WO2005097835A1 - 含フッ素エラストマー重合体の製造方法 - Google Patents
含フッ素エラストマー重合体の製造方法 Download PDFInfo
- Publication number
- WO2005097835A1 WO2005097835A1 PCT/JP2005/006677 JP2005006677W WO2005097835A1 WO 2005097835 A1 WO2005097835 A1 WO 2005097835A1 JP 2005006677 W JP2005006677 W JP 2005006677W WO 2005097835 A1 WO2005097835 A1 WO 2005097835A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fluorine
- vinyl group
- integer
- fluorinated
- compound
- Prior art date
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 211
- 239000011737 fluorine Substances 0.000 title claims abstract description 202
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 229920000642 polymer Polymers 0.000 title claims abstract description 130
- 229920001971 elastomer Polymers 0.000 title claims abstract description 107
- 239000000806 elastomer Substances 0.000 title claims abstract description 101
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 89
- 150000001875 compounds Chemical class 0.000 claims abstract description 76
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 63
- 239000000178 monomer Substances 0.000 claims abstract description 59
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 49
- 229920001577 copolymer Polymers 0.000 claims description 47
- 239000012736 aqueous medium Substances 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- 229910052783 alkali metal Inorganic materials 0.000 claims description 31
- 239000006185 dispersion Substances 0.000 claims description 30
- 150000001340 alkali metals Chemical class 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 22
- -1 carboxylic acid ester compound Chemical class 0.000 claims description 21
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 12
- 229920001973 fluoroelastomer Polymers 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 230000000379 polymerizing effect Effects 0.000 claims description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 239000004815 dispersion polymer Substances 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 238000004581 coalescence Methods 0.000 claims 2
- 239000003125 aqueous solvent Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 16
- 239000000839 emulsion Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 230000006835 compression Effects 0.000 description 9
- 238000007906 compression Methods 0.000 description 9
- 238000005345 coagulation Methods 0.000 description 8
- 230000015271 coagulation Effects 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 238000004073 vulcanization Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 5
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 5
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000001804 emulsifying effect Effects 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical class CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000001112 coagulating effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- FCBJLBCGHCTPAQ-UHFFFAOYSA-N 1-fluorobutane Chemical compound CCCCF FCBJLBCGHCTPAQ-UHFFFAOYSA-N 0.000 description 1
- CVXFRGDAMPVAMJ-UHFFFAOYSA-N 2-(sulfanylamino)phenol Chemical compound OC1=CC=CC=C1NS CVXFRGDAMPVAMJ-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-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
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- XUDOZULIAWNMIU-UHFFFAOYSA-N delta-hexenoic acid Chemical compound OC(=O)CCCC=C XUDOZULIAWNMIU-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001682 microtransfer moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 229920005548 perfluoropolymer Polymers 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N propionic acid ethyl ester Natural products CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004885 tandem mass spectrometry Methods 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
Definitions
- Patent Literature 2 does not suggest that polymerization can be stably performed even in the presence of a chain transfer agent while applying force. Further, there is no description of seed polymerization of a fluorine-free monomer in the presence of the aqueous dispersion of the VDF copolymer, but there is no description of seed polymerization of a fluorine-containing monomer.
- a first-stage polymerization is carried out in an aqueous medium in the presence of an emulsifier in an amount of 0.5% by weight or more of the aqueous medium, and the resulting seed particles have milk strength.
- a method of performing multi-stage polymerization by adding a monomer after diluting a suspension for example, see Patent Document 3. According to this method, the production efficiency can be increased by reducing the amount of the emulsifier to be used by performing multi-stage polymerization, but a certain amount of the emulsifier remains.
- Patent Document 3 does not suggest that this multi-stage polymerization is performed in the presence of a fluorine-containing vinyl group-containing emulsifier!
- Patent Document 2 JP-A-8-67795
- Patent document 3 International publication 00Z001741 pamphlet
- An object of the present invention is to provide a method for producing a fluoroelastomer polymer excellent in productivity and crosslinkability in view of the above situation.
- the present invention is a process for producing a fluorine-containing elastomer polymer, comprising polymerizing a fluorine-containing monomer in an aqueous medium in the presence of a fluorine-containing vinyl group-containing emulsifier and a chain transfer agent.
- the present invention is a process for producing a fluorine-containing elastomer polymer, comprising polymerizing a fluorine-containing monomer in an aqueous medium in the presence of a fluorine-containing vinyl group-containing emulsifier and a chain transfer agent.
- the fluorine-containing vinyl group-containing emulsifier has the following general formula (I)
- a represents an integer of 1 to 10
- Y represents —SO M or —COOM
- M represents H
- b represents an integer of 1 to 5
- Y represents —SO M or —COOM
- M represents H
- c represents an integer of 1 to 10
- Y represents —SO M or —COOM
- M represents H
- X represents F or CF
- d represents an integer of 0 to 2
- e represents an integer of 1 to 10.
- F represents an integer of 1 to 3
- Y represents -SO M or COOM
- M represents H
- a fluorine-containing vinyl group-containing compound (IV) represented by the following general formula (V):
- g represents an integer of 0 to 10
- Y represents -SO M or COOM
- M represents H
- h represents an integer of 1 to 6
- i represents an integer of 1 to 10
- Y represents SOM or C
- pl represents an integer of 1 to 10
- Y represents —SO M or —COOM
- M represents H
- q represents an integer of 1 to 4
- p2 represents an integer of 1 to 10
- Y is —SO M or
- the present invention provides an aqueous dispersion of a fluorinated elastomer, wherein the fluorinated elastomer is dispersed in an aqueous medium, wherein the fluorinated elastomer is a method for producing the fluorinated elastomer.
- a fluorinated elastomer polymer produced by the above wherein the fluorinated elastomer-polymer aqueous dispersion is a fluorinated vinyl group Containing or not containing a emulsifier, wherein the fluorinated vinyl group-containing oxidizing agent is less than 100 ppm of the fluorinated elastomer-polymer aqueous dispersion. It is a monopolymer aqueous dispersion.
- fluorine-containing elastomer polymer means an amorphous fluorine-containing polymer having rubber elasticity.
- the fluorine-containing polymer is a polymer having at least 58% by mass, preferably 64% by mass of fluorine atoms, and may be a partially fluorinated polymer or a perfluoropolymer.
- the fluorine-containing elastomer polymer has 30 to 80% by mass of a copolymerized unit of the first monomer.
- first monomer refers to the above-mentioned fluorinated elastomer which constitutes a copolymer unit which occupies the largest mass among all copolymer units in the molecular structure of the fluorinated elastomer polymer.
- VDF copolymer the copolymer in which the first monomer is VDF
- TFE the polymer in which the first monomer is TFE
- the above copolymer unit is a part of the molecular structure of the fluorine-containing elastomer polymer, and means a part derived from the corresponding monomer.
- the VDF unit is a part on the molecular structure of the VDF-based copolymer and is a part derived from VDF, and is represented by-(CH-CF)-.
- the above "all copolymerized units" is a fluorine-containing elastomer
- the content of the monomer unit can be obtained by measuring F 19 -NMR.
- a copolymer unit derived from a monomer other than the first monomer is any one of monomers copolymerizable with the first monomer. It may be derived from only the first monomer or two or more monomers copolymerizable with the first monomer.
- Examples of monomers copolymerizable with the first monomer include fluorine-containing olefins, fluorine-containing butyl ethers, and hydrocarbon olefins.
- the fluorine-containing olefin is not particularly limited. For example, hexafluoropropylene [HFP], tetrafluoroethylene [TFE], 1,2,3,3,3 pentafluorop pen [1-HPFP] , Trifluoroethylene [CTFE], and butyl fluoride [VF].
- the fluorine-containing butyl ether is not particularly limited, but includes perfluoro (alkyl butyl ether).
- a 6 par full O b alkylene group, m and n are independently an integer from 0 to 10, Rf e is the par full O b alkyl group having 1 to 6 carbon atoms. Are preferred.
- Rf d is a perfluoroalkyl group having 1 to 6 carbon atoms. And more preferably a compound represented by the formula:
- the PAVE is preferably perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], or perfluoro (propyl vinyl ether) [PPVE].
- Rf e is preferably CF
- u is an integer of 1
- V is an integer of 1
- n and n are independently integers from 0 to 10
- y is an integer from 0 to 3
- z is
- n and n are each independently an integer of 0 or 1, and z is preferably an integer of 1.
- the PAVE unit is preferably 20 to 70% by mass.
- the hydrocarbon olefin is not particularly limited, but is preferably propene such as ethylene and propene.
- the fluorine-containing elastomer single polymer, if having a hydrocarbon Orefin units is preferably hydrocarbons Orefuin unit force 20 mass 0/0.
- the above-mentioned fluorine-containing elastomer polymer is not particularly limited as long as it has at least 58% by mass of fluorine atoms, but TFEZ perfluoro (vinyl ether) -based copolymer, VdFZHFP-based copolymer, and VdFZCTFE-based copolymer Manufactured by emulsion polymerization of fluorine-containing copolymers such as polymers, VdFZHFPZTFE copolymers, VdFZCTFEZTFE copolymers, TFEZ propylene copolymers, TFEZ propylene ZVdF copolymers, and ethylene ZHFP copolymers. And the like.
- the fluorine-containing elastomer polymer is preferably a VDF-based copolymer or a TFE-based copolymer.
- a TFE-based copolymer a TFEZ propylene-based copolymer or a TFEZ perfluoro (Buruether) -based copolymer is preferable.
- VDF-based copolymer examples include, for example, VDFZHFP copolymer, VDFZHFPZTF E copolymer, VDFZHFPZTFEZ4—bromo-3,3,4,4-tetrafluorobutene 1 copolymer, VDFZHFPZTFEZ4 3,4,4-tetrafluorobutene 1 copolymer, VDFZPMVEZTFEZ4 bromo-3,3,4,4-tetrafluorobutene-1 copolymer, VDFZPMVEZTFEZ4 odo-3,3,4,4-tetrafluorobutene-1 copolymer And VDFZPMVEZTFEZI, l, 3,3,3 pentafluoropropene copolymer.
- VDFZHFP copolymer examples include, for example, VDFZHFP copolymer, VDFZHFPZTF E copolymer, VDFZHFPZTFEZ4—bromo-3,3,4,4
- Examples of the TFEZ propylene-based copolymer include a TFEZ propylene copolymer.
- examples of the above TFEZ perfluoro (butyl ether) copolymer include TFEZPMVEZ ethylene copolymer, TFEZPMVEZ ethylene Z4-bromo-3,3,4,4-tetrafluorobutene 1 copolymer, and TFEZPMVEZ ethylene Z4 copolymer 3,3,4,4.
- Tetraphnoleolobutene 1 copolymer Tetraphnoleolobutene 1 copolymer, TFEZPMVE copolymer, TFEZPMVEZ perfluoro (8-cyano 5 methyl 3,6 dioxa 1 otaten) copolymer, TF EZPMVEZ4 odo 3,3,4,4-tetrafluor Lobutene 1 copolymer, TFEZ PMVEZ perfluoro (2-phenoxypropylbutyl) ether copolymer and the like.
- the process for producing a fluorine-containing elastomer polymer of the present invention comprises polymerizing a fluorine-containing monomer in an aqueous medium in the presence of a fluorine-containing vinyl group-containing emulsifier and a chain transfer agent. .
- the above-mentioned fluorine-containing vinyl group-containing emulsifier is a compound having a radically polymerizable unsaturated bond and a hydrophilic group in the molecule.
- R 2 , R 3 , R 4 and R 5 are the same or different and each represent a perfluoroalkyl group which may be substituted with H, H, F, Cl, Br or I, wherein R is a main chain Represents a linear or branched fluoroalkylene group in which all or a part of H is substituted with F, and j represents an integer of 0 to 6 , K represents an integer of 0 or 1, and Y represents a hydrophilic group. It is preferred that the compound is a fluorine-containing vinyl group-containing compound (1) represented by the following formula:
- R 2 , R 3 , R 4 and R 5 are the same or different, and H or F is preferable.
- R is preferably a linear or branched perfluoroalkylene group having 1 to 23 carbon atoms in the main chain, which may have an oxygen atom [O] in the main chain.
- the oxygen atom may be a polyoxyalkylene group composed of 1 to 10 oxyalkylene units (preferably having 2 to 3 carbon atoms).
- a branch that is preferably a constituent oxygen atom -CF is preferable as a side chain.
- j is preferably an integer of 0 to 2.
- hydrophilic group represented by Y is SOM or COO
- M represents H, NH or an alkali metal
- the fluorine-containing vinyl group-containing emulsifier includes a fluorine-containing vinyl group-containing compound (I), a fluorine-containing vinyl group-containing compound ( ⁇ ), a fluorine-containing vinyl group-containing compound (III), and a fluorine-containing vinyl group-containing compound. (IV), fluorine-containing vinyl group-containing compound (V), fluorine-containing vinyl group-containing compound (VI
- ⁇ (Vm) may be one kind or two or more kinds different from each other.
- a represents an integer of 1 to 10
- Y represents —SO M or —COOM
- M represents H
- a is preferably an integer of 5 or less, more preferably an integer of 2 or less.
- the above-mentioned Y is preferably —COOM in that a suitable water solubility and surface activity can be obtained.
- M is preferable in that the heat resistance of the obtained molded body which is hardly retained as an impurity is improved. Or, it is preferably NH.
- CF CF—CF—COOH
- CF CF—CF—COONH
- CF CF—CF CF COOH
- CF CF—CF -COONH
- CF CF—CF CF -SO H
- CF CF—CF CF SO Na
- CF CFCF -COONH is preferred because dispersion stability is improved.
- the compound having a fluorine-containing butyl group ( ⁇ ) has the following general formula ( ⁇ ):
- CF CF— (CF C (CF) F) ⁇ (II) [Wherein, b represents an integer of 1 to 5, Y represents —SO M or —COOM, and M represents H, N
- b is preferably an integer of 3 or less in terms of emulsifying ability.
- Y is COOM in that a suitable water solubility and surface activity are obtained.
- M is preferably H or NH from the viewpoint that the heat resistance of a molded article obtained by remaining as impurities is improved.
- c represents an integer of 1 to 10
- Y represents —SO M or —COOM
- M represents H
- the above c is preferably an integer of 5 or less from the viewpoint of water solubility.
- the above Y is preferably from the viewpoint of obtaining appropriate water solubility and surface activity.
- M which is preferably COOM, is preferably H or NH from the viewpoint of improving dispersion stability.
- Examples of the above-mentioned fluorine-containing group-containing compound ( ⁇ ) include:
- X represents —F or CF
- d represents an integer of 0 to 2
- e represents an integer of 1 to 10.
- f represents an integer of 1 to 3
- Y represents -SO M or COOM
- M represents H
- the above X is preferably —CF from the viewpoint of surface activity.
- the above d is preferably an integer of 0 in terms of copolymerizability.
- the above e is preferably an integer of 5 or less in terms of water solubility.
- the above f which is preferably COOM from the viewpoint of obtaining surface activity, is preferably 2 or less.
- the above M is preferably H or NH.
- CF 2 CF-1 O—CF 2 CF (CF 3 ) —OCF 2 —COOH
- CF 2 CF— 0— CF 2 CF (CF 3 ) — OCF 2 —— COONH 4 ,
- CF 2 CF one OCF 2 CF (CF 3) one OCF 2 S0 3 Na,
- CF 2 CF ⁇ O ⁇ CF 2 CF (CF 3 ) -OCF 2 CF 2 -COOH
- CF 2 CF— O— CF 2 CF (CF 3 ) -OCF 2 CF 2 — COONH 4 ,
- CF 2 CF-O—CF 2 CF (CF 3 ) -OCF 2 CF 2 SO 3 H
- CF 2 CF one OCF 2 CF (CF 3) - OCF 2 CF 2 S0 3 Na,
- CF 2 CF— CF 2 —— O— CF 2 CF (CF 3 ) -OCF 2 CF 2 -COOH
- CF 2 CF— CF 2 —— O— CF 2 CF (CF 3 ) — OCF 2 CF 2- COONH 4
- CF 2 CF—CF 2 O—CF 2 CF (CF 3 ) —OCF 2 CF 2 SO 3 H
- CF 2 CF—CF 2 —— O—CF 2 CF (CF 3 ) —OCF 2 CF 2 SO 3 Na
- CF 2 CF—CF 2 -CF 2 ⁇ 0—CFsCFiCFg) -OCF 2 CF 2 -COOH
- CF 2 CF—CF 2 -CF 2 — O—CF 2 CF (CF3) -OCF 2 CF 2 -COONH 4
- CF 2 CF—CF 2 -CF 2 — 0—CFgCFCCFg) OCF 2 CF 2 S0 3 H
- CF 2 CF—O—CF 2 CF (CF 3 ) —OCF 2 —COOH
- CF 2 CF-0-CF 2 CF (CF 3 )-OCF 2- COONH 4 ,
- CF 2 ⁇ CF- 0- CF 2 CF (CF 3) - OCF 2 S0 3 H,
- CF 2 CF- OCF 2 CF ( CF 3) - OCF 2 S0 3 Na
- CF 2 CF— O— CF 2 CF (CF 3 ) — OCF 2 CF 2 —COOH
- CF 2 CF— O— CF 2 CF (CF 3 ) OCF 2 CF 2 — COONH 4
- CF 2 CF— OCF 2 CF (CF 3) one OCF 2 CF 2 SO 3 H
- CF 2 CF- OCF 2 CF (CF 3) one OCF 2 CF 2 SO 3 Na
- CF 2 CF- CF 2 - O — CF 2 CF (CF 3 ) — OCF 2 CF 2 -COOH
- CF 2 CF—CF 2 —O—CF 2 CF (CF 3 ) —OCF 2 CF 2 —COONH 4
- CF 2 CF—CF 2 —O—CF 2 CF (CF 3 ) —OCF 2 CF 2 —S0 3 H
- CF 2 CF— CF 2 — 0 to CF 2 CF (CF 3 ) — OCF 2 CF 2 -S0 3 a
- the fluorine-containing vinyl group-containing compound (V) has the following general formula (V):
- g 0 or an integer from 1 to 10
- Y represents one SOM or one COOM
- the above g is preferably 0 or an integer of 1 to 5 in terms of emulsifying ability, more preferably an integer of 0 to 2, and 0 or 1. More preferably, Y is one COOM in that a suitable water solubility and surface activity can be obtained. Is preferably H or NH from the viewpoint of improving the
- fluorine-containing vinyl group-containing compound (V) examples include, for example, [0054] [Formula 5]
- CH CFCF OCF (CF) —CF OCF (CF) -COONH is preferred.
- h represents an integer of 1 to 6
- i represents an integer of 1 to 10
- Y represents —SO M or C
- OOM OOM
- M H, NH or an alkali metal
- h is preferably an integer of 2 or less, more preferably 1 or less from the viewpoint of copolymerizability.
- the above Y which is preferably an integer of 3 or less, is preferably COOM in that a suitable water solubility and surface activity can be obtained.
- the above M hardly remains as an impurity and is obtained.
- H or NH is preferred from the viewpoint of improving the heat resistance of the molded body.
- Examples of the above-mentioned fluorine-containing group-containing compound (VI) include [0059] [I-Dani 6]
- the fluorine-containing vinyl group-containing compound (VII) has the following general formula (VII):
- pl represents an integer of 1 to 10
- Y represents —SO M or —COOM
- M represents H
- pl is preferably an integer of 5 or less from the viewpoint of emulsifying ability, more preferably an integer of 2 or less.
- the above Y is preferably COOM in that a suitable water solubility and surface activity can be obtained.
- the above M is less likely to remain as an impurity in that the heat resistance of the obtained molded body is improved.
- it is NH.
- the fluorine-containing vinyl group-containing compound (VII) includes, for example,
- the above-mentioned fluorinated vinyl group-containing emulsifier is preferred because of its good copolymerizability.
- the above-mentioned fluorinated bullet group-containing emulsifier has the following general formula (i) in that dispersion stability is improved.
- k is preferably an integer of 0 to 2, and preferably 0 or 1.
- Y is preferably COOH or COONH.
- the above-mentioned various fluorine-containing vinyl group-containing emulsifiers may be a mixture of compounds having different numbers of oxyalkylene groups in the above-mentioned general formulas (I) to (VIII) and (i).
- the “compound having a radically polymerizable unsaturated bond and a hydrophilic group in the molecule” such as the fluorine-containing vinyl group-containing compound (1) can be prepared by a known method.
- the fluorinated butyl group-containing emulsifier is preferably added in an amount of lppm to 10% by mass of the aqueous medium.
- the addition amount of the above-mentioned fluorine-containing vinyl group-containing emulsifier is less than lppm of the aqueous medium, the amount of the obtained fluorine-containing elastomer polymer attached to the inside of the reaction tank tends to increase and the productivity tends to decrease, When the amount exceeds 10% by mass of the aqueous medium, the thermal stability of the obtained fluorine-containing elastomer polymer may decrease.
- the more preferred lower limit of the amount of the fluorine-containing vinyl group-containing emulsifier is 10% of the aqueous medium. ppm, a more preferred lower limit is 50 ppm of the aqueous medium, a more preferred upper limit is 5% by mass of the aqueous medium, a still more preferred upper limit is 2% by mass of the aqueous medium, and a particularly preferred upper limit is the aqueous medium. 1% by mass.
- the method for producing a fluorinated elastomeric polymer of the present invention comprises polymerizing a fluorinated monomer in the presence of the fluorinated vinyl group-containing oxidizing agent, and thus has been conventionally used. Emulsion polymerization is possible without the addition of fluorinated surfactants and other emulsifiers, and the resulting fluorinated elastomeric polymers tend to have excellent dispersion stability in aqueous media and high bridging speeds. .
- the process for producing a fluorine-containing elastomer polymer of the present invention also comprises polymerizing a fluorine-containing monomer in the presence of a chain transfer agent in addition to the above-mentioned fluorine-containing vinyl group-containing emulsifier. .
- One of the above chain transfer agents may be used alone, or two or more thereof may be used in combination.
- the chain transfer agent is not particularly limited as long as it is used for producing a fluorine-containing elastomer polymer.
- an alcohol having 1 to 12 carbon atoms and an ester having 1 to 12 carbon atoms can be used.
- Each of the above compounds may be partially substituted with fluorine and Z or chlorine! /.
- the chain transfer agent is a saturated aliphatic compound having a bromine atom and Z or iodine atom such as perfluorocarbon in which 1-2 fluorine atoms are substituted with bromine atom and Z or iodine atom. Not including,.
- Examples of the alcohol having 1 to 12 carbon atoms include methanol, ethanol, propanol, and butanol.
- ester having 1 to 12 carbon atoms examples include methyl acetate, ethyl acetate, butyric acetate, ethyl ethyl propionate, dimethyl malonate, getyl malonate, dimethyl succinate, getyl succinate, and the like.
- alkane having 1 to 12 carbon atoms examples include methane, ethane, propane, butane, pentane, hexane and the like.
- ketone having 1 to 12 carbon atoms examples include acetone, acetylacetone, methyl ethyl ketone, and cyclohexanone.
- Examples of the mercaptan having 1 to 12 carbon atoms include dodecyl mercaptan and the like.
- Examples of the compound partially substituted with fluorine and Z or chlorine include carbon chloride, chloroform, carbon tetrachloride and the like.
- the chain transfer agent is a saturated hydrocarbon having 1 to 6 carbon atoms or an alcohol having 1 to 4 carbon atoms, a carboxylic acid ester compound having 4 to 8 carbon atoms, a chlorine-substituted hydrocarbon having 1 to 2 carbon atoms, It is preferable to use a ketone having 3 to 5 carbon atoms and Z or a mercaptan having 10 to 12 carbon atoms.
- chain transfer agents among others, dispersibility in a polymerization medium, chain transferability, removal from the target product
- isopentane, isopropanol, getyl malonate, carbon tetrachloride, acetone, ethyl acetate, and Z or dodecyl mercaptan are more preferable.
- the chain transfer is moderate and the decrease in polymerization rate is small. From the viewpoint, isopentane, dimethyl malonate, and ethyl acetate are more preferable.
- the chain transfer agent is added in an amount of 0.1 part by mass based on 100 parts by mass in total of the first monomer and the monomer other than the first monomer. It is preferable to add 0001 to 5 parts by mass.
- the chain transfer agent is more preferably 0.0005 parts by mass or more, more preferably 0.001% by mass, based on 100 parts by mass of the total addition amount, in terms of adjusting the molecular weight and the molecular weight distribution of the fluorinated elastomer monopolymer.
- the above addition and more preferably 1% by mass or less, more preferably 0.1% by mass or less with respect to 100 parts by mass of the total addition amount.
- the process for producing a fluorine-containing elastomer polymer of the present invention comprises polymerizing a fluorine-containing monomer in the presence of the above-described chain transfer agent. It is possible to suppress the increase in the molecular weight of the resulting fluorine-containing elastomer polymer, to make the molecular weight appropriate, and to further widen the molecular weight distribution of the obtained fluorine-containing elastomer polymer. Therefore, the fluorinated elastomer obtained by the method for producing a fluorinated elastomer of the present invention has a well-balanced molecular weight and molecular weight distribution. A molded article can be obtained with a high vulcanization rate during shaping and a low compression set.
- the method for producing a fluorine-containing elastomer polymer of the present invention comprises polymerizing a fluorine-containing monomer in an aqueous medium.
- the above-mentioned fluorine-containing monomer means the above-mentioned first monomer and a copolymerizable compound having at least one fluorine atom to be added as required.
- the method for producing a fluorine-containing elastomer polymer of the present invention may be one in which, in addition to the above-mentioned fluorine-containing monomer, if desired, a fluorine-free monomer is added for polymerization.
- fluorine-containing monomer and the non-fluorine-containing monomer include the same as those described above for the fluorine-containing elastomer polymer.
- the preferable lower limit of the total supply amount of the fluorine-containing monomer and the fluorine-free monomer is 10 to 100 parts by mass of the aqueous medium in view of the dispersion stability of the obtained fluorine-containing elastomer polymer.
- a preferable upper limit is 100 parts by mass with respect to 100 parts by mass of the aqueous medium, and a more preferable upper limit is 80 parts by mass. .
- the total supply amount of the fluorine-containing monomer and the fluorine-free monomer is the total amount of the initial charge amount at the start of the polymerization reaction and the continuous charge amount added during the polymerization reaction.
- the supply amount of the fluorine-free monomer can be appropriately set according to the desired composition of the fluorine-containing elastomer polymer.
- the polymerization is carried out by adding a radical polymerization initiator to an aqueous solution, if desired, in addition to the fluorine-containing vinyl group-containing emulsifier, the chain transfer agent, the fluorine-containing monomer, and the fluorine-free monomer to be added as required. You can do it by adding it to the medium.
- radical polymerization initiator examples include peroxides of a water-soluble inorganic compound or a water-soluble organic compound, for example, persulfates such as ammonium persulfate and potassium persulfate, peroxides of pisuccinic acid, and peroxides of bisdartalic acid. These are general, and these can be used alone or in combination of two or more. In the polymerization in a low temperature range, it is preferable to use a redox initiator. Furthermore, as long as the stability of the latex is not impaired, one or both of water-insoluble organic peroxides and azoizides are used alone or together with a water-soluble inorganic compound or a water-soluble organic compound baroxide.
- the amount of the radical polymerization initiator to be added should be appropriately set according to the composition and yield of the fluorine-containing elastomer polymer to be produced, the amount of the fluorine-containing monomer, and the amount of the fluorine-free monomer used. Can be.
- the radical polymerization initiator is preferably added in an amount of 0.01 to 0.4 part by mass, and preferably in an amount of 0.05 to 0.3 part by mass, based on 100 parts by weight of the obtained fluorine-containing elastomer polymer. More preferably, it is added.
- the above polymerization may be conducted by further adding an additive such as a fluorine-containing surfactant other than the above-mentioned fluorine-containing vinyl group-containing emulsifier, a radical scavenger and the like.
- an additive such as a fluorine-containing surfactant other than the above-mentioned fluorine-containing vinyl group-containing emulsifier, a radical scavenger and the like.
- fluorine-containing surfactant examples include:
- Z 2 represents F or H, and aa represents an integer of 3 to 20.
- Fluorocarboxylic acid represented by the formula: and alkali metal salts, ammonium salts, amine salts and quaternary ammonium salts thereof;
- Z 3 represents F or C1
- bb represents an integer of 3 to 13.
- Fluorocarboxylic acid represented by the formula: and alkali metal salts, ammonium salts, amine salts and quaternary ammonium salts thereof;
- Rf represents a perfluoroalkyl group having 1 to 7 carbon atoms
- cc represents an integer of 0 to 10
- Z 4 represents COOM or —SO M
- M represents H
- One or more of the above-mentioned fluorinated surfactants may be added during the above-mentioned polymerization.
- the amount of the fluorinated surfactant to be added can be appropriately set according to the composition and yield of the fluorinated elastomer polymer to be produced.
- the above polymerization is carried out in the absence of a fluorinated surfactant in that a fluorinated elastomer polymer which can be processed into a molded article having a high vulcanization rate during molding and a low compression set can be obtained. It is preferred to do so.
- the polymerization may be performed by any of batch operation, semi-batch operation and continuous operation, but is preferably performed by semi-batch operation.
- the fluorine-containing monomer, the fluorine-free monomer, the chain transfer agent, the polymerization initiator, the fluorine-buil group-containing emulsifier, the fluorine-containing surfactant, and / or the radical scavenger Additives such as agents can be appropriately added during the polymerization reaction according to the composition and yield of the desired fluoroelastomer polymer.
- the above-mentioned polymerization can be further performed in a multi-stage polymerization step described in WO 00001741 to obtain a desired monomer composition of the obtained fluorine-containing elastomer polymer.
- the above polymerization is usually carried out while maintaining the temperature in the range of 10 to 120 ° C. If the above temperature is less than 10 ° C, it is not possible to achieve a reaction rate of an effective size on an industrial scale, and if it exceeds 120 ° C, the reaction pressure required to maintain the polymerization reaction And the reaction cannot be maintained.
- the polymerization is usually carried out while maintaining the pressure in the range of 0.5 to: LOMPa.
- a preferred lower limit of the above range is 1. OMPa, and a preferred upper limit of the above range is 6.2 MPa.
- a desired polymerization pressure can be achieved in the early stage of the polymerization by adjusting the amount of the monomer gas at the time of initial supply.
- the pressure is adjusted by adjusting the additional supply of.
- the desired polymerization pressure is adjusted by adjusting the back pressure of the outlet pipe of the obtained fluorine-containing elastomer-polymer dispersion liquid.
- the above pressure is less than 0.5 MPa, the monomer concentration in the polymerization reaction system becomes too low to achieve a satisfactory reaction rate, and the molecular weight of the obtained fluoroelastomer polymer does not become sufficiently large. Sometimes. If the above pressure exceeds lOMPa, the equipment for maintaining the pressure will be costly.
- the above polymerization is usually performed for 0.5 to: LOO time.
- the fluorine-containing elastomer polymer obtained from the above polymerization is obtained by copolymerizing the above-mentioned first monomer.
- the unit power of the oxidizing agent derived from the above-mentioned fluorinated butyl group-containing emulsifier is used.
- the "emulsifier unit” is a part of the molecular structure of the fluorinated elastomer polymer, and means a portion derived from the corresponding fluorinated vinyl group-containing emulsifier.
- the compound constituting the fluorinated vinyl group-containing emulsifier was added to the polymer chain and became a part of the polymer chain of the fluorinated elastomer polymer. Things.
- the emulsifier unit is preferably 10 ppm or more and 10% by mass or less of the fluoroelastomer polymer.
- the amount is less than lOppm, the dispersion stability in an aqueous medium when a conventional non-copolymerizable emulsifier is not used may be inferior.
- the amount exceeds 10% by mass, physical properties such as heat resistance are deteriorated. Sometimes.
- the more preferable lower limit of the emulsifier unit is 25 ppm of the fluorine-containing elastomer polymer, and the further preferable lower limit is 50 ppm.
- a more preferred upper limit of the emulsifier unit is 5% by mass, and a still more preferred upper limit is 2.5% by mass.
- the above-mentioned fluorine-containing elastomer polymer has a viscosity at 100 ° C of usually 10 to: L00.
- the preferred lower limit is 30 from the viewpoint of the vulcanizability of the obtained molded article, and the preferred upper limit is 80 from the viewpoint of the molding force.
- the above-mentioned viscosity (ML (1 + 10)) is a value obtained by measuring according to ASTM D-1646.
- the fluorine-containing elastomer polymer obtained by performing the above polymerization is obtained in an amount almost equal to the additional amount, and is usually 10 to 30 parts by mass, preferably 20 to 25 parts by mass with respect to 100 parts by mass of the aqueous medium. Obtained in parts by weight.
- the amount of the fluorinated elastomer is less than 10 parts by mass with respect to 100 parts by mass of the aqueous medium, and when the amount exceeds 30 parts by mass with respect to 100 parts by mass of the undesired aqueous medium, the amount of the fluorinated elastomer is reduced. It may be difficult for one polymer to disperse.
- the polymerized fluorine-containing elastomer particles obtained by performing the above polymerization usually have an average particle diameter of 10 to 500 nm and have excellent dispersion stability.
- the process for producing the fluorinated elastomeric polymer of the present invention is a fluorinated elastomeric polymer that can be in any form as long as it has the above-mentioned polymerization force. It may be one that constitutes a turbid liquid! / It may be one that constitutes an aqueous dispersion of a fluorinated elastomer-polymer described below, or may be an aqueous dispersion of the fluorinated elastomer-polymer described above. It may constitute a gum or a crumb obtained by coagulating, drying, etc.
- the method for producing a fluorinated elastomeric polymer of the present invention is carried out in the presence of the fluorinated vinyl group-containing amide and the chain transfer agent.
- the molecular weight and the molecular weight distribution can be adjusted appropriately.
- the addition amount of the fluorine-containing surfactant is small, there is a problem that the obtained fluorine-containing elastomer polymer adheres to the inside of the reaction tank and the yield decreases.
- the fluorinated elastomer polymer is an aqueous dispersion of a fluorinated elastomer polymer in which particles having the same properties are dispersed in an aqueous medium, wherein the fluorinated elastomer polymer is a single layer of the fluorinated elastomer of the present invention.
- the aqueous dispersion of a fluorinated elastomer polymer that is obtained by the method for producing a combined product is also one of the present invention.
- the aqueous fluoroelastomer dispersion of the present invention contains or does not contain a fluorine-containing vinyl group-containing emulsifier.
- the aqueous fluorine-containing elastomer-polymer dispersion of the present invention can contain, for example, the above-mentioned fluorine-containing butyl group-containing emulsifier in less than 100 ppm.
- the fluorinated elastomer-polymer aqueous dispersion of the present invention has a good crosslinkability at the time of molding and processing, and the fluorinated butyl group-containing emulsifier is preferably less than 100 ppm, more preferably less than 10 ppm. Better!/,.
- the aqueous fluorinated elastomer-polymer dispersion of the present invention may be purified, for example, by coagulating an aqueous emulsion obtained after polymerization obtained immediately after the polymerization reaction of the fluorinated elastomer polymer by a known method. Can be prepared.
- the fluorinated elastomer-polymer aqueous dispersion of the present invention has a fluorinated vinyl group-containing emulsifier concentration within the above range, the fluorinated vinyl polymer-containing emulsifier is substantially free of the fluorinated vinyl group-containing emulsifier to form aggregates, compositions, molded articles, and the like Can be processed.
- the fluorinated elastomeric polymer rubber or crumb having the above-mentioned fluorinated elastomeric polymer power can be substantially free of a fluorinated surfactant.
- the above-mentioned fluorine-containing elastomer polymer rubber or crumb can be obtained by coagulating and drying the aqueous dispersion of a fluorine-containing elastomer polymer of the present invention.
- coagulants examples include aluminum salts such as aluminum sulfate and alum, calcium salts such as calcium sulfate, magnesium salts such as magnesium sulfate, sodium salt and potassium salt. And coagulation aids such as monovalent cation salts.
- the curing agent examples include polyol, polyamine, organic peroxide, organic tin, bis (aminophenol) tetraamine, and bis (thioaminophenol). Since the above-mentioned fluorine-containing elastomer polymer composition is composed of the above-mentioned fluorine-containing elastomer polymer, it does not substantially contain a fluorine-containing vinyl group-containing emulsifier, is easily crosslinked at the time of molding and processing, and is excellent in terms of: You.
- the fluorinated elastomeric polymer, the aqueous dispersion of the fluorinated elastomeric polymer of the present invention, or the fluorinated elastomeric polymer molded article is molded by using the rubber or crumb.
- the method of forming is not particularly limited, and includes a method using the above-described curing agent.
- the above-mentioned fluorinated elastomeric polymer molded article is made of the above-mentioned fluorinated elastomeric polymer, it has a low compression set and excellent mechanical strength. It is particularly suitable for parts for semiconductor manufacturing equipment, automobile parts and the like.
- the method for producing a fluorinated elastomeric polymer of the present invention is simple because it has the above-described configuration, and the obtained fluorinated elastomeric polymer has a low vulcanization rate during molding. In addition to the rapid and high crosslink density, the obtained fluorinated elastomeric polymer molded product exhibits excellent properties with low compression set and low compression set.
- Average particle size determined by performing a dynamic light scattering method.
- the obtained aqueous emulsion had a solid content of 28.8% by mass, an average particle size of 148 nm, and unreacted RS-1 was not detected (detection limit lppm).
- the Mooney viscosity at C was 52.5.
- Example 1 the fluorine-containing butyl group-containing emulsifier was replaced with perfluoro (6,6 dino, ido-2--2-trifluoronorelomethinole 3 oxalate) 5 hexenoic acid ammonium salt [RS-2] 0.07 g Polymerization was carried out for 3 hours in the same manner as in Example 1 except that the composition was changed to 1,370 g of an aqueous emulsion.
- the reaction was carried out for 2.8 hours in the same manner as in Example 1 except that in place of RS-1, an ammonium salt of perfluorooctanoic acid [AP FO] was used in place of RS-1, and the reaction was carried out for 1245 g. An aqueous emulsion was obtained.
- AP FO perfluorooctanoic acid
- the obtained aqueous emulsion had a solid content of 27.7% by mass and an average particle size of 234 nm.
- the components shown in Table 1 were blended with the fluorine-containing elastomer copolymer obtained from Example 1 and the fluorine-containing copolymer obtained from Comparative Example 1, and then uniformly blended with a rubber roll by a standard method to obtain a sulfur composition.
- the product was prepared and the vulcanizability was evaluated with a curast meter.
- the composition was vulcanized under the conditions shown in Table 1, and the physical properties of the molded body were measured.
- tensile strength, elongation, tensile stress, and compression set were based on JIS K 6301, and the Shore hardness was based on ASTM D-2240.
- the vulcanizability was measured at 170 ° C using a curast meter (JSR II type).
- T represents the induction time
- T represents the appropriate vulcanization time
- degree of vulcanization represents the degree of vulcanization.
- the method for producing a fluorinated elastomeric polymer of the present invention is simple because it has the above-mentioned constitution, and the obtained fluorinated elastomeric polymer has a high vulcanization rate during molding. In addition to the high crosslink density, the obtained fluorinated elastomeric polymer molded product exhibits excellent properties with low compression set and low compression set.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/547,637 US20080114118A1 (en) | 2004-04-07 | 2005-04-05 | Method For Producing Fluorine-Containing Elastomer Polymer |
EP05728777A EP1739099A4 (en) | 2004-04-07 | 2005-04-05 | PROCESS FOR PREPARING FLUOROUS ELASTOMER POLYMER |
US12/463,965 US20090227727A1 (en) | 2004-04-07 | 2009-05-11 | Method for producing fluorine-containing elastomer polymer |
Applications Claiming Priority (4)
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JP2004113683 | 2004-04-07 | ||
JP2004-113683 | 2004-04-07 | ||
JP2004270480A JP4834971B2 (ja) | 2004-04-07 | 2004-09-16 | 含フッ素エラストマー重合体の製造方法 |
JP2004-270480 | 2004-09-16 |
Related Child Applications (1)
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US12/463,965 Division US20090227727A1 (en) | 2004-04-07 | 2009-05-11 | Method for producing fluorine-containing elastomer polymer |
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WO2005097835A1 true WO2005097835A1 (ja) | 2005-10-20 |
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PCT/JP2005/006677 WO2005097835A1 (ja) | 2004-04-07 | 2005-04-05 | 含フッ素エラストマー重合体の製造方法 |
Country Status (5)
Country | Link |
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US (2) | US20080114118A1 (ja) |
EP (1) | EP1739099A4 (ja) |
JP (1) | JP4834971B2 (ja) |
CN (1) | CN1938336A (ja) |
WO (1) | WO2005097835A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008001895A1 (fr) | 2006-06-30 | 2008-01-03 | Daikin Industries, Ltd. | Procédé de fabrication d'un élastomère contenant du fluor |
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JP2005320501A (ja) * | 2004-04-07 | 2005-11-17 | Daikin Ind Ltd | 含フッ素エラストマー重合体の製造方法 |
JP2008297529A (ja) * | 2007-06-04 | 2008-12-11 | Daikin Ind Ltd | ビニリデンフルオライド系重合体の製造方法 |
EP3000828A1 (en) * | 2011-08-25 | 2016-03-30 | Daikin Industries, Ltd. | Method for producing aqueous polytetrafluoroethylene dispersion |
WO2014088820A1 (en) * | 2012-12-04 | 2014-06-12 | 3M Innovative Properties Company | Highly fluorinated polymers |
WO2014088804A1 (en) * | 2012-12-04 | 2014-06-12 | 3M Innovative Properties Company | Partially fluorinated polymers |
EP3067390A4 (en) | 2013-12-26 | 2017-09-20 | Daikin Industries, Ltd. | Processing aid for polyolefins, and polyolefin composition |
JP2015131895A (ja) * | 2014-01-10 | 2015-07-23 | ユニマテック株式会社 | 含フッ素共重合体水性分散液 |
JP6528552B2 (ja) | 2015-06-16 | 2019-06-12 | ダイキン工業株式会社 | ポリオレフィン用加工助剤及びポリオレフィン組成物 |
US20220195080A1 (en) * | 2019-04-26 | 2022-06-23 | Daikin Industries Ltd | Composition production method, and composition |
CN114096573A (zh) * | 2019-07-16 | 2022-02-25 | 大金工业株式会社 | 含氟弹性体的制造方法和组合物 |
CN114729071A (zh) * | 2019-11-19 | 2022-07-08 | 大金工业株式会社 | 聚四氟乙烯的制造方法 |
WO2022025111A1 (ja) * | 2020-07-28 | 2022-02-03 | ダイキン工業株式会社 | 含フッ素エラストマー水性分散液の製造方法および含フッ素エラストマー水性分散液 |
CN116134060B (zh) * | 2020-07-30 | 2024-06-18 | 大金工业株式会社 | 含氟弹性体水性分散液的制造方法、含氟弹性体和水性分散液 |
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- 2005-04-05 WO PCT/JP2005/006677 patent/WO2005097835A1/ja active Application Filing
- 2005-04-05 US US11/547,637 patent/US20080114118A1/en not_active Abandoned
- 2005-04-05 EP EP05728777A patent/EP1739099A4/en not_active Withdrawn
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WO2008001895A1 (fr) | 2006-06-30 | 2008-01-03 | Daikin Industries, Ltd. | Procédé de fabrication d'un élastomère contenant du fluor |
US8598290B2 (en) | 2006-06-30 | 2013-12-03 | Daikin Industries, Ltd. | Method for producing fluorine-containing elastomer |
Also Published As
Publication number | Publication date |
---|---|
EP1739099A4 (en) | 2007-05-30 |
US20090227727A1 (en) | 2009-09-10 |
CN1938336A (zh) | 2007-03-28 |
JP4834971B2 (ja) | 2011-12-14 |
JP2005320500A (ja) | 2005-11-17 |
EP1739099A1 (en) | 2007-01-03 |
US20080114118A1 (en) | 2008-05-15 |
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