CN1738840A - Method for producing vulcanizable fluorine-containing elastomer - Google Patents
Method for producing vulcanizable fluorine-containing elastomer Download PDFInfo
- Publication number
- CN1738840A CN1738840A CN 200480002487 CN200480002487A CN1738840A CN 1738840 A CN1738840 A CN 1738840A CN 200480002487 CN200480002487 CN 200480002487 CN 200480002487 A CN200480002487 A CN 200480002487A CN 1738840 A CN1738840 A CN 1738840A
- Authority
- CN
- China
- Prior art keywords
- fluoroelastomer
- polymerization
- fluorine
- iodine
- weight
- 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
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000011737 fluorine Substances 0.000 title claims abstract description 25
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229920001971 elastomer Polymers 0.000 title abstract description 8
- 239000000806 elastomer Substances 0.000 title abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 127
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 60
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 11
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 6
- 229920001973 fluoroelastomer Polymers 0.000 claims description 80
- 229920000642 polymer Polymers 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- -1 alkyl vinyl ether) class Chemical class 0.000 claims description 32
- 239000000126 substance Substances 0.000 claims description 32
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 31
- 230000006835 compression Effects 0.000 claims description 25
- 238000007906 compression Methods 0.000 claims description 25
- 238000005987 sulfurization reaction Methods 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 125000001153 fluoro group Chemical group F* 0.000 claims description 12
- 150000002978 peroxides Chemical class 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical class FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 8
- 238000004293 19F NMR spectroscopy Methods 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- QMIWYOZFFSLIAK-UHFFFAOYSA-N 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene Chemical compound FC(F)(F)C(=C)C(F)(F)F QMIWYOZFFSLIAK-UHFFFAOYSA-N 0.000 claims description 4
- QBTUCBKAWGUMMK-UHFFFAOYSA-N C=CC.[F] Chemical group C=CC.[F] QBTUCBKAWGUMMK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 229910052728 basic metal Inorganic materials 0.000 claims description 3
- 150000003818 basic metals Chemical class 0.000 claims description 3
- 150000001733 carboxylic acid esters Chemical group 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims 1
- 241001441571 Hiodontidae Species 0.000 claims 1
- 230000004304 visual acuity Effects 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 64
- 239000011630 iodine Substances 0.000 abstract description 52
- 238000012546 transfer Methods 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 150000005827 chlorofluoro hydrocarbons Chemical group 0.000 abstract 1
- 239000007792 gaseous phase Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 238000004073 vulcanization Methods 0.000 description 26
- 238000005502 peroxidation Methods 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- 239000002245 particle Substances 0.000 description 21
- 239000012071 phase Substances 0.000 description 17
- 239000000839 emulsion Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 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 13
- 238000000465 moulding Methods 0.000 description 13
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 12
- 239000011324 bead Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 241000183024 Populus tremula Species 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 7
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical class CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 230000006837 decompression Effects 0.000 description 6
- 230000005674 electromagnetic induction Effects 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-UHFFFAOYSA-N 0.000 description 5
- 229960004065 perflutren Drugs 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000003566 sealing material Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 229960003132 halothane Drugs 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- YDDULLXUFDTAKJ-UHFFFAOYSA-M octanoate tetrafluoroazanium Chemical compound F[N+](F)(F)F.CCCCCCCC([O-])=O YDDULLXUFDTAKJ-UHFFFAOYSA-M 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 3
- 150000002497 iodine compounds Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 2
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical compound CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-UHFFFAOYSA-N 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 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 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000254 damaging effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 238000000593 microemulsion method Methods 0.000 description 2
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 description 2
- 235000019407 octafluorocyclobutane Nutrition 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- VQUGQIYAVYQSAB-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-2-(1,2,2-trifluoroethenoxy)ethanesulfonyl fluoride Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)S(F)(=O)=O VQUGQIYAVYQSAB-UHFFFAOYSA-N 0.000 description 1
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- AAAXMNYUNVCMCJ-UHFFFAOYSA-N 1,3-diiodopropane Chemical compound ICCCI AAAXMNYUNVCMCJ-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- FCHGUOSEXNGSMK-UHFFFAOYSA-N 1-tert-butylperoxy-2,3-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1C(C)C FCHGUOSEXNGSMK-UHFFFAOYSA-N 0.000 description 1
- XSQHUYDRSDBCHN-UHFFFAOYSA-N 2,3-dimethyl-2-propan-2-ylbutanenitrile Chemical compound CC(C)C(C)(C#N)C(C)C XSQHUYDRSDBCHN-UHFFFAOYSA-N 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
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-Phenylethanol Natural products OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- MUPIEMDDBGZNRU-UHFFFAOYSA-N C(C)(C)C(=O)O.C(C)(C)(C)OO Chemical compound C(C)(C)C(=O)O.C(C)(C)(C)OO MUPIEMDDBGZNRU-UHFFFAOYSA-N 0.000 description 1
- XTEWRFWHPZOAGD-UHFFFAOYSA-N C(CCC)C(C(CP)OC)(CCCC)CCCC Chemical compound C(CCC)C(C(CP)OC)(CCCC)CCCC XTEWRFWHPZOAGD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000522254 Cassia Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VVQVXIUJLQFGGS-UHFFFAOYSA-N FC=C(F)F.[I] Chemical group FC=C(F)F.[I] VVQVXIUJLQFGGS-UHFFFAOYSA-N 0.000 description 1
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 241001676573 Minium Species 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 1
- OTXUPAZXSZPKIK-UHFFFAOYSA-N [I].FC(F)Cl Chemical compound [I].FC(F)Cl OTXUPAZXSZPKIK-UHFFFAOYSA-N 0.000 description 1
- XBVBMZBKUKOOKA-UHFFFAOYSA-N [I].FCF Chemical compound [I].FCF XBVBMZBKUKOOKA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 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
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 1
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical compound OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- NEZRFXZYPAIZAD-UHFFFAOYSA-N ethylcyclobutane Chemical compound CCC1CCC1 NEZRFXZYPAIZAD-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- JUMYIBMBTDDLNG-OJERSXHUSA-N hydron;methyl (2r)-2-phenyl-2-[(2r)-piperidin-2-yl]acetate;chloride Chemical compound Cl.C([C@@H]1[C@H](C(=O)OC)C=2C=CC=CC=2)CCCN1 JUMYIBMBTDDLNG-OJERSXHUSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- WRIRWRKPLXCTFD-UHFFFAOYSA-N malonamide Chemical compound NC(=O)CC(N)=O WRIRWRKPLXCTFD-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 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
- 238000012703 microemulsion polymerization Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BLYOHBPLFYXHQA-UHFFFAOYSA-N n,n-bis(prop-2-enyl)prop-2-enamide Chemical compound C=CCN(CC=C)C(=O)C=C BLYOHBPLFYXHQA-UHFFFAOYSA-N 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 125000001402 nonanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229960004692 perflenapent Drugs 0.000 description 1
- 229960004624 perflexane Drugs 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 description 1
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 description 1
- NJCBUSHGCBERSK-UHFFFAOYSA-N perfluoropentane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F NJCBUSHGCBERSK-UHFFFAOYSA-N 0.000 description 1
- 150000004978 peroxycarbonates Chemical class 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
- REJGOFYVRVIODZ-UHFFFAOYSA-N phosphanium;chloride Chemical compound P.Cl REJGOFYVRVIODZ-UHFFFAOYSA-N 0.000 description 1
- NAYYNDKKHOIIOD-UHFFFAOYSA-N phthalamide Chemical class NC(=O)C1=CC=CC=C1C(N)=O NAYYNDKKHOIIOD-UHFFFAOYSA-N 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical class CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229940099204 ritalin Drugs 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- JREYOWJEWZVAOR-UHFFFAOYSA-N triazanium;[3-methylbut-3-enoxy(oxido)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].CC(=C)CCOP([O-])(=O)OP([O-])([O-])=O JREYOWJEWZVAOR-UHFFFAOYSA-N 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention provides a process for preparing a fluorine-containing elastomer in a high productivity comparable to that of non-iodine transfer polymerization process by carrying out an iodine transfer polymerization at high pressure. The present invention also provides a fluorine-containing elastomer prepared by this process, and fluorine-containing molded articles. The process is a batch copolymerization process conducted under conditions that the reduced temperature of the critical constant is at least 0.95 and the reduced pressure of the critical constant is at least 0.80 wherein the reduced temperature and the reduced pressure are calculated using the Peng-Robinson formula from the critical temperature, the critical pressure and the composition ratio of each of the monomers in the gaseous phase in a reaction vessel, in which ethylenically unsaturated compounds containing at least one fluoroolefine are copolymerized in the presence of a compound having the formula: Rf<1>.Ix wherein Rf<1> is a saturated or unsaturated fluorohydrocarbon or chlorofluorohydrocarbon group having 1 to 16 carbon atoms, and x is the number of bonds of Rf<1> and an integer of 1 to 4.
Description
Technical field
The present invention relates under high pressure utilize the iodine transfer polymerization to make the method for fluoroelastomer.And then relate to the fluoroelastomer of making by this method that the elastomerics side chain is few and terminal iodine content is high, and by vulcanizing the compression set that this elastomerics obtains and the superior fluorine-containing moulding product of balance of tension fracture elongation rate.
Background technology
Biasfluoroethylene-hexafluoropropylene (VdF-HFP) class and tetrafluoroethylene (TFE)-perfluoro-ethylene ethers fluoroelastomer has shown remarkable chemical resistant properties, solvent resistance, thermotolerance, thereby it is formed in the O type ring that uses under the severe rugged environment, packing ring, flexible pipe, rod seal, shaft seal, diaphragm etc., is widely used in fields such as automotive industry, semi-conductor industry, chemical industry.
As the fluoroelastomer that is used to these purposes, have the fluoroelastomer that contains iodine that has highly active iodine atom in molecular end.This fluoroelastomer that contains iodine can have good cross-linking efficiency by the iodine atom of molecular end, and sulfuration property is superior.And,, also be widely used as peroxide cure moulding product owing to do not need to add chemical substance with metal ingredient.
Peroxide vulcanizing system (for example opening clear 53-125491 communique with reference to the spy) its chemical resistant properties and anti-steam (hot water) property are superior, but because its compression tension set is poorer than the polyvalent alcohol vulcanization system, and be not suitable for as the sealing material purposes.This problem is solved (for example opening clear 62-12734 communique with reference to the spy) by import the sulfuration point in the elastomerics main chain.But, to sacrifice tension fracture elongation rate in order to improve sulfuration density.Thereby both are very difficult to have compression tension set and tension fracture elongation rate concurrently.
In addition, make the method for fluoroelastomer as utilizing high pressure polymerisation, following method is arranged, and for example at least a monomer is in the polymerization (for example with reference to the international brochure that discloses No. 00/47641) and the emulsion polymerization (for example with reference to international disclose No. 01/34666 brochure) of the monomer concentration in the polymer particle more than benchmark value of supercritical state.Though in any one piece of documents, all have describe among the present invention can be at R
f 1I
xThere is the such record of polymerization down, but do not have specific embodiment, do not reach disclosed effect among the present invention fully.
The fluoroelastomer that contains iodine is made (for example with reference to special public clear 63-41928 communique) by emulsion polymerizations such as so-called iodine transfer polymerization methods, but in order to realize that high terminally iodized rate then needs the usage quantity (for example with reference to the tactical rule, the polymer association (1986) that build the polymkeric substance in the just auspicious P19 of unit, 86/6 microcosmic symposium, the radical polymerization) of controlled polymerization initiator, correspondingly productivity then can not be improved.Can easily increase polymerization velocity for the hard-core polymerization system of the usage quantity of polymerization starter by increasing amount of initiator, but because the ultimate density of initiator can produce big influence to the rerum natura of end article, thereby do not wish to increase the usage quantity of initiator for iodine transfer polymerization system.
Various motions have been carried out in order to boost productivity.The method that has for example proposed to carry out letex polymerization continuously and boosted productivity (for example with reference to the spy open flat 3-33108 communique, the spy opens flat 3-221510 communique), but can not get good tensile and compression set, and this good properties contains the fluoroelastomer characteristic of iodine just.
In addition, proposed more than or equal to 1.7MPa (gauge pressure, down with) high pressure carry out polymeric method (for example opening flat 5-222130 communique) with reference to the spy, but its with the pressure of 2.6MPa~2.7MPa scope as preferably, also be limited to disclosing in this scope in an embodiment.And polymerization time is also above 15 hours.And then, proposed microemulsion polymerization method (for example opening clear 63-8406 communique), but need use fluorocarbon oil etc. in order to form microemulsion in the early stage with reference to the spy, become source of pollution in the goods because this fluorocarbon oil etc. can remain in, thereby need washing to remove.
If, can increase the usage quantity of emulsifying agent, but because emulsifying agent self can produce the sulfuration obstacle, thereby also need its washing is removed only for the stable polymerization system or improve polymerization velocity, and aspect cost and the environment aspect also also imperfect.
In order to address these problems, proposed to carry out iodine transfer polymerization (for example with reference to the international brochure that discloses No. 00/01741) with the two-stage emulsion polymerization.So-called two-stage emulsion polymerization is following method, promptly in the polymerization of fs, use the synthetic a large amount of polymer particle of emulsifying agent of more amount, then dilute the emulsion that obtains and reduce polymer particle and emulsifier concentration, use this dilution emulsion to carry out the polymerization of subordinate phase.In the method, though not needing that the equipment that existing letex polymerization is used is carried out big change can form homogeneous particle diameter and keep its original characteristic, and polymerization velocity can be shortened more than 2 times, but specific production rate is still poor mutually with the polymerization of not using iodide.And, to compare with iodine transfer polymerization method in the past, the elastomerics that obtains with this polymerization does not have the part of special improvement, residual the problem of above-mentioned stopping property aspect.
Also there is not this manufacture method of taking into account the productivity of the fluoroelastomer that contains iodine and keeping characteristic.
Summary of the invention
The present invention is by under high pressure carrying out the manufacture method that the iodine transfer polymerization provides fluoroelastomer, and it has the high productivity that is equal to mutually with non-iodine-transfer polymerization method.And then the fluoroelastomer of making by this method that the polymkeric substance side chain is few and terminal iodine content is high is provided, and provide by vulcanizing the compression set that this elastomerics obtains and the superior fluorine-containing moulding product of balance of tension fracture elongation rate.
Promptly, the present invention relates to adopt the manufacture method of the fluoroelastomer of intermittent type copolymerization method, its use the Peng-Robinson equation by reactive tank in each monomeric critical temperature in the gas phase part, emergent pressure and the ratio of components separately critical constants of calculating reduced temperature for more than or equal to 0.95, reduced pressure carries out under more than or equal to 0.80 condition, wherein, be R at general formula
f 1I
xExistence under make the ethylene type unsaturated compound copolymerization that contains at least a fluoroolefin, in the described general formula, R
f 1Be that carbonatoms is 1~16 saturated or undersaturated fluorocarbon based or Chlorofluorocarbons (CFCs) base, x is R
f 1The bonding valence mumber, it is 1~4 integer.
Pressure during polymerization depends on monomeric kind and the ratio of components that carries out copolymerization, can be for for example more than or equal to 4MPa.The fluoroelastomer that above-mentioned pressure goes for for example will obtaining is the multipolymer that vinylidene and R 1216 form, and vinylidene: R 1216 is 9: 1 to 5: 5 situation with molar ratio computing.And polymerization pressure can be for for example more than or equal to 3MPa.The fluoroelastomer that above-mentioned pressure goes for for example will obtaining is the situation of the multipolymer that forms of vinylidene, R 1216 and tetrafluoroethylene, wherein vinylidene: R 1216 is that 9: 1 to 5: 5 and tetrafluoroethylene are smaller or equal to 40 moles of all % of elastomerics with molar ratio computing.
When polymerization finishes in preferred every 1g water the fluoroelastomer population be more than or equal to 5 * 10
13Individual.
Fluoroolefin is preferably CX
1X
2=CX
3X
4, X wherein
1~X
3Be hydrogen atom or halogen atom, X
4For hydrogen atom, halogen atom, carboxyl, carbonatoms be 1~9 and the alkyl that contains or do not contain ehter bond type Sauerstoffatom that replaced by fluorine atom of some or all of hydrogen atom or carbonatoms be 1~9 and the alkoxyl group that contains or do not contain ehter bond type Sauerstoffatom that replaced by fluorine atom of some or all of hydrogen atom, this alkene contains 1 fluorine atom at least.
Fluoroolefin is preferably and is selected from by R 1216, tetrafluoroethylene, trifluoro-ethylene, five fluorine propylene, vinyl fluoride, hexafluoro-isobutene, perfluor (alkyl vinyl ether) class, poly-fluorine dienes and following formula
Compound in the group of forming, Y is-CH in the formula
2I ,-OH ,-COOH ,-SO
2F ,-SO
3(M is NH to M
4Base or basic metal), carboxylate salt, carboxylic ester group, epoxy group(ing), itrile group, iodine atom, X
5And X
6Identical or different, be hydrogen atom or fluorine atom, R
f 2Be that carbonatoms is 0~40 the fluorine-containing alkylidene group of divalent, contain or do not contain ehter bond type Sauerstoffatom.
Fluoroelastomer is preferably more than at 100 ℃ mooney viscosity and equals 30.
In addition, the present invention relates to fluoroelastomer, described fluoroelastomer contains the vinylidene repeating unit of 20 moles of %~90 mole %, the R 1216 repeating unit of 10 moles of %~80 mole %, wherein, (a) contain the iodine atom of 0.01 weight %~10 weight % in elastomerics, (b) the polymkeric substance number-average molecular weight is 1,000~300,000, (c) use very high resolution
19F-NMR measures the acetone soln of polymer concentration about 20%, by following formula
δ F-96.5~-area between 99.5ppm
3 * (δ F-88.0~-area between 124.0ppm
" the VdF branching rate " of trying to achieve is that described fluoroelastomer can carry out peroxide cure smaller or equal to 200ppm.
The tension fracture elongation rate Eb of the formed body that preferred sulfuration obtains is 200%~550%, and is 5%~30% at 200 ℃, 72 hours compression set CS.
The invention still further relates to fluoroelastomer curing and use composition, it contains fluoroelastomer and vulcanizing agent.
Embodiment
The manufacture method of fluoroelastomer of the present invention is to adopt the manufacture method of the fluoroelastomer of intermittent type copolymerization method, its reduced temperature of the critical constants that uses the Peng-Robinson equation to calculate by each the monomeric critical temperature in the part of the gas phase in the reactive tank, emergent pressure and ratio of components separately for more than or equal to 0.95, reduced pressure carries out under more than or equal to 0.80 condition, wherein, be R at general formula
f 1I
xExistence under make the ethylene type unsaturated compound copolymerization that contains at least a fluoroolefin, in the described general formula, R
f 1Be that carbonatoms is 1~16 saturated or undersaturated fluorocarbon based or Chlorofluorocarbons (CFCs) base, x is R
fThe bonding valence mumber, it is 1~4 integer.
The invention provides by under high pressure carrying out the method that the iodine transfer polymerization is made fluoroelastomer, in the method, although polymerization starter seldom, polymerization velocity increases considerably; And has the high productivity that is equal to mutually with non-iodine-transfer polymerization method.And then pass through few, the terminal iodine content height of its side chain of elastomerics that this method is made, and can provide the superior fluorine-containing moulding product that compression set is little, tension fracture elongation rate is good.
The characteristics of manufacture method of the present invention are under high pressure to carry out iodine transfer polymerization method.Iodine transfer polymerization method there is not special qualification, but a number of the fluoropolymer particles when aspect productivity, preferably increasing polymerization and finishing, as the preferred international seeding polymerization method of putting down in writing in No. 00/01741 brochure that discloses of its method.
The reactive tank that uses among the present invention is owing to carry out polymerization adding to depress, thereby uses pressure vessel.Add the aqueous medium (being generally pure water) that letex polymerization is used in this reactive tank, form liquid phase part, described aqueous medium contains the polymer particle with the subject polymer same composition.
Reactive tank partly is made of this liquid phase part and gas phase, imports polymerizable monomer with displacement gas phase part backs such as nitrogen.Then the special liquid phase part that stirs in reactive tank is supplied with polymerizable monomer from the gas phase part to liquid phase part.The monomer that supplies to liquid phase part soaks into to polymer particle, and the polymerizable monomer concentration in the polymer particle increases.By to gas phase part sustainable supply monomer, the monomer concentration in the polymer particle is in state of saturation (we can say that also the monomer feed speed to liquid phase part is in equilibrium state), thereby drops into polymerization starter and iodide and begin polymerization.
Along with polymeric constantly carries out, monomer is consumed, and the monomer concentration that generates in the polymer particle can reduce gradually, thereby usually needs sustainable supply monomer (appending monomer) in polymer particle.
Append monomeric ratio and depend on the monomer that is added and the composition of subject polymer, preferably this ratio keeps in the reactive tank at polymerization initial stage monomer to form certain.
When in addition, polymerization finishes in preferred every 1g water the fluoroelastomer population be more than or equal to 5 * 10
13Individual, population is more than or equal to 1.0 * 10 in more preferably every 1g water
14Individual.Population is a less than 5 * 10
13When individual, not only speed of response reduces, and particle diameter becomes extremely unstable, and polymkeric substance is to the tendency that is attached with increase of polymerization tank.
The polymerization process of the population when increasing polymerization and finish also can be enumerated the microemulsion method put down in writing in special public clear 63-8406 communique, the public clear 62-288609 communique of spy and as the increase emulsification dosage of general method etc. except the seeding polymerization method.Wherein,, need use fluorocarbon oil etc., thereby in goods, understand oil residues, become source of pollution, thereby need washing to remove in order to form microemulsion in the early stage for microemulsion method.In addition, for increasing emulsification dosage, only stable polymerization system or raising polymerization velocity are effectively, but are easy to generate foamed phenomenon before and after polymerization, and the emulsifying agent that remains in the elastomerics that obtains is easy to generate the sulfuration obstacle.And, consider also also nonideal method from cost and environment aspect.On the other hand, the seeding polymerization method does not have above-mentioned problem, demonstrates remarkable effect in the iodine transfering system.
In manufacture method of the present invention, be the critical temperature of correction gas phase monomer mixture and some errors of emergent pressure, reduced temperature for more than or equal to 0.95, be preferably more than equal 0.97, reduced pressure for more than or equal to 0.80, be preferably more than and equal to carry out intermittence type polymerization under 0.85 the condition, the critical temperature of described gas phase monomer mixture and emergent pressure are derived by the independent critical temperature of each monomer, emergent pressure and initial stage monomer ratio of components by the Peng-Robinson equation.Reduced temperature, the reduced pressure of the mix monomer by making gas phase portion all exceed above-mentioned value, may carry out the polymerization of high monomer density, except polymerization velocity accelerates, can also obtain the side chain and the terminal few polymkeric substance of ion of main chain, thereby compression set is improved significantly.At this, so-called reduced temperature is by reduced temperature T
R=T/T
c(in the formula, the actual temperature when T is polymerization, T
cCritical temperature that be to use the Peng-Robinson equation to calculate) numerical value of decision, same so-called reduced pressure is to pass through P
R=P/P
c(in the formula, the true pressure when P is polymerization, P
cEmergent pressure that be to use the Peng-Robinson equation to calculate) numerical value of decision.
At this, describe at the Peng-Robinson equation that determines critical temperature and emergent pressure.Usually, the initial stage monomer density in the known polymerization tank is high more, then is easy to generate composition distribution and initial stage monomer more and can especially sharply rises near the monomer density stagnation point in the polymkeric substance that obtains.Yet, more than 2 kinds or 2 kinds during the monomer copolymerization of composition the stagnation point meeting of gas phase monomer mixture change according to monomeric kind and ratio of components.Method as the stagnation point of being calculated mix monomer by the independent critical temperature of each monomer, emergent pressure and initial stage monomer ratio of components adopts the Peng-Robinson equation.The principle of this equation is at D.Y.Peng and D.B.Robinson, " ANew Two-Constant Equation of state ", Ind.Eng.Chem.Fund., Vol.15, (1976) are described in p.59-64.Its summary as principle, can be used the programsimulator of Aspen Plus (Aspen science and technology society system) etc. with following formula during actual computation.
The summary of Peng-Robinson equation is as described below.
P=RT/(V
m-b)-a/[V
m(V
m+b)+b(V
m-b)]
At this, a in the above-mentioned formula
i, b
iRespectively as giving a definition.
a
i=α
i0.45724R
2T
ci 2/P
ci
α
i(T)=[1+m
i(1-T
ci0.5)]
2
m
i=0.37464+1.54226ω
i-0.26992ω
i 2
b
i=0.0778RT
ci/P
ci
In addition, each meaning of parameters is as follows.
P: pressure
T: temperature
V
m: volume
R: gas law constant
Xi: the ratio of components of monomer component i
T
Ci: the critical temperature of monomer component i
P
Ci: the emergent pressure of monomer component i
ω
i: the eccentric factor of monomer component i
As concrete calculated example, use Aspen Plus Ver.11.1 (making of Aspen technology company) to utilize the Peng-Robinson equation to carry out critical temperature, emergent pressure calculating when consisting of VdF/HFP=36/64 (mole %) in the polymerization tank, the result is T
c=87.7 ℃, P
c=3.05MPa.If utilize above-mentioned reduced temperature 0.95, reduced pressure 0.80 to carry out conversion, then Ci Shi polymerizing condition is T more than or equal to 69.7 ℃, P more than or equal to 2.44MPa.
When reduced temperature less than 0.95 or reduced pressure less than 0.80, the monomer concentration in the polymer particle does not reach saturated, and not only polymerization velocity can reduce, and often is difficult to obtain subject polymer.Satisfy that further preferred polymerization temperature is 10 ℃~120 ℃ the temperature and pressure of the conditional of calculating from above-mentioned formula, be preferably 30 ℃~100 ℃ especially; Preferred polymerization pressure is more than or equal to 3MPa, more preferably 3.5MPa, and then be preferably more than and equal 4MPa.In addition, the upper limit of pressure value does not have special restriction, but considers that monomeric operability and conversion unit cost etc. are preferably smaller or equal to 15MPa, more preferably smaller or equal to 12MPa.
And then preferably stir.This be because, can keep monomer concentration in the high polymer particle by stirring through polymerization.
As mixer means, can use for example anchor shape blade, turbine blade, dihedral vane etc., but consider that from the angle that the dispersion stabilization of monomeric diffusion and polymkeric substance is good the preferred large-scale blade that is called as Off Le ゾ one Application and マ Star Network ス Block レ Application De that utilizes stirs.
Horizontal type whipping appts can be used as whipping appts, also the longitudinal type whipping appts can be used.
Reaction system has monomer phase part in fact.At this, so-called have in fact monomer be illustrated in mutually the shared volume of medium such as water with respect to the volume of aggregation container for smaller or equal to carrying out polymerization under 90% the state, be preferably smaller or equal to 80%.Volume surpasses at 90% o'clock, and then monomer is difficult to be supplied to medium, and polymerization velocity can reduce, and perhaps the polymkeric substance rerum natura has the tendency of deterioration.
Use general formula: R what the present invention used
f 1I
xIn the iodide of expression, R
f 1Be that carbonatoms is 1~16 saturated or undersaturated fluorocarbon based or Chlorofluorocarbons (CFCs) base, preferred carbonatoms is 4~8 perfluoroalkyl.Carbonatoms surpasses at 16 o'clock, and then reactivity tends to reduce.
Use general formula: R
f 1I
xIn the iodide of expression, x is R
f 1The bonding valence mumber, it is 1~4 integer, is preferably 2~3.Even surpassing 4, also can use x, but also not preferred aspect synthetic cost.Consider that from the angle that the polymkeric substance side chain is few x most preferably is 2.
The carbon-iodine bond of these iodide is more weak keys, and cracking is free radical in the presence of free radical generation source.Because the free radical that produces is reactive high, monomer generation addition reaction is then by attracting to obtain iodine and stopped reaction from iodide.The bond with carbon in molecular end that obtains thus has its terminal iodine of fluoroelastomer of iodine to become effective sulfuration point, thereby can vulcanize effectively.
As using general formula: R
f 1I
xThe iodide of expression, can enumerate single iodine perfluoromethane, single iodine R 116, single iodine perfluoropropane, single iodine perfluorinated butane (2-iodine perfluorinated butane for example, 1-iodine perfluor (1,1-dimethyl ethane)), single iodine perflenapent (for example 1-iodine perfluor (4-methylbutane)), 1-iodine perfluor octane, single iodine perfluorocyclobutane, 2-iodine perfluor (1-cyclobutyl ethane) hexanaphthene, single iodine perfluor hexanaphthene, single iodine trifluoro tetramethylene, single iodine methylene fluoride, single iodine list fluoromethane, 2-iodo-1-hydrogen R 116,3-iodo-1-hydrogen perfluoropropane, single iodine monochloro methylene fluoride, single iodine dichloro list fluoromethane, 2-iodo-1,2-two chloro-1,1, the 2-Halothane, 4-iodo-1,2-dichloro perfluorinated butane, 6-iodo-1,2-dichloro perflexane, 4-iodo-1,2,4-trichlorine perfluorinated butane, 1-iodo-2,2-two hydrogen perfluoropropanes, 1-iodo-2-hydrogen perfluoropropane, single iodine trifluoro-ethylene, 3-iodine perfluoro propylene-1,4-iodine perfluor amylene-1,4-iodo-5-chlorine perfluor amylene-1,2-iodine perfluor (1-cyclobutene base ethane), 1,3-diiodo perfluo propane, 1,4-diiodo perfluo normal butane, 1,3-two iodo-2-chlorine perfluoropropane, 1,5-two iodo-2,4-dichloro perfluor Skellysolve A, 1,7-diiodo perfluo octane, 1,2-two (iodine difluoromethyl) perfluorocyclobutane, 2-iodo-1,1, the 1-Halothane, 1-iodo-1-hydrogen perfluor (2-methyl ethane), 2-iodo-2,2-two chloro-1,1, the 1-Halothane, 2-iodo-2-chloro-1,1,1-Halothane etc.And then, R
f 1Alkyl in can contain functional groups such as ehter bond Sauerstoffatom, thioether bond sulphur atom, carboxyl, can enumerate 2-iodine perfluoroethyl perfluorovinyl base ether, 2-iodine perfluor ethyl perfluor isopropyl ether, 3-iodo-2-chlorine perfluoro butyl perfluoro-methyl thioether, 3-iodo-4-chlorine perfluorobutyric acid etc.
Wherein, consider from easily synthetic, reactivity, economy, stable aspect preferred 1,4-diiodo perfluo normal butane.
These iodine compounds can be by suitable known method manufacturing.For example, 2-iodine perfluoropropane can be made by make HFC-236fa and Iod R in the presence of Potassium monofluoride, 1,5-two iodo-2,4-dichloro perfluor Skellysolve A can be by making 3,5-dichloro perfluor-1, the silver salt of 7-pimelic acid and Iod R and make, 4-iodo-5-chlorine perfluor-1-amylene can be by making iodine chloride and perfluor-1 in addition, and the 4-pentadiene reacts and makes.
The addition of iodine compound is 0.05 weight %~2.0 weight % with respect to fluoroelastomer preferably.During addition less than 0.05 weight %, then tend to vulcanize insufficient, compression set (CS) worsens; When surpassing 2.0 weight %, then cross-linking density is too high, tends to damage the performances such as elongation of rubber.
Contain fluoroolefin more than at least a kind or a kind as the monomer that forms fluoroelastomer with above-mentioned iodine compound, also can contain ethylene type unsaturated compound beyond the fluoroolefin as its comonomer.
This composition is preferred for forming fluoroelastomer.
Be preferably as the fluoroolefin that uses in the present invention and use CX
1X
2=CX
3X
4The alkene of expression.X in the formula
1~X
3Be hydrogen atom or halogen atom, X
4For hydrogen atom, halogen atom, carboxyl, carbonatoms be 1~9 and the alkyl that contains or do not contain ehter bond type Sauerstoffatom that replaced by fluorine atom of some or all of hydrogen atom or carbonatoms be 1~9 and the alkoxyl group that contains or do not contain ehter bond type Sauerstoffatom that replaced by fluorine atom of some or all of hydrogen atom, this alkene contains 1 fluorine atom at least.
As using CX
1X
2=CX
3X
4The fluoroolefin of expression, can enumerate R 1216 (HFP), vinylidene (VdF), tetrafluoroethylene (TFE), trifluoro-ethylene, five fluorine propylene, vinyl fluoride, hexafluoro-isobutene, chlorotrifluoroethylene (CTFE), trifluoro propene, five fluorine propylene, tetrafluoeopropene, hexafluoro-isobutene, perfluor (alkyl vinyl ether) (PAVE) etc., the angle that the elastomerics that is easy to get is calmly formed considers that preferred vinylidene (VdF), R 1216 (HFP), tetrafluoroethylene (TFE), perfluor (alkyl vinyl ether) are (PAVE).
In addition, perfluor (alkyl vinyl ether) class also is being preferred aspect winter hardiness, the chemical resistant properties.
As perfluor (alkyl vinyl ether), can enumerate perfluor (methylvinylether) (PMVE), perfluor (ethyl vinyl ether) (PEVE), perfluor (propyl vinyl ether) (PPVE) etc.
In addition, as CX
1X
2=CX
3X
4Fluoroolefin in addition can be enumerated usefulness
CF
2=CFOCF
2CF=CF
2Fluoroolefin, the usefulness of expression
(Y is-CH in the formula for the fluoroolefin that contains functional group of expression and poly-fluorine dienes etc.
2I ,-OH ,-COOH ,-SO
2F, SO
3(M is hydrogen, NH to M
4Base or basic metal), carboxylate salt, carboxylic ester group, epoxy group(ing), itrile group, iodine atom; X
5And X
6Identical or different, be hydrogen atom or fluorine atom; R
f 2Be that carbonatoms is the fluorine-containing alkylidene group of 0~40 divalent, can contain the ehter bond Sauerstoffatom).
The fluoroolefin that contains functional group is preferred as functional monomers such as surface modification, raising cross-linking densities, and poly-fluorine dienes is preferred aspect cross-linking efficiency.
As the fluoroolefin that contains functional group, can enumerate:
CF
2=CFOCF
2CF
2CH
2OH、CF
2=CFOCF
2 3COOH、
CF
2=CFOCF
2CF
2COOCH
3、
CF
2=CFCF
2CH
2OH、
CF
2=CFCF
2OCF
2CF
2CF
2COOH、
CF
2=CFCF
2CF
2COOH、CF
2=CFCF
2COOH、
CH
2=CFCF
2CF
2CH
2CH
2OH、CH
2=CFCF
2CF
2COOH、
CH
2=CFCF
2CF
2 2COOH、
CH
2=CHCF
2CF
2CH
2CH
2COOH、
CH
2=CHCF
2 4CH
2CH
2CH
2OH、
CH
2=CHCF
2 6CH
2CH
2COOCH
3、
As the fluoroolefin that contains functional group, in order to improve preferably disclosed monomer CF in patent documentation 2 of cross-linking density
2=CFOCF
2CF
2CH
2I.
As poly-fluorine dienes, can enumerate CF
2=CFCF=CF
2, CF
2=CFCF
2OCF=CF
2Deng.
Do not have special restriction as the ethylene type unsaturated compound beyond the fluoroolefin, can enumerate carbonatomss such as ethene (ET), propylene, butylene, amylene and be 2~10 'alpha '-olefin monomers; It is alkyl vinyl ether of 1~20 alkyl etc. that methylvinylether, ethyl vinyl ether, propyl vinyl ether, cyclohexyl vinyl ether, hydroxy butyl vinyl ether, butyl vinyl ether etc. have carbonatoms.
These compounds are being preferred aspect low cost, the amine resistance.
As the monomeric combination that forms fluoroelastomer of the present invention, there is the above-mentioned CX that uses that contains more than a kind or a kind
1X
2=CX
3X
4Fluoroolefin, the CX more than a kind or a kind of expression
1X
2=CX
3X
4Fluoroolefin in addition and use above-mentioned CX more than a kind or a kind
1X
2=CX
3X
4The fluoroolefin and the CX more than a kind or a kind of expression
1X
2=CX
3X
4The combination of fluoroolefin in addition, and the comonomer of each combination also can contain fluoroolefin ethylene type unsaturated compound in addition.
In the ethylene type unsaturated compound beyond above-mentioned fluoroolefin and the fluoroolefin, in order to form fluoroelastomer with good sulfuration with low cost, preferably by can and the ethylene type unsaturated compound of vinylidene (VdF) copolymerization formed.
Fluoroelastomer by manufacture method manufacturing of the present invention is preferably more than at 100 ℃ mooney viscosity and equals 30, more preferably more than or equal to 35, by carrying out peroxide cure, with compare with the product in the past of viscosity that elongation is big, compression set (CS) and roller processibility be superior.High viscosity field, big more about compression set (CS) with the difference of product in the past.
If mooney viscosity less than 30 improves with the cross-linking efficiency of the product in the past of viscosity, thereby and in the past the difference of product tend to diminish, but product can't variation more in the past.
Then, new fluoroelastomer of the present invention, contain the vinylidene repeating unit of 20 moles of %~90 mole %, the R 1216 repeating unit of 10 moles of %~80 mole %, wherein, (a) contain the iodine atom of 0.01 weight %~10 weight % in elastomerics, (b) the polymkeric substance number-average molecular weight is 1,000~300,000, (c) use very high resolution
19F-NMR measures the acetone soln of polymer concentration about 20%, by following formula
δ F-96.5~-area between 99.5ppm
3 * (the area between δ F-88.0~124.0ppm
" the VdF branching rate " of trying to achieve is that described fluoroelastomer can carry out peroxide cure smaller or equal to 200ppm.
Fluoroelastomer of the present invention can be by above-mentioned method manufacturing.
Fluoroelastomer of the present invention preferably contains vinylidene (VdF) repeating unit of 20 moles of %~90 mole %, more preferably 40 moles of %~85 mole %; The vinylidene (VdF) and R 1216 (HFP) repeating unit that preferably contain 10 moles of %~80 mole %, more preferably 15 moles of %~60 mole %.
The VdF branching rate of the preferred following qualification of fluoroelastomer that 2 membered copolymers of VdF and HFP form is smaller or equal to 200ppm, more preferably smaller or equal to 150ppm.When VdF branching rate surpasses 200ppm, particularly use in the elastomerics, reduce because iodine is terminal at the peroxide cure that contains iodine, thereby the reduction of sulfuration efficient, compression set various rerum naturas such as (CS) tend to worsen.
With respect to above-mentioned VdF branching rate is the fluoroelastomer that forms smaller or equal to the VdF/HFP of 200ppm, the scope of not damaging its characteristic also can with other monomer copolymerizations.As other multipolymers, can illustration tetrafluoroethylene for example.Form as multipolymer, can enumerate tetrafluoroethylene (TFE) repeating unit of R 1216 (HFP) repeating unit of vinylidene (VdF) repeating unit of 30 moles of %~89 mole %, 10 moles of %~50 mole %, 0.1 mole of %~40 mole %.
Use very high resolution
19F-NMR measures the acetone soln (concentration about 20%) of polymkeric substance, obtains " VdF branching rate " by following calculating formula.
δ F-96.5~-area between 99.5ppm
3 * (δ F-88.0~-area between 124.0ppm)
The branching of afore mentioned rules mainly be meant as
The CF adjacent in such structural unit with branching CH base
2The base area, its appear at δ F-96.5~-99.5ppm between.The area at this peak with respect to δ F-88.0~-all CF that 124.0ppm occurs
2It is the branching rate that base adds up to the shared ratio of area.Yet, because with respect to a CF
2Chain exists 3 branching in abutting connection with CF
2Base, thereby be calculated as 1/3 of this measured value corresponding to the branching rate of unit VdF.
Be meant that at this so-called very high resolution utilization measures more than or equal to the spectrometer of 500MHz.
In addition, fluoroelastomer preferably contains the iodine atom of 0.01 weight %~10 weight % in elastomerics, more preferably 0.05 weight %~2.0 weight %.During iodine atom content less than 0.05 weight %, then vulcanize insufficiently, compression set tends to worsen; When surpassing 2.0 weight %, then cross-linking density is too high, and elongation is too small etc., and the performance of rubber tends to worsen.
And then elastomeric number-average molecular weight is preferably 1,000~300,000.Molecular weight less than 1,000 o'clock, then viscosity is low excessively, and operability tends to worsen; Surpass at 300,000 o'clock, viscosity is too high, and operability has the tendency of deterioration equally.
Molecular weight distribution (weight-average molecular weight Mw/ number-average molecular weight Mn) is preferably more than and equals 1.5, more preferably more than or equal to 1.8.During molecular weight distribution less than 1.5, though no problem aspect rerum natura, the roller processibility tends to worsen.
In addition, on the fluoroelastomer that obtains further progressively polymerizable crystallizable segment and the segment elastomerics that obtains can be aptly as thermoplastics etc.
Do not have special restriction as the crystallinity segment, can enumerate tetrafluoroethylene, perfluor (propyl group) vinyl ether, R 1216, ethene (ET), propylene, butylene etc.
In manufacture method of the present invention, can use oil soluble radical polymerization initiator or water-soluble radical initiator as polymerization starter.
The oil soluble radical polymerization initiator of Shi Yonging can use generally well-known oil soluble superoxide in the present invention, can enumerate for example dialkyl group peroxycarbonates class such as diisopropyl peroxydicarbonate, di-secondary butyl peroxyization two carbonic ethers as representational material; Peroxyesters such as tert-butyl hydroperoxide isobutyrate, tert-butyl hydroperoxide trimethylacetic acid ester; Dialkyl classes such as di-t-butyl peroxide; Also has peroxidation two (ω-hydrogen-ten difluoro oenanthyl); peroxidation two (ω-hydrogen-ten tetrafluoro oenanthyl); peroxidation two (ω-hydrogen-ten hexafluoro nonanoyl); peroxidation two (perfluor butyryl); peroxidation two (perfluor valeryl) (ジ (パ one Off Le パ レ リ Le) パ one オ キ サ イ De); peroxidation two (perfluor hexanoyl); peroxidation two (perfluor oenanthyl); peroxidation two (perfluor decoyl); peroxidation two (perfluor nonanoyl); peroxidation two (ω-chloro-hexafluoro butyryl); peroxidation two (ω-chloro-ten fluorine hexanoyls); peroxidation two (ω-chloro-ten tetrafluoro decoyls); peroxidation ω-hydrogen-ten difluoro oenanthyl-ω-hydrogen ten hexafluoro nonanoyls; peroxidation ω-chloro-hexafluoro butyryl radicals-ω-chloro-ten fluorine hexanoyls; peroxidation ω-hydrogen ten difluoros oenanthyl-perfluor butyryl; peroxidation two (dichloro five fluorine butyryl); peroxidation two (trichlorine octafluoro hexanoyl); peroxidation two (tetrachloro 11 fluorine decoyls); peroxidation two (pentachloro-ten tetrafluoro caprinoyls); peroxidation two peroxidation two such as (11 chlorine, 30 difluoro docosane acyls) [perfluor (perhaps fluorine chlorine) acyl group] class etc.
But, the problem that has as the di-isopropyl peroxycarbonates (IPP) and the di peroxycarbonates peroxycarbonates classes such as (NPP) of representative oil-soluble initiator is, they have the danger of blast, cost an arm and a leg, and the dirt that generates in polyreaction adheres to the wall of polymerization tank etc. easily, thereby preferably uses water-soluble radical polymerization initiator.
Use generally well-known water-soluble peroxide as water-soluble radical polymerization initiator, can enumerate for example persulfuric acid, peroxyboric acid, the ammonium salt of crossing chloric acid, peroxophosphoric acid, percarbonic acid etc., sylvite, sodium salt, the peroxidation toxilic acid tert-butyl ester, tertbutyl peroxide etc.
The addition of water-soluble radical initiator does not have special restriction, can add the amount (being several ppm to water concentration for example) that can significantly not reduce polymerization velocity once, in batches or continuously at the polymerization initial stage.On be limited to polymerization reaction heat can be from the scope of surface radiating of device.
In manufacture method of the present invention, can also add emulsifying agent, molecular weight regulator, pH regulator agent etc.Molecular weight regulator can disposable in the early stage interpolation, also can add continuously or in batches.
Can use nonionic surface active agent, aniorfic surfactant, cationic surfactant etc., fluorine series anion type tensio-active agents such as particularly preferred example such as ammonium perfluorocaprylate as emulsifying agent.Addition is preferably 50ppm~5000ppm.
As molecular weight regulator, can enumerate for example ester classes such as dimethyl malonate, diethyl malonate, ritalin, vinyl acetic monomer, N-BUTYL ACETATE, Succinic acid dimethylester; Also have iso-pentane, Virahol, acetone, various mercaptan, tetracol phenixin, hexanaphthene, single methyl iodide, 1-methyl iodide, 1-iodine n-propane, the different propane of iodate, methylene iodide, 1,2-methylene iodide, 1,3-diiodo-n-propane etc.
The buffer reagent etc. that can also suit to add in addition, but its consumption should be the scope of not damaging effect of the present invention.
Fluoroelastomer composition of the present invention comprises described fluoroelastomer and vulcanizing agent, also can contain vulcanization aid.
Can be suitable selected as operable vulcanizing agent among the present invention according to the vulcanization system that adopts.Any of polyamine vulcanization system, polyvalent alcohol vulcanization system, peroxide vulcanizing system can be adopted as vulcanization system, particularly when vulcanizing, effect of the present invention can be significantly brought into play with peroxide vulcanizing system.
As vulcanizing agent, the polyvalent alcohol vulcanization system can be enumerated for example polyols such as bisphenol AF, Resorcinol, dihydroxyphenyl propane, diamino bisphenol AF; Peroxide vulcanizing system can be enumerated for example α, α '-two (t-butyl peroxy) diisopropyl benzene, 2,5-dimethyl-2, organo-peroxides such as 5-two (t-butyl peroxy) hexane, dicumyl peroxide; The polyamine vulcanization system can be enumerated for example hexamethylene-diamine carbamate, N, N '-two Chinese cassia tree fork-1, polyamine compounds such as 6-hexamethylene-diamine.But be not limited to these.
Wherein, consider from sulfuration property, operability aspect preferred 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane.
With respect to 100 mass parts elastomericss, the use level of vulcanizing agent is 0.01 weight part~10 weight parts, is preferably 0.1 weight part~5 weight parts.When vulcanizing agent is less than 0.01 weight part, sulphidity deficiency then, thereby the performance of fluorine-containing moulding product tends to be compromised; When surpassing 10 weight parts, it is too high then to vulcanize density, thereby except curing time is elongated, also often also not preferred economically.
Can use various quaternary ammonium salts, season phosphonium salt, cyclic amine, simple function amine compound etc. to be normally used for elastomerics sulfurized organic bases as the vulcanization aid of polyvalent alcohol vulcanization system.As object lesson, can enumerate for example quaternary ammonium salts such as Tetrabutyl amonium bromide, tetrabutylammonium chloride, benzyl tributyl ammonium chloride, benzyltriethylammoinium chloride, 4-butyl ammonium hydrogen sulfate, TBAH; Season phosphonium salt such as benzyltriphenylphospchloride chloride phosphine, chlorination tributyl allyl group phosphine, chlorination tributyl-2-methoxy-propyl phosphine, zephiran chloride phenyl (dimethylamino) phosphine; Simple function amine such as benzyl methylamine, benzyl ethyl alcohol amine; 1,8-diaza-bicyclo [5.4.0]-undecane-cyclic amine such as 7-alkene etc.
Vulcanization aid as peroxide vulcanizing system, can enumerate triallyl cyanurate, triallyl isocyanurate (TAIC), three (diallyl amine-s-triazine), triallyl phosphorous acid ester, N, N-diallyl acrylamide, six allyl group phosphamides, N, N, N ', N '-tetraallyl four phthalamides, N, N, N ', N '-tetraallyl Malonamide, trivinyl chlorinated isocyanurates, 2,4,6-trivinyl methyl trisiloxanes, three (5-norbornylene-2-methylene radical) cyanurate etc.Wherein, consider preferred triallyl isocyanurate (TAIC) from the rerum natura aspect of sulfuration property, sulfide.
With respect to 100 weight part elastomericss, the use level of vulcanization aid is 0.01 weight part~10 weight parts, is preferably 0.1 weight part~5.0 weight parts.When vulcanization aid is less than 0.01 weight part, then curing time tend to elongated so that can not be practical; When surpassing 10 weight parts, then except curing time was too fast, the compression set of moulding product often also can reduce.
And then, only otherwise damage purpose of the present invention, also can use as the such metal hydroxides of the such metal oxide of packing material, processing aid, carbon black, inorganic filler, the magnesium oxide of common additive, calcium hydroxide etc.
The modulation of composition of the present invention and vulcanization process do not have special restriction, can adopt known method in the past such as for example compressed moulding, extrusion moulding, transfer mould moulding, injection moulding.
The tension fracture elongation rate (Eb) that uses vulcanizing agent to vulcanize the moulding product of fluoroelastomer is preferably 200%~550%.During tension fracture elongation rate less than 200%, then so-called " caoutchouc elasticity " can disappear, and often is not suitable for as sealing material; Surpass at 550% o'clock, then cross-linking density is low excessively, and compression set (CS) tends to worsen.
In addition, the moulding product are preferably 5%~30% 200 ℃, 72 hours compression set (CS), and more preferably 7%~25%.During compression set less than 5%, then stopping property is good, but usually elongation is often too small; Surpass 30%, then the performance of sealing material tends to worsen.
At this, the sulfuration among so-called the present invention is meant according to standard as follows and cooperates, vulcanizes by the standard cure condition.
(standard cooperation)
Fluoroelastomer 100 weight parts
Triallyl isocyanurate (TAIC) 4 weight parts
パ one ヘ キ サ 25B (PERHEXA 25B) 1.5 weight parts
Carbon black MT-C 20 weight parts
(standard cure condition)
Compounding process: roller is mixing
Press vulcanization: carried out 10 minutes at 160 ℃
Cure sulfuration: carried out 4 hours at 180 ℃
The iodine transfer polymerization reacting phase that carries out under manufacture method of the present invention and the low pressure in the past relatively, polymerization time is shortened significantly, and then the roller processibility of the fluoroelastomer that obtains is improved.Thereby when the goods of getting identical mooney viscosity in the fluoroelastomer that obtains by low pressure iodine transfer polymerization and the goods of the present invention compared, low stampings were separated out vulcanizing agent (TAIC) in mixing, and rubber is fracture easily often; And goods of the present invention are not found such phenomenon.
The composition that contains the fluoroelastomer that obtains by the present invention and vulcanizing agent can suit as the coating agent, one-piece type packing ring of base material and the sealing member class by disperseing moulding to form on the base material that contains inorganic materials such as metal, pottery, containing inorganic materials such as metal, pottery base material on the multi-layer product, magnetic recording system that form by coating with packing ring, fuel cell with sealing material, treating plant sealing material.
Evaluation method
<weight-average molecular weight (Mw) and number-average molecular weight (Mn) 〉
Device: HLC-8000 (eastern ソ one (strain) system)
Clear and post: 2 of GPC KF-806M
1 of GPC KF-801
2 of GPC KF-801
Detector: differential refractometer
Launch solvent: tetrahydrofuran (THF)
Temperature: 35 ℃
Sample solution concentration: 0.1 weight %
Standard test specimen: various monodisperse polystyrenes ((Mw/Mn)=1.14 (Max)), TSK polystyrene standard (eastern ソ one (strain) system)
<mooney viscosity 〉
Measure according to ASTM-D1646 and JIS K6300 standard.
The system MV2000E of determining instrument: ALPHA science and technology society type
Rotor revolution number: 2rpm
Measure temperature: 100 ℃
<compression set (CS) 〉
Under following standard cure condition, following standard title complex is carried out 1 press vulcanization and cures sulfuration 2 times, make O type ring (P-24), according to the compression set behind 1 press vulcanization of JIS-K6301 standard test with the compression set (CS) after curing sulfuration for 2 times (, measuring this sample) in 25 ℃ thermostatic chamber, placing 30 minutes after keeping 72 hours in 200 ℃ under the 25% pressurization compression.
(standard cooperation)
Fluoroelastomer 100 weight parts
Triallyl isocyanurate (TAIC) 4 weight parts
パ one ヘ キ サ 25B (PERHEXA 25B) 1.5 weight parts
Carbon black MT-C 20 weight parts
(standard cure condition)
Compounding process: roller is mixing
Press vulcanization: carried out 10 minutes at 160 ℃
Cure sulfuration: carried out 4 hours at 180 ℃
<100% tensile stress (modulus) (M100) 〉
Under the standard cure condition, the standard title complex is carried out 1 press vulcanization and cures sulfuration 2 times, form the thin slice of thickness 2mm, measure according to the JIS-K6251 standard.
<tensile break strength (Tb) and tension fracture elongation rate (Eb) 〉
Under the standard cure condition, the standard title complex is carried out 1 press vulcanization and cures sulfuration 2 times, form the thin slice of thickness 2mm, measure according to the JIS-K6251 standard.
<hardness (Hs) 〉
Under the standard cure condition, the standard title complex is carried out 1 press vulcanization and cures sulfuration 2 times, form the thin slice of thickness 2mm, measure according to the JIS-K6253 standard.
<vulcanization characteristics 〉
Use JIR type vulcanizing ingredient (キ ユ ラ ス ト メ one ) II type and V-type are obtained the vulcanization curve at 170 ℃ when 1 press vulcanization, obtain MV minium viscosity (ML), sulphidity (MH), induction time (T
10) and optimum sulfurating time (T
90).
The median size of<polymkeric substance is measured 〉
Measure particle diameter with miniature tracer 9340UPA (HONEYWELL society system).
<population is calculated 〉
Use the measurement result of the median size of above-mentioned polymkeric substance to calculate population by following formula.
<VdF branching rate is measured 〉
To measure sample dissolution in acetone, and make its concentration be about 20%.By
19F-NMR (the system AMX500 of Bruker society type) measures it, uses MestRe-C2.3a (MestRe-C science and technology society system) for process software, calculates branching peak area and whole CF
2Peak area is obtained the branching rate by the result who obtains.
<compositional analysis 〉
Use
19F-NMR (the system AMX500 of Bruker society type) measures.But, contain the TFE polymkeric substance and use
19F-NMR (NEC (strain) system FX100 type) measures.
<ultimate analysis 〉
Use Yokogawa Off ユ one レ Star ト パ Star カ one G2350A of De society type to measure.
<Peng-Robinson Equation for Calculating 〉
Use Aspen Plus Ver.11.1 (Aspen science and technology society system).Each monomeric critical temperature, emergent pressure, eccentric factor all use the value that is stored in the software.
T
c:VdF 29.65℃,
TFE 33.3℃,
HFP 85.0℃
P
c:VdF 4.46MPa/SQCM,
TFE 3.94MPa/SQCM,
HFP 3.21MPa/SQCM
ω:VdF 0.136,
TFE 0.226,
HFP 0.382
Reference example 1
(polymerization of seed polymer particle)
Having the internal volume of electromagnetic induction whipping appts as whipping appts is in 1.8 liters the polymerization tank, adds perfluoro ammonium caprylate aqueous solution and the 0.6g diethyl malonate of 720g pure water, 290g 10 weight %, reduces pressure after fully replacing in the system with nitrogen.Repeating 3 times should operate, and added 20gVdF and 51gHFP under decompression state, and under agitation was warming up to 80 ℃.Then, be pressed into 0.02g with nitrogen and be dissolved in persulfuric acid ammonium salt (APS) in the 0.6g pure water, the beginning polymerization.Making polymerization pressure is 2MPa, and the pressure when remedying polymerization reduces, and supplies with VdF/HFP mix monomer (78/22 (mole %)) continuously, under agitation carries out polymerization.Finish until polymerization, in groove, supply with the 215g monomer.
The weight of the emulsion that obtains is 1233g, and polymer concentration is 18.1 weight %, and obtaining the polymer beads subnumber is 1.2 * 10
16The emulsion of individual/1g water.Stop after 30 minutes stirring, emit monomer, stop polymerization.
Reference example 2
(polymerization of seeding polymerization particle)
Having the internal volume of electromagnetic induction whipping appts as whipping appts is in 1.8 liters the polymerization tank, adds the perfluoro ammonium caprylate aqueous solution of 809g pure water, 200g 10 weight %, reduces pressure after fully replacing in the system with nitrogen.Repeating 3 times should operation, adds the 0.5mL iso-pentane under decompression state, drops into each monomer again, make 80 ℃ mutually in consist of VdF/TFE/HFP=29.0/13.0/58.0 mole %, the groove internal pressure is 1.4MPa.After heat up finishing, be pressed into 0.67g with nitrogen and be dissolved in persulfuric acid ammonium salt (APS) in the 20g pure water, beginning polymerization.Making polymerization pressure is 1.4MPa, and the pressure when remedying polymerization reduces, and supplies with VdF/TFE/HFP mix monomer (50/20/30 (mole %)) continuously, under agitation carries out polymerization.Finish until polymerization, in groove, supply with the 320g monomer.
The weight of the emulsion that obtains is 1285g, and polymer concentration is 24.8 weight %, and obtaining the polymer beads subnumber is 1.0 * 10
15The emulsion of individual/1g water.Stop after 360 minutes stirring, emit monomer, stop polymerization.
Embodiment 1
Having internal volume with the same electromagnetic induction whipping appts of reference example 1 is to add the aqueous liquid dispersion of the polymer particle that 1324g pure water, 33.5g make in reference example 1 and the perfluoro ammonium caprylate aqueous solution of 19.1g 10 weight % in 2.5 liters the polymerization tank, reduces pressure after fully replacing in the system with nitrogen.Repeating 3 times should operate, and added 171gVdF and 729gHFP under decompression state, and under agitation was warming up to 80 ℃.Then, be pressed into 2.98g octafluoro-1 with nitrogen, 4-two butyl iodides and 0.068g are dissolved in the APS in the 15g pure water, and initiated polymerization is proceeded polymerization under (a) and (b) and condition (c), stop after 4.3 hours stirring, and emits monomer, stops polymerization.
(a) VdF/HFP=36/64 (mole %) carries out critical temperature by the Peng-Robinson equation and emergent pressure is calculated at forming in the polymerization tank to use Aspen Plus Ver.11.1, and the result is T
c=87.7 ℃, P
c=3.05MPa.And then by reduced temperature T
R0.95, reduced pressure P
R0.80 when carrying out conversion, T=69.7 ℃, P=2.44MPa, the polymerizing condition of present embodiment are more than or equal to reduced temperature and more than or equal to reduced pressure.
(b) supply with VdF/HFP (95/5 (mole %)) monomer mixture continuously, gas phase pressure is partly maintained 6MPa.And, finish until polymerization, in groove, supply with the 302g monomer.
(c) keep stirring velocity at 560rpm.
Adding 0.034g was dissolved in the APS in the 15g pure water when (d) polymerization time surpassed 3 hours.
The weight of the emulsion that obtains is 1879g, and polymer concentration is 29.6 weight %, and the polymer beads subnumber is 2.7 * 10
14Individual/1g water.And fluoroelastomer is 566g, and the weight-average molecular weight Mw that measures with GPC is 23.6 ten thousand, and number-average molecular weight Mn is that 11.3 ten thousand, Mw/Mn are 2.1.With
19The polymkeric substance that F-NMR measures consist of VdF/HFP=77/23 (mole %).
Embodiment 2
Except making APS is the 0.17g, similarly to Example 1 polymerization fluoroelastomer.
Polymerization time is 1.5 hours, and the weight of the emulsion that obtains is 1909g, and polymer concentration is 30.1 weight %, and the polymer beads subnumber is 2.9 * 10
14Individual/1g water.And fluoroelastomer is 575g, and the weight-average molecular weight Mw that measures with GPC is 27.7 ten thousand, and number-average molecular weight Mn is that 10.3 ten thousand, Mw/Mn are 2.7.With
19The polymkeric substance that F-NMR measures consist of VdF/HFP=76/24 (mole %).
Embodiment 3
Except making octafluoro-1,4-two butyl iodides are beyond the 5.96g, similarly to Example 1 polymerization fluoroelastomer.
Polymerization time is 3.4 hours, and the weight of the emulsion that obtains is 1899g, and polymer concentration is 28.6 weight %, and the polymer beads subnumber is 2.6 * 10
14Individual/1g water.And fluoroelastomer is 543g, and the weight-average molecular weight Mw that measures with GPC is 10.5 ten thousand, and number-average molecular weight Mn is that 5.63 ten thousand, Mw/Mn are 1.9.With
19The polymkeric substance that F-NMR measures consist of VdF/HFP=77/23 (mole %).
Comparative example 1
Having internal volume with the same electromagnetic induction whipping appts of reference example 1 is to add the aqueous liquid dispersion of the polymer particle that 1324g pure water, 33.5g make in reference example 1 and the perfluoro ammonium caprylate aqueous solution of 19.1g 10 weight % in 2.5 liters the polymerization tank, reduces pressure after fully replacing in the system with nitrogen.Repeating 3 times should operate, and added 20gVdF and 57gHFP under decompression state, and under agitation was warming up to 80 ℃.Then, be pressed into 2.98g octafluoro-1 with nitrogen, 4-two butyl iodides and 0.068g are dissolved in the APS in the 15g pure water, and initiated polymerization is proceeded polymerization under (a) and (b), (c) and condition (d), stop after 16.5 hours stirring, and emit monomer, stop polymerization.
(a) VdF/HFP=50/50 (mole %) carries out critical temperature by the Peng-Robinson equation and emergent pressure is calculated at forming in the polymerization tank to use Aspen Plus Ver.11.1, and the result is T
c=57.3 ℃, P
c=3.83MPa.And then by reduced temperature T
R0.95, reduced pressure P
R0.80 when carrying out conversion, T=40.8 ℃, P=3.06MPa, the polymerizing condition of this comparative example are more than or equal to reduced temperature and smaller or equal to reduced pressure.
(b) supply with VdF/HFP (78/22 (mole %)) monomer mixture continuously, gas phase pressure is partly maintained 1.5MPa.And, finish until polymerization, in groove, supply with the 570g monomer.
(c) keep stirring velocity at 560rpm.
(d) the every mistake of polymerization time adding in 3 hours 0.034g is dissolved in the APS in the 15g pure water.
The weight of the emulsion that obtains is 2087g, and polymer concentration is 27.7 weight %, and the polymer beads subnumber is 1.4 * 10
14Individual/1g water.And fluoroelastomer is 578g, and the weight-average molecular weight Mw that measures with GPC is 18.3 ten thousand, and number-average molecular weight Mn is that 13.3 ten thousand, Mw/Mn are 1.4.With
19The polymkeric substance that F-NMR measures consist of VdF/HFP=77.3/22.7 (mole %).
Embodiment 4~6 and comparative example 2
Use the fluoroelastomer that obtains in embodiment 1~3 and the comparative example 1 to obtain fluorine-containing moulding product according to following cooperation, cure conditions.Evaluation result is shown in Table 1.
(standard cooperation)
Fluoroelastomer 100 weight parts
Triallyl isocyanurate (TAIC) 4 weight parts
パ one ヘ キ サ 25B 1.5 weight parts
Carbon black MT-C 20 weight parts
(standard cure condition)
Compounding process: roller is mixing
Press vulcanization: carried out 10 minutes at 160 ℃
Cure sulfuration: carried out 4 hours at 180 ℃
Table 1
Unit | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 2 | |
Polymkeric substance is formed | |||||
VdF/HFP | Mole % | 77.3/22.7 | 76.0/24.0 | 77.1/22.9 | 77.3/22.7 |
The branching rate | ppm | 138 | 136 | 124 | 337 |
Iodine content | Weight % | 0.21 | 0.20 | 0.53 | 0.17 |
Number-average molecular weight (Mn) | 1.13E+05 | 1.03E+05 | 5.63E+04 | 1.33E+05 | |
Polymkeric substance mooney viscosity ML1+10,100 ℃ | 65 | 58 | 11 | 71 | |
Vulcanizing ingredient II type (160 ℃) | |||||
Minimum torque (ML) | kgf | 0.08 | 0.08 | 0.03 | 0.09 |
Sulphidity (MH) | kgf | 4.02 | 3.22 | 4.13 | 3.48 |
Induction time (T10) | Divide | 1.00 | 0.80 | 1.10 | 0.80 |
Optimum sulfurating time (T90) | Divide | 2.30 | 2.10 | 2.90 | 2.00 |
100% tensile stress | MPa | 2.1 | 2.0 | 2.7 | 1.9 |
Tensile break strength | MPa | 22.9 | 21.9 | 18.5 | 22.6 |
Tension fracture elongation rate | % | 430 | 410 | 300 | 480 |
Hardness (shore A) peak value | 66 | 67 | 68 | 67 | |
Compression set | |||||
(25℃×72hr) | % | 9.3 | 9.4 | 7.2 | 14.4 |
(200℃×72hr) | % | 24.7 | 24.5 | 20.4 | 32.2 |
Embodiment 7
Having internal volume with the same electromagnetic induction whipping appts of reference example 1 is the aqueous liquid dispersion that adds the polymer particle that 970g pure water, 27g make in 1.8 liters the polymerization tank in reference example 2, reduces pressure after fully replacing in the system with nitrogen.Repeating 3 times should operate, and added 18g VdF, 22g TFE, 537g HFP under decompression state, and under agitation was warming up to 80 ℃.Then, be pressed into 2.8g octafluoro-1 with nitrogen, 4-two butyl iodides and 0.05g are dissolved in the APS in the 15g pure water, and initiated polymerization is proceeded polymerization under (a) and (b) and condition (c), stop after 3.6 hours stirring, and emits monomer and stops polymerization.
(a) VdF/TFE/HFP=6.5/5.0/88.5 (mole %) carries out critical temperature by the Peng-Robinson equation and emergent pressure is calculated at forming in the polymerization tank to use Aspen Plus Ver.11.1, and the result is T
c=87.7 ℃, P
c=3.05MPa.And then by reduced temperature T
R0.95, reduced pressure P
R0.80 when carrying out conversion, T=69.7 ℃, P=2.44MPa, the polymerizing condition of present embodiment are more than or equal to reduced temperature and more than or equal to reduced pressure.
(b) supply with VdF/TFE/HFP (68.0/23.8/8.2 (mole %)) monomer mixture continuously, gas phase pressure is partly maintained 3.5MPa.And, finish until polymerization, in groove, supply with the 247g monomer.
(c) keep stirring velocity at 560rpm.
The weight of the emulsion that obtains is 1368g, and polymer concentration is 26.8 weight %, and the polymer beads subnumber is 9.5 * 10
14Individual/1g water.And fluoroelastomer is 369g, and the weight-average molecular weight Mw that measures with GPC is 6.7 ten thousand, and number-average molecular weight Mn is 4.8 ten thousand, and Mw/Mn is 1.4.With
19The polymkeric substance that F-NMR measures consist of VdF/TFE/HFP=50.7/19.5/29.8 (mole %).
Embodiment 8
Except making octafluoro-1,4-two butyl iodides are beyond the 2.4g, similarly to Example 7 polymerization fluoroelastomer.
Polymerization time is 4.2 hours, and the weight of the emulsion that obtains is 1401g, and polymer concentration is 28.6 weight %, and the polymer beads subnumber is 3.5 * 10
14Individual/1g water.And fluoroelastomer is 396g, and the weight-average molecular weight Mw that measures with GPC is 8.7 ten thousand, and number-average molecular weight Mn is 5.7 ten thousand, and Mw/Mn is 1.5.With
19The polymkeric substance that F-NMR measures consist of VdF/TFE/HFP=51.0/19.8/29.2 (mole %).
Embodiment 9
Except following (a) and (b), (c), similarly to Example 7 polymerization fluoroelastomer: (a) add 2.4g octafluoro-1,4-two butyl iodides, (b) added 3.96gCF at 50% o'clock that adds amount of monomer
2=CFOCF
2CF
2CH
2I, (c) added 0.025g in 3 hours in the every mistake of polymerization time and are dissolved in APS in the 15g pure water.
Polymerization time is 3.8 hours, and the weight of the emulsion that obtains is 1391g, and polymer concentration is 27.3 weight %, and the polymer beads subnumber is 8.3 * 10
14Individual/1g water.And fluoroelastomer is 384g, and the weight-average molecular weight Mw that measures with GPC is 9.2 ten thousand, and number-average molecular weight Mn is 5.9 ten thousand, and Mw/Mn is 1.6.With
19The polymkeric substance that F-NMR measures consist of VdF/TFE/HFP=52.0/20.7/27.3 (mole %).
Comparative example 3
Having internal volume with the same electromagnetic induction whipping appts of reference example 7 is the aqueous liquid dispersion that adds the polymer particle that 970g pure water, 27g make in 1.83 liters the polymerization tank in reference example 2, reduces pressure after fully replacing in the system with nitrogen.Repeating 3 times should operation, adds each monomer under decompression state, makes and consist of VdF/TFE/HFP=11.0/19.0/70.0 (mole %) in 80 ℃ groove, the groove internal pressure is 1.5MPa.Then, be pressed into 1.7g octafluoro-1 with nitrogen, 4-two butyl iodides and 0.05g are dissolved in the APS in the 15g pure water, and initiated polymerization is proceeded polymerization under the condition of (a)~(d), stop after 15.3 hours stirring, and emit monomer and stop polymerization.
(a) VdF/TFE/HFP=11/19/70 (mole %) carries out critical temperature by the Peng-Robinson equation and emergent pressure is calculated at forming in the polymerization tank to use Aspen Plus Ver.11.1, and the result is T
c=69.0 ℃, P
c=3.48MPa.And then by reduced temperature T
R0.95, reduced pressure P
R0.80 when carrying out conversion, T=51.9 ℃, P=2.78MPa, the polymerizing condition of present embodiment are more than or equal to reduced temperature and smaller or equal to reduced pressure.
(b) supply with VdF/TFE/HFP (50.0/20.0/30.0 (mole %)) monomer mixture continuously, gas phase pressure is partly maintained 1.5MPa.And, finish until polymerization, in groove, supply with the 370g monomer.
(c) keep stirring velocity at 560rpm.
(d) the every mistake of polymerization time adding in 3 hours 0.025g is dissolved in the APS in the 15g pure water.
The weight of the emulsion that obtains is 1410g, and polymer concentration is 26.2 weight %, and the polymer beads subnumber is 3.9 * 10
14Individual/1g water.And fluoroelastomer is 370g, and the weight-average molecular weight Mw that measures with GPC is 8.5 ten thousand, and number-average molecular weight Mn is 6.1 ten thousand, and Mw/Mn is 1.4.With
19The polymkeric substance that F-NMR measures consist of VdF/TFE/HFP=50.2/19.8/30.0 (mole %).
Embodiment 10~12 and comparative example 4
Use the fluoroelastomer that obtains in embodiment 7~9 and the comparative example 3 to obtain fluorine-containing moulding product according to following cooperation, cure conditions.Evaluation result is shown in Table 2.
(standard cooperation)
Fluoroelastomer 100 weight parts
Triallyl isocyanurate (TAIC) 4 weight parts
パ one ヘ キ サ 25B 1.5 weight parts
Carbon black MT-C 20 weight parts
(standard cure condition)
Compounding process: roller is mixing
Press vulcanization: carried out 10 minutes at 160 ℃
Cure sulfuration: carried out 4 hours at 180 ℃
Table 2
Unit | Embodiment 10 | Embodiment 11 | Embodiment 12 | Comparative example 4 | |
Polymkeric substance is formed VdF/TFE/HFP | Mole % | 50.7/19.5/29.8 | 51.0/19.8/29.2 | 52.0/20.7/27.3 | 50.2/19.8/30.0 |
Iodine content | Weight % | 0.32 | 0.26 | 0.40 | 0.23 |
Number-average molecular weight (Mn) | 4.8E+05 | 5.7E+05 | 5.9E+05 | 6.1E+05 | |
Polymkeric substance mooney viscosity ML1+10,100 ℃ | 20 | 46 | 27 | 48 | |
Vulcanizing ingredient II type (160 ℃) | |||||
Minimum torque (ML) | kgf | 0.1 | 0.2 | 0.1 | 0.1 |
Sulphidity (MH) | kgf | 5.0 | 4.9 | 5.1 | 4.7 |
Induction time (T10) | Divide | 1.0 | 1.0 | 0.8 | 1.0 |
Optimum sulfurating time (T90) | Divide | 2.3 | 2.4 | 2.2 | 2.4 |
100% tensile stress | MPa | 3.9 | 3.6 | 5.1 | 3.3 |
Tensile break strength | MPa | 20.2 | 19.5 | 18.0 | 21.2 |
Tension fracture elongation rate | % | 310 | 320 | 210 | 320 |
Hardness (shore A) peak value | 74 | 73 | 73 | 73 | |
Compression set | |||||
(200℃×72hr) | % | 16.5 | 18.5 | 12.4 | 22.5 |
The possibility of utilizing on the industry
The present invention is by under high pressure carrying out the manufacture method that the iodine transfer polymerization provides fluoroelastomer, and in this manufacture method, although polymerization initiator is few, polymerization speed increases significantly, and has the high production rate that is equal to mutually with non-iodine-transfer polymerization method. And then few, the terminal iodine atom content of its side chain of elastomer of making by the method is high, and the superior fluorine-containing products formed of balance of fluoroelastomer and compression set and tension fracture elongation rate is provided in addition.
Claims (9)
1, the manufacture method of fluoroelastomer, it is the manufacture method that adopts the fluoroelastomer of intermittent type copolymerization method, its use the Peng-Robinson equation by reactive tank in each monomeric critical temperature in the gas phase part, emergent pressure and the ratio of components separately critical constants of calculating reduced temperature for more than or equal to 0.95, reduced pressure carries out under more than or equal to 0.80 condition, wherein, be R at general formula
f 1I
xExistence under make the ethylene type unsaturated compound copolymerization that contains at least a fluoroolefin, in the described general formula, R
f 1Be that carbonatoms is 1~16 saturated or undersaturated fluorocarbon based or Chlorofluorocarbons (CFCs) base, x is R
fThe bonding valence mumber, it is 1~4 integer.
2, the manufacture method of fluoroelastomer as claimed in claim 1, wherein, polymerization time slot internal pressure is more than or equal to 3MPa.
3, the manufacture method of fluoroelastomer as claimed in claim 1 or 2, wherein, when polymerization finishes in every 1g water the fluoroelastomer population be more than or equal to 5 * 10
13Individual.
4, as the manufacture method of claim 1,2 or 3 described fluoroelastomers, wherein, fluoroolefin is CX
1X
2=CX
3X
4, X
1~X
3Be hydrogen atom or halogen atom, X
4For hydrogen atom, halogen atom, carboxyl, carbonatoms be 1~9 and the alkyl that contains or do not contain ehter bond type Sauerstoffatom that replaced by fluorine atom of some or all of hydrogen atom or carbonatoms be 1~9 and the alkoxyl group that contains or do not contain ehter bond type Sauerstoffatom that replaced by fluorine atom of some or all of hydrogen atom, this alkene contains 1 fluorine atom at least.
5, as the manufacture method of claim 1,2 or 3 described fluoroelastomers, wherein, fluoroolefin contains and is selected from by R 1216, tetrafluoroethylene, trifluoro-ethylene, five fluorine propylene, vinyl fluoride, hexafluoro-isobutene, perfluor (alkyl vinyl ether) class, poly-fluorine dienes and following formula
Compound in the group of forming; Y is-CH in the formula
2I ,-OH ,-COOH ,-SO
2F ,-SO
3M, carboxylate salt, carboxylic ester group, epoxy group(ing), itrile group, iodine atom, M are hydrogen, NH
4Base or basic metal; X
5And X
6Identical or different, respectively do for oneself hydrogen atom or fluorine atom; R
f 2Be that carbonatoms is 0~40 the fluorine-containing alkylidene group of divalent, contain or do not contain ehter bond type Sauerstoffatom.
6, fluoroelastomer, it is obtained by claim 1,2,3,4 or 5 described manufacture method, is more than or equal to 30 at 100 ℃ mooney viscosities.
7, fluoroelastomer, described fluoroelastomer contains the vinylidene fluoride repeating unit of 20 moles of %~90 mole %, the R 1216 repeating unit of 10 moles of %~80 mole %, wherein, (a) in elastomerics, contain the iodine atom of 0.01 weight %~10 weight %, (b) the polymkeric substance number-average molecular weight is 1,000~300,000, (c) use high resolving power
19F-NMR measures the acetone soln of polymer concentration about 20%, by following formula
" the VdF branching rate " of trying to achieve is that described fluorine-containing resilient energy is carried out peroxide cure smaller or equal to 200ppm.
8, fluoroelastomer as claimed in claim 7, wherein, the tension fracture elongation rate Eb of the formed body that obtains of sulfuration is 200%~550%, and is 5%~30% at 200 ℃, 72 hours compression set CS.
9, composition is used in fluoroelastomer curing, and it contains claim 7 or 8 described fluoroelastomer and vulcanizing agents.
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Cited By (5)
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CN101977982B (en) * | 2008-03-27 | 2012-10-24 | 大金工业株式会社 | Fluorine-containing elastomer composition |
CN103354814A (en) * | 2010-12-17 | 2013-10-16 | 3M创新有限公司 | Partially fluorinated polysulfinic acids and their salts |
CN102317330B (en) * | 2009-02-13 | 2014-09-24 | 索尔维索莱克西斯公司 | Perfluoroelastomer |
CN104540861A (en) * | 2012-04-26 | 2015-04-22 | 阿肯马法国公司 | Controlled free-radical copolymerisation of trifluoroethylene |
CN105940027A (en) * | 2013-09-30 | 2016-09-14 | 霍尼韦尔国际公司 | Synthesis of chlorotrifluoroethylene-based block copolymers by iodine transfer polymerization |
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US5037921A (en) * | 1990-03-01 | 1991-08-06 | E. I. Du Pont De Nemours And Company | Base resistant fluoroelastomers with improved processibility and curability |
US6716942B1 (en) * | 1999-02-15 | 2004-04-06 | Daikin Industries, Ltd. | Process for producing fluoropolymer |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101977982B (en) * | 2008-03-27 | 2012-10-24 | 大金工业株式会社 | Fluorine-containing elastomer composition |
CN102317330B (en) * | 2009-02-13 | 2014-09-24 | 索尔维索莱克西斯公司 | Perfluoroelastomer |
CN103354814A (en) * | 2010-12-17 | 2013-10-16 | 3M创新有限公司 | Partially fluorinated polysulfinic acids and their salts |
CN103354814B (en) * | 2010-12-17 | 2017-04-26 | 3M创新有限公司 | Partially fluorinated polysulfinic acids and their salts |
CN104540861A (en) * | 2012-04-26 | 2015-04-22 | 阿肯马法国公司 | Controlled free-radical copolymerisation of trifluoroethylene |
CN104540861B (en) * | 2012-04-26 | 2016-08-24 | 阿肯马法国公司 | The controlled free-radical copolymerization of trifluoro-ethylene |
CN105940027A (en) * | 2013-09-30 | 2016-09-14 | 霍尼韦尔国际公司 | Synthesis of chlorotrifluoroethylene-based block copolymers by iodine transfer polymerization |
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