JP2008007767A - Manufacturing method of polymer - Google Patents
Manufacturing method of polymer Download PDFInfo
- Publication number
- JP2008007767A JP2008007767A JP2007146470A JP2007146470A JP2008007767A JP 2008007767 A JP2008007767 A JP 2008007767A JP 2007146470 A JP2007146470 A JP 2007146470A JP 2007146470 A JP2007146470 A JP 2007146470A JP 2008007767 A JP2008007767 A JP 2008007767A
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- JP
- Japan
- Prior art keywords
- group
- formula
- polymerization
- substituent
- anion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920000642 polymer Polymers 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 15
- 150000001450 anions Chemical class 0.000 claims abstract description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 9
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims abstract description 8
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 7
- 125000001424 substituent group Chemical group 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 239000000178 monomer Substances 0.000 abstract description 20
- 239000000654 additive Substances 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 239000003505 polymerization initiator Substances 0.000 abstract description 4
- 239000003999 initiator Substances 0.000 abstract description 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 238000010551 living anionic polymerization reaction Methods 0.000 abstract 1
- -1 ethyl α-lithioisobutyrate Chemical compound 0.000 description 72
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 9
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 150000003440 styrenes Chemical class 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 3
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 3
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 125000006039 1-hexenyl group Chemical group 0.000 description 2
- 125000006023 1-pentenyl group Chemical group 0.000 description 2
- 125000006017 1-propenyl group Chemical group 0.000 description 2
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 2
- 125000006040 2-hexenyl group Chemical group 0.000 description 2
- 125000006022 2-methyl-2-propenyl group Chemical group 0.000 description 2
- 125000006024 2-pentenyl group Chemical group 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 2
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 2
- 125000006041 3-hexenyl group Chemical group 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- WVRPFQGZHKZCEB-UHFFFAOYSA-N Isopropyl 2-methylpropanoate Chemical compound CC(C)OC(=O)C(C)C WVRPFQGZHKZCEB-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 229940024423 isopropyl isobutyrate Drugs 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- YYJWBYNQJLBIGS-PLNGDYQASA-N methyl (z)-2-methylbut-2-enoate Chemical compound COC(=O)C(\C)=C/C YYJWBYNQJLBIGS-PLNGDYQASA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- GBVSONMCEKNESD-UHFFFAOYSA-N 1,1'-biphenyl;lithium Chemical group [Li].C1=CC=CC=C1C1=CC=CC=C1 GBVSONMCEKNESD-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MNCMBBIFTVWHIP-UHFFFAOYSA-N 1-anthracen-9-yl-2,2,2-trifluoroethanone Chemical group C1=CC=C2C(C(=O)C(F)(F)F)=C(C=CC=C3)C3=CC2=C1 MNCMBBIFTVWHIP-UHFFFAOYSA-N 0.000 description 1
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- DTNCNFLLRLHPNJ-UHFFFAOYSA-N 1-ethenyl-4-(1-ethoxyethoxy)benzene Chemical compound CCOC(C)OC1=CC=C(C=C)C=C1 DTNCNFLLRLHPNJ-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- QQHQTCGEZWTSEJ-UHFFFAOYSA-N 1-ethenyl-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(C=C)C=C1 QQHQTCGEZWTSEJ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- LXUNZSDDXMPKLP-UHFFFAOYSA-N 2-Methylbenzenethiol Chemical compound CC1=CC=CC=C1S LXUNZSDDXMPKLP-UHFFFAOYSA-N 0.000 description 1
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 1
- DGAWPXLUGCQPIK-UHFFFAOYSA-N 2-ethenyl-1,3,5-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC(C(C)C)=C(C=C)C(C(C)C)=C1 DGAWPXLUGCQPIK-UHFFFAOYSA-N 0.000 description 1
- DBWWINQJTZYDFK-UHFFFAOYSA-N 2-ethenyl-1,4-dimethylbenzene Chemical compound CC1=CC=C(C)C(C=C)=C1 DBWWINQJTZYDFK-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- IGLWCQMNTGCUBB-UHFFFAOYSA-N 3-methylidenepent-1-ene Chemical compound CCC(=C)C=C IGLWCQMNTGCUBB-UHFFFAOYSA-N 0.000 description 1
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- RNMZRVDGSKKNNZ-UHFFFAOYSA-N C1=CC=CC2=CC=CC=C12.CC=CC1=CC=CC=C1 Chemical compound C1=CC=CC2=CC=CC=C12.CC=CC1=CC=CC=C1 RNMZRVDGSKKNNZ-UHFFFAOYSA-N 0.000 description 1
- 125000005915 C6-C14 aryl group Chemical group 0.000 description 1
- SPXDYPYJHCSREL-UHFFFAOYSA-N CCC(C)[Mg]C(C)CC Chemical compound CCC(C)[Mg]C(C)CC SPXDYPYJHCSREL-UHFFFAOYSA-N 0.000 description 1
- DBNGNEQZXBWPTJ-UHFFFAOYSA-N CCCC[Mg]C(C)CC Chemical compound CCCC[Mg]C(C)CC DBNGNEQZXBWPTJ-UHFFFAOYSA-N 0.000 description 1
- NTZRDKVFLPLTPU-UHFFFAOYSA-N CC[Na] Chemical compound CC[Na] NTZRDKVFLPLTPU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LXXNWCFBZHKFPT-UHFFFAOYSA-N Ethyl 2-mercaptopropionate Chemical compound CCOC(=O)C(C)S LXXNWCFBZHKFPT-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical class [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- OCIWBOQWEJQOQY-UHFFFAOYSA-N [Li].SC=1SCCN1 Chemical compound [Li].SC=1SCCN1 OCIWBOQWEJQOQY-UHFFFAOYSA-N 0.000 description 1
- NTVIBFNHMURTMP-UHFFFAOYSA-N [Li]CC=CC[Li] Chemical compound [Li]CC=CC[Li] NTVIBFNHMURTMP-UHFFFAOYSA-N 0.000 description 1
- ICKXMDGNIZPYRS-UHFFFAOYSA-N [Li]CCCCCC[Li] Chemical compound [Li]CCCCCC[Li] ICKXMDGNIZPYRS-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005083 alkoxyalkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000005085 alkoxycarbonylalkoxy group Chemical group 0.000 description 1
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 150000001356 alkyl thiols Chemical class 0.000 description 1
- 125000005530 alkylenedioxy group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002078 anthracen-1-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([*])=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- IBWZMBOYXIWJQE-UHFFFAOYSA-L bis(2,6-ditert-butylphenoxy)-ethylalumane Chemical compound CC[Al+2].CC(C)(C)C1=CC=CC(C(C)(C)C)=C1[O-].CC(C)(C)C1=CC=CC(C(C)(C)C)=C1[O-] IBWZMBOYXIWJQE-UHFFFAOYSA-L 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000000262 haloalkenyl group Chemical group 0.000 description 1
- 125000004438 haloalkoxy group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- UUQLCJCZFWUWHH-UHFFFAOYSA-N lithium;1-phenylhexylbenzene Chemical compound [Li+].C=1C=CC=CC=1[C-](CCCCC)C1=CC=CC=C1 UUQLCJCZFWUWHH-UHFFFAOYSA-N 0.000 description 1
- XWWCTWQBCBOOAG-UHFFFAOYSA-N lithium;diphenylazanide Chemical compound [Li+].C=1C=CC=CC=1[N-]C1=CC=CC=C1 XWWCTWQBCBOOAG-UHFFFAOYSA-N 0.000 description 1
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 description 1
- XAVQZBGEXVFCJI-UHFFFAOYSA-M lithium;phenoxide Chemical compound [Li+].[O-]C1=CC=CC=C1 XAVQZBGEXVFCJI-UHFFFAOYSA-M 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- IZWPPZMYNSBLNI-UHFFFAOYSA-N magnesium;2-methylpropane Chemical compound [Mg+2].C[C-](C)C.C[C-](C)C IZWPPZMYNSBLNI-UHFFFAOYSA-N 0.000 description 1
- WRYKIHMRDIOPSI-UHFFFAOYSA-N magnesium;benzene Chemical compound [Mg+2].C1=CC=[C-]C=C1.C1=CC=[C-]C=C1 WRYKIHMRDIOPSI-UHFFFAOYSA-N 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- YHNWUQFTJNJVNU-UHFFFAOYSA-N magnesium;butane;ethane Chemical compound [Mg+2].[CH2-]C.CCC[CH2-] YHNWUQFTJNJVNU-UHFFFAOYSA-N 0.000 description 1
- WCFJMDWWJOCLSJ-UHFFFAOYSA-N magnesium;methanidylbenzene Chemical compound [Mg+2].[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1 WCFJMDWWJOCLSJ-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MKIJJIMOAABWGF-UHFFFAOYSA-N methyl 2-sulfanylacetate Chemical compound COC(=O)CS MKIJJIMOAABWGF-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- SEXOVMIIVBKGGM-UHFFFAOYSA-N naphthalene-1-thiol Chemical compound C1=CC=C2C(S)=CC=CC2=C1 SEXOVMIIVBKGGM-UHFFFAOYSA-N 0.000 description 1
- IJJSYKQZFFGIEE-UHFFFAOYSA-N naphthalene;potassium Chemical compound [K].C1=CC=CC2=CC=CC=C21 IJJSYKQZFFGIEE-UHFFFAOYSA-N 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- ZYBHSWXEWOPHBJ-UHFFFAOYSA-N potassium;propan-2-ylbenzene Chemical compound [K+].C[C-](C)C1=CC=CC=C1 ZYBHSWXEWOPHBJ-UHFFFAOYSA-N 0.000 description 1
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical compound SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- QHSPZGZEUDEIQM-AATRIKPKSA-N tert-butyl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)(C)C QHSPZGZEUDEIQM-AATRIKPKSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- RUOHIDNTYAKSDG-UHFFFAOYSA-K tris(2,6-ditert-butylphenoxy)alumane Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O[Al](OC=1C(=CC=CC=1C(C)(C)C)C(C)(C)C)OC1=C(C(C)(C)C)C=CC=C1C(C)(C)C RUOHIDNTYAKSDG-UHFFFAOYSA-K 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- HEPBQSXQJMTVFI-UHFFFAOYSA-N zinc;butane Chemical compound [Zn+2].CCC[CH2-].CCC[CH2-] HEPBQSXQJMTVFI-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、リビングアニオン重合法に使用される新規な重合開始剤、または重合反応途中に添加し、重合末端を安定化等させる働きを有する新規なキャップ剤を用いた重合体の製造方法に関する。 The present invention relates to a method for producing a polymer using a novel polymerization initiator used in a living anion polymerization method or a novel cap agent added during the polymerization reaction to stabilize the polymerization terminal.
メタクリル酸エステル又はアクリル酸エステルのアニオン重合において開始効率を高める方法に関しては、例えば、α−リチオイソ酪酸エチル、１，１−ジフェニルヘキシルリチウム等の有機リチウム化合物をメチルビス（２，６−ジ−ｔｅｒｔ−ブチルフェノキシ）アルミニウム、エチルビス（２，６−ジ−ｔｅｒｔ−ブチルフェノキシ）アルミニウム、トリス（２，６−ジ−ｔｅｒｔ−ブチルフェノキシ）アルミニウム等の有機アルミニウム化合物と混合した後、メタクリル酸メチルと接触させる手順を経て、メタクリル酸メチルを、トルエン等の非極性有機溶媒中、室温前後の温度でアニオン重合させることにより、０．０５〜０．６３の開始効率を達成したことが知られている。（特許文献１を参照） Regarding the method for increasing the initiation efficiency in the anionic polymerization of methacrylic acid ester or acrylic acid ester, for example, an organic lithium compound such as ethyl α-lithioisobutyrate or 1,1-diphenylhexyl lithium is converted to methylbis (2,6-di-tert- After mixing with organoaluminum compounds such as butylphenoxy) aluminum, ethylbis (2,6-di-tert-butylphenoxy) aluminum, tris (2,6-di-tert-butylphenoxy) aluminum, contact with methyl methacrylate Through the procedure, it is known that methyl methacrylate was anionically polymerized in a nonpolar organic solvent such as toluene at a temperature around room temperature to achieve an initiation efficiency of 0.05 to 0.63. (See Patent Document 1)
また、α−リチオイソ酪酸エチル、ｔｅｒｔ−ブチルリチウム等の有機リチウム化合物を使用したメタクリル酸エステル又はアクリル酸エステルのアニオン重合を、トルエン等の炭化水素系溶媒中、トリアルキルアルミニウム等の有機アルミニウム化合物及びエステル化合物、エーテル化合物若しくは有機４級塩の存在下に、約−８０℃〜０℃の温度で行うことにより、分子量分布の狭い重合体を得たことが知られている。（非特許文献１、特許文献２を参照） In addition, anionic polymerization of methacrylic acid ester or acrylic acid ester using an organic lithium compound such as ethyl α-lithioisobutyrate and tert-butyllithium, in a hydrocarbon solvent such as toluene, an organoaluminum compound such as trialkylaluminum and It is known that a polymer having a narrow molecular weight distribution was obtained by carrying out the reaction at a temperature of about −80 ° C. to 0 ° C. in the presence of an ester compound, an ether compound or an organic quaternary salt. (See Non-Patent Document 1 and Patent Document 2)
しかしながら、従来のエノレートアニオンは、モノマーの種類や塩化リチウム等の添加剤の種類や量によっては、しばしばそこからの重合反応がうまく進行しないという問題があった。
本発明は、モノマー、または添加剤の種類に対応して、開始剤効率のよい新規な重合開始剤、またはキャップ剤を提供することを目的とする。
However, the conventional enolate anion has a problem that the polymerization reaction often does not proceed well depending on the type of monomer and the type and amount of additives such as lithium chloride.
An object of the present invention is to provide a novel polymerization initiator or capping agent having a high initiator efficiency corresponding to the type of monomer or additive.
本発明者らは、上記課題を解決すべく鋭意検討した結果、カルボニル基のβ位炭素上に置換基、またはエステル基に比較的嵩高い置換基を設けたエノレートアニオン種を用いることにより、上記課題を解決することを見出し本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have used an enolate anion species in which a substituent on the β-position carbon of the carbonyl group or a relatively bulky substituent is provided on the ester group, The inventors have found that the above problems can be solved and have completed the present invention.
すなわち、本発明は、
（１）式（I）
That is, the present invention
(1) Formula (I)
（式中、Ｒ１、Ｒ２及びＲ３は、それぞれ独立に水素原子又は置換基を有していてもよい炭化水素基を表し、Ｒ４は、置換基を有していてもよい炭化水素基を表す。但し、Ｒ１とＲ２は同時に水素原子となることはない。）、又は式（II） (Wherein R 1 , R 2 and R 3 each independently represents a hydrogen atom or a hydrocarbon group which may have a substituent, and R 4 represents a hydrocarbon which may have a substituent. Wherein R 1 and R 2 are not hydrogen atoms at the same time) or formula (II)
（式中、Ｒ５及びＲ６は、それぞれ独立に置換基を有していてもよい炭化水素基を表し、Ｒ７は、酸素原子に結合している原子が２級以上の炭素原子である置換基を有していてもよい炭化水素基を表す。）で表される化合物と、有機金属、アルカリ金属又はアニオン重合鎖末端のアニオンを反応させて得られるアニオンを重合の起点とすることを特徴とする重合体の製造方法であり、
（２）式（III）
（Ｒ）ｋＭ （III）
（式中、Ｒは、アルキル基、アリール基又は炭化水素オキシ基を表し、Ｍは、長周期型周期律表第１、２、１２又は１３族に属する元素を表し、ｋは、Ｍ元素の価数を表し、ｋが２以上の場合、Ｒ同士は、同一でも相異なっていてもよい。）で表される有機金属又はそのアート錯体の共存下で重合を行うことを特徴とする上記(１)に記載の重合体の製造方法である。
(In the formula, R 5 and R 6 each independently represent a hydrocarbon group which may have a substituent, and R 7 is a secondary or higher carbon atom whose atom is bonded to an oxygen atom. A hydrocarbon group which may have a substituent.) And an anion obtained by reacting an anion of an organic metal, an alkali metal or an anion polymerization chain end with a compound represented by A method for producing a characteristic polymer,
(2) Formula (III)
(R) k M (III)
(In the formula, R represents an alkyl group, an aryl group or a hydrocarbon oxy group, M represents an element belonging to Group 1, 2, 12 or 13 of the long-period periodic table, and k represents an M element. The valence is represented, and when k is 2 or more, Rs may be the same or different from each other.) The polymerization is performed in the presence of an organometallic represented by It is a manufacturing method of the polymer as described in 1).
本発明のアニオン重合方法を用いることにより、モノマーの種類や溶媒の種類が変化しても分子量や分子量分布を制御することができ、厳密な分子量や分子量分布が要求されるレジスト材料への応用やブロック重合体の製造が容易に行うことができる。 By using the anion polymerization method of the present invention, the molecular weight and molecular weight distribution can be controlled even if the type of monomer and the type of solvent change, and the application to resist materials that require strict molecular weight and molecular weight distribution The block polymer can be easily produced.
本発明は、式（I）又は（II）で表される化合物と式（III）で表される有機金属、アルカリ金属又はアニオン重合鎖末端のアニオンを反応させて得られるアニオンを重合の起点として、ブロック重合などを行うものである。 In the present invention, the starting point of polymerization is an anion obtained by reacting a compound represented by formula (I) or (II) with an organic metal, alkali metal or anion at the end of an anionic polymerization chain represented by formula (III). , Block polymerization and the like.
（式（I）又は(II)で表される化合物）
本発明の式（I）又は(II)で表される化合物における各Ｒについては以下のとおりであ
る。
Ｒ１、Ｒ２及びＲ３は、それぞれ独立して、水素原子又は置換基を有していてもよい炭化水素基を表す。
炭化水素基は、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、ｓｅｃ−ブチル、ｔ−ブチル、ｎ−ペンチル、ｎ−ヘキシル、ｎ−ヘプチル、ｎ−オクチル等のアルキル基、好ましくはＣ１−１２のアルキル基；シクロプロピル、シクロヘキシル、シクロヘプチル等のシクロアルキル基、好ましくはＣ３−１２のシクロアルキル基；ビニル、アリル、イソプロペニル、１−プロペニル、２−ブテニル、３−ブテニル、１，３−ブタンジエニル、２−メチル−２−プロペニル、１−ペンテニル、２−ペンテニル、３−ペンテニル、４−ペンテニル、１−ヘキセニル、２−ヘキセニル、３−ヘキセニル等のアルケニル基、好ましくはＣ２−１２のアルケニル基；エチニル、１−プロピニル、プロパルギル、１−ブチニル、２−ブチニル、３−ブチニル、２−ペンチニル、３−ペンチニル、４−ペンチニル、３−メチル−２−プロピニル、２−エテニルプロピル、２−ペンチル、３−ペンチル、４−ペンチニル、１−メチル−２−ブチニル、１−メチル−３−ブチニル、２−メチル−３−ブチニル、３−メチル−１−ブチニル、１−ヘキシニル、２−ヘキシニル、３−ヘキシニル、４−ヘキシニル、５−ヘキシニル等のアルキニル基、好ましくはＣ２−１２のアルキニル基；フェニル、１−ナフチル、２−ナフチル等のアリール基、好ましくはＣ６−１０のアリール基；ベンジル、フェニルエチル、フェニルプロピル等のアラルキル基、好ましくはＣ７−１２のアラルキル基等がある。
(Compound represented by formula (I) or (II))
Each R in the compound represented by the formula (I) or (II) of the present invention is as follows.
R 1 , R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group which may have a substituent.
The hydrocarbon group is an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, preferably C 1-12 alkyl group; cycloalkyl group such as cyclopropyl, cyclohexyl, cycloheptyl, etc., preferably C 3-12 cycloalkyl group; vinyl, allyl, isopropenyl, 1-propenyl, 2-butenyl, 3-butenyl, Alkenyl groups such as 1,3-butanedienyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, preferably C 2 -12 alkenyl groups; ethynyl, 1-propynyl, propargyl, 1-butynyl, 2-butyl , 3-butynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 3-methyl-2-propynyl, 2-ethenylpropyl, 2-pentyl, 3-pentyl, 4-pentynyl, 1-methyl-2- Alkynyl groups such as butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, Preferably C 2-12 alkynyl group; aryl group such as phenyl, 1-naphthyl and 2-naphthyl, preferably C 6-10 aryl group; aralkyl group such as benzyl, phenylethyl and phenylpropyl, preferably C 7 And -12 aralkyl groups.
置換基を有していてもよい場合の置換基としては、ハロゲン原子、シアノ、アルキル、アルケニル、アルキニル、ハロアルキル、アルコキシ、ニトロ、アルコキシカルボニル、アルキルカルボニルオキシ、アルキレンジオキシ、アルキルカルボニル、アミノ、アルキルアミノ、ハロアルコキシ、アルキルチオ、アルキルスルホニル、ハロアルケニル、アルコキシカルボニルアルキル又はアルコキシカルボニルアルコキシ、アリールオキシなどがある。
Ｒ４、Ｒ５及びＲ６は、置換基を有してよい炭化水素基を表し、炭化水素基及び置換基の意味は上記定義と同じである。
Ｒ７は、酸素原子に結合している原子が２級以上の炭素原子である、置換基を有してもよい炭化水素基を表す。
In the case where it may have a substituent, the substituent is a halogen atom, cyano, alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, nitro, alkoxycarbonyl, alkylcarbonyloxy, alkylenedioxy, alkylcarbonyl, amino, alkyl There are amino, haloalkoxy, alkylthio, alkylsulfonyl, haloalkenyl, alkoxycarbonylalkyl or alkoxycarbonylalkoxy, aryloxy and the like.
R 4 , R 5 and R 6 represent a hydrocarbon group which may have a substituent, and the meanings of the hydrocarbon group and the substituent are the same as defined above.
R 7 represents a hydrocarbon group which may have a substituent, wherein the atom bonded to the oxygen atom is a secondary or higher carbon atom.
このような炭化水素基としては、イソプロピル、ｓｅｃ−ブチル、ｔ−ブチル、イソプロペニル、シクロペンチル、シクロヘキシル、ジフェニルメチル、トリフェニルメチルなどがあり、比較的嵩高い炭化水素基はすべて含まれる。
置換基を有してもよい場合の置換基は、上記定義と同じである。
式（I）又は（II）で表される化合物として、具体的には、アンゲリカ酸メチル、クロ
トン酸ｔ−ブチル、イソ酪酸イソプロピルなどがある。これらの化合物を含め式（I）又は（II）で表される化合物は、公知の製法により製造することが可能である。
Such hydrocarbon groups include isopropyl, sec-butyl, t-butyl, isopropenyl, cyclopentyl, cyclohexyl, diphenylmethyl, triphenylmethyl and the like, and all relatively bulky hydrocarbon groups are included.
In the case where it may have a substituent, the substituent is the same as defined above.
Specific examples of the compound represented by the formula (I) or (II) include methyl angelate, t-butyl crotonate, and isopropyl isobutyrate. The compounds represented by the formula (I) or (II) including these compounds can be produced by a known production method.
（式（III）で表される化合物）
次に、式（III）で表される化合物のＲ及びＭについては以下のとおりである。
Ｒはアルキル基、アリール基又は炭化水素オキシ基を表す。
アルキル基としては、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ペンチル、ｎ−ヘキシル、ｎ−ヘプチル、ｎ−オクチル、ｎ−ドデシル、ｎ−ペンタデシルなど直鎖状または分岐状のアルキル基、好ましくはＣ１−１２のアルキル基、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシルなどシクロアルキル基、好ましくはＣ３−１２のシクロアルキル基がある。
アリール基としては、フェニル、１−ナフチル、２−ナフチル、１−アントリル、２−アントリル、９−アントリル、１−フェナントリル基、２−フェナントリル、３−フェナントリル、４−フェナントリル、９−フェナントリル、１０−フェナントリル等であり、好ましくはＣ６−１４のアリール基である。
(Compound represented by formula (III))
Next, R and M of the compound represented by the formula (III) are as follows.
R represents an alkyl group, an aryl group, or a hydrocarbon oxy group.
Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-pentadecyl and the like. There are chain or branched alkyl groups, preferably C 1-12 alkyl groups, cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like, preferably C 3-12 cycloalkyl groups.
As the aryl group, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl group, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 10- Phenanthryl and the like, preferably a C 6-14 aryl group.
炭化水素オキシ基における炭化水素は、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、ｓｅｃ−ブチル、ｔ−ブチル、ｎ−ペンチル、ｎ−ヘキシル、ｎ−ヘプチル、ｎ−オクチル等のアルキル基、好ましくはＣ１−１２のアルキル基；シクロプロピル、シクロヘキシル、シクロヘプチル等のシクロアルキル基、好ましくはＣ３−１２のシクロアルキル基；ビニル、アリル、イソプロペニル、１−プロペニル、２−ブテニル、３−ブテニル、１，３−ブタンジエニル、２−メチル−２−プロペニル、１−ペンテニル、２−ペンテニル、３−ペンテニル、４−ペンテニル、１−ヘキセニル、２−ヘキセニル、３−ヘキセニル等のアルケニル基、好ましくはＣ２−１２のアルケニル基；エチニル、１−プロピニル、プロパルギル、１−ブチニル、２−ブチニル、３−ブチニル、２−ペンチニル、３−ペンチニル、４−ペンチニル、３−メチル−２−プロピニル、２−エテニルプロピル、２−ペンチル、３−ペンチル、４−ペンチニル、１−メチル−２−ブチニル、１−メチル−３−ブチニル、２−メチル−３−ブチニル、３−メチル−１−ブチニル、１−ヘキシニル、２−ヘキシニル、３−ヘキシニル、４−ヘキシニル、５−ヘキシニル等のアルキニル基、好ましくはＣ２−１２のアルキニル基；フェニル、１−ナフチル、２−ナフチル等のアリール基、好ましくはＣ６−１０のアリール基；ベンジル、２−フェニルエチル、３−フェニルプロピル等のアラルキル基等、好ましくはＣ７−１２のアラルキル基がある。 The hydrocarbon in the hydrocarbon oxy group is an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl. , Preferably a C 1-12 alkyl group; a cycloalkyl group such as cyclopropyl, cyclohexyl, cycloheptyl, etc., preferably a C 3-12 cycloalkyl group; vinyl, allyl, isopropenyl, 1-propenyl, 2-butenyl, Alkenyl groups such as 3-butenyl, 1,3-butanedienyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, preferably alkenyl groups C 2-12; ethynyl, 1-propynyl, propargyl, -Butynyl, 2-butynyl, 3-butynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 3-methyl-2-propynyl, 2-ethenylpropyl, 2-pentyl, 3-pentyl, 4-pentynyl, 1 -Methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl Alkynyl groups such as C 2-12 alkynyl groups; aryl groups such as phenyl, 1-naphthyl and 2-naphthyl, preferably C 6-10 aryl groups; benzyl, 2-phenylethyl, 3-phenylpropyl And an aralkyl group such as C 7-12 .
Ｍは、長周期型周期律表第１、２、１２又は１３族に属する元素である。例えば、リチウム、ナトリウム、カリウム、セシウム、マグネシウム、亜鉛、アルミニウムなどがある。
式（III）で表される化合物として、具体的には、エチルリチウム、ｎ−ブチルリチウ
ム、ｓｅｃ−ブチルリチウム、ｔ−ブチルリチウム、エチルナトリウム、リチウムビフェニル、リチウムナフタレン、ナトリウムナフタレン、カリウムナフタレン、α−メチルスチレンナフタレンジアニオン、１，４−ジリチオ−２−ブテン、１，６−ジリチオへキサン、クミルカリウム、クミルセシウム等の有機アルカリ金属；ジ−ｎ−ブチルマグネシウム、ジ−ｔ−ブチルマグネシウム、ジ−ｓ−ブチルマグネシウム、ｎ−ブチル−ｓ−ブチルマグネシウム、ｎ−ブチル−エチルマグネシウム、ジ−ｎ−アミルマグネシウム、ジベンジルマグネシウム、ジフェニルマグネシウム、ジエチル亜鉛、ジ−ｎ−ブチル亜鉛、トリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウム、トリ−ｎ−へキシルアルミニウム等の有機金属がある。これらの化合物は、単独であるいは２種以上を混合して用いることができる。これら式（III）の化合物はアート錯体としても使
用することができる。
M is an element belonging to Group 1, 2, 12 or 13 of the long periodic table. For example, there are lithium, sodium, potassium, cesium, magnesium, zinc, aluminum and the like.
Specific examples of the compound represented by the formula (III) include ethyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, ethyl sodium, lithium biphenyl, lithium naphthalene, sodium naphthalene, potassium naphthalene, α -Organic alkali metals such as methylstyrene naphthalene dianion, 1,4-dilithio-2-butene, 1,6-dilithiohexane, cumyl potassium, cumyl cesium; di-n-butylmagnesium, di-t-butylmagnesium, di-s -Butylmagnesium, n-butyl-s-butylmagnesium, n-butyl-ethylmagnesium, di-n-amylmagnesium, dibenzylmagnesium, diphenylmagnesium, diethylzinc, di-n-butylzinc, trimethylaluminum, triethyl Aluminum, and organic metals such as hexyl aluminum triisobutyl aluminum, the tri-n-. These compounds can be used alone or in admixture of two or more. These compounds of formula (III) can also be used as art complexes.
式（III）の化合物の使用量は、重合に影響しない範囲内で任意に使用できるが、具体
的には重合開始剤に対してモル比で１０：１以上１：２０以下であるのが好ましい。１０：１より小さい場合には、重合体製造の際に分子量や分子量分布が制御された重合体を安定的に再現性よく製造できない場合があり、１：２０より大きい場合には、重合反応に、成長速度が著しく低下する場合がある。
The amount of the compound of the formula (III) can be arbitrarily used within a range not affecting the polymerization, and specifically, it is preferably 10: 1 or more and 1:20 or less in a molar ratio with respect to the polymerization initiator. . If the ratio is smaller than 10: 1, a polymer having a controlled molecular weight or molecular weight distribution may not be stably produced with good reproducibility during the production of the polymer. The growth rate may be significantly reduced.
（アルカリ金属）
アルカリ金属としては、リチウム、ナトリウム、カリウムなどがある。
(Alkali metal)
Examples of the alkali metal include lithium, sodium, and potassium.
（重合方法）
本発明に用いられるアニオン重合性単量体は、アニオン重合性不飽和結合を有するものであれば特に限定されないが、具体的には、スチレン誘導体、ブタジエン誘導体、（メタ）アクリル酸エステル誘導体等を好ましく例示することができる。
スチレン誘導体として、具体的には、スチレン、α−アルキルスチレン、核置換スチレン等を例示することができ、核置換基としては、重合開始能力があるアニオン種、および重合開始能力がないアニオン種に対して不活性な基であれば特に制限されず、具体的には、アルキル基、アルコキシアルキル基、アルコキシ基、アルコキシアルコキシ基、ｔ−ブトキシカルボニル基、ｔ−ブトキシカルボニルメチル基、テトラヒドロピラニル基等を例示することができる。さらにスチレン誘導体の具体例として、α−メチルスチレン、α−メチル−ｐ−メチルスチレン、ｐ−メチルスチレン、ｍ−メチルスチレン、ｏ−メチルスチレン、ｐ−エチルスチレン、２，４−ジメチルスチレン、２，５−ジメチルスチレン、ｐ−イソプロピルスチレン、２，４，６−トリイソプロピルスチレン、ｐ−ｔ−ブトキシスチレン、ｐ−ｔ−ブトキシ−α−メチルスチレン、ｍ−ｔ−ブトキシスチレン、ｐ−（１−エトキシエトキシ）スチレンなどを例示することができる。
(Polymerization method)
The anion polymerizable monomer used in the present invention is not particularly limited as long as it has an anion polymerizable unsaturated bond. Specifically, a styrene derivative, a butadiene derivative, a (meth) acrylic acid ester derivative, etc. It can be illustrated preferably.
Specific examples of the styrene derivative include styrene, α-alkylstyrene, and nucleus-substituted styrene. The nucleus substituent includes an anion species having a polymerization initiation ability and an anion species having no polymerization initiation ability. The group is not particularly limited as long as it is an inert group. Specifically, an alkyl group, an alkoxyalkyl group, an alkoxy group, an alkoxyalkoxy group, a t-butoxycarbonyl group, a t-butoxycarbonylmethyl group, a tetrahydropyranyl group. Etc. can be illustrated. Specific examples of the styrene derivative include α-methylstyrene, α-methyl-p-methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, 2 , 5-dimethylstyrene, p-isopropylstyrene, 2,4,6-triisopropylstyrene, pt-butoxystyrene, pt-butoxy-α-methylstyrene, mt-butoxystyrene, p- (1 -Ethoxyethoxy) styrene and the like can be exemplified.
ブタジエン誘導体として、具体的には、１，３−ブタジエン、イソプレン、２，３−ジメチルブタジエン、２−エチル−１，３−ブタジエン、１，３−ペンタジエンなどを例示することができる。
また（メタ）アクリル酸エステル誘導体は、エステルアルコール残基の炭素数が１〜２０のものが反応性の観点より好ましく、具体的には、メチルエステル、エチルエステル、イソプロピルエステル、ｎ−ブチルエステル、ｔ−ブチルエステル等を例示することができる。
例示したこれらの単量体は、１種単独、または２種以上用いることができる。
Specific examples of the butadiene derivative include 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, and the like.
In addition, the (meth) acrylic acid ester derivative preferably has an ester alcohol residue having 1 to 20 carbon atoms from the viewpoint of reactivity. Specifically, methyl ester, ethyl ester, isopropyl ester, n-butyl ester, A t-butyl ester etc. can be illustrated.
These exemplified monomers can be used alone or in combination of two or more.
本発明の式（I）又は（II）で表される化合物をスチレン誘導体から（メタ）アクリル酸エステル誘導体、ブタジエン誘導体から（メタ）アクリル酸エステル誘導体へのブロック重合を行なう際のキャップ剤に使用するとブロック化反応が副反応が低減されスムースに進行する。従ってブロック共重合体製造においても適用が可能である。 The compound represented by the formula (I) or (II) of the present invention is used as a cap agent when performing block polymerization from a styrene derivative to a (meth) acrylate derivative and from a butadiene derivative to a (meth) acrylate derivative. Then, the blocking reaction proceeds smoothly with reduced side reactions. Therefore, it can be applied to the production of block copolymers.
本発明における重合温度は、移動反応や停止反応などの副反応が起こらず、単量体が消費され重合が完結する温度範囲であれば特に制限されないが、−７０℃以上、重合溶媒沸点以下の温度範囲で行なわれることが好ましい。また、単量体の重合溶媒に対する濃度は、特に制限されないが、通常１〜４０重量％の範囲であり、特に２〜１５重量％の範囲が好ましい。 The polymerization temperature in the present invention is not particularly limited as long as it is a temperature range in which side reactions such as transfer reaction and termination reaction do not occur and the monomer is consumed and the polymerization is completed, but it is −70 ° C. or more and the polymerization solvent boiling point or less. It is preferably performed in the temperature range. The concentration of the monomer with respect to the polymerization solvent is not particularly limited, but is usually in the range of 1 to 40% by weight, and particularly preferably in the range of 2 to 15% by weight.
重合反応においてはエーテル基含有溶媒が使用される。エーテル基含有溶媒は、具体的にはジエチルエーテル、テトラヒドロフラン（ＴＨＦ）、ジオキサン、トリオキサンなどのエーテル系化合物を例示することができる。また、これらの溶媒は、１種単独で、または２種以上の混合溶媒として用いることができる。
また重合反応に関与せず、かつ重合体と相溶性のある極性溶媒であれば、特に制限されず、エーテル基含有溶媒と併用して用いることができる。具体的にはテトラメチルエチレンジアミン、ヘキサメチルホスホリックトリアミドなどの第３級アミンを例示することができる。
In the polymerization reaction, an ether group-containing solvent is used. Specific examples of the ether group-containing solvent include ether compounds such as diethyl ether, tetrahydrofuran (THF), dioxane, and trioxane. Moreover, these solvent can be used individually by 1 type or as a 2 or more types of mixed solvent.
Moreover, if it is a polar solvent which does not participate in a polymerization reaction and is compatible with a polymer, it will not restrict | limit, and it can use together with an ether group containing solvent. Specific examples thereof include tertiary amines such as tetramethylethylenediamine and hexamethylphosphoric triamide.
さらに、極性の低い脂肪族、芳香族又は脂環式炭化水素化合物であっても、重合体と比較的相溶性があれば、エーテル基含有溶媒と組み合わせることにより使用することができ、具体的には、へキサンとＴＨＦの組み合わせを例示できる。 Furthermore, even if it is an aliphatic, aromatic or alicyclic hydrocarbon compound having a low polarity, it can be used by combining with an ether group-containing solvent, as long as it is relatively compatible with the polymer. Can exemplify a combination of hexane and THF.
本発明においては、必要に応じてアルカリ金属塩やアルカリ土類金属塩、カルボン酸類、アミン類、アルコール類やチオール類のアルカリ金属塩などよりなる添加剤を、重合開始時、または重合中に添加することができる。そのような添加剤として、具体的にはナトリウム、カリウム、バリウム、マグネシウムの硫酸塩、硝酸塩、ホウ酸塩などの鉱酸塩やハロゲン化物、脂肪族アルコールのアルカリ金属塩、脂肪族又は芳香族チオールのアルカリ金属塩を例示することができ、より具体的にはリチウムやバリウムの塩化物、臭化物、ヨウ化物や、ホウ酸リチウム、硝酸マグネシウム、塩化ナトリウム、塩化カリウム、リチウムメトキシド、リチウムｔ−ブトキシドのようなアルコキシド、リチウムフェノキシドのようなフェノキシド、プロイオン酸リチウムのようなカルボキシド、リチウムジフェニルアミドのようなアミド、エタンチオールやプロパンチオールおよびシクロヘキシルシオールなどのＣ１〜Ｃ１８のアルキルチオールやシクロアルキルチオール、メルカプトエタノールやｐ−メルカプロフェノール等の水酸基を含有するチオール、メルカプト酢酸メチルやメルカプトプロピオン酸エチルなどのカルボン酸エステルを含有するチオール、ベンゼンチオールやトルエンチオールおよびナフタレンチオールなどの芳香族チオール、メルカプトチアゾリンメルカプトベンズチアゾリンおよびメルカプトピリミジンなどの含窒素芳香族チオールなどリチウム、ナトリウム、カリウム塩を挙げることができるが、これらの中でも、リチウムのハロゲン化物、アルコール類やチオール類のアルカリ金属塩が好ましい。これらの添加剤は、１種単独、または２種以上用いることができる。 In the present invention, an additive comprising an alkali metal salt, an alkaline earth metal salt, a carboxylic acid, an amine, an alcohol or an thiol alkali metal salt is added at the start of polymerization or during polymerization as necessary. can do. Specific examples of such additives include mineral salts and halides such as sodium, potassium, barium and magnesium sulfates, nitrates and borates, alkali metal salts of aliphatic alcohols, aliphatic or aromatic thiols. And more specifically, lithium, barium chloride, bromide, iodide, lithium borate, magnesium nitrate, sodium chloride, potassium chloride, lithium methoxide, lithium t-butoxide Alkoxides such as Lithium Phenoxide, Carboxides such as Lithium Proionate, Amides such as Lithium Diphenylamide, C1-C18 Alkylthiols and Cycloalkylthiols such as Ethanethiol, Propanethiol and Cyclohexylciol , Me Thiols containing hydroxyl groups such as captoethanol and p-mercaprophenol, thiols containing carboxylates such as methyl mercaptoacetate and ethyl mercaptopropionate, aromatic thiols such as benzenethiol, toluenethiol and naphthalenethiol, mercaptothiazoline Lithium, sodium and potassium salts such as nitrogen-containing aromatic thiols such as mercaptobenzthiazoline and mercaptopyrimidine can be mentioned, and among these, lithium halides, alcohols and alkali metal salts of thiols are preferred. These additives can be used alone or in combination of two or more.
本発明の方法で得られる重合体は分子量制御されているので、単分散で分子量分布の狭い重合体となる。この重合体の分子量分散度（重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ））は通常１．０１〜２．５０であり、好ましくは１．０１〜１．５０である。
本発明においては、得られる重合体の分子量を更に正確に規定するため、一定の単量体を重合した後、その分子量をＧＰＣなどで把握し、更に所望する重合体の分子量に必要とされる単量体を加え分子量を調整する多段重合を用いることにより、より精密に分子量を規定することが可能となる。多段重合またはブロック重合体を製造するときには、加える単量体に有機金属を加えておくのが好ましい。
Since the polymer obtained by the method of the present invention is controlled in molecular weight, it becomes a monodispersed polymer with a narrow molecular weight distribution. The molecular weight dispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of this polymer is usually 1.01 to 2.50, preferably 1.01 to 1.50.
In the present invention, in order to more accurately define the molecular weight of the obtained polymer, after polymerizing a certain monomer, the molecular weight is grasped by GPC or the like, and further required for the desired molecular weight of the polymer. By using a multistage polymerization in which a monomer is added to adjust the molecular weight, the molecular weight can be regulated more precisely. When producing a multistage polymerization or block polymer, it is preferable to add an organic metal to the monomer to be added.
本発明の製造方法から得られる重合体の中で異なる単量体の組合せから製造される多元ブロック共重合体は、精密なミクロ相分離を必要とする自己組織化ナノパターニング材料用の重合体として好適に使用される。特に、スチレン、ビニールナフタレンやブタジエンのような非極性単量体とｐ−ｔ−ブトキシスチレン、ｔ−ブチルメタクリレートおよび２−ヒドロキシエチルメタクリレートのアセタール保護モノマーなどの極性単量体を保護した単量体やグリシジルメタクリレーとなどの官能基を有する単量体との多元ブロック共重合体が好適である。保護基のある重合体は保護基を外すことにより誘導体に導くことができる。 The multi-block copolymer produced from a combination of different monomers among the polymers obtained from the production method of the present invention is a polymer for self-organized nanopatterning materials that require precise microphase separation. Preferably used. In particular, non-polar monomers such as styrene, vinyl naphthalene and butadiene and monomers protected with polar monomers such as acetal protecting monomers of pt-butoxystyrene, t-butyl methacrylate and 2-hydroxyethyl methacrylate A multi-block copolymer of a monomer having a functional group such as glycidyl methacrylate and glycidyl methacrylate is preferable. A polymer having a protecting group can be converted into a derivative by removing the protecting group.
以下実施例を用いて本発明を詳細に説明するが、本発明の範囲は実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, the scope of the present invention is not limited to an Example.
窒素雰囲気下、ＴＨＦ１００ｇに塩化リチウム０．１７ｇ（４．１ｍｍｏｌ）を溶解させ溶液中に、−５０℃で、ｓ−ＢｕＬｉ溶液１．１５ｇ（１．８ｍｍｏｌ）を加え、続いて、アンゲリカ酸メチル０．２２ｇ（１．９ｍｍｏｌ）を加え、攪拌した。その後、ジエチル亜鉛溶液０．７５ｇ（１．０ｍｍｏｌ）を加え攪拌した。次に、メチルメタクリレート５．６７ｇ（５６．６ｍｍｏｌ）を滴下し、滴下終了後、７０分間攪拌し、メタノールを加えキリングした。このキリング溶液をガスクロで測定してみるとモノマーは残存していなかった。また、ＧＰＣ測定を行なうと分子量（Ｍｗ）３０８００、分散度＝１．０８のポリマーが生成していた。 Under a nitrogen atmosphere, 0.17 g (4.1 mmol) of lithium chloride was dissolved in 100 g of THF, and 1.15 g (1.8 mmol) of s-BuLi solution was added to the solution at −50 ° C., followed by methyl angelate 0 .22 g (1.9 mmol) was added and stirred. Thereafter, 0.75 g (1.0 mmol) of diethyl zinc solution was added and stirred. Next, 5.67 g (56.6 mmol) of methyl methacrylate was added dropwise, and after completion of the dropwise addition, the mixture was stirred for 70 minutes, and methanol was added to kill it. When this killing solution was measured by gas chromatography, no monomer remained. Further, when GPC measurement was performed, a polymer having a molecular weight (Mw) of 30800 and a dispersion degree of 1.08 was produced.
窒素雰囲気下、ＴＨＦ１６０ｇに塩化リチウム０．５１ｇ（１２．１ｍｍｏｌ）を溶解させた溶液中に、−５０℃で、ｎ−ＢｕＬｉ溶液１．６８ｇ（４．０ｍｍｏｌ）を加え、続いてクロトン酸ｔ−ブチル０．５７ｇ(４．０ｍｍｏｌ)を加え、１０分間攪拌した。続いて、ジエチル亜鉛溶液０．３８ｇ（０．５ｍｍｏｌ）を加えた。その後、ＴＨＦ１５ｇにｔ−ブチルメタクリレート７．８３ｇ（５５．１ｍｍｏｌ）を溶解させ、ジエチル亜鉛溶液０．３８ｇ（０．５ｍｍｏｌ）を加えた溶液を滴下し、滴下終了後、９０分間攪拌し、メタノールを加えキリングした。このキリング溶液をガスクロで測定してみるとモノマーは残存していなかった。また、ＧＰＣ測定を行なうと分子量（Ｍｗ）６１００、分散度＝１．０７のポリマーが生成していた。 Under a nitrogen atmosphere, 1.68 g (4.0 mmol) of n-BuLi solution was added at −50 ° C. to a solution of 0.51 g (12.1 mmol) of lithium chloride in 160 g of THF, followed by crotonic acid t- 0.57 g (4.0 mmol) of butyl was added and stirred for 10 minutes. Subsequently, 0.38 g (0.5 mmol) of diethyl zinc solution was added. Thereafter, 7.83 g (55.1 mmol) of t-butyl methacrylate was dissolved in 15 g of THF, and a solution obtained by adding 0.38 g (0.5 mmol) of a diethylzinc solution was added dropwise. Added killing. When this killing solution was measured by gas chromatography, no monomer remained. Further, when GPC measurement was performed, a polymer having a molecular weight (Mw) of 6100 and a dispersion degree of 1.07 was produced.
窒素雰囲気下、ＴＨＦ１２０ｇに塩化リチウム０．６７ｇ（１５．８ｍｍｏｌ）を溶解させた溶液中に、−５０℃で、ｓ−ＢｕＬｉ溶液４．００ｇ（６．２ｍｍｏｌ）を加え、続いてイソ酪酸イソプロピル０．４４ｇ（３．４ｍｍｏｌ）を加え、２０分間攪拌した。続いて、ジエチル亜鉛溶液２．７６ｇ（３．８ｍｍｏｌ）を加えた。その後、ＴＨＦ５ｇにメチルメタクリレート５．７１ｇ（５７．０ｍｍｏｌ）を溶解させ、ジエチル亜鉛溶液０．３６ｇ（０．５ｍｍｏｌ）を加えた溶液を滴下し、滴下終了後、６０分間攪拌し、メタノールを加えキリングした。このキリング溶液をガスクロで測定してみるとモノマーは残存していなかった。また、ＧＰＣ測定を行なうと分子量（Ｍｗ）１７１００、分散度＝１．１３のポリマーが生成していた。 Under a nitrogen atmosphere, 4.00 g (6.2 mmol) of s-BuLi solution was added at −50 ° C. to a solution of 0.67 g (15.8 mmol) of lithium chloride in 120 g of THF, followed by isopropyl isobutyrate 0 .44 g (3.4 mmol) was added and stirred for 20 minutes. Subsequently, 2.76 g (3.8 mmol) of diethylzinc solution was added. Thereafter, 5.71 g (57.0 mmol) of methyl methacrylate was dissolved in 5 g of THF, and a solution obtained by adding 0.36 g (0.5 mmol) of a diethylzinc solution was added dropwise. After completion of the addition, the mixture was stirred for 60 minutes and killed by adding methanol. did. When this killing solution was measured by gas chromatography, no monomer remained. Further, when GPC measurement was performed, a polymer having a molecular weight (Mw) of 17100 and a dispersity of 1.13 was produced.
Claims (2)
（Ｒ）ｋＭ （III）
（式中、Ｒは、アルキル基、アリール基又は炭化水素オキシ基を表し、Ｍは、長周期型周期律表第１、２、１２又は１３族に属す元素を表し、ｋは、Ｍ元素の価数を表し、ｋが２以上の場合、Ｒ同士は、同一でも相異なっていてもよい。）で表される有機金属又はそのアート錯体の共存下で重合を行うことを特徴とする請求項１に記載の重合体の製造方法。 Formula (III)
(R) k M (III)
(In the formula, R represents an alkyl group, an aryl group or a hydrocarbon oxy group, M represents an element belonging to Group 1, 2, 12 or 13 of the long-period periodic table, and k represents an M element. The valence is represented, and when k is 2 or more, Rs may be the same or different from each other.) The polymerization is carried out in the presence of an organic metal represented by or an art complex thereof. A method for producing the polymer according to 1.
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