JP5121045B2 - Method for producing polymer by anionic polymerization - Google Patents
Method for producing polymer by anionic polymerization Download PDFInfo
- Publication number
- JP5121045B2 JP5121045B2 JP2007119503A JP2007119503A JP5121045B2 JP 5121045 B2 JP5121045 B2 JP 5121045B2 JP 2007119503 A JP2007119503 A JP 2007119503A JP 2007119503 A JP2007119503 A JP 2007119503A JP 5121045 B2 JP5121045 B2 JP 5121045B2
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- Prior art keywords
- compound
- anionic
- polymer
- solvent
- anionic polymerization
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims description 77
- 238000010539 anionic addition polymerization reaction Methods 0.000 title claims description 73
- 238000004519 manufacturing process Methods 0.000 title claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 109
- 238000006243 chemical reaction Methods 0.000 claims description 79
- 239000002904 solvent Substances 0.000 claims description 50
- -1 alkyl lithium Chemical compound 0.000 claims description 42
- 239000003505 polymerization initiator Substances 0.000 claims description 42
- 125000000129 anionic group Chemical group 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 35
- 229920006318 anionic polymer Polymers 0.000 claims description 19
- 150000001450 anions Chemical class 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 230000000379 polymerizing effect Effects 0.000 claims description 16
- 239000012295 chemical reaction liquid Substances 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000002798 polar solvent Substances 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- 239000000178 monomer Substances 0.000 description 22
- 238000006116 polymerization reaction Methods 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 229910052783 alkali metal Inorganic materials 0.000 description 15
- 238000005227 gel permeation chromatography Methods 0.000 description 15
- 239000002184 metal Substances 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 9
- 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 8
- 238000004817 gas chromatography Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 150000003440 styrenes Chemical class 0.000 description 4
- 150000003573 thiols Chemical class 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 150000002739 metals Chemical class 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
- 239000012454 non-polar solvent Substances 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 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
- BXAVKNRWVKUTLY-UHFFFAOYSA-N 4-sulfanylphenol Chemical compound OC1=CC=C(S)C=C1 BXAVKNRWVKUTLY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000010551 living anionic polymerization reaction Methods 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
- 150000002736 metal compounds Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 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
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 1
- 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
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 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
- 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
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 1
- LXUNZSDDXMPKLP-UHFFFAOYSA-N 2-Methylbenzenethiol Chemical compound CC1=CC=CC=C1S LXUNZSDDXMPKLP-UHFFFAOYSA-N 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
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([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
- NLHFDAUOBSZFKR-UHFFFAOYSA-N 3h-1,3-benzothiazole-2-thione;1,3-thiazolidine-2-thione Chemical compound S=C1NCCS1.C1=CC=C2SC(=S)NC2=C1 NLHFDAUOBSZFKR-UHFFFAOYSA-N 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
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- GSXOBSRPSWHPLE-UHFFFAOYSA-N C1=CC=CC2=CC=CC=C12.CC(=C)C1=CC=CC=C1 Chemical compound C1=CC=CC2=CC=CC=C12.CC(=C)C1=CC=CC=C1 GSXOBSRPSWHPLE-UHFFFAOYSA-N 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 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
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000005083 alkoxyalkoxy 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229920001400 block copolymer Polymers 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
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- CMKBCTPCXZNQKX-UHFFFAOYSA-N cyclohexanethiol Chemical compound SC1CCCCC1 CMKBCTPCXZNQKX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl 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])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- OBTSLRFPKIKXSZ-UHFFFAOYSA-N lithium potassium Chemical compound [Li].[K] OBTSLRFPKIKXSZ-UHFFFAOYSA-N 0.000 description 1
- URMHJZVLKKDTOJ-UHFFFAOYSA-N lithium;(3-methyl-1-phenylpentyl)benzene Chemical compound [Li+].C=1C=CC=CC=1[C-](CC(C)CC)C1=CC=CC=C1 URMHJZVLKKDTOJ-UHFFFAOYSA-N 0.000 description 1
- DSZMPZRQIDKROL-UHFFFAOYSA-N lithium;1-phenylhexylbenzene Chemical compound [Li+].C=1C=CC=CC=1C(CCCC[CH2-])C1=CC=CC=C1 DSZMPZRQIDKROL-UHFFFAOYSA-N 0.000 description 1
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-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
- 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
- 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
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 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
- 239000011707 mineral Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 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 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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
- 239000003973 paint Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 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
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propyl mercaptan Natural products CCCS SUVIGLJNEAMWEG-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
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 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
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-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
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003643 water by type Substances 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
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical group OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、アニオン重合による重合体の製造方法に関し、より詳細には、アニオン重合により所望の分子量の重合体を狭分散でかつ効率よく製造する方法に関する。 The present invention relates to a method for producing a polymer by anionic polymerization, and more particularly to a method for efficiently producing a polymer having a desired molecular weight in a narrow dispersion by anionic polymerization.
リビングアニオン重合法により分子量や分子量分布が制御された重合体を製造する場合は、溶媒中にアニオン重合開始剤を添加し、その中にモノマーを添加する方法が一般的である。リビングアニオン重合において分子量や分子量分布を制御するためには、アニオン重合開始剤と反応させようとするモノマーの反応がモノマー同士の反応よりも非常に速いこと、あるいはアニオン重合開始剤と反応させようとするモノマーの反応がモノマー同士の反応とほぼ同じであることが条件となる。これらが満たされない場合は分子量分布が広くなったり、設定した分子量とはかけ離れた高分子量体が生成したりすることになる。例えば、一般的なアニオン重合開始剤として知られているアルキルリチウム、特にハンドリングの容易なｎ−ブチルリチウムをテトラヒドロフラン（以下、「ＴＨＦ」という）等の極性溶媒中でリビングアニオン重合に使用した場合、モノマーとしてｐ−メトキシスチレンのようなアルコキシスチレンなどを用いると、分子量分布が広くなったり、設定した分子量とはかけ離れた高分子量体が生成するなどの問題が生じる。分子量分布が広がってしまうこの傾向は、製造する重合体の分子量が大きくなればなるほど顕著になる。また、メチルメタクリレートなどをアニオン重合した場合、設定分子量よりもはるかに大きい分子量のものが生成してしまう。 In the case of producing a polymer whose molecular weight or molecular weight distribution is controlled by the living anion polymerization method, a method in which an anionic polymerization initiator is added to a solvent and a monomer is added therein is generally used. In order to control the molecular weight and molecular weight distribution in living anionic polymerization, the reaction of the monomer to be reacted with the anionic polymerization initiator is much faster than the reaction between the monomers, or the reaction with the anionic polymerization initiator is attempted. It is a condition that the reaction of the monomers to be performed is almost the same as the reaction between the monomers. When these are not satisfied, the molecular weight distribution becomes wide, or a high molecular weight body far from the set molecular weight is generated. For example, when alkyl lithium known as a general anionic polymerization initiator, particularly n-butyl lithium which is easy to handle, is used for living anionic polymerization in a polar solvent such as tetrahydrofuran (hereinafter referred to as “THF”), When alkoxy styrene such as p-methoxystyrene is used as the monomer, problems such as broad molecular weight distribution and generation of a high molecular weight substance far from the set molecular weight occur. This tendency to broaden the molecular weight distribution becomes more prominent as the molecular weight of the polymer to be produced increases. Moreover, when anionic polymerization of methyl methacrylate or the like occurs, a molecular weight much larger than the set molecular weight is generated.
これらの問題を避けるためには、モノマーにとって最適な開始剤を用いることが考えられるが、現在知られているアニオン重合開始剤の種類は極限られたものになっており、十分に有効な解決法とはいえない。また、アニオン重合する際の溶媒として、極性溶媒ではなく非極性溶媒を用いると、分子量分布はやや狭くなることが知られている（例えば特許文献１参照）。これは、非極性溶媒を用いることによって、モノマー同士の反応（モノマーの成長反応）の反応速度が、モノマーとアニオン重合開始剤との反応の反応速度に対して相対的に遅くなることによるものであると考えられている。しかし、非極性溶媒を用いると、重合反応自体も遅くなってしまい、工業的な生産性という観点からは十分な方法ではなかった。 To avoid these problems, it is conceivable to use an initiator that is optimal for the monomer, but the types of anionic polymerization initiators that are currently known are limited and a fully effective solution. That's not true. Further, it is known that when a nonpolar solvent is used instead of a polar solvent as a solvent for anionic polymerization, the molecular weight distribution is slightly narrowed (see, for example, Patent Document 1). This is because the reaction rate of the reaction between monomers (monomer growth reaction) becomes relatively slower than the reaction rate of the reaction between the monomer and the anionic polymerization initiator by using a nonpolar solvent. It is thought that there is. However, when a nonpolar solvent is used, the polymerization reaction itself becomes slow, which is not a sufficient method from the viewpoint of industrial productivity.
このような状況下、アニオン重合において、様々なモノマーや溶媒を用いた場合であっても、所望の分子量の重合体をより狭分散で、かつ効率良く製造する方法が求められていた。 Under such circumstances, even in the case where various monomers and solvents are used in anionic polymerization, there has been a demand for a method for efficiently producing a polymer having a desired molecular weight more narrowly dispersed.
なお、特許文献２には、アニオン重合性化合物をリビングアニオン重合させて分子量分散度が１．５以下の単分散高分子を製造する方法であって、アニオン重合性化合物の添加を複数回に分けて行い、初回に添加したすべてのアニオン重合性化合物が反応するまで、２回目以降のアニオン重合性化合物の添加を行わない方法が開示されている。しかし、この方法は、初回に添加するアニオン重合性化合物の量が多く（例えば、目的の分子量の重合体を得るために必要だと推定されるアニオン重合性化合物の５０％から９５％に相当する量）、初回に添加するアニオン重合性化合物が極めて少ない（溶媒中の濃度が低い、及び／又は、アニオン重合開始剤に対するモル比が小さい）本発明の重合体の製造方法とは明らかに異なる。 Patent Document 2 discloses a method for producing a monodisperse polymer having a molecular weight dispersity of 1.5 or less by living anion polymerization of an anion polymerizable compound, and the addition of the anion polymerizable compound is divided into a plurality of times. A method is disclosed in which the second and subsequent anionic polymerizable compounds are not added until all the anionic polymerizable compounds added for the first time have reacted. However, in this method, the amount of the anionic polymerizable compound added in the first time is large (for example, it corresponds to 50% to 95% of the anionic polymerizable compound estimated to be necessary for obtaining a polymer having a target molecular weight). The amount of the anionic polymerizable compound added in the first time is very small (the concentration in the solvent is low and / or the molar ratio to the anionic polymerization initiator is small), which is clearly different from the method for producing the polymer of the present invention.
本発明の課題は、アニオン重合において、様々なモノマーや溶媒を用いた場合であっても、所望の分子量の重合体をより狭分散で、かつ効率良く製造する方法を提供することにある。 An object of the present invention is to provide a method for producing a polymer having a desired molecular weight more narrowly and efficiently even in the case of using various monomers and solvents in anionic polymerization.
本発明者らは、上記課題を解決すべく鋭意検討した結果、溶媒に対して低濃度の一般式（Ｉ）で表される化合物（ｉ）を、アニオン重合開始剤を含む溶媒に添加し、撹拌下で前記化合物（ｉ）と前記アニオン重合開始剤とを混合して、すべての前記化合物（ｉ）を反応させて反応液を得、該反応液に、アニオン重合性不飽和結合を有する化合物を添加して、アニオン重合体を重合することにより、所望の分子量の重合体をより狭分散で、かつ効率良く製造し得ることを見い出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the inventors of the present invention added the compound (i) represented by the general formula (I) at a low concentration relative to the solvent to the solvent containing the anionic polymerization initiator, The compound (i) and the anionic polymerization initiator are mixed with stirring, and all the compounds (i) are reacted to obtain a reaction solution, and the compound having an anionically polymerizable unsaturated bond in the reaction solution It has been found that a polymer having a desired molecular weight can be produced more narrowly and efficiently by polymerizing an anionic polymer with the addition of, thereby completing the present invention.
なお、前述のように、特許文献２には、アニオン重合性化合物をリビングアニオン重合させて分子量分散度が１．５以下の単分散高分子を製造する方法であって、アニオン重合性化合物の添加を複数回に分けて行い、初回に添加したすべてのアニオン重合性化合物が反応するまで、２回目以降のアニオン重合性化合物の添加を行わない方法が開示されている。しかし、特許文献２には、初回に添加するモノマーの量が、目的の分子量の重合体を得るために必要だと推定されるモノマーの５０％に相当する量より少ないと、２回目に添加するモノマーの量が多くなり過ぎて、分子量分布が広くなる旨が記載されていることからも明らかなように、本発明のごとく、アニオン重合性化合物の添加を複数回に分けて行い、初回に添加したすべてのアニオン重合性化合物が反応するまで、２回目以降のアニオン重合性化合物を添加しない重合体の製造方法において、初回に添加するアニオン重合性化合物をごく少量（溶媒中の濃度が低い、及び／又は、アニオン重合開始剤に対するモル比が小さい）とすることによって、逆に、所望の分子量の重合体を狭分散で、かつ効率良く製造することができるということは極めて意外であった。 As described above, Patent Document 2 discloses a method for producing a monodisperse polymer having a molecular weight dispersity of 1.5 or less by living anion polymerization of an anion polymerizable compound, and adding an anion polymerizable compound Is divided into a plurality of times, and a method is disclosed in which the second and subsequent anionic polymerizable compounds are not added until all the anionic polymerizable compounds added for the first time have reacted. However, in Patent Document 2, if the amount of the monomer added for the first time is less than the amount corresponding to 50% of the monomer estimated to be necessary for obtaining a polymer having the target molecular weight, it is added the second time. As is clear from the fact that the amount of monomers is too large and the molecular weight distribution is widened, as in the present invention, the addition of the anionic polymerizable compound is carried out in a plurality of times, and it is added for the first time. In the method for producing a polymer in which the anionic polymerizable compound is not added for the second and subsequent times until all the anionic polymerizable compounds have reacted, a very small amount of the anionic polymerizable compound added for the first time (the concentration in the solvent is low, and (Or the molar ratio with respect to the anionic polymerization initiator is small), conversely, a polymer having a desired molecular weight can be produced in a narrow dispersion and efficiently. It was extremely surprising.
すなわち本発明は、
（１）アニオン重合開始剤を含む溶媒に、一般式（Ｉ）で表される化合物（ｉ）を、溶媒に対して１質量％以下となるように添加し、撹拌下で前記化合物（ｉ）と前記アニオン重合開始剤とを所定の時間反応させて反応液を得る工程（Ａ）、工程（Ａ）より後に以下の工程（Ｂ）〜工程（Ｄ）のいずれかの工程とを有する、アニオン重合による重合体の製造方法であって、所定の時間が、アニオン重合反応後に分散度１．３以下の重合体が得られうる時間であることを特徴とする重合体の製造方法
・工程（Ｂ）：工程（Ａ）における反応液に、アニオン重合性不飽和結合を有する化合物を添加して、アニオン重合体を重合する工程
・工程（Ｃ）：アニオン重合性不飽和結合を有する化合物に、工程（Ａ）における反応液を添加して、アニオン重合体を重合する工程
・工程（Ｄ）：アニオン重合性不飽和結合を有する化合物と、工程（Ａ）における反応液とを混合して、アニオン重合体を重合する工程
That is, the present invention
(1) A compound (i) represented by the general formula (I) is added to a solvent containing an anionic polymerization initiator so as to be 1% by mass or less with respect to the solvent, and the compound (i) is stirred. An anion having the following steps (B) to (D) after the step (A) of obtaining a reaction liquid by reacting the anionic polymerization initiator with the anionic polymerization initiator for a predetermined time: A method for producing a polymer by polymerization, wherein the predetermined time is a time in which a polymer having a degree of dispersion of 1.3 or less can be obtained after an anionic polymerization reaction (B) ): A step of adding an anion polymerizable unsaturated bond compound to the reaction liquid in the step (A) to polymerize the anion polymer, step (C): a compound having an anion polymerizable unsaturated bond, step The reaction solution in (A) is added to form an anion Step-step of polymerizing the polymer (D): a compound having an anionic polymerizable unsaturated bond, by mixing the reaction solution in the step (A), polymerizing the anionic polymer process
［式中、Ｒ１は水素原子又はアルキル基を表し、Ｒ２はアニオン重合を阻害しない基で置換されていてもよいアルキル基又はシクロアルキル基を表し、Ｒ３は各々独立してアルキル基又はアルコキシ基を表し、ｍは０〜４のいずれかの整数を表す。］や、
（２）工程（Ａ）における溶媒中のアニオン重合開始剤を、溶媒中の一般式（Ｉ）で表される化合物（ｉ）に対して０．２倍モル以上含有させることを特徴とする上記（１）に記載の重合体の製造方法や、
（３）アニオン重合開始剤を含む溶媒に、一般式（Ｉ）で表される化合物（ｉ）を、溶媒に対して１質量％以下となるように添加し、撹拌下で前記化合物（ｉ）と前記アニオン重合開始剤とを混合して、すべての前記化合物（ｉ）を反応させて反応液を得る工程（ａ）と、工程（ａ）より後に以下の工程（ｂ）〜工程（ｄ）のいずれかの工程とを有する、アニオン重合による重合体の製造方法
・工程（ｂ）：工程（ａ）における反応液に、アニオン重合性不飽和結合を有する化合物を添加して、アニオン重合体を重合する工程
・工程（ｃ）：アニオン重合性不飽和結合を有する化合物に、工程（ａ）における反応液を添加して、アニオン重合体を重合する工程
・工程（ｄ）：アニオン重合性不飽和結合を有する化合物と、工程（ａ）における反応液とを混合して、アニオン重合体を重合する工程
[Wherein R 1 represents a hydrogen atom or an alkyl group, R 2 represents an alkyl group or a cycloalkyl group which may be substituted with a group that does not inhibit anionic polymerization, and R 3 each independently represents an alkyl group or Represents an alkoxy group, and m represents an integer of 0 to 4. ]
(2) The anionic polymerization initiator in the solvent in the step (A) is contained in an amount of 0.2 times mol or more with respect to the compound (i) represented by the general formula (I) in the solvent. The method for producing the polymer according to (1),
(3) The compound (i) represented by the general formula (I) is added to a solvent containing an anionic polymerization initiator so as to be 1% by mass or less with respect to the solvent, and the compound (i) is stirred. And the anionic polymerization initiator are mixed to react all the compounds (i) to obtain a reaction solution, and the following steps (b) to (d) after the step (a) A process for producing a polymer by anionic polymerization, step (b): adding a compound having an anionic polymerizable unsaturated bond to the reaction liquid in step (a), Step of polymerizing / step (c): adding the reaction solution in step (a) to the compound having an anionically polymerizable unsaturated bond to polymerize the anionic polymer / step (d): anionic polymerizable unsaturated A compound having a bond in step (a) By mixing the reaction solution, the step of polymerizing an anionic polymer
［式中、Ｒ１は水素原子又はアルキル基を表し、Ｒ２はアニオン重合を阻害しない基で置換されていてもよいアルキル基又はシクロアルキル基を表し、Ｒ３は各々独立してアルキル基又はアルコキシ基を表し、ｍは０〜４のいずれかの整数を表す。］や、
（４）工程（ａ）が、アニオン重合開始剤を含む溶媒に、一般式（Ｉ）で表される化合物（ｉ）を、溶媒に対して１質量％以下となるように添加し、撹拌下で前記化合物（ｉ）と前記アニオン重合開始剤とを混合して、少なくとも２分間反応させて反応液を得る工程（ａ’）であることを特徴とする上記（３）に記載の重合体の製造方法や、
（５）工程（ａ）又は（ａ’）における溶媒中のアニオン重合開始剤を、溶媒中の一般式（Ｉ）で表される化合物（ｉ）に対して０．２倍モル以上含有させることを特徴とする上記（３）又は（４）に記載の重合体の製造方法や、
（６）アニオン重合開始剤が、有機アルカリ金属化合物であることを特徴とする上記（１）〜（５）のいずれかに記載の重合体の製造方法や、
（７）有機アルカリ金属化合物が、アルキルリチウムであることを特徴とする上記（６）に記載の重合体の製造方法や、
（８）溶媒が、極性溶媒であることを特徴とする上記（１）〜（７）のいずれかに記載の重合体の製造方法や、
（９）アニオン重合性不飽和結合を有する化合物が、一般式（Ｉ）で表される化合物（Ｉ）であることを特徴とする上記（１）〜（８）のいずれかに記載の重合体の製造方法や、（１０）アニオン重合性不飽和結合を有する化合物が、工程（Ａ）又は（ａ）で用いられる一般式（Ｉ）で表される化合物（ｉ）と同一化合物であることを特徴とする上記（９）に記載の重合体の製造方法に関する。
[Wherein R 1 represents a hydrogen atom or an alkyl group, R 2 represents an alkyl group or a cycloalkyl group which may be substituted with a group that does not inhibit anionic polymerization, and R 3 each independently represents an alkyl group or Represents an alkoxy group, and m represents an integer of 0 to 4. ]
(4) In the step (a), the compound (i) represented by the general formula (I) is added to a solvent containing an anionic polymerization initiator so as to be 1% by mass or less with respect to the solvent, and the mixture is stirred. Wherein the compound (i) and the anionic polymerization initiator are mixed and reacted for at least 2 minutes to obtain a reaction solution (a ′). Manufacturing method,
(5) The anionic polymerization initiator in the solvent in the step (a) or (a ′) is contained in an amount of 0.2 times mol or more with respect to the compound (i) represented by the general formula (I) in the solvent. A method for producing the polymer as described in (3) or (4) above,
(6) The method for producing a polymer according to any one of (1) to (5) above, wherein the anionic polymerization initiator is an organic alkali metal compound,
(7) The method for producing a polymer as described in (6) above, wherein the organic alkali metal compound is alkyl lithium,
(8) The method for producing a polymer according to any one of (1) to (7) above, wherein the solvent is a polar solvent,
(9) The polymer according to any one of (1) to (8) above, wherein the compound having an anionic polymerizable unsaturated bond is the compound (I) represented by the general formula (I) And (10) the compound having an anionically polymerizable unsaturated bond is the same compound as the compound (i) represented by the general formula (I) used in the step (A) or (a) It is related with the manufacturing method of the polymer as described in said (9) characterized.
本発明のアニオン重合による重合体の製造方法を用いることにより、所望の分子量の重合体をより狭分散で、かつ効率良く製造することが可能となった。また、本発明の製造方法では、分子量と分子量分布がよくコントロールされるようになったため、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なった。 By using the method for producing a polymer by anionic polymerization of the present invention, a polymer having a desired molecular weight can be produced more narrowly and efficiently. Further, in the production method of the present invention, the molecular weight and the molecular weight distribution are well controlled, so that it is easy to apply to a resist material requiring a strict molecular weight and a molecular weight distribution and to produce a block polymer.
本発明の重合体の第１の製造方法は、アニオン重合開始剤を含む溶媒に、一般式（Ｉ）で表される化合物（ｉ）を、溶媒に対して１質量％以下となるように添加し、撹拌下で前記化合物（ｉ）と前記アニオン重合開始剤とを所定の時間反応させて反応液を得る工程（Ａ）と、工程（Ａ）より後に以下の工程（Ｂ）〜工程（Ｄ）のいずれかの工程とを有する、アニオン重合による重合体の製造方法であって、所定の時間が、アニオン重合反応後に分散度１．３以下の重合体が得られうる時間である限り特に制限されない。
・工程（Ｂ）：工程（Ａ）における反応液に、アニオン重合性不飽和結合を有する化合物を添加して、アニオン重合体を重合する工程
・工程（Ｃ）：アニオン重合性不飽和結合を有する化合物に、工程（Ａ）における反応液を添加して、アニオン重合体を重合する工程
・工程（Ｄ）：アニオン重合性不飽和結合を有する化合物と、工程（Ａ）における反応液とを混合して、アニオン重合体を重合する工程
In the first production method of the polymer of the present invention, the compound (i) represented by the general formula (I) is added to a solvent containing an anionic polymerization initiator so as to be 1% by mass or less based on the solvent. The step (A) of obtaining a reaction solution by reacting the compound (i) with the anionic polymerization initiator for a predetermined time under stirring, and the following steps (B) to (D) after the step (A) ), A process for producing a polymer by anionic polymerization, as long as the predetermined time is a time in which a polymer having a degree of dispersion of 1.3 or less can be obtained after the anionic polymerization reaction. Not.
-Step (B): Step of polymerizing an anionic polymer by adding a compound having an anionic polymerizable unsaturated bond to the reaction liquid in step (A)-Step (C): Having an anionic polymerizable unsaturated bond The reaction solution in step (A) is added to the compound to polymerize the anionic polymer. Step (D): The compound having an anionically polymerizable unsaturated bond and the reaction solution in step (A) are mixed. And the step of polymerizing the anionic polymer
また、本発明の重合体の第２の製造方法は、アニオン重合開始剤を含む溶媒に、一般式（Ｉ）で表される化合物（ｉ）を、溶媒に対して１質量％以下となるように添加し、撹拌下で前記化合物（ｉ）と前記アニオン重合開始剤とを混合して、すべての前記化合物（ｉ）を反応させて反応液を得る工程（ａ）と、工程（ａ）より後に以下の工程（ｂ）〜工程（ｄ）のいずれかの工程とを有する限り特に制限されない。
・工程（ｂ）：工程（ａ）における反応液に、アニオン重合性不飽和結合を有する化合物を添加して、アニオン重合体を重合する工程
・工程（ｃ）：アニオン重合性不飽和結合を有する化合物に、工程（ａ）における反応液を添加して、アニオン重合体を重合する工程
・工程（ｄ）：アニオン重合性不飽和結合を有する化合物と、工程（ａ）における反応液とを混合して、アニオン重合体を重合する工程
ここで、「前記化合物（ｉ）と前記アニオン重合開始剤とを混合して、すべての前記化合物（ｉ）を反応させる」とは、前記化合物（ｉ）とアニオン重合開始剤との反応、及び、生成したアニオン種と化合物(ｉ)との重合反応を包含する。
Moreover, the 2nd manufacturing method of the polymer of this invention makes the compound (i) represented by general formula (I) into a solvent containing an anionic polymerization initiator into 1 mass% or less with respect to a solvent. From step (a), wherein the compound (i) and the anionic polymerization initiator are mixed with stirring to obtain a reaction solution by reacting all the compounds (i); There is no particular limitation as long as it includes any of the following steps (b) to (d).
Step (b): Step of polymerizing an anionic polymer by adding a compound having an anionic polymerizable unsaturated bond to the reaction solution in the step (a) Step (c): Having an anion polymerizable unsaturated bond Step of adding the reaction liquid in the step (a) to the compound and polymerizing the anionic polymer Step (d): mixing the compound having an anionically polymerizable unsaturated bond and the reaction liquid in the step (a) Step of polymerizing an anionic polymer Here, "the compound (i) and the anionic polymerization initiator are mixed and all the compounds (i) are reacted" means that the compound (i) and It includes a reaction with an anionic polymerization initiator and a polymerization reaction between the produced anionic species and compound (i).
本発明に用いられる化合物（ｉ）において、Ｒ１は水素原子；又は、メチル基、エチル基等のＣ１からＣ６のアルキル基を表す。
Ｒ２はアニオン重合を阻害しない基で置換されていてもよいＣ１からＣ２４のアルキル基又はＣ３からＣ２４のシクロアルキル基を表す。アルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ペンチル基、イソペンチル基、ｔ−アミル基、ヘキシル基、イソヘキシル基、ヘプチル基、イソヘプチル基、ｔ−オクチル基、イソオクチル基、ノニル基、イソノニル基、デシル基、イソデシル基、ウンデシル基、イソウンデシル基、ドデシル基などを例示することができる。好ましくは、Ｃ１〜Ｃ８のアルキル基である。シクロアルキル基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロプロピルメチル基、シクロプロピルへキシル基、シクロヘキシルプロピル基等を例示することができる。好ましくは、Ｃ３〜Ｃ８のシクロアルキル基である。アニオン重合を阻害しない基としては、水酸基、アミノ基、カルボキシル基等の活性水素を含有する基を有しない基や、カルボニル基を有しない基であり、アルキル基、アルコキシ基、シクロアルキル基、シクロアルコキシ基、フェニル基、アリル基、シクロオレフィン基等を例示することができる。
ＯＲ２基の置換位置としては特に制限されないが、４位であることが好ましい。
Ｒ３は各々独立してアルキル基又はアルコキシ基を表す。アルキル基及びアルコキシ基のアルキル部分は、Ｃ１からＣ２４のアルキル基であり、Ｒ２で例示されたアルキル基と同じアルキル基を例示することができる。好ましくは、Ｃ１〜Ｃ８のアルキル基である。
ｍは０〜４のいずれかの整数を表す。
In the compound (i) used in the present invention, R 1 represents a hydrogen atom; or a C1 to C6 alkyl group such as a methyl group or an ethyl group.
R 2 represents a C1 to C24 alkyl group or a C3 to C24 cycloalkyl group optionally substituted with a group that does not inhibit anionic polymerization. As the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, isopentyl group, t-amyl group, hexyl group, isohexyl group, Examples include heptyl group, isoheptyl group, t-octyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, isoundecyl group, dodecyl group and the like. Preferably, it is a C1-C8 alkyl group. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopropylmethyl group, a cyclopropylhexyl group, and a cyclohexylpropyl group. Preferably, it is a C3-C8 cycloalkyl group. Examples of groups that do not inhibit anionic polymerization include groups that do not have active hydrogen-containing groups such as hydroxyl groups, amino groups, and carboxyl groups, and groups that do not have carbonyl groups, and are alkyl groups, alkoxy groups, cycloalkyl groups, cyclohexanes, and the like. Examples thereof include an alkoxy group, a phenyl group, an allyl group, and a cycloolefin group.
Is not particularly restricted but includes substitution position of OR 2 groups is preferably 4-position.
R 3 each independently represents an alkyl group or an alkoxy group. Alkyl moiety of the alkyl and alkoxy group is an alkyl group of from C1 C24, can be exemplified the same alkyl groups as exemplified alkyl group R 2. Preferably, it is a C1-C8 alkyl group.
m represents an integer of 0 to 4.
上記工程（Ａ）や工程（ａ）における化合物（ｉ）の濃度は、溶媒に対して１質量％以下であれば特に制限されないが、０．０００００５〜０．８質量％であることが好ましく、０．０００００５〜０．２質量％であることがより好ましい。
なお、本願明細書における「溶媒に対して」とは、「純粋に溶媒のみの質量に対して」を意味し、アニオン重合開始剤や化合物（ｉ）等の溶媒以外の物質の質量は、ここでいう溶媒の重量には含めない。
また、化合物（ｉ）は、アニオン重合性不飽和結合を有する化合物の１０質量％以下、好ましくは７質量％以下、さらに好ましくは５質量％以下使用される。
The concentration of the compound (i) in the step (A) or the step (a) is not particularly limited as long as it is 1% by mass or less with respect to the solvent, but is preferably 0.000005 to 0.8% by mass, More preferably, it is 0.000005-0.2 mass%.
In the present specification, “relative to the solvent” means “relatively to the mass of the solvent alone”, and the mass of the substance other than the solvent such as the anionic polymerization initiator and the compound (i) It is not included in the weight of the solvent.
Further, the compound (i) is used in an amount of 10% by mass or less, preferably 7% by mass or less, more preferably 5% by mass or less of the compound having an anionically polymerizable unsaturated bond.
本発明に用いられるアニオン重合開始剤は、好適な条件下で、アニオン重合性不飽和結合を重合させる能力のあるアニオン種であれば特に制限されず、具体的には、有機アルカリ金属；有機アルカリ土類金属；１，１−ジフェニルエチレン又はスチルベンから誘導される炭素アニオン種；等を例示することができる。さらに具体的には、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、１，１−ジフェニルヘキシルリチウム、１，１−ジフェニル−３−メチルペンチルリチウム、１，４−ジリチオ−２−ブテン、１，６−ジリチオへキサン、ポリスチリルリチウム、クミルカリウム、クミルセシウム等を例示することができる。
本発明に用いられるアニオン重合開始剤は、１種単独であってもよいし、２種以上を併用してもよい。
The anionic polymerization initiator used in the present invention is not particularly limited as long as it is an anionic species capable of polymerizing an anionic polymerizable unsaturated bond under suitable conditions. Specifically, an organic alkali metal; an organic alkali Examples thereof include earth metals; carbon anion species derived from 1,1-diphenylethylene or stilbene; and the like. More specifically, ethyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, ethyl sodium, lithium biphenyl, lithium naphthalene, sodium naphthalene, potassium naphthalene, α-methylstyrene naphthalene dianion, 1,1- Examples thereof include diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium, 1,4-dilithio-2-butene, 1,6-dilithiohexane, polystyryl lithium, cumyl potassium, cumyl cesium and the like.
One type of anionic polymerization initiator used in the present invention may be used alone, or two or more types may be used in combination.
上記工程（Ａ）や工程（ａ）におけるアニオン重合開始剤の濃度は、好適な反応条件下でアニオン重合反応させた後に分散度１．３以下の重合体が得られうる限り特に制限されないが、所望の分子量の重合体をより狭分散で得る観点から、溶媒中の化合物（ｉ）に対して０．２倍モル以上とすることが好ましく、１倍モル以上とすることがより好ましく、１〜２０倍モルの範囲内とすることがさらに好ましい。
過剰なアニオン重合開始剤は、反応液を３０分間以上撹拌することや、反応液に有機金属を添加することによって、不活性化させることができる。したがって、上記工程（Ａ）や工程（ａ）において、アニオン重合開始剤を含む溶媒に、一般式（Ｉ）で表される化合物（ｉ）を添加した後に、反応液を３０分間以上撹拌するか、反応液に有機金属を添加するか、又はその両方を行うことが好ましい。有機金属とは、有機基を金属原子上に有する金属化合物をいい、その具体例は後述のとおりである。
The concentration of the anionic polymerization initiator in the step (A) or the step (a) is not particularly limited as long as a polymer having a dispersity of 1.3 or less can be obtained after an anionic polymerization reaction under suitable reaction conditions. From the viewpoint of obtaining a polymer having a desired molecular weight more narrowly, it is preferably 0.2 times mol or more, more preferably 1 time mol or more, relative to compound (i) in the solvent. More preferably, it is within the range of 20 times mole.
Excess anionic polymerization initiator can be inactivated by stirring the reaction solution for 30 minutes or more or adding an organic metal to the reaction solution. Therefore, in the above step (A) or step (a), after adding the compound (i) represented by the general formula (I) to the solvent containing the anionic polymerization initiator, the reaction solution is stirred for 30 minutes or more. It is preferable to add an organic metal to the reaction solution or both. The organic metal refers to a metal compound having an organic group on a metal atom, and specific examples thereof are as described later.
工程（Ａ）における所定の時間とは、好適な反応条件下でアニオン重合反応させた後に分散度１．３以下、より好ましくは１．２以下、さらに好ましくは１．１以下の重合体が得られうる時間である限り特に制限されない。アニオン重合反応させた後に分散度１．３以下の重合体を得られうる時間は、用いる化合物（ｉ）の種類や濃度、用いるアニオン重合性不飽和結合を有する化合物の種類や濃度、用いるアニオン重合開始剤の種類や濃度、用いる溶媒、反応条件等により左右されるため一概にいうことはできないが、溶媒に含まれるすべての化合物（ｉ）が反応するまでに要する時間以上の時間を例示することができる。溶媒に対して１質量％以下で含まれるすべての化合物（ｉ）が反応するまでに要する時間以上の時間として、通常、２分間以上を要し、上限は反応が終了するまでの時間以上であるが、条件により異なるので、条件に合わせてその都度選択すればよい。
一方、詳細な作用機作については不明であるが、本発明の如く、特定濃度の化合物（ｉ）とアニオン重合開始剤とを所定の時間反応させる工程を有すると、所望の分子量の重合体をより狭分散で、かつ効率良く製造することが可能となる。
The predetermined time in the step (A) is a polymer having a dispersity of 1.3 or less, more preferably 1.2 or less, and even more preferably 1.1 or less after an anionic polymerization reaction under suitable reaction conditions. There is no particular limitation as long as it can be done. The time for which a polymer having a dispersity of 1.3 or less after an anionic polymerization reaction can be obtained is the type and concentration of the compound (i) used, the type and concentration of the compound having an anionic polymerizable unsaturated bond, and the anionic polymerization used. Since it depends on the type and concentration of the initiator, the solvent to be used, the reaction conditions, etc., it cannot be said in general, but the time required for all the compounds (i) contained in the solvent to react is illustrated. Can do. The time required for the reaction of all the compounds (i) contained at 1% by mass or less with respect to the solvent is usually 2 minutes or longer, and the upper limit is the time required for the reaction to end. However, since it varies depending on conditions, it may be selected each time according to the conditions.
On the other hand, although the detailed mechanism of action is unknown, as in the present invention, when the compound (i) having a specific concentration and an anionic polymerization initiator are reacted for a predetermined time, a polymer having a desired molecular weight is obtained. It becomes possible to manufacture more narrowly and efficiently.
また、工程（ａ）における「すべての前記化合物（ｉ）が前記アニオン重合開始剤と反応するまで少なくとも反応させ」とは、溶媒中に含まれるすべての化合物（ｉ）が、アニオン重合開始剤と反応するまでに要する時間以上の時間、反応させることを意味し、具体的には工程（Ａ）と同様であり、通常２分間以上である。 Further, in the step (a), “react at least until all the compounds (i) react with the anionic polymerization initiator” means that all the compounds (i) contained in the solvent are anionic polymerization initiators and This means that the reaction is performed for a time longer than the time required for the reaction. Specifically, the reaction is the same as in the step (A), usually 2 minutes or more.
本発明における「（溶媒に含まれる）すべての化合物（ｉ）が反応する」とは、該反応後における溶媒中に含まれる化合物（ｉ）が、例えばいずれかの通常のガスクロマトグラフィー（例えば株式会社島津製作所製 ＧＣ−１４Ａ）の検出限界以下であることをいうが、便宜上、溶媒に添加した化合物（ｉ）のうち９８質量％以上、好ましくは９９質量％以上、より好ましくは９９．５質量％以上の化合物（ｉ）が反応した場合も含まれ、中でも通常のガスクロマトグラフィー（例えば株式会社島津製作所製 ＧＣ−１４Ａ）の検出限界以下であることが好ましい。 In the present invention, “all compounds (i) (contained in the solvent) react” means that the compound (i) contained in the solvent after the reaction is, for example, any ordinary gas chromatography (for example, stock Although it is below the detection limit of Shimadzu Corporation GC-14A), for the sake of convenience, it is 98% by mass or more, preferably 99% by mass or more, more preferably 99.5% by mass in the compound (i) added to the solvent. % Or more of the compound (i) reacts, and it is preferably below the detection limit of ordinary gas chromatography (for example, GC-14A manufactured by Shimadzu Corporation).
工程（Ａ）や（ａ）における反応の反応温度は、工程（Ａ）や（ａ）で得られた反応液を、工程（Ｂ）〜（Ｄ）のいずれか又は工程（ｂ）〜（ｄ）のいずれかの重合反応に用いた場合に、好適な反応条件下でアニオン重合反応させた後に分散度１．３以下の重合体が得られうる温度範囲内であれば特に制限されないが、具体的には、−７０℃以上、重合溶媒沸点以下の温度範囲を好ましく例示することができ、−７０℃〜２５℃の範囲をより好ましく例示することができ、−７０℃〜−１０℃の範囲をさらに好ましく例示することができる。 The reaction temperature of the reaction in the step (A) or (a) is the same as that of the step (B) to (D) or the step (b) to (d) for the reaction solution obtained in the step (A) or (a). When the polymerization reaction is used in any of the polymerization reactions), there is no particular limitation as long as it is within a temperature range in which a polymer having a dispersity of 1.3 or less can be obtained after an anionic polymerization reaction under suitable reaction conditions. Specifically, a temperature range of −70 ° C. or more and a polymerization solvent boiling point or less can be preferably exemplified, a range of −70 ° C. to 25 ° C. can be more preferably exemplified, and a range of −70 ° C. to −10 ° C. Can be illustrated more preferably.
本明細書における重合体の分散度（分子量分散度）は、質量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）により算出することができる。質量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）は、例えばゲル浸透クロマトグラフィー（ＧＰＣ）により測定することができる。より具体的には、例えば、ＧＰＣ装置として、日本ウォーターズ株式会社製のウォーターズ６００Ｅコントローラー（ポンプユニット）、７１７オートサンプラー、９９６フォトダイオードアレイ検出器、及び４１０示差屈折計等を用い、カラムとして、昭和電工株式会社製のＫＦ−８０１、ＫＦ−８０２、ＫＦ−８０３の３本を連結したものを用い、ＧＰＣ装置の制御及びＧＰＣの解析に関するソフトウェアとして、日本ウォーターズ株式会社製のＥｍｐｏｗｅｒ（登録商標）を用いることができる。本明細書における重合体の分散度とは、いずれかの通常のＧＰＣ装置で測定された分散度をいうが、より好ましくは、上述の具体的な装置、カラム及びソフトウェアを用いて測定された分散度をいう。 The dispersity (molecular weight dispersity) of the polymer in the present specification can be calculated by mass average molecular weight (Mw) / number average molecular weight (Mn). The mass average molecular weight (Mw) and the number average molecular weight (Mn) can be measured, for example, by gel permeation chromatography (GPC). More specifically, for example, as a GPC apparatus, a Waters 600E controller (pump unit) manufactured by Nippon Waters Co., Ltd., a 717 autosampler, a 996 photodiode array detector, a 410 differential refractometer, etc. are used. Emperor (registered trademark) manufactured by Nihon Waters Co., Ltd. is used as software related to GPC device control and GPC analysis using a combination of KF-801, KF-802, and KF-803 manufactured by Denko Corporation. Can be used. In the present specification, the degree of dispersion of a polymer refers to the degree of dispersion measured with any ordinary GPC apparatus, and more preferably, the dispersion measured using the above-described specific apparatus, column, and software. Say degree.
本発明に用いられる溶媒は、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、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、トリオキサン等のエーテル系化合物；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等の第３級アミン；などを例示することができ、特にＴＨＦを好ましく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。
さらに、極性の低い脂肪族炭化水素化合物、芳香族炭化水素化合物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、極性溶媒と組み合わせることにより使用することができる。そのような組み合わせとして、具体的には、へキサンとＴＨＦの組み合わせを例示することができる。
The solvent used in the present invention is not particularly limited as long as it is a polar solvent that does not participate in the polymerization reaction and is compatible with the polymer. Specifically, diethyl ether, tetrahydrofuran (THF), dioxane, trioxane, etc. Ether compounds; tertiary amines such as tetramethylethylenediamine and hexamethylphosphoric triamide; and the like, and THF is particularly preferred. Moreover, these solvent can be used individually by 1 type or as a 2 or more types of mixed solvent.
Furthermore, even if it is an aliphatic hydrocarbon compound, an aromatic hydrocarbon compound, or an alicyclic hydrocarbon compound with a low polarity, if it is relatively compatible with a polymer, it can be used by combining with a polar solvent. . Specific examples of such a combination include a combination of hexane and THF.
工程（Ａ）や（ａ）における溶媒には、化合物（ｉ）及びアニオン重合開始剤のみを含有させてもよいが、本発明の効果を妨げない限り、他に任意の成分を含有させることができる。そのような任意成分として具体的には、有機金属、アルカリ金属塩及びアルカリ土類金属塩からなる群から選ばれるいずれか１種又は２種以上を好ましく例示することができる。これらの添加剤は、成長アニオン末端を安定化させ、重合を円滑に進行させる働きをする。また、これらの添加剤は、系内に存在する活性水素化合物等と反応するので、活性水素化合物等による重合反応の阻害を抑制又は防止することができる。 The solvent in step (A) or (a) may contain only compound (i) and an anionic polymerization initiator, but may contain other optional components as long as the effects of the present invention are not hindered. it can. Specific examples of such optional components include one or more selected from the group consisting of organic metals, alkali metal salts, and alkaline earth metal salts. These additives serve to stabilize the growth anion terminal and to facilitate the polymerization. Moreover, since these additives react with the active hydrogen compound and the like present in the system, inhibition of the polymerization reaction by the active hydrogen compound and the like can be suppressed or prevented.
ここで有機金属としては、有機基を金属原子上に有する金属化合物をいう。有機基としては、例えば、炭素数１〜２０のアルキル基、又は炭素数６〜２０のアリール基を挙げることができ、より具体的には、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓ−ブチル基、ｔ−ブチル基、イソブチル基、アミル基、ヘキシル基、ベンジル基、フェニル基、ナフチル基等を例示することができる。また、有機金属における金属原子としては、特に制限されないが、マグネシウム、亜鉛、アルミニウム等を好ましく例示することができる。
有機金属として、より具体的には、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を好ましく例示することができる。
Here, the organic metal refers to a metal compound having an organic group on a metal atom. Examples of the organic group include an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and more specifically, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. N-butyl group, s-butyl group, t-butyl group, isobutyl group, amyl group, hexyl group, benzyl group, phenyl group, naphthyl group and the like. In addition, the metal atom in the organic metal is not particularly limited, but preferred examples include magnesium, zinc, aluminum and the like.
More specifically, as an organic metal, di-n-butylmagnesium, di-t-butylmagnesium, di-s-butylmagnesium, n-butyl-s-butylmagnesium, n-butyl-ethylmagnesium, di-n Preferred examples include -amyl magnesium, dibenzyl magnesium, diphenyl magnesium, diethyl zinc, di-n-butyl zinc, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum and the like.
アルカリ金属塩又はアルカリ土類金属塩とは、具体的にはリチウム、ナトリウム、カリウム、バリウム、マグネシウム等のアルカリ金属やアルカリ土類金属の硫酸塩、硝酸塩、ホウ酸塩等の鉱酸塩；アルカリ金属やアルカリ土類金属のハロゲン化物；脂肪族アルコールのアルカリ金属塩；脂肪族若しくは芳香族チオールのアルカリ金属塩；等を例示することができ、より具体的にはホウ酸リチウム、硝酸マグネシウム；リチウム、カリウム若しくはバリウムの塩化物、臭化物、ヨウ化物；リチウムメトキシド、リチウムｔ−ブトキシド等のアルコキシド；リチウムフェノキシド等のフェノキシド；プロイオン酸リチウム等のカルボキシド；リチウムジフェニルアミド等のアミド；エタンチオールやプロパンチオール等のＣ１〜Ｃ１８のアルキルチオールのアルカリ金属塩；シクロヘキシルチオール等のＣ１〜Ｃ１８のシクロアルキルチオールのアルカリ金属塩；メルカプトエタノールやｐ−メルカプトフェノール等の水酸基を含有するチオールのアルカリ金属塩；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等のカルボン酸エステルを含有するチオールのアルカリ金属塩；ベンゼンチオールやトルエンチオール及びナフタレンチオール等の芳香族チオールのアルカリ金属塩；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等の含窒素芳香族チオールのアルカリ金属塩；など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等を好ましく挙げることができる。 Alkali metal salt or alkaline earth metal salt is specifically an alkali metal such as lithium, sodium, potassium, barium or magnesium, or a mineral salt such as sulfate, nitrate or borate of alkaline earth metal; Examples include metal and alkaline earth metal halides; aliphatic alcohol alkali metal salts; aliphatic or aromatic thiol alkali metal salts; and more specifically, lithium borate, magnesium nitrate; lithium Potassium, barium chloride, bromide, iodide; alkoxide such as lithium methoxide and lithium t-butoxide; phenoxide such as lithium phenoxide; carboxylate such as lithium proionate; amide such as lithium diphenylamide; C1-C18 alkyl such as propanethiol Alkali metal salts of thiols; Alkali metal salts of C1-C18 cycloalkyl thiols such as cyclohexyl thiol; Alkali metal salts of thiols containing hydroxyl groups such as mercaptoethanol and p-mercaptophenol; methyl mercaptoacetate and ethyl mercaptopropionate Alkali metal salts of thiols containing carboxylic acid esters; Alkali metal salts of aromatic thiols such as benzenethiol, toluene thiol and naphthalene thiol; Alkali metal salts of nitrogen-containing aromatic thiols such as mercaptothiazoline mercaptobenzthiazoline and mercaptopyrimidine Among them, preferred are lithium halides; alkali metal salts of alcohols and thiols, and the like.
以上に例示した各添加剤は、１種単独で用いてもよいし、２種以上を併用してもよい。 Each additive illustrated above may be used individually by 1 type, and may use 2 or more types together.
本発明の重合体の第１の製造方法は、工程（Ａ）と、工程（Ａ）より後に以下の工程（Ｂ）〜工程（Ｄ）のいずれかの工程とを有する。
工程（Ｂ）：工程（Ａ）における反応液に、アニオン重合性不飽和結合を有する化合物を添加して、アニオン重合体を重合する工程
工程（Ｃ）：アニオン重合性不飽和結合を有する化合物に、工程（Ａ）における反応液を添加して、アニオン重合体を重合する工程
工程（Ｄ）：アニオン重合性不飽和結合を有する化合物と、工程（Ａ）における反応液とを混合して、アニオン重合体を重合する工程
The 1st manufacturing method of the polymer of this invention has a process (A) and any process of the following processes (B)-processes (D) after a process (A).
Step (B): A compound having an anionic polymerizable unsaturated bond is added to the reaction liquid in the step (A) to polymerize the anionic polymer. Step (C): To a compound having an anionic polymerizable unsaturated bond , Adding the reaction solution in step (A) to polymerize the anionic polymer step (D): mixing the compound having an anionically polymerizable unsaturated bond with the reaction solution in step (A) to form an anion Process for polymerizing polymer
工程（Ｂ）〜工程（Ｄ）の中でも、操作の簡便性の観点から、工程（Ｂ）が好ましく挙げられる。 Among the steps (B) to (D), the step (B) is preferably mentioned from the viewpoint of easy operation.
本発明の重合体の第２の製造方法は、工程（ａ）と、工程（ａ）より後に以下の工程（ｂ）〜工程（ｄ）のいずれかの工程とを有する。
工程（ｂ）：工程（ａ）における反応液に、アニオン重合性不飽和結合を有する化合物を添加して、アニオン重合体を重合する工程
工程（ｃ）：アニオン重合性不飽和結合を有する化合物に、工程（ａ）における反応液を添加して、アニオン重合体を重合する工程
工程（ｄ）：アニオン重合性不飽和結合を有する化合物と、工程（ａ）における反応液とを混合して、アニオン重合体を重合する工程
The 2nd manufacturing method of the polymer of this invention has a process (a) and the process in any one of the following processes (b)-a process (d) after a process (a).
Step (b): Adding a compound having an anionic polymerizable unsaturated bond to the reaction solution in step (a) to polymerize the anionic polymer Step (c): Converting the compound having an anionic polymerizable unsaturated bond to , Adding the reaction liquid in step (a) to polymerize the anionic polymer step (d): mixing the compound having an anionic polymerizable unsaturated bond with the reaction liquid in step (a) Process for polymerizing polymer
工程（ｂ）〜工程（ｄ）の中でも、操作の簡便性の観点から、工程（ｂ）が好ましく挙げられる。 Among the steps (b) to (d), the step (b) is preferably mentioned from the viewpoint of easy operation.
本発明に用いられるアニオン重合性不飽和結合を有する化合物としては、アニオン重合性不飽和結合を有する化合物である限り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。 The compound having an anion polymerizable unsaturated bond used in the present invention is not particularly limited as long as it is a compound having an anion polymerizable unsaturated bond, and specifically, a styrene derivative, a butadiene derivative, (meth) acrylic acid. An ester derivative etc. can be illustrated preferably.
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る。核置換基としては、重合開始能力があるアニオン種及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）スチレン等を例示することができる。 Specific examples of the styrene derivative include styrene, α-alkylstyrene, and nucleus-substituted styrene. The nuclear substituent is not particularly limited as long as it is an anionic species having a polymerization initiating ability and an inactive group with respect to an anionic species having no polymerization initiating ability. , Alkoxyalkoxy groups, t-butoxycarbonyl groups, t-butoxycarbonylmethyl groups, tetrahydropyranyl groups, and the like. 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−ペンタジエン等を例示することができる。 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.
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−ブチルエステル等を例示することができる。 In addition, the (meth) acrylic acid ester derivative is preferably one having 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, etc. Can be illustrated.
本発明の製造方法において、アニオン重合性不飽和結合を有する化合物は、１種単独又は２種以上を用いることができる。従ってブロック共重合体、ランダム共重合体等の共重合体の製造にも適用することが可能である。 In the production method of the present invention, the compound having an anionic polymerizable unsaturated bond may be used alone or in combination of two or more. Therefore, it can be applied to the production of copolymers such as block copolymers and random copolymers.
アニオン重合性不飽和結合を有する化合物は、工程（Ａ）又は工程（ａ）における化合物（ｉ）と異なる化合物であってもよいし、工程（Ａ）又は工程（ａ）における化合物（ｉ）と同一化合物であってもよい。 The compound having an anionically polymerizable unsaturated bond may be a compound different from the compound (i) in the step (A) or the step (a), or the compound (i) in the step (A) or the step (a). The same compound may be sufficient.
本発明における工程（Ｄ）の「アニオン重合性不飽和結合を有する化合物と、工程（Ａ）における反応液とを混合する」とは、工程（Ｂ）の「工程（Ａ）における反応液に、アニオン重合性不飽和結合を有する化合物を添加する」及び工程（Ｃ）の「アニオン重合性不飽和結合を有する化合物に、工程（Ａ）における反応液を添加する」以外の態様であって、アニオン重合性不飽和結合を有する化合物と、工程（Ａ）における反応液とを接触させるいかなる態様も含まれる。工程（Ｄ）として具体的には、アニオン重合性不飽和結合を有する化合物と、工程（Ａ）における反応液とを、空の別の容器に同時に入れて混合する工程を挙げることができる。工程（ｄ）についてもこれと同様である。 In the step (D) of the present invention, “mixing the compound having an anion polymerizable unsaturated bond and the reaction solution in the step (A)” means “in the reaction solution in the step (A) of the step (B), An anion other than “adding a compound having an anionic polymerizable unsaturated bond” and “adding the reaction solution in step (A) to a compound having an anion polymerizable unsaturated bond” in step (C) Any embodiment in which the compound having a polymerizable unsaturated bond is brought into contact with the reaction solution in the step (A) is also included. Specific examples of the step (D) include a step of simultaneously mixing the compound having an anionically polymerizable unsaturated bond and the reaction liquid in the step (A) in another empty container. The same applies to step (d).
工程（Ｂ）〜工程（Ｄ）や工程（ｂ）〜工程（ｄ）における重合の重合温度は、好適な反応条件下でアニオン重合反応させた後に分散度１．３以下の重合体が得られうる温度範囲内であれば特に制限されないが、移動反応や停止反応などの副反応が起こらず、アニオン重合性不飽和結合を有する化合物（単量体）が消費されて重合が完結する温度範囲内であることが好ましい。工程（Ｂ）〜工程（Ｄ）や工程（ｂ）〜工程（ｄ）における重合の重合温度として、具体的には、−７０℃以上、重合溶媒沸点以下の温度範囲を好ましく例示することができる。 The polymerization temperature in the step (B) to the step (D) or the step (b) to the step (d) is a polymer having a dispersity of 1.3 or less after an anionic polymerization reaction under suitable reaction conditions. The temperature is not particularly limited as long as it is within the temperature range, but side reactions such as transfer reaction and termination reaction do not occur, and the compound (monomer) having an anionically polymerizable unsaturated bond is consumed and the polymerization is completed. It is preferable that As the polymerization temperature of the polymerization in the step (B) to the step (D) or the step (b) to the step (d), specifically, a temperature range of −70 ° C. or higher and a polymerization solvent boiling point or lower can be preferably exemplified. .
工程（Ｂ）〜工程（Ｄ）や工程（ｂ）〜工程（ｄ）におけるアニオン重合性不飽和結合を有する化合物の濃度は、好適な反応条件下でアニオン重合反応させた後に分散度１．３以下の重合体が得られうる限り特に制限されないが、工程（Ｂ）〜工程（Ｄ）や工程（ｂ）〜工程（ｄ）における重合溶媒に対して１〜４０質量％の範囲内であることが好ましく、２〜１５質量％の範囲内であることがより好ましい。 The concentration of the compound having an anionically polymerizable unsaturated bond in the step (B) to the step (D) and the step (b) to the step (d) is 1.3 degree after the anionic polymerization reaction is performed under suitable reaction conditions. Although it does not restrict | limit especially as long as the following polymers can be obtained, It exists in the range of 1-40 mass% with respect to the polymerization solvent in a process (B)-a process (D) or a process (b)-a process (d). Is preferable, and it is more preferable that it exists in the range of 2-15 mass%.
工程（Ｂ）〜工程（Ｄ）や工程（ｂ）〜工程（ｄ）における重合溶媒には、化合物（ｉ）、アニオン重合開始剤、アニオン重合性不飽和結合を有する化合物のみを含有させてもよいが、本発明の効果を妨げない限り、他に任意の成分を含有させることができる。そのような任意成分として具体的には、有機金属、アルカリ金属塩及びアルカリ土類金属塩からなる群から選ばれるいずれか１種又は２種以上を好ましく例示することができる。これらの添加剤は、成長アニオン末端を安定化させ、重合を円滑に進行させる働きをする。また、これらの添加剤は、系内に存在する活性水素化合物等と反応するので、活性水素化合物等による重合反応の阻害を抑制又は防止することができる。 Even if it contains only the compound which has a compound (i), an anionic polymerization initiator, and an anionic polymerizable unsaturated bond in the polymerization solvent in a process (B)-a process (D) or a process (b)-a process (d). Although it is good, as long as the effect of this invention is not prevented, other arbitrary components can be contained. Specific examples of such optional components include one or more selected from the group consisting of organic metals, alkali metal salts, and alkaline earth metal salts. These additives serve to stabilize the growth anion terminal and to facilitate the polymerization. Moreover, since these additives react with the active hydrogen compound and the like present in the system, inhibition of the polymerization reaction by the active hydrogen compound and the like can be suppressed or prevented.
有機金属、アルカリ金属塩及びアルカリ土類金属塩等の添加剤の濃度は、好適な反応条件下でアニオン重合反応させた後に分散度１．３以下の重合体が得られうる限り特に制限されない。 The concentration of additives such as organic metal, alkali metal salt and alkaline earth metal salt is not particularly limited as long as a polymer having a dispersity of 1.3 or less can be obtained after an anionic polymerization reaction under suitable reaction conditions.
本発明の重合体の第１の製造方法は、好適な反応条件下でアニオン重合反応させた後に分散度１．３以下の重合体が得られうる限り、工程（Ａ）と、工程（Ｂ）〜工程（Ｄ）のいずれかの工程の他に、任意の工程を含んでいてもよい。また、本発明の重合体の第２の製造方法は、好適な反応条件下でアニオン重合反応させた後に分散度１．３以下の重合体が得られうる限り、工程（ａ）と、工程（ｂ）〜工程（ｄ）のいずれかの工程の他に、任意の工程を含んでいてもよい。
任意の工程の具体例としては、工程（Ｂ）〜工程（Ｄ）のいずれかの工程、又は工程（ｂ）〜工程（ｄ）のいずれかの工程より後に、得られたアニオン重合体の分子量を測定し、その分子量を所望する重合体の分子量と比較して、所望する分子量の重合体を得るために必要なアニオン重合性不飽和結合を有する化合物の添加量を決定し、決定した量のアニオン重合性不飽和結合を有する化合物を、工程（Ｂ）〜（Ｄ）及び（ｂ）〜（ｄ）のいずれかの重合溶媒に含有させる工程（Ｅ）を好ましく例示することができる。このような工程（Ｅ）を設けていわゆる多段重合することによって、所望の分子量により近い重合体を得ることができる。
この工程（Ｅ）における、アニオン重合体の分子量の測定方法は特に制限されないが、例えばゲル浸透クロマトグラフィー（ＧＰＣ）等を用いることができる。
The first production method of the polymer of the present invention includes steps (A) and (B) as long as a polymer having a dispersity of 1.3 or less can be obtained after an anionic polymerization reaction under suitable reaction conditions. ~ In addition to any step of step (D), any step may be included. In addition, the second production method of the polymer of the present invention includes steps (a) and (as long as a polymer having a dispersity of 1.3 or less can be obtained after an anionic polymerization reaction under suitable reaction conditions. In addition to any step of b) to step (d), an optional step may be included.
As a specific example of the optional step, the molecular weight of the anionic polymer obtained after any step of step (B) to step (D) or after any step of step (b) to step (d) And comparing the molecular weight with the molecular weight of the desired polymer to determine the amount of compound having an anionic polymerizable unsaturated bond necessary to obtain a polymer with the desired molecular weight. The step (E) in which a compound having an anionic polymerizable unsaturated bond is contained in the polymerization solvent in any of the steps (B) to (D) and (b) to (d) can be preferably exemplified. By providing such a step (E) and performing so-called multistage polymerization, a polymer closer to a desired molecular weight can be obtained.
The method for measuring the molecular weight of the anionic polymer in this step (E) is not particularly limited, and for example, gel permeation chromatography (GPC) can be used.
本発明の製造方法により得られた重合体の用途は特に制限されないが、本発明の重合体の製造方法を用いると、所望の分子量の重合体をより狭分散で得ることができるため、本発明の製造方法により得られた重合体は、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に特に適している。また、本発明の製造方法により得られた重合体は、塗料や接着剤にも好適に用いることができる。 The use of the polymer obtained by the production method of the present invention is not particularly limited, but when the polymer production method of the present invention is used, a polymer having a desired molecular weight can be obtained in a narrower dispersion. The polymer obtained by this production method is particularly suitable for application to a resist material requiring a strict molecular weight and molecular weight distribution and for production of a block polymer. In addition, the polymer obtained by the production method of the present invention can be suitably used for paints and adhesives.
以下、実施例により本発明をより具体的に説明するが、本発明の技術的範囲はこれらの例示に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited to these illustrations.
窒素雰囲気下、ＴＨＦ３０ｇとトルエン１７０ｇの混合溶媒中に、−３０℃で、ｎ−ブチルリチウム（ｎ-ＢｕＬｉ）溶液１．１７ｇ（２．８ｍｍｏｌ）を加え、続いて、ｐ−（１−エトキシエトキシ）スチレン０．５２ｇ（２．７ｍｍｏｌ）を加え、３０分間攪拌した。その後、ｐ−（１−エトキシエトキシ）スチレン２１．４６ｇ（１０９．３ｍｍｏｌ）にジブチルマグネシウム溶液０．２１ｇ（０．３ｍｍｏｌ）を加えたものを６分かけて滴下し、滴下終了後、６０分攪拌し、メタノールを加えて反応を停止させた。反応を停止させたこの溶液をガスクロマトグラフィー（株式会社島津製作所製 ＧＣ−１４Ａ）で測定してみるとモノマーは残存していなかった。また、得られた溶液をゲル浸透クロマトグラフィー（ＧＰＣ）（日本ウォーターズ株式会社製）で測定したところ、分子量（Ｍｗ）１３１００、分散度＝１．０８のポリマーの生成が確認された。 Under a nitrogen atmosphere, 1.17 g (2.8 mmol) of n-butyllithium (n-BuLi) solution was added to a mixed solvent of 30 g of THF and 170 g of toluene at −30 ° C., followed by p- (1-ethoxyethoxy). ) 0.52 g (2.7 mmol) of styrene was added and stirred for 30 minutes. Thereafter, a solution obtained by adding 0.21 g (0.3 mmol) of dibutylmagnesium solution to 21.46 g (109.3 mmol) of p- (1-ethoxyethoxy) styrene was added dropwise over 6 minutes. Then, methanol was added to stop the reaction. When this solution in which the reaction had been stopped was measured by gas chromatography (GC-14A, manufactured by Shimadzu Corporation), no monomer remained. Moreover, when the obtained solution was measured by the gel permeation chromatography (GPC) (made by Nippon Waters Co., Ltd.), the production | generation of the polymer of molecular weight (Mw) 13100 and dispersity = 1.08 was confirmed.
窒素雰囲気下、ＴＨＦ２００ｇに２−メルカプトチアゾリン０．１２（１．０ｍｍｏｌ）を加えた溶液に室温でｎ−ＢｕＬｉ溶液１．２９ｇ（３．１ｍｍｏｌ）を加え、３０分間攪拌した。その後、−３０℃に冷却し、ｎ−ＢｕＬｉ溶液０．３８ｇ（０．９ｍｍｏｌ）を加え、続いて、ｐ−（１−エトキシエトキシ）スチレン０．２７ｇ（１．４ｍｍｏｌ）を加え、１５分間攪拌した。その後、−４０℃に冷却し、ｐ−（１−エトキシエトキシ）スチレン２１．８７ｇ（１１１．４ｍｍｏｌ）にジブチルマグネシウム溶液０．１５ｇ（０．２ｍｍｏｌ）を加えたものを７分かけて滴下し、滴下終了後、３０分攪拌し、メタノールを加えて反応を停止させた。反応を停止させたこの溶液をガスクロマトグラフィーで測定してみるとモノマーは残存していなかった。また、得られた溶液をＧＰＣで測定したところ、分子量（Ｍｗ）３８１００、分散度＝１．０６のポリマーの生成が確認された。 Under a nitrogen atmosphere, 1.29 g (3.1 mmol) of n-BuLi solution was added to a solution of 2-mercaptothiazoline 0.12 (1.0 mmol) in 200 g of THF at room temperature and stirred for 30 minutes. Thereafter, the mixture was cooled to −30 ° C., 0.38 g (0.9 mmol) of an n-BuLi solution was added, and then 0.27 g (1.4 mmol) of p- (1-ethoxyethoxy) styrene was added, followed by stirring for 15 minutes. did. Then, it cooled to -40 degreeC, what added 0.15 g (0.2 mmol) of dibutyl magnesium solutions to 21.87 g (111.4 mmol) of p- (1-ethoxyethoxy) styrene was dripped over 7 minutes, After completion of dropping, the mixture was stirred for 30 minutes, and methanol was added to stop the reaction. When this solution in which the reaction was stopped was measured by gas chromatography, no monomer remained. Moreover, when the obtained solution was measured by GPC, the production | generation of the polymer of molecular weight (Mw) 38100 and dispersion degree = 1.06 was confirmed.
窒素雰囲気下、ＴＨＦ１２０ｇとトルエン８０ｇの混合溶媒中に、０℃で、ｎ−ＢｕＬｉ溶液０．８１ｇ（２．０ｍｍｏｌ）を加え、続いて、ｐ−ｔ−ブトキシスチレン０．４１ｇ（２．３ｍｍｏｌ）を加え、１分間攪拌した。その後、ｐ−ｔ−ブトキシスチレン１７．８０ｇ（１０１．０ｍｍｏｌ）にジブチルマグネシウム溶液０．３２ｇ（０．５ｍｍｏｌ）を加えたものを９分かけて滴下し、滴下終了後、１０分攪拌し、メタノールを加えて反応を停止させた。反応を停止させたこの溶液をガスクロマトグラフィーで測定してみるとモノマーは残存していなかった。また、得られた溶液をＧＰＣで測定したところ、分子量（Ｍｗ）１７７００、分散度＝１．２４のポリマーの生成が確認された。 Under a nitrogen atmosphere, 0.81 g (2.0 mmol) of an n-BuLi solution was added at 0 ° C. to a mixed solvent of 120 g of THF and 80 g of toluene, followed by 0.41 g (2.3 mmol) of pt-butoxystyrene. Was added and stirred for 1 minute. Thereafter, a solution obtained by adding 0.32 g (0.5 mmol) of dibutylmagnesium solution to 17.80 g (101.0 mmol) of pt-butoxystyrene was added dropwise over 9 minutes. To stop the reaction. When this solution in which the reaction was stopped was measured by gas chromatography, no monomer remained. Moreover, when the obtained solution was measured by GPC, the production | generation of the polymer of molecular weight (Mw) 17700 and dispersion degree = 1.24 was confirmed.
窒素雰囲気下、ＴＨＦ２００ｇ中に、−５０℃で、ｎ−ＢｕＬｉ溶液１．４４ｇ（３．５ｍｍｏｌ）を加え、続いて、ｐ−（１−エトキシエトキシ）スチレン０．４１ｇ（２．０ｍｍｏｌ）を加え、１５分間攪拌した。その後、ジブチルマグネシウム溶液１．２９ｇ（１．８ｍｍｏｌ）を加え、ｐ−（１−エトキシエトキシ）スチレン２１．３３ｇ（１０８．７ｍｍｏｌ）にジブチルマグネシウム溶液０．３７ｇ（０．５ｍｍｏｌ）を加えたものを５分かけて滴下し、滴下終了後、−３５℃で２５分攪拌し、メタノールを加えて反応を停止させた。反応を停止させたこの溶液をガスクロマトグラフィーで測定してみるとモノマーは残存していなかった。また、得られた溶液をＧＰＣで測定したところ、分子量（Ｍｗ）８４５００、分散度＝１．０９のポリマーの生成が確認された。 Under nitrogen atmosphere, 1.44 g (3.5 mmol) of n-BuLi solution was added to 200 g of THF at −50 ° C., followed by 0.41 g (2.0 mmol) of p- (1-ethoxyethoxy) styrene. And stirred for 15 minutes. Thereafter, 1.29 g (1.8 mmol) of dibutyl magnesium solution was added, and 21.33 g (108.7 mmol) of p- (1-ethoxyethoxy) styrene was added with 0.37 g (0.5 mmol) of dibutyl magnesium solution. The solution was added dropwise over 5 minutes. After completion of the addition, the mixture was stirred at -35 ° C for 25 minutes, and methanol was added to stop the reaction. When this solution in which the reaction was stopped was measured by gas chromatography, no monomer remained. Moreover, when the obtained solution was measured by GPC, the production | generation of the polymer of molecular weight (Mw) 84500 and dispersion degree = 1.09 was confirmed.
窒素雰囲気下、ＴＨＦ２００ｇ中にｐ−メルカプトフェノール０．２２ｇ（１．７ｍｍｏｌ）を溶解させた溶液に、室温でｎ−ＢｕＬｉ溶液３．０１ｇ（７．２ｍｍｏｌ）を加え、６０分間攪拌した。その後、−４０℃に冷却し、ｎ−ＢｕＬｉ溶液１．０５ｇ（５．２ｍｍｏｌ）を加え、続いて、ｐ−（１−エトキシエトキシ）スチレン０．５１ｇ（２．６ｍｍｏｌ）を加え、２０分間攪拌した。その後、ｎ−ＢｕＬｉ／ジエチル亜鉛アート錯体１．１４ｇ（１．０ｍｍｏｌ）とジエチル亜鉛溶液０．３６ｇ（０．５ｍｍｏｌ）を加え、ｐ−（１−エトキシエトキシ）スチレン２１．３３ｇ（１０８．７ｍｍｏｌ）にジブチルマグネシウム溶液０．１５ｇ（０．２ｍｍｏｌ）を加えたものを９分かけて滴下し、滴下終了後、１０分攪拌し、メタノールを加えて反応を停止させた。反応を停止させたこの溶液をガスクロマトグラフィーで測定してみるとモノマーは残存していなかった。また、得られた溶液をＧＰＣで測定したところ、分子量（Ｍｗ）１６８００、分散度＝１．１４のポリマーの生成が確認された。 Under a nitrogen atmosphere, to a solution obtained by dissolving 0.22 g (1.7 mmol) of p-mercaptophenol in 200 g of THF, 3.01 g (7.2 mmol) of an n-BuLi solution was added at room temperature and stirred for 60 minutes. Thereafter, the mixture was cooled to −40 ° C., 1.05 g (5.2 mmol) of an n-BuLi solution was added, and then 0.51 g (2.6 mmol) of p- (1-ethoxyethoxy) styrene was added, followed by stirring for 20 minutes. did. Thereafter, 1.14 g (1.0 mmol) of n-BuLi / diethyl zinc ate complex and 0.36 g (0.5 mmol) of diethyl zinc solution were added, and 21.33 g (108.7 mmol) of p- (1-ethoxyethoxy) styrene was added. A solution obtained by adding 0.15 g (0.2 mmol) of a dibutylmagnesium solution was added dropwise over 9 minutes. After completion of the addition, the mixture was stirred for 10 minutes, and methanol was added to stop the reaction. When this solution in which the reaction was stopped was measured by gas chromatography, no monomer remained. Moreover, when the obtained solution was measured by GPC, the production | generation of the polymer of molecular weight (Mw) 16800 and dispersion degree = 1.14 was confirmed.
窒素雰囲気下、ＴＨＦ１２０ｇとトルエン８０ｇの混合溶媒中に、ｐ−ｔ−ブトキシスチレン０．３６ｇ（２．０ｍｍｏｌ）を加え０℃で、ｎ−ＢｕＬｉ溶液０．７２ｇ（１．７ｍｍｏｌ）を加え、１分間攪拌した。その後、ジブチルマグネシウム溶液１．５１ｇ（２．１ｍｍｏｌ）を加え、続いて、ｐ−ｔ−ブトキシスチレン１７．７１ｇ（１００．５ｍｍｏｌ）にジブチルマグネシウム溶液０．１９ｇ（０．３ｍｍｏｌ）を加えたものを４分かけて滴下し、滴下終了後、４５分攪拌し、メタノールを加えて反応を停止させた。反応を停止させたこの溶液をガスクロマトグラフィーで測定してみるとモノマーは残存していなかった。また、得られた溶液をＧＰＣで測定したところ、分子量（Ｍｗ）４７２００、分散度＝１．２３のポリマーの生成が確認された。 Under a nitrogen atmosphere, 0.36 g (2.0 mmol) of pt-butoxystyrene was added to a mixed solvent of 120 g of THF and 80 g of toluene, and 0.72 g (1.7 mmol) of an n-BuLi solution was added at 0 ° C. Stir for minutes. Then, 1.51 g (2.1 mmol) of dibutylmagnesium solution was added, and then, 17.19 g (100.5 mmol) of pt-butoxystyrene was added to 0.19 g (0.3 mmol) of dibutylmagnesium solution. The solution was added dropwise over 4 minutes. After completion of the addition, the mixture was stirred for 45 minutes, and methanol was added to stop the reaction. When this solution in which the reaction was stopped was measured by gas chromatography, no monomer remained. Moreover, when the obtained solution was measured by GPC, the production | generation of the polymer of molecular weight (Mw) 47200 and dispersion degree = 1.23 was confirmed.
Claims (7)
・工程（ｂ）：工程（ａ）における反応液に、アニオン重合性不飽和結合を有する化合物を添加して、アニオン重合体を重合する工程
・工程（ｃ）：アニオン重合性不飽和結合を有する化合物に、工程（ａ）における反応液を添加して、アニオン重合体を重合する工程
・工程（ｄ）：アニオン重合性不飽和結合を有する化合物と、工程（ａ）における反応液とを混合して、アニオン重合体を重合する工程
Step (b): Step of polymerizing an anionic polymer by adding a compound having an anionic polymerizable unsaturated bond to the reaction solution in the step (a) Step (c): Having an anion polymerizable unsaturated bond Step of adding the reaction liquid in the step (a) to the compound and polymerizing the anionic polymer Step (d): mixing the compound having an anionically polymerizable unsaturated bond and the reaction liquid in the step (a) And the step of polymerizing the anionic polymer
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