SCIENTIFIC ABSTRACTS ABKIN, A. D. - ABKIN, A. D.

• Document Type: CREST
• Collection: Scientific Abstracts
• Document Number (FOIA) /ESDN (CREST): CIA-RDP86-00513R000100130002-4
• Release Decision: RIF
• Original Classification: S
• Document Page Count: 102
• Document Creation Date: November 2, 2016
• Document Release Date: April 3, 2001
• Sequence Number: 2
• Publication Date: December 31, 1967
• Content Type: SUMMARY

83704
S11901601002100610091012
iT-Wl B015/BO64
AUTHORS: Medvedev, S. S., Abkia,_Adj,,,,Ahomikovskiy, P,, M..
a eras !MQY,-D-,JL , _dr~_m6v, V. F. Uikin _4,Tsingister,
,--Yu
V. A , Auer,_A. L.. 'Jakovleva, M. K., Ileghirova,
Matvoyeva, A. V., Bezzubik, Z. G,
TITLEs Polymerization of Ethyl enFAUnder the Influence of r-Radiation/1
PERIODICAL: Vysokomolekulyarnyye soyedineniya, 1960, Vol. 2:, Wo. 6,
pp. 904-915
TEXT% The raAiai;ion-chemical polymerization of ethylene in the gaseous
phase and in organic substances was investigated at different-pressure
and radiation doiie as well as some properties of the polymers fcrmed.
Co 60 r -radiation sources of the institut im. Karpova (Institute imeni
Karpov (1400, 1800, and 20000 gram qquiv, Ra) and pressures of
50-300 atm, radiation dose of 17 to 165 r/sec, and 250C (oowe experiments
were made at 500C) were the conditions. The experiments wAre carried out
in a corresponding device (Fig. 1). The ethylene used was mass-
Card 1/4

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,a rcWTted hdare (Ior. cii,). Me
purificd by labut, ixt ii4;-- and,--. -
-
-rhb~,rtlistd. from thit sivotmincr IT1.11 usrI in
-mel, -11m iliduction period,
'13 W11 "fativist, doilig away With
11txadZ-cj1 ixijrtite was sym~msizrd from bej4Jmxuo1 and-
l4eiiMlatein tile prcsviccof p-toluenestAfm0c acid. The-'
~~stcr %vas diud. in varxit in the presetive of motallic Cli,
arld the '.55-60* fraction at 1.4 inin, tig. m.)). IV. tili
MY11), d" - 0.859, waq collected. Pure 11Y101 was jir?ed
as tile reaction Initialor. For capjYmerkatioti, a toilleiv
------ -- --
-.,,The ivolyinerbittion rate ivas observmt tifiLitontelik-ally, at
-
'
PO -L- 0.05
.
The i"-vid(--cyl lirryfate polmuti~;itioi% rate.
-
WaS fomid to 1--,e 2~1 tiotc-s gremt-r than of h1v acryl;ile. 3114

this ral e wa, tomid to N --title at li)%Yvr conviv;. A)f mtll,
tile
n3. - Tf- r,lfe lvw% cak;l. 1'v III ill), i Iii,
ic crpol% -
tivrived forinuti, whicli involvv,) lilt- ll,v -if 01C
;I'dividlial polyllivrizitiol, rak% of the tIIolIo17l,lI;, and tile
(-lT.X tile ritio of tile coll-
of tile irplividital jnonniqvr~ 1-Il-111cri"alioll itliti Itit"I.
TI;- Ylltwor.% %%,vi foand to In: 6 froul 1110 Lilwtiv I "ta, :III,],
m wi)l the ~-illlc valkle float fill- 14%1. of
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I-Vd')'JT0VA, 0.; : ALKII, DVEDEV, S.
_J. ; ~I
Foi~nzerization Processes Laboratory, Moscow Physico-Chemical 'nstitute im. L. Ya.
Kurpovp (-1939-). "Ilhe Kinotics of PolymorlzatJoil )!.' I~uttld toile - 1.3 in the Presence
of Potassium Phe,~vlisopropyl (Fenilizopropilkallya)".
Zhur. Fiz. Dim., Vol. 14, 110- 1, 1940.

83704,
Polymerization of Ethylene Under the SligOV601002100610091012
InflLuence of r -Radiation B015/ .064
spectroscopically analyzed by M. V. Tikhomirov and M. V, Gurlyev, The
molecular weight of the polyethylene obtained was determined by the method
of light scattering by 1. G. Soboleva and N. V. Mekletsovat particular
data on this will be given in a separate paper. The experiments of
polymerization in heplane, cyclohexane, methanol, and ao~.etonp (50 atm.
250C, ejICO r/sec) showed (Table 1) that reaotion proceeds ten times more
rapidly than in the gaseous phase. The polymers formed have a molecular
weight of 20000-40000. Polymems of the atructure Cl 3C(C2H4)2 C3 (6Cr/,) and
Cl3C(C2H 4)3 CI (20%) form in good yield in carbon tetrschlorid6. Polymari-
zation in zhe gaseous phase was investigated at constant prc-asure
(100-300 atm 72 r/sec) and decreasing pressure (100 and 150 atm,
17-165 r/seo: 250 and 500C). The polymer yield increases rapidly if
experiments are made in the presence of polyethylene (Table 2). To begin
withi the polymerization rate increases with time ani reache,3 then a
,,.ongtant value. The mean molecular weight and the characteristic v1s,
cosity of the polymers increases with proceeding transformatl~;n (TAble 5)
The mean rea,~tion rato amounts to 16.9 g/l,hour tit 300 atm. 25"C' a
duration of 24 hours and radiation doso of 172 r/svc. and thj maximum rate
Card 2/4

83704
Polymerization of Ethylene Under the S//19 60/002/006/009/012
Influence of r-Radiation B01 5YBo64
20,.5 g1l.hour (Table 4), The mean molecular weight and viscosity of
polyethylene (Table 5) rise with pressure (i.e. the ethylene conevntration~
The maximum rate of polymerization increases somewhat with the radiation
dose with a proportionality factor of 0.3, while tho radiation-chemical
yield decreaneu with an increase in the radiation dose with a factor of
0.7. The molecular weight of polyethylene increases with a reduct-i~'n of
'L
the radiation dose with a factor of 0-7. The molecular v--' i ht Cf Pcly..
et-bylene increase Le 65..'A'tempera'ure
- with dpcreasing radiation dose (Tat-
increase from 250C to 5000 at constant ethylene concentration (330 9/1)
causes a lesser increase in the polymerization rate and the mole,,ular
VC!iJht (Table 7). Irvestigations carried out by Yu. W Malin-3RA."T "-ad
B. T . Everev I n t lie I abo ra to ry o f rad I o o hem il 'I --y i: li~-' . n:' hors ' i ns t I t,, i t e
ihowed that the polyethylene obtsned has a highpr den3ity '0~945-
0-975 g/c=3) and 40",ee Of Cry3tallAZatiOn than high-pressur,: pclyethylene'
Ilffers, however, only slightly from the latter with r-~spcct to the
tensile strength, In conclusion, tho authors thank A.. Kh. Broger,
LLpav, and V,,, A. Golldin for assisting in carryinC out the
V. _R. Or
experiments with the gamma emitters. There are 8 fi6nires, 7 t;ible~, and
11 referencep: 5 Soviet, 4 US, 1 'Britlah, and I Belgian.
Card 3/4

8--viO4
Polymerization of EtlWlene Under the
Influenoe of r -Radiation
3/'190/60/002/006/009/012
B015/BO64
ASSOCIATIONs Fiziko-khtmicheskly institut im. L, Ya, Karpcva
(~~eo-chemical Institute imeni L. Ya~ Karpov
SUBMITTED; February 24, 1960
card 4/4

AUTHOR: Abkint A. D.
TITLE: Radiation polymerization
3/84 62/000/000/075/129
D423YD307
SOURGIA Trudy 11 Vooooyuznogo Boveolichuniya po radiat8ionnoy khi-
mii. Ed. by L. 6. Polak. Moscowt lzd-vo A14 S'S)'1)'Rj 1962,
430-449
TEXT: Results of (mostly ',V*ester11) investigationu in the ficd"Of
radiation polymerizatiun tire reviewed. The E;ubjecto covered include
radical. polymerization, polymerization in-a variety of systems and
aiso in the three iihaaes. Ionic polynoriz4tion in the liquid jhase
is discussed for iso-butylene, utyrene., butadiene and trimethyl-
2,4,4-peritene-1. To-mie cinclusionu are drawn concerning the mechan-
isms of the polymerization proces3es and equations and graphs are
,presented to show the relations 'between the,vfirioua paramuters.
Experiments were carried out over the rtAnge +60 to -1120C. Carbani-
onic polymerization-is also considered, in some detail, for acrylo-
nitrile in various solvents. lt was shown that radiation pulymeri-
Card 1/ 3

Radi,ation polymerizatiun
6/644/62 "i OUU/OJJ/075/1 2-9
iA 2 3/ D5 07
zation proceeded by Ln ;tnionic i-icclianism, th~.- rate of which in tri-
mctJ',y1'11Aine, uvjr the r...no.*e +25 to -1120C, fell initially to a i:ii-
ninun Of Lboi,1.t -5000 it.id tLen increaocd ra,iidly. Increaue in the
rate of polymeriztition %~au, u1su accom,janied by a significant in-
crease in molecular veight of the polymer. Addition of styrene to
solutions of acrylinitrile in dine thyl-f orinumide at -'NOC reduced
the rate of polym--~rization. I section is devoted to the mechanism
of ionic polymerization in the liquid )hase and a theory is estab-
lished for the monomolbeular i:iechanism of chain rupture in the low-
temperature polymerization of iso-butylene and styrene, associated
with ejection by the giowing carbonium ion of a pro-con and the for-
mation in the final grcup of the polymer chain of a double bond.
An equation is given for the ratio of joint polymerization,
2 2
+ 1 ) (r A + 2AB + r. B ).w a)
2 1 2 2 A B
Br 1 A + Xt-w.;BAB + (OA r2B
Card 2/3

Radiation polymeri-sation
3/844/62/000/000/075/1;!9
D423/D307
where A and B are the monomer concentrations;co A andr.)Baro the in-
dividual rates of polymerization; Ais a quantity characterizing the
ratio of the rates of furmation of initial active centers "rom the
monomers A and B by their Joint polymerization; X is a quantity
characterizing the ratio of the constants of the rates of "cross'
chain rupture and the rates of -joint chain growth. There are 3 tab-
~es, 8 figures and 80 references.
ASSOCIATIONi
Fizilti-khimicheskiy institut irfv~L. Ya. K-,irpcv
sico-Chenical Institute im. L. Ya. Karpov)
Card 3/3

? .-ne r) zat Inn i sn-
Qrl. lone - -V1,"- ;TIE I !L,t-
tion constant, aikyl fiaiide
A 1 i,~, T P A ('T The rolle of solld adMixtures in 3,Lrh r-eArt',0-:1s was exr)lored in
*he Sppar-ate and w2r?j~~er,,,,4Wnbf the title products --,cei tneimtu, rice of
,~j rnm;~ _raves 7J ra~'; s t j e
ZnO in quaTAI-tiea cormapanding In v4DIume to the volume of the liquid pnak3e.
S t e me r i z n
Card 1/ 3

ACCESSION NR: AP4043843
We a 1.10
11 Z T- e .1i P
To~l ISPUUIYILq51]v cuju u1j.
t P r 17-a
wt
nf-

~MPM~N NR, AP4043843
v-,41c radia,'nn poivme-i?-.atIon, probably related tn the inter:iction nf monom. ers
th- in the chem!,-adsr-r!,P-! 1, 7- dat:i -n the
..gures,
ASS-OCLAI-K)'11' Fiziio-khimicheski-v nstoul Y- iPhysico-
Cneirxical Lnetitute;
SUBMITTTED~ 25Mar64 ENCL. 00
Card- 3/3-- -------- ----- -

L h282-66
T/ EWAh A I IR PL WWt1rG.1Ri
ACCESSION NR: AP5024006 U 0020/65/164/002/O3G5/03G7
--AUTIIOR: - Gerasimov. G. N.; Babirova, T. M.; Khomikovr
kiy, P. M.; Abkin, A. D.
TITLE: Radiation polymerizatiol of vtyl chlorldAn -a-61-id-s-o-Mut-lon-a -at lo --- w--t c-m-paraturef I
J, SOURCE: AN SSSR. Doklady, v. 14, no. 2, 1965P 365-367
TOPIC TAGS.- vinyl chloride, radiation polymerization, mineral oil, solid solution
ABSTRACT: The polymerization of vinyl chloride Nvas carric 14 out In mineral oil at a dose
rate of 70 rad/sco (Co(;O) and temperatures of -7 8 and -196C, if. c. , above and bclov;' the
inelting, point of vinyl chloride. Considerable -postpolymeTfiz-,Uion was found to take placo
i t:,uring thawing of the solutions, so that the latter was carried out very rapidly when kinetic,~
data were taken. The kinetic curves obtained show that at -196C the reaction rate do-
creases sharply during the first stage, and the polymerization practically ceases at
15 - 20'10 conve:~sion; the yield of polymer becomes markedly reduced when the vinyl
chloride content increises from 6 to 15%. At -78C, the reaction rate increases sharply "d.-
fi" St, then rcachc8 a maximum, and declines rapidly at 50 - 607k) conversion. The pro-
ducts formed are low-molecular polymers. It is postulated on the basis of the Iiinctic data;
that the polymerization of vinyl chloride in a solid mineral oil solution is determined by a
Card 1/2
J

L L-289-66
ACCESSION NR: AP5024006
definite ordered arrangernentof vinyl chloride molecules. The 8tructure of the frozen-----
systems also affects the polymerization process. In contrast to amorphous solutions of
vinyl chloride in low-molecular paraffins, the solid system vinyl chloride-mineral oil
is a. microheterogencous one; in the presence of microlietorogencity, significant kinetic
effects can tako place. Orig. art.- has: 2 figures.
ASSOCIATI N: Fiziko-khimicheskiy institut Im. L. Ya. Karpova (Physiochom teal In-
SUBMITTED: 10DccG4 ENCL: 00 - SUB CODE- MT, &4L
NO REP SOV: 001 OTHER- 005
Card 2/2

L 261LB-66 2 /13o (j )ty 11
ACC NR, AP6015oft IGOURCE CODr: UR, OH,9~-0-ItelOC~OtO-57()-961-16~62
AUTIIOR* Bruk, M. A.; Gromov, V. F.; Chernyak, I. V.; Yuhamikovskly, P.~Mi; Abkinj, A, I
ORG. . Hone
TtITLE: Radiation- induced polymerizationlof tetrafluoroethylenid acry'Lonitrilelat
4.2 -K
SOURCE: Vysokomolekulyarnyye soyedineniyal v. 8, no. 5, 1966, 961-962
TOPIC TAGS: tetrafluorothylene, acr7lonitrile, bulk polymerization, low temperature
polymerization
ABSTRACT: Polymers oftetrafluoroethylene or acrylon'itrile have been prepared by
bulk radiation-indyaced polymerization of the monomers at 4.2 K. Mlten monomer sample
were frozen at a given rate in liquid nitrogen, placed in a cryostat with liquid
helium, and irradiated. Defrocting of the smples was conducted under conditions wbic
excluded post-polymerization. The authors assume that in the course of polymerizatior
of the monomers at low temperatures the bulk temperature of the samples does not
determine the charecter of the polymer chain formation, which takes place in "hot"
regions. The polyrrer chains grow before relaxation of the vibration excitation of
moleculas in "hot" regions has time to o.ccur. The authors also assume that polymeri-
zation follows the cooperative mechanism which does not require activation for the
addition of indiviaual monomer molecules. Orig. art. has: 1 figure. [BO]
SUB CODE- 07. 11! Sum DATE:. o6jan66/ ORI 0 REF; - 003/. OTH. REF. 001 ATD PJTBE,)~
,Card -1/QE
5'~

ACOESSION NR: AP4012181 S/0lql/64/Ooo/oo2/ooo3/ooo6
'AURHORS: Lbkint A. D.; Auer, JL. L.; Breger, A. Kh.; Vaynahteyno
-1-;"Voropayev, Yu. V.; Golldin, V. A.; Gromov, V. P.;
B
.
OsIpov, V. B.; Sv*rkusv N. P.; Ushakov, V. D.; Xhomikovekiy,,'
P. M.; Teingister, V. A.; Ohikin, Yu. L.
.TITLB: Radiation polymerization of ethylene In enlarged laboratory
appar&tue.
.SOUROB: Plastlohasklys massy*, no. 2, 1964, 3-6
iTOPIC TAGS: ethylene, radiation polymerization, reactor designp
;reactor surface area, reaction rate, polymer yield, reactor tempora-
:t;ura field
!ABSTRkOT: Radiation polymerization of ethylene wag conducted lu
~laboratory reactors of 1-2 liter capacity (fig. 1 & 2). Based on
:tolerances admitted In this work, It vae found that the temperature
ifield can be calculated with sufficient accuracy@ Comparison of
~:reaction rates and yield of ethylene polymer shows thit these factors
I
,are Independent of the specific surface of the reaction space* Thus
I-Card- 14A

;'AOOZSBION'NR:"
!commercial scale apparatus can be designed by estimating the Dro-
i age
icess rate and yield dependence on pressure, temperature and don
:rate without o6noern for specific surface area of the reactor.
iOrig. art. has; 1 Table and 5 Pigures,
!ASSOOIATXON: None
!SUBMITTED: 00 DOE ACQ: 26Peb64 RNOL: 02
.SUB OODS: XL n REP SOV: 005 02HER:
Card 2/4

89593
511901611003100210111012
B101/B215
AUTHORSs Gantmakher, A. R., Madvedev, S. S., Abkin, A. D.
TITLEs Low-tomperature polymerization of ethylene tetrafluoride in
liquid phase by the action of gamma radiation
PERIODICALs Vysokomolokulyarnyye soyedineniyal ve 3t no. 29 1961, 320
TEXTt In this letter to the editor the authors state that they were the
first to axamine the liquid phase polymerization of ethylene tetrafluoride
under the action of gamma radiation. The polymerization was conducted in
sealed glass phials in the absence of oxygen, at -5500 and 10 roentgen/seo.
Under these conditions, the reaction took place at a high rate and was
accompanied by the formation of a solid polymer, Afer one hour, the yield
of polyethylene tetrafluoride was 35~- It was increased up to 95% by a
radiation of 6 hro The studies were continued by Ye. P. Volkova, As Ve
Fokin, V. M. Belikov (Tsaisy dokladov na II Vs(isoyuznom soveshchanii po
radiatsionnoy khimii, 1960 str. 65 (Theses of the Reports on the 2nd All-
Union Conference of Radiation Chemistry, Moscow, 1960, p. 65) Ref. 1). The
Card 1/2

89593
S11901611003100210111012
Low-temperature polymerization of B101/B215
publications show (S. S. Medvedev, A. D. Abkin, P. M. Khomikovskiy, G
Gerasimov, V. F. Gromov et al., Vysokomolek. soyed. 2, 904, 1960, Ref: 2,~
that ethylene under similar condiftone is polymerized more slowly. This
difference in the polymerization rates of ethylene tetrafluoride and
ethylene may be due to a slower rupture of ch&ins by recombination in the
polymerization of ethylene tetrafluoride due to repulsive forces. The
latter occur in the approximation of perfluorinated radicals of polyethy-
lene tetrafluoride. The slow rate of chain ruptures may also be dne to
topochemical peculiarities occurring in t~e polymerization of ethylene te-
trafluoride. (Atstraoter's notes thislIf's a full translation from the
original.] There are 2 So7iet-bloc referpi~ces,
SUBMITTED: October 29, 1960
Card 2/2

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) to 2(X)
A
oll
~-
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&
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s

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1LO-CU..e.CIf(OH).CflCHhIcCONHl (VIU)
t I
,
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6 r I
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s.
4 0

10 1 0
u
04. It
4. 11 11 to 44 6 it a is Its 61 A I 1 0 1 44 4
0 0 0 0 0 0 0 * 0 0 0 a 0 0 0 6 a 0 0 0 Vs 0 0 0 0 0 0 111 a 0 0 4 a 6 0 0 0 0 6 0 411
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'a if It 11 $0 to if It )f a )d It As v AS Sit Is It IS
IIIS It IN 0
I L 0 A-1 A A -A.. L a I
.61 Ji- ftltmi,

Polymerulng cWtoricipmese. "tAbj~w,,-;

S. Klitsirnkov. Ru%u Cyjml.. Nov. :Ifi.
9e,
I,
c4
umtk-
t
i
(T
I
h
i c
"
YmtT
n
cr
in t
r ptewtKv (4 tetrglill
P
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uthetic rulbber A.' It. AbLut. S klmnuL,.v,
S~ S~
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r
, ~tmhtit V &&SJ
S
fuly 311U1, A %lit I. uf, Lf.",qIwitc and Simi kltl,-ou6
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IF -00
.11-tances in tile Im-IRV of l1w al'u-IRV
-.00
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it ple Aft L I, a t~
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0 0, 0 0 0 0 0 0 a 0 0 Ill, Ol 0 0 * 0
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is W. &I it 0 G)JO
f. - =.04. N., 1), Is, 1". "1 11.. A j - A
J-v-"vq*%
vr"w 'is -4 P1,04,16 ts of
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Kiss" 4a at biwifto is
Ot- A..A"w SkAd
W ~ftw IM. 13, M-
'14mm.mw 04,M111mi, 296) k "kpu"
6's"
P*aftiostion is 60 16 surfs" ce the
Iwo -%us woksumt it. 7u &WL),
dbabbalwo wtbepp-ol
dwt js= bambnaaMmixiid zoo
PO-4W." Op 4 the poom"b"Ma mioctimi
Coo
I wd 2, - .%
im*w"A on ID&Z of do "ion isou""n. coo
The roU of uoa am 0
mp Soo
or the bepoly
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of Activaum have bwo Cole.
to 0
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14t.!
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a% owl a m11
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0, 9, 9, 9'~,,
01 a 41 a a a
A ILI LIMU
j
p4stad~M4 Is the
0. Mamoolova.
A40. U. X. S. 2
sow. the say..
h Now With a ought sec.
of Is hit. on adds. of trdtadkne to
the cbtffy4vd
MIS. dboopm"i .00
rdw 000 WR Pdrusertatka,
*M ad 0011 an tM walle by 000
bwncdm 7 * ow I isobt, vA that evah, too
06 al- lisop OM is this VOL ad the eft. amths 00
0001 = . W&wWw*O Is this vok. or
0" bosom as the norim; dw I Is " taft Goo
00,1 stud. JU MweAcs dWyo, Ow 6W011011 v - 1'4'70 ;
ha + 449. who - GI- toom of butficilm. ki AM &i
00 wMe ow Cheap with
we MIS oma& to farnalim Old - 900
so nvo as foams S*, 40. Sol 130. W, 10; 250.
of aeon" of the wbak -1800
Oft T"IST '"cMiEwiffild .1 ww* MW 'tm. I I',,**
.1000
VOW,
1100
I A 18. 1 t a041'ALLURMAL LITIAMAN CLASSOKATIO
!IrO9
_r_r_r_r_T_T__r_r_r_r Ir-T
a 00
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00 *
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"A of ~J=utwu id K-1,411 1,141 till
to KI tbo ImW hq* I.-"*I ~'h.n t
'"I'1 - a" AM him. 110), It," lei. iwl..~l
at ftA ==.Irh own again AMY: tilt
00:1. of as per scon. and 1wr
I" is Ad "m comf .. ~Dd (M *-t-
Io- h" a x w" I ' M . An hictow of W out-
ta" am of 00 ft C~ with mobtWo misod 11ir mto but
1~ -114, mwvw rmMm MMNWMM"ts at
a-Wo 7- -tho 4*;~;a o7
DA 10641411111 =IjW 6 zzarak.. sob. Twog.w.
M~fa"%j At thf MffWV. =
tho bum of M dew both at Ow
Arw I th* balk. Saturated *4utk*e 44 (1) in E101 bro
080. rd Q-T&M, AS pia, - &TO and 637 mot". Itit tvqwg "Voly

a ~ i~
a Is V Jo 39 a 11 U a w a v
4 W I- Is rA go CIP-j t. A _I, 1.
A let, 4.0 4 l*
1.111041111
I- the I + 11 and i-oo
The oviscloasslain 44 the volovoillson- "baties of (over 93"" is ApIrwrMI Ott
booolosaw" vft Vinyl 4yousi" MA ~-09=14ho ty 4'reir 9 - 7w ~ for the I f III ."t"n. Tb-Z ClAmpa. of (Iw
polymer depends littit ca the time at pligymeorgstion and
mww The atchin ed besigay, Persaw. I.. I-p-, but rairies sevardang to x. In the I + 11 system.
Ixosorpopor Ing. Ph L"brove.,
AM*, and! 8. Madve4ew the P01YUNCT03GIAliall 111101V I tILAII the Origiaill allot. at 9 < -00
Moscow). J. Phyl. 010111. 21"1XV47 k" than t ariti alixt.ats>U70. lathorl
t194 108 of butedivat Is wt. %) + system. the "Oluetropic" torist. has Or - Wv. Jale .09
eC'4 (w)
W%tb'61.XI1CN (Ill (100' - x %I Ur Clio: Cid . of (StOls In the polymer devniuve wbrot j 121(vess"
ow .- x ") and (ago)$ (y%) Were CV. IS N. bested I lio,,Ver. Polymertiation continues Ago after t&-C-Q-w.
it I am 21) bra.
hn.. owil 4itil. at r0,= t1raip. in a OR WAMI IKCvn*$ tem. Monomer. distd. froen The polynow and
Tive dists. fiesidive (- twilywor') Wal "JIlied
for 24 (i.e. again raised with it, polynierives at the same to sad viodistn. 400
Fcwtb~detn'ol&cdvc Occurred. but soln. sad reWn. A PAymitt otmo e its
9'9"
0.) the polymer mum be di"01"d 10 CliCh' tOot 'a A"t-e* catalytic activity. 71be coratio. of a copillymer depends
1019
The ratit .1 0. Iner"tion at poly- d-- swisea I in* on the coasw a and 0 expressing the rotlative rates of rv- 7 Ego
III cream, We for the gy9ton I + Ll beltill 0-01-0 action of 2 free radicals with ilic2compoisinstsol tbeuww-
The wad ral is 0.26% per log. at I VOYOOW 9-2'70 Pit weric mixt. A "Z methast kit Uing a and 0
to w
i nmw Cong. at raw '.xpt1. data Is 11. From
hr. at 5 - 2)"l- During Oat " =X. 1. . and 0
WnaU X and OKre~ with time IMIA tV x9 Tke I i--scs the distribution of monooterr groups Within llet copollysoff
With I="-; e.9. Uri is attained at 60' within can be cxkd. (cf- C-A - 42. SLOW. In the cvWy=er I +
w his. and st 760 wiWaV11%. The or is pri"tti"OhAhl to U 67% U is present as am nstnIt group between 2 but&- -0 0
0 Those rftwtg ;~rr
'~ and I* I + 11.11 Mlj U1 is in this alterouite
V/7 betweir" Y - U-1 &w 7 Lad Medmkv.' patt cesistion of polymerization when I of the
are ths"" C lr= the vkwpj.j of Abkia , Rhea we vol ;; 0 9
c.14. j6. movs. 7,bt P013,mert-liat, ceaw" I Is is LoorIl up %bows that both conopovests am wee
highest yield of jx'Av'"- =1 the twaialhing of The orractim chain.
at% is U'"NI up, The
the " patior
ne*
A I a - 11. a &ITALtUsAKAL LIIIIIIA101 CLASSIFICATION I I too*
~is. olv~*Jiq.
U 111 41 1
it 1, or of a it 19 a Is a ft It v a All AA I I I N a a 0 1 V Is I a a 3 9 9
4) 'ilo e 0 0 0 0 0 0 0 0 0 0 0
0 0 :
0 00 196 a 0 1111 a 0 0 9 0 000 0 91: 0 0 a 0 0 0 0 9 0 0 0 11111 0 0 0 a 0

-* v 0 9 * 0 0 9

I a it Is limou ult "b
V it
It

set

004
00 1 A. D AtAin
(I.R.ss.36. 11 4100
0-114714. Inflill. loortmof to givarn A Ow

%wro., .4 IllivI6.1 4.9'. 111 OKI% Ow 000

Okll" I~Iswfl. ad I III ow"to"voras al I. or""st. .11111112 I-dar.
:
w

lso
on" 461 41. vim 1140148 Ill v siveol Im 14.4-41AIII v .4 1.0 tumi 0
00 0-M 44 tile thforsent triatral (of Idowetutts lailbit 1.4 Itoom, 111.. 0
0

0 coo
we
*90

too

1 L
:

'
- IF woo
0 o

5,.
17. o
Z,
kit
'U It AV *I Is 4
'
em a.. Ill
0 0
0
* 0 0 0
:
10 0 111 6 0 0
0

-0
A
Kletitka and mockulato *I A. V.
At" (L. Va. Kallsuv Ill .-C". Insit., MaKew), Dab-
Ardy All". Nook S.S.ST 73, 403-AIM.-This late as
of %vuesimption of the sum of 2 sussommit A asid IS coo be
expressed by w - 64%A'A + k*jb1k*II + k%40'A + kasli'll.
a briv Ow the rissims.. wit! the dote dealoussil;
The tuklyuseg rattkals, With R - A, + 0,
ikad Alit ~*%Ulltmia t3i als1klimainvis (rate of Wilsilm mm.
MtV Of IC111-14--tilill). this tIMM" W - AA1110111(ft + ft)'11/
V/444). whae I's, gull Pit - sal-is of illisimillim in lisp.
polymerization, J. - rate twat, lit and a a
MAI + 2AH + Olls. and is - *AAPD + Voolik. trith a W
114,04% and ft - 4aIl1kJLA. In polymerization laidatad by
atiol, the 14clor usuldyoug (011s) In the abo" I=
blIvomes 1.42 O.Vk.)- X(A +
.(A.'slilifloolthersto
civilits, Ail Iniliatiliss for the -witionsers A and B. loop. With
A known. ibis, ptrinits ca!tu. of A - k44/bop. solf bence at'
the MIA's hir ally lAawy STUrm tit tr3ativit note, if, iff%
adda. to It. tbr aim. Yalulp -A on@ of the individual ji.
I
16a vollusts.. md it,, we klo-~wn. thit 11nnaluing; 3
ctxt~ts. cast be c%kd. fro" kinedc data. &Kh were
rallied out and found its ago"zisint wills literal data. At
rlassL min Jb + N - Cs. the rates of orp. itions
of A and All IA. Nvow. I" Ts) 17,M.11-111 14
W& - 1.420611
and wP - 1.42 sod the late of
V a w - X(A +
i~rnwit4lkm tirt-ollic
wbtrv .4' 1w, on + A','-w"A; 0 the rate of 16106-
,M a vgt~tjtr 1011i'l WWI 0 TheMit tit-if dw sullissinstim,
fit fact 11-17ing (011V) is ),(At 4- 111111AWSICIP'L
We equallins )"mile kakft. All 1911aly syslartus front the
tattoof arts. lotoutassfutsedutiolils
P-Pon6ts Ad A and of 11 for 91 ffervitt values of X (fruits 0 it
to )(9)) .constructed with the slid Ad IW equilt ilia. wet'
1"Ird %ith satisfactory results asainsl ralill. data for AILIVTT-
rut 1110410"Net psi . The consti. X and a an telated fly
-~/-% ^ A' 4, %%11h &aoa 0 knowis. the relative reactivi-
I" of -liffelvill radkVIll call I* rall't- and aft in
vinyl Crankle ftlethyl scivilite. Villyl alvialf. The-
(I)71Wrsl0.4Ihr~
lateracti=1set"It a and A, isilrest(te (he nuire highly the
monomer B In activated thrvagh boad delocalfution, and
ther laft oftbilind the radical A'; adda. of small &Into. of 0
reduM the total rate of Polymerisalkli whoseply. and: gives,
to a min. However, the rate of c"Wyawitatson "it
MrATrosed through predoniblant Initialion by one of the
monilown, Lr~ whcn a J, (2) Pfrarixt of a
Deg, : rRett nuiv ciftle rondittinto (avist abl# to an ins riaction
wn a modetattly reactive A and a stabdised Mdj,-aI 11',
depelodhil an & &lid the pallar effect, adda. of Ij tun III(-Fftiw
the role of copolyustrisalklis assid give time to a max. J -

14-0
u S 5 Iz
juid no-J,anUm ;n-,
chlutiole and vinylidene. Ollulld~
4" '1-
IfL " ' --- . - - , . -~ - 11..~A~, .
a, k
A~jl ";, "'. i ... !.
Is AMIn. :I, IJII- :
M
of lmnyiwl verax.Wc-(Ift)-in
-- --------- - on fttt.~ rp ILI- 1-T imia -
vroa: Strai,24 Eli a d, wrOwd mld Mu%trai'd VAmum
app. 71v initild liku!c 11ilcOu1j. (1) ef 1. 11, m,J 111. tjl~
M I, CIA, vinol, thr yidd
mclim, lbr (0), and the tc-,
Lit mpols-tamatul t1ir molt (t"~ of 1 mA 11 hi 0
c
Littv- Div tAtplitv,! ond graph'.0 is j~,int
fiijm, A. pind 0. Foratty valuld fl, i'll isxivv,
thC III it OfintititIOMI ',' ~C=Mnltd; ishra it i, -j!- d up, dl~
!v"Ctiol, Stops. The rate Of 4 1 - n ,
S. I", ClAll th- rate Of I" I or
i~ morc fivt thIM 1, bm Ottv n4o;-.-al of I is nwr ht
thalrz,~ 11, NN, JA~L"!,
of

USSR/Cbenistry - Polymerization Nov 53
"The Nature of the Reactions of Braniching in Diene
_Polymerization of. the Radical Typ!e,"A. D. Abkin,
'S. N. Kamenskaya,5~.$. S. Medvedev~ '*t Phys-Chem Inst
in-L. Ya.-Karpov
Zhur Fiz nim, Vol 27, NO 11, pp 16o4-16og
Detd the initial velocities of polymerization of
vinyl acetate (I), pentene-1 (II), and pentene-2
,(III) separately as well as in copolymerization of
.I with II and III. On the basis of the'lzitial velo-
cities, detd the consts of copolymerization. Found
that pentenes inhibit polymerization of I. Estimated
274T15
the relative velocities of interaction of pentenes
with radicals of I, styrene, and butadiene. Found
that branching in the polymerization of butadiene-
1,3 ic caused by chain transfer.

A. D.
The ;Nat-irv of tl,,c Dranchi.nr ~Zeaction, -Durlilf, 7M-iical of Dienes.
A. D. Ahl-~n, S.N. Kamenskayt., S.S.Nedvedev, Cor. 'r'br.,Acad. Sci.USM; Sci.
Res. Phy-sicochem. Tnst. im. L. Ya. Yarnov - DAN -I'SSR, vol.F81no.21 Jan 53,
pp 269-271
A Quant appraisal is made of the specific rates of tlic, rcaction between
the polybutadiene radical and polybutzidiene particles at tile nmo- and cIi-
substittited double bond.
255T15

Will 01'
k X ) i x e I 1 1 KIT"M V. r 10,
~'%"Vjygwi S~S,S.R, 1955, 6~ ,
trob'Tw xn~!e studird touth mote fully *6 the tKisis ot
Int d:
t2 trartioni (Ahkin, es al.,
CA, 40, 4.~2.%. W~~r) thatt merely Irmn the quant. rcla-
tions of thevarityus j~.-Iymtr formations and the dl-,qtribution 1,A
of the Immomer tault~ in the Ineq. The method and results yo
L4 kinnic inve-stiyatiou are dism%sed. All cquatkm de-
rived for the VrMcilv of luflynteril-Ation reaction gives sul-
0 fi~kfttly RMINOC illf,~FIMItLMI 011 the ~blaj)C 14 Me VOIXIty-
cvu:lpn, eutvt ten a fI.V rrAl biwry gyvtern a'"I Ows the value
0, a ernnbt, thqt chutartetl3to tilt tact-tivenz-A of a "M11-
cltoft" chx;n rupture. Mnnovierv with caribigmte.1 double
bon0%werr found to Ie tiTMst tt;_R-)~-r towitr1h, radicals of any
type. whereas ruai,incrs with isolated double bords ara
Imt tnt-Aive toward ndical,. This is illwmted on the
V)nyl chloride + t~,ttsdlrrte, vinyl c1daride + winylld"ie
chkwide. vinyl Deflate i- Slyrrue, rtr., jx4yrurrizations,
A table wasconstincted of the relative r-activitlexalcamo.-
Mrs and 4,10trA" and t1w for '!.e reactivity Alil.
Ityrnecs ate M 11,e t-Nii of their chetri. structures.
w SLUnbru

lail"VIA A.-D--j w,.d ~'OKCLOV, L. B.
"Gencr*l theory of addition pol.N-mcrizatitln," a pup-:~r presented Ot the
I
9th Congress on the Chemistry vna rhysics of 111j;h 2" Jan-2 Feb 57,
Moscow, Knrpov Inst.
B-3,(:04,395

I-fbl lu
M1,
a-d
4,j
A r6
'I, ~ .A.
ad

SOEDIOV, L.B.; ABKIN. AI D. --
Additivity of contraction in copolymerization. 77ookom. soed. I no.6:
863-864 Je 159. - (MIRA 12:10)
1.7iziko-khimichaskiy institut im. L. Ta. Karpova.
(Polymerization)

SOKOLOV, L.B.; AMIN, A.D.
Gopolymerization with the participation of bi-ftnational manomers.
Vysokom.soed. I no-7:io24-io26 j1 '59. (MIRA 12:11)
1. Miko-khImicheskiy, institut im L.Ya. Karpova.
(Polymerization)

DTURNBAUM,
V.S.;,,ABKIN, A.D.; KLINENKOV. V.S.- -
-
Production of copolymers of sorylonitrile with mothacrylamide and
of fibers derived from them. Khim. voloke.no.2124-28 '59.
(NIRA 12:9)
l.Vaeso7uzW nauohno-iseledovatellskiy institut iskusetvennogo
volokna.
(Aer7lOnitrile) (Mathacrylamide) (Rayon)

5(4) SOV/76-33,-6-54/44
AUTHORS: Sokolov, L. B.r Abkin. A. D.
TITLE: On tile Mechanism Of Copolymerization With PartIcipation of
Difunctional Monomers (0 mokhanizme novmstnoy polimorizatsii
a uchastiyem bifunktsionaltnykh monomerov),. 1. Copolymerize-
tion of a-Chloracrylate of 2-Ethoxyothanol With Styrone,
Mathylmethacrylate and Methylacrylate (I. sovmestnaya poli-
merizatsiya a.-khlorakrilovogo efira 2-etoksietanola so
stirolom, metilmotakrilatom i motilakrilutom)
PERIODICAL: Zhurnal fizichesko khim*i, 1959, Vol 33... Nr 6,
PP 1387-1392 (USSR
ABSTRACT: In connection with the problems of synthesis of branched
and reticular polymers (P), investigations of the polymeriza-
tion mechanism of systems with binfunctional monomers are
particularly important. The copolymerization (CP) of the
monomers styrene (I)r methylmethaerylate (II) and methyl-
acrylate (III) with ethylene.-glycol-di-a-chloracrylate (IVII
and 2-othoxyothanol-a-chloraorylate (V) was investigated.
The present paper presents the experimental results obtained
with ~V). The (CP) took place in methylethylketone solutions
Card 1/3 at 50 C. Benzoylperoxide was used as initiator. and the re-

SOV/76-33-6-34/44
On the Mechanism of Copolymerization With Participation of Bifunctional
Monomers. 1. Copolymerization of a-Chloracrylate of 2-Ethoxyethanol With
Styrene, Methylmethaorylate and Methylacrylate
action kinetics was determined by the dilatometric method.
On the system (III) - (V) it was observed that (V) is a more
active monomer than (III) but much loan active than the radical.
The (CP)-constants computed for this system are a - 0.1 and
P - 3-8. A closer consideration of the reaction mechanism is
put forward. In the (CP) of (II) with (V) there was com uted
a - 0-4 and P - 1.21 and in contrast to the system (1115 - (V),
a weak maximum was observed in the diagram polymarization
rate (PR) - composition Fig_2~. The latter is due to polar
factors. For the system M V), the values a - 0.12 and
P - 0.26 were obtained which point to the fact that (I) is
more active than (V) in the reaction with the monoester radical.
In the diagram (?R) - composition (Fig 3), a distinctly
marked maximum can be observed which is also produced by a
polar effect. A comparison of the (CP)-constants obtained
with those of the system with methyl-a-chloracrylate
(Refs B-10) (Table) shove good agreement. It ie ancertained
that the polymerization kinetics of the systems investigated
Card 2/3 can be well represented by the simplified oquation of the

I SOV/76-33-6--34/44
On the Mechanism of Copolymerization With Participation of Bifunctional
Monomers. I. Copolymerization of a.-Chloracrylate of 2.-Ethoxyethanol With
Styrene, Methylmethacrylate and Methylacrylate
copolymerization kinetics, under the assumption of equal
initiation rates of the process on both monomers. Finally,
the authora express their thanks to Academician S. S. Medvedev.
There are 3 figures, I table, and 17 references, 8 of which
are Soviet.
ASSOCIATION: Fiziko.-khimicheakiy institut im. L. Ya. Karpova,liloskva
(Physico-chemical Institute imeni L. Ya. KarpovyMoscow)
SUBMITTED: December 13, 1957
Card 3/3

4 .5
AUTHORS;
TITLE.
Sokolov: L. B., Abl:in, A. D. .90v//76- 33 -? -9/40
On 'ha Mechanism of Copolymerization Wit"! Pa:,ticipaticr. of
B`f-.--n-tiona1 Monomers. 11. PaTti~~ularit4ea of the Polymer."za.-
t-on cf Binary Systems With the Partl--ipatiori cf th,3 Ethylene
Glye.,ol Di-a-chloroaoryl Ester
PERIODICALt Zhurnal fizicheskoy khimii, 1~59i Vol 33., Nr 7., PP 1495 - 1503
(USSR)
ABSTRACT.- The authors investi-Eated the copolymerization (CP) of the cth-
ylent~ olycol di-a-chloroacryl ester (1) (diester) with styzene
II), methyl methacrylate (III), and izethyl acrylate (N).
!) was obtained from asryli-,~ ac-~'d and ethylere glycol
~
by e method described already earl4er (Ref 1). The author3
che~,,ked the polynerization (P) at 50 + 0.0500 in methyi-ethyl-
ketcne at a monomer concentration c-f T m,)1/1. Durin6 the (P) of
(1) it was found that the polymer is precipitated by (P) of
3 or 47", For the (CP) of (IV) with (1) "he (CP~-ccnetants
o - 0.1 and P w. 3.6 were obtained, for the (CP) of (III) with
(I). a - 0.35 and P = 1.4, and for the (CP) of (!I) with (I),
a - 0.0: and ~ ~ 0.2. Accordingly, tj-~ ttutlicis found the fol-
Card The (P)-rate -,f W is twice as t;Teac ne that of the

On +he MeAariam of Coplyme--nization With Part~-,i;~at,-'on SCV/76 33-7, 0
~f Bif M a, T-1 . F a it -Ica I a T. 1*13 S a of thf~
.).f Binary Sys4,e.-,3 With the Eth:,,Icrr,~~
D` -a~zhl-;rca:-rj1 Es-,er
By the moth-A ~-f it f~uwi
th~%t ram~,`fied -Ana -.P-+i*-,.-.,&!- -~ojvllymers a-t~
. * ~ F) .
'lip (-.C?' -~,f (I). th~ int-tisLll at-a6,E ~,f
of tha --inyl -f W; -.s
vinyl 6rvapb -~f th;,
,)f *he (Cp~ Of tIlti `1) 3.tj~- ~J17) (TI,
w~-*.'h 1.)ifjncti,~~nal m-3.noraa-rs
vh-~',:h is ascribod to the retie~ular stz,-t,-,'Ure th, Tsau'ttant,
.,-)p,,Iytaer and 7~eC.;arlcd ;As a
9-
syst n3 %11',11
r 11)
f
,UjaTit'i~8 (...I 4,1,11C Sy 1 ;3;,1
4, j t
.f tj)e pa-:~,jC, a slim ed
2 is
~tha', +he -reaction ac,~eieration w4-th timed is ,c be -trrlain-~d bY
rin ac~-;u-nala'-ior. of --adical8 within t:,,e syst,~-m~ -.F, -aused
ty chfA5.n transfer or. the part of th!~ p,~Iyu~~-, by an Jni-.4-a-
tim -ea~tion of the added vinyl groups. In :;crclusion., th?
autho-s thank A,,,alewician S. S, llclvr-~~ev foi, ~'.,s
7
Card 2/.1,

On the Mechanism of Copolymerization With Participation SOV/76--33-7-9/40
ofBifunctional Monomers. II. Particularities of the
Polymerization of Binary Systems With the Participation of the Ethylene
Glycol Di-a-chloroacryl Eater
There are 5 figures, 1 table, and 12 references, 4 of which
are Soviet.
ASSOCIATION: Fizikokhimicheskiy inatitut im. L. Ya, Karpova (Physico-
chemical Institute imeni L. Ya. Karpoy)
A
Card 3/,

66876
SOV/76-33-11-47/47
AUTHORSt Abkin. A. D., Sheynkerr A. P., MezhirovaV L. P.
TITLE: On the "Carbanion" Mechanism of Polymerization'Under the
Effect of Gamma Rays.
PERIODICAL: Zhurnal fizicheskoy khimii, 1959, Vol 33, Nr 11, p 2636
(USSR)
ABSTRACTt Data from publications (Ref 1) on the polymerization of iso-
butylene, and data of the joint polymerization of isobutylene
with vinylidene chloride and of the styrene with methyl
methacrylatel obtained by the authors (Ref 2) show that at low
temperaturesland influenced by nuclear radiation, the poly-
merization occurs according to the carbonium mechanism. Up to
present there is no information in publications on the course
of a "carbanion" mechanism at the polymerization under the in-
fluence of nuclear radiation. It has been established that the
polymerization may proceed according to both mechanisms
(carbonium or "carbanion" mechanism) and that this is not do-
termined by the chemical structure of the monomers, but by the
nature of the medium. Data on the polymerization of asulic
Card 1/2 acid nitrileland styrenelat -780C (Table) under the influence

66876
SOV/76-33-11-47/47
On the "Carbanion" Mechanism of the Polymerization Under the Effect of Gamma
Rays
of t;amma rays, show that the polymerization of the acrylic
acid nitrile in solving agents with electron donor substituents
(triethyl amine, dimethyl formamide) occurs and that none
occurs in ethyl chloride (which is usually used for carbonium
polymerization) containing electrophilic groups. Contrary,
styrene polymerizes only in ethyl chloride* These data show P-r
that acrylic acid nitrilep which has molecules containing
electronegative groups, polymerizes, under the Given conditions,
not according to the radical mechanism, but according to the
"carbanion" mechanism. It is mentioned that more detailed
results of the investigations carried out will be published
later and that the authors thank Academician S. S. Medvedev.
There are 1 table and 3 referencesp 2 of which are Soviet-.
Card 2/2

5W SOV/20--124-3-39/67
AUTHORS: Sheynker, A. P., Yakovleva, M. K., Kristal1nyyjE. V..
Abk1n, A. D.
TITLE: On the Mechanism of the Low-temperature Polymerization of
Monomers Under the Action of a Gamma-radiation (0 mekhanizme
nizkotemperaturnoy polimerizataii monomerov pod deystviyem
gamma-izlucheniya)
PERIODICAL: Doklady Akademii nauk SSSR, 1959, Vol 124, Nr 3, pp, 632-634
(USSR)
ABSTRACT: The present paper deals with the results obtained by in-
vestigating the mechanism of the low-temperature polymeriza-
tion of various vinyl compounds under the action of a
y-radiation. The authors investigated this mechanion by employ-
ing the method of joint polymerizationg according to which
it is possible to obtain the necessary information concern-
ing the nature of active particles (radicals, ions) participat-
ing in the active process from the composition of the Ko-poly-
mer and from the kinetic data. The authors investigated the
common polymerization of isobutyls with vinylidene chlogide
Card 1/4 (in the "mass") in the temperature interval of -78 to 0 ,

SOV/20-124--3-39/67.
On the Mechanism of the Low-temperature 'Polymerization of Monowers Under
the Action of a Gamma-radiation
and of methvl-metaorylate with styrene in othylchloride as
solvent at -78 tg +25 0- Polymerization was carried out in
ampoules on a Co *-source of 20,000 g-eqii1valent3 at an in-.
tensity nf 230-250 r/sec. The det;,ee of polymerivation was
not more than JO`f6. A diagram supplies data concernin,- the
dependence of the copolymers on the composition of the orij-,inal
mixture for the system isobutylene-vinylidetie chloride, which
were determined in the course of polymerization at different
temperature conditions. From these data the conntante of the
common polymerization a (for isobutylene) and 0 (for vinylidene
chloride) were then determined according to the vimplified
equation for the integral composition. The following holds:
0- - -, . I__-_._ I
Polymerization temperature in C a
-78 1 25
-40 1.-7
0 0.03
Card 2/4 The composition of the common polymers formed depend to a

SOV/20-124-3-39/67
On the Mechanism of the Low-temperature Polymerization of Monomers Under
the Action of a Gamma-radiation
considerable extent on temperature. Details are given. The
data discussed in the present paper permit the following
conclusions to be drawn: The joint polymerization of iao-
butylene with vinylidene chloride under the influence of
a I-radiation at low temperatures occurs according to the
carbonium (karboniyeviy) mechanism or a similar mechanism.
The authors further investigated the polymerization of
utyrene in an equimolecular mixture of styrene and methyl
metacrylate in ethyl chloride as solvent. With decreasing
tomperattAre, the methyl metacrylate component in the co-
polymer decreases, which indica'te~ an increase of the share
of ion reactions in this process. The authors thank Academician
S. S. Medvedev for discussing the results obtained. There
are 2 figures, 2 tables, and 8 references, 4 of which are
Soviet.
ASSOCIATION: Nauchno-iseledovatellskiy fiziko-khimicheskiy institut
im. L. Ya. Xarpova (Physico-Chemical Scientific Research
Card 3/4 Institute imeni L. Ya. Karpov)

307/20-124-5-39/67
On the Mechanism of the Low-temperature Polymerization of Monomers Under
the Action of a Camma-radiation
PRESENTED: October 30, 1958, by S. S. Medvedev, Academician
SUBMITTED: October 27, 1958
Card 4/4

0 'VAI M. K. t MEZHIROVAt L. P.
A I =NMR) A P., YAK3VLL
"On the carbonium and carbonion mechanisms of gamm-ray induced polymerization.
report presented at the International Polymer Synpositun, (IUPAC), Moscow, LESR,
14-i8 June 196o.

S/08 61/000/021/085/094
B145YI3144
AUTHORS: Rozovskaya, N. I., Abkin, A. D.
TITLE: Study of the copolymerization of styrene and a-eleostearic
acid
PERIODICALt Referativnyy zhurnal. Khimiya, no. 21, 1961, 456, abstract
2IPli5- (Lakokrasoohn. materialy i ikh primeneniyep no. 1~
1961, 9 - 12)
TEXT: The copolymerization of styrene (I) and a-eleostearic acid (N)
dissolved in toluene was studied in the presence of benzoyl peroxide.
Methods and results are presented. The copolymertzation constants were
determined, the differential and integral compositions of the polymers in,
the course of polymerization were calculated, and the conditions under
which the copolymerization limit is reached were established. Small
additions of II were found to inhibit the polymerization of I considerably.
As a monomerl II is more reactive than I even though the reactivity of the
radical of I is much higher than that of the radioalQfIL This fadt causes
Card 1/2

S/081/61/000/021/085/094
Study of the copolymerization of styrene ... 3145/B144
the inhibitory action of II on the polymerization of I. [Abstracter's not(%
Complete translation.]
Card 2/2

IS-B420
33125
S/638/61/001/000/056/056
B125/B104
AUTHORS: Sheynker, A., P., Abkin, A. D~
TITLE. Ion mechanism of polymerization under the action of
nuclear radiations
SOURCE: Tashkentskaya konferenteiya po mirnomy ispol;zovaniyu
atomnoy energii. Tashkent, 1959. Trudy. v I.. Tashkent,
19619 395-400
TEXT: The copolymerization of the following pairs of monomers was examined;,
isobutylene - vinylidene chloride (in the bulk) between -78 and OoCj
styrene - methyl methacrylate between -780 and 250c; and isobutylene -
styrene Et -78OC(with ethyl chloride as solvent); acrylonitrile - styrene
at -78OC(as solution ia dimethyl formamide) Specially designed
dilatometers and a C060 source were used for the experiments, The
copolymerization constants r, (for isobutylene), and r 2 (for vinylidene
chloride) at -70, -409 and 00C are 25, 1.27, 0.03, and 0, 0.21, 1.3,
respectively. The compositions of the resulting copolymers are largely
dependent on the polymerization temperature, and their concentration rises
Card 0

)_3 1 ?5
3/638/61/001/000/056/056
Ion mechanism of polymerization B125/BIO4
significantly on cooling from -40 to -780C~ Therefore, low- and high-
temperature polymerization under the action of radiation probably follow
the ion and the radical mechanism, respectively, On the strength of these
and other facts, gamma irradiation permits low-temperature copolymeriza-
tion of isobutylene with vinylidene chloride according to the carbonium
mechanism. The radiation polymerization of styrene and methyl methacrylate
at 250C follows the radical process. In the gamma polymerization of an
equimolecular mixture of styrene and methyl methacrylate in ethyl chloride,
the relative amount of the methyl methacrylate component in the copolymer
drops rapidly with decreasing polymerization tempefature. The resitlting
copolymers contain a component with a hieh concentration of styrene. Ion
chains are formed in the low-temperature polymerization of styrene and
methyl methacrylate according to the carbonium mechanism, The polymeriza-
tion rate is reduced sharply by the addition of small amounts of
tsobutylene to styrene. Low-temperature radiation polymerization may also
take place aLcording to the ion mechanism, Not only the chemical structurs
of the monomer to be polymerized, but also the nature of the surrounding
medium influences the polymerization mechanism, The mechanism of ion
--hain.formation and the nature of the resulting ion pairs will later be
studied. M, Y., Yakovleva and L, P Mezhirova assisted in the inveetiga-
Card 2/3

33125
S/63 61/001/000/056/056
Ion mechanism of polymerization B125%104
tion. Academician S. S. Medvedev is thanked for interest. There are
5 figures, 2 tables, and 14 references: 7 Soviet and 7 non-Soviet. The
four most recent references to En-glish-language publications read as
follows: Davison W. H. G., Pinner S.. If,p Worrell R,, Chem. % Ind. 38,
1274, 1957; Worrall R~, Charlesby A~, Journ.. Appl. Rad, a IOot- 4- 84,
19581 Worrall R., Pinner S. H., J. Pol. Sci., 34 N 127, 229, 1959. Burlant
W. J., Green D. 11~, J. Pole Sci., 31, 122, 227, 1958,
ASSOCIATION: N.-i-fiziko-khimicheakiy institut im. L. Ya. Karpova
(Scientific Physicochemical Research Institute imeni L. Ya.
Karpov)
Card 3/3

DYURNBAUM# V,S.; ABKIN, A.D., KLIKMCV, V.S.
Kinetics of copolymerization of acrylonitrile with sone vinyl
monomers. Xhim.volok. no-3-8-11 '61. (MIRA 14:6)
1. Vsesoyuznyy nauchno-issledovatellskiy institut iskusstvennogo
volokna.
(Acrylonitrile) (Vinyl compounds)

88731
S/190161/003/00-1/015/020
B119/B216
AUTHORSt Mezhirova, L. P., Sheynker, A. P., Abbk~ AD.-
TITLE: The carbanionic mechanism of polymerization under the action
of gamma rays
PERIODICALs Vysokomolekulyarnyye soyedineniya, v. 3, no. 1, 1961, 99-104
TEXTs The present work studies the polymerization of acrylonitrile and its
copolymerization with styrene under the action of y-radiation at low 60
temperatures for the purposeof explaining the reaction mechanism. Cc was
used as radiative source. The experimental temperatures ranged from -50 to
-1120C. Polymerization was performed in the solvents dimethyl formamide,
triethyl amine, isopropyl amine, acetone, toluene, acetonitrile, propio-
nitrile, ethyl chloride, heptane, ethyl acetate. The reaction rate was
measured dilatometrioally. (The volume change of the reaction mixture
during polymerization was measured by the change of electric resistance of
a platinum wire and a mercury thread inside the dilatometer capillary).
The acrylonitrile polymers were separated from their solutions by means of
Card 1/3

88731
S/190/61/003/001/015/020
The carbanionic mechaniam of... B119/B216
methyl alcohol and the styrene copolymers by a heptane - ether mixture.
The copolymers were microanalyzed for C, H and N. In some cases the results
were checked by infrared spectroscopy. At -780C, and a dose rate of
128 rad/sec, the polymerization gate of aorylonitrile (initial concentgation
3-5 mol/1) was 1.57 mol/l.sec-10 in isopropyl amine, 6.7 mol/1-see-10 in
triethyl amine, 9.7 mol/l-aec*106 in dimethyl formamide and 2.1 mol/1-880-4
in the "bulk". The copolymerization constants were r, - 33 (acrylonitrile)',
r2 - 0-'005 (styrene). Resultst Acrylonitrile polymerization occurs only in
the solvents dimethyl formamide, triethyl amine and isopropyl amine, but
not in solvents with electron acceptor properties. The composition of the
copol3mers obtained at -780C by the above method and that of the analogous
copolymers prepared by a radical reaction exhibit significant differences.
The polymerization rate of acrylonitrile increases proportionately with
the dose rate. A reduction of the reaction temperature from -50 to -1120C
produces a great increase of reaction rate and molecular weight. The
findings indicate a carbanionic reaction mechanism. The authors thank
Ya. A. Tearfin and K. G. Nogteva, both at Vladimirskiy nauchno-
Card 2/3

88731
S/190/61/003/001/015/020
The carbanionie mechanism of... B119/B216
issledovatel'skiy institut sinteticheskikh smol (Vladimir Scientific
Research Institute of Synthetic Resins) for carrying out the elementary
analyses. There are 4 figures, 2 tables, and 8 referenoees 5 Soviet-bloc,
and 3 non-Soviet-bloo.
ASSOCIATIONs Fiziko-khimicheskiy institut im. L. Ya. Karpova (Physico-
chemical Institute imeni L. Ya. Karpov)
SUBMiTTED: June 9, 1960
Card 3/3

M64
g 0 19
cpat/o
AUTHORS:
TITLE:
PERIODICAL:
2 z o s, 14
S/190/61/003/005/007/014
BIOI/B218
Sheynker, A. P.p Abkin, A~ D.
Study of the mechanism of polymerization by radiation. I.
Mechanism of carbonium. polymerization of isobutylene and
styrene under the influence of gamma radiation
Vysokomolekulyarnyye soyedinenipi., V. 3, no. 5, 1961, 716-722
TEXT: The authors studied the kinetics and mechanism of separate and joint
polymerization of styrene and isobutylene under the action of gamma radia-
tion. According to published data, these monomers polymerize at low temper-
ature following the oarbonium mechanism. The kinetics of the process was
studied dilatometrioally. Isobutylene and styrene (2.5 moleall) dissolved
in ethylahloride were filled into reaction ampoule 1 (equipped with spiral
capillary 21 Fig. 1) until the level A was reached. This process was car-
ried out in vacuo and at the same temperature at which polymerization was
performed. Capillary 3 was filled with Hg- In order to prevent boiling of
the reaction mixture, sphere 5 was filled with the same mixture so that a
counterpressure existed. The platinum wire 4 with the contacts 7 was con-
Card 1/8

22564
S/190/61/003/005/007/014
Study of B101/B218
nected to a measuring bridge and, thus, the resistance was measured, which
increased due to a decrease in volume during polymerization and simultaneous
lowering to the Hg level in capillayy 3 ' The mercury was collected in 6.
Irradiation was carried ou" with C060at -780C and a dosage of 106 rad/sec.
Volume changes not oausei by polymerization (i.e., due to heating during
radiation adsorption) were corrected by a control dilatometer filled with
ethylehloride, isopentene, and ethylbenzene. The composition of the co-
polymers was determined by Ya. A. Tearfin and K. G. Noateva (analitiches-
kaya laboratoriya Vladimirskogn WTTBRi Analytical Laboratory of Vladimir
NIIS) by elementary analysis. Fig. 5 shows the composition of copolymers
consisting of isobutylene and styrene. During the initial stage of co-
polymerization, the yield of copolymer is a linear function of time. The
same holds for separate polymerization of monomers: styrene 20.1.10-6 moleA.
-seel isobutylene 14.1*10-6 mole/1-sec. Fig. 7 shows the copolymerization
rateci for different molar fractions of isobutylene. Fig. 9 presents
log'CJ as P. function of the logarithm of the radiation doae 1 (14-110 rad/secj
Also logeJ - f(log a) (c, . concentration is a linear function for both
monomers. The authors calculated the reaction constants from the data
.on the composition of the copolymers: r, (isobutylene) - 3,51
r2 (styrene) - 0.33. In radiation polymerization and at low temperature,
Card 2/8

S f ...
/C
isobut-lene is more active Vian st-!rcne.
;lu the carboniu.-.,, mechanism, sin:ilar to that in ~-lrecencc cf SnC-1., -'1"!, e
m,olecular weiC;htr, of 'he copolymers ;,ere deter:Anel b-,~ :1. V.
and found to be: ratio isobutylene: utyrcn,,~ in initial
c
0-0 0-"' : 0-1 0-5 : 0-5 0.1 0-9 C-C : I - 0; mo` - cu! ar !'t:
801000 551000 27 000) 35,CCO 70,000.
As is sho,.,in in FiU. 10, cojcl-mc3~izaticn at COC t-,il:o~ an e-,tiroly
coll1r0e. In thio ca.-.c , the radical nechanisn. cc-mcz; in -,,,la,,, b-,it tl~,-z3
a' CcC
not lend to c-rC isobut-lene. IT- -. 0
le.
contalinea ch~or Tjr, f4
.1. 2. - There E;-res a-d rr,'crences: 8 Soviet-bloc
a'ld 17 non-Soviet-bloc. The .1 mos-L 'i-rport*n'nt refercnces to
'h'~.cat-;orz read as follows- R. 7;orrell S'. *i-*, -Pl--rer, j. poly-mer.
u L. - -
p
.a, 22~1,.1959; '-7- H. J. Davison, S. It. Pinner, R. 1.7orr*ell, Proc. Roy. Soc.
167 A. S. lloff mann, j . Polymer Sci. , Lil 2LIrl , 1959;
A. , 1959; .1 1 .1 -
D--inton, J. Polymer. Sci., 34, 241, 1959- A
ASGOCIATMI: Fiziko-khimicheski~ institut in. L. Ya. Kar-ova (Physico-
cherii--al Tnstitute imeni L. Ya. Karpov)
SUBMITT"D: Jul. 21, 19~O
Card 3/8

1/cc 3/1006"005/019
B 1 1 o/'B,- 16

AUTHORS - Yakov ov -i, Y, Shoynker, A. P , AbIr-in. A. D.

TITLE: Studj~,,, cf Tli -, meOianigm of rilin,,cri r(lyrneri7lticn, Il.
titla Dethyl
r t; z or, c. f r
PERIODICAL; -3 c k k r I , yy ov e3 i r, -~ m, i y J~ 1 . 82 8-8 5 2
TEXT -. Prev i ow, 7 t lid -'m t hOT-i (Ref . I : D~,rl All.,"ISR, 124, 632,
1959) le,)j !(: Ine ~at 1,1i finr 'form. during
- f:.p o I yme r i -! a f: ;i t" ir r o tv - r. - we t ha c ry I a t e
stuiles
thi 9 i nf nr
hp,- r tre%!~el %ith 3
E: r"I a 11 fl r j eil e Z: 1 1
:)r
d
'
The 'g-inc-liro of tl: (,,i J I

a) by rom v ?.ili,
i '.n r i il 9 n c f,
ca r-i I /f,

Stud I Ps Of lbe
of CuSCItl. nrd tA r o 1 :,'m e U10-01101
in the prooi-r.,(, r!' ~i-!!
rr i r-1 (Iii i; i n the
d-
i n Cr~j vc,13
-1 in ! v 7 'i Y
C
0 1 of C
n 'i v-i :tnd 7 0 0
rl
ri;i,- T%r I v v r rP. T:1 I- -4nined in
t j! v M? - ~q
"t reL,,7 t ion
1 2
r 1~ F re of th,~
r i:-3,? cc TiI v t he forma t ion
t1;.? me,1!71 m- than I r r r e
Z3
Tt containe-- .,Itl r r - i!,ht of tror
-I t -0 r ir, rind "00 m e r 1 n The
abscirp i ~!n
1 n i p rl r i -irv- ~-ti n in
.jjoW7_ t.~,
n In t, r.7 a in c. i - i 11 r m ~ x ', i i r eThe

23762
S119016110031006.10051019
Studies of the mechanism of radiation... B110/B216
styrene oorcentration is a linear function of the monomer concentration.
Table 2 illustrates the dependence of the styrene polymerization rate on
the surface of the reaction vessel. At -780C, the use of ampoules made
of stainless steel reduced the rate of styrene polymerization. The
polymer molecular weights at an initial molar ratio styrene :methyl
methaorylate of 0.9:0.1 were determined by N. V. Makletsova by the light
scattering method at 70,000 for polySt,rrene and 30,000 for the copolymer.
W
In copolymerization under the action of I-radiation, lowering of the
reaction temperature from 250C to -780C increases the relative content
of styrene component (rl(styrene) -20; r2 -0-005). On polymerization of
these monomers under the action of y-radiation at 250C, r 1 =0.631 r2 =0.50.
In the case of a peroxide-initiated polymerization at 600C, r 1- 0,52;
r2 -0-46. Witb cation catalysts, r 1 -10-5; r2 .0.1 and with anion
catalysts r1 .0.1; r2 '6.0. The copolymer composition and the dependence
of the copolymerization rate on the composition of the monomer mixture
(Pig- 5) indicate a carbonium mechanism of polymerization of styrene with
methyl methaorylate at low temperatures under the action of I rays. Fig. 5
Card 3/8

23762
s/190/61/003/006/005/019
Studies of the mechan-lem of radiation... 3110IB216
shows that the addition of (,j 10 moles) methyl methaorylate inhibits
polymerization to a greater extent than the addition of isobutylene, but
not as strongly as acrylonitrile addition. From this it is concluded that
the inhibition increases with increasing electronegativity of the sub-
stituent at the double bond of the added monomer. There are 6 figures,
2 tables, and 10 references: 5 Soviet-bloc and 5 non-Boviet-bloc. The
three references to English-language publications read as follows:
Ref. 3: R. Worrall, A. Charlesby, Journ. Appl. and Isot., A, 84, 19561
Ref- 5: W. J. Burlant, D. H. Green, J. Polymer Sci., 31, 227, 1958;
Ref. 7: A. Shapiro, V. Stannett, J. Chim. Phys., 56, 736, 1959.
ASSOCIATION: Nauchno-issledovatellskiy fiziko-khimicheskiy institut im.
L. Ya. Karpova (Scientific Research Institute imeni
L. Ya. Karpov)
SUBMITTED: July 21, 1960
Card 4/ a

I ~- ~,' b S/1,90/6-:/005/007/008/021
---------- 2 '526 4 B,l 0 -.1 /.B 2 2,0
//, Ow /
AUTHORS: Gromov, V. F., Khomakovskiy, P. M., Abkin, A. D.
TITLE: Copclyrziertzation oi acry-.- und-r tn-
E~ff(,~ct cf ga,nma radiation
PER10DICALs Vysokomulel-ilyarnyye nc, 7, l-)bl
IG-',5 - 1019
TEXT: The c;opulymerizltion of eth~vlenc ,;nier
6o. :%llid-,ed.
the effi~ut of Fi- ,;mvi radimicln of C,,) 000 r
The tests W,21". 70!JC P
r.-- 7~ u r e
of the et"'Vir-ne k; t ci 5 an'; t'hQ _0
rad/3ec. T'-.e cl'm 11 n i n e df r om t h:,, n r) fa a ow. In,-
impil I, I C, propylenc. "'Llt -IL:Tjt2,,
hydroc..r~,~~r c-,. .14 ~;U,, , 0. G Ti,,-~~ AN tirld :i b~-,il,,n~, i) n t. :,."i ~ u:; . L
to 77.11, T:;~~ polymerizition v;as offe-ted in sice. nmipullne vith
maj:rnetiz mixor. The ampullap iilled AN dintzclv,26 in toli~ene,
li',,erat,-,d from a-,i, by freezing and th3winj :Ln vac~;,an., and oatur,,%te~,, v,,ith
C,,ird 1/ 3

25264 S~/ ~ - / 7 "C',07 ID 0~51021
Copolymeriznt_~on ,,! acryl,
ethylene under t),e abc)va-mentioned presjure. Tho polymor !311:3ponsiono
obtained were rin.3ed with methanol, dried in vac!;=i. and then the,.r
content it) nltro.~-'-n u3 ;13 th(lit' ViSOOSitV 1'. diniethy- formamide
at 2600 and with a concentraticn of ihe polymor of 0.35 --:> 0,75 g/di,
were determinQd. Data obtainea: !)for :iclar r~~ti~.; o' etaylvnc: Ali -
0.1t0.9 and 0,511' 0 thc "l-ta of .11 lin,~-rly dependent cn the
titne of polyizerization r(!.iuirc:d to achieve a 4051o cGrIVOIrsion. For -a
ratio of 0.7s0.3 the rate of polymerization increases up to 215',o coll-
versi.on and then de.~reases; 2) the intrin!,ic viscosity of the polymers
increas;,,s with the derrje. of converaion; 3) %%,itil loni, radiation (about
20 hr and more) and a molar part of the AN >0-5 the polymers become
insolubic due to cross linking; 4) the rate of polymerization increases
with increasing concentratior of the AN; 5) for Lill ratios the polymer
contains relativeiy more AN than the initial mixture. In the range of
concertrati-3ns of the AN from 0.1 - 1.0 molar parts, the equation y -
0.716+ 0-046X + O.CD19x 2 holds, wherein x is the content of AN in the
initial wixture and y ttLe content of AN in the polymer; 6) the calcu-
lated constants of copolymerization are: r 7, r ' 0. r, de-
l(AN) 2~~
Card 2/3

Cci o' 25264 S/190/'61/003/007/'008/02",
P lymerization of acryi .... B101/15220
creases, however, if the content in AN exceeds 0.7 molar parts; 7) the
followinr -- constants were calculated for the copolyi,it-rization of ethylene
with CO, basod on the data given by 1J. Rrubaker et al. (see 'be1o-.,,,,):
r2(CO) - Q-25; r2(C 2H4) ' 0-57. G, S. Kolesni-Knv. A. P Siinrur. and T
A . ~j I e kr;- are mentioned. There are 7 figures, 2 tables and 10
COS.,
oov2.et-bloc, and 5 non S-viet-bloc. The most important rcferen-
ces to English-language publications read as follows: M. Brubaker, ii.
Coffman, H. Hoehn, J. Amur, Chem. Soc. 74, 11509, 1952; ~i. Kay, Industr.
and Engng. Cher,-,. 40, 14~-19, 1948.
A&;0CLMON; Fiziko--khiniicheskiy institut im. L. Ya. Karp:)va (Physico.-
chemical Institute im. L. Ya. Karpov)
jt1,dMIT'-`ED: September 20, 1960
Card 3/3

I
S/6'-~
190761/'003/008/005/019
B110/B220
AUTHORS: Abk1n, A, D... Shpynker, A, P., Yakovleva, M. K.
TITLE: Study of the mechanism of radiation polymerization,
Ill, Mechanism of carbonium radiation polymerization
PERIODICAL: Vysokomolekulyarnyye soyedineniya, v. 3, no.. 8, 1961,
1135-1139
TEXT: Previously, the authors had studied the effect of gamma radiation on
polymerization and copolymerization of isobutylene, styrene, and methyl
methyarylate (!.'11A) dissolved ir. ethyl chloride and shown triat they proceed
at low temperlLtUX'08 (-780C) according to the carbonium meohan,.em
Liezhdunarodnyy sympozium. po makromolekulyarnoy khimii, SSSR. Yloskva
International Symposium of I-laoromulecular Chemistry, USSR. June
~
14-18, 1960; V3,sokemolek. soyed, 5-, 716, 1961; ibid., ) 8128, 1961). Some
ideas with regard to this mechanism are put forward in the present paper.
The initiation of polymer chains is effected by interaction between a
monomer molecule and a proton presumably originating from the solvent. The
following ex.erimental data are given in confirmation of this assumption:
Card 114

262Y.'
S/190/61/0035/008/005/019
Study of the mechanism of B110220
1) The polymerization rate is a linear function of' the monomer coricentratia-4
2) radiolysis of ethyl chloride at 780C yields a product closely related to
20
-dichlorobutene as to molecular weight (132) and refractive index (n D. IA812);
3 at -78 0C the polymerization rate of isobutylene "in mass"
(46.7-10- 6 mole/1-sec) is lower than in a solution of ethyl chloride (con-
centration of isobuty)ene 12.6 mole/!: 71.2-10- 6 mole/1-sec), The
following mechanism to assumed: The growing carbonium ion ejects a proton
which forms a free radical with the negative molecular ion (counter _ion) of
the monomer. The participation of the negative monomer Ion is proved by the
fact that the polymerization is strongly inhibited in the presence of a
monomer wi.h electron-acceptor properties. The copolymerization of iso-
butylene and styrerie as %&e11 as of styrene and LIMA follows the equation:
W + 1 ) (r1A2 + 2AB. + r2B2 )-W ub]/[Abr,A 2 + )( (j LbAB + 0 r 21 where
a a a 2B
co is the total rate of copolymerization; A and B are the concentrations of
the monomers A arid B. respectively; ia a and Ob are the rateB of separate
Card 2/4

26,2111190/61/003/008/005/019
S
Study of the meohanism of ... B110/B220
polymerizatl,~. of A and B, respectively; X a v a /Vbis the ratio of the
f,,rmation rates of active centers of A and BI
X - (k brA+B/kinerA+B t kbrB-A /k,n crB+A)/vb' where k, nor -rate of chain
growth; kbr is the rate of chain rupture. The two unknowns ~ and I can be
determined experimentally from W , , and from the copolymerization rates
a "b
at different ratios of the monomers. Data obtained for the copolymers of
isobutylene (A) and styrene (3): A - 41 8~106; for styrene (A) and
6
MMA (B) 10; -X - 440-10 . It was observed that the polvmerization rate
of styrene increased at -780C with increasinQ, :iurface of the reaction vessel.
The authors established an effect that is analogous to that of solid ad-
mixt-uree observed by R, ~-orrall et al. (J. Apple Rad. a. Isot,, A, 84, 1958),
The monomer molecules adsorbed on the surface of the reaction v(-.Elsel have
a higher electron affinity than the molecules in the volume, and are able
to capture secondary electrons. Thus, the lifetime of the carbonium ions
effecting the rolymerization process is prolonged. Moreover, the influence
of the surface is confirmed by a reduction of the molecular weight of the
Card 3/4

S~19"0~61/003/008/005/019
Study of the mechanism of ... B110/B220
polymer at -780C when steel ampullae are used instead of g2ass ampullae.
S~ S. Medvedev is thanked for his interest. There are 2 figures and
7 references: 4 Soviot and 3 non-Soviet, The most important references to
English-language publications read as follows- Ref-4: A~ Shapiro,
V. Stannett. J. Chim. Phys., ~_6, 830P 1959- Ref.06: F, R. Ma-,,o, Ch, Walling,
Chem, Revs., 46, 191, 1950~ Ref.7: R. it'orrall, S. H. Pinner, J. Polymer
3ci. , a, 229, 1959.
ASSOCIATION: Fiziko-khimicheakiy institut im, L. Ya.. Karpova (Physico-
chemical Institute imeni L. Ya. Karpov)
SUBMITTED: September 5, 1960
Card 4/4

2 ~ 7 4- 1
uol 11 14 S G, S/1qD/61'C)D3/o)I/015/016
BIIO/BI41
Ushzkov, V. D., Mezhirova, L. P., Galata, L. A. t,K A-7
Z'`.%snutdinova, Z. S. , Medvedev, S. S. , Abk,.n, A. D. ,
Xhomikovckiy, P, M.
Polymerization of alyrene and butadiene svith styrene in
cmuluions under the action of initiating redox syjt-~,ms.
T. Effect of the nature of pcroxide compounds on the raln
of polymeri:,ation
11711 0 D I C A LVyjokomolekulyarnyye soyedineniya, v.3. no. 11, 1961,
1716-1722
NEXT: Ain of the present work was the determination of the mant active
redox syntems for the polye,.erization of butaliene "ith styroni,
in emulsiona, and especially 0, the effect of the nature of perox,,dea on
lae rate of polymerization. Nekal with 20 1,, of Na2so4and NaCl and
norLolnte (mixture of Na salts of vulfonic acids of the aliphatic serl0b.
(,,F 50 NI;) with < 5 % of RaCI Berved as emulsifiers. Perox:des were uac3
31

It
7111.
S/190/61/003/01 1/015/016
Polymerivition of styrene and... B 110/1) 1,17
!!a OxIdlint!) (Table). Potas5itim ferrocyanide and forrDis pyrophonphatc
ccT!v!-: (IV) --rvcd ris r-Mucing nrentv. The rnte of polyziLrization u-LI;
J"t-'rimint-d vither dilutometrically cr from tho yield a-,' polymur
1 .r~: , at ior, trck plrce lit 5'~c ;vl th im f.),conn of butnei flit', rilyreni, wi th
dii.,olved in '1. (10 1,, solution). nird the citloulated ~ivnoun'. of
n i f. r ri,njui ion .A nuoptntion of Ili,- ferrouc; pyrophLiqhatc win
at 1, rtIrtar IttImperature by meaw, of mod2cal ryr,.n(~e.-_ rL, n :; t 11:. r ~, 4
(11' mor;-ollaii (5 1, by r~-irht -idued to vriter, ratio mcriomer . ~mlilsif.,Pr
0) pota~isi,4m ;,rrocy-irode. Thp temperature va3 varieJ bvt~e-zr
C-tnd Percrider; urro inveatjga~rd ir, amourits equiva"n". I':
0 aioi O~I by weight of 'Inupropyl benzone hydrrperoxide. V-K
,n Izonctr.tratior!~ equimclef7ular tr hydroncroxIde- P-tert-lu-%yl
um ratL of vr)lyveri.-,iicn;
ztnz~~!-~ Yydroperx-.de (1) had th,,? cptim
i-topropyl honu-no peroxide, iropropyl tictiunp- (111), .1~a
hydroper oxide ran lower, that of dibonzyl hyrjrop,~roxidp still
iinl that of b,tnzoyl pQroxide the leivest. Polymerization with H 0,
nce 11 0 a,,d
pzoc~-,s fujt at trio beginning, then it decrenses 3trongly, si 2
,ne 7PdLC!nr qp-~nt are readily soluble in witer. With 0.2-0.5 1,, by weight
C:i ro 2 / If

It
S/ 1 90/61/003/011/013/016
Polymerizatinn of styrene and ... 13110/11147
11, only the initial rate incronseq. The total yield is lorT-r than
viith 0.1 by %eirht of II. Betvron 0.75 and 1 .' by %cight of II, initial
raten ani total yield are much lorer. 'With 0.07-0.2 "m by WeiciA of 1,
initinl rnten increase. Since the total rate decreazies at 0.2 1"o by rciehtj
the dependence of the reaction rate on the hydroperoxide concentration is
linked with the inhibiting effect of the decomposition products
of hydroperoxide. With 0.1 ~~ by voijht of I and an equirolocular amount
of rf 4Fo(C,1)G, both total yield and initial rate incroaued with increaning
tv-,peraturp. The activation energies viero determined according to the
Arrhenius eauntion and found to be: E -A.6 koal/=olo for II and
5-7 Pcal/mole for I. Reduction of E by 3 kcal/role at - OOC corresponds
to a 200-fold increase of the reaction rate. Since the ra%e iu %vice an
higli at OOC, the pre-expofiential factor in the Arrheniua equation increases
by *02 times with decreasing activation energy of I. For the copolymerize-
t3.on of butadiene with styrene (ratio 70 -.50) at 50C, the following was
1 (2.8 and 1.4 % by veight added to %ater). 0 .44 *' by weight
used : Nekal 71
of ferropyrophoophate (related to iron sulfate) of the monomer. The ratio
orranic phase :aqueous phase was 1 :4 (by weight). In the case of 0.34
Card 3/7

,9A1
S/190/61/005/oli/013/016
?olymerization of styrene and ... B110147
by Neil-.ht of hydroperoxide of 11 (equinolar ratio to the monorler) optimum
rate ran achieved rith IV. The highest yield was achieved with aryl-alkyl
hyd rope rox id es (I and 1.1-diphonyl ethano hydroperoxide (111)) (Table).
an emulaifi-r concentration of 2.8 j', i-nximum convoraion (70-75 '1) was
achieved after 2 hr wit% 0.2 ~ by veirlit of I und with 0.3 -,,' by rcielit cr
!!I. 'With 0.54 ~'- by weight of 11, optimum conversion (~j3O ~,) was itchieved
after 2 hr. polymerization of I and IV with 1.4 or 2.8 by voight of
,,mul3ifior was conatant up to 30 ~. conversion, then the rate dropped. With
1.4 by %ei(;ht, the initial rate was lower and the decrease more distinct.
'.7ith an addition of 0.1 % by weight of hydroperoxide +0.26 ~'~ by weight of
17 (Pfter 1 hr new addition of 0.1 % by weight of hydroperoxide and 0.16 %
by %eieht of IV), constant polymerization took place up to 60 1,4 conversion .
Thus, thc- consumption of the initiating system causes a decrease in rate.
'~'he efficiency vf redox systems and initiators depends on the rpactivity
of the rnlical va well its on the solubility of the neroxide compounds in
thc i~,jticoua iftif7v iind )n the monomers. The loiter the solubility in Waler,
thc !over Lite lorn and the ntronger the initiating action. I +IV cause a
hir",;cr r-te of reaction than II+IV due to lower activation energy and
lo.i.-r solubility in water. For II *IV, the redox reaction occurs at the
Card 4/7

14 Itf ti 7L2
I- S/I90/61/CiO3/011/014/016
B1 10/B14
Uoha%ov, V- D,, Yezhirova, L. P., Galata, L. A.,
X-lairuLtdinoyn. 7- _ Sheynker, A. P., Yedvedev, S. S.,
Abkin, A. D., Khonikovakiy, P. M.
IT LE: Polymeriz3tion of styrene And buttadiene with ntyrvne in
emulsions under the action of initiating redox syotems.
IL Ef'oct of the natiare of the reducine npent on the rate
of polymerization
PFRIODICAL: Vysokomo1eku1yarnyye soyedineniya, v. 5, no. 11, 1961,
1723-1729
'X7
Tne '!`fert of tho redlicinp Component of illittating "Ivvt"rl!~ antl of
inu addition of a aecond roducing agent on the rate of pol -vmerizn-tion Is
OtIl"'Jed Uscd upre Dyatema of hydroperoxides (lip) of isopropyl bonzeno
(1) or n-tcrt-hutyl iuopropyl benzene (11) with forrepyrophoipin'to
(111 potassium ferrucynnide (IV). ferrous o-difeto ivith
-phvnantnroline, or of complexes of a,a-dipyridyl with ferrou3 oxalate.
'-dium 'Disullite and the bisulfite Compound of acetone served ae reducing
1/5

2974 2
~Y`1/6.1;fon~ /0'.
"o I tor. 0: :1 nd
t,: :ic:~ ovtA af to r 4 hr nt a rr.;,. io 0. 5 IV I The hir-h rat, of
1y';'. r .7;i1ton for systemo %ith III i:~ cauf,cd by ttiv Io% of
I r he rudox jo 111, n t. o I in :';)0 mv 1:1 n % (I I L,
ot r-ic t L i t n 1 1 !Tnlvc~; only nlowiy, Tit,.- c~.ust tni,
TV ri1h h1rh po~qitive Potential (420 13... 1 .,n voluciv
i,, determined by JntcriLC:'-tcr. ,: 7:-.'
rate of initizxtinrz
I 'olvriori?,tition in not in-,tiated during ne unproductvt r"action
L I ~il q b 1 '0 and -.,.ell !-,olul-le UP 1. NaHSO 5 and poorly oolublt,
;I nit The efent of IV on .11 .0 200C corvIsts
t it~ 9f, "l-l"'etly th~ ;i. vtl;
v rc i t .,~i r7,
I .I Itw. in :11,; 1 1* a nJ Ni

;A:1) %'r. 993-6 19 June
R.A.DIATION POL11"MERIZATION OF TETRAFLUCROETHYLENTE IN THE
SO:,-TD STATL (USSRO
Druk, A., A-D-Ahkin., and P. M. Khomikovskiy. IN: Akademiya nauk
Doklady. v. 1,19, no. 6, 21 Apr 1961, 1322-1325.
S/020/63/149/006/014/027
:~a,liation polymerization of tetrafluoroathylene (TFE) in the solid state
i~Zis. studiied at the Physicochemical Institute imeni L. Yu. Karpov..
li
of pur,,~ TFE were frozen by immersion in quid nitrogen and
to
from a Cc;, source with an activity of 60, 000 g-equiv of Ra 6r
om ~F_n e- zron acceleralor with an energy of 1.5 Mev. The -:eld of the
Pol-1,7mers was determined gra,.rimetrically following: last defr,~ezing of ir-
radiated specinn ens. The RPR spectra were recroded with the us e of
:'::-1301 type devices; the absolute concentrations of radicals were evalu-
of a stakidard with
-1ted by cornp-rison of the signal areas of the sample and
Card 1/2

.1
C\8 -6
A
F-CIL)2CRIZATION [Coatldl. S/020/63/149/oo6/m4/027
a ~-nown concentraiion of paramagnatic particles. It was shown that - 1) the.
polymerization rate of TFE in the solid state increases with tempera-
-,,r e, a'tains a maximum near the melting point, and drops sharply a f t e r
2) th e totil activation energy of polymerization is 0.6 kcal/mol in
t - C~ - 19 5to -155*C ran,---e and 1.6 kcal/mol . at -155 to -131"C; 3) rapid anni-
1, 1 lat i cof rc~dicah~ takes place in the -180 to -1400C range and in the -80 to
-50'C ange; ard 4)the character of the radical annihilation and oh-angesin -the----.--
-s p e cTra observed at low temperatures suggest that these spectra are
associated with t:ie radical formed in the monomer, and the spectra ob-
served at -150*C ard -above, to the radical in the polymer; Fjnall~, it is assume!d
L&Mt the poly.-ner radical has the structure
F F
F F
and is formed ir the system as a result of the growth of the polymer chain.
Card 2/2

31885
S/183/ 2/000/001/001/001
B110/11147
AUTHORS: Dorokhina, 1. S., Abkin, A. D., Klimenkov, V. S.
TITLE: Copolymers of acrylonitrile and vinyl acetate
PERIODICAL: Khimicheskiye volokna, no. 1, 1962, 49 - 54
TEXT: The composition of copolymers of acrylonitrile (I) and vinyl
acetate (II) in (a) aqueous emulsions, and (b) homogeneous dimethyl fbmamib
solutions (DMF) with peroxide initiators in different steps of
polymerization was studied. The following values were found for a:
monomer:H20 = 1:3, emulsifier concentration = 3% by weight of the
monomer, X2 SO5concentration = 0.3% by weight of the monomer,
temperature = 50 C; the values for b were: concentration of monomers in
DMF = 4 moles/liter, benzoyl peroxide concentration - 0.048 moles/liter,
temperature - 50 0C. Copolymerization was first investigated in 30 - 40 ml
dilatometers for a conversion of 10 - 15%. The copolymer obtained from
an aqueous emulsion was coagulated by a 10% aqueous NaCl solution, that
obtained from DMF by a 60 - 70% DMF solution. In this case, the
copolymers were extracted by benzene. Further copolymerization in
Card 1/4

318
S/183/62/0007001/001/001
Copolymers of acrylonitrile ... B110/B147
aqueous emulsions was investigated in a 6 liter reaction vessel in N 2
atmosphere (4 0.05% 02) in the presence of K2SO5* The authors determined:
(1) the composition according to nitrogen content (Kjeldahl), (2)
characteristic viscosity of 0.5% solutions of the copolymers in DMF, (3)
their solubility (qualitatively), (4) density, (5) vitrification
temperature according to V. A. Kargin et al. (Ref. 6: ZhFKh, 23, 630
(1949)). When the degree of conversion was low, copolymerz of different
characteristic viscosities were obtained. The lower -~char of the
copolymers obtained in DMF solution are caused by chain transfer through
the solvent. The dependence of ~char on the initial monomer composition
is caused by different reactivities of monomers and radicals formed from
them. This dependence is practically the same for copolymers from a DMF
solution and from aqueous emulsions For an arbitrary initial component
ratio, the copolymer is always enriched with I. The copolymerization
constants (r1 = 4.2, r2 obtained according to L. Gindin et al.
(Ref, 8: ZhFKh, ~1, 1269 (1 47 ) show that the rate of addition of I to
its own and to a foreign radical is higher than that of II. Since with
Card 2/4

31885
S/183/62/000/001/001/001
Copolymers of acrylonitrile ... B110/B147
arbitrary initial monomer ratios I is faster consumed than II, only II
polymerizes in many cases. Integral copolymer composition changes with
the degree of transformation, with the contont of I decreasing. Differential
copolymer composition changes stronger than integral copolymer composition,
with howopolymerization of II taking place when I is exhausted. The intra-
molecular distribution of chain links was calculated from the formulas for
the distribution functions according to L. Gindin et al. (Ref. 11: DAN,
SSSR, 56, 2, 177 (1947)). With a high content of I in the initial mixture,
the macromolecules are made up of long links of I connected by 1 2 links
of II. Copolymerization of I and II (initial molar fraction of 1 0.679)
with 70% yield results in an equimolar ratio with an integral composition
of -80% M of 1. Macromolecules of the copolymer- (50:50) consist of
successive Bections of I and II with 1 - 10 links of each component.
Solubility increases, and specific gravity and vitrification temperature
decrease when the fraction of H is increased. The fraction of the
Copolymer enriched with II acts as a plasticizer in fiber production, and
deteriorates the properties of the fiber (resistance to heat). There are
6 figures, 5 tables, and 12 references: 5 Soviet and 7 non-Soviet. The
three most recent references to English-language publications read as
Card 3/4

318
S/183/62/000%01/001/001
Copolymers of acrylonitrile ... B110/B147
follows: F. R. Mayo et al., J. Am. Chem. Soc,; 12. 1523 0948); R. M. .
Fordyce et al., J. Am. Chem.-Soc., 10, 2489 9481; T. Alfrey et al., J
Polymer, Sci., 5, 719 (1950) ~'v
ASSOCIATION: VNIIV
Card 414

DYURKBAUM, V.S.; AU INt A.D.) KUHMOVY V.S.
Composition and intramolecular distribution of copolymers of
aer7loriltrile vith butylvinyloulfonate and mothacryiamide. Xhim.
voloke no.2slO-34 162. (MIRA 15:4)
1. Vsesoyuznyy nauchno-isaledovatellskiy institut iskusstvennogo
volokna.
(Acrylonitrile) (Sulfonio acids) (Hathaerylamide)

S/183/62/000/005/001/002
B101/B186
AUTHORS: Dorokhina, I. S., Klimenkov, V. S., Abkin D.
TITLE: Production of fiber-forming oopolymers from acrylonitrile
and vinyl acetate
PZRIODICAL; Khimicheakiye volokna; no. 5, 1962, 16 - 21
TEXT: This second paper on copolymerization of acrylonitrile (AN) with
vinyl acetate (VA) describes laboratory and pilot plant experiments in N
atmosphere at 50 OC aimed at the production of copolymer fibers containini
3 - 20X, VA, and listu the properties of the fibers. Results- A copolymer
of the ratio AN : VA = 90 :.10 was found to have optimum properties.
Because of the higher reactivity of AN, this was added in successive Ooses
during the prccess, together with.the regulator and the emulsifier, so as
to obtain copolymers of constant composition. The inhibiting effect of 0 2
-contained in N was suppressed by 0.03 - 0.05~ hydrosulfite. Since the
2
reaction velocity strongly increases owing to the redox system formed, N 2
was used with a maximum of 0.5 - 0-8% 02' The following optimum conditions
were found experimentally: ratio monomers : H 20 - 1 3; ratio AN : VA in
Card 1/3

S/183/62/000/005/001/002
Production of fiber-forming..'. BIOI/B186
the initial mixture equalling 68 : 32; content of initiator (water-soluble
peroxide) 0.7' of the monomer weight; emulsifier or Sulfano14)
3. e,; regulator (Diproxid) 0.03~4; duration of process 4 hr3, yield 70-78~j.
In the laboratory test, the fiber was spun from 14 167~~ solution of
copolymer in dimethyl formamide. Oxidized hydrocarbons (C 12 - C15) were
used for the precipitation bath (90-1000C), and triethylene glycol for the'
drawine bath (1000C). In the pilot plant test, spinning was performed
through spinnerets uith 4800 or 12,000 openings, following a procedure
-developed for polyacrylic fiberG, in a 40-60% dimethyl formamide
preCiDitation bath. The "nitron B (V)" fiber showed a breaking length of
25 - 30 km, an elongation after embossing of.20-25i4, and a shrinkage in
boiling viater of 25-30,*. Increased shrinkage occurred with increasing VA
content, fiber with 20;v VA was poorly heat-resistant. The vitrification
temperature was 80-020C for 101o VA, and 65-70 C for 2011~ VA, as against
85-900C for pure nitron (polyacrylio fiber). The new fiber can be
colored by basic or disperse oolorants. Colorability increases 'With
increasing VA content. A VA content of 10-12% is recommended for the
production of staple fiber, a VA content of 2Q~ for fur manufactured from
man-made fibers. There are 3 figures and 4 tables,
Card 2/3

S/183/62/000/005/001/004
Pro4uction of fiber-forming... B101/B186
ASSOCIATION: VNILIV
SUBMITTED: Auguat 26, 1961
Card 3/3

B/069/62/024/005/003/010
B107/BI86
AUTHORS: Dorokhina, 1. S., Abkin, A. D., Klimenkov,*V. S.
-TITLE: The part. played by the distribution of monomers between the
phases in the emulsion copolymerization of acrylonitrile and
vinyl acetate
PERIODICAL: Kolloidnyy zhurnal, v 24, no-.5t 1962, 549 - 553
TEXT: The distribution of monomeric acrylonitrile and of vinyl acetate
between the hydrocarbon phase and the liqnid phase was examined at 50 0 C,
both rith and without the addition of MR (MK)'as'emulsifier. A likely
reaction mechanism of the polymerization is suggested. The distribution
by voluise was determined after shaking togbther a mixture of monomerq and
water for one hour. The initial proportion by weight was 3:1. The
prODortionate amounts of acrylonitrile and vinyl acetate were determined
by refractometry, applying a correction for the solubility of the hydro-
carbon phase in water. The results are collected in Table 1 and Table 2.
The rat*io of acrylonitrile to vinyl acetate in the hydrocarbon phase is
Been to.be only slightly displaced, whereas considerable deviations appear
Card 1/4

S/06 62/024/005/003/010
The part played by the distribution... B107YI3186
in the aqueous phase. The solubility of the monomers is slightly greater
in soap solution than in water. Polymerization experiments carried out
with different quantities of emulsifier indicated that the polymerizing
reaction proceeds firstly in the soap micelle and later in the polymeric
monomer particles. There are 4 figures and 2 tables.
ASSOCIATION: Veesoyuznyy nauchno-iosledovatellskiy inatitut iskusst-
vennogo volokna, Moskva - Mytishchi (All-Union Scientific
Research Institute for Synthetic Fibers, Moscow - Mytishchi)
SUBMITTED: August 12, 1961
Table 1. Legend: a - composition of initial monomer mixture ~acrylonitrilo-
vinyl acetate); b - hydrocarbon phase; c aqueoue phase; d - solubility
of monomers in water in %; e, k, m, - mole~o; f, 1, n - wt.%; g, i -
composition of monomeric mixture (acrylonitrile - vinyl acetate); h, j
quantity of monomers in % of initial quantities.
Card 2/4

3/069/62/024/005/003/010
The part played by the distribution ... B107/B186
Table 2. Legend: a - romposi 'tion of initial monomer mix'ture (acryl~onitftle_
vinyl acetate); b - soap solution (11% 00; c - hydrocarbon phase in the
presence of the emulsifierl d - solubility of monomers in %; e, h, 1
mole%; f, i, m - wt.%; g, k - composition of the-monomer mixture
,acrylonitrile - vinyl acetate; J, n - quantity of monomers in % of
initial quixntities; o in 1~j M solution; p in*pure emulsifier.
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Card 3/4

S/06 62/024/005/003/010
The part played by the distribution... B107YB186

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Card 4/4

8/19OJ63/005/003/016/02%
DIOVD203
AUTHORSa Dorokbinat I.-B.9 Okin, A. D., Klimenkov, V. S.
TITLEs Kinetics of copolymerization of scrylonitrile and vinyl acetati
PERIODICALs Vyi;okomolekulyarnyye noyedineniyat vo 5, no. 3# 19639 385-392
TEXTs To study-the possibility of synthesizing fiber-forming copolymers,
the kinetics of copolymerization of acrylonitrile (AN) and vinyl acetate
(VA) was invesiigated in dimethyl formamide (DUP) and in aqueous emulsion.
In DW the concentration of components was 4 moles/liter and copolymeriza-
tion was performed at 500C with 0.048 moles/liter benzoyl peroxide. Ini
aqueous emulsion the monomer # water ratio was I s 3 and potassium per-
sulfate served as initiator. The following values were calculated from the
equ:Ations developed In the thesin by Min (Fiaiko-khim. in-t im.
Lo Ya. Karpoval Rep 1951) for the reaction in DUFs k - It 0 - 40, r, - 4~21
r2 - 0-05, constant of cross termination ktAB ' 6.78#108 liters/molesseo,
-8
constant of the initiation rate k - k' - 2.65-10 litere/mole-ace. For
-A B
copolymerization In the emulsion, the values weres 8P 9 - 1709 con-
Card lip...

S11901631005100310161024
Kinetios of copolymerization of ... B101/B203
stants of the rate of Brovth k BB , 1632t k 66t k 361o k 32)700t~
10 AD AA BA
k -7 '10 P kA - 22-4-10-7, kj - 2.8.10-7 liters/mole-seo. The index,
tAB ' 3 3
A refers to AN, the index B to VA. There are 3 figures and 2 tables.
ASSOCIATIONt VaesoyUznyy nauohno-icaledovateliskiy institut iskusetvennogD
volokna (All-Union Scientific Retjearoh Institute oi Synthetio.
Fib era.)
SOMITTEDs August 26j ig6i
Card 2/2

S/190/63/005/004/001/020
AUTHORS: -Mezhirova, L. F.p Smigasevich, Z., Sheynker, A. P.-,~~L.D.
TlTLS: Carbanion mechanism of gamma ray initiated polymerization
PERIODICAL: Vysolcomolekulyarnyye soyedineniya, v- 5, no. 4, 1963, 473-478
T;AT: The Co 60 gaimaa ray initiatod polymerization of acrylonitrile (AN)
and copolymerization of AN with styrene (St) and methyl mnthacrylate (4=,K)
are discussed. Results; (1) At -780C the polymerization of AN initiated
by gamma irradiation ran successful in triethyl amine only, while at 000
the electron donor or accoptor properties of the solvents (triethyl amine,
ethyl chloride, acetonitrile or butyronitrile) had no effect on the poly-
merization. (2) 'Jhon copolymerization of AN with St was initiptod by
(;amria rays, copolymers enriched with AN formed at low temporaturos, while
at normal temperatures an azootrope characteristic of the radical polymeri-
zation of these monomers wan formed. (3) Copolymerization of AN with
init`m.ated by ga=:L rays, yielded in triethyl canine at -"180C a polymer en-
riche(i with All, independently of the initial ratio of the monomers.
rkit 0 7.0, r.I,',,',A - 0.05, these values being close to those for catalytic
Card 1/2

3/190/63/005/004/'001/020-
Carbanion mechanism of gamma ray ... B101/B220
anionio polymerization. (4) The kinetics differs from that of radical
polymerization. MIA polymerizes moreslowly (0.04-1o-5 mo,Lj/i-sec) than
1,11 (0-96-10-5 mole/1'seo)- (5) These differences confirm the carbanion
machaniom suggested by the authors for the polymerization and copolymeri-
zation of All by gamma irradiation at, low temperatures. There are
3 figures and 2 tables.
ASSOCIATION: Fiziko-khimicheskiy institut im. L. Ya. Karpova (Pbysico-
chemi6al InstiLute iiaeni L. Ya. Karpov)
SUB.'--'ITTED:. Au6ust 26, 1961
Card 2/2

3/19'0/63/005/004/002/020
B101/B220
AUTHORS: Gere,simov, G. N., Abkin, A. D., Khomikovskiy, F. M.
TIME: Mechanism of heterogeneous polymerization of ethylene under
the effect of ionizing radiations
PERIODICAL: Vysokomolekulyarnyye eoyedineniya, v- 5, no. 4, 1963, 479-48")
TEXT: A method was developed for determining the diffusion coefficielit-OS
ethylene in polyethylene by plotting the desorption curve, after the poly..
ethylene had beten previously saturated under pressure (up to.200 atm) with
ethylene. Tha*desorption-induced change in weight of the polyethylene wasi
meaj=ed. The d_~ffusicn coefficient was at 250C r%13,5, at 38OC-,6.0, at
500C,,jg.O. The solubility of ethylene in polyethylene is proportional -to
its volatility, and with constant volatility independent of the temperatimn.-
71ith constant tFtmperb6ture, the diffusion coefficient is independent of tho
a oTi-i b i-ty- of -_ eth-y!6ne.--The---dp-ec--ific--su-r-ra-66 wil the-pore
polyethylene was determined with crypton by the method of A. Zettlemover,
A. Chanda, B. Gambble Wi Imer. Chem- Soo., 72, 2752, 1950). The speoifia
tace was dependent on the conditions of polymerization; it was
~g):20.2 vrith a dose of 62 r/seo,. 500 atm, 700C, irradiation time 10 hr;
Card 1/2

S/1190/63/005/004/002/020
11'jechaniom of hoteroConeous BlCl/B220
33-2 at 141/r see, 400 5 141 r/sec, 400 atm,
2500, 12 hr. Assuming cylindrical pores their internal diwjeter-~, and
wall thiokness d aro-calculated: ro - 1.66.'io-5 cm, d - 6.32-10 -
1.69*10-5 cm. Based on the cylindrical model and using the method of
J. Crane (Mathematics of Diffusion, Oxford Univ. Fress, London, 1957), a
rate of ethylene addition at the radicals inside the po%mer of 23.2 sell
was found, whereas the experimental data vary between 8.) and 45.0 g/1-hr.
This difference is explained by the fact that the concentration of the re.-
active radicals inside the polymer is less than 10 mole/l. From the
proportionality between rate of polymerization and specific surface it is
coneltded that the reactive radicula are mainly at the surface of the
polymer. Thero are 4 figures and 3 tables.
'ASSOCIATION: Fiziko-khimicheskiy institut im. L. Ya. Karpova (Physico-
chemical Institute imeni L. Ya. Ka--pov)
SUBMITTED: November 5, 1961
Card 2/2.

BRU, M.A.; A-B.~K!N, A.D.; KHOMIKOVSKIY, P.M.
Radiation-induced polymerization of tetrafluoroethylene In the
solid state. Dokl. AN SSSR 149 no.6:1322-1325 Ap 163.
(MIRA 16:7)
1. Fiziko-vimicheskiy iftstitut im. L.Ya.Karpova.
(Ethylene) (Polymerization)