Vinylidene fluoride and trifluoroethylene polymers

Patent metadata

Field	Value
Publication number	US-9751967-B2
Application number	US-201113996018-A
Country	US
Kind code	B2
Filing date	Dec 13, 2011
Priority date	Dec 22, 2010
Publication date	Sep 5, 2017
Grant date	Sep 5, 2017

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:
R 1 , R 2 and R 3 , equal to or different from each other, are independently selected from a hydrogen atom and a C 1 -C 3 hydrocarbon group, and R OH represents a hydrogen atom or a C 1 -C 5 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.

First claim

The invention claimed is:

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:
R 1 , R 2 and R 3 , equal to or different from each other, are independently selected from a hydrogen atom and a C 1 -C 3 hydrocarbon group, and
R OH represents a hydrogen atom or a C 1 -C 5 hydrocarbon moiety comprising at least one hydroxyl group, said fluoropolymer comprising end groups of formula —CF 2 H and/or —CF 2 CH 3 .

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

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

4. The fluoropolymer of claim 1 , comprising end groups of formula —CF 2 H and/or —CF 2 CH 3 in a combined amount of at least 30 mmoles per kg of VDF recurring units.

5. 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).

6. 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).

7. 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).

8. 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).

9. 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.

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

11. 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 .

12. 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.

13. 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.

Assignees

• Marrani Alessio
• Brinati Giulio
• Solvay Specialty Polymers It

Inventors

• Marrani Alessio
• Brinati Giulio

Classifications

• C08F214/225 Primary

  with non-fluorinated comonomers · CPC title

• C08F214/22 Primary

  Vinylidene fluoride · CPC title

• C08F220/10

  Esters · CPC title

• C08L27/16

  Homopolymers or copolymers or vinylidene fluoride · CPC title

• C08L33/04

  Homopolymers or copolymers of esters {(C08L43/04 takes precedence)} · CPC title