Curing agents for fluoroelastomers

Patent metadata

Field	Value
Publication number	US-9908992-B2
Application number	US-201514866902-A
Country	US
Kind code	B2
Filing date	Sep 26, 2015
Priority date	Sep 26, 2015
Publication date	Mar 6, 2018
Grant date	Mar 6, 2018

Abstract

Curing fluoroelastomers with curing agents of formulas (I), (II), (III), and (IV):

wherein each of R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , and R 9 , is selected from the group consisting of H; halogen atom; C1 to C4 alkyl groups in which the alkyl group is linear, branched, or cyclic; OR′; and aromatic groups;
R 5 is H; and R′ is selected from the group consisting of C1 to C4 alkyl groups in which the alkyl group is linear, branched, or cyclic; and phenyl.

First claim

What is claimed is:

1. A compound comprising:
A. one or more fluoroelastomers comprising copolymerized units of:
(1) one or more unsaturated fluorinated olefins;
(2) one or more unsaturated fluorinated olefin co-monomer different from (1) selected from the group consisting of fluorovinyl ethers, unsaturated fluorinated olefins, unsaturated olefins, and mixtures of these; and
(3) one or more cure site monomers selected from the group consisting of nitrile-containing fluorinated olefins and nitrile-containing fluorinated vinyl ethers; and
B. 0.1 to 10 parts of at least one curing agent selected from the group consisting of formulas (I), (II), (III), and (IV):

wherein:
each of R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , and R 9 is selected from the group consisting of H, halogen atom, C1 to C4 alkyl groups in which the alkyl group is linear, branched, or cyclic; OR′; and aromatic groups;
R 5 is H; and
R′ is selected from the group consisting of C1 to C4 alkyl groups in which the alkyl group is linear, branched, or cyclic; and phenyl.

2. The compound of claim 1 , further comprising 0.1 to 5 phr of a curing agent C different from curing agent B.

3. The compound of claim 1 , wherein the unsaturated fluorinated olefin is selected from the group consisting of tetrafluoroethylene, 1,1-difluoroethylene, and mixtures of these.

4. The compound of claim 2 , wherein the unsaturated fluorinated olefin is selected from the group consisting of tetrafluoroethylene, 1,1-difluoroethylene, and mixtures of these.

5. The compound of claim 1 , wherein the fluorovinyl ether is selected from the group consisting of perfluoro(methyl vinyl) ether and perfluoro(propyl vinyl) ether.

6. The compound of claim 2 , wherein the fluorovinyl ether is selected from the group consisting of perfluoro(methyl vinyl) ether and perfluoro(propyl vinyl) ether.

7. The compound of claim 1 , wherein curing agent B is selected from the group consisting of 1,3-diiminoisoindoline and 5,6-Dichloro-1,3-diiminoisoindoline.

8. The compound of claim 2 , wherein curing agent B is selected from the group consisting of 1,3-diiminoisoindoline and 5,6-Dichloro-1,3-diiminoisoindoline.

9. The compound of claim 1 , additionally comprising at least one filler.

10. The compound of claim 2 , additionally comprising at least one filler.

11. The compound of claim 9 , wherein the filler is selected from the group consisting of polymeric reinforcing filler, polymeric micropowders, mineral micropowders, carbon black, stabilizers, plasticizers, lubricants, processing aids, and combinations of these.

12. The compound of claim 10 , wherein the filler is selected from the group consisting of polymeric reinforcing filler, polymeric micropowders, mineral micropowders, carbon black, stabilizers, plasticizers, lubricants, processing aids, and combinations of these.

13. An article, comprising a cured compound that, before curing, comprised:
A. one or more fluoroelastomers comprising copolymerized units of:
(1) one or more unsaturated fluorinated olefins;
(2) one or more unsaturated fluorinated olefin co-monomer different from (1) selected from the group consisting of fluorovinyl ethers, unsaturated fluorinated olefins, unsaturated olefins, and mixtures of these; and
(3) one or more cure site monomers selected from the group consisting of nitrile-containing fluorinated olefins and nitrile-containing fluorinated vinyl ethers; and
B. 0.1 to 10 parts of at least one curing agent selected from the group consisting of formulas (I), (II), (III), and (IV):

wherein:
each of R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , and R 9 is selected from the group consisting of H, halogen atom, C1 to C4 alkyl groups in which the alkyl group is linear, branched, or cyclic; OR′; and aromatic groups;
R 5 is H; and
R′ is selected from the group consisting of C1 to C4 alkyl groups in which the alkyl group is linear, branched, or cyclic; and phenyl.

14. The article of claim 13 , wherein the cured compound further comprised before curing 0.1 to 5 phr of a curing agent C different from curing agent B.

15. The article of claim 13 in the form of a gasket, seal, tubing, sheet, washer, or O-ring.

16. The article of claim 14 in the form of a gasket, seal, tubing, sheet, washer, or O-ring.

17. The article of claim 13 , wherein the compression set, as measured in air at 70 hours according to method ASTM D395B, is less than 15 percent.

18. The article of claim 14 , wherein the compression set, as measured in air at 70 hours according to method ASTM D395B, is less than 15 percent.

19. A process comprising the step of:
curing a fluoroelastomer A with at least one curing agent B of formulas (I), (II), (III), and (IV):

wherein:
fluoroelastomer A comprises copolymerized units of:
(1) one or more unsaturated fluorinated olefins;
(2) one or more unsaturated fluorinated olefin co-monomer different from (i) selected from the group consisting of fluorovinyl ethers, unsaturated fluorinated olefins, unsaturated olefins, and mixtures of these; and
(3) one or more cure site monomers selected from the group consisting of nitrile-containing fluorinated olefins and nitrile-containing fluorinated vinyl ethers;
and
each of R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , and R 9 is selected from the group consisting of H, halogen atom, C1 to C4 alkyl groups in which the alkyl group is linear, branched, or cyclic; OR′; and aromatic groups;
R 5 is H; and
R′ is selected from the group consisting of C1 to C4 alkyl groups in which the alkyl group is linear, branched, or cyclic; and phenyl.

20. The process of claim 19 , wherein fluoroelastomer A further comprises 0.1 to 5 phr of curing agent C different from curing agent B.

21. The process of claim 19 , wherein the unsaturated fluorinated olefin A(1) is selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, 1,1-difluoroethylene; 1,1,2-trifluoroethylene; 1-fluoroethylene, and mixtures of these.

22. The process of claim 20 , wherein the unsaturated fluorinated olefin A(1) is selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, 1,1-difluoroethylene; 1,1,2-trifluoroethylene; 1-fluoroethylene, and mixtures of these.

23. The process of claim 19 , wherein the unsaturated fluorinated olefin co-monomer A(2) is selected from the group consisting of perfluoro(methyl vinyl) ether, hexafluoropropylene, perfluoro(propyl vinyl) ether, and mixtures of these and curing agent B is selected from the group consisting of amidinoamidine HCl, N′, N″-diaminoamidine; phenyloxoaminoamidine, 3-(5-phenyl-4H-1,2,4-triazolyl)amidine, 1H-pyrrolylamidine, benzimidazolylamidine, aminothioxoamidine; aminocarbonylmethylamidine HCl, N-aminoamidine bicarbonate, N″-1H-pyrazolyl-N′-t-butoxycarbonylamidine, 2-pyridylamidine HCl, sulfinoamidine, and mixtures of these.

24. The process of claim 20 , wherein the unsaturated fluorinated olefin co-monomer A(2) is selected from the group consisting of perfluoro(methyl vinyl) ether, hexafluoropropylene, per

Assignees

• Du Pont

Inventors

• Fox Peter Anthony
• Burkhardt Stephen E
• Junk Christopher P
• Wang Shuhong

Classifications

• C08K5/34

  Heterocyclic compounds having nitrogen in the ring · CPC title

• C08K5/3412

  having one nitrogen atom in the ring · CPC title

• C08K3/04

  Carbon · CPC title

• C08L27/12

  containing fluorine atoms · CPC title

• C08K5/3417 Primary

  condensed with carbocyclic rings · CPC title