JP5914088B2 - α−(トリフルオロメチル)アクリル酸ホモポリマーの製造方法 - Google Patents
α−(トリフルオロメチル)アクリル酸ホモポリマーの製造方法 Download PDFInfo
- Publication number
- JP5914088B2 JP5914088B2 JP2012070563A JP2012070563A JP5914088B2 JP 5914088 B2 JP5914088 B2 JP 5914088B2 JP 2012070563 A JP2012070563 A JP 2012070563A JP 2012070563 A JP2012070563 A JP 2012070563A JP 5914088 B2 JP5914088 B2 JP 5914088B2
- Authority
- JP
- Japan
- Prior art keywords
- trifluoromethyl
- acrylic acid
- homopolymer
- acrylate
- general formula
- 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.)
- Active
Links
- VLSRKCIBHNJFHA-UHFFFAOYSA-N 2-(trifluoromethyl)prop-2-enoic acid Chemical compound OC(=O)C(=C)C(F)(F)F VLSRKCIBHNJFHA-UHFFFAOYSA-N 0.000 title claims description 75
- 229920001519 homopolymer Polymers 0.000 title claims description 52
- 238000000034 method Methods 0.000 title claims description 12
- 239000003999 initiator Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 239000012986 chain transfer agent Substances 0.000 claims description 17
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 150000001340 alkali metals Chemical class 0.000 claims description 13
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 125000005385 peroxodisulfate group Chemical group 0.000 claims description 4
- ZESXUEKAXSBANL-UHFFFAOYSA-N trifluoromethyl prop-2-enoate Chemical compound FC(F)(F)OC(=O)C=C ZESXUEKAXSBANL-UHFFFAOYSA-N 0.000 claims 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 11
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 9
- BULLJMKUVKYZDJ-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-6-iodohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I BULLJMKUVKYZDJ-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052792 caesium Inorganic materials 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 ethylthiol Chemical compound 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 229940047670 sodium acrylate Drugs 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XEMRAKSQROQPBR-UHFFFAOYSA-N (trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=CC=C1 XEMRAKSQROQPBR-UHFFFAOYSA-N 0.000 description 1
- PGRFXXCKHGIFSV-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-iodobutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)I PGRFXXCKHGIFSV-UHFFFAOYSA-N 0.000 description 1
- XTGYEAXBNRVNQU-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-iodopropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)I XTGYEAXBNRVNQU-UHFFFAOYSA-N 0.000 description 1
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 description 1
- HHPUADFPUXGYTC-UHFFFAOYSA-N 1,2,3-tribromo-5-methylbenzene;1,2,5-tribromo-3-methylbenzene;1,3,5-tribromo-2-methylbenzene Chemical compound CC1=CC(Br)=C(Br)C(Br)=C1.CC1=CC(Br)=CC(Br)=C1Br.CC1=C(Br)C=C(Br)C=C1Br HHPUADFPUXGYTC-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- GBBZLMLLFVFKJM-UHFFFAOYSA-N 1,2-diiodoethane Chemical compound ICCI GBBZLMLLFVFKJM-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- COXCGWKSEPPDAA-UHFFFAOYSA-N 2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)C#N COXCGWKSEPPDAA-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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- DNYWXJPIRSNXIP-UHFFFAOYSA-N 2-bromo-1,1,1-trichloroethane Chemical compound ClC(Cl)(Cl)CBr DNYWXJPIRSNXIP-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
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229950010765 pivalate Drugs 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 1
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
(1)α−(トリフルオロメチル)アクリル酸からα−(トリフルオロメチル)アクリル酸ホモポリマーを製造する方法において、下記一般式(1)で示されるα−(トリフルオロメチル)アクリル酸塩のアルカリ性水溶液に、連鎖移動剤およびラジカル開始剤を加えて乳化重合させる工程を含むことを特徴とする下記一般式(2)で示される反復単位を有するα−(トリフルオロメチル)アクリル酸ホモポリマーの製造方法。
攪拌子を具備した100mlフラスコに60mlの水を入れ20分間窒素置換した後、α−(トリフルオロメチル)アクリル酸(5g、0.0357mol)を溶解させ、水酸化ナトリウムを用いて水溶液のpHを8〜9に調整した。次いで、ペルオキソ二硫酸ナトリウム(0.5g、0.0021mol)、1−ヨードパーフルオロヘキサン(0.75g、0.0017mol)をフラスコ内に添加し、80℃で16時間反応を実施した。反応後、フラスコを室温まで冷却した後に溶媒を留去し、冷却したn−ペンタン溶液(50ml)中にて沈殿させ、濾過物を乾燥後、淡黄黄色パウダー状のα−(トリフルオロメチル)アクリル酸ナトリウムホモポリマー(5.5g)を得た。19F−NMR法(溶媒D2O)にて原料のα−(トリフルオロメチル)アクリル酸[δ−65.1ppm(s,CF3)]およびα−(トリフルオロメチル)アクリル酸ナトリウムホモポリマーの面積比から算出して転化率97%であった(純度95wt.%、収率92%)。副生成物は観測されなかった。
19F−NMR(D2O)δ−68.5ppm(s,CF3)
攪拌子を具備した100mlフラスコに60mlの水を入れ20分間窒素置換した後、α−(トリフルオロメチル)アクリル酸(10.0g、0.0714mol)を溶解させ、水酸化カリウムを用いて水溶液のpHを8〜9に調整した。次いで、ペルオキソ二硫酸ナトリウム(0.51g、0.0021mol)、1−ヨードパーフルオロヘキサン(1.02g、0.0024mol)をフラスコ内に添加し、80℃で16時間反応を実施した。反応後、フラスコを室温まで冷却した後に溶媒を留去し、冷却したn−ペンタン溶液(60ml)中にて沈殿させ、濾過物を乾燥後、淡黄色パウダー状のα−(トリフルオロメチル)アクリル酸カリウムホモポリマー(11.3g)を得た。実施例1と同様に算出した転化率は74%であった(純度89wt.%、収率66%)。NMR測定の結果、副生成物は観測されなかった。
攪拌子を具備した100mlフラスコに60mlの水を入れ20分間窒素置換した後、α−(トリフルオロメチル)アクリル酸(5g、0.0357mol)を溶解させた(pH=2)。次いで、ペルオキソ二硫酸ナトリウム(0.5g、0.0021mol)、1−ヨードパーフルオロヘキサン(0.75g、0.0017mol)をフラスコ内に添加し、80℃で16時間反応を実施した。反応後、フラスコを室温まで冷却した後に溶媒を留去し、冷却したペンタン溶液中にて沈殿させ、濾過物を乾燥して19F−NMR法により分析したが、目的物であるα−(トリフルオロメチル)アクリル酸ナトリウムホモポリマーは観測されず、取得物は原料の−(トリフルオロメチル)アクリル酸のみであった。
Claims (6)
- α−(トリフルオロメチル)アクリル酸からα−(トリフルオロメチル)アクリル酸塩ホモポリマーを製造する方法であって、下記一般式(1)で示されるα−(トリフルオロメチル)アクリル酸塩のアルカリ性水溶液に、連鎖移動剤およびラジカル開始剤を加えて乳化重合させる工程を含むことを特徴とする下記一般式(2)で示される反復単位を有するα−(トリフルオロメチル)アクリル酸塩ホモポリマーの製造方法。
(式中、A1はアルカリ金属を表す)
(式中、A2はアルカリ金属を表し、反復単位においてA2は互いに独立して異なってもよい。) - α−(トリフルオロメチル)アクリル酸およびアルカリ金属の水酸化物を水中にて反応させて前記一般式(1)で示されるα−(トリフルオロメチル)アクリル酸塩のアルカリ性水溶液を製造する工程を含むことを特徴とする請求項1に記載のα−(トリフルオロメチル)アクリル酸塩ホモポリマーの製造方法。
- 下記一般式(1)で示されるα−(トリフルオロメチル)アクリル酸塩、連鎖移動剤、およびラジカル開始剤をアルカリ性条件下で水中にて乳化重合させることを特徴とする下記一般式(2)で示される反復単位を有するα−(トリフルオロメチル)アクリル酸塩ホモポリマーの製造方法。
(式中、A1はアルカリ金属を表す)
(式中、A2はアルカリ金属を表し、反復単位においてA2は互いに独立して異なってもよい。) - 前記一般式(1)中のA1で表されるアルカリ金属がLi、Na、KまたはCsであることを特徴とする請求項1〜3のいずれか1項に記載のα−(トリフルオロメチル)アクリル酸塩ホモポリマーの製造方法。
- 前記連鎖移動剤が1−ヨードパーフルオロアルカンであることを特徴とする請求項1〜4のいずれか1項に記載のα−(トリフルオロメチル)アクリル酸塩ホモポリマーの製造方法。
- 前記ラジカル開始剤がペルオキソ二硫酸塩であることを特徴とする請求項1〜5のいずれか1項に記載のα−(トリフルオロメチル)アクリル酸塩ホモポリマーの製造方法。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012070563A JP5914088B2 (ja) | 2012-03-27 | 2012-03-27 | α−(トリフルオロメチル)アクリル酸ホモポリマーの製造方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012070563A JP5914088B2 (ja) | 2012-03-27 | 2012-03-27 | α−(トリフルオロメチル)アクリル酸ホモポリマーの製造方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2013203744A JP2013203744A (ja) | 2013-10-07 |
JP5914088B2 true JP5914088B2 (ja) | 2016-05-11 |
Family
ID=49523229
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2012070563A Active JP5914088B2 (ja) | 2012-03-27 | 2012-03-27 | α−(トリフルオロメチル)アクリル酸ホモポリマーの製造方法 |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5914088B2 (ja) |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60161947A (ja) * | 1984-01-31 | 1985-08-23 | Sagami Chem Res Center | β,β−ジフルオロアクリル酸誘導体の製造方法 |
JPS63278913A (ja) * | 1987-05-09 | 1988-11-16 | Daikin Ind Ltd | 含フッ素ポリマ−ラテックス及びその用途 |
JP3843505B2 (ja) * | 1996-10-22 | 2006-11-08 | ソニー株式会社 | 高分子電解質及び電池 |
JP2008214420A (ja) * | 2007-03-01 | 2008-09-18 | Tosoh F-Tech Inc | 乳化剤を用いずに制御されたラジカル重合法によるフッ化ビニリデン系共重合体 |
JP2009029854A (ja) * | 2007-07-24 | 2009-02-12 | Daikin Ind Ltd | 含フッ素(メタ)アクリルポリマー及びフルオロポリマーの製造方法 |
JP2009029853A (ja) * | 2007-07-24 | 2009-02-12 | Daikin Ind Ltd | フルオロポリマーの製造方法 |
JP2010085921A (ja) * | 2008-10-02 | 2010-04-15 | Panasonic Corp | レジスト材料及びそれを用いたパターン形成方法 |
-
2012
- 2012-03-27 JP JP2012070563A patent/JP5914088B2/ja active Active
Also Published As
Publication number | Publication date |
---|---|
JP2013203744A (ja) | 2013-10-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Patil et al. | Advances in the (co) polymerization of alkyl 2-trifluoromethacrylates and 2-(trifluoromethyl) acrylic acid | |
David et al. | Use of iodocompounds in radical polymerization | |
US20090306297A1 (en) | Process for preparing a copolymer with controlled architecture, of telomer or block copolymer type, obtained from vinyl phosphonate monomers, by iodine transfer polymerization | |
EP3243850A1 (en) | Aqueous suspension polymerization of 2,3,3,3-tetrafluoropropene | |
WO2015122404A1 (ja) | リビングラジカル重合触媒及びそれを用いた重合体の製造方法 | |
JP5914088B2 (ja) | α−(トリフルオロメチル)アクリル酸ホモポリマーの製造方法 | |
KR102520611B1 (ko) | 함불소 중합성 단량체의 증류 정제법 | |
JP4984243B2 (ja) | ビニル系重合体の製造方法 | |
JP2017061422A (ja) | 高純度パラスチレンスルホン酸エステル及びその製造方法 | |
JP5261717B2 (ja) | ブロック共重合体およびその製造方法 | |
US8933264B2 (en) | Method for producing organic compound having sulfo group, method for producing liquid composition, and method for hydrolyzing organic compound having fluorosulfonyl group | |
JP4788129B2 (ja) | クロロプレン系重合体及びその製造法 | |
CN114402001B (zh) | 含氟化合物的制造方法和共聚物的制造方法 | |
CN116171287B (zh) | 含碘化合物的制造方法和含碘化合物 | |
JP6786194B2 (ja) | 有機テルル化合物の製造方法およびビニル重合体の製造方法 | |
JP2008127318A (ja) | 含フッ素フルオロスルホニルアルキルビニルエーテルの製造方法 | |
EP4053166A1 (en) | Method for making telechelic fluoride-based polymers | |
JP2003137916A (ja) | 両親媒性重合体の製造方法 | |
JP6568426B2 (ja) | ビス(2−ハロエチル)ベンゼンスルホン酸又はその塩、及びその製造方法、並びにビス(2−ハロエチル)ベンゼンスルホン酸を前駆体とするジビニルベンゼンスルホン酸又はその塩の製造方法 | |
JP2017075243A (ja) | ジアリルアミン類と二酸化硫黄との共重合体、及びその製造方法。 | |
JP2022101643A (ja) | 含フッ素重合体の製造方法及び組成物 | |
JP2003277438A (ja) | スルホン化重合体の製造方法 | |
CN116601144A (zh) | 含碲化合物、聚合物和聚合物的制造方法 | |
CN111499836A (zh) | 一种全氟碘化物的转化利用方法及所得产品和应用 | |
Han | Utilizing Hypervalent Iodine (III) Reagents in the Synthesis of Dynamers and Functional Polymers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150313 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20160127 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160202 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160302 |
|
RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20160303 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160322 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160404 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5914088 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |