SCIENTIFIC ABSTRACT KORSHAK,V.V. - KORSHAK,V.V.

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• Collection: Scientific Abstracts
• Document Number (FOIA) /ESDN (CREST): CIA-RDP86-00513R000824930004-1
• Release Decision: RIF
• Original Classification: S
• Document Page Count: 100
• Document Creation Date: November 2, 2016
• Document Release Date: June 14, 2000
• Sequence Number: 4
• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

26296
3/190/61/0j3/008/009/015
B11O/B216
AUTHORS: Korshak V. V., Krongauz, Ye. S., Gribkova, P. N., Basnev,
- i - ~.~ _' ~.- , , ~'
TITLE: Study in the field of coordination-chtin polymers. V.
Synthesis of metal-containing polymers of bis-/I-diketones
PERIODICAL& Vyaokomo1eku1yartyye soyedineniya, v. ~, nu. 8, 1961,
#203-1209
T.EXT: In previous papers (Ref. 1 % Vysokomolek. sojed. , 1, 1764, 1959;
lic-i. 21 ibid. 2, 662, 190,0) the authors had shown that c-covdination-chain
-I,oljmeru viere formed by interLetioil of bis-~-di:ze tones 4nd acet!.;t_-s (or
bcetyl acutonates) of bivalent metals. Bis-fi-diketones of the following
st.-,.ct_,.re wurt? studied: CH COCH CO-Y-COCH COCH vher,~ Y
3 2 2
Ci -CH _117~\, -H
2
of these polyLi..rs were unsoluble and hau decompoaiticn temperatures
of uetvii~eii ;eUO anA 43uc'(;- It was the aim of tht; Ire eat work. t-o produce
Card 1

26296
6/190/61/003/008/009/019
Study in the field of coordination-... B110/B218
polymers with flexible chains, ihich containad -(CH 2)n- or LO (CH 2)2]n 0-
groups between the benzene nuclei. For this purpose, three aromatic
bis *diicet ones were synthesized: 4,41-bio~ac-~;toacetjl) diphenyl ethane
Mi 4,41-bis(acet,acetyl) ethylene diphenji ether (II); and 4,41-bis-
kacetcacetyl) diphezVl dietIVlene glycol ether (111). 3yntheais was made
according to the au,.hor's certifLate of the USA, nu. 1206488, 1959, by
acetoacetylating the aromatic z:ompounds by means of acetanhydride in the
presence of BF 3. As compared to Claisente condensation, the reaction V~
is one-staged and results in a high yield. To prevent formation of
intermediates, a large excess of acetanhydride is necessary, molar ratio
1 : 20 - 30. 1 (melting point 147 - 1480C) was obtained in a yield of 0
10~ referred to liphenyl ethane. The reaction temperature was 40 - 50 C.
The infrared spectrum confirmed the structure of p-substituted bi s-fl-
diketone of' diphenyl ethane (for keto-enols, characteristic absorption
1
at 1600 cm- ,for 1,4-substituted benzene nuclei, characteristic
absorption at 845, and 790 cm- 1). As a by-product (10~), diphenyl ethane-
Card 2/P~,

26296
S11901611003100810091019
Study in the field of coordination-... B11O/B218
,I-diketone (melting point 81-5 - 82-50C) was,obtained. II (melting point
16.9 - 1700C) was obtained in optimum yield (16%) at -100C. The ethylene
diphenyl ether, brought into reaction with acetanhyaride, was synthesized
in the autoolave (1500C# 50 atm) by roaotion with natrium phenolate and
1,2-aichloro ethane. III (melting point 125.5 - 1260C, yield 7-9%)
was obtained at a reaction temperature of from -5 to +50C. Diethylene
glycol diphenyl ether was SylLthesized as initial compound by reaction
of Na phenolate with fl,At-dichloro diethyl ether (2000C, 50 atm). Since
the compounds had not yet been described, the authors synthesized I also
by Claisen condensation and found it to be identical with the compound
obtained by direct acetoacetylation. Compounds II and III could not be
produced according to Claisen. By reacting I, II, and III with acetates
of bivalent metals, the authors obtained the compounds given in the
Table. In this, they made the following observations: The solubility
of the polymer depends on the ionic radius of the metal which forms the
polymer chain. It was found that introduction of the groups -CH 2CH 2-;
Card 3/8/V

5/19 M003100810091019
~2
B,
Study in the field of coordination-... B110 B218
-OCH2CH20-, and -OCH2CH2OCH2CH20 between the benzene nuclei resulted in
coordination-chain polymerization.-The molecular weights, determined
ebullioscopically, were at about 2000 - 3000. The films produced at
200 - 3000C and 50 atm were brittle.' The thermomechanical curves and the
X-ray picture of the beryllium compounds of II confirmed the crystal
structure of the polymers. There*&re 3 figures, I table, and 6
references, 5 Soviet and 1 non-Soviet.
ASSOCIATIONt Institut elementoorganich6skikh soyedineniy AN SSSR
(Institute of Elemental Organic Compounds AS USSR)
SUBMITTEDs October 18, 1960
Card 41_0~

27570
I'S") 2. 22,09 2409 S11901611003100910051016
B11O/B1O1
AUTHORS: Korshakt.V. V.p Sosin, 3. L., Alekseyeva, V. P.
TITLE: Synthesis of new types of linear polymers
PERIODICAL: Vysokomolekulyarnyye soyedineniya, v. 3, no. 9, 1961,
1332-1340
TEXT: The first two authors showed in previous paDers (Ref. 1: Dokl.
AN SSSR., 121, 299, 1958; Ref. 2: Vysokomolek. soyed., 1, 938, 1959) that
when treating peroxides (PO) of compounds such as p-diis-opropyl benzene
(DIPB), diisopropyl ferrocene, p-dichloro benzene, etc., linear polymers
are formed, and, particularly in the case -of DIPBq non-fusible and
insoluble polymers with cross-linked trimer structure. Polyrecombinatioi-i
of diphenyl methane (DPIJ) , 'phenyl acetic acid methyl ester, benzyl
benzoate, etc., was studied in the present work. 71hen treating these
compounds with tort-butyl peroxide (TBPO) (molar ratio of TBPO to initial
compound >> 1-2) at 2001C., linear polymers were obtained. Diphenyl methane
(DPJJ) gave a linear polymer, an amorphous , yellowish powder which
dissolved in benzene (melting point 200-2200C) with'a molecular weight
Card 1/7

27570
S/190/61/003/009/005/016
Synthesis of new types, ... B110IB101
(m) Of 10,000-900,000, depending on the molar ratio.
-3 0.326
2.18-10 M The following reactions take place:
(CH 3)3 COOC(C11 3)3 2 CH 3 3CO'(R'); (CH 3)3 CO' (CH 3)2C0 + CHj(1?-). The
radicals reAct with the~h,
ydrocarbor~q:
2 (Call,), dil tic (("115)'C[1 Wflla)-!~
(CS
C (Callsh lite ((1411021111'- He (Callsh MCB110-l" - - -If M.
The resultant polydiphenyl methYlene.(PDPM) (I) does not decompo!ie to free
radicals in the presence of diphenyl picryl hydrazine, and is stable to
oxidants ('R'03) 1since the structure of ,tetraphenyl ethane (TPI-!,) which is
probably formed initially does not permit the formation of stable radicals.
Rearrangements might take-place-accordingto
G - C -
Card 2/7-

2 57
8/196/61/003/0Q9/005/016
Synthesis'. of~new types B1 I QJBI 01
a
d
n
-0~
, HG (C,Ho)
HC (C,Hs), CH (C4Hj)I
.,
HC (CtHa)oC (C11s) (CjHs)% " (CaHs), C-= CHI + (CjH&)j CH2;
C (CsH,)s;-~ CHI C (CdHs)t- CHI -
-The reppating'r t'in'I and.
uni II-. is E in III C H jVh.en
14 12
1310
,
compiring tfie'IR 'spectra of the polymers, from DPM, TPE, tetraphenyl

ethylene, an& 1,0
-diphenyl-ethylene, the. absorption maximum characteristic
'of - IA a found to be abseni.i
-substituted.benzene (833-840 om- W 8, n PDPM.1
1
'
.
structure Il
is therefore no sible.. -also excluded since~.th
t pce e

maxi
mum
060 "6ML,~) ch.aiiacteriet.i'c of the C H -C-CH configura.tion was.
6, 5, 2

ll
ig thus confi - 4, The i
d*.PDPM struPture'
:absent as well. Th
according,Lto rMe
-
.
dependence of'theyield on the molar,oratio of PO'to hydroca
rbon:indicated.
for' the
an almost complete oonsumptioln.of. the first peroxide mole.
L, dimer"ization(A). of the total:DPM.to TPB(-9C~Vyield). - At a ratio o f
.,2,-. I.the polymer yield W is.0onstant-(50%)- LThis accounts for the
Card
31T

2757Q
%3/1 90V611003100910051P1 6
Synthesis of new: types.~.. B110/B101

change in viscosity. ed (meltin'
In A, TPE is f orme 9-point.209-2110C, e.
higher than the reaction tempeia~tii~6) and viscosity considerably
-decreases since Ahe -low.,molecular -polyne
increases. In,B, however it. re
melt already at C .'The read .tion of TPE'which is first
180-1900
is then retarded by the Yormation:.Of high-*Moleoul a (melting
ar polymer
0
point 200 C). The visoosity'will'~be t r
reduced,toward the end of
tion'by adding a DPM-PO mixture'- to. ~FM; '.th'e'yield increasee. PeroAde 413,~~

aamixture of' > 2 moles/mo,le of aphically results in. a steep ascent.
DPM g;
0
of the molecular weight which!aaymptotically approaches the ordinat4,-
-the
Assuming that*ihe'rohain growi by doubling (dimer tetramer, octamer),

V,
follow~fig holds: N ix -2 2/n, wher6*N' number of free radicals/iole8l .1 _
R
n - polymerization coefficient. _A. mo'le'of free
radicale is formed on
.
deloomposition,of TBPO. Maximum,M is-thus obtained for-a PO consumption of!, Y-1
2 moles/mole of hydrocarbon. 0.68 mole tert-butoxyl radicals result' from
I mole P0,(in the form of tort-butyl alcohol). 1.32 mole of radicals' i
decomposes to -give 1.32.mole acetone and o.66 mole methane, as' follows..-.
4U,!
0
0. 190-2000C CO

0 CH') C04 OHS, and (B) (CH ) C 0,(CH
(A),(CH 3)3C - jA0 0 0 3 2 3 3 3)2

.

*
CH _0_C_(qH Acoording to Yu. A. Aleksandrova, Huan YU-1i,. A., P..
)
3 3
3
Card
_4/ T_______ ....... .

27:570
6
91190161100310091005101
Synthesis of new types B11O B101
T
Fravednikov, S.. S. Medvedev"(Dokl. AN SSSRI 123, 1029 f 1956) -no methyl
radicaleare formed in (BI which'takes place at higher temperatures.
Isobutylene oxide reEults on initiation of. the peroxide decomposition. Thli~~t 4'iv
authors separated the fraction (51-5300); ieobUtyl-methyl ether and T.
a01.
isobutylene oxide. In the same way, they obtained polymers which dis vea
When using ditolyl methane instead of DPMj' a
in benzene. C~olymer
0 8_~ A'F
insoluble in benzene and p-croool (melting point 186-2400 witi; cr a
9-
linked structure is obtained in addition to linear polymers (meltin
point - 150-1 800C, molecular ~weight - 2500). The elemental-organic
1 mers obtained from diisopropyl. ferrocene, ferrocene, and triphenyl-tki'4~
0 y
P
N-igopropyl borazol (TPNI) by means of polyrecombination showed IR.'.-
absorption maxima at 820# 1000, and lioO cm-1 , and, accordingly). struct~vbli- T
1~4
FO
C118h
I-D ID X
ji~
-red powders soluble in be ne (soften
M 1000-7000i they are dark nze i...
0
t ^-300 The electron paramagnetic resonance signal (line wi
poin
Card 5/7

27 '70
S/1,90/61/003/009/005/016
Synthesis of new types B1 I O/B1 01
120 oej 200C) confirmed them existence of unpaired electrons (concentrat
21
10 /g polymer). Treatment of TPNI with TBPO yielded only a soluble',*
low-molecular polymer.. Polyrecombination gives also.polymers with
aromatic rings in side ana principal'o'hains.' A soluble copolymer was
obtained by treating a mixture of DPM (0.1 mole) and DIFB (0-1 mole) with-
insol4ble polymer. 2
0.25,mole TBPOI DIPB alone gave a near* 6-aichlor6.-
.p-xylene gives a chlorinated analog of.poly-p-xylene soluble in benzene
..-Cl-in ortho-position to the CH3 groups blocks them and prevents their.
participation in the formation of linear chains. Polyrecombination thus:,:. i-;-;,
YNQ
'results in carbon chain polymers with aromatic rings in the principal
-made
chain, whose production is difficult. Gas chromatography of DPM was
on the X -2 (Kh-2) apparatus. There are 4 :figures j 1 table, and 18 ref
ences: 6 Soviet and 12 non-Soviet. The three most recent references to
English-language publications read as follows; Ref 7: G. A. Russel
J. Amer. Chem. Soc-, 78Y 1047) 1956; Ref. 9: J. k Brook, Trans; Faraday-,,.
Soc., 51, 327, 1957; Ref. 10: K. M. Johnston, G...'L Willia,s,,Chem. 'and
Cbem. Ins. 1958', No, 111 328.
ASSOCIATION: Institut elementoorganicheskikh soy'edineniy AN SSSR
(Institute of Elemental Organic Compounds AS USSR)
Card 6/7.

2700
S/190/61/003/009/015/016
C) & B124/B101
AUTHORSs
TITLEs
Korshak, V. V., Sosin, S. L., Chou Jun-p'ei
Production of polymers by thermal dehydropolymerization of
hydrocarbons
PERIODICALs Vysokomolekulyarnyye soyedineniya, v. 3, no. 9, 1961, 1427
TEXT: Heat-treated hydrocarbons are cracked and dehydrogenated, and
yield, besides low-molecular decomposition products, resins which are
low-molecullar condensation products with a complex structure which greatly
differs from that of the initial products. Such resins are formed both
by gaseous-phase pyrolysis and liquid-phase cracking. High-molecular
polymers cannot form under these conditions due to the inevitable decom-
position in the high-temperature zone. High polymers may be also obtained,
however, when the hydrocarbons are thermally dehydrogenated under con-
ditions preventing thermal degradation of the polymer. The method devel-
oped by the authors is based on the liquid-phaBe dehydropolymerization
in a flow of 0nitrogen on a platinum or tungsten coil electrically heated
to 650 - 700 C and immersed in the liquid hydrocarbon. The hydrocarbon
Card 1/3

2-7
S/19 ~1101003100910151016
6
Production of polymers ... B124/BIO1
is dehydrogenated on the coil, and simultaneously forms polymer products
which are immediately carried along from the heated surface by the liquid
hydrocarbon. The condensation products obtained are led from the high-
teniperature zone to a heated container where the drops of the condensation
.products are collected, and the unreacted hydrocarbon is distilled off and
recycled to the reactor (see Fig.). A number of alkyl and hydroaromatic
hydrocarbons was treated in this way. Tetralin is converted to naphthalene
described, whereas polymers are recovered from p-xylene,
-cumene, ethyl benzene, and p-diisopropyl benzenel the molecular weight of
thelpo i~41 a.re''oVta'ined from p-diisopropyl benzene is about 10,000. The
yield in polymer is 10 - 15% related to the hydrocarbon used, and 70 - 80%
related to the reacted hydrocarbon. There is 1 figure. ibstracter's
note: Essentially complete translation
SUBMITTEDt January 12, 1961
Card 2/3

283.76
I S-0 B11901611003101010041019
B130/B11O
AUTHORSs Korshak, V. V., Krongauz, Ye.,S.9 Sheina, V. Ye.
TITLEt Studies in the field of coordination polymers. VI.
Synthesis of coordination polymers of some bis-((-diketones)
PERIODICAL: Vysokomolekulyarnyye soyedineniyaq v- 3, no. 10, 1961,
1456-1461
TEXTs The authors synthesized aliphatic bis-(P-diketones): 191,292-
tetraacetyl ethane (I), adipyl- (II), and sebacyl diacetophenone (III), and
prepared and studied their metal polymers. They prepared I from a
suspension of 0.5-mole Na-acetyl acetonate in ether by adding a solution
of 0.5-mole iodine in ether at room temperature under vigorous stirring.
The melting point was 185-1860C, the yield 27-30%. 11 and III were
prepared according to V. V. Korshak at al. (Vysokomolek. soyed., 1, 1764~
1959). The melting point of III was 108-109.5 00 (Yield 20-22%). The
metal polymers of the bis-(P-diketones) produced were prepared by 3-hr
heating in a vacuum of 2-4 mm H9 of their equimolecular mixture with the
Card- 11,"

f8176
S/190/61/003/010/004/M
Studies in the field of coordination ... B130/B11O
respective Me-acetyl acetonate at 150-21000 until no acetyl acetone was
set free. To 'remove the remaining aaetyl aoetonef the resulting product
was treated with hot water, boiled in alcohol, washed with ether, and
dried to oonstant weight. The copper derivatives were obtained by
reaction of the diketones with copper acetate in an alcohol solution. It
was found that I with Be-, Ri-9 Go-, and Zn-acetyl acetonates formed
nonfusible powders which were unsoluble in ordinary organic solvents and
had a high decomposition temperature. I formed no coordination compounds
with Mn and Cd. The chemical analysis showed that the composition of the
resulting metal compounds corresponded to the theoretical values. Also
the metallic deriatives of II and III constituted colored powders. The
Be-derivatives of 1119 and the Be-, Zn-, and Cd-derivatives of III are
soluble in ohloroform2 tetrachloro ethane, dioxane, bromo benzene, and
dimethyl formamide, the Ni- and Co-derivatives only in dimethyl formamide
and dioxane. The peculiarities of these compounds are explained according
to Hammond, Borduin, and Guter (see below). In the interaction between
tetraacetyl ethane and the metal ions, a coordination binding of the
metal takes place between the keto groups of adjacent molecules of the
0 ard 2/4~ 2
J

2 8176
B/igOY61/003/019/004/019
Studies in the field of coordination B130/B11O
binding agent (Fig.,l). In II, and particularly in III, the formati.on
of closed, monomeric complexes is probable-because of the presence of
a flexible methylene chain (Fig. 2). rhere are 2 figures, .4 tables, and
6 referencesi 2 Soviet and 4 non-Soviet. 'The four refer enbbs to English-
lanLuage publications read'as f9llowst R. G. Charles, Organic Syntheses,
,a,61, 19591 G. S. Hammond, W. G. Borduin, G. A. Guter, J. Amex. Chem.
SOC. , 11 , 4682 f 1959; G. A. Guter, G. S. Hammond, J.- Amer6' thein. Boo.
81',- 4686, 1959; G. T-.' Bullen, Acta crystallogr.,12, 703, 1559..
AS�O-CIATION:, Institut elementoorganicheskikh soyedineniy' AN' S~SR'
(Inditute of Elemental Organic Compounds AS USSR)
SUBMITTED: October 25f 1960
Fig. 1. Model of a I 1 2, 2-tet-~aacetylene ethane complex with metalt'
carbon, o --hydrogen, - 0-- oxyGen metal.
Fig. 2. Model of a sebacyl diacetophenone complex with-metal. Designations
as in Fig. 1.
Card 31V

28177
S/19 61/003/010/005/'019
5ASSO B1 30YB1 10
AUTHORS: Korshak, V. V., Mozgova, K. K., Shkolina, M. A.
TITLE: Synthesis of graft copolymers. VII
PERIODICALt Vysokomolekulyarnyye soyedineniya, v. 3, no. io, 1961,
1462-1467
TEXT: The authors describe the possibility of producing graft copolymers
from polyamide and polyester films and vinyl monomers without the use of
ozone, Films of mixed polyamide r-669 (G-669) stored for different
periods of time were used for the investigation. The monomer uued was
styrene. Tests showed that a freshly prepared polyamide grafted only
2-31o polystyrene, a one-year old up to 9%, and a 6-year old 30-60%. In
the 6-year old polyamide, active centers formed by the action of
atmospheric oxygen and moisture. The effect of atmospheric oxygen and air
was studied at various temperatures. It was shown that a sample grafting
no more than 2-5% polystyrene, grafted 20% after thermal treatment in air
0
at about 80 C. In thermal treatment of caprone films, grafting was also
Card 1/3

28177
S/190/61/003/010/005/019
Synthesis of graft copolymers. VII B130/B110
increased but not to such an extent as in the treatment of 0-669, Lavsan
films heated in nitrogen showed better grafting than those not heatedl but
did not attain such a degree as when heated in an air flow. The tests
also showed that the heating did not only activate the polymers 'but also
improve their mechanical properties. The breaking elongation of Lavsan
films heated at 80 OC increased bY 48-8%, that of caprone films by 176~.
No positive results have been obtained yet when trying to find free
radicals by an epr spectrum. Infrared and ultraviolet spectra showed no
considerable change due to thermal treatment of caprone. The ultraviolet
spectrum of heated Lavsan suggested a formation of groups containing 00.
r-ray patterns showed higher orderliness of the molecular chain of heated
samples, The breaking elongation of samples was tested at the VMIS, the
infrared and ultraviolet speotra were taken at I. V. Obreimov's laboratory)
the X-ray pictures at A. 1. Kitayguiudskiy's laboratory. A. V. Zasechkina
and A. I. Volkova assisted in experiments. There are 2 figures, 8 tables,
and 6 Soviet references.
Card 2/3

28177
8/190/61/003/010/005/019
Synthesis of graft copolymers. VII B130/B110
ASSOCIATIONs Institut elementoorganicheskikh soyedineniy AN SSSH
(Institute of Elemental Organic Compo=ds AS USSR)
SUBMITTED: November 3, 1960

28180
Zq 05 113/190/61/003/010/009/019
B120110
AUTHORSi Korshakq V. V., Vinogradova, S. V., Morozova, D. T.
TITLEs Study of coordination polymers. VII. Coordination Polymers
based on quinizarin and 4,41-bis.-(acetoacetyl) dipheRyl ether
PERIODICAL3 Vysokomolekulyarnyye soyedineniya, v. 3, no. 107 1961,
1300 -- 1508
TEXTi The authors synthesized the homogeneous coordination polymers of
quinizarin (I) with Mg, Ca, and Be. the coordination polymers of (I) with
two different metals and,finally, the coordination polymers on the basis
of (I) and 4941-bis-(acetoacetyl)biphenyl ether (II) with Zn, Cu, htn. Ni,
Co, Mg, Ca, Cd, and Be, and studied their properties. The results obtained
with homogeneous coordination polymers and mixed coordination copolymers
are given in Tables 1 4. The studied polymers were homogeneous, solid.
powder-like substances of intense color, practically insoluble in chloro-
form, dichloro ethane, tetrachloro ethane. a mixture of tetrachloro ethane
and phenol, chloro benzene.. methanol, dimethyl formamide, ditolyl methane,
dioxaneg tetrahydrofuran, methyl-ethyl ketone, ethyl acetate, and cresol
111, VA
Card I/*

28180
S/190/61/003/010/009/019
Study of coordination... B120110
except for the coordination polymers of beryllium, which were rather
easily soluble in chloroform, cresol. and dimethyl formamide. The molecu-
lar weights of polymers of I with Be varied from 1700 - 1800 and from
3500 - 3600. As proved thermomechanically mixed coordination polymers of
I with Zn and Cd or Zn and Cu are more stable than the resRective homo-
polymers. This is reverse with Be polymers. Heat deformat Ion of all com-
pounds was found between 200 - 4500C (no chemical decomposition)4 As
proved by X-ray tests most of them consist of crystalline and amorphous
phases together. The synthesis was carried out by heating the ligands
solved in dimethyl formamide in N 2 current at 1200C, addition of the metal
compound solved in dimethyl formamide at 1000C, and I hr heating at 1200C,
1 hr at 120 - 140OCi 4 hr at 1400C. The authors thank the collabo:rators
cf the laboratories of INEOS AN SSSR under supervision of G. L. Slanimskiy,
A. I. Kitaygorodskiy, and N. E. Gellman. Ye. S. Krongauz and V. Ye. Sheina
(Ref. 39' Vysokomolek. soyed. 2, 662, 1960) are mentioned. There j~re 4
figures, 4 tables, and 5 Sovijt references.
ASSOCIATIONs Institut elementoorganicheskikh soyedineniy AN SSSR
Card 24 '~/ (Institute of Elemental Organic Compounds .AS USSR)

29
1 ~33
S/19 6 003/011/002/016
B124 B 101
AUTHORS: Korshak, V. V., Slinkin, A. A., Vinogradova, S, V,,
_!~a~cffn sera,
M
TITLB: Study in the field of coordination chain polymers.
VIII. Coordination polymers based on bis-(8-hydroxy-
quinolyl)methane, quinizarin, and 4,41-bis-)aceto-
acetyl)phenyl ether
PERIODICAL: Vysokomolekulyarnyye soyedineniya, v. 3, no. 11, 1961,
1624-1632
TEXT: The synthesis of mixed coordination polymers of bis-(8-hydi,,,oxy-
quinolyl)methane (I) and quinizarin (II), (I) and 4,41-bis_(aceto-
acetyl)phenyl ether (III) with various metals is described, and the
magnetic properties of some coordination polymers of (11), (1), and (III)
are studied. Compositions, structures, and properties of the synthesized
coordination polymers are given. X-ray data indicate that the
homogeneous coordination polymers exhibit a more or less ordered
structure. The solubilities of the homogeneous and the mixed coordinaticn
Card 1/2

27733
003/011/002/016
Study in the field of... B120101
polymers in organic solvents are extremely low; only the mixed cQordina-
tion polymers of (1) and (III) with Ou are soluble in Qreeol. ThQ
temperature dependence of the magnetic susceptibility (x) as well as the
magnetic moment and the Weiss constant calculated from the magnetic
susceptibility are given for a number of coordination polymers on the
basis of (II), (I)q and (III). Conclusions as to the configurations of
Co. bin, and Ni in the polymers were drawn from the magnetic properties-
The authors thank the staff of the Laboratories of INOES AN SSSR under the
guidance of A. 1. Kitaygorodskiy and N. E. Gellman~ There are 3 figures,
3 tables, and 7 references: 6 Soviet-bloc and I non-Soviet-bloo, The
reference to the English-language publication reads as follows:
1). F. Craig, A. Maccoll, R. S. Nyholm, L, E, Orgel, L. E, Sutton, J.
Chem. Soc, 1954, 332, 354.
ASSOCIATION: Institut elementoorganicheskikh soyedineniy AN SSSR
(Institute of Elemental Organic Compounds, AS USSR).
Institut organicheskoy khimii im.N. D. Zelinskogo AN SSSR
(Institute of Organic Chemistry imeni N. D_ Zelinskiy, AS USSR)
SUBMITTED- November 16, 1960
Card 2/2

29734
S/19 61/003/011/003/016
B124YB101
AUTHORS: -,,Korshak, -. V., Fedorova, L. S., Kolesnikov, G. S.
TITLE: Synthesis of polyarylenealkyls. XI. Chemical properties
of poly(halophenylene )ethyls
PERIODICAL: Vysokomolekulyarnyye soyedineniya, v. 3, no. 11 , 1961,1644-1649
TEXT: The degradation of poly(fluorophenylene)ethyl effected by phenyl
fluoride, as well as the aspects of hydrogenation and of substituting a
hydroxyl and an amino'group, respectively, for the halide atom in
poly(halophenylene)ethyl were studied in this paper. The effect of the
phenyl fluoride concentration on the degradation of poly(fluoro-
phenylene)ethyl (I) ha's been investigated using a weight ratio of AM 3 to
~I) equal to 1:4, constant temperature (1000C) and reaction time
4 hr), while the phenyl-fluoride - I ratio was varied. The molecular
weight of the initial (I) was 3810; results are presented in Table 1.
Data obtained for a phenyl-fluoride - I weight ratio of 5:1, at constant
temperature (1000C) and reaction time (4 hr), and varied AM I r
3
Card 1/0

29734
S11901611003101110031016
Synthesis of polyarylenealkyls... B124/B101
are given in Table 2 and,finally, results obtained with a constant phenyl-
fluoride - I weight ratio of 5:1, constant AM 3 concentration of 2.5 per
cent by weight of the polymer, constant temperature (1000C) and varied
reaction time are presented in Table 3. From these results, it can be
concluded that phenyl fluoride effects degradation of the polymer, and
that the intensity of this degradation is influenced by the ratio of the
initial substances, catalyst concentration, and the time of the degrada-
tion process. Hence, it follows that phenyl fluoride acts both as a
component of chain formation and as a degradation agent in polycondensation
with dichloroethane. From the fact that no hydrolysis occurs when
poly(chlorophenylene)ethyl is heated to 3000C with water in a ratio of
1:10 in the digester, the conclusion may be drawn that the mobility of the
chlorine atom in (II) is very low. When (II) is heated with aqueous KOH,
hydroxyl groups are substituted for chlorine, and linear molecules formed
are cross-linked by oxygen bridges; the properties of the products depend
on the amount of reacted KOH. Neither degradation of (II) nor substitution
of an amino group for chlorine has been effected by aqueous ammonia
solutions. Poly(cyclohexylene)ethyl
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29734
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Synthesis of polyarylenealkyls ... B124/B101
/-2r\ - CH CH _]X
W 2 2
1
forms when (II) is hydrogenated in benzene in the presence of Haney's
nickel catalyst which is not accompanied by degradation. There are
3 tables and 6 Soviet references.
ASSOCIATION: Institut elementoorganicheskikh soyedineniy AN SSSR
(Institute of Elemental Organic Compounds AS USSR)
SUBMITTED: December 1, 1960
Table 1. Degradation of poly(fluorophenylene)ethyl by phenyl fluoride.
Legend: (I) Weight ratio of phenyl fluoride to poly(fluorophenylene)ethyl;
(11) obtained, % of the initial substances; (III) of low-molecular
reaction products; (IV) of poly(fluorophenylene)ethyl; (V) molecular weight
of the polymer.
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Synthesis of polyarylenealkyls ... B120101
Table 2. Degradation of poly(fluorophenylene)ethyl by phenyl fluoride.
Legend: (I) Weight ratio of aluminum chloride to poly (flu orophenyl ene) ethyl;
(II) yield, % of the initial substances; (III) of low-molecular reaction
products; (IV) of poly(fluorophenylene)ethyl; (V) molecular weight of the
polymer.
d
Table 3. Degradation of poly(fluorophenylene)ethyl by phenyl fluorit!
(molecular weight of the initial polymer; 3250). Legend- (1) Reac I on
time, hr; (II) obtained, ~ of the initial substances; (III) of low-
molecular reaction products; (IV) of poly(fluorophenylene)ethyl;
molecular weight of the polymer.
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29735
S/190/61/003/011/004/016
2109 B120101
AUTHORS: zms-~~ , Fedorova, L. S., Kolesnikov, G. S.
TITLE: Synthesis of polyarylenealkyls. XII. Polycondensation of
1,2-dichloroethane with phenyl bromide
PERIODICAL: Vysokomolekulyarnyye soyedineniya, V. 3, no. 11, 1961, 1650-1654
TEXT: Polyoondensatee of 1,2-dichloroethane with phenyl bromide were
prepared in the presence of AIC13 using the same method as that described
by the authors in Refs. I (Izv. AN SSSR, Otd. khim. n., 1955, 359) and 2
(Izv. AN SSSR, Otd. khim. n., 1958, 53) except that dibromodiphenyl ethane
and diphenyl ethane were distilled off in vacuo after driving off the
solvent and after conclusion of the reaction. The molecular weight of the
polymer obtained man determined viscosimetrically, and the constant K m
in the Staudinger equation was assumed to be equal to 1.8-10-4. With
decreasing phenyl bromide excess in the reaction mixture, both the
molecular weight and the yield of polycondensation products are increased;
maximum values are obtained with a phenyl bromide - dichloroethane ratio
Chrd 1/# --Z.

S/1 92~97??15/003/011/004/oi 6
Synthesis of polyarylenealkyls... B120101
of 0.95. When phenyl bromide - dichloroethane ratios of 1.2 and less are
used, three-dimensional products are formed. The bromine content was
28.7 % in soluble poly(bromophenylene)ethyl and 21.5 % in the three-
dimensional polycondeneation product, while the theoretical bromine content
is 43-7 %. This circumstance is attributed to the fact that migration of
bromine takes place during polycondensation which leads to the formation of
an inhomogeneous, halogen-substituted polymer. The yields of polymers
(Fig. 1) and the molecular weights (Fig. 2) of the polycondeneates of
dichloroethane with phenyl chloride, fluoride, and bromide, respectively,
decrease in the order: phenyl fluoride> phenyl chloride >phenyl bromide
which is due to the fact that Bteric hindrance increases with the size of
the halogen substituent. Optimum catalyst concentration of 8 mole% with
respect to maximum molecular weight of poly(bromophenylene)ethyl was
established (Table 2). The low-molecular reaction products were rectified
to yield two fractions, one of which was identified to be dibromodiphenyl
ethane and the other to be diphenyl ethane. It was shown by structural
analysis by means of destructive oxidation with chromosulfuric acid that,
due to partial conversion of the phenyl bromide to benzene which takes part
in polycondensation, a copolymer forms in the course of the relative
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S11901611003101110041016
Synthesis of polyarylenealkyls... B120101
polycondensation. There are 2 figures, 2 tables, and 6 rdferences:
3 Soviet and 3 non-Soviet.
ASSOCIATION: Institut elementoorganicheskikh soyedineniy AN SSSR
(Institute of Elemental Organic Compounds AS USSR)
SUBMITTED: December 1, 1960
Fig. 1. Influence of the phenyl halide - dichloroethane ratio on the
yield of polymer and low-molecular fractions: (1), (2), (3) yield of
polymer; (1a), (2a), (3a) yield of low-molecular products; (1), (1a)phenyl
fluoride; (2), (2a) phenyl chloride; (3), (3a) phenyl bromide.
Legend: (A) Yield, ~-; (B) phenyl halide dichloroethane ratio.
Fig; 2, Influence of the phenyl halide dichlorcethane ratio on the
molecular weight nf the polymer. (1) benzene; (2) phenyl fluoride;
(3) phenyl chloridei (4) phenyl bromide. Legend: (A) Molecular weight;
(B) phenyl halide - dichloroethiin(, ratio
Card

29736
S/190/61/003/011/005/016
2705 B120101
AUTHORS: Korshak, V. V., Mozgova, K. K., Shkolina, M. A.
TITLE: Synthesis of graft copolymers. VIII
PERIODICAL: Vyeokomolakulyarnyye soyedineniya,v-3,no.11,1961, 1655-1660
TEXT: Results obtained when styrene is grafted to heat-activated caprone
fiber are given in this paper. The effect of the time of thermal treatment
of the fiber on the yield of grafted polystyrene is studied at temperatures
ranging from 80 to 1500C in a nitrogen stream and in air (Fig. 1). Up to
20 min from the beginning I active centers of copolymerization of the fib
with styrene are formed at 800C in nitrogen, with no further oxidation O;r
the fiber occurring on heating. When kept at a constant temperature of
800C in air, two maxima appear, the first of which is due to the presence
of active centers prior to heat treatment, and the second to the secondary
formation of active groups by oxidation. From data given in Fig. 1 it can
be further concluded that the yield of grafted polystyrene increases Aith
the time of copolymerization, and that the formation of active centers in
the fiber is accelerated by a temperature rise. Maximum yield of graft
Card 1/0"-?
Synthesis of graft copolymers. VIII
2M6
S/190/61/003/011/005/016
B124/B1O1
copolymer is obtained when the fiber is kept at 1100C in a thermostat for
3 min, with true temperature in the thermostat and, thus, also of the
sample being about 900C. From measured viscosity values of the graft
copolymers, optimum results were obtained under the same conditions as
mentioned (Table 1). A polystyrene layer can be grafted to the caprone
fiber with yields up to 30 7o and a molecular weight up to 60,000-80,000
(Table 2). It is shown that the described grafting takes place
essentially on the surface of the polymer. A. P. Zasechkina and A. I. Volkova
took part in experimental work. There are 3 figures, 2 tables, and
5 references: 4 Soviet and 1 non-Soviet. The reference to the English-
language publication reads as follows; A. J. Goldberg, W. P. Hohenstein,
H. Mark, J. Polymer Sci., 29 503, 1947.
ASSOCIATION- Institut elementoorganicheskikh soyedineniy AN SSSR
(Institute of Elemental Organic Compounds AS USSR)
SUBIMITTED: December 7, 1960
Card 2/#"

/012/00~/619
0 61/003
3 P9
101 B110
B
1 YB
AUTHORSs Koinhak, V.' V. Rogozhinj S.,V., Volkovj V. I
j~':V
InvestigationsAn the,field of coordination polymers. NIM
TITLE:
on the basis of -dihydroxydi-~
Polymers ..aromatic, o,ol
carboxylic aoids, and bivalent metals
PERIODICAL i Vysokomolekulyarnyye:soyedineniyat vo 31 no. 12, 196111--
1808 1615)
TEXT: The deal with.the synthesis of high-molecular,compounds i,
which metal atoms are.'combined,with-the-organic pa'rt'of the,*maer6moleou
by means of coordination.b fid-. . The, present investigation describes.the,
interaction of acetyl acetonates acetates, and chlorides of Cu, Zn,-Ni
Cc# Cd, and Be with 2,5-dihydroxy terephthalic acid (I) and 410 4 1 -dihydroX
a
triphenyl methane-3.,31-dicar-boxylic acid (II), also their dimethyl eater
-(III) sn'd dimethoxy, derivativlbs (IV)-0 In.:the reaction of I with acetyl
Znt.Ni or Cui dimethyl.formamidet acetyl acetone was f reed:p'
aoetonates of
and polymers containing metal were formed,.for which 'the structural
formulas
Card 1/ 4

SAM
_0761/003/012/005/012
Investigations in the -f i eld )I/B1 10
'0 oil
it C-0 0'
Ate" ot
0" ?0--L -0.
7
~O_C. '-O=C
are suggested. The polym.er,with,Zrt"d4~~o'm-p"'oses :at 359*C the -polymer vi.#h~
Cu at 2530C. The reaction:of,II with Zn, or Cu compounds.jacetyla66tonates
and acetates) in:methyl formamid,%' (some tests also in methanol or water)
resulted in unsoluble, nonfusible substances which decomposed above 35000-
1I was obtained by condensation of salicylid.: acid with benzaldehyde in
acid medium at,850.C- In order-to study the role of carbonyl and hydroxyl
oxygen, III and IV.were.synthesized. III.was obtained by esterification
of II by means of methanol in, th6 pieibnce of H 60"-~_ -IV_ by treating the,
2 41
disodium salt of. II with dim-6thyl sulfate.'~ - since III and o -IV*melted with-
out decompositiont polymerization could also be achieved in 'the'. melt by
means of these substances. Reaction.of III with Co, Ni Cu* and 1 M_
Zi co
pounds resulted in unsolubliet nonfusible substances for which formula
Card 21 4~

0
911
S 196/6.1/003/012/005/012
Investigations in the field... B1O1/B11O
is suggested. The compounds'.obt.ained from aqueous solution deviated in
their composition from the theoretical composition, probably due to'Water
dontent. The oonsiderable.ino'rease-in volume of the Be and Zn, compounds
above 20000 is ascribed to continuation. of the incomplete chemical reaotion.~
at, elevated temperature. In the eaters of aromatic o-hydroxy acidsp:
.carbonyl oxygen of the carboxyl group effects the formation of the coordi-
nation bond In o-methoxy acid, the oxygen of the methoxy group has an
effect. Al olymers were colored powders. The polymera obtained from
the melt had a composition which came nearest to theory. There are
1 figure, 6 tables, and 15 references a 9 Soviet 'and 6 non-Soviet. The
four most recent referenceg to En,-".ish-language publications read as-
followas S. Xanda, Y. Saitop Bull.~Chem. Soc. Japan, 30, 192, 1957;
H. Klng, L. Alexander, G. Summer, Acts. crystallogr., 11, 41, 1958;
R. G. Charlest M. A. Pawlikowskil J. Phys. Chem., L, 440, 1958;
J. Wilkins, E. Wittbecker, US Patent 2659711, 1953-
ASSOCTATIONs Inatitut elementoorganicheskikh eoyedineniy AN.SSSR
(institute'of Elemental Organic Compounds AS USSR)
SUB4ITTEDz January 6, 1561
Card 4/4

KORSHAKI V.V.; VINOGRADOUI S.V.
Polyarylatea, Uvp. khIm. 30 no, 4s422-461 Ap 161. Offlu 14:4)
1. Inatitut elementoorganicheakikh soyedineniy AN SSSR.
(Eatera) (Polymers)

1- 0 7
AUTHORSt
TITLEs
10 4 1) 114 9
20638
3/0201''61/136/0061/014/0-:1
B! 03)!B203
Kcrshak, V. V., Corresponding Member AS USSR, Kasatochil-ii.Xl,
-Sladkov, A. M., Kudryavtaev, Yu, P., and Usei,bayev* K~
Synthesis and properties of polyacetylene
PERIODICALs Doklady Akademii nauk SSSRj v,, 136, no. 6, 1961~ 1342-1344
TEXT: The authors produced polyacetylene (FA) and studied its chemical
structure and physical properties. They assumed that PA formed Jn the
oxidation of bis-acetylene acetylenidee of the type HC'==C - (02 )n ---C
which are said to be among the polymeric products not yet at-udled, They
had already ouggested a formation meahan4sm of PA in Ref, .3. In the pre8ent
investigation, they produced the required acetylenide by passing a-etylene
through the ammoniacal solution of a salt of- bivalent copper. '",;,baequently,
the acetylenide was oxidized by an aquoou3 solution of potassium ferri-
cyanide at boiling temperature, The authors assumed that the reriulting
black powder (containing 98~~ of C) was a mixture of' polymer homologe of
polyacetylene. On the basin of the tomparature-depend6ra weight lougas
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S/020/~1/136/0006/014/024
Synthesis and properties of ... B1031/B203
(Fig. 1) and the electron paramagnetic resonance, they conclude that this
product is a polymer with Qumulene structure, probably
PA showed high heat resistance, being transformed into graphite only at
23000C. Below 23000C, the carbon in PA remains in the form of P013,acetylene.
Graphite is also formed by long boiling of annealed Pit samples in con-
centrated HCI. The authors point to the readiness of transformat-on of
carbon atom chains of PA into graphite monolayers, and the corresj,-.ond:irg
transformation of valence forms under the aotion of HCI. The electric
resistivity p measured by the zero method on an MTS(MTV) bridge d:i,cpped
with rising tempera-ture. This is explained by the concentration of crystall-
line copper due to thermal dissociation and the separation of terminal
copper atoms from PA., p continued dropping at higher temperaturea when
copper had.already evaporated and no graphite was formed., This indi.,lated
an extension of PA chains during the pyrogeneDic synthegis which -,ocl~ place
due to thermal dissociation and copper separation, as well as sub6e4u'int
recombination of the resulting free polymeric radicals. The enifa was
measured by the compensation method on a MT13 (PPTV) high-resistance
potentiometer. On the basis of the values obtained for P and a, -the authorizi
C.ard 2/5

ho
[20
.20638
S/020J61/136/00(5/014/024
~"Synthesisand properties B103/B203
-conclude that the PA.sample Investigated is an n-type semi conduo to'r.~ 'The
.40 9pper-atome imbedded in the molecular carbon chain with polyalltine struc.'
ture play the role of the electron donor. This is confirmed by thefact
Ithat the a of PA samples which,were produced with the use of stronger,
1copper-free oxidizers (nitrate iong H202) is equal to zero. The change of
0
the sign of a (near zero at 1300 and 15000C + above 1500 UP to 23100 C
corresponds to the transition of the PA sampYe to a p-type semiconductor.
The authors think that this is coupled with the thermal dissociation and
the separation of copper- and hydrogen atoms from the carbon chain# and
is certainly connected with the acceptor properties of the terminal C
atoms. There are 3 figures, 1 tablep and 3 referenoesu 1 Soviet-bloo
and 1 non-Soviet-bloo.
ASSOCIATIONt Institut goryuchikh iskopayemykh Akademii nauk S~SR
(Institute of Mineral Fuels of tbeAoademy 'of Sciences USSR).
Inatitut elementoorganicheskikh soyedineniy Akademii nauk.
SSSR (Instituteof Elemental-organio Compounds of the
Academy of Sciences USSR)
'Card 3/5
30

15.5114
a'4L
AUTHORS:
22,05
S/02YAM7/006/013/020
B1 03 "217
Neamevanovi As If., Academician,_KqZ&hAk_L_V. V.,Corresponding
Member AS USSR, Volevodakiy, V. V., Corresponding Member ."
AS USSR, Kochetkovat N. S.9 Sosin, S. L., Materikova- B.. B.,
Bolotnikovat T. K.f Chibrikin, V. M.,-and Bazhin, N. M.-
TITLE: Synthesis and some optical-magnetic properties of poly-
ferrocenes
PERIODICAL: Doklady Akademii nauk SSSR, v. 137, no. 6, 1961, 1370-1373
.TEXT: The authors studied the magnetic .properties of ferrocene derivv,tivest.7~
".1) of the polyferrocenylenes (Table-1, nos. 1-6), 2) the polydiisopropyl-
ferrocene (Table 11 nos- 7-8), -3) the polymethano- and 4) the polyethano-
polyferrorlenes (Table 1, no s* 9-1.3). They were synthetized by: 1) Poly-
recombination., To 1). and 2). 1 qiole ferrocene (Or Of its diisopropyl.
homolog) was treAted with I mole tertiary butyl peroxide in nitrogen
atmosphere at 2000C.1 1) and 2) are assumed to be formed as follows: the
Butoxyl and methyl radicals formed during peroxide decomposition separate
the hydrogen.from ferrocene (or the a-hydrogen). The radicals thus formed
-Card I

Synthesis and some
S102~0'Rl" P/437/006/013/D20
Z
B103 B217
recombine and form linear 1) or 2), easily soluble in benzene. An in-
soluble polymer (Table 1, nos- 5-6) with a two- or tridimensional network
structure is formed simultaneously. The conversion of ferrocene to high-
molecular products amounted to 25~S. Nos. 1-3 have a softening temperature
of 290-3000C and are a dark-red powder, whereas nos- 5-6 had their softening
temperature at about 4000C and were light-yellow. B) Polyalkylenation of
ferrocene by methylene chloride and 1,2-dichloroethane in the presence of
anhydrous aluminum chloride. Aluminum chloride solution in 50 ml of di-
halogen alkane was added gradually to 40 gferrocene dissolved in 250 m2 dry
dihalogen alkane. The mixture was stirred for 6 hr at the boiling tempera-
ture of the solvent. The next day, 10 g aluminum chloride in 25 ml dihalo-
gen alkane were added and treated for 6 hr as above. The mixture was
decomposed by ice.and HC1 and treated with sodium sulfite. The obtained 3)
and 4) were well soluble in be nzene, differed, however, by their solubility
in ether. Table 1 shows the molecular weights, the always equal g-factor
and the magnetic characteristics of all substances produced. The decolliposi-
tion temperature of 9-13 was 115-120OC-. All substances are amorphous
powde'rs, nos. 9 and 10 light-yellow, no. 11 grey-brown. Nos. 10 and 11 are
of a chemical composition similar to that of no. 9 (pentaethanodifferrcicene).
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S/02 61/137/006/013/020
Synthesis and some B103YB217
They consist possibly of 2 and 4 molecules similar to the latter, connected
by ethane bridges, 4-5 methylenes in the molecule of nos. 12 and 13 belong
to 2 ferrocene radicals. They do not contain halogen. The infrared spectra
of nos. 9-13 have frequencies within the range 1000-1100 cm-1. To I).
Derivatives 1) having a n-conjugation between the ferrocene links give a
signal the electron paramagnetic resonance (e-p-r), similarly to the poly-
aromatic hydrocarbons, This cannot be explained by the presence of a
corresponding quantity of the oxidized form of the ferricinium'cation.
Table 1 shows that also polymers in which the-ferroceiLe 1 'inks are sepaxated
by the --CH2--GH27 group give an a. p. r. signal. It is known that the
delocalization of the unpaired'electrono between the two phenyl rings'is not:
prevented by this group. In the.substances described here, which give an
e-. p. r. signal, this signal is the smaller, the smaller the number of
.-ferrocene links is. This signal Vanishes in 2). Polymers with a low
molecular weight give no. e.'p., r. signal 'in the solution (benzene), but in
solid state. This is explained'by the fact that the intramolecular
interactions cause in solid state a conjugation of the adjacent polymer
molecules. This Causes for its part an e. p. r. signal. kll polymers
Card 31.6,-"

2-
S/020/61/1~37/006/013/020
Synthesis and some B103/B21,7
giving.this signal show a single,symmetrioal-line of-the e. p.r. of the
Lorenz type.. Thell).obtained from the reaction A yields a wide e. p. r.,
line of 1,26-160 oersteds., ite.width.bding dependent on the polymer structure.
This line becomes broader on reducing the measuring temperature. Its width
is ch'anged mos.t considerably in low-molecular polymers~. The authors
believe the nature,of the measured signals to be unclarified,,they cannot
maintain that the number N of the unpaired electrons per.1 member, deter-
mined by a comparison with the standard, corresponds to their actual number.
N may, however, be a certain characteristic of the magnetic properties of
the system,~,,.(nos. 2-4).- N reaches an-anomalous size in the insoluble -
!j?Tolymer no. 5- This is assumed to be:connected with & collective effect.of
.the.ferromagnetic type. The ultraviolet (UV-) spectra of 1),dissolved. in
n-octane, which g~~q. an e'e.pe r.. signal in solid state, differ from the
ultraviolet spectra~of such that give no signal in solid state% In the
first.case the UV-spectrum.agrees completely with that of ferrocene dis-
solved in CCl* It was proved for these spectra (Ref- 7) that the oharile
4 +
transfer takes,place here under formation-of an ion pair Per CCl_. On the
-4
contrary, tae UV-spectrum of such 1) that give no e. p. r. signal is similar
Card 4/9-j5'
-AAN, ----------

25
I S/020/61 138 006/015/013
B103/B215
AUTHORS: Jorshak, V. V., Corresponding Member AS USSR, and
Vinogradovi-I-S. V.
TITLE: Some laws of the polycoordination reaction
PERIODICAL: Akademiya nauk SSSR. Doklady, v. 138, no. 6, 1961,1353-1356
TEXT: The authors determined the conditions for the synthesis of coordina~
tion polymers with a molecular weight of more than 100,000. The tetra-
ketone 4,41-bis-(acetoacetyl)-phenyl ether (BAPE) was used as initial
ligand, since solubility of the final product is of great advantage for
the examination. The authors allowed BAPE to react with beryllium- and
..zinc acetoacetonatee and also with zinc acetate. Polycoordination in some
respects reminds of polycondensation. In both cases, the polymer is
synthesized due to the interaction between two types of reactive groups
where, besides the growth of polymer chains, low-molecular products are
separated: in the former oase water, alcohol, etc., in the latter case
acetylacetone, acetic acid, etc. The authors had already found poly-
condensation to be a balanced process. If the low-molecular product is
Card 1/4

25
5339
S/020/61/138/006/015/01,51
Some laws of the polycoordination reaction B103/B215
removed from the reaction sphere, the equilibrium may shift and thus
increase the polymer yield by favoring the formation of polymer molecules.
The authors found that polycoordination like polycondensation is a
reversible prooese, and that coordination polymers are completely
destroyed by the low-moleouLar reaction product. TLey also proved that;
coordination polymers react with chemically similar substances. The
low-molecular product should therefore be completely removed from the
reaction sphere. The reaction was conducted (a) in a solution, (b) in a
melt. Ad (a): BAPE and zinc acetate dissolved in dimethyl formamide viere
subjected to polycoordination in nitrogen flow at 120 and 1400C. In bath
cases, the polymer yield was 84-87 % after 5 hr. The intrinsic viscosity
of the polymer in cresolic solution was 0.06-0.09 and remained constant
durin,cy a reaction time of 0.5-11 hr. In their attempts to increase the
viscosity by higher reaction temperatures (dissolution in dinyl at 2200C
for 5 hr), the authors obtained a polymer poorly soluble in cresol.
Therefore they continued -their experiments with beryllium polymers (instead
of zinc) in dinyl at 200-2400C. Thus, they found that polymers of higher
viscosity are formed in solutions of higher concentration (0.74 to
2.00 mole/1). Distillation of acetylacetone also favors the increase in
Card 2/4

Sonic laws of the polyaoordination reaction
25339
3/020/61/138/006/015/0-19
B103/B215
molecular weight. The quantitative ratio of the initial products also has
a great effect upon viscosity. A polymer of the highest molecular weight
forms at an equimolar ratio of the two components. A 0.2 mole excess of
one component reduces the viscosity almost to 1~4- If the excess' is
higher, viscouity is no longer affected. Ad (b : In the melt, BAPE and
beryllium form a polymer with a viscosity of 0.06 already within the first
hour at 2000C. It remains constant during 5 hr of reaction. At 26000,
viscosity is doubled and increases atthis temperature as the time of
reaction increases. In vacuo (1-2 mm Hg), the maximum increase in
viscosity is reached in the second stage of reaction. Thus, the allthDre
obtained a viscosity of 0.44 of the coordination polymers by conducting
the reaction first in nitrogen flow for 5 hr at 20000, then in vacuo for
another 5 hr at 2600C. When using 6 g of BAPE instead of 0.5 g, a
viscosity of 0.48 was obtained in vacuo at a reaction time of 14 hr and
2600C. The fractionation of this polymer from chloroform with n-hexane
yielded three fractions; (1) 27.3 % (molecular weight: 12600), (11)
26.2 ~~, and (111) 44-5 %~ with a viscosity in chloroform of 1.2, 0.5, and
0.32, respectively. The authors explain the increase of the molecular
weight by the above equilibrium character of the process. The removal of
Card 3/4

B1Q
3A! qj,
AUTHbR-S'-:4`:
A k6~shiak, V V.,,Corres ond g MepibpTi, k
p
V n
0
7Tamb
e..:
TITLE a.Pol*e:e Zation of. ox
st
u qy~"oge;iquq.. -gapoiilicofi~.
0 a
OMP
d
VERIODI BASH 4,_
CAL: a 6 Ic", ~141-
Ak d
TEXT' a ~Naq
d1ken3d -iilaine-~ erivativ4
genous~
atu( ie(I.::, Thee', gee
i~_Iis~dicai_,;ii~ii' * r zoisobutyrodini't~iie'-"-
th iifo
(2)._ t . I . , , .. . _ j.~
at zio= 1 -.prea__.e'u;e
p iia' ~enzo~l p roxide (b)'
P1 , , . e - a
with,.Pt/d.O~ -6 4Lt~%J, .0 B.; --:It was found thaV. cyano-Up
propoxy alke4l~ eflatt.4.44kivitt ly!46rize.. at -compaiatiVely' low,
tempera urea*
t -.u.-Abovle',,;t2o .0.~Ih'46.~-,oompounas frequenti -'decomp'Ose;P
y .- al
at'80'?G.;' For
tinderlthe cbridi ti6nio -'o6l'6il'ed polymers vere'obtained
-,the,,,.'.r' ei V, t.46y'-,_ier'e' bi*o*n_.~ Some.of the experiments ended. up
'a'nd',*.`charring:,of., the Pr6ducisl.. .1lost of the
'rod~i 1-~ - -1 -2~
6tw,'4r~,,,s1'fghtl,y-solubl no The authors also,
p

3tudy of the polymerization ...
71n
(1) or. There are I table and 9 references: 7 Soviet and 2 non-Soviet.
The two references to English-language publications read as'fo'llows:
J. C. Williams, R. A' Pike 'F. Fekete, Ind. and Eng. Chem. , ~Ll-, 939
(1959); R. M. Savagey Rubber Age, a, 975 (1959).
ASSOdIATION: Institut elem*entoorganicheskikh soyedineniy Akademii nauk
SSSR (Institute of Elemental Organic,Compounds of the
Academy of Soiences USSR).Institut organicheskoy khimii
im. If. D. Zelinskogo Akademii nauk SSSR (Institute of
S/020/611141/003/009/021
-~31 03/B1 01"
RO R' OCHCH,CN
F 11f.ptcl.
H -1L-0-11 H + M CH - CHt - S1 - CH, - CH Ckt,
&HJC%C~ Pf/c 3
R, OCHICHICN
_OL~,._CH%'_CH.,CH. MiCHPis
(3)
~CHICHsCN
Orfanic.Chemiltry imeni N. D. Zelinskiy of the Academy of
Card 310-3 Sc ence USSR

ANDRIANOV, Kuzlma Andrianovich; KORSHAK, V Vp otv red ZHDANOVI
A.A., red.; BALLOV., A.I.P teKhn. DOiOKKil, I.N., tekhn.
red.
(Polymers with inorganic main chains of molecules)Polimary 9
neorganicheskimi glavnymi tsepiami molekul. Moskva, Izd-vo
Akad. nauk SSSR, 1962. 326 po (MIRA 16:2)
1. Chlen-korrespondent Akademii nauk SSSR (for Korshak).
(Silicon organic compounds) (Polymers)
(Organometallic compounds)

PHASE I BOOK EXPLOITATION SOV16119
Korshak,' Vasilly Vladimirovich.. and Tailyana Mikhaylovna Frunze
Sinteticheskiye geterotdepnyye poliamidy (Synthetic Hetero-
Chain,.Polyamided). Moscow, Izd-vo AN SS'SR, 1962. 523 P.
.Rrrata slip inserted. 5000 copies printed.
Sponsgring Agency: Akademiya nauk SSSR. Institut elementoor-
ganicheskikh soyedinaniya
ResP6 Ed.s S. R. Rafikov, Doctor of Chemical Sciences; Bds.;
V. M. Zhulin and I. P. Iooskutova; Tech. Ed.: S. 0, Tikhomirova.
PURPOSE: This book Is intended for scientific research workers,
students and teachers at schools of higher technical educationp
and technicians In the synthetic fiber, paint, plastics, and
other industries which produce or utilize polyamides.
COVERAGEs The monograph gives a comprehensive simmary of the
literature through 1959, and a selection of the more interesting
materials published in 1960, on the chemistry and physics of
heterd-chain polyamides. Types of polyamides, polymerization,
the mechanics of polycondensation, and the chemical and physical
Card 1/5

Synthetic Hetero-Chain Polyamides SOV16119
properties and the production of polyamides are discussed.
References are given following each chapter (Cho. VII and VIII
each have a bibliography of over 700 items). -Altogether
-..about 4'00 Soviet and 1500 non-Soviet authors are cited. No
personalities are mentioned.
TABLE OF CONTENTS (Abridged]:
Foreword 3
Ch. I* Introduction 5
History of the discovery of the individual types of polyaqides 5
Classification of polyamides 7
References 12
Ch. II. Production of Polyamides by Polycondensation 13
Types of polyamide-forming reactions 14
Struct~ure and polyamide-forming capacity of ~nonomers 16
Reference data (tables) 24
References 70
Card 2/5

I
Synthetic Hetero-Chain Polyamides
SOV16119
Ch. III, Polycondennation Mechanism
" 78
78
Polycondensation and its
types 80
Equilibrium polyeondeneation
Polycondensation at-the phase boundary 127
147
References

Produetion of Polyamides by Polymerization
Ch. 3:
153
Types ar polymeritation reactions 153
Hydrolytic polymerization 155
18o
Catalytic polymerization of cyclic lactams 188
Deoarboxylation polymerization
Copolymerization of polyinocyanates with polyhydric alaO)11D18
of polyamines 193
Copolymerization of 2,2-bis-5(4.4)-oxazolones with diamines
or glycols 207
208
Polymerization of isoeyanates
Polymerizatiou of unsaturated amides 210
References 211
Card 3/5

Synthetic Hetero.Chaln.Polyamides 16119
MDV/
Oh.,Vj--Produation7of- . Mx~d--:Polyamides 217
Equilibrium reactions 217
Wone4uilibrium reactions 24o

Graf t~ 4iopolymers 94

N
Block copolymers 2
R6ferenoes 255
Ch. VI. Chend-3al Propertie-s of Hetero-Chain Polyamides ~260
~Cleavage of the amide bond '261
substitutXon.by hydrogen radicals
Amide 268
-
gradatlop' 'and itruotuire formation
De 272
,
Other polyamide reaotions 292
~Abs6rption-of Viriouwsubhtanees by polyamides 294
Referenees 298
Ch, VII. Phyilcal.Preperties bf Polyamides 308
References 391
dird 4/5

PHASE I BOOK EXPLOITATION SOV/6034
Konferentsiya po khimii i primeneniyu fosfororganicheskikh soyedineniy. 2d,
Kazan', 1959,
Ehimiya i primeneniye fosfororganicheskikh soyedineniy; trudy (Chemistry
and Use of Organophosphorus Compounds; Conference Transactions) Moscow,
Izd-vo AN SSSR, 1962. 630 p. Errata slip inserted. 2800 copies printed.
Sponsoring Agency: Akademiya nauk SSSR. Kazanskiy filial.
Resp. Ed. : A. Ye. Arbuzov, Academician; Ed. of Publishing House: L- S.
Povarov; Tech. Ed.: S. G.,Tikhomirova.
PURPOSE: This collection of conference transactions is intended for chemists,
process engineers, physiologists, pharmacists, physicians, veterinarians,
and agricultural scientists.
COVERAGE: The transactions include the full texts of most of the scientific
papers presented at the Second Conference on the Chemistry and Use of
Card 1/14

Chemistry and the Use of Organophosphorus (Cont.) SOV/6034
Organophosphorus Compounds held at Kazan' from 2 Nov through I Dec.,1959.
The material is divided into three sections: Chemistry, containing 67 arti-.
cles; Physiological Activity of Organophosphorus Compounds, containing 26
articles; and Plant Protection, containind,12 articles. The reports reflect
the strong interest of Soviet scientists in the chemistry and application of
organophosphorus compounds. References accompany individual reports.
Short summaries of some of the listed reports have been made and are given,
below.
TABLE OF CONTENTS, [Abridged]:
Introduction (Academician A. Ye. Arbuzov) 3
TRANSACTIONS OF THE CHEMISTRY SECTION
Gefter, Ye. 1, [N11 plastmass (Scientific Research Institute of Plastics,
Moscow]. Some Prospects for the Industrial Use of Organophosphorus
Compounds 46
Card 2/14

Chemistry and the Use of Organophosphorus (Cont.) SOV/6034
triorganosilanols (113SiOH) with acids of phosphorus under condi-_
tions of azeotropic distillation of water in the presence of inert
solvents. Another is based on the interaction of triorganosilanes
with orthophosphoric and m ethylphos phonic acids in the presence
of active colloidal nickel.
Korshak. V. V., I. A. Gribova, and M. A. Andreyeva [Institut ele-
mentoorganicheskikh soyedineniy (Institute of Organoelemental Com-
pounds, Academy of Sciences USSR, Moscow)]. Study of Phosphorus-
Containing Compounds 242
The polycondensation of dichlorides of phosphonic acids with diols
has been studied by following the interaction of methylphosphonic
dichloride with hydroquinone in a nitrobenzene solution at a tempera-
ture of 140 to 170*C. The properties of polyesters of phosphonic acid
have also been studied.
Card 4/14

Chemistry and the Use of Organophosphorus (Cont.) SOV16034
-Korshak,_ V. V., T. M. Frunze, V. V, Kurashev, and I, V. Kozlov
[Institute of Organoelemental Compounds]. Synthesis of Some Phos-
phorus- Containing Dicarboxylic Acids and Derivation of Polyamides
Based on Such Acids 247
Phosphorus -containing dicarboxylic acids have been obtained by
synthesis and used for the preparation of polyamides. The effect
of the phosphorus and the structure of the acids on the properties
of the polyamides has beenstudied.
Kolesnikov, G. S., Ye. F. Rodionova, and L_ S. Fedorova [Institute
of Organoelemental Compounds]. Synthesis, Polymerization, and Co-
polymerization of Esters of Vinylphosphonic Acid 255
The authors obtained esters of vinylphosphonic acid and demonstrated
th'at these esters are capable of entering the polymerization and co-
polymerization reaction with other monomers. Polymers and co-
polymers of the dichloride and esters of vinylphosphonic acid have
been synthesized and their properties determined.
Card 5/14

Chemistry and the Use of Organophosphorus (Cont.) SOV/6034
Andreyeva, M. A., I. A. Gribova, M. 1. Kabachnik, G. S. Kolesnikov,
-_V, V, Korsb,-&, T. Ya. Medv,-d', Yu. M. Polikarpov, Ye. F. Ro&6nova,
and I- S. Fedorova [Institute of Organoelemental Compounds]. Some
Methods of Synthesis of New Organophosphorus Monomers and Polymers 263
This study attempts to develop new methods of synthesis of organo-
phosphorus monomers and polymers for obtaining high-moiecular
fireproof materials. The authors synthesized vinyl compounds of
pentavalent phosphorus and studied their properties, as well as those
of the polymers obtained.
Moshkin, P. A., Ye. I- Gefter, and I. K. Rubtsova [Scientific Research
Institute of Plastics). StuJy of the Synthesis and Uses of Some Organ o-
phosphorus Compounds in the Plastics Industry 279
Industrial methods for the preparation of esters of phosphoric acid
and for testing qualities of these acids as plasticizers have been de-
veloped, along with methods for obtaining phosphorus -containing
rhonomers for use in polymerization, copolymerization, and poly-
condensation reactions. Polyesters based on dichlorides of
Card 6 /14

A
32358
S/191/62/000/001/002/006
B1451B110
AUTHORS: Akutin, M. S., Vinogradovat S. V.9
Rodivilovav L. A., Valetskiy, P. M., Lebedeva, A. S.,
Salazkin, S. N.
TITLE: Polyarylates - new thermoetable polymers
PERIODICAL: Plasticheskiye massy, no. 1, 1962, 9-13
TEXT: A survey of the properties of polyarylates is given. They are best
synthetized from bifunctional phenols and dicarboxylic acid chlorides.
Some of the synthetized polyarylates and their softening temperatures are
given in Table 1. The great number of rings in the polymer ensure high
resistance to most organic solvents as well as to gasolines and oils. At
room temperature, the polyarylate WA (ID) is stable against H 202' dilute
and concentrated caustic soda solutions, acetic acid, formic acid, nitric
acid, and sulfuric acid. The effect of dilute and concentrated ammonia
solutions considerably reduces the molecular weight of ID. Polyarylates
on the basis of phenolphthalein are readily soluble in a number of
solvents which facilitates the production of foils. At the NIIPM it was
Card I ~Yj

32358
S/19 62/000/001/002.,/006
Polyarylates - new thermostable ... B145YB110
established that the polyarylates TA (TD) and ID withstand high tempera-
tures. Decomposition increases with rising temperature, at first slowly
and then sharply at about 4000C. The oxidation of ID sets in at 2500C
and proceeds slowly. Measurement of breakdown voltage, temperature
dependence of tan 6, dielectric constant, and volume resistivity for some
polyarylates prove that they are better dielectrics than polyethylene
terephthalate, polycarbonate, etc. Polyarylates have good mechanical
properties at various temperatures. Working processes are being elaborated
at present. Specimens of mixed polyarylates were obtained by pressure
casting, the tensile strength of which reached 850 kp/CM2. Specimens
sprayed on metal showed an adhesion to metal of 75 to 150 kp/CM2. Work is
also in progress on polyarylates with double bonds and free functional
groups. They might be used as a basic material for the production of
varnishes, glues, glass-reinforced plastics, and foam plastics. Thigre are
5 figures, 6 tables, and 5 Soviet references.
Table 1. Softening temperature of polyarylatee of different structures,
Legend: (1) polyarylate; (2) structure of the chain link; (3) softening
temperature in OC; (4) TD; (5) ID; (6 TG; (7) IG; (8) TR; (9) IR; ('10) TF;
(11) IF; (12)-(14) ITD; (15) IDR; (16~ TDR; (17) IFDj \18) IAD; * the
Card 2x~

32358
s/iqi/62/000/001/002,(Oo6
Polyarylates - new thermostable ... B1451B110
molecular ratio of the initial dicarboxylic acid chlorides related to
1 mole of diol is given in parentheses; * * the molecular ratio of the
initial diols related to 1 mole of dicarboxylic acid chloride is given in
parentheses.
Card 3113

34946
s/191/62/000/003/004/0-10
B101/W47
P/ 0
AUTHORS: Kamenskiy, I. V., Sanin, I. K., Xorshak. V. V.
TITLE: Polymers based on silicon-containing, furan compounds.
Synthesis of esters of furfuryl alcohol and ortho-silicic
acid
PERIODICAL; Plasticheakir massy, no. 3, 1962, 8-12
TEXT: (1) The synthesis of tetrafurfuryl oxysilane (I) in the presence of'
KOH by alcoholysis of tetraethoxy silane (TES) with furfuryl alcohol is
described. To avoid resinification, the alcohol is first only mixed with
half the TES, after evaporation of Mj,' of the theoretical C 2 H5OH amount
with the next quarter, and after evaporation of 3% C2 H5OR with the rest.
it. H OH at 115-140 0 C.
The reaction is continued until evaporation of 750 C2 5
.0
The yield is 60-620i'o, the substance consists OA. jellowi3h crystals, m.p.
38-390C, b.p. 204-2060C (4 mm, Hg), d40 1.231, n 0 1-5025. A by-product is
the hitherto unknown ethoxy trifurfuryl oxysilane, a yellowish liquid, b.p.
Card 1/4

S/191/62/000/003/004/010
Polymers based on silicon- B101/B147
152-1540C (1 mm Hg), d 20 1.1400, n 20 1-4890- (2) Synthesis of I by
4 D
esterification of SiCl 4 with furfuryl alcohol. SiCl 4 is added dropwise to
alcohol dissolved in benzene, excess pyridine is admixed as HC1 acceptor.
Pyridine hydrochloride was separated (a) by washine, dehydration of the
benzene layer by CaC12, distillation of I in vacuo, or (b~ with higher
yields (94~j/4), by filterine off the pyridine hydrochloride. (3) Synthesis.
of tetrahydrofurfuryl orthosilicate (II) by alcoholysis of TES with tetra-
hydrofurfuryl alcohol in the presence of lead monoxide at 120-1.450C for
4 hrs. The product (75',/, yield) was a heavy, colorless liquid, b.p.
215-2160c (1-5 mm 11g), d 20 1.1399, n 20 1.4680. (4) Synthesis of II by
4 D
esterification of SiCl 4, ratio S'Cl4 : tetrahydrofurfuryl alcohol
pyridine = 1.1 : 4 : 4.8, 4 hrs at 100C, 80~f, yield referred to alcohol.
(5) Synthesis of ethyl furfuryl oxysilanes by alcoholysis, similar to i:1),
of ethyl triethoxy silane or diethyl diethoxy silane with furfuryl alcohol
during 5 hrs. The product was ethyl trifurfuryl ethoxy silane (54.5,c4), bp.
159-5-1600C (1 mm 11g), d 20 1-1743, n 20 1-4988; and diethyl difurfuryl
Card 2/4

S/191/62/000/003/004/01,D
Polymers based on silicon B101/B147
0 20 20
oxysilane (48~'O), b.p. 138-139 C (3 Mm He), d4 1.0835, nD 1.4845.
(6) Synthesis of alkyl(aryl)furfuryl oxysilanes by esterification of methy4
ethyl, or phenyl trichloro silane, dimethyl, diethyl dichloro silane, or
trimethyl chloro silane with furfuryl alcohol, similar to (1). Products
obtained: methyl trifurfuryl oxysilane (9(Yi,), b.p. 157-1580C (1 mm Hg),
d20 1.1601, n20 1.4992; dimethyl difurfuryl oxysilane, b.p. 102-103
4 D 20
(1 mm Hg), d20 1.1021, n 1-4809; trimethyl furfuryl oxysilane (69%.),
1 4 D 20 20
b.p. 39-0-39-50C 0 mm HO) ' d4 0.9519, nD 1.4449; ethyl trifurfuryl
oxysilane (91%), b.p. 159-5-1600C, d 20 1-1743, n20 1.4988; diethyl
4 D 20 20
difurfuryl oxysilane (6911'.), b.p. 138-1390C (3 mm Hg), d 4 1.0835, nD 1.4615;
and phenyl trifurfuryl oxysilane (5%"), b.p. 199-5-2000C , d20 1.2040,
20 4
nD 1-5358- (7) Esterification of methyl chlorosilanes with tetrahydro-
furfuryl alcohol produced (in 88-90% yields): methyl-tri-(tltrahydro-
furfuryl)-oxysilane, b.p. 179-1810C (2 mm. He), d20 1.1068, n 0 1-4648;
4 D
Card 3/4

5/191 /62/000/003/004/010
Polymers based on silicon ... B101/B147
dimethyl'-di-(tetrahydrofurfuryl)-oxysilane, b.p. 123-1250C (1 mm HU),
d20 1-0324, n20 1.4505; and trimethyl-(tetrahydrofurfuryl)-oxysilane, b.:,).
4 0 D. 20 - 20
172-173 C (76o mm Hg), d4 0*9214, nD 1-4271. The infrared spectra of -the
compounds are shown. Papers by Yu. X. Yurlyev (ZhOKhj ~_8, 3 (1950) and
A. L. Mdzhoyan (DAN ArmSSRj 27P 305 (1958)) are mentioned. There are
7 figures, I table, and 25 references: 8 Soviet and 17 non-Soviet. The
four most recent references to English-language publications read as
follows: (1~55); K. 0. Wilks
H. Olson, Ind. Eno. Chem., AZ, 1411 J. Am.
Chem. Soc., J2, 1208 (1950); US Patent 2601497 (1952); US Patent 2569455t
C. A., 46, 3084 (1952).
SUBMITTED: October 19, 1960
Card 4/4

Of-LI
S/062/62/000/004/012/013
B110/B101
AUTHORSs Ko.rshakv V. Vep Sladkov, A. Me, and Luneval Le Ke
TITLEt Synthesis of elemental organic polymers with acetylene
bonds in their chain
PERIODICAM Akademiya nauk SSSRe Izvestiyao Otdeleniye khimioheskikh
naukp no- 49 1962, 728
TEXT: New polymers were obtained by polyoondeneation of halides of element41:.:'.,'
21 with Na acetylenides of bis-acetylenes in polar
organic compounds, RMeCl
solvents (tetrahydrofurany dimethyl etherp diethylene glycol, ethyl etherp~,
etc.). The acetylenide was obtained from finely distributed sodium or
sodium amide and bis-aoetylene in the solvent. Elemental organic compounds
On the same solvent were added at room temperature, heated to 6o-iooOct
filtered offp and the polymer was separated from the filtrate. Thuov the...- .1
acetylenide was obtained from p-di-ethinyl benzene and sodium. After th
_2~
addi-tion of dimeth~rll dichloro silane, the substance was boiled for 7 hr:
-yellow polymer not melting at
cooled, and diluted with water* A light
Card 1/2
Ti
p 1"I
U
S/062/62/000/0
04/012/013
Synthesis of elemental organic.... B110/B101
3000C and slightly darkening at 2400C (C 66-45P H - 7-74, Si 20.92%)
1 40~
precipitated. The infrared spectra showed C~^ (2250 cm- ) and Bi-CH
stretching vibrat 1 3
ions (1250 cm- ). The range of elastic deformation W
thermodynamically determined at 150-3000c. Similarlyp an acetylenide W"L!,
obtained from phenyl acetylene and sodium;, Addition of dimethyl dichloro
silane at room temperature and subsequent boiling for 4 hrs yielded 4 5
di-p-phenyl ethinyl dimethyl ailane (be pt 180-1650C at 4 mm Hg). in an i:'
i analogous manner, polymers can also be obtained from other compounds of
elements Of Group IV. The resulting-Monomers Were used for producing
Polymers and Copolymers.
ASSOCIATIONs Institut eleme'ntoorganioheskikh aoyedinaniy Akadexii nauk
SSSR (Institute Of Elemental Organic Gompounds-of the
Academy of Sciences USSR)
SUBMITTEDs December 25, 1961
--Card

KORSHAK, V-V ; K%RROVA~ L.I.; SIDOROV, T.A.
Infrared spectra of organic~complexee of beryllium. Izv. AN SSSIR.,
Otd.khim.nauk n0.5:813-815 147 062. (MIRA 15:6)
1. Institut elementoorganicheskikh soyedineniy AR SSSR.
(Beryllium*organic compounds-Spectra)

KORSHAKY V.V.; KROMAUZO Ye.S.; BERLIN., A.M.
Organophosphorus polywro with F - N bonds. Izv.AN SWR.Otd.
kbim.nauk no.8:W2-3la6 Ag 162. (MA 15%8)
1. Institut elewntoorganicheokikh ooyedineniy AN &WR.
I (Phosphorus organic compounds) (-%lymers)

s/o62/62/000/008/009/016,f
BIOI/B180
AUTHORS: Korshak V V Vinogradovat S. V.? Salazkin, S. N.t and
Sidorov, T. A.
TITLE: Production of polyaryls based on phenol phthalein by inter-
phase polycondensation
PERIODICAL: kkademiya nauk'SSSR. Izvestiya. Otdeleniye khimicheskikh
nauk, no. 8, 1962, 106-1423
TEXT: This is the 47th report on heterochain polyesters. -Interphase pol
condensation of phenol p '(P) with*chlorides of dicarboxyli a ids
hthalein a c
yielded-polymers of low intrinsic viscosity Reacting P with
isophthalic acid in this way in p-xylol solution,*at initial reactant
concentrations of 0.1 mole/l, with 29 NaOH per M phenol phthalein,
resulted in [1j4C0.23 (in tricresol) and yields of up to 80. Higher
alkaline concentrations reduced both [q] and yield. Nor did an emulsifier,--"
(Nekal) or catalyst (triethylbenzyl ammoniumchloride) cause an
appreciable increase in E,%]. Polycondensates from P and terephthallio
acid (T), and mixed polycondensates from Pt 4-41-dihydroxydipheilylpropane
Oard 1/ 3

S/062/62/odq/608/009/616.
Production of polyaryls based ... B101/B180
Dian) and I or T all had a lo' [,q] (0.26-0-32) was.1.ower still
0.12-0.16) when the d:iohlorid:s of I and T were IoNally or partially.
~
replaced by fumaryl dichloride, due to the slight hydrolysis caused by
the latter. These results are attributed to the slow rate of the
tautomeric transformation of P. In alkaline solution it is assumed that
there is equilibrium between the quinoid and the lactone forms. The
chloride of the dicarboxylic acid only reacts with the lactone. Since
transition from quinoid to lactone occurs 9lowly,-hydrolY818 of the acid
chloride sets in, and the molecular weight remains low. This is supported
by the absence of a band characterizing the quinoid structure at 1680 am-1
in the IR spectra of the polycondeneates. The 1300 cm-1 band, attributed
by S. Lo Elisabeth to the quinoid form (Industr. and Engng, Chem.9 52,
319 (1960)), was ascribed to the residue of I, since it was also obser7ed
in the polycondeneate of Dian and Is The doublet 1710-1760 cm-' is
attributed to the different bonds of the carbonyl groups (ester and
laotone bonds), Thekd 6ke 0 tidukdo AM 4 thbl~~,
ASSOCIATION: Institut elementoorginicheakikh soyedineniy Akademii naule-
SSSR (Institute of Elemental Organio Compounds of the Aoiadeqr
of Sciences USSR)
Card 213

Production of polyaryls based as,
SUBMITTED: February 11, 1962
Card 3/3 ~

S10621621000100810111016
B117/B180
AUTHORS: Korshak V V Kudryavtsev, R. V.p Sergeyev, V* A*9 and
I s ra ron' ~.' 4
TITLE: Investigation of hydrolytic polymerization mechanism of
E-caprolactam in the presence of-water,contAining a heavy
F
oxygen isotope
PERIODICAL: Akademiya nauk SSSR. Izvestiya. Otdeleniye khimicheakilth
naukt no. 8# 19629 1468-1470
18
TEXT: In this investigation the water contained 6% 0 F--oaprolactam
and the labeled water, in a 1:1-5 ratio, were heated'for 6 bra at 9000C
The molecular weight of the resulting poly-E-capioamide was relatively
18
low, and its 0 content the same as with an exchange reaction. From this--
it is concluded that the monomer links on to the end groups of the
growing polymer chain during the reaction. When the polymer was heated
for 3 brs at 2500C in argon, the viscosity of the Solution was found to
be higher than that of the initial-polymer, (from Nj - 1.76),
tr 0-38 to
Card -1 A-

S/062/62/000/008/011/016
Investigation of hydrolytic B117[B180
as also the molecular weight. In the final stage of the reaction, if all
the water can be removed, polycondensation of the macromolecule will
occur due to the reaction between amino and carboxyl end-groups. The
course of the hydrolytic polymerization of &-caprolactam ddscribed above
confirms earlier predictions (V. V. korshak and T. M. Prunze, Izv. AN SSSR.
Otd, khim. n- 1955P 376). There is I table.
ASSOCIATION: Institut elementoorganicheskikh soyedineniy Akademii nauk
SSSR (Institute of Elemental Organic Compounds of the
Academy of sciences USSR)..
SUBMITTED: January 31, 1*962-
Card 2/2

~CRSHAKp V.V.1 ROGOZHIN, S,V.; VINOGRADOV, M.G.
FIrthalocyanins po2y=ra of diphthalyl ketone. Izv.AN WSR.Otd.khim..
nai& no.S-.3.473--2475 Ag 162, OMA 15:8)
1. institut slamentoorganichookikh soyedineniy AN SSSR.
(Ketone-Y (Phthalocyanine)

~0730
510621621000100910071009
B119/B186
AUTHORS: Korshak, V. V.,_Krongauz, Yee Set and Gr~bkova, P. N.
TITLE: Production of a polymer by polyrecombination from diphenyl
benzyl phosphine oxide.
PERIODICAL: Akademiya nauk SSSR. Izvestiya. Otdeleniye khinicheskikh
nauk, 'no. 9) 1962, .1638 1644
TEXT: (C H P(O)CH C was polyrecombined by heating to 210 2120C in
6 5 2 2 05
a current of N2 and in the presenc6'of Vertiary butyl peroxide. The time
of reaction (3 - 11 hrs) and the perogide c .onteht (I r 4 moles' per I molt,
of diphenyl benzyl phosphine oxide'(D)) were varied. . A polymer with
-polecular weight between 33,000 and 35,000 was obtained. The melting
e- the specific viscosity a
Point wa-s 320 - 3300C, of 0-5 ~a solution in
croaol< 0.1. The maximum polymer yield was gel ~4 referred to the amount
of D use(L. Nothing certain could be learned as to the dependence of the
yield on the mixing ratio,D: peroxide.or as to the time of reaction, or
rate.of-paroxide admixture. The'highly ramified polymer molecules are
assumed to form according to the following reaction schemes
Card 1/3

13/062/62/000/009/007/009
Production.of a polymer by,. B119/B186
CH
3\, CH
3 OR
3\
CH -C-0-0 -C-CH
CH to,-W)
0 H
CH
3 3 3
CH3\
CH C-0-
3
:

y
CH13.
+(OR COH ,
v
33
0
.
CH 3\
CH C-0- CH +(CH.) C-ito
.3 Y2_1
3

C
d
/ H
+ CH' -4 H-C-CH
ar
2
3

7 S/191/62/000/011/oo6/oig
B101/B186
AUTHORS: Akutin, M. S.,,.Korshak, V. V., Rodivilova, I. A.,
Vinogradova, S. V., Budnitskiy, Yu. M., Valetskiy, P. M.,
Lebedeva,.A. S.
TITLE: New data on processing and properties of polyarylates
PERIODICAL: Plasticheskiye massy .,no. 11, 19.62, 20-26
TEXT: This paper deals with experiments for determining the optimum
processing conditions of polyarylates from isophthalic acid and diane (ID),
terephthalic acid and diane (TD), and the mixed'polymer ITD (ratio iso-
to terephthalic acid 1:1). Preliminary experiments showed that the
interfacial polycondensation in more concentrated solutions than hitherto
usual gave polymers with low molecular weight: thus 13.5~* by weight of
diane in NaOH solution + 15-20% by weight of isophthalic dichloride in
methylene chloride yielded a polymer with MVI -18,000. A better result was
obtained for ITD in the presence of 1% trieihyl benzyl ammonium chloride
as cataliat: the reduced viscosity in tricresol was 0-53- InJection-
molded products were made from ID, TD, and ITD, and tested. Results:
Card 1/3.

s/191162/000/011/oo6/oig
New data on processing and ... B101[B186
(1) At 280-360'OC, ID and TD can be processed only in inert gas atmosphere
since thermal destruction occurs if air is present. ITD can still be -
processed at these temperatures in the presence of air. (2) The strength
of products depends on the molecular weight (or on the reduced viscosity).
Adequate tensile strength (- 400 kg/Om 2) is attained above Ired 0 1.0.
Products with a tensile strength of 850-900 kg1cm 2 were obtained from ITD
with '~Lred ' 1.9-2.0. (4) The tensile strength drops from 820 kg/cm2 at
2800C to 480 kg/cm 2 at 340 0C- (5) The effect of the molding time becomes
manifest the tensile strength dropping from 850 kg/CM2 after 10 min to
300 kg/cm2 after 30 min molding time (6) A change in molding pressure
has no effect on the tensile strengtL (7) Increasing the temperature of
the mold from a0 to 1600C increases the tensile streneth from 650 to
820 kg/cm2, but a further increase (to 2000C) reduces the tensile strength.
(8) A study of the chemical stability of injection-molded specimens and
films showed: good stability to mineral and organic acids, oxidants, and
dilute alkalis; poor stability to concentrated alkalis, particularly
ammonia; swelling in some solvents, injection-molded specimens being more
stable than films. The chemical stability of polyarylates resembles that
of polycarbonates, and is inferior to that of polyethylene terephthalate
Card 2/3

S/I 9y62/000/011/006/01 9
New data on processing and ... B101 B1 86
only as regards the swelling in some organic solvents. There are
6 figures and 6 tables.
Card 3/3

42649
B/062/62/000/011/012/021
B101/B144
AUTHORS: Korshak,,V. V., Frunze,-T. M., and Kozlov, L. V.
TITLEt Heterachain polyamides. Communication 32. Interfacial forma.
tion of mixed polyamides-from mixtures of various diamines
FERIODICALs Akademiya nauk SSSR. izvestiya. Otdeleniye khimicheskikw
nauk, no. 11, 1962, 2o62 - 2o69
TEXT: The rules governing the interfacial polycondensation of adipyl
chloride (AC) with a mixture of ethylene diamine (1) and m-phenylene
diamine (II), or I and hexamethylene diamine (III), were studied. Poly-
amides were also synthesized from sebacyl.chloiide-(SC) and a mixture of
III and piperazine (IV). The polycondensation-was carried out at rooin
temperature; the chloride was dissolved in*benzene, the.diamines in aqueous
alkali. The molar ratio of the diamines was vatied.between Osl and 1s0.
The relative reaction rate of II and III was determined by acylating their
-mixture with benzoyl chloride. The nitrogen content of the reaction prod-
uct and its IR spectrum proved that main.ly-dibenzoyl,.hexamethylene amine
was formed and that the reaction rate of III was consequently much higher
Card 1/3

-W/062/62/000/011/012/021
Heterochain*polyamides ... B100144
than that of II. In the polycondensation of AC with diamines the following
were-determineds the initial ratio K of the diaminesq-the-ratio K 2 of
the diamines in the copolymer, and a K2/Kj. The following values were
foundt K1 . 1/13: K2 . I/II K1. I/III K2 M I/III
4 0.54 0.14 ,4 - 2.03 0.51
1.50 0.41 0*27 1.50 o.613 0.41
1.00 0-15 0.15 1.00 0.32 0o48
o.67 0018 0.27 0.67 0.32 0.48
0.25 0.00 0.00 0.25 0.075 0.30
amean 0 0,17 Oe.41
The polymers had a higher content of Il or III, respectively, than would
correspond to the initial ratio. After prolonged polycondensation of AC
with I and II, the I content in t *he polymer increased owing to exhaustion
of the diamine mixture with respect to II, which had the principal share in
the early reaction stage. The system of SC behaved similarly with III and
IV. These results are explained by the different rates of diffusion of
Card 2/3

S106 62/000/011/012/921
Heterochain polyamides*** B101YB144
the diamines into'the organic phase., It is (in M/cm 2. mi.n) 3.9-10-7 for 1,
6-07-10-5 for II, and 1.07-10-5 for III. The dissociation constants area
8.5.10-5, 6.0-10"10, and 5- 1-10-4, respectively. In the polymer, the con-
tent of radicals of the diamine primarily depends on the rate of diffusion.
The reactivity is of secondary importance and has a compensating effect on
the polymer composition if the slowly diffusing diamine has a higher re&6-
tion rate (dissociation constant). There are-3 figures and 5-tables.
ASSOCIATION: Institut elementoorganicheskikh soyedineniy Akademii nauk SSSR
(Institute of-Elemental Organic Compounds of the Academy of~
Sciences USSR)
SUBMITTEDs April 9, 1962
Card 3/3

3/19c) 93404/001/004/020
B101/B110
AUTHORSt Korshak, V. V., Rogozhinq S. V., Volkov, V. I.
TITLE. Studies of coordination polymers. IX. Metal-containing
polymers based on aliphatic dicarboxylic, a, a'-dihydroxydi-
carboxylic, and a, m'Ldialkoxydicarboxylic acids
PERIODICAL: Vysokomolekulyarnyye soyedineniya, v. 4, no. 1, 1962, 20-24
TEXTt Synthesis and properties of polymers containing Zn, Cu, Cd, Co, or
Ni on the basis of W, W 1-hexadecanedicarboxylic acid (I), terephthalic
acid (II , a, at-dihydroxysebacie acid (III), and a, a'-dimethoxysebacie
acid (IV~ are described. III was synthesized from m, at-dibromosebacie
acid by saponification with 5~ KOH solutionp production of Cu salt with
CUSO 4, and formation of the free acid by precipitating Cu with H2S.
Dimethyl eater of IV was obtained from a, (xl-dibromosebacie acid by sodium
methylate (n 20 - 1.4425; boilinf; point=128-1300C/1-2 mm Hg). Dipotassium
D
salts of I,II,TII,dr IV were reacted with the chlorides or acetates of the
Card 1/4

3230
S11901621004100110041020
Studies of coordination ... B101/B110
metals in an aqueous or aqueous-alcoholic medium. Linear structure is
assumed due to the thermal behavior and insolubility of the powdery pre-
cipitates obtained. The following data are listed: (A) Polymers from I,
structure 0 0141(0016 -In; copper compound light blue, crystalline,
melting point 223 - 2250C (in capillary), maximum deformation (1) max ) at
2010C; Cd compound crystallineg whitet melting point 211 - 213 Oct
Dmax ~ 175 0C; Zn compound crystalline, white, melting point 242 - 24 0C,
Dmax 221 0C; (B) the Cu compound with II is light blue, crystalline,
melting point 3000C (with decomposition), D max ' 335 OC; (C) the composi-
tion of polymers of III differed with the conditions of synthesis. It is
assumed that complexes with groups of adjacent chains or with molecules
of the solvent are formed as a consequence of the incompletely occupied
coordination sphere of the metal ion. Cd compound white, melting point
280-2900C (decomposition), Dmax m 2920C; Zn compound white, melting
Card 2/4

3?343
S/190/62/004/001/004/020
Studies of coordination B101/t110
point 330 - 350 OC (decomposition), Dmax ' 3270c; Ga compound light blue,
melting point 3300C (decomposition), Dmax - 341 0C; Co compound red-violet,,
meltinp Zn compound white, melting point
g point 25'oCj 'max ~ 3510C; 0
280 C, Dmax ~ 3270c; Ni compound green, melting point 300 C (decomDosi-
tion), D m 365 OC; M the Co compound with IV is light violet,
max
melting point 300 OC (decomponition)p Dmax ' 2430C! Zn compound light
yellow, melting point 140 - 2200C, ])max m' 1570C. The low stability of
the compound with IV is explained by the fact that substitution of CH 3
for the hydrogen of hydroxyl groups prevents the formation of-H bonds -
X-ray patterns of Zn polymers showed a decreasing crystallinity in the
series I,~III> IV (the latter polymer being amorphous). There are 2
figures, 2 tables, and 4 referencess I Soviet and 3 non-Soviet. The
two xeferences to English-language publications read as follows: R.
Martin, 11. Watermanng J9 Chem, Soc., 2545, 1957; Ch. K. Ingold, J. Chem.
Card 3/4

Studies of coordination...,
2343
S/19 62/004)0017004/020
B101YB110
Soc., 11r), 964, 1921-
ASSOCTATION: IngtiLut elementoorganicheskikh soyedineniy AN SSSR
(Institute of Elemental Organic Compounds AS USSR)
SUBII,' ITT ED tJanuary 18, 1961
Card 4/4

D 'S?&/62/OO4/0O1/OO9/O2O
B101/B110
AUTHORS: Korshakq V. V., Gribova, I. A., Andreyeva, M. A., Popova,
TITLE: Polymers containing phosphorus. XXVII. Heterochained
polyesters of vinyl phosphinic acid with some dihydroxy
compounds
PERIODICAL: Vysokomolekulyarnyye soyedineniyal Va 4, no. 1, 1962, 58-63
TEXT: The authors report on the properties of eaters of diethylene glycol
(I) and 4,41-dihydroxy-2,2-diphonyl propane (II) with mixtures of vinyl
and methyl phosphinic acids. The syntheses of these eaters have already
been described (Vysokomolek. soyed., K, 427, 1960; Izv. AN SSSR, Otd.
khim. n., 1958, 880). Eaters with I are colorless, viscous liquids. Their
freezing point drops from -390C (100% CH 3POC1 2) to -510C with 100%
CH2-CHPOC12 in the initial mi.xture. Eaters with II are transparent, britle
solids soluble in dichloro ethane, chloroform, and tricresol, insoluble in
ether, benzene, and dioxane. Their softening points drop from 55-560C to
Card 1/2

32 47
8/190 2/004/001/009/020
Polymers containing phosphorus. B101 B110
41-420C (- 100% vinyl phosphinic acid) as the content of vinyl phosphinio
acid increases. Struoturization of the eater of I (in sealed ampule, N2
atmosphere, at 600C for 15 hreq or in an open teat tube and in C2H4Cl2
solution) by benzoyl peroxide, text-butyl peroxide, azoisobutyric dinitrile,
tert-butyl hydroperoxide, or cumene hydroperoxide, only occurred with a
vinyl phosphinic acid content ;~t 40% (gelatinous substances, softening
Points; 150-2000C the latter value with 100% CH 2 CHFO-). Eaters with 11
could not be structurized under the experimental conditions, applied. Them
are 2 figures, 4 tables, and 4 Soviet references.
ASSOCIATION:
SUBMITTED:
Institut elementoorganicheakikh soyedineniye AN SSSR
(Institute of Elemental Organic Compounds AS -%J--SBR)
January 26, 1961
Card 2/2

33375
S/190/62/004/002/004/021
B110/B101
AUTHORS: Korshak, V. V., Zamyatina, V. A., Ma Jui-janp Oganesyan, R.M.
I--
TITLEi Polyesters and polymeric salts of boric and 1,4-phenylene
diboric acids
PERIODICALi Vysokomolekulyarnyye soyedineniya, V. 4, no. 2, 1962, 188-191
TEXT: V. A. Zamyatina and N. I. Bekaaova (Usp. khimii, LO, 48, 1961)
described the synthesis of highly thermostable polyesters of boric and
substituted boric acids. In the present study, the polyesters of boric
acid and 1,4-phenylene diborid acid (I) with pentaerythrite (II), the Zn-
and Sn-organic salts of pentaerythrite 'hydroxydiboric acid (III) and I
were synthesized, and their properties compared. Polypentaerythrite pheny-
-dibora H m--N B /OCH2 > C < OR 2 JOR
lene-1,4 tel > Be
~O 00192 CH 2 60"
H
0
is unmeltable and resistant to heat and hydrolysis. For producing a linear
Card 1/3

SY375
19y62/004/002/004/021
Polyesters and polymeric salts ... B110 B101
polyester, boric acid was condensed with pentaerythrite equimolecalarly
for 10 hr at 1-0 - 1800C in N2 flow. The polymeric salts of III had linear
structure. The molecular weight of unsoluble polymers hydrolyzing in
aqueous alkali could not be determined. The Zn salt of III contains more
organic and fewer mineral fractions than had been calculated, Folyconden...
sation of I with II yielded a polyester of calculated composizion which was,
however, not linear and unsoluble. Anhydride was formed during the ,
synthesis of polymeric salt of I from metal acetates, and some tributyl
borate was separated out during that of Zn salt. Polyesters and salts
resemble each other in mechanical and thermomechanical respect, and in ou-'er
appearance. The brittle white polyesters malt at >300'C. The polyester
of 1 does not hydrolyze in the cold, that of boric acid does. The yellow
brittle Sn-organic salts hydrolyze in the cold, and have low softening
temperatures. The white ZinseltsexeMahl hydrolyze well, and melt at>5()Ooc-
There are I figure, 2 tables, and 2 references: I Soviet and t non-So-Tiet.
The reference to the English-language publication reads as followss W. R.
Bamfordq S. Fordham. High Temperature Resistance and Thermal Degradation
of Polymers, Symposium, Sept. 1960, London, p. 127.
Card 2/3

Polyesters and polymeric salts ...
33375
S/19 621004100210041021
BliOX101
ASSOCIATION: Institut.element6organicheskikh soyedineniy AN SSSR
(Institute of Elemental Organic Compounds AS USSR)
SUBMITTED: February 2, 1961
Card 3/3

33376
S09~0*0.21994/002/005/00
BI 0 .31Q.1
AUTHOld: to ak, T, To
v v lj~ Ma Jui-jan Zaiqatinaj V. A.
TITLEt P.1y nhydrides iDfAr4-ph9njy1ene diborio-aoid
PERIODICALi
Vyiok6iolskulyarriyye'soyedineniyat V* 4j no. 2p 1962t
.195-
TEXT Aacordin to B. M. MikhayloV* and P. M. Aronovich obshch. khimii
(zh
9
ZIP 3124;*'1959), enters of subi3tituted.borio aoids mayexchange the alkoxy
group f6i,t'heamino group of aromatio smines, and dispropmti6nate to organor7:
b6ron diaminess
OC4111
RIB
RIB 30000, those from monoamines are linear'. those from diamines
are steric and unsoluble, and hydrolyze in boiling water. During poly-
condensation of tetraethoxy-1,4-phenylene diborate with anhydrous hydrazinq
NH3 and a volatile boron compound are probably separated. There are 1
figureq 1 tablej and 3 referencess 2 Soviet and 1 non-Soviet. The
reference to the English-language publication reads as follows: D. R.
Nielsen, W. E. McEwen, J. Amer. Chem. Soc., 12, 3081, 1957-
ASSOCIATION: Institut elementoorganicheskikh soyedineniy AN SSSR
(Institute of Elemental Organic Compounds AS USSR)
SUBMITTED: February 2, 1961
Card 3/3

Vz P-1130
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puv 'ajqe4 L Isoanj?Tj V eau ojoqL -ouoTj-e.?TqGOAUT 0TdO0GOX400dG
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t710Tj, SO V:910W Zj'g q~TA PaUT134qo siauig
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TS65

8/19 62/004/003/002/023
B1 10YB144
AUTHORS: K Vinogradova, S. V., Salazkin, S. N.
TITLE: Heterochain polyesters. XXXIII. Polyarylates on
phenolphthalein base
PERIODICAL: Vysokomolokulyarnyye soyedineniya, v- 4, no. 3, 1,0062,339-344
TEXT: HomoCeneous and mixed polyarylates (I) on phenolphthale-in base were
synthesized, ~Lnd the effect of the initial compound 3tructure on their
properties was examined. The authors hoped to obtain a polymer which
would be well soluble by virtue of the large phenolphthalein side groups
and which would have a sufficiently high softening temperature owing to
the polar group in the side group. The lactone group was to be modified
to reactive carboxyl and hydroxyl groups as follows:
-0 C 00=0 C-e--\~00
.00 CRC0-'
0 into 01
e Y1\ /\OH
COOH
0.
lk~o CI-10
The decrease in packing density raises the solubility of ! on DhenolphUnleia
base as compared with I on "dian" base. I on zhenolphthalein tase and
isophthalic acid base dissolves in methylene ckoride, chloroform, tetra-
chloro ethane, tetrahydrofuran, cyclohexanone. The partial substitution of
phenolphthalein for bivalent phenols raises solubility. Films obtained
from 5 ~t solutions of I with phenolphihalein and terephthalic acid retain
Card 2/3

S/190/62/004/003/002/02~
Heterochain polyesters... B110/B144
50 % of their strength at 1800C. Amorphous structure of most of I on
phenolphthalein base was established by X-ray structural analysis. Thanks
are due to the teams of laboratoriya fiziki polimerov (Laboratory of
Pol~mar Physics) and laboratoriya rentgenostrukturnogo analiza
(Laboratory of X-ray Structural Analysis) for thermodynamic and X-ray
analyses. There are 3 tables and 17 references: 13 Soviet and 4 non-
Soviet. The two references to English-language publications read as
follows: A. Conix, Industr. and Engng. Chem., ~1, 147, 1959;
V1. M. Eareckson, J. Polymer Sci., AO, 399, 1959.
ASSOCIATION: Institut element oorgani che sk ikh soyedineniy AN SSSR
(institute of Elemental Organic Compounds AS USSR)
SUBMITTED: April 24, 1961
Card 3/3,

AUTHORS:
TITLE:
PERIODICAL:
34983
S/190/62/004/003/003/023
B110/B144
Korshak, V. V., Vinogradovaj S. V., Iskenderov, M. A.
Heterochain polyesters. XXXIV. Polyesters of aromatic
dioxy condensed-ring compounds
Vysokomolekulyarnyye soyedineniya, v. 4, no. 3, 1962, 345-350
TEXT: Polyarylates were obtained on the base of isomeric diols of the
naphthalene, anthra,:ene, and phenanthrene series using .interface poly-
concentration. The 'effect of the feeding rate of initial compound solu-
tions, of their concentration and ratio, and of the reaction lemperature
on yield and molecular weight of polyarylates of 1,6-dio'xy naphthalene M
and dicarboxylic acide (adipic (II), sebacic, and isouhthalic (III) acid)
was investigated. Best results were achieved by the addition of acid
chloride solution to an aqueous alkali solution of I for 11-14 min. The
highest polymer yield and viscosity were obtained at 0.10 N concentration
of the initial solutions. 200C was ideal for the interface condensation
of 1,6-dioxy naphthalene with II, III, and sebacia acid. If one of the
phases is aqueous, various competing reactions may, in polyesterification,
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S/190/62/004/003/003/023
Heterochain polyesters... B110/B144
take place at the interface. Some of them produce a polyesterl while
others,prevent it from forming as, e.g., chain rupture due to hydrolysis o1.
the acid chloride groups and of the initial dicarboxylic acid chloride:
1. ...-OC,,ti,OOCRCOCI+HO....-OCIOHOOCRCOOH+HCI
2. C10MCOCI + 2H20 - HOOCRCOOH + 2HC1
3. CIOCRCOCI + HO C10CRC00H + HC1
0GRC00Ct0H$0Na + C10CRC00H ... 0CRG00CjoH&00CRC00H + NaCl
The decrease in viscosity and yield of the polyarylates of I with an
increase of the reaction temperature from 20 to 400C is effected by the
increase of the rate of these reactions in the polycondensation process at
higher temperatures, while the decrease in viscosity and yield at low
temperatures is effected by a drop iii thd ixate of:the polymer- forming reaction.
Yield and viscosity of polyarylatea depend on the different hydrolyzing
capacities of the acid chlorides.. A.0.2-mole excess of dicarboxylic acid
chloride,required as compensation for the acid chloride lost through
hydrolysis, provided maximum viscosity (0.22 in polyarylates of III, and
0.16 in those of II) and yield (84 % in III and 35 % in II). Excess Of
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Heterochain polyesters...
S/19 62/004/003/003/023
Bi 10Y13144
1 or of acid chloride (> 0.2 mole) leads to chain rupture by the formation
of phenolate or acid chloride groups at the chain terminals. The best
NaOH amount is 0.1 mole excess in III and 0.2 mole excess in 11. The
amount of reactive phenolate of I drops with NaOH deficiency, as I does not
react. spontaneously. NaOff excess causes the initial acid chloride and
the polymer chain to hydrolyze. There are 4 figures, 2 tables, and
16 rc,~ferencea; 10 Soviet and 6 non-Soviet. 'The two references to
English-language publications read as follows: A. Conix, Industr. and
Engng. Chem.,.~1, 147, 1959; 1. A. Ambler, I. T. Seanlan, Industr. and
Engng. Chem., jj, 417, 1927.
ASSOCIATION; Institut elementoorganicheskikh soyedineniy AIN SSSR
(Institute of Elemental Organic Compounds AS USSR)
SUBMITTED: February 9, 1961
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