Grafted fluoroelastomers

1. A process for making a grafted fluoroelastomer, said process comprising:

a) mixing in the bulk i) a polyhydroxy curable fluoroelastomer gum, said fluoroelastomer being substantially free of nucleophilic endgroups with ii) a monophenol having a pendant group, iii) an accelerator and iv) an acid acceptor to form a graftable fluoroelastomer composition; and

b) heating said graftable composition at a temperature between 80° C. and 250° C., thereby producing a grafted fluoroelastomer having a plurality of pendant groups bonded to carbon atoms on said grafted fluoroelastomer through monophenols, said grafted fluoroelastomer being substantially free of nucleophilic endgroups and having a Mooney viscosity, ML(1+18) at 135° C., of less than 160.

2. A process of claim 1 wherein said mixing step A) is at a temperature less than 80° C.

3. A process of claim 1 wherein said heating step B) is performed with gentle mixing.

4. A process of claim 1 wherein said heating step B) is to a temperature between 130° C. and 200° C.

5. A process of claim 1 wherein said fluoroelastomer gum is selected from the group consisting of copolymers of i) vinylidene fluoride with hexafluoropropylene; ii) vinylidene fluoride with hexafluoropropylene and tetrafluoroethylene; iii) vinylidene fluoride with a perfluoro(alkyl vinyl ether), 2-hydropentafluoroethylene and tetrafluoroethylene; iv) tetrafluoroethylene with propylene and 3,3,3-trifluoropropene; and v) ethylene with tetrafluoroethylene, perfluoro(methyl vinyl ether) and 3,3,3-trifluoropropylene.

6. A process of claim 1 wherein said monophenol is selected from the group consisting of 2-methoxy-4-allyl phenol; 2-allylphenol; 2,5-diallylphenol; p-acetamidophenol; m-hydroxy-N-methylacetanilide; p-hydroxymethylbenzoic acid phenyl ester; hydroxybenzoic acid phenylesters; 3-hydroxy-2-naphthoic acid phenyl ester; a monoacrylate ester of a bisphenol; a monoacrylate ester of a dihydroxybenzene; a monoacrylate ester of a dihydroxynaphthalene; 4-hydroxystyrene; a monoallyl ether of bisphenol AF; and a monovinyl ether of bisphenol AF.

7. A process for making a grafted fluoroelastomer, said process comprising:

mixing in the bulk, at a temperature between 80° C. and 250° C., i) a polyhydroxy curable fluoroelastomer gum, said fluoroelastomer being substantially free of nucleophilic endgroups with ii) a monophenol having a pendant group, iii) an accelerator and iv) an acid acceptor to form a grafted fluoroelastomer having a plurality of pendant groups bonded to carbon atoms on said grafted fluoroelastomer through monophenols, said grafted fluoroelastomer being substantially free of nucleophilic endgroups and having a Mooney viscosity, ML(1+18) at 135° C., of less than 160.

8. A process of claim 7 wherein said fluoroelastomer gum is selected from the group consisting of copolymers of i) vinylidene fluoride with hexafluoropropylene; ii) vinylidene fluoride with hexafluoropropylene and tetrafluoroethylene; iii) vinylidene fluoride with a perfluoro(alkyl vinyl ether), 2-hydropentafluoroethylene and tetrafluoroethylene; iv) tetrafluoroethylene with propylene and 3,3,3-trifluoropropene; and v) ethylene with tetrafluoroethylene, perfluoro(methyl vinyl ether) and 3,3,3-trifluoropropylene.

9. A process of claim 7 wherein said monophenol is selected from the group consisting of 2-methoxy4-allyl phenol; 2-allylphenol; 2,5-diallylphenol; p-acetamidophenol; m-hydroxy-N-methylacetanilide; p-hydroxymethylbenzoic acid phenyl ester; hydroxybenzoic acid phenylesters; 3-hydroxy-2-naphthoic acid phenyl ester; a monoacrylate ester of a bisphenol; a monoacrylate ester of a dihydroxybenzene; a monoacrylate ester of a dihydroxynaphthalene; 4-hydroxystyrene; a monoallyl ether of bisphenol AF; and a monovinyl ether of bisphenol AF.

10. A process for making a grafted fluoroelastomer from a polyhydroxy curable fluoroelastomer gum, said process comprising:

a) mixing in the bulk, at a temperature between 80° and 250° C., i) a polyhydroxy curable fluoroelastomer gum, said fluoroelastomer being substantially free of nucleophilic endgroups, with ii) an accelerator and iii) an acid acceptor, in the absence of a grafting agent, to form an unsaturated fluoroelastomer;

b) mixing i) said unsaturated fluoroelastomer composition with ii) a monophenol having a pendant group, iii) an accelerator and iv) an acid acceptor to form a graftable composition; and

c) heating said graftable composition at a temperature between 80° C.-250° C., thereby producing a grafted fluoroelastomer having a plurality of pendant groups bonded to carbon atoms through monophenols, said grafted fluoroelastomer being substantially free of nucleophilic endgroups and having a Mooney viscosity, ML(1+18) at 135° C., of less than 160.

11. A process of claim 10 wherein said fluoroelastomer gum is selected from the group consisting of copolymers of i) vinylidene fluoride with hexafluoropropylene; ii) vinylidene fluoride with hexafluoropropylene and tetrafluoroethylene; iii) vinylidene fluoride with a perfluoro(alkyl vinyl ether), 2-hydropentafluoroethylene and tetrafluoroethylene; iv) tetrafluoroethylene with propylene and 3,3,3-trifluoropropene; and v) ethylene with tetrafluoroethylene, perfluoro(methyl vinyl ether) and 3,3,3-trifluoropropylene.

12. A process of claim 10 wherein said monophenol is selected from the group consisting of 2-methoxy-4-allyl phenol; 2-allylphenol; 2,5-diallylphenol; p-acetamidophenol; m-hydroxy-N-methylacetanilide; p-hydroxymethylbenzoic acid phenyl ester; hydroxybenzoic acid phenylesters; 3-hydroxy-2-naphthoic acid phenyl ester; a monoacrylate ester of a bisphenol; a monoacrylate ester of a dihydroxybenzene; a monoacrylate ester of a dihydroxynaphthalene; 4-hydroxystyrene; a monoallyl ether of bisphenol AF; and a monovinyl ether of bisphenol AF.