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Title:
POLYMERIZATION OF FLUORINATED VINYL MONOMERS IN AQUEOUS SALT SOLUTIONS
Document Type and Number:
WIPO Patent Application WO/2013/090941
Kind Code:
A1
Abstract:
An improved process for polymerization of a fluorinated vinyl monomer to produce a fluorinated polymer is described. The polymerization process comprises the free radical polymerization of a fluorinated vinyl monomer in an aqueous salt solution, which contains a water-soluble salt having a metal cation and a fluorinated anion. The water-soluble salt increase the solubility of the fluorinated vinyl monomer in the aqueous solution, thereby reducing the pressure required for the polymerization.

Inventors:
MATHER BRIAN D (US)
SHIFLETT MARK BRANDON (US)
REINARTZ NICOLE M (US)
USCHOLD RONALD EARL (US)
Application Number:
PCT/US2012/070202
Publication Date:
June 20, 2013
Filing Date:
December 17, 2012
Export Citation:
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Assignee:
DU PONT (US)
International Classes:
C08F14/18; C08F2/10; C08L27/12
Foreign References:
US4025709A1977-05-24
US20040225053A12004-11-11
US20080269408A12008-10-30
US20080114143A12008-05-15
US3475396A1969-10-28
Attorney, Agent or Firm:
LANGWORTHY, John A. (Legal Patent Records Center4417 Lancaster Pik, Wilmington Delaware, US)
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Claims:
CLAIMS

What is claimed is:

1. A process for polymerization of a fluorinated vinyl monomer comprising the steps of:

(a) providing a reaction mixture comprising a fluorinated vinyl monomer, an aqueous salt solution, and at least one water-soluble free radical initiator;

wherein :

(i) the aqueous salt solution comprises at least one water-soluble salt having a metal cation and a fluorinated anion; and

(ii) the concentration of the at least one water-soluble salt in the aqueous salt solution is greater than 20 wt%; and

(b) agitating the reaction mixture at a temperature and pressure sufficient to produce a slurry comprising a

fluorinated polymer.

2. The process of claim 1, wherein the fluorinated vinyl monomer is selected from the group consisting of C2H3F, C2H2F2, C2HF3, C3HF5, C3H2F4, C3H3F3, C3H4F2, C3H5F, and mixtures thereof;

3. The process of claim 1, wherein the reaction mixture is agitated at a temperature of about 25 °C to about 250 °C and a pressure of about 2.5 MPa to about 100 MPa to produce a slurry comprising a fluorinated polymer.

4. The process of claim 1, further comprising the step of recovering the fluorinated polymer from the slurry.

5. The process of claim 1, wherein the fluorinated vinyl monomer is vinyl fluoride and the fluorinated polymer is poly (vinyl fluoride) .

6. The process of claim 1, wherein the fluorinated anion is selected from the group consisting of 1,1,2,2- tetrafluoroethanesulfonate; 2-chloro-l,l,2- trifluoroethanesulfonate; 1,1,2,3,3,3- hexafluoropropanesulfonate; 1 , 1 , 2-trifluoro-2-

(trifluoromethoxy) ethanesulfonate; l,l,2-trifluoro-2- (pentafluoroethoxy) ethanesulfonate; 2- (1,2, 2,2- tetrafluoroethoxy) -1, 1, 2, 2-tetrafluoroethanesulfonate; 2- (1,1,2, 2 -tetrafluoroethoxy) -1, 1, 2, 2-tetrafluoroethanesulfonate; 2- (l,l,2,2-tetrafluoro-2-iodoethoxy) -1,1,2,2- tetrafluoroethanesulfonate; 1,1,2, 2-tetrafluoro-2- (pentafluoroethoxy) ethanesulfonate; Ν,Ν-bis (1, 1, 2, 2- tetrafluoroethanesulfonyl) imide; N,N-bis (1,1,2,3,3,3- hexafluoropropanesulfonyl) imide; tetrafluoroborate ;

tetrafluoroethanesulfonate; [BF4]~, [PF6]", [SbF6] , [HCF2CF2S03] ; [CF3HFCCF2SO3] ", [HCCIFCF2SO3] "; [ (CF3CF2SO2) 2N] "; [CF3OCFHCF2SO3] ", [CF3CF2OCFHCF2SO3] ", [CF3CFHOCF2CF2SO3] ", [CF2HCF2OCF2CF2SO3] ",

[CF2ICF2OCF2CF2SO3] , [CF3CF2OCF2CF2SO3] ", [ (CF2HCF2S02) 2N] "; and [ (CF3CFHCF2SO2) 2N] ".

7. The process of claim 1, wherein the metal cation is lithium, sodium, potassium or zinc.

8. The process of claim 1, wherein the at least one water-soluble salt is lithium bis (trifluoromethylsulfonyl) imide or lithium 1 , 1 , 2 , 2-tetrafluoroethanesulfonate .

9. The process of claim 1, wherein the concentration of the at least one water-soluble salt in the aqueous salt solution is about 40 wt% to about 90 wt% .

10. The process of claim 1, wherein the concentration of the at least one water-soluble salt in the aqueous salt solution is about 40 wt% to about 80 wt% .

11. The process of claim 1, wherein the concentration of the at least one water-soluble salt in the aqueous salt solution is about 60 wt% to about 90 wt% .

12. The process of claim 1, wherein the concentration of the at least one water-soluble salt in the aqueous salt solution is about 60 wt% to about 80 wt% .

13. The process of claim 1, wherein the water-soluble free radical initiator is selected from the group consisting of organic peroxides, hydroperoxides, water-soluble salts of inorganic peracids, and azo compounds.

14. The process of claim 1, wherein the water-soluble free radical initiator is selected from one or more members of the group consisting of 2, 2' -azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis [2-methyl-N- (2- hydroxyethyl ) propionamide] , 2,2'-azobis(N,N'- dimethyleneisobutyroamidine) dihydrochloride, 2,2'-azobis (Ν,Ν'- dimethyleneisobutyramidine, and 2, 2 ' -azobis [N- (2-carboxyethyl) - 2-methylpropionamidine ] hydrate .

15. The process of claim 1, wherein the reaction mixture further comprises a surfactant.

16. The process of claim 15, wherein the surfactant is a nonionic surfactant comprising polymeric blocks of alkylene oxide units.

17. The process of claim 4, further comprising a step of forming or fabricating an article from the fluorinated polymer.

Description:
TITLE

POLYMERIZATION OF FLUORINATED VINYL MONOMERS IN AQUEOUS SALT SOLUTIONS

This application claims priority under 35 U.S.C. §119 (e) from, and claims the benefit of, U.S. Provisional Application No. 61/576,406, filed 16 December 2011, and U.S. Provisional

Application No. 61/638,003, filed 25 April 2012, each of which is by this reference incorporated in its entirety as a part hereof for all purposes.

Technical Field

The subject matter of this disclosure relates to a process for the polymerization of fluorinated vinyl monomers using free radical initiators.

Background

Fluorinated vinyl monomers, such as vinyl fluoride and vinylidene fluoride, are widely used to make polymers and copolymers that are useful in many applications. For example, poly (vinyl fluoride) finds wide use as a protective or

decorative coating on substances such as cellulosics, flexible vinyls, plastics, rubbers and metals. Additionally,

poly (vinyl fluoride) transparent film is used as the cover for solar plate collectors and photovoltaic cells.

Poly (vinylidene fluoride) is used as a coating for metallic roofing, window frames, panel siding, and wire insulation. The polymers and copolymers of fluorinated vinyl monomers are typically produced by free radical polymerization in an aqueous solution at high pressure. For example, poly (vinyl fluoride) can be produced by free radical polymerization of vinyl fluoride in an aqueous medium at a temperature between 50°C and 150°C and a pressure of 3.4 to 34.4 MPa using

catalysts such as peroxides or azo compounds. Additionally, vinyl fluoride can be polymerized using a continuous process as described in U.S. Patent No. 3,265,678. Vinylidene fluoride can be polymerized in an aqueous medium using a variety of free radical initiators, such as di-t-butyl peroxide (U.S. Patent No. 3,193,539), peroxy dicarbonates and peroxy esters (GB 1,094,558), and disuccinic acid. High pressure is used in these processes to increase the solubility of the fluorinated vinyl monomer in water; however, the high pressure limits the size of the reactor used to make the polymers, thereby limiting capacity. Additionally, there is a high initial capital cost associated with the high pressure reactor that is required for the process.

A need thus remains for a process for polymerizing fluorinated vinyl monomers at lower pressure to increase production capacity and reduce cost.

Summary

The subject matter of this disclosure meets the above described needs by offering various advantageous technical effects, included among which are

providing a process for the polymerization of fluorinated vinyl monomers that can be run at lower pressure, and

providing a process for the polymerization of fluorinated vinyl monomers in which the solubility of fluorinated monomers in the reaction mixture can be increased.

Accordingly, one embodiment of the subject matter of this disclosure provides a process for the polymerization of fluorinated vinyl monomers wherein the reaction mixture in which polymerization occurs contains an aqueous salt solution.

In another embodiment of the processes hereof, an aqueous salt solution as used in the polymerization reaction mixture contains at least one water-soluble salt having a metal cation and a fluorinated anion.

In a further embodiment of the processes hereof, a process for the polymerization of fluorinated vinyl monomers is provided that includes the steps of:

(a) providing a reaction mixture that includes a

fluorinated vinyl monomer, an aqueous salt solution, and at least one water-soluble free radical initiator; wherein:

(i) the aqueous salt solution comprises at least one water-soluble salt having a metal cation and a fluorinated anion; and

(ii) the concentration of the at least one water- soluble salt in the aqueous salt solution is greater than 20 wt%; and (b) agitating the reaction mixture at a temperature and a pressure sufficient to produce a slurry comprising a

fluorinated polymer. In yet another embodiment of the processes hereof, a fluorinated vinyl monomer as used in the processes hereof can be selected from the group consisting of C 2 H 3 F, C 2 H 2 F 2 , C 2 HF 3 , C 3 HF 5 , C 3 H 2 F 4 , C 3 H 3 F 3 , C 3 H 4 F 2 , C 3 H 5 F, and mixtures thereof.

Detailed Description

As used above and throughout the description of the subject matter of this disclosure, the following terms, unless otherwise indicated, shall be defined as follows:

The term "fluorinated vinyl monomer" refers to a vinyl monomer containing 2 or 3 carbon atoms. Examples of

fluorinated vinyl monomers suitable for use in the processes hereof can be selected from the group consisting of C 2 H 3 F, C 2 H 2 F 2 , C 2 HF 3 , C 3 HF 5 , C 3 H 2 F 4 , C 3 H 3 F 3 , C 3 H 4 F 2 , C 3 H 5 F, and mixtures thereof. Exemplary fluorinated vinyl monomers include without limitation HFC=CH 2 (vinyl fluoride) , HFC=CHF, H 2 C=CF 2

(vinylidene fluoride), and HFC=CH-CH 3 . The term "slurry" refers to a thick suspension of an insoluble fluorinated polymer product in an aqueous medium.

The terms "free radical initiator" and "radical

initiator" are used interchangeably herein to refer to a chemical compound that can generate free radical species (i.e. chemical species having an unpaired electron) and thereby promote radical reactions. The term "water-soluble free radical initiator" refers to a free radical initiator that is sufficiently soluble in water to produce a concentration of at least 0.001 wt% .

Disclosed herein are processes for polymerization of a fluorinated vinyl monomer to produce a fluorinated polymer. A polymerization process hereof can include the free radical polymerization of a fluorinated vinyl monomer in an aqueous salt solution, wherein the aqueous salt solution contains a water-soluble salt having a metal cation and a fluorinated anion. The water-soluble salt is understood to increase the solubility of the fluorinated vinyl monomer in the aqueous solution, thereby reducing the pressure required for the polymerization.

A process hereof for polymerization of a fluorinated vinyl monomer can include the following steps. First, a reaction mixture is formed by combining a fluorinated vinyl monomer, a water-soluble free radical initiator and an aqueous salt solution. The reaction mixture is typically formed in a high pressure reaction vessel. Typically, the aqueous salt solution and the water-soluble free radical initiator are combined in the reaction vessel and then the fluorinated vinyl monomer gas is added to the reaction vessel from an external reservoir under pressure.

Examples of fluorinated vinyl monomers suitable for use in the processes hereof can be selected from the group

consisting of C 2 H 3 F, C 2 H 2 F 2 , C 2 HF 3 , C 3 HF 5 , C 3 H 2 F 4 , C 3 H 3 F 3 , C 3 H 4 F 2 ,

C 3 H 5 F, and mixtures thereof. These monomers exist as a gas at ambient conditions and have a relatively low solubility in water. In one embodiment, the fluorinated vinyl monomer is vinyl fluoride (HFC=CH 2 ) . In another embodiment, the

fluorinated vinyl monomer is vinylidene fluoride (H 2 C=CF 2 ) . A variety of water-soluble free radical initiators can be used in the processes disclosed herein. Suitable free radical initiators include without limitation organic peroxides, such as diacetyl peroxide; hydroperoxides, such as t-butyl

hydroperoxide and acetyl hydroperoxide; water-soluble salts of inorganic peracids such as ammonium persulfate, potassium persulfate, potassium perphosphate , and potassium percarbonate ; and azo compounds such as -azoisobutryamidine hydrochloride, 2 , 2 ' -diguanyl-2 , 2 ' -azopropane dihydrochloride, 4 , 4-azobis ( 4- cyanovaleric acid), 2 , 2 ' -diguanyl-2 , 2 ' -azobutane

dihydrochloride, azo- -cyclopropylpropionamide hydrochloride,

2, 2' -azobis (2-methylpropionamidine) dihydrochloride (sold under the trade name V-50 by Wako Chemical Co., Richmond, VA) , 2,2'- azobis [2-methyl-N- (2-hydroxyethyl) propionamide] (sold under the trade name VA-086 by Wako Chemical Co., Richmond, VA) , 2,2'- azobis (Ν,Ν' -dimethyleneisobutyroamidine) dihydrochloride (sold under the trade name VA-044 by Wako Chemical Co., Richmond, VA) , 2 , 2 ' -azobis (N, ' -dimethyleneisobutyramidine (sold under the trade name VA-061 by Wako Chemical Co., Richmond, VA) , 2,2' -azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (sold under the trade name VA-057 by Wako Chemical Co.,

Richmond, VA) , 4 , 4 ' azobis ( 4-cyanopentanoic acid) (sold under the trade name V-501 by Wako Chemical Co., Richmond, VA) ; and substituted azonitrile compounds such as those sold under the trade name Vazo® free radical sources by E.I. du Pont de

Nemours and Co. (Wilmington, DE) . Mixtures of any of these aforementioned initiators may also be used. The amount of the free radical initiator used can vary from about 0.001% to about 5% based on the weight of the monomer used.

In one embodiment, the water-soluble free radical initiator is selected from one or more members of the group consisting of

2, 2' -azobis (2-methylpropionamidine) dihydrochloride (V-50), 2,2' -azobis [2-methyl-N- ( 2-hydroxyethyl ) propionamide] (VA-086) , 2, 2' -azobis (Ν,Ν' -dimethyleneisobutyroamidine ) dihydrochloride (VA-044) ,

2 , 2 ' -azobis (N, ' -dimethyleneisobutyramidine (VA-061), and 2,2' -azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (VA-057) .

An aqueous salt solution as used in the polymerization reaction mixture hereof can contain water and at least one water-soluble salt having a metal cation and a fluorinated anion .

Examples of metal cations suitable for use herein as a component of an aqueous salt solution include without

limitation lithium, sodium, potassium and zinc.

Examples of fluorinated anions suitable for use herein as a component of an aqueous salt solution include without limitation the following:

1,1,2, 2-tetrafluoroethanesulfonate;

2-chloro-1,1, 2-trifluoroethanesulfonate,·

1,1,2,3,3, 3-hexafluoropropanesulfonate;

1,1, 2-trifluoro-2- (trifluoromethoxy) ethanesulfonate;

1,1, 2-trifluoro-2- (pentafluoroethoxy) ethanesulfonate;

2- (1,2,2, 2-tetrafluoroethoxy) -1,1,2,2- tetrafluoroethanesulfonate ; 2- ( 1 , 1 , 2 , 2-tetrafluoroethoxy) -1,1,2,2- tetrafluoroethanesulfonate ;

2- (l,l,2,2-tetrafluoro-2-iodoethoxy) -1,1,2,2- tetrafluoroethanesulfonate ;

1,1,2, 2-tetrafluoro-2- (pentafluoroethoxy) ethanesulfonate;

Ν,Ν-bis (1, 1, 2, 2-tetrafluoroethanesulfonyl) imide;

Ν,Ν-bis (1, 1, 2, 3, 3, 3-hexafluoropropanesulfonyl ) imide;

tetrafluoroborate, [BF 4 ] ~ ;

tetrafluoroethanesulfonate, [HCF 2 CF 2 S0 3 ] ;

[PF 6 ] ~ ; [SbF 6 ]; [ CF 3 HFCCF 2 S0 3 ] " ; [HCC1FCF 2 S0 3 ] ~ ;

[ (CF 3 CF 2 S0 2 ) 2 N] " ; [ CF 3 OCFHCF 2 S0 3 ] " , [ CF 3 CF 2 OCFHCF 2 S0 3 ] " ,

[CF 3 CFHOCF 2 CF 2 S0 3 ] " , [CF 2 HCF 2 OCF 2 CF 2 S0 3 ] " , [CF 2 ICF 2 OCF 2 CF 2 S0 3 ] , [CF 3 CF 2 OCF 2 CF 2 S0 3 ] " , [ ( CF 2 HCF 2 S0 2 ) 2 N] " ; and [ ( CF 3 CFHCF 2 S0 2 ) 2 N] " . In one embodiment, a water-soluble salt as used in the reaction mixture of the processes hereof can include a lithium cation, and an anion selected from any one or more members of the group of anions consisting of:

1,1,2, 2-tetrafluoroethanesulfonate;

2-chloro-1,1, 2-trifluoroethanesulfonate ;

1,1,2,3,3, 3-hexafluoropropanesulfonate;

1,1, 2-trifluoro-2- (trifluoromethoxy) ethanesulfonate;

1,1, 2-trifluoro-2- (pentafluoroethoxy) ethanesulfonate;

2- (1,2,2, 2-tetrafluoroethoxy) -1,1,2,2- tetrafluoroethanesulfonate;

2- ( 1 , 1 , 2 , 2-tetrafluoroethoxy) -1,1,2,2- tetrafluoroethanesulfonate ;

2- (l,l,2,2-tetrafluoro-2-iodoethoxy) -1,1,2,2- tetrafluoroethanesulfonate ;

1,1,2, 2-tetrafluoro-2- (pentafluoroethoxy) ethanesulfonate;

Ν,Ν-bis (1, 1, 2, 2-tetrafluoroethanesulfonyl) imide;

Ν,Ν-bis (1, 1, 2, 3, 3, 3-hexafluoropropanesulfonyl ) imide; tetrafluoroborate, [BF 4 ] ;

tetrafluoroethanesulfonate, [HCF 2 CF 2 S0 3 ] ;

[PF 6 ] " ; [SbF 6 ]; [ CF 3 HFCCF 2 S0 3 ] " ; [HCC1FCF 2 S0 3 ] " ;

[ (CF 3 CF 2 S0 2 ) 2 N] " ; [ CF 3 OCFHCF 2 S0 3 ] " , [ CF 3 CF 2 OCFHCF 2 S0 3 ] " ,

[CF 3 CFHOCF 2 CF 2 S0 3 ] [CF 2 HCF 2 OCF 2 CF 2 S0 3 ] [CF 2 ICF 2 OCF 2 CF 2 S0 3 ] ,

[CF 3 CF 2 OCF 2 CF 2 S0 3 ] [ ( CF 2 HCF 2 S0 2 ) 2 N] " ; and [ ( CF 3 CFHCF 2 S0 2 ) 2 N] " .

In one embodiment, a water-soluble salt as used in the reaction mixture of the processes hereof can include a sodium cation, and an anion selected from any one or more members of the group of anions consisting of:

1,1,2, 2-tetrafluoroethanesulfonate;

2-chloro-1,1, 2-trifluoroethanesulfonate,·

1,1,2,3,3, 3-hexafluoropropanesulfonate;

1,1, 2-trifluoro-2- (trifluoromethoxy) ethanesulfonate;

1,1, 2-trifluoro-2- (pentafluoroethoxy) ethanesulfonate;

2- (1,2,2, 2-tetrafluoroethoxy) -1,1,2,2- tetrafluoroethanesulfonate ;

2- ( 1 , 1 , 2 , 2-tetrafluoroethoxy) -1,1,2,2- tetrafluoroethanesulfonate;

2- (l,l,2,2-tetrafluoro-2-iodoethoxy) -1,1,2,2- tetrafluoroethanesulfonate ;

1,1,2, 2-tetrafluoro-2- (pentafluoroethoxy) ethanesulfonate; Ν,Ν-bis (1, 1, 2, 2-tetrafluoroethanesulfonyl) imide;

N,N-bis(l,l,2,3,3, 3-hexafluoropropanesulfonyl ) imide;

tetrafluoroborate, [BF 4 ] " ;

tetrafluoroethanesulfonate, [HCF 2 CF 2 S0 3 ] ;

[PF 6 ] " ; [SbF 6 ]; [ CF 3 HFCCF 2 S0 3 ] " ; [HCC1FCF 2 S0 3 ] " ;

[ (CF 3 CF 2 S0 2 ) 2 N] " ; [ CF 3 OCFHCF 2 S0 3 ] " , [ CF 3 CF 2 OCFHCF 2 S0 3 ] " ,

[CF 3 CFHOCF 2 CF 2 S0 3 ] " , [CF 2 HCF 2 OCF 2 CF 2 S0 3 ] " , [CF 2 ICF 2 OCF 2 CF 2 S0 3 ] , [CF 3 CF 2 OCF 2 CF 2 S0 3 ] " , [ ( CF 2 HCF 2 S0 2 ) 2 N] " ; and [ ( CF 3 CFHCF 2 S0 2 ) 2 N] " . In one embodiment, a water-soluble salt as used in the reaction mixture of the processes hereof can include a potassium cation, and an anion selected from any one or more members of the group of anions consisting of:

1,1,2, 2-tetrafluoroethanesulfonate;

2-chloro-1,1, 2-trifluoroethanesulfonate;

1,1,2,3,3, 3-hexafluoropropanesulfonate;

1,1, 2-trifluoro-2- (trifluoromethoxy) ethanesulfonate;

1,1, 2-trifluoro-2- (pentafluoroethoxy) ethanesulfonate;

2- ( 1 , 2 , 2 , 2-tetrafluoroethoxy) -1,1,2,2- tetrafluoroethanesulfonate ;

2- ( 1 , 1 , 2 , 2-tetrafluoroethoxy) -1,1,2,2- tetrafluoroethanesulfonate ;

2- (l,l,2,2-tetrafluoro-2-iodoethoxy) -1,1,2,2- tetrafluoroethanesulfonate;

1,1,2, 2-tetrafluoro-2- (pentafluoroethoxy) ethanesulfonate;

Ν,Ν-bis (1, 1, 2, 2-tetrafluoroethanesulfonyl) imide;

Ν,Ν-bis (1, 1, 2, 3, 3, 3-hexafluoropropanesulfonyl ) imide;

tetrafluoroborate, [BF 4 ] ~ ;

tetrafluoroethanesulfonate, [HCF 2 CF 2 S0 3 ] ;

[PF 6 ] " ; [SbF 6 ]; [ CF 3 HFCCF 2 S0 3 ] " ; [HCC1FCF 2 S0 3 ] " ;

[ (CF 3 CF 2 S0 2 ) 2 N] " ; [ CF 3 OCFHCF 2 S0 3 ] " , [ CF 3 CF 2 OCFHCF 2 S0 3 ] " ,

[CF 3 CFHOCF 2 CF 2 S0 3 ] " , [CF 2 HCF 2 OCF 2 CF 2 S0 3 ] " , [CF 2 ICF 2 OCF 2 CF 2 S0 3 ] , [CF 3 CF 2 OCF 2 CF 2 S0 3 ] " , [ ( CF 2 HCF 2 S0 2 ) 2 N] " ; and [ ( CF 3 CFHCF 2 S0 2 ) 2 N] " .

In one embodiment, a water-soluble salt as used in the reaction mixture of the processes hereof can include a zinc cation, and an anion selected from any one or more members of the group of anions consisting of:

1,1,2, 2-tetrafluoroethanesulfonate;

2-chloro-1,1, 2-trifluoroethanesulfonate;

1,1,2,3,3, 3-hexafluoropropanesulfonate; 1,1, 2-trifluoro-2- (trifluoromethoxy) ethanesulfonate;

1,1, 2-trifluoro-2- (pentafluoroethoxy) ethanesulfonate;

2- (1,2,2, 2 -tetrafluoroethoxy) -1,1,2,2- tetrafluoroethanesulfonate ;

2- ( 1 , 1 , 2 , 2 -tetrafluoroethoxy) -1,1,2,2- tetrafluoroethanesulfonate ;

2- (l,l,2,2-tetrafluoro-2-iodoethoxy) -1,1,2,2- tetrafluoroethanesulfonate ;

1,1,2, 2-tetrafluoro-2- (pentafluoroethoxy) ethanesulfonate;

Ν,Ν-bis (1, 1, 2, 2-tetrafluoroethanesulfonyl) imide;

Ν,Ν-bis (1, 1, 2, 3, 3, 3-hexafluoropropanesulfonyl ) imide;

tetrafluoroborate, [BF 4 ] ~ ;

tetrafluoroethanesulfonate, [HCF 2 CF 2 S0 3 ] ;

[PF 6 ] " ; [SbF 6 ]; [ CF 3 HFCCF 2 S0 3 ] " ; [HCC1FCF 2 S0 3 ] " ;

[ (CF 3 CF 2 S0 2 ) 2 N] " ; [ CF 3 OCFHCF 2 S0 3 ] " , [ CF 3 CF 2 OCFHCF 2 S0 3 ] " ,

[CF 3 CFHOCF 2 CF 2 S0 3 ] " , [CF 2 HCF 2 OCF 2 CF 2 S0 3 ] " , [CF 2 ICF 2 OCF 2 CF 2 S0 3 ] , [CF 3 CF 2 OCF 2 CF 2 S0 3 ] " , [ ( CF 2 HCF 2 S0 2 ) 2 N] " ; and [ ( CF 3 CFHCF 2 S0 2 ) 2 N] " .

In one embodiment, the water-soluble salt is lithium bis (trifluoromethylsulfonyl) imide . In another embodiment, the water-soluble salt is lithium 1,1,2,2- tetrafluoroethanesulfonate .

The concentration of the water-soluble salt in the aqueous salt solution is typically greater than about 20 wt% . The upper concentration limit is determined by the aqueous solubility of the salt. In one embodiment, the concentration of the water-soluble salt in the aqueous salt solution is about 40 wt% to about 90 wt% . In another embodiment, the

concentration of the water-soluble salt in the aqueous salt solution is about 40 wt% to about 80 wt% . In a further embodiment, the concentration of the water-soluble salt in the aqueous salt solution is about 60 t% to about 90 t%. In yet another embodiment, the concentration of the water-soluble salt in the aqueous salt solution is about 60 wt% to about 80 wt% . In another embodiment, the concentration of the water- soluble salt in the aqueous salt solution is about 20 wt% or more, or is about 40 wt% or more, or is about 60 wt% or more, and yet is about 90 wt% or less, or is about 80 wt% or less. The reaction mixture may also contain one or more other vinyl monomers to produce copolymers including, for example, vinyl chloride; vinylidene chloride; mono-olefins such as ethylene, propylene and butylene, as described by Hecht (U.S. Patent No. 3,265,678); tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, fluorinated vinyl ethers, fluorinated alkyl acrylates/methacrylates , perfluoroolefins having 3-10 carbon atoms, perfluoro Ci-C 8 alkyl ethylenes and fluorinated dioxoles . Particularly preferred comonomers include

tetrafluoroethylene, hexafluoropropylene ,

perfluorobutylethylene , and C 2 ~C 6 perfluoro vinyl alkyl ethers.

Additionally, the reaction mixture may contain various additives such as iodine or compounds containing iodine, as described by Trautvetter et al . (U.S. Patent No. 3,755.246); and surfactants. Suitable surfactants include without limitation halogen-free surfactants with a critical micelle concentration of less than about 0.05 wt% at 25°C, as described by Uschold (U.S. Patent Application No. 2012/0116016) .

Preferred halogen-free surfactants are nonionic surfactants having polymeric blocks of alkylene oxide units, for example, ethylene oxide and propylene oxide units . Exemplary nonionic surfactants include without limitation the Pluronic® series and the Pluronic® R series from BASF (Florham Park, NJ) , such as Pluronic® 31R1. The surfactant, if used, is typically present in the reaction mixture at a concentration less than or equal to about 0.1 t% based on the total weight of the reaction mixture.

In the next step of the process, the reaction mixture is agitated at a temperature and pressure and for a time

sufficient to form a slurry containing a fluorinated polymer product. Agitation may be done by any suitable method known in the art. For example, a stirring device such as a motor- driven stirrer may be used. Alternatively, a shaking or rocking motion may be imparted to the reaction vessel. The temperature used in the process depends on several factors as follows: the lower temperature limit depends on the initiation temperature of the free radical initiator used; and the upper temperature limit depends on the temperature at which the fluorinated vinyl monomer or the fluorinated polymer produced undergoes a significant degree of thermal decomposition, for example about 250 °C for vinyl fluoride. Typically, the temperature used in the process is about 50°C to about 200°C, more particularly about 50°C to about 150°C, and more

particularly, about 50°C to about 100°C. The pressure used in the processes disclosed herein can be in the range of about 2.5 MPa to about 100 MPa, more particularly about 2.5 MPa to about 50 MPa, and most particularly about 2.5 MPa to about 10 MPa.

In another embodiment, the pressure used in the processes hereof can be about 0.1 MPa or more, or about 0.5 MPa or more, or about 1.0 MPa or more, or about 2.0 MPa or more, and yet can be about 50 MPa or less, or about 10 MPa or less, or about 5 MPa or less, or about 2.5 MPa or less. The fluorinated polymer may be recovered from the slurry by filtration, centrifugation, or the like. The recovered fluorinated polymer in the form of a powder or cake may be washed with water or an organic solvent and dried. Once recovered, the polymer so produced can be subjected to

operations to form or fabricate an article therefrom. For example, the polymer could be cast or blown as a film, could be sprayed or spun as a coating, or could be blow molded or injection molded as an object.

EXAMPLES

The operation and effects of certain embodiments of the subject matter hereof may be more fully appreciated from a series of examples, as described below. The embodiments on which these examples are based are representative only, and the selection of those embodiments to illustrate the processes hereof does not indicate that materials, components, reactants, configurations, conditions, techniques or protocols not described in the examples are not suitable for use herein, or that subject matter not described in the examples is excluded from the scope of the appended claims and equivalents thereof.

The meaning of abbreviations used is as follows: "min" means minute (s), "hr" means hour(s), "s" means second(s), "mL" means milliliter ( s ) , "μΙ ' means microliter ( s ) , "L" means liter(s), "g" means gram(s), "mg" means milligram ( s ) , " g" means microgram ( s ) , "wt%" means weight percent, "psi" means pounds per square inch, "Pa" means pascal (s), "kPa" means kilopascal ( s ) , and "MPa" means megapascal ( s ) , "rpm" means revolutions per minute, ,1 Η NMR" means proton nuclear magnetic resonance spectroscopy, " 19 F NMR" means fluorine isotope 19 nuclear magnetic resonance spectroscopy, " S" means micro siemen ( s ) .

Materials

Lithium bis (trifluoromethylsulfonyl) imide (LiTf 2 N) , 1- ethyl-3-methyl imidazoleum bis (trifluoromethanesulfonyl) imide (Emlm Tf 2 N) , trihexyltetradecyl phosphonium

bis (trifluoromethanesulfonyl ) imide (6,6,6,14-P Tf 2 N) , lithium 1 , 1 , 2 , 2-tetrafluoroethanesulfonate (Li TFES) , l-octyl-3-methyl imidazoleum 1 , 1 , 2 , 2-tetrafluoroethanesulfonate (Omlm TFES) and l-butyl-4-methylpyridinium tetrafluoroborate were obtained from Iolitec Inc. (Tuscaloosa, AL) . Lithium bromide (LiBr) was obtained from Sigma-Aldrich (St. Louis, MO) . Vazo-67 and Vazo- 64 (AIBN) were obtained from E. I. du Pont de Nemours and Co.

(Wilmington, DE) . Vinyl fluoride (VF) was manufactured by E.I. du Pont de Nemours and Co. VF was stabilized with D-limonene which was removed by passing the gas through silica gel. The initiators V-50, VA-044, VA-061, VA-057, and VA-086 were obtained from Wako Chemical Co. (Richmond, VA) .

EXAMPLE 1

Solubility of Vinyl Fluoride in Lithium

bis (trifluoromethylsulfonyl) imide Solutions

The purpose of this Example was to demonstrate the solubility of vinyl fluoride in aqueous solutions of lithium bis (trifluoromethylsulfonyl) -imide .

Solubility measurements were made using a glass

equilibrium cell (E.W. Slocum, Ind. Eng. Chem. Fundam. (1975) 14, 126) . The glass equilibrium cell had a known volume and was agitated so that the upper phase (gas or liquid) mixed into the lower liquid phase. A known amount of an aqueous solution of lithium bis (trifluoromethylsulfonyl ) imide (i.e.,

concentration of 20 wt%, 40 wt%, or 80 wt%) was loaded into the cell and the cell was evacuated with heating to degas and remove any residual air in the solution. Knowing the density of the solution, the volume of the solution was calculated, and the difference from the initial glass cell volume was used to calculate the vapor space volume. A known amount of vinyl fluoride gas was fed into the cell and the temperature was held constant with a circulating oil bath at 100 °C. The pressure of the cell was measured and recorded. When the pressure was determined to no longer change, the cell was at equilibrium and the amount of gas absorbed was calculated by taking into account the amount of gas in the equilibrium cell vapor space. The measurements were repeated using water in place of the aqueous solution of lithium bis (trifluoromethylsulfonyl) imide for comparison. Further discussion of this equipment and procedure is available in W. Schotte, Ind. Eng. Chem. Process Des. Dev. (1980) 19, 432-439. The results of the measurements are shown in Tables 1-4.

Table 1

Solubility of Vinyl Fluoride in 20 wt% Lithium bis (trifluoromethylsulfonyl) imide Solution at 100 °C

Table 2

Solubility of Vinyl Fluoride in 40 t% Lithium bis (trifluoromethylsulfonyl) imide Solution at 100 °C

Table 4

Solubility of Vinyl Fluoride in Water at 100 °C

As can be seen from the results presented in Tables 1-4, vinyl fluoride has a higher solubility in aqueous solutions of lithium bis (trifluoromethylsulfonyl) imide than in water. The solubility of vinyl fluoride increased as the concentration of lithium bis (trifluoromethylsulfonyl) imide increased.

EXAMPLE 2

Polymerization of Vinyl Fluoride in a 60 wt% Aqueous Solution of Lithium

bis (trifluoromethylsulfonyl) imide

A 240 mL stainless steel shaker tube was loaded with 100 mL of a 60 wt% aqueous solution of lithium

bis (trifluoromethylsulfonyl) imide and 0.100 g of V-50 radical initiator (Wako Chemical Co.) . The tube was sealed, and then evacuated and refilled with nitrogen 3 times. Next, the tube was cooled using a dry ice bath to -78 °C and 15 g of vinyl fluoride gas was condensed into the tube. The tube was once again sealed, and heated to 80 °C for a period of 6 hours with vigorous shaking. During this time, pressure and temperature were monitored. The pressure decreased from 531 psi (3.66 MPa) to 142 psi (0.979 MPa) over the course of the reaction, while the temperature was maintained at 80 °C, indicating significant consumption of the vinyl fluoride monomer. At the end of the reaction, the unreacted vinyl fluoride was vented into a fume hood, and the product was decanted into a sample jar. The product was an opaque white sludge. The polymer was purified by mixing with water, filtering and conducting a soxhlet

extraction for 5 days with boiling water. The yield of the polymerization was determined by drying the resultant

poly (vinyl fluoride) powder in a vacuum oven. The yield was determined to be 63% .

EXAMPLE 3

Polymerization of Vinyl Fluoride in an 80 wt% Aqueous Solution of Lithium

bis (trifluoromethylsulfonyl) imide

A 240 mL stainless steel shaker tube was loaded with 100 mL of an 80 wt% aqueous solution of lithium

bis (trifluoromethylsulfonyl) imide and 0.100 g of V-50 radical initiator. The tube was sealed, and then evacuated and refilled with nitrogen 3 times. Next, the tube was cooled using a dry ice bath to -78 °C and 15 g of vinyl fluoride gas was condensed into the tube. The tube was once again sealed, and heated to 80 °C for a period of 8 hours with vigorous shaking. During this time, pressure and temperature were monitored. The pressure decreased from 512 psi (3.53 MPa) to 227 psi (1.56 MPa) over the course of the reaction, while the temperature was

maintained at 80 °C, indicating significant consumption of the vinyl fluoride monomer. At the end of the reaction, the unreacted vinyl fluoride was vented into a fume hood, and the product was decanted into a sample jar. The product was an opaque white sludge. The polymer was purified by mixing with water, filtering and conducting a soxhlet extraction for 5 days with boiling water. The yield of the polymerization was greater than 50%.

EXAMPLE 4, COMPARATIVE

Polymerization of Vinyl Fluoride in Water

A 240 mL stainless steel shaker tube was loaded with 100 g of deionized water and 0.100 g of V-50 radical initiator. Th tube was sealed, and then evacuated and refilled with nitrogen 3 times. Next, the tube was cooled using a dry ice bath to -78 °C and 15 g of vinyl fluoride gas was condensed into the tube. The tube was once again sealed, and heated to 80 °C for a period of 6 hours with vigorous shaking. During this time, pressure and temperature were monitored. The pressure decrease from 565 psi (3.90 MPa) to 218 psi (1.50 MPa) over the course of the reaction, while the temperature was maintained at 80 °C indicating significant consumption of the vinyl fluoride monomer. At the end of the reaction, the unreacted vinyl fluoride was vented into a fume hood, and the product was decanted into a sample jar. The product was an opaque white liquid. The yield of the polymerization was determined by evaporating the water from the product, and drying the

resultant poly (vinyl fluoride) powder in a vacuum oven. The yield was determined to be 60%. EXAMPLE 5, COMPARATIVE

Unsuccessful Polymerization of Vinyl Fluoride in Emlm Tf 2 N

A 240 mL stainless steel shaker tube was loaded with 113 g of the ionic liquid l-ethyl-3-methyl imidazoleum

bis (trifluoromethanesulfonyl ) -imide (Emlm Tf 2 N) and 0.075 g of Vazo® 64 radical initiator (azobisisobutyronitrile, AIBN) initiator (E.I. du Pont de Nemours and Co.) . Vazo® 64 radical initiator has been successfully used to polymerize vinyl fluoride according to Usmanov et al . (Russian Chemical Reviews, 46, 1977, p.462-478) . The tube was sealed, and then evacuated and refilled with nitrogen 3 times. Next, the tube was cooled using a dry ice bath to -78 °C and 15 g of vinyl fluoride gas was condensed into the tube. The tube was once again sealed, manually shaken, and allowed to sit for 1 hour to equilibrate. Next, the tube was heated to 80 °C for a period of 6 hours with vigorous shaking. During this time, pressure and temperature were monitored. The pressure remained at 400 psi (2.76 MPa) over the course of the reaction, while the temperature was maintained at 80 °C, indicating that negligible consumption of the vinyl fluoride monomer occurred. At the end of the

reaction, the unreacted vinyl fluoride was vented into a fume hood, and the product was decanted into a sample jar. The product was a clear liquid, slightly discolored from the original ionic liquid. A few drops of the reaction mixture were dissolved in 2 mL of CDC1 3 and a 1 E NMR spectrum was obtained. The NMR spectrum indicated the presence of vinyl fluoride monomer and ionic liquid. No other products were observed.

This Example suggests that an ionic liquid containing the organic cation l-ethyl-3-methyl imidazoleum and the fluorinated anion bis (trifluoromethanesulfonyl ) imide may not be useful as a solvent for the polymerization of vinyl fluoride. EXAMPLE 6, COMPARATIVE

Polymerization of Vinyl Fluoride in 6, 6, 6, 14-P Tf 2 N

A 240 mL stainless steel shaker tube was loaded with 68 g of the ionic liquid trihexyltetradecyl phosphonium

bis (trifluoromethanesulfonyl ) imide (6, 6, 6, 14-P Tf 2 N) and 0.100 g of Vazo® 67 radical initiator (E.I. du Pont de Nemours and Co . ) . The tube was sealed, and then evacuated and refilled with nitrogen 3 times. Next, the tube was cooled using a dry ice bath to -78 °C and 15 g of vinyl fluoride gas was condensed into the tube. The tube was once again sealed, manually shaken, and allowed to sit for one hour to equilibrate. Next, the tube was heated to 80 °C for a period of 6 hours with vigorous shaking. During this time, pressure and temperature were monitored. The pressure decreased from a maximum of 400 psi (2.76 MPa) to 365 psi (2.52 MPa) over the course of the reaction, while the temperature was maintained at 80 °C, indicating the consumption of some of the vinyl fluoride monomer. At the end of the reaction, the unreacted vinyl fluoride was vented into a fume hood, and the product was decanted into a sample jar. The product was a slightly cloudy liquid, suggesting the presence of poly (vinyl fluoride) . A few drops of the reaction mixture were dissolved in 2 mL CDC1 3 and a 1 E NMR spectrum was obtained. The NMR spectrum indicated the presence of small quantities of poly (vinyl fluoride) , in addition to vinyl fluoride monomer and ionic liquid. No other products were observed. This Example suggests that an ionic liquid containing the organic cation trihexyltetradecyl phosphonium and the fluorinated anion

bis (trifluoromethanesulfonyl ) imide may not be useful as a solvent for the polymerization of vinyl fluoride. EXAMPLE 7

Polymerization of Vinyl Fluoride in an 80 wt% Aqueous Solution of Lithium

bis (trifluoromethylsulfonyl) imide at Higher Pressure

Due to the greater solubility of vinyl fluoride in the ionic salt solutions at higher pressure, higher molecular weight products can be produced. The purpose of this Example was to obtain higher molecular weight poly (vinyl fluoride) using higher pressure vinyl fluoride during the reaction.

A 240 mL stainless steel shaker tube was loaded with 100 mL of an 80 wt% solution of lithium

bis (trifluoromethylsulfonyl) imide and 0.100 g of V-50 radical initiator. The tube was sealed, and then evacuated and refilled with nitrogen 3 times. Next, the tube was cooled using a dry ice bath to -78 °C and 35 g of vinyl fluoride gas was condensed into the tube. The tube was once again sealed, and heated to 80 °C for a period of 6 hours with vigorous shaking. During this time, pressure and temperature were monitored. The pressure decreased from 1003 psi (6.92 MPa) to 837 psi (5.77 MPa) over the course of the reaction, while the temperature was

maintained at 80 °C. At the end of the reaction, the unreacted vinyl fluoride was vented into a fume hood, and the product was decanted into a sample jar. The product was an opaque white sludge. The polymer was purified by mixing with water,

filtering and conducting a soxhlet extraction for 5 days with boiling water. The yield of the polymerization was 38%. EXAMPLE 8, COMPARATIVE

Polymerization of Vinyl Fluoride in Water at Higher Pressure

A 240 mL stainless steel shaker tube was loaded with 100 mL of water and 0.100 g of V-50 radical initiator. The tube was sealed, and then evacuated and refilled with nitrogen 3 times. Next, the tube was cooled using a dry ice bath to -78 °C and 35 g of vinyl fluoride gas was condensed into the tube. The tube was once again sealed, and heated to 80 °C for a period of 6 hours with vigorous shaking. During this time, pressure and temperature were monitored. The pressure decreased from 1047 psi (7.22 MPa) to 944 psi (6.51 MPa) over the course of the reaction, while the temperature was maintained at 80 °C. At the end of the reaction, the unreacted vinyl fluoride was vented into a fume hood, and the product was decanted into a sample jar. The product was an opaque white sludge. The polymer was obtained by removing the water by evaporation at room

temperature, followed by drying in a vacuum oven. The yield of the polymerization was 36%.

EXAMPLE 9

Polymerization of Vinyl Fluoride in a 70 wt% Aqueous Solution of Lithium 1 , 1 , 2 , 2-tetrafluoroethanesulfonate

A 240 mL stainless steel shaker tube was loaded with 75 mL of a 70 wt% solution of lithium 1,1,2,2- tetrafluoroethanesulfonate (Li TFES) in water and 0.080 g of V- 50 radical initiator. The tube was sealed, and then evacuated and refilled with nitrogen 3 times. Next, the tube was cooled using a dry ice bath to -78 °C and 35 g of vinyl fluoride gas was condensed into the tube. The tube was once again sealed, and heated to 80 °C for a period of 8 hours with vigorous shaking. During this time, pressure and temperature were monitored. The pressure decreased from 1021 psi (7.04 MPa) to 739 psi (5.10 MPa) over the course of the reaction, while the temperature was maintained at 80 °C, indicating significant consumption of the vinyl fluoride monomer. At the end of the reaction, the unreacted vinyl fluoride was vented into a fume hood, and the product was decanted into a sample jar. The product was an opaque white sludge. The polymer was purified by mixing with water, filtering and conducting a soxhlet for 5 days with boiling water. The yield was 46%.

EXAMPLE 10, COMPARATIVE

Unsuccessful Polymerization of Vinyl Fluoride in

an Aqueous Solution of LiBr

A 240 mL stainless steel shaker tube was loaded with 100 mL of a 43 wt% solution of lithium bromide and 0.091 g of V-50 radical initiator. The tube was sealed, and then evacuated and refilled with nitrogen 3 times. Next, the tube was cooled using a dry ice bath to -78 °C and 15 g of vinyl fluoride gas was condensed into the tube. The tube was once again sealed, and heated to 80 °C for a period of 8 hours with vigorous shaking. During this time, pressure and temperature were monitored. The pressure stayed constant at 680 psi (4.69 MPa), indicating little consumption of the vinyl fluoride monomer. At the end of the reaction, the unreacted vinyl fluoride was vented into a fume hood, and the product was decanted into a sample jar. The product was a clear liquid, resembling the initial LiBr solution. No polymer was obtained from this reaction. This result suggests that aqueous solutions containing salts having a metal cation and a non-fluorinated anion may not be useful for the polymerization of vinyl fluoride. EXAMPLE 11, COMPARATIVE

Unsuccessful Polymerization of Vinyl Fluoride in Omlm TFES

A 240 mL stainless steel shaker tube was loaded with 113 g of the ionic liquid l-octyl-3-methyl imidazoleum 1,1,2,2- tetrafluoroethanesulfonate (Omlm TFES) and 0.150 g of Vazo® 67 radical initiator. The tube was sealed, and then evacuated and refilled with nitrogen 3 times. Next, the tube was cooled using a dry ice bath to -78 °C and 15 g of vinyl fluoride gas was condensed into the tube. The tube was once again sealed, manually shaken, and allowed to sit for one hour to

equilibrate. Next, the tube was heated to 80 °C for a period of 6 hours with vigorous shaking. During this time, pressure and temperature were monitored. The pressure stayed at 426 psi (3.28 MPa) over the course of the reaction, while the

temperature was maintained at 80 °C, indicating that negligible consumption of the vinyl fluoride monomer occurred. At the end of the reaction, the unreacted vinyl fluoride was vented into a fume hood, and the product was decanted into a sample jar. The product was a clear liquid, and slightly discolored from the original ionic liquid. No polymer was produced. This Example suggests that an ionic liquid containing the organic cation 1- octyl-3-methyl imidazoleum and the fluorinated anion 1,1,2,2- tetrafluoroethanesulfonate may not be useful as a solvent for the polymerization of vinyl fluoride.

EXAMPLE 12, COMPARATIVE

Unsuccessful Polymerization of Vinyl Fluoride in l-Butyl-4- methylpyridinium Tetrafluoroborate

A 240 mL stainless steel shaker tube was loaded with 45 g of the ionic liquid l-butyl-4-methylpyridinium

tetrafluoroborate and 0.100 g of Vazo® 67 radical initiator. The tube was sealed, and then evacuated and refilled with nitrogen 3 times. Next, the tube was cooled using a dry ice bath to -78 °C and 15 g of vinyl fluoride gas was condensed into the tube. The tube was once again sealed, manually shaken, and allowed to sit for one hour to equilibrate. Next, the tube was heated to 80 °C for a period of 6 hours with vigorous shaking. During this time, pressure and temperature were monitored. The pressure stayed at 402 psi (2.77 MPa) over the course of the reaction, while the temperature was maintained at 80 °C, indicating that negligible consumption of the vinyl fluoride monomer occurred. At the end of the reaction, the unreacted vinyl fluoride was vented into a fume hood, and the product was decanted into a sample jar. The product was a clear liquid, and no polymer was produced. This Example suggests that an ionic liquid containing the organic cation l-butyl-4- methylpyridinium and the fluorinated anion tetrafluoroborate may not be useful as a solvent for the polymerization of vinyl fluoride .

EXAMPLE 13

Polymerization of Vinyl Fluoride in an 80 wt% Aqueous Solution of LiTf 2 N in an Autoclave Reactor Using V-50 Initiator

A 1-L stainless steel autoclave, fitted with a ribbon blade stirrer having 3 blades and baffles and a 3/16 inch (4.8 mm) diameter cooling coil with two turns was sealed and flushed with nitrogen. The autoclave was also equipped with a

thermocouple and temperature control . The autoclave was assembled and leak tested at 500 psi (3.45 MPa) with nitrogen. Then, vacuum was used to pull a solution of 3.0 g V-50 (Wako Chemical Co.) in 500 mL of water into the reactor. Next, the reactor was heated at 95 °C for 3 hours with stirring at 500 rpm. The reactor was then cooled to 35 °C and the contents were removed by opening a drain valve that led to a tube running to the bottom of the reactor and flushing the reactor with nitrogen. Next, the reactor was re-pressurized with nitrogen and flushed a second time to remove any remaining liquid. Then, vacuum was applied to the reactor and 500 mL of 80 wt% lithium bis (trifluoromethylsulfonyl ) imide in water was pulled into the reactor. The reactor was flushed with nitrogen gas again three times at 80 psi (0.55 MPa) with stirring at 100 rpm. Then, the reactor was heated to 80 °C and pressurized to 509 psi (3.51 MPa) with vinyl fluoride (VF) and then isolated from the VF feed. A solution of V-50 in water (1 wt% ) was added at a rate of 1 mL/min using an Isco 260D syringe pump (Teledyne Isco, Inc., Lincoln, NE) until 5.0 mL was added.

Subsequently, the initiator feed rate was decreased to 0.1 mL/min and continued for the duration of the reaction. After 1 hr, the pressure decreased 10 psi (69 kPa) below the initial pressure, indicating that the reaction was proceeding and the VF feed was resumed to maintain the pressure at 500 psi (3.45 MPa) using an Isco 1000D syringe pump. The addition of VF continued for 1.5 hr, until 50 g of VF had been added. The VF and initiator feeds were then stopped. The heating was turned off and cooling was turned on until the temperature dropped to 35 °C and then the excess VF was vented. The reactor was purged three times with 80 psi (0.55 MPa) nitrogen while stirring at 100 rpm. The product, which was a sludge, was then discharged from the reactor into a pre-weighed jar. The product was filtered and rinsed with water until the

conductivity of the rinse water dropped below 8 μΞ . Finally, the product was dried in a vacuum oven at 60 °C for 3 days .

EXAMPLE 14

Polymerization of Vinyl Fluoride in an 80 wt% Aqueous Solution of LiTf 2 N in an Autoclave Reactor Using VA-086 Initiator

A 1-L stainless steel autoclave, fitted with a ribbon blade stirrer having 3 blades and baffles and a 3/16 inch (4.8 mm) diameter cooling coil with two turns was sealed and flushed with nitrogen. The autoclave was also equipped with a

thermocouple and temperature control . The autoclave was assembled and leak tested at 500 psi (3.45 MPa) with nitrogen. Then, vacuum was used to pull a solution of 3.0 g V-50 (Wako Chemical Co.) in 500 mL of water into the reactor. Next, the reactor was heated at 95 °C for 3 hours with stirring at 500 rpm. The reactor was then cooled to 35 °C and the contents were removed by opening a drain valve that led to a tube running to the bottom of the reactor and flushing the reactor with nitrogen. Next, the reactor was re-pressurized with nitrogen and flushed a second time to remove any remaining liquid. Next, vacuum was applied to the reactor and 450 mL of 80 wt% lithium bis (trifluoromethylsulfonyl ) imide in water was pulled into the reactor. The reactor was flushed with nitrogen gas again three times at 80 psi (0.55 MPa) with stirring at 100 rpm. The reactor was heated to 100 °C and pressurized to 508 psi (3.50 MPa) with vinyl fluoride (VF) and then isolated from the VF feed. A solution of VA-086 (Wako Chemical Co.) in water (1 wt%) was added at a rate of 1 mL/min using an Isco 260D syringe pump until 5.0 mL was added. Subsequently, the initiator feed rate was decreased to 0.1 mL/min and continued for the duration of the reaction. After 1 hr, the pressure decreased 10 psi (69 kPa) below the initial pressure,

indicating that the reaction was proceeding and the VF feed was resumed to maintain the pressure at 500 psi (3.45 MPa) using an Isco 1000D syringe pump. The addition of VF continued for 2 hr, until 35 g of VF had been added. The VF and initiator feeds were then stopped. The heating was turned off and cooling was turned on until the temperature dropped to 35 °C and then the excess VF was vented. The reactor was purged three times with 80 psi (0.55 MPa) nitrogen while stirring at 100 rpm. The product, which was a viscous semi-opaque liquid, was then discharged from the reactor into a pre-weighed jar. The product was purified by using dialysis tubing (Spectra/Por® 12,000-14,000 MWCO, Spectrum Laboratories, Inc., Rancho

Dominguez, CA) which was placed in a 1-L beaker filled with water. The water was changed every 2 days for 1 week. The product began to flocculate in the dialysis tubing and was filtered using a plastic fritted filter and rinsed with water. Finally, the product was dried in a vacuum oven at 60 °C for 3 days to obtain a white, flaky product.

EXAMPLE 15

Polymerization of Vinyl Fluoride in an 80 wt% Aqueous Solution of LiTf 2 N in an Autoclave Reactor Using VA-044 Initiator

A 1-L stainless steel autoclave, fitted with a ribbon blade stirrer having 3 blades and baffles and a 3/16 inch (4.8 mm) diameter cooling coil with two turns was sealed and flushed with nitrogen. The autoclave was also equipped with a

thermocouple and temperature control . The autoclave was assembled and leak tested at 500 psi (3.45 MPa) with nitrogen. Then, vacuum was used to pull a solution of 3.0 g V-50 (Wako Chemical Co.) in 500 mL of water into the reactor. Next, the reactor was heated at 95 °C for 3 hours with stirring at 500 rpm. The reactor was then cooled to 35 °C and the contents were removed by opening a drain valve that led to a tube running to the bottom of the reactor and flushing the reactor with nitrogen. Next, the reactor was re-pressurized with nitrogen and flushed a second time to remove any remaining liquid. Then, vacuum was applied to the reactor and 500 mL of 80 wt% lithium bis (trifluoromethylsulfonyl ) imide in water was pulled into the reactor. The reactor was evacuated and flushed with nitrogen gas again three times at 100 psi (0.69 MPa) with stirring at 100 rpm. Then, the reactor was heated to 68 °C and pressurized to 502 psi (3.46 MPa) with vinyl fluoride (VF) and then isolated from the VF feed. A solution of VA-044 in water (1 wt%) was added at a rate of 1 mL/min using an Isco 260D syringe pump (Teledyne Isco, Inc., Lincoln, NE) until 5.0 mL was added (5 min) . Subsequently, the initiator feed rate was decreased to 0.1 mL/min and continued for the duration of the reaction. After 15 min, the pressure decreased 4 psi (0.03 kPa) below the initial pressure, indicating that the reaction was proceeding, and the VF feed was resumed to maintain the pressure at 500 psi (3.45 MPa) using an Isco 1000D syringe pump. The addition of VF continued for 42 min, until 25 g of VF had been added. The VF and initiator feeds were then stopped. The heating was turned off and cooling was turned on until the temperature dropped to 63 °C and then the excess VF was vented. When the reactor reached 47 °C, it was purged three times with 100 psi (0.69 MPa) nitrogen while stirring at 100 rpm. The product, which was a thick, chunky white sludge, was then discharged from the reactor into a pre-weighed jar. EXAMPLE 16

Polymerization of Vinyl Fluoride in a 40 wt% Aqueous Solution of LiTf 2 N in an Autoclave Reactor Using VA-044 Initiator

A 1-L stainless steel autoclave, fitted with a ribbon blade stirrer having 3 blades and baffles and a 3/16 inch (4.8 mm) diameter cooling coil with two turns was sealed and flushed with nitrogen. The autoclave was also equipped with a

thermocouple and temperature control . The autoclave was assembled and leak tested at 500 psi (3.45 MPa) with nitrogen. Then, vacuum was used to pull a solution of 3.0 g V-50 (Wako Chemical Co.) in 500 mL of water into the reactor. Next, the reactor was heated at 95 °C for 3 hours with stirring at 500 rpm. The reactor was then cooled to 35 °C and the contents were removed by opening a drain valve that led to a tube running to the bottom of the reactor and flushing the reactor with nitrogen. Next, the reactor was re-pressurized with nitrogen and flushed a second time to remove any remaining liquid. Then, vacuum was applied to the reactor and 500 mL of 40 wt% lithium bis (trifluoromethylsulfonyl ) imide in water was pulled into the reactor. The reactor was evacuated and flushed with nitrogen gas again three times at 100 psi (0.69 MPa) with stirring at 100 rpm. Then, the reactor was heated to 68 °C and pressurized to 516 psi (3.56 MPa) with vinyl fluoride (VF) and then isolated from the VF feed. A solution of VA-044 in water (1 wt%) was added at a rate of 1 mL/min using an Isco 260D syringe pump (Teledyne Isco, Inc., Lincoln, NE) until 5.0 mL was added (5 min) . Subsequently, the initiator feed rate was decreased to 0.1 mL/min and continued for the duration of the reaction. After 75 min, the pressure decreased 8 psi (0.06 kPa) below the initial pressure, indicating that the reaction was proceeding, and the VF feed was resumed to maintain the pressure at 500 psi (3.45 MPa) using an Isco 1000D syringe pump. The addition of VF continued for 182 min, until 25 g of VF had been added. The VF and initiator feeds were then stopped. The heating was turned off and cooling was turned on until the temperature dropped to 63 °C and then the excess VF was vented. When the reactor reached 22 °C, it was purged three times with 100 psi (0.69 MPa) nitrogen while stirring at 100 rpm. The product, which was a smooth white sludge, was then discharged from the reactor into a pre-weighed jar.

EXAMPLE 17

Polymerization of Vinyl Fluoride in an 80 wt% Aqueous Solution of LiTf 2 N in an Autoclave Reactor Using VA-061 Initiator

A 1-L stainless steel autoclave, fitted with a ribbon blade stirrer having 3 blades and baffles and a 3/16 inch (4.8 mm) diameter cooling coil with two turns was sealed and flushed with nitrogen. The autoclave was also equipped with a

thermocouple and temperature control . The autoclave was assembled and leak tested at 500 psi (3.45 MPa) with nitrogen. Then, vacuum was used to pull a solution of 3.0 g V-50 (Wako Chemical Co.) in 500 mL of water into the reactor. Next, the reactor was heated at 95 °C for 3 hours with stirring at 500 rpm. The reactor was then cooled to 35 °C and the contents were removed by opening a drain valve that led to a tube running to the bottom of the reactor and flushing the reactor with nitrogen. Next, the reactor was re-pressurized with nitrogen and flushed a second time to remove any remaining liquid. Next, vacuum was applied to the reactor and 500 mL of 80 wt% lithium bis (trifluoromethylsulfonyl ) imide in water was pulled into the reactor. The reactor was evacuated and flushed with nitrogen gas again three times at 100 psi (0.69 MPa) with stirring at 100 rpm. The reactor was heated to 87 °C and pressurized to 498 psi (3.43 MPa) with vinyl fluoride (VF) and then isolated from the VF feed. A solution of VA-061 (Wako Chemical Co.) in water (0.4 wt%) was added at a rate of 2.3 mL/min using an Isco 260D syringe pump until 11.5 mL was added (5 min) . Subsequently, the initiator feed rate was decreased to 0.23 mL/min and continued for the duration of the reaction. After 9 min, the pressure decreased 9 psi (0.06 kPa) below the initial pressure, indicating that the reaction was proceeding, and the VF feed was resumed to maintain the pressure at 500 psi (3.45 MPa) using an Isco 1000D syringe pump. The addition of VF continued for 124 min, until 25 g of VF had been added. The VF and initiator feeds were then stopped. The heating was turned off and cooling was turned on until the temperature dropped to 67 °C and then the excess VF was vented. When the reactor reached 19 °C, it was purged three times with 100 psi (0.69 MPa) nitrogen while stirring at 100 rpm. The product, which was an off-white sludge, was then discharged from the reactor into a pre-weighed jar.

EXAMPLE 18, COMPARATIVE

Unsuccessful Polymerization of Vinyl Fluoride in Water Using VA-061 Initiator in an Autoclave Reactor

A 1-L stainless steel autoclave, fitted with ribbon blade stirrer having 3 blades and baffles and a 3/16 inch (4.8 mm) diameter cooling coil with two turns was sealed and flushed with nitrogen. The autoclave was also equipped with a

thermocouple and temperature control . The autoclave was assembled and leak tested at 500 psi (3.45 MPa) with nitrogen. Then, vacuum was used to pull a solution of 3.0 g V-50 (Wako Chemical Co.) in 500 mL water into the reactor. Next, the reactor was heated at 95 °C for 3 hours with stirring at 500 rpm. The reactor was then cooled to 35 °C and the contents were removed by opening a drain valve that led to a tube running to the bottom of the reactor and flushing the reactor with nitrogen. The reactor was re-pressurized with nitrogen and flushed a second time to remove any remaining liquid. Next, vacuum was applied to the reactor and 500 mL of deionized water was pulled into the reactor. The reactor was flushed with nitrogen gas again three times at 100 psi (0.69 MPa) with stirring at 100 rpm. The reactor was heated to 87 °C and pressurized to 502 psi (3.46 MPa) with vinyl fluoride (VF) and then isolated from the VF feed. A solution of VA-061 in water (0.4 wt%) was added at a rate of 2.3 mL/min using an Isco 260D syringe pump until 11.5 mL was added (5 min) . Subsequently, the initiator feed rate was decreased to 0.23 mL/min and continued for the duration of the reaction. After 1 hr and 42 min, the VF pressure had not decreased, indicating that VF polymerization was not proceeding. The initiator feed was then stopped. The heating was turned off and cooling was turned on until the temperature dropped to 37 °C and then the excess VF was vented. The reactor was purged three times with 100 psi (0.69 MPa) nitrogen while stirring at 100 rpm. The product, which consisted of a clear liquid (water) with a small amount of particulates present, was then discharged from the reactor into a pre-weighed jar. Based on visual observations, it was clear that little polymer had been produced.

EXAMPLE 19

Polymerization of Vinyl Fluoride in an 80 wt% Aqueous Solution of LiTf 2 N in an Autoclave Reactor Using VA-057 Initiator A 1-L stainless steel autoclave, fitted with a ribbon blade stirrer having 3 blades and baffles and a 3/16 inch (4.8 mm) diameter cooling coil with two turns was sealed and flushed with nitrogen. The autoclave was also equipped with a

thermocouple and temperature control . The autoclave was assembled and leak tested at 500 psi (3.45 MPa) with nitrogen. Then, vacuum was used to pull a solution of 3.0 g V-50 (Wako Chemical Co.) in 500 mL of water into the reactor. Next, the reactor was heated at 95 °C for 3 hours with stirring at 500 rpm. The reactor was then cooled to 35 °C and the contents were removed by opening a drain valve that led to a tube running to the bottom of the reactor and flushing the reactor with nitrogen. Next, the reactor was re-pressurized with nitrogen and flushed a second time to remove any remaining liquid. Next, vacuum was applied to the reactor and 450 mL of 80 wt% lithium bis (trifluoromethylsulfonyl ) imide in water was pulled into the reactor. The reactor was evacuated and flushed with nitrogen gas again three times at 100 psi (0.69 MPa) with stirring at 100 rpm. The reactor was heated to 80 °C and pressurized to 706 psi (4.87 MPa) with vinyl fluoride (VF) and then isolated from the VF feed. A solution of VA-057 in water (1 wt%) was added at a rate of 1.0 mL/min using an Isco 260D syringe pump until 5.0 mL was added (5 min) . Subsequently, the initiator feed rate was decreased to 0.1 mL/min and continued for the duration of the reaction. After 35 min, the pressure decreased 8 psi (0.06 kPa) below the initial pressure,

indicating that the reaction was proceeding, and the VF feed was resumed to maintain the pressure at 700 psi (4.83 MPa) using an Isco 1000D syringe pump. The addition of VF continued for 81 min, until 35 g of VF had been added. The VF and initiator feeds were then stopped. The heating was turned off and cooling was turned on until the temperature dropped to 80 °C and then the excess VF was vented. When the reactor reached 44 °C, it was purged three times with 80 psi (0.55 MPa) nitrogen while stirring at 100 rpm. The product, which was a thick white sludge, was then discharged from the reactor into a pre-weighed jar. The product was filtered and then divided into two fractions. To one product fraction (319.40 g) was added 640 mL of deionized water and the resulting suspension was mixed at 250 rpm for 20 min using an overhead mixer

(Servodyne, model 50003-20, Cole-Parmer, Vernon Hills, IL) . The mixture was then filtered and the conductivity of the filtrate was measured. The collected solid was re-dispersed in water and the process using the overhead mixer was repeated as described above until the conductivity of the filtrate dropped below 8 ]iS . To the second product fraction (350.87 g) was added 700 mL of deionized water and the resulting suspension was mixed for 1 min at 9,500 rpm using a disperser (Ultra- Turrax T-25 Basic IKA-WERKE, IKA® Works Inc, Wilmington, NC) . The mixture was then filtered and the conductivity of the filtrate was measured. The collected solid was re-dispersed in water and the process using the disperser was repeated as described above until the conductivity of the filtrate dropped below 8 μΞ . Finally, each fraction was dried in a nitrogen- purged oven at 110 °C overnight. Polymer yield from the combined fractions was 93%. The two fractions were judged to be equivalent. The product produced using the overhead mixer wash was characterized and the results are shown in Example 21.

EXAMPLE 20, COMPARATIVE

Unsuccessful Polymerization of Vinyl Fluoride in Water Using VA-057 Initiator in an Autoclave Reactor

A 1-L stainless steel autoclave, fitted with ribbon blade stirrer having 3 blades and baffles and a 3/16 inch (4.8 mm) diameter cooling coil with two turns was sealed and flushed with nitrogen. The autoclave was also equipped with a

thermocouple and temperature control . The autoclave was assembled and leak tested at 500 psi (3.45 MPa) with nitrogen. Then, vacuum was used to pull a solution of 3.0 g V-50 (Wako Chemical Co.) in 500 mL water into the reactor. Next, the reactor was heated at 95 °C for 3 hours with stirring at 500 rpm. The reactor was then cooled to 35 °C and the contents were removed by opening a drain valve that led to a tube running to the bottom of the reactor and flushing the reactor with nitrogen. The reactor was re-pressurized with nitrogen and flushed a second time to remove any remaining liquid. Next, vacuum was applied to the reactor and 500 mL of deionized water was pulled into the reactor. The reactor was flushed with nitrogen gas again three times at 100 psi (0.69 MPa) with stirring at 100 rpm. The reactor was heated to 81 °C and pressurized to 505 psi (3.48 MPa) with vinyl fluoride (VF) and then isolated from the VF feed. A solution of VA-057 in water (1 wt%) was added at a rate of 1.0 mL/min using an Isco 260D syringe pump until 5.0 mL was added (5 min) . Subsequently, the initiator feed rate was decreased to 0.1 mL/min and continued for the duration of the reaction. After 25 min, the pressure decreased 16 psi (0.11 kPa) below the initial pressure, indicating that the reaction was proceeding, and the VF feed was resumed to maintain the pressure at 500 psi (3.45 MPa) using an Isco 1000D syringe pump. However, after addition of only a small amount of VF (5.3 g) , VF pressure stopped dropping and remained constant, indicating that polymerization had ceased. After waiting for 1 h 40 min, the VF and initiator feeds were stopped. The heating was turned off and cooling was turned on until the temperature dropped to 31 °C and then the excess VF was vented. The reactor was purged three times with 100 psi (0.69 MPa) nitrogen while stirring at 100 rpm. The product, which consisted of a clear liquid (water) with a small amount of white particulates present, was then discharged from the reactor into a pre-weighed jar. Based on visual

observations, it was clear that little polymer had been produced .

EXAMPLE 21

Characterization of Poly (Vinyl Fluoride) Polymers

The poly (vinyl fluoride) polymers described in the preceding Examples were characterized by viscosity measurement, NMR, and differential scanning calorimetry.

Viscosity Measurement:

Solution viscosity measurements were performed using a Kayeness Galaxy V capillary rheometer (Alpha Technologies, Akron OH) in N, -dimethylacetamide (DMAC) at 40 wt% of the poly (vinyl fluoride) polymers described above at 150 °C . For comparison, viscosity measurements were also made on a

commercial poly (vinyl fluoride) polymer, i.e., Tedlar® PVF resin (E.I. du Pont de Nemours and Co., Wilmington, DE) . The viscosity results for the polymers described above are shown in Table 5. Table 5

Viscosities of Various Poly (Vinyl Fluoride) Polymers

as a Function of Shear Rate

Example 9 23.44 106

93.75 58

352 31

1172 19

3516 12

Commercial Tedlar® 23.44 1025

93.75 393

352 153

1172 65

3516 30

*nd means not determined.

The results in Table 5 indicate that for the poly (vinyl fluoride) polymers made at low initial vinyl fluoride pressure (-500 psi, 3.45 MPa) , the polymer made by polymerization in water (Example 4, Comparative) had a higher viscosity than the polymer made in 80% lithium bis (trifluoromethylsulfonyl) imide (Example 3) and also exhibited more shear thinning. In

contrast, for the polymers made at high initial vinyl fluoride pressure (-1000 psi, 6.89 MPa) , the polymer made in water (Example 8, Comparative) had a lower viscosity than the polymer made in 80% lithium bis (trifluoromethylsulfonyl) imide (Example 7) . The poly (vinyl fluoride) made in 80% lithium

bis (trifluoromethylsulfonyl) imide at an initial vinyl fluoride pressure of -1000 psi had a higher viscosity than even the commercial Tedlar® PVF resin.

NMR Studies of Branching:

Since viscosity is a function of molecular weight and branching, additional characterization of the polymers in terms of branching determination was performed using 1 E and 19 F NMR in dimethyl sulfoxide-d 6 at 116-119 °C . The results of the branching determination are shown in Table 6.

Table 6

Results of Branching and End Group Analysis by 1 E and 19 F NMR

inverted monomers refers to the monomer units that are reversed, except, not including those with branches.

2Mol% normal branch refers to the mol% of branch points

(relative to total monomer units) connected to normal (non- inverted) monomer units.

3 Mol% HH branch refers to the mol% of branch points (relative to total monomer units) connected to inverted monomer units. 4Total mol% branch refers to the sum of Mol% normal branch and Mol% HH branch.

5 Mol% CHFCH 3 ends refers to the mol% of end groups resulting from a head-to-head monomer addition.

6nd means not determined.

Differential Scanning Calorimetry:

The thermal properties of the poly (vinyl fluoride) polymers described above were measured using differential scanning calorimetry (DSC) . DSC was performed using a model Q100 differential scanning calorimeter (TA Instruments, New Castle, DE) equipped with a TA Instruments Refrigerated Cooling System. Samples were prepared by accurately weighing 2 to 25 mg of polymer into a standard aluminum DSC pan. The

temperature program was designed to erase the thermal history of the sample by first heating it above its melting point from 35 °C to 220 °C at 20 °C/min and then allowing the sample to re-crystallize during cooling from 320 °C to 35 °C at 10 °C /min. Reheating the sample from 35 °C to 220 °C at 10 °C /min afforded the melting point of the sample, which was recorded. The results are shown in Table 7. The entire temperature program was carried out under a nitrogen purge at a flow rate of 50 mL/min. All melting points were quantified using TA' s Universal Analysis software via the software linear peak integration function.

Table 7

Thermal Properties of PVF Polymers Measured by Differential Scanning Calorimetry

As can be seen from the results in Table 6, the total mol% branching was similar, if not slightly lower for the PVF samples made in lithium bis (trifluoromethylsulfonyl) imide solution compared to the PVF polymer made in water. The pressure played a larger role in affecting the degree of branching than did the choice of reaction solvent. The lower degree of branching was consistent with the higher melting points and heats of fusion (measured by DSC) for the PVF made in lithium bis (trifluoromethylsulfonyl ) imide solution compared to the PVF made in water (Table 7) . Combining this branching information with the viscosity data, one can conclude that the molecular weight of the PVF polymers made at similar pressures trended with the viscosity results. In particular, the polymer made in Example 7 had a higher molecular weight than the polymer made in Example 8, Comparative. This is consistent with the higher solubility of vinyl fluoride in the lithium

bis (trifluoromethylsulfonyl) imide solution (Example 1), which may have led to faster rates of propagation relative to termination, leading to higher degrees of polymerization. For the polymer made at -1000 psi in 70 t% LiTFES (Example 9) , a very low viscosity product was obtained. This suggests the occurrence of chain transfer to the LiTFES, which, unlike the lithium bis (trifluoromethylsulfonyl) imide, does contain hydrogen .

EXAMPLE 22

Polymerization of Vinyl Fluoride in an 80 wt% Aqueous Solution of LiTf 2 N in an Autoclave Reactor Using a Nonionic Surfactant A 1-L stainless steel autoclave, fitted with a ribbon blade stirrer having 3 blades and baffles and a 3/16 inch (4.8 mm) diameter cooling coil with two turns was sealed and flushed with nitrogen. The autoclave was also equipped with a

thermocouple and temperature control . The autoclave was assembled and leak tested at 500 psi (3.45 MPa) with nitrogen. Then, vacuum was used to pull a solution of 3.0 g V-50 (Wako Chemical Co.) in 500 mL of water into the reactor. Next, the reactor was heated at 95 °C for 3 hours with stirring at 500 rpm. The reactor was then cooled to 35 °C and the contents were removed by opening a drain valve that led to a tube running to the bottom of the reactor and flushing the reactor with nitrogen. Next, the reactor was re-pressurized with nitrogen and flushed a second time to remove any remaining liquid. Next, vacuum was applied to the reactor and 450 mL of 80 wt% lithium bis (trifluoromethylsulfonyl ) imide containing 0.1 wt% Pluronic 31R1 (BASF Corporation, Florham Park, NJ) in water was pulled into the reactor. The reactor was flushed with nitrogen gas again three times at 80 psi (0.55 MPa) with stirring at 100 rpm. The reactor was heated to 100 °C and pressurized to 500 psi (3.45 MPa) with vinyl fluoride (VF) and then isolated from the VF feed. A solution of V-50 in water (1 wt%) was added at a rate of 1 mL/min using an Isco 260D syringe pump until 5.0 mL was added. Subsequently, the initiator feed rate was decreased to 0.1 mL/min and continued for the duration of the reaction. After 30 min, the pressure decreased 5 psi (34 kPa) below the initial pressure, indicating that the reaction was proceeding and the VF feed was resumed to maintain the pressure at 500 psi (3.45 MPa) using an Isco 1000D syringe pump. The addition of VF continued for 37 min, until 25 g of VF had been added. The VF and initiator feeds were then stopped. The heating was turned off and cooling was turned on until the temperature dropped to 35 °C and then the excess VF was vented. The reactor was purged three times with 80 psi (0.55 MPa) nitrogen while stirring at 100 rpm. The product, which was a viscous opaque liquid, was then discharged from the reactor into a pre-weighed jar.

In this specification, unless explicitly stated otherwise or indicated to the contrary by the context of usage, where an embodiment of the subject matter hereof is stated or described as comprising, including, containing, having, being composed of or being constituted by or of certain features or elements, one or more features or elements in addition to those explicitly stated or described may be present in the embodiment. An alternative embodiment of the subject matter hereof, however, may be stated or described as consisting essentially of certain features or elements, in which embodiment features or elements that would materially alter the principle of operation or the distinguishing characteristics of the embodiment are not present therein. A further alternative embodiment of the subject matter hereof may be stated or described as consisting of certain features or elements, m which embodiment, or m insubstantial variations thereof, only the features or elements specifically stated or described are present.

Where a range of numerical values is recited or

established herein, the range includes the endpoints thereof and all the individual integers and fractions within the range, and also includes each of the narrower ranges therein formed by all the various possible combinations of those endpoints and internal integers and fractions to form subgroups of the larger group of values within the stated range to the same extent as if each of those narrower ranges was explicitly recited.

Where a range of numerical values is stated herein as being greater than a stated value, the range is nevertheless finite and is bounded on its upper end by a value that is operable within the context of the invention as described herein.

Where a range of numerical values is stated herein as being less than a stated value, the range is nevertheless bounded on its lower end by a non-zero value.

In this specification, unless explicitly stated otherwise or indicated to the contrary by the context of usage, (a) lists of compounds, monomers, oligomers, polymers and/or other chemical materials include derivatives of the members of the list in addition to mixtures of two or more of any of the members and/or any of their respective derivatives; and (b) amounts, sizes, ranges, formulations, parameters, and other quantities and characteristics recited herein, particularly when modified by the term "about", may but need not be exact, and may also be approximate and/or larger or smaller (as desired) than stated, reflecting tolerances, conversion factors, rounding off, measurement error and the like, as well as the inclusion within a stated value of those values outside it that have, within the context of this invention, functional and/or operable equivalence to the stated value;