Sulfonated silicones and methods for their production
AssigneeRensselaer Polytechnic Institute
InventorsGary E. Wnek, Jun-Kang Liu
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Abstract
A process for the preparation of sulfonated silicones is disclosed. The process comprises the steps of (a) hydrosilylating an olefin-terminal silylketene acetal with a hydrosiloxane; (b) treating the ketene acetal with a trialkylsilylsulfonyl chloride and (c) hydrolyzing the resulting .alpha.-trialkylsilyl ester to provide a salt of an .alpha.-sulfonate. Useful products of the process are also disclosed; they comprise several genera of .alpha.-sulfonate esters pendant from siloxanes and polysiloxanes. The products are useful as polymer electrolytes and as sustained or controlled release substrates for the administration of medicines.
Claims40
A compound of formula ##STR23## wherein R.sup.1 is phenylene, naphthylene, or linear or branched alkylene;
- R.sup.2 is hydrogen or lower-alkyl;
- R.sup.3 is alkyl;
- R.sup.4a is lower-alkyl, lower alkoxy, or tri(lower-alkyl)siloxy;
- R.sup.5 and R.sup.6 are independently chosen from the group consisting of lower-alkyl, lower-alkoxy and ##STR24## R.sup.7 is lower-alkyl;
- m is zero or an integer from 1 to 100;
- and
- A.sup.+ is hydrogen, alkali metal, ammonium or tetra(lower-alkyl)ammonium.
A compound of formula ##STR25## wherein R.sup.1 is phenylene, naphthylene or linear or branched alkylene;
- R.sup.2 is hydrogen or lower-alkyl;
- R.sup.4a is lower-alkyl, lower-alkoxy, or tri(lower-alkyl)siloxy;
- R.sup.5 and R.sup.6 are independently chosen from the group consisting of lower-alkyl, lower-alkoxy and ##STR26## R.sup.7 is lower-alkyl;
- R.sup.8 is hydrogen or alkyl;
- m is zero or an integer from 1 to 100;
- and
- A.sup.+ is hydrogen, alkali metal, ammonium or tetra(lower-alkyl)ammonium.
A random copolymer of formula ##STR27## wherein R.sup.1 is phenylene, naphthylene or linear or branched alkylene;
- R.sup.2 is hydrogen or lower-alkyl;
- R.sup.3 is alkyl;
- R.sup.4 is lower-alkyl;
- R.sup.12 is lower alkyl or CH.sub.2 CH.sub.2 R.sup.13 where R.sup.13 is hydrogen, lower-alkyl, ferrocenyl, poly(alkyleneoxy) or --R.sup.1 --CH(R.sup.2 )COOR.sup.3 ;
- n is an integer from 2 to 2000;
- p is zero or an integer from 1 to 2000;
- and
- A.sup.+ is hydrogen, alkali metal, ammonium, or tetra(lower-alkyl)ammonium.
A random copolymer of formula ##STR28## wherein R.sup.1 is phenylene, napthylene or linear or branched alkylene;
- R.sup.2 is hydrogen or lower-alkyl;
- R.sup.4 is lower-alkyl;
- R.sup.8 is alkyl;
- R.sup.14 is lower alkyl or --CH.sub.2 CH.sub.2 --R.sup.15 where R.sup.15 is hydrogen, lower-alkyl, ferrocenyl poly(alkyleneoxy) or --R.sup.1 --OC(O)CHR.sup.2 R.sup.8 ;
- n is an integer from 2 to 2000;
- p is zero or an integer from 1 to 2,000;
- and
- A.sup.+ is hydrogen, alkali metal, ammonium or tetra(lower-alkyl)ammonium.
A random copolymer of formula ##STR29## wherein R.sup.1 is phenylene, napthylene or linear or branched alkylene;
- R.sup.2 is hydrogen or lower-alkyl;
- R.sup.3 is alkyl;
- R.sup.4 and R.sup.16 are independently lower-alkyl;
- R.sup.12 is lower alkyl or --CH.sub.2 CH.sub.2 --R.sup.13 where R.sup.13 is hydrogen, lower-alkyl, ferrocenyl poly(alkyleneoxy) or --R.sup.1 --CH(R.sup.2)COOR.sup.3 ;
- n and q are integers from 2 to 2000;
- p is zero or an integer from 1 to 2,000;
- and
- A.sup.+ is hydrogen, alkali metal, ammonium or tetra(lower-alkyl)ammonium.
A random copolymer of formula ##STR31## wherein R.sup.1 is phenylene, napthylene or linear or branched alkylene;
- R.sup.2 is hydrogen or lower-alkyl;
- R.sup.8 is alkyl;
- R.sup.4 and R.sup.16 are independently lower-alkyl;
- R.sup.14 is lower alkyl or CH.sub.2 CH.sub.2R.sup.15 where R.sup.15 is hydrogen, lower-alkyl, ferrocenyl poly(alkyleneoxy) or --R.sup.1 --OC--(O)CHR.sup.2 R.sup.8 ;
- n and q are integers from 2 to 2000;
- p is zero or an integer from 1 to 2,000;
- and
- A.sup.+ is hydrogen, alkali metal, ammonium or tetra(lower-alkyl)ammonium.
A compound of formula ##STR33## wherein R.sup.1 is phenylene, napthylene or linear or branched alkylene;
- R.sup.2 is hydrogen or lower-alkyl;
- R.sup.3 is alkyl;
- R.sup.4 is lower-alkyl;
- r is an integer from 3 to 5;
- and
- A.sup.+ is hydrogen, alkali metal, ammonium or tetra(lower-alkyl)ammonium.
A compound of formula ##STR34## wherein R.sup.1 is phenylene, napthylene or linear or branched alkylene;
- R.sup.2 is hydrogen or lower-alkyl;
- R.sup.4 is lower-alkyl;
- R.sup.8 is alkyl;
- r is an integer from 3 to 5;
- and
- A.sup.+ is hydrogen, alkali metal, ammonium, or tetra(lower-alkyl)ammonium.
A process for the preparation of sulfonated silicones comprising the steps of:
- (a) reacting a silicone having Si--H bonds with an olefin-terminated (trialkyl silyl) ketene acetal of formula ##STR35## wherein R.sup.2 is hydrogen or lower-alkyl;
- R.sup.9 is lower-alkyl;
- and
- one of
- R.sup.10 and R.sup.11 is alkyl and the other is an olefin-terminal linear or branched alkylene, phenylene or naphthylene radical;
- in the presence of a hydrosilylation catalyst to produce a silicone attached to said ketene acetal at the terminal carbon of said olefin-terminal radical R.sup.10 or R.sup.11 ;
- (b) treating said ketene acetal attached to said silicone with a trialkylsily sulfonyl chloride to produce an .alpha.-trialkylsilysulfonyl ester;
- and
- (c) hydrolyzing said .alpha.-trialkylsily sulfonyl ester with a mild base to provide a salt of an .alpha.-sulfonate.
A process for the preparation of sulfonated silicones comprising the steps of:
- (a) reacting a silicone having Si--H bonds with an olefin-terminal .alpha.-trialkylsilylsulfonyl ester of formula ##STR36## wherein R.sup.2 is hydrogen or lower-alkyl;
- R.sup.9 is lower-alkyl;
- and
- one of
- R.sup.10 and R.sup.11 is alkyl and the other is an olefin-terminal linear or branched alkylene, phenylene or naphthylene radical;
- in the presence of a hydrosilylation catalyst to produce a silicone attached to said .alpha.-trialkylsily sulfonyl ester at the terminal carbon of said olefin-terminal radical R.sup.10 or R.sup.11 ;
- and
- (b) hydrolyzing said .alpha.-trialkylsilylsulfonyl ester with a mild base to provide a salt of an .alpha.-sulfonate.
A process for the preparation of sulfonated silicones comprising the steps of:
- (a) reacting a silicone having Si--H bonds with an olefin-terminated ester of formula XXII ##STR37## wherein R.sup.7 is hydrogen or lower-alkyl;
- and one of R.sup.10 and R.sup.11 is alkyl and the other is an olefin-terminal linear or branched alkylene, phenylene or naphthylene radical, in the presence of a hydrosilylation catalyst to produce a silicone attached to the ester at the terminal carbon of the olefin-terminal radical R.sup.10 or R.sup.11 ;
- and
- (b) treating the ester with a strong base followed by a trialkylsilyl halide to form a ketene acetal;
- (c) treating the ketene acetal with a trialkylsilyl sulfonyl chloride to produce an .alpha.-trialkylsilyl-sulfonyl ester;
- and
- (d) hydrolyzing the .alpha.-trialkylsilyl sulfonyl ester with a mild base to provide a salt of an .alpha.-sulfonate.
Dependencies are inferred from the claim text.