Fluoroelastomer compositions

• US 7,022,773 B2
• Filed: 05/12/2004
• Issued: 04/04/2006
• Est. Priority Date: 02/23/1999
• Status: Expired due to Term

• Current Assignee: Solvay Solexis SPA (Solvac SA)
• Original Assignee: Solvay Solexis SPA (Solvac SA)
• Inventors: Arcella, Vincenzo, Albano, Margherita, Apostolo, Marco, Marchese, Enrico
• Primary Examiner(s): Nutter, Nathan M.
• Application Number:
  US10/843,440
• Publication Number:
  US 20040210003A1
• Time in Patent Office: 692 Days
• Field of Search: 525/199, 525/200, 525/214, 525/221, 525/222, 525/240, 525/241
• US Class Current: 525/199
• CPC Class Codes: C08L 2205/02 containing two or more polymers of the same C08L -group
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 27/12 containing fluorine atoms
• CPC Class Codes: C08L 27/18 Homopolymers or copolymers or tetrafluoroethene
• CPC Class Codes: C08L 29/10 Homopolymers or copolymers of unsaturated ethers C08L35/08 takes precedence

Abstract

Fluoropolymers comprising a fluoroelastomer matrix incorporating therein particles of a semicrystalline fluoropolymer formed of tetrafluoroethylene (TFE) homopolymers or copolymers, wherein the average particle sizes of the semicrystalline fluoropolymer latex range from 10 to 100 nm.

Claims

1. Fluoropolymer compositions comprising a fluoroelastomer and a semicrystalline fluoropolymer latex formed by tetrafluoroethylene (TFE) homopolymers, or TFE copolymers with one or more monomers containing at least one unsaturation of ethylene type in amounts ranging from 0.01% to 10% by moles, obtainable by mixing the semicrystalline fluoropolymer latex with the fluoroelastomer, subsequent coagulation and drying.

2. Fluoropolymer compositions according to claim 1 obtainable by polymerizing in a first step the semicrystalline fluoropolymer and in a second step the fluoroelastomer.

3. Fluoropolymer compositions according to claim 1 wherein the semicrystalline fluoropolymer amount inside the fluoroelastomer matrix is in the range 2–

40% by weight of the total of the polymeric mixture.

4. Fluoropolymer compositions according to claim 3 wherein the semicrystalline fluoropolymer amount inside the fluoroelastomer matrix is in the range 5–

30% by weight of the total of the polymeric mixture.

5. Fluoropolymer compositions according to claim 1 wherein the semicrystalline polymer is based on PTFE modified with comonomers with ethylene unsaturation both of hydrogenated and fluorinated type.

6. Fluoropolymer compositions according to claim 5 wherein the hydrogenated comonomers are selected from the group consisting of ethylene, propylene, methylmethacrylate, methacrylic acid, butylacrylate, hydroxyethylhexylacrylate, and styrene.

7. Fluoropolymer compositions according to claim 5 wherein the fluorinated comonomers are selected from the group consisting of:

perfluoroolefins C₃–

C₈;

hydrogenated fluoroolefins C₂–

C₈;

chloro- and/or bromo- and/or iodo-fluoroolefins C₂–

C₈;

(per)fluoroalkylvinylethers (PAVE CF₂═

CFOR_f, wherein R_f is a (per)fluoroalkyl C₁–

C₆;

(per)fluoro-oxyalkyvinylethers CF₂═

CFOX, wherein X is a alkyl C₁–

C₁₂, or an oxyalkyl C₁–

C₁₂, or a (per)fluoro-oxyalkyl C₁–

C₁₂ having one or more ether groups;

fluorodioxoles.

8. Fluoropolymer compositions according to claim 5 wherein the fluorinated comonomers are selected from the group consisting of perfluoromethyl-, ethyl-, propyl-vinylether and perfluorodioxoles.

9. Fluoropolymer compositions according to claim 1 wherein the fluoroelastomer is selected from the following classes:

(1) vinylidene fluoride (VDF)—

based copolymers, wherein VDF is copolymerized with at least one comonomer selected from the group consisting of;

perfluoroolefins C₂–

C₈, chloro- and/or bromo- and/or iodofluoroolefins C₂–

C₈, (per)fluoroalkyl-vinylethers (PAVE) CF₂═

CFOR_f, wherein R_f is a (per)fluoroalkyl C₁–

C₆, perfluoro-oxyalkylvinylethers CF₂═

CFOX, wherein X is a perfluoro-oxyalkyl C₁–

C₁₂ having one or more ether groups, non fluorinated olefins (Ol) C₂–

C₈;

(2) tetrafluoroethylene (TFE)—

based copolymers, wherein TFE is copolymerized with at least one comonomer selected from the group consisting of (per)fluoroalkyvinylethers (PAVE) CF₂═

CFOR_f, wherein R_f is as above defined;

perfluoro-oxyalkyvinylethers CF₂═

CFOX, wherein X is as above defined;

fluoroolefins C₂–

C₈ containing hydrogen and/or chlorine and/or bromine and/or iodine atoms;

non fluorinated olefins (Ol) C₂–

C₈.

10. Fluoropolymer compositions according to claim 9 wherein the fluorelastomer is selected from the following compositions expressed by moles:

(a) vinylidene fluoride (VDF) 45–

85%, hexafluoropropene (HFP) 15–

45% tetrafluoroethylene (TFE) 0–

30%;

(b) vinylidene fluoride (VDF) 50–

80%, perfluoroalkylvinylether (PAVE) 5–

50%, tetrafluoroethylene (TFE) 0–

20%;

(c) vinylidene fluoride (VDF) 20–

30%, non fluorinated olefins (Ol) C₂–

C₈ 10–

30%, hexafluoropropene (HFP) and/or perfluoroalkylvinylether (PAVE) 18–

27%, tetrafluoroethylene (TFE) 10–

30%;

(d) tetrafluoroethylene (TFE) 50–

80%, perfluoroalkylvinylether (PAVE) 20–

50%;

(e) tetrafluoroethylene (TFE) 45–

65%, non fluorinated olefins (Ol) C₂–

C₈ 20–

55%, vinylidene fluoride 0–

30%

(f) tetrafluoroethylene (TFE) 32–

60%, non fluorinated olefins (Ol) C₂–

C₈ 10–

40%, perfluoroalkylvinylether (PAVE) 20–

40%;

(g) tetrafluoroethylene (TFE) 33–

75%, perfluoroalkylvinylether (PAVE) 15–

45%, vinylidene fluoride (VDF) 5–

30%.

11. Fluoropolymer compositions according to claim 1 wherein the fluoroelastomer comprises also monomer units deriving from a bis-olefin having the formula:

wherein

R₁, R₂, R₃, R₄, R₅, R₆, equal to or different from each other, are H or alkyl C₁–

C₅;

Z is a linear or branched, alkylene or cycloalkylene C₁–

C₁₈ radical, optionally containing oxygen toms optionally at least partially fluorinated, or a (per)fluoropolyoxyalkylene radical.

12. Fluoropolymer compositions according to claim 11 wherein the unit amount in the chain deriving from the bis-olefin is in the range 0.01–

1.0% by moles of the other monomer units forming the fluoroelastomer base structure.

13. Fluoropolymer compositions according to claim 1 wherein the fluoroelastomers are cured by peroxidic route.

14. Fluoropolymer compositions according to claim 1 wherein when the fluoroelastomers contain cyano groups they are cured by tin organic compounds and/or di-aromatic aminic compounds.

15. Fluoropolymer compositions according to claim 1 wherein the fluoroelastomers are cured by tin organic compounds and/or diaromatic aminic compounds and optionally by peroxidic route if in the polymeric chain iodine and/or bromine atoms are present.

16. Fluoropolymer compositions according to claim 1 wherein the one or more monomers containing at least one unsaturation of ethylene type are present in amounts ranging from 0.5% to 5% by moles.

17. Fluoropolymer compositions according to claim 7 wherein the perfluoroolefins C₃–

C₈ are selected from the group consisting of hexafluoropropene (HFP) and hexafluoroisobutene.

18. Fluoropolymer compositions according to claim 7 wherein the hydrogenated fluoroolefins C₂–

C₈ are selected from the group consisting of vinyl fluoride (VF), vinylidene fluoride (VDF), trifluoroethylene and perfluoroalkylethylene CH₂═

CH-R_f, wherein R_f is a perfluoroalkyl C₁–

C₆.

19. Fluoropolymer compositions according to claim 7 wherein the chloro-fluoroolefin C₂–

C₈ is chlorotrifluoroethylene (CTFE).

20. Fluoropolymer compositions according to claim 7 wherein the (per)fluoroalkylvinyl-ethers (PAVE)(CF₃═

CF)R_f) are selected from the group consisting of CF₃, C₂F₅ and C₃F₇.

21. Fluoropolymer compositions according to claim 7 wherein the (per)fluoro-oxyalkyl C₁–

C₁₂ having one or more ether groups is perfluoro-2-propoxy-propyl.

22. Fluoropolymer compositions according to claim 9 wherein the perfluoroolefin C₂–

C₈ is selected from the group consisting of tetrafluoroethylene (TFE) and hexafluoropropene (HFP).

23. Fluoropolymer compositions according to claim 9 wherein the chloro- and/or bromo-fluoro-olefins C₂–

C₈ are selected from the group consisting of chlorotrifluoroethylene (CTFE) and bromotrifluoroethylene.

24. Fluoropolymer compositions according to claim 9 wherein the (per)fluoroalkyl-vinylethers (PAVE) CF₂—

CFOR_f are selected from the group consisting of trifluoromethyl, bromodifluoromethyl and pentafluoropropyl.

25. Fluoropolymer compositions according to claim 9 wherein the perfluoro-oxyalkylvinylether CF₂═

CFOX is perfluoro-2-propoxy-propyl.

26. Fluoropolymer compositions according to claim 9 wherein the nonfluorinated olefins (Ol) C₂–

C₈ are selected from the group consisting of ethylene and propylene.

27. A sealing manufactured article comprising the fluoropolymer compositions according to claim 1.

28. The sealing manufactured article according to claim 27, wherein the sealing manufactured article is an O-ring.

29. Cured fluoropolymer compositions according to claim 1.

30. Fluoropolymers comprising a fluoroelastomer matrix incorporating therein particles of a semicrystalline fluoropolymer latex formed by tetrafluoroethylene (TFE) homopolymers, or TFE copolymers with one or more monomers containing at least one unsaturation of ethylene type in amounts ranging from 0.01% to 10% by moles.

31. Fluoropolymers according to claim 30 obtainable by mixing the semicrystalline fluoropolymer latex with the fluoroelastomer latex and subsequent coagulation.

32. Fluoropolymers according to claim 30 obtainable by polymerizing in a first step the semicrystalline fluoropolymer and in a second step the fluoroelastomer.

33. Fluoropolymers according to claim 30 wherein the semicrystalline fluoropolymer amount inside the fluoroelastomer matrix is in the range 2–

40% by weight of the total of the polymeric mixture.

34. Fluoropolymers according to claim 33 wherein the semicrystalline fluoropolymer amount inside the fluoroelastomer matrix is in the range 5–

30% by weight of the total of the polymeric mixture.

35. Fluoropolymers according to claim 30 wherein the semicrystalline polymer is based on PTFE modified with comonomers with ethylene unsaturation both of hydrogenated and fluorinated type.

36. Fluoropolymers according to claim 35 wherein the hydrogenated comonomers are selected from the group consisting of ethylene, propylene, methylmethacrylate, methacrylic acid, butylacrylate, hydroxyethylhexylacrylate, and styrene.

37. Fluoropolymers according to claim 35 wherein the fluorinated comonomers are selected from the group consisting of

perfluoroolefins C₃–

C₈;

hydrogenated fluoroolefins C₂–

C₈;

chloro- and/or bromo- and/or iodo-fluoroolefins C₂–

C₈;

(per)fluoroalkylvinylethers (PAVE) CF₂═

CFOR_f, wherein R_f is a (per)fluoroalkyl C₁–

C₆;

(per)fluoro-oxyalkyvinylethers CF₂═

CFOX, wherein X is an alkyl C₁–

C₁₂, or an oxyalkyl C₁–

C₁₂, or a (per)fluoro-oxyalkyl C₁–

C₁₂ having one or more ether groups;

fluorodioxoles.

38. Fluoropolymers according to claim 35 wherein the fluorinated comonomers are selected from the group consisting of perfluoromethyl-, ethyl-, propyl- vinylether and perfluorodioxoles.

39. Fluoropolymers according to claim 30 wherein the fluoroelastomer is selected from the following classes:

(1) vinylidene fluoride (VDF)—

based copolymers, wherein VDF is copolymerized with at least one comonomer selected from the group consisting of;

perfluoroolefins C₂–

C₈, chloro- and/or bromo- and/or iodofluoroolefins C₂–

C₈, (per)fluoroalkyl-vinylethers (PAVE) CF₂═

CFOR_f, wherein R_f is a (per)fluoroalkyl C₁–

C₆, perfluoro-oxyalkyvinylethers CF₂═

CFOX, wherein X is a perfluoro-oxyalkyl C₁–

C₁₂ having one or more ether groups, non fluorinated olefins (Ol) C₂–

C₈;

(2) Tetrafluoroethylene (TFE)—

based copolymers, wherein TFE is copolymerized with at least one comonomer selected from the group consisting of (per)fluoroalkylvinylethers (PAVE) CF₂═

CFOR_f, wherein R_f is as above defined;

perfluoro-oxyalkyvinylethers CF₂═

CFOX, wherein X is as above defined;

fluoroolefins C₂–

C₈ containing hydrogen and/or chlorine and/or bromine and/or iodine atoms;

non fluorinated olefins (Ol) C₂–

C₈;

perfluorovinylethers containing hydrocyanic groups.

40. Fluoropolymers according to claim 39 wherein the fluoroelastomers is selected from the following compositions expressed by moles:

(a) vinylidene fluoride (VDF) 45–

85%, hexafluoropropene (HFP) 15–

45% tetrafluoroethylene (TFE) 0–

30%;

(b) vinylidene fluoride (VDF) 50–

80%, perfluoroalkylvinylether (PAVE) 5–

50%, tetrafluoroethylene (TFE) 0–

20%;

(c) vinylidene fluoride (VDF) 20–

30%, non fluorinated olefins (Ol) C₂–

C₈ 10–

30%, hexafluoropropene (HFP) and/or perfluoroalkylvinylether (PAVE) 18–

27%, tetrafluoroethylene (TFE) 10–

30);

(d) tetrafluoroethylene (TFE) 50–

80%, perfluoroalkylvinylether (PAVE) 20–

50%;

(e) tetrafluoroethylene (TFE) 45–

65%, non fluorinated olefins (Ol) C₂–

C₈ 20–

55%, vinylidene fluoride 0–

30%;

(f) tetrafluoroethylene (TFE) 32–

60% by moles, non fluorinated olefins (Ol) C₂–

C₈ 10–

40%, perfluoroalkylvinylether (PAVE) 20–

40%;

(g) tetrafluoroethylene (TFE) 33–

75%, perfluoroalkylvinylether (PAVE) 15–

45%, vinylidene fluoride (VDF) 5–

30%.

41. Fluoropolymers according to claim 30 wherein the fluoroelastomer comprises also monomer units deriving from a bis-olefin having the formula:

wherein

R₁, R₂, R₃, R₄, R₅, R₆, equal to or different from each other, are H or alkyl C₁–

C₅;

Z is a linear or branched, alkylene or cycloalkylene C₁–

C₁₈ radical, optionally containing oxygen atoms optionally at least partially fluorinated, or a (per)fluoropolyoxyalkylene radical.

42. Fluoropolymers according to claim 41 wherein the unit amount in the chain deriving from the bis-olefin is in the range 0.01–

1.0% by moles of the other monomer units forming the fluoroelastomer base structure.

43. Fluoropolymers according to claim 30 wherein the fluoroelastomers are cured by peroxidic route.

44. Fluoropolymers according to claim 30 wherein when the fluoroelastomers contain cyano groups they are cured by tin organic compounds and/or di-aromatic aminic compounds.

45. Fluoropolymers according to claim 30 wherein the fluoroelastomers are cured by tin organic compounds and/or diaromatic aminic compounds and optionally by peroxidic route if in the polymeric chain iodine and/or bromine atoms are present.

46. Fluoropolymers according to claim 30 wherein the one or more monomers containing at least one unsaturation of ethylene type are present in amounts ranging from 0.5% to 5% by moles.

47. Fluoropolymers according to claim 37 wherein the perfluoroolefins C₃–

C₈ are selected from the group consisting of hexafluoropropene (HFP) and hexafluoroisobutene.

48. Fluoropolymers according to claim 37 wherein the hydrogenated fluoroolefins C₂–

C₈ are selected from the group consisting of vinyl fluoride (VF), vinylidene fluoride (VDF), trifluoroethylene and perfluoroalkylethylene CH₂═

CH-R_f, wherein R_f is a perfluoroalkyl C₁–

C₆.

49. Fluoropolymers according to claim 37 wherein the chloro-fluoroolefin C₂–

C₈ is chlorotrifluoroethylene (CTFE).

50. Fluoropolymers according to claim 37 wherein the (per)fluoroalkylvinylethers (PAVE)(CF₂═

CFOR_f) are selected from the group consisting of CF₃, C₂F₅ and C₃F₇.

51. Fluoropolymers according to claim 37 wherein the (per)fluoro-oxyalkyl C₁–

C₁₂ having one or more ether groups is perfluoro-2-propoxy-propyl.

52. Fluoropolymers according to claim 39 wherein the perfluoroolefin C₂–

C₈ is selected from the group consisting of tetrafluoroethylene (TFE) and hexafluoropropene (HFP).

53. Fluoropolymers according to claim 39 wherein the chloro- and/or bromo- fluoro-olefins C₂–

C₈ are selected from the group consisting of chlorotrifluoroethylene (CTFE) and bromotrifluoroethylene.

54. Fluoropolymers according to claim 39 wherein the (per)fluoroalkylvinylethers (PAVE) CF₂═

CFOR_f are selected from the group consisting of trifluoromethyl, bromodifluoromethyl and pentafluoropropyl.

55. Fluoropolymers according to claim 39 wherein the perfluorooxyalkylvinylether CF₂═

CFOX is perfluoro-2-propoxy-propyl.

56. Fluoropolymers according to claim 39 wherein the nonfluorinated olefins (Ol) C₂–

C₈ are selected from the group consisting of ethylene and propylene.