IPC분류정보
국가/구분 |
United States(US) Patent
등록
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국제특허분류(IPC7판) |
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출원번호 |
US-0122489
(2002-04-11)
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발명자
/ 주소 |
- Grootaert, Werner M. A.
- Kolb, Robert E.
- Hintzer, Klaus
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출원인 / 주소 |
- 3M Innovative Properties Company
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인용정보 |
피인용 횟수 :
12 인용 특허 :
47 |
초록
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A composition of (a) a fluoropolymer having interpolymerized units derived from a nitrogen-containing cure site monomer; and (b) a nonfluorinated catalyst composition that includes a compound having the general formula: {RA}(?){QR′k}(+) or in certain cases the precursors thereof, wherein R is hydrog
A composition of (a) a fluoropolymer having interpolymerized units derived from a nitrogen-containing cure site monomer; and (b) a nonfluorinated catalyst composition that includes a compound having the general formula: {RA}(?){QR′k}(+) or in certain cases the precursors thereof, wherein R is hydrogen, an alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl or aralkyl, A is an acid- or acid-derivative anion, Q is phosphorous, sulfur, nitrogen, arsenic, or antimony, and each R′ is hydrogen or an alkyl, aryl, aralkyl, or alkenyl group, k is the valence of Q; and optionally (c) an alcohol of the formula R2?OH, wherein R2 is an alkyl group which can be partially fluorinated. Also provided are a method of making a fluoropolymer, a method of increasing induction time, and fluoropolymer articles containing curable or cured fluoropolymer compositions.
대표청구항
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1. A composition consisting essentially of:(a) a perfluoropolymer comprising interpolymerized units derived from a nitrogen-containing cure site monomer; (b) a non-fluorinated catalyst composition that includes a compound having the general formula: {R(A)n}(?n){QR′k(+)}n or the precursors thereof ad
1. A composition consisting essentially of:(a) a perfluoropolymer comprising interpolymerized units derived from a nitrogen-containing cure site monomer; (b) a non-fluorinated catalyst composition that includes a compound having the general formula: {R(A)n}(?n){QR′k(+)}n or the precursors thereof added separately or as a mixture; wherein R is hydrogen, a C1-C20 alkyl or alkenyl, C3-C20 cycloalkyl or cycloalkenyl, or C6-C20 aryl or aralkyl, {R(A)n}(?n) is an acid anion or an acid derivative anion, n is the number of A groups in the anion, Q is phosphorus, sulfur, nitrogen, arsenic, or antimony, each R′ is, independently, hydrogen or a substituted or unsubstituted C1-C20 alkyl, aryl, aralkyl, or alkenyl group, provided that when Q is nitrogen and the only fluoropolymer in the composition consists essentially of a terpolymer of TFE, a perfluorovinylether, and a perfluorovinylether cure site monomer comprising a nitrile group not every R′ is H, and k is one greater than the valence of Q, and, optionally, an additional curative material selected from the group consisting of: ammonium salts, ammonia-generating compounds, substituted triazine derivatives, unsubstituted triazine derivatives, bis-amidooximes, and organotin compounds; and optionally a coagent; optionally (c) an alcohol of the general formula R2?OH, wherein R2 is an alkyl group having from 1 to 20 carbon atoms, and wherein R2 is optionally partially fluorinated; and optionally (d) a filler selected from fluoropolymer filler, carbon black, and combinations thereof. 2. A composition according to claim 1 wherein A is selected from the group consisting of: COO, O when R is hydrogen, aryl, or alkylaryl, SO3, SO2, SO2NH, PO3, CH2OPO3, (CH2O)2PO2, C6H4O, OSO3, 3. A composition according to claim 1 wherein a precursor of R(A)n has the general formula selected from the group consisting of: RCOOM, ROSO3M, RSO3M, and ROM, wherein M is hydrogen, or an alkali or alkaline earth metal.4. A composition according to claim 1 wherein R(A)n is selected from the group consisting of: C6H5COO; PhO; CH3?(CH2)p?O?SO3 where p is 1 to 10; RCOO wherein R is an alkenyl, a C1-C10 alkyl, or a C6-C20 aryl; (?)OOC?(CH2)p?COO(?) wherein p is 0 to 10; and Ph?((CH2)p?COO(+))q wherein p and q are independently 1 to 4.5. A composition according to claim 1 wherein R(A)n is selected from the general formula (+)Ox?Ph?Gy?Ph?Oz(?) wherein G is a bond or a difunctional aliphatic, cycloaliphatic, or C1-C13 aromatic radical, or a thio, oxy, carbonyl, sulfinyl, or sulfonyl radical, G and/or Ph are optionally substituted with at least one Cl atom, y is 0 or 1, z is 1 or 2, and any aromatic ring of the polyoxy compound is optionally substituted with at least one atom of Cl, or Br atom, or carboxyl, or an acyl radical, or an alkyl radical; and blends of two or more such compounds.6. A composition according to claim 1 wherein R(A)n is selected from the general formula (?)O?Ph?C(CX3)2?Ph?O(?), wherein X is H, or Cl; and blends of two or more such compounds.7. A composition according to claim 1 wherein a precursor of QR′k is selected from the group consisting of tetramethylphosphoniums, tributylallylphosphoniums, tributylbenzylphosphoniums, dibutyldiphenylphosphoniums, tetrabutylphosphonium, tributyl(2-methoxy) propylphosphoniums, triphenylbenzylphosphoniums, and tetraphenylphosphoniums.8. A composition according to claim 1 wherein a precursor of QR′k is selected from the group consisting of phenyltrimethylammoniums, tetrapentylammoniums, tetrapropylammoniums, tetrahexylammoniums, tetraheptylammoniums, tetramethylammoniums, tetrabutylammoniums, tributylbenzyl ammoniums, tributylallylammoniums, tetrabenzylammoniums, tetraphenylammoniums, diphenyl diethylamino ammoniums, triphenylbenzylammoniums, 8-benzyl-1,8-diazabicyclo[5.4.0]undec-7-eniums, benzyltris(dimethylamino) phosphoniums, and bis(benzyldiphenyl phosphine)iminiums.9. A composition of claim 1 wherein the catalyst composition is prepared in situ.10. A composition according to claim 1 wherein the catalyst composition is prepared from components dissolved in a solvent.11. A composition according to claim 1 wherein the perfluoropolymer comprises interpolymerized units derived from (i) tetrafluoroethylene, and optionally (ii) one or more perfluorovinyl ethers of the formula:CF2?CFO(R2fO)a(R3fO)bR4f wherein R2f and R3f are the same or are different linear or branched perfluoroalkylene groups of 1-6 carbon atoms; a and b are, independently, 0 or an integer from 1 to 10; and R4f is a perfluoroalkyl group of 1-6 carbon atoms.12. A composition according to claim 11 wherein the perfluoropolymer further comprises interpolymerized units derived from perfluoroolefins.13. A composition according to claim 1 wherein said cure site monomer is a fluorinated olefin.14. A composition according to claim 1 wherein said cure site monomer is a nitrile-containing monomer having the formula CF2?CFO(CF2)LCN; CF2?CFO(CF2)uOCF(CF3)CN; CF2?CFO[CF2CF(CF3)O]q(CF2O)yCF(CF3)CN; or CF2?CF[OCF2CF(CF3) ]rO(CF2)tCN; wherein L=2-12; q=0-4, r=1-2; y=0-6; t=1-4, and u=2-6.15. The composition of claim 1 wherein the perfluoropolymer is selected from a fluoroelastomer and a fluoroplastic.16. The composition of claim 1 wherein the composition has an induction time below about 15 minutes at a temperature of about 175° C.17. The composition or claim 1 wherein the composition has a scorch resistance greater than the scorch resistance of a comparative composition tested at the same temperature, which comparative composition has the same perfluoropolymer with a urotropin curative.18. A shaped article comprising the perfluoropolymer composition of claim 1.19. The composition according to claim 1, wherein the curative increases MDR torque in the fluoropolymer composition at 177° C. by at least about 0.01 Nm.20. The composition of claim 1 wherein the coagent is selected from the group consisting of: triallyl cyanurate; triallyl isocyanurate; tri(methylallyl) isocyanurate; tris(diallylamine)-s-triazine; triallyl phosphite; N,N-diallyl acrylamide; hexaallyl phosphoramide; N,N,N′,N′-tetraalkyl tetraphthalamide; N,N,N′,N′-tetraallyl malonamide; trivinyl isocyanurate; 2,4,6-trivinyl methyltrisiloxane; and tri(5-norbornene-2-methylence)cyanurate.21. The composition of claim 1 wherein R(A)n is selected from the group consisting of: acetate, benzoate, and carbonate.22. The composition of claim 1 wherein {R(A)n}(?n){QR′k(+)}n is selected from the group consisting of: (QR′k)(+)(AQR′k)(?), (QR′4+)(CO32?)R, (QR′4+)2CO32?, (QR′4+)2SO42?, (QR′4)+OH?, (PR′4+)2CO32?, (PR′4)′OH?, and (PR′4+)2SO42?.23. The composition of claim 1 wherein QR′k is selected from the group consisting of: tetrabutylphosphonium and tributyl(2-methoxy)propylphosphonium.24. A method of making a perfluoropolymer composition comprising forming a mixture consisting essentially ofa perfluoropolymer having interpolymerized units derived from a nitrogen-containing cure site monomer, a nonfluorinated catalyst composition comprising a compound having the formula: {R(A)n}(?n){QR′k(+)}n or the precursors thereof added separately or as a mixture, wherein R is hydrogen, a C1-C20 alkyl or alkenyl, C3-C20 cycloalkyl or cycloalkenyl, or C6-C20 aryl or alkylaryl, {R(A)n}(?n) is an acid anion or an acid derivative anion group, which may be heterocyclic, n is the number of A groups in the anion, Q is P, S, N, As, or Sb, and each R′ is, independently, hydrogen or a substituted or unsubstituted C1-C20 alkyl, aryl, aralkyl, or alkenyl group, provided that when Q is nitrogen and the only fluoropolymer in the composition consists essentially of a terpolymer of TFE, a perfluorovinylether, and a perfluorovinylether cure site monomer comprising a nitrile group, not every R′ is H, and k is one greater than the valence of Q; optionally, an additional curative material selected from the group consisting of: ammonium salts, ammonia-generating compounds, substituted triazine derivatives, unsubstituted triazine derivatives, bis-amidooximes, and organotin compounds; optionally a coagent; optionally a filler selected from the group consisting of fluoropolymer filler, carbon black, and combinations thereof, and optionally in the presence of an alcohol of the general formula R2?OH, wherein R2 is a C6-C20 alkyl group. 25. The method of claim 24 further comprising:a) shaping the mixture; b) optionally curing the shaped mixture; and c) optionally heat aging the cured mixture. 26. A method according to claim 25 wherein the catalyst is added in a form selected from the group consisting of: a compound and a mixture of catalyst precursors.27. A method according to claim 25 wherein individual components of the catalyst are separately added to the fluoropolymer composition.28. A method according to claim 25 wherein the step of curing further comprises press-curing and optionally post-curing.29. A cured article prepared according to the method of claim 25.30. A method for increasing the induction period in a curable perfluoropolymer composition comprising the steps of:a) providing a perfluoropolymer comprising interpolymerized units derived from a nitrogen-containing cure site monomer; and b) incorporating, into the fluoropolymer, a nonfluorinated catalyst composition that consists essentially of a compound having the general formula: {RA}(?n){QR′k(+)}n or the precursors thereof added separately or as a mixture, wherein R is hydrogen, a C1-C20 alkyl or alkenyl, a C3-C20 cycloalkyl or cycloalkenyl or a C6-C20 aryl or alkylaryl; {RA}(?n) is an acid anion or an acid derivative anion; n is the number of A groups in the anion; Q is P, S, N, As, or Sb; each R′ is, independently, hydrogen or a substituted or unsubstituted C1-C20 alkyl, aryl, aralkyl, or alkenyl group, provided that when Q is N and the only fluoropolymer in the composition consists essentially of a terpolymer of TFE, a perfluorovinylether, and a perfluorovinylether cure site monomer comprising a nitrile group, not every R′ is H; and k is one greater than the valence of Q; and, optionally, an additional curative material selected from the group consisting of: ammonium salts, ammonia-generating compounds, substituted triazine derivatives, unsubstituted triazine derivatives, bis-amidooximes, and organotin compounds; and optionally a coagent. 31. The method of claim 30 further comprising the step of incorporating an alcohol of the general formula R2?OH, wherein R2 is a C1-C20 alkyl group, and wherein R2 is optionally partially fluorinated.32. The method of claim 30 further comprising:c) shaping the composition; d) optionally curing the shaped composition; and e) optionally heat aging the cured composition. 33. The method of claim 32 wherein the step of curing comprises press-curing, and optionally post-curing.34. A shaped article prepared according to the method of claim 30.35. A composition comprising:(a) a perfluoropolymer comprising interpolymerized units derived from a nitrogen-containing cure site monomer; (b) a non-fluorinated catalyst composition selected from the group consisting of tributyl-(2-methoxy)-propyl phosphonium benzoate, tetrabutyl phosphonium carbonate, optionally (c) an alcohol of the general formula R2?OH, wherein R2 is an alkyl group having from 1 to 20 carbon atoms, and wherein R2 is optionally partially fluorinated; and optionally (d) a filler selected from fluoropolymer filler, carbon black, and combinations thereof.
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