JP2007277533A - Method for producing living radical polymer and polymer - Google Patents
Method for producing living radical polymer and polymer Download PDFInfo
- Publication number
- JP2007277533A JP2007277533A JP2007060938A JP2007060938A JP2007277533A JP 2007277533 A JP2007277533 A JP 2007277533A JP 2007060938 A JP2007060938 A JP 2007060938A JP 2007060938 A JP2007060938 A JP 2007060938A JP 2007277533 A JP2007277533 A JP 2007277533A
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- formula
- compound represented
- living radical
- producing
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 29
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 29
- 125000003118 aryl group Chemical group 0.000 claims abstract description 22
- 239000002841 Lewis acid Substances 0.000 claims abstract description 21
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 21
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 18
- 150000003498 tellurium compounds Chemical class 0.000 claims abstract description 16
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims abstract description 14
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 claims abstract description 11
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims abstract description 10
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000002252 acyl group Chemical group 0.000 claims abstract description 7
- 125000003368 amide group Chemical group 0.000 claims abstract description 7
- -1 halogen salt Chemical group 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 30
- 150000001463 antimony compounds Chemical class 0.000 claims description 15
- 150000001622 bismuth compounds Chemical class 0.000 claims description 14
- 239000007869 azo polymerization initiator Substances 0.000 claims description 11
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical group [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 9
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 7
- 229920001400 block copolymer Polymers 0.000 claims description 6
- 150000002602 lanthanoids Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 229920005604 random copolymer Polymers 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 238000010550 living polymerization reaction Methods 0.000 claims 2
- 239000003505 polymerization initiator Substances 0.000 claims 2
- IPENDKRRWFURRE-UHFFFAOYSA-N fluoroimide Chemical compound C1=CC(F)=CC=C1N1C(=O)C(Cl)=C(Cl)C1=O IPENDKRRWFURRE-UHFFFAOYSA-N 0.000 claims 1
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 8
- 229910052714 tellurium Inorganic materials 0.000 abstract description 7
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052787 antimony Inorganic materials 0.000 abstract description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052797 bismuth Chemical group 0.000 abstract description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 29
- 150000003254 radicals Chemical class 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 23
- 238000010526 radical polymerization reaction Methods 0.000 description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 13
- 239000007870 radical polymerization initiator Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000004926 polymethyl methacrylate Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- LCMDQKIQBKULEI-UHFFFAOYSA-N dimethyl ditelluride Chemical compound C[Te][Te]C LCMDQKIQBKULEI-UHFFFAOYSA-N 0.000 description 5
- JPIIVHIVGGOMMV-UHFFFAOYSA-N ditellurium Chemical compound [Te]=[Te] JPIIVHIVGGOMMV-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- SFLRURCEBYIKSS-UHFFFAOYSA-N n-butyl-2-[[1-(butylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound CCCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCCC SFLRURCEBYIKSS-UHFFFAOYSA-N 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 4
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 4
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 4
- DRAQBUIVUGPBEB-UHFFFAOYSA-N (ethylditellanyl)ethane Chemical compound CC[Te][Te]CC DRAQBUIVUGPBEB-UHFFFAOYSA-N 0.000 description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- VYKRXVMQJHSOQR-UHFFFAOYSA-N CC[Bi](CC)[Bi](CC)CC Chemical compound CC[Bi](CC)[Bi](CC)CC VYKRXVMQJHSOQR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 3
- 229940080818 propionamide Drugs 0.000 description 3
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- VUKYWZYFZZJLRZ-UHFFFAOYSA-N 2-[(1-amino-2-methyl-1-methyliminopropan-2-yl)diazenyl]-n',2-dimethylpropanimidamide;dihydrochloride Chemical compound Cl.Cl.CNC(=N)C(C)(C)N=NC(C)(C)C(=N)NC VUKYWZYFZZJLRZ-UHFFFAOYSA-N 0.000 description 2
- KWZULKIVMJKFKM-UHFFFAOYSA-N 2-[(1-amino-2-methyl-1-oxobutan-2-yl)diazenyl]-2-methylbutanamide Chemical compound CCC(C)(C(N)=O)N=NC(C)(CC)C(N)=O KWZULKIVMJKFKM-UHFFFAOYSA-N 0.000 description 2
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 102100040409 Ameloblastin Human genes 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OZKNNTSQASVDEL-UHFFFAOYSA-N C1=CC=CC=C1[Bi](C=1C=CC=CC=1)[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 OZKNNTSQASVDEL-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
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- 101000891247 Homo sapiens Ameloblastin Proteins 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 102100020870 La-related protein 6 Human genes 0.000 description 2
- 108050008265 La-related protein 6 Proteins 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 101100490446 Penicillium chrysogenum PCBAB gene Proteins 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- ALBJGICXDBJZGK-UHFFFAOYSA-N [1-[(1-acetyloxy-1-phenylethyl)diazenyl]-1-phenylethyl] acetate Chemical compound C=1C=CC=CC=1C(C)(OC(=O)C)N=NC(C)(OC(C)=O)C1=CC=CC=C1 ALBJGICXDBJZGK-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- WPKWPKDNOPEODE-UHFFFAOYSA-N bis(2,4,4-trimethylpentan-2-yl)diazene Chemical compound CC(C)(C)CC(C)(C)N=NC(C)(C)CC(C)(C)C WPKWPKDNOPEODE-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- 239000011261 inert gas Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
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- 239000000203 mixture Substances 0.000 description 2
- CYTJMBLSQUBVMS-UHFFFAOYSA-N n-[[2-cyanopropan-2-yl(formyl)amino]hydrazinylidene]formamide Chemical compound N#CC(C)(C)N(C=O)NN=NC=O CYTJMBLSQUBVMS-UHFFFAOYSA-N 0.000 description 2
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- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FXEIVSYQEOJLBU-UHFFFAOYSA-N 1-$l^{1}-selanylethanimine Chemical compound CC([Se])=N FXEIVSYQEOJLBU-UHFFFAOYSA-N 0.000 description 1
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- IXHNVIRJONELOD-UHFFFAOYSA-N 1-chloro-2-ethenylbenzene Chemical compound ClC1=CC=CC=C1C=C.ClC1=CC=CC=C1C=C IXHNVIRJONELOD-UHFFFAOYSA-N 0.000 description 1
- NDRBQRBSUPZULR-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1.ClC1=CC=C(C=C)C=C1 NDRBQRBSUPZULR-UHFFFAOYSA-N 0.000 description 1
- FNKZDQXLSGBIBB-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C.CC1=CC=CC=C1C=C FNKZDQXLSGBIBB-UHFFFAOYSA-N 0.000 description 1
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- DDCWGUIPLGMBPO-UHFFFAOYSA-K samarium(3+);trifluoromethanesulfonate Chemical compound [Sm+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F DDCWGUIPLGMBPO-UHFFFAOYSA-K 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005930 sec-butyloxycarbonyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- JLYAVYSVLLIWEK-UHFFFAOYSA-K terbium(3+);trifluoromethanesulfonate Chemical compound [Tb+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F JLYAVYSVLLIWEK-UHFFFAOYSA-K 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- 150000003556 thioamides Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- JPJIEXKLJOWQQK-UHFFFAOYSA-K trifluoromethanesulfonate;yttrium(3+) Chemical compound [Y+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F JPJIEXKLJOWQQK-UHFFFAOYSA-K 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
【課題】精密な分子量分布（ＰＤＩ＝Ｍｗ／Ｍｎ）及び立体規則性の制御されたポリマーを製造する方法を提供する。
【解決手段】（Ａ）式（１a)で表される有機テルル化合物、（テルルはアンチモン、ビスマスに置換できる）から選ばれる少なくとも１種と、（Ｂ）ルイス酸を用いて、ビニルモノマーを重合することを特徴とするリビングラジカルポリマーの製造方法。
（式中、Ｒ１及びＲ２は、Ｃ１〜Ｃ８のアルキル基、アリール基、置換アリール基又は芳香族ヘテロ環基を示す。Ｒ３及びＲ４は、水素原子又はＣ１〜Ｃ８のアルキル基を示す。Ｒ５は、アリール基、置換アリール基、芳香族ヘテロ環基、アシル基、アミド基、オキシカルボニル基又はシアノ基を示す。）
【選択図】なしDisclosed is a method for producing a polymer having a controlled molecular weight distribution (PDI = Mw / Mn) and stereoregularity.
A vinyl monomer is polymerized using (A) at least one selected from organic tellurium compounds represented by formula (1a) (where tellurium can be substituted with antimony or bismuth) and (B) a Lewis acid. A method for producing a living radical polymer.
(In the formula, R 1 and R 2 represent a C 1 to C 8 alkyl group, aryl group, substituted aryl group or aromatic heterocyclic group. R 3 and R 4 represent a hydrogen atom or C 1 to C 8. R 5 represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an amide group, an oxycarbonyl group or a cyano group.
[Selection figure] None
Description
本発明は、リビングラジカルポリマーの製造方法に関する。 The present invention relates to a method for producing a living radical polymer.
リビングラジカル重合は、ラジカル重合の簡便性と汎用性を保ちつつ分子構造の精密制御を可能にする重合法で、新しい高分子材料の合成に大きな威力を発揮している。本発明者は、リビングラジカル重合の例として、有機テルル化合物を開始剤として用いたリビングラジカル重合を報告している（例えば、特許文献１参照）。また、有機アンチモン化合物を開始剤として用いたリビングラジカル重合も報告している（例えば、特許文献２参照）。一方、Ｎ−アルキルアクリルアミドおよびメタクリルアミド類のアゾ系重合開始剤を用いたラジカル重合にルイス酸を添加することで、ポリマーの立体規則性を制御できることが知られている（例えば、非特許文献１参照）。
この非特許文献１の方法は、アゾ系重合開始剤にルイス酸を添加し、Ｎ−アルキルアクリルアミドおよびメタクリルアミド類を重合することにより、生成するラジカルポリマーの立体規則性を制御している。しかし、分子量分布（ＰＤＩ＝Ｍｗ／Ｍｎ）および立体規則性の両方を、より精密に制御されたポリマーが望まれている。
本発明の課題は、（Ａ）式（１ａ）で表される有機テルル化合物、式（１ｂ）で表される有機アンチモン化合物および式（１ｃ）で表される有機ビスマス化合物から選ばれる少なくとも１種と、（Ｂ）ルイス酸を用いて、ビニルモノマーを重合することにより、精密な分子量分布（ＰＤＩ＝Ｍｗ／Ｍｎ）及び立体規則性の制御されたポリマーを製造する方法を提供することにある。
In the method of Non-Patent Document 1, the stereoregularity of the generated radical polymer is controlled by adding a Lewis acid to an azo polymerization initiator and polymerizing N-alkylacrylamide and methacrylamide. However, polymers with more precise control over both molecular weight distribution (PDI = Mw / Mn) and stereoregularity are desired.
An object of the present invention is (A) an organic tellurium compound represented by formula (1a), an organic antimony compound represented by formula (1b), and an organic bismuth compound represented by formula (1c). And (B) providing a method for producing a polymer having a precise molecular weight distribution (PDI = Mw / Mn) and stereoregularity by polymerizing a vinyl monomer using a Lewis acid.
本発明は以下の発明に係る。
１．（Ａ）式（１ａ）で表される有機テルル化合物、式（１ｂ）で表される有機アンチモン化合物および式（１ｃ）で表される有機ビスマス化合物から選ばれる少なくとも１種と、（Ｂ）ルイス酸を用いて、ビニルモノマーを重合することを特徴とするリビングラジカルポリマーの製造方法。
The present invention relates to the following inventions.
1. (A) at least one selected from an organic tellurium compound represented by formula (1a), an organic antimony compound represented by formula (1b), and an organic bismuth compound represented by formula (1c), and (B) Lewis A method for producing a living radical polymer, characterized in that a vinyl monomer is polymerized using an acid.
（式中、Ｒ１及びＲ２は、Ｃ１〜Ｃ８のアルキル基、アリール基、置換アリール基又は芳香族ヘテロ環基を示す。Ｒ３及びＲ４は、水素原子又はＣ１〜Ｃ８のアルキル基を示す。Ｒ５は、アリール基、置換アリール基、芳香族ヘテロ環基、アシル基、アミド基、オキシカルボニル基又はシアノ基を示す。） (In the formula, R 1 and R 2 represent a C 1 to C 8 alkyl group, aryl group, substituted aryl group or aromatic heterocyclic group. R 3 and R 4 represent a hydrogen atom or C 1 to C 8. R 5 represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an amide group, an oxycarbonyl group or a cyano group.
２．（Ａ）式（１ａ）で表される有機テルル化合物、式（１ｂ）で表される有機アンチモン化合物および式（１ｃ）で表される有機ビスマス化合物から選ばれる少なくとも１種、（Ｂ）ルイス酸、（Ｃ）式（２ａ）で表される化合物、式（２ｂ）で表される化合物および式（２ｃ）で表される化合物から選ばれる少なくとも１種を用いて、ビニルモノマーを重合することを特徴とするリビングラジカルポリマーの製造方法。 2. (A) at least one selected from an organic tellurium compound represented by formula (1a), an organic antimony compound represented by formula (1b), and an organic bismuth compound represented by formula (1c), (B) a Lewis acid (C) polymerizing a vinyl monomer using at least one selected from a compound represented by formula (2a), a compound represented by formula (2b), and a compound represented by formula (2c). A method for producing a living radical polymer.
３．（Ａ）式（１ａ）で表される有機テルル化合物、式（１ｂ）で表される有機アンチモン化合物および式（１ｃ）で表される有機ビスマス化合物から選ばれる少なくとも１種、（Ｂ）ルイス酸、（Ｄ）アゾ系重合開始剤を用いて、ビニルモノマーを重合することを特徴とするリビングラジカルポリマーの製造方法。 3. (A) at least one selected from an organic tellurium compound represented by formula (1a), an organic antimony compound represented by formula (1b), and an organic bismuth compound represented by formula (1c), (B) a Lewis acid (D) A method for producing a living radical polymer, wherein a vinyl monomer is polymerized using an azo polymerization initiator.
４．（Ａ）式（１ａ）で表される有機テルル化合物、式（１ｂ）で表される有機アンチモン化合物および式（１ｃ）で表される有機ビスマス化合物から選ばれる少なくとも１種、（Ｂ）ルイス酸、（Ｃ）式（２ａ）で表される化合物、式（２ｂ）で表される化合物および式（２ｃ）で表される化合物から選ばれる少なくとも１種、（Ｄ）アゾ系重合開始剤を用いて、ビニルモノマーを重合することを特徴とするリビングラジカルポリマーの製造方法。 4). (A) at least one selected from an organic tellurium compound represented by formula (1a), an organic antimony compound represented by formula (1b), and an organic bismuth compound represented by formula (1c), (B) a Lewis acid (C) at least one selected from the compound represented by formula (2a), the compound represented by formula (2b) and the compound represented by formula (2c), and (D) an azo polymerization initiator. A method for producing a living radical polymer, wherein a vinyl monomer is polymerized.
本発明によれば、ビニルモノマーの重合が促進され、反応時間を短縮することができ、精密な分子量分布（ＰＤＩ＝Ｍｗ／Ｍｎ）及び立体規則性の制御されたポリマーの製造方法を提供する。また、本発明の製造方法により得られたポリマーに、更に、ビニルモノマーを追加することにより、分子量の増大されたポリマー或いは任意のブロック（コ）ポリマーの製造を可能とする。また得られたポリマーは様々な応用分野で興味のある製品を製造することができる。 According to the present invention, there is provided a method for producing a polymer in which polymerization of a vinyl monomer is promoted, reaction time can be shortened, and a precise molecular weight distribution (PDI = Mw / Mn) and stereoregularity are controlled. Further, by adding a vinyl monomer to the polymer obtained by the production method of the present invention, it becomes possible to produce a polymer having an increased molecular weight or an arbitrary block (co) polymer. The resulting polymer can also produce products of interest in various fields of application.
本発明で使用する有機テルル化合物は、式（１ａ）で表される。 The organic tellurium compound used in the present invention is represented by the formula (1a).
Ｒ１で示される基は、具体的には次の通りである。
Ｃ１〜Ｃ８のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、シクロプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、シクロブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基等の炭素数１〜８の直鎖状、分岐鎖状又は環状のアルキル基を挙げることができる。
好ましいアルキル基としては、炭素数１〜４の直鎖状又は分岐鎖状のアルキル基が良い。
より好ましくは、メチル基、エチル基又はｎ−ブチル基が良い。
Specific examples of the group represented by R 1 are as follows.
Examples of the C 1 to C 8 alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclobutyl group, and n-pentyl. Examples thereof include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms such as a group, n-hexyl group, n-heptyl group and n-octyl group.
A preferable alkyl group is a linear or branched alkyl group having 1 to 4 carbon atoms.
More preferably, a methyl group, an ethyl group, or an n-butyl group is good.
アリール基としては、フェニル基、ナフチル基等を挙げることができる。
好ましいアリール基としては、フェニル基が良い。
置換アリール基としては、置換基を有しているフェニル基、置換基を有しているナフチル基等を挙げることができる。
Examples of the aryl group include a phenyl group and a naphthyl group.
A preferred aryl group is a phenyl group.
Examples of the substituted aryl group include a phenyl group having a substituent and a naphthyl group having a substituent.
上記置換基を有しているアリール基の置換基としては、例えば、ハロゲン原子、水酸基、アルコキシ基、アミノ基、ニトロ基、シアノ基、−ＣＯＲａで示されるカルボニル含有基（Ｒａ＝Ｃ１〜Ｃ８のアルキル基、アリール基、Ｃ１〜Ｃ８のアルコキシ基、アリーロキシ基）、スルホニル基、トリフルオロメチル基等を挙げることができる。
好ましい置換アリール基としては、トリフルオロメチル置換フェニル基が良い。
また、これら置換基は、１個又は２個置換しているのが良く、パラ位若しくはオルト位が好ましい。
芳香族へテロ環基としては、ピリジル基、ピロール基、フリル基、チエニル基等を挙げることができる。
Examples of the substituent of the aryl group having the above substituent, for example, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, a carbonyl-containing group represented by -COR a (R a = C 1 alkyl group -C 8, aryl group, alkoxy group of C 1 -C 8, an aryloxy group), a sulfonyl group, and a trifluoromethyl group.
A preferred substituted aryl group is a trifluoromethyl-substituted phenyl group.
These substituents may be substituted one or two, and the para position or ortho position is preferable.
Examples of the aromatic heterocyclic group include a pyridyl group, a pyrrole group, a furyl group, and a thienyl group.
Ｒ３及びＲ４で示される各基は、具体的には次の通りである。
Ｃ１〜Ｃ８のアルキル基としては、上記Ｒ１で示したアルキル基と同様のものを挙げることができる。
Specific examples of each group represented by R 3 and R 4 are as follows.
Examples of the C 1 to C 8 alkyl group include the same alkyl groups as those described above for R 1 .
Ｒ５で示される各基は、具体的には次の通りである。
アリール基、置換アリール基、芳香族へテロ環基としては上記Ｒ１で示した基と同様のものを挙げることができる。
アシル基としては、ホルミル基、アセチル基、ベンゾイル基等を挙げることができる。
アミド基としては、アセトアミド、マロンアミド、スクシンアミド、マレアミド、ベンズアミド、２−フルアミド等のカルボン酸アミド、チオアセトアミド、ヘキサンジチオアミド、チオベンズアミド、メタンチオスルホンアミド等のチオアミド、セレノアセトアミド、ヘキサンジセレノアミド、セレノベンズアミド、メタンセレノスルホンアミド等のセレノアミド、Ｎ−メチルアセトアミド、ベンズアニリド、シクロヘキサンカルボキサニリド、２,４'−ジクロロアセトアニリド等のＮ−置換アミド等を挙げることができる。
オキシカルボニル基としては、−ＣＯＯＲｂ（Ｒｂ＝Ｈ、Ｃ１〜Ｃ８のアルキル基、アリール基）で示される基を挙げることができる。
具体的には、カルボキシル基、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ｎ−ブトキシカルボニル基、ｓｅｃ−ブトキシカルボニル基、ｔｅｒ−ブトキシカルボニル基、ｎ−ペントキシカルボニル基、フェノキシカルボニル基等を挙げることができる。
好ましいオキシカルボニル基としては、メトキシカルボニル基、エトキシカルボニル基が良い。
Specific examples of each group represented by R 5 are as follows.
Examples of the aryl group, substituted aryl group, and aromatic heterocyclic group include the same groups as those described above for R 1 .
Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group.
Examples of the amide group include carboxylic acid amides such as acetamide, malonamide, succinamide, maleamide, benzamide, and 2-fluamide, thioamides such as thioacetamide, hexanedithioamide, thiobenzamide, and methanethiosulfonamide, selenoacetamide, hexanediselenoamide, Examples include selenoamides such as selenobenzamide and methaneselenosulfonamide, N-substituted amides such as N-methylacetamide, benzanilide, cyclohexanecarboxanilide, and 2,4′-dichloroacetanilide.
Examples of the oxycarbonyl group include a group represented by —COOR b (R b = H, C 1 to C 8 alkyl group, aryl group).
Specifically, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, ter-butoxycarbonyl group, n-pentoxycarbonyl group, phenoxycarbonyl group, etc. Can be mentioned.
Preferred oxycarbonyl groups are a methoxycarbonyl group and an ethoxycarbonyl group.
好ましいＲ５で示される各基としては、アリール基、置換アリール基、オキシカルボニル基又はシアノ基が良い。
好ましいアリール基としては、フェニル基が良い。
好ましい置換アリール基としては、ハロゲン原子置換フェニル基、トリフルオロメチル置換フェニル基が良い。
また、これらの置換基は、ハロゲン原子の場合は、１〜５個置換しているのが良い。アルコキシ基やトリフルオロメチル基の場合は、１個又は２個置換しているのが良く、１個置換の場合は、パラ位若しくはオルト位が好ましく、２個置換の場合は、メタ位が好ましい。
好ましいオキシカルボニル基としては、メトキシカルボニル基、エトキシカルボニル基が良い。
Each group represented by R 5 is preferably an aryl group, a substituted aryl group, an oxycarbonyl group or a cyano group.
A preferred aryl group is a phenyl group.
Preferred examples of the substituted aryl group include a halogen atom substituted phenyl group and a trifluoromethyl substituted phenyl group.
In addition, in the case of a halogen atom, these substituents are preferably substituted by 1 to 5 pieces. In the case of an alkoxy group or a trifluoromethyl group, one or two substituents may be substituted. In the case of one substitution, the para position or the ortho position is preferable, and in the case of two substitutions, the meta position is preferable. .
Preferred oxycarbonyl groups are a methoxycarbonyl group and an ethoxycarbonyl group.
好ましい（１ａ）で示される有機テルル化合物としては、Ｒ１が、Ｃ１〜Ｃ４のアルキル基を示し、Ｒ３及びＲ４が、水素原子又はＣ１〜Ｃ４のアルキル基を示し、Ｒ５が、アリール基、置換アリール基、オキシカルボニル基で示される化合物が良い。
特に好ましくは、Ｒ１が、Ｃ１〜Ｃ４のアルキル基を示し、Ｒ３及びＲ４が、水素原子又はＣ１〜Ｃ４のアルキル基を示し、Ｒ５が、フェニル基、置換フェニル基、メトキシカルボニル基、エトキシカルボニル基が良い。
As the preferred organic tellurium compound represented by (1a), R 1 represents a C 1 -C 4 alkyl group, R 3 and R 4 represent a hydrogen atom or a C 1 -C 4 alkyl group, R A compound in which 5 is an aryl group, a substituted aryl group, or an oxycarbonyl group is preferable.
Particularly preferably, R 1 represents a C 1 to C 4 alkyl group, R 3 and R 4 represent a hydrogen atom or a C 1 to C 4 alkyl group, and R 5 represents a phenyl group or a substituted phenyl group. A methoxycarbonyl group and an ethoxycarbonyl group are preferable.
式（１ａ）で示される有機テルル化合物は、具体的な代表例は次の通りである。
（メチルテラニルメチル）ベンゼン、（１−メチルテラニルエチル）ベンゼン、１−クロロ−４−（１−メチルテラニルエチル）ベンゼン、１−トリフルオロメチル−４−（１−メチルテラニルエチル）ベンゼン、３,５−ビス−トリフルオロメチル−１−（１−メチルテラニルエチル）ベンゼン、１,２,３,４,５−ペンタフルオロ−６−（１−メチルテラニルエチル）ベンゼン、２−メチルテラニルプロピオニトリル、（２−メチルテラニルプロピル）ベンゼン、メチル ２−メチルテラニル−２−メチル−プロピオネート、エチル ２−メチルテラニル−２−メチル−プロピオネート、２−メチルテラニル−２−メチル−プロピオニトリル等を挙げることができる。また、上記において、メチルテラニルの部分がエチルテラニル、ｎ−ブチルテラニル、ｎ−オクチルテラニル等と変更した化合物も全て含まれる。その他ＷＯ２００４／０１４９６２に記載された有機テルル化合物の全てを例示することができる。
Specific representative examples of the organic tellurium compound represented by the formula (1a) are as follows.
(Methylterranylmethyl) benzene, (1-methylterranylethyl) benzene, 1-chloro-4- (1-methylterranylethyl) benzene, 1-trifluoromethyl-4- (1-methylterranylethyl) Benzene, 3,5-bis-trifluoromethyl-1- (1-methylteranylethyl) benzene, 1,2,3,4,5-pentafluoro-6- (1-methylterranylethyl) benzene, 2 -Methyl teranyl propionitrile, (2-methyl teranyl propyl) benzene, methyl 2-methyl teranyl-2-methyl-propionate, ethyl 2-methyl teranyl-2-methyl-propionate, 2-methyl teranyl-2-methyl-propio A nitrile etc. can be mentioned. In addition, in the above, all compounds in which the methyl terranyl moiety is changed to ethyl terranyl, n-butyl terranyl, n-octyl terranyl or the like are also included. In addition, all of the organic tellurium compounds described in WO2004 / 014962 can be exemplified.
本発明で使用する有機アンチモン化合物は、式（１ｂ）で表される。 The organic antimony compound used in the present invention is represented by the formula (1b).
Ｒ１及びＲ３〜Ｒ５で示される基は、上記と同様である。
Ｒ２で示される基は、Ｒ１と同様である。
The groups represented by R 1 and R 3 to R 5 are the same as described above.
The group represented by R 2 is the same as R 1 .
式（１ｂ）で示される有機アンチモン化合物は、具体的な代表例は次の通りである。
（ジメチルスチバニル−メチル）ベンゼン、（１−ジメチルスチバニル−エチル）ベンゼン、１−クロロ−４−（１−ジメチルスチバニル−エチル）ベンゼン、１−トリフルオロメチル−４−（１−ジメチルスチバニル−エチル）ベンゼン、３,５−ビス−トリフルオロメチル−１−（１−ジメチルスチバニル−エチル）ベンゼン、１,２,３,４,５−ペンタフルオロ−６−（１−ジメチルスチバニル−エチル）ベンゼン、２−ジメチルスチバニル−プロピオニトリル、（２−ジメチルスチバニル−プロピル）ベンゼン、メチル ２−ジメチルスチバニル−２−メチル−プロピオネート、エチル ２−ジメチルスチバニル−２−メチル−プロピオネート、２−ジメチルスチバニル−２−メチル−プロピオニトリル等を挙げることができる。また、上記において、ジメチルスチバニル−の部分がジエチルスチバニル−、ジｎ−ブチルスチバニル、ジｎ−オクチルスチバニル等と変更した化合物も全て含まれる。その他ＷＯ２００６／００１４９６に記載された有機アンチモン化合物の全てを例示することができる。
Specific representative examples of the organic antimony compound represented by the formula (1b) are as follows.
(Dimethylstivanyl-methyl) benzene, (1-dimethylstibanyl-ethyl) benzene, 1-chloro-4- (1-dimethylstibanyl-ethyl) benzene, 1-trifluoromethyl-4- (1-dimethylsti Vanyl-ethyl) benzene, 3,5-bis-trifluoromethyl-1- (1-dimethylstivanyl-ethyl) benzene, 1,2,3,4,5-pentafluoro-6- (1-dimethylstibanyl) -Ethyl) benzene, 2-dimethylstivanyl-propionitrile, (2-dimethylstibanyl-propyl) benzene, methyl 2-dimethylstivanyl-2-methyl-propionate, ethyl 2-dimethylstibanyl-2-methyl- Examples include propionate and 2-dimethylstivalyl-2-methyl-propionitrile. Further, in the above, all compounds in which the dimethyl stivanyl- moiety is changed to diethyl stivanyl-, di-n-butyl stivanyl, di-n-octyl stivanyl, etc. are also included. Other examples include all organic antimony compounds described in WO2006 / 001496.
本発明で使用する有機ビスマス化合物は、式（１ｃ）で表される。 The organic bismuth compound used in the present invention is represented by the formula (1c).
（式中、Ｒ１及びＲ２は、Ｃ１〜Ｃ８のアルキル基、アリール基、置換アリール基又は芳香族ヘテロ環基を示す。Ｒ３及びＲ４は、水素原子又はＣ１〜Ｃ８のアルキル基を示す。Ｒ５は、アリール基、置換アリール基、芳香族ヘテロ環基、アシル基、アミド基、オキシカルボニル基又はシアノ基を示す。） (In the formula, R 1 and R 2 represent a C 1 to C 8 alkyl group, aryl group, substituted aryl group or aromatic heterocyclic group. R 3 and R 4 represent a hydrogen atom or C 1 to C 8. R 5 represents an aryl group, a substituted aryl group, an aromatic heterocyclic group, an acyl group, an amide group, an oxycarbonyl group or a cyano group.
Ｒ１〜Ｒ５で示される基は、上記と同様である。 The groups represented by R 1 to R 5 are the same as described above.
式（１ｃ）で示される有機ビスマス化合物は、具体的な代表例は、上記、式（１ｂ）で示される有機アンチモン化合物の、スチバニルの部分がビスムタニルと変更した化合物を挙げることができる。その他ＰＣＴ／ＪＰ２００５／０２３０９３に記載された有機ビスマス化合物の全てを例示することができる。 Specific examples of the organic bismuth compound represented by the formula (1c) include compounds in which the stantivanyl moiety of the organic antimony compound represented by the formula (1b) is changed to bismutanyl. In addition, all the organic bismuth compounds described in PCT / JP2005 / 023093 can be exemplified.
本発明で使用するルイス酸は、ＭＸｎ（ｎ＝２、３または４）で表される。
Ｍは、２族、ランタノイドを含む３族、４族、１２族、１３族および１４族から選ばれる１種の元素である。具体的には、マグネシウム、スカンジウム、イットリウム、ランタン、セリウム、プラセオジウム、ネオジウム、プロメチウム、サマリウム、ユウロビウム、ガドリニウム、テルビウム、シスプロシウム、ホルミニウム、エルビウム、ツリウム、イッテルビウム、ルテチウム、アルミニウム、スズを挙げることができる。
好ましくは、２族、ランタノイドを含む３族が良い。より好ましくは、ランタノイドが良い。
Ｘは、ハロゲン塩、トリフルオロメタンスルホン酸塩（トリフラート、ＯＴｆ）、トリフルオロイミド、テトラアリルボレート、ヘキサフルオロアンチモナート等を挙げることができる。
好ましくは、トリフルオロメタンスルホン酸塩（トリフラート、ＯＴｆ）が良い。
ＭＸｎで表される、具体的な化合物は、例えば臭化マグネシウム、塩化イットリウム、トリフルオロメタンスルホン酸イットリウム、トリフルオロメタンスルホン酸ランタン、トリフルオロメタンスルホン酸セリウム、トリフルオロメタンスルホン酸プラセオジウム、トリフルオロメタンスルホン酸ネオジウム、トリフルオロメタンスルホン酸プロメチウム、トリフルオロメタンスルホン酸サマリウム、トリフルオロメタンスルホン酸ユウロビウム、トリフルオロメタンスルホン酸ガドリニウム、トリフルオロメタンスルホン酸テルビウム、トリフルオロメタンスルホン酸シスプロシウム、トリフルオロメタンスルホン酸ホルミニウム、トリフルオロメタンスルホン酸エルビウム、トリフルオロメタンスルホン酸ツリウム、トリフルオロメタンスルホン酸イッテルビウム、トリフルオロメタンスルホン酸ルテチウム等を挙げることができる。
好ましくは、トリフルオロメタンスルホン酸ランタノイド塩が良い。
The Lewis acid used in the present invention is represented by MXn (n = 2, 3 or 4).
M is one element selected from Group 2, Group 3, Group 4, Group 12, Group 13 and Group 14 including lanthanoids. Specific examples include magnesium, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, eurobium, gadolinium, terbium, cisprosium, holmium, erbium, thulium, ytterbium, lutetium, aluminum, and tin.
Preferably, Group 2 and Group 3 including lanthanoid are preferable. More preferably, a lanthanoid is good.
Examples of X include halogen salts, trifluoromethanesulfonate (triflate, OTf), trifluoroimide, tetraallylborate, hexafluoroantimonate, and the like.
Trifluoromethanesulfonate (triflate, OTf) is preferable.
Specific compounds represented by MXn include, for example, magnesium bromide, yttrium chloride, yttrium trifluoromethanesulfonate, lanthanum trifluoromethanesulfonate, cerium trifluoromethanesulfonate, praseodymium trifluoromethanesulfonate, neodymium trifluoromethanesulfonate, Promethium trifluoromethanesulfonate, samarium trifluoromethanesulfonate, eurobium trifluoromethanesulfonate, gadolinium trifluoromethanesulfonate, terbium trifluoromethanesulfonate, cisprosium trifluoromethanesulfonate, formium trifluoromethanesulfonate, erbium trifluoromethanesulfonate, trifluoromethane Thulium sulfonate, trifluorometa Acid ytterbium, mention may be made of trifluoromethanesulfonic acid lutetium like.
A lanthanoid trifluoromethanesulfonic acid salt is preferable.
本発明で使用する式（２ａ）〜（２ｃ）で表される化合物は、次の通りである。 The compounds represented by formulas (2a) to (2c) used in the present invention are as follows.
Ｒ１で示される基は、上記に示した通りである。
式（２ａ）で示される化合物は、具体的には、ジメチルジテルリド、ジエチルジテルリド、ジ−ｎ−プロピルジテルリド、ジイソプロピルジテルリド、ジシクロプロピルジテルリド、ジ−ｎ−ブチルジテルリド、ジ−ｓｅｃ−ブチルジテルリド、ジ−ｔｅｒｔ−ブチルジテルリド、ジシクロブチルジテルリド、ジフェニルジテルリド、ビス−（ｐ−メトキシフェニル）ジテルリド、ビス−（ｐ−アミノフェニル）ジテルリド、ビス−（ｐ−ニトロフェニル）ジテルリド、ビス−（ｐ−シアノフェニル）ジテルリド、ビス−（ｐ−スルホニルフェニル）ジテルリド、ジナフチルジテルリド、ジピリジルジテルリド等が挙げられる。
好ましい式（２ａ）で示される化合物としては、Ｒ１がＣ１〜Ｃ４のアルキル基、フェニル基が良い。好ましくは、ジメチルジテルリド、ジエチルジテルリド、ジ−ｎ−プロピルジテルリド、ジ−ｎ−ブチルジテルリド、ジフェニルジテルリドが良い。特に好ましくは、ジメチルジテルリド、ジエチルジテルリド、ジ−ｎ−プロピルジテルリド、ジ−ｎ−ブチルジテルリドが良い。
The group represented by R 1 is as described above.
Specific examples of the compound represented by the formula (2a) include dimethylditelluride, diethylditelluride, di-n-propylditelluride, diisopropylditelluride, dicyclopropylditelluride, di-n- Butyl ditelluride, di-sec-butyl ditelluride, di-tert-butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride, bis- (p-methoxyphenyl) ditelluride, bis- (p-aminophenyl) ditelluride, bis- (p -Nitrophenyl) ditelluride, bis- (p-cyanophenyl) ditelluride, bis- (p-sulfonylphenyl) ditelluride, dinaphthylditelluride, dipyridylditelluride and the like.
As a preferable compound represented by the formula (2a), R 1 is preferably a C 1 to C 4 alkyl group or a phenyl group. Preferred are dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, di-n-butyl ditelluride, and diphenyl ditelluride. Particularly preferred are dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride and di-n-butyl ditelluride.
Ｒ１及びＲ２で示される基は、上記に示した通りである。
式（２ｂ）で示される化合物は、具体的には、テトラメチルジスチビン、テトラエチルジスチビン、テトラ−ｎ−プロピルジスチビン、テトライソプロピルジスチビン、テトラシクロプロピルジスチビン、テトラ−ｎ−ブチルジスチビン、テトラ−ｓｅｃ−ブチルジスチビン、テトラ−ｔｅｒｔ−ブチルジスチビン、テトラシクロブチルジスチビン、テトラフェニルジスチビン、テトラ−（ｐ−メトキシフェニル）ジスチビン、テトラ−（ｐ−アミノフェニル）ジスチビン、テトラ−（ｐ−ニトロフェニル）ジスチビン、テトラ−（ｐ−シアノフェニル）ジスチビン、テトラ−（ｐ−スルホニルフェニル）ジスチビン、テトラナフチルジスチビン、テトラピリジルジスチビン等が挙げられる。
The groups represented by R 1 and R 2 are as described above.
Specific examples of the compound represented by the formula (2b) include tetramethyl distibin, tetraethyl distibin, tetra-n-propyl distibin, tetraisopropyl distivin, tetracyclopropyl distibin, tetra-n-butyl distibin, tetra -Sec-butyl distivine, tetra-tert-butyl distivine, tetracyclobutyl distivine, tetraphenyl distibin, tetra- (p-methoxyphenyl) distibin, tetra- (p-aminophenyl) distibin, tetra- (p-nitrophenyl) Examples include distibin, tetra- (p-cyanophenyl) distibin, tetra- (p-sulfonylphenyl) distibin, tetranaphthyl distibin, and tetrapyridyl distibin.
好ましい式（２ｂ）で示される化合物としては、Ｒ１及びＲ２がＣ１〜Ｃ４のアルキル基、フェニル基が良い。好ましくは、テトラメチルジスチビン、テトラエチルジスチビン、テトラ−ｎ−プロピルジスチビン、テトラ−ｎ−ブチルジスチビン、テトラフェニルジスチビンが良い。特に好ましくは、テトラメチルジスチビン、テトラエチルジスチビン、テトラ−ｎ−プロピルジスチビン、テトラ−ｎ−ブチルジスチビンが良い。 As a preferable compound represented by the formula (2b), R 1 and R 2 are preferably C 1 to C 4 alkyl groups and phenyl groups. Tetramethyl distibin, tetraethyl distibin, tetra-n-propyl distibin, tetra-n-butyl distibin, and tetraphenyl distibin are preferable. Particularly preferred are tetramethyl distivin, tetraethyl distibin, tetra-n-propyl distibin, and tetra-n-butyl distibin.
Ｒ１及びＲ２で示される基は、上記に示した通りである。
式（２ｃ）で示される化合物は、具体的には、テトラメチルジビスムチン、テトラエチルジビスムチン、テトラ−ｎ−プロピルジビスムチン、テトライソプロピルジビスムチン、テトラシクロプロピルジビスムチン、テトラ−ｎ−ブチルジビスムチン、テトラ−ｓｅｃ−ブチルジビスムチン、テトラ−ｔｅｒｔ−ブチルジビスムチン、テトラシクロブチルジビスムチン、テトラフェニルジビスムチン、テトラ−（ｐ−メトキシフェニル）ジビスムチン、テトラ−（ｐ−アミノフェニル）ジビスムチン、テトラ−（ｐ−ニトロフェニル）ジビスムチン、テトラ−（ｐ−シアノフェニル）ジビスムチン、テトラ−（ｐ−スルホニルフェニル）ジビスムチン、テトラナフチルジビスムチン、テトラピリジルジビスムチン等が挙げられる。
The groups represented by R 1 and R 2 are as described above.
Specific examples of the compound represented by the formula (2c) include tetramethyldibismuthine, tetraethyldibismuthine, tetra-n-propyldibismuthine, tetraisopropyldibismuthine, tetracyclopropyldibismuthine, tetra- n-butyldibismuthine, tetra-sec-butyldibismuthine, tetra-tert-butyldibismuthine, tetracyclobutyldibismuthine, tetraphenyldibismuthine, tetra- (p-methoxyphenyl) dibismuthine, tetra- (P-aminophenyl) dibismuthine, tetra- (p-nitrophenyl) dibismuthine, tetra- (p-cyanophenyl) dibismuthine, tetra- (p-sulfonylphenyl) dibismuthine, tetranaphthyldibismuthine, tetrapyridyldibismuthine, etc. Is mentioned.
好ましい式（２ｃ）で示される化合物としては、Ｒ１及びＲ２がＣ１〜Ｃ４のアルキル基、フェニル基が良い。好ましくは、テトラメチルジビスムチン、テトラエチルジビスムチン、テトラ−ｎ−プロピルジビスムチン、テトラ−ｎ−ブチルジビスムチン、テトラフェニルジビスムチンが良い。特に好ましくは、テトラメチルジビスムチン、テトラエチルジビスムチン、テトラ−ｎ−プロピルジビスムチン、テトラ−ｎ−ブチルジビスムチンが良い。 As a preferable compound represented by the formula (2c), R 1 and R 2 are preferably C 1 to C 4 alkyl groups and phenyl groups. Tetramethyldibismuthine, tetraethyldibismuthine, tetra-n-propyldibismuthine, tetra-n-butyldibismuthine, and tetraphenyldibismuthine are preferable. Particularly preferred are tetramethyldibismuthine, tetraethyldibismuthine, tetra-n-propyldibismuthine, and tetra-n-butyldibismuthine.
本発明で使用されるアゾ系重合開始剤は、通常のラジカル重合で使用するアゾ系重合開始剤であれば特に制限なく使用することができる。
例えば２,２'−アゾビス（イソブチロニトリル）（ＡＩＢＮ）、２,２'−アゾビス（２−メチルブチロニトリル）（ＡＭＢＮ）、２,２'−アゾビス（２,４−ジメチルバレロニトリル）（ＡＤＶＮ）、１,１'−アゾビス（１−シクロヘキサンカルボニトリル）（ＡＣＨＮ）、ジメチル−２,２'−アゾビスイソブチレート（ＭＡＩＢ）、４,４'−アゾビス（４−シアノバレリアン酸）（ＡＣＶＡ）、１,１'−アゾビス（１−アセトキシ−１−フェニルエタン）、２,２'−アゾビス（２−メチルブチルアミド）、２,２'−アゾビス（４−メトキシ−２,４−ジメチルバレロニトリル）、２,２'−アゾビス（２−メチルアミジノプロパン）二塩酸塩、２,２'−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］、２,２'−アゾビス［２−メチル−Ｎ−（２−ヒドロキシエチル）プロピオンアミド］、２,２'−アゾビス（２,４,４−トリメチルペンタン）、２−シアノ−２−プロピルアゾホルムアミド、２,２'−アゾビス（Ｎ−ブチル−２−メチルプロピオンアミド）、２,２'−アゾビス（Ｎ−シクロヘキシル−２−メチルプロピオンアミド）等が挙げられる。
The azo polymerization initiator used in the present invention can be used without particular limitation as long as it is an azo polymerization initiator used in normal radical polymerization.
For example, 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis (2-methylbutyronitrile) (AMBN), 2,2′-azobis (2,4-dimethylvaleronitrile) (ADVN), 1,1′-azobis (1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2′-azobisisobutyrate (MAIB), 4,4′-azobis (4-cyanovaleric acid) (ACVA) 1,1′-azobis (1-acetoxy-1-phenylethane), 2,2′-azobis (2-methylbutyramide), 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2,2′-azobis (2-methylamidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis [ 2-Methyl-N- 2-hydroxyethyl) propionamide], 2,2′-azobis (2,4,4-trimethylpentane), 2-cyano-2-propylazoformamide, 2,2′-azobis (N-butyl-2-methyl) Propionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) and the like.
これらのアゾ系開始剤は反応条件に応じて適宜選択するのが好ましい。例えば低温重合（４０℃以下）の場合は２,２'−アゾビス（２,４−ジメチルバレロニトリル）（ＡＤＶＮ）、２,２'−アゾビス（４−メトキシ−２,４−ジメチルバレロニトリル）、中温重合（４０〜８０℃）の場合は２,２'−アゾビス（イソブチロニトリル）（ＡＩＢＮ）、２,２'−アゾビス（２−メチルブチロニトリル）（ＡＭＢＮ）、ジメチル−２,２'−アゾビスイソブチレート（ＭＡＩＢ）、１,１'−アゾビス（１−アセトキシ−１−フェニルエタン）、高温重合（８０℃以上）の場合は１,１'−アゾビス（１−シクロヘキサンカルボニトリル）（ＡＣＨＮ）、２−シアノ−２−プロピルアゾホルムアミド、２,２'−アゾビス（Ｎ−ブチル−２−メチルプロピオンアミド）、２,２'−アゾビス（Ｎ−シクロヘキシル−２−メチルプロピオンアミド）、２,２'−アゾビス（２,４,４−トリメチルペンタン）を用いるのがよく、また水系溶剤を用いた反応では４,４'−アゾビス（４−シアノバレリアン酸）（ＡＣＶＡ）、２,２'−アゾビス（２−メチルブチルアミド）、２,２'−アゾビス（２−メチルアミジノプロパン）二塩酸塩、２,２'−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］、２,２'−アゾビス［２−メチル−Ｎ−（２−ヒドロキシエチル）プロピオンアミド］を用いるのがよい。 These azo initiators are preferably selected as appropriate according to the reaction conditions. For example, in the case of low temperature polymerization (40 ° C. or lower), 2,2′-azobis (2,4-dimethylvaleronitrile) (ADVN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), In the case of medium temperature polymerization (40-80 ° C.), 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis (2-methylbutyronitrile) (AMBN), dimethyl-2,2 In the case of '-azobisisobutyrate (MAIB), 1,1'-azobis (1-acetoxy-1-phenylethane), high temperature polymerization (80 ° C or higher), 1,1'-azobis (1-cyclohexanecarbonitrile) ) (ACHN), 2-cyano-2-propylazoformamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropion) Amide), 2,2′-azobis (2,4,4-trimethylpentane), and in a reaction using an aqueous solvent, 4,4′-azobis (4-cyanovaleric acid) (ACVA), 2,2'-azobis (2-methylbutyramide), 2,2'-azobis (2-methylamidinopropane) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] may be used.
本発明で使用するビニルモノマーとしては、ラジカル重合可能なものであれば特に制限なく使用することができる。 The vinyl monomer used in the present invention can be used without particular limitation as long as it is capable of radical polymerization.
例えば、下記のものを挙げることができる。
（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸オクチル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸−２−ヒドロキシエチル等の（メタ）アクリル酸エステル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸メチルシクロヘキシル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸シクロドデシル等のシクロアルキル基含有不飽和モノマー。
（メタ）アクリル酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸、クロトン酸、無水マレイン酸等メチル等のカルボキシル基含有不飽和モノマー。
For example, the following can be mentioned.
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic acid-2- Cycloalkyl group-containing unsaturated monomers such as (meth) acrylic acid esters such as hydroxyethyl, cyclohexyl (meth) acrylate, methyl cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and cyclododecyl (meth) acrylate.
(Meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, maleic anhydride and other carboxyl group-containing unsaturated monomers.
Ｎ,Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ,Ｎ−ジメチルアミノエチル（メタ）アクリルアミド、２−（ジメチルアミノ）エチル（メタ）アクリレート、Ｎ,Ｎ−ジメチルアミノプロピル（メタ）アクリレート等の３級アミン含有不飽和モノマー。
Ｎ−２−ヒドロキシ−３−アクリロイルオキシプロピル−Ｎ,Ｎ,Ｎ−トリメチルアンモニウムクロライド、Ｎ−メタクリロイルアミノエチル−Ｎ,Ｎ,Ｎ−ジメチルベンジルアンモニウムクロライド等の４級アンモニウム塩基含有不飽和モノマー。
（メタ）アクリル酸グリシジル等のエポキシ基含有不飽和モノマー。
3 such as N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, 2- (dimethylamino) ethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, etc. Secondary amine-containing unsaturated monomer.
Quaternary ammonium base-containing unsaturated monomers such as N-2-hydroxy-3-acryloyloxypropyl-N, N, N-trimethylammonium chloride and N-methacryloylaminoethyl-N, N, N-dimethylbenzylammonium chloride.
Epoxy group-containing unsaturated monomers such as (meth) glycidyl acrylate.
スチレン、α−メチルスチレン、４−メチルスチレン（ｐ−メチルスチレン）、２−メチルスチレン（ｏ−メチルスチレン）、３−メチルスチレン（ｍ−メチルスチレン）、４−メトキシスチレン（ｐ−メトキシスチレン）、ｐ−ｔｅｒｔ−ブチルスチレン、ｐ−ｎ−ブチルスチレン、ｐ−ｔｅｒｔ−ブトキシスチレン、２−ヒドロキシメチルスチレン、２−クロロスチレン（ｏ−クロロスチレン）、４−クロロスチレン（ｐ−クロロスチレン）、２,４−ジクロロスチレン、１−ビニルナフタレン、ジビニルベンゼン、ｐ−スチレンスルホン酸又はそのアルカリ金属塩（ナトリウム塩、カリウム塩等）等の芳香族不飽和モノマー（スチレン系モノマー）。 Styrene, α-methylstyrene, 4-methylstyrene (p-methylstyrene), 2-methylstyrene (o-methylstyrene), 3-methylstyrene (m-methylstyrene), 4-methoxystyrene (p-methoxystyrene) P-tert-butylstyrene, pn-butylstyrene, p-tert-butoxystyrene, 2-hydroxymethylstyrene, 2-chlorostyrene (o-chlorostyrene), 4-chlorostyrene (p-chlorostyrene), Aromatic unsaturated monomers (styrene monomers) such as 2,4-dichlorostyrene, 1-vinylnaphthalene, divinylbenzene, p-styrenesulfonic acid or alkali metal salts thereof (sodium salt, potassium salt, etc.).
２−ビニルチオフェン、Ｎ−メチル−２−ビニルピロール、１−ビニル−２−ピロリドン、２−ビニルピリジン、４−ビニルピリジン等のヘテロ環含有不飽和モノマー。
Ｎ−ビニルホルムアミド、Ｎ−ビニルアセトアミド等のビニルアミド。
（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−イソプロピル（メタ）アクリルアミド、Ｎ,Ｎ−ジメチル（メタ）アクリルアミド等の（メタ）アクリルアミド系モノマー。
１−ヘキセン、１−オクテン、１−デセン等のα−オレフィン。
ブタジエン、イソプレン、４−メチル−１,４−ヘキサジエン、７−メチル−１,６−オクタジエン等のジエン類。酢酸ビニル、安息香酸ビニル等のカルボン酸ビニルエステル。（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリロニトリル、メチルビニルケトン、塩化ビニル、塩化ビニリデン。
Heterocycle-containing unsaturated monomers such as 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1-vinyl-2-pyrrolidone, 2-vinylpyridine and 4-vinylpyridine.
Vinylamides such as N-vinylformamide and N-vinylacetamide.
(Meth) acrylamide monomers such as (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N, N-dimethyl (meth) acrylamide.
Α-olefins such as 1-hexene, 1-octene and 1-decene.
Dienes such as butadiene, isoprene, 4-methyl-1,4-hexadiene and 7-methyl-1,6-octadiene. Carboxylic acid vinyl esters such as vinyl acetate and vinyl benzoate. Hydroxyethyl (meth) acrylate, (meth) acrylonitrile, methyl vinyl ketone, vinyl chloride, vinylidene chloride.
好ましくは、極性ビニルモノマーであり、３級アミン含有不飽和モノマー、ヘテロ環含有不飽和モノマー、（メタ）アクリルアミド系モノマー、カルボン酸ビニルエステルが良い。尚、上記の「（メタ）アクリル酸」は、「アクリル酸」及び「メタクリル酸」の総称である。 Preferred are polar vinyl monomers, and tertiary amine-containing unsaturated monomers, heterocyclic-containing unsaturated monomers, (meth) acrylamide monomers, and carboxylic acid vinyl esters are preferred. The “(meth) acrylic acid” is a general term for “acrylic acid” and “methacrylic acid”.
本発明のリビングラジカルポリマーの製造方法は、具体的には次の通りである。
不活性ガスで置換した容器で、ビニルモノマー、式（１ａ）で表される有機テルル化合物、式（１ｂ）で表される有機アンチモン化合物および式（１ｃ）で表される有機ビスマス化合物から選ばれる少なくとも１種（リビングラジカル重合開始剤）およびルイス酸、必要に応じて、式（２ａ）〜式（２ｃ）で表される化合物、アゾ系重合開始剤を混合する。
The method for producing the living radical polymer of the present invention is specifically as follows.
In a container substituted with an inert gas, selected from a vinyl monomer, an organic tellurium compound represented by formula (1a), an organic antimony compound represented by formula (1b), and an organic bismuth compound represented by formula (1c) At least one (living radical polymerization initiator) and a Lewis acid, and if necessary, a compound represented by formula (2a) to formula (2c) and an azo polymerization initiator are mixed.
次に、上記混合物を撹拌する。反応温度、反応時間は、適宜調節すればよいが、通常、２０〜１５０℃で、１分〜１００時間撹拌する。好ましくは、４０〜１００℃で、０.１〜３０時間撹拌するのが良い。また、光を照射することにより、反応温度を低温にすることができる。光の照射方法としては、特に制限されることが無く、イマージョン型の光反応装置や通常の反応容器に光照射を行うことで重合を行うことができる。光照射をした場合、反応温度は、低温にする程ポリマーの立体規則性を制御することができるが、反応時間が長くなるおそれがあるため、０〜８０℃、より好ましくは、０〜３０℃とするのが良い。この時、圧力は、通常、常圧で行われるが、加圧或いは減圧しても構わない。この時、不活性ガスとしては、窒素、アルゴン、ヘリウム等を挙げることができる。好ましくは、アルゴン、窒素が良い。特に好ましくは、窒素が良い。 Next, the mixture is stirred. The reaction temperature and reaction time may be adjusted as appropriate, but are usually stirred at 20 to 150 ° C. for 1 minute to 100 hours. Preferably, it is good to stir at 40-100 degreeC for 0.1 to 30 hours. Further, the reaction temperature can be lowered by irradiating light. The light irradiation method is not particularly limited, and polymerization can be carried out by irradiating light to an immersion type photoreaction apparatus or a normal reaction vessel. When light irradiation is performed, the lower the reaction temperature, the more the polymer's stereoregularity can be controlled. However, the reaction time may become longer, so 0-80 ° C, more preferably 0-30 ° C. It is good to do. At this time, the pressure is usually a normal pressure, but may be increased or decreased. At this time, examples of the inert gas include nitrogen, argon, helium, and the like. Argon and nitrogen are preferable. Nitrogen is particularly preferable.
ビニルモノマーと式（１ａ）〜式（１ｃ）で表されるリビングラジカル重合開始剤の使用量としては、得られるリビングラジカルポリマーの分子量或いは分子量分布により適宜調節すればよいが、通常、式（１ａ）〜式（１ｃ）で表されるリビングラジカル重合開始剤１ｍｏｌに対して、ビニルモノマーを５〜１０,０００ｍｏｌ、好ましくは５０〜５,０００ｍｏｌとするのが良い。 The amount of the vinyl monomer and the living radical polymerization initiator represented by the formulas (1a) to (1c) may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the resulting living radical polymer. ) To 1 mol of the living radical polymerization initiator represented by the formula (1c), the vinyl monomer may be 5 to 10,000 mol, preferably 50 to 5,000 mol.
式（１ａ）〜式（１ｃ）で表されるリビングラジカル重合開始剤とルイス酸の使用量としては、通常、式（１ａ）〜式（１ｃ）で表されるリビングラジカル重合開始剤１ｍｏｌに対して、ルイス酸を０.０１〜５００ｍｏｌ、好ましくは０.１〜５０ｍｏｌとするのが良い。 The amount of the living radical polymerization initiator represented by formula (1a) to formula (1c) and the Lewis acid used is usually 1 mol of the living radical polymerization initiator represented by formula (1a) to formula (1c). Thus, the Lewis acid may be 0.01 to 500 mol, preferably 0.1 to 50 mol.
式（１ａ）〜式（１ｃ）で表されるリビングラジカル重合開始剤と式（２ａ）〜式（２ｃ）で表される化合物を併用する場合、その使用量としては、通常、式（１ａ）〜式（１ｃ）で表されるリビングラジカル重合開始剤１ｍｏｌに対して、式（２ａ）〜式（２ｃ）で表される化合物０.０１〜１００ｍｏｌ、好ましくは０.１〜１０ｍｏｌ、特に好ましくは０.１〜５ｍｏｌとするのが良い。 When the living radical polymerization initiator represented by the formula (1a) to the formula (1c) and the compound represented by the formula (2a) to the formula (2c) are used in combination, the amount used is usually the formula (1a). To 0.01 to 100 mol, preferably 0.1 to 10 mol, particularly preferably, the compound represented by the formula (2a) to the formula (2c) with respect to 1 mol of the living radical polymerization initiator represented by the formula (1c). It is good to set it as 0.1-5 mol.
式（１ａ）〜式（１ｃ）で表されるリビングラジカル重合開始剤とアゾ系重合開始剤を併用する場合、その使用量としては、通常、式（１ａ）〜式（１ｃ）で表されるリビングラジカル重合開始剤１ｍｏｌに対して、アゾ系重合開始剤０.０１〜１００ｍｏｌ、好ましくは０.０５〜１０ｍｏｌ、特に好ましくは０.０５〜２ｍｏｌとするのが良い。 When the living radical polymerization initiator represented by the formula (1a) to the formula (1c) and the azo polymerization initiator are used in combination, the amount used is usually represented by the formula (1a) to the formula (1c). The azo polymerization initiator may be 0.01 to 100 mol, preferably 0.05 to 10 mol, particularly preferably 0.05 to 2 mol with respect to 1 mol of the living radical polymerization initiator.
反応は、通常、無溶媒で行うが、ラジカル重合で一般に使用される有機溶媒或いは水性溶媒を使用しても構わない。使用できる有機溶媒としては、例えば、ベンゼン、トルエン、Ｎ,Ｎ−ジメチルホルムアミド（ＤＭＦ）、ジメチルスルホキシド（ＤＭＳＯ）、アセトン、２−ブタノン（メチルエチルケトン）、ジオキサン、ヘキサフルオロイソプロパオール、クロロホルム、四塩化炭素、テトラヒドロフラン（ＴＨＦ）、酢酸エチル、トリフルオロメチルベンゼン等が挙げられる。また、水性溶媒としては、例えば、水、メタノール、エタノール、イソプロパノール、ｎ−ブタノール、エチルセロソルブ、ブチルセロソルブ、１−メトキシ−２−プロパノール、ジアセトンアルコール等が挙げられる。溶媒の使用量としては適宜調節すればよいが、例えば、ビニルモノマー１ｇに対して、溶媒を０.０１〜５０ｍｌ、好ましくは、０.０５〜１０ｍｌが、特に好ましくは、０.１〜５ｍｌが良い。 The reaction is usually carried out without a solvent, but an organic solvent or an aqueous solvent generally used in radical polymerization may be used. Examples of the organic solvent that can be used include benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, hexafluoroisopropol, chloroform, tetrachloride. Examples thereof include carbon, tetrahydrofuran (THF), ethyl acetate, trifluoromethylbenzene and the like. Examples of the aqueous solvent include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, diacetone alcohol and the like. The amount of the solvent used may be adjusted as appropriate. For example, the solvent is 0.01 to 50 ml, preferably 0.05 to 10 ml, particularly preferably 0.1 to 5 ml with respect to 1 g of the vinyl monomer. good.
反応終了後、常法により使用溶媒や残存モノマーを減圧下除去して目的ポリマーを取り出したり、目的ポリマー不溶溶媒を使用して再沈澱処理により目的物を単離する。反応処理については、目的物に支障がなければどのような処理方法でも行う事ができる。 After completion of the reaction, the solvent or residual monomer is removed under reduced pressure by a conventional method to take out the target polymer, or the target product is isolated by reprecipitation using a target polymer insoluble solvent. The reaction treatment can be performed by any treatment method as long as there is no problem with the object.
本発明のリビングラジカルポリマーの製造方法では、ビニルモノマーを複数使用することができる。例えば、２種以上のビニルモノマーを同時に反応させるとランダム共重合体を得ることができる。該ランダム共重合体は、モノマーの種類に関係なく、反応させるモノマーの比率（モル比）通りのポリマーを得ることができる。ビニルモノマーＡとビニルモノマーＢを同時に反応させランダム共重合体を得るとほぼ原料比（モル比）通りのものを得ることができる。また、２種のビニルモノマーを順次反応させるとブロック共重合体を得ることができる。該ブロック共重合体は、モノマーの種類に関係なく、反応させるモノマーの順番によるポリマーを得ることができる。ビニルモノマーＡとビニルモノマーＢを用いてブロック共重合体を得る場合、反応させる順番によりＡ−Ｂのもの、Ｂ−Ａのものを得ることができる。 In the method for producing a living radical polymer of the present invention, a plurality of vinyl monomers can be used. For example, a random copolymer can be obtained by simultaneously reacting two or more kinds of vinyl monomers. The random copolymer can obtain a polymer in accordance with the ratio (molar ratio) of the monomer to be reacted, regardless of the type of monomer. When the vinyl monomer A and the vinyl monomer B are reacted at the same time to obtain a random copolymer, it is possible to obtain a raw material ratio (molar ratio). A block copolymer can be obtained by sequentially reacting two kinds of vinyl monomers. The block copolymer can obtain a polymer according to the order of monomers to be reacted, regardless of the type of monomer. When a block copolymer is obtained using vinyl monomer A and vinyl monomer B, those of AB and BA can be obtained depending on the order of reaction.
本発明で得られるリビングラジカルポリマーの分子量は、反応時間及び有機ビスマス化合物の量により調整可能であるが、数平均分子量５００〜１,０００,０００のリビングラジカルポリマーを得ることができる。特に数平均分子量１,０００〜５０,０００のリビングラジカルポリマーを得るのに好適である。
本発明で得られるリビングラジカルポリマーの分子量分布（ＰＤＩ＝Ｍｗ／Ｍｎ）は、１.０１〜１.５０の間で制御される。より好ましくは１.０１〜１.４０、１.０１〜１.３０、１.０１〜１.２０、１.０１〜１.１０、１.０１〜１.０５である。
本発明で得られるリビングラジカルポリマーの立体規則性は、ポリマー中のメソ二連子（ｍ）とラセモ二連子（ｒ）の比（ｍ：ｒ）で表される。これらは、１Ｈ−ＮＭＲ分析で決定することができる。好ましい立体規則性は、ｍ＝６０〜１００、より好ましくは、ｍ＝６５〜１００、更に好ましくは、ｍ＝７０〜１００が良い。
Although the molecular weight of the living radical polymer obtained by this invention can be adjusted with reaction time and the quantity of an organic bismuth compound, the living radical polymer of number average molecular weight 500-1,000,000 can be obtained. It is particularly suitable for obtaining a living radical polymer having a number average molecular weight of 1,000 to 50,000.
The molecular weight distribution (PDI = Mw / Mn) of the living radical polymer obtained in the present invention is controlled between 1.01 and 1.50. More preferably, they are 1.01 to 1.40, 1.01 to 1.30, 1.01 to 1.20, 1.01 to 1.10, 1.01 to 1.05.
The stereoregularity of the living radical polymer obtained in the present invention is represented by the ratio (m: r) of the meso duplex (m) and the racemo duplex (r) in the polymer. These can be determined by 1 H-NMR analysis. Preferred stereoregularity is m = 60-100, more preferably m = 65-100, and still more preferably m = 70-100.
本発明で得られるリビングラジカルポリマーの成長末端は、リビングラジカル重合開始剤由来の反応性の高い有機金属（有機テルル、有機アンチモン或いは有機ビスマス）であることが確認されている。従って、式（１ａ）〜式（１ｃ）の化合物をリビングラジカル重合に用いることにより従来のリビングラジカル重合で得られるリビングラジカルポリマーよりも末端基を他の官能基へ変換することが容易である。これらにより、本発明で得られるリビングラジカルポリマーは、マクロリビングラジカル重合開始剤（マクロイニシエーター）として用いることができる。 It has been confirmed that the growth terminal of the living radical polymer obtained in the present invention is a highly reactive organic metal (organic tellurium, organic antimony or organic bismuth) derived from the living radical polymerization initiator. Therefore, by using the compounds of the formulas (1a) to (1c) for living radical polymerization, it is easier to convert the terminal group to another functional group than the living radical polymer obtained by conventional living radical polymerization. By these, the living radical polymer obtained by this invention can be used as a macro living radical polymerization initiator (macroinitiator).
即ち、本発明のマクロリビングラジカル重合開始剤を用いて、例えばＮ−アルキル（メタ）アクリル酸アミド−スチレン等のＡ−Ｂジブロック共重合体、スチレン−Ｎ−アルキル（メタ）アクリル酸アミド等のＢ−Ａジブロック共重合体、Ｎ−アルキル（メタ）アクリル酸アミド−スチレン−Ｎ−アルキル（メタ）アクリル酸アミド等のＡ−Ｂ−Ａトリブロック共重合体を得ることができる。 That is, using the macro living radical polymerization initiator of the present invention, for example, an AB diblock copolymer such as N-alkyl (meth) acrylamidoamide-styrene, styrene-N-alkyl (meth) acrylamide, etc. A-B-A triblock copolymers such as N-alkyl (meth) acrylic acid amide-styrene-N-alkyl (meth) acrylic acid amide can be obtained.
本発明のリビングラジカルポリマーの製造方法では、ビニルモノマーの重合が促進され、反応時間を短縮することができる。また、得られるポリマーの分子量分布を制御し、且つ、立体規則性をも制御することができる。 In the method for producing a living radical polymer of the present invention, polymerization of a vinyl monomer is promoted, and the reaction time can be shortened. Moreover, the molecular weight distribution of the obtained polymer can be controlled, and the stereoregularity can also be controlled.
以下、本発明を実施例に基づいて具体的に説明するが何らこれらに限定されるものではない。また、実施例および比較例において、各種物性測定は以下の機器により測定を行った。
１Ｈ−ＮＭＲ：Ｖａｒｉａｎ ＶＸＲ−３００Ｓ（３００ＭＨｚ）
ＭＳ（ＧＣＭＳ）：Ｈｅｗｌｅｔｔ Ｐａｃｋａｒｄ ５９７２
分子量及び分子量分布：
装置：ゲルパーミエーションクロマトグラフィー 日本Ｗａｔｅｒｓ ＧＰＣＶ２０００
カラム：ＴＳＫｇｅｌ ＧＭＨＸＬ；ＴＳＫｇｅｌ Ｇ３０００ＨＸＬ
EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, it is not limited to these at all. In Examples and Comparative Examples, various physical properties were measured using the following equipment.
1 H-NMR: Varian VXR-300S (300 MHz)
MS (GCMS): Hewlett Packard 5972
Molecular weight and molecular weight distribution:
Apparatus: Gel permeation chromatography Japan Waters GPCV2000
Column: TSKgel GMHXL; TSKgel G3000HXL
合成例１（エチル ２−メチル−２−メチルテラニル−プロピオネート）
金属テルル〔Ａｌｄｒｉｃｈ製、商品名：Ｔｅｌｌｕｒｉｕｍ（−４０ｍｅｓｈ）〕 ６.３８ｇ（５０ｍｍｏｌ）をＴＨＦ ５０ｍｌに懸濁させ、これにメチルリチウム（上記と同じ） ５２.９ｍｌ（１.０４Ｍジエチルエーテル溶液、５５ｍｍｏｌ）を、室温でゆっくり滴下した（１０分間）。この反応溶液を金属テルルが完全に消失するまで撹拌した（２０分間）。この反応溶液に、エチル−２−ブロモ−イソブチレート １０.７ｇ（５５ｍｍｏｌ）を室温で加え、２時間撹拌した。反応終了後、減圧下で溶媒を濃縮し、続いて減圧蒸留して、黄色油状物 ６.５３ｇ（収率５１％）を得た。
Synthesis Example 1 (Ethyl 2-methyl-2-methylterranyl-propionate)
Metal tellurium (Aldrich, trade name: Tellurium (−40 mesh)) 6.38 g (50 mmol) was suspended in 50 ml of THF, and 52.9 ml of methyllithium (same as above) (1.04 M diethyl ether solution, 55 mmol). ) Was slowly added dropwise at room temperature (10 minutes). The reaction solution was stirred until the metal tellurium disappeared completely (20 minutes). To this reaction solution, 10.7 g (55 mmol) of ethyl-2-bromo-isobutyrate was added at room temperature and stirred for 2 hours. After completion of the reaction, the solvent was concentrated under reduced pressure, followed by distillation under reduced pressure to obtain 6.53 g (yield 51%) of a yellow oil.
合成例２（ジメチルジテルリド）
金属テルル（上記と同じ） ３.１９ｇ（２５ｍｍｏｌ）をＴＨＦ ２５ｍｌに懸濁させ、メチルリチウム（関東化学株式会社製、ジエチルエーテル溶液） ２５ｍｌ（２８.５ｍｍｏｌ）を０℃でゆっくり加えた（１０分間）。この反応溶液を金属テルルが完全に消失するまで撹拌した（１０分間）。この反応溶液に、塩化アンモニウム溶液２０ｍｌを室温で加え、１時間撹拌した。有機層を分離し、水層をジエチルエーテルで３回抽出した。集めた有機層を芒硝で乾燥後、減圧濃縮し、黒紫色油状物 ２.６９ｇ（９.４ｍｍｏｌ：収率７５％）を得た。
Synthesis Example 2 (Dimethylditelluride)
3.19 g (25 mmol) of metal tellurium (same as above) was suspended in 25 ml of THF, and 25 ml (28.5 mmol) of methyl lithium (manufactured by Kanto Chemical Co., Ltd., diethyl ether solution) was slowly added at 0 ° C. (10 minutes) ). The reaction solution was stirred until the metal tellurium disappeared completely (10 minutes). To this reaction solution, 20 ml of ammonium chloride solution was added at room temperature and stirred for 1 hour. The organic layer was separated and the aqueous layer was extracted 3 times with diethyl ether. The collected organic layer was dried over sodium sulfate and concentrated under reduced pressure to obtain 2.69 g (9.4 mmol: yield 75%) of a black purple oily substance.
合成例３（トリメチルスチバニルジブロマイド）
ジエチルエーテル ９００ｍｌにマグネシウム ３７.７ｇ（１.５５ｍｏｌ）とヨウ化メチル ２３５.４ｇ（１.６５ｍｏｌ）を仕込み、ヨウ化メチルマグネシウム溶液を調製する。三塩化アンチモン １１４ｇ（０.５ｍｏｌ）をＴＨＦ １００ｍｌに溶解した液を０℃で、ゆっくり滴下する（４０分間）。その後１.５時間室温で撹拌した。副製した塩を濾別し溶媒を濃縮後、減圧下（２０−３０℃、２００−３００ｍｍＨｇ）で蒸留した。得られら液に撹拌しながら、臭素を加えた（臭素による着色が見られるまで）。得られた沈殿物を冷却したエーテルで数回洗浄後、室温で減圧乾燥することで白色固体 １１５.６ｇ（収率７１％）を得た。
Synthesis Example 3 (Trimethylstivanyl dibromide)
900 ml of diethyl ether is charged with 37.7 g (1.55 mol) of magnesium and 235.4 g (1.65 mol) of methyl iodide to prepare a methyl magnesium iodide solution. A solution obtained by dissolving 114 g (0.5 mol) of antimony trichloride in 100 ml of THF is slowly added dropwise at 0 ° C. (40 minutes). The mixture was then stirred at room temperature for 1.5 hours. The by-produced salt was filtered off and the solvent was concentrated, followed by distillation under reduced pressure (20-30 ° C., 200-300 mmHg). Bromine was added to the resulting liquid while stirring (until coloring with bromine was observed). The obtained precipitate was washed several times with cooled ether and then dried under reduced pressure at room temperature to obtain 115.6 g (yield 71%) of a white solid.
合成例４（ジメチルスチバニルブロマイド）
トリメチルスチバニルジブロマイド １６.３ｇ（５０ｍｍｏｌ）を減圧下（５０ｍｍＨｇ）で１８０℃に加熱する。その後蒸留することで、黄色油状物のジメチルスチバニルブロマイド ９.２７ｇ（収率９０.０％）を得た。
Synthesis Example 4 (Dimethylstivalyl bromide)
16.3 g (50 mmol) of trimethylstivanyl dibromide are heated to 180 ° C. under reduced pressure (50 mmHg). Thereafter, distillation was performed to obtain 9.27 g (yield: 90.0%) of dimethyl stivanyl bromide as a yellow oily substance.
合成例５（エチル ２−ジメチルスチバニル−２−メチル−プロピオネート）
イソ酪酸エチル ３.４８ｇ（３０ｍｍｏｌ）をＴＨＦ ５０ｍｌに加え−７８℃に冷却し、これにリチウムイソプロピルアミド（Ａｌｄｒｉｃｈ製、２.０Ｍヘプタン・ＴＨＦ・エチルベンゼン溶液） １６.５ｍｌ（３３ｍｍｏｌ）をゆっくり滴下した（１０分間）。この反応液を−７８℃に保ちながら撹拌した（１時間）。この溶液にジメチルスチバニルブロマイド ６.９ｇ（２９.８ｍｍｏｌ）を０℃で加え、その後２時間室温で撹拌した。反応終了後、減圧下で溶媒を濃縮し、続いて減圧蒸留して、無色油状物 ３.９８ｇ（収率５０.０％）を得た。
Synthesis Example 5 (Ethyl 2-dimethylstivanyl-2-methyl-propionate)
3.48 g (30 mmol) of ethyl isobutyrate was added to 50 ml of THF and cooled to −78 ° C., and 16.5 ml (33 mmol) of lithium isopropylamide (manufactured by Aldrich, 2.0 M heptane / THF / ethylbenzene solution) was slowly added dropwise. (10 minutes). The reaction solution was stirred while maintaining at -78 ° C (1 hour). To this solution, 6.9 g (29.8 mmol) of dimethyl stivanyl bromide was added at 0 ° C., and then stirred at room temperature for 2 hours. After completion of the reaction, the solvent was concentrated under reduced pressure, followed by distillation under reduced pressure to obtain 3.98 g (yield 50.0%) of a colorless oil.
実施例１〜１７及び比較例１
リビングラジカルポリマーの合成
窒素置換したグローブボックス内で、エチル ２−メチル−２−メチルテラニル−プロピオネート ２５.８ｍｇ（０.１０ｍｍｏｌ）を１当量として、ルイス酸 １ｍｍｏｌ（１０当量）、ＡＩＢＮ ４.１ｍｇ（０.０２５ｍｍｏｌ）（０.２５当量）、Ｎ−イソプロピルアクリルアミド ２.２６ｍｇ（２０ｍｍｏｌ）（２００当量）及びエタノール １ｍｌの割合で仕込んだ溶液を、６０℃で２時間反応させた。反応終了後、テトラヒドロフラン １０ｍｌに溶解した後、その溶液を攪拌しているジエチルエーテル ２００ｍｌ中に注いだ。沈殿したポリマーを吸引ろ過、乾燥することにより目的物を得た。
１Ｈ−ＮＭＲとＧＰＣ分析（ポリメタクリル酸メチル標準サンプルの分子量を基準）による結果を表１に示した。
Examples 1 to 17 and Comparative Example 1
Synthesis of Living Radical Polymer In a nitrogen-substituted glove box, 25.8 mg (0.10 mmol) of ethyl 2-methyl-2-methylterranyl-propionate was used as 1 equivalent, 1 mmol of Lewis acid (10 equivalents), 4.1 mg of AIBN (0 0.025 mmol) (0.25 equivalent), N-isopropylacrylamide 2.26 mg (20 mmol) (200 equivalents), and a solution charged with ethanol 1 ml were reacted at 60 ° C. for 2 hours. After completion of the reaction, the reaction mixture was dissolved in 10 ml of tetrahydrofuran, and the solution was then poured into 200 ml of stirring diethyl ether. The precipitated polymer was suction filtered and dried to obtain the desired product.
The results of 1 H-NMR and GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample) are shown in Table 1.
実施例１８〜３２及び比較例２
リビングラジカルポリマーの合成
窒素置換したグローブボックス内で、エチル ２−メチル−２−メチルテラニル−プロピオネート ２５.８ｍｇ（０.１０ｍｍｏｌ）を１当量として、ルイス酸 １ｍｍｏｌ（１０当量）、ジメチルジテルリド ２８.５ｍｇ（０.１０ｍｍｏｌ）（１当量）、ＡＩＢＮ ４.１ｍｇ（０.０２５ｍｍｏｌ）（０.２５当量）、Ｎ−イソプロピルメタクリルアミド ２.５４ｍｇ（２０ｍｍｏｌ）（２００当量）及びエタノール １ｍｌの割合で仕込んだ溶液を、６０℃で６時間反応させた。反応終了後、ジエチルエーテル １０ｍｌに溶解した後、その溶液を攪拌しているメタノール ２００ｍｌ中に注いだ。沈殿したポリマーを吸引ろ過、乾燥することにより目的物を得た。
１Ｈ−ＮＭＲとＧＰＣ分析（ポリメタクリル酸メチル標準サンプルの分子量を基準）による結果を表２に示した。
Examples 18 to 32 and Comparative Example 2
Synthesis of Living Radical Polymer In a nitrogen-substituted glove box, 25.8 mg (0.10 mmol) of ethyl 2-methyl-2-methylteranyl-propionate was used as 1 equivalent, 1 mmol (10 equivalents) of Lewis acid, dimethyl ditelluride 28. 5 mg (0.10 mmol) (1 eq), AIBN 4.1 mg (0.025 mmol) (0.25 eq), N-isopropylmethacrylamide 2.54 mg (20 mmol) (200 eq) and ethanol 1 ml were charged. The solution was reacted at 60 ° C. for 6 hours. After completion of the reaction, the reaction mixture was dissolved in 10 ml of diethyl ether, and the solution was then poured into 200 ml of stirring methanol. The precipitated polymer was suction filtered and dried to obtain the desired product.
The results of 1 H-NMR and GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample) are shown in Table 2.
実施例３３〜３６及び比較例３
リビングラジカルポリマーの合成
窒素置換したグローブボックス内で、エチル ２−ジメチルスチバニル−２−メチル−プロピオネート ２６.７ｍｇ（０.１０ｍｍｏｌ）を１当量として、ルイス酸 １ｍｍｏｌ（１０当量）、ＡＩＢＮ ４.１ｍｇ（０.０２５ｍｍｏｌ）（０.２５当量）、Ｎ−イソプロピルアクリルアミド ２.２６ｍｇ（２０ｍｍｏｌ）（２００当量）及びＤＭＦ １ｍｌの割合で仕込んだ溶液を、６０℃で１時間反応させた。反応終了後、ジエチルエーテル １０ｍｌに溶解した後、その溶液を攪拌しているメタノール ２００ｍｌ中に注いだ。沈殿したポリマーを吸引ろ過、乾燥することにより目的物を得た。
１Ｈ−ＮＭＲとＧＰＣ分析（ポリメタクリル酸メチル標準サンプルの分子量を基準）による結果を表３に示した。
Examples 33 to 36 and Comparative Example 3
Synthesis of Living Radical Polymer In a nitrogen-substituted glove box, 26.7 mg (0.10 mmol) of ethyl 2-dimethylstavanyl-2-methyl-propionate was used as 1 equivalent, 1 mmol (10 equivalents) of Lewis acid, and 4.1 mg of AIBN. A solution prepared by mixing (0.025 mmol) (0.25 equivalent), N-isopropylacrylamide 2.26 mg (20 mmol) (200 equivalent) and 1 ml of DMF was reacted at 60 ° C. for 1 hour. After completion of the reaction, the reaction mixture was dissolved in 10 ml of diethyl ether, and the solution was then poured into 200 ml of stirring methanol. The precipitated polymer was suction filtered and dried to obtain the desired product.
The results of 1 H-NMR and GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample) are shown in Table 3.
実施例３７
リビングラジカルポリマーの合成
窒素置換したグローブボックス内で、エチル ２−メチル−２−メチルテラニル−プロピオネート ２５.８ｍｇ（０.１０ｍｍｏｌ）を１当量として、ルイス酸 ２ｍｍｏｌ（２０当量）、ＡＩＢＮ ４.１ｍｇ（０.０２５ｍｍｏｌ）（０.２５当量）、Ｎ−イソプロピルアクリルアミド ２.２６ｍｇ（２０ｍｍｏｌ）（２００当量）及びエタノール １ｍｌの割合で仕込んだ溶液を、６０℃で２時間反応させた。反応終了後、テトラヒドロフラン １０ｍｌに溶解した後、その溶液を攪拌しているジエチルエーテル ２００ｍｌ中に注いだ。沈殿したポリマーを吸引ろ過、乾燥することにより目的物を得た。
１Ｈ−ＮＭＲとＧＰＣ分析（ポリメタクリル酸メチル標準サンプルの分子量を基準）による結果を表４に示した。
Example 37
Synthesis of Living Radical Polymer In a nitrogen-substituted glove box, 25.8 mg (0.10 mmol) of ethyl 2-methyl-2-methylterranyl-propionate was used as 1 equivalent, 2 mmol (20 equivalents) of Lewis acid, 4.1 mg of AIBN (0 0.025 mmol) (0.25 equivalent), N-isopropylacrylamide 2.26 mg (20 mmol) (200 equivalents), and a solution charged with ethanol 1 ml were reacted at 60 ° C. for 2 hours. After completion of the reaction, the reaction mixture was dissolved in 10 ml of tetrahydrofuran, and the solution was then poured into 200 ml of stirring diethyl ether. The precipitated polymer was suction filtered and dried to obtain the desired product.
Table 4 shows the results of 1 H-NMR and GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample).
実施例３８
ルイス酸を２ｍｍｏｌ（２０当量）から３ｍｍｏｌ（３０当量）に変更した以外は、実施例３７と同様にしてリビングラジカルポリマーを得た。
１Ｈ−ＮＭＲとＧＰＣ分析（ポリメタクリル酸メチル標準サンプルの分子量を基準）による結果を表４に示した。
Example 38
A living radical polymer was obtained in the same manner as in Example 37 except that the Lewis acid was changed from 2 mmol (20 equivalents) to 3 mmol (30 equivalents).
Table 4 shows the results of 1 H-NMR and GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample).
実施例３９
リビングラジカルポリマーの合成
窒素置換したグローブボックス内で、パイレックス（登録商標）ガラス管に、エチル ２−メチル−２−メチルテラニル−プロピオネート ２５.８ｍｇ（０.１０ｍｍｏｌ）を１当量として、ルイス酸 １ｍｍｏｌ（１０当量）、Ｎ−イソプロピルアクリルアミド ２.２６ｍｇ（２０ｍｍｏｌ）（２００当量）及びエタノール １ｍｌの割合で仕込んだ溶液を、シャープカット光学フィルター（Ｙ−５２、５０％光遮断波長＝５２０ｎｍ）を通して、２５℃で２時間反応させた。反応終了後、テトラヒドロフラン １０ｍｌに溶解した後、その溶液を攪拌しているジエチルエーテル ２００ｍｌ中に注いだ。沈殿したポリマーを吸引ろ過、乾燥することにより目的物を得た。
１Ｈ−ＮＭＲとＧＰＣ分析（ポリメタクリル酸メチル標準サンプルの分子量を基準）による結果を表５に示した。
Example 39
Synthesis of Living Radical Polymer In a nitrogen-substituted glove box, 25.8 mg (0.10 mmol) of ethyl 2-methyl-2-methylterranyl-propionate was used as an equivalent in a Pyrex (registered trademark) glass tube. Equivalent), N-isopropylacrylamide 2.26 mg (20 mmol) (200 equivalents) and 1 ml of ethanol were passed through a sharp cut optical filter (Y-52, 50% light blocking wavelength = 520 nm) at 25 ° C. The reaction was performed for 2 hours. After completion of the reaction, the reaction mixture was dissolved in 10 ml of tetrahydrofuran, and the solution was then poured into 200 ml of stirring diethyl ether. The precipitated polymer was suction filtered and dried to obtain the desired product.
The results of 1 H-NMR and GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample) are shown in Table 5.
実施例４０
温度を２５℃から０℃に変更した以外は、実施例３９と同様にしてリビングラジカルポリマーを得た。
１Ｈ−ＮＭＲとＧＰＣ分析（ポリメタクリル酸メチル標準サンプルの分子量を基準）による結果を表５に示した。
Example 40
A living radical polymer was obtained in the same manner as in Example 39 except that the temperature was changed from 25 ° C to 0 ° C.
The results of 1 H-NMR and GPC analysis (based on the molecular weight of a polymethyl methacrylate standard sample) are shown in Table 5.
Claims (14)
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| WO2010013651A1 (en) | 2008-07-28 | 2010-02-04 | 大日精化工業株式会社 | Aqueous pigment dispersion and applications thereof |
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