Vinylidene fluoride copolymers

Patent metadata

Field	Value
Publication number	US-9441054-B2
Application number	US-201113995275-A
Country	US
Kind code	B2
Filing date	Dec 13, 2011
Priority date	Dec 22, 2010
Publication date	Sep 13, 2016
Grant date	Sep 13, 2016

Abstract

The present invention pertains to a fluoropolymer [polymer (F)] comprising:
recurring units derived from vinylidene fluoride (VDF), and from 0.01% to 5% 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,

said polymer (F) comprising end groups having formula —CF 2 H and/or —CF 2 CH 3 in an amount of at least 30 mmoles per Kg of vinylidene fluoride (VDF) recurring units.

The invention also pertains to a process for the manufacture of said polymer (F) and to use of said polymer (F) as binders for the manufacture of electrodes or for the manufacture of membranes.

First claim

The invention claimed is:

1. A fluoropolymer comprising:
recurring units derived from vinylidene fluoride (VDF), and
from 0.01% to 5% by moles of recurring units derived from at least one (meth)acrylic monomer (MA) having formula (I):

wherein:
R 1 , R 2 and R 3 , equal to or different from each other, are independently selected from the group consisting 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,

and wherein said fluoropolymer comprises end groups having formula —CF 2 H and/or —CF 2 CH 3 in an amount of at least 30 mmoles per Kg of vinylidene fluoride (VDF) recurring units.

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

3. The fluoropolymer of claim 1 , comprising at least 0.02% by moles of recurring units derived from said at least one (meth)acrylic monomer (MA) having said formula (I).

4. The fluoropolymer of claim 1 , comprising at most 1% by moles of recurring units derived from said at least one (meth)acrylic monomer (MA) having said formula (I).

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

6. A process for the manufacture of the fluoropolymer of claim 1 , said process comprising polymerizing, at a pressure of from 20 to 70 bar and a temperature of from 60° C. to 135° C., said vinylidene fluoride (VDF), said 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.

7. An aqueous latex comprising the fluoropolymer of claim 1 and at least one fluorinated surfactant (FS).

8. A composition (C) comprising the fluoropolymer of claim 1 and at least one VDF polymer different from said fluoropolymer.

9. A method for forming electrodes comprising the step of using the fluoropolymer of claim 1 or a composition comprising said fluoropolymer and at least one VDF polymer different from said fluoropolymer as binder.

10. An electrode-forming composition comprising the fluoropolymer of claim 1 or a composition comprising said fluoropolymer and at least one VDF polymer different from said fluoropolymer, a powdery electrode material and, optionally, an electroconductivity-imparting additive and/or a viscosity modifying agent.

11. A hydrophilic membrane comprising the fluoropolymer of claim 1 or a composition comprising said fluoropolymer and at least one VDF polymer different from said fluoropolymer.

12. The process of claim 6 , wherein the radical initiator is at least one organic radical initiator selected from the group consisting of di-tert-butyl peroxide (DTBP), diterbutylperoxyisopropylcarbonate, terbutyl(2- ethyl-hexyl)peroxycarbonate and terbutylperoxy-3,5,5-trim ethylhexanoate.

13. The process of claim 6 , wherein the radical initiator is a mixture of one or more organic radical initiators and one or more inorganic radical initiators.

14. The process of claim 6 , wherein the polymerizing is carried out at a pressure of from 25 to 65 bar.

15. The process of claim 6 , wherein the polymerizing is carried out at a temperature of from 90° C. to 130° C.

Assignees

• Stanga Milena
• Kent Bradley Lane
• Marrani Alessio
• Brinati Giulio
• Solvay Specialty Polymers It

Inventors

• Stanga Milena
• Kent Bradley Lane
• Marrani Alessio
• Brinati Giulio

Classifications

• C08F214/22

  Vinylidene fluoride · CPC title

• H01M10/0565

  Polymeric materials, e.g. gel-type or solid-type · CPC title

• C08J5/2237

  containing fluorine · CPC title

• C08L27/16

  Homopolymers or copolymers or vinylidene fluoride · CPC title

• C08F214/225

  with non-fluorinated comonomers · CPC title