SCIENTIFIC ABSTRACT NEYMAN, M. B. - NEYMAN, M. B.

• Document Type: CREST
• Collection: Scientific Abstracts
• Document Number (FOIA) /ESDN (CREST): CIA-RDP86-00513R001136810020-9
• Release Decision: RIF
• Original Classification: S
• Document Page Count: 100
• Document Creation Date: January 3, 2017
• Document Release Date: August 1, 2000
• Sequence Number: 20
• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

275 7 6
si, 1 ),3/6 1/003/00?/ oi 1,'016
B124/B101
AMORS Mo is eye v, V. D. , Neyman, !A. B
TITLE: Y-olecul:_-r weight , run' uer of double bonds , and thermal
degradation mechanisc. of vinyl pclymers
PERIODICAL: Vyscikomolekulyarnjye soyedineniyE.., v . 3, no. 9, 1961
1365 - 1"'88
TD.T: A free-radical chain react -on mechanisra is assu:aed fcr the thermal
legradation of vinyl polymers consists of t~.e ini-iation, t,-ie de-
polymerization, -the isomerization, the intermolecular chain transfer, and
tho termination f3telA. This paper deals exclasively with the t~.ermal
degradation of line&r high polyners with short side chains (:)rerared with
Ziegler-Natta type catalysts) containing at least 5000 to 10000 units in
the chE.in. The light destruction products were frozen under high vacuum.
whereby thE! polymerLzation of otefins in the distillate is greatly
eliminated. For th,~ degraciatiozi mechanism of these polymers, the
following f.acts holis (1) thE! 2hief reason for the decrease in molecular
weight during thermlil degradation is the chain transfer; (2) ~'-e light
Card 1,14

27576, /
5/19 1 oil /016
0/- 1 1,, 00 3/ 0091'
Mclecular weigh%, rumber ... B f-/3101
degradation products are disti' '1-3d off' witho.it an~ c~,ange; ~5) t~,,e I light
degradati2n produc",s are forrrea almost exclu3ively during i:iomerization,
whereas tt.e monome;.- forms durin~~ depolymerizatic,ni (4) the reaction
mechanism and, tha;5, the composition and mear. molecular w~,ight of the
d(~,jradation (at ocristant
diatillat%on produz-ts remain unchanged during;
tijmperatu.,~(j), fir] 1,11)8 an tho polym(:r uhaln:i ILVE) long (1110FIn
LA/
degree above 5 - 10-103); (5) nflnconaidpratJon J th,j polyiriori zat ioll or
the olefins contained in the solid residue )eads to -rIcjr,, in t~ie de.,--r-
mination of the c~.ain transfer rate which a-e, hcwevc~r, sxEll a~ lo~x
e.egradat..on degrecs, and (6) on the aSSUMT)t-Lon cf long kinetic hains, the
fol1cwing relations are found: n = -a dep ~ 1viso ' I'm f ra r, a; ~- ,'A N-d (" P
-&I is o + AN trans WN 01 (wdep - depolymerizatior. rate, 'a iso , isomerizat4-ori
Tate., w ~ c hain transfer rate, 3 = thermal degradation a e g r e e ,
trans
d e,p ' 'lumber of bonds rup~.-,ired -or, dep~ly~rn,~riza'~ion, 6N, so - rumber of
bon(~-; ruptured. on isom-~~rizal:ion,, A-11 t-r -a ns , number of bonds ruptured on
chain transfer, No . number of bonds Der gram Df the poly.7.er at. the
Card 21,~

27576
S~iqq/61/00 3/0C 9/0 1 1/0 16
Molecular weight, number ... BiWB101
moment 1; 0 - The number of bonds ruptured on depolymerizati~,n e-~uals
that of monorrier zoleculps 'ormed: WI mon (mon - monomer,' (1), and
dop
wdep ' (dN del) /dt) dmon/dt - ~1'). Th(; relations w iso ' dS iso /dt
(d/dt.) (01 1 + R 1 H 1 /-Y" 1)(d/dt)(g +- g, mon (2') (01 1 = light olefin
(up to "~ 30 - C4C 1 mean molecular weight of the diFitillate molecule,
R1 H - "Light paraffin (up to C 30 - C 40 ), g - weight of the solid residue
at the momen**, t~ holds for the iso erization rate. A general rela-.ion:
W /"--M - !A-()(g - ~;O)//gjl ~(d7/it) tE (dg/dt)] (6') is
trans ~'30 L 0/90)
derivei for'the chain trans'-er rate, where g is the weight of tht~ solid
residue at the noment to, M the mean molecular weight of t~-E? solid resi-
due at the moment t, anT TI the same at the moment t These three
4uant it ies can :) e det er:,,ine d experi rir,~-ntal ly , F r (j;;i L 'o and w t ran,
~?d/dt,)(401 - ;.I H) (10") (where 401 - Cl 01 f~;f' t'-c cf.'.ain
190 trans
C a r d

27576
S/1,)0/61,/005/0(D9//G1 1/0 16
Molecular welght, number... B124/B101
transf-2r rate, the relation 9 Vgo 4. *1 4 1,-,
D /1 11 0 )
(11') (01 - high-molecular- (mo-nio) olefin) is derived for the molecular
weight of the polymer on the assumption that the molar quantities of
olefins and paraffins in the volatile degradation products (with the
lighteEt gases being subtracted) are equal to each-other. T'hcre are
3 references: 1 Soviet and 2 non-Soviet. The two references to _English-
language public3tion3 read as followsi R. Simha, L. A. '.Uall' P. J. Blatz,
, 615, Jellinek, Degradation of vinyl
J. Polymer Sci. ~ 1950; H. H. G. I
polyme.rs, New York, 1955.
ASSOCLMON: Institut khiminheskoy fiLiki All SSSR (Institute of
Chemical PhysicG of thp kS USSR)
SUBL71TTED: DEcember 8, 1963
Card L14

20,26) S/062/61/000/010/003/018
B117/B101
AUTHORSs Neyman, M. B., and Buchachenko, A, L.
TITLE: Investigation of the structure and reactivity of some stable
radicals
Pr,HIODICAL-, Akademiya nauk SSSR. Izvestiya. Otdeleniyt, khimichuskikh
nauk, no. 10, 1961, 1742 - 1748
TEXTi The present paper was presented it the general meeting of the
Otdeleniye kbimicheskikh nauk Akademii nauk 555R (Departai~_:nt of Chemical
Scionces of the Academy of Sciences USSR) in Moscow, June 22, 1961. It
contained some new data on stable radicals, their structare, physical
properties, and chemical reactions, 40 kinetically stable radicals were
obtained by oxidation of phenol derivatives and secondary aromatic amines
with organic peroxides, percarbonates, or PbO 2 in benzene or toluene
solutions, The radical solutions are colored. Some radicals form colored
crystals after 9vaporation of the solvent, The electron paramagnetic res-
onance (epr) spectra of the resulting radicals exhibit a fine structure,
owing to interaction of the electron apin with the magnetic moments of
V~/
Card 1/4

2:72)~~9 5/062/61/0-00/01c/005/cia
Investigation of the.., B117/B101
hydrogen and nitrogen nuclei. If the magnetic moment of an unpaired
electron interacts only with one proton whose spin is 1/2, the epr spec
trum will show a doublet. Interaction of an unpaired electron with two
hydrogen atoms of the benzene ring in meta-position results in a triplet
structure of' the epr spectrum, Interaction of the unpaired electron with
three hydrogen atoms of the methyl group in para position gives rise to a
quadruplet structure in the epr spectrum.. On weak interaction with two
hydrogen atoms of the benzene ring in meta-position each line of the
quadruplet is split up into three components . The interaction of the un-
paired electron with a nitrogen nucleus whose spin is 1, gives a triplet
in the epr spectrum The lines of this triplet are split up into 15 com-
ponents on weak interaction of the electron .,ith non-equivalent protons of
the benzene ring, Even more lines were observable in the epr spectrum on
interaction of the dislocated electron with the nitrogen nucleus ana with
hydrogen nuclei in benzene rings anc. Lethoxy g:-oups. In the absence of
oxygen, tnt~ radicals in que~tian have a bng lifetime at room temper~iture,
which pcrmitzi tn, investig-ition of tceir physical and chemical properties -
_rie of' the radicals can be sublimed in vacuo at,,j1000C without decomposi-
tion, They form crystals on cold surfaces, and can be determined by the
Card 2/,; Or

2~269 S/062/61/000/010/OC3/018
Investigation of the ... B117/B101
epr method. In co-operation with E. G. Gintsberg and B. M. Kovarskaya,
absorption spectra of some antioxidants and their radicals were studied in
the ultraviolet and infrared. The shift of the absorption bands from the
ultraviolet to the visible region, observed during radical formation, ex-
plains the coloration of their solutions and crystals. Infrared spectra
disclosed that the intensity of the absorption line of hydroxyl at 2 B~L
is reduced with a partial formation of the radical and that now lines
appear round 6.2 The polarographic reduction of kinetically stable
radicals in alcorO*1 solutions on anLiCl background was shown to be
possible in the potential range of 0.35 - 0.45 v. If the radical contains
a polarographically active group, the free valency and this group can be
reduced independently at corresponding potentials, The radicals in
question cannot dimerize, presumably owing to steric hindrances, They
are, however, able to break off the hydrogen from other molecules, e.g.
from the solvent, thus forming molecules of the initial phenole. The
kinetics of this reaction was studied at different temperatures (90 -
1500C). This reaction was found to be described by a second-order equa-
tion. A number of reactions between kinetically stable radicals and
molecules of various substances in solutions were examined by the epr
Card 3/4

2~ 269 S/C'62/61/000/010/003/018
Investigation of the... B117/BIOI
method. These radicals can be used to investigate the reactivity of
various bonds. When kinetically stable radicals are used, their separa-
tion from each other and from ordinary molecules is an extremely important
problem which can often be solved with the aid of paper chromatography.
This was exemplified by the separation and identification of the radicals
formed in the oxidation of ionol (2,6-di-tert-butyl-4-methyl-phenol) by
this method. Ye. K. Zavoyskiy, Razuvayev, Khidekel, Gorbunova, and
M, S. Khloplyankina and the monography by 0. A. Reutov: Teoreticheskiye
problemy organicheskoy khimii (Theoretical Problems of Organic Chemistry),
Izd. 11GU, K., 1956, are mentioned~ There are 9 figures and 7 referencest
3 Soviet and 4 non-Soviet. The two references to English-language publica-
tions read as followst J. K. Becconsall, S. Clough, G. Scott, Trans.
Faraday Soc., 56, 459 (1960); C. Cook, J. Organ. Chem., 18, 261 (1953).
ASSOCIATIONs Institut khimicheskoy fiziki Akademii nauk SSSR (Institute
of Chemical Physics of the Academy of Sciences USSR)
SUBMITTEDs June 22, 1961
Card 4/4

IS ko(bk
211417
S/1 91 /6 1 //- -_ -'
Bi C)i //Ii i C
AITTHORS. Dudorov , V. V '!,-y::;an 13. , Lukovni kov , A ~ F -
T IT IIE: Oxiuation of Dcly-ropylene at high oxygen pressures he
dependence of indl~ction _eriods on temFerature and ress-;re
PERIODICAL: Plasticheskiye massy, no. 12, 1,)61, 3-7
TEXT: The oxidation rkinetics of olyprcLylere is cl'sei relatej
the iroblems of tY~erE:,ooxidative destruction and j_~raftinv- of otiier
~oly%~ers onto PP. The present ;Ia:,er deals viith the examination of tne
induction oeriod of FF oxidal-l'--r. at a of atm, and IIC-14COC. The
authors used ~sotac 4
C Pr with a molecu'ar weieht of C,
separatQd from tLe ccmmercial -,;roduct by a .,Iethod describt,-1 !~y
et al.
(VysokDnaL soyel., 1, 14'z/ At abo,it I
150 kg/cm'~, this PP was used for ~roducinu films (C.10 nam thickness, 3r
10 . Cl M.VCM2 The induction period was measured by the apj.'aratus of Fig, 1
(detailed description see Plast. massy, no. 1C (1)61,''. A certain pre_~-
C2 .
sure was applied to the ~~P film sa:nple. '.he .ressure 7 in reactln_-
bard I/ ~_

211417
S/1') 61
Oxidat4 on of ~;olypro:ylen~~,
space due to 0,~ absorTtion Causes a deflection of me[-,,bra.,-,e

-as o,.tically ~he
transferred to sc---Ie (14~ craduated in H6, ~niuct:~~n
~ericd -.,ias de -fined as t~.e tim- in which the ~)ressure 4 1-, the reac -i'~n si~a(.-
drcp~E!d b~,
rim. ReiroducJ bJ 14 t' of measurements de~,(--nied --n th
~
reliminary t reatment of the reaction vessel and ,n the con-Ilit' n"
~iims storal
_7e C- -
, There-'o:-e , a speciall,, tr ated vessel ard fil~-.s
a:~
ndu ~)n zer iod of + C :.-.in at I and 2- at7 -xc-re --ised
e x,., e r4e
~ - . ants S e c i al ~ x e - i-,,. e,-. * s qe 2 a i -,_i c e:" d s
affec- --' V
U aillat- ':.s of an,! ar-a ',-.s n
I - - . - -
- - - a:
-
I 0,
-C atm and at I cf e ress-~r ,f lr,:~-
~,ielded rin a p pa rp n t I,,-; t i c ne r I --d t

7)-- t I
-SO afmi) si ' --h~-
nce -'-f lam~:iati~~n occ'irrel at h! --her j~ s,-are
0'
the c,.)rves s-ov7ed autrcatalvtIc )xida-~4 Dn tc, set in at a 7
decreased unt 4l 1V4C atm, and increaseql a~rair. at a hi~-her
-
C-
is due to an intense geraiation of voiatile Frodu,~ts at 'n
Card 2/5

21J417
C at n Z)l:i ru ene
pr,iducts was measureJ b~, Q,,, af ter s~i.---rt timc- cf acti-~~nI ~n 4 n
I ~ followed t~ie linear l7unct4 --n lo- 4'1 4~ 41
m, EL za x
tu rr? T,.e constant of -.ress,~re rise ~7aS dete=J nei f t s n t 4 n
',ind ~ress,-;re r4se fr-m ti-.e ~,ressure
7. -tted by Teans -' al-' ra, - aid--
curve f,-,r C- absor,-tion IF4 -a a s
of the ~-rdinutes of ressure Jr,-~ and r4.s-, llherefr7~:., n
r, :)d T was fcund -c T Z'x ~.e ri me n t al duta viel ;c!
T T T T00 -uh ore7 i~eriod at -4 -r-
difference betvieen t-p induction -eri,,A ---r
4
)o
Since i,,"T was constant within the ex:.er'mental er,-,()rs
(2, , I is a iinear func*icn
t ran Drmed irito~ T = 7
w as (1 . 11 /
fT ',L~ temperat,~,r~: coefficient y and th;~ fact-,r
f
the exponential function
-(14 - 3.0,'1--) 1', ;/
we.-e
4 C /X

L
17
S 1 1 1 1 1 ~ - -/ ~ - - I -
exi(iation of !,olyi).-opyiene ic
:r, :)I' ;.ressure and tem-erature,
-14
T ~ I 11/p)(6,,) - 23CC/T) ':ilde Z'
.4.1c exp(i 00/7 exp
exi erimental conditions, 23OC/T rhan~;es by 8' only 7 h e, v a I -i r- c, f tn J s
frartion was cal cu 1 at ed f o r 1 200C and su bs t i tu ted i r i E" q By
Eq~ (5) into a series and by usinL~ its first tdo terms, the e:.-jpirica'L
EQ. (2) is obtained. There are ) fii,,ures, 2 tables, and 7 references:
Scvie* and non-Soviet '-e reference to the -nEl`sh-lan.-~ia-e uc 1 a -
lion reads as follows: 3 Natta, E'. 13eati, F, Severini, j IP Sc:
54 . n o 7, 68 5 9 5))
FiE- 1- Diairram of ,.;easurinC a,. aratus Polymer sam p!
s--ace; t~iermostat; (4) rec-jlatin-,~ valves;
('~) standard -.anc7.eter;
(6,' sto2 valves; (7) mernb-rane; f6~ reaction vessel; space wit- -~nstan*
~~ressure; (10~ 41luminator; (11 i~' as a; 2 mi rrors -r~e
scale; (15' funnel,
LeE-,end (a) Vacuum; (b) oxygen
Fic-- 7 Changes of pressure (curves 1 arid and oxy...e.-, a~scr,ti'
11 and 21) during oxidaticn at 1100C. Pressure 1 -and I' at 60 atm; and
at 121 C at,
Card 4/5

NEYM, M.B.$ FEKLISOV,, G.I.; Prinimal uchastlye,-, KATYUSHIN, A.A.,
Kinetic tracer meth,~d for Investigations on the mechanism of
coWlex chemical and blochemical processea. Part 10, Rate
constant of the reaction between an acetyl radical and mole-
cular oxygen. Zhur. Atiz. khim. 35 no.5'1064-1067 W 161.
(MIRA 16:7)
1. Tnstitut khimichaskoy fiziki AN SSSR (for Neymang Feklisov).
2. Gor1kovskiy gosudarstvenny'y universitet (for Katyushin).
(Acataldehyde) (Carbon oxide)
(Chemical reaction, Rate of)

S/020/61/136/003/022/027
B004/BO56
AUTHORS: Neyman, Miller, V. B., Shlyapnikov, Yu. A., and
Torsuyeva, Ye. S.
TITLE: The Dependence of the Induction Period of the Oxidation on
the Concentration of the Antioxidant
PERIODICAL: Doklady Akademii nauk SSSR, 1961, Vol. 136, No. 3,
pp. 647-650
TEXT: The authors proceed from the fact that the problem of the
mechanism of the effect produced by inhibitors of the oxidation,
especially the connection between induction period and concentration of an
inhibitor is as yet not clear. The present paper therefore studies the
effect produced by very low concentrations of oxidation inhibitors upon
the induction of the oxidation. According to the chain theory by N. N.
Semenov dn/dt = wi + fn (2) is written down for the oxidation. wi is the
rate of initiation, n is the concentration of the active centers, (f the
factor of self-acceleration. With addition of an inhibitor, which breaks
Card 1/4

V/
The Dependence of the Induction Period of S/02 61/136/005/022/027
the Oxidation on the Concentration of the B004YB056
Antioxidant
off the reaction chain, the reaction follows the system of equations:
dn/dt - wi + Tn - kxn (3); -dx/dt - kxn (4). x is the concentration of the
inhibitor, k the rate constant of its reaction with the active centers.
The following dimensionless variables are introduced: )- n/wi-ro
(concentration of the active centers)l K - x~w
4ro (concentration of the
inhibitor); 0; _t/,ro (time). Equations (3), thus assume the form:
dV/dg = 1 + a bKV(5) ; -di(/dg - bK10 (6). a - fro; b - kvi T2 ~ The
c
discussion of these equations leads to the following result: 1) with
K,,a/b low steady
rate of the reaction. Here, '0 = 1/(bt% - a) (7) holds for the
concentration of the active centers. The induction period is finished as
soon as br.0 = a. For the purpose of checking these theoretical
assumption, experiments were carried out. The induction period of the
thermal oxidation of polypropylene was determined in the presence of
various inhibitors of the oxidation (phenolderivatives and aromatic
amines). As an example, Fig. 3 shows the course taken by this reaction at
Card 2/4

The Dependence*of the Induction' Period of S/020/61/136/003/022/027
the Oxidation on the Concentration of the B004/BO56
Antioxidant
P0 300 mm H9; 190, 200,.and 2100C in the presence of the anlioxidant A:
2
OH OH
I C11
(CH C(CH
3 3 3 3
CH3 r~E3
The induction periodIrlarepresented as a function of the concentration X
of the inhibitor. From the inclination of the initial sectionq of the
curves x . k-ro/f is found. The rate constant k equals 21, 14, and'15
0
9/mole.sec. for the temperatures given. For high values of x (steep
k
sections in Fig. 3), an activation energy of about 40,000 kcal/mole is
calculated, which corresponds to the activation energies for the
oxidation of hydrocarbons. The effectiveness of various oxidation
inhibitors may be compared on the basis of k. In this way, the authors
i~oved that at low concentrations N,NI-phenyloyclohexyl-p-phonylcndiamine
p
as inhibitor, with polypropylene-.oxidation is more effective khan the
Card. 3/4-
.3;

The Dependence of the Induction Period of 3/020/61J'136/003/022/027
the Oxidation on the Concentration of the B000056
Antioxidant
3 figures
7 references: 6.Soviot and
British. C
ASSOCIATION: Institut khimicheakoy fiziki Akademii nauk SSSR (Institute
of Chemical Physics of the Academy of Sciences USSR)
PRESENTED: July 29, 1960, by V. N. Kondratlyev, Academician
SUBMITTED: July 29, 1960
inhibitor A. There are
I
and
Legend to Fig* 3: a) mole/kg
CA7CAA
is,

v

25862
j , 02 Oil `04 2 2 ~ 2
B, 271 B2 12
AUTHORS: Buc~iachenko, A. L. and Neyman, M. 2.
TITLE: Separation of free radirals by the paper chromat~rapny
method
PERIODICAL; Akademiya nauk SSjR. Doklady, v, '59, no, 4, 1961, 916-918
TEXTs The authore studied the radicals of 2.6-uitertiur.,~-tutyl 4-methyl-
phenol (Ionol), Radicals are formed by cracking if hydroxyl hydroEen.
which, in turn, may form radicals, 5oth reactions prc,-c(-ed sim~,ltaneo-,491y;
therefore, the electron paramagnetic resonance spectra c,verlap. rne
e.p.r., 3pectrum of the first ionol radical showed a juadr-plet structure
with a distance of 11.4 oerateda betaeen the compotienta Mina an intensity
ratio of 113--3:1. The quadruplet res,ilts from interactic~n of an unpaired
electron with protons of the methyl gro,,ip in witn respect
to the oxygen atom. Each quadruplet c-omponent was sp'Lit into three 'lines
of an intensity ratio of 112t' \fdistani,.e. '." cie,,, TIiis iiyperfine
structure is caused by the two equiva.'ent protons 1r, In the
Card I /~

25862
3/0~01// 6 1/ 13),, 004,1'022 1' Oe-15
Separation of free radica Is oy the. . B! 271 B21
henzene rind-,. In order to --epardte tne rudichIs b., ;;!ip,r
toliene, lathyl alcohol', or carton tt~tr,i.,i.1i11o-idc, wf-re ased ui mo~,ilp zhase
f low med i um) .Best separution WRS attillned V71th tn%j rise of 9bil ethyl,
alcohol. In thiL3 casc- the liand of the iot~,--Ioxido )n qfto-,,iod ~Ieur
3optirtition into two frontut rj lovior oran~7,~ fron'. "".ith ~(f - 0, and fn
tipper yelioll one with Hf After dr~ring, eacri i~art of the chromatogram
.vas investiErated with an3PP-.-, -2) apectrometer, and the
spectra were recorded. The e.p.r. 8pectr,irr, of the second lonol raiicul
showed a doublet (1:1; distance 14, ~) oej in uolid state, L,,,d -t tL'IP!Pt
(1 t211 ;, 6.2 oe) in uolution (b(,rizenu, tol~iene, Th-~l componcnts of
the latter are likewiae 8plit into threu lines -each :2:' ; 1.6 ce, The
do-iblet-triplet transition wus found to be rever.9i" , I El .Thus, an
spectrum analysis makes it possible tc) L3tudy the bQhL.vi(,r of radicu16
in solid or liquid states. The authuro ,iiention that the above met~,od
of paper chromatography jiay )~e ui3e~ al.,jo for tjupitrat,.rig radical %nd
fnolecule. Here, the firut front couipriooo the r.,idicttl, find the 9econd,
im.movable front, the molecule. There are 4 figure~3 ar,i 7 references:
Card 21/3

25862
S/O 2 6/ J64,,~02 2,-02:~-
Separation of free radicals by the... 3127,'31-l'.2
3 Soviet-bloc and 4 non-Soviet-bloc. The rwc most _-ecent references to
English-language publications read as follows- Ref, 21 r.. ~. Beecorisall,
S. Clou,_zh, G. Scott, Trans. Farad. Soc., 56, 4`19 "1960); Ref. 6:
'r. - 4`43 ~195`
11 Gordy, C. G. McCornic, J. Am. Chem. ~;oc,, d, -- % 0).
AiSOCIATION: Instit,*L. khimicheskoy fiziKi AkLvIemii nuuk SSSR (Institute
of Chemical Physics of tne AcEideimy Df 6,_-ences ',63R~
PRESLIiTED: April 7. 1`1461, V.
SUBMITTED. April '/, 1961
;-ard 3/3

KHIDEKELI, H.L.; BTJClIACHEl-;K0, A.L.; RAZbTAYEV, G.A.; GORBUNOVA, L.V.;
NEWMI B.
Oxidation of f-nal.hthol and some of its derivatives by
peroxide compounds. Dokl. A1,; SSSR 140 no.541096-1099 0
.1
161. WIM 15:2)
1. flauchno-issiedo-vatellskly institut khimii p1-- Gortkovskom
gosudarstvennom universitete ira. N.I.Lobachevskogo i Institut
khimicheskoy fiziki All SSSR~ 2. Chlen-kon*espondent 4~11 SSSIR
(for Razuvayev).
(Naphthol)
(Peroxides)

NF,T1Wj H.B.; MMOVA.. Yu.G.; BLEIM, P.; BUCHACHENKO A.L.
- I
Kinetics of reactions between a tritertiary butyl phanoxy
radical and certain hydrocarbons. DokI,AH SSSR no,,2:392-394 My
162. OnA 15-5)
1. Institut khimicheskoy fiziki AD SSSR. Predstavleno akademikom
V.N.Kondrutlyevymo
(Hytirocarborw) (Radicals (Chemistry))

P 0
S r,,X ~ja, .1. r i z hk ov ii, A. Low,') tov.)!' ',J;l ,
:;Oxm m, 7. V. , Vlnri r-12("'1
V. , 7alj tF, - iY
TITLE s JtiA,/ of th, thermal dcF-radatio-i of cinle,7:~ation
1-hermal larra!;.tion of licterochain polyestLra
so,,er11ncniya, V. 4, no. 5, 196?,
TEXT t Thormal deFralatton of polyarylates on the baais of
3henyl-2,21-pronano (DD?) awl tere-ohthalic (polyarjlate TD) or
(poljirylate ID~ -ici,~a prc~)arc~l either in a hirln-boilinr, solvcnt ~:~~trolar-
ethcr) (-D(s) and ID(.), reipctively) nr by intcrfacial condon5a'.:On
(TD(i) and 1D(i), re3pectivuly) is 5tnliei in this )ape:. Tn I 1 0 -. na
of the pol;,arylates wores 7D I o ),- 340"C ; TD '5()o G; 1~, (,3 ),02Y60 C. C;
0
.270 C). Thornal, Ole,-radation of Vic mentionel pol.7mcrs
bct-,vecn 250 and 5250C. ---volution of gas set3 in above 400 6C', where 3. ?C.-
0.42 mole CO, 0.30-0.60 mole CO 2# and 0.06-0.13 CH 4 per mole of the poly-
arylate structural unit are liberated. The liquid producta of thermal
Card 1/3

'62/004/0r; 3/o1 ryw
6tuiy of th.,) thermal ... ~124/IBI 01
eo(-ralation of Tj(r;) nur'ormed at 4500C show absorption ban&3 at I 16~*
-I c 1 5
rind 2970 cm haractert3tiC Of tne methyl proup, and at 17,7~5 an.1 12 0 cm
characteristic of the ester bond. The uplit ab:;or,ition band at 1735 -.- 1
in,iicate3 the pronence of terephthaltc act i , -nKcre,s the cp' -t b;;n~i at
1600 cm-I sho~~;3 free :)DP to be pi*ccient. The infrare I spec trum of rolid.
residue of Tj(o) after thQrmal ~e--raiation at "1,0"C for' I hour lo,s not
cant-tin bands which -ire ch~ir-,cterijtic of meth,~l ~~rouns, ',a7-s
c-aracterlatic of the ezter ~-,ond are est,blished In .he infrared !;p-ctr,--.M
a' the solid rcoiduo eApoae! to thermal elel-ra.lation at 50000 for '. hnur.
These ')ands are lacz~inr in the spectrum of the nroduct expozqe.~' to I.-er:7-1
dei-rilition at 60000 for 20 Absorption spectra a, the :-"li' -c-
3;lue of T;)(a) ar." DD? in tne -,'-ion a' 700 - 900 ind !600 cf-.-l 3,,o--
tho concentration of :)hcnyl rinr3 increases after ~e~;-adation 1-ia..Irg to
the for~atior of polYphcny1r.,ne-like structures. Those conclutiw~a
7
ere confirmed bj ~he -7,:R Onectra of the residues of 'hernal ~e-
7
rfidaiion of TD(s) at 450, 500, and 600'C. k. A. Bcrlin and L. A. hlyiimen-
fel'd Vjroko-molek. soyod., 2_L 1494, 19601 Zhurnal strukturnoy khimit 1, 105,
Card 2/3

Z/190/62/004/003/016/023
3t,iey of the ther-m-al ... B124/B101
ire mentioned. Thcro are 7 fii.-jrcs, I table. ~;nd 11 referr.,ncoji
9 jovict and 2 non-3oviet.
ASSOCIATION: ,auchno-isz;ledovatel1skiy institut plastichoskikh mas3
(Scientific Research Institute of Plastics)
SUB~IITTEDt Yarch 4, 1961.
Card 3/3

IL
39850
s/igo/62/004/06/011/016
A.
Lrr~ D101/B138
UT H OR S y a j) n i k o vY uit 1 e r , V . B. e y m an B
I2orsuyeva, Ye.
Correlations in the effecta of inhibitors in oxidation
reactiona. I. Alkyi phenols
j'--":-OJjC"T Vysokomolekulyarnyye soyedineniya, v. 4, no. 8, 1962,
1228-1234
TEXT: The authors studied the effect of 2,6-di-tert--octYI-4-Ma'IhY--
. .nol (I~ and 2,21-d-methylene-bis-(4-methyl-6-'Uert.-butyI pl-,ernl) 'II)
on the induction period of the oxidation of isotactic polypropylene.
Vie inhibitor consum,~tion was measured for the induction period at
1,7~: - 2-po0c in the presence of I, and at 19C - 21G0C in the prezence of
!I, accordind to Vysokomolek. soyed., 2, 1409, 19060. The amorunt
unconsumed was determined by weijhing the inhibitor sublimed from the
rel-c*.4.on mixture at 2000C. Results: (1) The induction period increases
."i tn inhibitor concentration but without linear relation. With JI, the
Card 113

.1-1.c: AationL; in the eff;_~Cts of . . . Bici/B13B
i-duction period 'r depemls on pros:-ure: at 170 ard 0.01 molei;
-jly,,ropylene, 7 vkas 56 and 32 min at 300 and 63' 7.m Hj, respectivolli-

-ptioi spectra of t~-.2 oxidation prolucts s',-Io,;. it"at I'---
e b s oi

ijed lurin. _Jie -,heir amount is ;)roportio~:il
i t C, 1. re ;:1,1 .1 r, 2 Vr. C w
k, ~,tior of
t.,, decreasi-ii., ij~,,Jb:lor corcentration, The o-~&nge in Concentr.

-order rule. ~3' Durin- T' tle ~ccreaz-e
o.,'_d~tion follow- a f~xst
o 1 e _,al ar i.7j~ t of poly:)ropylene is accelerated as the i...'-_i~itor
0 -

~oly:rer cE:in ru-itur,- -ij~roximalei- - ::~ols.
ion rises. At --Avery
I" t 4-tor are con_,umed. ~4) Considerably snortened '.-y ad jing 1 to
,,olypropyiene already contt~,inin(3 !1. '5) The io~.~ intensity of tae epr
of 1 and IT su-Zost& that only a small portion of inhillbitor is
,re_-ant in ':ie form of froe rnlicL.I~j. 3onciuzionz: A amown-, of
I
c3naume~ b,, direct oxidation and terminLLion iTliti:ite~l
t -on b~, t-ose not initiated by it. h~
but only a small port.
'Oe-,~.Vjor3 of 7' ar,-: 7- ar
renj C du e -. o t f e n t f'e,-- on
_:IitiLation and branciiin,, Jurin'- ",4droperoxid- dqcomlporition. anj
~-L-cc~ oxidal.ion by nolecular oxydtm io zis~7,umed for I!. There are
important Im-lio..-la gua e reference's
md 1 table. The mozit
-'aters, C. j. Buoso, Induz;tr. and Zngng. Chem., 41, 9071,
rd 2/3

-/62/r)04//008/0, I 1-,-, 6
or~-el;-Lion in tile effect,,: of . . . 3 13 1 /-3138
J. R. 'roatfjon, induztr. and En-zng. Chem., 411, 1114, 1949;
~i. Ro,,enwald, J. R. Hoatson, J. A. Chenicok, ibid., 42, 162, 1950-
3C 1-1 --0.' : inatitut khirmicheskoy fizilri :LY, 25511Z (Institute of
~;xm ical ?hysics of the AS USSR)
SU,B. ~: I T T L D-ay 18, 1961
Card 3/3

S/190/62/004/012/015/015
B101/B186
AUTHORSs AlisNoyev, V. R., Gurlyanova, V. V., Kovarskaya, B. M.,
Neyman, B
TITLEi Non-additive effpct in the stabilization of poljformaldehyde
by additi6no-of ~olyamide6 and antiolidants
P--'RL,D1,','AL: Vysokomolckulyarnyye soyedineniya, v. 4v no. 12, 1962, 1887
TEM It has been found that a joint addition of pclyamide and anti-
oxidant more effecLively reduces the evolution of gas in the deradation
U
of polyformaldehyde by thermooxidation than an addition of polyamide or
antioxidant alone (Fie.). There is 1 figure..
SUBMITTED: June 1-', 1962
Fig. Increase of pressure in the oxidation of polyformaldehyde at
2000C, P 0 - 200 mm' He. (1) Without addition, (2) with polyamide,
(.3) with antioxidant, (4) with polyamide - antioxidant mixture. Ordinate:
6p mm Rgi abscissa; time, min.
1 112
Card

S/190/62/004/012/01~),/CI5
Non-additive effect in the,.r B101/BI86
de rfm pm cla
Card 2/2
V GF IF0 M
Opem.f. mem

NEDUNP I.I.B.; PUDOV, V.S.
Effect of inhibitors on the decomponition of polyproVilene
hydroperoxide. Izv. AN SSSR. Otd.khim.nauk, no.5:932 My 162.
(MIRA 15:6)
1. Institut khimichaskoy fiziki AN SSSR.
(Propylene oxide) (Inhibition (Chemistry))

3Eo6L'4
7:
Ye., Ourlyar,3111ii, ~,-
of ti,e Of L~-~ox~j
1-)b2, 11-15
a S -~ I C ". u sk _4 Ya :z aS Y
-e dij s c t ~- c,:, c',.ani E: .-~G n~-,
-.Yr,- z in OXY rQ3!n
res4 :,i vas heat ed 4r -)U, 0 v C J a t t; C. ci
a
Q
I . "-e s t r,~; c t n o 1~1 u cs
at 700 and 600
t Y Xh au S t e d Coll e C -r.,~ by a L:i,-X-Ur~~ of rY
i cc , !-,nd 2 ) Into a si.~i lar flask cool b Z I i -, u --' d 2 a n f 1 1 d V, I
o t h a f _i r 2 - vi a r, a,~ d,~ d d i i I I r, G h 4 C. n L!
icL I I
2atura-.k~d z~olution of Na-Cl. The Lasewd.;
solution were examined by absorption (,!-is 'Ln(i *,Lu
follc-wini~ were found to be oresent: + C 0 2 C
2
.urd ,/5

/6,2 13~-i- -
-herzal destruction of C, - 5
oil (4) 01" t V' e
ly
2 4
ru firat colluct~aC flask wi~.j uy Lu.~- v,-,
4, 2,h 1 1 , 2 9 (1956 I~h,! :~rcQrtLc;,L!z by f~,r 'H.-
0-
L; 0 1 id, d a' d.~'-yde a-, iere r~ - c
1 .16 0. 41 1 O.C25; 0.016; 0.01 ~~; -D.063; ~.ind G.U-06-'3; a'
G-OOCb; 1 .17; 0.55; 0.059; 0.024; 0-02.2; C-055; 1--o-I an,.: C
1.4; ')-bg; 5.27; - 67-44;
e- r, t I-I tiQs showod that no los3us had o,,curr,~d. 5 oe wiao
c re sonance o1 S 7-,ara:7,a,:ne c --,a rt o e 3 pe r c f --t~a
to the si -na-7 of ~L. -.)roa,~Cts
dipi.onylol propane. if n is tLk,-.n ~-s tie Iber of
,ho ::Iolecuia, then p a -t- 1 2 n where 5 is the molar f2zctIon c.:
dip,-,anylol Propane. . T h e n n-284, and P,, - (66-10C,11Z +
--.,heru P io tho contont lin by viei6h'.) of' terminul opoxy jrou~z.
e
bound for p: from the radioactivity, p - 3.43; thio
C.52; from tne content of epoxy -ro-aps, 7,
rLisfn consists chiefly of molecules n = 0 ar-,-- molecu-',--r
--.;ur.i-ies aith n . 1 . "he small fractions of iabala-,~ materi~! in t'-e
0 E,
C rd 2/5

c t
z;

'2 al i e 3 'ru c z --' on

Ci

rd 41
/15
0

)s-~ Lion of raul icLi- I b ~,oi~ on ? b y t '-I o
t" C; t C) i" e 1'! n r) r;i I i ca I I I b.;
11) reo 7 kca' --D' c" z'o~- i.~ r,~ a ;on, on y a sm, a.
o I a b e I e d e c- -, e i s c, r m e 3 n -a o I) r h (j a r L r, e c
&.L,2c"-,C,n rLsunance spec--,r", ta,--ei centrui of d' .~)'-,enylo'
pa---cinL--es in of aror.-,atic
~;r,., :Dthcr -ivith double bon-~- )12 cm-1 banJ or -.he
e:,,Dxy ~rou-) -1-Joappears in -"-,e infra.-ed s-,ectra o." the so-'id decom:;osition
rou4uctj of the resin, stable free radicals are formed as reported by
3. et al. gures
~Vyso'Komol. soyed., 1, 10 (195)~). There are 5 fi
~,Lnd 3 table3.
Ca--d 5/5

5/19 62/000/007/002/011
B1 24XB1 4 4
AUN0113i Alishoyev, V. R., Neyman, M. B., Kovarskaya, B. M.
T IT 1, E: Thf~rmooxidativo destruction and fitnbili?.ation of
p o I y fo r ma I d o hy d e
PERIODICAL: PlasticKeskiye massy, no. 7, 1962, 11-14
--,.XT: The authors sought to obtain kinetic (jata on thermooxidative
I- U
destruction and stabilization of polyfoi-maldehyde in laboratory devices
and durinL; castin.g. The same temperature was kept in all part6 of the
reaction vessel to prevent polymerization. Five cells (Fig. 2) and a
%eighed portion of about IC, mg were used. Reaction ve-ssel 1 with ground
section was connected to t'lle principal part of the apparatus, the weighed
portion was added, and an Sn-Pb-Cd-Bi alloy introduced in the curved tube 2;
the alloy on melting at test temperature isolated the reaction vessel from
the measuring part of the apparatus. The pressure in the reaction vessel
automatically haldnced itself with that in the measuring part through the
action of gases formed in the electrolyzer 3, this being checked in the
manometer 4. Thereupon the reaction vessel was evacuated, oxygen was
Card 141

5/19 62/000/007/G02/011
Thermooxidative destruction and ... B124YB144
introoLaced through an opening in the allol, the temperature in the reaction
vessel and irf the lower part of the curved tube was adjusted to + 0-50C
by way of a silicone oil thermostat. Fig. 3 shows the results f-rom
using a derivatograph on 140 Mg of acetylated polyformaldehyde in the
course of heating from 20 to 27qoC at a rate of 3.30C/min. The
experiments showed that the kinetice of thermooxidative destruction
were characterized by the curves for weight losses as well as by those
for pressure increase. Whereas in the absence of oxygen the pressure
at 1450C rises very slowly with an oxygen pressure of 600 mm Rg it rises
it I
at JA 50C as follows; Z~P - Ae' , where rfm 0.044 min- . In the same
experi-nient, the induction period z-, during which the pressure rises
SlowlYt is 115 min. An analysis showed that HCOH was the main product of
thermal destruction, whereas CO, CO 2' H20 , and H2 were formed besides HCOR
in the thermooxidative destruction. No hydroperoxide was detected
analytically. Oxygen takes part in the oxidation of the polymer and
stimulates its thermal destruction.. The results indicate a self-
accelerating chain process with degenerate branching. When either the
partial pressure of oxygen or the temperature rises, the autocatalysis
Card 2/&l
J

36053
7/A
AUTHOIi: Neyman, ?.-o.*os.,;or
T 1 -1 L;-- A6ing and sta~~-i Lion cc-f po--yrrears
~;62, '64 - '72
of
Of po:ymorn, madc- in the U6SI", am- d1scussed, a sc-eme of oxfdation and sta:D-,' 1 iza-
tion of poly-,-,iers is pres,-:ntk~d, and inhWtors are recol:L7?~!ndQd. It LS
mentioned tiat in sp--W~ of a ~;uccdszfui developmcnt of thest- studies 7,a;-.y a.;Lual
problems still have to be ~;olvec:, ~opQcially -~-,e stabilization C,-' poly,-~ers
temperature. -,.:c types of of poiy:7~:~rs are ~.:-O-an
structuration. Destr,.~ction by theri,-.al axLuation occurs,
accordin- to the mnechani.-La, sLat~~L oy as "01--0'.."S: RH + ":C",
initiation (I) , R' + 02 ROO' c~-.aln developiTient ( !I) , ROU + M = ROUI
cha in de ve lopment, ROOH RO' +'01ii branching ( IV), ROG' + BOO' = 02 +-loc,!~ ruiAun-
of the chain (V). It was observed that thermal oxidation
tic polypropylene fdlows this scheme, except for reaction (TI) instt-ad of
Card 1/14

r
Aging and stabilization..... A 0~7/All 216
ttie + + h2O +
(-or polypropylene - subst_'tu-,,P_(, p~.u..ols and aromatic
icals RGO ~~H = !MI-'' + thus o-
L
,,.,ith inhibitifiL: destruction 0:' Ln'- ')0 ly,,.c-.,-. ii0wov,:r,
,he present author -and s~,u-,!ed t~,at the simple c
not a',,..,ays valid. Thus, increasin-g t~~mperature dc:ci-eases -he e,"'ecz, Of a..
antioxidant in spite of tne concentration of the lalt,.L~r. anc
other observations could be uxplainvd -.:ith-The a3su.--ption 3.1, a ~~co"'d o:
t'-e anticxidant, i.e., Initiat-'on of polymner oxidation. Several sp?ctra of para-
m
magnetic electron resonance ta~-.en for stabilized sulistances tre :or:.-.aT.'cr:
of radicals by oxidation of the antioxidant used. Studios of the kinetics o~ --e-
action beti-.,een trl-tert-butylp)ienoxyl and n-decan, 2,4,6-trimv thy or
ethylbenzene proved the Initlation c)" polymi,- oxidation by
antioxidamt radical and tr.e pol_yrar. accordin,~ to: X'+ i,_: ~ _-D, + :1'
v:-,reovo,r, chain init-fation cir. by reaction
+ i4y ~- :i()* + 1!20 + i* (X) or by oxidation of tide inhib-Itor Xh + O~f = i.():-
addit.-.rity rule of ~;em-nov's ~%,chanism is not valid, ot~~cauze of L:~
e-ect of mutual intensification of t~r2 stabilizing propar-ty of _an'.i3X_'da'-t
tures. Corresponding results ware obtained recently by the present at.,.or an_~
bard 2/4

4
~'ing and stabilization .....
co-'.-ior~~ors innibitir,.6 polyp.--opylene deztructlon :~Y 01:iarv 7,ixt-,~res o" an-,ioxidants.
`evk2ral studies by othQr authors correspondin,; on t~,e
-ructure of t:,,! poly-..-:er and artioxidarit or ('(1)
;,,,ill control- Lhe initiaLiOn. _onus, substances dastroyin-- z;hc,! pe-oz-fue in-
cnztase the stabilizing effect of antioxiaant where "K), and ~X-~) pr-~-vai_,
while radical -capturing substances will he convenient a:-, at.~mlxtt,ves to stabi'izer~-,
where reaction (VIII) Playz the Prevailent role. Conslder'n,~ t~-.ese prinolples in-
ar~-; 'j';JIV a.;d
vestigations were carried out in laboratories of tree jT-PP, I.*--
the :'ound for poly,): ef~ne_,;: a_k,,y1pheii:)L.,;, ara-
mines, azomethy 's, hydrazines, pnusphit~es, and combinations of aramines and
phosphil;e-s with sulp,ur-containIng co,;;poundz. Aging of PVC ~an be inh;bited
suitably at low temperatures with polypheny lace tylene, and at nigh temperatures
by polyphenylenes, or polyazophenyienes. The effectiveness o:' stabilizers against
thermal and/or p~otodestvuction apparently dcp*,~nds upon the mobi~:ty in ti,(., poiyrreip
since high mobility inerra-ases the probability -). a contact wit~i actlve radicalliq
and facilitates homogeneous distribution of the stabilizer. In connection here-
with was studied recently the di."lusion of several stabilizers '.n poiypropylene,
polyfon,laldehyde, and polycaproiactam by the method of labeled atoms -in the
Card 3/4

S/A ~/6 2/-,07/~- VJ ',
Aging and stabilization ..... AO~VA11~6
Institut knimicheskoy fiz-1ki (Institute of Chernical Physics) . There are 18
figures.
Y
6
Card 4/4

% ugop,
s/igi/62/000/010/001/010
310-1/B186
ATJTiiGil,~: Ve, n Li- H-,- Kov--trnlcaya, 3. N1. , Levantov3kaya, 1. 1. , Dral-
n .
yiik, G. V., Ya-.vikuva, ~4. P., Sidorov, V. A., Kochetkov, V. 11.
G. I-, Tatovoslvnn, G. 0., Kuznetsovi, 1. B.
T ITL L jt,,b.Ljjz,-jtiOn of jMly,-jinide films for agriculture
m'3ssy, no.. 10, 1962, 6 - r3
s Pr-tection of PuIY,'~iliidc films, t.YPe 54, as used in hothouses and
t3ilos, froci o"fects or photo- :ind thermooxidation. was tested by tryine,,
11.1irinius ldditives under various test conditions.- The following were Added
zt,i ~,Itrnviolct liflit absorbers: 2-hydroXY-4-methoxy-benzophenone
(OMBF) (1), .2-bydroxy-4-~ilkoxy-benzaphenone (a fnixture.of benzophenonos
viti~ various nU.oxy eroups of the. type OC7H151 0C 6H179 or OC9H 19) (IT), and
2-liydroxy-51-metiiyl-benzotriazole (Tinuvin) (III). As antioxidants, Kl
titid cop,)er iiajlhtherv~te and organic stabilizers of the follovoing type were
11.9ed: -1) derivativen of aromitic amines; 2) phenol derivativesi 3) aromatic
oxa-Jines; j) 2,6-ilitert-bui.yl-4-methyl-phenyl-pyrocatechin phosphite (Ionoi~
C a rd '1 / 2

ROZINTSZV, E. G.; MAMSDOVA, Yu. G.; H=4AN, M. B.
hmservation of the free valency in the reduction of the
29206p6-tat tbTl- r-piparldone-nitric oxide radical
according to Kizhner's reaction. Izv. AM SSSII Otd. khIm. nauk
no,12:2250-22-51 D 162. (MIRA 16:1)
1. Institut khimicheakoy fiziki AN SSSR.
tiperidone) (Radicals(Chamistry))

KSDVEDEEVAI N.I.; NEYMAN, M.B.i TORSUEVA, Ye.S.
Kinetic tracer method in the study of the irechanisz of
chemical and biochemical processes. Part 11: Rate of formaticn
and consumption of propylene In the cracking of propane. Zhur.-
fiz.khim. 36 no.5.-1016-1021 My '62. (MIRA 15:3)
1. Institut khimicheskoy fiziki tJJ SSSIR.
(Propene) (Propane) (Cracking process)

S/02 62,/143/0G1/024/030
/4" D 101 X31 47
AUTH' 0 i IS: Buc~.achenko, A. Khlopl,,,,ankina, 01. S. , Neyman, .% B.
TITLF: Formation of inhibitor radicals in polypropylen,2 oxidation
PEilODICAL: Akademiya nauk 33jR. Doklady, v. 1~,, no. I., 1~6 - 1,19
TIE' X71' :laritactiv polypropylene powder with an inhibitor di~-).'Jolved in
2, 'Jphk!r-kJ.
alcohol was pressed into 1G(~u films (150 kg/om 120'JC in IL CO2atmo.
The inhibitor concentration of the films was 7*10- 2 _9.10- 2 mole3l/kg.
The epr spectrum was taken at 20 - 2500C (heating by blowinr in hot air).
C; -naphthol, 3-naphthol, binaphthol, 2,6-di-tert-octyl-A,-Methyl phenol,
and diphenyl lamine, Ph2NE, were used as inhibitor3. Cwing to loss of the
H atGrn in the hydroxyl group, radicals formed with epr spectra consist~-nt
with those of the individual inhibitors in the model test. 4,-naphthol and
3-naphthol showed singlets (widths: 3 and 5 oe, respectively)% Conjunction
of` the unpaired electron (UE) on the a, -naphthoxyl radical with theTbonds
Card 1/3

5/02o/62/1;3/()01/Q24/030
Formation of inhibitor ... 3101)'B147
of the naph'.hyl ring is more intense than that of the 1-aJical. The
triplet of binaphthol is caused by the reaction of UE with t.7o eqt;ivalent
pr:)tons. Intensive interaction of UE and the protons of the p-m,:"hyl
group in di-octyl mothyl phenol yielded a quadruplet every line of which
was split into three lines due to interaction with meta protDn3. Cn
reacting Ph2 1TH with peroxide radicals, Ph 2N0 was formed which showed a
uniform triplet (Yridth 10.3 oe) caused by reaction of Ui~ with the N 14
nucleL~s. Every component was split into 15 lines due to interaction with
the o-protons ard p-protons of the benzene ring. The hyperfine structilre
occurring with greater dilution is caused by m-protons. In the initial
section, the radical concentration curves were of autocatalytic char~.~Cter.
The cancentration then increases and goes through a maximum. Comparison
with polypropylene powder containing an inhibitor showed its inductiOn
perioc, to be considerably reduced. The inhibitor efficiency thus depends
on its introduction into the polymer. As compared ,qith-;,-na,)hthol, the
radical concentration in the presence of 13-naphthol was lower according to
the lower stability of,3-naphthol radicals. The same hold~l for [III aoovo
Curd 2/3

6/020,/62/143/001/024/030
Formation of inhibitor ... B101/310
inhioitors. The ma *4ority of radicals -~re formud by chain rupture during
oxidation, a complicated process with degenerate branches. 11. B. Neyman's
kinetic isotope method might yield quantitative data on the kinetics of
inhibitor consumpti~Dn and 02absorption. There are 1, fig-area and 4
references: 3 Soviet and I non-Soviet. The reference to the Enr,,Iigh-
1 an 'qu a pe publication reads as foilows: 0. L. Harle, J. R. T-omas,
J. Am. Chem. Soc., 79, 2973 (1957).
PRESENTED: October 9, 1961, by V. N. Kondratlyev, Academician
SUD,'LITTEDi October 9, 1561
Card 3/3

(6-0
413 '17
S/020/62/146/003/013/019
B101/B144
AUTHORS: KuzIminskiy, A. S.9 Neyman, Lt. B., Fedoseyeva, T. S.,
Lebedev, Ya. S., BuclKe-.ahenko, A. L., Chertkova, V. F.
TITLE: Conversions of free radicals in gamma-irradiated polyioo-
prenes
PERIODIAL: Akademiya nauk SSSR. Doklady, v. 146, no. 3, 1962', 611-614
TEXT: The initial stage of cis- and trans-polyisoprene structuration
caused by 10-50 Mrad C060 irradiation was studied. The appearance and
disappearance of free radicals was ascertained Vy recording the epr
spectrum. An epr spectrum with a signal width of Woersteds was
observed on trane-polyisoprene after irradiation at room temperature in
vacuo. The structure of the radical causing this signal could not b~
clarified; probably it was formed by separation of a hydrogen atom from
the a-methylene group. At -1960C, irradiated trans-polyisoprene showed
a broad singlet due to superposition of various radical spectra. If air
was admitted to the ampoule at roon temperature, the spectrum passed
..over into a peroxide spectrum. No epr spectrum appeared in cis-poly-
Card 1/3 -

3/020/62/146/003/()13/019
Conversioru of free radicals ... B101/B144
number of cross links also proves that with increasine density of the
network the mobility of molecular chains is impeded and the recombination
of free radicals is rendered difficult. There are 4 figures.
ASSOCIATION': Nauclino-isaledovatellakiy institut rezinovoy
promyshlennosti (Scientific Research Institute of the
Rubber Industry). Institut khimicheskoy fiziki kkademii
nauk SSSR (Institute of Chemical Physics of the Academy of
Sciences USSR)
PRESENTED: May 21,.:1962, by V. 14. Kondratlyev, Academician
SUBMITTED: May 25, 1962
Card 3/3

L-0=3109 lat AP3001M s/olqi/63/ow/oo6/oaWoozq
AMAMR: Outing H. S.1 r4trelev, T. I.$ Xmraksya, S. H.1 Xostryukars, T. D.1
Tarasov, V. T.1 SLdnevv A. 1.1 Rodin, Z.; Mitchev 0. 9.4 141wano H. 13.
TI=: Casting of polycarbowtas under proosure.
SOURC& PlastLohookiye massy, no. 6, 1963, 26-29
TOPIO TALSs Diflon, polparbonate, thermal axIdstion.
AMTRACTs Tha change In molecular weigM and meahan.1cal properties of a poly-
carbonate ODif2oe under laboratory o3ddation and an prosaure-casting was studied
Polloarbonatas are dastroyad ma: rapidly by pressure casting than by thermal - -
oxidation. Apparently, this acceleration in combined vith the presence of machaal-
cal deatzvatizz4 The amount of time and temperature for tr*WfCrZbl& the
polymer to the vIA=vi~fUvIn& state abould be used In ardor to r*dwe the azt&nt
of destruatLan. Orig. art,* bass 9 figures, I table and I equation.
'ASSWIATMEs as
smufr=& 00 DATE AQs M;Wh3 =is 00
QM

)/EWT(m)/BDS/ES(s~-,2~--AFFTC/A~)D/SSD--Ps-h/
L 10623-11-3-1 FPR/PPF(G)/W(J'
PrZ~Pc-4/Pt-h_-RM/14AY/WW
ACCESSMI N'R: 03000687 S101901031OD510051064JV064S
AUTHOR: AlishU.8_1, L.L.-L NeZ~=M~.Bj Ysovarskaya, D. M.; Gurlyanova, V. V.
Thermaoxidative degradation and stabilization of polyforr.,aldehyde
SMURCE: VysokomoIekulyarrqye soyedineniya., v* 5, no. 5, 1963, 6U.!-648
TCPIC TAGS: thermaoxidative degradation, degradationf stabi lizat."on, poly-
',-am4de, polyformaldehyde, FFAF 549-27, antiox-4dant,, p~oxineozon, Santovar 0, 22-46
_ABSTRkCT: 'A method has beeir Ca"reloped and used to evaluate the effectiveness of
individual - p2jyamida resi,^,& angtheir
P(as acceptors of the evolving forw_l3Ide!qde)
cor-Dination with various ant~pxidants in stabilizing FFA pL1Xforr-aldehydeAgainst,
thermooxOativedegradation_~~ The method is based on measuremant of the pressure
changte in a special vessel enclosed in a. thermostat containing a PFAsanpla exposed
to oyygen and/or heat. Rressure ciAnge veraus time curves are plotted and evaluated,
?reliminary tests showed Mhat at 145C in the absence of* oxygen PFA decomposes very
slowly. With oxygen present decomposition is =uch faster, shovs an irduction
period, Id
nd yie . carbon oridesi hydrogen, and water. Screenin of
polyamide resina nd "1548-27I.L%y formaldohyde-abaooption tosts ahowed
a ~F
that 1154E-2711 Idehyde acceptor. Antioxidantaksuch aa 1122-46,t
Carci
7 7 1~ 7

...............
L 10623-63
11 41P
Azassim im. j660687
i(2,2f-methyjene-bis(L-met ,'Yl-6-tertbutyl)-phanal) or "p-oxineozon" Ca ~-hydroxy-
in combination with 11548-2711 were screened by the above
r phenylnaphtlrflar"Ine?~
method as additives to PFA at 2000 and 2OG =. Fg of oxygen. The most effectUva
in comb Iination with "549-27' proved to be "22-46," "p-oidneozon' and
nO.." In the case of the "548-271t/t422-4_60 Pombinatiozi added to FFA in 2.5e'
total concentration the optimum polyamide to antioxidant ratio was o.6/6-4- This
derived by the pre ssure-change-curve method, was in good agreement with the
~resultsaof control studies of thermaoxidation by thermogravimetric and differential!;
~thermal analysis. This work was done at the Scientific Research Institute of
..Plastics, Orig. -art. has-.. 8 figures and 1 table.
ASSOGIATIC.1-7-. Nauchno-issladovatelfskiy inatitut plastichaskikh maus (Scientific
Research In6titu:te of Plastics)
S UBYI=, 050dtol~:-- DATE ACQ: 17.Tun6,~
ENCL: 00
"SUB CCDE: CHIIVMA NO REF SOV. 004
(7rHMz 007.
Card 2/2

LIQL24-6 ?F(C")/EPR/jWk (m)/LIDS/F:3(s)-2--AFF,rC/ASD/SSD--Pr-4/
'j)/
ACCESSION NR',, AP3000688 S/0190163/005/00510649/0654
'ik=
AUTH01: V varskaXA-'a, X.; Ak_u_t_i_nA_ff__-_SL-_j- Sidney, A. 1,
1 YM
1 .19,
1, Heyman
TITLE.-I
Iniiestigation of the thermooxidati-
4a decomp sitio of
SOURCE
Vysokomolekulyarnyye Boyedineniya, v- 5, no. 5, 1963, 649-654
TOFIG TAcs.- Diflon
polycarbonate, thermooxidative degradation---
decompositi themooxidative
an
..ABSTRAM. The chermooxidat:,Lve degradarton of.the Soviet POLYCarbonate 10JEJ te
000) has been studied. Thermooxidation was carried out at 240 to
(mot* wt., !a
300C and 92'~ to approkimate'
Ly 700 mm Ng, of oxygen with equipmeam described pre-
viously by the authors,(M. B. Neyman, B. M. Kovarskaya, H. P. Y"vikovat A.
Sidnev, M. S. Akutin, Tygsokomolek. soyadlp 3, 6021 1961). It was found that the
initial rate.of change of.pressure in the system, i.e., the oxidation rate (W 0)
is directly proportional to the oxygen pressure and increases with temperature
according to the law Wo exp(-E/RT), where K 36,500 kcal/mol. The. weight
carct

-63
L io624
-AP3000688
ACCESSIM NR::.
3000 and consta nt initial oxygen pressure. increases line
loss of Difloniat arty
-wit
h, time ~.Idf tiracertaininitial 1
periodi the higher the initial pressure, the
greater the loss. Analysis of the degradation products revealed CO CO, it
V 2
i (trace'), propan~j hydroperoxideo were not
H 20 CH20, and bis(hydroxyphenyl)
1 detected. It was concluded that the degradation is an auteaccelerating chain
reaction with degenerate branchings which are evidently due to hydroperoxLde
decomposition. The reaction is speeded up by da poesence of impurities introduced
in the- starting materials. Special preliminary purification of Diflon by multiples
reprecipitation improved oxidation stability by about 507.. An oxidation mechanism-!
I is suggested which shows that oxidation-not only gives rise to gaseous products
but also alters th aldehyde and hydroxy
e structure of the polymer chains in which
groups accumulate. This is confirmed by the fact that the thermal stability (in
the.absence of oxy0anI of oxidized Diflon is far Lower-than, that ofthe intLtLal
roups and to addi-
Diflon, owing probably to the decomposition of the aldehyde g
tional oxygen.;containinir groups which facilitate ester bond cleavage. Orig. art.
hast 10 foMulaa and 8 figures.
Scientif ic ResearchInatitute of Plastics
2,
Card

AKUTIN, M.S.; KOTRELEV, V.N.; KOVARSKAYA, B.M.; KOSTRYUKOVA, T.D.;
TARASOV, V.V.; SIDNEV, A.I.; RODA, E.; HITCHE, O.N.; NEYMAN, M.B.
Casting of' polycarbonates under pressures. Plast. massy no.6:
26-29 f63. (MIRA 16:10)

?W/F'WPM/EWTWjBDS Pr-h/pc-h RM/WV[
t. FPj
ACCESSION NR-. A?;'1002296' S[0062/631000/006[1118/ilM
AUTHOR: Buchachanko, A. L.; Sdobnov.. "Ke. I Rafikov, S. R.., Neyman, M. B.
TITLE: Reactivity of diethyl phoMhJ-te actions with tritertiary butyl
$n radical m
n
-SOURCE: ~x SSSR& Iz.V. Otdeleniye kh1micheskikh nau4, no. 6, 1963, 1n8-11W
TOPIC TAGS,. dietlql phosphite, tritertiary butyl phenoiql, dimerization, kinetic,
method, degree of solvation
ABSTRACT: The reaction of tertiary butyl phenozyl with diethyl phosphite proceeds
with abstraction of the phosphine hydrogen from mom-aria tautomer containing
pentavalent. phosphorous. The rate constant in benzene at 20 degrees was found to
be k sub I = 1.12 x 10 sup _25- cc/see and the 6quilibriun constant for the dimeriza-
tion of dietbyl plwsphite, K = 7.5 x 10 sup -21 cm ntP -3. The procedure developed
provides a general kinetic method for determining degree of solvation of the reac,-
tion center. Orig. art. has: 3 figures.
ASSOCIATION: Ins-titut khimicheskoy fiziki, kkademii. nauk SSSR (Institute of Chemi-
c~il-Physics); Ins:titut elementoorganicheskikh soyedineniy kkademii. nauk SSSR
Catd

ROZA14TSFV, E.G.; EYMAN, M.B.; KAMDOVA, YU.G.
Reaction of free organic radicals -with Grignard reagents. Izv.AN
SSSR.Ser.khim. no.8:1509-1511 Ag 163. (MIRA 16:9)
1. Institut khimicheskoy fiziki AN SSSR.
(Radicals (Chemistry)) (Grignard reagents)

WDUIDOV, A.A.; BUCHACHENKO, A.L.; ROZANTSEV, E.G.j NEYM~C M B.
Chromatographic separation of the radicals form-d during the
oxidat-Ion of hydrogenated 2,2,4-trimethylquimollnes. Izv,. AN SST,
Ser.khim. no.10;1713-1717 0 163. MRA 17-.3)
1. Institut khimicheakoy fiziki AN SSSR.

ROZANTSEV, E.G.-i MED'11111DOV, A.A.; NEYMAN, M.B.
Kinetically stable radicals of the pyrrole series. izv, AN SCI~R
Ser.khIm. no.].O-.1876-18?? 0 163. (MIRLk 11:31)
1. Institut khimicheskoy fiziki AN SSSR.

ACCESSION NRs AP3006755 1916190163100510003591154
'AUTHORS i ~N(!pan V.; ftchach~nkoj At Le;
U. B.1 Fedoseyeval T. S.; Chubarovaq Q
Lebadev# Yi S.
TITLEt A study of the radicals in irradiated polyformaldehyde
;SOURCEt Vy*sokomoleka1yarny*ye soyedineniyao T. 5, no* 9t 1963, 1339-1544
ITOPIG TAGSs free radicalt polyformaldshyde, electron paramagnetic resonance,.chain
I hain/ EM 2 1W spectrometer
polymerq (pumas irradiatient polymer c
~ABSTRACT: Structural and kinetic characteristics of free radicals in'irradiated
:polyformaldehyde (PFA) were investigated. Powdered PFA was placed in soldered and
acuated ampules and was subjected to gamma radiation from a Cc 60 source. Th
ev e 1
i
study of electron paramagnetic resonance (M) radical spectra at low temperatures
6
was candu(ste4 an PFA irradiated at 77K with doses of 5 x 10 and I x 107 roentgen..
:Spectra were recorded on the spectrometer M-2 RW. A special ampule was used for
,room temperature radiation expertmentse The ampule was cotuleoted to vacuum equip-
!ment to al'low varying gas concentrations-around the specimens, Means were provided
for controlling the.amblent air temperature, Test results indicatede, 1) two types
!Card 1/2

STILYAPNIKOV, Yu.A.; MILLER, V.B.; NEYMAN, M.B.; TOR-'IJYEV'A, Ye.S.
Regularities of the effect of inhibitors in oxidation
reactions. Part 2: Mixtures of alkvl phenols with didecyl
al-ilfide. Vysokom. soed. 5 no.10:15G7-1512 0 lfZ')3.
(14M1 17: 1)
1. Institut khirdcheskoy fizikL AN SSSR.

NEIMAN, M.B.; LIKHTENSHTEYN, G.I.; KONSTANTINOV, Tu.S.; KARFETS, N.P.;
URHAN, ra.G.
Thermal oxidative degradation of polypropylene studied by the
method of nuclear magnetic resonance. Vysokom.sced. 5 no.11:
1706-1710 N 163. (MIRA 17:1)
1. Institut khimichaskoy fiziki AN SSSR.

BUCHACHERKO, A.L.; ITMN, M.B.; SUKHANOVAp O.P.; MAHEDOVA, Yu.G.
Effect of solvents on the reactivity of nitrophenols of different
structure in their reaction with the tri-tert-butylphenoxyl eadic&l.
Zhur.fizAbIti. 37 no.1&221-224 Ja 163. (MIRA 17:3)
1. Institut khimicheskoy fizikI AN SS3SR.

".AL IM-63 EM/EWP(J)AFF(a)/WT(m)/
A

FF
ZGIASD
Ps Q?c
ACCESSION kRi AP3006624 S/0076f63/0371009.12077f,2081
AUTHORt Gromov,,V, K.',*,Reyman, H, B Vakula, V. L, Voy-utsk.y,
S.. S.
trTLE t 'Study of the nature of the failure o f, apolymer--substrate
adhesive. bond bythe method of tagged_atomoly

COURMs Zh. Z zLeheskoy khLmii,. v.-37, no. 9, 1963, 2077-ZO41
:TOPIC TAGSt a dhesive bond, adhesive bond failure, bond failure,
joint.failure, failure, polymer substrate:adhesive bond, radio--
metric. method, : adhesiviss tagged atom, tagged oolymer,, &tactic
olypropyleue,
P -tagged at.actic polypropylene substrate, monradio-,
i actLve atactLe polypropyltne,.sheet silicate glass, copper foil,
stripping test ,adhesion testing machine-, TsHIKZ adhtsi6n testing
machine, bond strength,,-radLoactivLty, substrate radioactivity,
bonding time, bonding temperature, mLeromosaic type faiLure'
AIISTRACT: The failure of polymer-subs trace adhesive bonds has
been studied b y a. highly sensitive radiometric method developed
C.,d

AOCESSION M, AP3006624-
the auth loyLag a tagged polymer., Atactic.;ialypropylene
(Iftolecul. r Vei 3 X 104) with tagged tortLary C allom &I Used,
d'a art
all in a hasiv and nofiradioixettve atactia polypropXLeft sheat
sIlfcate, 1-11asst or copper foil, as a substrate. Str),ppi X11 tests
percale strips coated with the adhesive were conducted with a
TOM adhesion testing, machine; the radioactivity of the stripped!
si.Abstrates van.then matoured. The results are given in the form
of tables and graphs. The fact that all stripped substrates were i
radtoactive indicates that after' bond failure a certain amount
of
adhesive remains an the substrate. Radioactivity measurements
howed that.the,quantity of adhesive remaining on the substrate
increased wLth !an increase,Ln the time and temperature 'of contact
between adhe sive and substrate during specimen preparation. rt is
a~sumad that: 1) the adhesIve remaining as nonpolymerLe substrate!,
is distributed in the form of "EsLets" rather than as a uniform
layer and that Ln such case bond ifaLLure is "micromosaic" in type; I'---
Z) in the case of polytteric substrates of a higher molecular
weight with thtae-dim6nsional or supermolecular network structure
Ca"I

S/020 6311,16100110191052
B1019BI86
AUTHORS: Buchachenko, A. L., Gurlyanova, Ye. N., Kalashnikova, L.A.,
Neyman, M. B.
TITLE: Dipole moments of the diphenyl nitrogen oxide radical and
of the. diprenyl hydroxylamine molecule
PERIODICAL: Akademtya nauk SSSR.' Doklady, v. 146, no. 1, 1963, 95-96
TEXT: The molar polarization P 00 at infinite dilution and the molar
refraction RD for the D line of sodium of C 6H5 -F-.C6H5 (1) and of
0
cisH5 -,1,- C6H 5(11) were determined in benzene at 250C. The dipole moment
OH
was calculated according to g 0.22 rP~7i~. Data found for I:*M.P.
11
oil0CI.P(n . 240.8, RD 55.8, 3.0*10-18, and for II: m.p. - 600 C,
-18
p 9108, RD - 56.9, 1A = 1.3-1o The discussion of these p values
leads to the conclusion that no additivity exists and that p for I cannot
Card 1/2

1'. 1' 00-6 P"/P~-4 - F&VWd.
S
AOX381W NE% vwm2i 61=016V15110011014,810150
AMIMRSt S kovg Ymo A~j Killer Ye B*j gaptan# Me BrI Torvuyeva,, Yea so
TZ=t ~a~lclpatlou of Inhi bitor aegenerate branch
Ing of a obain
OURM AN SSSR. Dokladyj vii 15lg no' I U03t 148~
150
TOPIC. TAGS t inhibitor, oxidizing (mF
reacti chain branching.
ABSIWT-., The anthor investig4ted, IV-ba Wluewm of tbe. inhibitor Immapbsoo1w
or. the IvAntity tit arftLaal omaewtratlonot another Inhibitor Oblyhonollre
it
is, RhOWA that the factor ot sOlf-moslarating oxidizing roa*tLQZL of hijoL-woloeulu-
OallbokAzateldepende on the ox7pa Imeamure and on tbo concentratiAm ot the
-Wlwhouol" inhibitor& Tte growth of the salt-aaaelerating oxidizing re
actiom
i fadtar in. the pre3emos of the inhititor "monophanol* is explained by the Wti-
aipe~Uou of vbs Libibitor in the act of degenerate branching, of chainuo The,
I paper was 15resentod by Academillian 9. 11. Semenov ofx 11 Karch 1943,~ Orig. art.
haff.: 11 formulas and 2 fi%#es.
SS6, Acadeqr of Sciences,
'TAT N: Inst., of -Chemical -Phnics,
A
Card,

NEYMAN, M.B., ot7l. red.
[Few developmen*.s in -nemist.-Il Nr-vof, ; ihimii) swrnil
statei. Moskva, llauyr,; 1964, 361 P. ~XIhA 17.12)
1. kkaden.iya nau-k SSSit.

_65 `
L 21811

i

049841.
AT4
ACCEMOR O

d% -residue aft r dagradatica a
Inf rare :spqictr&-of-p6Iycarbonate and of the. solid e
t

7
P

500C :show&r that' the
:Absorption bands~of the CHq groi~p (2970j: 1365 1385 Carl) -

t-in the initial polycarbonate are missing in the solid residue,,
which are presen
and that thli intensity of the. absorption bands of the,groups C-0 and C-O-C (1760,
and 1259 ciO) decreases. The: increase in the intensity of-absoiption at 1600 and
1300 eel Orresponding to the. benzene ring#An the solid a oiduit shows that the'
residue contains.more phanyl tinge af ter, degradation. The changa Ln the structure i
and mole-dutir mobilit Iuring: degradation of polycarbonate %ras also investigated
by nuclear'-paramagnatic resorAnce spectra.: Here, the r0idth of the line depends on,
the degree of mobility-of the molecular group contairting th~i resonant ring* At a
temperatur~higher than 150C and lower than -130C, for the Initial polycarbonate
a COIV~Miti~signal is. seen which consists of two tomponentm: a narrow and a wide
band. Two regions,of decreased vidth of the line from o-150-to -.50C and from 150
to 170C are-16jind.for the initial polycarb3iatee The narrovdng of the EPR line
at low temoaratures is
due to the mobility )f the CHq groupai in the polymr. This
-.

7~j
R%t
L 2767+40~'--
b w- -
-AT40,49 645
f
80 miti,- at 200 250s 265, 280v 200 and 3000 be
I 11f ter 'hoating-for I came 3.20.8
2.61, 2&2# :1*9"~and 1o72,- respectively. At 20OC-the intrinsic viscosity remained
unch Said; ~a~ 30QC a loci a- the weight loss insignift nt
the gou evolution Va. nd ca
Al: 3450 the - po y0wr obt sp than 3% of- its weighta:aAd the. averagemolecular
the at,% obtained show that
wli.ght .*f 'evolved :gOes was closeto 44i. The kinetii~~ 4
dutia th -ion of polypropylene togethe:r witli other processeall,
ermd deiradat.
polywrization - of the degradation products takes place* , Ior polymer 1,,on the
bavis of the-pqints of the dWrgm corresponding to temperatures of 315, 330 and
34!.'c (dissociatior, enir-1;y) - 18.0 kcal/mole; for polyzier, 11 SLt the same tiwer
turesi Q xa 19-7 kcal/00'le. Tabulated data.are given for the sclutiou of the prob-
lent of the -case Of the U101: rato of thermal degr"ation,,, *The:total rate of the
degradation-of jplypk~opyiexte is a I to the am of. the -rates - dejolymerizat
qua 6
iataetiiati6n and cho" transfero At -34SC-Whas & value of 10 tured
rup
bmids per g,', seei - It-Vita concluded for,,polypropylenatbat the high rate of
butt degradation,-of pdymsre cannot be explkindd.by this cloncepts.of the normal-

Sw

!;s,Eom NR,, AT4049845'-
-ACCE'

khimicheakoy-fiziki AN SSSR -(CheM.cal J~hys institute
-Abl S3)S9L

6jun-62 :00 StM CODSt;
StMM:ETMDt ENCL: OC Gi2i -

vnm,.,~ OW
Rl

-Card,
3/3

Car

1/3
al,d
c
wa:
L
AT4049847
equation describino,the cons
toPtIon. of ene inhibitor-in the oxidizing
C mixture
'lutsining two 1-6hibitors of -the iiame. type is 0
given. In a mixture of these tw
luhlbltOro~ 2021-thio-bis-(4 methYl-6-tert.-butylphenol) is conaumed wore alowiv,
rand 2.2ia-matAvlana-

L 'PaL6.-tZ~
ACCESSION Al. AT4049855 9/0000/64/000/ooo/0156/015
9
164, R,
AUTHDR: ~09
so; Neyman M, 3.
TTTLE: Theriw-Oxidative degradat I Polyethylene oxide
SoWn
E: Khimicheskiye ovoystva imodifikatsiya polimerov (Chemical properties
and the modification of polymers); ebornik statey. Moscow, Izd-vo Ila A& 1964,
156-159
Tqlc TA(;,S:. polyetbjlene oxide, thermal degradation, propylgall te, ar~nwtii:
amint-p ocidative,degradation, polymer oxidatioa, antioxidant
ABSTA~C!T:' The indui~.tion. period of the oxidation of.pilyethylene oxide (PEO) was
investigated as a funation'of temperature and oxygen-- pressure., The initial
e
vroduct (malecular weight 25000) was obtained by bulk polymerization of ethylen

- ~Q 4~kM_.
Card
N-116-66
ACCESSION NR: AT4010855
was aalculs''ted ---at 331,000 caVmole, The dittit obtained for the retardation of
Oxidation bf M by cntioxidants are, tabulated. The induction period am a con.
centration. of antioxidant'of 9'5. x 1o-3 moleft, 135C and Por340 "o chosen
as cliarantaristic for evaluating the effectiveness of stabilizers V The plotted

ACCESSION XR: iLP4018159
S/0191/64/000/003/0014/0017
AUTHORS: T~evantovskaya, I.I.; Kovarskaya, B.M.;.~eyman, M.B.;
Rozantsev, ErG.; YazviLkova, ".,.P.
t
TIPLEE: Inhibiting the thermal oxidative destruction of polyamides
with aromatic,amines and radical type stabilizers
SOURCE: Plasticheskiya massy*, no.3, 1964, 14-17
TOPIC TAGS: polyamide, thermal oxidation, oxidation inhibition,
antioxidant, phenyl beta naphthylamine, piperidine nitric oxide,
piiDeridone nitric oxide, radicnl t7fpl- stabilizer, induction Period
I
P.BSTRuXT: The inhibition of ther,,-ial oxidation Of P017amides -.-!itb
phanyl-beta-naphthylamine and wl.th th'a fr.--- radical type stabilizers
2,2,6,6-'%"etramethylpi,oeridone ni.trIc oxide and 2,2,,6,6-tatramethyl-4-
et'hyl.-I-hydroxypiperiaine nitric oxide vas investigateq. The radical
stabilizers display marked inh-ibition of thermal oxidalion. Lass
than half of the original amount of aromatic amine is spent during
tha induction period in inhibitin;-, polyamide thermal o7,idation; inhi-
Card 1/p,

ACCESSION YR: AP4018159
bition of oxidation at the en,' of th-3 induction period apparently
depends on the remaining unspcr.*-- antio)*,idant. Unlike the aromatic
amines, the free radical inhib~-tors retard the oxidation of polyam-
ides until they are completely consumed. At the end of the induc-
tion teriod tbee rate of oxldat~on v;ith these radical inbibitors
aporoaches the rate of oxida-.-ion of the uninhibited polymer. Orig.
art. has: B figures and 2 formulas.
ASSOCIATION: None
SUBmIWED: 00
DATE 271.1ar64
ENCL: 00
SUB COIE: CH
NR REP SOV: 008
OTHER: 000
Card 2/2

ACCESSION NR: A114042869
S/0062/64/000/007/1178/1184
AUTHOR: Neyman, M. B.; Rozantsev, E. G.
TITLE: The use of stable radicals as antioxidants
SOURCE: AN SSSR. Izvestiya. Seriya khimicheskaya, no. 7, 1964,
1178-1184
TOPIC TAGS: anti'oxidant, free radical, nitroxide, acetoneamine,
polymer stabilization,'polymeric material, polyformaldehyde
stabilization, polyamide 68 stabilization, polypropylene stabilization
ABSTRACT: The authors had previously found that a new type of anti-
oxidant - the nitroxides - terminate the oxidation chain reaction
without increasing the probability of branching of the reaction
chains. These new antioxidants contain a -N-O- group with a free-
radical valence. The simplest nitroxide was synthesized from acetone
and ammonia by the catalytic oxidation of the intermediate triacecone-
amine to the structure:
Me
0 N-0,
Card M. e2

ACCESSION NR: AP4.042869
where He represents the CH3group. Further, a series of aromatic
nitroxides of the type
Ar Ar
0
was prepared, where Ar designates a substituted aromatic radical
with alkyl and alkoxy substituents. The previous experiments of the
authors, in which ethylbenzene was oxidized by air in the presence
of azobisisobutyronitrile used as the chain initiator, indicated that
the -aitroxide radicals of the triacetoneamine series practically do
not react with the formed hydroperoxide radicals ROO. However,
when oxygen was excluded and replaced by helium, the reaction of
nitr3xide free radicals with hydrocarbon radicals R, took place.
Similar behavior of nitroxide radicals was observed also in the oxi-
dation of isotactic polypropylene in films ; it was found that nitroxide
radicals accelarated the dacompooition of hydroparoxida (which
results in branching of the chain) only 302, while the aro-
matic amines which are also used as antioxidants accelerated this
:Z/4

ACCESSION NR: AP4042869
decomposition by 30-40 times. Experiments with the oxidation of
polyamide-68 at 160C and 200 mm Hg oxygen pressure indicated that
bis-2,2,6,6,-teti-amethyl-14-ethyl-4-hydroxypiperidine nitroxide
produced an induction period of approximately 200 min, i.e., equal
to that produced by one of the most effective antioxidants - Neozone
D. In experiments involving the thermooxidative decomposition of
polyformaldehyde the nitroxide radical was to be combined with a poly-
amide to bind the evolving formaldehyde. An increase in nitroxide
antioxidant concentration produces an increase in the induction
period, and saturation is attained after the initial increase of the
effact. The authors state that the effectiveness of the nitroxide.
antioxi-lant5 depends on the structure of the compounds; however, the
reaction found by the authors for their synthesis of nitroxides makes
it -,)ossible to prepare a variety of these antioxidants, including
coml)ounds with low volatility and high antioxidant effectiveness.
Some water-soluble nitroxides might be of interest for biochemical
studies; aromatic: nitroxides are promising antioxidants, for rubber.
Orig. art. has: 11 figures..
Card 3 / 4

ACCESSION NR: AP4042869
ASSOCIATION: Institut khimicheskoy fiziki AN SSSR (Institute of
Chemical Physics AN SSSR)
SUBMITTED: 20Feb64 ATD PRESS: 3070 ENCL; 00
SUB CODE: OC, MT NO REF SOV: 016 OTHER: 007
C-6 4/4

oeen i,otuoLea. an.u P
piper,lAtuo I-oxido
tiea. had fenaibUf~

ULLOWN 49T. 4LOV. -BUDIFTI.- %,.Qnr. Vu Visa IFsuala POEM 4luQ Jkh

, , : J. , .
I cor& fts,:~- -,
; I ... - ;~~
.1 ~ :w " ,, ~'. , ~~-

ic

Card
3/3~~

t)qi "-
tlie--p,eisence-oi wiyK
ONE

ACCESSION NR: AP4017634
S/0190/64/006/002/OZ41/0246
AM70R";s Fedoseyeva, T. 3.1 Kuzlninakly, A. S.; Heyman. V. B.1 Sucha*henko, A. L.;
Lebedev# Ya. 3.1 Chertkmq V. F. Qlj._'~_i_.`- -~6_'_,
TITLEa Effoot of throe-dimensional network on free radical annihilation process in
clautomors
SOURM Vy*aokomola)mlyarny*yo soyellneniyap Y. 6, no. 2, 1964, 241-246
TOPIC TkGSs free radical, sodium-butadiono, thermal vuleanizate, EPR spectra,
irradiated upecimanp chain segment, activation energy, pro-exponential factor
ABSTIUM The kinetic properties of free radicals formed in the ~-irradiatiou of
thermally vulcaaized sadium-butadiens of various degrees of cross-linkages have
been ir.yeatigated by the EFR method. The thermal vulcanizate was obtained by p a-
lizinary hoc-Aing of the purified pol~(zor in the press at 220C and under 50 t/5
prossuras from 5 to 60 haws. The specimen was irradiated in vacu= at -196C from
a co6o source of 25 Ur&l dose. The JOR spectra of the irradiat6d. specimen were
obtained on the EPH-2 EMP AN SSSIt Instrument at -196C In 20 to 1000 Intorvias. It
is showa that for2ation of a three-dAzensional network Vralonge the lifetize of the
C.,d 1/2

ACCESSICO HRs A.P4017634
!captured radicals. The rate of &=ihilation of these radicala deoreaaes with
increase in the number of aroee-linla%,es. The rate for the same network density is
'limited'by the mobility of the various chain segatents. Parthermore, the activation
~energies and pro-expodential factors for the vxnih~Uaticn of free radicals in
~"mobile" and "sluggish" regions of the chain have been determined. Orig. art. bass
:5 figures Wd 1 table.
~ASSOCIATICK: Thstitmt kh-Imicheakoy fiziki AIT SSSR (rnstituto 0i Chemical mysics,
4N SSSR); Nauchno-issledavatellskiy institmt rezinovoy IwaWshlenT sti (Scientitio
Research Institute of the Rubber Mmdustry)
SUBIrr=t 131TON62
DLTS ACqt 23U&r(4 ESOLs 00
SUB CODEs CH NO RE? SOVs OTEER 1 000
005
:,-Card.

ACCESSION NR: AP404,1774 S/0190/64/00ra/00,3/1391/1393
AUTHOR: Goglev, R. S.. Neyman, M. B.
TITLE: Thermo-oxidative degradation of polypropylene oidde
SOURCE: Vy*sokomoletatlyarny*ye soyeeineniya, v. 6, no. 8, 1964, 1391-1393
TOPIC TAGS: oxidation, oxidative degradation, polymer oxidation, polypropylene,
polypropylene oxide, propylene oxide, antioxidant
ABSTRACT: The duration of the induction time ri") of the reaction as a function of tempe,-
ature, oxygen pressure and the presence of antioxidants was investigated in a study of the
oxidative degradation polypropylene oxide, using a method described in an earlier
paper. The polymer, with a melting point of 69C and a molecular weight of 40, 000, wa-
prepared by catalytic polymerization of propylene oidde in the presence of ferric chloride
and purified by repeated precipitation by water from an acetone solution acidified with '
hydrochloric acid. The effective activation energy for the oxidation of the polymer, fouud
from a carve of lg* vs. 1/T, Is 22 k-cal/mol. The Induction time was inversely proportional
to both temperature and oxygen pressure; yielding hyperbolic curves. Curves showIng
the retardation of the ox1dition by additions of 2. 2-methylena-bls- (4-methyl- 6-tert. -butyl