Fluorine-containing polymers and preparation and use thereof

Abstract

Group IV organometallic compounds, e.g. alkylsilane, or alkylsiloxane compounds, are used as chain transfer agent in the radical initiated polymerization of ethylenically unsaturated monomers, to give polymers comprising non-ionic end groups.

What is claimed is: 
     
       1. A method for the preparation of fluorine-containing polymer comprising, polymerizing .Iadd.in an aqueous emulsion or suspension.Iaddend., under free-radical conditions, a polymerizable mixture comprising fluorine-containing ethylenically unsaturated monomer, and a non-free-radically polymerizable organometallic compound .[.comprising a.]. .Iadd.containing 1 to 10 .Iaddend.silicon .[.atom.]. .Iadd.atoms .Iaddend.and .[.an.]. .Iadd.at least one .Iaddend.aliphatic carbon atom bonded directly to .Iadd.at least .Iaddend.said silicon atom and to .[.a.]. .Iadd.at least one .Iaddend.hydrogen atom. 
     
     
       2. The method of claim 1 wherein said fluorine-containing monomer is selected from the group consisting of vinylidene fluoride, hexafluoropropene, chlorotrifluoroethylene, 2-chloropentafluoropropene, perfluoroalkyl vinyl ethers, tetrafluoroethylene, 1-hydropentafluoropropene, dichlorodifluoroethylene, 2-hydropentafluoropropene, vinyl fluoride, trifluoroethylene, 1,1-dichlorofluoroethylene, perfluorodiallylether, and perfluoro-1,3-dioxoles of formula ##STR4## where each R f  is F, C n  F 2n+1  where n is from 1 to 4, or where the two R f  groups together .Iadd.with the depicted carbon atom to which they are bonded .Iaddend.form a ring of formula C n  F 2n-2  where n is from 5 to 8. 
     
     
       3. The method of claim 1 wherein said polymerizable mixture further comprises fluorine-free ethylenically unsaturated monomer. 
     
     
       4. The method of claim 1 wherein .[.said organometallic compound comprises from 1 to 200 silicon atoms, and.]. said silicon atoms are bonded directly to each other or through an alkylene group, arylene group, sulfur atom, oxygen atom, phosphorus atom, nitrogen atom, or combinations thereof. 
     
     
       5. The method of claim 4 wherein said organometallic compound is a siloxane, silazane, or silane. 
     
     
       6. The method of claim 4 wherein said organometallic compound has the formula   R-[(R).sub.2 M].sub.z --[(Q).sub.x --M(R).sub.2 ].sub.y --CH(R).sub.2     where M is said silicon atom, Q is a divalent linking group, each R is independently H, alkyl, aryl, or combinations thereof, x is 0 or 1, z is 0 or 1, and y is an integer from 1 to 9. .[.7. The method of claim 1 wherein said polymerizing comprises polymerizing in an aqueous emulsion or   
     
     
        suspension..].8. The method of claim .[.7.]. .Iadd.1 .Iaddend.wherein said organometallic compound is selected from the group consisting of hexamethyldisilane, tetramethylsilane, and hexamethyldisiloxane and wherein said fluorine-containing monomer is selected from the group consisting of vinylidene fluoride, hexafluoropropene, tetrafluoroethylene, 
     
     
        and chlorotrifluoroethylene. 9. In a method of preparing fluorine-containing polymer by polymerizing .Iadd.in an aqueous emulsion or suspension.Iaddend., under free-radical conditions, a polymerizable mixture comprising fluorine-containing ethylenically unsaturated monomer, the improvement comprising polymerizing said mixture in the presence of a non-free-radically polymerizable organometallic compound .[.comprising a.]. .Iadd.containing 1 to 10 .Iaddend.silicon .[.atom.]. .Iadd.atoms .Iaddend.and .[.an.]. .Iadd.at least one .Iaddend.aliphatic carbon atom bonded directly to .Iadd.at least one of .Iaddend.said silicon .[.atom.]. .Iadd.atoms .Iaddend.and to .[.a.]. .Iadd.at least one .Iaddend.hydrogen 
     
     
        atom. 10. The method of claim 9 wherein said .[.organometallic compound comprises from 1 to 200.]. silicon atoms .Iadd.are .Iaddend.bonded directly to each other or through an alkylene group, arylene group, sulfur atom, oxygen atom, phosphorus atom, nitrogen atom, or combinations thereof.