Crosslinkable fluoropolymers

Patent metadata

Field	Value
Publication number	US-10696768-B2
Application number	US-201515121266-A
Country	US
Kind code	B2
Filing date	Feb 25, 2015
Priority date	Feb 28, 2014
Publication date	Jun 30, 2020
Grant date	Jun 30, 2020

Abstract

The present invention pertains to a process for the manufacture of a crosslinkable fluoropolymer, to said crosslinkable fluoropolymer and the crosslinked fluoropolymer obtainable therefrom, to a film comprising said crosslinkable fluoropolymer or said crosslinked fluoropolymer and to uses of said crosslinked fluoropolymer film in various applications.

First claim

The invention claimed is:

1. A crosslinkable fluoropolymer [polymer (FC)] comprising:
first recurring units derived from vinylidene fluoride (VDF), and
from 0.01% to 10% by moles, with respect to the total moles of recurring units of said polymer (FC), of second recurring units derived from at least one functional hydrogenated monomer (H′ F ), said second recurring units comprising a pendant side chain comprising an end group (E) of any of formulae (III-A) to (V-A):
—O—C(O)—C(R 3 )═CR 1 R 2   (III-A)

—O—C(O)—NH—C(O)—C(R 3 )═CR 1 R 2   (IV-A)

—O—C(O)—Z—C(R 3 )═CR 1 R 2   (V-A)

wherein each of R 1 , R 2 and R 3, equal to or different from each other, is independently a hydrogen atom or a C 1 -C 3 hydrocarbon group, and Z is a bonding group of any of formulae (j) and (jj):
—NH—X—O—C(O)—  (j), and

—NH—X—NHC(O)O—X′—O—C(O)—  (jj)

wherein X and X′, equal to or different from each other, are independently hydrocarbon groups selected from the group consisting of C 1 -C 20 aliphatic groups, C 5 -C 40 cycloaliphatic groups and C 6 -C 50 aromatic, alkylaromatic and heteroaromatic groups.

2. The crosslinkable fluoropolymer [polymer (FC)] according to claim 1 , wherein the pendent side chain of at least one monomer (H′ F ) is a pendant side chain of any of formulae (VI) to (X):
—C(O)—O—Y—E  (VI)

—C(O)—NH—Y—E  (VII)

—[C(O)] n —O—R—O—Y—E  (VIII)

—[C(O)] n —O—R—O—C(O)—NH—Y—E  (IX)

—[C(O)] n —O—R—O—C(O)—O—Y—E  (X)

wherein Y is a C 1 -C 10 hydrocarbon bonding group, optionally comprising at least one functional group, R is a C 1 -C 5 hydrocarbon group, optionally comprising at least one hydroxyl group, n is 0 or 1, and E is an end group of any of formulae (III-A) to (V-A).

3. A process for the manufacture of the crosslinkable fluoropolymer [polymer (FC)] according to claim 1 , said process comprising reacting:
(A) at least one fluoropolymer [polymer (F)] comprising:
first recurring units derived from vinylidene fluoride (VDF), and
from 0.01% to 10% by moles, with respect to the total moles of recurring units of said polymer (F), of second recurring units derived from at least one functional hydrogenated monomer (H F ), said second recurring units comprising a pendant side chain comprising an end group of any of formulae (I) and (II):
—C(O)—O—R x   (I)

—O—R x   (II)

wherein R x is a hydrogen atom or a C 1 -C 5 hydrocarbon group comprising at least one hydroxyl group, and
(B) at least one (meth)acrylic compound (MA) of any of formulae (III) to (V):
R 1 R 2 C═C(R 3 )—C(O)—O—T  (III)

R 1 R 2 C═C(R 3 )—C(O)—NH—C(O)—O—T  (IV)

R 1 R 2 C═C(R 3 )—Z—C(O)—O—T  (V)

wherein each of R 1, R 2 and R 3, equal to or different from each other, is independently a hydrogen atom or a C 1 -C 3 hydrocarbon group, T is a C 1 -C 10 hydrocarbon end group comprising at least one functional group, and Z is a bonding group of any of formulae (j) and (jj):
—NH—X—O—C(O)—  (j), and

—NH—X—NHC(O)O—X′—O—C(O)—  (jj)

wherein X and X′, equal to or different from each other, are independently hydrocarbon groups selected from the group consisting of C 1 -C 20 aliphatic groups, C 5 -C 40 cycloaliphatic groups and C 6 -C 50 aromatic, alkylaromatic and heteroaromatic groups.

4. The process according to claim 3 , wherein monomer (H F ) is selected from the group consisting of (meth)acrylic monomers of formula (I-A) and vinyl ether monomers of formula (II-A):

wherein each of R 4, R 5 and R 6, equal to or different from each other, is independently a hydrogen atom or a C 1 -C 3 hydrocarbon group, R X is a hydrogen atom or a C 1 -C 5 hydrocarbon group comprising at least one hydroxyl group, and R′ x is a C 1 -C 5 hydrocarbon group comprising at least one hydroxyl group.

5. The process according to claim 3 , wherein T is a C 1 -C 10 hydrocarbon end group comprising at least one functional group selected from the group consisting of hydroxyl groups, cyclic alkyl ether groups, isocyanate groups, carboxylic acid groups, amine groups, aryl ether groups and alkoxy silane groups.

6. The process according to claim 3 , said process being carried out in a liquid medium comprising at least one organic solvent (S).

7. The process according to claim 3 , wherein monomer (H F ) comprises an end group of formula (I), wherein R x is a hydrogen atom, and compound (MA) has any of formulae (III) to (V), wherein T is a C 1 -C 10 hydrocarbon end group comprising at least one functional group selected from the group consisting of hydroxyl groups, cyclic alkyl ether groups, and amine groups.

8. The process according to claim 7 , wherein compound (MA) has any of formulae (III) to (V), wherein T is a C 1 -C 10 hydrocarbon end group comprising at least one hydroxyl group, said process being carried out in the presence of at least one activating agent selected from the group consisting of N,N′-dicyclohexylcarbodiimide, thionyl chloride, oxalyl dichloride and inorganic acids.

9. The process according to claim 3 , wherein monomer (H F ) comprises an end group of any of formulae (I) and (II), wherein R x is a C 1 -C 5 hydrocarbon group comprising at least one hydroxyl group, and compound (MA) has any of formulae (III) to (V), wherein T is a C 1 -C 10 hydrocarbon end group comprising at least one functional group selected from the group consisting of hydroxyl groups, cyclic alkyl ether groups, isocyanate groups and carboxylic acid groups.

10. The process according to claim 9 , wherein compound (MA) has any of formulae (III) to (V), wherein T is a C 1 -C 10 hydrocarbon end group comprising at least one isocyanate group, said process being carried out in the presence of at least one activating agent selected from the group consisting of organic tin compounds.

11. A crosslinkable composition (CC) comprising:
at least one crosslinkable fluoropolymer [polymer (FC)] according to claim 1 , and
at least one additive selected from the group consisting of crosslinking co-agents and crosslinking initiators.

12. A crosslinkable fluoropolymer film [film (FC)] comprising at least one crosslinkable fluoropolymer [polymer (FC)] according to claim 1 .

13. The crosslinkable fluoropolymer film [film (FC)] according to claim 12 , said film (FC) being free from any organic solvent (S).

14. The crosslinkable fluoropolymer film [film (FC)] according to claim 12 , said film (FC) further comprising at least one organic solvent (S).

15. The film (FC) according to claim 14 , wherein the solvent (S) is selected from the group consisting of diesters of formula (DE-I) and ester-amides of formula (EA-I):
R A —OOC—Z de —COO—R B   (DE-I)

R A —OOC—Z ea —CO—NR C R D   (EA-I)

wherein:
R A and R B , equal to or different from each other, are independently selected from the group consisting of C 1 -C 20 hydrocarbon groups,
R C and R D , equal to or different from each other, are independently selected from the group consisting of hydrogen, C 1 -C 36 hydrocarbon groups, optionally substituted, wherein R C and R D are optionally part of a cyclic moiety including the nitrogen atom to which they are bound, said cyclic moiety being optionally substituted and/or optionally comprising one or more than one additional heteroatom, and mixtures thereof, and
Z de and Z ea , equal to or different from each other, are independently a linear or branched C 3 -C 10 divalent alkylene group.

16. The crosslinkable fluoropolymer film [film (FC)] ac

Assignees

• Solvay Specialty Polymers It
• Solvay Speciality Polymers Italy S P A

Inventors

• Apostolo Marco
• Triulzi Francesco Maria
• Cojocaru Paula
• Wlassics Ivan
• Marchionni Giuseppe
• Tonelli Claudio Adolfo Pietro

Classifications

• H10F19/804

  Materials of encapsulations · CPC title

• C08F214/186

  with non-fluorinated comonomers · CPC title

• C08F214/22

  Vinylidene fluoride · CPC title

• C08F214/18

  Monomers containing fluorine · CPC title

• Y02E10/50

  Photovoltaic [PV] energy · CPC title