SCIENTIFIC ABSTRACT MINSKER, K. S. - MINSKIY, N. A.

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• Collection: Scientific Abstracts
• Document Number (FOIA) /ESDN (CREST): CIA-RDP86-00513R001134420019-6
• Release Decision: RIF
• Original Classification: S
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• Document Creation Date: November 2, 2016
• Document Release Date: June 14, 2000
• Sequence Number: 19
• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

Stereospecific Polymerization of Styrene s/o6Y460/000/005/003/009
B015 B058
of the molar ratio of triethyl aluminum to TiCl 3 above 1 : I at a con-
centration of the former of 7% and an experimental temperature of 90 0
and 1200C leads to increased formation of amorphous fraction, but it
does not change the yield of isotactic fraction (Table 2). Temperature
Oith variations of from 600 to 1500C) exerted a marked influence on the
yield of amorphous fraction# but not on that of the isotactic fraction.
The following polymerization conditions are recommended: concentration
of triethyl aluminum in the solution: 5-0-7.0%t molar ratio between
triethyl aluminum and TiCl 3 " I : 1, weight ratio between styrene and
TiCl3 - 12-20 : It reaction temperature 90-150 0C, duration of reaction
3-5 hours. The
synthesis are
product (Table
20 references:
1 Japanese.
properties of polystyrene obtained in the stereospecific
finally discussed and the advantages of the crystalline
3) are pointed out. There are 3 figures, 3 tables, and
6 Soviet, 5 US, 2 British, 2 German, 4 Italian, and
V/
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!UVLYAKOV. A.3.; ZTLIS. V.S.- KINSKIR, I.S.; DBGTTAIWA, L.M.;
FIDOSIMA, G. T. : -~ -
Steraospecifle polymerlution of styrenes Xhim.prome no.5:362-
367 JI-Ag l6o. (MIRA 13:9)
(Styrene) (Polymerization)

RMV, Ye.Ye.; BORT, D.N.; MINSKERp K.S.; KROIRMT, A.G.; TEPLOV, B.F.
1~
I.me data on the crystalline polyvinyl chloride structure.
Zh~r.strukt.khim. 2 no.5:615-616 S-0 161. (MIRA 14:11)
(Ethylene) (CrystaII3)

,;495)4
3119016210041003/0041023
B110/B144
AUTHORS: Minsker,_K. S., Shapiro, I. Z., Razuvayev, G. A.
TITLE: Modification of polypropylene
PERIODICAL: Vysokomolekulyarnyye soyedineniya, v. 4, no. 3, 1962, 351-356
TEXT: The modification of polypropylene (I) was investigated by introducing
functional groups into the macromolecule. The destruction of the hydro-
peroxides,first formed owing to the rather easy oxidation of I, was
possible (1) by graft copolymerization of I with vinyl monomers
polymerizing through the radical mechanism, and (2) by characteristic
I
hydro-jeroxide reactions. Thereby, the number ol - U - n Donds of the
1 V41
unsymmetric C atom, oxidation, and aging are reduced, and ordinary dyes
can be fixed at the surface of newly formed polar groups. I can be graft-
copolymerized with methyl methacrylate (II), with methacryl amide,
methacrylic acid, and acrylonitrile. In the last three compounds,
however, the copolymers are poorly separable from the homopolymers. Tho
graft polymer of I and II can be dyed well with azo dyes, the fiber color
Card 1112-

S/1 qY62/CO4/GO7j/CO4/O2 71
Modification of polypropjlenc- 3110 B 144
being characterized by brilliance and resistance to boiling soapsuds. The
mechanical strength (a) was found tc increase, but the relative elongation
(k) in the case of rupture decreased considerably due to elasticity loss.
Oxidation of I only affected d and L if it 2was protracted (> 6 hrs) 2or
- 0 '~; c'
60 k
combined with UV irradiation (a g1mm 6 - 425 79 kg/mm
350 %). Only surface oxidation took place without secondary aging. The
macromolecular hydroperoxide groups were identified by iodine separation.
Oxidized I was treated for 6 hrs with KI acetate solution at 200C, and the
following reaction took place:
CH3 CH3
I HI I
C C --I + H20 + 12*
1 1
00H OH
The OH groups thus formed were identified by IR spectroscopy. Here also,
coloring with azo dyes was successful, and a and E increased. 1 fibers were
made suitable for dyeing by being treated with nolutions of triethjl
aluminum in n-heptane and with 0.1 N HC1. The initial strength was
preserved, and even partly increased. The frequency 333 cm~% identifying
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34990
S/1 90/6-2/004/C03/01 O/C23
Yrs- 0 B1 1 O/B1 44
MYTHORS: Minsker- V- g., Kronmanq A, G., Teplov, B. F., Rylov, Ye. Ye.,
Bort, D. N.
TITLE: Stereospecific homogeneous vinyl chloride polymerization
PERIODICAL: Vysokomolekulyarnyye coyedineniya, v. 4, no. 3, 1962, 383-368
TEXT: The effect of various polar solvents (nitro compounds, amines,
amides,initriles, ethers, esterap ketones, aldehydes, acids, anhydrideo,
and heterocyclic compounds) on the polymerization of vinyl chloride (I) was
studied to determine the structure of the polymer formed. Polymerization
was conducted for 16 hrs between 0 and 600C in an 112 atmosphere with radical
initiators (a.lo-4 moles/mole of monomer). Films kept at 1200C for 2.5 hrs
were used for the electronoaraphic determination of crystallinity. Only
few dolvents yielded stereoregular PVC structures. Electron diffraction
patterns showed four diffuse rings. HCOOH, CH 3cooii, c21l5Cool!, C3H7Cool!
lead to a higher order of the polymer chain and produce two more diffuse
bands of aliphatic aldehydes yielded cryptalline PV~. Electron diffraction
patterns showed some new lines with d - 5.07, 5.27 A (instead of 5.16);
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s/1 90/62/0,C4/0031/01 O/C27
Stereospecific homot-eneous ... D110/B144
Q
2.52, 2.62 2. (instead of 2.56); 2.26, 2.31 2. (instead of 2.28); 1.74 and
1.60 ?.. Low yields''and molecular weights suCgest: (1 ) that aldeh,rde3
w .0
reOulate the molecular weiGht in radical polymerization of I; and (2) clain
transfer. CHCl 3 and CIII3were used for chain rupture, since the formation
of a regular structure is easier at low molecular weights. PVC with "he
characteristic viscosity of 0.1 was obtained with 1 mole MIC1 3per monomer-
mole. Absence of aldehyde in the system (monomer initiator and aidehyde)
leads to amorphous PVC. Substitution of azoisobutyric dinitrile by peroxide
initiators yielded poorly crystalline PVC. Peroxide on the basis of
butyric aldehyde yielded hiehly crystalline PVC. Electron diffraction
patterns of PVC twice reprecipitated PVC showed further new bands with
Q
d = 1.89, 1.54, and 1-44 A . Free radicals formed by the decomposition of
the hydroperoxide group in peracids initiate th& radical polymerization of
I in the uresence of aidehydes so that addina of initiators becomes
unnecessary. Complexes of aldehyde and vinyl chloride cause the formation
of crystalline PVC. Conclusions. (1) The C-0 [:roups do not affect the
crystallinity, since amides, esters, ketones, acids, and anhydrides are
ineffective. (2) Regularity (but not crystallinity) is increased in the
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S/190/62/004/003/CIO/023
Stereospecific homogeneous B110/B144
systems containing COOII r~roups. (3) Crystallinity is caused by aliphatic
aldehydes only. Stercospecificityie affected by substituents in aldehydes
and acids ((C11 3)2CHCIIO, CM3C0011). There are 1 figure and 1 table. The
reference to the Enj-,lish-languaCe publication reads ar, follows: P. It.
Burleigh, J. Amer. Chem. Soc., 82, 749, 196o.
SUB,1ITTED: February 23, 1961
Card 313

8/190 62~004/010/006/010
B101%18
AUTHORS: Razuvayev, Go A., Minsker, K. So, Fedoseyeval Go To
VITLE: Heterogeneous catalytic polymerization of ethylene in the
presence of TiCl + Al + AM or TiCl + (Al + HC1)
3 3 3
PERIODICAL: Vysokomolekulyarnyye-soyedineniYa, v- 4, no. 10, 1962,
1495-1502
TEXT: Polyethylene (PE) and ethylene.were synthesized at 600C and a
pressure of 10 atm in different solvents to obtain more exact data on the
polymerization of ethylene with a catalyst suggested V K. Fukui et al.
(J. Polymer Sci-, 37, 341, 959; ibid.t 37, 353, 1959). The system
TiCl3 + Al + AlCl 3was very active, wheread its components alone or paired
did not form PE. TiCl 3 + Al which yields small amounts of PEp is an
*exception. For the first, timepthe activity of thJ 3batalyst was found to
depend on the type of solvent (Fig. 1). The catailjA system is assumed to
form a catalytically effective complex with the solvent, where klC1 acts
3
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S/1-,q0j62/004/OIo/oo6/oio
Ifeterogeneoud-oatalytio poi~terization Blui/B186
u'rA;6e and of TiCl M
as activator Vf the Al a and fok(a complexes with
3
3
aromatic hydrocarbons. Hence, the catalytic effect of the system
TiCl 3 + (Al ~--Ucl) was tested, with Al having been"Ilreated with anhydrous
HCl in an a:~&iatic or satuA4ted hydrocarbon medium, 43 Treatment of Al with
HG1 in benzend yielded a y4liowish brown AM de sit which, without
' : 3 V 3 t 11
TiCl was a highly active catalyst of alkylation.tiBenzene yielded
31
considerable amounts of hexaethylene benzene. An addition of TiCl 3 caused
the formationof PE. The cotaplex thus formed, excludes structures causing
alkylation of aromatics. The effectiveness of the system TiCl 3 + (Al + HCI)
depended on tHe contact time of the components befole the reaction. After
a contact timd of 0-5 hra, the ratio PE : hexaethyl benzene was 4 1i0,
after 24 hrs 11 : 70, after 90 hra 75 : 3, and after 120 hra 350 0-
TiCl + (Al 411M) was morelactive than TiCl + AV4 AM ita presence
3 .2 3 3'
intensified the ethylene a4forption. After an add'~Aion of TiCl 30 A'
activated wish HC1 in n-hebtane, did not yield Wlwiiich was only obtained
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3/1 9OJ62/004/010/006/oi 0
Heterogeneous catalytic polymerization ... B101/B186
when benzene was used for the activation, and th was suspended in
n-heptane. Both systems yielded PE with m.p. . 728yatem and with
0 - 1350C'
physicomechanical properties.consistent with those of PE produced with
.Ziegler catalysts. The active centers of polymerization are on the metal
..surface on which TiCl is deposited. Micro- and,macroformationeg fibrilsj.~
3
spherolites, etc were observed, under the polarization microscopes There
are 5 figures and 3 tables.
SUBMITTED: June 10, 1961
Fig. 1: Yield of PE versus time when different solvents are' used.
~Ij Benzene; (2) chloro benzene; (3) toluene; (4) O-xylenel (5) cyclohexanel
6 p-dichloro benzene; (7) n-heptane.
Legend: (a) polymer yield; (b) time, hre.
C1
.Card 3/V

S/190/62/004/012/009/015
B101/B186
AUTHORSs Razuvayev, C. A., Minsker, K. S., Shapiro, I. Z.
TITLE'a Copolymerization of styrene and propylene in the presence
of the heterogeneous Ziegler-Natta catalytic system
PERIODICAL: Vysokomolek~lyarnyye soyedineniyat v. 4, no. 12, 1962,
1633-1838
'TEXTs Styrene and pkopylene in the initial ratio 6505 were polym4rized
in the autoclave at 600C in the presence of TiCl + AI(C it The
2 5 3*
~bove-mqntioned rati6was chosenin order to obtain a polymer the
softening point of which is only slightly below that of isotactic poly-
styrene. Reaults: (1) The polymerization of propylene is anomalously
accelerated in the presence of styrene. The initial product contains
almost no styrene. Only after prolonged heating (10-15 hrs) is a
copolymer obtained, which differs from the iniiial product and also from
a mechanical mixture of the homopolymers. -The.thermomechanical curve for
the mixture shows transition points at 1600 and at 200-2100C, whereas the
copolymer has a softening point only at 195-2050C. The same product is
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3/19 62/004/012/009/015
Copolymerization of styrone and ... BlOlym6
obtained by addition of propylane in portions. This suggests that a block
copolymer is formed. (2) If an aromatic hydrocarbon (benzene, xylene) is
used Ss solvent instead of'a saturated hydrocarbon (benzine, n-heptane),
polymerization in acceleraidd. (3) The rate of polymerization also
depends on the method of producing TiC 13 . The,latter was obtained by
reduction of TiC14 with H2, Al, Sb, or Si. The use of TiC13 obtained by
reduction with H2 or Si yielded a copolymer with s.p. 150-15500 and
relativb breaking elongation of 200-680$, whereas the chtalyst reduced
with Al or Sb yielded a! copolymer with s.p. 195-2080C and relative
breaking elongation 30-70%. This is axplained by the difference in qu,--lity
of the catalyst surface. (4) The softening point of the copolymer depends
on the styrene content. In copolymers.witY, a styrene-propylene ratio >1011,
an amorphous product is formed, the s.p. of which lies below that of
polypropylene. (5) Composit 'ion and physico-mechanical properties of the
copolymer can thus be reFulated by the method of adding propylene, the
reaction time, and the type of TiCl3 used. There are 5 figures and
3 tables. The most important English-language reference iss N.G.Gaylord,
H.F.Mark, Linear and Stereoregular Addition Polymers, Intersci. Publ.
Inc., E.Y., 1959.
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An
Copolymerization of styrene and...
SUBMITTED: July 7, 1961
S/19 62/004/012/009/015
B101YI3186
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RAZUVAYEVI, G.A.; GRAYEVSKIY, A.I.; MINSYFR. Ki-; ZAKHAROVA, V.N.
Syntehois and dow properties of diethaxyalunint, paroxycuma. . .Izv.AN
SWR.Otd.k,hi-.nauk no-9-1555-1559 S '62- (MIRA 15:10)
1. Neuchno-issledovatellskiy institut Irbi-ii., g. GoOkly.
(Aluminum organic compounds)

RAZUVAnV, G.A.; MINSKER, K.S.; KRONMAN, A.G.; SANGALOV, YU.A.; BORT, D.N.
Mechanism of homogeneous radical atereospecific polymerization
of vinyl chloride in aldehydes. Dokl. AN SSSR 143 no.5:1116-
1118 Ap 162. OURA 15:4)
1. Nauchno-isaledovatellskiy institut kbWi pri Gorlkovakom
gosudarstvennom universitete Im. N.I.Lobachevokogo. 2. Chlen-
korrespondent AN SSSR (for Razuvayev).
(Vinyl compound polymers)

S/02 62/143/006/015/024
Bio6jB138
AUTHORS: Bort, D. P., Kronman, A. G., Minaker, K. S., Shtarkman, B. P.,
and Kargin, V. A., Academic
TITLEt Electron microscopic study of crystalline polyvinyl chloride
PERIODICAL; Akademiya nauk SSSR. Doklady, v. 143, no. 6, 1962, 1345-1347
TEXT: Electron microscopic investigations of highly crystalline polyvinyl
chloride were carried out for the first time. To prepare the specimens,
one drop of a solution of the polymer in oyclohexanone was put on the
surface of distilled water saturated with cyclohexanone. The resulting
film was applied to a collodion base. Such specimens were crystallized by
heating to 80, 100, and 1200C for different periods.and were compared
against amorphous specimens obtained by drying the film at room tempera-
ture. In the electron microscope specimens heated to 1000C for 30 min
showed, compact formations consisting of parallel bands, the number and
dimensions of which increased with heating time. In shape, they were
either reminiscent of extended concertinas, crabs, claws, or macro-
molecules in bundles. These bundles were sometimes bent, the bands re-
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5/020J62/143/006/015/024
Electron microscopic study... B106/B138
maining parallel and the density in the bends being lower owing to the
more defective crystal structure. The specimens heated to 1200C showed
basically the same structures. Specimens crystallized at BOOC (near the
brittle temperature of the polymer) showed triangles and rhombs as
morphological formations. Strangely bent stripes and disks always formed
4he background of the preparations. When the surface of the crystalline
foils was etched in dichlorethane, the bands showed a transversely folded
structure (thickness of the folds 300 R, length 600 R). The position of
the folds in the bands fitted very well into the formation mechanism for
bands proposed by V. A. Kargin and G. L. Slonimskiy (Vvedeniye v fiz1ko_ all
khimiyu polimerov (Introduction to the physical chemistry of polymers),
m., 196o, p. lie). After etching, the background surface also changed a
fibrous structure. It is probable that these fibrous structures cannot
produce more perfect shapes (bands) due to the prevailing kinetic condi-
tions. The stability of the crystalline structures was studied by intense
electron irradiation of the film base in the electron microscope. The
crystallites showed high strength in all cases. In crystalline forms ob-
ta-ined from a solution of polyvinyl chloride in dichlorethane, no new
forms were observed other than the morphological ones described. There
are 3 figures. The English-language reference reads as followas P.'U.Tillf;,
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S/020/62/143/006/015/024
Electron microscopic study ... B106/B138
J. Polym. Sci., 24, 301 (1957)-
SUBMITTEDs January 19, 1962
V/
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3/02 62/145/004/015/024
B 1109144
AUTHORS Bort, D. N. I'Ainsker K. B., Okladnov, N. A., Shtarkman, B. F,,
and Kargin, i.~.,'!i=adem~ician
TITLE: Direct formation of secondary polyethylene structures in
polymerization processes
PERIODICAL: Akademiya nauk SSSR. Dcklady, v. 145, no. 4, 1962, 787 - 788
TEXT: Crystalline polymer structures ranging from primary supermolecular
Vo-ms (packets) to.higiner secondary structures were studied directly in
the cour3c. of It-he polymerization. Polyethylene syntheSized in benzene
(600c, 10 atm) with a, catalytic mixture of partially chlorinated metallic
i'll and TiCl3forms a layer fv 4-5 mm thick on the Al surface. This layer
consists of fibers perpendicular to the Al surface with cross-stripes
1-5 g wide. kf'.er dispersion of the fibers in water and separation of the
larger particles, helical bands with distinct transverse folds (3-5- 4-5-4)
of striated structure.(150 - 2501 packets) were observed by electron
microscone. This proves the stepwise development of the supermolecular
S.
.ructure, corresponding to the structure of the crystalline polymer phase
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S/020/62/145/004/015/024
Direct formation of secondary ... B110/B144
according to V. A. Kargin, G. L. Slonimskiy (Kratkiye ocherki po fiziko-
khimii nolimerov (The physical chemistry of polymers in brJef outline),
eo
190 ). The distribution of molecular weight indicates ;hat poly-
ethylene consists of homologs having.an average molecular weight of
100,000. The melting point (121 - 1320C), the heat of fusion (35-9 cal/g),
and the degree of crystallization (67 %) were determined th~ermographicaily.
The density was 0.955 g/cm3. The assumption of V. A. Kargin, G. L.
Slonimiskiy (Us?. khim., 24, 785 (1955)) that internal stresses affect the
3hape of the crystals is confirmed. There are 3 figures.
SUB.'JITTED: April 6, 1962
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3/020/62/147/003/026/o-, T
B101/B166
AUTHORS% Razuvayev, G. A., Corresponding Member AS USSR, Minsker, K. 51
Chernovskaya, R. P.
TITLES Xffect of organic compounds with a closed conjugated system
of T--bonds on the stereospecific polymerization of propylene
PtRIODICALt Akademiya nauk SSSR. Doklady, v. 147, no. 3, 1962, 636 - 638
TEXT: The effects of compounds containing conjugatedIr-bonds of benzene,
diphenyl, naphthalene, and anthracene were at 'udied on the basis of the
effect of styrene on the polymerization of propylene with Ziegler catalysts
as studied in previous papers (Vysokomolek. a*oyed., 4, no. 12, (1962)).
For this purpose, the k 9/k0 ratio was determined, where k 9 is the constant
of propylene polymerization in the presence of the aromatic compound, and
k is the constant of polymerization in a pure aliphaSic solvent (benzine,
b?p. 96 - 1020C). Polymerization was conducted at 45 C, a propylene
pressure of 4.5 - 5 atm, and a catalyst concentration C TiCl 3 w 0.0265mDkWl-
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S/020/62/147/003/026/0-7
Effect of organic.compounds with a ... B101/B186
Figure 1 shows that the polymerization rate is decelerated by small addi-
tions (0.3 moles/1) of aromatic compounds, and is accelerated by higher
compounus. Anthracene additions could be used only up to 0.1 moles/1
owing to their poor solubility in benzine. A complex with intensive donor
or.acceptor properties is assumed to be formed by. aromatic hydrocarbon and
one catalyst component. The equlibrium of this reaction depends on the
structure and concentration of the additive, thus affecting the electron
state of the active cen.ters, and their ability to initiate polymerization.
There is 1 figure. The most important English-language reference ist K.
Vesely, J. Ambroz et al., J. Polymer Sci., 55, 25 (1961).
SUBMITTEDt August 29, 1962
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ACCESSION NR: AT4020699 S/0000/63/000/000/0045/0047
i AUTHOR: Minske K. S. ; Kronman,'A. 0. ; Sangalov, Yu. A. ; Bort, D. N. ; Razuvayev,
G. A.
TITLE: Crystalline polyvinyl bromide
SOURCE: Karbotsepny*ye vy*sokomolekulyarny*ye soyedinenlya (Carbon-chain macro-
molecular compounds); sbornik statey. Moscow, Izd-vo AN SSSR, 1963s 45-47
TOPIC TAGS: polymerization, stereospecific polymerization, crystalline polymer, block
polymerization, polyvinyl chloride, polyvinyl bromide, butyraldehyde
ABSTRACT: Crystalline polyvinyl bromide was prepared by homogeneous free-radical stereo-
specific polymerization at room temperature in a butyraldehyde medium. After 5 hours,
the yield of polyvinyl bromide was 5-6% with a 0. 02% active oxygen content in the aldehyde.
The resulting polymer w.an a white'powder with an absolute viscosity of 0. 912 cp at 20C in di-
chlorethane. The absolute viscosity of highly crystalline polyvinyl chloride obtained under
the same conditions was 0. 939 cp. X-ray patterns of annealed unoriented polyvinyl bromide
films obtained by block polymerization and by the polymerization of the monomer in a butyral-
dehyde solution are given. The maximum degree of crystallinity of polyvinyl bromide was
obtained at a molar ratio of monomer to aldehyde - I : 1. Addition of water and'alcohols to
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ACCESSION NR: AT4020699
the homogeneous stereospecific system produced a strongly amorphous polymer structure.
By polymerizing the monomer in ether solutions, a sufficiently high degree of crystallinity
Orig. art. has: 1 figure.
could be retained.
ASSOCIATION: Nauchno-isoledovatellakly institut khimli pri Gor1kovskom gosudaretvannom,
universitete im. N. 1. Lobachevskogo (Scientific Research Institute of Chemistry, Gortkiy
Soto University)
SVBMrrTED: 09Apr62 DATE ACQ: 20Mar64 ENCL: 00
SUB CODE: OC NO REF SOV: 006 OTHER.- 003
Caird 2/2

4i
L-5
AMMSION XRs AP3000689
AMOR-. Wasker, K. 0. Tot'razavaYevi G~ A.
TMX: The role of the hatero Ion
-mcamponent In stereaspeciflo ]Robmrl 1 4
'ziefier-Iktte. catalyitis
BOOM. _vYlackmolakulyarny" "dinenlyas ,V' 9630 655-658
ITOPIC TAGSs ~.cataljtic-aotivlty, hetero--oaqxment, stareaspecific Polywrization-
activation of bonds etyrene,'VICOL sub, 3,, Cr(M sub 3,'prqpy1ens,, ethylene
~,]AtSTRACT: Thavresent vork. was carried aut~because'.Qr the scarcity or information
-Al A.-,
ron th 'catautle performance of the alpha." ficatIon.of TICLsub 3 aad.the
purpi
y1ene,
and pit tfication ot CrCl sub 3 In Initiating the polymerization of 6th
styrene ',\The polymerization of ethylene was conducted In metaIll
nd
reactors,, liters In bapacityl, that of propylens and styrene In ampules. A
;nonstereospecIflo polymeiftation was obtained,, accompanied by the formation of
-low-moleculw reaction products,, confirmed by *4 electroacamo Th~ thaory, is
iadvwced Thai. -a of-the-
4tivatiou double bonol occurs amcberloorption of tha manomr
Tiby the active haterogeneous catal,".t -centers 11!he doubllng'of the yield In the
~presence of benzene lends support to this Z;;ory. Orlg* art. ban: 1-table and 3.
;figure* Scientific %search Ihst. of Chardstry, Gorkiy State Un.

-L 1707"3 M Pc-4/Pr-4 RH/WW/JD
FWP(J)/EPF(c)/tW(q)/EW(m)/BDS
S/020/63/149/006/018/027
71
-AWHCR I.Iinsker,_ K8 Fedoseyevaj, G. T Vorob yeva, N A.., and Corresponding
M!ft WAcademy of sciences USSR G. A.
SOURCEs., ANSSSR, Doklad:t, v. i49, n*. 6 P. 1351$ 1963
RQI=ri=tIQI4of _2thylenelon a chlorinated mixture of titanium and
o aluminuln,
By:polymariziing ethyleneat-1-ni pressura in the presence of a chlorinated
mixture of titanium -and aluminum the authors obtained a'hidi yield of solid poly-
ethylene witL a pour point of 120-135*C- The titani=. -al:uminun mixtures used for
this.purpose~vere prepared from 0(-TiClo + AlC13AAl.,t 0,(-TiCI3 (Al i- EC1) j and
,treated vith,chlorine,before being.useeas catalys 'he polymerization. The authors
-coneliiAethatin the process of the treatment of tthe e of metals Ali- Ti.vith
,:,hydrogen.,chloride-or chlorine in benzene there forms a new type of an active ethylene-
polymerization catalyst ,.Iiose structure most closely approaches the formAa
(Ti?_"A-12C181 I ~C6n.,. In this connection the, form1tion of phenol is occasioned not
by.the oxidation of0the aryl-metal M.-Ph by oxygen but by the wddation of benzene
-in the.presence of AlC13 and titanium chlorides..
sidi~. : J'Une 25., 1962
card i/I

MINSKER K S!; GRAYEVSKIY, A.I.; RAZUVAYEV, G.A.
Polymerization of methyl wthaerylat.!g in the presence of organo-
aluminum compounds. Izv.AN SSSR.Ser.khim. no.8-.1483-1487 Ag
163. (MIRA 16:9)
(Nothacrylic acid) (Polymerization) ,
(Aluminum organic compounds)

MINSKERP K.S.; FEDOSEYEVA, G.T.; RAZUVAYEV, G.A.
Role of the heterogeneous component in stereospecific polymeriza-
tion taking place in the presence of Ziegler-Natta catalysts.
Vysokom.soed. 5 no.5:655-658 My 163. NIRA 17:3)
1. Nauchno-issledovatellskiy institut khimii pri GorIkovskom gosu-
darstvennom universitete,

RAZIIVAYEV, G.A.; MINSKER, K.S.; FEDOSEYEVA, G.T.; SHTARKMAN, B.P.
HeterdgOneoue catalytic polymertz~.tion of ethylene in the presence of
the m6til - metal chloride sy4tqm. Vosokom.soed. 5 no.9:1371-1375 S
163. (MMA 17:1)
1. 9&11~~A4-issledovatellskiy institut khimii pri Gorlkovskoin gosndarst-
vennon universitete.

RAZUVAYEV, G.A.; MINSKER, K. -S.; KRONMAN, A.G.; SANGALOVp Tu.Ai
Stereospecific effect in the homogeneous free radical polywrization
of vinyl chloride in aidehydes. Vysokom.soed. 5 no.1121615-1619 N
163. (KIRA 17:1)
1. Nauchno-tooledovatellskir institut khimii pri Gortkovskom
gosudaretvannom universitete imeni Lobachevskogo.

)UNSKER., K.S.; CHERNOVSKATA, R.P.; ZAKHAROVA, A.S.
Kinetics and mechanism of propylene polymerization in the pre-sence
of styrene on the oC-TiCI3 + AlR3 system. Vysokom.soed. 5
no.11:1627-1631 N 163. OURA 17:1)
1. Nauchno-isaledovatellskiy institut khimii pri GorIkovskom
gosudarstvennom universitete imeni N.I.Lobacheyokogo.

RAZUVAYEVV, G.A.; GRAYEVSKIYp A.I.; MINSKER, K.S.; BELOVA, M.D.
Oxidation of aluminum alkyls. Dokl. AN SSSR 152 no.W14-116
S 163. (MIRA 16:9)
1. Chlen-korrespondent AN SSSR (for RazuYayew).
(Aluminum organic compounds) (Oxidation)

TIM: Catalytic systems for the polymerizationlof ethylene
BMWE: fleftekhimiya, Y. 4, no. 4, 1964, 372-575
TOPIC TAOS: catalysis, polymerization, ethylene, aluminum, titanium, chloride, Po
ethylene plastic, poliw-rization kinetics, macromolecular chemistry
Abstraef: The polys-eirlisition of iihylene was studied on catalytic b'ystams
produced by thda reaction of titanium trichloride with chlorinated aluminum
or by joint chlorination of titanium and aluminum In bezene. A mi-xture of
- - I A-1-11__,A_ - -A . I - " -,.- - k I -- . A- , - ~ I. ( - ~ 1, --- I "-,. , I . . +- f

L 36474-65
-=as W,
ifAto
periodat a br ef incr6aae in the rate, constant po y
1,merinatLon rate at a maximum value, then a decrease in the polymerization

q6ir-ULUUMAII&F APA~ -k#Cl& %-- VA,-LIAM- =U I. GAY %oula, 4W.
formed. The apparent actLvatLoneneegy of the polymerization of ethylene was
12.8 kcal/~iole. The properties bf the polymer obtained were enalogous to the
properties of polyethylene produced in the presence of a Ziegler catalyst
?'TC2115) Al + TiCI47..
3 ga'art. has 2 graphs and 2 tables.
AS=IATIOlf.- none
SUMUTMOt U6"3 ENGLi 00 SUB COM OC, GC
No ~-AWIVV OTM., 002

AccFssiox NR: AP4ol7626 -s,/C-)1-90/64/006/002/0189/0192
X. S.
ALMHORS: Kargin, V. A.; Bort, D. N.; Shtarkman,, B.
TITLE: Supermolecular structures arisi4 directly in the polymerization process
SOURCEs Vy*sokomolskulyarr" sayedineniyas ve 6p no. 2j, 1964,0 189-192
TOPIC TAGS: polymerization, polymor, polyvinylcl-aoride, polyethylene,, super-
molecular formation, catalyst, alumimun,, chlorinated aluminumj tape formationp
fibrillar formation., fagot, fibrillar orientation., solution., film., suspension,
folded structure,, crystalline structure
ABSTRACT: This investigation was conducted on crystaLline polyviny1chloride
(obtained in a butyraldehyde medium) and on polyethylene prepared in a benzene
medium, In both instances partly chlorinated aluminum in combination with the
alpha-alpha modification of titanium trichloride was used as catalyst. The
obt~fdned polyvinylehloride was dried, ground in a porcelain mortar, suspended in
aqugous alcohol, spread on a collodion film, dried and subjected to examination
on a Teala-24M electron microscope at a 10 000-20 000 magnification. The poly-
etlV~ene was split into fibers by means of a'needle,, and treated as in the pre-
ceding cane. The electron microscopic picture of polyvixWlchloride showed that thi
Card

ACCESSION NRs AP4017628
particles consisted of fibrillar aggregate formations, the structure of which
resembled accumillations of tapes-and macrofagot packages. The authors assume that
these structures were formed directly during the process of polymerization and wer,
reconstructed only in the course of the subsequent procedure. Samples of Doly-
etlWlene showed a similar structure but -,-ere more distinct. Here the tape .0-
formations revealed distinct transverse etriations of folded fibers 150-200 A in
diameter. Another structural type of polyethylene was dendritic,, seemingly growin,
from the bit of alumimm. Similar structures were also obtained fr= solution in
ortho-.Vleno. Orig. arts bass 3 pictures,
ASSOCIATION: none
SUBHITTED s 3OJun62 DATE ACQ: 23mar64 ENCL: 00
-SUB CODE: CH NO REP SOV2 018 OTHER: 003

MINSKER,-.K.S.; SANGADOV, Yu.A.; GRAYEVSYIY, A.I.; RAZUVAYEV, G.A.
Low-temperature polymerization of vinyl chloride in the presence of the
system organoaluminum compound - oxygen. Vysokom.soed. 6 no.2:269-273
F 64. (MRA 17:2)

CHF01OVSKAYA, H.P.; LEBEDEV, V.P.; RAZUVAYEV, G.A.
Copolymerization of propylens with styrene in tho preaence
of OC-TiC1 3 # Aa(C2H5)3* Vyaokom. soed. 6 no.70313-1317
Jl f64 (MIRA 18v2)

SANGALOV, Yu.A.; HINSKER, K.S.; RAMVAYEV, G.A.
Catalytic activity of the evatem aluminum - organic acimpound -
peroxide. Vysokom. sood. 6 no.7tl323-1326 JI 164(KRA 18:2)

ACCESSION NR-. AP4045432 S/0190/64/006/009/1656/1661
AUTHOR: Chernovskaya, R.P., Minaker. K.9., Roauvayev, G.A.
TITLE: Nature of the modifying action of aromatic compounds on the stereospecific
polymerization of propylene
SOURCE: Vy*ookomolekdyarny*y.e soyedineniya, v. 6, no. 9, 1964, 1656-1661
TOPIC TAGS: propylens,'propylene polymerization, stereospeQUic polymerizatio n.
benzene, naphtriethyl aluminum, alkyl aluminum, thalene, ti um trichloride,
poly7nerization catalyst tall
ABSTRACT: The effect of naphthalene, a very effective modifier, on the catalysto(-
TiC13 + Al (C2H5)3 was studied during the stereospecific polymerization of propylene,
and the relative propylene polymerization rate (k.:Iko where k. and ko are rate constants
in the presence and absence of naphthalene, respectively) was plotted against both C
OHS
concentration and Me molar ratio of Al(C H MCI with a constant TiC13 c0nt"1,1
with an Increasing molar ratio of,wmlt~zs 3
3- ?iC13, a smaller amount of C, 6 to
needed to Increase Me polymerization Me. A plot of do polymerization rakc-
catalyst eonioentration and do molar ratio of C1009: catalyst showed that naphthalene.

ACCESSION NR: AP40415432
increases the activity of the catalyst. Two series of experiments were carried out to
clarify the fole of each catalyst component. In the first series, the concentration of
alkylaluminfim was varied with a constant TiC13 and C content; in the other, the
amount of TICI was varied with a constant ampunt of 10, H and C H . It was
( 2 3 10
found that lie Arlation in the AI(C2H5)3: C10H ratio plays emore ImpoXint role than-
the variatiop in the TiCI3: naphthalene ratio. An increase in the AI(C2H,5)3, concentra-
tion above A certain value decreases the molecular weight of the polymer, ihd In the
presence of C 011 the molecular weight decreases more sharply. IMe proportion of
isotactic fricaon U the polymer obtained in th~ presence of C, A varies relatively
slightly with an increasing concentration of AI(C2H5)3. With varying TiC13 content
in the presence of C 01189 the molecular weight of polypropylene remains almost un-
changed. This reaj can be explained by the essential role of the surface electron
defects and the impurity crystals in the mechwdsm of polymerization. Most probably,
the System ~71CIVAI(C0115)3 - aromatic compound to an equilibrium system in which
alkylifindf6m, aromatic compound and their.comples in solution are adsorbed to the
surface of the MCI . 7be strength of their bond with the active centers of the 7IC13
varies. -ne vari;Jon in the activity of the catalyst with the concentration of aromatic

ACCESSION NR: AP4045432
compounds in discussed In detail. As expected, in experiments with C H in the range
of maximum catalytic activity, the degree of stereoregulation Is lower Van' that found
In parallel, experiments Without naphthalene. On the other hand, for varying TIC13
content, an Increase in the amount of TIC13 at a constant coneentratidn of AI(C2HSb
and C10118 (L 66 mole/liter) leads to dispropoytionation of the activating portion of
naphthalene. With a decrease In the TiCl content, the activity of the modified catalyst
decreases. The concentration of very active centers increases more,-slowly than the
total TiCI content. Thus, the variation In the relative rate of polymerization depending
on the mofar ratio AI(C ji5)3- TiCIA - is smoother than that due to a varying concentration
of AI(C2H03 at a cons;&t Zount o? TiCI3- When experimental data ~Rr coarsely dis- ,
persed TiC13 (8=12 m2) and TIC13 ground in a vibration mill JS = 18 m-) were compared,
it was found that the position and size of the rate extremes and the other characteristics
of the proceed depend on the individual specimens of TiC13 emPlOyOd- Orig. art. has:
6 figures.
ASSOCUTION: none
SUBMn"XZD:. OMM ENCL: 00 BUD COD91 OCO MT~
NO REr save. oos OTHER:'007
Cwd 3/3..

ACCESSIOR NR: AP4019979
8/0020/64/154/000/IMM/1401
;AUTHORgs Razu"YeTt G.A. (oorrespondlug 11ftbor)$ np~Lr~a, K.B.;
SMS&IOT# YU*Ae
TITLE: , Polynerisation of am* olefing &M vjUyjL monomers is djethyl
butens_l-~,yl.lwajus1UUM (DIDA) In the PrOBOX09 of tltwdva balides
~30URCZ: AN SSSR- Doklady0o Y-154, no.6. 190, 1398-14oig insert f&.
cing P-1329
TOPIC TAGS: POlYmOrIzatlon oleflne monomer,, vinyl monomer, diethyl.
bitenealumlnum, titanium halide, slectrophilic property..
'ABSTRkOT: The CatlytIc action of DEM In a polymerisatlon reaction of'z
some monomers van studied. The catalytic system on a D3BL bass com-
bined with titanium chlorides possesses unusual properties which per-
mit both the polar and nonpolar amers to be polqnsrIxede Such beha.~
yLor can be szplained. by a reduatlon of Its olectrophilic pro arties 1
.(as compared to trIeftylaluslum),, as wourred :in the use of 10295)2LIt;
0005 or (0245)Ul with additions of don agenti#' Sao, properties
i cmd I/:R.

ACCESSIOR JIR: AP40199T9
of DZU Include both the properties of Its hydroxy and halide deriva-
tives. Such a peculiarity of properties of the unsaturated alumilnum-
organic compound signifies that the catalytic systeang while being ao-1
tive In olefinio polynerixatlon, are also ospable of amsing polynaft-,
zation, are &Lao capable of causing pol4nerloation of polar nonmerse
grig. art. ~ has: 4 f1CA"sq I table
ASSOGIATION: gone
SUMaTM: 20NOvG3, 1122 AGQ: 2XAr64 MOW ~.'00
IM RW sov:~: 61,F.,
W13 wmu %,02=1, 001
'CWd'- 2/0,

SOURCE: AN SSSR. Doklady*,. v. 158, no. 1, 1964, 170-172
TOPIC.TAGS: ~ v chloride':, polymerization, polymerization initiation, triethyl-
aluminum catalyst system, titanium trichloride catalyst system, chloroorganic
catalyst system, polyvinyl chloride, catalyst
--the-viny~,chl
-ABSTRACT-:~---The,-initiatidri~of oridd--pplym -by the'.
eriza-tion reaction.
I- u _68A)
---iftteeidi6n, 6fAe. et -minum: t certain halo rgan ,a compounds was
studied. Vinyl chloride did not polymerize in the presence of TEA-TiC13 and
non-polar hydrocarbons. Polymerization with yields of 4-516 to 80-8510 was ob-
tained in TEA-TiCl3_RCI systems (RC1= alkyl or aryl chlorides and di- and poly-
chloro derivatives of saturated and unsaturated hydrocarbons). The compounds
cad 113

L 1959.0~65
containing d;h'e'micaUy Inert chlorine atoms did not initiate polymerization; the
activity of the chlorine increased in the following series:
C H Cl,