# US 9,751,967 B2 · Vinylidene fluoride and trifluoroethylene polymers

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- Number: US 9,751,967 B2
- Document ID: US9751967B2
- Status: Granted
- Kind: B2
- Application number: 13/996,018
- Filed: 2011-12-13
- Published: 2013-11-07
- Granted: 2017-09-05
- Earliest claimed: 2010-12-22
- Assignees: Solvay Specialty Polymers Italy S.P.A.
- Applicants: Alessio Marrani; Giulio Brinati
- Inventors: Alessio Marrani; Giulio Brinati
- Web page: https://patentgrep.com/patent/US9751967B2

## CPC

- C08F 214/225: {with non-fluorinated comonomers}
- C08F 214/22: Vinylidene fluoride
- H10N 30/857: Macromolecular compositions
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- H10N: ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR

## Abstract

The present invention pertains to a fluoropolymer [polymer (F)] comprising: recurring units derived from vinylidene fluoride (VDF); from 10% to 50% by moles of recurring units derived from trifluoroethylene (TrFE); and from 0.01% to 10% by moles of recurring units derived from at least one (meth)acrylic monomer [monomer (MA)] having formula (I) here below: wherein: R1, R2 and R3, equal to or different from each other, are independently selected from a hydrogen atom and a C1-C3 hydrocarbon group, and ROH represents a hydrogen atom or a C1-C5 hydrocarbon moiety comprising at least one hydroxyl group. The invention also pertains to a process for the manufacture of said polymer (F) and to use of said polymer (F) as ferroelectric, piezoelectric, pyroelectric or dielectric material in electrical and electronic devices.

## Claims

### Claim 1

A fluoropolymer comprising:
recurring units derived from vinylidene fluoride (VDF);
from 10% to 50% by moles of recurring units derived from trifluoroethylene (TrFE); and
from 0.01% to 10% by moles of recurring units derived from at least one (meth)acrylic monomer (MA) having formula (I) here below:
wherein:
R1, R2 and R3, equal to or different from each other, are independently selected from a hydrogen atom and a C1-C3 hydrocarbon group, and
ROH represents a hydrogen atom or a C1-C5 hydrocarbon moiety comprising at least one hydroxyl group, said fluoropolymer comprising end groups of formula —CF2H and/or —CF2CH3.

### Claim 2 (depends on 1)

The fluoropolymer of claim 1, wherein the (meth)acrylic monomer (MA) is acrylic acid (AA) or hydroxyethylacrylate (FLEA).

### Claim 3 (depends on 1)

The fluoropolymer of claim 1, further comprising recurring units derived from one or more other fluorinated comonomers (F).

### Claim 4 (depends on 1)

The fluoropolymer of claim 1, comprising end groups of formula —CF2H and/or —CF2CH3 in a combined amount of at least 30 mmoles per kg of VDF recurring units.

### Claim 5 (depends on 1)

The fluoropolymer of claim 1, consisting of:
from 40% to 85% by moles of recurring units derived from vinylidene fluoride (VDF),
from 10% to 50% by moles of recurring units derived from trifluoroethylene (TrFE), and
from 0.01% to 1% by moles of recurring units derived from at least one (meth)acrylic monomer (MA) having said formula (I).

### Claim 6 (depends on 5)

The fluoropolymer of claim 5, consisting of:
from 45% to 83% by moles of recurring units derived from vinylidene fluoride (VDF),
from 15% to 48% by moles of recurring units derived from trifluoroethylene (TrFE), and
from 0.02% to 0.8% by moles of recurring units derived from said at least one (meth)acrylic monomer (MA) having formula (I).

### Claim 7 (depends on 1)

The fluoropolymer of claim 1, consisting of:
from 40% to 85% by moles of recurring units derived from vinylidene fluoride (VDF),
from 10% to 50% by moles of recurring units derived from trifluoroethylene (TrFE),
from 2% to 20% by moles of recurring units derived from chlorotrifluoroethylene (CITE), and
from 0.01% to 1% by moles of recurring units derived from at least one (meth)acrylic monomer (MA) having said formula (I).

### Claim 8 (depends on 7)

The fluoropolymer of claim 7, consisting of:
from 45% to 80% by moles of recurring units derived from vinylidene fluoride (VDF),
from 15% to 48% by moles of recurring units derived from trifluoroethylene (TrFE),
from 4% to 15% by moles of recurring units derived from chlorotrifluoroethylene (CTFE), and
from 0.02% to 0.8% by moles of recurring units derived from at least one (meth) acrylic monomer (MA) having formula (I).

### Claim 9 (depends on 1)

A process for the manufacture of the fluoropolymer of claim 1, said process comprising polymerizing vinylidene fluoride (VDF), trifluoroethylene (TrFE), at least one (meth)acrylic monomer (MA) having said formula (I) and, optionally, one or more other fluorinated comonomers (F) in the presence of at least one radical initiator in a polymerization medium comprising:
water,
at least one fluorinated surfactant (FS), and
at least one non-functional perfluoropolyether (PFPE) oil.

### Claim 10 (depends on 9)

The process of claim 9, wherein a mixture of one or more organic radical initiators and one or more inorganic radical initiators is used.

### Claim 11 (depends on 1)

An electrical or electronic device comprising ferroelectric, piezoelectric, pyroelectric or dielectric material wherein the ferroelectric, piezoelectric, pyroelectric or dielectric material comprises the fluoropolymer of claim 1.

### Claim 12 (depends on 11)

The electrical or electronic device according to claim 11, wherein the fluoropolymer is in the form of a film or sheet having a thickness of at most 100 μm.

### Claim 13 (depends on 11)

The electrical or electronic device of claim 11, wherein the fluoropolymer is in the form of a film or sheet having a thickness of at most 40 μm.