JP2021017498A - Production method of polymer using disulfide compound - Google Patents
Production method of polymer using disulfide compound Download PDFInfo
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- JP2021017498A JP2021017498A JP2019133836A JP2019133836A JP2021017498A JP 2021017498 A JP2021017498 A JP 2021017498A JP 2019133836 A JP2019133836 A JP 2019133836A JP 2019133836 A JP2019133836 A JP 2019133836A JP 2021017498 A JP2021017498 A JP 2021017498A
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- -1 disulfide compound Chemical class 0.000 title claims abstract description 67
- 229920000642 polymer Polymers 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 44
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 35
- 239000003999 initiator Substances 0.000 claims abstract description 34
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 125000002947 alkylene group Chemical group 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 238000011282 treatment Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 125000003282 alkyl amino group Chemical group 0.000 claims description 5
- 125000004185 ester group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 229920005604 random copolymer Polymers 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000012987 RAFT agent Substances 0.000 abstract description 14
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 57
- 150000003254 radicals Chemical class 0.000 description 34
- 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 23
- 239000000203 mixture Substances 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000004817 gas chromatography Methods 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 238000005227 gel permeation chromatography Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- LWGLGSPYKZTZBM-UHFFFAOYSA-N benzenecarbonothioylsulfanyl benzenecarbodithioate Chemical compound C=1C=CC=CC=1C(=S)SSC(=S)C1=CC=CC=C1 LWGLGSPYKZTZBM-UHFFFAOYSA-N 0.000 description 6
- UUNRYKCXJSDLRD-UHFFFAOYSA-N dodecylsulfanyl-(dodecylsulfanylcarbothioyldisulfanyl)methanethione Chemical compound CCCCCCCCCCCCSC(=S)SSC(=S)SCCCCCCCCCCCC UUNRYKCXJSDLRD-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000007870 radical polymerization initiator Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012719 thermal polymerization Methods 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 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-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
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002019 disulfides Chemical class 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- YFTIOFHTBMRALM-UHFFFAOYSA-N ethene;formaldehyde Chemical compound C=C.O=C YFTIOFHTBMRALM-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 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
- 239000011259 mixed solution Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- KFJJYOKMAAQFHC-UHFFFAOYSA-N (4-methoxy-5,5-dimethylcyclohexa-1,3-dien-1-yl)-phenylmethanone Chemical compound C1C(C)(C)C(OC)=CC=C1C(=O)C1=CC=CC=C1 KFJJYOKMAAQFHC-UHFFFAOYSA-N 0.000 description 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- ONCICIKBSHQJTB-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]propan-1-one Chemical compound CCC(=O)C1=CC=C(N(C)C)C=C1 ONCICIKBSHQJTB-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 1
- GIMQKKFOOYOQGB-UHFFFAOYSA-N 2,2-diethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)(OCC)C(=O)C1=CC=CC=C1 GIMQKKFOOYOQGB-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- LZWVPGJPVCYAOC-UHFFFAOYSA-N 2,3-diphenylanthracene-9,10-dione Chemical compound C=1C=CC=CC=1C=1C=C2C(=O)C3=CC=CC=C3C(=O)C2=CC=1C1=CC=CC=C1 LZWVPGJPVCYAOC-UHFFFAOYSA-N 0.000 description 1
- DXUMYHZTYVPBEZ-UHFFFAOYSA-N 2,4,6-tris(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 DXUMYHZTYVPBEZ-UHFFFAOYSA-N 0.000 description 1
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-UHFFFAOYSA-N 0.000 description 1
- MFUCEQWAFQMGOR-UHFFFAOYSA-N 2,4-diethyl-9h-thioxanthene Chemical compound C1=CC=C2CC3=CC(CC)=CC(CC)=C3SC2=C1 MFUCEQWAFQMGOR-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- CCTFAOUOYLVUFG-UHFFFAOYSA-N 2-(1-amino-1-imino-2-methylpropan-2-yl)azo-2-methylpropanimidamide Chemical class NC(=N)C(C)(C)N=NC(C)(C)C(N)=N CCTFAOUOYLVUFG-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- 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 1
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Abstract
Description
本発明は、ジスルフィド化合物を用いる重合体の製造方法に関する。より詳しくは、特定のジスルフィド化合物をラジカル開始剤であらかじめ処理した後にモノマーを加えて重合する逐次仕込を用いることで、所望の分子量の重合体を得る製造方法に関する。 The present invention relates to a method for producing a polymer using a disulfide compound. More specifically, the present invention relates to a production method for obtaining a polymer having a desired molecular weight by using a sequential preparation in which a specific disulfide compound is previously treated with a radical initiator and then polymerized by adding a monomer.
ジスルフィド化合物は、可逆的付加開裂連鎖移動（ＲＡＦＴ）剤として利用できることが知られている（特許文献１、２）。ＲＡＦＴ剤を使用した重合方法は、リビング性のラジカル重合であり、数平均分子量および重量平均分子量の制御が容易で分子量分布の狭い重合体が得られるという特徴を示す。しかし、先行技術文献に記載されたジスルフィド化合物をＲＡＦＴ剤として使用した重合方法（ここでは一括仕込法と呼ぶ）では、モノマーとＲＡＦＴ剤との仕込モル比で決定される設計分子量、すなわち所望される分子量の約２倍の分子量の重合体が得られており、ジスルフィド化合物が重合制御剤として十分に機能していないという問題がある（非特許文献１）。 It is known that the disulfide compound can be used as a reversible addition cleavage chain transfer (RAFT) agent (Patent Documents 1 and 2). The polymerization method using a RAFT agent is a living radical polymerization, which is characterized in that the number average molecular weight and the weight average molecular weight can be easily controlled and a polymer having a narrow molecular weight distribution can be obtained. However, in the polymerization method using the disulfide compound described in the prior art document as a RAFT agent (referred to here as a batch charging method), the design molecular weight determined by the charged molar ratio of the monomer and the RAFT agent, that is, desired. A polymer having a molecular weight about twice the molecular weight has been obtained, and there is a problem that the disulfide compound does not sufficiently function as a polymerization control agent (Non-Patent Document 1).
本発明は、ジスルフィド化合物をＲＡＦＴ剤として使用する重合方法において、モノマーとＲＡＦＴ剤との仕込みモル比で決定される設計分子量、すなわち所望される分子量の重合体を得る製造方法を提供することを課題とする。 An object of the present invention is to provide a production method for obtaining a polymer having a design molecular weight determined by a charged molar ratio of a monomer and a RAFT agent, that is, a polymer having a desired molecular weight in a polymerization method using a disulfide compound as a RAFT agent. And.
本発明者らは、鋭意検討を行った結果、ジスルフィド化合物をラジカル開始剤であらかじめ処理したものを重合制御剤として使用する重合体の製造方法により、モノマーとＲＡＦＴ剤との仕込みモル比で決定される設計分子量、すなわち所望される分子量の重合体を得ることができることを見出し、本発明を完成したものである。 As a result of diligent studies, the present inventors have determined the molecular weight ratio of the monomer and the RAFT agent by a method for producing a polymer using a disulfide compound pretreated with a radical initiator as a polymerization control agent. The present invention has been completed by finding that a polymer having a design molecular weight, that is, a desired molecular weight can be obtained.
かくして、本発明によれば、一般式（１）：
で表されるジスルフィド化合物をラジカル開始剤であらかじめ溶媒中または無溶媒中で処理した後、その処理物に少なくとも１種のラジカル重合性単量体を加えてラジカル重合させる重合体の製造方法が提供される。
Thus, according to the present invention, the general formula (1):
Provided is a method for producing a polymer in which a disulfide compound represented by is treated with a radical initiator in advance in a solvent or in the absence of a solvent, and then at least one kind of radically polymerizable monomer is added to the treated product to carry out radical polymerization. Will be done.
また、本発明によれば、ラジカル重合性単量体１００質量部に対して、ジスルフィド化合物０．１〜５０質量部を、溶媒１〜２００質量部、温度−２０〜２００℃、処理時間０．１〜１００時間の条件でラジカル開始剤０．１〜５０質量部であらかじめ処理した後、その処理物に少なくとも１種のラジカル重合性単量体を加え、重合温度５〜２００℃、重合時間０．１〜１００時間の条件でラジカル重合させ、数平均分子量Ｍｎが５００〜１００万、重量平均分子量Ｍｗと数平均分子量Ｍｎの比（Ｍｗ／Ｍｎ）が１．０〜５．０で数平均分子量Ｍｎと設計分子量Ｍ（ｔｈ）の比（Ｍｎ／Ｍ（ｔｈ））が０．７〜１．３の重合体を得る前記の重合体の製造方法が提供される。 Further, according to the present invention, 0.1 to 50 parts by mass of the disulfide compound is added to 100 parts by mass of the radically polymerizable monomer, the solvent is 1 to 200 parts by mass, the temperature is 20 to 200 ° C., and the treatment time is 0. After pre-treatment with 0.1 to 50 parts by mass of a radical initiator under the conditions of 1 to 100 hours, at least one radically polymerizable monomer is added to the treated product, the polymerization temperature is 5 to 200 ° C., and the polymerization time is 0. After radical polymerization under the conditions of 1 to 100 hours, the number average molecular weight Mn is 5 to 1,000,000, the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw / Mn) is 1.0 to 5.0, and the number average molecular weight. Provided is a method for producing the above-mentioned polymer, which obtains a polymer having a ratio (Mn / M (th)) of Mn to a design molecular weight M (th) of 0.7 to 1.3.
また、本発明によれば、２種類以上のラジカル重合性単量体を用いてランダム共重合体、ブロック共重合体を得る前記の重合体の製造方法が提供される。 Further, according to the present invention, there is provided a method for producing the above-mentioned polymer, which obtains a random copolymer or a block copolymer using two or more kinds of radically polymerizable monomers.
本発明によれば、ジスルフィド化合物をラジカル開始剤であらかじめ処理した後にラジカル重合性単量体を重合させることにより、所望の分子量の重合体を提供することができる。 According to the present invention, a polymer having a desired molecular weight can be provided by pre-treating a disulfide compound with a radical initiator and then polymerizing a radically polymerizable monomer.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の製造方法は、次の、一般式（１）：
で表されるジスルフィド化合物をラジカル開始剤であらかじめ溶媒中または無溶媒中で処理した後、その処理物に少なくとも１種のラジカル重合性単量体を加えてラジカル重合させて重合体を製造することを特徴とする。
The production method of the present invention has the following general formula (1):
The disulfide compound represented by is treated with a radical initiator in a solvent or no solvent in advance, and then at least one kind of radically polymerizable monomer is added to the treated product and radically polymerized to produce a polymer. It is characterized by.
前記「ジスルフィド化合物をラジカル開始剤であらかじめ溶媒中または無溶媒中で処理した後、その処理物に少なくとも１種のラジカル重合性単量体を加えて重合させて」とは「ジスルフィド化合物とラジカル開始剤をあらかじめ溶媒中または無溶媒中で反応させ、続いて少なくとも１種のラジカル重合性単量体を加えて重合させて」と同じ意味である。 The phrase "a disulfide compound is previously treated with a radical initiator in a solvent or no solvent and then polymerized by adding at least one radically polymerizable monomer to the treated product" means "disulfide compound and radical initiation". The agent is reacted in advance in a solvent or in the absence of a solvent, and then at least one radically polymerizable monomer is added and polymerized. "
本発明における「芳香族炭化水素基」は１価の芳香族炭化水素基であり、その好適な例としては、次のものに限定されないが、フェニル、ナフチル、アントリル、フェナントリルなどが挙げられ、中でもフェニルがより好ましい。これらは適当な置換基（例えば、アルキル、アルコキシ、ハロゲンなど）で置換されてもよい。 The "aromatic hydrocarbon group" in the present invention is a monovalent aromatic hydrocarbon group, and suitable examples thereof include, but are not limited to, phenyl, naphthyl, anthryl, phenanthryl and the like, among others. Phenyl is more preferred. These may be substituted with suitable substituents (eg, alkyl, alkoxy, halogen, etc.).
本発明における「炭素数１〜２０の直鎖状または分枝鎖状のアルキレン基」の好適な例としては、メチレン、エチレン、トリメチレン、プロピレン、テトラメチレン、ペンタメチレン、ヘキサメチレン、ヘプタメチレン、オクタメチレン、ノナメチレン、デカメチレン、ウンデカメチレン、ドデカメチレン、トリデカメチレン、テトラデカメチレン、ペンタデカメチレン、ヘキサデカメチレン、ヘプタデカメチレン、オクタデカメチレン、ノナデカメチレン、イコサメチレン、エチルエチレン、ジメチルエチレンなどが挙げられ、中でもメチレン、エチレンおよびドデカメチレンがより好ましい。これらは適当な置換基（例えば、アルコキシ、ハロゲンなど）で置換されてもよい。 Preferable examples of the "linear or branched alkylene group having 1 to 20 carbon atoms" in the present invention are methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene and octa. Methylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecamethylene, nonadecamethylene, icosamethylene, ethylethylene, dimethylethylene, etc. Among them, methylene, ethylene and dodecamethylene are more preferable. These may be substituted with a suitable substituent (eg, alkoxy, halogen, etc.).
本発明で用いられる「可能な場合は酸素原子がアルキレン基の炭素結合の間に存在してもよい炭素数１〜２０の直鎖状または分枝鎖状のアルキレン基」の用語において、酸素原子がアルキレン基の炭素結合の間に存在する場合のアルキレン基の炭素数は２〜２０である。
したがって、「酸素原子がアルキレン基の炭素結合の間に存在する炭素する２〜２０の直鎖状または分枝鎖状のアルキレン基」の好適な例としては、次のものに限定されないが、ジエチレンオキシド、ジ（トリメチレン）オキシド、ジプロピレンオキシド、ジ（テトラメチレン）オキシド、ジ（ペンタメチレン）オキシド、ジ（ヘキサメチレン）オキシド、ジ（ヘプタメチレン）オキシド、ジ（オクタメチレン）オキシド、ジ（ノナメチレン）オキシド、ジ（デカメチレン）オキシド、エチレンメチレンオキシド、トリエチレンジオキシド、トリプロピレンジオキシド、トリ（トリメチレン）ジオキシド、テトラエチレントリオキシド、テトラプロピレントリオキシド、ペンタエチレンテトラオキシド、ヘキサエチレンペンタオキシドなどが挙げられ、中でもエチレンメチレンオキシドがより好ましい。これらは適当な置換基（例えば、アルコキシ、ハロゲンなど）で置換されてもよい。
In the term "linear or branched alkylene group having 1 to 20 carbon atoms in which an oxygen atom may be present between carbon bonds of the alkylene group when possible" used in the present invention, the oxygen atom. The alkylene group has 2 to 20 carbon atoms when is present between the carbon bonds of the alkylene group.
Therefore, suitable examples of "2 to 20 linear or branched alkylene groups in which an oxygen atom exists between carbon bonds of an alkylene group" are not limited to the following, but are limited to ethylene oxide. Ethylene oxide, di (trimethylene) oxide, dipropylene oxide, di (tetramethylene) oxide, di (pentamethylene) oxide, di (hexamethylene) oxide, di (heptamethylene) oxide, di (octamethylene) oxide, di (nonamethylene) ) Oxide, di (decamethylene) oxide, ethylene methylene oxide, triethylene dioxide, tripropylene dioxide, tri (trimethylene) dioxide, tetraethylene trioxide, tetrapropylene trioxide, pentaethylene tetraoxide, hexaethylene pentaoxide, etc. Among them, ethylene methylene oxide is more preferable. These may be substituted with a suitable substituent (eg, alkoxy, halogen, etc.).
本発明における「炭素数３〜１２の環状アルキレン基」の好適な例としては、次のものに限定されないが、シクロプロピレン、シクロブチレン、シクロペンチレン、シクロヘキシレン、シクロヘプタレン、デカヒドロナフチレンなどが挙げられ、これらは適当な置換基（例えば、アルコキシ、ハロゲンなど）で置換されてもよい。 Preferable examples of the "cyclic alkylene group having 3 to 12 carbon atoms" in the present invention are not limited to the following, but are limited to, but are not limited to, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptalene, and decahydronaphthylene. These may be substituted with suitable substituents (eg, alkoxy, halogen, etc.).
前記の適当な置換基におけるアルキルの好適な例としては、次のものに限定されないが、メチル、エチル、プロピル、イソプロピル、ブチル、ペンチル、ヘキシルなどの炭素数１〜６の直鎖状または分枝鎖状のアルキル基が挙げられる。 Suitable examples of alkyl in the above-mentioned suitable substituents are, but are not limited to, linear or branched with 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl and the like. Examples include chain alkyl groups.
前記の適当な置換基におけるアルコキシの好適な例としては、次のものに限定されないが、メトキシ、エトキシ、プロポキシ、イソプロポキシ、ブトキシ、ペンチルオキシ、ヘキシルオキシなどの炭素数１〜６の直鎖状または分枝鎖状のアルキルオキシ基が挙げられる。 Suitable examples of alkoxy in the above-mentioned suitable substituents are, but are not limited to, linear chains having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, and hexyloxy. Alternatively, a branched alkyloxy group can be mentioned.
前記の適当な置換基におけるハロゲンとしては、フッ素、塩素、臭素およびヨウ素が挙げられる。 Halogen in the suitable substituents mentioned above includes fluorine, chlorine, bromine and iodine.
本発明における「炭素数１〜２０の直鎖状または分枝鎖状のアルキル基」の好適な例としては、次のものに限定されないが、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシル、ノナデシル、イコシルなどの直鎖状アルキルおよびそれらの構造異性体である分枝鎖状アルキルが挙げられる。 Preferable examples of the "linear or branched alkyl group having 1 to 20 carbon atoms" in the present invention are not limited to the following, but are limited to methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl. , Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecil, icosyl and other linear alkyls and their structural isomers, branched chain alkyls.
本発明における「アルキルアミノ基」としては、炭素数１〜２０の直鎖状または分枝鎖状のアルキル基で一または二置換されたアミノ基が挙げられ、ここで、ジアルキルにおけるアルキルは同一または異なっていてもよい。
上記「アルキルアミノ基」の好適な例としては、次のものに限定されないが、メチルアミノ、エチルアミノ、プロピルアミノ、イソプロピルアミノ、ブチルアミノ、ペンチルアミノ、ネオペンチルアミノ、ヘキシルアミノ、ヘプチルアミノ、オクチルアミノ、ノニルアミノ、デシルアミノ、ジメチルアミノ、ジエチルアミノ、ジプロピルアミノ、ジイソプロピルアミノ、ジブチルアミノ、ジペンチルアミノ、ジネオペンチルアミノ、ジヘキシルアミノ、ジヘプチルアミノ、ジオクチルアミノ、ジノニルアミノ、ジデシルアミノ、エチルメチルアミノ、メチルプロピルアミノ、エチルプロピルアミノなどが挙げられ、中でもジエチルアミノがより好ましい。
Examples of the "alkylamino group" in the present invention include amino groups mono- or di-substituted with a linear or branched-chain alkyl group having 1 to 20 carbon atoms, wherein the alkyl in the dialkyl is the same or It may be different.
Preferable examples of the above "alkylamino group" are not limited to the following, but are limited to methylamino, ethylamino, propylamino, isopropylamino, butylamino, pentylamino, neopentylamino, hexylamino, heptylamino and octyl. Amino, nonylamino, decylamino, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, dipentylamino, dineopentylamino, dihexylamino, diheptylamino, dioctylamino, dinonylamino, didecylamino, ethylmethylamino, methylpropylamino , Ethylpropylamino and the like, with diethylamino being more preferred.
本発明における「エステル基」は−ＣＯＯＲ’で表され、ここで、Ｒ’は上記の炭素数１〜２０の直鎖状または分枝鎖状のアルキル基である。前記アルキル基において、メチル、エチル、プロピルおよびブチルが好ましく、ブチルがより好ましい。 The "ester group" in the present invention is represented by -COOR', where R'is the above-mentioned linear or branched alkyl group having 1 to 20 carbon atoms. Among the alkyl groups, methyl, ethyl, propyl and butyl are preferable, and butyl is more preferable.
本発明の重合体の製造方法において利用可能なラジカル重合性単量体としては、置換または非置換のスチレン、置換または非置換のアルキルアクリレート、置換または非置換のアルキルメタクリレート、アクリロニトリル、Ｎ−アルキルアルキルアミド、Ｎ−アルキルメタクリルアミド、Ｎ，Ｎ−ジアルキルアクリルアミド、Ｎ，Ｎ−ジアルキルメタクリルアミド、イソプレン、ブタジエン、エチレン、ビニルアセテートおよびこれらの組み合わせから選択することが可能である。 Examples of the radically polymerizable monomer that can be used in the method for producing a polymer of the present invention include substituted or unsubstituted styrene, substituted or unsubstituted alkyl acrylate, substituted or unsubstituted alkyl methacrylate, acrylonitrile, and N-alkylalkyl. It is possible to select from amide, N-alkylmethacrylamide, N, N-dialkylacrylamide, N, N-dialkylmethacrylamide, isoprene, butadiene, ethylene, vinyl acetate and combinations thereof.
ラジカル重合性単量体の詳細な例としては、メチルメタクリレート、エチルメタクリレート、プロピルメタクリレート（全ての異性体を含む）、ブチルメタクリレート（全ての異性体を含む）、２−エチルヘキシルメタクリレート、イソボルニルメタクリレート、メタクリル酸、ベンジルメタクリレート、フェニルメタクリレート、メタクリロニトリル、α−メチルスチレン、メチルアクリレート、エチルアクリレート、プロピルアクリレート（全ての異性体を含む）、ブチルアクリレート（全ての異性体を含む）、２−エチルヘキシルアクリレート、イソボルニルアクリレート、アクリル酸、ベンジルアクリレート、フェニルアクリレート、アクリロニトリル、スチレン、グリシジルメタクリレート、２−ヒドロキシエチルメタクリレート、ヒドロキシプロピルメタクリレート（全ての異性体を含む）、ヒドロキシブチルメタクリレート（全ての異性体を含む）、Ｎ，Ｎ−ジメチルアミノエチルメタクリレート、Ｎ，Ｎ−ジエチルアミノエチルメタクリレート、トリエチレングリコールメタクリレート、イタコン酸無水物、イタコン酸、グリシジルアクリレート、２−ヒドロキシエチルアクリレート、ヒドロキシプロピルアクリレート（全ての異性体を含む）、ヒドロキシブチルアクリレート（全ての異性体を含む）、Ｎ，Ｎ−ジメチルアミノエチルアクリレート、Ｎ，Ｎ−ジエチルアミノエチルアクリレート、トリエチレングリコールアクリレート、メタクリルアミド、Ｎ−メチルアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−ｔ−ブチルメタクリルアミド、Ｎ−ｎ−ブチルメタクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ−エチロールアクリルアミド、４−アクリルモルフォリン、ビニル安息香酸（全ての異性体を含む）、ジエチルアミノスチレン（全ての異性体を含む）、α−メチルビニル安息香酸（全ての異性体を含む）、ジエチルアミノα−メチルスチレン（全ての異性体を含む）、ｐ−ビニルベンゼンスルホン酸、ｐ−ビニルベンゼンスルホン酸ナトリウム塩、トリメトキシシリルプロピルメタクリレート、トリエトキシシリルプロピルメタクリレート、トリブトキシシリルプロピルメタクリレート、ジメトキシメチルシリルプロピルメタクリレート、ジエトキシメチルシリルプロピルメタクリレート、ジブトキシメチルシリルプロピルメタクリレート、ジイソプロポキシメチルシリルプロピルメタクリレート、ジメトキシシリルプロピルメタクリレート、ジエトキシシリルプロピルメタクリレート、ジブトキシシリルプロピルメタクリレート、ジイソプロポキシシリルプロピルメタクリレート、トリメトキシシリルプロピルアクリレート、トリエトキシシリルプロピルアクリレート、トリブトキシシリルプロピルアクリレート、ジイソプロポキシシリルプロピルアクリレート、マレイン無水物、Ｎ − フェニルマレイミド、Ｎ−ブチルマレイミド、ブタジエン、イソプレン、クロロプレン、エチレン、ビニルアセテート、およびこれらの組み合わせを挙げることができるが、これらに限定されるものではない。 Detailed examples of radically polymerizable monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate (including all isomers), butyl methacrylate (including all isomers), 2-ethylhexyl methacrylate, and isobornyl methacrylate. , Methacrylic acid, benzyl methacrylate, phenyl methacrylate, methacrylonitrile, α-methylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate (including all isomers), butyl acrylate (including all isomers), 2-ethylhexyl Acrylate, isobornyl acrylate, acrylic acid, benzyl acrylate, phenyl acrylate, acrylonitrile, styrene, glycidyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate (including all isomers), hydroxybutyl methacrylate (all isomers) Includes), N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, triethylene glycol methacrylate, itaconic acid anhydride, itaconic acid, glycidyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate (all isomers) Includes), hydroxybutyl acrylate (including all isomers), N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, triethylene glycol acrylate, methacrylicamide, N-methylacrylamide, N, N- Dimethylacrylamide, N-t-butylmethacrylate, Nn-butylmethacrylate, N-methylolacrylamide, N-ethylolacrylamide, 4-acrylic morpholine, vinyl benzoic acid (including all isomers), diethylaminostyrene (Includes all isomers), α-methylvinylbenzoic acid (including all isomers), diethylamino α-methylstyrene (including all isomers), p-vinylbenzenesulfonic acid, p-vinylbenzenesulfon Sodium acid salt, trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate, tributoxysilylpropyl methacrylate, dimethoxymethylsilylpropylmethacrylate, diethoxymethylsilylpropylmethacrylate, dibutoxymethylsilylpropylmethacrylate, diisopropoxymethylsilylpro Pill methacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropyl methacrylate, dibutoxysilylpropyl methacrylate, diisopropoxysilylpropyl methacrylate, trimethoxysilylpropyl acrylate, triethoxysilylpropyl acrylate, tributoxysilylpropyl acrylate, diisopropoxysilylpropyl Examples include, but are not limited to, acrylate, maleine anhydride, N-phenylmaleimide, N-butylmaleimide, butadiene, isoprene, chloroprene, ethylene, vinyl acetate, and combinations thereof.
本発明の重合体の製造方法において好ましいラジカル重合性単量体としては、置換または非置換のスチレン、置換または非置換のアルキルアクリレート、置換または非置換のアルキルメタクリレート、Ｎ−アルキルアクリルアミド、Ｎ−アルキルメタクリルアミド、Ｎ，Ｎ−ジアルキルアクリルアミド、Ｎ，Ｎ−ジアルキルメタクリルアミドおよびこれらの組み合わせから選択されるものが挙げられる。 Preferred radically polymerizable monomers in the method for producing a polymer of the present invention include substituted or unsubstituted styrene, substituted or unsubstituted alkyl acrylate, substituted or unsubstituted alkyl methacrylate, N-alkylacrylamide, and N-alkyl. Methacrylamide, N, N-dialkylacrylamide, N, N-dialkylmethacrylamide and those selected from combinations thereof can be mentioned.
本発明の重合体の製造方法では、ラジカル重合性単量体の種類や添加方法を制御することにより、単独重合体、ランダム共重合体、ブロック共重合体を生成することができる。 In the method for producing a polymer of the present invention, a homopolymer, a random copolymer, or a block copolymer can be produced by controlling the type and addition method of the radically polymerizable monomer.
本発明の重合体の製造方法では、更に溶媒を加えてもよい。重合に用いられる溶媒としては、アルコール類（エタノール、プロパノール、イソプロパノール、ブタノール、イソブタノールなどのアルキルアルコール類、エチレングリコール、プロピレングリコールなどのグリコール類など）、炭化水素類（ヘキサンなどの脂肪族炭化水素類、シクロヘキサンなどの脂環式炭化水素類、トルエン、キシレンなどの芳香族炭化水素類など）、ハロゲン化炭化水素類（塩化メチレン、クロロホルムなど）、エーテル類（ジメチルエーテル、ジエチルエーテルなどの鎖状エーテル類、ジオキサン、テトラヒドロフランなどの環状エーテル類など）、エステル類（酢酸メチル、酢酸エチル、酢酸ブチル、乳酸エチル、酪酸エチルなど）、ケトン類（アセトン、エチルメチルケトン、メチルイソブチルケトン、シクロヘキサノン、Ｎ−メチル−２−ピロリドンなど）、セロソルブ類（メチルセロソルブ、エチルセロソルブ、ブチルセロソルブなど）、カルビトール類（メチルカルビトール、エチルカルビトール、ブチルカルビトールなど）、プロピレングリコールモノアルキルエーテル類（プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノｎ−ブチルエーテルなど）、グリコールエーテルエステル類（エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルセロソルブアセテート、ブチルカルビトールアセテートなど）、アミド類（Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミドなど）、スルホキシド類（ジメチルスルホキシドなど）、ニトリル類（アセトニトリル、ベンゾニトリルなど）、Ｎ−メチルピロリドンなどの有機溶媒が挙げられる。有機溶媒は、単独または混合溶媒として使用できる。ジスルフィド化合物の溶解性の点からトルエン、酢酸エチル、テトラヒドロフランが好ましい。 In the method for producing a polymer of the present invention, a solvent may be further added. Examples of the solvent used for the polymerization include alcohols (alkyl alcohols such as ethanol, propanol, isopropanol, butanol, and isobutanol, glycols such as ethylene glycol and propylene glycol), hydrocarbons (aliphatic hydrocarbons such as hexane). , Alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene), halogenated hydrocarbons (methylene chloride, chloroform, etc.), ethers (chain ethers such as dimethyl ether, diethyl ether, etc.) , Dioxane, cyclic ethers such as tetrahydrofuran), esters (methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, ethyl butyrate, etc.), ketones (acetone, ethyl methyl ketone, methyl isobutyl ketone, cyclohexanone, N- Methyl-2-pyrrolidone, etc.), cellosolves (methylcellosolve, ethylserosolve, butylcellosolve, etc.), carbitols (methylcarbitol, ethylcarbitol, butylcarbitol, etc.), propylene glycol monoalkyl ethers (propylene glycol monomethyl ether, etc.) , Propropylene glycol monoethyl ether, propylene glycol mono n-butyl ether, etc.), Glycol ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, butyl carbitol acetate, etc.) , Amids (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), sulfoxides (dimethylsulfoxide, etc.), nitriles (acetritale, benzonitrile, etc.), organic solvents such as N-methylpyrrolidone. The organic solvent can be used alone or as a mixed solvent. Toluene, ethyl acetate and tetrahydrofuran are preferable from the viewpoint of solubility of the disulfide compound.
本発明の重合体の製造方法においてはラジカル開始剤を必須成分とする。
上記ラジカル開始剤としては特に制限はなく、各種のものを用いることができる。ラジカル開始剤は熱重合開始剤（熱ラジカル発生剤）であってもよく光重合開始剤（光ラジカル発生剤）であってもよい。
In the method for producing a polymer of the present invention, a radical initiator is an essential component.
The radical initiator is not particularly limited, and various types can be used. The radical initiator may be a thermal polymerization initiator (thermal radical generator) or a photopolymerization initiator (photoradical generator).
熱重合開始剤（熱ラジカル発生剤）としては、ジアルキルパーオキサイド類（ジ−ｔ−ブチルパーオキサイド、ジクミルパーオキサイドなど）、ジアシルパーオキサイド類［ジアルカノイルパーオキサイド（ラウロイルパーオキサイドなど）、ジアロイルパーオキサイド（ベンゾイルパーオキサイド、ベンゾイルトルイルパーオキサイド、トルイルパーオキサイドなど）など］、過酸エステル類［過酢酸ｔ−ブチル、ｔ−ブチルパーオキシオクトエート、ｔ−ブチルパーオキシベンゾエートなどの過カルボン酸アルキルエステルなど］、ケトンパーオキサイド類、パーオキシカーボネート類、パーオキシケタール類などの有機過酸化物；アゾニトリル化合物またはアゾ化合物［２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（イソブチロニトリル）、２，２’−アゾビス（２−メチルブチロニトリル）、２，２’−アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、ジメチル２，２’−アゾビス（２-メチルプロピオナート）、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）、４，４’−アゾビス（４−シアノバレリックアシッド）など］、アゾアミド化合物｛２，２’−アゾビス｛２−メチル−Ｎ−［１，１−ビス（ヒドロキシメチル）−２−ヒドロキシエチル］プロピオンアミド｝など｝、アゾアミジン化合物｛２，２’−アゾビス（２−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］二塩酸塩など｝、アゾアルカン化合物［２，２’−アゾビス（２，４，４−トリメチルペンタン）、４，４’−アゾビス（４−シアノペンタン酸）など］、オキシム骨格を有するアゾ化合物［２，２’−アゾビス（２−メチルプロピオンアミドオキシム）など］などのアゾ化合物などが含まれる。熱重合開始剤は、単独または２種以上組み合わせて使用してもよい。 Examples of the thermal polymerization initiator (thermal radical generator) include dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, etc.), diacyl peroxides [dia-alkanoyl peroxide (lauroyl peroxide, etc.), di Azobisisobuty (benzoyl peroxide, benzoyl toluyl peroxide, toluyl peroxide, etc.), etc.], peracid esters [t-butyl peracetate, t-butyl peroxyoctate, t-butyl peroxybenzoate, etc. Acid alkyl esters, etc.], organic peroxides such as ketone peroxides, peroxycarbonates, peroxyketals; azonitrile compounds or azo compounds [2,2'-azobis (2,4-dimethylvaleronitrile), 2, , 2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2, 2'-azobis (2-methylpropionate), 1,1'-azobis (cyclohexane-1-carbonitrile), 4,4'-azobis (4-cyanovaleric acid), etc.], azoamide compound {2 2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, etc.}, azobisin compound {2,2'-azobis (2-amidinopropane) dihydrochloride Salt, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, etc.}, azoalcan compound [2,2'-azobis (2,4,4-trimethylpentane), 4, 4'-azobis (4-cyanopentanoic acid) and the like], azo compounds having an oxime skeleton [2,2'-azobis (2-methylpropionamide oxime) and the like] and the like are included. The thermal polymerization initiator may be used alone or in combination of two or more.
光重合開始剤（光ラジカル発生剤）としては、例えば、ベンゾイン類（ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテルなどのベンゾインアルキルエーテル類など）；アセトフェノン類（アセトフェノン、ｐ−ジメチルアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、２，２−ジエトキシアセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、２−フェニル−２−ヒドロキシ−アセトフェノン、１，１−ジクロロアセトフェノン、１−ヒドロキシシクロヘキシルフェニルケトンなど）；プロピオフェノン類（ｐ−ジメチルアミノプロピオフェノン、２−ヒドロキシ−２−メチル−プロピオフェノン、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オンなど）；ブチリルフェノン類［１−［４−（２−ヒドロキシエトキシ）フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチル−プロパン−１−オンなど］；アミノアセトフェノン類［２−メチル−２−モルホリノ（４−チオメチルフェニル）プロパン−１−オン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタン−１−オン、２−ジメチルアミノ−２−メチル−１−フェニルプロパン−１−オン、２−ジエチルアミノ−２−メチル−１−フェニルプロパン−１−オン、２−メチル−２−モルホリノ−１−フェニルプロパン−１−オン、２−ジメチルアミノ−２−メチル−１−（４−メチルフェニル）プロパン−１−オン、１−（４−ブチルフェニル）−２−ジメチルアミノ−２−メチルプロパン−１−オン、２−ジメチルアミノ−１−（４−メトキシフェニル）−２−メチルプロパン−１−オン、２−ジメチルアミノ−２−メチル−１−（４−メチルチオフェニル）プロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−ジメチルアミノフェニル）−ブタン−１−オンなど］；ベンゾフェノン類（ベンゾフェノン、Ｎ，Ｎ’−ビス（ジメチルアミノ）ベンゾフェノン（ミヒラーズケトン）、３，３−ジメチル−４−メトキシベンゾフェノン、ベンジルなどのＮ，Ｎ’−ジアルキルアミノベンゾフェノンなど）；ケタール類（アセトフェノンジメチルケタール、ベンジルジメチルケタールなど）；チオキサンテン類（チオキサンテン、２−クロロチオキサンテン、２，４−ジエチルチオキサンテンなど）；アントラキノン類（２−エチルアントラキノン、１−クロロアントラキノン、１，２−ベンズアントラキノン、２，３−ジフェニルアントラキノンなど）；（チオ）キサントン類（チオキサントン、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２−クロロチオキサントン、２，４−ジイソプロピルチオキサントンなど）；アクリジン類（１，３−ビス−（９−アクリジニル）プロパン、１，７−ビス−（９−アクリジニル）ヘプタン、１，５−ビス−（９−アクリジニル）ペンタンなど）；トリアジン類（２，４，６−トリス（トリクロロメチル）−ｓ−トリアジン、２−（４−メトキシフェニル）−４，６−ビス（トリクロロメチル）−ｓ−トリアジン、２，４−ビス−トリクロロメチル−６−（３−ブロモ−４−メトキシ）スチリルフェニル−ｓ−トリアジンなど）；スルフィド類（ベンジルジフェニルスルフィドなど）；アシルホスフィンオキシド類（２，４，６−トリメチルベンゾイルジフェニルホスフィンオキシドなど）；チタノセン系光重合開始剤；オキシムエステル類などが例示できる。これらの光重合開始剤は、単独または２種以上組み合わせて使用できる。 Examples of the photopolymerization initiator (photoradical generator) include benzoins (benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin alkyl ethers such as benzoin isobutyl ether, etc.); acetophenones (acetophenone, p. -Dimethylacetophenone, 2-Hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone , 2-Phenyl-2-hydroxy-acetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, etc.); Propiophenones (p-dimethylaminopropiophenone, 2-hydroxy-2-methyl-propio) Phenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc.); Butyrylphenones [1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane- 1-one, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propane-1-one, etc.]; Aminoacetophenones [2-Methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) -butane-1-one, 2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropane- 1-one, 2-methyl-2-morpholino-1-phenylpropan-1-one, 2-dimethylamino-2-methyl-1- (4-methylphenyl) propan-1-one, 1- (4-butyl) Phenyl) -2-dimethylamino-2-methylpropan-1-one, 2-dimethylamino-1- (4-methoxyphenyl) -2-methylpropan-1-one, 2-dimethylamino-2-methyl-1 -(4-Methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-dimethylaminophenyl) -butane-1-one, etc.]; benzophenones (benzophenone, N, N'- Bis (dimethylamino) benzophenone (Mihilazuke) Tons), 3,3-dimethyl-4-methoxybenzophenone, N, N'-dialkylaminobenzophenone such as benzyl, etc.); Ketals (acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.); Thioxanthenes (thioxanthene, 2- Chlorothioxanthene, 2,4-diethylthioxanthene, etc.); Anthraquinones (2-ethylanthraquinone, 1-chloroanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, etc.); (Thio) xanthones (thioxanthone) , 2,4-Dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.); Sulfides (1,3-bis- (9-acridinyl) propane, 1,7-bis -(9-acrydinyl) heptane, 1,5-bis- (9-acrydinyl) pentane, etc.); Triazines (2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl)) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, etc.); Sulfides (benzyldiphenyl sulfide, etc.) Etc.); Acylphosphine oxides (2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc.); Titanosene-based photopolymerization initiators; Oxym esters and the like can be exemplified. These photopolymerization initiators can be used alone or in combination of two or more.
重合温度の点から２，２’−アゾビス（イソブチロニトリル）、ジメチル２，２’−アゾビス（２-メチルプロピオナート）、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）、４，４’−アゾビス（４−シアノバレリックアシッド）が好ましい。 From the point of view of polymerization temperature, 2,2'-azobis (isobutyronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 1,1'-azobis (cyclohexane-1-carbonitrile), 4 , 4'-azobis (4-cyanovaleric acid) is preferred.
本発明の組成物は、必要であれば、種々の添加剤を含んでいてもよい。添加剤としては、例えば、熱重合禁止剤（ヒドロキノン、ヒドロキノンモノエチルエーテルなど）、消泡剤、塗布性改良剤、増粘剤、滑剤、安定剤（抗酸化剤、熱安定剤、耐光安定剤など）、可塑剤、界面活性剤、溶解促進剤、着色剤、充填剤、帯電防止剤、シランカップリング剤、レベリング剤、分散剤、分散助剤などが例示できる。添加剤は単独または２種以上組み合わせてもよい。 The composition of the present invention may contain various additives, if necessary. Additives include, for example, thermal polymerization inhibitors (hydroquinone, hydroquinone monoethyl ether, etc.), defoamers, coatability improvers, thickeners, lubricants, stabilizers (antioxidants, heat stabilizers, light-resistant stabilizers). Etc.), plasticizers, surfactants, dissolution accelerators, colorants, fillers, antistatic agents, silane coupling agents, leveling agents, dispersants, dispersion aids and the like. Additives may be used alone or in combination of two or more.
本発明の製造方法である、前記式（１）のジスルフィド化合物をラジカル開始剤であらかじめ溶媒中または無溶媒中で処理した後、その処理物に少なくとも１種のラジカル重合性単量体を加えてラジカル重合させる重合体の製造方法の製造条件について説明する。
処理および重合は全て不活性ガス（例えば、窒素など）雰囲気下で行うのが好ましい。
The disulfide compound of the formula (1), which is the production method of the present invention, is previously treated with a radical initiator in a solvent or no solvent, and then at least one radically polymerizable monomer is added to the treated product. The production conditions of the method for producing a polymer to be radically polymerized will be described.
All treatments and polymerizations are preferably carried out in an atmosphere of an inert gas (eg, nitrogen).
前記ジスルフィド化合物をラジカル開始剤で処理する条件については以下のとおりである。
ジスルフィド化合物は、ラジカル重合性単量体１００質量部に対して、好ましくは０．１〜５０質量部、より好ましくは１〜１０質量部用いられる。
The conditions for treating the disulfide compound with a radical initiator are as follows.
The disulfide compound is preferably used in an amount of 0.1 to 50 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the radically polymerizable monomer.
溶媒を用いる場合は、溶媒は、ラジカル重合性単量体１００質量部に対して、好ましくは１〜２００質量部、より好ましくは３０〜１００質量部用いられる。ラジカル開始剤は、ラジカル重合性単量体１００質量部に対して、好ましくは０．１〜５０質量部、より好ましくは１〜５質量部用いられる。
なお、本処理においてラジカル開始剤は過剰に用いてもよい。その場合、過剰のラジカル開始剤は、本処理に続くラジカル重合性単量体との重合でラジカル重合開始剤として作用し得る。
When a solvent is used, the solvent is preferably 1 to 200 parts by mass, more preferably 30 to 100 parts by mass with respect to 100 parts by mass of the radically polymerizable monomer. The radical initiator is preferably used in an amount of 0.1 to 50 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the radically polymerizable monomer.
The radical initiator may be used in excess in this treatment. In that case, the excess radical initiator can act as a radical polymerization initiator in the polymerization with the radically polymerizable monomer following this treatment.
処理温度は、好ましくは−２０〜２００℃、より好ましくは５０〜９０℃である。
処理時間は、好ましくは０．１〜１００時間、より好ましくは１〜５時間である。
The treatment temperature is preferably -20 to 200 ° C, more preferably 50 to 90 ° C.
The treatment time is preferably 0.1 to 100 hours, more preferably 1 to 5 hours.
上記の処理に続く、少なくとも１種のラジカル重合性単量体を重合させる重合条件は以下のとおりである。
重合はラジカル重合開始剤を使用するのが好ましく、そのラジカル重合開始剤としては、前記のラジカル開始剤が挙げられる。
ラジカル重合開始剤はラジカル重合性単量体１００質量部に対して、好ましくは０．１〜１０質量部、より好ましくは０．４〜１質量部用いられる。
重合温度は、好ましくは５〜２００℃、より好ましくは５０〜１３０℃である。
重合時間は、好ましくは０．１〜１００時間、より好ましくは1〜２０時間である。
The polymerization conditions for polymerizing at least one radically polymerizable monomer following the above treatment are as follows.
It is preferable to use a radical polymerization initiator for the polymerization, and examples of the radical polymerization initiator include the above-mentioned radical polymerization initiator.
The radical polymerization initiator is preferably used in an amount of 0.1 to 10 parts by mass, more preferably 0.4 to 1 part by mass with respect to 100 parts by mass of the radically polymerizable monomer.
The polymerization temperature is preferably 5 to 200 ° C, more preferably 50 to 130 ° C.
The polymerization time is preferably 0.1 to 100 hours, more preferably 1 to 20 hours.
上記の重合方法により数平均分子量Ｍｎが５００〜１００万で、重量平均分子量Ｍｗと数平均分子量Ｍｎの比（Ｍｗ／Ｍｎ）が１．０〜５．０の重合体を得ることができる。 By the above polymerization method, a polymer having a number average molecular weight Mn of 5 to 1,000,000 and a ratio of weight average molecular weight Mw to number average molecular weight Mn (Mw / Mn) of 1.0 to 5.0 can be obtained.
本発明のジスルフィド化合物をラジカル開始剤であらかじめ処理した後、その処理物にラジカル重合性単量体を加えてラジカル重合させる方法は、従来のジスルフィド化合物、ラジカル開始剤およびラジカル重合性単量体を一括して加えて重合させる方法で得られる重合体の数平均分子量Ｍｎと設計分子量Ｍ（ｔｈ）の比［Ｍｎ／Ｍ（ｔｈ）］が１．７以上であるのに対して、その比を１．７未満、さらには１．５以下、特に０.７〜１．３とすることができる。
このことは、所望される分子量の重合体を得ることができることを意味している。
The method of subjecting the disulfide compound of the present invention with a radical initiator in advance and then adding a radically polymerizable monomer to the treated product for radical polymerization is a method of radically polymerizing a conventional disulfide compound, a radical initiator and a radically polymerizable monomer. The ratio [Mn / M (th)] of the number average molecular weight Mn of the polymer obtained by the method of adding and polymerizing all at once to the design molecular weight M (th) is 1.7 or more, whereas the ratio is calculated. It can be less than 1.7, more 1.5 or less, especially 0.7-1.3.
This means that a polymer having a desired molecular weight can be obtained.
なお、上記の所望される分子量の重合体を得ることができる理由としては、下記一般式（２）に示すようにジスルフィド化合物をラジカル開始剤で前もって処理するとラジカル開始剤から発生するラジカル（Ｉ・）はラジカル重合性単量体がないため、ジスルフィド化合物とのみ反応してＲＡＦＴ剤として働く化合物を２分子生成し、その後、２分子のＲＡＦＴ剤がラジカル重合性単量体（Ｍ）と反応して所望した設計分子量の重合体を得ることができるためと考えられる。 The reason why the above-mentioned polymer having the desired molecular weight can be obtained is that the radical (I.) generated from the radical initiator when the disulfide compound is previously treated with the radical initiator as shown in the following general formula (2). ) Does not have a radically polymerizable monomer, so it reacts only with the disulfide compound to produce two compounds that act as RAFT agents, and then two molecules of the RAFT agent react with the radically polymerizable monomer (M). This is considered to be because a polymer having a desired design molecular weight can be obtained.
これに対して、ジスルフィド化合物、ラジカル開始剤およびラジカル重合性単量体を一括して加えて重合させた場合は下記一般式（３）に示すように、ラジカル開始剤から発生するラジカル（Ｉ・）とラジカル重合性単量体（Ｍ）が反応した成長末端ラジカル（Ｐｎ・）がジスルフィド化合物と反応し、生成した化合物（ａ）はＲＡＦＴ剤として働くが、一方で生成したチオカルボニルチオラジカル（ｂ）はラジカル重合性単量体と反応してもＲＡＦＴ剤としては働かないため、結果的にジスルフィド化合物1分子からＲＡＦＴ剤として働く化合物としては１分子が生成するため、設計分子量の２倍の分子量をもつ重合体が生成すると考えられる。 On the other hand, when the disulfide compound, the radical initiator and the radical polymerizable monomer are collectively added and polymerized, the radical (I.) generated from the radical initiator is as shown in the following general formula (3). ) And the radically polymerizable monomer (M) react with the growing terminal radical (Pn.), Which reacts with the disulfide compound, and the produced compound (a) acts as a RAFT agent, while the generated thiocarbonylthio radical (Pn.) b) does not act as a RAFT agent even if it reacts with a radically polymerizable monomer, and as a result, one molecule is produced as a compound that acts as a RAFT agent from one molecule of the disulfide compound, which is twice the design molecular weight. It is considered that a polymer having a molecular weight is produced.
以下に合成例、実施例および比較例を示して本発明を詳細に説明するが、本発明はこれらの合成例、実施例および比較例に限定されるものではない。なお、各合成例、実施例および比較例における物性の測定に用いた装置は次のとおりである。 The present invention will be described in detail below with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these Synthesis Examples, Examples and Comparative Examples. The devices used for measuring the physical properties in each synthesis example, example and comparative example are as follows.
［分子量測定］
ゲルパーミエーションクロマトグラフ装置（ＬＣ−２０Ａ、島津製作所社製）を用いて、下記の条件よりポリスチレン換算による数平均分子量（Ｍｎ）及び重量平均分子量（Ｍｗ）を得た。また、得られた値から分子量分布（Ｍｗ／Ｍｎ）を算出した。
○測定条件
カラム：東ソー社製ＴＳＫｇｅｌ ＳｕｐｅｒＭｕｌｔｉｐｏｒｅＨＺ−Ｍ×１本
カラム温度：４０℃
溶離液：テトラヒドロフラン
検出器：ＲＩ
[Measurement of molecular weight]
Using a gel permeation chromatograph device (LC-20A, manufactured by Shimadzu Corporation), a polystyrene-equivalent number average molecular weight (Mn) and a weight average molecular weight (Mw) were obtained under the following conditions. Moreover, the molecular weight distribution (Mw / Mn) was calculated from the obtained values.
○ Measurement condition Column: Tosoh TSKgel Super Multipore HZ-M x 1 Column temperature: 40 ° C
Eluent: Tetrahydrofuran Detector: RI
［液体クロマトグラフィー（ＬＣ）測定］
液体クロマトグラフィー装置（ＧＬ−７４８０、ＧＬサイエンス社製）を用いて、下記の条件で測定した。
○測定条件
カラム：Ｉｎｅｒｔｓｉｌ ＯＤＳ−２
カラム温度：４０℃
溶離液：テトラヒドロフラン/アセトニトリル ２０／８０（ｖ／ｖ） １ｍｌ／分
検出器：ＵＶ、３００ｎｍ
[Liquid Chromatography (LC) Measurement]
The measurement was carried out under the following conditions using a liquid chromatography device (GL-7480, manufactured by GL Science Co., Ltd.).
○ Measurement condition column: Inertsil ODS-2
Column temperature: 40 ° C
Eluent: Tetrahydrofuran / Acetonitrile 20/80 (v / v) 1 ml / min Detector: UV, 300 nm
［ガスクロマトグラフィー（ＧＣ）測定］
ガスクロマトグラフィー装置（ＧＣ−２０１４、島津製作所社製）を用いて、下記の条件で測定した。
○測定条件
カラム：ＨＰ−1 １０ｍ 内径０．５３０ｍｍ 膜厚２．６５μｍ
オーブン：８０℃１分 １０℃／分 ３００℃ ５分
インジェクション温度：２８０℃
検出器：水素炎イオン化検出器
検出器温度：３００℃
[Gas chromatography (GC) measurement]
Measurement was performed under the following conditions using a gas chromatography device (GC-2014, manufactured by Shimadzu Corporation).
○ Measurement conditions Column: HP-1 10m Inner diameter 0.530mm Film thickness 2.65μm
Oven: 80 ° C for 1 minute 10 ° C / min 300 ° C for 5 minutes Injection temperature: 280 ° C
Detector: Hydrogen flame ionization detector Detector temperature: 300 ° C
［合成例１］
ビス（ｎ−ドデシルメルカプト−チオカルボニル）ジスルフィドの合成
Synthesis of bis (n-dodecyl mercapto-thiocarbonyl) disulfide
還流冷却管、温度計及び攪拌機を備えた１Ｌフラスコにｎ−ドデシルメルカプタン１０１ｇ、二硫化炭素４６ｇ、テトラヒドロフラン２００ｇを投入して反応液を調製した。そこに４８％水酸化カリウム水溶液５８ｇを滴下ロートにより滴下した。滴下中は内温４０℃以下になるように水バスで冷却した。滴下終了後、1時間撹拌し反応させた。そこにヨウ素６４ｇをテトラヒドロフラン２２ｇに溶解させた溶液を滴下した。この時も水バスで冷却し、内温４０℃以下になるように調整した。滴下終了後、１時間反応させた後、水１００ｇとトルエン１００ｇを加え分液した。さらに上層を２％亜硫酸ソーダ水８１ｇで洗浄した後に水８０ｇで二回の洗浄を行った。分液終了後、上層をエバポレーターによりトルエンを除去し、そこにメチルメタノール２５０ｇとトルエン６０ｇを加え５℃冷却下で４時間撹拌し、結晶を析出させた。析出した結晶をろ過し、３０℃以下減圧下で乾燥させることにより、標記のビス（ｎ−ドデシルメルカプト−チオカルボニル）ジスルフィドを１２７ｇ得た（収率９１％）。液体クロマトグラフィー分析より求めた純度は９７％であった。 A reaction solution was prepared by putting 101 g of n-dodecyl mercaptan, 46 g of carbon disulfide, and 200 g of tetrahydrofuran into a 1 L flask equipped with a reflux condenser, a thermometer, and a stirrer. 58 g of a 48% potassium hydroxide aqueous solution was added dropwise thereto with a dropping funnel. During the dropping, the mixture was cooled with a water bath so that the internal temperature was 40 ° C. or lower. After completion of the dropping, the mixture was stirred for 1 hour and reacted. A solution prepared by dissolving 64 g of iodine in 22 g of tetrahydrofuran was added dropwise thereto. At this time as well, the mixture was cooled with a water bath and adjusted so that the internal temperature was 40 ° C. or lower. After completion of the dropping, the reaction was carried out for 1 hour, and then 100 g of water and 100 g of toluene were added to separate the liquids. Further, the upper layer was washed with 81 g of 2% sodium sulfite water, and then washed twice with 80 g of water. After completion of the liquid separation, toluene was removed from the upper layer by an evaporator, 250 g of methylmethanol and 60 g of toluene were added thereto, and the mixture was stirred under cooling at 5 ° C. for 4 hours to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure at 30 ° C. or lower to obtain 127 g of the title bis (n-dodecyl mercapto-thiocarbonyl) disulfide (yield 91%). The purity determined by liquid chromatography analysis was 97%.
［合成例２］ビス（チオベンゾイル）ジスルフィドの合成
還流冷却管、温度計、窒素封入管及び攪拌機を備えた１Ｌフラスコにマグネシウム４．９ｇを投入し、窒素雰囲気下でフェニルブロマイド３１ｇとテトラヒドロフラン１４０ｇの混液を滴下ロートで滴下した。この時、水バスまたは空冷で内温４０〜５０℃に調整した。滴下終了後、２時間撹拌し反応させた。そこに二硫化炭素１５ｇとテトラヒドロフラン１０ｇの混液を滴下した。この時、水バスで冷却し、内温４０℃以下になるように調整した。１時間撹拌して反応させた後、ヨウ素２５ｇをテトラヒドロフラン３５ｇに溶解させた溶液を滴下した。１時間撹拌して反応させた後、水１２０ｇとトルエン１１５ｇを加えて分液した。上層を水１２０ｇで洗浄し、５％亜硫酸ソーダ１００ｇで二回洗浄し、水１００ｇで二回洗浄した。上層からエバポレーターでトルエンを除去し、酢酸エチル４７ｇを加え５℃に冷却することにより結晶を析出させた。析出した結晶をろ過し、３０℃で減圧乾燥することにより標記のビス（チオベンゾイル）ジスルフィド２１ｇを得た（収率６９％）。液体クロマトグラフィー分析により求めた純度は８５％であった。 4.9 g of magnesium was put into a 1 L flask equipped with a reflux condenser, a thermometer, a nitrogen-filled tube and a stirrer, and a mixed solution of 31 g of phenyl bromide and 140 g of tetrahydrofuran was added dropwise with a dropping funnel under a nitrogen atmosphere. At this time, the internal temperature was adjusted to 40 to 50 ° C. by a water bath or air cooling. After completion of the dropping, the mixture was stirred for 2 hours and reacted. A mixed solution of 15 g of carbon disulfide and 10 g of tetrahydrofuran was added dropwise thereto. At this time, it was cooled by a water bath and adjusted so that the internal temperature was 40 ° C. or lower. After stirring for 1 hour and reacting, a solution prepared by dissolving 25 g of iodine in 35 g of tetrahydrofuran was added dropwise. After stirring for 1 hour and reacting, 120 g of water and 115 g of toluene were added to separate the liquids. The upper layer was washed with 120 g of water, twice with 100 g of 5% sodium sulfite, and twice with 100 g of water. Toluene was removed from the upper layer with an evaporator, 47 g of ethyl acetate was added, and the mixture was cooled to 5 ° C. to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure at 30 ° C. to obtain 21 g of the title bis (thiobenzoyl) disulfide (yield 69%). The purity determined by liquid chromatography analysis was 85%.
［実施例１］
還流冷却管、温度計、窒素導入管及び攪拌機を備えた２００ｍｌのフラスコを窒素置換し、これに、ジスルフィド化合物としてビス（ｎ−ドデシルメルカプト−チオカルボニル）ジスルフィド４．３質量部とトルエン５０質量部とアゾビスイソブチロニトリル１．５質量部とを収容して、９０℃で２時間反応させた後、その反応液に重合成分としてアクリル酸ブチル１００質量部とラジカル開始剤としてアゾビスイソブチロニトリル０．４質量部、トルエン５０質量部を加えラジカル重合用組成物を得た。次いで、窒素気流下に、攪拌しながら、上記重合用組成物が収容されたフラスコをオイルバスを用いて、７５℃で２時間加熱し、ラジカル重合を行った。重合反応終了後、室温に戻し分析を行った。ガスクロマトグラフィー（ＧＣ）により求めたアクリル酸ブチルの転化率は９４％、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により求めた数平均分子量（Ｍｎ）は７，７００、分散度（Ｍｗ／Ｍｎ）は１．０８であった。
[Example 1]
A 200 ml flask equipped with a reflux cooling tube, a thermometer, a nitrogen introduction tube and a stirrer was replaced with nitrogen, and 4.3 parts by mass of bis (n-dodecyl mercapto-thiocarbonyl) disulfide and 50 parts by mass of toluene were added as disulfide compounds. And 1.5 parts by mass of azobisisobutyronitrile and reacted at 90 ° C. for 2 hours, and then 100 parts by mass of butyl acrylate as a polymerization component and azobisisobuty as a radical initiator are added to the reaction solution. 0.4 parts by mass of bnitrile and 50 parts by mass of toluene were added to obtain a composition for radical polymerization. Next, the flask containing the above-mentioned polymerization composition was heated at 75 ° C. for 2 hours using an oil bath while stirring under a nitrogen stream to carry out radical polymerization. After completion of the polymerization reaction, the temperature was returned to room temperature for analysis. The conversion rate of butyl acrylate determined by gas chromatography (GC) is 94%, the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) is 7,700, and the dispersity (Mw / Mn) is 1. It was .08.
［実施例２］
実施例１と同様にビス（ｎ−ドデシルメルカプト−チオカルボニル）ジスルフィド５．６質量部、トルエン５０質量部、アゾビスイソブチロニトリル２質量部からなる組成物を９０℃で２時間反応させた後、その反応液にメタクリル酸メチル１００質量部、アゾビスイソブチロニトリル０．５質量部、トルエン５０質量部を加えラジカル重合用組成物とした。それを７５℃で６時間加熱し、ラジカル重合を行った。重合反応終了後、室温に戻し分析を行った。ＧＣにより求めたメタクリル酸メチルの転化率は８４％、ＧＰＣにより求めたＭｎは５，６００、Ｍｗ／Ｍｎは１．１８であった。
[Example 2]
A composition consisting of 5.6 parts by mass of bis (n-dodecyl mercapto-thiocarbonyl) disulfide, 50 parts by mass of toluene, and 2 parts by mass of azobisisobutyronitrile was reacted at 90 ° C. for 2 hours in the same manner as in Example 1. After that, 100 parts by mass of methyl methacrylate, 0.5 parts by mass of azobisisobutyronitrile, and 50 parts by mass of toluene were added to the reaction solution to prepare a composition for radical polymerization. It was heated at 75 ° C. for 6 hours for radical polymerization. After completion of the polymerization reaction, the temperature was returned to room temperature for analysis. The conversion rate of methyl methacrylate determined by GC was 84%, Mn determined by GPC was 5,600, and Mw / Mn was 1.18.
［実施例３］
実施例１と同様にビス（チオベンゾイル）ジスルフィド３．１質量部、トルエン５０質量部、アゾビスイソブチロニトリル２質量部を９０℃で２時間反応させた後、その反応液にメタクリル酸メチル１００質量部、アゾビスイソブチロニトリル０．５質量部、トルエン５０質量部を加えラジカル重合用組成物とした。それを７５℃で９時間加熱し、ラジカル重合を行った。重合反応終了後、室温に戻し分析を行った。ＧＣにより求めたメタクリル酸メチルの転化率は８５％、ＧＰＣにより求めたＭｎは５，１００、Ｍｗ／Ｍｎは１．１４であった。
[Example 3]
Similar to Example 1, 3.1 parts by mass of bis (thiobenzoyl) disulfide, 50 parts by mass of toluene, and 2 parts by mass of azobisisobutyronitrile were reacted at 90 ° C. for 2 hours, and then methyl methacrylate was added to the reaction solution. 100 parts by mass, 0.5 parts by mass of azobisisobutyronitrile, and 50 parts by mass of toluene were added to prepare a composition for radical polymerization. It was heated at 75 ° C. for 9 hours for radical polymerization. After completion of the polymerization reaction, the temperature was returned to room temperature for analysis. The conversion rate of methyl methacrylate determined by GC was 85%, Mn determined by GPC was 5,100, and Mw / Mn was 1.14.
［実施例４］
実施例1と同様にビス（チオベンゾイル）ジスルフィド２．４質量部、トルエン５０質量部、アゾビスイソブチロニトリル１．５質量部を９０℃で２時間反応させた後、その反応液にアクリル酸ブチル１００質量部、アゾビスイソブチロニトリル０．４質量部、トルエン５０質量部を加えラジカル重合用組成物とした。それを７５℃で２０時間加熱し、ラジカル重合を行った。重合反応終了後、室温に戻し分析を行った。ＧＣにより求めたアクリル酸ブチルの転化率は８８％、ＧＰＣにより求めたＭｎは６，７００、Ｍｗ／Ｍｎは１．１５であった。
[Example 4]
Similar to Example 1, 2.4 parts by mass of bis (thiobenzoyl) disulfide, 50 parts by mass of toluene, and 1.5 parts by mass of azobisisobutyronitrile were reacted at 90 ° C. for 2 hours, and then acrylic was added to the reaction solution. 100 parts by mass of butyl acid, 0.4 parts by mass of azobisisobutyronitrile, and 50 parts by mass of toluene were added to prepare a composition for radical polymerization. It was heated at 75 ° C. for 20 hours for radical polymerization. After completion of the polymerization reaction, the temperature was returned to room temperature for analysis. The conversion rate of butyl acrylate determined by GC was 88%, Mn determined by GPC was 6,700, and Mw / Mn was 1.15.
［比較例１］
還流冷却管、温度計、窒素導入管及び攪拌機を備えた２００ｍｌのフラスコを窒素置換し、これに、ジスルフィド化合物としてビス（ｎ−ドデシルメルカプト−チオカルボニル）ジスルフィド４．３質量部と、重合溶媒としてトルエン１００質量部と、重合成分としてアクリル酸ブチル１００質量部とラジカル開始剤としてアゾビスイソブチロニトリル０．４質量部を収容して、ラジカル重合用組成物を得た。次いで、窒素気流下に、攪拌しながら、上記重合用組成物が収容されたフラスコをオイルバスを用いて、７５℃で４時間加熱し、ラジカル重合を行った。重合反応終了後、室温に戻し分析を行った。ＧＣにより求めたアクリル酸ブチルの転化率は９４％、ＧＰＣにより求めたＭｎは１７，２００、Ｍｗ／Ｍｎは１．１５であった。
[Comparative Example 1]
A 200 ml flask equipped with a reflux cooling tube, a thermometer, a nitrogen introduction tube and a stirrer was replaced with nitrogen, and 4.3 parts by mass of bis (n-dodecyl mercapto-thiocarbonyl) disulfide as a disulfide compound was added as a polymerization solvent. A composition for radical polymerization was obtained by accommodating 100 parts by mass of toluene, 100 parts by mass of butyl acrylate as a polymerization component, and 0.4 parts by mass of azobisisobutyronitrile as a radical initiator. Next, the flask containing the above-mentioned polymerization composition was heated at 75 ° C. for 4 hours using an oil bath while stirring under a nitrogen stream to carry out radical polymerization. After completion of the polymerization reaction, the temperature was returned to room temperature for analysis. The conversion rate of butyl acrylate determined by GC was 94%, Mn determined by GPC was 17,200, and Mw / Mn was 1.15.
［比較例２］
比較例１と同様にビス（ｎ−ドデシルメルカプト−チオカルボニル）ジスルフィド５．５質量部、トルエン１００質量部、メタクリル酸メチル１００質量部、アゾビスイソブチロニトリル０．５質量部からなるラジカル重合用組成物を７５℃で６時間加熱し、ラジカル重合を行った。重合反応終了後、室温に戻し分析を行った。ＧＣにより求めたメタクリル酸メチルの転化率は９０％、ＧＰＣにより求めたＭｎは９，５００、Ｍｗ／Ｍｎは１．１１であった。
[Comparative Example 2]
Similar to Comparative Example 1, radical polymerization consisting of 5.5 parts by mass of bis (n-dodecyl mercapto-thiocarbonyl) disulfide, 100 parts by mass of toluene, 100 parts by mass of methyl methacrylate, and 0.5 parts by mass of azobisisobutyronitrile. The composition for use was heated at 75 ° C. for 6 hours to carry out radical polymerization. After completion of the polymerization reaction, the temperature was returned to room temperature for analysis. The conversion rate of methyl methacrylate determined by GC was 90%, Mn determined by GPC was 9,500, and Mw / Mn was 1.11.
［比較例３］
比較例１と同様にビス（チオベンゾイル）ジスルフィド３．１質量部、トルエン１００質量部、メタクリル酸メチル１００質量部、アゾビスイソブチロニトリル１．３質量部からなるラジカル重合用組成物を７５℃で９時間加熱し、ラジカル重合を行った。重合反応終了後、室温に戻し分析を行った。ＧＣにより求めたメタクリル酸メチルの転化率は８３％、ＧＰＣにより求めたＭｎは７，６００、Ｍｗ／Ｍｎは１．３０であった。
[Comparative Example 3]
Similar to Comparative Example 1, a composition for radical polymerization consisting of 3.1 parts by mass of bis (thiobenzoyl) disulfide, 100 parts by mass of toluene, 100 parts by mass of methyl methacrylate, and 1.3 parts by mass of azobisisobutyronitrile was prepared. Radical polymerization was carried out by heating at ° C. for 9 hours. After completion of the polymerization reaction, the temperature was returned to room temperature for analysis. The conversion rate of methyl methacrylate determined by GC was 83%, Mn determined by GPC was 7,600, and Mw / Mn was 1.30.
［比較例４］
比較例１と同様にビス（チオベンゾイル）ジスルフィド２．４質量部、トルエン１００質量部、アクリル酸ブチル１００質量部、アゾビスイソブチロニトリル１．６質量部からなるラジカル重合用組成物を７５℃で２０時間加熱し、ラジカル重合を行った。重合反応終了後、室温に戻し分析を行った。ＧＣにより求めたアクリル酸ブチルの転化率は９０％、ＧＰＣにより求めたＭｎは１１，５００、Ｍｗ／Ｍｎは１．２３であった。
[Comparative Example 4]
Similar to Comparative Example 1, a radical polymerization composition consisting of 2.4 parts by mass of bis (thiobenzoyl) disulfide, 100 parts by mass of toluene, 100 parts by mass of butyl acrylate, and 1.6 parts by mass of azobisisobutyronitrile was prepared. Radical polymerization was carried out by heating at ° C. for 20 hours. After completion of the polymerization reaction, the temperature was returned to room temperature for analysis. The conversion rate of butyl acrylate determined by GC was 90%, Mn determined by GPC was 11,500, and Mw / Mn was 1.23.
上記実施例と比較例の重合組成物の配合処方と重合結果を以下の表１にまとめた。
＊設計分子量Ｍ（ｔｈ）とは［（ラジカル重合性単量体とジスルフィド化合物との仕込モル比）×（ラジカル重合性単量体の分子量）×０．５×（モノマー転化率）］＋（実効ＲＡＦＴ剤の分子量）より計算される値である。
§Ｍｎ／Ｍ（ｔｈ）とはＧＰＣ測定より求められた数平均分子量Ｍｎと設計分子量Ｍ（ｔｈ）との比である。
The compounding formulations and polymerization results of the polymerization compositions of the above Examples and Comparative Examples are summarized in Table 1 below.
* The design molecular weight M (th) is [(molar ratio of radically polymerizable monomer to disulfide compound) x (molecular weight of radically polymerizable monomer) x 0.5 x (monomer conversion rate)] + ( It is a value calculated from the molecular weight of the effective RAFT agent).
§ Mn / M (th) is the ratio of the number average molecular weight Mn obtained by GPC measurement to the design molecular weight M (th).
表１の結果は、ジスルフィド化合物とラジカル開始剤とモノマーを逐次反応させた実施例１〜４では、数平均分子量Ｍｎと設計分子量Ｍ（ｔｈ）がほぼ同じ値で、その比［Ｍｎ／Ｍ（ｔｈ）］は１．１〜１．２であった。それに対して、ジスルフィド化合物、ラジカル開始剤、モノマーを一括反応した比較例１〜４ではＭｎ／Ｍ（ｔｈ）が１．７〜２．７であり、所望した分子量よりも２〜３倍の分子量をもつ重合体が得られた。すなわち、比較例の一括仕込反応の重合法ではジスルフィド化合物の半分がＲＡＦＴ剤として機能していないことを示している。 The results in Table 1 show that in Examples 1 to 4 in which the disulfide compound, the radical initiator, and the monomer were sequentially reacted, the number average molecular weight Mn and the design molecular weight M (th) were almost the same, and the ratio [Mn / M ( th)] was 1.1 to 1.2. On the other hand, in Comparative Examples 1 to 4 in which the disulfide compound, the radical initiator, and the monomer were collectively reacted, the Mn / M (th) was 1.7 to 2.7, which was 2 to 3 times the desired molecular weight. A polymer having the above was obtained. That is, it is shown that half of the disulfide compounds do not function as RAFT agents in the polymerization method of the batch charging reaction of the comparative example.
本発明のポリマーの製造方法は、メタクリレート、アクリレート、スチレンなどのラジカル重合性モノマーのフリーラジカル重合の分野で幅広く適用することができる。例えば、保護シート用粘着剤などの粘着剤分野または、フォトレジスト用ポリマーやシーラントとして好適に用いることができる。更に、ブロック、星形ポリマー、及び分岐ポリマー等は、熱可塑性エラストマー、塗料用顔料分散剤、レオロジー調整剤等として使用することができる。 The method for producing a polymer of the present invention can be widely applied in the field of free radical polymerization of radically polymerizable monomers such as methacrylate, acrylate, and styrene. For example, it can be suitably used in the field of adhesives such as adhesives for protective sheets, or as polymers and sealants for photoresists. Further, blocks, star-shaped polymers, branched polymers and the like can be used as thermoplastic elastomers, pigment dispersants for paints, rheology adjusters and the like.
Claims (3)
で表されるジスルフィド化合物をラジカル開始剤であらかじめ溶媒中または無溶媒中で処理した後、その処理物に少なくとも１種のラジカル重合性単量体を加えてラジカル重合させる重合体の製造方法。 The following general formula (1):
A method for producing a polymer, in which a disulfide compound represented by (1) is previously treated with a radical initiator in a solvent or no solvent, and then at least one radically polymerizable monomer is added to the treated product to carry out radical polymerization.
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| JP2009069547A (en) * | 2007-09-14 | 2009-04-02 | Jsr Corp | Radiation-sensitive resin composition for colored layer formation and color filter |
| JP2010120977A (en) * | 2008-11-17 | 2010-06-03 | Jsr Corp | Curable resin composition for forming protection film, protection film and method for forming protection film |
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