2-(aryl)propylhydridopolysiloxane type silicone fluids and methods for preparing the same

The present invention relates to novel 2-(aryl)hydrogenpolysiloxane type silicone fluids as represented by the formula I and their preparation methods by hydrolyzing mixtures of 2-(aryl)hydrogendichlorosilane and diorganodichlorosilane as represented by the formula II and formula III respectively. ##STR1## wherein X.sup.1 and X.sup.2 represent independent hydrogen or alkyl (C.sub.1 -C.sub.3), phenyl, phenoxy, fluoro, chloro, bromo, mercapto, mercaptomethyl group; R.sup.1 and R.sup.2 represent independently methyl or phenyl group; M represents H or SiMe.sub.3 group wherein Me represents methyl and when M is hydrogen, the silanol groups at the both ends of the molecule easily undergo dehydration so that they can cyclize to form the cyclic silicone fluids. The mixing ratio (x/y) of the compounds as represented in formula II and formula III respectively can be 1:0.01-1:100.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to novel cyclic or linear 
2-(aryl)hydrogenpolysiloxane type silicon fluids as represented by the 
formula I and their preparation methods by hydrolyzing mixtures of 
2-(aryl)hydrogendichlorosilane and diorganodichlorosilane as represented 
by the formula H and formula Ill respectively. 
##STR2## 
wherein X.sup.1 and X.sup.2 represent independently hydrogen or alkyl 
(C.sub.1 -C.sub.3), phenyl, phenoxy, fluoro, chloro, bromo, mercapto, or 
mercaptomethyl group; R.sup.1 and R.sup.2 represent independently methyl 
or phenyl group; M represents H or SiMe.sub.3 group wherein Me represents 
methyl and when M is hydrogen, the silanol groups at the both ends of the 
molecule easily undergo dehydration so that they can cyclize to form the 
cyclic silicone fluids. The mixing ratio (x/y) of the compounds as 
represented in formula II and formula III respectively can be 
1:0.01-1:100. 
2. Description of the Prior Art 
It is well known in the art that polymethylhydrogensiloxanes when applied 
to textile fabrics or masonry, are capable of imparting water repellency 
thereto. (Walter Noll, Chemistry and Technology of Silicone, Academic 
Press, 1968, p-196) When they are condensed on the fiber, 
polymethylhydrogensiloxanes give a hard nonsticky film. Regarded 
chemically, this is a case of cross-linking through the formation of 
Si--O--Si bonds in place of the Si--H bond. The cross-linking reaction can 
be initiated by water, more quickly in an alkaline medium; the former 
gives rise to hydrolysis of the Si--H bonds to silanol groups, which is 
subsequently condensed to give siloxanes. The cross-linking reaction of 
Si--H bond can be brought about not only by hydrolytic rupture but also by 
oxidation at elevated temperatures, possibly under the action of a 
catalyst. 
##STR3## 
In general, the preparation of organosilicone fluids is performed by the 
hydrolysis and condensation of organosilanes, such as those having two 
methyl or other organic radicals bonded to the silicon atoms, has 
heretofore been described. The hydrolysis is conducted by reacting a 
chlorosilane, such as dimethyldichlorosilane, with water, generally in the 
presence of an inert solvent. The organosilicone fluids are thus obtained 
without difficulty. (Wilcock, U.S. Pat. No. 2,491,843, Patnode and 
Wilcock, J. Am. Chem. Soc., 68, 358 (1946)) Dimethyldichlorosilane gives 
with water a mixture of polydimethylcyclosiloxanes and linear 
polydimethylsiloxane-.alpha.,.omega.-diols. Depending upon the hydrolysis 
methods, the ratio of cyclic and linear fluids in the products varies. 
Hydrolysis with dilute hydrochloric acid or the employment of organic 
solvent in hydrolysis can increase the proportion of cyclic fluids. The 
so-called "reversed" hydrolysis, in which a calculated amount of water is 
added to the mixture of organochlorosilanes, is recommended for the 
co-hydrolysis of organochlorosilanes having widely differing rates. Thus, 
the "reversed" hydrolysis has been recommended for the co-hydrolysis of 
silane mixtures of dichlorodimethylsilane and methyltrichlorosilane, 
methyltrichlorosilane and chlorotrimethylsilane, or of 
diorganidichlorosilanes with different organic substituents. (Walter Noll, 
Chemistry and Technology of Silicone, Academic Press, 1968, p-196) The 
special modified silicone fluids can be prepared by replacing a proportion 
of the methyl groups in polydimethylsiloxanes by other organic groups such 
as phenyl, vinyl, hydrido, etc. When the fluids of type 
polymethylhydrogen-siloxanes is applied to textile fabrics or masonry, the 
substrates become water repellent. Since they are hydrosilated with 
polymethylvinylsiloxanes a rubbery material is obtained, they are used for 
the manufacture of two-components room temperature vulcanizing rubber. 
The chlorosilanes may be dissolved in an inert organic solvent such as 
toluene, benzene, carbon tetrachloride, ether, liquid aliphatic 
hydrocarbons. By hydrolysis of methyldichlorosilane equivalent fluids 
should be producible, in as much as the silicon-bonded hydrogen is not 
readily hydrolyzed by water. Instead, when methyldichlorosilane is 
hydrolyzed with water, hard, brittle products are produced instead of the 
expected fluids. Obviously, under these conditions the hydrogen has been 
cleaved from the silicon. Various methods have been proposed for avoiding 
this result. Thus, the use of an inert solvent has been suggested. 
Likewise, it has been proposed that the cleavage of the hydrogen may be 
avoided by maintaining low temperature during hydrolysis. A third method 
which has been proposed to avoid the production of the resinous products 
is the co-hydrolysis of trimethylchlorosilane with the 
methyldichlorosilane. The first two proposals above mentioned are not 
entirely sufficient. The third method effects solubilizing of the product 
only by virtue of end-blocking, and not by reduction in hydrogen loss from 
the siloxane. Accordingly, these methods have not led to entirely 
satisfactory results. At best, only a small amount of oil is obtained, the 
remainder being useless. 
Nitzsche and Pirson later reported on improved methods for the hydrolysis 
of methyldichlorosilane to obtain improved hydrolysis products in improved 
yield in U.S. Pat. No. 2,647,911. In accordance with the process of the 
invention, methyldichlorosilane is reacted with an alcohol to effect 
interchange of alkoxy radicals for chlorine atoms, the alcohol being 
employed in amount less than two moles of alcohol per mole of 
methyldichlorosilane. The reaction product, which then contains both 
chlorine atoms and alkoxyl radicals bonded to the silicon, is hydrolyzed 
by reacting it with water in amount sufficient to hydrolyze both the 
chlorine atoms and the alkoxy radicals in the presence of an inert 
solvent. Operation in this manner results in the preferential formation of 
oils. 
John C. Goossens reported in U.S. Pat. No. 3,462,386 the preparation of the 
copolymers containing diorganosiloxy units and organohydogensiloxy units. 
The organic groups were selected from monovalent hydrocarbon radicals or 
halogenated monovalent hydrocarbon radicals. Fukuda and his coworkers 
reported in U.S. Pat. No. 4,528,156 that dimethylpolysiloxanes containing 
Si--H bonds could be added to vinyl containing silicones in the presence 
of platinum catalyst to give room temperature vulcanizing silicone rubber. 
The present inventors reported that allyldichlorosilane as the major 
product and allyltrichlorosilane were prepared by reacting allyl chloride, 
incorporated with hydrogen chloride, with elemental silicon in the 
presence of copper catalyst at a temperature from 260.degree. C. to 
360.degree. C. Cadmium was a good promoter and the reaction could be 
carried out in a fluidized bed or a stirred bed reactor. The incorporation 
of hydrogen chloride suppressed the decomposition of allyl chloride and 
prevented the production of diallyldichlosilane. Diallyldichlosilane 
easily caused the polymerization of the products at the reaction 
temperature. (Korean Patent Appln. No. 92-10292 (filed Jun. 13, 1992)) 
##STR4## 
We also reported the preparation of 2-(aryl)propyldichlorosilane by the 
Friedel-Craft reaction of allyldichlorosilane with aromatic compounds 
using aluminum chloride as a catalyst. Aromatic compounds could be 
benzene, alkyl substituted benzenes, halogen substituted benzenes, thiol 
or mercaptoalkyl substituted benzenes, naphthalene, byphenyl, byphenyl 
ethers, etc. (Korean Patent Appln. No. 92-12996 (7.21. 1992)) 
##STR5## 
SUMMARY OF THE INVENTION 
The present invention relates to novel 2-(aryl)hydrogenpolysiloxane type 
silicone fluids as represented by the formula I and their preparation 
methods by hydrolyzing mixtures of 2-(aryl)hydrogendichlorosilane and 
diorganodichlorosilane as represented by the formula II and formula III 
respectively. 
##STR6## 
wherein X.sup.1 and X.sup.2 represent independently hydrogen or 
alkyl(C.sub.1 -C.sub.3), phenyl, phenoxy, fluoro, chloro, bromo, mercapto, 
or mercaptomethyl group; R.sup.1 and R.sup.2 represent independently 
methyl or phenyl group; M represents H or SiMe.sub.3 group wherein Me 
represents methyl and when M is hydrogen, the silanol groups at the both 
ends of the molecule easily undergo dehydration so that they can cyclize 
to form the cyclic silicone fluids. The mixing ratio (x/y) of the 
compounds as represented in formula II and formula III respectively can be 
1:0.01-1:100. 
DETAILED DESCRIPTION OF THE INVENTION 
2-(Aryl)hydrogenpolysiloxanes type silicone fluids as represented by 
formula I according to the present invention can be prepared by any 
suitable methods described as below. For example, 
2-(aryl)propylhydrogenpolysiloxanes endblocked with hydroxy group or 
trimethylsiloxy groups are prepared by hydrolyzing 
2-(aryl)propyldichlorosilane or a mixture of trimethylchlorosilane and 
2-(aryl)propyldichlorosilane. The chlorosilanes may be dissolved in an 
inert organic solvent such as toluene, benzene, carbon tetrachloride, 
ether, liquid aliphatic hydrocarbons, etc. and then hydrolyzed by pouring 
the solution into water or the other way around. After hydrolysis the 
solution has been thoroughly washed with water to remove all, or 
substantially all, of the hydrochloric acid and then the solvent may be 
distilled to give the fluids. 2-(Aryl)propylhydrogenpolysiloxanes 
end-blocked with hydroxy group are prepared by hydrolyzing 
2-(aryl)propyldichlorosilane only. The same fluids end-blocked with 
trimethylsiloxy groups may be prepared by co-hydrolyzing 
2-(aryl)propyldichlorosilane and trimethylchlorosilane or equilibrating 
2-(aryl)propylhydrogenpolysiloxanes end-blocked with hydroxy group and 
hexamethyldisiloxane using concentrated sulfuric acid or CF.sub.3 SO.sub.3 
H. The copolymers containing diorganosiloxy- and 
2-(aryl)propylhydridosiloxy-groups may be prepared by co-hydrolyzing 
diorganodichlorosilane and 2-(aryl)propyl-dichlorosilane and then 
eqiulibrating the products with hexamethyldisiloxane. The same fluids may 
be prepared by eqiulibrating 2-(aryl)propylhydrogenpolysiloxanes 
end-blocked with trimethylsiloxy group and cyclic diorganopolysiloxanes 
using concentrated sulfuric acid or CF.sub.3 SO.sub.3 H

The invention will be further illustrated by the following examples. It is, 
however, not intended that this invention will be limited by the examples. 
EXAMPLE 1 
To a 300 ml, three neck, round bottomed flask equipped with a mechanical 
stirrer, a dropping funnel, and a condenser were added 5 g (0.02 mol) of 
3-phenyl-1,1-dichloro-1-silabutane and 30 ml of ether. Through the 
dropping funnel was added dropwise 20 ml of water over 30 min. After the 
solution was reacted for another hour with stirring, the organic layer was 
separated and washed three times with 20 ml of distilled water. The 
solution was dried over Mg.sub.2 SO.sub.4 and distilled under reduced 
pressure to remove the solvent. This product was very viscous liquid. The 
amount of the obtained product was 3.6 g. The GPC analysis result of this 
product represented by mean molecular weight of 5,000. As the analysis 
results by nuclear magnetic resonance spectroscopy (300 MHz) were observed 
peaks corresponding to Si--CH.sub.2 at 0.89-1.20 ppm, C-CH.sub.3 at 
1.25-1.43 ppm, CH at 2.92-3.10 ppm, Si--H at 4.54-4.69 ppm, aryl-H at 
7.11-7.35 ppm. 
EXAMPLE 2 
The same procedure as Example 1 was repeated except that 
3-(4-methylphenyl)-1,1-dichloro-1-silabutane was used instead of 
3-phenyl-1,1-dichloro-1-silabutane. The amount of the obtained product was 
3.6, with means molecular weight of 5,000. 
The products prepared by hydrolyzing various organochlorosilanes according 
to the procedures described above are listed in Table 1. 
TABLE 1 
__________________________________________________________________________ 
##STR7## 
X.sub.1 
X.sub.2 
SiCH.sub.2 
CH.sub.3 
CH SiH ArylH 
X.sub.1 and X.sub.2 
__________________________________________________________________________ 
H H 0.89-1.20 
1.25-1.43 
2.92-3.10 
4.54-4.69 
7.11-7.35 
H m & p-CH.sub.3 
0.99-1.24 
1.25-1.44 
2.98-3.16 
4.62-4.77 
7.00-7.35 
2.35(bf.s, 3H, CH.sub.3) 
H m & p-Et 
1.00-1.23 
1.25-1.43 
3.00-3.17 
4.63-4.78 
6.96-7.38 
1.25-1.43(br.m, 3H, CH.sub.3), 
2.66-2.78(br.s, 2H, CH.sub.3) 
H m & p-iso-pr 
1.03-1.27 
1.28-1.51 
3.02-31.7 
4.63-4.78 
6.96-7.38 
1.28-1.51(br.m, 3H, CH.sub.3), 
2.91-2.03(br.s, 1H, CH) 
H o-F 0.86-1.09 
1.21-1.34 
3.30-3.40 
4.53-4.72 
6.94-7.30 
H p-F 0.86-1.09 
1.21-1.34 
2.83-3.05 
4.53-4.72 
6.94-7.30 
H o-Cl 0.86-1.10 
1.23-1.39 
3.34-342 
4.53- 4.72 
7.07-7.39 
H p-Cl 0.86-1.10 
1.23-1.39 
2.87-3.00 
4.53-4.72 
7.07-7.39 
H o-Br 0.86-1.05 
1.20-1.31 
3.45-3.56 
4.53-4.72 
7.00-7.54 
H p-Br 0.86-1.05 
1.20-1.31 
2.85-2.98 
4.53-4.72 
7.00-7.54 
H m & p-Ph 
1.03-1.23 
1.27-1.47 
3.01-3.15 
4.53-4.72 
7.25-7.65 
7.25-7.65(m, 5H, Phenyl-H) 
H m & p-OPh 
1.01-1.24 
1.26-1.44 
3.10-3.42 
4.54-4.80 
6.90-7.43 
6.90-7.43(m, 5H, Phenyl-H) 
H m & p-SH 
0.90-1.26 
1.27-1.45 
2.92-3.10 
4.52-4.79 
7.02-7.47 
2.80-3.00(br.s, 1H, SH) 
H m & p-CH.sub.2 SH 
0.93-1.23 
1.27-1.43 
2.89-3.03 
4.53-4.78 
718-7.43 
3.25-3.37(br.s, 2H, CH.sub.2), 
2.85-3.05(br.s, 1H, SH) 
2 & 3-CH.sub.3 
3 & 4-CH.sub.3 
0.89-1.08 
1.20-1.33 
2.85-3.04 
4.58-4.71 
6.87-7.08 
2.24(br.s, 6H, CH.sub.3) 
2 & 3-CH.sub.3 
4 & 5-CH.sub.3 
0.88-1.09 
1.20-1.33 
2.85-3.04 
4.58-4.70 
6.87-7.08 
2.25(br.s, 6H, CH.sub.3) 
2-CH.sub.3 
5-CH.sub.3 
0.91-1.13 
1.20-1.39 
3.25-3.38 
4.58-4.71 
6.95-7.15 
2.37 & 2.39(br.s, 3H, 
__________________________________________________________________________ 
CH.sub.3) 
EXAMPLE 3 
The same procedure as Example 1 was repeated except that a mixture of 
3-(3,4-dimethylphenyl)-1,1-dichloro-1-silabutane (2.5 g, 0.01 mol) and 
dimethyldichlorosilane (1.3 g, 0.01 mol) was used instead of 
3-phenyl-1,1-dichloro-1-silabutane. The amount of the obtained product was 
3.6 with mean molecular weight of 20,000. 
NMR data of this type co-polymeric products were similar to those of the 
corresponding homopolymer listed in Table 1 except the peaks due to the 
dimethylsiloxy group at 0.05-0.22 ppm. 
EXAMPLE 4 
The same procedure as Example 1 was repeated except that a mixture of 3-(2 
& 4-fluorophenyl)-1,1-dichloro-1-silabutane (4.7 g, 0.02 tool)and 
dimethyldichlorosilane (0.03 g, 0.0002 mol) was used instead of 
3-phenyl-1,1 -dichloro-1-silabutane. The amount of the obtained product 
was 3.3 g with mean molecular weight of 5,000. 
NMR data of this type co-polymeric products were similar to those of the 
corresponding co-polymer of Example 3. 
EXAMPLE 5 
The same procedure as Example 1 was repeated except that a mixture of 3-(3 
& 4-mercaptophenyl)- 1,1-dichloro-1-silabutane (0.13 g, 0.0005 mol) and 
dimethyldichlorosilane (6.5 g, 0.05 mol) was used instead of 
3-phenyl-1,1-dichloro-1-silabutane. The amount of the obtained product was 
3.0 g, with mean molecular weight of 30,000. 
NMR data of this type co-polymeric products were similar to those of the 
corresponding co-polymer of Example 3. 
EXAMPLE 6 
The same procedure as Example 1 was repeated except that a mixture of 
3-(4-bromophenyl)-1,1-dichloro-1-silabutane (3.5 g, 0.012 mol) and 
dimethyldichlorosilane (1.52 g, 0.011 mol) was used instead of 
3-phenyl-1,1-dichloro-1-silabutane. The amount of the obtained product was 
2.84 g with mean molecular weight of 20,000. 
NMR data of this type co-polymeric products were similar to those of the 
corresponding homopolymer listed in Table 1 except the peaks due to the 
methyl of methylphenylsiloxy group at 0.09-0.40 ppm. The peaks due to the 
phenyl of methylphenylsiloxy group were overlapped with the other phenyl 
peaks. 
EXAMPLE 7 
The same procedure at Example 1 was repeated except that a mixture of 3-(2 
& 4-chlorophenyl)-1,1-dichloro-1-silabutane (2.7 g, 0.0011 mol), 
dimethyldichlorosilane (1.3 g, 0.011 mol), and trimethylchlorosilane (0.2 
g, 0.002 mol) was used instead of 3-phenyl-1,1-dichloro-1-silabutane. The 
obtained product was trimethylsiloxy end-blocked fluid and the amount of 
the product was 2.3 g with mean molecular weight of 8,000. 
NMR data of this type co-polymeric products were similar to those of the 
corresponding homopolymer listed in Table 1 except the peaks due to the 
trimethylsiloxy group at 0.01-0.23 ppm.