SCIENTIFIC ABSTRACT KLEBANSKII, V.A.L. - KLEBANSKIY, A.L.

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CIA-RDP86-00513R000723010010-7
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RIF
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S
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100
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December 30, 2016
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June 19, 2000
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10
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Publication Date: 
December 31, 1967
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SCIENTIFIC ABSTRACT
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M. -U&0 is Applied 92 U946) The object of Me work is the elaboration of methods of obtaining diviMlacetylons derivso capable of polymerizing with the fomtion of filn- forming substancov which would be of greater tech* irportance than the divUWl- acetylene polymer, A table is given of the 6 theoretioally possible Du others of divinylacetylone, namely 10 CH CHsCsCtCHCH2OC4Hq (l 6 isomer), CH31CHCHIC- (OC4Hq)CHr CH2 0-0, CH)MICSC?;~~;q)CHICR2 (1-09 C4H9W~CHtCtCHCHtCH2 (4-1)9 CH3GH(OC4Hq)CICCHtcH2 (4-2)) and %H~=2CH2CiCCHiCH, (2-1). Structurowas studied by oxidation; oxidation with Pln%showed that the I lo 3 lo and 1 6 derive. vere important. A. S. 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V. 17479). Aw. I P. 1430,1440 00 . *("PMWMi$ MINE IbAb ww1h, 400 t"r W-molish"Ir tbr law"Wrl"am Ot Avilljrl 000 Oov hoj -w eas for b"h "Wi". 20 C 001 rw 000 ago* ICAIOV 6 909 $014" wit ON 1 is . foe 4169 Goo 0*0 0*6400:6*69006 000000060000 . A- L. ~ rf) -its ana Milo 1~114111111 Is Is M Irnflev's x1mme (C..J. 29. 711117) he Ilollymer oattlon f4 co'clill-I ill the twt-4t3wt C4 StrMst twtd%. larmiallon of MKIM frotu Wh In ao:441 *+t. he isowmA to istottv I TqAtIlly hydrAY10140 vhfyl ftlefs of 4k % yjrhl, 44 MCC fo lift tViVif. jittolt, C1111 MO;A"l at J.'Y" jave tntly Mccift). The rule n( heavy MrIni Ralt talaly%l% Ill asitilmorwi its the main to an it"row of The silly. 0( Cjfj lIMWgI1 wish No (it the 141110 1~2. at On". with CUA) 01111061vostj Id formation of romp" em"4%. of cill, Rawl the me-tat - anti to activatlon of MR, C if rt*lflor ill It"PAtIrm C4 11t 71111:; the C-1111 fftwied I" mle mo trP at ertilat of ' . . l f an H Simi of Cliff. frftcrfivl- C.O.Mytits arr. "Itt; jig, TW ~. (;L4 Witio %ithmi CtsA)) vrith a ~Jtlkj 44 7% McC110. lInlytowtimikon is ft-iluctA w-LA4krably. ;kPA Wjj of 7n. Col, awl ri tirnlarly Cot tow) As. In The Ill -ft"ll it *fill poloitcrigallots 11( uill phikw (he Vi(ht of httCI(O In thr gAi 1+4104!; (It X'W C i . j fflnrillatt!l f- M1136011 Of 16tt!CII(J; Wish 10 1I I im IG110, on a wAid cattirf, Ill-- yield of Me II( ' " 2 . S * M% 10141111 tt*Mt to thl! CjItj P*Md, In 01 lkillstk 19" VWSS. alid, rcf4w" to the C-11, reaefed. With a tails. lyst of 11410, awl a mitt. 4 Zn mul At nt Cti Wts ons so soud t%tro-ler ("wilem oll i0ica oirl). at V&-3ldn'. with C.Its 4111(l. Wkh I Ito * , ~-x ill the ". fStia 1: 10 and with No Its the rotfilt 1:2 (gvt rnit(. rnotic. 5 vvil. WV C111r), tN &Y. 11 h (: l1 Id o d f M t h e re"Vto to t & Pointe o ec l is Ylv 0"t, wit i . 1 Thii i c r i le r*c1cd. 02-W# wiff I rrvmt it) f '1 Ant 1 entalslu protht"d NO g. MCCRON./j. c3oatyd at a rwluct 11M of 0.2 W N. Iflot'M "0 Sowsisirip 41 P*Wwo of RJ &a 20, 111442*11611. M 1441 ow 1.4 - to op iali"Isr. orAof -4ol.1so rumfolt "bra pft"I. In wMal*w w No 4:06.w", 4w"w. 00ift 114,440praoft pow IWi C11,41. 41 11, llcq%ll. Sow U-7111i owdek ". *kWh io"Ir. IkAf MW I.:, sm1word"IWO tAlwo V1W* Ak" ottle thir mme cwwm~ 1.4~km. The I f 44 obf 1.2.3-flich8we Aftb% i-wift"AOIC1106(for"AlwWrt"I f4do"Olsoulf. OffilliMI1111)$ III OSOWY44 WASMIrOl 13; "Wiful 1.4. .1tw4we ow lbw e4fly Owyow" f we~, cropirom 0. Sook .t"M$6104 PAY11" ~1 MRIAM 14MW INOMOW41 I-' frAtIMM Palms$. ot Sh"11 hv it. towdy. rbr -da "ibi *.uU$fd *JW 110"UtOr. bkftIi(WSI A* sot, avkl &- 14* As -h G. M. Law&pd -,0" "M 4" dk-- R 246 -C 44' KL f A vrtl-~tc of a qfi*a of diottislIve* brn"d an a 4-diWwa- of f4~ xt m v CA." 4", U~mrit furm RSH jv?d --arvq~ tip --i'-4 Willa V L ~- ,p IN ii -S %nickel skeleton-> platinum black catalyst, which Is in contrast with references 5 Card 1/3 and 4o The hydrogenation with the palladium catalyst in the SOV/79-29-3-16/6* 61ftift tt' o Pi#* XeAc~ Rules of tho soioiTive i;yjTLen4aM1?on. of Vinyl Acotylene in Solution vapor phase at 1300 was not possible owing to side rosotf,1100 Therefore tho hydrogenation of vinyl acetylene was carried out on the palladium catallst with finely powdsr*l allies, Sol as carrier, It takes place in the first stop of the process on vinyl acetylene and on hydrogen. In the kinetic range of hydro- genation the reaction 'rate is directly proportional to the quantity of the catalyst and does not depend on the intensity of stirring of the solutions In the diffusion range an the hydrogen the reaction rate Increases proportionally to the In- creasing intensity of stirring of the solution and does note depend an the quantity of the catalyst* In both hydrogenation ranges the reaction rate increases proportionally to th*ln- creasing partial pressure of the hydrogen. In order to find cut those conditions which product the highest selectirity in tha -process and to facilitate tho,!:paration of the principal product of the reactiong the inyl# (butadion*-193) In a puro .atatoj the composition of the reaction products obtained at different intensity of hydrogenation was daterminedo In the Card 2/3 initial stage of the process, up to a hydrogenation intensity SOV/79-29-5-16/6*11 4&Wy%d *dropastion of VJVIAtetylene I.Ueneral i6inetio Rules of the Solectiyo Hydrcgenatlorn of Vinyl Acetylene In Solution -30~ (calculated with Tespect t4 the acellylene bond) *.h~ affiliation of the hydrogen was foun4 to take place mairly ti~ the triple bond# On further hydrogenation in addition to 44his affiliation a hydrogenation of the divinyl being form,~d takes place wherein the reaction proditts represent a veri comploi mixture of hydrocarbons which are difficult to separate. By hydrogenation of the mixture of vinyl acetylene and diviny'l the above mentioned reactlon charaoter 'was zonfirmed. On a low intensity of hydrogenation (up to 30%) praQti~~a','Y C-ly il- vinyl Is obtained# There aro 4 flg~;res., 2 tatlaq, :%M -9 re-f- erences, 5 of which &To Soviet. ASSOCIATION: Voesoyuznyy nauohno-isslledo-rat~~*,'-skiy 'natitut sittettcbeskogo kauchuka (All-Union Scienttfl;.a Researc; Ine'.141-.1ta 'Of syrthoWc Rubber) SUBMITTED: February 3,,1958 Card 3/3 AUTHORS: TITLE: PERIODICAL: ABSTRACT: Card 1/3 Oarmonov, 1. Vt-K-1ebanekJy# A# L-j Chavychalovs, X " K# the Catalytic Xyd"gamtlcu of Vinyl (Katall t1oheakoye gidrirovaniyi~ -tin.11- atsetilena a isellyu poluohe;.iya divinila). I* Influence . A Exerted by Various Factors Upon Rate and.Selective Sohavlwr of Hydrogenation of Vinyl Aostylono (1.*Vliyaniye rat'lichnykh faktorov na skoros'ti lzbiratellnostf gidrlrovaniya atsetilena) Zhurnal obabohey kh1mii, 19501, Vol 29, Mr 3, m830-836 (VSSR) In the present paper the authors present data on the influence exerted by the nature of the carTier and solvent, the reaction temperature and the intensity -if the mixing of the solutlon upon the rate and the seloo.1-live tehavlor of the hydrogenation of vinyl acetylene. In order to itvestigate the Influonce t~f the conditions at the preparation of the catalyst and that of the character of the carrier upon the rate and the seloctive behavior of this hydrogenation, experiments with palladi= on oil'ica gel, with barium sulfate and with polyvinyl alt-thol wet* carried out. It was found that a zodification of the preparation conditions of the catalyst and of the nature of the carr-14r SOV/79-29-3-17/61 --Precaution of Divinyl by, -t1i*jrAt&1j+A* Hydrogenaticn, of Vinyl Acetylene 1. Influence Exerted by Various Fac tura Upon ilatc- and Seloctly* behavior of Hydrogenation of Vinyl Acetylene influences the reaction rate, but that the selective behavior of hydrogenation is not markedly influenced ty these modif cations. The results obtained theoretically completely Cor- respond with the publications available in this field (Hof 2). From among all factors Investigated the intensity of the sizing of the solution and the percentage of the quantity of the medium exert a noticeable influence upon the selectivity of the reaction* At a low intensity the'reaotion did not proceed selectively* In the alcohol solution with the pH > 7 the re- action proceeded more rapidly but with less selection than In acid and neutral medium, The determined hydrogenation character of the dissolved vinyl'aostylene in the presenoe of the pal- ladium catalyst as well as the determined dependen" of tb* selective behavior of the process on the intensity of the. mixing of the solution completely agree with the absorption theory concerning the catalytlo hydrogenation (Ref 4). Card 2/3 There are I figure 5 tables, and 5 Soviet referenc*so -40V./7 9 - 29 - 5 -17 /61 Pr4polation Of Di'vinyl by tbw 4aitaiytio' Hydropation of VIMV Addrt7lsw it Influence Exerted by Various Factors Upon Rate and Selective Behavior of Hydrogenation of Vinyl Acetylene ASSOCIATION: Vaesoyuznyy nauohno-isoledovatellskiy institut sinteticheskogo kauchuka (All-Union8:1entific Research Institute of Synthetic Rubber) SUBMITTED: February 31 1958 Card 3/3 15.9210 75679 SOV/80-32-10-28/51 AUTHORS: Klebanokly_,_A. L,j Timoreyevj 0. A. TITLE: Emulsion Copolymerization of Hexarluorobutadiene With Diene Compounds. Communication II PERIODICAL: Zhurnal prikladnoy khimii, 1959, Vol 32, fir 10, pp 2294- 2299 (USSR) ABSTRACT: The study deals with the comparison or the reactivity constants or solution copolymerization and emulsion copolymerization or chloroprene with hexarluorobutadiene, and with the characteristics or copolymers thus obtained. The experimental part was described-prevlously by the authors (in thid journalo 1959, Vol 321 Nr 9). Esteramine (eater or diethylamInoethanol and lauric acid) was found to be the most suitable emulsifying agent, at an optimum-con- centration of 5%. The rate of polymerization Increased with the acidity of the water phace; the optimum value was PH.- 3. The optimum ratio of the water phase of the mono- Imer mixture was 2*1. Among copolymerization catalysts, IK S 0 was the mo;t effective. The rate of p;lymerization Card 1/3 10c9sed with catalyst concentration; It depended also on Emulsion Copolymerization of Rexariuorobutadiene 75679 With Diene Compounds. Communication II 50V/80-3)2-10-28/51 the Initial ratio of the monomers. The reaction slowed down with the Increasing hexarluorobutadiene content, and increased with rise in temperature. The polymerization. constants or emulsion and solution copolymevl~:ation de- termined on the basis,or experimental data had practically the same value; this confirmed the authoro' a3sumption that these constants do not depend on the manner In which the copolymerization Is conducted. It was aloo established that the tendency to the alternation of chloroprene and hexa- riuorobutadlene molecules In the copolymer, as well as the tendency of ttexarluorobutadlene molecules t'o JoIn toGether, increased with the concentration of liexat'luorobutadiene in the initial monomer mixture. Copolymers of hexafluoro- butadiene with fluoroprene, Isoprene, and chlovoprene vulcanized at a high rate. It would be of Int.-ce-cst, there- fore, to Investigate the feasibility of vulcanizing fluorin- ated olefins by incorporation In the chain of small amounts of hexafluorobutadiene as vulcanization Inducing agent. V. H. Kartsev and F. Ye. Berman cooperated In the preparation of Card 2/3 copolymer samplen. Vtcrf~ are 10 rf~fert%nces, &wlslon Copolymerization or Hexa- 75679 fluorobutadiene With Diene Compounds. SOV/80-32-10-28/51 Communication Il I U.S.j ana 3 Soviet. The U.S. reference Is F. R. Mayop Ch.'Walling., Chem. Rev., 46, 2, 191 (1950). SUBMITTEDt August 9, 1956 Card 3/3 3/138/60/000/007/001/010 4051/AM AUTHM t Xlebanskly# AL., Zartseve VN., Yomina, i.?., Tr*nke. YA.V. 1 -7 1jr Tr= I The smat or Admixtures Prisent In Chloroprsno_op the Staullity of NaIrite PMIOMCALs Kauohuk I RosIna, 1960, No. 7, PP. 1-3 t In the Present u-tialo the authors have submitted data collected tzon a study of the effect of sionov1nylaortyleno, di"Uc*tylene and air oxygen aftixtures on the properties of,nalrlt** In addition to this, the effetts or I- ron malts on the polymerization process conducted In an toulsion WO on tbe aging Process were determined for "1t concentrations of 0.02 - o,2%, Although the ef- fect of admixtures such as those investigated In the Initial ohlorepreno monomer were previously studied andfowtd to have the most, harmful effeot on the proper- ties of rubber, for polymen of chloroprens, however, obtained by the pDlyftriz&- tion process in an emulsion, this "peat was not sufficiently clarifted. The presence of 0,1 - 0.2% monoy Iny lacetylene admixtures in chloroprene was invosti- gated and found not to have any effect on the natrito properties in th1s ton2ea- Card X/3 S/138/60/000/007/001/010 A051/AO29 'The Effect of Admixtures Present In Chloropreno on the Stability of Wairit* iration, lmsrg~r &w=tx were not considered since they actually do tot, occur In the monomer (Fig. 1). An much as 0,05 - 0,2% of divinylacetylons in chloropren# decreases the ~ plasticity of nalrito and also. decreases its stability during ther- =1 aging (Pig. 2 MA 3)- The latter effoot Is 9xplaineds 1) by the participation of the admixtures in the process of copolymerization with the-foruation of rial- fled structures due to the multi-functIonal nature of these compounds; 2) by tho activation of the oxidizing process, since It Is known that the divinylk4etylOr-o admixtures activate the oxidizing processes of chloroprene with the oxygen from air. These data point to the necessity of purifying the monovWlacotylem adndx- tures, The stability of nairito Is also lower when it is polymerized In an air medium, sad it has a ptator tendency to scorching, than when polymrlzod in a ni- trogen medium (Fig. 4), Mairite Is oxidized and forms active pero4des, 7h# a- mount of saponifiable.chlorine increases in proportion to the amount of ong~n at- 19orbed. The increased quantity of the saponifiable chlorine causes tho polymers to undergo structuralisation *bon being stored or processed and also oauses tho premature vulcanization an a result of the interaction between tho metal Oxidte Card 2/3 3/138/60/000/007/001/010 A051/AO29 The Effect of Admixtures Present in Chloroprene an the Stability of Write during the processing, Pin~liy,,VI9U-r* 5 sho'W9 ttAt the presence of a 0.02 - 0,2$ concentration of iron salts In chloropm* does not affect the plasticity of Write. There are 5 graphs, MWIATIONI Vaesoyu%W nsuchno-Isslodovat*11skly institut sintatichoskogo kauchuka Ia. S.V. L*bodeva (The All-Union Scientific Ressamh Ins tute of Synthetic Ibbber im.,S.V. Labodev) 3/138/60/ODD/008/003/015 A051/AD29 AUMORS Jaebanskiy. A.L.; Pomina, L.P.1 Kartsev, V.N.; Tra**, Yu.V. Tl=t The Effect of Various Types Properties During Aging PERIODICALt Kauchuk I Retina, 19601-OANo. of Stabilizers on the Change in Write 8, PP. 9 - 13 TEM . The authors studied the selection of more effective stabilizers of Nalrite (ohloroprene rubber) then those commonly used., such &s thluram 9 (2.5%) combined with neozone (an antlox1dant, phenyl-beta-naphthylamine, 2%). Since tho oxidizing effect of air on the stability of Nalrit.e to considered one of the main factors during Its storage and vulcanization for avoiding scorching especially at elevated temperatures, the proper selection of stabilizers acquires great signIfi- canoe. The effect of the above-mentioned commonly-used stabilizers was described in Refs. 2 mid 3. These stabilizers, during longer storage periods at room tem- perature, as well as during the 'long-lasting processing of the mixtures at high temperatures (over 12090, do not ensure a sufficient stabilizing effect of the Nalrites the plasticity of the standard rubber mixtures drops when these are h*at- ed for I hour. This drop In plasticity is assumed to be connected with the Bcotvil- Ing effect of Mairits. In choosing the proper stabilizers, the structural charac- cam I/ S/138/60/ODO/008/003/015 A051/AO29 The Effect of Various Typos of Stabilizers on the Change In Mairits Properties During Aging teristio of Nairlts are considered, ordthus the structuralizing features of the latter. It Is deducted therefrom that in order to stabilize Write, a complex of substances must be used which Is capable of preventing the oxidizing processes of the chloroprenep and bind the easily detachable hydrogen chloride. Two groups 6f compounds wore !nvestlgated an anti-oxidants-, phenyl-,S-naphthylandne deriva- tives (neoiono D) and polyphenols. During the oxidation of the rubber Molatule an inactive polymer molecule Is formed as well an a noozone D radlial, which to no longer capable of continuing the growth of the chain due to the stability. It Is assumed that the anti-oxldlalng effect of neozone could be 1noreaaed by Intrrduoing polar substitutes (Cl, OH, eta) or substitutes containing conjugated systems of double bonds (Rer- 3)- Howeverk it was found in Investigating other -ompvands. ,such as dlphonylthissine JC6H phenylnaphthylthWIne (CA I C 1 dinaphthylphenylenedlej ne dlphenylphenylenedl wine W 5NMHC C. -C ':~ NHC oxynoozone CIO W 'H t In the formation of radicals from 10 these (rgy~ spent, than from neozone D, wyi it Is tirther astum- o unds loan ene ed that these radicals formed would to more s*tsble, a:ul 1#,S9 given to a shift, In Card 2/5 S11 38/60/000/008/003/015 A051/AQ9 The Effect of Various Typos of Stabillsors on the Change In MaIrIte Properties During Aging the chains. Based on these assumptions, It Is stated that the listed compounds would be better and more effective inhibitors of the oxidizing processes, than noozone D. Th.9 application of noosono D derivatives, with polar substitutes (oxy- -group, sulfide bonds) as stabilizers, or increasing the degree of linkage (41- phenrl- snd dinaPhthrlphonylonedlamines), does not increase the stability of Hai- rite. It does, however, Increase Its tendency 'to scorching during thermal aging (120 hours at TOO. Prom these observations it is concluded that the scorching mechanism of the chloroprone polymers Is not dependent on the ox1dising processes,, but Is due rather to the radical decay of the molecules along the polysulfide bonds forming pollar radicals$ Woh In -the presence of thluram and other cook- pounds, recombine with their radicals. Further deliberation follows on the dIs- advantages of noozons, am an oxidising Inhibitor. As to the polyphonols In the role of stabilixerso It was1ound that in testing compounds cont"ng phenol and oxide groups (lignin, dimethylphonyl-n-crosolp paraditertlarybuty1dioxyphonylono- sulfide), -these also had a ne"tive effect on the stability of Write, incroasIng the scorching tendencies (Via. 3). The accelerating effect of the phonols in this connection Is thought to be associated with the fact that in the presence of a Card 3 /5