Functionalised fluorinated copolymers

Patent metadata

Field	Value
Publication number	US-10730979-B2
Application number	US-201615769275-A
Country	US
Kind code	B2
Filing date	Oct 18, 2016
Priority date	Oct 29, 2015
Publication date	Aug 4, 2020
Grant date	Aug 4, 2020

Abstract

The invention relates to a fluorinated copolymers which are particularly based on vinylidene fluoride (VDF) or trifluoroethylene (TrFE) and particularly functionalized by functional and/or functionizable vinyl ethers. The invention also relates to methods for producing said copolymers, and to the applications thereof.

First claim

The invention claimed is:

1. A fluorinated copolymer of formula (I) below:
poly[A-co-X-co-(X-E-X)]  (I)

in which A is a fluorinated monomer, X is chlorotrifluoroethylene (CTFE); X is capable of copolymerizing with, said monomer A and, also with a monomer E in an alternating manner, E is vinyl ether of formula CH 2 ═CH—O—R in which R is selected from the group consisting of: alkyls; glycerol, saccharide; halogenated groups; thiols, silanes, sulfonic acid, phosphonic acids, azides, alkynes, carbonates, amines, ammoniums, amidine, aldehyde, isocyanate, urea, sulfonates, phosphonates, silicones, and fluorinated or hydrocarbon-based polymers and oligomers;
wherein A is selected from the group consisting of vinylidene fluoride (VDF), trifluoroethylene (TrFE) or mixtures thereof and wherein the proportion of moieties derived from the monomer A is greater than 85 mole %.

2. The copolymer as claimed in claim 1 , wherein the monomer E is an vinyl ether of formula CH 2 ═CH—O—R in which R is selected from the group consisting of: ethyl, butyl, iso-butyl, 2-ethylhexyl, tert-butyl, 2-chloroethyl, chloro-(2,2-dimethylpropyl) and triethoxysilane.

3. The copolymer as claimed in claim 1 , wherein the monomer E is an vinyl ether of formula CH 2 ═CH—O—R in which R is chosen from the group consisting of: saccharide thiols, silanes, phosphonic acids, sulphonic acids, azides, alkynes, carbonates, amines, ammoniums, amidine, aldehyde, isocyanate, urea, sulfonates, phosphonates, silicones, and fluorinated or hydrocarbon-based polymers and oligomers.

4. The copolymer as claimed in claim 1 , comprising:
a proportion of moieties derived from monomer E of less than 5%, and greater than or equal to 0.1%;
an X:E molar ratio of greater than or equal to 2.

5. A process for producing the copolymer of formula (I) as claimed in claim 1 , comprising a step of radical copolymerization of a reaction mixture comprising the fluorinated monomer A, the monomer E and the monomer X; the X:E molar ratio being greater than or equal to 2; the molar ratio of the monomer A being greater than 0.85; wherein the monomer A is selected from the group consisting of VDF, TrFE or a mixture thereof, the monomer X is CTFE and the monomer E is an alkyl vinyl ether (VE) of formula CH 2 ═CH—O—R in which R is selected from the group consisting of: alkyls; glycerol, saccharide; halogenated groups; thiols, silanes, sulfonic acid, phosphonic acid, azides, alkynes, carbonates, amines, ammoniums, amidine, aldehyde, isocyanate, urea, sulfonates, phosphonates, silicones, and fluorinated or hydrocarbon-based polymers and oligomers.

6. The process as claimed in claim 5 , for producing a copolymer of formula (I), wherein the monomer E is a vinyl ether (VE) of formula CH 2 ═CH—O—R in which R is selected from the group consisting of: ethyl, butyl, iso-butyl, 2-ethylhexyl, tert-butyl, 2-chloroethyl, chloro-(2,2-dimethylpropyl) and triethoxysilane.

7. The process of claim 5 , wherein:
the molar proportion of VE, in the reaction mixture, is less than 5%, and greater than or equal to 0.1%;
the X:E, chlorotrifluoroethylene:vinyl ether, molar ratio is greater than or equal to 2;

the molar proportions being related to the sum of moles of VDF, of TrFE, of CTFE and of VE.

8. The process as claimed in claim 5 , wherein said copolymer is obtained by radical solution polymerization comprising a step of copolymerization of said reaction mixture in the presence of a radical initiator and of a solvent.

9. The process as claimed in claim 8 , wherein said solvent is selected from the group consisting of 1,1,1,3,3-pentafluorobutane, acetonitrile, methyl ethyl ketone, dimethyl carbonate, 2,2,2-trifluoroethanol, tert-butanol, hexafluoroisopropanol, methyl acetate, ethyl acetate, cyclohexanone and water, and mixtures thereof.

10. The process as claimed in claim 5 wherein said copolymer is obtained by radical suspension polymerization comprising a step of copolymerization of said reaction mixture in the presence of water, of an initiator, optionally of a dispersing agent, and optionally of a chain transfer agent.

11. The process as claimed in claim 5 wherein said copolymer is obtained by radical emulsion polymerization comprising a step of polymerization of said reaction mixture in the presence of water, of a surfactant and of an aqueous dispersion of initiator.

12. The process as claimed in claim 5 comprising an additional step of functionalization of said VE monomer.

13. Coatings comprising at least one copolymer as claimed in claim 1 .

14. Membranes comprising at least one copolymer as claimed in claim 1 .

15. Electroactive devices comprising at least one copolymer as claimed in claim 1 .

16. The copolymer of claim 1 , wherein the copolymer comprises a proportion of moieties derived from the monomer A of greater than 90%.

17. The copolymer of claim 1 , wherein the copolymer comprises less than 10 mole % (X-E-X) moieties.

18. The copolymer of claim 1 , wherein the chlorotrifluoroethylene:vinyl ether molar ratio X:E is equal to 2.

19. The copolymer of claim 1 , having a molar mass from 150 000 to 500 000 g/mol.

Assignees

• Arkema France
• Centre Nat Rech Scient
• Univ Montpellier
• Enscm

Inventors

• Lannuzel Thierry T
• Domingues Dos Santos Fabrice
• Soulestin Thibaut
• Ladmiral Vincent
• Ameduri Bruno

Classifications

• C08F216/1408

  Monomers containing halogen · CPC title

• C08F214/22

  Vinylidene fluoride · CPC title

• C08F8/40

  Introducing phosphorus atoms or phosphorus-containing groups · CPC title

• C08F8/22

  by reaction with free halogens · CPC title

• C08F214/227 Primary

  with non-fluorinated vinyl ethers · CPC title