(SANITIZED)UNCLASSIFIED PUBLICATION ON SOVIET RESEARCH ON PLASTICS(SANITIZED)

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP80T00246A075000330001-2
• Release Decision: RIPPUB
• Original Classification: C
• Document Page Count: 5
• Document Creation Date: December 27, 2016
• Document Release Date: February 7, 2014
• Sequence Number: 1
• Publication Date: May 15, 1964
• Content Type: REPORT

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The Synthesis of Borosiloxane Oligomers and their Resistance
to Hydrolysis
..A.AndrianpV, L.E.PananashVili, A.V.Varlamov and V.S.TikhanoV
Plasticheskie gassy, ..(No. -3) 20(1964)
Polymers with inorganic units in the molecular chains have.
considerable practical importance.:_ Parallel with the development
of the polyorganosiloxanes (themsekted) attention was soon drawn to
those polymers set up,with main bonds holding boron, in addition
to silicon and_oxygen
Organoi2b-VOlt1loxanes easily (undergo) hydrolysis in water.:
The explanation lies in the high degree of polarity of the bonds
B-O-Si and the ability of boron easily to utilize pi orbitals
forming bonds coordinatingwith nucleophilic : reagents. Present
interest stems from the question as to whether the bonds B-0-Si
are always stable with regard to water. Such stability (resistance)
could probably be heightened by the introduction as a side ;hain
to the inorganic chain, 4 group containing nitrogen, intended to
furnish a coordinating bond to the boron, utilizing this pair of
electrons.
For this purpose, there were synthesized four oligomers with
phenylaminomethyl groups on a silicon atom as indicated:
(I) CH3000B(091(CH5)(002H5)CH2NHC6H5)2
H3 90=15
(II) C2H50-( i-O-B-0,4-Si(CH5)(002H5)0H2NH 6H5
H2NHC6H5 2
90CCHS
(III) CH5C00-(41-0-gi(CH5)-0-)402H0
CH2NHO6H5
(IV) ((OH3000)2B0)2Si(OWCH2NHC6H5.
Declassified in Part - Sanitized Copy Approved for Release 2014/02/07: CIA-RDP80T00246A075000330001-2
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Structures of, the chain groups and side' chains were determined
according .to the customary- chemical-methods-and confirmediv-
infrared data. Theee-.compounds showed frequencies of
1345 cm-II CBS-Si, 820-800 em-1 and 1282-1250_0M-1- The hydrolytic
resistance of the B-0-Si linkage in these oligomers is defined at
room temperature by the amount of 1p611,p acid formed in water
solution from a known amount of the substance, immerged in waters'
Solubility
Viscosity Brittle Pt
I C2H5OH, OH3dOOH3, 0(dH20H2) 0H3000H
0,15
-35*
II
as I
040
..12o
III
02H5OH, CH3COCH3
0.21.
+500
IV
as I .
0f07
+44*
On the curve (below) is the evidence of definite hydrolytic
resistance On the part) of the oligomers prepared._ As seen, fram
the runs, on the curve, the hydrolytic resistance of all four
compounds was tested.
100
75
% B(OH)3 50
25 ?
f2
0 5
Time, hours
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Comparison grf the hydrolytic resistancein the compounds
studied with theirstructuresHshors that theinfluence of the
phenylaminompthyl group on the hydrolytic resistance of
B707Sii.s manifested strongly in each case where the number_
of .phpnylaminomethyl,groups is sufficient to coordinate with
(a110) the boron atoms. However, when the number oT boron
atoms exceeds the number of phenylatinomethyl.groupsj as will
be_sepn in-compound IT, the stabilizing effect Of the phenylaMino-
methyl groups is not operave.
Experimental Part
Boron triacetate_rap prepared by the methO400; An4ri4n0Y.
and Yolkova (2) with m.p. 1300-1310,- Methylphenylaminompthyl-
diethcixysi1ane, b.p. 1450-1470(12 mm-13 mm), n(2001))1.4981,
d(2004?) 1.006.
,synthesis Of 01,14gmer1I. _ In a flask furnished with an
upright condenser and measuring flask with recekving flask,
were-placed 18,80 g. (0.1 mole) of boron triapetate and. 47.88 g.
i'nekh3)
(0,2 mole) of methylphenylaminopethpxysilane. The contents Of
the flask were heated to 145? C., then discontinued to distill
off ethyl acetate (94% of thevry)(followed by) vacuum
distillation of the reaction product over a four hour (period)(
(500 C. at 20 mm.)
%: 3.87; 137 2.21, 2.25; Si- 11.58, 11.82;
02#50- 18.57, 17.84; C22H3506N2SiB.
Calculated; %, N- 5.70; B- 2.21; Si- 11.46; 02H50- 18.35.
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MIR
:4.
The synthesis of each oligomer was carried out under
analogous conditions with the proper molar ratio of boron
triacetate and methylphenylaminomethyldiethoxysilane.
Hydrolytic resistance was determined by methods given
by Andrianov and Volkova (2).
In the Table are presented the characterization of these
oligomers.
Summary
1. The synthesis of borosiloxy oligomers containing the
phenylaminomethyl group attached to 4 silicon atom.
2. A study Pf:TPPiPt.ance,to hydrolysip.of the borOsiloxy
oligomers and evidence :that (these):oligomers with various
phenylaminpmethyl_groups in equal number to the,, boron atoms
in the ,molecule or grater, possess ample resistance to ,
hydrolysis. Oligomers with boron atoms in excess than the '
number of phen37.7-laminotethyl groups are hydrolytically unstable.
, Bibliography
. 1. M. Wick, cunststoffe, 50 433 (1960)
2. K.A.Andrianov and L.M.Volkova, Izvestiya Akademii
Nauk, SSSR, 0411, 303 (1957)
3. "c..A.Andrianov, V.S,Tikhanov, L.M.Plananashvili,
En-Tsze Han and Shu-Yu Han, Plastkheskie Massy,
(No. 12) 25 (1962)
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