Highly fluorinated polymers

Patent metadata

Field	Value
Publication number	US-9260553-B2
Application number	US-201314646980-A
Country	US
Kind code	B2
Filing date	Nov 21, 2013
Priority date	Dec 4, 2012
Publication date	Feb 16, 2016
Grant date	Feb 16, 2016

Abstract

A method of making a highly fluorinated polymers and resulting aqueous mixtures. The method comprising polymerizing one or more perfluorinated monomers in an aqueous emulsion polymerization in the presence of a polymerizable fluorinated emulsifier to form a perfluorinated polymer. The polymerizable fluorinated emulsifier has the formula X 2 C═CX(CF 2 ) m (CH 2 ) n [O—(CX 2 ) p ] q —[O—(CX 2 ) r ] s —[O—(CX 2 —CX 2 )] t —[(O) w —(CX 2 ) u ] v —[CH 2 ] z —Y. The method also provides for isolating the highly fluorinated polymer and post-fluorinating the isolated highly fluorinated polymer.

First claim

What is claimed is:

1. A method of making a highly fluorinated polymer comprising:
(i) polymerizing one or more perfluorinated monomers in an aqueous emulsion polymerization in the presence of a polymerizable fluorinated emulsifier to form the highly fluorinated polymer, wherein the polymerizable fluorinated emulsifier having the formula:
X 2 C═CX(CF 2 ) m (CH 2 ) n [O—(CX 2 ) p ] q —[O—(CX 2 ) r ] s —[O—(CX 2 —CX 2 )] t —[(O) w (CX 2 ) u ] v —[CH 2 ] z —Y

where X is independently selected from H, F, or CF 3 ; Y is COOM or SO 3 M where M is H, an alkali metal or NH 4 ; m is 0 to 5, n is 0 to 5, p is at least 1, q is 0 to 5, r is 0 to 5, s is 0 to 5, t is 0-5, u is 0 to 5, v is 0 to 5, w is 0 or 1, and z is 0 to 5; wherein at least one of m, n, q, s, t, u, v, and z is at least 1; wherein the polymerizable fluorinated emulsifier (a) comprises at least 1 fluorine atom; (b) is substantially free of telogenic activity, and (c) is less than 1 wt % based on the total weight of monomers used;
(ii) isolating the highly fluorinated polymer; and
(ii) post-fluorinating the isolated highly fluorinated polymer.

2. The method of claim 1 wherein the polymerizable fluorinated emulsifier is perfluorinated.

3. The method of claim 1 , wherein the polymerizable fluorinated emulsifier is selected from the group consisting of:
CF 2 ═CF—(CF 2 ) m —O—(CF 2 ) p —[O—(CF 2 ) r ] s —Y  (II)

CF 2 ═CF—(CF 2 ) m —O—(CF 2 ) p —[O—(CF(CF 3 )—CF 2 )] t —[O—CF(CF 3 )] v —Y  (III); and

CX 2 ═CX—(CF 2 ) m —Y  (IV)

where X is independently selected from H, F, or CF 3 ; where Y is COOM or SO 3 M, m is an integer selected from 0 to 5, p is at least 1, r is an integer selected from 0 to 5, s is an integer selected from 1 to 5, t is an integer selected from 1 to 5, v is an integer selected from 1 to 5, and M is H, an alkali metal, or NH 4 .

4. The method of claim 1 , wherein the polymerization is substantially free of a non-telogenic emulsifier.

5. The method of claim 1 , wherein the polymerization is substantially free of a non-telogenic fluorinated emulsifier.

6. The method of any one of the previous claims, wherein the polymerizable fluorinated emulsifier is added throughout the polymerization.

7. The method of claim 1 , wherein the amount of polymerizable fluorinated emulsifier is at least 50 ppm and no more than 5000 ppm based on the amount of perfluorinated monomer used.

8. The method of claim 1 , wherein the polymerizable fluorinated emulsifier forms a microemulsion.

9. The method of claim 1 , wherein the perfluorinated monomers are selected from the group consisting of: tetrafluoroethylene, hexafluoropropylene, perfluoroalkoxy alkenes, perfluoro alkyl vinyl ethers, perfluoroalkoxy vinyl ethers, MV4S, MV5CN, and combinations thereof.

10. The method of claim 1 , wherein the highly fluorinated polymer is a fluoroplastic.

Assignees

• 3M Innovative Properties Co

Inventors

• Hintzer Klaus
• Kaspar Harald
• Koenigsmann Herbert
• Traunspurger Helmut
• Zipplies Tilman C

Classifications

• C08F214/262 Primary

  with fluorinated vinyl ethers · CPC title

• C08L27/18 Primary

  Homopolymers or copolymers or tetrafluoroethene · CPC title