Organopolysiloxane polymers and method for making

An organopolysiloxane homopolymer or copolymer comprising recurring units of the general formula: ##STR1## wherein R.sup.1 and R.sup.2 are independently selected from monovalent hydrocarbon groups, Q is a divalent aromatic hydrocarbon group, and letter n is an integer of from 1 to 4 has a high melting point and a high glass transition temperature and cures into products having a high modulus of elasticity and mechanical strength and thus suitable for various industrial applications. The polymer is prepared by a simple method involving the steps of reacting an alkali metal salt of a dihydroxy aromatic compound with a halogenated alkyl diorganoalkoxysilane, hydrolyzing the resulting bis(alkoxysilylalkoxy)arylene compound, and polycondensing the resulting bis(hydroxysilylalkoxy)arylene compound.

This invention relates to organopolysiloxane homopolymers and copolymers 
having a high melting point and a high glass transition temperature which 
can be cured into products having a high modulus of elasticity and 
mechanical strength and being suitable for various industrial 
applications. It also relates to a method for preparing the polymers. 
BACKGROUND OF THE INVENTION 
Heretofore, organopolysiloxanes, especially dimethylpolysiloxanes have been 
utilized in fluid or cured form in a wide variety of industrial settings 
including electric, electronic, automobile, machinery, and building 
industries. However, as a result of the characteristics (low melting 
point, low glass transition temperature, and low van der Waals forces) of 
the base polymer or dimethylpolysiloxane thereof, these cured products are 
rubbery elastomers which only find a limited range of application because 
of their low modulus of elasticity and mechanical strength. 
It was reported that organopolysiloxanes capable of forming cured products 
having a high melting point and a high modulus of elasticity can be 
obtained by introducing a divalent aromatic hydrocarbon group such as a 
phenylene group into the backbone of organopolysiloxanes. Based on this 
teaching, the following organopolysiloxanes were proposed. 
(1) Polysilphenylenesiloxane 
##STR2## 
See R. L. Merker, M. J. Scott, and G. G. Habeland; Journal of Polymer 
Science, Part A, Vol. 2, page 31 (1964). 
(2) Poly(m-silxylenesiloxane) 
##STR3## 
See H. Rosenberg and E. W. Choe; Organometallic Polymer "Symposium on 
Organometallic Polymers," New Orleans, 1977, Academic Press, page 239 
(1978). 
However, synthesis of these polymers (1) and (2) is cumbersome because of a 
need for Grignard reagents or metallic sodium. 
There is a need for the development of a divalent aromatic hydrocarbon 
group-bearing organopolysiloxane which is easy to synthesize, has improved 
properties (such as a high melting point), which cures into a quality 
article, and thus can be useful in a wide variety of industrial 
applications. 
SUMMARY OF THE INVENTION 
A primary object of the present invention is to provide a novel and 
improved organopolysiloxane homopolymer or copolymer having a divalent 
aromatic hydrocarbon group incorporated in its backbone, which has a high 
melting point and a high glass transition temperature, cures into products 
having a high modulus of elasticity and high mechanical strength, is easy 
to synthesize and thus suitable for use in electrical, electronic and 
other industries. Another object is to provide a method for preparing 
these polymers. 
According to the present invention, there is provided an organopolysiloxane 
polymer comprising recurring units of the general formula: 
##STR4## 
wherein R.sup.1 and R.sup.2 independently selected from monovalent 
hydrocarbon groups having 1 to 10 carbon atoms, Q is a divalent aromatic 
hydrocarbon group having 6 to 20 carbon atoms, and letter n is an integer 
of from 1 to 4. The polymer may be either a homopolymer or a copolymer. 
This polymer has a high melting point and a high glass transition 
temperature and cures into products having a high modulus of elasticity 
and high mechanical strength so that the polymer may find a wide variety 
of applications in electrical, electronic and other industries. 
According to another aspect of the present invention, the polymer 
comprising recurring units of general formula (I) is prepared simply by 
reacting an alkali metal salt of a dihydroxy aromatic compound of the 
general formula: 
EQU M--O--Q--O--M (1) 
wherein M is an alkali metal atom and Q is as defined above with a 
halogenated alkyl diorganoalkoxysilane of the general formula: 
##STR5## 
wherein R.sup.1, R.sup.2, and n are as defined above, R.sup.3 is a lower 
alkyl group, and X is a halogen atom, preferably in a polar solvent, to 
thereby form a bis(alkoxysilylalkoxy)arylene compound of the general 
formula: 
##STR6## 
wherein R.sup.1, R.sup.2, R.sup.3, Q, and n are as defined above, 
hydrolyzing the compound of formula (3) to thereby form a 
bis(hydroxysilylalkoxy)arylene compound of the general formula: 
##STR7## 
wherein R.sup.1, R.sup.2, R.sup.3, Q, and n are as defined above, and 
polycondensing the compound of formula (4), preferably in the presence of a 
condensation catalyst. 
DETAILED DESCRIPTION OF THE INVENTION 
The organopolysiloxane polymer of the invention includes recurring units of 
general formula (I). 
##STR8## 
In formula (I), letter n is an integer of from 1 to 4, and R.sup.1 and 
R.sup.2 are independently selected from monovalent hydrocarbon groups 
having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, for example, 
alkyl groups such as methyl, ethyl, propyl, and butyl, alkylene groups 
such as vinyl and allyl, aryl groups such as phenyl and tolyl, and aralkyl 
groups such as benzyl and 2-phenylethyl. Substituent Q is a divalent 
aromatic hydrocarbon group having 6 to 20 carbon atoms, preferably 6 to 15 
carbon atoms, examples of which are illustrated below. 
##STR9## 
Some illustrative, non-limiting examples of the organopolysiloxane 
homopolymers and copolymers comprising recurring units of formula (I) are 
the following compounds of formulae (i) through (x). In the formulae, l 
and m are integers (inclusive of 0) meeting m+l.gtoreq.2, preferably 
m+l.gtoreq.10, most often 100.ltoreq.m+l.ltoreq.1000. 
##STR10## 
The organopolysiloxane homopolymers and copolymers of the invention which 
are preferred for physical properties including melting point, glass 
transition temperature, modulus of elasticity, and mechanical strength are 
those of formula (I) wherein n is equal to 1. 
The organopolysiloxane polymers of the invention can be readily synthesized 
by the following method. 
The polymer comprising recurring units of general formula (I) is prepared 
simply by reacting an alkali metal salt of a dihydroxy aromatic compound 
of the general formula: 
EQU M--O--Q--O--M (1) 
wherein M is an alkali metal atom such as lithium, sodium, and potassium, 
and Q is as defined above with a halogenated alkyl diorganoalkoxysilane of 
the general formula: 
##STR11## 
wherein R.sup.1, R.sup.2, and n are as defined above, R.sup.3 is a lower 
alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, 
and X is a halogen atom such as fluorine, chlorine, bromine and iodine, in 
a polar solvent to thereby form a bis(alkoxysilylalkoxy)arylene compound 
of the general formula: 
##STR12## 
wherein R.sup.1, R.sup.2, R.sup.3, Q, and n are as defined above, in high 
yields. The compound of formula (3) is then hydrolyzed to form a 
bis(hydroxysilylalkoxy)arylene compound of the general formula: 
##STR13## 
wherein R.sup.1, R.sup.2, R.sup.3, Q, and n are as defined above, in high 
yields. Thereafter, one or more compounds of formula (4) are then 
condensed in the presence of a condensation catalyst to form an 
organopolysiloxane homopolymer or copolymer comprising recurring units of 
general formula (I). 
Several examples of the alkali metal salt of a dihydroxy aromatic compound 
of formula (1) are shown below. 
##STR14## 
Several examples of the alkoxysilane of formula (2) are shown below. 
##STR15## 
The compound of formula (1) and the compound of formula (2) may be mixed in 
any desired ratio although at least two mol of the formula (2) compound is 
preferably used per mol of the formula (1) compound. 
Reaction between the compounds of formulae (1) and (2) is often effected in 
a polar solvent. Examples of the solvent include dimethylsulfoxide, 
dimethylformamide, dimethylacetamide pyrrolidone, methylpyrrolidone, 
tetrahydrofuran, propyl ether, and butyl ether. 
A reaction promoter may be added to the reaction charge for the purpose of 
promoting the reaction. The promoters include tertiary amines such as 
triethylamine and tributylamine; quaternary ions such as tetrabutyl 
ammonium bromide, benzyl triethylamine bromide, tetraphenyl phosphonium 
bromide, and tetrabutyl phosphonium chloride; and cyclic polyethers such 
as dibenzo-12-crown-4, and dibenzo-18-crown-6, dicyclohexyl-18-crown-6. 
The promoter is desirably added in an amount of 0.5 to 5% by weight based 
on the reaction charge. 
The reaction conditions include a temperature of 50.degree. to 150.degree. 
C., preferably 80.degree. to 130.degree. C. and a time of about 8 to about 
16 hours. 
Reaction of the compound of formula (1) with the compound of formula (2) 
under the above-mentioned conditions produces a 
bis(alkoxysilylalkoxy)arylene compound of formula (3) wherein substituent 
R.sup.3 is a lower alkyl group. Hydrolysis of the silicon compound of 
formula (3) produces a bis(hydroxysilylalkoxy)arylene compound of formula 
(4) having substituent R.sup.3 in formula (3) replaced by a hydrogen atom. 
Hydrolysis may be conventional hydrolysis for alkoxysilanes, that is, 
hydrolysis in a basic or acidic aqueous solution using a suitable diluent. 
This method has a possibility that silanol groups once formed condense in 
a basic or acidic condition according to the following scheme, reducing 
the yield of the end product. 
##STR16## 
For this reason, it is recommended to effect hydrolysis by a method for the 
synthesis of silanols from alkoxysilanes as described in W. Bread, R. L. 
Elliot and M. E. White head, Journal of Polymer Science, Part A-1, Vol. 2, 
2745-2755 (1967). Utilizing this method, a bis(alkoxysilylalkoxy)arylene 
compound of formula (3) is converted into a sodium siloxide, which is, in 
turn, neutralized with a phosphate buffer solution to synthesize a 
bis(hydroxysilylalkoxy)arylene compound of formula (4) having substituent 
R.sup.3 in formula (3) replaced by a hydrogen atom, in high yields. The 
reaction scheme is as shown below. 
##STR17## 
Finally, the bis(hydroxysilylalkoxy)arylene compound of formula (4) is 
polycondensed in the presence of a condensation catalyst to produce the 
end organopolysiloxane according to the present invention. Of course, two 
or more such compounds are polymerized when a copolymer is desired. The 
condensation catalysts used herein include n-hexylamine 2-ethylhexoate 
(see Rober L. Merker and Mary Jane Scot, Journal of Polymer Science, Part 
A, Vol. 2, 15 (1964)) and tetramethylguanidine di-2-ethylhexoate (see 
Rober L. Merker, Mary Jane Scot, and G. G. Haberland, Journal of Polymer 
Science, Part A, Vol. 2, 31 (1964)), to name a few. The reaction scheme is 
as shown below. 
##STR18## 
The condensation catalyst is used in a catalytic amount, typically 0.1 to 
10% by weight of the reaction system. 
The condensation reaction is preferably carried out in a reaction medium 
which azeotrops with water, for example, benzene, toluene, and xylene, so 
that product water may be taken out of the reaction system. In this 
respect, the reaction temperature is desirably higher than the azeotropic 
temperature of the medium with water. The reaction time usually ranges 
from 8 to 16 hours. 
The organopolysiloxane homopolymers and copolymers prepared in this way 
according to the invention have a higher melting point, glass transition 
temperature, modulus of elasticity, and mechanical strength than currently 
commercially available conventional organopolysiloxanes and their cured 
products or elastomers. They are thus suitable for use in various 
industrial fields including automobile, ship, aircraft, electric and 
electronic fields. They are usually formed into film, fibers and various 
other articles. 
The organopolysiloxane homopolymers and copolymers according to the 
invention may be combined with any desired one or more of well-known 
additives to further improve mechanical strength, solvent resistance or 
the like, depending on a particular intended purpose. Such additives 
include fillers such as fumed silica, precipitated silica, and calcium 
carbonate, coloring agents such as titanium oxide and carbon black, heat 
resistance modifiers, binders, and adhesives. 
The organopolysiloxane homopolymers and copolymers according to the 
invention have a high melting point and a high glass transition 
temperature, cure into products having a high modulus of elasticity and 
high mechanical strength so that they are suitable for various industrial 
applications, typically in electrical and electronic industries. Ease of 
synthesis is another important advantage.

EXAMPLE 
Examples of the present invention are given below by way of illustration 
and not by way of limitation. All parts and percents are by weight unless 
otherwise stated. 
Example 1 
(1) Synthesis of 2,2-bis{4'-[(dimethylmethoxysilyl)methoxy]phenyl}propane 
A mixture of 114 grams (0.5 mol) of 2,2-bis(4'-hydroxyphenyl)propane 
(bisphenol A), 228 grams of toluene, 228 grams of dimethylsulfoxide, and 
80 grams of a 50% aqueous solution of sodium hydroxide was stirred and 
heated at 110.degree.-120.degree. C. for 8 hours in a flask while 
azeotroping off water. There was synthesized sodium salt of bisphenol A. 
The reaction solution was then cooled to 80.degree. C., to which 145.4 
grams (1.05 mol) of chloromethyldimethoxysilane was added dropwise. The 
mixture was stirred at 80.degree. C. for a further 8 hours. The reaction 
solution was further cooled to room temperature and filtered to remove the 
precipitating sodium chloride. Vacuum distillation of the filtrate 
afforded 130 grams (yield 60%) of a white solid as a fraction at a boiling 
point of 205.degree. C./1 mmHg. 
This solid had the following physical properties and was identified to be 
2,2-bis{4'-[(dimethylmethoxysilyl)methoxy]phenyl}propane of the following 
structural formula. 
##STR19## 
Melting point: 106.degree. C. 
.sup.1 H--NMR (CCl.sub.4): .delta. (ppm) 
0.15 (Si--CH.sub.3, S, 12H), 1.53 (C--CH.sub.3, S, 6H), 
3.25 (SiOCH.sub.3, S, 6H), 3.31 (Si--CH.sub.2 --, S, 4H) 
MS: m/e=432 
(2) Synthesis of 2,2-bis{4'-[(dimethylhydroxysilyl)methoxy]phenyl}propane 
A flask was charged with 18.2 grams of sodium hydroxide, 12.6 grams of 
water, and 84 ml of methanol. A solution of 50 grams (0.116 mol) of 
2,2-bis{4'-[(dimethylmethoxysilyl)methoxy]phenyl}propane resulting from 
step (1) in 60 ml of tetrahydrofuran and 60 ml of ethanol was added 
dropwise to the flask at room temperature. The mixture was stirred for one 
hour. 
To the solution was added a solution of 18.2 grams of sodium hydroxide in 
84 ml of water. The mixture was stirred for one hour. The solution was 
added dropwise to a solution of 132.5 grams of potassium dihydrogen 
phosphate in 2100 grams of ice water and the mixture was allowed to stand 
for one day. The resulting solid was filtered, dried in vacuum, and 
recrystallized from toluene, obtaining 40.8 grams (yield 87%) of white 
crystals. 
This solid had the following physical properties and was identified to be 
2,2-bis{4'-[(dimethylhydroxysilyl)methoxy]phenyl}propane of the following 
structural formula. 
##STR20## 
Melting point: 106.degree. C. 
Elemental analysis: C.sub.21 H.sub.32 Si.sub.2 O.sub.4 
______________________________________ 
C H Si 
______________________________________ 
Calc. 62.32 7.99 13.88 
Found 62.41 7.92 13.69 
______________________________________ 
.sup.1 H--NMR (CD.sub.3 COCD.sub.3): .delta. (ppm) 
-0.12 (Si--CH.sub.3, S, 12H), 1.25 (C--CH.sub.3, S, 6H), 
3.13 (Si--CH.sub.2 --, S, 4.3H), 4.63 (O--H, S, 2H), 
6.38-6.83 (.phi.H, m, 8.4H) 
IR (KBr): Vmax 
3340 cm.sup.-1 (O--H), 2960 cm.sup.-1 (C--H) 
(3) Polymerization of 
2,2-bis{4'-[(dimethylhydroxysilyl)methoxy]phenyl}propane 
A flask was charged with 20 grams of 
2,2-bis{4'-[(dimethylhydroxysilyl)methoxy]phenyl}propane resulting from 
(2), 40 grams of toluene, and 0.2 grams of n-hexylamine 2-ethylhexoate. 
The contents were stirred for 12 hours at a temperature of 
120.degree.-140.degree. C. while azeotroping off water. 
The solution was then cooled to room temperature and added in increments to 
1000 ml of methanol with vigorous stirring, causing the resultant polymer 
to precipitate again. The polymer was collected by filtration and dried in 
vacuum, obtaining 17.8 grams of a white solid. 
The molecular weight of this solid was measured by means of a gel 
permeation chromatograph (GPC) model HLC-8020 (manufactured by Toyo Soda 
K.K.) loaded with a polystyrene gel column, finding a weight average 
molecular weight (Mw) of 164,000 and a number average molecular weight 
(Mn) of 60,700. Using a differential thermobalance model TA-3000 
(manufactured by Metra Co.), it was also measured for melting point (Tm) 
and glass transition temperature (Tg), which were 93.degree. C. and 
37.degree. C., respectively. 
This solid was dissolved in tetrahydrofuran to form a 20% solution, which 
was cast into a mold where the solvent was evaporated off to form a film 
of about 200 .mu.m thick. The film was measured for modulus in tension and 
tensile strength by means of a tensile tester. 
Modulus in tension (modulus at 1.25% elongation): 
145 kg/mn.sup.2 
@25.degree. C., gage mark span 25 mm, pulling rate 
1 mm/min. 
Tensile strength: 1.47 kg/mm.sup.2 
@25.degree. C., gage mark span 25 mm, pulling rate 
50 mm/min. 
Example 2 
(1) Synthesis of 4,4'-bis[(dimethylmethoxysilyl)methoxy]benzophenone 
A reaction procedure similar to step (1) of Example 1 was followed using 
107 grams (0.5 mol) of 4,4'-dihydroxybenzophenone, 214 grams of toluene, 
214 grams of dimethylsulfoxide, 80 grams of a 50% aqueous solution of 
sodium hydroxide, and 145.5 grams (1.05 mol) of 
chloromethyldimethoxysilane. Vacuum distillation afforded 86 grams (yield 
41%) of a pale yellow solid as a fraction at a boiling point of 
286.degree.-288.degree. C./1 mmHg. 
This solid had the following physical properties and was identified to be 
4,4'-bis[(dimethylmethoxysilyl)methoxy]benzophenone of the following 
structural formula. 
##STR21## 
Melting point: 52.degree. C. 
.sup.1 H--NMR (CCl.sub.4): .delta. (ppm) 
0.1 (Si--CH.sub.3, S, 12H), 3.33 (SiOCH.sub.3, S, 6H), 
3.52 (Si--CH.sub.2 --, S, 4H), 6.85-7.60 (.phi.H, m, 8H) 
MS: m/e=418 
(2) Synthesis of 4,4'-bis[(dimethylhydroxysilyl)methoxy]benzophenone 
A reaction procedure similar to step (2) of Example 1 was followed using 
18.8 grams of sodium hydroxide, 13 grams of water, 86 ml of methanol, 50 
grams (0.12 mol) of 4,4'-bis[(dimethylmethoxysilyl)methoxy]benzophenone 
resulting from step (1), 120 ml of ethanol, 18.8 grams of sodium 
hydroxide, 86 ml of water, 137 grams of potassium dihydrogen phosphate, 
and 2,200 grams of ice water. Recrystallization from toluene gave 28.8 
grams (yield 61%) of pale yellow crystals. 
This solid had the following physical properties and was identified to be 
4,4'-bis[(dimethylhydroxysilyl)methoxy]benzophenone of the following 
structural formula. 
##STR22## 
Melting point: 126.degree. C. 
Elemental analysis: C.sub.19 H.sub.26 Si.sub.2 O.sub.5 
______________________________________ 
C H Si 
______________________________________ 
Calc. 57.97 6.67 15.03 
Found 58.18 6.83 14.90 
______________________________________ 
.sup.1 H--NMR (CD.sub.3 COCD.sub.3): .delta. (ppm) 
-0.3 (Si--CH.sub.3, S, 12H), 3.17 (Si--CH.sub.2 --, S, 3H), 
4.47 (OH, S, 1.9H), 6.43-7.27 (.phi.H, m, 8.3H) 
IR (KBr): Vmax 
3250 cm.sup.-1 (O--H), 2960 cm.sup.-1 (C--H) 
(3) Polymerization of 4,4'-bis[(dimethylhydroxysilyl)methoxy]benzophenone 
A reaction procedure similar to step (3) of Example 1 was followed using 20 
grams of 4,4'-bis[(dimethylhydroxysilyl)methoxy]benzophenone resulting 
from (2), 40 grams of toluene, and 0.2 grams of n-hexylamine 
2-ethylhexoate. There was obtained 17.3 grams of a pale yellow solid. 
Similarly, this solid were measured for physical properties. 
Mw: 86,600 
Mn: 38,000 
Tm: 92.degree. C. 
Tg: 44.degree. C. 
Modulus in tension: 155 kg/mm.sup.2 
Tensile strength: 3.18 kg/mm.sup.2 
Example 3 
(1) Synthesis of 
2,2-bis{4'-[(vinylmethylmethoxysilyl)methoxy]phenyl}propane 
A reaction procedure similar to step (1) of Example 1 was followed using 
114 grams (0.5 mol) of 2,2-bis(4'-hydroxyphenyl)propane (bisphenol A), 228 
grams of toluene, 228 grams of dimethylsulfoxide, 80 grams of a 50% 
aqueous solution of sodium hydroxide, and 158.0 grams (1.05 mol) of 
chloromethylvinylmethylmethoxysilane. Vacuum distillation afforded 98 
grams (yield 43%) of a white solid as a fraction at a boiling point of 
240.degree.-243.degree. C./1 mmHg. 
This solid had the following physical properties and was identified to be 
2,2-bis{4'-[(vinylmethylmethoxysilyl)methoxy]phenyl}propane of the 
following structural formula. 
##STR23## 
Melting point: 87.degree. C. 
.sup.1 H--NMR (CCl.sub.4): .delta. (ppm) 
0.23 (Si--CH.sub.3, S, 6H), 1.55 (C--CH.sub.3, S, 6H), 
3.45 (SiOCH.sub.3, S, 6H), 3.55 (Si--CH.sub.2 --, S, 4H), 
5.66-6.25 (Si--CH.dbd.CH.sub.2, m, 6H), 
6.6-7.1 (.phi.H, m, 8H) 
MS: m/e=456 
(2) Synthesis of 
2,2-bis{4'-[(vinylmethylhydroxysilyl)methoxy]phenyl}propane 
A reaction procedure similar to step (2) of Example 1 was followed using 
17.2 grams of sodium hydroxide, 11.9 grams of water, 86 ml of methanol, 50 
grams (0.11 mol) of 
2,2-bis{4'-[(vinylmethylmethoxysilyl)methoxy]phenyl}propane resulting from 
step (1), 60 ml of tetrahydrofuran, 60 ml of ethanol, 17.2 grams of sodium 
hydroxide, 80 ml of water, 125.2 grams of potassium dihydrogen phosphate, 
and 1,980 grams of ice water. Recrystallization from toluene gave 38.6 
grams (yield 82%) of white crystals. 
This solid had the following physical properties and was identified to be 
2,2-bis{4'-[(vinylmethylhydroxysilyl)methoxy]phenyl}propane of the 
following structural formula. 
##STR24## 
Melting point: 108.degree. C. 
Elemental analysis: C.sub.23 H.sub.32 Si.sub.2 O.sub.4 
______________________________________ 
C H Si 
______________________________________ 
Calc. 64.44 7.53 13.10 
Found 64.52 7.47 13.01 
______________________________________ 
.sup.1 H--NMR (CD.sub.3 COCD.sub.3): .delta. (ppm) 
-0.13 (Si--CH.sub.3, S, 6H), 1.17 (C--CH.sub.3, S, 6H), 
3.23 (Si--CH.sub.2 --, S, 4.2H), 4.73 (O--H, S, 2H), 
5.56-6.0 (Si--CH.dbd.CH.sub.2, m, 6.1H), 
6.36-6.8 (.phi.H, m, 8.2H) 
IR (KBr): Vmax 
3340 cm.sup.-1 (O--H), 2960 cm.sup.-1 (C--H) 
(3) Copolymerization of 
2,2-bis{4'-[(dimethylhydroxysilyl)methoxy]phenyl}propane with 
2,2-bis[4'-[(vinylmethylhydroxysilyl)methoxy]phenyl}propane 
A reaction procedure similar to step (3) of Example 1 was followed using 
40.4 grams (0.1 mol) of 
2,2-bis{4'-[(dimethylhydroxysilyl)methoxy]phenyl}propane resulting from 
step (2) of Example 1, 0.856 grams (0.002 mol) of 
2,2-bis{4'-[(vinylmethylhydroxysilyl)methoxy]phenyl}propane resulting from 
step (2) of this example, 96 grams of toluene, and 0.4 grams of 
n-hexylamine 2-ethylhexoate. There was obtained 32 grams of a white solid. 
Similarly, this solid were measured for physical properties. 
Mw: 159,600 
Mn: 74,600 
Tg: 29.degree. C. 
Modulus in tension: 32 kg/mm.sup.2 
Tensile strength: 1.1 kg/mm.sup.2 
Example 4 
(1) Synthesis of p-bis[(methylphenylmethoxysilyl)methoxy]benzene 
A reaction procedure similar to step (1) of Example 1 was followed using 
55.0 grams (0.5 mol) of hydroquinone, 110 grams of toluene, 110 grams of 
dimethylsulfoxide, 80 grams of a 50% aqueous solution of sodium hydroxide, 
and 210.5 grams (1.05 mol) of chloromethylphenylmethylmethoxysilane. 
Vacuum distillation afforded 140 grams (yield 32%) of a clear colorless 
liquid as a fraction at 217.degree.-218.degree. C./0.8 mmHg. 
This liquid had the following physical properties and was identified to be 
p-bis[(methylphenylmethoxysilyl)methoxy]benzene of the following 
structural formula. 
##STR25## 
Specific gravity: 1.1043 @25.degree. C. 
Refractive index (n.sup.25.sub.D): 1.5541 
.sup.1 H--NMR (CCl.sub.4): .delta. (ppm) 
0.27 (Si--CH.sub.3, S, 6H), 3.27 (SiOCH.sub.3, S, 5.8H), 
3.5 (Si--CH.sub.2, S, 4.1H), 6.5-7.4 (.phi.H, m, 13.9H) 
MS: m/e=438 
(2) Synthesis of p-bis[(methylphenylhydroxysilyl)methoxy]benzene 
A reaction procedure similar to step (2) of Example 1 was followed using 
17.9 grams of sodium hydroxide, 12.4 grams of water, 82 ml of methanol, 
50 grams (0.11 mol) of p-bis[(methylphenylmethoxysilyl)methoxy]benzene 
resulting from step (1), 120 ml of ethanol, 17.9 grams of sodium 
hydroxide, 82 ml of water, 125.2 grams of potassium dihydrogen phosphate, 
and 2,100 grams of ice water. There was obtained a clear colorless viscous 
liquid. This liquid was dissolved in 200 ml of toluene, washed a few times 
with water, dried over anhydrous sodium sulfate, heated to 150.degree. C., 
and vacuum stripped at the temperature, obtaining 38 grams of a clear 
colorless viscous liquid. 
This liquid was measured for infrared absorption spectrum and NMR spectrum 
and was identified to have the following structural formula. 
##STR26## 
IR (KBr): Vmax 
3325 cm.sup.-1 (O--H) 
.sup.1 H--NMR (CD.sub.3 COCD.sub.3): .delta. (ppm) 
-0.07 (SiCH.sub.3, S, 6H), 3.26 (SiCH.sub.2, S, 4.1H), 
4.8 (SiOH, S, 3.8H), 6.31-7.23 (.phi.H, m, 14.3H) 
(3) Polymerization of p-bis[(methylphenylhydroxysilyl)methoxy]benzene 
A reaction procedure similar to step (3) of Example 1 was followed using 20 
grams of p-bis[(methylphenylhydroxysilyl)methoxy]benzene resulting from 
(2), 40 grams of toluene, and 0.2 grams of n-hexylamine 2-ethylhexoate. 
There was obtained 16.8 grams of a white solid. Similarly, this solid were 
measured for physical properties. 
Mw: 26,400 
Mn: 12,900 
Tg: 28.degree. C. 
Modulus in tension: 4.5 kg/mm.sup.2 
Tensile strength: 1.15 kg/mm.sup.2 
Several preferred embodiments have been described. Obviously many 
modifications and variations of the present invention are possible in the 
light of the above teachings. It is therefore to be understood that within 
the scope of the appended claims, the invention may be practiced otherwise 
than as specifically described.