Hydroxy-functionalized triazine compounds, curable fluoropolymer compositions comprising such compounds and cured articles therefrom

Patent metadata

Field	Value
Publication number	US-12428384-B2
Application number	US-202017615127-A
Country	US
Kind code	B2
Filing date	Jun 22, 2020
Priority date	Jun 28, 2019
Publication date	Sep 30, 2025
Grant date	Sep 30, 2025

Abstract

Described herein are compounds according to Formula (I) wherein each Rf is independently selected from a perfluorinated divalent group comprising 2 to 12 carbon atoms; and m is an integer independently selected from 1 to 3. A method of making the compound from a hydroxy-containing vinyl ether and excess ammonia is disclosed. In one embodiment, the hydroxy-functionalized triazine compound is used in a curable fluoropolymer composition and cured to form articles.

First claim

What is claimed is:

1. A curable composition comprising (a) an amorphous fluorinated polymer capable of being dehydrofluorinated, and (b) a compound of Formula (I)

wherein each Rf is independently selected from a perfluorinated divalent group comprising 2 to 12 carbon atoms; and m is an integer independently selected from 1 to 3.

2. The curable composition of claim 1 , wherein the molecular weight of compound of Formula (I) is less than 1500 grams/mole.

3. The curable composition of claim 1 , wherein Rf is —(CF 2 ) n —, where n is an integer from 2-8.

4. The curable composition of claim 1 , wherein Rf comprises
—(CF 2 ) p —O—(CF 2 ) q , —(OCF 2 CF 2 ) q —, —(OCF 2 CF(CF 3 )) p — and/or —(CF 2 CF(CF 3 )) p —O—(CF 2 ) q —, wherein p is an integer of 1-11 and q is an integer from 1-11, such that the sum of p+q is 2-12.

5. The curable composition of claim 1 , wherein m is 1.

6. The curable composition of claim 1 , wherein the compound according to Formula I is at least one of the following: [HOCH 2 (CF 2 ) 2 OCFH] 3 —C 3 N 3 , [HO(CH 2 ) 2 (CF 2 ) 2 OCFH] 3 —C 3 N 3 , [HO(CH 2 ) 3 (CF 2 ) 2 OCFH] 3 —C 3 N 3 , [HO(CH 2 )(CF 2 ) 3 OCFH] 3 —C 3 N 3 , [HO(CH 2 )(CF 2 ) 4 OCFH] 3 —C 3 N 3 , [HO(CH 2 )(CF 2 ) 5 OCFH] 3 —C 3 N 3 , [HO(CH 2 )(CF 2 ) 6 OCFH] 3 —C 3 N 3 , [HO(CH 2 )(CF 2 ) 6 OCFH] 2 —C 3 N 3 —[CHFO(CF 2 ) 2 (CH 2 )OH], [HO(CH 2 )(CF(CF 3 )O(CF 2 ) 6 OCFH] 2 —C 3 N 3 —[CHFO(CF 2 ) 2 OCF(CF 3 )CH 2 OH], [HOCH 2 CH 2 CF(CF 3 )O(CF 2 ) 2 OCFH] 3 —C 3 N 3 , [HOCH 2 CF(CF 3 )O(CF 2 ) 2 OCFH] 3 —C 3 N 3 , [HOCH 2 (CF 2 ) 3 OCF(CF 3 ) CF 2 OCFH] 3 —C 3 N 3 , [HOCH 2 CH 2 (CF 2 ) 4 OCFH] 3 —C 3 N 3 , [HOCH 2 (CF 2 ) 2 OCF(CF 3 ) CF 2 OCFH] 3 —C 3 N 3 , [HOCH 2 CH 2 (CF 2 ) 2 OCF 2 CF(CF 3 ) OCFH] 3 —C 3 N 3 , and [HOCH 2 (CF 2 ) 5 OCF(CF 3 ) CF 2 OCFH] 3 —C 3 N 3 , where C 3 N 3 represents the triazine ring.

7. 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 amorphous fluorinated polymer capable of being dehydrofluorinated.

8. The curable composition of claim 1 , wherein the amorphous fluorinated polymer capable of being dehydrofluorinated comprises at least one of (i) vinylidene fluoride, tetrafluoroethylene, and propylene copolymer; (ii) vinylidene fluoride and hexafluoropropylene copolymer; (iii) hexafluoropropylene, tetrafluoroethylene, and vinylidene fluoride copolymer; (iv) hexafluoropropylene and vinylidene fluoride copolymer; (v) tetrafluoroethylene, propylene, and 3,3,3-trifluoropropene copolymer; (vi) tetrafluoroethylene, and propylene copolymer; and (vii) blends thereof.

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

10. The curable composition of claim 9 , wherein the fluorinated comonomer having an acidic hydrogen atom comprises at least one of trifluoroethylene; vinyl fluoride; 3,3,3-trifluoropropene-1; pentafluoropropene; and 2,3,3,3-tetrafluoropropene.

11. The curable composition of claim 1 , wherein the dehydrofluorinating agent is selected from an organo onium compound.

12. The curable composition of claim 11 , wherein the organo onium compound is selected from at least one of quaternary ammonium hydroxides or salts, quaternary phosphonium hydroxides or salts, and ternary sulfonium hydroxides or salts.

13. The curable composition of claim 1 , further comprising an organic or inorganic base.

14. The curable composition of claim 1 , further comprising a sulfonamide.

15. A cured article derived from the curable composition of claim 1 , optionally, wherein the cured article is an o-ring, a seal, a gasket, a hose or a sheet.

16. A molded article comprising the cured compositions of claim 15 .

17. A method of making the compound according to Formula (I), the method comprising:
reacting a vinyl ether monomer according to Formula (II), with ammonia to form an amidine molecule; and heating the amidine molecule to form the compound according to Formula (I), where Formula (II) is

wherein Rf is a perfluorinated divalent group comprising 2 to 12 carbon atoms; and m is an integer independently selected from 1 to 3.

18. A method of preparing a shaped article comprising the steps of:
providing the curable composition of claim 1 , heating said composition to a temperature sufficient to cure the curable composition; and
recovering the shaped article.

19. A compound according to Formula (I)

wherein each Rf is independently selected from a perfluorinated divalent group comprising 2 to 12 carbon atoms; and m is an integer independently selected from 1 to 3.

Assignees

• 3M Innovative Properties Company

Inventors

• Guerra Miguel A
• Fukushi Tatsuo
• Mitchell Michael H
• Qiu Zai-Ming

Classifications

• C07D251/24 Primary

  to three ring carbon atoms · CPC title

• C08K5/3492 Primary

  Triazines · CPC title