SCIENTIFIC ABSTRACT ZHDANOV, A.A. - ZHDANOV, A.A.

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• Sequence Number: 18
• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

20-5-24/60
The Synthesis of Pblygrganoaluminum Siloxanes.Exchange.
Decomposition 'Reaction Between Sodium Salts of Alkyl-Silantriole,
and Aluminum Chloride.
The',investigationa showed that on,the occasion of
organic solvents,
'
the interaction of chloroaluminum with sodium salts of phenyl-ailan-
troil,ethyl.ailantroil androith thedisodium salt of 1,3,5-triphonyl
-1,3,5-trimothyl silanoxanottho formation of the substances mentio-
ned
in the title proce6dd according to j)attarn:C6H;Si(O11)8ONa+A1.Cl3
"
---'~C H 5'(011) 073 AI+SNaOltn/c6H5S'(OH)3/3kl-- 6H53i( )01 1 +
%
e
i
M
-
e RU
ing polymers represent colid,brittle,glass-li
reaul
+nH20.
otanoespsoluble in benzenepalcohol and acetono.On the 0ocasion of
the evaporation of their solutions there develop transparent films
on solid surfaces.The sodium salts of alkyl-silantriols used by the
authors in the exchatge decomposition reaotion,wore synthetized by
the influence of an equimolecular amount of caustio soda upon.poly.-
organosiloxaneo.These,sodium salts represent solid crystalline oub-
stances containing crystallization water.According to the amount of
,crystallization water these substances are soluble in alcohol and
acetone.Experimental part with the usual data.(3 Slavic references.)
ASSOCIATION Institute for Elemontary-Organic Gompounds of the Academy of Science
PRESF11TED BY of the U.S.S.R.
13UBYkITTED
101AILABLE Librtiry of Congress.

ar
C id ~/2

ZFIDAN A. A.., ANURIMIOV) K. A.)
"The Synthesis of Polyorganometalosiloxanes and the Investigation of
their properties,,-, paber,submitted at the Symposium on Organic and
Nonsilicate Silicon Chemistry on 12th-14th May 1958, Dresden.
1. The reaction of metals- sodium, magnesium and aluminum- with
organosilanols- diethylsilanediol, 1,3-dihydronrtetraethj1l- dinilo-
xane and polyphenylsiloxane resins, is under investigation. It will
be shown that -the above compounds react with the metals under anhydrous
conditions with the formation of metal-siloxane (metal-oxygen-ailicon)
linkages.
2. The reactivity of the silanols is dependent on the stability of their
hydroxyl. groups. Compounds which easily iLmdergo condensation do not react
with metals. Compounds which have stable hydroxyl groups react easily
with metals.
3. It will be shown that by the action of aluminum chloride on the
sodium salts of phezWl- and ethylsilanetriols and of 1,3,5-tririethyl-43,
5-triphenyltrisiloxane,, polymers are formed- the polyorganoaluminouiloxanea.
Abstract: B-3,108,944 (Encl.)

AUTHORSs Andrianovt K. APj-Zhdanov# A#A# SOV/62-58-6-24/37
TITLEt The.Synthesis of Te traki r-rT;rG'6j1- oil oxy) Titanium and
Tetrkkis-(Viethyl-Silo 'xy)-Tin (Sintez tetrakia-(trietilsilokai)
titanaA tetrakis (frietilailokbi) olova)
:PERIODICALs Izvestiya, Akademii nauk 355H, Otdoloniye khimichookikh nailk,
1958P Nr 6tzpp. 779-780 (USSR)
ABSTRACT: The synthesis.of-siiicon-organic titanium derivatives are
dealt,with by several scientific papers. In the course of
the present report fle authors dencribe the syntheais of
triethyl-ailoxy titanium and tetratriethyksiloxy tin brout-ht
about by the'exchange,reaction of godium-trieth.yj-."
silanolate with tetrachlorotitanium and zinc chlorides
4(C H ) SiONa + SnCl C H Sn t 4NuCl-
S'01
---> 1(
2 5 3
2 5 3 4
4
Further data relating to the investigation of the reaction
as well as to the
interaction between sodium triethylsilanol~te
,
and other halides are intended to be discussed by the authors.
in a paper.V)-follow. There are 5 referencest 3 of which are
Card 1/2 Soviet.

AUTHORSi Andria anov A. A. SOV
nov, K., A.., Zhd /62-58-9-9/26

"~.TITLE:
The Reaction of
etals With Hydroxyl-Containing Organo-
silicon Compounds (0 vzaimodeystvii metallov s gidroksil-
soderzhashchimi kremneorganicheskimi soyedineniyami)
PERIODICAL: Izvestiya,Akademii nauk SSSR. Otdeleniye khimicheskikh nauk9
1958, Nr 9, pp 1o76 1079 (USSR),
ABSTRACT: In the previous papers the authors showed that triethyl-
silanol can react.with aluminum to form aluminum
with the liberation of hydrogen.
The high reactivity of hydroxyl-containing organosilicon
compounds toward metals can only be explained by the
fact thatthe silicon atom in these compounds exhibits
a high degree of polarizability. The authors were
interested in investigating the reactivity of several
polymers of brganosilicon compounds which had hydroxyl
groups a
t the silicon atom. It was found that in the
reaction of these compounds with metallic sodium, magnesium,
and aluminum that hydrogen was liberated and a metal
Card 1/2 ailoxane was formed. The reactivity of the siloxy-con-

The Reaction of Metals With Hydroxyl-Containing SOV/62-58-9- 9/26
Organosilicon Compounds
taining organosilicon compounds depends upon the re-
sistivity at these hydroxyl groups. Compounds which
enter into intermolecular condensation reactions easily
do not react with metals. On the other hard, hydroxyl
groups which are resistive to condensation reacti6ns
react relatively easily with metals. There tire 6 tables
and 4 references, 2 of which are Soviet.
ASSOCIATION: Institut elementoorganicheskikh soyedineniy Akademji nauk
SSSR (Institute of Elemen'0.-orgsnic Compoundsp AS USSR)
..SUBMITTED: FebruarY 5, 1957
Card 2/2

AUTHCRSe Andrianovo K. A., Corresponding Member 2o-ii&.6-21/43
of the AS USSR, Zhdanov, At A.s Asnovichp E* Z.

TITLE: On,the Synthesis of Infusible but Soluble Polymers
(0 sinteze neplavkikh, no rastvorimykh polimerov)
PERIODICAL'. Doklady kkademii Nauk SSSR,.1958, Vol- 118, Nr 6,
pp. 1124~.1127 (VIRSR).

ABSTRACT: ThOt, fusibility and solubility of polymers in organic solvents
are considered to be dependent on the molecular structur4a of
the chains. Polymers with a linear structure are soluble and
meltable by heating, rigardless of their molecular weight. The
branching of the chain, viz'. the formation of laced (pabit4u
structures and spatial structures makes the polymer lose-.
these.properties. This dependence concerns allpolymers, The
author3 tested the synthesis of pol,,~mers-which were readily
soluble'in non-lo'r slightly-oolar aolvents but which did not
malt, when: heated. The results obtained by thourough invostigas
tions-show that no polymers with the aforesaid propertins can be
obtained with the production of cyclic poly-organo-ailaxanes.
Card 1/ 4 A general composition of the polymers x which corm
(C05S'Olj5)

on the Synthesis of Infusible but Soluble Polymers 20-118-6-21/43
responds to a cyclic structure of the golecules) was proved
during the hydrolysis of phenyltrichlorosilane. Such po4mers,
however, are soluble in organic solvents and melt when heated.
A long lasting heating of the polyphenyL~siloxanes at 25ooC
and above.6'auses an increase-of the melting temperatures, but
the polymer loses its solubilityat the same time. The polymeric
molecule grows Apparently in first line due to bursting of the
rings and their polymerization under the formation of structures
which are laced, For increasing the melting-temperature -of the
complicated eyelid polyphenyl-siloxinem., aluminum was introduced
into the molecule of the polymer.Aluminum-siloxane reacts with
phenyl-trihydrox3r-silane by precipitating water. A further cons
densation at the cost of the hydroxyli-groups under formation a
polymer with a molecular weight of 599o, a content of hydroxyl-
groups of 5j5o/o And A ratio Si: Al 0 4,1. The obtained aluminum-
phenyl.-ailexaneeis a colorless,, brittlei vitreous substance which
does notmelt with heating up to 5ooOC and does not sihter either
(figure'l). It'is readily soluble in. benzene, toluene, acetone,
ethanol, chlorobenzehe and carbon tetrachloride, yet insoluble in
petroleum ether and -white spirit. Though the content of OH-groups
in the polymer decreases from 5,53 to 2,70/o with a heating at
Card 2/4 15oOC for lo hours (reference 1), its solubility remaini uno

On the Synthesis of Infusible but Soluble Polymers 20-1184-21/43
changed. Thesolubility in acetone is preserved also with
heating at 2ooOC for.4 hours, With an action of heat of 3oo0C
for 15 minutes, it is soluble in 850/o. in the case of a lonu
ger lasting heating at 2ooOC and with a 15 minutes lasting
heating at 4oo'and 5oocC, the solubility gets completely lost,
The constants and the chemical analysis (table 1) are given. An
empirical'formula.for.a term'of the concerned polymer is given.
A spatial structure of the polymeric molecule seerw impossible)
whereas such a term is a constituent of a complex cyclic or vo=
lumetric-polymeric molecule. Polvaluminun-ethylailoxane was
synthesized analogously. With equal properties as polyaluminum-
phenylsiloxane it does notLMelt with heating (figure 1). The
solubility of the former'in various,solvents at various tempen
ratures is shown in table 1. Polyaluminum-ethylsiloxane*loses
its solubility more rapidly. An experimental part with.usual
data follow
There are 1 figure, 1 table, and. 2references,
Card 3/4

50)
.
AUTHOR:
Zhdanov SOV/30-59-1-2 /57
Candidate of Chemical 9
%._
~
So on cats
TITLE:, Cratkiya soobshcheniya) Scientific Conference
News in Brief (I
.
on Organosilicon Compounds (Nauchnays konforentoiya po kremnty-
organicheskim soyadineniyam)
PERIODICAL:, Vestnik Akademli nauk SSS-Ro 1959, lir 1, PP 115 -117 (USSR)
ABSTRACT: The conference was organized by the Association of I'Jerman
Chemists in Dresden (German Democratic Republic), may
Scientists from the following countries
partiApated: the,German Democratic Republic, the German
Federal Republic, the USSR aad Czechoslovakia. R. MUller
(R. Myuller), (Dresden), director of the Institute for Organo-
silicon and Organofluorine Compounds reported in his opening
address on the increasing scientific and technical importance
of the investigated class of chemical compounds. F.Renglein
(Karlsruhe) spoke about the synthesis of polymers containing
groups the type of which is shown. G. Kolschtitter (Darmstadt)
Card 1/2~ dealt in his report with theinvestigation of'the surfaces

News in Brief. Scientific Conference on Organosilicon SOV/3o-53-1-29/57
compounds
of compositions which form In the case of processing hydrated
silicagel by the effect of trimethyl chloroeilane' The dele-
gates of the Soviet Union D. N, Andreyev, M. 0. Voronkov,
-A. A. Zhdanov, D. Ya. Zhinking N. S. Laznov, N. S. Nametkin,
V. A. Ponomarenko reported on papers which had been published
in Soviet'periodicals already at an earlier time.After the
conclusion of'the conference R. MUller received the Soviet
delegates and showed them the laboratories and equipment
of the institute under his direction. They also undertook
an excursion to Leipzigv Berlin and Potsdam which was organized
by the Association of German Chemists.
Card 2/2

5M-
A.UTHORS: Andrianov, K * Ae, A*j sov/62-59-3-13/37
Kazakovat A' A
TITLE: Synth Iesis of.New,Polymers With Inorganic Chains of Molecules
novykh polimerov a neorganicheskimi tsepyami molekul)
PERIODICAL: Izvestiya Akademii nauk SSSR. Otdeleniye khimicheskikh nauk,
1959, 11r 39 pp 466-471, (USSR)
A13STRACT: In thepresent paper some reactions of the formation of new
polymers with mineral chains of molecules containing aluminums
titanium,-phosphorus, and oxygen atoms were investigated.
By means of double decomposition ofsodium ethyl silanolate
with ti.tanium-tetrachloride as wellas'of sodium trimithyl
silanolate with titanium tetrachloride and aluminum chloride
.dodecamethyl-titanoxy-tetrasiloxane, dodecaethyl-,titanoxy-
and nonamethyl alumoxy-trisiloxane weresyn-
thesized. In the investigation of tho hydrolytic stability of
nonaethyl-alumoxy-trislloxane it was found that during hydro-7
lysis a simultaneous formation of polyorganosilylalumoxanes
polymers withthe elomentary group of the formula
-Card 1/2

5-0)
AUTHORS: Andrianov, K. Lot .507/79-29-4-53/77
Kazakova,Af, A.
TITLE; 'Synthesis of the Polymers With Inorganic Molecule Chains
(Sintez polimerov a noorganicheskimi tsepyami molekul).
I.Polyorganosiloxyphosphoaluminumoxans (I.Poliorganosiloksifos-
foralyumoksany)~
PERIODICAL: Zhurnal obahchey khimii) 1959, Vol 29, Nr 4, pp 1281 1284
(USSR)
ABSTRACT: In continuation of the preceding report (Ref 1) the investiga--
tions under review show that the polyalkylailoxyaluminum phos-
phates are.obtained V the polycondensation of the tris-(trial-
kylsiloxy)-aluminum with or ano-phosphosilicon compounds ac-
cording to schemes 1) and 2~. The nature of the resulting poly-
mere depends.on the nature of the organic radical in the sur-
rounding.trialkyloiloxane groups, By the condensation of tria-
-(triethylailoxy)-aluminum with triethylailoMhosphinic acid
or tris- (triethylsilyl)-phosphate at 200-2200 polymers were ob-
tained which changed to an unsoluble, not meltablet and solid
state above the afore-mentioned temperature. Under the same
Card'113 conditions solidp not meltable, and unsoluble products were

,Synthesis of the Polymers With Inorganio Molecule BOV/79-29-4-53/77
Chains. I.Polyorganosiloxyphosphoaluminumoxans
alsoobtained by the use of trimethylsiloxyphosphinic acid. In,
order.to confirm the scheme mentioned 2 mole of tris-(triethyl-
siloxy)-aluminum were condensed with 1 mol of triethylailoxy-
phosphinic acid.~In this way the condensation produot (III) Of
low molecular weight was obtainedl hexaethyldisiloxan6 and wa-
ter were eliminated in quantities corresponding.to scheme 2.
The analysis of the product corresponds to the formula given
in scheme 2. By the same condensation, which wasl in this casel
carried out with equimolecular quantities, solid polymers of
the composition
0
R SiO- -Al-O..P-0- lRdenoting H or SiR 'were. obtained.
3 3
Osin3 OSiR
Powder,,not meltable products which were, at the same time,in-
soluble in organic solutions resulted from the, condensation of
Card 2/3 tris-(trimethyls'iloxy)-aluminum with trimethylailoxyphosphinic

-5 (3)
AUTHORS I Andrianov, K'. --A. g, Odinetsy I. A01 SOV/79-29-5-21/75
...Zhdanov, A
A.
TXTLEt On the:Aeadtion.of.Acylatlon of A~ylaliphatic Disiloxanes:

reaktsii atailirovaniya arilalifaticheaki%h disiloksanov),'
(0
'Synthecis of Bis-(4#4Acatobentyl)-tetrfLmethyl-disiloxane
(Sintez bis-(4,4tatsetobenzil)-tatranatildisiloksaiia)
.:PERIODICALt Zhurnal obshchey,khimii, 1959, Vol 29, Ur 5,
~Pp 1499-1503 (USSIO
ABSTR.ACTt' The-authors concluded fro.m the forination of benzyl.methyl
chlord--silanes and acylation of b6nzyl-trimethyl silane that
. ...the Priedel-Orafte redotion,may, be sucoewifully Aprlied to the
ensyl alloxane,derivqtives in which the
synihesis of varldue.b
'
aromatio.nuolous is separated,from the silicon atom by the
methy1d'fie, group* ExperimieAts indicated,that berfzyl-dimethyl-
chloro~-Sllane is not destroyed in thepresence of aluminum,.
chlorido-and can be used as initial product for tho cynthenin
of ~is-(acetobenzyl)-tetrametliyl..~disiloxane. The benzyl-
4imethyl-bhloro silane was prepRred according to the Grigziard
reaction from dimethyl-diohloro-silane~ and benzyl magnesium
Card 1,13 chloride., The synt~etic,bio-(aoot-obenzyl)-tatramethyl-

-------------
On the Reaction 'of Acylation of.,Arylalilohatic SOV/79-29-5-214/75
.Disildxanes. Synthesis of,.Bii-(4,4-Acetabonzy~)otdtramethyl-disiloxe-ne
disiloxane.has the properties of. aliphatic-aromatic ketones
and - f o'rm a'the dinitro-phonyl hydrazone In which case the
Teaction!proseeds via both onrbonyl-qr9ups. On oxidation of.
the bia-(acetobenzyl)-tetramothyl-disiloxane with sodium
%,yVobr0mid4 in alkali, the toluic 'acid is fornea Which'irras
-ot'its mothyl enter. A comraratively
idebtified in1he form
easy'separation of.the benzyl carb6xy-trroup is connected with
the'displace-ment of the reactivity in the sy3tem of the
.,oonjueated nuclear bondaft.In consequence of it-a decieaae of
-the elQctron density on the.silicon nucleus and subnequent
rupture of the Si-c-bond-takes place under the influence of
nucleothific agents ~ When -using, alkaline 'T)o+,asziu:,i solution,
the~oxldation is complete,an.d.tere~hthalic acid is formed. The
formatibn'of t~e p.;-toluic and-terephthalic acid indicates
that1h4.aceto-groupcomes into para-position with respect to
the methylene gtoup durinC the Prieael-Crafts reaction.
Properties of the compounds synthenized are given'in the
table., There are I table and 6 rdfaroncesp 4 of which are Soviet,
..Card 2/3

50) SOV/79-29-8-57/81
AUTHORSt Andrianov, K. A.,-Odinetsq V. A., Zhdanov, A. A.
TITLEt On the Acylation Reaction of the Aryl Aliphatic Disiloxanes.
II. Synthesis of Silioon-organic Aromatic Ketones and Di-
functional Kletooarboxylia Acids
PERIODICAL: Zhurnal obehohey khimii, 1959, Vol 29, Wr 8,
:pp2
7o2 27o6 (uSSR)
ABSTRACT
t As the authors showed in a previous paper (Ref 1), benzyldi-
. methylahlorosilane easily reacts with acetic anhydride~in
the presence of AM while bis-(4-acetobenzyl)-tetramethyl-
3
disiloxane is-formed with a yield of 50%. In the prese nt
.. .paper this reaction was used in the synthesis of.silicon di-
carboxylic-acid and aromatic ketones. Benzy1dimethylehloro-.
silane and the acylating compounds (succinic acid - phthalic
anhydride and benzoylc~loride) were used as a basis (Scheme 1).
-By means of the reaction the best yield was achieved in a
benzene medium (50-60%).,The acylation of benzyldimethyl-
chlorosilane with benzoylchloride leads to the aromatic di-
Card 1/2 ketone according to scheme 2. Bis-(benzoylbenzyl)-tetramethyll-

pn the Acylation Reaction of the Aryl Aliphatic Diailoxanes.SOY/79-29-8-57/81
II~ Synthesis of Silicon-organic Aromatic Ketones and Difunctional Keto-,
carboxylic Acids.
disilo,xane was-preoipitated (40%). It forms easily the di-
nitrophenylhydrazon.e which contains 11-44 % nitrogen, and
thus indicates-the presence of two ketone groups in themolecule
of the synthesized,compound. The molecular refraction of this
siloxane was found to be 4 units higher than that cf E. Warrick
(Ref 6).(A. Do Petrov (Ref,5) found it to be higher by two
units in 4-substituted silanes with one group). The data ob-
tained.show,that the acylation of benzyldimethylohlorosilane
is also possible 'with the anhydrides of the dicarboxylio acids
and the acid,ohlorides~of the monocarboxylic acids without
a noticeabledestruction of the compounds taking part in the
reaction ,under the influence of hydrogen chloride ' The pro-
perties of,the compounds obtained are given in the table.
There are I table and 7 references, 4 of which are Soviet.
ASSOCIATIONt Institut elementoorganicheskikh soyedineniy Akademft nauk SSSR
(Institute.of Elemental.Organio Compounds of the Academy of
Sclences, USSR)
SUBMITTEDt July 11, 1958
Card 2/2

SOV/80-32-2-52/56
'AUTHORSt Andrianov, K.A.79 Zhdanovp A.A## Kashutinal E.A.
~'TITLE:. 'Synthesis of Derived Molecular Di(triethylailoxy)-Lead With
Lead,Hydroxide and Its Interaction With Titanium Tetrachloride
ASintez molekulyarnogo proizvodnogo di(trietiloiloksi)svintsa
a gidrookii1y.u evintsa i yego vzaimodeyetviye is chetyrekh-
khloristym-titanom)
PERIODICALt Zhurnalprikladnoy khimilp 1959, Vol XXXII, Nr 2,
PP 463-464 (USSR)
ABSTRACTs During.the development of new methods for the synthesis of
trialkylsiloxymetals of the general formula (R,SiO) aosynthesis
for tetra(,trieihylsiloxY)titanium from di(trie hylsil xy)-lead
and titanium tetrachloride was found. The various steps of
1he-experiment are described.
.1hers, are 3 referencesp 2 of which are Soviet and 1American.
SUBMITTEDs ;ApAl 24, 1958
.Card
a

(2,3)
''AUTHORS: 'Andrianovp X.4j,:0orreaponding Member sovI26-i26-6-3216(
AS USSRp Zhdanov A, Aty Kashutinaq E. A.
TITLE; Synthesis of Triethyl Siloxy Derivatives of Vanadium and
Antimony (Sintez trietilailoksiproizvodnykh vanadiya i surfmy)
PERIODICAL:. Doklady Akademii nauk SSSR, 1959, Vol 126, Nr 6,, 'pp 1261 1263
US. R)
ABSTRACT: Among the syntheses for the produotion of compounds of type
ency of the netall which,
Meb wheren denotes the val
(R Sio)
.
, n
'
are known at present# the interaction reaction of the
trialkyl
silanolates of sodium and of some other metals in of speoial
interest (see scheme)..These monomers have an Si-O-Me bond and
the.synthesis of polymers which have alternating metal or oz-
ygen atoms in the main chain is direatly conneoted with their
synthiaia. By the method, illustrated by the above schemev the
authors synthesized for the first time the following compounds:'
a) tetrakia-(trimethvl-,ailoxy)-titanium (Ref 1)1 b) tetrakis-
trakis-(tri-
-(dimethyl-phonyl-ailox )-titanium (Ref 3)j c) t
y
ethyl-ailoxy)-titanium (Ref 2), and d) tetrakis- triethyl-ei-
7

-Card I loxy)-tin (Ref 2). In the present paper the above mentioned

Synthesis of Triethyl,,Siloxy Derivatives of Vanadium SOY/20-126-6-32/67
and Antimony
metood was further developed forthe synthesis mentioned (000
schemee).'The experiments carried out.produced yields of 60-
70A 'of the 'theoretically possible yields. The lead-triethyl-
-ailanolate (Ref 4) showed a considerable reactivity: by the ao-
tion.ofl titanium-tetraohloride or of II vanadium oxychloride
on its complex compound the following was formed: I Tetrakis-
-(triethyl-ailoxy titanium or II trio-(triethyl-siloxy)-vanao~
date (see schemes~_. These reactions which were investigated by
the authors with respeet.to the titanium-tetra- or vanadium-
-oxychloride, are,of general importance for the production of
trialkyl-ailyl-derivativea of various elements. The investiga-
tions of the infra-red spectra of some of the compounds-synthe-
sized (by N. *'Gashnikova in the Vaesoyusnyy elaktrotekhnicheakly
institut im. V. I. Lenins, - All-Union Electrotechnical Insti-
tute imeni V. 1, Lenin),proved the characteristic oscillation
frequences of V008i(c H ))3 which are mentioned in the papero
2 5
''Tablell shows properties of the materials synthesized among
others also of tria (triethyl-ailoxy)-stibine. There are I
rd 2/3 table and 4 Soviet ;eferences.

International Symposium ou maormajecul" CA4012tky.' !"Fow.
1960.,
lakulyarnay kniall 33M.
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ly-
PURP=s This book is intendbd for chemists Interested Irk PQ
the synthesis or b140 molecular
mertzation reactions and
couna, =a is section nx or a nuitzvoucae work contain-
US Pape", an xftcx locular chemistry. The ArUcl*& In
ven*ral deal with the kinetics of polyzerIzation reactions.
the anthaglig of polymer*, *.S.. ton ex-
Change realms, r materials, etc., methods of car-
a2yzIng polym satlan "aations, properties and chemical
Interactions of blo molecular materials. 'and the'arrocts or
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:3~ _V10, articles.
7
ikov, and S. S. Medv*dev
v ~ koih v .0 A ---
R~ zir~& ortW A41d and"P-or= on 4=-Vre
Cadatloo of Aydrocarbons and Aydrocarbon Polymer* 364,
Zoacy- 7 V.. and D_ KU;q-v::2*Z (Mn). ZZ047 of the
a., 36-ma organio Ortanoolomental Compounds an
the Thormal Degradation or Polyvinyl Chlorldo 372
Z. uttler, and P. &relsn (Czechoslovakia).
ly-E-Cagrol"tan an a Result of Ex-,
Ch4ants, GaCtIO12 Between A&Lds Boa" 380
Neutralization or Residual Catmayst " Polydiwtkar ljajox=e;
Effect Of Thermal Neutroalzatloo an the Therms' 3tabillty or
the Folvmr VtR
7-
TA&r%oo=a&cxoaa! DegraAatlon or Polyesters. 3tudy or De.
trodation R"ations ror Difrgrect Types of Ljng&r Polyesters 4"
IE92 ~M_ B. 17 1.dvanzov
"lose --Poly"r C mazens" 414
L; 0. In-vestisation
51-M-EfrZolt"y of Inn'bitarm or Rubber =4atloo at Varl-
T1119 Wgn-k'ang (UM). Sech".jan *T __
the, Prozeetiv Action of Benzene 111nex During the Radio-
:
of PQlj
t7 433
and A. 1~r~-_v (UMA). On Lhe Eydro-
.y or
f lymers With
Zmarganic
and CO. 1. 'Vo,
opolynal
tIcp Durlog.the fretclas or $t Solutions 334
and U_A=9X_(VSV).
1
W
M
M
l
E
I
1. of A A.
.-f C. lulase, by :ft%ft1nd 344

67947
SOV20-130-1-2q169
AUTHORSs Andrianov, K. A.9 Corresponding Member AS USSRa Zhdanov, At A"
:Odinetag Yo As
TITLEt Chloromsthylation~.f iryl-aliphatioDielloxano6. Synthesis of
Uh
l -
oromethylbeni Idimethyloblorosilans and Its Derivatives
PERIODICAL: Doklady Akademii,~auk,-SOSRj, 19009,Vol 130g Nr I pp 75-78. (VSS10
ABSTRACTs The authors proved that 'the chloranethylation. of the bentyl group
'
aasefully used for thesynth4sis
bound,io -,aili4o-n can 146 4ue
mentioned inf'.the,oubtitlejese Scheme). This reaction proceeds
well in fuming,hydroohlorio.aold. Paraform ia used as an agent of
ohl6rgmethylation.,.Tbe.ohl.bromethyle6tion in the presence of zinc
t~
6hiorl ,do-ia'aQcompar4ed by,~secondary processes. They form viscousl

yl-!-methane g ups (see
noxidiaitillible pr4duqte,coataiping.diphen ro
86b'ome)~.I'Tb~.le6lation,.')Ot-,Purb~chlo:comethylbenzyldimethylehloro-
silani from the rie"adtion, mixture was',atta'Jued'by hydrolysis with
excess"Wator'whilotho Ajoilorane',mixture was oplit by strong
sultUtio'a6id~,in
,thel;~rerjeiioe of,ammonium chloride (see Scheme).
.
The'tqtal'yield ~n~ohloromethylberzyldimethylehlorosilane was 60%
of 'the benzyldim4thylohlord'silans reacted, and 30/; of the qilantity
used respectively. Direct;fractionation of the chlorqmothylation
,
Card 1/2 vacuum delivered sm"aller.
produots purified with ~watsr.in~ the,

- ----------
Chloromethylation of Ax7l-aliphatic Disiloxanne. BOV/20-130-1-20/69
Synthesis of Chloromethylbersyldlnethylohlorosilane and Its Derivatives
yields.,The end product obtained had all pro.?erties of the
alkylohlorosilane halideo. By bydrolysis with waterp it readily
forms,the disiloxanea Bis-(chloromethylbonsyl)-tetramethyldi-
siloxane was isolated as a consequence of this reaction ( see
Scheme). By the action of potaselum acetate on this latter
substance in aa6tio-medium, bie-(ace,3*xymithylbe~l)-tatramethyl-
disiloxane was formed. On hydrolysis of the latter compound# the
JK
acetate group is split off. In the first 'stage, bis-(oxymethyl-
benzyl)-tatramethy1disiloxane develops which aftaiwards decomposes
by the catalytic aotion of the alkali during distillation. Toluyl
methanol and polydImethylelloxanes with functionai and groups as
shown in the scheme are probably formed. Table I shown the
properties of the nubatanoes syntheetzed. A.V. ToDchivey and
X. S. Nametkin are mentioted in the paper. There are 1 table and
8-iaferenoes, 5 of which are Soviet.
September 30, 19W
Card 2/2

87861
S/191J60/000/005/007/020
Ito B004/BO64
AUTHORSt Andrianov, K. A.t Zhdanov, A. A., Baksheyeva, T. S.
11 -------------
TITLE: Synthesis of Organosilicon Oligomers Containing Oxyphenyl
Groups
PERIODICALs Plasticheskiye, massy, 1960, No. 5, pp. 18 21
TEXT: Aim of the -13resent study was the synthesis of organosilicon pol-
H
H
3
ymers with end groups of the following structures -0-9 0 OR.
3~
iH
H3
Synthesis was carried out in.two stages. First, organosilicon oligomers
with butoxy end groups were.produced. They were reacted with dihydroxyl-
diphenyl propane. Phenyl-tributoxy silane, phenyl-methyl dibutoxy silane,
and dimethyl-dibutoxy,.ailane were the initial compounds used. They
resulted from esterification of the respective chloro silanes. The
oligomers with different degree of polymerization were produced by partial
hydrolysis. Hydrolysis of I mole of dimethyl-dibutoxy silane with 0.5 moles
Card 1/3

47881
Synthesis of OrganosiliaonMigomers 3/19 60/000/005/007/020
Containing,Oxyphenyl aroups B004YB064
of water yielded, in the.presence of EC1, the dimer in a 73 % yiold.
41moles of dimethyl-dibutoxy.silane yielded, with ~ moles of water,
41:0etramiers 50 % hexamer,wai obtained from 6 moles of dimethyl-dibutoxy
silane and' '5 moles o.f water. Partial hydrolysis of 1 mole of phenyl-
tributoxy sflan; with 11 mole of water gave an 66 % yield in polyphenyl-
butoxy siloxane on heating in.the presence of HC1. Phanyl-met-hyl dibutoxy
silane was polymerized in'thesame w*ay, but, in the presence of NaCH.
Thecomposition determined by equationA - nAn - m) was confirmed by
elementary analysis (A - number.of silicon atoms in the polymer chain,
n number of-moles of the substance subjected to hydrolysis, m - number
of.moles of water used for hydrolysis). The oligomers with butoxy end
groups were reacted, in the presence of Na- or Al butylate, with
dihydroxydiphenyl propane. The, ratio of components waa 1sI. 1--n-butoxy-
polydimethyl siloxane yielded a polymer with the degree of polymerization
246,- 1-n-butoxy-polyphenyl-methyl siloxane gave a polymer whose dogree
of.polymerization was 2468. Determination of the butanol set free during
the reaction showed that the reaction proceeds up to a yield of 80
The resulting organosilicon compounds which contained the end group
Card 2/3

~/190/60/002/007/011/017
B020052
AUTHORSt Andrianov,.K. -A.O~Zhdanov, A- A,
TITL.Ht Inv.e stigation of .the Polymerization of Polyorganobiloxanes
Under the Influence of Polyaluminum Ethyl Siloxanes
PERIODICALs Vysokomolokulyarnyye soyedineniyat 1960, Vol, 2, No* 7t
PP, 1071-1076
.'TEXTs Theauthors foundthat poly'aluminum organosiloxanes reduce the re.
action:time of thepolymerization of polyorganosiloxanes obtained from
trifunctional, and bi- and trifunctional monomers. The reaction time of
the polyorganosiloxane polymerization in dependence on'the-amount of the
polyaluminum organosiloxane 'introduced, was investigated to explain the
rules governing the above polymerization, Polymers produced by cohydro-
lysis of methylchloro silane and phenyl trichloro silane, methyl tri-
acetoxy silane, and phenyl.acetoxy silane (polymer 1-A were used for
this,investigation. Polyaluminum siloxane A_ 16 (Refo 1~ was used as
catalyst. Table I gives the 'tharacteristice of the polymers used. Fig.
Shows the dependence of the polymerization time on the amount of the
Card 1/3

Investigation of the.Polymerization of Poly- S/190J60/002/007/011/017
organosiloxanes Under the Influence of B0201BO52
:-,Polyaluminum Ethyl,Biloxanes
added polymer A-160 Already with.0.5~ of the polymer A-16# a considerable
reduction of-the polymerization time was found*:Pige 2 shows the dependence
of the polymerization time of a 99% mixture of 1- X (I-Kh) and 1% of A-16
on the amount of dimethyl aniline and pyridinet respectively. Tho amount
~of the tertiary amine addition also reduoes the polymerization.time of the
polymers 1-Kh and 1-A (Figs- 4,5)- For the evaluation of the maxims of the
curves shown in Figs. 2 and 3,'the molar ratio between tertiary amine and
aluminum in the mixtures invehtigat6dp:.wds calculated for points cor-
responding to the maximum value of the polymerization.time (Table 2), The
maximum polymerization time in all cases approximately corresponds to the
equimolar ratio between the amount of the amine addition and the aluminum
in the polymer molecule. The mechanism of the interaction between poly-
aluminum ethyl siloxane and the organosilicon. polymer was explained by-
the data obtained. Finally#,the syntheses of poly-mars 1-Kh,' I-Ap and A-16
are described. Their elementary composition is given in Table 1, The de-
.termination of the polymerization time is also described, respective
results being graphically presented in Figs, 1 to 5. There are 5 figures#
2 tablesp and 1 Soviet reference.
.card 2/3

3/661/61/000/006/051/081
D235/D302
AUTHORS: Zhdanov, A.: A,and Andrianov, K. A.
----------
TITLE: Polyorgano-mbtallo-siloxanes and polyorgano-siloxy-,me-
talloxanes At_
SOURCE. 'Khimiy i p,rakticheskoye primenoniye kur onn e o,~ jani c he s-
soyedineniy; trudy konferentaii, no. 6: Do1clady, K
diskuseii, reisheniye. II Vses. konfer. po khimii. i
p krei~neorg. soyed., Len. 1958. L(.,nJn6rad
rakt. prim. -
Izd-vo AN 8SSRI 1561 220-224
'oVe
TEXT A d'i se ssion of-the a
3' u
paper (this publicoti on, no. 2
1,00)-between:the.author's and N. P. Orlov (IKhS All 33SR,
grad) , S. ~.X. Borisovi(VNIISK~~Leningrad) and M. G. Voronko*v (MiS
AN SSSR, Leningrad). The following points are di.9cassed- Thernol
and hydrolytic stability of the bonds silicon-oxygen-mattal; intro-
duction of the elem nts magnesium and zinc into the siloxane sttruc-
e
ture; the formation. of oly-diethyl-alumina-siloxane; reazons for
p
riors;
..the-increase in thermal stability obtained by the aut. thermal
Card 1/3

S/661/61/000/006/051/081
Polyorgano-metallo-siloxanes ... D235/D302
and hydrolytic stability.of poly-org'ano-titaniurq siloxanes. The
thermal stability of the bonds Si-.O-M is fairiy hi,,h und a co=pound
tj
h as (R'SiO )Ti is h dr lized only,very slowly by water. Tiagllle-
SUO Y 0 kJ
reactYllie aluminum with hydroxyl containing silicon compounds
to give hydrogen and the siloxane polymer containint, maoe-,, m. Re-~
0 Au,
ference is made -to a patent.by Viberg and Katnslav whera poly-di-
ethyl-alumina-siloxane is obtained by reacting. the metal %-.rilth di-
ethyl siloxane at 3100C; the authors only obtained a 1.5 - 2c.-
yield
~by such abreaction. Alkaline hydrolysis of dimethyl-siloxane with
-aluminum chloride in the.ratio ~Si-Al of 3:1 to 45:1 leads to the
..formation of gel-like polymers and in the ratio Si-Al of 60:1 to
100:1 to +1 ibbers,
co-polymere similar, o poly-dimethyl-siloxana rt
but the exterior is~frequently.gummy. Thermal stability of poly-
organo-titanium-siloxanes is.considerably higher than for the alu-
minum compounds. The bond -Si- 0_'Ti has higher thurr,,.al :jtability than
the compounds'with a siloxano bond due to the offect of oxygen on
Si-C'under the.actibn of titanium. The hydrolytic stability depends
on,the nature of the radical connected to silicon and the molecular
structure. Derivatives from elements of group V possess the greatest
Card 2/3

S/079,/61/031/001/018/025
T.18114. 24019 B001[B066
AUTHORS: Andrianov, K. A.,,Zhdanovt A. A-j Khanat%shVill, L. It., and
Shapatint A. S.
'TITLE: Reactions of Aluminum Isopropylate With SomeOrgano-
phosphorus Compounds,
PERIOPICALs Zhurnal obshohey khimiij 1961, Vol. '.31 ,No. 1, pp. 224 228
TEM The authors studied the,-zreaction of aluminum isopropylate with the
acid chlorides of meihyl-m-cresoxy phosphinic acid and dimethyl phosphinic
acid, in order to use them as initial products for the synthesis-of
polymers with inorganic molecular chains. One of the initial organo
phosphorus compounds, the acid chloride of methyl-m-cresoxy phosphinic
acid, was obtained by reaction of methyl phosphinic acid dichloride with
m-cresol at 120 - 1400C, 0
CH Ll + m CH C CH P Rol (1)
3 2 3 6H4OK .3
CH M
4 3
Card 1/3

81484
Reactions of Aluminum Isopropylato With Some S/079/61/031/001/018/025
Organophosphorus Compounda BOOI/BO66
As by-product,leonsiderable'quantities of di-m-oresyl ester of methyl.
phosphinic acid Iare-formed. Higher excess of the diohloride of methyl
phosphinic acid gives a larg 6 yield of the chloride of mothyl-m-cresoxy
phosphinic Acid and a low yield of the afore-mentioned by-product. The
reaction of the chloride of:methyl-m-cresoxy-phosphinic acid with
aluminum isopropylate was expected to proceed according to the following
equation:
0
C1 ;H
C H + WOO H iso (i-C3H Al-O-P\ 3
3 \,,OC~H CH 3 17 C3H7Cl + 70)2 dc H CH -M
4 3- 6 4 3
However, in.addition.to isopropyl chloride, also the isopropyl-m-cresyl
ester was separated.which Islindicative of side reactions. At an elevated
reaction temperature (140 - MOO still more complicated compounds
resultedl which renders the separation of individual reaction products
very difficult. To confirm the assumption on the course of reaction,
tris(methyl-m-cresoxy-phosphinoxy)aluminum was synthesized. The reaction
was carried out at'90 - 1000C to avoid separation of the cresoxy group.
Under these conditions, tria(methyl-m-cresoxy-phosphinoxy)aluminiim
resulted in a yield of'59 isopropylehloride in a yield of 67 which.
Card 2/3

Reactions of Aluminum Isopropylate With Some 3/079/61/031/001/018/025
Organophosphorus Compounds Booi/Bo66
oonfirmed~the predicted course of reaction. The reaction of dimethyl
phosThinio acid with aluminum isoprop ylate takes place according to
equati n (5): 0
POH + (i-C 3H70)3Al (1 -03 H7 O)2Al-O-P(CH3)2 + i-C 3H7 OH.
This is confirmed by a,,nearly quantitative separtiion of isopropyl alcohol
(99'%). According towultimateanalysist the product distilling from the
reaction mass-at 1640C corresponds to dimethyl-phosphinoxy-(diisoprbpyl)
aluminum which is conta.minated. The vitreous,, colorless product is soluble
ill common aromatic solvents. G. B. Ravich and I. F. Manucharova are
thanked for their cooperation...There are.1 figure,and 10 references:
Soviet,2 British# 2 German, and TCzech6slovakian.
ASSOCIATION: Moskovskiy institut tonkoy khimicheskoy tekhnologii
(Moscow Institute of Fine Chemical Technology)
SUBMITTED; February 20, 1j60
Card 3/3

31193
S/079/61/031/012/007/011
D258/D301
~AUTHORS: Andrianov, K. A., Zhdanov,- A.A., and Odinet8, V. A.
TITLE; The addition of aromatic derivatives to vinyl methyl
diohlorosilane
PERIODICAL: Zhurnal obahchey khimii, v. 31, no, 12, 19619 4033-
4038
VEXT,.- The authors showed that.theaddition of either berzene, to-
luene, chlordbenzeneor diphenyl to vinyl methyl dichlorosilane
yields the corresponding (0-aryl ethyl)-methyldichlorosilanes and
also a higher boiling by-product; ArH + OH2 - CHSi(OH 3)C12
A101
.;3.ArCH2 CH2si(CH 3)C1 2 ... (1). The by-product was isolated in
the case of benzene and identified as bie-(2-dichloromethyl silyl
,ethyl)-benzenet formed on further reaction of the primary product
with a second molecule of the silane:
Gard 1/3

311913
3/079/61/031/012/007/011
Th-e-addition of aromatic D258/D3O1
A101
C H CH CH Si(CH )Cl + PH CHSi(CH )C1 1
5 2- 3 2 3)S'( 02, 2
6 2 2 3 2 2( CH
C H (2)
6 4
The primary addition products were converted to the corresponding
silane diols by acetylation with CH COOK and subsequent hydrolysis.
The infrared-a ectra of all these diols confirm the presence of
1258 cm-
Si-CH groups of..an aromatic nucleus and of SiOR
.,groups-(830 - 880 cm The authors conclude that the phenyl com-
pound adds on in the B-position (with respect to Si). The syn-
theses ofthe primary addition products are then described: The
melting points of the benzene,"toluene, chlorobenzene and di-
phenyl derivatives were 80-81, 709 89-919 and 132-1346C reapec-
tively. There are 4 figuresi 1 table and 3 references: 1 Soviet-
.bloc and 2 non-Soviet-bloc. The references to the English-language
publications read as.followe; G. H. Wagner, D. L. Bailey, A. H.
Card 2/3

37775
5r I 1 10. S/661/61/000/006/0613/081
D247/D302
AUTHORS; Konstantinova, N. G., Zhdanov, A. Andrianov, K.
Sharov, IA. Ya., Kyutnd-T-;, M7 Wo 4ainid~Zzakharov, A. A.
e 1 cquer coatings based on silico-organic,
TITLE Thermostabl a
polymers
SOURCE: Khimiya i prakticheskoye,primeneniye kremneorganiches-
kikh soyedineniy;l,trudy konferentaii, no. 6: Doklady,
diskusaii, resheniye. II Vses. konfer. po khimii i
prakt. prim. kremneorg. soyed., Len. 1958. Leni,ngrad,.,-
Izd-vo 'AN SSSR119619 296-299
TEXT: Astudy was made...of the thermostability of several lacquer.-
painted materials on the basis of different film-forming substan-
ces. The silico-organic resin K-47 was modified by the use oforga-
nic polymers to give a hard I oold-drying coat of increased thermo-
stability. The metallic Isurface and its preparation was found-to-
have a great influence on thq~adhesion, the protective properties
and the thermostability of the coatings. In the discussion, the
Card 1/2

61/138/002/020/024
2209
B103YB220
AUTHORS: Andrianov, K. A~ Corresponding Member AS USSRp and
''Zhdanov A.4.'
TITLE: m r
Polyoondensation as a ethod of p oducing polydialkyl
6116xane and polyaluminum dialkyl ailoxane elastomers
PERIODICAL: Akademiya nauk,SSSR. Doklady, v. 138f no. 2t 1961, 361-362
TEXT: A new.mathod of synthetizing polydialkyl siloxane elastomers having
chains is discussed. It is based on the polycondensa-.
tion of bi-funational oligomers with bi-funational silicoorganic monomerso
This prooese-takes.plaoe in 2 stages: 1) production of oligomers by the
known methods (see diagram no. 1);~2) polycondensation or heterofunctional
polycondensation of the monomers produced, whereby elastomers of high
molecular weight are.formed. Of the elastomers having inorganic principal
chains and.framing organic radicals only polydimethyl siloxane elastomers
including modifications are known. Up to-the present, it has not been
possible to produce e 'lastomers by hydrolysis and polycondensation or by
heterofunctional polycondensation of different bi-functional monomeral the
Card 116

8/020/61/138/002/020/024.
Polyodndeneation an a method of producing..* B103/B220
side reactions caused the formation of linear as well as.oyclic products.
The characteristic of the:method described by the FAuthore in based on the
faot,that in the.two-stage process mentioned.the formation of cycles of
low,molecular weight in the final stage is impossible., The oligomers
subject to polycondensation have suoh.a degree of polymerization that ring
formation becomes Impossible. From elaBtomers produoed by this method)
types of rubber can be produced by vulcanization, which have properties
analogous tothose of standard,polydim6thyl siloxane rubber. Furthermore,
the authors Ptated that differently~high polycondensated a,&)-dihydroxy
polydimethyl siloxanes undergo:the following reaotionu, whereby linear
..~,polymers are formed with atoms of aluminum, titanium, or boron in the in-
organio,polymer chain-, aluminum:butylate gives VCH (0C Hq) 01
3)25'0128[A' 4
with a molecular weight.of 30000; tributoxy boron given
-[(CH 3)2S'0335 [B (0C4 H90 molecular weight-,34000i tetrabutoxy titanate
gives L(CH H ) 01 Dependent on the functional end groups
3)ZS'01351~'_(004 9
ofthe oligomerat thepolyoondensation can proceed with formation of
various products of low molecular weight (see diagram no. 2). The
'Card 216

~3/020 MIJ8/002/020/024
Polycondensation as a method of producing... B103 B220
Polymers produced by the~authore are-elastic solable substances with a
molecular weight of 100000,to 2,00000. Those having a metal atom in the
chain are highly reactive due to the retaining of the functional group,
atthe metal atom.' The rubber ma:terialop thus obtained, are similar to
those produced,from polydimethyl siloxanes, but have still better
Propertieea'- aqw-dichloro polydimethyl siloxanes were produced bythe
abovementione,d"Methodes K. A Andrianov,:V. V. Severn B G. Zavin
41 Izv. AN SSSR, OKhNj being printed)$ Cl[(cII ~'S'ioj Si (CH
3 2 41 3)2C'
Therefrom,-.oli produ
gomers were ced with siloxane chains of various lengths
~.from which a,io-dihydropolydimethyl siloxanes.were obtained by hydrolysis.
'These siloxanes were produced equally from dimethyl diacetoxy siloxane.
Mention is made of white soot Y-333 40 (U-333 40) and of the method of
determining.the molecular weights by Terentlyevy which isp however, not
explained in detail. The polymer L(C6 H)(CH )3iOAl (00 H9) 0]. was
5 3 4
produced from phenylmet.hyl diacetoxy.silane with aluminum butylate. There
are 1 table and 5 referenoess- 3 Soviet-bloo and'2 non-Soviet-bloo. The
1,tworeferences to English-language publications read as follows: Ref. 2s
J. P. Hydey J. Am. Chem. Boo-P 75, 2166 (1953); Ref. 31 T. Takiguchil
Card 3/6

23837
3/020/61/136/002/o20/024
Polyoondensation as a method of producing.#. B103/B220
Bull. Chem. Boo. Japan, 32, 556 (1959).
..ASSOCIATIONs Institut.elementoorganicheakikh soyedineniy Akademii nauk
SSSR:(Institute of Element4l-organio Compounds, Academy of
Sciences USSR)

z--4
S/06 61/000/007/0C4/009
-'t' 17 0 2521h BI 17YI3215
AUTHOR,t Zhdanov, A. A#O,Andrian6vp K& A.# and Bogdanova, A. A,'
TITLEs Reaction.of aluminum chloride with dialkyl oyclosiloxanes
PERIODICALs' Akademiya nauk SSSR. Izvestiya. Otdeleniye khimicheskikh
nauk, not-7s' :1961t 1261 1266
TEXTt -The.interaction of aluminum chloride with dimethyl- and diet4yl
eyblosiloxanes was investigated in a study of the methods of producing
polyalumo-organ.osiloxanea#. Alflask with mixery thermometer# rooooler, and
cooling vessels for collecting thereaction produot.e. were used for-the
experiments. It was found that aluminum chloride riaote easily with
dimethyl- and diethyl cyclosiloxanes at equimolecular.ratios. Crystallino
reaction products are formed which.are quantitatively sublimated in vacuo.
In the'examinationof the reaction mixture obtained by reaction between
t
00trethyl oyclotetraoiloxane and aluminum chloride (mixing 'iMe I10 hr at.
120 C), the following reaction ProductSrW8re is8latedt 1~3-diohloro
tetramethyl disiloxane# boiling point: 32, 360C ~10 mm IP5-dichloro
trisiloxaneg boiling point, 72 75 Go 10 mm 197-dichloro
octamethyl tetrasiloxane, boilingrpoints go - 95 C 10 MM)l a
Card 1/4

S/062/61/000/007/OC4/009
Reaction of aluminum chloride ... B117/B215
crystalline substance, boiling points 152 0 153"C, of the empirical
composition 0 H- 0 C1 Si k1 The formation of theae products in the
e 24 6 , y 4 3'
reaction mixture followed the scheme
2 [(CIr +3AlCl --)G H 0 01 Si Al + 2C I Si 001
3)2B'01 4 7 3 -8 24 6 5 4 3 4 12 2 2
The crystalline substance-of...the above empirical formula showed a constant
composition in repeated sublimation. On the basis of analytical data and
studies it may be assumed that the respective substance contains,
a complex,aluminum.ohloride molecule. The reaction between alumigum
0
chloride and hexamethyl cyclotrisiloxane (mixing times 6 hr at 50 - 60 C)
is similar to the previous one, with the only difference that besides the
crystalline substance also dimethyl dichlorosilane and highest ato -
dichloro poly.siloxanes.are.formed. This process may be expressed by the
scheme 2 [(CH + 3 A101 C H 01 Bi Al + 2C H Biel
3)2S'O1 3 3 - 8 2406 5 4 3 .2 6 2*
Similar ethyl derivatives were isolated in the reaction between alum num
chloride and oo'taethyl cyclotetrasiloxane (mixing times 11 hr at 120~ C)
Card 2A

25214 8/062J61/000/007/004/009
Reactionlof aluminum chloride B117/B215
13-diohloro.tetraethyl,,dioiloxanej boiling points 85 0 - 9009 00 mm),
0
1:5,dichloroboxaethyl tribiloxanet boiling points 124 - 131 C (10 MM)l
0 0
Ig4-diohloro octaethyl tetrasiloxanes boiling points 131 C 145 C
(10 mm); a crystalline substance which is sublimated at 225 6a - 2330 CS
melting points 112,'C (unstable), of the empirical composition
C H 0 Cl Si Al . The stritntures of.the crystalline substances are
6 61n5
811miloar . both.hses. An icienticalo crystalline substance of the
above composition and highest polydiethyl siloxanes were obtained in
the reaction between aluminum chloride and hexaethyl cyclotrisiloxane
(mixing time, 5 hr at 8000., Conclusion: Rupture of the cycle takes
place in the interaotionlof aluminum chloride and the above cyclic
dialkyl siloxanesq and a-chloro- W-dichloro alumoxydialkyl polysilox-
anesare formed. The latter then separate ajW -dichloro polysiloxanea
and form cyclic compoundes.1-chloro-313i5,5-tetramethyl cycloalumo-
disiloxane and 1-chloro-30,5,5-tetraethyl cycloalumodisiloxane.
These compounds werelioolated and characterized in the form of com-
plexes with aluminum chloride. There is I non-Sovist-bloc reference.
Card 3/4

KORSHILK, V.V.; VINOGRADOVA, S.
-V.j FRUNZE, T.M.j GRIWVAp I
ZHDANOV A A MOZGOVA''K.K,.,- KRO14
i 0 'GAUZ) Ye.S., red.izd-va,-
VA S' khn.red.
17MMIRO P *G. to
[Chemistry aid technology of synthetic macromolecular.compoundes
Haterocyclia'~4*pounds],.'Khimiia i tokhnologiia sintatichaskikh
Vy8ok=olsku1iarnykh soedinenii. (1,eteratsepnye soedineniia;
Moskva; Izd-vo Akad.nauk SSSR. 1940 721 p. (Itogi nauki:
Khimicheakie nauki, no.7) (mIRA 3J+: 11)
~Chlen-korrespondent, AN SSSR (for Korshak).
~(Macrowlecular cornpounds)
compounds)

27491
S/062/61/000/009/006/01~,
8 Ila B1171BI01
AUTHORS: Andrianov, K. A.p Zhdan ovi A, -'A. Iand Odinetef V. As.
-TITLE: Synthesis of liquid lin-hexamethyl-poly(phenyl-athyl)-methyl
siloxanes and investigationrof their properties
PERIODICAL: -Akademiya nauk SSSR. Izvestiya. Otdeleniye khimicheskikh
nauk, no. 9v 1961v 1615-1624,
TEXT: The lowest-molecularmembers of the polymerhomologous-series of
i,n-h7examethyl-poly(phenyl-'ethyl)-methyl s"iloxan'es were synthesized-and
their properties studied. Thework was undertaken to study the dependence
of the polar properties of theseliquid organo-silicon polymers on various
polar substituents at the benzenexing. The polar properties were
studied on the basis' of the aotivation.energy of viscous flow and the
temperature dependence of the viscosity.- The flowing initial substances
were used forthe synthesie, (phenyl-ethyl methyl-dichloro silane
(C H C H (CH )SiCl , b.p. 900-9200 (5 mm'99~)p (tolyl-ethyl)-methyl-di-
6 5 2 4 3 2
chloro silane,(CH 3C6H4 C2H 4(CH3)SiCl2, b.p~i 1030-10500 (2 mm Hg), (chloro-
Card 11/6

27491
8/062/61/000/009/006/014
Synthesis of liquid 1jn-hexamethyl-
B1171BI01
phenyl-pt~yl)-~ethyl-dichloro silane* a H (CH )SiCl2p b.pe_
-4 2 4 3
1240-1-2'60C (2 M'm Hg).- The synthesis a theoaliflompoundb is described in
Ref. 11 (K#*A. Andrianov et al,.~Zh~- imii (in print)). The
liquid polymers were obtained bylthe ~biit'hy drolysis of toluene solution
of mixtures of these compoundsmith trime"thyl-chloro silane (b.p. 580-590C)
at 90-950C., Polymers of varying degreeslof polymerization, according to
the reactant ratio, may be,isolated'from~the reaction mixture (Table I)-
Hydrolysis of ethereal solution of (phenyl).-methyl-dichloro silane yielded
clic polymers also:, tri(phenyl-ithyll)-trimethyl cyclotrisiloxane
c
rC6 H5C2H4(CH3)SiO], and totra(phenyl-et.hyl)-tetramethyl cyclotstrasiloxane
1C6H5C2H4 (CH 3)"'014 - Evaluation.of the.,infrarea spectra of the compounds
investigated indicates that the addition of the vinyl aromatic nucleus
takes place in P position? giving P-substituted derivatives. The density
of the liquids was determined pyonometrically. Viscosity measurements
were carried out by standard methods with an Oetwuld-Pinkovich
viscosimeter. Data on the activation energy of viscous flow and the
temperature coefficients of the viscosity are shown in Table 2. It was
found that for the lowest-molecular members of the homologoua series the
Card 216

7 r
S/062/62/000/003/008/014
B117/B144
A.5. P/ P7 0
AUTHORS: Andrianov, K#:AF1 -A ~ot and Kashutina,E A.
TITLE: Synthesis of ~o-lyorganosiloxano-oligomerswith terminal
lonate
ma
groups
PERIODICAL: Akademiya nauk 355R.
Izvestiya. Otdeleniye khimicheskikh
nauk, noi 3t 1962, 454-456
TEM, The joint hydrolysis 'of dimethyl-diethoxy silane and (diethyl
thyl)dimethyl-ethoxy silane was studied, Dimethylchloromethyl-
malonylme
ethoxy silane synthetized by the method described by K. A. Andrianov and
M. A. Golubenko (Ref. 4: Dokl. AN SSSR 112, 257 (1957)), boiling pplnt
131-1330C, dimethyl-diethoxy silane, boiling point 112-1160C and freshly
distilled malonic.ester were used. The reaction was shown to take a smooth
course in slightly acid medium,without cleavage of ethoxy groups in malonic
eater rests. Polyorganosiloxane-oligomers with terminal malonate groups
are formed here... Investigation of infrared spectra of the compounds
..produced showed.that the malonic ester residue is not added to the 0
xygen
atom, but 'to the carbon atom. The following compounds were synthe ti zed:
.--Card .1

5/062/62/000/003/008/014
Synthesis of,polyorganosilbxane-oligomere*~o B117 /B 144
(diethylmalonylmethyl) dimet'hylethoxysilanef C H 0 Si, yield 42 clear,.
10 19 4
20 20
colorless liquid, boiling,point 120-1230C (5 mm Ha n 1.4312, d 1-00581
D 4
-MR 71-29; 1,3-bis-(diethylmalonylmethyl)tetramethylailoxane, C H 0
20 38 9 2'
93
Yield 78-4 %,,cleari colore a liquid, boiling point 184-1880C (2 mm Hg),
20 20
..1-4425t d 1-0588, MR 119-94;,1,5-bis-(diethylmalonylmethyl)
nD
4
hexamethyltrisiloxane, C28'44010 Si 31 heavy, colorless liquid, boiling poinV
20
20-234cc (7-13 mm Hg) n2 1. CI I
4363, 0425, MR 138-93; 1,7-bis-
D 4
(diethylm lonylmeth 1)ootamethiltetrasilaxane, C Si , clear color-
a Y
24H5 0 11 4
0 26
2.
less liquidp boiling point 2142-12550Q (8-10 mm Hg), nD 1-4338, d 4 1-0375?
MR 157-56; 1 17-bis (diethylmal'onylmethyl)octadecamethylnonasiloxaneI
20
a H Si n 1.425 d20 1.0190, LIR 250-66; 1,37-bis-(diethyl-
34 800~16 9 D of 4
malonylmethyl)octatricontamethylnonadeoasiloxane, C H 0 Si clear,
19P
20 20 54 140 26
-viscous liquid, n d 1.0068f Al N. S. Leznoy and
D 1o4165f R434-40-
4
Card-- 2/3-_...I_.':I . . . .. .

11 If tot ~~WiIJP
16635
s/o62/62/000/004/004/013
BIIO/B1O1
AUTHORSs Andrianov, K,A., and Zhdanov, Ae A.
r=
~TITLE% Polyboron dimethyl ailoxanes
.-PERIODICALs. Akademiya nauk SSSR. Izvestiya. Otdeleniye
khimicheskikh n6ukp no. 4, 1962, 615-619
TEXT: Polyboron dimethyl a iloxanes, which are of interest as slastomers
(molecular~weight 200,000-400,000), were produced by heterofunctional
polycondensation as described by the,authors (Dokl. AN SSSR 134, 361
(1961)). In the first staget,326 g 1.1 moles) of octamethyl
cyclotatrasiloxa Ine was tolomerized,in the presence of 2-37 9 (0-0184 moles)
of dimethyl dichlorosilane in anautoclave for 4 hre at 2000C. The
resultant substance, 79 9 of,colorless,,viscous U,w-dichloro polydimethyl
siloxane.(Clsi(CH 3)20 [Si(CH 3)2 0] 705 i(CH P201) was hydrolyzed in
acetone and benzene-by means of sodium bicarbonate, whereby 72 g of
colorleas, viscous o(f(,J-dioxy polydimethyl siloxane, [(CH Sio] was
2 m
obtained. ..The molecular weight of the compound was oalculated from
Card 1/#

:9 ~,F --l I - i_.,.

S/062/62/000/004/004/013
'Polyboron dimethyl siloxanes B110/B101
-association, The characteristic viscosity of the roaetion mixture of
(4-dioxy polydimethyl.siloxane and tributoxy boron does not increase
at 200C at ratios of 10 or.10. Measurements of viscosity showed that
the removal of the resulting butanol with carbon dioxide accelerated the
reaction. After 30-min heating at 2000C, the specific viscosity of
the 8% solution increased to 0,946, butanol being obtained in a quantity
of 43% of the theoretical amount. The gel-like, polymeric substance,
which is soluble in polar and apolar solvents, was also formed after
30-40 min heating at 15000 in vacuo. Its vitrification temperature
(-1250C) and yield point (-5000) were established by thermomechanical
investigations. It is elastic on sudden deformation, capable of
springbacks on shocks, but flows under slow stress as in the case of
polyaluminosiloxanes, coordination bonds are assumed toexist between
oxygen andboron atoms in the siloxane chainst
Card 4/5

37h03
5/062/62/000/005/005/008
B110/B101
/5-9c~ os-
AUTHORS: Andrianov, K. A.,,and Zhdanov, A. A.'
IIITLE;~ Synthesis of po~raluminoorganosiloxanes with molecules of a
periodic network structure
PERIODICALs Akademiya nauk SSSR. Izvestiya. Otdeleniye khimicheskikh
nauk, no- 5, 1962, 837 840
TEXT: The polycondensation,of,a,Q-dioxypolydimethy1 siloxanee (K. A.,;
Andrianov et al. (Dokl. AN.5.53R 134, 1347 (1961)) with aluminum butylate
vras investigated. When the components were'in a proportion 30, the
followihg"reaotion took plaoe.at 2000c,
Clls~ 0 Isi (CIWI 0172 ll
AI(OC,11,)3+3110 -~i-o li Al 0 ISI (Clip)$ 0171 It + 3Cjll,0lj
In'the first stage of.polyco ndensation, the intrinsic viscosity changed
very slowly, increasing from 0.05~ to 0.092 within 48 ~re. This indicateal
the formatiQn of a branched oligomer with a central aluminum atoms whereby,
Card 1/4

S,/062/62/000/005/005/008
Synthesis of ~po3Vaiumiriodrganosiloxanes ... B110[B101
rease in viscosity from 0.092 to 0.263 during polycondenvation for
I
nc
32 hre. At a ratio. 1:1, linearpolycondensation takes places
At (0C,11,), + HO ISI (CHs): 0172 11
At - 0 JSI (CI13)sOI71-Al 0 [SI (CHj)s 0113-w-Al0+ C&1160H
oc,~ If, OC4116
This results from the change,in viscosity during polyconden&ation at 180
and 2000C. At 2000C, viscosity rises from 0.092 to 0.164 after pollycon-
densation for 14 hrs, but at a ratio 30 this value is only reached after
72 hrs. At room temperature, the 3:1 polymer with an intrinnic viscosity
and ether, but
of 0.263 is very elastic, soluble in benzene, toluene,
0
becomes insoluble when kept on at a temperature of 200 C., It 0 is.elastic
over a wide range and has a vitrification temperature ofv-60 C. The high'
elasticity of its periodic network structure is due to the large spacing
flexibility
of theAlatoma and the.,considerable
of the polydimethyl
room temperature, the linear molecule is elastic,
siloxane chaifts. At
readily soluble in organic solvents, and has a wider range of elasticity
than 'the network polymer.- There~arei 3 figures.
Gard )/4

38718
9/191/62/000/007/005/011
B124/BI44
AUTHOR.S., Andrianov, K. -A.,_~4 ~anov, ~A. A~.
:11TLE
Some peculiarities in the structure of polyorgan6ailoxanes
and polyorganometal ailoxanee
Placticheakiye massy, no. 7, 1962, 24-27
Froblems.concerning the structure of polyorganosiloxanes and
polyorganometal siloxanes are discussed on the basis of earlier papers
by the authors and in publications from the USA. The flexibility of.
Si-O-Si bonds surrounded by organic groups is proved by the formation of
cyclic compounds (e.g. octamethyl oyclotetrasiloxane) -in the hydrolysis
of aqueous dimethyl dichlorouilone solutions, the.eize of the resulting
ring being dependent on the type of organio. groups on the Siatom.
Cyclic polymers of the structure
Card 116

I

S/191j62/000/007/005/011
Some peculiarities in the structure ... B124/BI44
are formed in the synthesis of polymers with inorBanic chain moloculeD
by hydrolysis and condeneation. Polyalumaphenyl- or polyalumoethyl
siloxanes:
R R R R
-0-sj-o-Sj-O-SI-O-SI-O-AI-

OH: 01A 0 0
16.5 10.5 10.5-
l' from the cb
.reau hydrolyeis of phenyl trichlorosilane or ethyl trichloro-
silane with AlCl3f as well as.from reactions of Cl 11 011a. with
6 5S'(OF')2
1 2CS04)3 they a re
readily soluble in organic solvents and do not melt
at 700OC; their s I
tructure may be stated as.follows:
R R
S
0 0
SI Al
\
/l\
Card 416 b
R 0 0

S/191/62/000/007/005/011
Sbme peculiaritiou in the structure B124/BI44
Polytitanophdnyl ailoxanen with the struoturet
0 R 0 R 0
\S.
Si i
0
Si, Ti.
0 R 0 0 0
are also formed in the cohydrolysis of phenyl triohlorooilane or phenyl
sodium oxydihydroxysilane with'TiC1 A, similar structure was determined
4*
for polytitanoethyl- and polytitanomethyl siloxanea. This also occurred
in polvareenophenyl ailoxane of cyclolinear structure obtained by
cohydrolyeis of AsCl and phenyl trichlorosilane, as well as in poly-
phenyl siloxane synthesized from phenyl. trichlorosilane. Thus it has
been proved that the synthesis of the polymers here mentioned proceeds via
cyclic compounds with functional-groups which react with one another ~o
Card 5/6

ACCESSION NR:' AT4033984 sloooo/63/000/000/0045/0052
VAUTHORI, Zhdanov,.A. A.,,. Andr I anov, K., A.
.~'TITL9: Mechanlord of formation of A) contalilng silicones In the reaction of_
aluminum butylate with dialkyV, (alkyaryl) dIacetoxy9I lanes
CE Get kom6l kulyarny*ye so edinent a (Heterochain macro-
s ar6tsepny*ye.vy*so 6 y y
'molecular compounds); sbornik statay. Moscow, lzd-vo "Nauka.11
1963, 45-s2
TOPIC TAGS*:' aluminum butylate, polymer, silicone, acatoxysilane, butyl acetate,
aluminum containing silicone, dimethyidlacetoxystiane, phenylmethyidiacatoxysilane.
diethyidiacetoxysitaine, trimethylacetoxystiane, polycondensation, heterorunctional
polycondensation, acetate grotip, acatoxy group, butoxy group, polyorg nosi)oxane
u
ABSTRACT: Mixtures of aluminuih b tylate (I; bep, 296-297c/24 mm) with phenyl-
methy)dlacetoxysilane (11; b.p. 127C/7 mm, acetate group (49-78%). dFethy).diace-
toxysilane (111; b-P, 95-97C/20 mm; a9 58-52%), dimethyldlacatoxysi lane (IV; b.poi
65-67C/.20 mm; ag 66-76%) or trimethylacetoxysilane (V; bop, 102-105C/ag 45.18%),
were heated in an oil bath to'200C and kept at that temperature for 30 hours to
study the formation of polymets containing the Si.O-Al bond. Reaction withilb
III and IV proceeded rapidly at 140-160C, with formation of a polymerproduct
j (Al-contalnlng sll 'Icona).and precipitation of butyl acetate* Dimethyidibutoxysi-
Card 1/2:

. . 0, , I I
I
I -r --, - ~7 7~ ~ . a ., , I

i
I
ill 'I.
ill=, 1,111.1-19

ACCESSiox NR: Ap4o35102 8/0191/64/000/009/0023/0026
A.34.; Andrianov K. A. Ba"heyevaj. T. Be; Polikimin
No Ai;
AUZHOR 'ZbdAwv#- P
lavitr,47j. MO, MI.
TITIZ*., lnveatl~ption of ths'propertles of ors''='Goilicon polymers containing
hydro5' henyl &oupa&
SOURCE:~ Plasticheakiye massyr*,0 no. 5..., 1964 00-26
TOPIC ~06: silicon polvwr) hydroxyphi4yl containing siloxane, eater
e.reiction, polymer chain grovth,, di~henylolpropane., polyphenylbutox3r-
Siloxaqao dianoi: rcaction product,, mol4od compa''teitionj.pbysical property) mechanical-.
property#, crejoi liWmge, polymerizatioix
The4eaction of forming org ano silicon compounds containing the hydroxy-
p enyllgroupp end the properties of the proiuA polymers were inventigated. The
hydro enyl group can be introduced into th~ siloxano chain by ester interchanSe
_of'thq diphen*1pMane (diane) with orgwosilicon polymers or oligomqra contain-
ing bu;_ x7 grovps~oa the silicon atom., -If the olicamer has only teminal butoxy
SroUYS Iths pw?,~ct formed VIU have di=e gropps at the ends of the chain, If the

-A t.11,
ACCESSION NRs S/0190/64/006/1005/0940/0944
AP4037291'-
AUTHOR: ZhdanoV At 9 AndrLanov, K. As$ Kazakova# A* A* 'I
~-Baksheyavao To So;,
110'
~TITLZt Poly Oro with inorganic backbone, Synthesis of polYorgano
','phosphoroalu
mLnoxones
SOURCE I Vy*sokooolekulyarny*ye soyedinenLya, v, 6, no# 5# 1964
940-944
TOPIC TAGSt polymers, inorganic backbone containing polymer,~pho
phorus containing polymer, alumLaum,containLng polymer, alumLnoxanet
1 rganophosphoroaluminoxanel, aluminum containing polymsthylpho#-',j--
PO YO
IV
phonate, aluminum othylateg aluminum butylate, diethyl methylphos-
phonatep dLbutyl methylphoaphonateg diphanyl methylphosphonate,
polycondensationt methylphosphonyl chloride
ABSTRAM 'The reaction of aluminum alcoholates with some derivade,
.'j,,tivas.,of methylphosphonic acids and the properties of the con dens
products obtained have been studied#. 'Aluminum athylate or i
CAM, 1/3