.JIHT0JI0I3, BJIxfiHxe IfOTOpbIX IfOJIxileCTBEHHO x3yLIxJI Pblxlaxelf [111.
C ueJIbIO xpOBepxx 3TIIX J~axHbIX 6bIJI0 IiCCJIeJ[OBaxO BJ1xxHxe
IfOHl[exTpal[xx xHxuxaTOpOB' xa O6xI,ylo CIfOpOCTb IIOJIxnlepI33auIIII
Ii Ha .O6pa3OBaxIIe TIaCTxu IIprI IIOCTOSIHxOM IfO7IxTIeCTBe xCIIOJIb-
30BaHxOrO 3MyJIbraTOpa. yrJi0BOI3 ICO3C~1(~1xI~I3eHT O6exX JlHxei3-
1lbix i~yxxuxH, HpeAcTaB~Iexxbix xa pxc. 4 B ~IOrapxc~MxuecxoH
CxCTenie ICOOpJ~xHaT, COOTBOTCTByeT IIpx~OJIx3xTeJIbHO 0,4-I3 CT0II0xx
If.OHi[eHTpal[xx IlHxuxaTOpa HO TOOpIIx GMxTa - ~8Bap1a.
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~'xxTR~xex 11 co~P3tRxxxII [12] IIayga~lII BJIYIBxIIe xoHuexTpa-'.
I~IIYI 3DIyJIbPaTOpa IIpr3 3MyTIbCIIOHHOI3 IIOJII3MepII3aI~I313 XnOpOIIpexa
Fla 06pa30BaxIIe ~IaCTIII[ ~B OTCyTCTBIIe IIIiIII~HaTOpa;. OIIbITbI Beni
JT
Pxc. 3. ~KCIIepI3M0HT8JIbH8FI 31BIICI3MOCTb 07' = f ~T~ 3MyJIbCIlOIlIl0I3 BOIIi3ME-
pxaauxx x.noponpexa.
OTnomeane ?~as 1:3,31 (68:225); TeMnepaTypa mepmocTaTa 40?. CocTan soAnoH $asb~r
amynbraTOp 5,8 z/n, KESQOa 0,360 z/n, npn6asnexne KESpOe 0,360 z/n, KHSOe. 0,445 z/n;.
sa~4xcneao ns,ypasaenntt .(3).
C CIICTOMOYI~ IIOJIIIMepII3yI0II~eIICfl IIOR BJIII8HII0M ,IIpHCyTCTBylO-
II;NX? B MOHOMepe IIepeI{IICeYI. nOCJIe IIepeCiIOTa' J~axxbIX 3TIIX aBTO-
pOB O COAep51(aIII313' 3MyJIbPaTOpa B CIICTOMe IIa HOHI[eHTpaI~13I0 eI'O
B BOJ~HOyI (~a3e MO?KHO 3aMOTFITb IIpOIIOpIjIIOHaJIbIIyIO 3aBIIC1'IMOCTb
nlexcAy ? COOTBOTCTByEOII~I~MYI JIOPapII(~nfYITIeCKIIMS3 , BeJII3iIYixaAll3
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c yr~osbinl Icoac~c~xuxexzon'i.0;9. YxonlxxyTax cxcTenia B.6onbmenl
ilpx6.ai~xcexxr~ IIOJIxMepx3yeTCFI x0 MOXaHx3My, IIpe~[JlOxcexHOniy
McRBeAeBbIM [8) Rnx c~Iy~Iax, s xoTOponl xxllullaTOp pacTriopHM
$ yr~IeB,oAopoAxoH c~a3e.
0.2, 0,4 , 0,6 0,8 10 Z,0 40 6,0.8,0
CKZ s2 oR .
PIIC: 4. Y - 3aBHCIIMOCTb CIfOpOCTH 3MyJIbCHOHHOI3~ IIOJIISMepN-
3aI(HH XJIOpOIIpeHa OT HOHI;eHTpan;HI3 KZS20g, 2, - 3aBHCIIMOCTb
KOJIHileCTBa tIaCTIII; JIaTEItCa OT IfOHl[eHTpaII,HH K~S20g: '
OTHOIDCHHC q>a31t: 8,81; 'TCMIICpBT}'pa"4O?. ICOHIjQHTpBIjAH OM9]IhP8TOp8
5,81 a/n s HoAi7oia cease.
I{xxeTx~ecxax xoxcTaxza pocza uexx x~IOpoxpexa xpr3 40?,
sbr~r3c~Iexxasi xa ocxosaxllx xaxixx IlaMepexlli~ o6~IIx cxopocTei~
Qo~IxMepxaai~xll, ~xc~Ia *IacTr~r; t3 xoxi~exTpauxA Moxoniepa s qa-
? cTxt~ax ~IaTexca (7,G ?10-3 .~corcb ?c.~t-3) oTBegaeT axa~exliio
220 rc ?.nsorcb_I ?ce~c-1.-
JIIITepaTypa ..
1. V. K a m e n i k, c~I. H r u b y, Chem. prumysl., 5., 510, 1955.
2. H. ,i~. K o a o B, O. B. P H B H H, ?I~. c~HS. xIIMIIIi, 33, 83, 1959.
3. S. E k e g r e n, 0. O h. r n, K. Granath, P: V. K i p e 1 1, Acta
Chem. stand., 4, 138, 1950.
4. W. I. B e n g o u g h, H. W. M e l v i l l e, Proc. Roy. Soc., 225A,
330, 1954.
5. E. Bar?tholome, H. Gerrens, R. Herbeclc, H. M.
Weitz, Z. Elektrochem., 60, 334, 1956.
6. H. G e r r e n s, Z. Elektrochem., 60, 400, 1956.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
7. W. V. S m i t b, R. B. H. E w a r t, J. Chem. Phys:; 26, 592,.
1948:
8. C. C. M c R s e A e s, MexcRyxapoAxviu cnMnosnybr no .MaxpoMOnexy-
napxoii xnMnn, IIpara, 1957, C6. 22, 160, 1957.
9. M. Morton, P. P. Salatiello, H. Landf field, J. Poly-
mer Sci., 8, 279, 1952.
10. M. Morton, J. A. Calla, M. W. A.ltier, J. Piirma, J_
Polymer. Sci., 19, 547, 1956.
11. A. R y s a n e k, I. Polymer Sci., 29, 557, 1958.
12. R. W intgen, L. Iiirgen-Locmann, Kolloid. Z., 122.
148, 1951. ,
Summary
Investigation of the polymerization process was carried out.
o~i emulsions placed in water-thermostatted flasks. The tempera-
tures of the central part of the flask and of the thermostat were
measured with the aid of thermocouples. The heat balance of the
reaction system under investigation is given by the following.
differential equation:
' dq/dT=Cd(~T)/dT~-KIT. (1~
The quantity of heat dq evolved during the time d ~ in the
course of the reaction raises the temperature of the system by
d(~T), part of the heat being removed by the cooling bath: The
.constant K expresses the over-all heat transfer, C is the overalP
heat capacity of the polymerizing system.
The left side of equation (1) contains the time function of the?
reaction. We investigated the cases for zero, first and second order
reactions and derived the corresponding solution of the basic?
equation for DT = f(T)
a) zero order reaction:
DT = (~HKo/K) (1 - e-xT~c) + OTP e-KT~c (2~
b) first order reaction:
OT = [(OHKI - NIP)l(K - CKi)l' (e-Kh -
c) second order reaction:
OT = (OHMn/C) [e-xz/C - 1/(NIp,K1zT -f- ~)1 ~-
-}- ATP e-Kl0 -{- (OHh'/C2 Ku) e-x;cn1~(MP?~{ iiT -F. 1) X
X {L+'i [(K/CNIp Kii) (n'Tp Kt~ 2 --~' ti)1- Ei (h'/CI'~1n (Kll )} (4)'
~~
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Ko, KI and KII in equations (2), (3), and (4) are the zero,
first and second order rate constants, DH, the heat of polymeri-
zation, .Mp and OTp, ,the number of moles and the temperature
difference at the start of the reaction; the difference
. .S .
_~
is the so-called reduced exponential integral, values of which are
tabulated.
The constants K and c may be calculated from the experimen-
tal curve OT = f (2) and from two-three values for the degree of
conversion in the course of polymerization. From this any
number of values may be obtained for the degrees of conversion
with time. For such values we derived the following relation:
where ~p~OT is the over-all reaction rate- expressed.by the increase
with time of the amount of polymer. Expression (5) has a conve-
nient linear plot and from the slope and the intercept on the ordi-
nate axis the reaction order i and the rate constant Ki may be
determined' directly.
The theory was applied to a kinetic study of the emulsion
polymerisation of styrene and chloroprene. An aqueous solution
of potassion laurate served as emulsifier and potassium persul-
fate as initiator. The reaction was carried out at 40?C. The me-
thod permits accurate determination of the overall polymeriza-
tion rate and of the monomer concentration in the ]at.ex par-
ticales.
1n a number of experiments the reaction rates and quantity
of latex particles as function of initiator concentration were
determined. The results were compared with conclusions follow-
ing from the Smith-Evart quantitative theory of emulsion poly-
merization.
The constants of chain growth of polystyrene and polychlo-
roprene were determined.
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L'etude de polymerisation s'executait avec 1'emulsion, pla~
cee daps un ballon thermostats par 1'eau. On mesurat la tempe-
rature au milieu de ballon et du thermostat par un couple ther-
moelectrique.
L'equilibre thermique du systems reactionnaire a etudier
est exprime en forme differentielle par 1'squation:
La quantity de chaleur dq qui se degage au de la rsaciton
en temps dT augments la temperature du syst'eme de d(0 T);
,quelque peu de chaleur est evacue par un bain refroidissant. La
constants K exprime le total du transfert de chaleur. C designs
une capacite thermique sommaire du systems se polymerisant.
La partie gauche de .l'equation (1) comports la fonction de
temps de la reaction. Nous aeons.examine le cas des ~ordres: nul,
.premier et? deuxieme et elabore une- solution correspondante de
1'equation principals pour DT = f (T)~. .
. a) Reaction de 1'ordre nul:
b) Reaction du premier ordre:
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ou K?, Kl et Kll en equation (2), (3) et (4) presentent les vitesses
constantes des reactions des ordres: nul, premier et deuxieme;
3-i est la chaleur de polymerisation, Mp et OTp designent une
quantite des mols et une difference des temperatures au debut
~de la reaction: La difference
~lesigne , dont les var-
leurs sont contenues daps les tableaux:
A partir de la courbe DT = f(2) et deux-trois valeurs du~
Alegre de transformation, determinees au tours de polymerisa-
tion, on peut calculer les valeurs des constantes K et C et calcu-
ler, ainsi, une serie arbitraire de valeurs du degre de transforma-
tion par rapport au temps. Pour ces valeurs nous aeons fait la
relation
ou 0p/OT est la vitesse generals de reaction exprimee par une aug-
mentation de la quantite du polymers selon le temps: La rela-
tion (5) a une presentation lineaire commode; a partir du coef-
ficient angulaire et tronCOn sur 1'axe des ordonnees on peut
determiner directement 1'ordre de reaction i et une constants de
vitesse de reaction K2.
Cette theorie a ete appliques pour 1'etude de la cinetique~
de polymerisation en emulsion du styrolene et chloroprene.
A titre d'emulsionnant a ete utilises une solution aqueuse de po-
tassium laurique et pour amorcer la polymerisation on a employe
persulfate de potassium a 40? C. La methods permet de mesurer
exactement une vitesse totals de polymerisation et de determiner
la concentration de monomers Bans les particules du latex.
Durant quelques essais on a mesure les vitesses de reaction et
la quantite des particules du latex suivant la concentration d'ini-
~,iateur. Les resultats ont ete compares aux deductions de la theo-
mie quantitative Smith - Evarte pour la polymerisation en
emulsion.
Des constantes'de croissants de chains du' polystyrolene et~
celles du polychloroprene ont ete determinees.
i2' Me}spyHapoAn~H cnMnosnyH, cexunR 2 q~q
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Next 5 Page(s) In Document Denied
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HOJII~IMEPI~I3AI~I~IFI
B IIPHCYTCTBHH OPI'AHI~IiIECffHX COEJ~I~IHEHHYI
II~EJIOLIHbIX METAJIJIOB
IO. Jl. Cnupun, j{. I#. IZo.2s+xoe, A. P. I'a~Ina,a~axep,
C. C. McBee~ea
(CCCY)
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CyTCTBIIH OpraHHiIQCHxX COeZ(IIH0HIII3 II~eTIOiIHbIx MOTaJIJIOB -
3$BIICIIMOCTb_ CTpoeHxx IIOJIxMepHOx I~exx OT IIpxpoRbl Bb16pax-
Iioro IcaTanxaaTOpa x cpeRbl.
' BbIJIO IIoxaaalio, xTO cTpyxTypa IIo~Ix6yTaRHexa [1] x IIo~III-
H3oxpexa [2], a Taxaxe cocTaB pxAa coIIO~rlrnlepoB [1, 3, 4] peaxo
MexxloTCx IIpx aaMexe nIITxHa~Ixxstbxbrx xaTa~IIIaaTOpoB 6o~iee
IIOJIFIpHbIMx xaTpHr~a~Ixx~IaMH, a Taxxce xpx IIepexoAe oT yr~Ie-
BoRopoRHOro pacTBOpHTe~ISI x aMxxy, 3c~Hpy x Rpyrxni coeAx-
xeHxxM THIIa JIIOHCOSCxxx ocxoBaHxi~.
B IIpeRbIRyII~eil pa6oTe [4], Ha ocxose axa~Ix3a Raxxbix o 3aBx-
cxnlocTx cocTasa pxRa coxo~IxMepoB oT yc~IOBxiI IIo~IxMepxaauHx,
oco6exxocTx IIpoueccoB IIo~IHaiepxaaulix B.IIpxcyTCTBxII ~IxTxil-
a~IxH~Ibxr~ix xaTanHaaTOpoB 6bIJIH o6~xcxeHbl yxacTxeM ~IIITxeBOir
xoMIIOxeHTbl xaTa~IHSaTOpa, xapslRy c xap6axxoxxoH, B axTax po-
cTa ueIIII.
B xacTOxlue%I pa6oTe xcc~IeRosa~Ix paaRenbxyIO H cosalecTxylo
IIOJIHMepx3ai(xI0 H30IIpeHa x CTxpOJIa C JIHTHI33TIIJIOM B. TOJIyOJIe
11 B CMBCH TOJIyOJIa C Tpx3TxJIa11IxHOM C I~eJIbIO Z(aJlbxel3xler0 BbIFIC-
HBHxSI MOXaIII33Ma 3TIIX .IIpOI[e000B.
I{xHOTHKy x3yTIa7Ix j~IIJIaTOMOTpxileCHHM MOTOJ~OM B yCJIOBHfIX,
~iCI{JIIOtIaI0II7xX IIOIIaJ~aHxe BJlarx x B03J~yXa. MOTOJ;xKa 3KCIIepx-
McIITa OIIHCaAa B IIpeJ[bIJ~yII;eYI pa6oTe [4]. COCTaB ,COIIOJIIIMepOI3
oxpeAe~ISI~Ix McTO7~aaIH IIxc~paxpacxoil cxexTpoclcoIIHx, 3~Ieniex-
Tapxoro axa~IH3a II pec~palcTOMeTpIIII [5l.
Pa3J[CJIbHaR IIOJIIIMepII3aI~YIII
IIpx xccneRoBaxxH paaRe~Ibxox IIOJIIinIepH3al[xII II30IIpeIIa
s To~Iyo~Ie IIpx 27? 6bI~I0 IIoxaaallo, sTO clcopocTb IIo~IHnrepxsauHl3
Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
xpoxopuxoxa~Ibxa xoxuexzpauxx MoxoMepa x, xpx xIIal;Iix xox-
i;exTpa>;xxx xaTa~Ixaazopa, BospacTaeT c?pocTO1,I ero xoxi~exTpa-
>~xx; xa*Ixxas c xoxuexTpai~xx ~IxTxi~3Tx.aa ?--0,006 ,n~o~cb(,~.
cxopocTb xe aaBxcxT oT xoxi>;exTpauxx xaza.nxaaTOpa x Aaxce xoxll-
xcaeTCSI xpx BoapacTaxxx xoxuexTpauxx JIIITIII33TxJIa BbIIIIe axa-
xexxx 0,03 .~corcb/rc (pxc. 1).
W f0 ?mona/n cem
o a
7,6 c
l,P o
o ~ -
1 I I I I I 1 I
I I __-~?
05 0,010 0,015 O.OPO OOPS 0,030 0,035 0,040 0,045 0,050 0,144
C, mans/n
Pxc. 1. 3aBHCHMOCTI, cxopocTx no.nlrMepusauux uaoupeua (VV) oT xouueuTpa-
uHH JII3TI3Ii3TI3JIa (C). B TOJIyOJIe.
(IIpII HH9HIIX~HOH$QHTpaIjHHX JIHTHL18THJ18 paf)OYYIO HOHI?;CHTpaIrHN) H8T87HI3YTOp~
' YTU4HHIIH HO J[BHHhIM HBMQpQHHFi MOJICH}'JIHpHIilX BQCOB),
~TCyTCTBxe 3aBxCI3MOCTx CxOpOCTI3 xOJIxMepx3allxlI OT xOH-
~eHTpauxx xaTa7lx3aTOpa BbIIIIe OIIpeJ[eJIexHOI3 ero xOxl[exTpai[I-Ix
Ha~JIIOJ~aJIOCb Taxlxe KOpOTxOBbIM xpx xOJlxMepx3aljIIII II30xpe-
Ha [6] x BOJibXOM [~]~ IIpx IIOJIxMepx3aI);xx ?CTxpOJIa C JIIITIIY16y-
Tx~IOaI B yrnesoRopoRxoH cpeRe.
M>I, xax x Be~Ibx, o6~bxcxsrel`I aTy oco6exxocTb xo~Illnleprraa-
uxx cTxpona x xaoxpexa o6paaosaxxei,I accotjxaTOB ~IIITxi~xo~rli-
cTxpona II ~IxTxi~xo,nxgaoxpexa, cooTBeTCTBexxo, BcneAczBxe Nero
TOJIbICO iIaCTb xaTaJlx3aTOpa (xeaCCOIlxxpOBaHxble 11IOJIeICyJrbI)
axTYIBHa IIpH IIOJIxMepx3all;I3x.
IlpeRe~Ibxaa xoxztexTpai~xx JIIITxiI3TIIJIa, Bbl~e xoTOpoi~ xe
xa6~IloRaeTCSI BoapacTaxxx cxopocTx xo~IxMepxaaullll c pocTOl\I
xoxz;exTpaz;xx xaTa~IxaaTOpa, R~Ix cTxpo~Ia (--0,02 .n~o.~b/rc) Br~Ixle,
ileM J.~JISI x3OIIpexa, *ITO, IIO-BxAxMOMy, CBSI3ax0 C ~OJIbxIe~I CTe-
II0xbI0 accoi;xauxII JIxTxI3IIOJIxx3Oxpexa. MOJIexyJiFlpxbI~i B0C
IIOJixII3OIIpexa, xax x MOJIexyJlSIpxbIyI B0C IIO7IxCTYIpOJIa, BO3paCTaeT
c r~Iy6xxoi~ xo~IxMepxaai~xx, *ITO cBSlaaxo c o6pasosaxlleM Tax
xasblBaeMblx .
FibIJIO IIoxaaaxo, uTO Mo~Iexy.nxpxble Beca xo~Ixxaoxpexa, pac-
cexTaxllble xo c~opnry~Ie [~] = 5,02 ?10_4 ?Mo,ss~~ cosxaRaloT co~
Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
~xagexxslMII Mo~Iexy~Ixpxblx BecoB, IIo~Iyxexxblx I33 cooTHOUIe-
xIIx M = M/a, rRe ~ M - xo~IxgecTBO IIo~IxMepx3oBaBIIrerocsi
~rloxoMepa; a - xo~IxxecTBO xaTa~I133aTOpa B Monxx; aTO o6o3xa-
~IaeT, xTO Bce Mo~Iexy~ibl xaza~III3aTOpa izoc~IeRosaTe~IliHO upxxx-
~IaioT ygacTge B peaxuIIII pocTa ueizx. '
B COOTBOTCTBgII C IIOJIyileHHbIMx .RaHHbIMI3, IIpOI[eCC IIOJIxhIe=
px3auIIII II30IIpexa IIpoTexaeT, IIO-BxAxNIOMy,. cor~Iacxo c~IeRylo-
II~eK cYeMe: _ . ~ .
(LiMnR)~ ~ (Li1VInR)~_I -}- LiMnR' (1)
LiMnR -}- M -~ LiM?+1R - pocT i;eIIg (2)
K COOTBOTCTBOHHO CItOpOCTb IIOJIIIMepYI3aI;III3, B 06JIaCTx KOHI[eH-
~Tpai~IIla xaTa~III3aTOpa 0,006-0,03 ~co.nb/r~, WP = K[M], rRe
,[M] - xoai;eHTpai~gsl NloxoMepa.
IIpg HII3xgx xoxi~exTpai;IIxx xaTa~Ix3azopa accouxauxx Mo~Ie-
fiy.n JII3TgI3IIOJII3~I30IIpexa IIOHI35KOHa, B CBSI3I3 C IOM CxOpOCTb II0-
_JII3Mepx3aI~gH B03paCTaeT C yBeJII3iI0xxeM xoHueHTpauxH xaTa~Ix-
3aTOpa.
B o6.nacTx xoxueIITpauIIK xaTa~Ix3azopa -~-0,006-0,03 .~uoribl~
xoxi~eHTpal~IIx HeaccouxIIpoBaxxr~x Mo~Iexy~I Ma~IO MexaeTCSI, ,
.H C J.~a~IbHOI3IIIHM pOCTOM ICOHI~eHTpaI~I3x IfaTa7lx3aTOpa - ]IOHYI-
':xaeTCx (pI3C. 1), TITO BQpOFITAO.CBfI3aH0 C OGpa30BaHIIOM B 3TxX
yCJIOBIIHX ~OJIee CJIOHSHbIX a000I~I3aTOB. ~3 COIIOCTaBJIOxAH J.~axxbIX
? IIO pa3J.~eJibHOI3 IIOJIxMepI33aI~I3I3 CTI3pOJIa' x x30IIpOxa ? B TOJIyOJie,
IIpx HII3KOI3 HOHI~eHTpaIjIIYI JIYIT~II33TIIJIa (~-0,003 .hLO/Gbl/G) CJle~yeT,
iITO CICOpOCTb IIOJIIIMepI33aI>;I3x x30IIpOxa ^- B 4 pa3a MexbIIre cxo-
}pocTx IIo~IIIMepII3a>;IIII cTllpo~Ia (pIIC. 2),
B o6~IacTx 6o~Iee BblcoxIIx xoxuexTpai;xK nIITxi3TII~Ia
~{-0,006-0,03 .~or~blrc), ~B cBx3II c accouxai~IIei~ ~IxTxxIIO~Ixx3o-
rlpeHa pa3dII3iII30 B CKOpOCTFIX IIOJIIIMepI33aI[I3I3 CTYIpOJIa x yI30IIpeHa
_yse~IggIIBaeTCSI,
IIpx IICCJIOJjOBaHI3g IIOJIIIMepg3al[gId II30IIpexa B IIpxcyTCTBgI?I
'Tpg3TI3JIaMI3Ha rObIJIO IIOIta3aH0, iiTO IIpx xox>~eHTpal;IIx .JIgTgI-i-
3TgJIa -0,01 .hGOJGbI/G CISOpOCTb IIOJIIIMOp1'I3aI~YII3 H30IIpOHa Bo3pa-
cTaeT c pocTOM xoxRexTpauxII aMIIxa Ro cooTxoIIlexIISl aMxx/LiR,.
pasxoro 160. ]~a~Ibxel~IIlyle Ro6aBxII aMZ3Ha IIo~Tg He B~IIISI~Ix xa
CKOpOCTb IIOJII3MepI33aI~Kx.
I{ax BIIJ~xO II3 pIIC. 3, IIpOJ~eJIbxaSI ICOI3I~eHTpaI;YIFI aMI3Ha, BbIIIIe
xoTOpoi3 He Ha6.nloRaeTCx Bo3pacTaHxsl. cxopocTx, R~IS x3oIIpexa
3Ha~Te~Ibxo 6o~IbIIre, ~eNI R.ns cTxpona.
8TO pa3~xxIIe B xIIxeTxxe IIo~IIIMepIISa~xII II3oIIpexa x czxpo-
.JIa B03MOxcHO CBtI3aH0 C TOM, ~ITO J{JIH IIOJIHOI3 .~[I3000I~IIaI~HI3
I IIpeRIIO7laraeTCH, *ITO B aTOi~ CII~TOMe IIMOIOTCH pa3JiIIYIIble accouxaTbl,
,pearllpycoll~Ile uo ypasaeaBlo (1).
Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
:2 d !0 14 IB 22 26 3(] 34 3B 42
Bpemn, n+un
~PHC. 2. 3aHHCHMOCTb IIpOI[eHTa IIpeBpaII~OHHH OT CpeZ(bI IIpH 2~?,
~{OHI~eHTpaI~IIH JIHTHI33THJIa ~,~~3 .A2Onb/n, HOHL~eHTpaI~HH MOHO-
Mepa 1 .~corcb/h.
~ - CTISpCJI a CMBCx ~TOJIyOxa C TplfaTxxaMNHOM (xpxBaH paCC9xTa Ha
H3 J(aHH6IX Ta6JI. 1) I; 2 - CTxpO7I B TOJIyOxe; 3 - xsoxpeH B Toxyone;
4 - xsoxpeH B. cMecx Toxyona c anHlxoM: .
OI i i i i i i ~ i ,
ai/IOpmone~acea Q4 0,6 0,8 1,0 1,2 1,4 1,6 18
0
PIIC. 3. .3aBHCHMOCTb CHOpOCTH IIOJIHMepIi3aIjHH OT HOH-
I~eHTpaijHIi aMI3Ha:
~q-~q CTIIp OJIa, HI1II xCHI~eHTpaI[xx MOHOMepa i ,xonb/n, xoxgeHTpauxx .nxTniiaTH.na
O.A~8 .ftOnb/n, xpx -31?; 6-jI7IH N30HpP.Ha, xpIi xoHgeHTpagxx MOHCMepa 1 .M1tOnb/n, xOH-
IIeHTpaIIHN JIxTNlI3THJIa ~,~1~ M.Onb/n> IIpII -2~?.
Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
Ta6nn>;a 2"
3 HepraH axTHBagnH H KOHCTaHTbI C&OIIOCTeIf peaICuHiI pOCTa genes cTHpona?
H HsonpeHa c xaTanllaaTOpoal nHTHiIaTHnonl ?
CTxpon
(xoxgexTpagxll
xaTa~IxaaTOpa
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(~coxuenTpauxx
I;aTa~InaaTOpa
0,03 .nconb / n)
CTxpon
I'I30npeH
(xoHgexTpar;Ilx
I;aTa7In3aTOpa
0,0001 ,nconb/n)
I'Iaonpell
I'Iaonpell
(soxgellTpai~xx
xaTanlisaTOpa
0,015 .~eonb /rc)
Tonyo~I .
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Q-FL =19>~ 1
13,6
14,3
9,2
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n /.?on b ? ce>r
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105
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n/ntonb?cex
0,5
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' 3xavexnst Q.-{- E - 19,7 !I 19,2 r~~an/.MOnb, nonyYennble AnR cTnpoaa II naonpexa.-
cooTeeTCTSexxo, s o6nacTx sblcoxxx ~xoxuexTpaun~ xaTanxsaTOpa (0,015 II 0,03 Mone/n).-
npeACTasnnioT coboil cyma+y aaeprnn axTnsaunn pocTa n Tennosoro scy~yexTa accoun-.
aunn. BbITInTflA ns Q-(-E AnR nsonpena.seainvxxy axeprxx axTnnauxn E = 14.3 xxan/Juond,
nonyvaeM, qTO ' Tennonoil acp~pexT accounaunn nxTnz'knonnnsonpexa Q =_ 5 rxan/.alone.
Baino noxasaxo', PTO s oOnacTn xoliuexTpauni3 xaTannsaTOpa 0,015-0,008'a+onb/n sxageane~
Q -(- E Anne nsonpexa.ne sasxceno oT xoxlfexTpauxn xaTanxsaTOpa. Axanornvnt~m o6pa?
soM ouennsaeTCR' TennosoCl ac~~pexz accounaunn ,nnTllCrnonxcTUpona.'
HeaxTHBHbIX II~II IIOJIIIMepII3aI~IiII aCCOI~IIaTOB JIIITIIIiIIOJIIII130IIpeHa~
Tpe6yeTCfl 60JIbIIIOe HOJIH~IeCTBO aMIIHa.
~7,IJI0 yCTaHOBJI0H0, iITO CICOpOCTb IIOJIIIMepII3al[IIII II30IIpeHa~
II CTIIpOJIa B IIpIICyTCTBHH H36bITxa TpH3TYIJIaMIIHa B IIIH~IOKODf
HxTepllane xoHueHTpaRHKj IIpouopulloHa~Ibxa xoHueHTpauIIx xa-
Ta~iH3aTOpa H MoxoNiepa. B sTIIx yc~IOBHxx Taxaxe xa6nloRanocb
o6pa3osaIIIIe ~i>%ITxi-lIIO~iHCTHpona H ~iH-
THYIIIO7IHH3OIIpeHa.
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Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
~zo~iyo~Ia c ~arrlrilo~ni; ~s ~cBxali c soapaczaHHeM xap6aHHOHHOro xa-
paxTepa xoMIIOaeHTbl R B LiR, cxopocTb IIOJIHMepH3aI~HH cTHpo~Ia
sospaczaeT (pIIC. 2).. IIpH azoM xoxcTaHTa cxopocTH pocTa ueHII ANSI
~cTHpo~ia soapacTaeT --- B 65 paa.
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:MaJiO AfeHHeTCFI ,(pHC_ 2), a xOHCTaHTa CKOpOCTH pOCTa I~eIIII H30-
:IIpexa IIpII BBeJ~eH~IIS3 c`ihiiiHa IIOHHSxaeTCFI (Ta6~i. 1).
.CoBmecTHasl IIonllMepIISaui3H
;Zjaxxble o xHHeTHxe cosniecTxo~i IIo~IHMepHaauHH cTHpona
c HaoupexoM B To~Iyoae H s criecH To~iyo~Ia c aMgHOM IIpxseRexbl
$a pnc. 4.
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CTH OTHOCHTeJIbHO BbICOxHX xOHI~eHTpal[HYI CTHpOJIa, IIO Mepe
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~poB BcneAcTSxe MeabIIrel~ accouHauIIII ~iHTHHIIO~iHCTHpo~Ia IIo cpaB-
.HeHHIO c ~iHTHI3Haoupeaoni.
COCTaB couo~iHTiepoB IIsorlpe$a co cTlipo~ioal IIpHBe~eH B Ta6~I. 2.
Ta6nNua 2
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27?. 2. B cntecx Tonyona c aMaaoM, npii 27?
iB ISCROAHON
CMQCI3
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TaHbI HHxceupxBeReHHble sxaxeHHSi xoxcTaaT corio~iHMepxsauHH
3THX CFiCTeM.
I - B To~Iyo~Ie ri (HaoilpeH) = 9;5, rz (cTHpo~i) = 0,25,
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
II=B CMOCII Tonyo~Ia C a114IIHOhi r3 (HSOrlpex) = 1,4, r4 ('cTFI-
Pon) - ~,8
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-~-B 9,5 pa3 BbIIIIe peaxuxOHA0I3 CII0006'gIOCTH CTgpOna. B IIpgCyT-
CTBYIYI TpII3TxnaMIIHa, B. cornacxII C J~aHHbIMH I~#ennII II To6oAb-
cxoro [3l, Ha6nloRaeTCx pesxoe IIahsexeraide coo.THOIIIexrax axTgs-
Hoczeg.
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Raehlax aasxcxMOCTb oTxocxTenbIIOi~ ~ peaxt~xo:HHO~I cnoco6HOCTg
oT xapaxTepa cpeRbl o6yc~IOSnexa, IIO-BxAIIMOhry, pasnH~IN
MOXaHx3MOM peaxullx pOCTa IT,eIII3 B IIpIICyTCTBIIYI II B OTCyTCTBHe.
aMIIHa.
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OT COOTHOIIIOHIIH ItOMII0H2HTOB IIpII I(OHIZ2HTpaIjIIII xaTanA3aTOpa ~,o~.KOAb/JL>
B TOJIy0Ji0 ~OIIbITbI 1-3), H B CMOCII K3 60%TOnyoaa II 40% aMxna nP$-
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4 1:1
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
IIpx IIo~IHMepHaauHII ~IxTH~ia~IxII~IanIH B yr~IesoAopoAHO%I,
cpeAe peaxuHx pocTa ueIIII ollpeAenxezcx xe To~Iblto a~IexTpoxo-
AoxopablMH csoHCTBaMH rpyIIIIbl MnR axTIIBHOro i~exTpa LiMnR,
HO II 3JIexTpOHOaKI~eIITOpHI,IMH CBOyICTBaNIII er0 JIHTHOBOIi ItOMIIO-
HOHTbI, '
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aMHHa C JIIITHOBOYI ItOMIIOH0HT0I3 KaTaJIII3aTOpa, B3aI3MOAeI3CTBIIe~
MOHOMepa C HOPI oclia6neHO H pOCT I;eIII3 OIIpeAeJlxeTCa B 3HaTIII-
TeJIbH0I3 CT0II8HII B3aIIMOAeI3CTBII0M MOHOMepa C xap6aHHOHHOI--l,
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MepIISai;IIII JIHTIII3aJIKIIJIOM B -yr~IesoAopoRHOH cpeAe BbIIIIe, ~Ienl
B Tex xte pacTBOpHTe~Ixx B IIpxcyTCTBxII aMIIHa, 3c~IIpa IIIIII IIpII-
IIposeAexHH IIo~IxMepr3aauIIl~ B, IIpIlcyTCTSxH HazpxKOpraxH*Iecxllx.
coeAHHeHH~T.
Heo6xoAHnlo OTMOTHTb, ~ITO IIpII IIOJIIIMepH3aI~IIH B IIpxcyT--
cTBxH ~IIITH~Ia~IxH~IOB B yr~IesoAopoAxo~I cpeAe, oco6exxo Bblcoxoi~
peaxi;xoaHOH crloco6HOCTbIO o6~IaAaIOT Mogonlepbl AHexosoro.
pxAa, TaK, HanpIIMep, IIpH cono~IHMepIIaauIIx IIsonpeHa co cTIIpo-
JIOM H CG-MOTHdICTIIpOJia CO CTHpOJIOM, IIpH 3aMeHe TOJIyOJIOM CMECIT'
TOJIyOJIa C abIHHOM, COAep1KaHIIe II30IIpeHa H CC-MOTHJICTIIpOJIa. B CO-
IIOJII3Mepe B03paCTaeT, IIpH ileM OTHOCIITeJIbHaH AOJISI II30IIpeHa
B COIIOJIIIMepe S03paCTaeT 3HaTiIITeJIbHO 60JIee pe3K0, TIeM OTHOCII-?
TeJIbHaFi AOJiFi p,-bIOTIIJICTIIpOJLa ~4~.
3Ta BbICOxax peaxuIIOHxax CIIOCOGHOCTb AIIOHOBbIX Mo.nexy~I
B IIpricyTCTBHII LiR'o6ye~IOB~Iexa, HO-BIIAHMOMy, TOM, *ITO B axTax
pOCTa I[eIIH 3THX MOHOMepOB yiIaCTByIOT ABe COIIpxSIteHHble ABOH-~
Hble CBH3H, H3 xOTOpbIX OAHa ~B II30IIpeHe - CBH3b 1,2~ B3aHM0-
AeI3CTByeT C JIIITIIOBOII, a BTOpax - c Kap6axlloaxoH xONIIIOHOHTOIi?
HaTaJIH3aTOpa.
IIpH 3TOM 06JIaK0 COIIpR?xeHHbiX 7C-3JIexTpOHOB CnleluaeTCt~
B CTO~IOHy JIIITHOBOI%I xOMII0H0HTbI, tITO yBeJII3iIIIBaeT CIIOCOGHOCTb.
BTOp0I3 ABO~IHOI3 CBSI3H B3aI3M0AeI3CTBOBaTb C xap6axxoHHOm'
xoMIIOxeHTOi~ xaTa~IHaaTOpa. '
Ha6nloAaenlasl B yr~IeBOAopoAxoK cpeAe Bblcoxax oTxocIITe.nb--
Hasl peaxi~I3oHIIOCII0006HOCTb Haoupexa IIo cpaBHeHxIO co cTII--
po~IOM, a 'TaKxte IIoxIIxteHHe xoxcTaHTbI cxopocTII pocTa ueIIII IIpI~
IIo~II3MepHaauHII Haoupeaa IIpH BBeAeHIIII B To~Iyo~I aMxHa Taxxte-
o6yc~IOB~Iexbl, ?IIO-BHAxMOMy, BbIIIIeyxa3axHbIMH oco6eHHOCTxnIII?
IIo~IHMepHaauIIII AHexosblx MoxoMepoB B yr~IeBOAopoAHOK cpeAe.
TaxIIM o6paaonz, B pa6oTe xsyxexbl aaxoxonlepxocTII paaAe.ab-~
xoH H coBnieczaoH IIo~IIIMepHSauIIH cTIIpo~Ia H IIsoIIpexa B HpH-
- CyTCTBHII JIHTH733THJIa B yrJIeB0AOp0AH0I3 CpeAe H B CMOCII TOJIyOJIa~.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
c arillxoM i3 xpeA~IOxcex nlexaxxaM, o6~slcxsllolt~Ilir oco6exxocTx
IIOJIYIDIepI33aI~IIII RI3eHOBbIX II BI3HI3JIbBbIX 1110HOMepOB B npI3CyT-
?CTBIIx d[I3TnIIOpraHI3ileCICxX COeRI3xeHI373.
JliiTepaTypa
-1. A. A. if 0 p O T K 0 B, CnMII03IIyM IIO MaI(poMOJlexyJlflplIO}I RIIb1NII.
IIpara, 1957.
.L. Il. AI o I? i t a, A. V. T o b o 1 s k y, J. Amer: Chem. Soc., 79, 5853,
? 1957.
3. D. J. Kelley, A. V. T o b o l s k y, J. Amery. Chem. Soc., 81,
1957, 1959.
4. I0. JI. CIIIIpxx, A. P. FaIITivlaxep, C. C. &IeAseAen.
BhlcoxoMO.nex. coeA., 1, 1259, 1959.
5. F. AI. Lewis, C. Walling, W. Cummings, E. R.
Briggs, W. J. W e n i s c b, J. Amer. Chem. Soc., 81, 1345, 1959.
6. A. A. ICopoTxoB, H. H_ LIecxoxoBa, JI. B. TpyxMaIIOBa,
BblcoxoMOnex. c~eA., 1, 46, 1959.
7. F. ~V e 1 c h; J. Amer. Chem. Soc., 70, 1527, 19~i8.
Summary
A study has been made of the effect of the nature of the alkaline
:metal and of the medium on the rate of polymerization and
-on the structure of the polymer chain. The rate of polymerization
of styrene and isoprene with an ethyllithium catalyst in
.hydrocarbon medium has been shown to increase on adding the
polar compounds, triethylamine, ether, and tetrahydrofuran,
to the solvent. The high rates of polymerization of styrene in the
presence of triethylamine are .due .to a lowering of the activation
?energy. The limiting concentration of triethylamine above which
increase in the polymerization rate in the presence of ethyllithium
is no longer observed is considerably higher in the case of isoprene
than styrene. This is in agreement with the data on the kinetics
of ethyllithium-catalyzed polymerization of styrene and
isoprene in hydrocarbon medium, according ~to which the limiting
concentration of ethyllithium above tivhich dependence of the
?polymerization rate on the catalyst concentration is no longer
observed is considerably lower for isoprene than for styrene.
The difference in polymerization kinetics of isoprene and
.styrene is explained by the fact. that more amine is required
to dissociate polymerization-inactive polyisoprene-lithium
associates.
By the joint polymerization method it has been shown, in
harmony with published data, that the mechanism of chain growth
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'in the presence of ethyllithium changes on passing over from
a hydrocarbon to a polar solvent and also on changing alkylli-
thium for organosodium compounds.
The specific features of alkyllithium catalysts in hydrocarbon
medium are interpreted as due to the participation of the lithium
component of the catalyst besides the ,carbanion in the chain
growth.
The different natures of~the carbanion components in the poly=
merization of styrene with organolithium and organosodium
compounds is confirmed by data on the electron absorption spec-
tra of these systems..
Dares le travail a ete etudiee 1'influence de la nature de metal
alcalin et de milieu sur la vitesse de polymerisation et la striictu.re
de chaine polymerique.
Il a ete montre, que la vitesse de polymerisation de styrolene
et isoprene en presence de lithium -.ethyle comme catalyseui?
et daps un milieu des hydrocarbures s'accroit au fur et a mesure
d'insertion en solvant des composes polaires: de triethylamine,
d'ether, de tetrahydrofurane.
On a etabli que les ? grandes vitesses de polymerisation du
styrolene en presence de triethylamine daps le milieu hydrocar-
bure etaient causees par affaiblissement d'energie d'activation.
La concentration finale de triethylamine, an-dessus de laquel-
le on n'observe pas 1'accroissement de vitesse de polymerisation
en presence de lithium -ethyle est sensiblement plus grande
pour 1'isoprene qu'elle nest pour le styrolene.
Ce resultat conforme aux donnees sur la cinetique de poly-
merisation de styrolene et isoprene daps le milieu hydrocarbure
en presence de lithium -ethyle. Solon cos donnees la concentra-
tion limite de lithium -ethyle, au-dessus de laquelle on
n'observe pas la dependance de vitesse de polymerisation de la
concentration de catalyseur, est sensiblement plus basso pour
1'isoprene quo pour le styrolene. .
La diversite daps la cinetique de polymerisation d'isoprene
et de styrolene est expliquee par ce fait quo pour .la dissociation
des complexes de polyisoprene avec le lithium qui ne sont pas
actives au tours de polymerisation, une plus grande quantite
d'amine est necessaire.
En concordance avec les donnees de literature par la methode
de polymerisation mixte it a ete montre quo le mecanisme de la
73 MexcAyaapoAas~# cmmnosFrym, cexuc+R 2 193
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reaction de croissance de chaine en presence de lithium - ethyle
change pendant le remplacemeiit du milieu hydrocarbure aux
solvants polaires ainsi que pendant la substitution des compo-
ses soude - organiques aux composes de lithium - alcoyles.
Les particularites specifiques des catalyseurs de lithium -
alcoyles au milieu hydro-carbure sont expliquees par la par-
ticipation de la composante de lithium du catalyseur ainsi que
de la composante carbanionique a la croissance de chaine.
La differente nature de la composante carbanionique au tours
de polymerisation de styrolene en presence des composes de lit-
hium et de soude - organique a ete confirmee par les donnees
des spectres elect.roniques d'absorption de ces systemes.
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Next 12 Page(s) In Document Denied
Q
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
~ I{I~IHETI~II{E .H MEXAHI~I3ME IIOJIJIMEPI~I3AI~I~II~I
METI~IJIMETAKPIIJIATA BYTI[JIJIIITI%IEM
A. A.,ICopomxoe, C. II. Muayexxex8raep,
B? S. I#pacyrcuxa .
(CCCP)
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xaTaJIII3aTOpaMII. B HaCTOHH~eM COOCIL~eHIIII, IIa IIpIIMepe xIIH6TIIxg
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B03HHxaIOII;IIe axTIIBHble L~eHTpbI MOI'yT , Tax1I{e peaPH-
pysl C MOHOMepOM B IIOJIO1iCeHIIII 1,4 IIEII 3,4. ~03TOMy TeileHIIe
peaxi;HII nonHnlepIISauIIII MOHCHO OIIIIC1Tb CJIeI;yI0I1;HMII 3JIeM0H-
TapHbIMII peaxuIIxMII:
1. 3apoxcReHIIe ueHTpoB no~IIIMepIIaauIIII:
BuLi -{- M .~~M [BuLi]` dT = klnm (A)
2. PocT IIOTIIIMepHbIX IjeIIeyI:
3. O~pbIE pOCTa IIOJIIIMepnbIX I;eIIOII:
Mi [BuLi]` -}- M ~3 BuMi+IO Li - dT = k3n`m (Fi)
4. B3aIIMOJ~eHCTBIIe xaTaJIII3aTOpa C MOHOMepOM, IIpHBORfiII~ee
x O~pa30BaHIIIO IIeaxTIIBHbIX MOJIexyJi:
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
rRe rri, n, H n * - xoHueHTpauHH MoaoMepa, I{aza~IHaaTOpa g ueHT-
poB IIo~IHMepHSauHH (a-.~o.~.ulr~). CgcTeMa He HMeeT xBasg-cTaugo-
tiapaoro cocTOSIHgx. ECJIH BBecTH aosylo IIepeMexaylo:
T
cp = S mdT
o
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B aa~a~IbHbII~ IIepgoR peaxi;He, xorRa k3cp ~ 0,5 H (ki -F- k4)cp
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pa3JIOH{eaHA HX B pRR, TOPJ;a ,
IIpH IIOJIHMepH3al[gH MCTHJIMOTaRpHJIaTa GyTHJIJIHTHEM B TOJIyOJIe
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KOrJ~a COGdIIORaJIOCb YKa3aHHOe yCJIOBHe 3I{CIIepNMOHTaJIbable TOTI-
I{H ~Ier~Ia C J(OCTBTOiIHOI3 TOiIaOCTbIO BOI{pyP IIpSIMOH (CM, pHC. 1)
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1 -xl2
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8xcaepIIMeHTa~IbHble To=IxH . (pxc. 2) ~Ier.nH Boxpyr IIpxMOg
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Te~IbaocTH peal{r~HII, pasaog 10-12 MHII. Ha~IAeHbI caleRyloII~He Be~IH-
LIHIIbI KOHCTaHT: k1 = O,OOG7, kz = 800 g k4 = 0,051. BOCIIOJIb30-
BaBIIIHCb IIOJIHbIM ypaBHeHIIeM ICHHeTHI{H Ha OCHOBaHHg cseReHHI~
OG OJ~HOI3 H3 TOLIeIC IIpH . GOJIbHI073 rny6aHe IIOJIaMepH3aI~HH MOH{HO
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uHx o6pblBa pocTa IIo~IHMepablX ueae~I xB.nxeTCx 6o~Iee c~IOaI{HoH,
14 MerxAyxapoAxs~i[ cfimnosF~ym, cexgxR 2 20~
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
~ieni Ronycxa~iocb IIepBOxa~Ianbxo IIpII BbIBORe xIIHeTIIxecxoro? ypaB-
IIexHSI: ..
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HbIX 3HaLI0HIIH ICIIH0TIIt38CICIIX I{OHCTBHT, BIIOJIHe yJ~OBJIOTBOpIITeJIbi30
oIIIICbIBaIOT IIpouecc (cM. pgc. 4II 5). Ha6~IioAalolgl~HCx cpasxII-
Te~Ibxo 60JIbIIIOyI pa36poc Toxex slB~ixeTCH xeII36e}HxbIM IIpII
npIIHxTOM McTORe II3yileHIIFI icIIxeTIIxII peaxuIIII IIo Becy o6pa3yloII~e-
rOCSI IIO~TIIMepa. B peaISI~IIOHHOYI? aMIIyJie, IICIIOJIb3yeMOII RJISI HaXO-
5I{Z[eHHH ICaiICJ~OII 3KCIIepHMOHTaJIbHOH TOLII{II.
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'/z
no~xMeprlsaglltl T oT (Homo)-'l~ ]n 1 +.x,
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1-x
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~ i i. ~
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no yt
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PHC. 2. 3aBHCIIMOCTb
(Mo/'V1) oT( n0 ~'/2 IIpslMax
\max f
u~Ix (2k1k2)'/z = 4,08.10-a
II k' '~' k4 __- 0,725.10-4
Hpli R.aIITesibxoM (xecxonbxo ~acoB) Bbl,~epaicIIBaHIIII IIpK =50?
peaxuIIOxxol~ cMecII; Hoc,ne rlpaxTII~IecxII IIo.nxoro 3aBepIIleHIIu
peaH~IIII IIOJIIIMepII3aB;IIII II1lOIICXOJ~IIT IIpIIMepHO yZ[BOOHIIe MOdie-
ICyJIApHOrO BECa IIOJIHMepa. C,ISeJIaHHOE' Ha~TIIOReHIIe II03BOJIHJIO
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
~Pf1C. 3. SaBI3CHMOCTb BeIlFITIAHbI x03(~(~AI~FIOHTa k3 OT no (KpHBax Y)
tr rno (xpxsan 2). ICpxs~e R~~x ks = 12no-x-2,14 ? no Z x ks=0,02nxo
tlpe,~H, hrun
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~~tu =:1,01 [1(~)h: 0,71 (2 (x)1> D>5 [3~(0)1> 0,31 [4 (~' )],. 0.11,[5 (+)1 nionti/n
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AaMeaeHge xoxueHTpausg Ho~gMepxr~x ueHei~ B cgczeMe (L)
MoxcHO oHgcaTb c.aeRyiorggM ypasxeHgeM
dL - klnm - kb n` {L - a (mo -?m) L} p
dT
perIIeHge xaTOporo gMeeT BgR:
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- k2 mo2 [ In (1 - x) -}- x -~- ~ x2). ..
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ugH~ Hauaa~bH~x xoH~eHTpa~ng Moxoa~epa g . xaTa~g$aTOpa (cM.
pHC. 6), IIpHUeM aTa aaBgcgMOCTb aganorg~Ha Taxosog~ Anx k3
mo g no.
Bpe,~A Mae
!0 20 30 40 50 60 70 BO 90 100 !!0
Pxc. 5. ICxxezx*~ecxxe xpKBr~e Aix oIIS~TOB c mo = 0,5ncon n/.~; no = 0,0156'
[1(~)], 0,0081 [2 (x)], .0,004 [3( ~)], 0,003 [~ (~)], 0,002 [5(~}-)]
I~pHB~e saBBCgMOCTg cpeRHero Mo.aexynxpxoro Beca oT r.ay6g-
III~I IIo~IIMepgsauHg Hpg pasxbix aHaxeHgxx mo, B no IIocTpoeHHSze
c xcIIO.abaoBaageM aaKAexH~x sHaxegg~ ks g a, BIIOnae yAoB~eTBO-
pgTe~vHO.OIIIICbIBax)T IIpOI~eCC (CM. pIIC. 7 g cg).
1J' CJII3 BOCIIOJIb30BaTbCFI ? HaI3ReHHbIMII BeJIIIYIIHaMIi x03(~1(~gI;g-
eHTOB /C3, /C5 II C; .J~JISi BbIiIgCJieHIISI OTIf.OCIITBJIbHOE CxopOCTg J~e3aK-
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MOHOMepa, TO IIOJIy~IaIOTCfi pe3yJIbTaTbI (CM. Ta6]IgI~y), II03BOJIHIO-
212
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0,? 0,4 0,6 O,B 10 7,Z 1,4 l,6
PxC. 6. 3aBHCHMOCTb BCIIxYxHbI H03(~1(~1xI;H0HTOB k5 x. ? OT mp
x no, I, 2 - xpx no = 0,004; 3 x 4 - HpH mo =0,5 .ntionn/n.
age yTBepxcRaTb, uTO xp.m no.araMepgaaugH McTg~MeTaxpgxaTa oc-
xoBxoe xo~guecTSO axTxsxbix uexTpoB ReaaxTIIBgpyeTCx xa xo.nH-
mepxbix ~euxx.
OTHOCETe71bHaH CHO[IOCTL J{e3aIfTABa[{flx, aIfTNBHSIX IjeHTpOR, BbIiIHCJIeHHaSI
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mo
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0,11
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0,00305
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0,14
0,80
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0,039
0,050
0,061
_ do * ? F (ks, a)
dz
0,18
0,82
0,028
0,035
0,073
0,069
213
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~~Ix IIIITepBa,na TeMIIepaTyp oT -80? Ro -50? HaKRexbl c.aeuylo-
BzIIe Be~Ixuxxbl isaxtyxSIIxcsl 3xeprIIH axTxBauIIg (xpg6~IIIxtexxble
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poB 5,5 Kn;arcl.~orcb, pocTa no.nIIMepxblx uenei~ 10,0 ~c>#ar~l.~orcv K
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5,6 ~cxar~l.~co.~b.
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xy.nxpxoro Beca nonnMepa oT r.ay6x-
IIbI , no~nHMepxsaulll~ npll - rno = 0,5
(no - cmi. pxc. 5).
PIIC. t~. ~aBIICnM()CTb cpeAnero
Mo.nexy~Ixplloro,seca no~inMepa oT
rny6nllbl , no.nnMepllaa~nrl npn
no = 0,004; nzo = 1,01 [I], 0,71
(2), 0,5 (3), 0,1 (4) .uorzl,/n
Ha ocxollaxIIi~ npIIBeAexxoro itxxeTHUecxoro axa.nIIaa .g IIoaly-
uexxoro axcxepIIMexza~Ibxoro MaTepxa,aa Moxtxo c.neAyioB~IIM o6-?
pa30M xpe~CTaBII1'b IIpOTexaHIIG' peaxuHII xOJIIIMepII3al(IIII MOTIIJI-
METaxpxJlaTa ~yTHJI1IIITIIEM B TOJIyOJie IIpx IIII3xIIX T0MII0paTypaX,
T. e. B yCJIOBIIHx O~pa30BaHIIFI x30TaxTHiICCItOPO IIOJIIIMepa.
I~aTa~IxaaTOp (6yTr~~I~IIITIIH) pearIIpyeT c McTII~IMezaxpII.aaTOM
rJIaBHbIM O~Opa30M C O~pa30BaHH8M HeaxTIIBHbiX COeRII13eHIIII
(pIIC. 9, xpIIBax 1) H To~Ibxo ero xe6o~IbIIlax uacTb (oxo.no 10
IIpII xoHuexTpauxH MoxoMepa 0,5 .ncorcblr~ II xaTa~IxaaTOpa
0,004 rwo.~v/n) RaeT axTIIBxbre ueHTpbl no.aIInzepIISauIIII (pxc. 9,
xpIIBax ~2):. ?~(esaxTHBauIIx aitTHBxbIx uexTpoB IIpogcxoRxT r~IaB-
IIbIM 06pa30M IIpg B3axMOZ[eHCTBIIII C IIOJIIIMepHbIMII MOJIexyJIaMII,
xTO xpIIBORr~T ~x cxx>xexxlo xoxuexTpaur~x IIoc~IeRxxx a cxcTenle,
oco6exxo x xo~Iuy npouecca (pIIC. 9, ItpIIBasl 3). B o6~IacTp oTxo-
cHTe.nbxo Bi~ICOxgx xoxuexTpauIIK xaTa~iIIaaTOpa (0,004 ,Ao
0,0156 .nco.2l,lr~ IIpII rho = 0,5 .~tor~1 /.n) It xoxuy IIpouecca coxpa-
294
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
IlsieTCSi cnbilue 40 % oT MaICexMa..abxoro coAepxcaxHx aICTHBiIbis I~exT-
poB B cgcTeMe (cni, pxc, 10), IIoaTOMy B sTHx c~iyiiaxX Mori:xo 2Ia-
6~IIO~aTb cyir~ecTBOIIaxIIe ualcHBbix IIosiiiMepoB>.
CyiuecTBexxo c~Ie~yIOll~ee o6czoslTenbcTBO. I{aaiCyH;axcx Be~Ili-
~IIIIIa sxeprIIH axTyiBauHII peaiCuxII aapo>ICReHHSi axTiiBIIbIX ueHTpo>3,
a TaxxCe peaxugII 6yTx~i,nIITIISi
C MOHOMepOM HO ICapJOICCHJIb-
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.no 5,5 BMecTO oaicxRaeiKOi3 12-
15 Kha:~latio~il~) IIpI3 Ma.noi-i Be.ar3-
lIYIHe ICOHCTdHTCICOpOCTIi. 1103TOMy!
.PIiC. 9. 3aBIiCIIMOCTb r.ny61lxbi peax-
I[IiII 6yTIIJIJII3THfI (HpIIBaII Y), xOHI~E;ITT-
pagIIll axTIIBIIbIx uexTpoB, IIpH oTCyT-
cTBIIII peaxullfl o6pblBa (xpIIBaH 2) H
xoirgeHTpauIIII IIo~HMepHblx Moxexy~i
(xpHSax 3) oT rny61iHbi IIonHMepIIaa-
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_izon~lrz; xoxueHTpauHa BbipaxceHa n
,go~IBx oT no..
~ ~
9 0,7 0~ 0,5 0.8 x {0
PIIC. 10. 3aBHCIlniocTb xolluellT-
paI[IiII IIOJIHMOp HbIR MOJIEKyJi OT
rJIy6IIHbI IIOJIIIMepH3aI(IIII IIpII
nzo = 0,5 .ntionb/n; no - cni. plic. 5.
$xa=Iexgx IIpeAaxcxoxexuxa.~Ibxoro Mxo7ICxTe.asi B ypallxexr~H Ap-
peHIIyca Rix IIeplloii peaxuliII - 1,7 ?103, a A.rra BTOpoi3 - oxo-
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OT O)ICFIZ4aeMbIX 3aICOIIOMepHOCTe~i M01iCH0 OC7>HCHIITb TOJIbICO OJ(I301-I
IIpII?IIIHOI3: IIa13J);eHHble BeJIxLIHHbI OTI30CIITCH Iie IC 6HMOJIOKyJIHpHbIM
pealCljHHM, a Ii CyMMe ,RByX IIOCJIeJ~OBaTeJIbHbIX peaICB;III3, 133 ICOTO-
pbIX O~B.a HBJIA.eTCH ,OCIL[('YI II paBHOBeCHOH.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
OtIeBIIJ~HO, B3agMOj{eHCTBge ~yTIIJIJIIITIIfi C MBTgJIM8T8xpSJIa=
TOM Bx.nlo*IaeT RBe IIOCJIeZ[OBaTeJlbHbie peaxugH: ,
llepsoH cTaRgel~ peaxuHH xB~ISIeTCH o6paaoBaHge AocTaTOxxa
IIpo*Ixoro xoMII~Iexcaoro coeRHHeHgx, THUa sc~HpaTOB ~IgTgl~op-
raHH~Iecxgx .coeRgHeHIII~.
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Hblx peaxug~I BbIBeRegHble paaee xgHeTH~ecxge ypaBHexHSI ocTa-
IOTCFI CIIpaBeRJIIIBbIMg, TOJIbxO B 3HatIeHIISi xOHCTaHT k1 g k4 BXOJ~gT'
B xaxeCTBe COMHOHfIITeJIFI xOHCTaHTa paBHOBeCgA IIepBOI3 CTaJ~HB'
peaxr;gg, T. e. kI = Kk1 g k4 = Kky. Ecing AOIIyCTgTb, tiTO I[eHT-
paMx- ~-IIOJIHMepII3aI~IIH sIB7IHIOTCH MOTaTIJI00praHg~IBCxge COeJ~g-
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peaxz;HII J~OJIHCHbI 6bITb 6JIII3xgMII x TaxOBOII ~[JIx Cny*IaH IIpgCOe-
Z{gHEHIIFI~ MOTIIJIMOTaxpHJIaTa x 6yTHJIJIHTHIO. HO peaxi;gx .pocTa.
,i~enei~ xapaxTepHayeTCx oTHOCHTe~Ibao HeBblcoxol~ aHeprgel~ ax-
TIIBaI~IIII ~10,7il#ClJGI.hLO./lb~ g ~OTIbIIIIIM 3HaTieHIIeM IIpeJ~3xCIIOHOHI~g-
a.nbHOro MHOixgTe~ISI; ~pasablM 0,54.1013. PTO RaeT ocaoBaHge~,
yTBepxcRazb, PTO axTHBiibIM i~eazpoM xBnxloTCx xe McTa~I~IOOpraxB-
*lecxse coeAgHeHHa, a,mable, oT~IguHble uo cBOeI~ IIpgpoRe H peax-
IjIIOHHOg CIIOCOCHOCTH. AKTYIBaI[Hx) MOHOMepHbIX MOJIexyJI Me-
TaJIJI00praHII~IeCKIIM COej~BHOHgeM Hy?xH0 IIpeJ~CTaBJIHTb Ce~e IIOZ{06-
HOH axTHBaI~IIII Ha TBepi[bIX xaTaJIH3aTOpaX C J~ByMSI I~eHTpaMH.
OpgeHTaun~I IIpIICOeRgHeHIIx Mo~Iexy~I McTg~IMeTaxpII~IaTa s nao-
TaxTHLIeCHOe IIOJI05xeHHe M07xeT ~blTb pe3.yJIbTaTOM IIOJIfIpId3yI0II~er0?
J{eI3CTBIIA axTIIBHbIX B;eHTIIOB, xOTOjIOe MO?ISeT paCIIpOCTpaHSITbCfI~
He TOJIbItO Ha ~JIg3JIe?ISaII;ire MOHOMepHble MOJIexyJibI~ HO g Ha Ha-
xoRaTi;necx 6o~Iee Ra~Iexo. .
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iIaCTb xaHfJ~OII IIOJIgMepHOI3 I[eIIH, IIpIIJIeSi{aII~aSI x axTIIBHOMy I;eHT-
py, sIB~IReTCx cBOeo6paaHO~ uxazanHTIIUecxo~I IIosepxxocTblo>,.
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OIIpeReJIeHHbIM 06pa30M, ( IIO I~eIIi4 x axTHBHOMy ueHTpy..
B TOM H B Z~pyrOM CdlyiTae J~OJI5xH0 Ha~7II0I~aTbCFI 3aMOTHOe IIOBbI-
IIIeHIIe ac~c~exTHBHOCTH coyAapeHIIl~ peargpyloII~IIx Mo.nexy~I? g cllg-
alcexHe axeprgg axTgBa~gg peaxl~H pocTa uelieii..
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
Sum-wary
Polymers of rather high molecular weight. are formed in the
butyllithium-catalyzed polymerization of methylmethacrylate
in toluene at -40?. If it be.assumed that one molecule of butyl-
lithium isconsumed for each polymer molecule than an approximate
calculation shows that about 2% of the initial catalyst participates
in the reaction, the major part of the catalyst being decomposed
by interaction- with the carbonyl groups of the monomer or of the
resultant polymer.
Over the monomer and catalyst concentration ranges 0.3 to
1.0 and 0.004 to 0.016 g. mole/1 respectively and for a reaction
time up to 10-15 minutes at. -50? the rate of polymerization is~
described by the equation:
1 x'l:
In + ~ = (2k1 `kznomo)I/II t
1-xi4 .
and the mean weight of the polymer by the equation:
ka (xMu)1/s '
M Mo ~2kikanu)I/s - k4 ~xMu)1/Y
where x is the degree of polymerization ki, k2 and k4 the rate..
constants for the elementary reactions of active center formation,.
of propagation and of the interaction of butyllithium with the car-
bonyl group of the monomer, respectively; no and mo are the ini-
tial monomer and catalyst concentrations, t-time and Mo-_the-
molecular weight of the monomer.
The polymerization proceeds at considerably lower rates with
lower initial monomer (0.1 g. mole/1) and catalyst (0.003. and
0.00? g. mole/1) concentrations than is predicted by 'the derived,
kinetic equation.
The existence of a very large difference (more than 105 times
between the rate constants for the elementary reactions of the
formation and growth of active centers and the considerable dif-
ference (twofold) between the activation energies completely ob-
viates the possibility of the reaction taking place by consecutive-
formation of organometallic compounds of ever increasing mole-
cular weight. The nature of the elementary act of active center
formation by interaction between methyl methacrylate and butyl-
. lithium molecules should be different in principle from that bet-
ween methylmethacrylate and the active centers. with the forma-
tion of polymer chains.
On the basis of the experimental data the following assump-
tion may be made as to the mechanism of the polymerization
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
Teaction, taking into account the fact that the frequency facbor of
the Arrhenius equation for the second reaction is several. orders
higher than:"for the ,first. - , . ?
. "The active centers of polymerization formed from. biityllithi=
um and methylmethacrylate molecules are transitions states of
.an ion-dipole character with high reactivities. It is possible that
the polarizing action .of a center extends not only over its near:
neighbor molecules" but further orr.: It is this which distinguishes
the: actiye, center from the .ordinary organolithium .compounds.
.Such activity in the presence of free monomer at a concentration.
not less than a certain" critical one (similar to crystal growth from
saturated:solritions) maybe maintained,. for a,considerable time:
At low? concentrations or in the absence of a morionrer the active'
centers should either isomerize to stable organometalli c com-
pounds, capable of again becoming an. active center of polymeriza-
tion, or react by its? carbonyl group with the monomer and
polymer 'with the formation of alcoholates, i. e. inactive com-
pounds.
The interaction of active centers' or isomerization products
with polymer. chains is confirmed by increase in molecular weight
often to twice the original, .during standing of the reaction solu-
tions, at which over 80-J0?o of the monomer has been consumed.
Par suite de polymerisation du methylmethacrylate en solu-
~tion de toluene par lebutyl-lithium a t.einperature inferieure a
40? se forwent les polymeres a poids moleculaire suffisamment"
haut. Si admetre .que pour former chaque molecule polymerique
on depense une molecule de butyl-lithium it resulte sur la base
?de calcul approximatif, qu'a la reaction de polymerisation parti-
cipe 2% environ du catalyseur initial, quant a sa partie principale
elle se detruise par suite de 1'interaction aveo 1es groupes carbo-
~yligries du monomere ou du polymere obtenu'.
Vans 1'intervalle des concentrations du monomere de 0,3 a 1,0
et du catalyseur de 0,004? a 0,016 g. mol/1 et pour la ?duree de re-
action viers 10-15 min. a 50 sec.. la cinetique de reaction. de
polymerisation est decrite par I'equation:
~/2
? In 1 + x,/2 - (2k1k2 nomo)`/z t .
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et, le .poids ~rnoleculaire?ri7oyen du polymere obtenu:
~ou-x est la profon~leur de polymerisation; k,, k2,et k.r sont?,les
vitesses 'des reactions elementaires (i?espectivement) de, la.aiais-
~?sance des centres `actifs., de lour croissance et.interaction de
butyl-lithium ~avec .le groupe carbonylique de monomere; no
yet mo ?sont les concentrations initiates, de catalyseur et de mono-
mere, t est le temps et Mo est le poids moleculaire du monomere.
Pour des concentrations initiates du monomere plus faibles
(0,1 g mot/1) et du catalyseur (0,003 et 0,002 g mot/1) la reaction
?de polymerisation s'effectue considerabtement plus tentement
~qu'il result.e de 1'equation cinetique deduite.
L'existence d"une tres grande difference (plug de 105 fois) entre
les constantes pour les vitesses des reactions elementaires de uais-
?sance des centres .actifs et de lour croissance de memo que dune
difference essentielle en:tre les valeurs des energies d'activation
(en deux fois) exclut absolument la possibilite de realisation de
reaction de polymerisation a travers le stade deformation des or-
ganometalli?qu.es apoids moleculaire de plus en plus haut. La na-
ture de 1'acte elementaire d'interaction entre les molecules du me-
thacrylate de methyle et du butyl-lithium suivi par la format~-
?on des centres actifs .doit se distinguer par principe de la nature
de reaction entre Ies molecules du methyl-methacrylate et les,
?centres actifs form.ant les chaines polymeriques.
En se basant sur les donnees experimentales et en tenant comp-
~te du fait que le facteur de frequence en equation Arrenius pour la
deusieme reaction est de quelques ordres superieurs a celui pour
la premiere reaction; on pout dormer la representation suivante
?su.r le mecanisme du d,eroulement de la reaction de polymerisa-
tion.
Le centre actif de polymerisation forme par les molecules du
butyl-lithium et du methylmethacrylate est un etat de trans-
fert du caractere ion - dipole a haute reactivite. I1 est possible
que son action de polarisation se propage non seulement sur des
molecules de monomere qui 1'entourent mail aussi sur des mole-
cules plus eloigneer. Ainsi, le centre actif se distingue. des organo -
]ithiens ordinaires. Cette reactivite en presence de monomere Lib-
re non. inferieure a certaine concentration critique (de memo que
la croissance des cristaux a partir des solutions saturPes) pout se
maintenir pendant une longue periode. A faible concentration ou
en 1' absence de monomere Les centres actifs doivent s'isomeriser
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en organometalliques stables, capables de redevenir des ~ centres
actifs de .polymerisation ou reagir avec le groups carbonylique
du monomers ou du polymers, en fournissant les alcoolats soit
les composes inactifs.
L'interaction des centres actifs ou des produits d'isomerisa-~
tion. avec les chaines polymeriques est confirmee par 1'augmenta--
tion de plus de 2 fois du poids moleculaire des ~olymeres formes,
si le solution reactionnelTe'Teste en repos apres ]'execution de lay
reaction de monomers au-dessus de 80-90?,0.
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Next 10 Page(s) In Document Denied
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
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~couxauHx xa HoHbI, TeTpariep $'llpxcyTCTBiIH BoRbI IIpx 100? Taxaxe
.xe Ho~IxMepxsyeTCx.
IIpH xcc~IeRoBaxxll ReiICTBIISI BoRbI Ha AerIO~IIIMepKaauxlo Ho~Ix-
.~HMeTx~ICH~IOxcaxa, co~epxcaH~ero cx.aaxo~IaTOSbie axT'xsxbie
II;eHTpbi, MO?xH0 xaC~IORaTb IIOJ~O~OHbIYi 3(~(~lexT ~pHC. 1). IIpx 150?
HaCTyIIaeT pe3x0e IIOHx?xeHlIe MOJIexyJlHpHbIX BOCOB. B T0X axe yC-
~IOBHxx, xo HpH 10?? HoalHnlep ocTaeTCH 6ea xsMexexHx.
~pxBeJ~eHHbie pe3y.ilbTaTbI MO1xH0 OC'bSICHHTb TOJIbxO 3Ha~IH-
TeJIbHbIMH 'x3M0HeH'HHMIi AeI3CTBHFI axTxBHbIX IT,eHTpOB.
B J~aJlbxeYIlIIex pa~~OTe ~bIJIH xCCJIeJ~OBaHbI ~(OHOp-aKI[eHTOp-
I3ble COOTHOIIIeHxSi ~YexcRy 'axTHBHbIMH ueHTpaMH H HeKOTOpbI1~1II
xI3CJIOpOJ;- x a3OTC0J[exl~K;a7I~xMx CoeJ~HHOHxHMx. 1ibIJIH H3MepexbI
&I3MeHexxFI MD3IexyJlflpHbIX BOf'iOB, BbI3BaxHble IIpHGyTCTBHOM TpH-
ckexII~IaMxxa, Rxc~exH~IahlHxa, axH~IHxa, RHC~exH~IOSOro ac~Hpa,
axHao~Ia H aTx~IOSOro cIIxpTa HpH IIO~IHMepxsaz~xH TeTpaMepa.
Peay~IbzaTbl >soxasaxbl Ha pHC. 2.
pa3~IHTIHFI B cxopocTxx peaxi~Hi~ IIpH Ho~IxMepxaauxH =IlicTOro
TeTpaMepa H B IIpxCyTCTBHx BCOX IIpHBeRexHbIX coeRHHexxil IIpII
X50? Oilexb MaJlbt:
HHTepOCHbie pa3nHLIHH 6bIJIH Hai3ReHbI IIpI3 100?. PHC. 3 IIO-
xa3blBaeT KpHBble', CTOIIexH IIpeBpall;eHHA HpH IIOJIHMepH3aIjHH
TeTpaMepa s paczsope (AHa~IexTpHxecxaa HocTOFIHxaH 8,7) B
SIpHCyTCTBI3x aHH30Jia H JSH(~exHJIaDiHHa. 06a COeRHHeHHH 3aMeJ~-.
JISIIOT IIOJIIIMepx3aIjHiO. '
1ibIJIU yCTaHOBJIeHO, LITO CHJIbHOe 3aMej~JIAIOII~ee J~exCTBHe Oxa-
3bIBaIOT ,TaK>ILe rHJ.~p00KHCH HexoTOpbIX MOTaJIJIOB. PHC. 4 IIOxa3bI-
BaeT xOJ; IIOJIHMepFI3aIjHIi TOTpauepa B IIpIICyTCTBHH NaOH HJIH
LiOH IIpH 150?.
U~OCy}KZ[eHHB
I~IxrH6Hposaxxe IIonHNtepHaai~HA soAoi~ B cpeAe, o6nerxaloH~ei~
AllccouHa~Hlo. xaTHOxa axTHBxoro z~exTpa, yAoB~IezsopxTenbxo
J~Oxa3biBaeT; HeB03bIOHfHOCTb IIpsIMOrO o6niexa KaTHOHa IIpOTO-
930M:
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vucmb~u
o Phi N
o Ph20
? PhpNN
PhoMe
v EfOH
r PhNH2
,6 ,8
LM01-CM1
~ Mo .
..ii,,~~
P.HCi. 2. oHBIICHMOCTb bIOJIexyJIHpHOrO BBCa IIOJIHJ{F3M0THJICHJIOxCflHB OT CT::-
IIeHH IIpeBpalgeH$cI IIpH IIOJIIIMepH3al[HH TeTpaMepa B IIpI3CyTCTBHH OCHOlc
HgFi- ROHI;eHTpagHS3 KPH ~ISaTaJIII3aTOp~ 1,8 +IthLOJlb~x2. TOTpaMepa, OCHOBI-
AHH HpH6aBnel3bl s axBHMOnxpIloM oTI3oIIIeIIHH x KOH.
~ - gacTl~Iia.Te~'PaMeP~ AIg$eHanoer~I# arpNp, TpNCpeHxnan3NH; 2 - aHNaon, J(N~QNAJIa:~~HH;
3 -BTNNOBSi~i CNHpT, aHN7INH.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
Piic. 3. -I{pxs>~e cTi;IIeIIx xpespaII~e x IIpx xonxMepxaauxx
TeTpu>xepa B IIpxCyTCTBxx asxaona x Axc~exxnaMxxa. I{osuex-
Tpagxs KOH 8,9/.rocnionb xz pacTSOpa, Monxpxoe oTSOmesRe MexcRy
axxaonoM xnx Rx~iexxnaMxsoM x KOH 1 : 1.
l - HOmiMepx3aulift TCTPaMePa B OTC)'TCTBIIC afIN30JIa ISJM J{If1~1CFIHJIa MIiHa;
Pxc. 4. I{pxBi~e cTexexx
IIpespax~e~iR,IIpx IIonxMe-
pxaauxx TeTpaMepa s IIpx-
CyTCTBxx NaOH, LiOH.
fino*~xag IIo.nxMepxaauxa.
AxaxexTpx*~ecxaA IIOCTO-
aIISax cpeR>~ 2,4; xoII-
uexTpauxa KOH 17,9
.H~tonb/xz TeTpaMepa (0,1
sec. % ).
1 - xOIIAMepA3auxft 4NCTOPO
TCTPaMePa; 2 - MOJIxp-
xoe oTxomeAiie KOH : NaOH
i : 0,7; 3 - MoJlftpxoe oTAO-
mexxe KOH:NaOH i i; 4-
MonApxoe oTHOmexxe KOH?
LiOH 1 : 0,7; 5 - MoJlftp-
xoe oTAOmexlie KOH : LiOH
i : 1; 6- MOJIftpHOe '-OTHOme-
AAe KOH: NaOII i s 10; 7 -
MOdiftpAOP. OTAOmeHlte KOH:,
LiOH f 10.
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f'aaltr~rlu a~cr~IaKOro uexrpa RoJlxcKr~ IIpoTexaTb gepe3 Bpenlex-
EIIO .o6pa3yloII;xiresl IIxTIIBaJIexTIIhIYI , aTOM Si. IIpII s3aI3MORe~I-
~CTBIIII C BOJ~OT3: ,
~ I~ ~ I
- - i i -OI(+ HO H ~- ~? - i - ~ WOK ~- -' - i 1-OH ~- KOH
O-iH
I
?H
BoAa xe Bo3Rei~cTByeT B 3xa~TeJlbxo 6oJlee pe3xIIx ycJlosxxx
as cHJloxcaxosylo csx3b [1l. IfoopRxxaz~IIOxxasl
CBSi3b o6pa3yezcx Jleree y xpeMxHx rpyIIIIbI - 'i - OK~,geri y
C aTOMOM xpeMxHU, c xoTOpblhl coeRxxexa cIIJlaxoJlaTOSax
TpyIIIIa, CIIOCOCHbI COeJ~IIxxTbCSi II TaKIIe J~OHOpbI, xOTOpble H0 MO-
TyT B03~(eI3CTBOBaTb Ha xpeMxI3Ft CIIJIOI{CaHOB0i3
~CBA3I3.
06pa30BaHIIe IIHTYIBaJI6HTHOPO Sl 0603HaiiaeT IIpexpaII~eHxe
cylRecTBOSaHHx axTi3Bxoro >~exTpa. Bo BpeMx cym~ecTBOSaIIIISI 3TOro
xonlIIJlexca He rloxceT IIpox3oirTx IIpxcoeRxxeHIIx AaJlbxei~IIrxx Mo-
JlexyJl TeTpaMepa x cxJlaxoJlaTOSOir rpyIIIIe. LjeIIx, oxaHTixsa10lijl3e-
~CfI OIIIICaHHOI3 rpyIIII0I3,- . C,Ta6IIJIbxOCTb 06pa3yI0II[IIX-
Cfi HOMIIJIexCOB C IIFITIIBaJIexTHbIM Si B RaHxbIX yCJIOBHSiX OIIpOJ~e-
.JIfIeT CTa6IIJIbIIOCTb. CIICTOMbi IIOJII3Mep - TOTpaMep ~xJIII TOJIbxO
IIoJIIIMepa) .
I3a CTa6IIJIbHOCTb xOMIIJIexCa 3Ha~IIITeJIbHO BJIxSIeT TeDlIIepaTypa.
KOMIIJIeHC, 06pa3yI0II~I3IICSI Ha axTIIBHOM I~eHTpe, Oilexb JI0rx0, pa3-
JlaraeTCFI npx 150?; IIpII 3TOM BbIJ~eJISIeTCx MOJIexyJla CIIJIbHOrO OC-
xOBaHiIFI ~KOH), Co3RaI0II[aSI CHOBa axTI3Bxble I~eHTpbl. ORIIaxo
9 I -
fIpII 100? xOMIIJIexCbI C IISITIIBaJIOHTHbIM - i I - 60JIee CTa613Jib-
HbI, II pe3yJlbTaTOM 3TOr0 FIBJIFIeTCx 3aMeJ~JIexxe IInII xxrII6xp0-
~BailIIe IIoJIIIMepII3aRIIII.
I{oxexxo, IIpxpoAa Roxopa x BxR aTOMOB IIJIII rpyIIII, csx3ax-
HbIX C Z[OHOpOri, TaxSxe OIIpeReJIFIIOT CTa~IIJIbHOCTb KOMIIJIexCOB.
'Ha pllc. 2 MO1xH0 xa6JIIOJ~aTb BJIIIHHI3e 3JIexTpOOTpIII~aTeJIbHOCTII
Roxopa. xa o6pa3oBaxxe xoMIIJlexca. ICxcJlopoA 6oJlee 3JIexTpo-
oTpIIuaTeJlex, neM a3oT. RJIx AocTIIxceHIIR . 3JIex-
~Tpoxxoro cpoRcTBa y a3ora xeo6xoRxMO csx3aTb c a3oTOM xa oRxy
3JI0HTpO0TpIIgaTeJIbxyIO rpyIIIIy 60JIbBIe.
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~e33CTBxeM 3.718KTpOOTpxIfaTeJIb$bIX (~enxJIOB' IIOB'bIIIIaeTCFS CpOJ~-
CTBO x " 37IexTpOHaM' y I~eHTpaJIbHOPO aTONia Rxc~ennnosoro ac~xpa!
n Tpxc~eHxnan~xxa
Ao Taxog cTexexx, *~TO 0 x,ax N xe cnoco6Hbi o6~eRxnxTb csoiov
a~exTpoaxyio napy c azoMOM axuenTOpa B oRxy cxcTeMy. 9Tx co-
I
eRxnexxx ae BaaxMORer~czByioT c - i~ - axTxsxoro uexTpa.
~xc~enxxaMxx n anxso~ xerxu BaaxMORe?~cTByioT c axTxsar~M
~exTpoM x aaanorx~xo, , xax x B c~ygae c H2O:..
IIpx 100? xoMnnexc axTxBxoro ueazpa c axxaoxonz x Axc~eaxn-
anzxxoM cpasxxTenbxo npo~ex, xax RoxaabiBaeT aaMeRxexxe none-
Mepxaauxx (pxc. 3):
? Taxnhs o6pasoM, xxcsopoR Axc~enxnosoro ac~xp.a ~rxniex snex--
TponoB oTpxuaTe~bxbiMx c~exxnaMn, Tax xax ox xe a~ic~exTxsen B
xaxecTBe Aonopa. I{nc~opoR B axx~iaTx*~ecxxx coeAxxeaxAx, na-
'npxMep B cnxpTax, ~erxo o6T~eRxaReT cBOio cso6oRxyio axex.poa-
ayio napy c xpeMxxerz axTxsxoro ~exTpa.
Pnc. 5 noxaar~BaeT xpxBbie cTenexn npespan~exxx npx ? nonx-
Mepxaauxx TeTpaMepa B npxcyTCTBxn c~exona (xaTa~xsaTOp=cKna-
xonaT K).
Ilpx IIpxcoeRxxexxx=c~exona x axTxsnoasy ~exTpy o6paayeTCx
cpasxxTenbxo cza6xnbxbri~ xoazn~exc, xoTOps~H pacm~ennReTCx
oxenb McRnexxo:
IIo~xNiepxaauxx nocne nepxoRa nnrx6~posaxxx nenpep~Bno
ycxopsieTCx oT nyxesoK cxopoczn BnaoT~ Ro Maicaxn~a~hnoi~, on-
peRe~xenioi~ icoxuexTpauxeH cBO6oAxsix axTxsx~x_ uenTpoB..
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
0 cTa6IIalbxocTII xoMII~Iexca c c~exononl cBII~~eTe~I~bcTByeT IIoRaB-
JIeHIIe Z[eIIOJIxMepH3al[IIII IIpII IIOMOII~II c~exo~Ia IIpII TertrlepaTypax.
150? [81.
I~
THRpooxxcH nleTa.a.noB Tax;xe o6pasyloT c - Si - axTllBxoro~
E
ueHTpa 60 nee IiJIIi DIOHee CTa6IIJIbHble xOAIIIJIeKCbI. C.Ta61IJIbHOCTh.
40 80 120 160 200 240 L ~ MQMi
PIIC. 5. I~pxBble cTetlexli xpespax~exxx xpx xonxMepxaauxx TeTpanlepa:
s npxcyTCTBxx c~exona. Bno*Ixax xo~IxMepxsauxx xpx 150?.
1;-dnoniiMepxaauHx vazcTOCO TeTpaMepa; 2 - MonRpxoe oraomex~3e axTxsar~x geaTpoB
K ~eaony = f 0,5; 3 - nionRpxoe oTeomexxe arcrusx~x i~exrpos K ~eaony = f ~-,.,
3TIIX HOMIITIexCOB 3aBIICIIT OT TeDiIIepaTypbI, HO PJIaBHbIM o6paaoM
oT paRIIyca I~oaa nleTa~I,na. ' I'I?IApooxHCII nleTa~I~IOS o6pasyloT c~.
- Si - axTIIBII01'O I~eIITpa K011fIIJIexCbI, CTa6IIJIbHOCTh xOTOpbIX:
IIosblIIlaeTCx B psl~y Na < Li < Zn < Fe < Al~< Be.
I~Ia IIpeRblAyu~ero c~IeAyeT, ~ITO cTa61I~Ibxble xonlII~Iexcbl, Boa--
. HIIxIIIIIe Ha axTIIBHODI I[eHTpe, TIIIIa:
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
A - BoaMOaKxo 6o~Iee a~IexTpoozpxuaTe.nbxblK (xHC,nopoA, ra-
.~IOrex), B - B03ni0?KHO 6o.aee aneKTpoOTpHuaTe~IbxaA yr~Ieso-
.RopoAxasl rpyxxa HJIx caMblH nla~IblH aTOnI aleza.a~Ia.
Ha ocxoBaxHx xpxBeRexxoYl pa6oTbl MoaKxo o6~bricxxTb TaKxce
~cTa6x~Ixaxpylox~ee Aei3cTBxe xoRa. Mexaxxsnl Rei~cTBIIx xoRa xoxa
xe 6bIJI yRoB~IeTBOpIITe.nbxo o6~bxcxex. Moxcxo xpeRxo~IOaKxTb
to
-Si-OK
~o6paaosaxxe icoalx.aexca ~\~o ~ oTUSex~Ixlox~ero KJO.
~~~
Tlpx RxcxpoxopulloxllpoBaxxx KJO o6paayloTCx KJ H KJ03,
xTO, Aoxaaaxo axa~IxTxgecxxnl xyTeM [9].
CTa6H.abxble KoNlx,nexcbr y aKTxBxblx uexTpos o6pasyloTOSI
He' TOJIbKO x3 COe]~xHOHxYI OIIxCBHHbIX THHOB. MoaKxo xepegHC~IxTb
MxOrO J~OxOpOB, o6paaylou~xx c aKTxBHbIM uexTporf KOMIIJIeKCbI
!pa3JI~i=IHOI3 CTa6HJIbHOCTx. OAHHM x3 HYIX HBJIFIeTCA, xaxpHMep,
RByoxricb yrsiepoRa. 1TpII 150? o6paayeTCx cpauxxTenbxo cTa-
~6x.nbxblH KOMx~Iexc, Bc.aeAczsxe zero BBeAexxeM RByoKKCII ~ yr~te-
poRa Moxcxo xpexpaTKTb xo~IxMepxaauIIlo. OAxaxo xpll TeMxepa-
Type cBblxle 200?, aTOT Konlx~Iexc pa3~IaraeTCa I3 cTa6x~IlIaxpylou~ee
ReHCTBIae HcxeaaeT [7].
06paaosaxHe cTa6x.abxblx KoMx~IexcoB xa ftKTIIBxbIx uexTpax
xMeez 6osbxloe 3xa~exxe R~Ix cTa6H~Ixa'ai;xx cIl~IOxcaxoBblx xo~Ix-
MepoB. I'xxoTe3a o6 o6paaoBaxxx aTxx KoMx.nexcoB xMeeT Taxxce
TeopeTxgecxoe a'xaeexxe. IIpeRocTaB~Ixezcsl B03MOHCHbIM o6~AC-
HIITb HOKOTOpble RO CIIX xop Hex3B0CTHble SIBJIexxFI IIpx IIOJIAMe-
px3aD;xH, xpx KOTOpbIX 3B0HOM aKTI3BHOr0 I(eHTpa FIBJIFIeTCSI aTODI
c KoopRxxat~HOxxbini xllc.nonr Bblxie geTrlpex.
JlgTepaTypa
1. D. T. H u n d, R. C. O s t h o f f, M. L. C o r g i n, J. Amer. Chem.
Soc., 76, 243, 1954.
2. M. Kucera,' J~IICCepTagiis~ HI~II'IMX, Bpao, 1959.
3. M. Kucera, M. I e l i n e k, Coll. Czechosl., B IIe~iaTx, 1960.
4. M. Kucera, Coll. Czechosl. s nexaTx, 1960.
5. M. Kucera, ,i~ox~iaA xa I#oxc~epexuiix no xpeMirxi~opraxii~ecxxM co-
,eRiixexiiaM, CCCP, JIexxxrpaA, 1958.
6. K. V e s e 1 u, M. Kucera, ZjoxnaA xa CxMno3xyMe IIo MaxpoMO~ie-
xy.naM, Weisbaden, 1959.
7. M. Kucera, I. Lanikova, M. Ielinek. J~oxnaA xa CHM-
n03IIyMe IIO MaxpOMOJIexyJlSipHOYI XnMnn, CCCP, Mocxsa, 1960.
8. M. Kucera, I. Lanikova, M. Ielinek, .B IIe*iaTx.
9. R. C. O s t h o f f, A. M. B u c h e, W. T. C r u b b, J. Amer.
Chem. Soc., 76, 4659, 1954.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
Summary
The ionic polymerization of octamethylcyclotetrasiloxane
(the tetramer) proceeds through successive additions of tetramer
on active centres. The active centres consist of the ion-pair
Si - OM (M stand for Na, K, Rb, Cs, Me4N-, Bu4P- etc.) formed
through the reaction of the hydroxide (oxide) of the respective al-
kali metal (or the respective ammonium of phosphonium base)
with the siloxane bond.
Measurement of the rate of polymerization of tetramer indi-
-+
Gated changes in the efficiency of Si = OK active centres caused
by additions of small amounts of substances capable of changing
the character of donor-acceptor reactions taking place during
polymerization. These substances were added in the order of their
decreasing acidity ranging fxom very strong acids such as HzSO4
to very strong bases such as e. g. hydroxides of alkaline metals. .
The influence of substances being added - as judged by their
influence on the over-all rate of reaction -can bee seen to fall
into several classes. The most acidic substances (ranging from ve-
ry strong mineral acids to weak organic acids e. g. phenol) neutra-
lize the active centres; weak acids (H2O, ROH ...) act - as judged
by changes of the over-all rate of reaction -only through physi-
co-chemical effects in the polymerizing system (for instance
through changes in the quantitative composition of the solvate
shell of ions and ion-pairs and through changes of the dielect-
ric constant). Very strong bases, as strong as, or stronger than,
KOH increase the number of active centres.
The most interesting effects are displayed on addition of rela-
tively strong bases of the type of LiOH and NaOH. They cause
a strong reduction of the efficiency of active centres, a deceleration
of the polymerization and even its complete inhibition, in the who-
le range of dielectric constants of the polymerizing medium in-
vestigated by the authors (viz. in the range of dielectric constants
from 3,4 to 8,7). This phenomenon of deceleration and even stop-
ping of polymerization on addition of relatively strong bases to
a basic active centre has been called the .
Similar effects were observed also in the case of the cationic poly-
merization of the tetramer, viz. aslowing-down or even stop-
ping of the H2SO4 -induced polymerization on addition of wea-
ker acids. '
The mechanism of the is discussed,
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Resume
La polymerisation anionique de 1'octamethylcyclotetrasilo=
xane (tetramere) se fait par 1'addition succesive du tetramere aux
centres actifs. Les centres actifs soot formes par les couples ioni-
ques Si - OM (M = Na, K, Rb, Cs, Me4N-, Bu,~P-) produits
par la reaction du hydroxyde (oxyde) du metal alcalin respectif
(eventuellement par la reaction de la base d'ammoniu.m ou de phos-
phonium) avec la liaison siloxane.
Par la mesure de la vitesse de polymerisation du tetramere
on obtient les changements de 1'efficacite des centres actifs Si -
OK, causes par 1'addition de petites quantitees des composes
qui ont le pouvoir de changer le caractere de lareaction donneur -
accepteur pendant la polymerisation. Les composes ont ate ajoutes
d'apres leur acidite abaissante, depuis des acides forts comme
H2SO4 jusqu'aux bases fortes comme les hydroxydes des metaux
alcalins.
L'effet des composes ajoutes, juge du point de vue de la vitesse
totale de la reaction, peut etre divise en quelques groupes. Les
composes les plus acides neutralisent le centre actif (depuis des
acides mineraux forts jusqu'aux acides organiques faibles comme
par example le phenol). Les acides faibles (H2O, ROH...) operant
seulement avec des influences physico-chimiques daps le sys-
teme en tours de polymerisation, c'est-a-dire par le changement
de la constitution quantitative de 1'enveloppe des ions solva-
tants et des couples ioniques et par le changement de la constante
dielectrique. Les bases aussi fortes ou plus fortes qua KOH aug-
mentent le Hombre des centres actifs.
Les phenomenes les plus int,,~~;essants ont ate observes apres
1'addition des bases relativement~ fortes du type de LiOH, NaOH.
Celles-ci decroissent 1'effet des centres actifs. et causent une di-
minution de la vitesse de polymerisation jusqu'a une inhibition
darts tout le domaine mesure de la constante dielectrique du milieu
(de la constante dielectrique 3,4-8,7j. Le phenomena quj~ consis-
te daps un ralentissement jusqu'a 1'arret de la polymerisation ap-
res 1'addition des bases relativement fortes au centre actif basique
a ate appelle . Des effets similaires ont
. ate observes aussi chez la polymerisation cathionique du tetrame-
re -ralentissement jusqu'a 1'arret de la polymerisation amorce
avec H2SO4, par 1"addition des acides faibleso
On discute du mecanisme de la .
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KI~IHETI~IKA 110JIHMEPIi3Al:~I~lI~I
~OPMA.nbJ~EI'LIJ~A
MogoMepabt~ c~opMa.~bAergR Bc~neAcTBge o~eHb IIo~xpao~ cBx-
ag C = 0 nerxo IIo.ngMepgayeTCx. 8TO Re~cTBIIe yxce Ha6nfoRa.n
EyTxepoB [1], B 1920-1930 rr. erO Hayxan IIITayAHHrep g coTpyR-
HsxH [2], Ranee Yoxep [3] g B IIoc~eRxee BpeMA eMy yAe~x~g BHII-
MaHHe aMepBxaxcxHe aBTOpbt, IIpexcRe Bcero B IIaTeHTax [~f]. OA-
Haxo~ xHHeTII~ecxse SsMepeHgx IIongMepHaaugg c~opManbRergAa
Ao cHx nop He 6bi~II B ~gTepaType ony6ngxoBaabi. OHg axcIIepgMeH-
TaJIbHO OileHb Tpy~Hbl BBIIJ~y He06bIxHOB0HH0i3 CxJIOHHOCTB MOHO-
MepHOPO (~OpMaJIbJ.~erIIZ{a x IIOTIIIMepld3aI~IIII, HOTOpaSi IIpII HOp=
MaJIbH0i3 TBMIIepaType MOH{eT IIpOTexaTb C IIOLITH B3pbIBAOIi CHO-
pocTbio.
J~~x IIsy~eHHx nongMepgsaugg c~opMa.~bReraAa MbI Bbi6pa.~II
MOTOZ[ J~IIJIaTOMOTpIIII IIpII HH3xIIX TBMIIepaTypaX ~OKOJIO -6~~~,
B 3TOg 06JIaCT1d TOMIIepaTyp MO?xH0 IIOHII3HTb CxOpOCTb IIOJIHMepII-
3aD;gH HaCTOJIbKO, iITO HIIHOTgiI2CxIIe II3MepeHTdfl MOH{HO BOCTg Ce3
60JIbmgX 3aTpyJ{HeHIII3, Ilpg HOMHaTH073 HJIg , HOCxOJIbKO 6oaiee
Hgsxog TeMIIepaTypax IIo.nsMep ocaxcRaeTCS~ Ha.cTe$ax AgnaTO-
Mezpa g Ae.aaeT xeBOSMOSxabiM gcuo~baosaHge AIInaTOMeTpg~ecxo-
ro McTOAa.
B Ha~eM Rox~aAe oIIgcaxbt axcuepIIMeHTa~baax ycxaaoBxa g
peay~bzaTbi, IIonyxexxbie IIpg IIcc,~eRoBaHHH B.agxHxR xoH~eHTpa-
I(Lig KaTaJIg3aTOpa, BORbI II MypaBbIIHOI3 KIICJIOTbI Ha CHOpOCTb IIO-
.~gMepg3augg H BSI3KOCTHble XapaxTepIICTgKH IIOJIIIMepa. ~OpMaJIb-
AerIIR IIOJIgMepII30BaJIII B paCTBOpe B 3TgJIOBOM 3(~gpe IIpg TEMIIe-
paType -58?. B xa~ecTBe xaTaJIg3aTOpa 6bin IICIIOJIb30BaH AII6y-
THJIaMgH, SIBJISIIOII~13I3Cfi OJ(HHM II3 yJ~O~HbIX HBTaJIII3aTOpOB IIOJIH-
~epgaaugg [4l. '
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
3xcnepHMexTaxbxa$ *~acTv
MOHOMep IIpIIPOTOBJIfIJIII xIIpOJIH3OM CyCII0x3xPI xapac~opManb-
RerBRa s RgoxTHxc~TaxaTe (1 : 1) xpR TeMaepaType Ro 150?, s cTex-
xuxxoH axxapaType. IIapac~opMa~bAergR 6bz~ xepeR gcxosbaoBa-
xgeM Bbicyixex B BaxyyMe xaR P203. I'asoo6paaxvi~ c~opMa~bRera~.
Borcyytir
PSC.1.CxeMa annapaTypr~ Rix nonxMepxsauAg:
1 - xpxocTaT, 2 - cocyu J~sioapa aecepe6peas~A, 3 - AnnaTOMeTp c Memanxoii,
4 - 6iopeTxa, 5 - c6opHnx c pacTBOpoM aaTaau3saTOpa, s - c6opanx c pacTBOpoM acn~-
Tyemoro xoMnoaeaTa (aanpaMep, BoAa, MypaBbnaaa xncnoTa), 7 - c6opaax c eacT~M
paCTBOpnTeJIeM, 8- a90T A7IA Ca(~OHHpOHBHHH, 9 - pTyTHF,i13 3aTBOp, IO - orsou asoTa;.
11 - BBTBOp C AHOHTa7I(kTaaaTOM.
xpoaycxang xepes Rse xpoMblBa~icH, xaxonxexxs~e cTex~Axx~MII
KOJIb7~aMg H ?xIIJ.[x]dM (~OpMaJIb~[erIIZ[OM C TeMIIepaTypOx, IIoARep-
aicgsaeMOi~ as yposxe Touxx xgxexgx (-19,2?). IIoc~e aTOro Mo-
xoMep xoxRexcgposa~g s c6opxHice B oTTyRa oT6Hpang erO xop-
u~g'R~x no~igMepgsa~gg. TeMxepaTypa e6opxgxa cocTas~x~a
oxo~o -80?.
IIpgMeaxeMax axxapaTypa, cxeMa xoTOpoi~ xoxasaxa xa pgc. 1~,'
COCTOgT H3 xpgOCTaTa C RIIJIaTOMBTpOM H 3axpbITOB RoagpyFOx[ei~-
CgCTOMbI.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
,uII~IaTOMeTp IIpoxa~IIIBaIOT B BaxyyMe, co3RaIIHOM Mac~IaHbIM
HBCOCOM; BaxyyM CHIIMaIOT TII~aTeJIbHO BbICyIIIeHIIbIM a3OTOM. IIO-
TOM IIOMeII;aIOT RIIJIaTOMOTp B xpIIOCTaT H IIpII IIOMOII~II xOJIbB;eBOI'O
IIlJIII(~a IIpIICOeRIIHSiIOT erO x J~O3IIpyI0II~eI3 CIICTOMe. B TezIeHIIe 3TO13
MaHIIIIyJIHI~IIII RBOJ~SIT B AIIJIaTOMOTp a3OT. I/I3 c6opHIIxa axIIAxoro
c~opManbRerIIRa IIeperoxxloT MoxoMep B AII~IaTOMeTp. 06~eM Moxo-
Mepa II3MepxloT B HIIxcael~ rpaAygposaHHOI~ uacTII AII,naTOMeTpa.
BBOAaT McIIia~Ixy II3 HepxcaBeloIISe>3 cTa~III II II3 3axpblTOi3 Ro3IIpylo-
II~ei3 CIICTeMbI IIpII6aBJISIIOT paCTBOpIITeJIb, paCTBOp xaTaJIII3aTOpa
IIIIII xce IIOCJIeJ~yIOII;IIe xOMIIOHeHTbI H CHOBa TlgCTbI1=i paCTBOpHTEJIb.
Ilpg6aBJIfIeMbIO xOMII0H0HTbI OTMepHx)T IIO O6'beMy.II IIepeR BBeJ~e-
HIIOM B JJ,IIJIaTOMETp IIX HarpeBaloT ~O TOMIIepaTypbI OIIbITa. MoHU-
Mep C 6OJIbIIIIIM y~[eJIbHbIM BOCOM OCTaeTCSI OTJJ;eJIeHHbIM CJIOCnI
YIICTOI'O paCTBOpIITeJIR OT xaTaJIII3aTOpa, TiTO yCTpaHfieT BO3M0?x-
HOCTb IIpe}xJ~eBpeMEHHO73 IIOJIIIMepII3aB;Hg. FibICTpbIM BepTHx'aJIb-
HbIM J{BII7xeHII0M McIIIaJIxII peaxuHOHHyIO CMOCb IIepeMeIIiIIBaIOT I[
McIIlaJlxy IIpIIBOJ~TIT BO BpaII~eHIIe. IlepeMeIIIIIBaHIIOM COJ~epHCaHIISI
JJ;IIJIaTOMOTpa HaTIIIHaIOT IIOJIIIMepII3aI;IIIO, XOJ~ xOTOpOI3 xOHTpOJIH-
pyloT IIO COxpaDjeHIIIO O6~eMa, OTCiIIITbIBaeMOMy B BepXHei=I rpaRyII-
pOBaHHOH iIaCTII J~IIJIaTOMETpa. IIOCJIe OICOHLIaHIIfI OIIbITa J1;IIJIaTO-
McTp 6bICTIlO BbIHIIMaIOT, tIaCTb peax>;IIOAHOI3 CMOCII OT6IIpaIOT B
KOT16y C M@TIIJIOBbIM CIIIIpTOM II B J~IIJIaTOMOTp BBOj{FIT MOTIIJIOBbIlI
CIIIIpT. IIOJIIIMep BbIi;eJISIIOT, (~HJIbTpyIOT H IIOCJIe TII~aTe7IbHOrO IIp0-
MbIBaHIISI 3(~IIpOM CyIIIaT B BaxyyMe, CO3j~aHIIOM BOAOCTpyIIHbIM Ha-
000OM, IIpH 60?~AO IIOCTOSIHHOI'O BOCa.
,~~Ix oupeAe~IeHIISI Bx3xocTHOI~ xapaxTepgcTIIxII H3MepxloT BH3-
xocTb pacTBOpoB IIo~IIIMepa B eMecg c~eao~Ia c TeTpaxnopsTaxonl
(1 : 3) IIpH 90?.
B~II3sIxHe Ri36yTH~IaMIIHa
IIpH IIonIIMepH3ai~IIII MbI cgaxa~Ia g3Mepx,ng B~IHxHHe xoHuex-
Tpa>~IIII AII6yTIInaMIIHa B IIHTepBa~Ie oT 2,7.10-e Ro 25.10-s .M-o.~blrc
IIpH xoH>~eHTpauIIII MoaoMepa B ac~IIpe 4,7 .~co/cbl/c; BoAbI - B HH-
Tepsa~Ie oT 2,5.10-3 Ro 3.10-3 .ntiorcblrc H TeMIIepaType -5810,1?.
IIo~IyxeHable xpIIBSIe IIpespalgeHIIx IIMeIOT xapaxTep, cooTBeTCT-
ByI0II;II73 peaxuIIII BbICIHero IIopslAxa, II IIx zHIIIIiIHasl c~opMa g3o6-
paxcexa Ha pgc. 2. 3aBHCHMOCZb MexcRy coxpaII~exIIeM o6~eMa g
czeneablo IIpeBpa>>;exIIH .nIIHegHax, b1o~Iexy~ISlpxbll~ sec. 3aBIICHT
oT cTeueHH IIpespargeHIIx, IIO3TOMy OIIbITbI 6bIJiII IIpexpaIL~eHbI B
o6~IacTg oxo.no 30%-HOZ~ cTeneHII IIpespaII~eHIIx.
MexsRy cxopocTblo IIo~IIIMepII3auIIH, IIo~IyueHHOiz rpac~Hxecxo>s
AepIIBaI~IIeI~ xpgBblx cTeneHII .IIpeBpaII~exIIx B o6~IacTII 10 % -HO1i
czeIIeHII IIpeBpaII~eHIIx, g xoHI~eHTpauIIei~ j{II~yTIIJIaMIIHa MbI o6ila-
pyxsIInH .nIIHe~IHylo 3aBIICIIMOCTb, IIOxa3aHHyx) Ha pIIC, 3. I/I3 3xC-
TpaIIOnsIuIIII x HyaeBOr~ cxopocTII BblTexaeT, uTO B peaxuIIOxxoii
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
ZO 4D 60 80 100 IZO 140 160
BpeMS , muH
Pgc. 2. 3asxcAMOCTb cTeIIe~ npespau~exxu oT speMeHx(-); Repxsauux
3TOI3 3aBgC33MOCTI3 ~- - -)?
? / ~
/ o
o
I~ f 1 I y I I I ~
0 2 4 6 8 !0 12 lk l6
? Qu6ymunamuN,MOna/n i0
Pxc. 3. 3asxcxnsocTb cxopocTx no~xMepxaar~xx oz xoxueHTpa~x
Ax6yTxnaMxxa.
?t(C?H?)z NH] oz 2,7.10-8, ,??onn/n Ao 25 ?AO-' Moan/n; [Hz0] s npeAenax oT 2,5.10-'
uo 3.10-' ,xonn/n; [HCHOI 4,7 ,?onn/n. PacTSOpuTena - orxnoeu>~ acpap, 'reM-
nepaTypa - 58t0,i?.
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cgcTeMe MoxteT IIpoIIao>3Tg xacTIIUIIbII~ pacxoR IcaTa~IIISaTOpa,
BepoaTHO Bc~ieRcTBIIe HaJtIIxIIx IIpIIMecel~ B MoxoMepe II~II xce pac-
TBOpIITCTie. I{OJIgLIeCTBO BCOX IIpIIM0CEI3 OIIpeJ[e7IeH0 OTpe3kOM Ha
OCII aOCI~I[CC, uaJlbHegIIIIIMII OIIbITaMII 6bIJI0 yCTaHOBJIeHO, LITO Be-
JIII~IIIIia 3TOI'O OTpe3ka HBJIFIeTCFI IIepeM0HH033, IIO TiIIHeI3HbIi3 XapaIC-
Tep saf~i-rcllmiocTK ckopocTII IIo.ngMepgaaugg oT koHueIITpaztgg ka-'
TaJIII3aTOpa COOJIIOJ~aeTCH, e~TO MO)I{II0.06'bHCIIIITb TEM, ~iTO pa6oTy
Be~Ig B o6.aacTII oxexb xIIaxgx koaueHTpaugl~ xaTa~IIIaaTOpa II yuo-
Tpe6~Ia~III MoIIOMep, xoTOpbli~ IIpIIrozoB.zsl.aII Rix xaxcRoro psiRa oIIbi-
TOB OTJ.~eJIbHO.
3aBIICIIMOCTII BfT3kOCTHOYI XapaKTepIICTIIkII OT kOIIl(eIITpaI~IIII
kaTaJIII3aTOpa IIIIII OT CICOpOCTII peakl~IIT3 IIe I~aBaJIII OJ~H03IIaiTHT~IX
pe3yJlbTaTOB, HO MO?ISHO IIOJIaI'aTb, iiTO 3Hat18HIIe Bfi3kOCTII yMOHb-
iIIaeTCS c uoBblBieaIIeM cxopocTII peakl~IIx.
IIo peay~ibTaTaM sTIIx oIIbITOB Nioxcao IIpeRIIO~IaraTb, PTO IIpII-
MecII, IIa xoTOpbie pacxoAyeTCSi ~acTb kaTa.nIIaaTOpa, IIMeIOT xgc-
~Ibli~ xapaxTep. TaKIIMII Beir~ecTBaMH, IIpIIeyzcTBIIx koTOpbix B pe-
axl~IIOIIIIO>3 cpeRe Moxcao oSkIIAaTb, xB~IxloTCii Bona IIIIII MypaBbII-
IIasi xgc~IOTa.
BJITI$IIIIe BOJjbI
OIIbITbI Be~III c koIIi~exTpauxel~ BoRbI B IIpeRe~Iax 2,5.10-3-
104.10-3 .~cor~blrc, IIpII IIocTOSIHxoI3 koxueHTpauIIII .~II6yTII~IaMIIIIa
r i i i i i i i r ~ i
!0 ZO 30 40 50 60 70 80 90 100 JJO
Boda, Mona/n JO'
PAC. 4. 3asTlcxrlocTb cxopocTll no~ITlnIepllsauxx oT xollT~eB-
zpal;xx Bogbl.
[HIO~ oz 2,5.10-' Ao 104.10-8 h+onb/n; [(CaH9)8 NH] 4.10-' ,MOnb/n;
[HCHOI 4,7 .m,onb/n. PacTSOpxTenb-aTxnosbtft a~xp, TeMnepaTypa-58?O,f?.
4.10-~ .mcor~blrc. OcTa~ibIIbie yc~IOBIISI 6bIJIII TaISIIMII xce, kak IIpII
OIIbITax C J[II6yTYIJIaMIIHOM. c3aBIICIIMOCTb CICOpOCTII IIOJIIIMepII3al[IIII
~B 06JIaCTII 10 ~ -HOTS CTOIIOAII IIpeBpaii~eHIIfT) OT kOIII~eHTpaI~IIII BOJjbI
17 MexcAysapoAac~~ emMnos~yM, cexiu~s~ 2 257
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PBC. J. 3aB1ic11btOCTb OOpaTHOI3 BIi3KOCTHO7i XaPaKTEi)11CTIiK i
OT KOHIjGHTPa]],I3H BOJ~bI.
ID, 20 .iO ,40' ~ i 22b
NHI
H
)
HCOOHf(C
y
z
[
~
Pxc. 6., 3aBxCxMOCTb CKOpOCTx IIOJIxMBpx3aI);xx OT ?OTHOIIIOHIIH MyP alibIlHOH
' - KIICdIOTbI K. Z[x6yTxJlahfxHy ~B MOJIAX).
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
$3o6paxceHa Ha pgc. 4: Moxcxo aaMeT$Tb, ~ITO IIp$cy,TCTB$e
BoAbI, Bo$pexg oxcgAaH$aM, He B.aHHeT cyII;ecTBexHbIM o6pa3oM Ha
CKOpOCTb_ peaKi;gg. c~TOT pe3yJIbTaT MO}ICIIO OC'bHCHI3Tb TOM, 'iITO
OIIbITbI BeJI$ C 60JIbIII$M $36bITxOM BOJ~bI IIO OTHOIIIeH$IO x xaTaJiII~
3aTOpy (M$H$MyM 5OO 1), IIp$ xOTOpOM B03M0}KHOe BJiHHH$e BOAbI
Ha CKOpOCTb peaxl[$$ He j~OJIHiHO IIpOHBIITbCSI.
3aB$C$MOCTb 06paTH0$ BH3xOCTHOI3 XapaxTOp$CTgx$ OT ;I{Ong
gexTpau$$ BoRbI, IIp$BeReH'Ha$ Ha? p$c. 5, IIoxaaana, xTO c IIo~Ibc
HI@H$eM xOHI~eHTpalj$$ BOJ~bI BH3xOCTHaH XapclxTep$CT$Ka $OHI[-
1I{aeTCH. TOT OIIbIT IIOj{TBeplxJ~aeT IIpeJ~IIOJIOH4eIIge, i1T0 BOJ[a J~ell~
CTByeT B xa~ecTBe IIepeAaTxgxa ueII$. ,
BJIHHHHQ MypaBbHHOI3 RHCJIOTbI ,
OIIbITbI BeJIII C xOHi[eHTpaI~I3eg MypaBb$HOI3 xSCJIOTbI ISO' 4O ~3xil',
H3 paCLIeTa Ha I~$6yT$JIaM$H, $ C IIOCTOHHHOI3 HOHI~eHTpau$eI~ J~13=
~~yT$~IaM$Ha 5,44.10_8 .~orcblr~; ~IO$oMepa 4,7 .~orcbl/c, soAbl .25',
? 10_3 ,uo,~b/.~. 3aB$cgMOCTb cxopocT$ IIoJI$Mep$aaiz$$ '(B o6.aacTl~
Too-xol~ cTeneH$ IIpeBpall~exi~sl) oT Mo~ISlpxoro oTHOmeil~sl,Mypa~
nbHHOg xgcnoTbl x A$6yT$naM$Hy IIoxasaHa Ha p$c. 6. ~IIo.ny~ex-
iiasl xp$Bax gMeeT xeoxcgRa$xblH xoR, xozopblg Ha oclioBaHxg `cy'-
i.gecTByloli~gX AaxxblX xe~Ibax o6~bslcxgTb. 8Ta $xTepecxaH `,3aBg-
CHMOCTb HBJIHeTCH J~Oxa3iITeJIbCTBOM TOPO, LITO yCTaHOBJIeH$0 ~paB-
IiOBOC$H A$CCOI~EaI~$$' MextRy xOMIIOHOHTaM$, y*IacTByioII~Mi3 ,'B
rix$u$gpoBaH$$, T. e. MexcAy R$6yT$.naM$xoM, MypaBl;HHO~'?irg?-~
71OTOg $ '(~OpMaJIbJ[erBJ{OM, 6yAeT, B J.~aHHhIX yCJIOB$HX'CJI0,3ICHbIM
npotXecCOa1. ~ .. ,.. ~ ,: ~ ~ .
~ B aTOM c~Iyuae, xax $ J{dIII R$6yT$~IaM$xa, He 6bi,no ycxaH'oB?=
.nexo cooTxomex$II MexrRy BSi3KOCTIIOH xapaxTep$cT$xoiI $ cx~o-
pOCTbx) IIOJIIIMepII3aLj$g IIJI$ KOHI~eIITpaI[$eYI MypaBb$HOI3 KHCJIOTBP,
1. A. 1J y.T..n e p o B, Ann., 111, 242, ..1859..
2. H. S t a u d' i n g e r, Die hochmolekuiaren' organischeii `Verbind'nngen
Kautschuk une Zellulose, Berlin, Springer, 1932. , ~: ' . ; : ~; J it ~.:.; ;
3. J. F. W a 1 k e r; J. Amer. Chem. Soc., 55,L821;; 1933.. , , ~ ;?; ,. ~.?,~ ;
4. R. N. M a c D o..n a 1 d, naT. CILIA 2768994 x Aa~Iaaeiiu,ne. ;
.~; ~1,'~?,i
?~~.~, ...:.I,
Polymerization. af. formald'ehyde,;has; been studied..in.`~,et~iyl
.ether solution at -58?C. ~ Monomeric formaldehyde has been,, pre-
.pared through pyrolysis, of. carefully, dried ~paraformaldehyde,,and
purified. by passage.throu~h, liquid,,formaldehyde ab its ?.boil'ing
Summary . '. , ..:.- .. ,
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'point 'and subsequent condensation in a reservoir. A catalytic sys-
tem consisting of n-butylamin and water has been used.
The course of polymerization has been studied in a dilatometer
provided with a stainless steel stirrer, since the polymer formed
is insoluble in the reaction mixture. The components. (i. e. liquid
monomer, solvent and solution of catalyst) has .been dosed into
the dilatometer under dry nitrogen gas so as to form separate
layers one on top of the other. The polymerization reaction was
started by mixing the contents. The rates of reaction. have been
chosen so that the initial over-all rate of reaction did not exceed
5 % of conversion per minute.
It has been observed that at constant n-butylamine concentra-
tion the over-all rate of reaction increases with increasing wa=
ter concentration while the molecular weight as checked by visco-
metry practically did not change. The, n-butylamine -water ratio
lay in the range from 1 : 10. to. 1 : 1000 at a formaldehyde concen-
tration .of 5 molell..
With increasing n-butylamine concentration (in the range
from 2,5 ? mole.ll to 14 ?mole/l) and at a constant concentration
of water (3,5 molell) -the over-all rate of reaction,. increases and
the: molecular weight decreases.,
The results. obtained allow to study dissociation. equilibria ul
amines with water in non-aqueous media. Ih the lecture the role
played bywater in the formation of the anion -OH (which initiates
the. polymerization) and the?influence of the structure of the catiun
RxNH?+ on molecular termination or possibly transfer are discus-
sed..
Resume
La polymerisation de 1'aldehyde formigne a ete etudiee dans la
solution. d'ether ethylique a la temperature de -58? C. L'alde-
hyde formique monomere a, ete prepare par la pyrolyse du par-
aldehyde formique soigneusement seche et purifie en le passant par
1'aldehyde formique liquide maintenue a son point d'ebullitiorr
et puffs condense. Comme catalyseur on a utilise le systeme n-ami-
. ne dibutiligne -eau.
La marche de la polymerisation a ete suivie dans un dilato-
metre, agite par un agitateur inoxydable puisque le polymere for-
me est insoluble dans le melange reactionnel. Les composantes
individuelles (c'est-a-dire le monomere liquide, le solvant et la
solution du catalyseur) ont ete ajoutees successivement sous azo-
te seche de fagon a former des couches separees. En melangeant.
260
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le contenu du dilatometre on commence la polymerisation. Les
vitesses de reaction ont ete choisies de fa~on a maintenir la vitesse
totale de la reaction a une vaeeur ne depassant pas ~% conversion
par minute.
On a observe qu'a une concentration constante de la n-amine
dibutylique la vitesse totale 'de la reaction augmente avec la con-
centration de 1'eau tandis que le poids moleculaire du polymere
(qui a ete mesure viscosimetriquement) ne change pratiquement
pas. Le rapport de.la n-amine dibutylique a 1'eau se trouvait dans
t'interval de 1:10 jusqu'a 1:1000 et la concentration de 1'alde-
hyde formique comportait 5 mol/1.
Avec la concentration croissante de la n-amine dibutylique
(depuis 2,5?mo1/1 jusqu'a 14 ? mol/1) et une concentration cons-
tante de 1'eau (3,8 mol/1) la vitesse totale de la reaction augmen-
te et la poids moleculaire. decroit. ~ ?
Les resultats obtenus facilitent 1'etude des equilibres des
dissociation des amines de 1'eau .dans des milieux non-aqueux.
Dans 1'expose on discute de plus pr%s la participation 'de 1'eau
a la formation des anions -OH, qui amorcent la polymerisation,
et 1'influence de la structure des cathions RxNH?+ pendant la ter-
minaison moleculaire eventuellement le transfert.
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 0 MEXAHI~I3ME I~IOH'HO~I IIOJI[~IMEPI~IBAI~I~II~I
' ~ K. Bece.zzr
(*iexocnosaxRS~)
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'CB13J~eTeJIbCTByIOT, HaIIpIIMep, Rolc~IaRbI Mara [1] >;I II~IeIIIa .[2l,
~CJ[P,JIaHHble Ha CIIMII03IIyMe B BIIC6aJ~eHe.
B XOTeJi 6bI IIpIIBOCTII 0630p pe3yJIbTBTOB, ~[OCTIIrHyT)iIX B 3TOH
iIOJIaCTII B HaIIIOM IIHCTIITyTe, IIpII IIOMOII;II KOTOpbIX, HaM yRa~IOCb
9aCTx?IAO 06'bHCHIITb 3Ty IIp06JIeMy.
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CTbIM aJIIOMIIHHOM.II ileTbIpeXXJIOpIICTbIM TIITaHOM CyII;eCTByeT IIp13H-
r>;IIIIIIa~Ibaoe paanIIUIIe, xoTOpoe irpoxB~IxeTCSI xalc B s~IexTpoxpo-
BOj{HOCTII CIICTOM IfaTaJIII3aTOp - COICaTaJIII3aTOp, TaK'II B MEXaHII3-
M0 HaTaJIx3a HOJIIIMep133aIjIIPf. e~TII pa3JI13LIyISI IIOKa3axbI Ha pIIC. 1
II 2.
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~Ia~IbxaH cxopocTb IIoaIIMepgsaugH IIpaxTIIxecI:II He aaBIICIIT oT
xoHI~eHTpaI~IIII .~eTblpexx~IOpgcTOro THTaxa HpII HeRocTaTxe BoRbI,
a IIpII IIa6biTxe r'e~e J3axoAIITCJ3 B nIIHei3HOJ3 aaBIICIIMOCTII oT xoHl~eH-
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a) II36bITOK KIICJIOTbI (ileTbIpeXXJIOpIICTbII3 TIITJIH) He BdIIIHeT
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pxcTOe on.oao - soRa; xax sxAxo xs peaynbTaTOS Hop13>aa x Paccena [13].
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
Z 3 4 Tt l,, f~'Et20)
PHC. 1. YAenbxax anexTpoxposoRxocTb x o6paTxoe sHaxexxe Monexy~rl-p -
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(anexTponposoRxocTb npB -~-25?),
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A1C13 : EtzO.
HoaLtexTpaipLx 25 n~ntionb/n, pacTSOpnTe,nb - EtCl, TeMneparypa -78,5?.
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
8TII peaynbTaTbl IIoxaablBaloT, PTO B ypasaeHgII, BbIBeAeaxoM
paHee [5]
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iIIIBaeT J~IICCOI;IIaL~IIIO II Aaxce 3JIeKTpOIIpOBOJ~IIOCTb. CIICTOMbI. ~O-
3TOMy J{JISI 3TOII CIICTOMbI B KaileCTBe OCHOBaHgH B,, B ypaBHeHIIII
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xaxx IIo~IyxaeM saBIICIIMOCTb:
I~oae~IIO, Hallo RoIIycTIITb, uTO BBIIRy BapblBIIOro xapaxzepa azbx
peaxuIIII II IIpaKTII~ecxII 100%-Hblx cTeueael~ IIpeBpaIISeHIIx ~o
cIIx IIop He yAa~IOCb paanII~IIITb, HacTyIIaeT ~II Z(eI3cTBIITeJIbHbII3 06-
pbIB I~eIIII C IIIIII IIpII IIOBbIIIIOHIIII IIOHII3aI~IIII o6pa-
syezcsl 6o~IbIIlee uIIC~IO axTIIBIIbIx ueHTpoB II HecTauIIOaapxasi pe-
axuIISl IIpexpaH;aeTCx BcneRcTBIIe IIeAocTaTxa MoxoMepa.
OxTaMeTII~IuHx~IO,TeTpacII~IOxcaII. Ha oc-
HosaxIIII xgHeTIIxecKIIx II3MepexIIl~, o xoTOpblx . MbI RoxnaRblBa~III
B BIIC6aReae [11], J[JIH 3TOH peaxuIIII 6bIJi AoxaaaH ~MexaHgaM
IIIBapua, T. e. MOXaHII3M ((SxIIBbIX IIOJIIIMepOB> [14], IIpII xoTOpoM
x xoxi;y
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xy~IHpIIbI~I Bec pacTeT ~IIIIIeHxo co cTeneHblo npesparr;eHIISI. J~a.aee
6bIJI0 ycTaxoB~IeHO, nTO czaRIIeH, onpeRenxloII~eH cxopocTb, HBJIII-
eTCSi IIeperpyIIirIIpoBxa aIIIIOxa:
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
0
E o
P?OSi\ I K ~ PR+iO
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BoaxBxIIlero IIpx soaAel~cTBr3i~ MoxoMepa xa xoxiteBylo xoHxylo
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snexTponpoBORHOCTHpacTBOpaKOH a.nexTponposoRHOCTH 1%-HOro pac-
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- HHnII TeTpaMepoM.
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70?.
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paTypax BbiIIle xa 200?.
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IIbIX IIpgMexxBIIIgMCx s c~Iy~Iae 8306yTI3JICHa. llpslMOe yiIaCTG]e
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
-+
?MOxoMepa B Hoxxaauxx xoxuenoii xoxxo~I IIapbl OK 6bino Roxa-
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xax IIoxaa'blraez pxc. 3.
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xoxi;eazpaugg xa RBa IIopxRxa. Benx~IHII xaalce.
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pocT ' ueIIH: HO -I- CH2O -~ HO - CH2O ,
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occ g I#payc [19], g:IIpeRxonarasi a = 7 t~ (cynlMa aorlxblx paRlay-
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 Approved For Release 2009/08/28 :CIA-RDP80T00246A010900180001-1
HcxaxcaeT KIIHeTIIxecKIIe peaynbTaTbl, uTO IIx Henbax npIIMeHIITI,.
B KauecTBe apryMeHTa Rnsl pocTa IIoHHbIx Hap.
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c IIso6yTIIneIIOM [5l, a TaxaKe peaynbTaTbl IIneIIla II coTpyRHII-
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peaKl[HHX, KOTOpbIO BEJ~yT K