Crosslinkable compositions based on vinylidene fluoride-trifluoroethylene polymers

Patent metadata

Field	Value
Publication number	US-10081691-B2
Application number	US-201214365482-A
Country	US
Kind code	B2
Filing date	Dec 6, 2012
Priority date	Dec 16, 2011
Publication date	Sep 25, 2018
Grant date	Sep 25, 2018

Abstract

The present invention relates to crosslinkable compositions comprising vinylidene fluoride (VDF)/trifluoroethylene (TrFE) polymers and a fluorine-containing crosslinking agent of formula (A) [agent (Cz)]: {N 3 [S(O) g1 ] s1 } na —(R H ) nh —R f —(R′ H ) nh′ —{[S(O) g2 ] s2 N 3 } na′ , formula (A) wherein each of g1 and g2, equal to or different from each other, is 1 or 2, each of s1 and s2, equal to or different from each other, is 0 or 1, each of na and na′ is independently zero or an integer of 1 to 3, provided that the sum na+na′ is at least 2, each of R H and R′ H , equal to or different from each other, is a C 1 -C 12 hydrocarbon group free of fluorine atoms, nh and nh′, equal or different from each other are independently 0 or 1, and R f is selected from the group consisting of i) a C 3 -C 20 fluorocarbon group, possibly comprising one or more ethereal oxygen atoms, ii) an oligomer comprising copolymerized units of vinylidene fluoride and trifluoroethylene, to a process for the manufacture of said compositions, to a method for curing the same, and to the use of said copolymers in electrical and electronic devices.

First claim

The invention claimed is:

1. A crosslinkable composition comprising:
at least one semi-crystalline fluoropolymer (F) possessing a detectable melting point when submitted to DSC measurements according to ASTM D3418 and comprising recurring units derived from vinylidene fluoride (VDF) and from 10% to 50% by moles with respect to the total moles of recurring units of fluoropolymer (F) of recurring units derived from trifluoroethylene (TrFE); and
at least one crosslinking agent (Cz) of formula (A):
{N 3 [S(O) g1 ] s1 } na —(R H ) nh —R f —(R′ H ) nh′ —{[S(O) g2 ] S2 N 3 } na′   (A)

wherein each of g1 and g2, equal to or different from each other, is 1 or 2, each of s1 and s2, equal to or different from each other, is 0 or 1, each of na and na′ is independently zero or an integer of 1 to 3, provided that the sum na+na′ is at least 2, each of R H and R′ H , equal to or different from each other, is a C 1 -C 12 hydrocarbon group free of fluorine atoms, nh and nh′, equal or different from each other are independently 0 or 1, and R f is selected from the group consisting of i) a C 3 -C 20 fluorocarbon group, optionally comprising one or more ethereal oxygen atoms, and ii) an oligomer comprising copolymerized units of vinylidene fluoride and trifluoroethylene.

2. The crosslinkable composition of claim 1 , wherein crosslinking agent (Cz) is an agent of formula (B):
N 3 —(CH 2 ) m —R B f —(CH 2 ) m′ —N 3   (B)

wherein each of m and m′ is independently an integer of 1 to 6, and R B f is a C 3 -C 10 fluorocarbon group, optionally comprising one or more ethereal oxygen atoms.

3. The crosslinkable composition of claim 2 , wherein crosslinking agent (Cz) is an agent of formula (C):
N 3 —(CH 2 ) m —(CF 2 ) nc —(CH 2 ) m′ N 3   (C)

wherein each of m and m′ is independently an integer of 1 to 6, and nc is an integer of 4 to 10.

4. The crosslinkable composition of claim 1 , wherein crosslinking agent (Cz) is an agent of formula (D):
N 3 [S(O) g1 ]—R D f —[S(O) g2 ]—N 3   (D)

wherein each of g1 and g2, equal to or different from each other, is 1 or 2, and R D f is a C 3 -C 20 fluoroalkyl group, optionally comprising one or more ethereal oxygen atoms.

5. The crosslinkable composition of claim 4 , wherein crosslinking agent (Cz) is an agent of formula (E):
N 3 —SO 2 —R E f —SO 2 —N 3   (E)

wherein R E f is a C 3 -C 20 fluoroalkyl group, optionally comprising one or more ethereal oxygen atoms.

6. The crosslinkable composition of claim 1 , wherein fluoropolymer (F) comprises from 0.01% to 15% by moles with respect to the total moles of recurring units of fluoropolymer (F) of at least one cure-site monomer (CS), wherein monomer (CS) is an ethylenically unsaturated monomer comprising at least one reactive group selected from the group consisting of:
an azide group;
a nitrile group; and
an alkyne group.

7. The crosslinkable composition of claim 6 , wherein fluoropolymer (F) comprises from 0.01% to 15% by moles with respect to the total moles of recurring units of fluoropolymer (F) of at least one monomer (Az) comprising an azide group, wherein monomer (Az) is a monomer of formula (I):
CX 1 X 2 ═CX—(O) p —R f —(CH 2 ) n —[S(O) q ] s N 3   (I)

wherein: X, X 1 and X 2 , equal to or different from each other, are independently H or F, p is 0 or 1, n is 0 to 4, s is 0 or 1, q is 1 or 2, R f is a divalent (hydro)fluorocarbon group, optionally interrupted by one or more ethereal oxygen atoms.

8. The crosslinkable composition of claim 7 , wherein monomer (Az) is a monomer of formula (II):
CX 1 X 2 ═CX—O—R f —(CH 2 ) n —[S(O) q ] s N 3   (II)

wherein: X, X 1 and X 2 , equal to or different from each other, are independently H or F, n is 0 to 4, s is 0 or 1, q is 1 or 2, R f is a divalent (hydro)fluorocarbon group, optionally interrupted by one or more ethereal oxygen atoms.

9. The crosslinkable composition of claim 7 , wherein monomer (Az) is a monomer of formula (IV):
CX″ 1 X″ 2 ═CX″—R″ f —(CH 2 ) n″ —[S(O) q″ ] s″ N 3   (IV)

wherein: X″, X″ 1 and X″ 2 , equal to or different from each other, are independently H or F, n″ is 0 to 4, s″ is 0 or 1, q″ is 1 or 2, R″ f is a divalent (hydro)fluorocarbon group, optionally interrupted by one or more ethereal oxygen atoms,
wherein the sp 2 hybridized carbon atom of the terminal double bond ═CX″— is bound to a sp 3 carbon atom of the R″ f group.

10. A process for the manufacture of the crosslinkable composition of claim 1 , comprising mixing:
at least one semi-crystalline fluoropolymer (F) comprising recurring units derived from vinylidene fluoride (VDF) and from 10% to 50% by moles with respect to the total moles of recurring units of fluoropolymer (F) of recurring units derived from trifluoroethylene (TrFE); and
at least one crosslinking agent (Cz) of formula (A):
{N 3 [S(O) g1 ] s1 } na —(R H ) nh —R f —(R′ H ) nh′ —{[S(O) g2 ] S2 N 3 } na′   (A)

wherein each of g1 and g2, equal to or different from each other, is 1 or 2, each of s1 and s2, equal to or different from each other, is 0 or 1, each of na and na′ is independently zero or an integer of 1 to 3, provided that the sum na+na′ is at least 2, each of R H and R′ H , equal to or different from each other, is a C 1 -C 12 hydrocarbon group free of fluorine atoms, nh and nh′, equal or different from each other are independently 0 or 1, and R f is selected from the group consisting of i) a C 3 -C 20 fluorocarbon group, optionally comprising one or more ethereal oxygen atoms, and ii) an oligomer comprising copolymerized units of vinylidene fluoride and trifluoroethylene.

11. A method of forming a cured shaped part, the method comprising crosslinking the crosslinkable composition of claim 1 , such that a cured shaped part is formed.

12. A method for manufacturing an electrical or electronic device, the method comprising processing the crosslinkable composition of claim 1 , and crosslinking the processed crosslinkable composition.

13. The process of claim 10 , wherein crosslinking agent (Cz) is an agent of formula (B):
N 3 —(CH 2 ) m —R B f —(CH 2 ) m′ —N 3   (B)

wherein each of m and m′ is independently an integer of 1 to 6, and R B f is a C 3 -C 10 fluorocarbon group, optionally comprising one or more ethereal oxygen atoms.

14. The process of claim 13 , wherein crosslinking agent (Cz) is an agent of formula (C):
N 3 —(CH 2 ) m —(CF 2 ) nc —(CH 2 ) m′ N 3   (C)

wherein each of m and m′ is independently an integer of 1 to 6, and nc is an integer of 4 to 10.

15. The process of claim 10 , wherein crosslinking agent (Cz) is an agent of formula (D):
N 3 [S(O) g1 ]—R D f —[S(O) g2 ]—N 3   (D)

wherein each of g1 and g2, equal to or different from each other, is 1 or 2, and R D f is a C 3 -C 20 fluoroalkyl group, optionally comprising one or more ethereal oxygen atoms.

16. The process of claim 15 , wherein crosslinking agent (Cz) is an agent of formula (E):
N 3 —SO 2 —R E f —SO 2 —N 3   (E)

wherein R E f is a C 3 -C 20 fluoroalkyl group, optionally comprising one or more ethereal oxygen atoms.

17. The process of claim 10 , wherein fluoropolymer (F) comprises from 0.01% to 15% by moles with respect to the total moles of recurring units of fluoropolymer (F) of at least one cure-site monomer (CS), wherein monomer (CS) is an ethylenically unsaturated monomer comprising at least one reactive group selected from the group consisting of:
an azide group;
a nitrile group; and
an alkyne group.

18. The process of claim 17 , wherein fluoropolymer (F) comprise

Assignees

• Solvay Specialty Polymers It

Inventors

• Tortelli Vito
• Marrani Alessio
• Wlassics Ivan
• Falco Ivan

Classifications

• C08J5/18

  Manufacture of films or sheets · CPC title

• C08K5/28 Primary

  Azides · CPC title

• C08J2327/24

  halogenated · CPC title

• C08F214/22 Primary

  Vinylidene fluoride · CPC title

• C08K5/43

  Compounds containing sulfur bound to nitrogen · CPC title