(SANITIZED)UNCLASSIFIED ENGLISH-LANGUAGE SOVIET ARTICLE ENTITLED " THE SYNTHESIS OF ORGANOGLYCOXYSILANCES AND THEIR CONDENSATION"(SANITIZED)
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November 4, 1964
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STAT
THE SYNTHESIS OF,ORGANOGLYCOXYSILANES AND THEIR CONDENSATION,
I.A.Andrianov, Iii-M.hananashvili and A.S.ochetkov, Plastic
Materials, (No. 8) 13 '(1964)
Organoglycoxysilanes have been described before this (1)(2).
They have aroused interest in the investigation of their possible
condensation reactions and (thus) the opportunity of their
incorporation into long chain polymers. -
In the present work are described the results of synthesOs
of trifunctional organoglycoxysilanes by the reaction of ether
,interchange between methyl-, ethyl- and phenyltriethOxysilane
and glycols, their properties and their condensation. The
syntheses lead, in excess glycol, to calculation so that by-
products of the reaction were removed along with any heterocyclic
compounds formed. As shown here, the reaction proceeds in
accordance with the equation:
RS1(002H5)o + 3HOR'OH RSi(ORIOH)3 + 302H50H,
where R = CH3-, C2H5-, 06H5-,
-CH2CH2CH2CH2-. ,
There was thus obtained a variety of organoglycoxysilanes,
as shown in Table 1. A study of the thermomechanical properties
of the compounds prepared indicated that their temperatures of
brittle point were in the neighborhood of -900 to -700 C.
(-1300 to -940F).
-01-120H2-,
-CH2CH2OCH2OH2-,
Table 1
(analytical data omitted)
REAGENT CONC. OF
GRAMS
Ethylene Glycol 20.351
Ethyltriethoxysilane 20
Ethylene Glycol 23.75
Phenyittiethoxysilane 27.9
Diethyiene GlYdol 25.6
Ethyltriethoxysilane 15.3
Diethylene Glycol 27.53
Phenyitriethoxysilane 19.8
1,4-Butane Diol 31.03
Phenyltriethoxysilane 26.3
REACTANT
mpLs.
0.328
0.104
0.383
0.116
0.25
0.796
0.259
0.0824
0.344
0.109
PRODUCT
Ethyltris-(-oxyethoxy)-silane
Phenyltris-(-oxyethoxy)-silane
Ethyltris-(diethyleneglycoxy-
siiane
Phenyltris-(diethyleneglycoxy)-
silane
Phenyitris-( -oxybutoxy)-silane
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The condensation of pure phenyltris-(-oxybutoxy)-silane was-
carried out under conditions guaranteeing-the .removal-of-reaction
by-products at 2000 C. and 1 mm. In-the process of condensation,
qualitatively, of the byproducts, there was isolated I,4-butane
diol,to the extent of 1.4 mol for,each moi?of.phenyltr,is-
((roxybutoxy)-silane. As In the condensation of methyltris-
(diethyleneglyzoxy)-silane at 1200 C. under 0.025 mm-0.020 mm.
there was also diethylene glycol, 1.25 mol for one mol of
methyltris-(digthyleneglycoxy )-silane. In each case the
reaction was-flinished after the production of by-product had
ceased. The products of condensation were transparent, hard
Polymers. The polymers prepared from methyltris-(diethylene-
gIyco34)-silape were dissolved in alcohol; the polymers from
phenyitris-(-oxybutoxy)-silane were insoluble in organic
solvents. The products formed by these reactions show that
polycondensatign proceeded in accordance with the equation:
2x ES1(ORIOH)3 -+ 3x HOR1OH + (-
i 0-R1-0
i 0 RI -0 -)x.
Infrared
-
Infrared spectra presented conformed to the chemical
structures pertaining to the units of the chain. In the polymers
there were observed, of ten,1429 cm-1 (corresponding to the
unit Si-06H5) and 3400 cm-1 (corresponding to the unit-
valence oscillation of the hydroxyl group in the associated
state). The thermomechanical properties of the polymers are
presented using phenyltris-(b-oxybutoxy)-silane as shown in
Curve 1. As seen, the polymer does not flow up to 00? C.,
which property grees with the structure of the polymer.
Relative
Deformation
500 1000 1500 2000 2500 300?
Curve 1
Thermomechanical Properties of the Polymer
Prepared by the Condensation of
Phenyltris-0-oxybutoxy)-silane
The condensation of methyl- and phenyltris-(diethyleneglyco-
silane with the methyl ester of terephthaIic acid took place in
equivalent concentrations at 250? C. in the absence of catalyst.
In this case the reactions suns easily with production of
by-product methanol as shown below:
2n R6i(OR1OH)3 + 3n CH316H4g001-13
6CH30H + (RSi(OR108C6H10-)3)n
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1.
where R = OH3-, C6H5-; RI -01.120H200H20112=; Methanol
was collected in yields of 72% of theory, paralleling the
production of polymer.which was .soluble in a toluene-ethanol
mixture.
Subsequent Condensation produced polymers, insoluble in
solvents. .If the soluble polymers are-heated-at 2000 C.
at 1 mm, they pass over to the insoluble polymers. This shows
that condensation of methyl- and.phenyltris-(diethyleneglycoxy)-
silane with dimethyl terephthalate produces a "pro" polymer
and that heating rearranges this. The thermomechanical
properties of the soluble polymers, prepared from methitris-
(diethyIeneglycoxY)-silane and dimethyl terephthalate and the
properties of the polymers after supplementary condensation at
2500 C. and heating-two hours are shown in Curve 2. In the
condensation of the oxysiIane with-dimethyl terephthalate no
further production of glycol was Observed as with the condensation
of the original organoglygoxysilane.
Relative
Deformation
Curve 2
ThermomechanicaI Properties of the
Polymers Produced from Methyltris- -
(diethyleneglycosy)-Silane and Dimethyl
Terephthalate. 1- as formed, 2-after
heat treatment.
The condensation synthesis of organoglycoxysilanes with
tolylene diisocyanate produced cyclic polymers as shown below:
2n RS1(ORIOH)3 3n OCK61-13N00
OH3
(RSi(ORIOFH96H3NHgORIO-)3)
GH3 0
In the reactions as run, the effect of heat was noticed, the
amount of which depended on the numerical amounts of the reactants.
The thermomechanical properties of the polymers'are.shown in- -
Curve 3, from which it is seen that the polymers are liquids at
300-400 C., that after six hour treatment at 1500 C. the liquids
have.practicarly disappeared, and that it shows that these are
the final possible structures of the polymers.
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Relative 15
Deformation
a 10 -
5
- 4 -
I
3
0 500 1000 1500 200?
Curve 3. Thermomechanicai Properties,of Polymers:
1. Prepared from Ethyltris-(p-oxyethoxy)-silane and
Tolyl ene Diisocyanateaas ForLed. 2. Same, after
Heating. 3. Prepared from Phenyltris-(diethyleneglyocoxy)-
silane and Tolyiene Diisocyanate after Heating.
Ffom these polymers one can prepare many different
manufactured articles.
Curve 4
Temperature
Dielectric charactbristics of the polymers
prepared from pheny1tris-(i,oxybutoxy)-silane
and tolyiene diisocyanate. Tangent angle
of dielectric loss: 1. at f = 400 gts.
2. f = 1.5 x 106 gts. Dielectric permeability:
3. at f = 400 gts. 4. at f = 1.5 x 106 gts.
An investigation of the electrical properties of typical
polymers classified as plastics shows a sharp maximum dependence
of dielectric loss on temperature. The Debaevskii maximum
(Curve 4). at the point 400 gts lies at 780 0; at the point
1.5 x 100 it is shifted to one side at the higher temperature
of 125? C.
Each property of these polymers was investigated.
Table 2
(analytical data omitted)
Compound n20 al
D
CH3Si(OCH2CH2OH)i5
1.4515 1.1980
C2H5Si(OCH20H2OH)3 1.4538 1.1642
06H551(00H2CH2OH)3 1.5025 1.2068
C2H5Si(OCH9OH200H2CH2OH)3 1.4588 1.1478
C6H5Si(00H3CH20CH20H2OH)3 1.4969 1.1862
C6H5Si(0CH2CH20H2CH20H)3 1.4967 1.1115
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Experimental Part
For the reactions of esterification (we) took pure alkyl
taryl)triethoxysiiane and dry glycol.
Pre aration of Meth ltris- ox ethox -silane. In a flask
were placed 4.01 z. 0.34 mol f ethylene glycol and through a
dropping funnel there was intVoduced with heating and intensive
stirring, 20.1 g. (0.113 mol) of methyltriethoxysilane. There
was forked at first an emulsion with distillation of by-product
alcohol. The temperature was maintained for four hours at
1750 C. After this, 13.15 g. of alcohol had been collected
(85.2% of theory). The main product of the reaction Was vacuum
distilled at 5 mm. and 10001200 C.
The product of the reaction was a viscous colorless liquid,.
n20 1.4515,d22 1.1980. MR 50.96; Calculated MR 61.168.
Analysisl-Found % OH 22.16, 22.73; Si 12.95, 12.65; Mol. Wt.
227. C H/E306Si
Calculated, %; OH 22.5; Si 12.4; Mol. Wt. 226.30
By similar methods (rhe other) organoglyzoxysilanes were
synthesized and identified (Table 2).
Condensation of Phen itris- to-ox buto -silane. 12.1 g.
(0.0325 mol) of phenyltris-(oxybutoxy)-silane was condensed by
heating two hours at a temperature of2Q0? C. in a vacum of 2 mm.
TOA yield was 4.02 g. (0.0446 mol) of 1,4-butanediol, ric13 1.4458,
(11 1.0106, m.r. 23.76; calculated 23.6,
The product of the reaction, a transparent, light-yellow
hard polymer, was insoluble in most organic solvents.
Condensation of Meth Itris-(diehYleneglycoxy)=pilane and
the DIME-1 Ester of Tere thaIic Acid. In a reaction flask,
8.4 g. 0.03 mol of methyltris- diethyleneglycoxy)-silane and
6.82 g. (0.0422 mol) of dimethyl' t6rephthalate were mixed and the
reaction mass stirred at 250? C. for one hour. The yield was
1.46 g. (0.0456 mol) of methanol (72% of theory) and a reaction
mass of yellow-brown material (which was) heated to fusion. A
test of its solubility showed that the product of the reaction was
soluble in a mixture of alcohol and toluene. Subsequent vacuum
distillation of the reaction product for two hours at 1500-2000
C. and 2 mm. brought out the desired polymer, insoluble in organic
solvents. _
Condensation of Phen-itris-(dieth iene leux -silane and
Dimetjrl Tere hthalate. This was accomplished by a method
analogous to the above. For the condensation, 5.85 g. (0.0139 mol)
of phenyltris-(diethyleneglycoxy)-silane and 4.05 g. (0.0244 mol)
of dimethyl terephthalate were taken, yield 0.8 g. (0.025 mol)
of methanol (60% of theogy).
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The product of thereaction..was a.light,yellow, hard polymer.
andenstion.of Methyltris7' -oxyethoxyJsilane with Tolylene
Diisoc-anate, There were mixed 416.g 0.0051.mol of methyltris-
-oxyet oxy ,silane and 12:.g.-(0.007,mol) of. tolyiene
d isocyanate; then the temperature-was raised.from;180 to-400:C.-
At the beginning the mixture-formed-an-eMU1SiOn. which disappeared-after
five minutes. The transparent liquid mass was poured out ontp a
plate and left to harden by drying at room.temperature'for 20 hours,
then placed in an oven and dried for six hours at 1500 C. The
reaction.produpt was a hard transparent polymer._
Found, .%: N 9.18,9.16. -Calculated, %: N 8.62.
,The condensations of other (related) organoglycoxysilanes
with tolyiene diisocyanate were carried out by the same method
(Table 3).
Table 3
Characteristics of Organoglycoxysilanes, Condensed with
Tolylene Diisocyanate
(analyIical data omitted)
Initial Reactants Ambunt Taken for the Reaction
mol
-
Ethyltris-(-oxyethoxy)-silane? 1.07
0.0045
Tolylene Dilsocyanate 1.28 .
_ _
0.0074
Phenyitris-oxyethoxy)-silane 107
'
0.0037
Tolylene Diisocyanate 1.02
0,006
Ethyltris-(diethyleneglycoxy)-silane 1.13
0.003
Tolylene Diisocyanate 0.84
0.0048
Phenyltris-(diethyleneglocoxy)-silane 1:18
0.0028
Tolylene Dlisocyanate . 0177
0.0044
Phenyltris-(-oxybutoxy)-silane 1.17
0.0031
Tolylene Diisocyanate 0.86
0.0049
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4 I, ?
4 ' f
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Summary
. 1. The reaction of methyl-, ethyl- and phenyitriethOxSriiiane
with glycols serves to synrhesize the, following: methyl-, ethyl-
and pheny1tris-(0-oxyethoxy)-silane, ethyl-1 andphenyitris-
(diethyleneglycoky)-silane and phenyltris-(b-oxybutoxy)-silane
from which were prepared polycondensation pfoducts(Polymers).
?2. The: condensation of synthetic organoglycoxysilanes with
the dimethyl ester of terephthalic acid, (with) toiyiene
diisocyanate aef!ve as the source of other polymers:
. Literature
1. M.M.Sprung, S.. Org. Chem., 26 (to. 1) 58 (1958)
2. Si?. Heterolinear High MolecTilr (Weight) Compounds,
"Science", 18 (1964)
STAT
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