JP2010209283A - Living radical polymerization initiator, and method for producing polymer using the same - Google Patents
Living radical polymerization initiator, and method for producing polymer using the same Download PDFInfo
- Publication number
- JP2010209283A JP2010209283A JP2009059704A JP2009059704A JP2010209283A JP 2010209283 A JP2010209283 A JP 2010209283A JP 2009059704 A JP2009059704 A JP 2009059704A JP 2009059704 A JP2009059704 A JP 2009059704A JP 2010209283 A JP2010209283 A JP 2010209283A
- Authority
- JP
- Japan
- Prior art keywords
- group
- living radical
- formula
- polymerization initiator
- telluride
- Prior art date
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- Granted
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- 238000010526 radical polymerization reaction Methods 0.000 title claims abstract description 46
- 239000007870 radical polymerization initiator Substances 0.000 title claims abstract description 40
- 229920000642 polymer Polymers 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 10
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 9
- 125000000547 substituted alkyl group Chemical group 0.000 claims abstract description 7
- -1 ditelluride compound Chemical class 0.000 claims description 74
- 239000000178 monomer Substances 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 11
- 239000007869 azo polymerization initiator Substances 0.000 claims description 9
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 7
- 239000003505 polymerization initiator Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 description 34
- 150000001875 compounds Chemical class 0.000 description 21
- 150000003254 radicals Chemical class 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 238000009826 distribution Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- VRLFOXMNTSYGMX-UHFFFAOYSA-N diphenyl ditelluride Chemical group C=1C=CC=CC=1[Te][Te]C1=CC=CC=C1 VRLFOXMNTSYGMX-UHFFFAOYSA-N 0.000 description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000003999 initiator Substances 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- DCXPWEXGIZAZJM-UHFFFAOYSA-N propan-2-yltellanylbenzene Chemical compound CC(C)[Te]C1=CC=CC=C1 DCXPWEXGIZAZJM-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 239000005297 pyrex Substances 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 7
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 7
- 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 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000003498 tellurium compounds Chemical class 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- JPIIVHIVGGOMMV-UHFFFAOYSA-N ditellurium Chemical compound [Te]=[Te] JPIIVHIVGGOMMV-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- 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
- 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
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000003125 aqueous solvent Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 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 4
- 239000003960 organic solvent Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910052714 tellurium Inorganic materials 0.000 description 3
- DRAQBUIVUGPBEB-UHFFFAOYSA-N (ethylditellanyl)ethane Chemical compound CC[Te][Te]CC DRAQBUIVUGPBEB-UHFFFAOYSA-N 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- 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
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 102100040409 Ameloblastin Human genes 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 101000891247 Homo sapiens Ameloblastin Proteins 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- 102100020870 La-related protein 6 Human genes 0.000 description 2
- 108050008265 La-related protein 6 Proteins 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 101100490446 Penicillium chrysogenum PCBAB gene Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 239000007864 aqueous solution Substances 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
- LWMFAFLIWMPZSX-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LWMFAFLIWMPZSX-UHFFFAOYSA-N 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 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 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229920000359 diblock copolymer Polymers 0.000 description 2
- LCMDQKIQBKULEI-UHFFFAOYSA-N dimethyl ditelluride Chemical compound C[Te][Te]C LCMDQKIQBKULEI-UHFFFAOYSA-N 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 2
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- 238000001226 reprecipitation Methods 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
- 238000003756 stirring Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
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- 229920001567 vinyl ester resin Polymers 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- GJEZBVHHZQAEDB-SYDPRGILSA-N (1s,5r)-6-oxabicyclo[3.1.0]hexane Chemical compound C1CC[C@H]2O[C@H]21 GJEZBVHHZQAEDB-SYDPRGILSA-N 0.000 description 1
- UXOFRFPVWFJROK-UHFFFAOYSA-N (2-ethenylphenyl)methanol Chemical compound OCC1=CC=CC=C1C=C UXOFRFPVWFJROK-UHFFFAOYSA-N 0.000 description 1
- JBVMSEMQJGGOFR-FNORWQNLSA-N (4e)-4-methylhexa-1,4-diene Chemical compound C\C=C(/C)CC=C JBVMSEMQJGGOFR-FNORWQNLSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 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
- GRFNSWBVXHLTCI-UHFFFAOYSA-N 1-ethenyl-4-[(2-methylpropan-2-yl)oxy]benzene Chemical compound CC(C)(C)OC1=CC=C(C=C)C=C1 GRFNSWBVXHLTCI-UHFFFAOYSA-N 0.000 description 1
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- 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
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- SDQCGKJCBWXRMK-UHFFFAOYSA-N propan-2-yl 4-methylbenzenesulfonate Chemical compound CC(C)OS(=O)(=O)C1=CC=C(C)C=C1 SDQCGKJCBWXRMK-UHFFFAOYSA-N 0.000 description 1
- SWWHCQCMVCPLEQ-UHFFFAOYSA-N propan-2-yl methanesulfonate Chemical compound CC(C)OS(C)(=O)=O SWWHCQCMVCPLEQ-UHFFFAOYSA-N 0.000 description 1
- NDJBHBQUEAGIOB-UHFFFAOYSA-N propan-2-yl trifluoromethanesulfonate Chemical compound CC(C)OS(=O)(=O)C(F)(F)F NDJBHBQUEAGIOB-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
- 238000000746 purification Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000000956 solid--liquid extraction Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 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
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 1
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000000108 ultra-filtration Methods 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
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
Abstract
Description
本発明は、リビングラジカル重合開始剤及びそれを用いるポリマーの製造方法に関する。 The present invention relates to a living radical polymerization initiator and a method for producing a polymer using the same.
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。我々は、有機テルル化合物が、温和な条件下で、精密な分子量及び分子量分布（ＰＤＩ＝Ｍｗ／Ｍｎ）の制御を可能とすることを見出し報告をしている（特許文献１）。
また、該有機テルル化合物と有機ジテルリド化合物との併用や、アゾ開始剤との併用により、より温和な条件下で、精密な重合が可能となることも見出し報告している（特許文献２〜４）。
Living radical polymerization is a polymerization method that allows precise control of the molecular structure while maintaining the simplicity and versatility of radical polymerization, and is very effective in the synthesis of new polymer materials. We have found and reported that organic tellurium compounds enable precise control of molecular weight and molecular weight distribution (PDI = Mw / Mn) under mild conditions (Patent Document 1).
It has also been found and reported that precise polymerization is possible under milder conditions by using the organic tellurium compound and organic ditelluride compound in combination or an azo initiator (Patent Documents 2 to 4). ).
しかし、既に報告している有機テルル化合物は空気に不安定であり、化合物の取扱いにより化合物が分解してしまう虞があった。また、該有機テルル化合物を開始剤として使用しビニルモノマーを重合するにあたり、空気量の制御を怠ると目的とするリビングラジカルポリマーを得られにくいという問題があった。 However, the already reported organic tellurium compounds are unstable to air, and the compounds may be decomposed by handling the compounds. Further, when the vinyl monomer is polymerized using the organic tellurium compound as an initiator, there is a problem that it is difficult to obtain a desired living radical polymer if the air amount is not controlled.
本発明の課題は、空気に安定なリビングラジカル重合開始剤、及びそれを用いたリビングラジカルポリマーの製造方法を提供することにある。 An object of the present invention is to provide a living radical polymerization initiator that is stable to air and a method for producing a living radical polymer using the same.
本発明は以下の発明に係る。
１．式（１）で表されるリビングラジカル重合開始剤。
The present invention relates to the following inventions.
1. Living radical polymerization initiator represented by Formula (1).
２．ビニルモノマーを、
（ａ）式（１）で表されるリビングラジカル重合開始剤、
（ｂ）式（１）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の混合物、
（ｃ）式（１）で表されるリビングラジカル重合開始剤と式（２）で表される有機ジテルリド化合物の混合物、又は
（ｄ）式（１）で表されるリビングラジカル重合開始剤、アゾ系重合開始剤及び式（２）で表される有機ジテルリド化合物の混合物
のいずれかを重合開始剤として用いて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. Vinyl monomer,
(A) a living radical polymerization initiator represented by formula (1),
(B) a mixture of a living radical polymerization initiator represented by formula (1) and an azo polymerization initiator,
(C) A mixture of a living radical polymerization initiator represented by formula (1) and an organic ditelluride compound represented by formula (2), or (d) a living radical polymerization initiator represented by formula (1), azo A method for producing a living radical polymer, wherein polymerization is carried out using any one of a mixture of a system polymerization initiator and an organic ditelluride compound represented by formula (2) as a polymerization initiator.
（Ｒ１Ｔｅ）２ （２）
（式中、Ｒ１は、上記と同じ。）
(R 1 Te) 2 (2)
(In the formula, R 1 is the same as above.)
本発明者は、鋭意研究の結果、特定の有機テルル化合物がリビングラジカル重合開始剤として使用することができること、該開始剤が空気に安定であること、該開始剤を使用しビニルモノマーの重合を制御することができることを見出し、本発明を完成するに至った。 As a result of diligent research, the present inventor has found that a specific organic tellurium compound can be used as a living radical polymerization initiator, that the initiator is stable to air, and that polymerization of vinyl monomers can be performed using the initiator. The present inventors have found that it can be controlled and have completed the present invention.
本発明によれば、空気に安定なリビングラジカル重合開始剤を提供することができる。また、該開始剤を使用しビニルモノマーの重合を行うと分子量分布（ＰＤＩ）の制御されたリビングラジカルポリマーを提供することができる。 According to the present invention, a living radical polymerization initiator stable to air can be provided. Further, when a vinyl monomer is polymerized using the initiator, a living radical polymer having a controlled molecular weight distribution (PDI) can be provided.
本発明で使用するリビングラジカル重合開始剤は、式（１）で表される。 The living radical polymerization initiator used in the present invention is represented by the formula (1).
Ｒ１で示される基は、具体的には次の通りである。
炭素数１〜８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 alkyl group having 1 to 8 carbon atoms 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。
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＝炭素数１〜８のアルキル基、アリール基、炭素数１〜８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。
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.
Examples of the substituent of the aryl group having the above substituent include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl-containing group represented by —COR a (R a = carbon number 1 -8 alkyl groups, aryl groups, C1-8 alkoxy groups, aryloxy groups), sulfonyl groups, trifluoromethyl groups, and the like.
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.
芳香族へテロ環基としては、ピリジル基、ピロリル基、フリル基、チエニル基等を挙げることができる。
Ｒ２及びＲ３で示される各基は、具体的には次の通りである。
炭素数１〜４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、シクロブチル基等の炭素数１〜４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。
炭素数１〜４の置換アルキル基としては、水酸基等を有する炭素数１〜４のアルキル基を挙げることができる。
炭素数１〜４のアルコキシ基としては、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、シクロプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、シクロブトキシ基等の炭素数１〜４の直鎖状、分岐鎖状又は環状のアルコキシ基を挙げることができる。
また、Ｒ２及びＲ３で環を形成しても良い。環としては例えば、シクロペンタン環、シクロヘキサン環、シクロヘプタン環、シクロオクタン環、グリコシド環を例示することができる。
Examples of the aromatic heterocyclic group include a pyridyl group, a pyrrolyl group, a furyl group, and a thienyl group.
Each group represented by R 2 and R 3 is specifically as follows.
Examples of the alkyl group having 1 to 4 carbon atoms include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, cyclopropyl groups, n-butyl groups, sec-butyl groups, tert-butyl groups, and cyclobutyl groups. Examples of the alkyl group include 1 to 4 linear, branched or cyclic alkyl groups. 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.
Examples of the substituted alkyl group having 1 to 4 carbon atoms include an alkyl group having 1 to 4 carbon atoms having a hydroxyl group and the like.
Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, cyclopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, and cyclobutoxy group. A linear, branched or cyclic alkoxy group having 1 to 4 carbon atoms can be exemplified.
Further, R 2 and R 3 may form a ring. Examples of the ring include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, and a glycoside ring.
好ましい式（１）で示されるリビングラジカル重合開始剤としては、Ｒ１が炭素数１〜４のアルキル基またはフェニル基を示し、Ｒ２及びＲ３が、炭素数１〜４のアルキル基で示される化合物が良い。 As a preferred living radical polymerization initiator represented by the formula (1), R 1 represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R 2 and R 3 represent an alkyl group having 1 to 4 carbon atoms. Good compound.
式（１）で示されるリビングラジカル重合開始剤は、具体的には次の通りである。
イソプロピルメチルテルリド、２−ブチルメチルテルリド、メチル−３−ペンチルテルリド、メチル−２−ペンチルテルリド、２−ヘキシルメチルテルリド、３−ヘキシルメチルテルリド、２−ヘプチルメチルテルリド、３−ヘプチルメチルテルリド、４−ヘプチルメチルテルリド、
The living radical polymerization initiator represented by the formula (1) is specifically as follows.
Isopropyl methyl telluride, 2-butyl methyl telluride, methyl-3-pentyl telluride, methyl-2-pentyl telluride, 2-hexyl methyl telluride, 3-hexyl methyl telluride, 2-heptyl methyl telluride, 3 -Heptylmethyl telluride, 4-heptylmethyl telluride,
エチルイソプロピルテルリド、２−ブチルエチルテルリド、エチル−３−ペンチルテルリド、エチル−２−ペンチルテルリド、エチル−２−ヘキシルテルリド、エチル−３−ヘキシルテルリド、エチル−２−ヘプチルテルリド、エチル−３−ヘプチルテルリド、４−ヘプチルエチルテルリド、 Ethyl isopropyl telluride, 2-butylethyl telluride, ethyl-3-pentyl telluride, ethyl-2-pentyl telluride, ethyl-2-hexyl telluride, ethyl-3-hexyl telluride, ethyl-2-heptyl telluride Lido, ethyl-3-heptyl telluride, 4-heptylethyl telluride,
ｎ−ブチルイソプロピルテルリド、ｎ−ブチル−ｓｅｃ−ブチルテルリド、ｎ−ブチル−３−ペンチルテルリド、ｎ−ブチル−２−ペンチルテルリド、ｎ−ブチル−２−ヘキシルテルリド、ｎ−ブチル−３−ヘキシルテルリド、ｎ−ブチル−２−ヘプチルテルリド、ｎ−ブチル−３−ヘプチルテルリド、ｎ−ブチル−４−ヘプチルテルリド、 n-butylisopropyl telluride, n-butyl-sec-butyl telluride, n-butyl-3-pentyl telluride, n-butyl-2-pentyl telluride, n-butyl-2-hexyl telluride, n-butyl-3 -Hexyl telluride, n-butyl-2-heptyl telluride, n-butyl-3-heptyl telluride, n-butyl-4-heptyl telluride,
イソプロピルフェニルテルリド、２−ブチルフェニルテルリド、３−ペンチルフェニルテルリド、２−ペンチルフェニルテルリド、２−ヘキシルフェニルテルリド、３−ヘキシルフェニルテルリド、２−ヘプチルフェニルテルリド、３−ヘプチルフェニルテルリド、４−ヘプチルフェニルテルリド、 Isopropylphenyl telluride, 2-butylphenyl telluride, 3-pentylphenyl telluride, 2-pentylphenyl telluride, 2-hexylphenyl telluride, 3-hexylphenyl telluride, 2-heptylphenyl telluride, 3-heptyl Phenyl telluride, 4-heptylphenyl telluride,
シクロペンチルメチルテルリド、エチルシクロペンチルテルリド、ｎ−ブチルシクロペンチルテルリド、シクロペンチルフェニルテルリド、１−ヒドロキシ−２−メチルテラニルシクロペンタン、１−ヒドロキシ−２−エチルテラニルシクロペンタン、１−ヒドロキシ−２−（ｎ−ブチルテラニル）シクロペンタン、１−ヒドロキシ−２−フェニルテラニルシクロペンタン、 Cyclopentylmethyl telluride, ethylcyclopentyl telluride, n-butylcyclopentyl telluride, cyclopentylphenyl telluride, 1-hydroxy-2-methylterranylcyclopentane, 1-hydroxy-2-ethylterranylcyclopentane, 1-hydroxy- 2- (n-butyl terranyl) cyclopentane, 1-hydroxy-2-phenyl terranyl cyclopentane,
シクロヘキシルメチルテルリド、エチルシクロヘキシルテルリド、ｎ−ブチルシクロヘキシルテルリド、シクロヘキシルフェニルテルリド、１−ヒドロキシ−２−メチルテラニルシクロヘキサン、１−ヒドロキシ−２−エチルテラニルシクロヘキサン、１−ヒドロキシ−２−（ｎ−ブチルテラニル）シクロヘキサン、１−ヒドロキシ−２−フェニルテラニルシクロヘキサン、 Cyclohexylmethyl telluride, ethylcyclohexyl telluride, n-butylcyclohexyl telluride, cyclohexylphenyl telluride, 1-hydroxy-2-methylterranylcyclohexane, 1-hydroxy-2-ethylterranylcyclohexane, 1-hydroxy-2- (N-butyl terranyl) cyclohexane, 1-hydroxy-2-phenyl terranyl cyclohexane,
シクロヘプチルメチルテルリド、エチルシクロヘプチルテルリド、ｎ−ブチルシクロヘプチルテルリド、シクロヘプチルフェニルテルリド、シクロオクチルメチルテルリド、エチルシクロオクチルテルリド、ｎ−ブチルシクロオクチルテルリド、シクロオクチルフェニルテルリド、１−ヒドロキシ−２−メチルテラニルシクロオクタン、１−ヒドロキシ−２−エチルテラニルシクロオクタン、１−ヒドロキシ−２−（ｎ−ブチルテラニル）シクロオクタン、１−ヒドロキシ−２−フェニルテラニルシクロオクタン、 Cycloheptylmethyl telluride, ethylcycloheptyl telluride, n-butylcycloheptyl telluride, cycloheptylphenyl telluride, cyclooctylmethyl telluride, ethylcyclooctyl telluride, n-butylcyclooctyl telluride, cyclooctylphenyl telluride Lido, 1-hydroxy-2-methylterranylcyclooctane, 1-hydroxy-2-ethylterranylcyclooctane, 1-hydroxy-2- (n-butylterranyl) cyclooctane, 1-hydroxy-2-phenylterranylcyclo Octane,
１−フェニルテルロ−２,３,４,６−テトラ−Ｏ−ベンゾイル−β―Ｄ−グルコピラノシド、１−フェニルテルロ−２,３,４,６−テトラ−Ｏ−アセチル−β−Ｄ−グルコピラノシド、１−メチルテルロ−２,３,４,６−テトラ−Ｏ−ベンゾイル−β―Ｄ−グルコピラノシド、１−メチルテルロ−２,３,４,６−テトラ−Ｏ−アセチル−β−Ｄ−グルコピラノシド、１−エチルテルロ−２,３,４,６−テトラ−Ｏ−ベンゾイル−β―Ｄ−グルコピラノシド、１−エチルテルロ−２,３,４,６−テトラ−Ｏ−アセチル−β−Ｄ−グルコピラノシド、１−ブチルテルロ−２,３,４,６−テトラ−Ｏ−ベンゾイル−β―Ｄ−グルコピラノシド、１−ブチルテルロ−２,３,４,６−テトラ−Ｏ−アセチル−β−Ｄ−グルコピラノシド。 1-phenyltelluro-2,3,4,6-tetra-O-benzoyl-β-D-glucopyranoside, 1-phenyltelluro-2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside, 1-methyltelluro-2,3,4,6-tetra-O-benzoyl-β-D-glucopyranoside, 1-methyltelluro-2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside, 1- Ethyltelluro-2,3,4,6-tetra-O-benzoyl-β-D-glucopyranoside, 1-ethyltelluro-2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside, 1-butyltelluro- 2,3,4,6-Tetra-O-benzoyl-β-D-glucopyranoside, 1-butyltelluro-2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside.
本発明は、ビニルモノマーを下記（ａ）〜（ｄ）のいずれかを重合開始剤として用いて重合することができる。
（ａ）式（１）で表されるリビングラジカル重合開始剤、
（ｂ）式（１）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の混合物、
（ｃ）式（１）で表されるリビングラジカル重合開始剤と式（２）で表される有機ジテルリド化合物の混合物、又は
（ｄ）式（１）で表されるリビングラジカル重合開始剤、アゾ系重合開始剤及び式（２）で表される有機ジテルリド化合物の混合物
In the present invention, a vinyl monomer can be polymerized using any of the following (a) to (d) as a polymerization initiator.
(A) a living radical polymerization initiator represented by formula (1),
(B) a mixture of a living radical polymerization initiator represented by formula (1) and an azo polymerization initiator,
(C) A mixture of a living radical polymerization initiator represented by formula (1) and an organic ditelluride compound represented by formula (2), or (d) a living radical polymerization initiator represented by formula (1), azo Of organic polymerization initiator and organic ditelluride compound represented by formula (2)
式（１）で表されるリビングラジカル重合開始剤は、非特許文献１等に記載の公知の化合物や、特許文献５等に記載された公知の方法等により製造することができる。
例えば、式（１）で表されるリビングラジカル重合開始剤は、式（３）の化合物、式（４）の化合物および金属テルルを反応させることにより製造することができる。式（１）の化合物のうち、Ｒ３がヒドロキシ基を持つもので、そのヒドロキシ基がＴｅＲ１基に対してβ位にあるものに関しては、エポキシ化合物と式（４）の化合物および金属テルルを反応させることにより製造することができる。
上記、式（３）の化合物としては、具体的には次の通りである。
For example, the living radical polymerization initiator represented by the formula (1) can be produced by reacting the compound of the formula (3), the compound of the formula (4) and metal tellurium. Of the compounds of formula (1), those in which R 3 has a hydroxy group and the hydroxy group is in the β-position with respect to the TeR 1 group, It can be produced by reacting.
Specific examples of the compound of the formula (3) are as follows.
Ｘで示される基としては、フッ素、塩素、臭素又はヨウ素等のハロゲン原子、又は、トリフラート、メシラート、トシラートなどのアルカンスルホナート基を挙げることができる。好ましくは、塩素、臭素が良い。
Ｍ（Ｒ１）ｍ （４）
（Ｒ１は、上記と同じ。Ｍは、アルカリ金属、アルカリ土類金属又は銅原子を示す。Ｍがアルカリ金属の時、ｍは１、Ｍがアルカリ土類金属の時、ｍは２、Ｍが銅原子の時、ｍは１または２を示す。）
Examples of the group represented by X include halogen atoms such as fluorine, chlorine, bromine and iodine, or alkanesulfonate groups such as triflate, mesylate and tosylate. Preferably, chlorine and bromine are good.
M (R 1 ) m (4)
(R 1 is the same as above. M represents an alkali metal, alkaline earth metal or copper atom. When M is an alkali metal, m is 1, when M is an alkaline earth metal, m is 2, M When is a copper atom, m represents 1 or 2.)
Ｍで示されるものとしては、リチウム、ナトリウム、カリウム等のアルカリ金属、マグネシウム、カルシウム等のアルカリ土類金属、銅を挙げることができる。好ましくは、リチウムが良い。
なお、Ｍがマグネシウムの時、化合物（４）はＭｇ（Ｒ１）２でも、或いはＲ１ＭｇＸ（Ｘは、ハロゲン原子）で表される化合物（グリニャール試薬）でもよい。Ｘは、好ましくは、塩素、臭素が良い。
Examples of M include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, and copper. Lithium is preferable.
When M is magnesium, the compound (4) may be Mg (R 1 ) 2 or a compound represented by R 1 MgX (X is a halogen atom) (Grignard reagent). X is preferably chlorine or bromine.
式（３）の化合物は具体的には次の通りである。２−ブロモプロパン、２−ヨードプロパン、ｐ−トルエンスルホン酸イソプロピル、メタンスルホン酸イソプロピル、トリフルオロメタンスルホン酸イソプロピル、２−クロロブタン、２−ブロモブタン、２−ヨードブタン、ｐ−トルエンスルホン酸ｓｅｃ−ブチル、メタンスルホン酸ｓｅｃ−ブチル、トリフルオロメタンスルホン酸ｓｅｃ−ブチル、２−クロロペンタン、２−ブロモペンタン、２−ヨードペンタン、ｐ−トルエンスルホン酸−２−ペンチル、メタンスルホン酸−２−ペンチル、トリフルオロメタンスルホン酸−２−ペンチル、３−クロロペンタン、３−ブロモペンタン、３−ヨードペンタン、ｐ−トルエンスルホン酸−３−ペンチル、メタンスルホン酸−３−ペンチル、トリフルオロメタンスルホン酸−３−ペンチル、２−クロロヘキサン、２−ブロモヘキサン、２−ヨードヘキサン、ｐ−トルエンスルホン酸−２−ヘキシル、メタンスルホン酸−２−ヘキシル、トリフルオロメタンスルホン酸−２−ヘキシル、３−クロロヘキサン、３−ブロモヘキサン、３−ヨードヘキサン、ｐ−トルエンスルホン酸−３−ヘキシル、メタンスルホン酸−３−ヘキシル、トリフルオロメタンスルホン酸−３−ヘキシル、 Specifically, the compound of Formula (3) is as follows. 2-bromopropane, 2-iodopropane, isopropyl p-toluenesulfonate, isopropyl methanesulfonate, isopropyl trifluoromethanesulfonate, 2-chlorobutane, 2-bromobutane, 2-iodobutane, sec-butyl p-toluenesulfonate, methane Sec-butyl sulfonate, sec-butyl trifluoromethanesulfonate, 2-chloropentane, 2-bromopentane, 2-iodopentane, p-toluenesulfonate-2-pentyl, methanesulfonate-2-pentyl, trifluoromethanesulfone 2-pentyl acid, 3-chloropentane, 3-bromopentane, 3-iodopentane, p-toluenesulfonic acid-3-pentyl, methanesulfonic acid-3-pentyl, trifluoromethanesulfonic acid-3-pentyl, 2 Chlorohexane, 2-bromohexane, 2-iodohexane, p-toluenesulfonic acid-2-hexyl, methanesulfonic acid-2-hexyl, trifluoromethanesulfonic acid-2-hexyl, 3-chlorohexane, 3-bromohexane, 3-iodohexane, p-toluenesulfonic acid-3-hexyl, methanesulfonic acid-3-hexyl, trifluoromethanesulfonic acid-3-hexyl,
２−クロロヘプタン、２−ブロモヘプタン、２−ヨードヘプタン、ｐ−トルエンスルホン酸−２−ヘプチル、メタンスルホン酸−２−ヘプチル、トリフルオロメタンスルホン酸−２−ヘプチル、３−クロロヘプタン、３−ブロモヘプタン、３−ヨードヘプタン、ｐ−トルエンスルホン酸−３−ヘプチル、メタンスルホン酸−３−ヘプチル、トリフルオロメタンスルホン酸−３−ヘプチル、４−クロロヘプタン、４−ブロモヘプタン、４−ヨードヘプタン、ｐ−トルエンスルホン酸−４−ヘプチル、メタンスルホン酸−４−ヘプチル、トリフルオロメタンスルホン酸−４−ヘプチル、 2-chloroheptane, 2-bromoheptane, 2-iodoheptane, p-toluenesulfonic acid-2-heptyl, methanesulfonic acid-2-heptyl, trifluoromethanesulfonic acid-2-heptyl, 3-chloroheptane, 3-bromo Heptane, 3-iodoheptane, p-toluenesulfonic acid-3-heptyl, methanesulfonic acid-3-heptyl, trifluoromethanesulfonic acid-3-heptyl, 4-chloroheptane, 4-bromoheptane, 4-iodoheptane, p -Toluenesulfonic acid-4-heptyl, methanesulfonic acid-4-heptyl, trifluoromethanesulfonic acid-4-heptyl,
クロロシクロペンタン、ブロモシクロペンタン、ヨードシクロペンタン、ｐ−トルエンスルホン酸シクロペンチル、メタンスルホン酸シクロペンチル、トリフルオロメタンスルホン酸シクロペンチル、クロロシクロヘキサン、ブロモシクロヘキサン、ヨードシクロヘキサン、ｐ−トルエンスルホン酸シクロヘキシル、メタンスルホン酸シクロヘキシル、トリフルオロメタンスルホン酸シクロヘキシル、クロロシクロヘプタン、ブロモシクロヘプタン、ヨードシクロヘプタン、ｐ−トルエンスルホン酸シクロヘプチル、メタンスルホン酸シクロヘプチル、トリフルオロメタンスルホン酸シクロヘプチル、クロロシクロオクタン、ブロモシクロオクタン、ヨードシクロオクタン、ｐ−トルエンスルホン酸シクロオクチル、ｐ−メタンスルホン酸シクロオクチル、トリフルオロメタンスルホン酸シクロオクチル、２,３,４,６−テトラ−Ｏ−ベンゾイル−α−Ｄ−ブロモグルコピラノシド、２,３,４,６−テトラ−Ｏ−アセチル−α−Ｄ−ブロモグルコピラノシド。 Chlorocyclopentane, bromocyclopentane, iodocyclopentane, cyclopentyl p-toluenesulfonate, cyclopentyl methanesulfonate, cyclopentyl trifluoromethanesulfonate, chlorocyclohexane, bromocyclohexane, iodocyclohexane, cyclohexyl p-toluenesulfonate, cyclohexyl methanesulfonate Cyclohexyl trifluoromethanesulfonate, chlorocycloheptane, bromocycloheptane, iodocycloheptane, cycloheptyl p-toluenesulfonate, cycloheptyl methanesulfonate, cycloheptyl trifluoromethanesulfonate, chlorocyclooctane, bromocyclooctane, iodocyclo Octane, cyclooctyl p-toluenesulfonate, p-methanesulfonate Looctyl, cyclooctyl trifluoromethanesulfonate, 2,3,4,6-tetra-O-benzoyl-α-D-bromoglucopyranoside, 2,3,4,6-tetra-O-acetyl-α-D-bromoglucopyranoside .
上記、エポキシ化合物としては、具体的には次の通りである。
１,２−エポキシシクロペンタン、１,２−エポキシシクロヘキサン、１,２−エポキシシクロオクタン。
Specifically, the epoxy compound is as follows.
1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxycyclooctane.
本発明で使用する有機ジテルリド化合物は、式（２）で表される。
（Ｒ１Ｔｅ）２ （２）
（Ｒ１は、炭素数１〜８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。）
The organic ditelluride compound used in the present invention is represented by the formula (2).
(R 1 Te) 2 (2)
(R 1 represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, or an aromatic heterocyclic group.)
Ｒ１で示される基は、式（１）において示した通りである。
好ましい式（２）で示される化合物としては、Ｒ１がＣ１〜Ｃ４のアルキル基、フェニル基の化合物である。
The group represented by R 1 is as shown in Formula (1).
A preferable compound represented by the formula (2) is a compound in which R 1 is a C 1 to C 4 alkyl group or a phenyl group.
式（２）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。 Specifically, the compound represented by the formula (2) includes 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. Preferred are dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, di-n-butyl ditelluride, and diphenyl ditelluride.
また本発明では重合速度の促進を目的にアゾ系重合開始剤を使用してもよい。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。 In the present invention, an azo polymerization initiator may be used for the purpose of accelerating the polymerization rate. The azo polymerization initiator can be used without particular limitation as long as it is an azo polymerization initiator used in normal radical polymerization.
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。 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）、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］、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）、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 '-Azobisisobutyrate (MAIB), 1,1'-azobis (1-acetoxy-1-phenylethane), 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], high temperature polymerization ( 1,1'- in the case of 80 ° C or higher) Zobis (1-cyclohexanecarbonitrile) (ACHN), 2-cyano-2-propylazoformamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl) 2-methylpropionamide), 2,2′-azobis (2,4,4-trimethylpentane), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] Is good.
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、ビニルモノマーであり、（メタ）アクリル酸エステル、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、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。
A vinyl monomer is preferable, and (meth) acrylic acid ester, tertiary amine-containing unsaturated monomer, heterocyclic-containing unsaturated monomer, and carboxylic acid vinyl ester are preferable.
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、例えば、（Ａ）加熱での重合、（Ｂ）光照射での重合等を挙げることができる。具体的には下記に示す。 Examples of the method for producing the living radical polymer of the present invention include (A) polymerization by heating, (B) polymerization by light irradiation, and the like. Specifically, it is shown below.
（Ａ）加熱での重合
不活性ガスで置換した容器で、ビニルモノマーと式（１）で表されるリビングラジカル重合開始剤を混合する。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、特に好ましくは、窒素が良い。
ビニルモノマーと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（１）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１０〜１０,０００ｍｏｌ、好ましくは、３０〜５,０００ｍｏｌが良い。
アゾ系重合開始剤を使用する場合、式（１）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の使用割合は、通常、式（１）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０.１〜１０ｍｏｌ、特に好ましくは０.１〜５ｍｏｌとするのが良い。
また、式（２）で表される化合物を使用する場合、通常、リビングラジカル重合開始剤１ｍｏｌに対して、式（２）で表される化合物を０.０５〜１０ｍｏｌ、好ましくは、０.１〜５ｍｏｌが良い。
(A) Polymerization by heating In a container substituted with an inert gas, a vinyl monomer and a living radical polymerization initiator represented by the formula (1) are mixed. At this time, examples of the inert gas include nitrogen, argon, helium, and the like. Argon and nitrogen are preferable, and nitrogen is particularly preferable.
The usage amount of the vinyl monomer and the living radical polymerization initiator may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the resulting living radical polymer, but is usually 1 mol of the living radical polymerization initiator represented by the formula (1). The vinyl monomer content is 10 to 10,000 mol, preferably 30 to 5,000 mol.
When the azo polymerization initiator is used, the ratio of the living radical polymerization initiator represented by the formula (1) and the azo polymerization initiator is usually 1 mol of the living radical polymerization initiator represented by the formula (1). In contrast, the azo polymerization initiator may be 0.01 to 100 mol, preferably 0.1 to 10 mol, particularly preferably 0.1 to 5 mol.
Moreover, when using the compound represented by Formula (2), 0.05-10 mol of compounds normally represented by Formula (2) are preferable with respect to 1 mol of living radical polymerization initiators, Preferably, it is 0.1. ~ 5 mol is good.
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ノール、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、０.１〜１ｍｌ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, hexafluoroisopropanol, chloroform, carbon tetrachloride, Tetrahydrofuran (THF), ethyl acetate, trifluoromethylbenzene and the like can be mentioned.
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, 0.01 to 50 ml, preferably 0.05 to 10 ml, particularly preferably 0.1 to 1 ml of the solvent is used per 1 g of the vinyl monomer. good.
次に、上記混合物を撹拌する。反応温度、反応時間は、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、６０〜１５０℃で、５〜１００時間撹拌する。好ましくは、８０〜１２０℃で、１０〜３０時間撹拌するのが良い。この時、通常、常圧で行われるが、加圧或いは減圧しても構わない。
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のリビングラジカルポリマーを取り出したり、目的のリビングラジカル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。
Next, the mixture is stirred. The reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the resulting living radical polymer, but are usually stirred at 60 to 150 ° C. for 5 to 100 hours. Preferably, it is good to stir at 80-120 degreeC for 10 to 30 hours. At this time, it is usually performed at normal pressure, but it may be increased or decreased.
After completion of the reaction, the solvent used or residual monomer is removed under reduced pressure by a conventional method to take out the target living radical polymer, or the target product is isolated by reprecipitation treatment using the target living radical polymer insoluble solvent. The reaction treatment can be performed by any treatment method as long as there is no problem with the object.
（Ｂ）光照射での重合
不活性ガスで置換した容器で、ビニルモノマーと式（１）で表されるリビングラジカル重合開始剤を混合する。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、特に好ましくは、窒素が良い。
容器としては、特に制限無く使用することができる。例えば、ＵＶ透過ガラス、パイレックス（登録商標）ガラス等の硬質ガラス、石英ガラス等の軟質ガラスを利用することができる。
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。
ビニルモノマーと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整すればよいが、通常、式（１）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１０〜１０,０００ｍｏｌ、好ましくは、３０〜５,０００ｍｏｌが良い。
(B) Polymerization by light irradiation In a container substituted with an inert gas, a vinyl monomer and a living radical polymerization initiator represented by the formula (1) are mixed. At this time, examples of the inert gas include nitrogen, argon, helium, and the like. Argon and nitrogen are preferable, and nitrogen is particularly preferable.
The container can be used without any particular limitation. For example, UV glass, hard glass such as Pyrex (registered trademark) glass, or soft glass such as quartz glass can be used.
The light irradiation method is not particularly limited, and the polymerization can be performed by irradiating light to an immersion type photoreaction apparatus or a normal reaction vessel.
The usage amount of the vinyl monomer and the living radical polymerization initiator may be appropriately adjusted according to the molecular weight or molecular weight distribution of the resulting living radical polymer, but is usually 1 mol of the living radical polymerization initiator represented by the formula (1). The vinyl monomer content is 10 to 10,000 mol, preferably 30 to 5,000 mol.
また、式（２）で表される化合物を使用する場合、通常、リビングラジカル重合開始剤１ｍｏｌに対して、式（２）で表される化合物を０.０５〜１０ｍｏｌ、好ましくは、０.１〜５ｍｏｌが良い。 Moreover, when using the compound represented by Formula (2), 0.05-10 mol of compounds normally represented by Formula (2) are preferable with respect to 1 mol of living radical polymerization initiators, Preferably, it is 0.1. ~ 5 mol is good.
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ノール、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、０.１〜１ｍｌ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, hexafluoroisopropanol, chloroform, carbon tetrachloride, Tetrahydrofuran (THF), ethyl acetate, trifluoromethylbenzene and the like can be mentioned.
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, 0.01 to 50 ml, preferably 0.05 to 10 ml, particularly preferably 0.1 to 1 ml of the solvent is used per 1 g of the vinyl monomer. good.
次に、上記混合物を攪拌する。光照射、反応温度、反応時間は、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。
光照射は、光照射するために用いられるランプ類としては、光波長３００〜７００ｎｍに発光分布を有するものが好適に用いられ、その例としては、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ブラックライトランプ、マイクロウェーブ励起水銀灯、メタルハライドランプ、キセノンランプ、クリプトンランプ、日光等が挙げられる。
Next, the mixture is stirred. Light irradiation, reaction temperature, and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the resulting living radical polymer.
In the light irradiation, lamps having a light emission distribution at a light wavelength of 300 to 700 nm are preferably used as lamps used for light irradiation. Examples thereof include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, and an ultrahigh pressure. Examples include mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, xenon lamps, krypton lamps, and sunlight.
また、照射する光源と、カットオフフィルターや減光フィルター、溶液フィルターを組み合わせることで、照射波長の領域を制御して行うこともできる。
式（１）で表される化合物を用いる場合は、３００〜６００ｎｍに発光分布を持つ光源を用いるのが良く、好ましくは３００〜５００ｎｍの領域に照射することが良い。また式（２）の式で表される化合物を用いる場合は、３００〜７００ｎｍに発光分布を持つ光源を用いるのが良く、好ましくは３００〜６００ｎｍの領域に照射することが良い。
反応温度は、３５℃以下が好ましい。特に好ましくは、０〜３５℃が良い。
反応時間は光の照射強度や照射波長により変化するため、特に制限はない。通常は１分〜１００時間程度で行うことができる。好ましくは、０.１〜３０時間が良い。更に好ましくは、０.１〜１５時間が良い。
このように低い重合温度及び短い重合時間であっても高い収率と精密な分子量分布を得ることができるのが、本発明の特徴である。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。
Further, the irradiation wavelength region can be controlled by combining a light source for irradiation, a cut-off filter, a neutral density filter, and a solution filter.
In the case of using the compound represented by the formula (1), a light source having a light emission distribution at 300 to 600 nm is preferably used, and preferably a region of 300 to 500 nm is irradiated. When the compound represented by the formula (2) is used, a light source having a light emission distribution in the range of 300 to 700 nm is preferably used, and the region of 300 to 600 nm is preferably irradiated.
The reaction temperature is preferably 35 ° C. or lower. Especially preferably, 0-35 degreeC is good.
The reaction time is not particularly limited because it varies depending on the light irradiation intensity and the irradiation wavelength. Usually, it can be performed in about 1 minute to 100 hours. Preferably, 0.1 to 30 hours are good. More preferably, 0.1 to 15 hours are good.
It is a feature of the present invention that a high yield and a precise molecular weight distribution can be obtained even at such a low polymerization temperature and a short polymerization time. At this time, the pressure is usually a normal pressure, but may be increased or decreased.
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のリビングラジカルポリマーを取り出したり、目的のリビングラジカル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 used or residual monomer is removed under reduced pressure by a conventional method to take out the target living radical polymer, or the target product is isolated by reprecipitation treatment using the target living radical polymer insoluble solvent. The reaction treatment can be performed by any treatment method as long as there is no problem with the object.
本発明においては、分子量分布（ＰＤＩ）２.５以下、好ましくは２.０以下、より好ましくは１.０１〜１.５、更に好ましくは１.０１〜１.３のリビングラジカルポリマーを得ることができる。 In the present invention, a living radical polymer having a molecular weight distribution (PDI) of 2.5 or less, preferably 2.0 or less, more preferably 1.01 to 1.5, and still more preferably 1.01 to 1.3 is obtained. Can do.
本発明のリビングラジカル重合開始剤を用いる場合、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；−ＴｅＲ１）であることが確認されている。従って、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。 When the living radical polymerization initiator of the present invention is used, it is confirmed that the growth terminal of the resulting living radical polymer is a highly reactive organic metal (organic tellurium; -TeR 1 ) derived from the living radical polymerization initiator. Yes. Therefore, the living radical polymer obtained in the present invention can be used as a macro living radical polymerization initiator (macro initiator).
また、該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。 Further, using the macro living radical polymerization initiator, for example, an AB diblock copolymer such as N-alkyl (meth) acrylamidoamide-styrene, styrene-N-alkyl (meth) acrylamide, etc. ABA triblock copolymers such as B-A diblock copolymer and N-alkyl (meth) acrylic acid amide-styrene-N-alkyl (meth) acrylic amide can be obtained.
一方、該リビングラジカルポリマーの分子末端に残存するテルル原子は、重合反応終了後、以下に示す方法を行うことで除去することができる。
例えば、トリブチルスタナンやチオール化合物などの用いるラジカル還元方法や、さらに活性炭、シリカゲル、活性アルミナ、活性白土、モレキュラーシーブスおよび高分子吸着剤なで吸着する方法、イオン交換樹脂などで金属を吸着させる方法や、また、過酸化水素水や過酸化ベンゾイル等の過酸化物を添加したり、空気や酸素を系中に吹き込むことでポリマー末端のテルル原子を酸化分解させ、水洗や適切な溶媒を組み合わせることにより残留テルル化合物を除去する液−液抽出法や固−液抽出法、特定の分子量以下のもののみを抽出除去する限外ろ過等の溶液状態での精製方法や、また、これらの方法を組み合わせることもできる。
On the other hand, tellurium atoms remaining at the molecular ends of the living radical polymer can be removed by the following method after completion of the polymerization reaction.
For example, radical reduction method using tributylstannane or thiol compound, method of adsorbing with activated carbon, silica gel, activated alumina, activated clay, molecular sieves and polymer adsorbent, method of adsorbing metal with ion exchange resin, etc. In addition, peroxide such as hydrogen peroxide or benzoyl peroxide is added, or air or oxygen is blown into the system to oxidize and decompose the tellurium atom at the end of the polymer, combined with water washing or an appropriate solvent. Liquid-liquid extraction method or solid-liquid extraction method that removes residual tellurium compounds by extraction, ultrafiltration that extracts and removes only those having a specific molecular weight or less, and a combination of these methods You can also.
以下、実施例により本発明をさらに具体的に説明するが、本発明はこれらの実施例によって何ら限定されるものではなく、その要旨を変更しない範囲において適宜変更可能である。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples, In the range which does not change the summary, it can change suitably.
実施例において、各種物性測定は以下の機器により測定を行った。
１Ｈ−ＮＭＲ：ブルカー・バイオスピン ＡＶＡＮＣＥ ５００（５００ＭＨｚ）
分子量及び分子量分布：ゲルパーミエーションクロマトグラフ 日本ウォーターズ ＧＰＣＶ−２０００（カラム：東ソー ＴＳＫ−ＧＥＬ ＧＭＨＸＬ ＋ ＴＳＫ−ＧＥＬ ＭｕｌｔｉｐｏｒｅＨＸＬ−Ｍ、ポリスチレンスタンダード：東ソーＴＳＫ Ｓｔａｎｄａｒｄ）
In the examples, various physical properties were measured with the following equipment.
1 H-NMR: Bruker BioSpin AVANCE 500 (500 MHz)
Molecular weight and molecular weight distribution: Gel permeation chromatograph Nippon Waters GPCV-2000 (column: Tosoh TSK-GEL GMH XL + TSK-GEL Multipore H XL- M, polystyrene standard: Tosoh TSK Standard)
合成例１
テルルパウダー（７.０２ｇ、５０ｍｍｏｌ）、ＴＨＦ ５０ｍＬの懸濁液にフェニルリチウム（５３.６ｍＬ、１.０３Ｍシクロヘキサン、ジエチルエーテル溶液、５５ｍｍｏｌ）を０℃で２５分かけてゆっくりと滴下し、生じた混合物を室温で１時間攪拌した。この溶液に、２−ブロモプロパン（４.６９ｍＬ、５０ｍｍｏｌ）を０℃で添加した後、反応溶液を室温で２時間攪拌した。使用前に０.５時間窒素バブリングで脱気した水を反応溶液に添加し、窒素雰囲気下で水層を分離した。脱気した飽和ＮＨ４Ｃｌ水溶液、飽和ＮａＣｌ水溶液で有機層を洗浄し、ＭｇＳＯ４で乾燥後、窒素雰囲気下でろ過を行った。溶媒を減圧下で留去し、目的のイソプロピルフェニルテルリドを蒸留精製により取得した（黄色油状液体、収量 ７.０９ｇ、収率５７％、ｂｐ．７５−７６℃／２.８ｍｍＨｇ）
Synthesis example 1
To a suspension of tellurium powder (7.02 g, 50 mmol) and THF 50 mL, phenyl lithium (53.6 mL, 1.03 M cyclohexane, diethyl ether solution, 55 mmol) was slowly added dropwise over 25 minutes at 0 ° C. The mixture was stirred at room temperature for 1 hour. To this solution was added 2-bromopropane (4.69 mL, 50 mmol) at 0 ° C., and then the reaction solution was stirred at room temperature for 2 hours. Before use, water deaerated by nitrogen bubbling for 0.5 hour was added to the reaction solution, and the aqueous layer was separated under a nitrogen atmosphere. The organic layer was washed with a degassed saturated NH 4 Cl aqueous solution and a saturated NaCl aqueous solution, dried over MgSO 4 , and filtered under a nitrogen atmosphere. The solvent was distilled off under reduced pressure, and the desired isopropylphenyl telluride was obtained by distillation purification (yellow oily liquid, yield 7.09 g, yield 57%, bp. 75-76 ° C./2.8 mmHg).
実施例１（光照射）
窒素雰囲気下、Ｐｙｒｅｘチューブ内で、アクリル酸ブチル（１.４３ｍＬ、１０.０ｍｍｏｌ）、合成例１で製造したイソプロピルフェニルテルリド（１５.４μＬ、０.１０ｍｍｏｌ）の溶液を５０℃で攪拌しながら、４７０ｎｍ以下の波長の光をフィルターでカットしながら、光照射を行った。反応終了後、転化率を１Ｈ ＮＭＲで、ＭｎとＰＤＩをＧＰＣで分析した。２時間後にモノマー転化率は９７％に達し、Ｍｎ＝１７,５００、ＰＤＩ＝１.７２のポリアクリル酸ブチルを取得した。
Example 1 (light irradiation)
While stirring a solution of butyl acrylate (1.43 mL, 10.0 mmol) and isopropyl phenyl telluride (15.4 μL, 0.10 mmol) prepared in Synthesis Example 1 at 50 ° C. in a Pyrex tube under a nitrogen atmosphere. Light irradiation was performed while cutting light having a wavelength of 470 nm or less with a filter. After completion of the reaction, the conversion was analyzed by 1 H NMR, and Mn and PDI were analyzed by GPC. After 2 hours, the monomer conversion reached 97%, and polybutyl acrylate having Mn = 17,500 and PDI = 1.72 was obtained.
実施例２（加熱）
窒素雰囲気下、Ｐｙｒｅｘチューブ内で、アクリル酸ブチル（１.４３ｍＬ、１０.０ｍｍｏｌ）、合成例１で製造したイソプロピルフェニルテルリド(１５.４μＬ、０.１０ｍｍｏｌ)の溶液を１００℃で攪拌した。反応終了後、転化率を１Ｈ ＮＭＲで、ＭｎとＰＤＩをＧＰＣで分析した。３５時間後にモノマー転化率は９５％に達し、Ｍｎ＝１５,５００、ＰＤＩ＝１.９６のポリアクリル酸ブチルを取得した。
Example 2 (heating)
Under a nitrogen atmosphere, a solution of butyl acrylate (1.43 mL, 10.0 mmol) and isopropylphenyl telluride (15.4 μL, 0.10 mmol) prepared in Synthesis Example 1 was stirred at 100 ° C. in a Pyrex tube. After completion of the reaction, the conversion was analyzed by 1 H NMR, and Mn and PDI were analyzed by GPC. After 35 hours, the monomer conversion reached 95%, and polybutyl acrylate having Mn = 15,000 and PDI = 1.96 was obtained.
実施例３（アゾ開始剤使用）
窒素雰囲気下、Ｐｙｒｅｘチューブ内で、アクリル酸ブチル（１.４３ｍＬ、１０.０ｍｍｏｌ）、合成例１で製造したイソプロピルフェニルテルリド(１５.４μＬ、０.１０ｍｍｏｌ)、ＡＩＢＮ（１.６４ｍｇ、０.０１ｍｍｏｌ）の溶液を６０℃で攪拌した。反応終了後、転化率を１Ｈ ＮＭＲで、ＭｎとＰＤＩをＧＰＣで分析した。２時間後にモノマー転化率は９６％に達し、Ｍｎ＝２１,５００、ＰＤＩ＝２.１９のポリアクリル酸ブチルを取得した。
Example 3 (using azo initiator)
In a Pyrex tube under a nitrogen atmosphere, butyl acrylate (1.43 mL, 10.0 mmol), isopropylphenyl telluride prepared in Synthesis Example 1 (15.4 μL, 0.10 mmol), AIBN (1.64 mg, 0.8 mmol). 01 mmol) was stirred at 60 ° C. After completion of the reaction, the conversion was analyzed by 1 H NMR, and Mn and PDI were analyzed by GPC. After 2 hours, the monomer conversion reached 96%, and polybutyl acrylate having Mn = 21,500 and PDI = 2.19 was obtained.
実施例４（光照射条件下、ジフェニルジテルリドを使用）
窒素雰囲気下、Ｐｙｒｅｘチューブ内で、アクリル酸ブチル（１.４３ｍＬ、１０.０ｍｍｏｌ）、合成例１で製造したイソプロピルフェニルテルリド(１５.４μＬ、０.１０ｍｍｏｌ)、ジフェニルジテルリド（４.１ｍｇ、０.０１ｍｍｏｌ）の溶液を５０℃で攪拌しながら、４７０ｎｍ以下の波長の光をフィルターでカットしながら、光照射を行った。反応終了後、転化率を１Ｈ ＮＭＲで、ＭｎとＰＤＩをＧＰＣで分析した。３時間後にモノマー転化率は９５％に達し、Ｍｎ＝１３,９００、ＰＤＩ＝１.２６のポリアクリル酸ブチルを取得した。
Example 4 (using diphenyl ditelluride under light irradiation conditions)
In a Pyrex tube under a nitrogen atmosphere, butyl acrylate (1.43 mL, 10.0 mmol), isopropylphenyl telluride (15.4 μL, 0.10 mmol) prepared in Synthesis Example 1, diphenyl ditelluride (4.1 mg) , 0.01 mmol) was stirred at 50 ° C., and light was irradiated while cutting light having a wavelength of 470 nm or less with a filter. After completion of the reaction, the conversion was analyzed by 1 H NMR, and Mn and PDI were analyzed by GPC. After 3 hours, the monomer conversion reached 95%, and polybutyl acrylate having Mn = 13,900 and PDI = 1.26 was obtained.
実施例５（加熱条件下、ジフェニルジテルリドを使用）
窒素雰囲気下、Ｐｙｒｅｘチューブ内で、アクリル酸ブチル（１.４３ｍＬ、１０.０ｍｍｏｌ）、合成例１で製造したイソプロピルフェニルテルリド(１５.４μＬ、０.１０ｍｍｏｌ)、ジフェニルジテルリド（４.１ｍｇ、０.０１ｍｍｏｌ）の溶液を１００℃で攪拌した。反応終了後、転化率を１Ｈ ＮＭＲで、ＭｎとＰＤＩをＧＰＣで分析した。４８時間後にモノマー転化率は９１％に達し、Ｍｎ＝１２,９００、ＰＤＩ＝１.２８のポリアクリル酸ブチルを取得した。
Example 5 (using diphenyl ditelluride under heating conditions)
In a Pyrex tube under a nitrogen atmosphere, butyl acrylate (1.43 mL, 10.0 mmol), isopropylphenyl telluride (15.4 μL, 0.10 mmol) prepared in Synthesis Example 1, diphenyl ditelluride (4.1 mg) , 0.01 mmol) was stirred at 100 ° C. After completion of the reaction, the conversion was analyzed by 1 H NMR, and Mn and PDI were analyzed by GPC. After 48 hours, the monomer conversion reached 91%, and polybutyl acrylate having Mn = 12,900 and PDI = 1.28 was obtained.
実施例６（アゾ開始剤及びジフェニルジテルリドを使用）
窒素雰囲気下、Ｐｙｒｅｘチューブ内で、アクリル酸ブチル（１.４３ｍＬ、１０.０ｍｍｏｌ）、合成例１で製造したイソプロピルフェニルテルリド(１５.４μＬ、０.１０ｍｍｏｌ)、ジフェニルジテルリド（４.１ｍｇ、０.０１ｍｍｏｌ）、ＡＩＢＮ（１.６４ｍｇ、０.０１ｍｍｏｌ）の溶液を６０℃で攪拌した。反応終了後、転化率を１Ｈ ＮＭＲで、ＭｎとＰＤＩをＧＰＣで分析した。２４時間後にモノマー転化率は９２％に達し、Ｍｎ＝１２,５００、ＰＤＩ＝１.２８のポリアクリル酸ブチルを取得した。
Example 6 (using azo initiator and diphenyl ditelluride)
In a Pyrex tube under a nitrogen atmosphere, butyl acrylate (1.43 mL, 10.0 mmol), isopropylphenyl telluride (15.4 μL, 0.10 mmol) prepared in Synthesis Example 1, diphenyl ditelluride (4.1 mg) , 0.01 mmol), a solution of AIBN (1.64 mg, 0.01 mmol) was stirred at 60 ° C. After completion of the reaction, the conversion was analyzed by 1 H NMR, and Mn and PDI were analyzed by GPC. After 24 hours, the monomer conversion reached 92%, and polybutyl acrylate having Mn = 12,500 and PDI = 1.28 was obtained.
実施例７（光照射条件下、ジフェニルジテルリドを使用）
窒素雰囲気下、Ｐｙｒｅｘチューブ内で、アクリル酸ブチル（１.４３ｍＬ、１０.０ｍｍｏｌ）、合成例１で製造したイソプロピルフェニルテルリド(１５.４μＬ、０.１０ｍｍｏｌ)、ジフェニルジテルリド（４１.０ｍｇ、０.１０ｍｍｏｌ）の溶液を５０℃で攪拌しながら、４７０ｎｍ以下の波長の光をフィルターでカットしながら、光照射を行った。反応終了後、転化率を１Ｈ ＮＭＲで、ＭｎとＰＤＩをＧＰＣで分析した。２３時間後にモノマー転化率は９３％に達し、Ｍｎ＝１３,４００、ＰＤＩ＝１.２１のポリアクリル酸ブチルを取得した。
Example 7 (using diphenyl ditelluride under light irradiation conditions)
In a Pyrex tube under a nitrogen atmosphere, butyl acrylate (1.43 mL, 10.0 mmol), isopropylphenyl telluride (15.4 μL, 0.10 mmol) prepared in Synthesis Example 1 and diphenyl ditelluride (41.0 mg) , 0.10 mmol) solution was stirred at 50 ° C., and light irradiation was performed while cutting light having a wavelength of 470 nm or less with a filter. After completion of the reaction, the conversion was analyzed by 1 H NMR, and Mn and PDI were analyzed by GPC. After 23 hours, the monomer conversion reached 93%, and polybutyl acrylate having Mn = 13,400 and PDI = 1.21 was obtained.
Claims (5)
（ａ）式（１）で表されるリビングラジカル重合開始剤、
（ｂ）式（１）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の混合物、
（ｃ）式（１）で表されるリビングラジカル重合開始剤と式（２）で表される有機ジテルリド化合物の混合物、又は
（ｄ）式（１）で表されるリビングラジカル重合開始剤、アゾ系重合開始剤及び式（２）で表される有機ジテルリド化合物の混合物
のいずれかを重合開始剤として用いて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。
（Ｒ１Ｔｅ）２ （２）
（式中、Ｒ１は、上記と同じ。） Vinyl monomer,
(A) a living radical polymerization initiator represented by formula (1),
(B) a mixture of a living radical polymerization initiator represented by formula (1) and an azo polymerization initiator,
(C) A mixture of a living radical polymerization initiator represented by formula (1) and an organic ditelluride compound represented by formula (2), or (d) a living radical polymerization initiator represented by formula (1), azo A method for producing a living radical polymer, wherein polymerization is carried out using any one of a mixture of a system polymerization initiator and an organic ditelluride compound represented by formula (2) as a polymerization initiator.
(R 1 Te) 2 (2)
(In the formula, R 1 is the same as above.)
The manufacturing method of the living radical polymer of Claim 2 which obtains the polymer of PDI = 1.01-1.3.
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| JP2012236984A (en) * | 2011-04-28 | 2012-12-06 | Kyoto Univ | Process for producing polymer, and polymer produced by the same |
| JP2017200961A (en) * | 2016-05-02 | 2017-11-09 | 国立大学法人京都大学 | Method for producing vinyl polymer and vinyl polymer |
| WO2018164147A1 (en) * | 2017-03-09 | 2018-09-13 | Ａｇｃ株式会社 | Method for producing polymer |
| WO2021049537A1 (en) * | 2019-09-10 | 2021-03-18 | 国立大学法人京都大学 | Three-dimensional control catalyst used in radical polymerization, polymer production method, and acrylic polymer |
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| JP2012236984A (en) * | 2011-04-28 | 2012-12-06 | Kyoto Univ | Process for producing polymer, and polymer produced by the same |
| JP2017200961A (en) * | 2016-05-02 | 2017-11-09 | 国立大学法人京都大学 | Method for producing vinyl polymer and vinyl polymer |
| WO2018164147A1 (en) * | 2017-03-09 | 2018-09-13 | Ａｇｃ株式会社 | Method for producing polymer |
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| WO2021049537A1 (en) * | 2019-09-10 | 2021-03-18 | 国立大学法人京都大学 | Three-dimensional control catalyst used in radical polymerization, polymer production method, and acrylic polymer |
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