초록 ▼

Fluoroelastomers, curable by peroxidic route, obtainable by polymerizing the following monomers: a) C2-C8 hydrogenated fluoroolefins; b) fluorovinylethers of general formula: description="In-line Formulae" end="lead"CFX═ CXOCF2OR (I)description="In-line Formulae" end="tail" c) bis-olefins h

Fluoroelastomers, curable by peroxidic route, obtainable by polymerizing the following monomers: a) C2-C8 hydrogenated fluoroolefins; b) fluorovinylethers of general formula: description="In-line Formulae" end="lead"CFX═ CXOCF2OR (I)description="In-line Formulae" end="tail" c) bis-olefins having general formula: description="In-line Formulae" end="lead"RI 1RI2C═CRI3--Z--CR I4═CRI5RI6 (IA) description="In-line Formulae" end="tail" and optionally: d) one or more fluorinated olefinic comonomers selected from perfluoroalkylvinylethers (PAVE) CF2═CFOR2 f, perfluorooxyalkylvinylethers CF2═CFOXa, e) C2-C8 perfluorolefins; f) one or more C2-C8 non fluorinated olefinic comonomers said fluoroelastomers comprising iodine and/or bromine atoms in the chain and/or in end position.

대표청구항 ▼

The invention claimed is: 1. Curable fluoroelastomers having good properties at low temperature, in particular a lower Tg and high resistance to low temperatures (TR10), said fluoroelastomers comprising units derived from the following monomers: a) vinylidene fluoride VDF b) fluorovinylethers of ge

The invention claimed is: 1. Curable fluoroelastomers having good properties at low temperature, in particular a lower Tg and high resistance to low temperatures (TR10), said fluoroelastomers comprising units derived from the following monomers: a) vinylidene fluoride VDF b) fluorovinylethers of general formula: description="In-line Formulae" end="lead"CFX═ CXOCF2OR (I)description="In-line Formulae" end="tail" wherein R is: C2-C6 linear or branched (per)fluoroalkyl, C5-C6 cyclic (per)fluoroalkyl, or C2-C6 linear or branched (per)fluoro oxyalkyl, containing from one to three oxygen atoms, and X=F, H; c) bis-olefins having general formula: description="In-line Formulae" end="lead"RI 1RI2C═CRI3--Z--CR I4═CRI5RI6 (IA) description="In-line Formulae" end="tail" wherein RI1, RI2, RI 3, RI4, RI5, RI6 equal to or different from each other, are H or C1-C5 alkyl; Z is a C1-C18 linear or branched alkylene or C4-C18 cycloalkylene radical, optionally containing oxygen atoms or a (per)fluoropolyoxyalkylene radical; d) optionally, one or more fluorinated olefinic comonomers selected from the following: (per)fluoroalkylvinylethers (PAVE) CF2═CFOR 2f, wherein R2f is a C1-C6 perfluoroalkyl; (per)fluoro-oxyalkylvinylethers CF2═CFOX a, wherein Xa is a C1-C12 alkyl, or a C1-C12 oxyalkyl, or a C1-C12 (per) fluoro-oxyalkyl having one or more ether groups; e) optionally, C2-C8 perfluoroolefins; f) optionally, one or more C2-C8 non fluorinated olefinic comonomers; said fluoroelastomers comprising iodine and/or bromine atoms in the chain and/or in end position, said halogen atoms deriving from "cure site" comonomers and/or from chain transfer agents used in polymerization. 2. Fluoroelastomers according to claim 1, wherein the fluorovinylethers component b) have general formula: description="In-line Formulae" end="lead"CFX═ CXOCF2OCF2CF2Y (II)description="In-line Formulae" end="tail" wherein Y=F, OCF3; X as above. 3. Fluoroelastomers according to claim 2, wherein the perfluorovinylethers have the following formulas: description="In-line Formulae" end="lead"CF2 ═CFOCF2OCF2CF3 (MOVE 1)description="In-line Formulae" end="tail" description="In-line Formulae" end="lead"CF2 ═CFOCF2OCF2CF2OCF3 (MOVE 2).description="In-line Formulae" end="tail" 4. Fluoroelastomers according to claim 3, wherein the perfluorovinylether is CF2═CFOCF2OCF2 CF3 (MOVE 1). 5. The curable fluoroelastomers of claim 1, wherein the C 4-C18 cycloalkylene radical is partially fluorinated. 6. Fluoroelastomers according to claim 1, wherein in formula (IA) of the bis-olefin component c) RI1, RI 2, RI3, RI4, RI 5, RI6, are hydrogen and Z is a C4-C 12 perfluoro-alkylene radical or a (per)fluoropolyoxyalkylene radical of formula: description="In-line Formulae" end="lead"--(Q) p--CF2O--(CF2CF2O)ma(CF2 O)na--CF2--(Q)p--(IIA)description="In-line Formulae" end="tail" wherein: Q is a C1-C10 alkylene or oxyalkylene radical; p is zero or 1; ma and na are numbers such that the ma/na ratio is from 0.2 to 5; the molecular weight of the (per)fluoropolyoxyalkylene radical of formula (IIA) being from 500 to 10,000. 7. The fluoroelastomers of claim 6, wherein Q is--CH 2OCH2--or--CH2O(CH2CH2O) sCH2--, wherein s is an integer from 1 to 3". 8. The fluoroelastomers of claim 6, wherein the molecular weight of the (per)fluoropolyoxyalkylene radical of formula (IIA) is from 1,000 to 4,000. 9. Fluoroelastomers according to claim 6, wherein the bis-olefin has formula: description="In-line Formulae" end="lead"CH2 ═CH--(CF2)t0--CH═CH2 description="In-line Formulae" end="tail" wherein t0 is an integer from 6 to 10. 10. The curable fluoroelastomers of claim 1, wherein the C1-C6 (per)fluoroalkyl of the optional one or more fluorinated olefinic comonomers is selected from the group consisting of trifluoromethyl and heptafluoropropyl; the C1-C12 (per)fluoro-oxyalkyl of the optional one or more fluorinated olefinic comonomers is perfluoro-2-propoxy-propyl; the optional C2-C8 perfluoroolefins are selected from the group consisting of tetrafluoroethylene (TFE), hexafluoropropene (HFP), and chlorotrifluoroethylene (CTFE); and the optional one or more C2-C8 non-flourinated olefinic comonomers are selected from the group consisting of ethylene propylene and isobutene. 11. Fluoroelastomers according to claim 1, wherein the brominated and/or iodinated "cure site" comonomers are selected from the following: C2-C10 bromo and/or iodo olefins, containing at least one bromine and/or iodine atom, C1-C10 linear or branched (per) fluoroalkylvinylethers and/or (per)fluorooxyalkylvinylethers containing at least one iodine and/or bromine atom. 12. The fluoroelastomers of claim 11, wherein the C2-C10 bromo and/or iodo olefins contain from one to three bromine and/or iodine atoms. 13. Fluoroelastomers according to claim 11, containing iodine atoms in the chain and/or in end position. 14. Fluoroelastomers according to claim 1, wherein iodinated and/or brominated chain transfer agents are selected from the following: p1 compounds of formula Rbf(I)x(Br) y, wherein Rbf is a (per)fluoroalkyl or a (per) fluorochloroalkyl having from 1 to 8 carbon atoms, while x and y are integers between 0 and 2, with 1<x+y<2; iodides and/or bromides of alkaline or alkaline-earth metals. 15. Fluoroelastomers according to claim 1, wherein the optional component d) is perfluoromethylvinylether (MVE) CF2 ═CF--O--CF3. 16. Fluoroelastomers according to claim 1, wherein the amount of units deriving from the fluorovinylether component b) is higher than 15% by moles. 17. The fluoroelastomers according to claim 16, wherein the amount of units deriving from the fluorovinylether component b) is higher than 17% by moles. 18. Fluoroelastomers according to claim 1, wherein the total amount of units deriving from the fluorovinylether component b), from the optional monomers component d), from HFP and CTFE (component e), is higher than 15%. 19. The fluoroelastomers according to claim 18, wherein the total amount of units deriving from the fluorovinylether component b), from the optional monomers component d), from HFP and CTFE (component e), is higher than 17% by moles. 20. Fluoroelastomers according to claim 1, wherein the amount of units in the chain deriving from the bis-olefin component c) is from 0. 01% to 2.0% by moles. 21. The fluoroelastomers according to claim 20, wherein the amount of units in the chain deriving from the bis-olefin component c) is from 0.05% to 0.8% by moles. 22. Fluoroelastomers according to claim 1, wherein the amount of units deriving from brominated and/or iodinated "cure-site" comonomers is from 0% to 5% by moles, the iodine and/or bromine amount from transfer agent present in the chain end groups is from 0% to 2% by weight. 23. Fluoroelastomers according to claim 22, wherein the total amount of iodine and/or bromine present in the polymer is in the range 0. 05% to 4% by weight. 24. The fluoroelastomers according to claim 22, wherein the iodine and/or bromine amount from transfer agent present in the chain end groups is from 0.05% to 0.8% by weight. 25. Fluoroelastomers according to claim 1, having the following monomeric composition, in % by moles: VDF 5-85 component b) 1-45 component c) 0.01-2 iodine amount (as % by weight) 0.05-0.6 component d) 0-45 component e) 0-60 component f) 0-40 the sum of the molar percentages of component b)+component d)+ component e) when component e) is different from TFE, being higher than 15%, and the sum of the molar percentages of the monomers being equal to 100%. 26. Fluoroelastomers according to claim 25, having the following monomeric composition, in % by moles: VDF 20 to 85 component b) 5 to 40 component c) 0.01 to 2 iodine amount (as % by weight) 0.05 to 0.6 component d) 5 to 30 component e) 0 to 60 component f) 5 to 20 the sum of the molar percentages of component b) +component d) +component e) when component e) is different from TFE, being higher than 17%, and the sum of the molar percentages of the monomers being equal to 100%. 27. Blends curable by peroxidic route containing the fluoroelastomers according to claim 1; and (A) curing coagents, in an amount in the range 0.5% to 10% by weight with respect to the polymer; (B) optionally a metal compound, in an amount in the range 0% to 15%, selected from oxides and hydroxides of divalent metals, optionally combined with a weak acid salt of Ba, Na, K, Pb, Ca; (C) optionally acid acceptors, in an amount from 0% to 10% by weight with respect to the polymer, of the non metal oxide type; (D) optionally additives, the amount of each of said additives being between 0% and 10% by weight with respect to the polymer; (E) optionally fillers in amounts from 0% to 80% by weight with respect to the polymer. 28. Blends curable by peroxidic route containing the fluoroelastomers according to claim 27; and (A) curing coagents, in an amount in the range 0.5% to 10% by weight with respect to the polymer; (B) optionally a metal compound selected from oxides and hydroxides of Mg, Zn, Ca or Pb, optionally combined with stearates, benzoates, carbonates, oxalates or phosphites of Ba, Na, K, Pb, or Ca; (C) optionally acid acceptors selected from 1,8-bis(dimethylamino)naphthalene or octadecylamine; (D) optionally additives selected from thickeners, pigments, antioxidants, or stabilizers; (E) optionally a filler selected from carbon black, silica, barium sulphate, titanium dioxide, or semicrystalline fluoropolymers in amounts from 15% to 50% by weight with respect to the polymer. 29. Fluoroelastomers according to claim 1 cured by ionic route. 30. Fluoroelastomers cured according to claim 1. 31. Manufactured articles obtained from fluoroelastomers according to claim 27.