CN1108263A - 含有源自二烯烃的单体单元的新的含氟弹性体 - Google Patents
含有源自二烯烃的单体单元的新的含氟弹性体 Download PDFInfo
- Publication number
- CN1108263A CN1108263A CN94119959A CN94119959A CN1108263A CN 1108263 A CN1108263 A CN 1108263A CN 94119959 A CN94119959 A CN 94119959A CN 94119959 A CN94119959 A CN 94119959A CN 1108263 A CN1108263 A CN 1108263A
- Authority
- CN
- China
- Prior art keywords
- fluoroelastomer
- tfe
- entirely
- vdf
- pave
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 32
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 30
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 18
- 229910052740 iodine Inorganic materials 0.000 claims description 18
- 239000011630 iodine Substances 0.000 claims description 16
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 13
- 150000002978 peroxides Chemical class 0.000 claims description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 125000001246 bromo group Chemical group Br* 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- 125000001118 alkylidene group Chemical group 0.000 claims description 7
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 7
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 6
- -1 fluoroalkyl vinyl ether Chemical compound 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 25
- 238000003490 calendering Methods 0.000 abstract description 4
- 238000004073 vulcanization Methods 0.000 abstract description 3
- 238000001746 injection moulding Methods 0.000 abstract description 2
- 238000001125 extrusion Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 25
- 239000000126 substance Substances 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000004530 micro-emulsion Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 239000012986 chain transfer agent Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000004160 Ammonium persulphate Substances 0.000 description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 12
- 235000019395 ammonium persulphate Nutrition 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000003999 initiator Substances 0.000 description 10
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000005189 flocculation Methods 0.000 description 7
- 230000016615 flocculation Effects 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000004816 latex Substances 0.000 description 6
- 229920000126 latex Polymers 0.000 description 6
- 238000012423 maintenance Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005987 sulfurization reaction Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002083 iodinating effect Effects 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 1
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical compound CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UZVATUMAIUENKR-UHFFFAOYSA-N NClCC1=CC=CC=C1 Chemical compound NClCC1=CC=CC=C1 UZVATUMAIUENKR-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001616 alkaline earth metal bromide Inorganic materials 0.000 description 1
- 229910001619 alkaline earth metal iodide Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical class [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- RUFWIGMRKSSQJC-UHFFFAOYSA-N benzene-1,2,3,4,5-pentol Chemical class OC1=CC(O)=C(O)C(O)=C1O RUFWIGMRKSSQJC-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- ODCCJTMPMUFERV-UHFFFAOYSA-N ditert-butyl carbonate Chemical compound CC(C)(C)OC(=O)OC(C)(C)C ODCCJTMPMUFERV-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000005816 fluoropropyl group Chemical group [H]C([H])(F)C([H])([H])C([H])([H])* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- WRIRWRKPLXCTFD-UHFFFAOYSA-N malonamide Chemical compound NC(=O)CC(N)=O WRIRWRKPLXCTFD-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 description 1
- JPQBRSQJGWOTGC-UHFFFAOYSA-N methyl(silyloxysilyloxy)silane Chemical class C[SiH2]O[SiH2]O[SiH3] JPQBRSQJGWOTGC-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- VBQCHPIMZGQLAZ-UHFFFAOYSA-N phosphorane Chemical class [PH5] VBQCHPIMZGQLAZ-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000002426 superphosphate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert-Butyl hydroperoxide Substances CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
- C08F291/02—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to elastomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/184—Monomers containing fluorine with fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
- C08F214/222—Vinylidene fluoride with fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
- Graft Or Block Polymers (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明描述了包含源自通式(I)二烯烃单体单
元的新的含氟弹性体。该产物尤其在硫化混合物的
压延过程中具有改善的可加工性,并且具有优异的力
学性能和挤出和注塑时的可加工性,易于脱模。式
(I)如下,其中各取代基定义见说明书。
Description
本发明涉及具有改善的可加工性和很好的力学性能和高弹性的新含氟弹性体。
本领域已知多种含氟弹性体。它们被广泛地应用于既需要很好的弹性又需要高的热化学稳定性的所有场含。对这些产品的广泛的综述可参见例如“Ullman′s Encyclopedca of Industrial Chemistry”,Vol.A-11,pp.417-429(1988,VCH Verlagsgesellschaft)。
含氟弹性体的硫化可用离子或过氧化物进行。就前者而言,是将适宜的硫化剂(例如多羟基化合物)与促进剂(例如四烷基铵盐)一起加到含氟弹性体中。就过氧化物硫化而言,聚合物必须包含能够在过氧化物的存在下生成自由基的硫化部位。为此,可将含有碘和/或溴的“硫化部位(cure-site)”的单体引入聚合物链中,如US-4,035,565,US-4,745,165和EP-199,138所述;或者在聚合过程中可以使用含有碘和/或溴的链转移剂,这样便可生成碘化和/或溴化的端基(参见例如US-4,243,770和US5,173,553)。
在硫化混合物的配制过程中常常遇到的问题是可加工性差,尤其是在需要较长时间的压延时可加工性差,特别是要将添加剂和填料混入混合物时,更是如此。所谓“添加剂”是指所有那些加到硫化混合物中起硫化剂、抗氧剂、稳定剂等作用的物质;而“填料”通常是指起颜料、增稠剂、增强剂、增塑剂等作用的物质(炭黑、二价金属氧化物和氢氧化物、硅、滑石粉等)。
人们知道,具有宽分子量分布的聚合物通常表现出较好的可加工性,因此,通过用聚合过程参数来改变含氟弹性体的分子量分布,尤其是用引发剂和链转移剂的送入反应器的数量和方式来改变分子量分布,则有可能克服上述缺陷。然而,这些手段将促使产物显示出明显的挤出膨胀现象,可用Garvey速率测定出来。
人们知道,通过适当地混合分子量分布不同的聚合物可以改善含氟弹性体的可加工性。但是这将除了有挤出膨胀现象外,还不可避免地使最终产品的力学性能和可模塑性变差。
本申请人现在惊异地发现,有可能获得具有改善的可加工性(尤其是在压延硫化混合物时的可加工性)以及很好的挤出和注塑时的力学性能和加工性能并具有很好的脱模性的新的含氟弹性体。通过向聚合物链中引入少量结构如下文定义的二烯烃便可获得所述效果。
因此,本发明的目的是提供一种含氟弹性体,它包含源自通式如下的二烯烃单体单元:
式中:
R1,R2,R3,R4,R5和R6彼此相同或不同,是H或C1-C5烷基;
Z是C1-C18亚烷基或亚环烷基,它们可以是直链或支链的,并可选地
含有氧原子,最好是至少部分氧化的;
或者Z是(全)氟聚氧化亚烷基;
在式(Ⅰ)中,Z是优选C4-C12全氟亚烷基,更优选C4-C8全氟亚烷基,而R1,R2,R3,R4,R5,R6优选为氢。
当Z是(全)氟聚氧化亚烷基时,它优选具有下式结构;
式中:Q是C1-C10亚烷基或氧化亚烷基;p是0或1;m和n是整数,其取值应使m/n比率在0.2-5之间并且使所述(全)氟聚氧化亚烷基的分子量在500-10,000之间,优选在1000-4000之间。Q优选-CH2OCH2-;-CH2O(CH2CH2O)5CH2-,S=1-3。
Z是亚烷基或亚环烷基的式(Ⅰ)二烯烃可按照I.L.Knunyants等人,Izv.Akad.Nauk.SSSR,Ser.Khim.,1964(2),384-6所述的方法制备;而含有(全)氟聚氧化亚烷基序列的二烯烃的制备方法可参见US-3,810,874所述。
源自这样的二烯烃的单元在链中的含量,按照每100mol其它基础单体单元计算,通常为0.01-1.0mol,优选0.03-0.5mol,更优选0.05-0.2mol。
含氟弹性体的基础结构尤其可选自:
(1)基于VOF的共聚物,其中VDF与至少一种选自下列化合物的共聚单体共聚:C2-C8全氟烯烃,如四氟乙烯(TFE)、六氟丙烯(HFP);C2-C8氯和/或溴和/或碘氟烯烃,如一氯三氟乙烯(CTFE)和一溴三氟乙烯;(全)氟烷基乙烯基醚(PAVE)CF2=CFORf,其中Rf是C1-C6(全)氟烷基;例如三氟甲基、一溴二氟甲基、五氟丙基;全氟-烷氧基乙烯基醚CF2=CFOX,其中X是具有一个或多个醚基团的C1-C12全氟烷氧基;例如全氟-2-丙氧基丙基;C2-C8非氟代烯烃(Ol),例如乙烯和丙烯;
(2)基于TFE的共聚物,其中TFE与至少一种选自下列化合物的共聚单体共聚:(全)氟烷基乙烯基醚(PAVE)CF2=CFORf,其中Rf定义如上;全氟-烷氧基乙烯基醚CF2=CFOX,其中X定义如上;含有氢和/或氯和/溴和/或碘原子的C2-C8氟化烯烃,C2-C8非氟代烯烃。
在上文定义的各类化合物中,优选的基础单体如下(摩尔%):
(a)VDF 45-85%,HFP 15-45%,0-30% TFE;(b)VDF 50-80%,PAVE 5-50%,TFE 0-20%;(c)VDF 20-30%,ol 10-30%,HFP and/or PAVE 18-27%,TFE 10-30%;(d) TFE 50-80%,PAVE 20-50%;(e)TFE 45-65%,ol 20-55%,0-30% VDF;(f)TFE 32-60%,ol 10-40%,PAVE 20-40%;(g)TFE 33-75%,15-45% PAVE,10-22% VDF.
重要的是,必须指出,对于适氧化物可硫化含氟弹性体来说,加入少量本发明的二烯烃可获得更进一步的突出优点。人们的确知道,为了达到较好的硫化水平,必须尽可能增加每条链上活性部位的数量,即碘和/溴的量。为此目的,我们可以努力增加碘化和/或溴化链转移剂的量,同时尽可能避免反应速率降低。除了该方法包含的操作困难之外,每条链上碘和/或溴原子的数目最多为两个,因为本领域已知的链转移剂最多含有两个碘和/或溴原子。实际上,从未达到过该理论极限,因为不可能在不引起反应速率的不可接受的降低的同时,将链转移剂/引发剂之经提高到超过一定的限度。按照该方法,通过每条链上最多只能获得1.8个碘和/或溴原子。因此,最终产物的硫化水平对于许多需要高弹性的应用场合显得不足。例如,该产物的压缩形变通常至少为28-30%(按照标准ASTM D395,方法B,在200℃下70小时测定)。
将本发明的工作实施例与下文报导的比较例比较,显然引入少量本发明的二烯烃可使产物发生一种预硫化(所达到的高分子量便是证明);对于过氧化物硫化的情况,使得与未使用本发明二烯烃制备的同一聚合物相比每条链终端碘和/溴的量显著地增加。因此,能够达到高的硫化水平,从而达到低的压缩形变值。例如,用于O型环来说,压缩形变值通常低于25%(按照标准ASTM D395方法B,在200℃下70小时测定)。
本发明的目标含氟弹性体的制备方法如下:按照本领域熟知的方法,在自由基引发剂(例如碱金属或铵的过硫酸盐、过磷酸盐、过硼酸盐或过碳酸盐)及可选的铁、铜或银盐或其它易氧化金属的存在下,在水性乳液中将单体共聚合。在反应介质中,通常还加有各种表面活性剂,其中特别优选下式氟代表面活性剂:
Rf-X-M+
式中Rf是C5-C16(全)氟烷基链或(全)氟聚氧化亚烷基链,X-是-COO-或-SO- 3,M+选自H+,NH+ 4和碱金属离子。其中最常用的有:全氟辛酸铵、带有一个或多个羧端基的(全)氟聚氧化亚烷基等。
加到反应混合物中的二烯烃的量取决于期望的最终产物中源自二烯烃的单元的数量,要记住的是,若以本发明目的而采用的量较少,则实际上反应介质中所有的二烯烃都将进入大分子链中。
聚合反应完成后,用常规方法如加入电解质或冷却絮凝的方法将含氟弹性体从乳液中分离出来。
或者,可按照熟知的技术进行本体聚合或者在包含适当自由基引发剂的有机液体中进行悬浮聚合。
聚合反应通常在不超过10MPa的压力下于25-150℃的温度下进行。
本发明的目标含氟弹性体的制备最好是按照US-4,789,717和US-4,864,006所述,在全氟聚氧化亚烷基的乳液、分散液或微乳液的存在下以水性乳液的方式进行聚合。
本发明的目标含氟弹性体优选用过氧化物硫化,因而最好在大分子链中和/或端基中含有碘和/或溴原子。可以这样引入所述碘和/或溴原子:向反应混合物中加进溴化和/或碘化的“硫化部位”共聚单体,如具有2-10个碳原子的溴代和/或碘代烯烃(参见例如US-4,035,565和US-4,694,045所述),或碘和/或溴氟烷基乙烷基醚(参见US-4,745,165,US-4,564,662和EP-199,138所述),其用量通常应使最终产物中“硫化部位”共聚单体的含量为每100mol其它基础单体单元0.05-2mol。
或者,可以与“硫化部位”共聚单体一起引进端基碘和/或溴原子,方法是向反应混合物中加入碘化和/或溴化的链转移剂,例如式Rf(I)x(Br)y化合物,其中Rf是具有1-8个碳原子的(全)氟烷基或(全)氟氯烷基,而x和y是是0-2的整数,且1≤x+y≤2(参见例如US-4,243,770和US-4,943,622)。也可以使用US-5,173,553中所述的碱金属或碱土金属碘化物和溴化物作为链转移剂。
或者,可以与含有碘和/或溴的链转移剂一起使用其它本领域公知的链转移剂,例如乙酸乙酯、丙二酸二乙酯等。
过氧化物硫化按照公知技术通过加入适宜的经加热可产生自由基的过氧化物来进行。在最常用的过氧化物中,我们可以提及:二烷基过氧化物,例如过氧化二叔丁基和2,5-二甲基-2,5-二(叔丁基过氧)己烷;过氧化二枯基;过氧化二苯甲酰;过苯甲酸二叔丁酯;碳酸二[1,3-二甲基-3-(叔丁基过氧化)丁]酯。其它过氧化物体系可参见例如专利申请EP-136,596和EP-410,351。
在硫化混合物中还加有其它物质,例如:
(a)硫化活性助剂,其用量为聚合物的0.5-10%(重量),优选1-7%(重量);其中常用的是:氰尿酸三烯丙酯;异氰尿酸三烯丙酯(TAIC);三(二烯丙胺)-S-三嗪;亚磷酸二烯丙酯;N,N-二烯丙基烯酰胺;N,N,N′,N′-四烯丙基丙二酰胺;异氰尿酸三乙烯酯;2,4,6-三乙烯基甲基三硅氧烷等;特别优选TAIC
(b)金属化合的,其用量为聚合物的1-15%(重量),优选2-10%(重量),它们可选自二价金属的氧化物或氢氧化物,例如Mg,Zn,Ca或Pb的氧化物或氢氧化物,同时可选地与弱酸盐例如Ba,Na,K,Pb,Ca的硬脂酸盐、苯甲酸盐、碳酸盐、草酸盐或亚磷酸盐一起使用;
(c)其它常规添加剂,诸如增稠剂、颜料、抗氧化剂、稳定剂等。
在打算离子硫化本发明的目标含氟弹性体时,除上述(b)项和(c)项所述的化合物外,还向硫化混合物中加入本领域熟知的适宜的硫化剂和促进剂。例如,作为硫化剂,可以使用芳族或脂族多羟基化合物或其衍生物,例如EP-355,705和US-4,233,427所述。其中,我们可特别提及二、三和四羟基苯类、萘类或蒽类;双酚类,其中两个芳族通过脂族、环脂族和芳族二价基团相连,或通过氧或硫原子或者还有羰基相连。所述芳环可以被一个或多个氯、氟、溴原子或被羰基、烷基、酰基取代。
作为促进剂,可以使用例如:季铵盐、季鏻盐、季鉮盐或季锑盐(参见例如EP-335,705和US-3,876,654);氨基鏻盐(参见例如US-4,259,463);正膦类(参见例如US-3,752,787);EP-182,299和EP-120,462所述的亚胺化合物等。
也可以使用混合的离子型或过氧化物型硫化体系,如EP-136,596所述。
现在用下列工作实例来更好地说明本发明,它仅仅是对本发明范围的说明而不是限定。
压延可加工性通过测定炭黑加入时间(BIT),即压延过程中聚合物混入填料所需的时间来评定。所述测定在操作上是用辊子直径为150mm的压延机进行的,辊子上粘附大约0.5kg聚合物。一旦在辊子上形成均匀的聚合物层,便立即加进表中所列量的填料:BIT定义为从填料加入到聚合物层不再从辊子自动脱落所经过的时间。当然,BTT越短,填料混入的速率越高,从而压延加工生产率便越高。
实施例1
将装有在630转/分钟下工作的搅拌器的5升高压釜抽真空,然后充入4升软化水和41.1ml预先制好的全氟聚氧化亚烷基微乳液。所述微乳液是通过将下列物质混合而获得的:
- 8.9ml酸封端的全氟聚氧化亚烷基
CF3O(CF2-CF(CF3)O)n(CF2O)mCF2COOH
式中n/m=10,其中均分子量为600;
- 8.9ml 30%(体积)的NH4OH水溶液;
- 17.8ml软化水;
- 5.5ml下式Galden(R)DO2:
CF3O(CF2-CF(CF3)O)n(CF2O)mCF3
式中n/m=20,其中均分子量为450。
然后,将高压釜加热至85℃,在整个反应过程中保持该温度不变。然后,送入下述单体混合物:
偏氟乙烯(VDF) 14.7%(摩尔)
六氟丙烯(HFP) 78.3%(摩尔)
四氟乙烯(TFE) 7.3%(摩尔)
从而使压力升至22巴。
然后,向高压釜中引入:
- 浓度为50g/l的过硫酸铵(APS)水溶液作为引发剂;添加分10次进行,第一次加30ml,随后,单体转化率每增加10%则每次加3.4ml;
- 溶液形式的1,4-二碘全氟丁烷(C4F8I2)作为链转移剂,所述溶液通过将4.26ml碘化产物溶解在45.74ml上面制备微乳液所用的Galden(R)DO2中制得;添加分20次进行,每次2.5ml,从开始聚合起,单体转化率每增加5%便添加一次;
- 溶液形式的式CH2=CH-(CF2)6-CH=CH2二烯烃,所述溶液通过将2.5ml该二烯烃溶解在45.5ml上面所述的Galden(R)DO2中制得;添加分20次进行每次2.5ml,从开始聚合起,单体转化率每增加5%便添加一次;
通过送入由下列物质组成的混合物使得在整个聚合过程中保持22巴的压力不变:
VDF 50%(摩尔)
HFP 26%(摩尔)
TFE 24%(摩尔)
反应23分钟后,将高压釜冷却,放出胶乳并将聚合物絮凝、洗涤、干燥。这样便得到622g产物,其特性列于表1中。
聚合物的单体组成用19F-NMR和IR分析测定。含碘百分数用X-射线萤光分析测定。平均分子量Mn(数均)、Mw(重匀)和Mz用凝胶渗透色谱(GPC)测定。渗透压分子量(Mosm)用校准曲线计算。
然后,将聚合物用过氧化物硫化,硫化混合物组成和硫化产物的特性列于表2。
实施例2(比较例)
按照与实施例1所述相同的方法,制备不含所述二烯烃的同一种聚合物。这样制得的产物的特性及经过氧化物硫化的产物的特性分别列于表1和表2。
(*)比较例
n.d.:无法测定
(*)比较例
n.d.:无法测定
实施例3
将装有在630转/分钟下工作的搅拌器的5升高压釜抽真空,然后充入3.5升软化水和36.0ml预先制好的全氟聚氧化亚烷基微乳液。所述微乳液是通过将下列物质混合而获得的:
- 7.8ml酸封端的全氟聚氧化亚烷基
CF3O(CF2-CF(CF3)O)n(CF2O)mCF2COOH
式中n/m=10,其中均分子量为600;
- 7.8ml 30%(体积)的NH4OH水溶液;
- 15.6ml软化水;
- 5.5ml下式Galden(R)DO2:
CF3O(CF2-CF(CF3)O)n(CF2O)mCF3
式中n/m=20,其中均分子量为450。
然后,将高压釜加热至80℃,在整个反应过程中保持该温度不变。然后,送入下述单体混合物:
偏氟乙烯(VDF) 45%(摩尔)
全氟甲基乙烯基醚(MVE) 36%(摩尔)
四氟乙烯(TFE) 19%(摩尔)
从而使压力升至22巴。
然后,向高压釜中引入:
- 50ml浓度为2g/l的过硫酸铵(APS)水溶液作为引发剂;一次加完。
- 溶液形式的1,4-二碘全氟丁烷(C4F8I2)作为链转移剂,所述溶液通过将4.26ml碘化产物溶解在45.74ml上面制备微乳液所用的Galden(R)DO2中制得;添加分20次进行,每次2.5ml,从开始聚合起,单体转化率每增加5%便添加一次;
- 溶液形式的式CH2=CH-(CF2)6-CH=CH2二烯烃,所述溶液通过将2.9ml该二烯烃溶解在47.1ml上述的Galden(R)DO2中制得;添加分20次进行每次2.5ml,从开始聚合起,单体转化率每增加5%便添加一次;
通过送入由下列物质组成的混合物使得在整个聚合过程中保持22巴的压力不变:
VDF 58%(摩尔)
MVE 18%(摩尔)
TFE 24%(摩尔)
反应116分钟后,将高压釜冷却,放出胶乳并将聚合物絮凝、洗涤、干燥。这样便得到1500g产物,其特性列于表3中。
然后,将聚合物用过氧化物硫化,硫化混合物组成和硫化产物的特性列于表4。
实施例4(比较例)
按照与实施例3所述相同的方法,制备不含所述二烯烃的同类型聚合物。这样制得的产物的特性及经过氧化物硫化的产物的特性分别列于表3和表4。
(*)比较例
(*)比较例
实施例5
将装有在630转/分钟下工作的搅拌器的5升高压釜抽真空,然后充入3.5升软化水和36.0ml预先制好的全氟聚氧化亚烷基微乳液。所述微乳液是通过将下列物质混合而获得的:
- 7.8ml酸封端的全氟聚氧化亚烷基
CF3O(CF2-CF(CF3)O)n(CF2O)mCF2COOH
式中n/m=10,其中均分子量为600;
- 7.8ml 30%(体积)的NH4OH水溶液;
- 15.6ml软化水;
- 5.5ml下式Galden(R)DO2:
CF3O(CF2-CF(CF3)O)n(CF2O)mCF3
式中n/m=20,其中均分子量为450。
然后,将高压釜加热至80℃,在整个反应过程中保持该温度不变。然后,送入下述单体混合物:
偏氟乙烯(VDF) 27%(摩尔)
全氟丙烯(HFP) 57%(摩尔)
四氟乙烯(TFE) 16%(摩尔)
从而使压力升至25巴。
然后,向高压釜中引入:
- 140ml浓度为1g/l的过硫酸铵(APS)水溶液作为引发剂;一次加完。
- 溶液形式的1,4-二碘全氟丁烷(C4F8I2)作为链转移剂,所述溶液通过将4.4ml碘化产物溶解在50ml上面制备微乳液所用的Galden(R)DO2中制得;探测到聚合开始便一次加完。
- 溶液形式的式CH2=CH-(CF2)6-CH=CH2二烯烃,所述溶液通过将3.7ml该二烯烃溶解在46.3ml上述Galden(R)DO2中制得;添加分20次进行,每次2.5ml,从开始聚合起,单体转化率每增加5%便添加一次;
通过送入由下列物质组成的混合物使得在整个聚合过程中保持25巴的压力不变:
VDF 50%(摩尔)
HFP 26%(摩尔)
TFE 24%(摩尔)
反应130分钟后,将高压釜冷却,放出胶乳并将聚合物絮凝、洗涤、干燥。这样便得到1550g产物,其特性列于表5中。
然后,将聚合物用过氧化物硫化,硫化混合物组成和硫化产物的特性列于表6中。
实施例6(比较例)
按照与实施例5所述相同的方法,用2.6ml碘化的链转移剂制备不含所述二烯烃的同类型聚合物。这样制得的产物的特性及经过氧化物硫化的产物的特性分别于表5和表6。
(*)比较例
(*)比较例
实施例7
将装有在630转/分钟下工作的搅拌器的5升高压釜抽真空,然后充入4.0升软化水和410.1ml预先制好的全氟聚氧化亚烷基微乳液。所述微乳液是通过将下列物质混合而获得的:
- 8.9ml酸封端的全氟聚氧化亚烷基
CF3O(CF2-CF(CF3)O)n(CF2O)mCF2COOH
式中n/m=10,其中均分子量为600;
- 8.9ml 30%(体积)的NH4OH水溶液;
- 17.8ml软化水;
- 5.5ml下式Galden(R)DO2:
CF3O(CF2-CF(CF3)O)n(CF2O)mCF3
式中n/m=20,其中均分子量为450。
然后,将高压釜加热至85℃,在整个反应过程中保持该温度不变。然后,送入下述单体混合物:
偏氟乙烯(VDF) 53.5%(摩尔)
六氟丙烯(HFP) 46.5%(摩尔)
从而使压力升至22巴。
然后,向高压釜中引入:
- 浓度为50g/l的过硫酸铵(APS)水溶液作为引发剂;添加分10次进行,第一次加40.4ml,随后,单体转化率每增加10%则每次加4.4ml;
- 溶液形式的乙酸乙酯作为链转移剂,所述溶液通过将66ml乙酸乙酯溶解在1000ml水中制得,探测到聚合开始便一次加完50ml所述溶液。
- 溶液形式的式CH2=CH-(CF2)6-CH=CH2二烯烃,所述溶液通过将2.5ml该二烯烃溶解在45.5ml上述的Galden(R)DO2中制得;添加分20次进行,每次2.5ml,从开始聚合起,单体转化率每增加5%便添加一次;
通过送入由下列物质组成的混合物使得在整个聚合过程中保持22巴的压力不变:
VDF 78.5%(摩尔)
HFP 21.5%(摩尔)
反应30分钟后,将高压釜冷却,放出胶乳并将聚合物絮凝、洗涤、干燥。这样便得到622g产物,其特性列于表7中。
然后,将聚合物离子硫化,硫化混合物组成和硫化产物的特性列于表8。
实施例8(比较例)
按照与实施例7所述相同的方法,制备不含所述二烯烃的同类型聚合物。这样制得的产物的特性及经离子硫化的产物的特性分别于表7和表8。
(*)比较例
(*)比较例
M1:双酚AF/含氟弹性体(50/50)母料
M2: N,N-二乙基-二苯基苄基-氨基氯/含氟弹性体(30/70)母料。
实施例9
将装有在630转/分钟下工作的搅拌器的5升高压釜抽真空,然后充入3.5升软化水和36.0ml预先制好的全氟聚氧化亚烷基微乳液。所述微乳液是通过将下列物质混合而获得的:
- 7.8ml酸封端的全氟聚氧化亚烷基
CF3O(CF2-CF(CF3)O)n(CF2O)mCF2COOH
式中n/m=10,其中均分子量为600;
- 7.8ml 30%(体积)的NH4OH水溶液;
- 15.6ml软化水;
- 5.5ml下式Galden(R)DO2:
CF3O(CF2-CF(CF3)O)n(CF2O)mCF3
式中n/m=20,其中均分子量为450。
然后,将高压釜加热至80℃,在整个反应过程中保持该温度不变。然后,送入下述单体混合物:
偏氟乙烯(VDF) 30.0%(摩尔)
六氟丙烯(HFP) 54.0%(摩尔)
四氟乙烯(TFE) 16.0%(摩尔)
从而使压力升至21巴。
然后,向高压釜中引入:
- 140ml浓度为1.0g/l的过硫酸铵(APS)水溶液作为引发剂;
- 溶液形式的1,6-二碘全氟己烷(C6F12I2)作为链转移剂,所述溶液通过将5.5ml碘化产物溶解在14.5ml上面制备微乳液所用的Galden(R)DO2中制得;
- 溶液形式的式CH2=CH-(CF2)6-CH=CH2二烯烃,所述溶液通过将2.5ml该二烯烃溶解在47.5ml上述的Galden(R)DO2中制得;添加分20次进行每次2.5ml,从开始聚合起,单体转化率每增加5%便添加一次;
通过送入由下列物质组成的混合物使得在整个聚合过程中保持21巴的压力不变:
VDF 50%(摩尔)
HFP 26%(摩尔)
TFE 24%(摩尔)
反应160分钟后,将高压釜冷却,放出胶乳并将聚合物絮凝、洗涤、干燥。这样便得到1522g产物,其特性列于表9中。
然后,将聚合物用过氧化物硫化,硫化混合物组成和硫化产物的特性列于表10中。
实施例10
将装有在630转/分钟下工作的搅拌器的5升高压釜抽真空,然后充入3.5升软化水和36.0ml实施例9所述的全氟聚氧化亚烷基微乳液。
然后,将高压釜加热至80℃,在整个反应过程中保持该温度不变。然后,送入下述单体混合物:
偏氟乙烯(VDF) 30.0%(摩尔)
六氟丙烯(HFP) 54.0%(摩尔)
四氟乙烯(TFE) 16.0%(摩尔)
从而使压力升至21巴。
然后,向高压釜中引入:
- 140ml浓度为1.0g/l的过硫酸铵(APS)水溶液作为引发剂;
- 溶液形式的1,6-二碘全氟丁烷(C6F12I2)作为链转移剂,所述溶液通过将5.5ml碘化产物溶解在14.5ml上面制备微乳液所用的Galden DO2中制得;
- 溶液形式的式CH2=CH-CH2OCH-CF2O-(CF2CF2O)m(CF2O)n-CF2-CH2OCH2-CH=CH2二烯烃,其中m/n比率为0.5,全氟聚氧化亚烷基基团的分子量为2,000。所述溶液通过将12.0ml该二烯烃溶解在38.0ml上述的Galden(R)DO2中制得;添加分20次进行,每次2.5ml,从开始聚合起,单体转化率每增加5%便添加一次;
通过送入由下列物质组成的混合物使得在整个聚合过程中保持21巴的压力不变:
VDF 50%(摩尔)
HFP 26%(摩尔)
TFE 24%(摩尔)
反应200分钟后,将高压釜冷却,放出胶乳并将聚合物絮凝、洗涤、干燥。这样便得到1589g产物,其特性列于表9中。
然后,将聚合物用过氧化物硫化,硫化混合物组成和硫化产物的特性列于表10。
Claims (13)
1、一种含氟弹性,它包含源自通式(Ⅰ)二烯烃的单体单元,通式(Ⅰ)如下:
式中:
或中:
R1,R2,R3,R4,R5和R6彼此相同或不同,是H或C1-C5烷基;
Z是C1-C18亚烷基或亚环烷基,它们可以是直链或支链的,并可选地
含有氧原子;
或者Z是(全)氟聚氧化亚烷基基团。
2、根据权利要求1的含氟弹性体,其中Z是至少部分氟化的C1-C10亚烷基或氧化亚烷基基团。
3、根据权利要求1的含氟弹性体,其中Z是C4-C12全氟亚烷基基团。
4、根据权利要求1的含氟弹性体,其中Z是式(Ⅱ)(全)氟聚氧化亚烷基基团:
式中:Q是C1-C10亚烷基或氧化亚烷基;p是0或1;m和n是整数,其取值应使m/n比率在0.2-5之间并且使所述(全)氟聚氧化亚烷基基团的分子量在500-10,000之间。
5、根据权利要求4的含氟弹性体,其中Q选自-CH2OCH2-;-CH2O(CH2CH2O)5CH2-,S=1-3。
6、根据上述任一项权利要求的含氟弹性体,其中R1,R2,R3,R4,R5,R6是氢。
7、根据上述任一项权利要求的含氟弹性体,其中源自所述二烯烃的单体单元的含量为每100mol其它基础单体单元0.01-1.0mol。
8、根据权利要求7的含氟弹性体,其中源自所述二烯烃的单体单元的含量为每100mol其它基础单体单元0.03-0.5mol。
9、根据权利要求1的含氟弹性体,其中单体结构是基于偏氟乙烯(VDF)与至少一种下述单体共聚的共聚结构:C2-C8全氟烯烃;C2-C8氯和/或溴和/或碘氟烯烃;(全)氟烷基乙烯基醚(PAVE)CF2=CFORf,其中Rf是C1-C6(全)氟烷基;全氟-烷氧基乙烯基醚CF2=CFOX,其中X是具有一个或多个醚基团的C1-C12全氟烷氧基;C2-8非氟代烯烃(O1)。
10、根据权利要求9的含氟弹性体,其中基础单体结构选自(摩尔百分数):
(a)VDF 45-85%,HFP 15-45%,TFE 0-30%;(b)VDF 50-80%,PAVE 5-50%,TFE 0-20%;(c)VDF 20-30%,ol 10-30%,HFP和/或 PAVE 18-27%,TFE 10-30%.
11、根据权利要求1的含氟弹性体,其中单体结构是基于四氟乙烯(TFE)与至少一种下述共聚单体的共聚结构:(全)氟烷基乙烯基醚(PAVE)CF2=CFORf,其中Rf是C1-C6(全)氟烷基;全氟-烷氧基乙烯基醚CF2=CFOX,其中X是具有一个或多个醚基团的C1-C12全氟-烷氧基;含有氢和/或氯和/或溴和/或碘原子的C2-C8氟代烯烃,C2-C8非氟代烯烃。
12、根据权利要求11的含氟弹性体,其中基础单体结构选自(摩尔百分数):
(d) TFE 50-80%,PAVE 20-50%;(e)TFE 45-65%,ol 20-55%,0-30% VDF;(f)TFE 32-60%,ol 10-40%,PAVE 20-40%;(g)TFE 33-75%,15-45% PAVE,10-22% VDF.
13、根据上述任一项权利要求的含氟弹性体,其中,碘和/或溴原子位于大分子链中和/或链端,可用过氧化物硫化。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITMI93A002750 | 1993-12-29 | ||
IT93MI002750A IT1265461B1 (it) | 1993-12-29 | 1993-12-29 | Fluoroelastomeri comprendenti unita' monomeriche derivanti da una bis-olefina |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1108263A true CN1108263A (zh) | 1995-09-13 |
CN1053200C CN1053200C (zh) | 2000-06-07 |
Family
ID=11367423
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN94119959A Expired - Lifetime CN1053200C (zh) | 1993-12-29 | 1994-12-29 | 含有源自二烯烃的单体单元的含氟弹性体 |
Country Status (12)
Country | Link |
---|---|
US (1) | US5585449A (zh) |
EP (2) | EP0661304B1 (zh) |
JP (1) | JP3574198B2 (zh) |
KR (1) | KR100359143B1 (zh) |
CN (1) | CN1053200C (zh) |
AT (2) | ATE186309T1 (zh) |
BR (1) | BR9405300A (zh) |
CA (1) | CA2139260C (zh) |
DE (2) | DE69421553T2 (zh) |
IT (1) | IT1265461B1 (zh) |
RU (1) | RU2136702C1 (zh) |
TW (1) | TW287172B (zh) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101835841B (zh) * | 2007-08-29 | 2012-12-26 | 索维索莱克西斯公开有限公司 | (全)氟弹性体组合物 |
CN103038266A (zh) * | 2010-08-02 | 2013-04-10 | 3M创新有限公司 | 包含改性剂和碘或溴端基的可过氧化物固化的含氟弹性体 |
CN103890021A (zh) * | 2011-06-09 | 2014-06-25 | 索尔维特殊聚合物意大利有限公司 | 超支化的氟弹性体添加剂 |
CN108137723A (zh) * | 2015-10-01 | 2018-06-08 | 旭硝子株式会社 | 含氟弹性共聚物、其制造方法、交联橡胶及其制造方法 |
CN108291069A (zh) * | 2015-11-19 | 2018-07-17 | 旭硝子株式会社 | 含有含氟共聚物的交联性组合物、交联物及半导体制造装置用密封材料 |
CN109715718A (zh) * | 2016-07-18 | 2019-05-03 | 索尔维特殊聚合物意大利有限公司 | 氟弹性体组合物 |
CN117534929A (zh) * | 2023-12-18 | 2024-02-09 | 上海芯密科技有限公司 | 一种低腐蚀性含氟密封圈组合物及其制备方法 |
Families Citing this family (171)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1273608B (it) * | 1995-04-28 | 1997-07-08 | Ausimont Spa | Fluoroelastomeri sostanzialmente privi di terminali polari e relativo processo di preparazione |
JP3178312B2 (ja) * | 1995-10-13 | 2001-06-18 | 日本メクトロン株式会社 | フルオロエラストマーおよびその架橋性組成物 |
IT1276979B1 (it) * | 1995-10-20 | 1997-11-03 | Ausimont Spa | Composizioni fluoroelastomeriche |
IT1276980B1 (it) * | 1995-10-20 | 1997-11-03 | Ausimont Spa | Composizioni fluoroelastomeriche |
IT1286042B1 (it) * | 1996-10-25 | 1998-07-07 | Ausimont Spa | O-rings da fluoroelastomeri vulcanizzabili per via ionica |
US6087406A (en) * | 1997-03-12 | 2000-07-11 | Dyneon Llc | Recycle of vulcanized fluorinated elastomers |
IT1292391B1 (it) * | 1997-06-20 | 1999-02-08 | Ausimont Spa | Elastomeri termoplastici |
US6239223B1 (en) | 1997-09-05 | 2001-05-29 | Chemfab Corporation | Fluoropolymeric composition |
US6703461B1 (en) * | 1998-03-25 | 2004-03-09 | Daikin Industries, Ltd. | Method of reducing metal content in fluoroelastomer |
IT1301780B1 (it) * | 1998-06-23 | 2000-07-07 | Ausimont Spa | Fluoroelastomeri vulcanizzabili per via perossidica |
IT1308627B1 (it) | 1999-02-23 | 2002-01-09 | Ausimont Spa | Composizioni fluoroelastomeriche. |
CA2377410A1 (en) | 1999-07-02 | 2001-01-11 | Dyneon Llc | Fluoroelastomer compositions and articles made therefrom |
US6720360B1 (en) | 2000-02-01 | 2004-04-13 | 3M Innovative Properties Company | Ultra-clean fluoropolymers |
US6593416B2 (en) | 2000-02-01 | 2003-07-15 | 3M Innovative Properties Company | Fluoropolymers |
IT1318488B1 (it) * | 2000-04-21 | 2003-08-25 | Ausimont Spa | Fluorovinileteri e polimeri da essi ottenibili. |
IT1318487B1 (it) * | 2000-04-21 | 2003-08-25 | Ausimont Spa | Fluoroelastomeri. |
US7534845B2 (en) | 2000-04-21 | 2009-05-19 | Solvay Solexis S.P.A. | Fluorovinyl ethers and polymers obtainable therefrom |
IT1318594B1 (it) * | 2000-06-23 | 2003-08-27 | Ausimont Spa | Processo di polimerizzazione di monomeri solfonici. |
IT1318593B1 (it) | 2000-06-23 | 2003-08-27 | Ausimont Spa | Ionomeri fluorurati. |
EP1167441B1 (en) | 2000-06-29 | 2015-07-29 | 3M Innovative Properties Company | Fluoroelastomer composition comprising a mineral oil |
IT1318669B1 (it) | 2000-08-08 | 2003-08-27 | Ausimont Spa | Ionomeri fluorurati solfonici. |
JP3742861B2 (ja) * | 2000-08-29 | 2006-02-08 | ダイキン工業株式会社 | 硬化性含フッ素ポリマー、それを用いた硬化性樹脂組成物および反射防止膜 |
DE60133019T2 (de) | 2000-09-18 | 2009-02-19 | 3M Innovative Properties Co., Saint Paul | Metallaminkomplex enthaltende fluorpolymer- zusammensetzungen |
EP1353998B1 (en) | 2000-12-01 | 2005-09-14 | 3M Innovative Properties Company | Curable fluoroelastomer compositions comprising hydro siloxanes or hydro silazanes |
US6730760B2 (en) | 2001-01-31 | 2004-05-04 | 3M Innovative Properties Company | Perfluoroelastomers having a low glass transition temperature and method of making them |
US6890995B2 (en) * | 2001-01-31 | 2005-05-10 | 3M Innovative Properties Company | Fluoropolymer compositions |
US6844388B2 (en) | 2001-04-12 | 2005-01-18 | 3M Innovative Properties Company | Fluoropolymer compositions containing a nitrogen cure site monomer |
US6803425B2 (en) | 2001-04-12 | 2004-10-12 | 3M Innovative Properties Company | Fluoropolymers having pendant imidate structures |
US6794457B2 (en) * | 2001-04-30 | 2004-09-21 | 3M Innovative Properties Company | Fluoropolymer curing system containing a nitrogen cure site monomer |
CN1256355C (zh) | 2001-05-02 | 2006-05-17 | 3M创新有限公司 | 制备氟聚合物的无乳化剂水乳液聚合方法 |
CA2446014A1 (en) | 2001-05-02 | 2002-11-07 | 3M Innovative Properties Company | Aqueous emulsion polymerization in the presence of ethers as chain transfer agents to produce fluoropolymers |
DE60221066T2 (de) | 2001-05-07 | 2008-03-13 | Solvay Solexis S.P.A. | Amorphe perfluorierte Polymere |
ITMI20011061A1 (it) | 2001-05-22 | 2002-11-22 | Ausimont Spa | Composizioni fluoroelastomeriche |
ITMI20011059A1 (it) | 2001-05-22 | 2002-11-22 | Ausimont Spa | Composizioni fluoroelastomeriche |
ITMI20012165A1 (it) * | 2001-10-18 | 2003-04-18 | Ausimont Spa | Perfluoroelastomeri |
ITMI20012164A1 (it) * | 2001-10-18 | 2003-04-18 | Ausimont Spa | Fluoroelastomeri |
US6906145B2 (en) | 2001-10-31 | 2005-06-14 | 3M Innovative Properties Company | Bonding of a fluoropolymer layer to a substrate |
US6916871B2 (en) | 2001-10-31 | 2005-07-12 | 3M Innovative Properties Company | Composition and method for making a fluoroelastomer |
ITMI20020598A1 (it) * | 2002-03-22 | 2003-09-22 | Ausimont Spa | Fluoroelastomeri vulcanizzabili |
WO2004000896A1 (en) | 2002-06-21 | 2003-12-31 | 3M Innovative Properties Company | Process for producing fluoropolymers having a reduced amount of polar end groups |
US6646077B1 (en) * | 2002-07-11 | 2003-11-11 | Dupont Dow Elastomers Llc | Peroxide curable fluoroelastomers |
US6803435B2 (en) | 2002-07-18 | 2004-10-12 | 3M Innovative Properties Company | Curable fluoropolymers containing bromine groups having improved compression set |
EP1525237B2 (en) | 2002-07-29 | 2021-01-27 | 3M Innovative Properties Company | Process for the preparation of ultraclean fluoroelastomer suitable for use in the manufacturing of electronic components |
US6884860B1 (en) | 2002-07-29 | 2005-04-26 | 3M Innovative Properties Company | Fluoroelastomer copolymer based on tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and vinylidene fluoride |
KR20050033622A (ko) | 2002-07-29 | 2005-04-12 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | 플루오로엘라스토머의 제조 방법 |
US6887927B2 (en) | 2002-08-27 | 2005-05-03 | 3M Innovative Properties Company | Fluoropolymer compositions containing a nitrogen cure site monomer and a sulfone or sulfoxide compound |
US6864336B2 (en) | 2002-09-12 | 2005-03-08 | 3M Innovative Properties Company | Fluoroelastomers having low temperature characteristics and solvent resistance |
US6846880B2 (en) * | 2002-10-11 | 2005-01-25 | 3M Innovative Properties Company | Fluoropolymer compositions |
EP1556426B1 (en) | 2002-10-31 | 2009-04-29 | 3M Innovative Properties Company | Emulsifier free aqueous emulsion polymerization to produce copolymers of a fluorinated olefin and hydrocarbon olefin |
WO2004046206A1 (en) | 2002-11-20 | 2004-06-03 | 3M Innovative Properties Company | Process for making a fluoropolymer having nitrile end groups |
US6734254B1 (en) | 2003-01-13 | 2004-05-11 | 3M Innovative Properties Company | Co-curable blends featuring bromine-and iodine-containing fluoroplastic polymers |
US20040142135A1 (en) | 2003-01-21 | 2004-07-22 | 3M Innovative Properties Company | Fuel management system comprising a fluoroelastomer layer having a hydrotalcite compound |
US6956085B2 (en) * | 2003-02-14 | 2005-10-18 | 3M Innovative Properties Company | Fluoroelastomer compositions |
EP1454740B1 (en) | 2003-03-04 | 2006-02-08 | 3M Innovative Properties Company | Method of bonding a fluoroelastomer layer to a silicone rubber layer, laminate for use in said method and article produced therewith |
US7375157B2 (en) * | 2003-06-09 | 2008-05-20 | 3M Innovative Properties Company | Melt-processible polymer composition comprising fluoropolymer having long chain branches |
EP1533325B1 (en) | 2003-11-17 | 2011-10-19 | 3M Innovative Properties Company | Aqueous dispersions of polytetrafluoroethylene having a low amount of fluorinated surfactant |
KR20070012640A (ko) * | 2003-12-30 | 2007-01-26 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | 플루오로중합체 응집 방법 및 조성물 |
US20050143529A1 (en) * | 2003-12-30 | 2005-06-30 | 3M Innovative Properties Company | Fluoropolymer compositions with nitrogen curing |
US8158728B2 (en) | 2004-02-13 | 2012-04-17 | The University Of North Carolina At Chapel Hill | Methods and materials for fabricating microfluidic devices |
ITMI20040789A1 (it) | 2004-04-22 | 2004-07-22 | Solvay Solexis Spa | Membrane fluorurate |
ITMI20040830A1 (it) | 2004-04-27 | 2004-07-27 | Solvay Solexis Spa | Fluoroelastomeri vulcanizzabili |
ITMI20041252A1 (it) * | 2004-06-22 | 2004-09-22 | Solvay Solexis Spa | Composizioni perfluoroelastomeriche |
ITMI20041251A1 (it) * | 2004-06-22 | 2004-09-22 | Solvay Solexis Spa | Gel di perfluoroelastomeri |
ITMI20041253A1 (it) * | 2004-06-22 | 2004-09-22 | Solvay Solexis Spa | Gel di fluoroelastomeri |
WO2006011547A1 (ja) | 2004-07-28 | 2006-02-02 | Daikin Industries, Ltd. | 過酸化物加硫可能な含フッ素エラストマー組成物 |
ITMI20041571A1 (it) | 2004-07-30 | 2004-10-30 | Solvay Solexis Spa | Perfluoroelastomeri |
ITMI20041573A1 (it) | 2004-07-30 | 2006-01-31 | Solvay Solexis Spa | Fluoroelastomeri |
ITMI20041801A1 (it) * | 2004-09-21 | 2004-12-21 | Solvay Solexis Spa | Uso di lattici submicrometrici di perfluoropolimeri nella determinazione di interazione molecolari mediante laser light scattering (lls) |
US7402630B2 (en) * | 2004-12-16 | 2008-07-22 | 3M Innovative Properties Company | Curing compositions for fluoropolymers |
US7300985B2 (en) * | 2004-12-21 | 2007-11-27 | 3M Innovative Properties Company | Fluoropolymers having pendant amidoxime or amidrazone structures |
JP5061446B2 (ja) * | 2005-03-04 | 2012-10-31 | 旭硝子株式会社 | 含フッ素エラストマーラテックス、その製造方法、含フッ素エラストマーおよび含フッ素ゴム成形品 |
US7294677B2 (en) * | 2005-08-25 | 2007-11-13 | 3M Innovative Properties Company | Catalyst for making fluoroelastomer compositions and methods of using the same |
US7381774B2 (en) * | 2005-10-25 | 2008-06-03 | Dupont Performance Elastomers, Llc | Perfluoroelastomer compositions for low temperature applications |
US20070100062A1 (en) * | 2005-10-28 | 2007-05-03 | Lyons Donald F | Process for the manufacture of fluoroelastomers having bromine or lodine atom cure sites |
US8557938B2 (en) * | 2005-11-10 | 2013-10-15 | Arkema Inc. | Branched fluoropolymers |
ITMI20052509A1 (it) | 2005-12-28 | 2007-06-29 | Solvay Solexis Spa | Assemblati per dispositivi elettrochimici |
ITMI20052508A1 (it) | 2005-12-28 | 2007-06-29 | Solvay Solexis Spa | Processo per ottenere ccm con subgasket |
US8944804B2 (en) | 2006-01-04 | 2015-02-03 | Liquidia Technologies, Inc. | Nanostructured surfaces for biomedical/biomaterial applications and processes thereof |
ITMI20060480A1 (it) * | 2006-03-16 | 2007-09-17 | Solvay Solexis Spa | Usom di perfluoropolimeri nella dtermibnazione della costante di legame recettore-ligando |
KR20090008236A (ko) | 2006-04-19 | 2009-01-21 | 아사히 가라스 가부시키가이샤 | 함불소 엘라스토머 조성물 및 함불소 고무 성형품 |
EP2028200B1 (en) | 2006-06-12 | 2011-09-07 | Asahi Glass Company, Limited | Curable composition and fluorine-containing cured product |
US20080021148A1 (en) * | 2006-07-24 | 2008-01-24 | 3M Innovative Properties Company | Scorch safe fluoropolymer compositions |
US7592386B2 (en) * | 2006-11-20 | 2009-09-22 | 3M Innovative Properties Company | Dual cure hydrotalcite containing fluoropolymer compositions |
US8128393B2 (en) | 2006-12-04 | 2012-03-06 | Liquidia Technologies, Inc. | Methods and materials for fabricating laminate nanomolds and nanoparticles therefrom |
GB0709033D0 (en) * | 2007-05-11 | 2007-06-20 | 3M Innovative Properties Co | Melt-Processible fluoropolymers having long-chain branches, Methods of preparing them and uses thereof |
EP2065441A1 (en) | 2007-11-30 | 2009-06-03 | Solvay Solexis S.p.A. | Fluoroelastomer composition |
GB0801194D0 (en) * | 2008-01-23 | 2008-02-27 | 3M Innovative Properties Co | Processing aid compositions comprising fluoropolymers having long-chain branches |
KR101595137B1 (ko) * | 2008-02-29 | 2016-02-17 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | 낮은 카르보닐 말단기 비를 갖는 퍼플루오로엘라스토머 |
CN102159641B (zh) | 2008-07-31 | 2013-12-18 | 3M创新有限公司 | 含氟聚合物组合物及其制备和使用方法 |
US8575273B2 (en) | 2008-11-26 | 2013-11-05 | Schlumberger Technology Corporation | Coupling agents and compositions produced using them |
US8263708B2 (en) | 2008-12-05 | 2012-09-11 | Solvay Solexis S.P.A. | Vulcanized (per) fluoroelastomer sealing articles |
EP2194094A1 (en) | 2008-12-08 | 2010-06-09 | Solvay Solexis S.p.A. | (Per)fluoroelastomer composition |
TWI482784B (zh) | 2009-02-13 | 2015-05-01 | Solvay Solexis Spa | 全氟彈性體 |
TWI496796B (zh) * | 2009-02-13 | 2015-08-21 | Solvay Solexis Spa | 全氟彈性體 |
EP2445939B1 (en) | 2009-06-25 | 2020-09-23 | 3M Innovative Properties Company | Curing compositions for fluoropolymers |
US20110274861A1 (en) | 2009-12-02 | 2011-11-10 | Dupont Performance Elastomers Llc | Fuel management systems having a fluororubber component in contact with fuel |
US20110143138A1 (en) * | 2009-12-10 | 2011-06-16 | 3M Properties Company | Perfluoroelastomer bonding |
KR101853987B1 (ko) * | 2010-07-14 | 2018-05-02 | 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. | 플루오로 엘라스토머 조성물 |
TWI523900B (zh) | 2010-07-20 | 2016-03-01 | 首威索勒希斯股份有限公司 | 氟彈性體組合物 |
US10533064B2 (en) | 2010-10-15 | 2020-01-14 | Solvay Specialty Polymers Italy S.P.A. | Fluoroelastomers |
JP5866375B2 (ja) | 2010-12-17 | 2016-02-17 | スリーエム イノベイティブ プロパティズ カンパニー | スルフィネート含有分子を含むフッ素含有ポリマー |
WO2012084587A1 (en) | 2010-12-20 | 2012-06-28 | Solvay Specialty Polymers Italy S.P.A. | Low viscosity fluoroelastomers |
WO2012141129A1 (ja) | 2011-04-11 | 2012-10-18 | ユニマテック株式会社 | 含フッ素エラストマーの製造方法 |
WO2012150253A1 (en) | 2011-05-03 | 2012-11-08 | Solvay Specialty Polymers Italy S.P.A. | Method for manufacturing fluoroelastomers |
GB201108963D0 (en) | 2011-05-27 | 2011-07-13 | 3M Innovative Properties Co | Composite materials comprising polyamides and fluoroelastomers |
EP2557109B1 (en) | 2011-08-11 | 2019-01-23 | 3M Innovative Properties Company | Method of bonding a fluoroelastomer compound to a metal substrate using low molecular weight functional hydrocarbons as bonding promoter |
JP6530191B2 (ja) * | 2011-08-17 | 2019-06-12 | ソルベイ スペシャルティ ポリマーズ イタリー エス.ピー.エー. | ミリング方法 |
SG11201402891XA (en) | 2011-12-16 | 2014-08-28 | Solvay Specialty Polymers It | Crosslinkable vinylidene fluoride and trifluoroethylene polymers |
CA2856176A1 (en) | 2011-12-16 | 2013-06-20 | Solvay Specialty Polymers Italy S.P.A. | Fluoroallylsulfonyl azide monomers and polymers there from |
US9403962B2 (en) | 2011-12-22 | 2016-08-02 | Schlumberger Technology Corporation | Elastomer compositions with silane functionalized silica as reinforcing fillers |
KR20150015440A (ko) * | 2012-04-27 | 2015-02-10 | 아사히 가라스 가부시키가이샤 | 축전 디바이스용 바인더 |
JP2016500390A (ja) | 2012-12-18 | 2016-01-12 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company | フルオロエラストマーの製造方法 |
WO2014099311A1 (en) | 2012-12-19 | 2014-06-26 | 3M Innovative Properties Company | Method of making fluoropolymers with a polyiodide, compositions and articles thereof |
CN103923578A (zh) | 2013-01-10 | 2014-07-16 | 杜邦公司 | 包括含氟弹性体的导电粘合剂 |
RU2522590C1 (ru) * | 2013-02-19 | 2014-07-20 | Федеральное государственное унитарное предприятие "Ордена Ленина и ордена Трудового Красного Знамени научно-исследовательский институт синтетического каучука имени академика С.В. Лебедева" (ФГУП "НИИСК") | Сополимеры на основе винилиденфторида для термоагрессивостойких материалов |
JP6356220B2 (ja) | 2013-04-22 | 2018-07-11 | ソルベイ スペシャルティ ポリマーズ イタリー エス.ピー.エー. | スルホン酸官能基を含む架橋性ポリマー |
JP2016523305A (ja) * | 2013-06-28 | 2016-08-08 | ソルベイ スペシャルティ ポリマーズ イタリー エス.ピー.エー. | フルオロエラストマー |
EP3080601B1 (en) | 2013-12-09 | 2018-09-26 | 3M Innovative Properties Company | A fluoroelastomer component for contacting ammonia and/or urea |
KR102279977B1 (ko) | 2014-03-06 | 2021-07-22 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 고도 플루오르화 엘라스토머 |
WO2015173194A1 (en) | 2014-05-12 | 2015-11-19 | Solvay Specialty Polymers Italy S.P.A. | Fluoroelastomers |
EP3143054B1 (en) | 2014-05-12 | 2019-07-10 | Solvay Specialty Polymers Italy S.p.A. | Method for the controlled polymerization of fluoromonomers |
WO2016087439A1 (en) | 2014-12-05 | 2016-06-09 | Solvay Specialty Polymers Italy S.P.A. | One-dimensional planar photonic crystals including fluoropolymer compositions and corresponding fabrication methods |
CN107580613B (zh) | 2015-05-08 | 2020-11-13 | 索尔维特殊聚合物意大利有限公司 | 氟弹性体组合物 |
CN107690451B (zh) * | 2015-05-29 | 2021-03-12 | 索尔维特殊聚合物意大利有限公司 | 氟弹性体组合物 |
WO2017011379A1 (en) | 2015-07-13 | 2017-01-19 | 3M Innovative Properties Company | Fluorinated block copolymers |
JP6722754B2 (ja) | 2015-08-05 | 2020-07-15 | ゼロックス コーポレイションXerox Corporation | PVDF−TrFE共重合体の末端基の交換法 |
EP3135477B1 (en) | 2015-08-27 | 2018-04-18 | 3M Innovative Properties Company | Multilayer articles with improved thermal resistance containing one or more fluoropolymers |
KR20180071291A (ko) | 2015-10-23 | 2018-06-27 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 비결정질 플루오로중합체 및 플루오로플라스틱 입자를 포함하는 조성물 및 이의 제조 방법 |
KR102605186B1 (ko) | 2015-11-30 | 2023-11-24 | 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. | 비닐리덴 플루오라이드와 트리플루오로에틸렌의 공중합체 및 플루오린화된 엘라스토머를 포함하는 플루오로중합체 조성물 |
WO2017102820A1 (en) | 2015-12-14 | 2017-06-22 | Solvay Specialty Polymers Italy S.P.A. | Method of manufacturing fluoroelastomers |
EP3390533B1 (en) | 2015-12-14 | 2020-02-12 | Solvay Specialty Polymers Italy S.p.A. | Fluoroelastomer compositions |
CN108884198A (zh) | 2016-03-11 | 2018-11-23 | 索尔维特殊聚合物意大利有限公司 | 用于固化氟弹性体组合物的多不饱和化合物 |
US20200299467A1 (en) | 2016-03-24 | 2020-09-24 | Solvay Specialty Polymers Italy S.P.A. | Fluoroelastomer composition |
EP3469018A1 (en) | 2016-06-13 | 2019-04-17 | Solvay Specialty Polymers Italy S.p.A. | Curable fluoroelastomer composition |
EP3354687A1 (en) | 2017-01-26 | 2018-08-01 | Solvay Specialty Polymers Italy S.p.A. | Fluorine-containing thermoplastic elastomer composition |
WO2018046355A1 (en) | 2016-09-07 | 2018-03-15 | Solvay Specialty Polymers Italy S.P.A. | Fluorine-containing thermoplastic elastomer composition |
US11261280B2 (en) | 2017-01-18 | 2022-03-01 | 3M Innovative Properties Company | Fluorinated block copolymers |
CN110214155B (zh) | 2017-01-18 | 2022-05-13 | 3M创新有限公司 | 衍生自腈固化位点单体的氟化嵌段共聚物 |
EP3392312A1 (en) | 2017-04-21 | 2018-10-24 | Solvay Specialty Polymers Italy S.p.A. | Polymer alloy comprising a sulphur-containing aromatic polymer and a fluoroelastomer |
EP3392311A1 (en) | 2017-04-21 | 2018-10-24 | Solvay Specialty Polymers Italy S.p.A. | Polymer alloy comprising a sulphur-containing aromatic polymer and a thermoplastic vulcanizate |
WO2019007728A1 (en) | 2017-07-05 | 2019-01-10 | Solvay Specialty Polymers Italy S.P.A. | COMPOSITION CONTAINING FLUORINATED THERMOPLASTIC ELASTOMERS AND VULCANISATES |
WO2019009248A1 (ja) * | 2017-07-05 | 2019-01-10 | Agc株式会社 | 含フッ素弾性共重合体、その組成物および架橋ゴム物品 |
WO2019162491A1 (en) | 2018-02-23 | 2019-08-29 | Solvay Specialty Polymers Italy S.P.A. | Fluorinated monomers comprising anthracene moieties |
EP3875536B1 (en) | 2018-11-02 | 2023-12-20 | Daikin Industries, Ltd. | Fluororubber composition and molded article |
WO2020127108A1 (en) | 2018-12-19 | 2020-06-25 | Solvay Specialty Polymers Italy S.P.A. | Curable composition |
CN113195629A (zh) | 2018-12-20 | 2021-07-30 | 3M创新有限公司 | 非晶态全氟化聚合物的胶乳共混物以及来源于其的制品 |
WO2020132203A1 (en) | 2018-12-20 | 2020-06-25 | 3M Innovative Properties Company | Dry powder blends of amorphous perfluorinated polymers, methods of making the same, and articles derived from the dry powder blends |
EP3935106A1 (en) | 2019-03-07 | 2022-01-12 | Solvay Specialty Polymers Italy S.p.A. | Fluorine-containing thermoplastic elastomer composition |
CN113544205A (zh) | 2019-03-20 | 2021-10-22 | 索尔维特殊聚合物意大利有限公司 | 氟弹性体组合物 |
KR20220003590A (ko) * | 2019-06-14 | 2022-01-10 | 다이킨 고교 가부시키가이샤 | 전기 화학 디바이스용 피압축 부재 |
US20220372267A1 (en) | 2019-07-17 | 2022-11-24 | Solvay Specialty Polymers Italy S.P.A. | Composite material comprising polyamide and fluoroelastomer |
WO2021099336A1 (en) | 2019-11-22 | 2021-05-27 | Solvay Specialty Polymers Italy S.P.A. | Method for improving coefficient of friction in cured fluororubber parts |
WO2021224164A1 (en) | 2020-05-07 | 2021-11-11 | Solvay Specialty Polymers Italy S.P.A. | Polyamide/fluoroelastomer blends and corresponding articles and formation methods |
JP7425375B2 (ja) | 2020-09-18 | 2024-01-31 | ダイキン工業株式会社 | フッ素ゴム架橋用組成物および成形品 |
WO2022128307A1 (en) | 2020-12-14 | 2022-06-23 | Solvay Specialty Polymers Italy S.P.A. | Sulphur-containing aromatic polymer composition having improved processability |
CN117083340A (zh) | 2021-04-02 | 2023-11-17 | 大金工业株式会社 | 氟橡胶交联用组合物、成型品和密封材料 |
EP4317284A1 (en) | 2021-04-02 | 2024-02-07 | Daikin Industries, Ltd. | Composition for fluorine rubber crosslinking and molded article |
WO2022210040A1 (ja) | 2021-04-02 | 2022-10-06 | ダイキン工業株式会社 | フッ素ゴム架橋用組成物、成形品およびシール材 |
KR20230158065A (ko) | 2021-04-15 | 2023-11-17 | 다이킨 고교 가부시키가이샤 | 불소 고무 가교용 조성물, 성형품 및 시일재 |
KR20240019815A (ko) | 2021-06-15 | 2024-02-14 | 다이킨 고교 가부시키가이샤 | 불소 고무 가교용 조성물, 성형품 및 시일재 |
CN117500877A (zh) | 2021-06-16 | 2024-02-02 | 大金工业株式会社 | 氟橡胶交联用组合物、成型品和密封材料 |
KR20240035802A (ko) | 2021-07-16 | 2024-03-18 | 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. | 이차 전지용 바인더 조성물 |
KR20240090174A (ko) | 2021-10-14 | 2024-06-21 | 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. | 플루오로탄성중합체 조성물 |
EP4417650A1 (en) | 2021-10-15 | 2024-08-21 | Daikin Industries, Ltd. | Fluoro rubber crosslinking composition and molded article |
KR20240096503A (ko) * | 2021-11-04 | 2024-06-26 | 사이언스코 에스에이 | (퍼)플루오로탄성중합체를 함유하는 보호층을 갖는 2차 배터리 |
WO2023100589A1 (ja) | 2021-11-30 | 2023-06-08 | ダイキン工業株式会社 | フッ素ゴム架橋用組成物および成形品 |
KR20240118784A (ko) | 2021-12-17 | 2024-08-05 | 솔베이 스페셜티 폴리머스 이태리 에스.피.에이. | 플루오로단량체의 유화 중합 방법 |
WO2023247225A1 (en) | 2022-06-23 | 2023-12-28 | Solvay Specialty Polymers Italy S.P.A. | Process for manufacturing aqueous dispersion comprising particles of a fluorinated polymer (f) |
TW202419517A (zh) * | 2022-09-28 | 2024-05-16 | 義大利商首威專業聚合物義大利公司 | 全氟聚醚聚合物 |
TW202413464A (zh) * | 2022-09-28 | 2024-04-01 | 義大利商首威專業聚合物義大利公司 | 全氟聚醚聚合物 |
WO2024120805A1 (en) | 2022-12-05 | 2024-06-13 | Solvay Specialty Polymers Italy S.P.A. | Composition (c) for manufacturing aqueous dispersion comprising particles of a fluorinated polymer (f) |
Family Cites Families (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3235537A (en) * | 1961-06-23 | 1966-02-15 | Du Pont | Fluorine containing terpolymer of a perfluorovinyl ether, vinylidene fluoride and a monomer of the structure cfx=cfy |
US3810874A (en) * | 1969-03-10 | 1974-05-14 | Minnesota Mining & Mfg | Polymers prepared from poly(perfluoro-alkylene oxide) compounds |
US3876654A (en) * | 1970-12-23 | 1975-04-08 | Du Pont | Fluoroelastomer composition |
US3752787A (en) * | 1972-01-28 | 1973-08-14 | Du Pont | Fluoroelastomer composition containing a triarylphosphorane vulcanization accelerator |
US4035565A (en) * | 1975-03-27 | 1977-07-12 | E. I. Du Pont De Nemours And Company | Fluoropolymer containing a small amount of bromine-containing olefin units |
JPS53125491A (en) * | 1977-04-08 | 1978-11-01 | Daikin Ind Ltd | Fluorine-containing polymer easily curable and its curable composition |
NL189567C (nl) * | 1977-12-14 | 1993-05-17 | Montedison Spa | Vulcaniseerbare mengsels op basis van elastomere copolymeren van vinylideenfluoride, werkwijze om deze te vulcaniseren en voorwerpen geheel of gedeeltelijk bestaande uit de zo verkregen gevulcaniseerde mengsels. |
FR2414519A1 (fr) * | 1978-01-16 | 1979-08-10 | Rhone Poulenc Ind | Copolymeres organopolysiloxaniques polysequences cristallins et leurs procedes de preparation |
US4281092A (en) * | 1978-11-30 | 1981-07-28 | E. I. Du Pont De Nemours And Company | Vulcanizable fluorinated copolymers |
JPS55108410A (en) * | 1979-02-14 | 1980-08-20 | Daikin Ind Ltd | Fluorine-containing polymer and composition thereof |
IT1163158B (it) * | 1983-03-22 | 1987-04-08 | Montedison Spa | Acceleranti per la vulcanizzazione di copolimeri elastomerici |
IT1206517B (it) * | 1983-09-07 | 1989-04-27 | Montedison Spa | Composizioni covulcanizzabili da fluoroelastomeri a base di fluoruro di vinilidene e copolimeri tetrafluoeoetilene-propilene. |
US4564662A (en) * | 1984-02-23 | 1986-01-14 | Minnesota Mining And Manufacturing Company | Fluorocarbon elastomer |
CA1265288A (en) * | 1984-11-22 | 1990-01-30 | E. I. Du Pont De Nemours And Company | Curable fluoroelastomer composition |
EP0199138B1 (en) * | 1985-03-28 | 1989-02-22 | Daikin Industries, Limited | Novel fluorovinyl ether and copolymer comprising the same |
IT1187684B (it) * | 1985-07-08 | 1987-12-23 | Montefluos Spa | Procedimento per la preparazione di fluoroelastomeri vulcanizzabili e prodotti cosi' ottenuti |
US4694045A (en) * | 1985-12-11 | 1987-09-15 | E. I. Du Pont De Nemours And Company | Base resistant fluoroelastomers |
IT1189092B (it) * | 1986-04-29 | 1988-01-28 | Ausimont Spa | Processo di polimerizzazione in dispersione acquosa di monomeri fluorurati |
IT1204903B (it) * | 1986-06-26 | 1989-03-10 | Ausimont Spa | Processo di polimerizzazione in dispersione acquosa di monomeri florati |
JPS63304009A (ja) * | 1987-06-04 | 1988-12-12 | Nippon Mektron Ltd | パ−オキサイド加硫可能な含フッ素エラストマ−の製造方法 |
CA1328533C (en) * | 1988-04-01 | 1994-04-12 | Werner Marie Aschille Grootaert | Fluoroelastomer composition |
IT1235545B (it) * | 1989-07-10 | 1992-09-09 | Ausimont Srl | Fluoroelastomeri dotati di migliore processabilita' e procedimento di preparazione |
IT1231174B (it) * | 1989-07-24 | 1991-11-22 | Ausimont Srl | Mescole vulcanizzabili di fluoroelastomeri contenenti bromo o iodio e di perossidi organici |
DE4114598A1 (de) * | 1991-05-04 | 1992-11-05 | Bayer Ag | Unvernetzte copolymerisate mit reaktiven doppelbindungen aus fluormonomeren und nicht konjugierten dienen und verfahren zu ihrer herstellung |
JPH05230151A (ja) * | 1991-08-06 | 1993-09-07 | Asahi Glass Co Ltd | 含フッ素ポリマーおよび硬化物 |
US5274179A (en) * | 1993-04-06 | 1993-12-28 | Alliedsignal Inc. | Fluorinated photoinitiators and their application in UV curing of fluorinated monomers |
US5264508A (en) * | 1992-06-25 | 1993-11-23 | The Dow Chemical Company | Polymers of haloperfluoro and perfluoro ethers |
-
1993
- 1993-12-29 IT IT93MI002750A patent/IT1265461B1/it active IP Right Grant
-
1994
- 1994-12-22 US US08/361,663 patent/US5585449A/en not_active Expired - Lifetime
- 1994-12-23 EP EP94120504A patent/EP0661304B1/en not_active Expired - Lifetime
- 1994-12-23 DE DE69421553T patent/DE69421553T2/de not_active Expired - Lifetime
- 1994-12-23 AT AT97103588T patent/ATE186309T1/de active
- 1994-12-23 TW TW083112098A patent/TW287172B/zh not_active IP Right Cessation
- 1994-12-23 DE DE69406408T patent/DE69406408T2/de not_active Expired - Lifetime
- 1994-12-23 EP EP97103588A patent/EP0784064B1/en not_active Expired - Lifetime
- 1994-12-23 AT AT94120504T patent/ATE159537T1/de not_active IP Right Cessation
- 1994-12-27 RU RU94045137A patent/RU2136702C1/ru active
- 1994-12-28 JP JP32905694A patent/JP3574198B2/ja not_active Expired - Lifetime
- 1994-12-29 KR KR1019940038927A patent/KR100359143B1/ko active IP Right Grant
- 1994-12-29 BR BR9405300A patent/BR9405300A/pt not_active Application Discontinuation
- 1994-12-29 CN CN94119959A patent/CN1053200C/zh not_active Expired - Lifetime
- 1994-12-29 CA CA002139260A patent/CA2139260C/en not_active Expired - Lifetime
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101835841B (zh) * | 2007-08-29 | 2012-12-26 | 索维索莱克西斯公开有限公司 | (全)氟弹性体组合物 |
CN103038266A (zh) * | 2010-08-02 | 2013-04-10 | 3M创新有限公司 | 包含改性剂和碘或溴端基的可过氧化物固化的含氟弹性体 |
CN103890021A (zh) * | 2011-06-09 | 2014-06-25 | 索尔维特殊聚合物意大利有限公司 | 超支化的氟弹性体添加剂 |
CN103890021B (zh) * | 2011-06-09 | 2016-03-23 | 索尔维特殊聚合物意大利有限公司 | 超支化的氟弹性体添加剂 |
CN108137723A (zh) * | 2015-10-01 | 2018-06-08 | 旭硝子株式会社 | 含氟弹性共聚物、其制造方法、交联橡胶及其制造方法 |
CN108137723B (zh) * | 2015-10-01 | 2021-03-23 | Agc株式会社 | 含氟弹性共聚物、其制造方法、交联橡胶及其制造方法 |
CN108291069A (zh) * | 2015-11-19 | 2018-07-17 | 旭硝子株式会社 | 含有含氟共聚物的交联性组合物、交联物及半导体制造装置用密封材料 |
CN108291069B (zh) * | 2015-11-19 | 2021-04-09 | Agc株式会社 | 含有含氟共聚物的交联性组合物、交联物及半导体制造装置用密封材料 |
CN109715718A (zh) * | 2016-07-18 | 2019-05-03 | 索尔维特殊聚合物意大利有限公司 | 氟弹性体组合物 |
CN109715718B (zh) * | 2016-07-18 | 2021-09-21 | 索尔维特殊聚合物意大利有限公司 | 氟弹性体组合物 |
CN117534929A (zh) * | 2023-12-18 | 2024-02-09 | 上海芯密科技有限公司 | 一种低腐蚀性含氟密封圈组合物及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
DE69421553D1 (de) | 1999-12-09 |
DE69406408D1 (de) | 1997-11-27 |
JP3574198B2 (ja) | 2004-10-06 |
DE69406408T2 (de) | 1998-05-07 |
EP0784064B1 (en) | 1999-11-03 |
CN1053200C (zh) | 2000-06-07 |
ATE159537T1 (de) | 1997-11-15 |
ATE186309T1 (de) | 1999-11-15 |
KR950018107A (ko) | 1995-07-22 |
CA2139260C (en) | 2005-10-25 |
RU2136702C1 (ru) | 1999-09-10 |
RU94045137A (ru) | 1996-10-10 |
BR9405300A (pt) | 1995-09-19 |
EP0661304A1 (en) | 1995-07-05 |
ITMI932750A0 (it) | 1993-12-29 |
JPH0812726A (ja) | 1996-01-16 |
EP0784064A1 (en) | 1997-07-16 |
ITMI932750A1 (it) | 1995-06-30 |
KR100359143B1 (ko) | 2003-02-05 |
CA2139260A1 (en) | 1995-06-30 |
US5585449A (en) | 1996-12-17 |
TW287172B (zh) | 1996-10-01 |
IT1265461B1 (it) | 1996-11-22 |
DE69421553T2 (de) | 2000-06-21 |
EP0661304B1 (en) | 1997-10-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1053200C (zh) | 含有源自二烯烃的单体单元的含氟弹性体 | |
JP4021960B2 (ja) | フルオロエラストマー用の硬化剤及びフルオロエラストマー | |
US8476356B2 (en) | (Per)fluoroelastomeric compositions | |
JP5197587B2 (ja) | (パー)フルオロエラストマー組成物 | |
KR101161674B1 (ko) | 퍼플루오로탄성중합체조성물들 | |
JP4015213B2 (ja) | フルオロエラストマー用硬化性組成物及びフルオロエラストマー | |
KR101205569B1 (ko) | 플루오로엘라스토머 | |
CN1712430A (zh) | 全氟弹性体凝胶 | |
KR20060048875A (ko) | 퍼플루오로엘라스토머 | |
CN1690093A (zh) | 可固化氟弹性体 | |
US6710132B2 (en) | Fluoroelastomeric compositions | |
US6323283B1 (en) | Peroxide curable fluoroelastomers | |
CN1712446A (zh) | 含氟弹性体凝胶 | |
US20020065372A1 (en) | Fluoroelastomers | |
CN1387551A (zh) | 交联用氟系弹性体组合物 | |
JP5101770B2 (ja) | フッ素化エラストマーとアクリルエラストマーのブレンド | |
CN1735662A (zh) | 交联性弹性体组合物及该交联性弹性体组合物所形成的成型品 | |
CN1946793A (zh) | 含氟弹性体组合物及含有该组合物的成型品 | |
CN100345876C (zh) | 可硫化的含氟弹性体的制造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C06 | Publication | ||
PB01 | Publication | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CX01 | Expiry of patent term |
Expiration termination date: 20141229 Granted publication date: 20000607 |