Curable fluoropolymer compositions comprising bis phthalonitrile-containing compound and cured articles therefrom

Patent metadata

Field	Value
Publication number	US-12084561-B2
Application number	US-201917296564-A
Country	US
Kind code	B2
Filing date	Dec 4, 2019
Priority date	Dec 14, 2018
Publication date	Sep 10, 2024
Grant date	Sep 10, 2024

Abstract

Described herein are fluoropolymer compositions comprising a bis phthalonitrile-containing compound. In one embodiment, the bis phthalonitrile-containing compound is used to crosslink a dehydrohalogenated polymer, and optionally with a polyhydroxy curative. In another embodiment, the bis phthalonitrile-containing compound is added to a composition comprising (i) a fluorinated elastomeric gum, wherein the fluorinated elastomeric gum comprises a fluoropolymer having a cure-site and (ii) a peroxide curing system.

First claim

What is claimed is:

1. A curable composition comprising (a) a partially fluorinated polymer, wherein the backbone of the partially fluorinated polymer comprises carbon-carbon double bonds or is capable of forming carbon-carbon double bond, and (b) a compound of Formula I

wherein X 1 and X 2 are independently selected from O or S, and L is

wherein R is selected from the group consisting of —S—, —O—, —C(CF 3 ) 2 —, —C(CH 3 ) 2 —, —CH 2 —, —SO 2 —, —C(═O)—, or —C(CH 3 ) 2 —C 6 H 4 —C(CH 3 ) 2 —; each R″ is independently selected from a methyl, methoxy, ethyl, and ethoxy group; and each R″ is independently selected from a methyl, methoxy, ethyl, or ethoxy group.

2. The curable composition of claim 1 , wherein the curable composition further comprises a polyhydroxy curative.

3. The curable composition of claim 2 , wherein the polyhydroxy curative is selected from at least one of 4,4′-hexafluoroisopropylidenyl bisphenol, 4,4′-dihydroxydiphenyl sulfone, 4,4′-isopropylidenyl bisphenol, 4,4′ (perfluoropropane-2,2-diyl)diphenol, dihydroxybenzophenone, hydroquinone, 2,4,6-trimercapto-S-triazine, 4,4′-thiodiphenol, or a metal salt thereof.

4. The curable composition of claim 1 , wherein the partially fluorinated polymer is derived from (i) vinylidene fluoride, tetrafluoroethylene, and propylene; (iii) vinylidene fluoride with hexafluoropropylene; (iv) hexafluoropropylene, tetrafluoroethylene, and vinylidene fluoride; (v) hexafluoropropylene and vinylidene fluoride, (ix) tetrafluoroethylene, propylene, and 3,3,3-trifluoropropene; (x) tetrafluoroethylene, and propylene; or (xvi) combinations thereof.

5. The curable composition of claim 1 , wherein the partially fluorinated polymer comprises (i) at least one of vinylidene fluoride or tetrafluoroethylene, and (ii) a fluorinated comonomer having an acidic hydrogen atom.

6. The curable composition of claim 1 , comprising at least 0.1 part by weight of the compound of Formula I to 100 parts by weight of the partially fluorinated polymer.

7. A curable composition comprising (a) a fluorinated elastomeric gum comprising a fluoropolymer, wherein the fluoropolymer comprises at least one of —I, —Br, and —CN cure site, (b) a peroxide curing system comprising a peroxide and a coagent, and (c) a compound of Formula I

wherein X 1 and X 2 are independently selected from O or S, and L is

wherein R is selected from the group consisting of —S—, —O—, —C(CF 3 ) 2 —, —C(CH 3 ) 2 —, —CH 2 —, —SO 2 —, —C(═O)—, or —C(CH 3 ) 2 —C 6 H 4 —C(CH 3 ) 2 —; each R′ is independently selected from a methyl, methoxy, ethyl, and ethoxy group; and each R″ is independently selected from a methyl, methoxy, ethyl, or ethoxy group.

8. The curable composition of claim 7 , wherein the coagent comprises (i) diallyl ether of glycerin, (ii) triallylphosphoric acid, (iii) diallyl adipate, (iv) diallylmelamine and triallyl isocyanurate, (v) tri(methyl)allyl isocyanurate, (vi) tri(methyl)allyl cyanurate, (vii) poly-triallyl isocyanurate, (viii) xylylene-bis(diallyl isocyanurate), (xi) CH 2 ═CH—Rf1-CH═CH 2 wherein Rf1 may be a perfluoroalkylene of 1 to 8 carbon atoms, or combinations thereof.

9. The curable composition of claim 7 , wherein the peroxide comprises 2,5-dimethyl-2,5-di(t-butylperoxy)hexane; dicumyl peroxide; di(2-t-butylperoxyisopropyl)benzene; dialkyl peroxide; bis (dialkyl peroxide); 2,5-dimethyl-2,5-di(tertiarybutylperoxy)3-hexyne; dibenzoyl peroxide; 2,4-dichlorobenzoyl peroxide; tertiarybutyl perbenzoate; α,α′-bis(t-butylperoxy-diisopropylbenzene); t-butyl peroxy isopropylcarbonate, t-butyl peroxy 2-ethylhexyl carbonate, t-amyl peroxy 2-ethylhexyl carbonate, t-hexylperoxy isopropyl carbonate, di[1,3-dimethyl-3-(t-butylperoxy)butyl] carbonate, carbonoperoxoic acid, O,O′-1,3-propanediyl OO,OO′-bis(1,1-dimethylethyl) ester, or combinations thereof.

10. The curable composition of claim 7 , wherein the fluoropolymer comprises (i) a copolymer comprising tetrafluoroethylene, vinylidene fluoride, and hexafluoropropylene monomeric units; (ii) a copolymer comprising tetrafluoroethylene, and propylene monomeric units; (iii) a copolymer comprising tetrafluoroethylene, vinylidene fluoride, and propylene monomeric units; (iv) a copolymer comprising vinylidene fluoride, perfluoro (methyl vinyl) ether, and hexafluoropropylene monomeric units; (v) a copolymer comprising tetrafluoroethylene, vinyl fluoride, and hexafluoropropylene monomeric units; (vi) a copolymer comprising vinyl fluoride, perfluoro (methyl vinyl) ether, and hexafluoropropylene monomeric units; (vii) a copolymer of TFE with perfluorovinyl ether, (viii) a copolymer of TFE with perfluoroallyl ether, or combinations thereof.

11. The curable composition of claim 7 , wherein an amount of the compound of Formula I is at least 0.05 parts by weight per 100 parts of the fluoropolymer.

12. The curable composition of claim 1 , wherein L is a divalent, trivalent or tetravalent benzene group.

13. The curable composition of claim 1 , wherein the partially fluorinated polymer is amorphous.

14. A cured article derived from the curable composition of claim 1 .

15. The cured article of claim 14 , wherein the cured article is an o-ring, a seal, a gasket, a hose, or a sheet.

16. The curable composition of claim 5 , wherein the fluorinated comonomer having an acidic hydrogen atom is selected from: trifluoroethylene; vinyl fluoride; 3,3,3-trifluoropropene-1; pentafluoropropene; or 2,3,3,3-tetrafluoropropene.

Assignees

• 3M Innovative Properties Company

Inventors

• Mitchell Michael H
• Anderson Benjamin J
• Dahlke Gregg D
• Fukushi Tatsuo

Classifications

• C09K2200/0637

  Fluoro-containing polymers, e.g. PTFE · CPC title

• C09K3/1009

  Fluorinated polymers, e.g. PTFE · CPC title

• C08J2327/20

  Homopolymers or copolymers of hexafluoropropene · CPC title

• C08J2327/16

  Homopolymers or copolymers of vinylidene fluoride · CPC title

• C08J5/18

  Manufacture of films or sheets · CPC title