# US 9,434,679 B2 · Allyl-bearing fluorinated ionomers

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- Number: US 9,434,679 B2
- Document ID: US9434679B2
- Status: Granted
- Kind: B2
- Application number: 14/420,708
- Filed: 2013-07-30
- Published: 2015-08-06
- Granted: 2016-09-06
- Earliest claimed: 2012-08-10
- Assignees: Solvay Specialty Polymers Italy S.P.A.
- Applicants: Solvay Specialty Polymers Italy S.P.A.
- Inventors: Luca Merlo; Vito Tortelli; Ivan Wlassics; Claudio Oldani
- Web page: https://patentgrep.com/patent/US9434679B2

## CPC

- C08F 216/1475: {Monomers containing sulfur and oxygen}
- C07C 41/30: by increasing the number of carbon atoms, e.g. by oligomerisation
- C07C 43/17: containing halogen
- C07C 213/02: by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
- C07C 217/46: the carbon skeleton being acyclic and unsaturated
- C08G 65/007: {containing fluorine}
- C08J 5/2237: {containing fluorine}
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)

## Abstract

The present invention provides a fluorinated ionomer [polymer (I)] comprising recurring units derived from at least the following monomers: (i) 5 to 50% by weight of a fluorinated monomer [monomer (A)] containing at least one —SO2X functionality, preferably having the formula of CF2═CF—O—(CF2CF(CF3)O)m—(CF2)mSO2X (I) wherein m is 0 or 1, n is an integer between 0-10, and X is selected from F, OH, and O−Me+, wherein Me+ indicates an alkali metal ion or an ammonium cation of formula NR4− where each R independently represents a hydrogen atom or a monovalent organic radical selected from aliphatic radicals having from 1 to 8 carbon atoms and arylic or alicyclic radicals having from 3 to 8 carbon atoms; (ii) a non-functional fluorinated monomer [monomer (B)] having at least one ethylene unsaturation; and (iii) a fluorinated polyfunctional compound having the general formula: (CR1R2═CFCF2—O)a—Rf—((O)c—CF═CR3R4)b (II) wherein: a is an integer equal to or larger than 1, preferably a is 1, 2, or 3; b is 0 or 1 and the sum of a and b is an integer equal to or larger than 2; c is 0 or 1; R1, R2, R3 and R4 are independently selected from F, H, alkyl, alkoxy, polyoxy alkyl, perfluoroalkyl, perfluoroalkoxy or perfluoropolyoxy alkyl, preferably F; and Rf represents a hydrocarbon or fluorocarbon group having at least two carbon atoms. The low-EW perfluorinated ionomers made of polymer (I) are adapted to be processed into thin films, which are found to have superior physical stability than the existing products and are thus well suited for low humidity or high temperature electrochemical applications. Moreover, these low-EW ionomers are melt processable and have limited loss of volatile substances at their melt processing temperatures.

## Claims

### Claim 1

A fluorinated polymer (I) comprising recurring units derived from at least the following monomers:
(i) 5 to 50% by weight of a fluorinated monomer (A) containing at least one —SO2X functionality wherein X is selected from F, OH, and O−Me+, wherein Me+ indicates an alkali metal ion or an ammonium cation of formula NR4+ where each R independently represents a hydrogen atom or a monovalent organic radical selected from aliphatic radicals having from 1 to 8 carbon atoms and arylic or alicyclic radicals having from 3 to 8 carbon atoms;
(ii) a non-functional fluorinated monomer (B), wherein monomer (B) comprises a fluorocarbon chain having a carbon skeleton, is free from functional groups that represent potential reaction sites in an organic compound and that may alter the properties of the carbon skeleton, and has at least one ethylene unsaturation; and
(iii) a fluorinated polyfunctional compound of formula (II):
(CR1R2═CFCF2—O)a—Rf—((O)c—CF═CR3R4)b (II)
wherein: a is 1, 2 or 3; b is 0 or 1 and the sum of a and b is an integer equal to or larger than 2; c is 0 or 1; R1, R2, R3 and R4 are independently selected from F, H, alkyl, alkoxy, polyoxy alkyl, perfluoroalkyl, perfluoroalkoxy or perfluoropolyoxy alkyl; and Rf represents a hydrocarbon group or fluorocarbon group having at least two carbon atoms, wherein the hydrocarbon group refers to a non-fluorinated group containing carbon and hydrogen atoms, and wherein the fluorocarbon group refers to a chemical group having carbon and fluorine atoms.

### Claim 2 (depends on 1)

The polymer (I) of claim 1, wherein polymer (I) comprises from 5 to 50% by weight of recurring units derived from monomer (A).

### Claim 3 (depends on 1)

The polymer (I) of claim 1, wherein monomer (A) is selected from:
compounds of formula: CF2═CF—O—(CF2CF(CF3)O)m—(CF2)nSO2X, wherein m is 0 or 1 and n is an integer between 0-10;
compounds of formula: CF2═CF(CF2)pSO2X wherein p is an integer between 0 and 10;
fluoroalkoxyvinylethers of formula: CF2═CF—(OCF2CF(RF1))w—O—CF2(CF(RF2))ySO2X wherein w is an integer between 0 and 2, RF1 and RF2, equal or different from each other, are independently F, Cl or a C1-C10 fluoroalkyl group, optionally substituted with one or more ether oxygens, y is an integer between 0 and 6;
aromatic fluoroolefins of formula CF2═CF-Ar-SO2X
wherein Ar is a C5-C15 aromatic or heteroaromatic substituent.

### Claim 4 (depends on 1)

The polymer (I) according to claim 1, wherein monomer (A) is selected from the group of compounds of formula: CF2═CF—O—(CF2CF(CF3)O)m—(CF2)n—SO2X, wherein m is 0 or 1 and n is an integer between 0-10.

### Claim 5 (depends on 1)

The polymer (I) according to claim 1, wherein monomer (A) in —SO2F form is selected from the group consisting of:
CF2═CF—O—CF2—CF2—SO2F;
CF2═CF—O—CF2—CF2—CF2—SO2F;
CF2═CF—O—CF2—CF2—CF2—CF2—SO2F; and
CF2═CF—O—CF2CF(CF3)—O—CF2—CF2—SO2F.

### Claim 6 (depends on 1)

The polymer (I) according to claim 1, wherein polymer (I) comprises from 30 to 95% by weight of recurring units derived from monomer (B).

### Claim 7 (depends on 1)

The polymer (I) according to claim 1, wherein monomer (B) is selected from the group consisting of:
C2-C8 perfluoroolefins;
vinylidene fluoride (VDF);
C2-C8 chloro- and/or bromo- and/or iodo-fluoroolefines;
fluoroalkylvinylethers of formula CF2═CFORf1 in which Rf1 is a C1-C6 fluoroalkyl; and
fluoro-oxyalkylvinylethers of formula CF2═CFORO1, in which RO1 is a C1-C12 fluorooxyalkyl having one or more ether groups.

### Claim 8 (depends on 1)

The polymer (I) according to claim 1, wherein monomer (B) is TFE.

### Claim 9 (depends on 1)

The polymer (I) according to claim 1, wherein polymer (I) comprises from 0.01 to 5% by weight of recurring units derived from fluorinated polyfunctional compound of formula (II).

### Claim 10 (depends on 1)

The polymer (I) according to claim 1, wherein in said formula (II), the sum of a and b is an integer from 2 to 4, and wherein Rf represents a divalent, trivalent, or tetravalent fluorocarbon group having at least two carbon atoms and containing a backbone of perfluoroalkyl, perfluoroalkoxy or perfluoropolyoxy alkyl, optionally containing sulfonimide groups; or Rf represents a divalent, trivalent, or tetravalent group having at least two carbon atoms, being selected from a non-fluorinated aromatic moiety, a fluorinated aromatic moiety and a perfluorinated aromatic moiety, optionally substituted with one or more nonhydrogen substituents.

### Claim 11 (depends on 1)

The polymer (I) according to claim 1, wherein Rf is selected from the group consisting of:
—(CF2)n′— with n′ being an integer from 2 to 12;
—CF2—O—CF2—;
—CF2—O—CF2—CF2—;
—CF(CF3)—;
—(CF2)2—O—CF(CF3)—CF2—;
—CF(CF3)—CF2—O—CF(CF3)—;
—(CF2)2—O—CF(CF3)—CF2—O—CF(CF3)—CF2—O—CF2—;
—(CF2)m′—SO2—NH—SO2(CF2)m′—; and,
—(CF2)m′—SO2—CH(SO2(CF2)m′—SO2(CF2)m′—,
wherein each m′ is independently an integer from 1 to 12.

### Claim 12 (depends on 1)

The polymer (I) according to claim 1, wherein the fluorinated polyfunctional compound of formula (II) is selected from the group consisting of:
(CF2═CFCF2—O)2-PFPE (a);
CF2═CF—O-PFPE-O—CF2CF═CF2 (b); and
(CF2═CFCF2—O—CF2CF2SO2)2NH (c).

### Claim 13 (depends on 12)

The polymer (I) according to claim 12, wherein the fluorinated polyfunctional compound of formula (II) is selected from compound (a) and compound (b), and wherein compounds (a) and (b) have PFPE units selected from the following groups:
—O—[CF(CF3)CF2O]b1′(CFYO)b2′— (1)
wherein:
Y, equal or different at each occurrence, is selected from a fluorine atom and a —CF3 group;
b1′ and b2′, equal to or different from each other, are independently integers ≧0 such that the b1′/b2′ ratio is comprised between 20 and 1000 and the (b1′+b2′) sum is comprised between 5 and 250; should b1′ and b2′ be both different from zero, the different recurring units are generally statistically distributed along the perfluoropolyoxyalkylene chain,
—O—[CF(CF3)CF2O]c1′(C2F4O)c2′(CFYO)c3′— (2)
wherein:
Y, equal or different at each occurrence, has the same meaning as defined above;
c1′, c2′ and c3′, equal to or different from each other, are independently integers ≧0 such that the (c1′+c2′+c3′) sum is comprised between 5 and 250; should at least two of c1′, c2′ and c3′ be different from zero, the different recurring units are generally statistically distributed along the perfluoropolyoxyalkylene chain, and
—O—(C2F4O)d1′(CF2O)d2′— (3)
wherein:
d1′ and d2′, equal to or different from each other, are independently integers ≧0 such that the d1′/d2′ ratio is comprised between 0.1 and 5 and the (d1′+d2′) sum is comprised between 5 and 250; should d1′ and d2′ be both different from zero, the different recurring units are generally statistically distributed along the perfluoropolyoxyalkylene chain.

### Claim 14 (depends on 1)

A membrane comprising the polymer (I) of claim 1.

### Claim 15 (depends on 1)

A method of manufacturing the polymer (I) according to claim 1, comprising polymerizing Monomer (A), Monomer (B) and the fluorinated polyfunctional compound of formula (II) in an aqueous emulsion in the presence of radical initiators.

### Claim 16 (depends on 1)

The polymer (I) of claim 1, wherein monomer (A) is a compound of formula (I):
CF2═CF—O—(CF2CF(CF3)O)m—(CF2)—SO2X (I)
wherein m is 0 or 1, n is an integer between 0-10, and X is selected from F, OH, and O−Me+, wherein Me+ indicates an alkali metal ion or an ammonium cation of formula NR4+ where each R independently represents a hydrogen atom or a monovalent organic radical selected from aliphatic radicals having from 1 to 8 carbon atoms and arylic or alicyclic radicals having from 3 to 8 carbon atoms.

### Claim 17 (depends on 2)

The polymer (I) of claim 2, wherein polymer (I) comprises from 15 to 35% by weight of recurring units derived from monomer (A).

### Claim 18 (depends on 3)

The polymer (I) of claim 3, wherein n is an integer between 2 and 4; p is 2 or 3; w is 1; RF1 is —CF3; y is 1 and RF2 is F.

### Claim 19 (depends on 6)

The polymer (I) according to claim 6, wherein polymer (I) comprises from 65 to 85% by weight of recurring units derived from monomer (B).

### Claim 20 (depends on 9)

The polymer (I) according to claim 9, wherein polymer (I) comprises from 0.02 to 0.1% by weight of recurring units derived from fluorinated polyfunctional compound of formula (II).