Method for preparation of siloxanyl phosphate

Abstract: A method for producing siloxanyl phosphate under moderate conditions and at a fast rate to yield a high viscosity siloxanyl phosphate having a low phosphoric acid content. The siloxanyl phosphate prepared by our method is particularly suitable as an agent for neutralizing basic catalysts used in manufacturing processes for producing high viscosity diorganopolysiloxanes. Our method comprises reacting a mixture comprising phosphoric acid and a hydroxyl-ended diorganosiloxane. A preferred method reacts a mixture of phosphoric acid, a hydroxyl-ended diorganosiloxane, and a triorganosiloxy-ended diorganosiloxane.

Description: This invention introduces a method of manufacturing siloxanyl phosphate under moderate conditions at a fast rate which is of high viscosity and of low phosphoric acid content. This siloxanyl phosphate product can be used as a neutralization agent for the basic catalyst used in manufacturing processes for high viscosity diorganopolysiloxanes. The ring-opening polymerization of cyclic diorganopolysiloxanes is catalyzed by a basic catalyst, namely, alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, and cesium hydroxide, lithium hydroxide, or silanolates or siloxanates of these alkali metals. The condensation polymerization of α,ω-hydroxyl-capped diorganopolysiloxane is also catalyzed by the above basic catalyst, followed by the neutralization of the basic catalyst with acidic substances. These are well known methods for manufacturing high viscosity diorganopolysiloxanes. The acidic substance used as the neutralization agent for the above basic catalyst can be hydrochloric acid, acetic acid, phosphoric acid, carbon dioxide. However, the hydrochloric acid and acetic acid added have to be exactly weighed to their theoretical quantity against the basic catalyst in the diorganopolysiloxane. Otherwise, the heat resistance of the diorganopolysiloxane obtained is degraded by excess basic catalyst or by excess acidic substance. Also, when carbon dioxide (which is a weak acid) is used, the neutralization salt produced decomposes at elevated temperatures and again forms a basic substance. Therefore, this neutralization salt has to be completely removed from the diorganopolysiloxane, or the heat resistance of the diorganopolysiloxane obtained is generally poor. Phosphoric acid is a preferable neutralization agent in that the phosphate produced by neutralization functions as a buffer for the residual phosphoric acid or basic catalyst when its addition amount is not weighed out exactly to the theoretical quantity. Therefore the phosphate does not suppress the heat resistance of the diorganopolysiloxane. However, phosphoric acid, and other acidic substances such as hydrochloric acid, and acetic acid are insoluble in diorganopolysiloxane. Therefore, its mixing and contacting efficiency during the neutralization process is low, and it is a problem if its neutralization time is too long. Because of this situation, phosphoric acid-containing organic silicon compounds such as silylphosphate, and siloxanyl phosphate, have been studied as the neutralization agent for basic catalysts in diorganopolysiloxanes. In particular, siloxanyl phosphate is of merit since its viscosity is higher when compared to silylphosphate. Therefore, the neutralization time can be shortened drastically by the improved miscibility with the diorganopolysiloxane when it is used as a neutralization agent. Also, siloxanyl phosphate is of merit since its phosphoric acid content in a molecule is less than that of silylphosphate, and even if it is not weighed out correctly to its theoretical quantity against the basic catalyst, this error is usually smaller. Manufacturing methods for siloxanyl phosphates are illustrated, for example, by a method where phosphoric acid or a phosphorus halide compound and hexaorganodisiloxane or triorganosiloxy-capped diorganopolysiloxane are heated to react while removing generated water (refer to JP-A 54-89000). A method of manufacturing siloxanyl phosphate is taught where phosphoric acid and triorganosiloxy-capped diorganopolysiloxane are reacted in the presence of silylphosphate catalyst (refer to JP-A 54-109924). A further method of manufacturing siloxanyl phosphate is taught where a silylphosphate mixture (prepared by adding phosphoric acid to hexaorganodisiloxane under heated reflux and heating while removing generated water) and cyclic diorganosiloxane are reacted (refer to JP-A 5-194557). However, the manufacturing methods of proposed in the above patents have slow reaction rates without addition of more phosphoric acid to the reaction system. Also, the reaction has to proceed at temperatures in the range of 150°C-200°C for several hours because siloxanyl phosphate formulation is extremely slow under moderate conditions. Consequently, it is a problem that the residual phosphoric acid content in the siloxanyl phosphate is naturally greater. Furthermore, the methods of JP-A 54-109924 and JP-A 5-194557, do not proceed at all without silylphosphate. Therefore, it is also necessary to prepare silylphosphate beforehand, and this further complicates the manufacturing process for siloxanyl phosphate. The objective of this invention is to provide a manufacturing method for a high viscosity and low phosphoric acid content siloxanyl phosphate, which can be used as a neutralization agent for the basic catalyst in the manufacturing process for high viscosity diorganopolysiloxanes, and which can neutralize the basic catalyst quickly under moderate conditions. This invention provides to a method for producing siloxanyl phosphate under moderate conditions and at a fast rate to yield a high viscosity siloxanyl phosphate having a low phosphoric acid content. Our siloxanyl phosphate is particularly useful as an agent for neutralizing basic catalysts adapted for producing high viscosity diorganopolysiloxanes. Our preparatory method comprises reacting a mixture comprising phosphoric acid and a hydroxyl-ended diorganosiloxane. A preferred method comprises reacting a mixture comprising phosphoric acid, a hydroxyl-ended diorganosiloxane, and a triorganosiloxy-ended diorganosiloxane. The present invention is a method for preparing siloxanyl phosphates described by formula : where each R 1 is an independently selected monovalent hydrocarbon group, and is an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a halogen substituted alkyl group, R 2 is a hydroxyl group or monovalent hydrocarbon group where at least one of R 2 is a hydroxyl group, z is an integer of 1 or greater, and a is an integer of 1 to 3. This method comprises reacting a mixture comprising: (A) phosphoric acid and (B) a hydroxyl-endblocked diorganosiloxane described by formula: where each R 1 is an independently selected monovalent hydrocarbon group and is an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a halogen substituted alkyl group, and x is an integer of 1 or greater. The mixture comprising the phosphoric acid and hydroxyl-endblocked diorganosiloxane may optionally comprise as needed (C) a triorganosiloxy-endblocked diorganosiloxane described by formula: where each R 1 is an independently selected monovalent hydrocarbon group and is an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a halogen substituted alkyl group, and y is an integer of 1 or greater. Constituent (A), phosphoric acid, is the predominant raw material in the method of this present invention. Its purity is not particularly limited, and also, if it is used as an aqueous phosphoric acid solution, its concentration is not limited. In general, a commercially available aqueous phosphoric acid (about 85 weight %) can be used as the constituent (A). The constituent (B), a hydroxyl-endblocked diorganosiloxane, is the raw material which is incorporated into the siloxanyl phosphate of our invention by forming P-O-Si bonds in a fast reaction under moderate conditions by contact with constituent (A). Constituent (B) is described by formula (2) above. Therein each R 1 is an independently selected monovalent hydrocarbon group, and is an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl; an alkenyl group such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, and octenyl; an aryl group such as phenyl, tolyl, xylyl, and naphthyl; an aralkyl group such as benzyl, and phenethyl; or a halogen substituted alkyl group such as 3-chloropropyl, or 3,3,3-trifluoropropyl. Preferred is when R 1 is a methyl group or a phenyl group. Also, x is an integer of 1 or greater, and preferably an integer in the range of 1 to 100. Specific examples of constituent (B) are 1,3-dihydroxy-1,1,3,3-tetramethyldisiloxane, 1,5-dihydroxy-1,1,3,3,5,5-hexamethyltrisiloxane, α,ω-hydroxydimethylsiloxy-capped dimethylpolysiloxane, α,ω-hydroxydimethylsiloxy-capped methylphenylpolysiloxane, α,ω-hydroxydimethylsiloxy-capped dimethylsiloxane-methylphenylsiloxane copolymer, α,ω-hydroxydimethyleiloxy-capped methylvinylpolysiloxane, α,ω-hydroxydimethylsiloxy-capped dimethylsiloxanemethylvinylsiloxane copolymer, α,ω-hydroxydimethylsiloxy-capped methylphenylsiloxane-diphenylsiloxane copolymer, and α,ω-hydroxydimethylsiloxy-capped methylvinylpolysiloxane. The method of preparing of constituent (B) is not particularly limited. It can be a method in which, after a hydrolyzable silane such as diorganodichlorosilane, or diorganodialkoxysilane, is hydrolyzed, it is then subjected to a condensation reaction; a method in which, after a cyclic diorganosiloxane is subjected to a polymerization reaction with a basic catalyst, the basic catalyst is neutralized by acetic acid, hydrochloric acid, or carbon dioxide; or a method in which, after cyclic diorganosiloxane is subjected to a polymerization reaction with an acidic catalyst, the acidic catalyst is neutralized by sodium hydroxide, potassium hydroxide, or ammonia gas. Furthermore, constituent (C), a trimethylsiloxy-ended diorganosiloxane, can optionally be reacted with constituent (B). Constituent (C) is described by formula (3). It is preferable to use constituent (C) in our present method since the viscosity of the siloxanyl phosphate thereby obtained can be readily adjusted. When only constituent (A) is reacted with constituent (B) this is not the situation. In formula (3), each R 1 is an independently selected monovalent hydrocarbon group. R 1 is an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl; an alkenyl group such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, and octenyl; an aryl group such as phenyl, tolyl, xylyl, and naphthyl; an aralkyl group such as benzyl group, or phenethyl; or a halogen substituted alkyl group such as 3-chloropropyl, or 3,3,3-trifluoropropyl. Preferred is when R 1 is a methyl group or a phenyl group. Also, y is an integer of 1 or greater, and preferably an integer in the range of 1 to 100. Specific examples of constituent (C) are 1,1,1,3,3,3-hexamethyldisiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 1,1,3,3-tetramethyl-1,3-diphenylsiloxane, 1,1,1,3,3,5,5,5-octamethyltrisiloxane, α,ω-trimethylsiloxy-capped dimethylpolysiloxane, α,ω-trimethylsiloxy-capped methylvinylpolysiloxane, α,ω-trimethylsiloxy-capped methylphenylpolysiloxane, α,ω-trimethylsiloxy-capped dimethylsiloxane-methylphenylsiloxane copolymer, α,ω-trimethylsiloxy-capped dimethylsiloxanemethylvinylsiloxane copolymer, α,ω-trimethylsiloxy-capped methylphenylsiloxane-diphenylsiloxane copolymer, α,ω-dimethylvinylsiloxy-capped -capped dimethylpolysiloxane, α,ω-dimethylvinylsiloxy-capped methylphenylpolysiloxane, α,ω-dimethyivinylsiloxy-capped methylvinylpolysiloxane, α,ω-dimethylvinylsiloxy-capped dimethylsiloxane-methylphenylsiloxane copolymer, α,ω-dimethylvinylsiloxy-capped dimethylsiloxane-methylvinylsiloxane copolymer, α,ω-dimethylvinylsiloxy-capped methylphenylsiloxane-diphenylsiloxane copolymer, α,ω-dimethylphenylsiloxy-capped -capped dimethylpolysiloxane, α,ω-dimethylphenylsiloxy-capped methylphenylpolysiloxane, α,ω-dimethylphenylsiloxy-capped methylvinylpolysiloxane, α,ω-dimethylphenylsiloxy-capped dimethylsiloxane-methylphenylsiloxane copolymer, α,ω-dimethylphenylsiloxy-capped dimethylsiloxanemethylvinylsiloxane copolymer, and α,ω-dimethylphenylsiloxy-capped methylphenylsiloxane-diphenylsiloxane copolymer. There is no particular limitation for the preparation of constituent (C). For example, it can be a method in which hydrolyzable triorganosilane such as triorganochlorosilane, or triorganoalkoxysilane, together with diorganodichlorosilane or diorganodialkoxysilane, as needed, are subjected to a hydrolytic condensation reaction; a method in which, after the polymerization reaction of hexaorganodisiloxane and cyclic diorganosiloxane with basic catalyst, the basic catalyst is neutralized; a method in which, after the polymerization reaction of hexaorganodisiloxane and cyclic diorganosiloxane with acidic catalyst, the acidic catalyst is neutralized; and a method in which constituent (B), hydroxyl-endblocked diorganosiloxane, is reacted with triorganochlorosilane or hexaorganodisilazane and then capped with triorganosiloxy groups at the terminals of the molecule. Furthermore, in the present method, cyclic diorganosiloxane described by formula: is added to our method in order to increase the siloxane units in the siloxanyl phosphate and to manufacture high viscosity siloxanyl phosphate. In this latter formula, each R 1 is an independently selected monovalent hydrocarbon group and is an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl; an alkenyl group such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, and octenyl; an aryl group such as phenyl, tolyl, xylyl, and naphthyl; an aralkyl group such as benzyl, or phenethyl; or a halogen substituted alkyl group such as 3-chloropropyl, or 3,3,3-trifluoropropyl. Preferred is where the R 1 groups of formula (4) are a methyl group or a phenyl group. Also in formula (4), p is an integer of 4 or greater. Specific examples of cyclic diorganosiloxane include 1,1,3,3,5,5,7,7-octamethyltetracyclosiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyltetracyclosiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenyltetracyclosiloxane, 1,1,3,3,5,5,7,7,9,9-decamethylpentacyclosiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentavinylpentacyclosiloxane, and 1,3,5,7,9-pentamethyl-1,3,5,7,9-pentaphenylpentacyclosiloxane. In the present method, the reaction conditions are not particularly limited, and the preferable reaction temperature is in a range from room temperature to 200°C, and more preferably in a range of 80 to 150°C. Also, the reaction time varies depending on the reaction temperature, but preferably is in the range of several tens of minutes to several hours. In our method, it is preferable to remove water from the reaction and condensation water generated during the reaction process. The method to remove water is by azeotropic removal by organic solvent, or removal by heating under atmospheric pressure or reduced pressure. Also, the storage stability of our siloxanyl phosphate prepared in this manner can be improved by storing in sealed containers to avoid moisture. When constituent (A) and constituent (B), and optionally constituent (C), are reacted, organic solvent can be added to the reaction. So long as the reaction is not impaired, there is no particular limitation on the organic solvent which is used. It can be an aromatic organic solvent such as toluene, or xylene; an aliphatic hydrocarbon organic solvent such as heptane, hexane, and octane; a cyclic aliphatic hydrocarbon organic solvent such as cyclohexane, or cycloheptane; a ketone organic solvent such as acetone, methylethylketone, and methylisobutylketone; an ester organic solvent such as methyl acetate, ethyl acetate, and isobutyl acetate; and other organic solvents such as tetrahydrofuran, dimethylformamide, and dimethyl sulfoxide. The siloxanyl phosphate prepared by our method is described by formula (1). In formula (1), R 1 is a monovalent hydrocarbon group, and is specifically an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl; an alkenyl group such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, and octenyl; an aryl group such as phenyl, tolyl, xylyl, and naphthyl; an aralkyl group such as benzyl, or phenethyl; or a halogen substituted alkyl group such as 3-chloropropyl, or 3,3,3-trifluoropropyl. Preferred to where R 1 is a methyl group or a phenyl group. Also, R 2 is a hydroxyl group or a monovalent hydrocarbon group, and at least one of R 2 is a hydroxyl group. Specific examples of R 2 can be the same groups as described for R 1 . Preferred is where R 2 is a hydroxyl group, a methyl group, or a phenyl group. Further, z is an integer of 1 or greater, and a is an integer of 1 to 3. These siloxanyl phosphates are obtained from the present method as a mixture, and the major constituents of the mixture are described by formulas: In formulas (5), (6), and (7) each R 1 is an independently selected monovalent hydrocarbon group as previously described. Each R 2 is an independently selected monovalent hydrocarbon group as previously described or a hydroxyl group, and z is an integer of 1 or greater. In addition to our siloxanyl phosphates described by the above formulas, siloxanyl phosphates are also formed having a structure where two phosphorus atoms are bonded by a diorganosiloxane chain, of formula: where R 1 is a monovalent hydrocarbon group as previously described, and z is an integer of 1 or greater. Each of the siloxanyl phosphates comprising the product mixture of our present method does not have to be isolated and purified. The product mixture can be readily used as the neutralization agent for the basic catalyst in a manufacturing process for a high viscosity diorganopolysiloxane. The viscosity of the siloxanyl phosphate prepared by our method is not particularly limited, but preferably is in a range of from several tens of centipoises to several tens of thousand centipoises (mPa.s). A siloxanyl phosphate of an appropriate viscosity can be used depending on its application and handling method. Also, the phosphoric acid content of the siloxanyl phosphate prepared by the method of this invention is not particularly limited. Preferably it is in a range of 0.01 to 10 weight %. A siloxanyl phosphate of an appropriate phosphoric acid content can be used depending on its application and handling method. The siloxanyl phosphate prepared by our method is of a high viscosity and a low phosphoric acid content. When it is used as a neutralization agent for the basic catalyst in a manufacturing process for high viscosity diorganopolysiloxane, it can be mixed with said diorganopolysiloxane quickly, and the basic catalyst will be neutralized in a short time. Therefore, our siloxanyl phosphate is especially suitable as a neutralization agent in a manufacturing process for diorganopolysiloxanes having a viscosity of 1000 centipoises (mPa.s) at 25°C to diorganopolysiloxane gums of high viscosity. To neutralize the basic catalyst with the siloxanyl phosphate, the phosphoric acid in the siloxanyl phosphate should be preferably more than the equivalent amount of basic catalyst. For example, when potassium catalyst is used as the basic catalyst, the phosphoric acid content of the siloxanyl phosphate is preferably in a range of 0.5 to 1 mole per mole of potassium. The present method for preparing siloxanyl phosphate is explained in detail by the following Examples. In the Examples, the viscosity is the value measured at 25°C. Example 1. 2.96 g of a 85 weight % aqueous solution of phosphoric acid and 397.0 g of α,ω-hydroxydimethylsiloxy-capped dimethylpolysiloxane described by the average formula: were loaded in a 1 liter round-bottom flask equipped with a Dean-Stark trap, thermometer, and stirrer. The solution was heated and stirred at 80°C for 6 hours. Then the viscosity of the system increased and generation of condensation water was observed, and a clear and viscous liquid having a viscosity of 824,000 centipoises (mPa.s) was obtained. This viscous liquid was analyzed by "Si-nuclear magnetic resonance spectra (hereafter NMR) and 31 P-NMR. No absorption attributable to O=P(OH) 3 was observed, whereas O=P(OH) 2 (OSi) bonding, O=P(OH)(OSi) 2 bonding, and O=P(OSi) 3 bonding were identified and the mole ratio of each bonding was 6.5 : 81.5 : 12.0. The viscous liquid was identified as a dimethylsiloxanyl phosphate mixture (phosphoric acid content = 0.63 weight %) of which the major constituents were dimethylsiloxanyl phosphate described by the average formula: dimethylsiloxanyl phosphate described by the average formula and dimethylsiloxanyl phosphate described by the average formula Example 2. 2.96 g of a 85 weight % aqueous solution of phosphoric acid and 397.0 g of α,ω-hydroxydimethylsiloxy-capped dimethylpolysiloxane described by the average formula were loaded in a 1 liter round-bottom flask equipped with a Dean-Stark trap, thermometer, and stirrer, and heated and stirred at 80°C for 6 hours. Then the viscosity of the system increased and generation of condensation water was observed. Subsequently, 22.15 g of α,ω-trimethylsiloxy-capped dimethylpolysiloxane described by the average formula was added, heated and stirred at 90°C for 5 hours. Then, this system was heated and stirred at 140°C to remove condensation water from the system. A clear viscous liquid with a viscosity of 3,000 centipoises (mPa.s) was obtained. This viscous liquid was analyzed by 29 Si-NMR and 31 P-NMR. No absorption attributable to O=P(OH) 3 was observed, whereas O=P(OH)(OSi) 2 bonding and O=P(OSi) 3 bonding were identified and the mole ratio of each bonding was 78.0 : 22.0. The viscous liquid was identified as a dimethylsiloxanyl phosphate mixture (phosphoric acid content = 0.60 weight %) of which the major constituents were dimethylsiloxanyl phosphate described by the average formula and dimethylsiloxanyl phosphate described by the average formula In the above formulas, X is hydroxyl groups or methyl groups. Example 3. 3.0 g of a 85 weight % aqueous solution of phosphoric acid, 350.0 g of α,ω-hydroxydimethylsiloxy-capped dimethylpolysiloxane described by the average formula and 50.0 g of α,ω-trimethylsiloxy-capped dimethylpolysiloxane described by the average formula were loaded in a 1 liter round-bottom flask equipped with a Dean-Stark trap, thermometer, and stirrer, and heated and stirred at 140°C for 4 hours. Then the viscosity of the system increased and generation of condensation water was observed. A clear viscous liquid with a viscosity of 440 centipoises (mPa.s) was obtained. This viscous liquid was analyzed by 29 Si-NMR and 31 P-NMR. No absorption attributable to O=P(OH) 3 was observed, whereas O=P(OH)(OSi) 2 bonding and O=P(OSi) 3 bonding were identified and the mole ratio of each bonding was 80.0 : 20.0. The viscous liquid was identified as a dimethylsiloxanyl phosphate mixture (phosphoric acid content = 0.63 weight %) of which the major constituents were dimethylsiloxanyl phosphate described by the average formula and dimethylsiloxanyl phosphate described by the average formula In the above formulas, X is hydroxyl groups orthyl groups. Comparison Example 1. 2.45 g of a 85 weight % aqueous solution of phosphoric acid, 50.0 g of α,ω-trimethylsiloxy-capped dimethylpolysiloxane described by the average formula and 47.5 g of 1,1,3,3,5,5,7,7-octamethyltetracyclosiloxane were loaded in a 1 liter round-bottom flask equipped with a Dean-Stark trap, thermometer, and stirrer, and heated and stirred at 100°C for 6 hours. No equilibrium polymer was obtained. Comparison Example 2. 2.72 g of a 85 weight % aqueous solution of phosphoric acid and 397.7 g of α,ω-trimethylsiloxy-capped dimethylpolysiloxane described by average formula were loaded in a 1 liter round-bottom flask equipped with a Dean-Stark trap, thermometer, and stirrer, and heated and stirred at 90°C for 6 hours. No equilibrium polymer was obtained. Comparison Example 3. 30.0 g dimethylsiloxanyl phosphate catalyst (phosphoric acid content = 0.63 weight %), of which the major constituent was dimethylsiloxanyl phosphate described by the average formula 3.0 g of a 85 weight % aqueous solution of phosphoric acid, 50.0 g α,ω-trimethylsiloxy-capped dimethylpolysiloxane described by the average formula and 350.0 g of 1,1,3,3,5,5,7,7-octamethyltetracyclosiloxane were loaded in a 1 liter round-bottom flask equipped with a Dean-Stark trap, thermometer, and stirrer, and heated and stirred at 150°C for 6 hours. No equilibrium polymer was obtained. Application Example. Cyclic dimethylsiloxane, of which the major constituent is 1,1,3,3,5,5,7,7-octamethyltetracyclosiloxane, and 1,1,3,3-tetramethyl-1,3-divinylsiloxane, and potassium hydroxide in the amount of 100 ppm were loaded in a small Ross mixer, and heated and stirred at 150°C for polymerization. Subsequently, dimethylsiloxanyl phosphate mixture as prepared in Example 2 (phosphoric acid content = 0.60 weight %) was added to this system in the amount of 1 mole of potassium per 0.7 mole of phosphorus in the above and stirred for 10 minutes. In this manner, α,ω-dimethylvinylsiloxy-capped dimethylpolysiloxane with a viscosity of 10,000 centipoises (mPa.s) was prepared. This dimethylpolysiloxane was analyzed by thermogravimetric analysis (hereafter TGA), and it was found that the temperature at which 10 % weight loss occurred was 470°C. Also in the above polymerization, neutralization was performed using trimethylsilyl phosphate instead of our dimethylsiloxanyl phosphate as prepared in Example 2. By the TGA analysis of α,ω-dimethylvinylsiloxy-capped dimethylpolysiloxane obtained in this manner, it was found that the temperature at which 10 % weight loss occurred was 370°C. Also in the above polymerization, the TGA analysis of α,ω-dimethylvinylsiloxy-capped dimethylpolysiloxane obtained by neutralization using trimethylsilyl phosphate and stirring for 2 hours showed that the temperature at which 10 % weight loss occurred was 470°C. Further in the above polymerization, the TGA analysis of α,ω-dimethylvinylsiloxy-capped dimethylpolysiloxane obtained by neutralization by introducing carbon dioxide gas into the system and stirring for 2 hours showed that the temperature at which 10 % weight loss occurred was 320°C.

Claims: A method for preparing siloxanyl phosphates described by formula where each R 1 is an independently selected monovalent hydrocarbon group and is an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a halogen substituted alkyl group, R 2 is a hydroxyl group or monovalent hydrocarbon group and at least one R 2 is a hydroxyl group, z is an integer of 1 or greater, and a is an integer of 1 to 3, the method comprising reacting a mixture comprising (A) phosphoric acid and (B) a hydroxyl-endblocked diorganosiloxane described by formula where each R 1 is an independently selected monovalent hydrocarbon group and is an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a halogen substituted alkyl group, and x is an integer of 1 or greater. A method according to Claim 1, where the mixture further comprises (C) a triorganosiloxy-endblocked diorganosiloxane described by formula where each R 1 is an independently selected monovalent hydrocarbon group and is an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a halogen substituted alkyl group and y is an integer of 1 or greater. A method according to Claims 1 or 2, the mixture further comprising (D) a cyclic diorganosiloxane described by formula where each R 1 is an independently selected monovalent hydrocarbon group and is an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a halogen substituted alkyl group and p is an integer of 4 or greater. A method according to Claims 1-3, where each R 1 is independently selected from methyl or phenyl. A method according to Claim 1, where the mixture is reacted at a temperature within a range from room temperature to 200°C. A method according to Claims 1-3, the mixture further comprising (E) an organic solvent. A method according to Claim 6, where the siloxanyl phosphate has a phosphoric acid content in a range of 0.01 to 10 weight percent.

Inventors: NOMURA TOSHIO, NOMURA, TOSHIO, NOMURA, TOSHIO, DOW CORNING TORAY
Applicants: DOW CORNING TORAY SILICONE, DOW CORNING TORAY SILICONE COMPANY, LIMITED
Application year: 1995
Main classification: C07F9
IPC codes: C08G77, C07F9