SCIENTIFIC ABSTRACT BARKALOV, I. M. - BARKAN, D. D.

• Document Type: CREST
• Collection: Scientific Abstracts
• Document Number (FOIA) /ESDN (CREST): CIA-RDP86-00513R000203620012-5
• Release Decision: RIF
• Original Classification: S
• Document Page Count: 100
• Document Creation Date: November 2, 2016
• Document Release Date: June 8, 2000
• Sequence Number: 12
• Publication Date: December 31, 1967
• Content Type: SCIENCEAB

B/190/63/005/003/013/024
BIOI/Bi86
AUTHORSt Berlint A.~ A*# Golldanakiy, V. 1.9 Kuo Min-kao
a
TITLEs Kinetics of phenylacetylene polymerization initiated with
benzeyl peroxide
PERIODICALs Vyookomolekulya--nyye soyedi-neniya, v- 5, no. 3, 1963, 368 -372
TEXT: The decompositlon of benzoyl peroxide (BP) in phenylacetylene
was studied in the absence of oxygen at 60 - 800C by iodometrically deter-
mining the remaining BP, by titrating the benzoic acid formed and by
cryoscopically determining the molecular weight of tne polymer formed. The
concentration of the components dissolved in benzene was 1.72 - 9.11 mole/li
PA, 0.0137 - 0-0840 mole7l BP. It has been found that the polymerization
stops at a low degree of conversion, that the decomposition of BP i& PA
takes place more rapidly than in vinyl monomersp and that the reaction is
of first order with respect both to PA and to BP. The maximum yield of
poly-PA is directly proportional to the BP concentration where 6.8 mole PA
are polymerized per mole BP. The molecular weight of the polymer was 730-
The activation energy of polymerization to 21 + 1 kcal/mole. Hence the
'Folymerization proceast
following reaction order is suggested for the
Card 1/2

S/19 63/005/00%;/013/024
Kinetics of phenylacetylene... BIOI~B186
k k k
Re 1 2
(0) M + P -4 Re + Be I X R*; (2) M + Re RH + M*;
k k k
(3) M + B*::~4 Bk + Me; (4) R*U,.--- termination; (5) Me + M :14
termination;
(6) Re + Re k6) termination. M is the m Ionomerp P i's benzoyl
peroxide, Re is
the polymer radical, Be the benzoyl radical, BA benzoic acid.
Since[R ,4,M
reaction (6) and reaction (4) can be neglected., W - (3 + ki/k2)k
OLM31p] ,
holds for the reaction rate, V - 3 + k,/k. for the chain lengVh,
from which
it follows that at v;:~_-7, k,/k2 w 4. Conclusions In the
radiation polymeri-
...zatign studied earlier (Vysokomolek. soyed., 2, 1103, 1960) as
well as in
the peroxide-initiated polymerization the same mechanisms are
active, which
is obviously a characteristic feature of tho polymerization of
acetylene
hydrocarbons. There are 5 figures and 2 tables.
:_ASSOCIATION: Institut khimicheskoy fiziki AN SSSR (Institute of
Chomical
Physics AS USSR)
SUBMITTEDt August 18, 1961
212

;/190/63/005/003/014/024
B100203
AUTHORSi ___Bajkajqj#- Jj_jA.L_Qoj1danskiyg Vo Iop Kotovaq Lo Met
Kuzlminat So So
TITLE:' Radiation polymerization of acetylene derivatives
PERIODICAL: Vysokomolekulyarnyye soyedineniyal v. 5, no. 3, 1963,
373-377
TEXTs The radiation polymerization of hexyne-1, cyclohexyl
acetylene, and
octyne-1 up to 10-12% degree of conversion was studied by a method
descriWi
earlier (Vysokomolek. soyed., 2,. 1103, ig6o). The results were
compared
with those obtained for phenyl acetylene. The rate of polymerization
de-
creases in the order phenyl acetylene >octyne>hexyne, cyclohexyl
acetylene,
and is proportional to the first degree of irradiation intensity. The
0
polymer yield between -196 and 0 0 in independent of the radiation
done.
Admissio,
n of oxygen does not inhibit the process. A reaction sequence is
suggested which corresponds to the degradationalohain transfer:
k 0 k1 k2 k
(0) M. Re ; (I M + Re ; (2) M + Re - RH + Me; (3) Re + Me :4 ter-;i
k k
+ Me termination; (5) R' + Re U4 terminationj where
mination; (4) me
Card 1/2

8/19 63/005/003/014/024
Radiation-polymerization of... ~B101%203
polymer radical; M' radical type R-CgC*; M monomer. since ER M
reaction (1) can be ne~leoted:' If termination occurs according to
(3),
Y'r . (2 + kj/k2)ko1(Mj holds for the reaction rate, and V . 2 + k
/k for the
1 2
chain length. If termination ocoura according to Mv W - (3 + 2k,/k
2)kOIEM]
.:and V - 3 + 2kj/k2* The latter equation corresponds better to the
experimental length, v 10
13. k I/k2 does not depend on the nature of
:':;:the-radical. The free valence of the polymer chain is situated
on a link of
i`~the structure -CR-CRO. Owing to intense self-inhibition by the
monomer, the
Anhibiting effect of 0 2 is not effioienti,. On the contrary, the
yield in-
creas 6s in octyne-1 and phenyl acetylene. in the presence of
oxygen due to
the formation of the more aotive:peroxide.-radioals. Thero arc 1
figure and
I table.
ASSOCIATIONs Inatitut khimicheskoy fiziki AN,SSSR (Institutf, of
Glv~ff~ical
Physics LS USSR)
'18, 1961
SUBMITTEDs ku a t
C-ard 212

R&RUMV, I.M., GGLDANSKIY, V.I., YENIKOLOPYAN, N.S.,
TJ-6F1MO',7A, G.M.,
TEREKHOVA, S.F.
Radiation-induced solid-state polymerization.
PartI..Polymerization of acrylonitrile.
PartII..Polymerization of vinyl acetate.
Various kinds of polymerization rate temperatures dependences.
Report submitted for the International Symposium of
Macromolecular chemistry,
Paris, 1-6 July 63

BARKALCIV, I,M.; GOLIDAT13HU, V.I,; GO YJN'-GA0 [Iruo
Mdn-kao]
-)nzoyl per,,xide daoomponiUon in ncetvIenic hydro-
Kinatics of Lk L
carbons. Dokl. AN SSSR 151 no.5.M23-11"t) Ag 1~3. (MA
16,9)
1. In.3titut khLmichoskoy fiziki AN 2.
Chlen--korreFponOont
AN SSSR (for Golldanskiy).
(Benzoyl peroxide) (Hydrocarbons)

/,EPP (n) 41k*hV9%T (J IT Fc-4/Pr-VPs-4 /Pu-h-. RFL/
88 65- EW(YA)/EPF6
A ho
ACGMION'NH:: AP4009153: - S/0190/64/006/001/0098/01&:
AUTHORS BAdMINIA-IL i G-631-16-nakly.- Ve L; Yo Terekhoval St..
ps; - Trof1mi;Va-, - a., M -
ITITLE:, Radiation pol -tioln. solid phase 2. Polymerizatio inyl
ymer za n of v
lacetatA tuff variation dependence o polymerization rate
V okomolokulyarny*ye soyedinaniya v. 6s no lp 1964,, 98-102
SOURCE. V
TOPIC TAGS.- -kinetics, polymerizationp vinyl acetatep solid state,
irradiation
Ther" kinetics ~of. the,:polymarisation of,vinyl acetate (VA)
induced by
Aev el e on acceleratoro e
ectrons.,in th. electr f the Inst4tut of Chemical Physics
S.MR
~.. . ..... __) was-investigated for, the, liquid, -crystalline, and
glassy states in the
G
course of studies which were purpose to clarify the problems of, .
-:-:--:-the radiation polymerization of monomers in the.solid phase;
in particular, the
temperature dependence,(-O*to the initial rate of polymerization was
iviv6stigated ~ in connectio-n-u-W -an- attempt ~ to establish "the
radical or ionic type
of~the mechanim.of polymerization* Polymerization in the solid state
occura with
racticaDy no temperature:dapendencej and the absolute rate values
are about an
ordler.of magnitude higher for glassy VA than for the, crystalline
product. There is 1
rization at wW,of the temperatures invastigated$ahd direct calori-
-M
aral7lo

_1~8879-65
IACCMION NR: AP4CW153
4ric wasu 6rients have shom that cure
A r '~polymerizaltlon of VA in the solid phase oc
only inthe process-of irradiation;- by.n mearw is the process pur y
radical., as
el
the process of'-pol~%Prization in the liquid-phase.is. The temperature
dependence ot~
the rate of radiation polymerization in-both solid and liquid phases
has also beenJ
investigated in the case ~of ~ methZI methacrylatel(MHA),
formaldehydel(FAL), ph.2MI-__~j
and isobutylene UB)e Two basil-, types of such dependence have 1
een es I ishedi. 1) It 0 for W.Iiquid and for the solid phases (VA,
HKA,
PAL -A
and -crylonitrily ;qA64.1) RX0 for-the liquid and E) 0 for the
solid.phasest
with maxii4um rate at th& melting point (ID an& other,monomers, which
polymerize by 1
an ionic mechanism)* -The specific-features of the rapid solid phase
polymerization!
in the course*of.irradiati on may. .be due ait her_to the effective
participation of
shprt-lived', excited statesAn the propag,~ktlon of the energy
chainsor to the
chh a in state of the:6 61JA "dukirg the course of theArradiationo
OrIg* art& has: I
4 figures*
ASSOCIATIONf. inati-.Wt ut. i4iiii6hebkok fisiki AN SSSR (Institute of
Chemial Ptysics$
AN SSSR)e
SUBMITTEDf 10A462
oo
ENOM
SUB CT'! D0)':4 AD,IREF SOVII 006.., OTHEM 007
cord 2 2

ELARKAlfill, I.M.; GOLIDANSKIY, V.I.., GO
'-~JN'-GAO [Kuo M~in-kacj
Kinetics of acetylenic hydrocarbon polymerizatJon
initiated by
azoisobut,,ric acAd dinitrile. Dolcl. AN SSSR 155
no.. ,,.883. FF5
I ~,l (',!IRA 17:
1 . TnSj.-tut khimicheskoy fiziki AN SSSR~, 2.
Chlen--kcrresponden~
A',,' ~ "o- Go 1 1 danskiy)
"'R A

ADADUROV, G.A.; BARKALOV I.M.; GCLlDAl:,TIY, V.I.;
DRE,11,N, A.1%; IGN!"TOVI'll'
- I
T.H.; f4jYHAYLOV, A.M.; 'I'ALIROZE, V.L.; YM."POLISHY,
P.A.
Polymrizzation in a shock wav~~. V-vsvkom.,-,oed. 7
no.1:180 Ja 165.
(IITR_.l IS- a;)

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L 3174-66 EWT(m)/ZPF(c)/ZWPQ)/T. FM
I ACCESSION NRt AP5=166 UR/0020/65/161/
?D02/0373/0376
Ye Golldanskiy,
AUTHORSi Berlins Al, A1,; Barkalov,.I&.,M.; No S**
V. 1. (Corresponding mem er AWSSSR)
TIT Kinetic features of nonisotropic p2~ymerization in the solid
phase
SOURCE: AN SSSR. Doklady, v. 161, no. 2, 19659 373-376
TOPIC TAGSt polymarizations kinetics., defect healing
ABSTRACT-. The kinetic features of solid phase- polymerization
were examined,
considering the nonisotropio growth of the polymer chain. The
post -po4-m rization
process, during which the formation of active centers and the
growth of chains
are separated in time, was investigated, The authors consider
three cases. The
first relates to the growth of the polymer chain from an active
center to a defect
in a Gr7stal lattice. Starting with equations for concentration
of active centers
along coordinate directions,, an equation is derived to express
bho kinetic curvet
)? + Re
whore R. is tho initial concentration of radicals per unit
volumes C~( the
Card
113

L 3174-66
ACCESSION NRt AP5010166
probability of encountering a defect., 6 the probabi-lity of
complete destruction
of an active center, k, and kZ growth cons'.-ants for two
directions of growth, and
t time. This equation is valid only when i~he prepared active
centers quickly
change to growing polymers. The second case considered relates
to the situation
when this changeis slows The kinetic curve then has the fom
t + k' " A. (I - e"')
kim
where ki~`~is the initiation constant and A0 is the initial
concentration.. When
iki > k2l the curve is similar to that above. When ki a k2, the
curve is straight..
2.1 the curve has an induction period. When the defects are
amealed
and when k-,