Curable composition

Patent metadata

Field	Value
Publication number	US-9458307-B2
Application number	US-201013517239-A
Country	US
Kind code	B2
Filing date	Dec 16, 2010
Priority date	Dec 23, 2009
Publication date	Oct 4, 2016
Grant date	Oct 4, 2016

Abstract

The invention relates to the use of 1,5-enediyne compounds of formula (I) as curing agents in polymeric systems. In particular the invention relates to a curable composition comprising a curing agent of formula (I) and a polymer suitable to be cross-linked and to the cured article obtained therefrom.

First claim

The invention claimed is:

1. A curable composition comprising:
(a) at least one fluorinated polymer (P) comprising cure sites in the backbone, either in the polymer chain or in one or more end groups; and
(b) at least one curing agent of formula (II):

wherein each R, equal to or different from each other, is independently selected from the group consisting of hydrogen; halogen; C 1 -C 20 alkyl, linear or branched, optionally substituted and/or optionally fluorinated; C 1 -C 20 oxyalkyl, linear or branched, optionally substituted and/or optionally fluorinated; (per)fluoropolyether chain; aromatic or heteroaromatic radical, monocyclic or polycyclic, optionally substituted and/or optionally fluorinated; —SiR 1 3 , —(R 1 2 SiO) b R 1 , —PR 1 2 wherein each R 1 , equal to or different from each other, is independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, linear or branched, optionally substituted and/or optionally fluorinated and wherein b is an integer of at least 1; wherein X is a divalent bridging group selected from the group consisting of a carbon-carbon bond; a C 1 -C 20 alkylene radical, optionally substituted and/or optionally fluorinated; a divalent (per)fluoropolyether radical; an organopolysiloxane radical —(R 1 2 SiO) b —; a —O— radical; a —S— radical; a —SO 2 — radical; a —C(O)— radical; a fused aromatic or heteroaromatic structure optionally substituted and/or optionally fluorinated; and
wherein the curable composition is a dry curable composition.

2. The composition according to claim 1 wherein X is selected from the group consisting of a carbon-carbon bond; a fluorinated C 1 -C 20 alkylene radical, optionally substituted; a divalent (per)fluoropolyether radical; an organopolysiloxane radical —(R 1 2 SiO) b — wherein R 1 and b are as defined in claim 1 .

3. The composition according to claim 1 wherein each R, equal to or different from each other, is independently selected from the group consisting of hydrogen; halogen; C 1 -C 8 alkyl, linear or branched, optionally substituted and/or optionally fluorinated; C 1 -C 3 oxyalkyl, linear or branched, optionally substituted and/or optionally fluorinated; (per)fluoropolyether chain; —(R 1 2 SiO) b R 1 wherein b and R 1 are as defined in claim 1 ; aromatic or heteroaromatic radical, monocyclic or polycyclic, optionally substituted and/or optionally fluorinated.

4. A process for the manufacture of the curable composition of claim 1 comprising mixing said at least one polymer (P) with said at least one curing agent of formula (II); and removing solvent, if present.

5. A process for curing a curable composition comprising heating a composition of claim 1 .

6. A process of making a cured article comprising: shaping the curable composition of claim 1 to form a shaped composition; curing the shaped composition to form an article; and optionally post curing the article.

7. A cured article obtainable form the composition of claim 1 , wherein the cured article comprises cross-links derived from dimerization of ethynyl moieties in the curing agent.

8. The composition according to claim 1 , wherein X is selected from an optionally substituted C 1 -C 20 fluorinated alkylene radical or a divalent (per)fluoropolyether radical.

9. The composition according to claim 1 , wherein polymer (P) is a fluoropolymer comprising recurring units derived from at least one fluorinated monomer selected from:
C 2 -C 8 fluoro- and/or perfluoroolefins;
C 2 -C 8 hydrogenated fluoroolefins;
(per)fluoroalkylethylenes of formula CH 2 ═CH—R f0 wherein R f0 is a C 1 -C 6 (per)fluoroalkyl or a C 1 -C 6 (per)fluorooxyalkyl having one or more ether groups;
chloro-C 2 -C 6 fluoroolefins; bromo-C 2 -C 6 fluoroolefins; iodo-C 2 -C 6 fluoroolefins;
fluoroalkylvinylethers of formula CF 2 ═CFOR f1 wherein R f1 is a C 1 -C 6 fluoro- or perfluoroalkyl;
hydrofluoroalkylvinylethers of formula CH 2 ═CFOR f1 wherein R f1 is a C 1 -C 6 fluoro- or perfluoroalkyl;
fluoro-oxyalkylvinylethers of formula CF 2 ═CFOX i , wherein X 1 is a C 1 -C 12 oxyalkyl or C 1 -C 12 (per)fluorooxyalkyl having one or more ether groups;
fluoroalkyl-methoxy-vinylethers of formula CF 2 ═CFOCF 2 OR f2 wherein R f2 is a C 1 -C 6 fluoro- or perfluoroalkyl, or a C 1 -C 6 (per)fluorooxyalkyl having one or more ether groups;
functional fluoro-alkylvinylethers of formula CF 2 ═CFOY 0 wherein Y 0 is a C 1 -C 12 alkyl or (per)fluoroalkyl, a C 1 -C 12 oxyalkyl, or a C 1 -C 12 (per)fluorooxyalkyl, and wherein Y 0 comprises one or more ether groups and a carboxylic or sulfonic acid group, in its acid, acid halide or salt form;
fluorodioxoles of formula:

wherein each of R f3 , R f4 , R f5 , R f6 , equal or different each other, is independently a fluorine atom, a C 1 -C 6 fluoro- or per(halo)fluoroalkyl, optionally comprising one or more oxygen atom.

10. The composition according to claim 1 , wherein polymer (P) is a fluoroelastomer.

11. The composition according to claim 1 , wherein polymer (P) is a semi-crystalline fluoropolymer.

12. The composition according to claim 9 , wherein polymer (P) is a fluoropolymer comprising recurring units derived from at least one fluorinated monomer selected from:
tetrafluoroethylene; hexafluoropropylene; pentafluoropropylene;
hexafluoroisobutylene; vinyl fluoride; 1,2-difluoroethylene; vinylidene fluoride;
trifluoroethylene; chlorotrifluoroethylene; fluoroalkylvinylethers of formula CF 2 ═CFOR f1 in which R f1 is selected from —CF 3 , —C 2 F 5 , and —C 3 F 7 ; hydrofluoroalkylvinylethers of formula CH 2 ═CFOR f1 in which R f1 is selected from —CF 3 , —C 2 F 5 , and —C 3 F 7 ; fluoro-oxyalkylvinylether of formula CF 2 ═CFOX 1 in which X i is perfluoro-2-propoxy-propyl;
fluoroalkyl-methoxy-vinylethers of formula CF 2 ═CFOCF 2 OR f2 in which R f2 is selected from —CF 3 , —C 2 F 5 , —C 3 F 7 and —C 2 F 5 —O—CF 3 ; fluorodioxoles of formula:

wherein each of R f3 , R f4 , R f5 , R f6 , equal or different each other, is independently selected from a fluorine atom, —CF 3 , —C 2 F 5 , —C 3 F 7 , —OCF 3 , and —OCF 2 CF 2 OCF 3 .

13. The composition according to claim 1 , wherein polymer (P) does not contain any 1,5-enediyne moiety.

14. A curable composition comprising:
(a) at least one fluorinated polymer (P), wherein polymer (P) is a fluoroelastomer; and
(b) at least one curing agent of formula (II):

wherein each R, equal to or different from each other, is independently selected from the group consisting of hydrogen; halogen; C 1 -C 20 alkyl, linear or branched, optionally substituted and/or optionally fluorinated; C 1 -C 20 oxyalkyl, linear or branched, optionally substituted and/or optionally fluorinated; (per)fluoropolyether chain; aromatic or heteroaromatic radical, monocyclic or polycyclic, optionally substituted and/or optionally fluorinated; —SiR 1 3 , —(R 1 2 SiO) b R 1 , —PR 1 2 wherein each R 1 , equal to or different from each other, is independently selected from the group consisting of hydrogen, C 1 -C 20 alkyl, linear or branched, optionally substituted and/or optionally fluorinated and wherein b is an integer of at least 1; wherein X is a divalent bridging group selected

Assignees

• Giannetti Enzo
• Sanguineti Aldo
• Wlassics Ivan
• Marchionni Giuseppe
• Solvay Specialty Polymers It

Inventors

• Giannetti Enzo
• Sanguineti Aldo
• Wlassics Ivan
• Marchionni Giuseppe

Classifications

• C08K5/0025

  Crosslinking or vulcanising agents; including accelerators · CPC title

• C08K5/5475

  containing at least one C≡N bond · CPC title

• C08K5/01 Primary

  Hydrocarbons {(C08K5/0091 takes precedence)} · CPC title

• C08K5/02

  Halogenated hydrocarbons {(C08K5/0091 takes precedence)} · CPC title