# US 10,246,572 B2 · Foamable fluoropolymer compositions

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 10,246,572 B2
- Document ID: US10246572B2
- Status: Granted
- Kind: B2
- Application number: 13/993,331
- Filed: 2011-12-09
- Published: 2013-10-10
- Granted: 2019-04-02
- Earliest claimed: 2010-12-16
- Assignees: Solvay Specialty Polymers Italy S.P.A.
- Applicants: Pasqua Colaianna; Giambattista Besana; Emanuele Di Nicolo; Letanzio Bragante; Giuseppe Marchionni; Giulio Brinati
- Inventors: Pasqua Colaianna; Giambattista Besana; Emanuele Di Nicolo; Letanzio Bragante; Giuseppe Marchionni; Giulio Brinati
- Web page: https://patentgrep.com/patent/US10246572B2

## CPC

- C08K 5/42: Sulfonic acids; Derivatives thereof
- C08J 9/0019: {halogenated}
- C08J 2327/12: containing fluorine atoms
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- 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 invention pertains to foamable thermoplastic fluoropolymer composition comprising: at least one fluoropolymer [polymer (A)]; and at least one perfluoroalkoxysulphonic derivative of either of formulae: (Xn+)1/n−O3S—CF2CF2O—Rdf—OCF2CF2—SO3−(Xn+)1/n and Rmf—OCF2CF2—SO3−(Xn+)1/n wherein Rdf is a divalent C1-C12 perfluorocarbon group, possibly comprising one or more ethereal oxygen atom; Rmf is a monovalent C1-C12 perfluorocarbon group, possibly comprising one or more ethereal oxygen atom, optionally comprising heteroatoms, generally selected from S, N, P; X=H, a metal cation, or an ammonium group; n is the valence of the cation X, preferably 1 or 2.

## Claims

### Claim 1

A foamable thermoplastic fluoropolymer composition comprising:
at least one melt-processible fluoropolymer [polymer (A)]; and
at least one perfluoroalkoxysulphonic derivative selected from the following compounds:
CF3—(CF2)w—OCF2CF2—SO3−(Zp+)1/p (i)
wherein w is an integer from 1 to 3, Z is NH4 or an alkaline or alkali-earth metal cation, and
p is the valence of the cation Z;
CF3—(CF2)w′OCF2CF2—OCF2CF2—SO3−(Zp+)1/p (ii)
wherein w′ is an integer from 0 to 2, Z is NH4 or an alkaline or alkali-earth metal cation, and
p is the valence of the cation Z; and
CF3—(CF2)q—(OCF2CFXF)r—OCF2CF2—SO3−(Zp+)1/p (iii)
wherein q and r are each independently an integer from 1 to 3, XF is F or CF3, Z is NH4 or an alkaline or alkali-earth metal cation, and p is the valence of the cation Z.

### Claim 2 (depends on 1)

The foamable thermoplastic fluoropolymer composition of claim 1, wherein the perfluoroalkoxysulphonic derivative is selected from the group consisting of the following compounds: CF3—CF2—OCF2CF2—SO3K, CF3—CF2—OCF2CF2—SO3Na, CF3—CF2—OCF2CF2—SO3NH4, (CF3—CF2—OCF2CF2—SO3)2Ba, (CF3—CF2—OCF2CF2—SO3)2Ca, CF3—OCF2CF2—OCF2CF2—SO3K, CF3—OCF2CF2—OCF2CF2—SO3Na, CF3—OCF2CF2—OCF2CF2—SO3NH4, (CF3—OCF2CF2—OCF2CF2—SO3)2Ba, (CF3—OCF2CF2—OCF2CF2—SO3)2Ca, CF3CF2—OCF2CF(CF3)—OCF2CF2—SO3K, CF3CF2—OCF2CF(CF3)—OCF2CF2—SO3Na, CF3CF2—OCF2CF(CF3)—OCF2CF2—SO3NH4, (CF3CF2—OCF2CF(CF3)—OCF2CF2—SO3)2Ba and (CF3CF2—OCF2CF(CF3)—OCF2CF2—SO3)2Ca.

### Claim 3 (depends on 1)

The foamable thermoplastic fluoropolymer composition according to claim 1 wherein the perfluoroalkoxysulphonic derivative from 1 to about 3 000 ppm, by weight based on the total weight of the composition.

### Claim 4 (depends on 1)

The foamable thermoplastic fluoropolymer composition according to claim 1 wherein said polymer (A) is a polymer comprising recurring units derived from at least one fluorinated monomer selected from the group consisting of:
C2-C8 fluoro- and/or perfluoroolefins;
C2-C8 hydrogenated monolluoroolefins;
(per)fluoroalkylethylenes complying with formula CH2═CH—Rf0, wherein Rf0 is a C1-C6 (per)fluoroalkyl or a C1-C6 (per)fluorooxyalkyl having one or more ether groups;
chloro- and/or bromo- and/or iodo-C2-C6 fluorooletins;
fluoroalkylvinylethers complying with formula CF2═CFORf1 wherein Rf1 is a C1-C6 fluoro- or perfluoroalkyl;
hydrofluoroalkylvinylethers complying with formula CH2—CFORf1 wherein Rf1 is a C1-C6 fluoro- or perfluoroalkyl;
fluoro-oxyalkylvinylethers complying with formula CF2═CFOX0, wherein X0 is a C1-C12 oxyalkyl, or a C1-C12 (per)fluorooxyalkyl having one or more ether groups;
fluoroalkyl-methoxy-vinylethers complying with formula CF2—CFOCF2ORf2 wherein Rf2 is a C1 -C6 fluoro- or perfluoroalkyl or a C1-C6 (per)fluorooxyalkyl having one or more ether groups;
functional fluoro-alkylvinylethers complying with formula CF2═CFOY0, wherein Y0 is a C1-C12 alkyl or (per)fluoroalkyl, or a C1-C12 oxyalkyl or a C1-C12 (per)fluorooxyalkyl, said Y0 group comprising a carboxylic or sulfonic acid group, in its acid, acid halide or salt form; and
fluorodioxoles, of formula:
wherein each of Rf3, Rf4, Rf5, Rf6, equal to or different from each other, is independently a fluorine atom, a C1-C6 fluoro- or per(halo)fluoroalkyl, optionally comprising one or more oxygen atom.

### Claim 5 (depends on 4)

The foamable thermoplastic fluoropolymer composition according to claim 4, wherein said polymer (A) is a per(halo)fluoropolymer substantially free from hydrogen atoms.

### Claim 6 (depends on 4)

The foamable thermoplastic fluoropolymer composition according to claim 4, wherein said polymer (A) is a homopolymer of a per(halo)flaoromonomer (PFM) or a copolymer comprising recurring units derived from more than one per(halo)fluoromonomer (PFM), said per(halo)fluoromoncaner (PPM) being selected from the group consisting of:
C2-C8 perfluaroolefins;
chloro- and/or bromo- and/or iodo- C2-C6 per(halo)fluoroolefins;
per(halo)fluoroalkylvinylethers complying with general formula CF2═CFORf1 wherein Rf1 is a C1-C6 por(halo)fluoroalkyl;
per(halo)fluoro-oxyalkylvinylethers complying with general formula CF2—CFOX01, wherein X01 is a C1-C12 per(halo)fluorooxyalkyl having one or more ether groups;
per(halo)fluoro-methoxy-alkylvinylethers complying with general formula CF2—CFOCF2ORf2 wherein Rf2 is a C1-C6 per(halo)fluoroalkyl or a C1-C6 per(halo)fluorooxyalkyl having one or more ether groups;
per(halo)fluorodioxoles of formula:
wherein each Rf3, Rf4, Rf5, Rf6, equal to or different from each other, is independently a fluorine atom, a C1-C6, perfluoroalkyl group, optionally comprising one or more oxygen atom.

### Claim 7 (depends on 6)

The foamable thermoplastic fluoropolymer composition according to claim 6, wherein said polymer (A) is a TFE copolymer comprising recurring units derived from at least one per(halo)fluoromonomer (PFM) selected from the group consisting of:
1. per(halo)fluoroalkylvinyiethers complying with general formula CF2═CFORf1 wherein Rf1 is a C1-C6 per(halo)fluoroalkyl;
2. per(halo)fluoro-oxyalkylvinylethers complying with general formula CF2—CFOX01, wherein X01 is a C1-C12 per(halo)fluorooxyalkyl having one or more ether groups;
3. C3-C8 perfluoroolefins; and
4. mixtures thereof.

### Claim 8 (depends on 7)

The foamable thermoplastic fluoropolymer composition according to claim 7, wherein said polymer (A) is selected from the group consisting of TFE copolymers consisting essentially of recurring units derived from tetrafluoroethylene (TFE) and hexafluoropropylene (HFP) in an amount ranging from 3 to 15 wt % and, optionally, from 0.5 to 3 wt % of at least one perfluoroalkylvinylether complying with general formula CF2═CFORf1 wherein Rf1 is a C1-C6 perlluoroalkyl.

### Claim 9 (depends on 7)

The foamable thermoplastic fluoropolymer composition according to claim 7, wherein said polymer (A) is a TFE copolymer consisting essentially of:
(a) from 3 to 13% by weight of recurring units derived from perfluoromethylvinylether;
(b) from 0 to 6% by weight of recurring units derived from one or more than one fluorinated comonomer different from perfluoromethylvinylether and selected from the group consisting of perfluoroalkylvinylethers complying with general formula CF2—CFORf1, wherein Rf1, is a C1-C6 perfluoroalkyl and perfluoro-oxyakylvinylethers complying with general formula CF2═CVOX01′, wherein X01′is a C1-C12 perfluorooxyalkyl having one or more ether groups; and
(c) recurring units derived from tetrafluoroethylene, in such an amount that the sum of the percentages of the recurring units (a), (b) and (c) is equal to 100% by weight.

### Claim 10 (depends on 7)

The foamable thermoplastic fluoropolymer composition according to claim 7, wherein said polymer (A) is a TFE copolymer consisting of:
(a) from 0.5 to 5% by weight of recurring units derived from perfluorornethylvinylether;
(b) from 0.4 to 4.5% by weight of recurring units derived from one or more than one fluorinated comonomer different from perfluoromethylvinylether and selected from the group consisting of perfluoroalkylvinylethers complying with general formula CF2—CFORf1, wherein Rf1, is a C1-C6 perfluoroalkyl and perfluoro-oxyalkylvinylethers complying with general formula CF2═CFOX01′, wherein X01′is a C1-C12 perfluorooxyalkyl having one or more ether groups;
(c) from 0.5 to 6% weight of recurring units derived from at least one C3-C8 perfluoroolcfins; and
(d) recurring units derived from tetrafluoroethylene, in such an amount that the sum of the percentages of the recurring units (a), (b), (c) and (d) is equal to 100% by weight.

### Claim 11 (depends on 1)

The foamable thermoplastic fluoropolymer composition according to claim 1, further containing at least one additional nucleating agent ingredient different from the perfluoroalkoxysulphonic derivative.

### Claim 12 (depends on 11)

The foamable thermoplastic fluoropolymer composition according to claim 11, said composition further comprising titanium dioxide, and optionally at least one inorganic salt selected from the group consisting of lithium carbonate, calcium carbonate, calcium telraborate, strontium carbonate, sodium carbonate, sodium tetraborate (Na2B4O7), sodium sulfite, potassium tetraborate potassium pyrosulfate, potassium sulfate, barium nitrate, aluminum phosphate, sodium fluorosilicate and combinations thereof.

### Claim 13 (depends on 1)

A process for the manufacture of the foamable composition according to claim 1, said process comprising the step of blending the polymer (A) and the perfluoroalkoxysulphonie derivative.

### Claim 14 (depends on 1)

A process for making a foamed fluoropolymer by foaming the foamable composition according to claim 1.

### Claim 15

A foamable thermoplastic fluoropolymer composition consisting essentially of:
at least one melt-processible fluoropolymer [polymer (A)]; and
at least one perfluoroalkoxysulphonic derivative selected from the following compounds:
CF3—(CF2)w—OCF2CF2—SO3−(Zp+)1/p (i)
wherein w is an integer from 1 to 3, Z is NH4 or an alkaline or alkali-earth metal cation, and
p is the valence of the cation Z;
CF3—(CF2)w′OCF2CF2—OCF2CF2—SO3−(Zp+)1/p (ii)
wherein w′ is an integer from 0 to 2, Z is NH4 or an alkaline or alkali-earth metal cation, and
p is the valence of the cation Z; and
CF3—(CF2)q—(OCF2CFXF)r—OCF2CF2—SO3−(Zp+)1/p (iii)
wherein q and r are each independently an integer from 1 to 3, XF is F or CF3, Z is NH4 or an alkaline or alkali-earth metal cation, and p is the valence of the cation Z; and
optionally, at least one additional nucleating agent selected from titanium dioxide, lithium carbonate, calcium carbonate, calcium tetraborate, strontium carbonate, sodium carbonate, sodium tetraborate, sodium sulfite, potassium tetraborate potassium pyrosulfate, potassium sulfate, barium nitrate, aluminum phosphate, sodium fluorosilicate and combinations thereof.