Method of polymerizing polydiorganosiloxane fluid-filler mixture using sulfuric or sulfonic acids

Claim 1

A method of producing a non-crepeing silicone polymer-filler mixture by bulk polymerization comprising (A) mixing (i) 100 parts by weight of polydiorganosiloxane (a) of the formula HO(R.sub.2 SiO).sub.x H, wherein each R is a radical selected from the group consisting of methyl, ethyl, propyl, phenyl, vinyl, allyl, and 3,3,3-trifluoropropyl, and x is an average value in the range of from 3 to 100 inclusive; optionally (i) can have present siloxane selected from the group consisting of polydiorganosiloxane (c) of the formula R.sub.3 'SiO(R.sub.2 SiO).sub.z SiR.sub.3 ', polydiorganosiloxane (d) of the formula R.sub.3 'SiO(R.sub.2 SiO).sub.z H, and mixtures thereof wherein each R is as defined above, each R' is a monovalent hydrocarbon radical of 6 or less carbon atoms, and z is an average value in the range of from 0 to 50 inclusive; (ii) from 2 to 70 parts by weight of reinforcing filler, said filler being acidic or neutral; and (iii) a catalytic amount of sulfuric acid or a sulfonic acid of the formula XSO 3 H, wherein X is selected from the group consisting of halogen, alkyl, aryl, alkoxy, and alkaryl radicals, (B) allowing polymerization to take place, and (C) inactivating the catalyst with a Lewis base to produce a non-crepeing dispersion of reinforcing filler in a polydiorganosiloxane having a higher molecular weight than the starting material in (i).

Claim 2

A method of producing a non-crepeing silicone polymer-filler mixture by bulk polymerization comprising (A) mixing (i) 100 parts by weight of polydiorganosiloxane (a) of the formula HO(R.sub.2 SiO).sub.x H, wherein each R is a radical selected from the group consisting of methyl, ethyl, propyl, phenyl, vinyl, allyl, and 3,3,3-trifluoropropyl, and x is an average value in the range of from 3 to 100 inclusive; optionally (i) can have present siloxane selected from the group consisting of polydiorganosiloxane (c) of the formula R.sub.3 'SiO(R.sub.2 SiO).sub.z SiR.sub.3 ', polydiorganosiloxane (d) of the formula R.sub.3 'SiO(R.sub.2 SiO).sub.z H, and mixtures thereof wherein each R is as defined above, each R' is a monovalent hydrocarbon radical of 6 or less carbon atoms, and z is an average value in the range of from 0 to 50 inclusive; (ii) from 2 to 70 parts by weight of reinforcing filler, said filler being acidic or neutral; and (iii) a catalytic amount of sulfuric acid or a sulfonic acid of the formula XSO 3 H, wherein X is selected from the group consisting of halogen, alkyl, aryl, alkoxy, and alkaryl radicals, (B) allowing polymerization to take place, and (C) inactivating the catalyst with a Lewis base to produce a non-crepeing dispersion of reinforcing filler in a polydiorganosiloxane having a higher molecular weight than the starting material in (i).

Claim 16

A method of producing a non-crepeing silicone polymer-filler mixture by bulk polymerization comprising (A) mixing together (i) and (ii) using sufficient shear to cause dispersion of (ii) in (i) before (iii) is added, (i) 100 parts by weight of polydiorganosiloxane (a) of the formula HO(R.sub.2 SiO).sub.x H, wherein each R is a radical selected from the group consisting of methyl, ethyl, propyl, phenyl, vinyl, allyl, and 3,3,3-trifluoropropyl, and x is an average value in the range of from 3 to 100 inclusive; (ii) from 5 to 20 parts by weight of fumed silica filler having a surface area of from 175 m 2 /g to 300 m 2 /g, and (iii) from 0.5 to 0.7 part by weight of dodecylbenzene sulfonic acid (B) allowing polymerization to take place, and (C) inactivating the catalyst with from 0.3 to 0.5 of diethylamine to produce a non-crepeing dispersion of reinforcing filler in a polydiorganosiloxane having a higher molecular weight than the starting material in (i).

Claim 17

A method of producing a non-crepeing silicone polymer-filler mixture by bulk polymerization comprising (A) mixing together (i) and (ii) using sufficient shear to cause dispersion of (ii) in (i) before (iii) is added, (i) 100 parts by weight of polydiorganosiloxane (a) of the formula HO(R.sub.2 SiO).sub.x H, wherein each R is a radical selected from the group consisting of methyl, ethyl, propyl, phenyl, vinyl, allyl, and 3,3,3-trifluoropropyl, and x is an average value in the range of from 3 to 100 inclusive; (ii) from 5 to 20 parts by weight of fumed silica filler having a surface area of from 175 m 2 /g to 300 m 2 /g, and (iii) from 0.5 to 0.7 part by weight of dodecylbenzene sulfonic acid (B) allowing polymerization to take place, and (C) inactivating the catalyst with from 0.3 to 0.5 of diethylamine to produce a non-crepeing dispersion of reinforcing filler in a polydiorganosiloxane having a higher molecular weight than the starting material in (i).

Claim 19

A method of producing a non-crepeing silicone polymer-filler mixture by bulk polymerization comprising (A) mixing (i) 100 parts by weight of polydiorganosiloxane (a) of the formula HO(R.sub.2 SiO).sub.x H, wherein each R is a radical selected from the group consisting of methyl, ethyl, propyl, phenyl, vinyl, allyl, and 3,3,3-trifluoropropyl, and x is an average value in the range of from 10 to 100 inclusive; optionally (i) can have present siloxane selected from the group consisting of polydiorganosiloxane (c) of the formula R.sub.3 'SiO(R.sub.2 SiO).sub.z SiR.sub.3 ', polydiorganosiloxane (d) of the formula R.sub.3 'SiO(R.sub.2 SiO).sub.z H, and mixtures thereof wherein each R is as defined above, each R' is a monovalent hydrocarbon radical of 6 or less carbon atoms, and z is an average value in the range of from 0 to 50 inclusive; (ii) from 2 to 70 parts by weight of reinforcing colloidal silica filler, said filler being acidic or neutral; and (iii) a catalytic amount of monoalkyl substituted benzene sulfonic acid, (B) allowing polymerization to take place, and (C) inactivating the catalyst with a Lewis base to produce a non-crepeing dispersion of reinforcing filler in a polydiorganosiloxane having a higher molecular weight than the starting material in (i).

Claim 20

A method of producing a non-crepeing silicone polymer-filler mixture by bulk polymerization comprising (A) mixing (i) 100 parts by weight of polydiorganosiloxane (a) of the formula HO(R.sub.2 SiO).sub.x H, wherein each R is a radical selected from the group consisting of methyl, ethyl, propyl, phenyl, vinyl, allyl, and 3,3,3-trifluoropropyl, and x is an average value in the range of from 10 to 100 inclusive; optionally (i) can have present siloxane selected from the group consisting of polydiorganosiloxane (c) of the formula R.sub.3 'SiO(R.sub.2 SiO).sub.z SiR.sub.3 ', polydiorganosiloxane (d) of the formula R.sub.3 'SiO(R.sub.2 SiO).sub.z H, and mixtures thereof wherein each R is as defined above, each R' is a monovalent hydrocarbon radical of 6 or less carbon atoms, and z is an average value in the range of from 0 to 50 inclusive; (ii) from 2 to 70 parts by weight of reinforcing colloidal silica filler, said filler being acidic or neutral; and (iii) a catalytic amount of monoalkyl substituted benzene sulfonic acid, (B) allowing polymerization to take place, and (C) inactivating the catalyst with a Lewis base to produce a non-crepeing dispersion of reinforcing filler in a polydiorganosiloxane having a higher molecular weight than the starting material in (i).

Claim 22

A method of producing a non-crepeing silicone polymer-filler mixture by bulk polymerization comprising (A) mixing (i) 100 parts by weight of polydiorganosiloxane (a) of the formula HO(R.sub.2 SiO).sub.x H, wherein each R is a radical selected from the group consisting of methyl, ethyl, propyl, phenyl, vinyl, allyl, and 3,3,3-trifluoropropyl, and x is an average value in the range of from 3 to 100 inclusive, and (ii) from 2 to 70 parts by weight of reinforcing colloidal silica filler using sufficient shear to cause dispersion of (ii) in (i), then heating the resulting mixture in a closed container to a temperature of from 100° C. to 170° C. while removing water from the system, for a time sufficient to remove water, then cooling the resulting dry minute to a temperature of from 80° C. to 100° C., then admixing (iii) from 0.5 to 1.0 part by weight of dodecylbenzene sulfonic acid, (B) allowing polymerization to take place by cooling the catalyzed mixture to a temperature in the range of from 30° C. to 35° C. and holding at temperature for a period of greater than 15 minutes until the desired increase in molecular weight is reached, and (C) inactivating the catalyst by admixing from 0.4 to 1.4 parts by weight of calcined magnesium oxide to produce a non-crepeing dispersion of reinforcing filler in a polydiorganosiloxane having a higher molecular weight than the starting material in (i).

Claim 23

A method of producing a non-crepeing silicone polymer-filler mixture by bulk polymerization comprising (A) mixing (i) 100 parts by weight of polydiorganosiloxane (a) of the formula HO(R.sub.2 SiO).sub.x H, wherein each R is a radical selected from the group consisting of methyl, ethyl, propyl, phenyl, vinyl, allyl, and 3,3,3-trifluoropropyl, and x is an average value in the range of from 3 to 100 inclusive, and (ii) from 2 to 70 parts by weight of reinforcing colloidal silica filler using sufficient shear to cause dispersion of (ii) in (i), then heating the resulting mixture in a closed container to a temperature of from 100° C. to 170° C. while removing water from the system, for a time sufficient to remove water, then cooling the resulting dry minute to a temperature of from 80° C. to 100° C., then admixing (iii) from 0.5 to 1.0 part by weight of dodecylbenzene sulfonic acid, (B) allowing polymerization to take place by cooling the catalyzed mixture to a temperature in the range of from 30° C. to 35° C. and holding at temperature for a period of greater than 15 minutes until the desired increase in molecular weight is reached, and (C) inactivating the catalyst by admixing from 0.4 to 1.4 parts by weight of calcined magnesium oxide to produce a non-crepeing dispersion of reinforcing filler in a polydiorganosiloxane having a higher molecular weight than the starting material in (i).

Claim 25

A method of producing a non-crepeing silicone polymer-filler mixture by bulk polymerization comprising (A) mixing (i) 100 parts by weight of polydiorganosiloxane (a) of the formula HO(R.sub.2 SiO).sub.x H, wherein each R is a radical selected from the group consisting of methyl, ethyl, propyl, phenyl, vinyl, allyl, and 3,3,3-trifluoropropyl, and x is an average value in the range of from 10 to 100 inclusive; (ii) from 2 to 70 parts by weight of reinforcing filler, said filler being acidic or neutral; and (iii) a catalytic amount of sulfuric acid or a sulfonic acid of the formula XSO 3 H, wherein X is selected from the group consisting of halogen, alkyl, aryl, alkoxy, and alkaryl radicals, (B) allowing polymerization to take place, and (C) inactivating the catalyst with a Lewis base to produce a non-crepeing dispersion of reinforcing filler in a polydiorganosiloxane having a higher molecular weight than the starting material in (i).

Claim 26

A method of producing a non-crepeing silicone polymer-filler mixture by bulk polymerization comprising (A) mixing (i) 100 parts by weight of polydiorganosiloxane (a) of the formula HO(R.sub.2 SiO).sub.x H, wherein each R is a radical selected from the group consisting of methyl, ethyl, propyl, phenyl, vinyl, allyl, and 3,3,3-trifluoropropyl, and x is an average value in the range of from 10 to 100 inclusive; (ii) from 2 to 70 parts by weight of reinforcing filler, said filler being acidic or neutral; and (iii) a catalytic amount of sulfuric acid or a sulfonic acid of the formula XSO 3 H, wherein X is selected from the group consisting of halogen, alkyl, aryl, alkoxy, and alkaryl radicals, (B) allowing polymerization to take place, and (C) inactivating the catalyst with a Lewis base to produce a non-crepeing dispersion of reinforcing filler in a polydiorganosiloxane having a higher molecular weight than the starting material in (i).