JP5890324B2 - Process for producing carboxyl group-containing polymer - Google Patents
Process for producing carboxyl group-containing polymer Download PDFInfo
- Publication number
- JP5890324B2 JP5890324B2 JP2012554622A JP2012554622A JP5890324B2 JP 5890324 B2 JP5890324 B2 JP 5890324B2 JP 2012554622 A JP2012554622 A JP 2012554622A JP 2012554622 A JP2012554622 A JP 2012554622A JP 5890324 B2 JP5890324 B2 JP 5890324B2
- Authority
- JP
- Japan
- Prior art keywords
- carboxyl group
- meth
- producing
- containing polymer
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims description 57
- 229920000642 polymer Polymers 0.000 title claims description 44
- 238000000034 method Methods 0.000 title claims description 29
- 239000000178 monomer Substances 0.000 claims description 67
- 229920002554 vinyl polymer Polymers 0.000 claims description 55
- -1 sulfonyl halide compound Chemical class 0.000 claims description 54
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 39
- 238000004519 manufacturing process Methods 0.000 claims description 28
- 238000010526 radical polymerization reaction Methods 0.000 claims description 20
- 150000003624 transition metals Chemical class 0.000 claims description 18
- 229910052723 transition metal Inorganic materials 0.000 claims description 17
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims description 16
- 239000003505 polymerization initiator Substances 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 150000001412 amines Chemical class 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 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 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003729 cation exchange resin Substances 0.000 claims description 8
- 150000004820 halides Chemical class 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 150000004699 copper complex Chemical group 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 56
- 238000006116 polymerization reaction Methods 0.000 description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- 239000000126 substance Substances 0.000 description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- BOWQDFRKKXVCCI-UHFFFAOYSA-N butyl 2-bromo-2-methylpropanoate Chemical compound CCCCOC(=O)C(C)(C)Br BOWQDFRKKXVCCI-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 3
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229920001429 chelating resin Polymers 0.000 description 3
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 3
- 229940018557 citraconic acid Drugs 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 3
- 229940045803 cuprous chloride Drugs 0.000 description 3
- 238000006392 deoxygenation reaction Methods 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- IOLQWGVDEFWYNP-UHFFFAOYSA-N ethyl 2-bromo-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)Br IOLQWGVDEFWYNP-UHFFFAOYSA-N 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 3
- VMGSQCIDWAUGLQ-UHFFFAOYSA-N n',n'-bis[2-(dimethylamino)ethyl]-n,n-dimethylethane-1,2-diamine Chemical compound CN(C)CCN(CCN(C)C)CCN(C)C VMGSQCIDWAUGLQ-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000010511 deprotection reaction Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- PQUSVJVVRXWKDG-UHFFFAOYSA-N methyl 2-bromo-2-methylpropanoate Chemical compound COC(=O)C(C)(C)Br PQUSVJVVRXWKDG-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 150000002896 organic halogen compounds Chemical class 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 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
- 150000004992 toluidines Chemical class 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- IDXCKOANSQIPGX-UHFFFAOYSA-N (acetyloxy-ethenyl-methylsilyl) acetate Chemical compound CC(=O)O[Si](C)(C=C)OC(C)=O IDXCKOANSQIPGX-UHFFFAOYSA-N 0.000 description 1
- JVPKLOPETWVKQD-UHFFFAOYSA-N 1,2,2-tribromoethenylbenzene Chemical compound BrC(Br)=C(Br)C1=CC=CC=C1 JVPKLOPETWVKQD-UHFFFAOYSA-N 0.000 description 1
- HWKPTYUKPGEEOA-UHFFFAOYSA-N 1,2,3-tris(1-bromoethyl)benzene Chemical compound CC(Br)C1=CC=CC(C(C)Br)=C1C(C)Br HWKPTYUKPGEEOA-UHFFFAOYSA-N 0.000 description 1
- ZWBRCDAPBCSXTA-UHFFFAOYSA-N 1,2,3-tris(2-bromopropan-2-yl)benzene Chemical compound CC(C)(Br)C1=CC=CC(C(C)(C)Br)=C1C(C)(C)Br ZWBRCDAPBCSXTA-UHFFFAOYSA-N 0.000 description 1
- FABVRSFEBCDJLC-UHFFFAOYSA-N 1,2,3-tris(bromomethyl)benzene Chemical compound BrCC1=CC=CC(CBr)=C1CBr FABVRSFEBCDJLC-UHFFFAOYSA-N 0.000 description 1
- WIGFTANVVOPELD-UHFFFAOYSA-N 1,2-bis(1-bromoethyl)benzene Chemical compound CC(Br)C1=CC=CC=C1C(C)Br WIGFTANVVOPELD-UHFFFAOYSA-N 0.000 description 1
- SSXHAKPMTMAEPK-UHFFFAOYSA-N 1,2-bis(2-bromopropan-2-yl)benzene Chemical compound CC(C)(Br)C1=CC=CC=C1C(C)(C)Br SSXHAKPMTMAEPK-UHFFFAOYSA-N 0.000 description 1
- KGKAYWMGPDWLQZ-UHFFFAOYSA-N 1,2-bis(bromomethyl)benzene Chemical compound BrCC1=CC=CC=C1CBr KGKAYWMGPDWLQZ-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- LNOKVKHZEYOLIQ-UHFFFAOYSA-N 1-(2,6-diethylphenyl)pyrrole-2,5-dione Chemical compound CCC1=CC=CC(CC)=C1N1C(=O)C=CC1=O LNOKVKHZEYOLIQ-UHFFFAOYSA-N 0.000 description 1
- VMDQUQBEIFMAIC-UHFFFAOYSA-N 1-(2,6-dimethylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC(C)=C1N1C(=O)C=CC1=O VMDQUQBEIFMAIC-UHFFFAOYSA-N 0.000 description 1
- LJDGDRYFCIHDPX-UHFFFAOYSA-N 1-(2-methoxyphenyl)pyrrole-2,5-dione Chemical compound COC1=CC=CC=C1N1C(=O)C=CC1=O LJDGDRYFCIHDPX-UHFFFAOYSA-N 0.000 description 1
- QYOJZFBQEAZNEW-UHFFFAOYSA-N 1-(2-methylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC=C1N1C(=O)C=CC1=O QYOJZFBQEAZNEW-UHFFFAOYSA-N 0.000 description 1
- BLLFPKZTBLMEFG-UHFFFAOYSA-N 1-(4-hydroxyphenyl)pyrrole-2,5-dione Chemical compound C1=CC(O)=CC=C1N1C(=O)C=CC1=O BLLFPKZTBLMEFG-UHFFFAOYSA-N 0.000 description 1
- KCFXNGDHQPMIAQ-UHFFFAOYSA-N 1-(4-methylphenyl)pyrrole-2,5-dione Chemical compound C1=CC(C)=CC=C1N1C(=O)C=CC1=O KCFXNGDHQPMIAQ-UHFFFAOYSA-N 0.000 description 1
- MKRBAPNEJMFMHU-UHFFFAOYSA-N 1-benzylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC1=CC=CC=C1 MKRBAPNEJMFMHU-UHFFFAOYSA-N 0.000 description 1
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- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 1
- VGIYPVFBQRUBDD-UHFFFAOYSA-N ethenoxycyclohexane Chemical compound C=COC1CCCCC1 VGIYPVFBQRUBDD-UHFFFAOYSA-N 0.000 description 1
- WGXGKXTZIQFQFO-CMDGGOBGSA-N ethenyl (e)-3-phenylprop-2-enoate Chemical compound C=COC(=O)\C=C\C1=CC=CC=C1 WGXGKXTZIQFQFO-CMDGGOBGSA-N 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- NNBRCHPBPDRPIT-UHFFFAOYSA-N ethenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C=C NNBRCHPBPDRPIT-UHFFFAOYSA-N 0.000 description 1
- LAZYBXUYSUIANF-UHFFFAOYSA-N ethenyl-diethoxy-hydroxysilane Chemical compound CCO[Si](O)(C=C)OCC LAZYBXUYSUIANF-UHFFFAOYSA-N 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
- ARFLASKVLJTEJD-UHFFFAOYSA-N ethyl 2-bromopropanoate Chemical compound CCOC(=O)C(C)Br ARFLASKVLJTEJD-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052740 iodine Chemical group 0.000 description 1
- 239000011630 iodine Chemical group 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ACEONLNNWKIPTM-UHFFFAOYSA-N methyl 2-bromopropanoate Chemical compound COC(=O)C(C)Br ACEONLNNWKIPTM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- DWFKOMDBEKIATP-UHFFFAOYSA-N n'-[2-[2-(dimethylamino)ethyl-methylamino]ethyl]-n,n,n'-trimethylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN(C)CCN(C)C DWFKOMDBEKIATP-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229940117803 phenethylamine Drugs 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-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
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- BZAROSBWJASVBU-UHFFFAOYSA-N tribromo(ethenyl)silane Chemical compound Br[Si](Br)(Br)C=C BZAROSBWJASVBU-UHFFFAOYSA-N 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 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
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
Description
本発明は、カルボキシル基含有重合体の製造方法に関するものであり、更に詳しくは、カルボキシル基を有するビニル単量体を原子移動ラジカル重合法によるリビングラジカル重合で製造する方法に関するものである。 The present invention relates to a method for producing a carboxyl group-containing polymer, and more particularly to a method for producing a vinyl monomer having a carboxyl group by living radical polymerization using an atom transfer radical polymerization method.
一般的なラジカル重合により製造されるビニル系重合体は、通常比較的広い分子量分布を有している。また、ビニル系重合体の各末端の構造は一様ではない。これに対して、分子量分布の狭いビニル系重合体が得られ、特定の官能基を重合体のほぼ任意の位置に導入することができるリビングラジカル重合法が種々提案さている。このリビングラジカル重合法の中でも、原子移動ラジカル重合（Ａｔｏｍ Ｔｒａｎｓｆｅｒ Ｒａｄｉｃａｌ Ｐｏｌｙｍｅｒｉｚａｔｉｏｎ：ＡＴＲＰ）は、重合開始剤や触媒の設計の自由度が高いことから、ビニル系重合体の製造方法として好ましく用いられている。 Vinyl polymers produced by general radical polymerization usually have a relatively wide molecular weight distribution. Moreover, the structure of each terminal of the vinyl polymer is not uniform. On the other hand, various living radical polymerization methods have been proposed in which vinyl polymers having a narrow molecular weight distribution are obtained and specific functional groups can be introduced at almost arbitrary positions in the polymer. Among these living radical polymerization methods, atom transfer radical polymerization (ATRP) is preferably used as a method for producing a vinyl polymer because it has a high degree of freedom in designing a polymerization initiator and a catalyst. .
原子移動ラジカル重合法としては、例えば特許文献１において、有機ハロゲン化合物及び銅の錯体を重合開始剤として、スチレン、アクリロニトリル及び（メタ）アクリル酸アルキル等をラジカル重合し、それにより分子量分布の狭く、末端構造を制御した重合体を得られることが開示されている。しかしながら、非特許文献１には、（メタ）アクリル酸等のカルボキシル基を有するビニル単量体の重合に、原子移動ラジカル重合法を適用することはできないと記載されている。その理由は、遷移金属原子がカルボキシル基と反応してしまい、リビング的にラジカル重合が進まないからである。 As the atom transfer radical polymerization method, for example, in Patent Document 1, radical polymerization of styrene, acrylonitrile, alkyl (meth) acrylate, and the like using an organic halogen compound and a copper complex as a polymerization initiator, thereby narrowing the molecular weight distribution, It is disclosed that a polymer having a controlled terminal structure can be obtained. However, Non-Patent Document 1 describes that the atom transfer radical polymerization method cannot be applied to polymerization of a vinyl monomer having a carboxyl group such as (meth) acrylic acid. The reason is that the transition metal atom reacts with the carboxyl group and radical polymerization does not proceed in a living manner.
そこで、非特許文献２には、カルボキシル基を保護し、重合後に脱保護をすることで、分子量分布の狭く、末端構造を制御したカルボキシル基含有重合体を得られることが記載されている。また、非特許文献３には、カルボキシル基を水酸化ナトリウムと中和し、水中で重合を行うことが記載されており、分子量分布の狭い重合体が得られている。更に、別の方法として、特許文献２には、銅以外の遷移金属（鉄、コバルト、ロジウム、ルテニウムなど）を用いることで、分子量分布の狭い重合体を得ることが開示されている。 Therefore, Non-Patent Document 2 describes that a carboxyl group-containing polymer having a narrow molecular weight distribution and a controlled terminal structure can be obtained by protecting a carboxyl group and deprotecting it after polymerization. Non-Patent Document 3 describes that a carboxyl group is neutralized with sodium hydroxide and polymerization is performed in water, and a polymer having a narrow molecular weight distribution is obtained. Furthermore, as another method, Patent Document 2 discloses that a polymer having a narrow molecular weight distribution is obtained by using a transition metal (iron, cobalt, rhodium, ruthenium, etc.) other than copper.
しかしながら、非特許文献２に開示されるような方法では、重合後に脱保護反応をする必要があり、重合工程が複雑となる問題がある。また、非特許文献３に開示されるような方法では、水中で重合を行うため、製造可能な末端構造に制限が生じるという問題がある。更に、特許文献２に開示されるような方法では、用いる遷移金属が高価であるという問題がある。 However, the method disclosed in Non-Patent Document 2 requires a deprotection reaction after the polymerization, and there is a problem that the polymerization process becomes complicated. In addition, the method disclosed in Non-Patent Document 3 has a problem that the terminal structure that can be produced is limited because the polymerization is performed in water. Furthermore, the method disclosed in Patent Document 2 has a problem that the transition metal used is expensive.
本発明は、上記問題点に鑑みなされたものであって、その目的は、（メタ）アクリル酸等のカルボキシル基を有するビニル単量体の重合に、原子移動ラジカル重合法を適用して、分子量分布の狭く、任意の末端を有する重合体を安価かつ容易に得る方法を提供することにある。 The present invention has been made in view of the above problems, and its purpose is to apply an atom transfer radical polymerization method to the polymerization of a vinyl monomer having a carboxyl group such as (meth) acrylic acid to obtain a molecular weight. An object of the present invention is to provide a method for easily and inexpensively obtaining a polymer having a narrow distribution and an arbitrary terminal.
本発明者らは、上記課題を解決するために鋭意検討した結果、カルボキシル基を有するビニル単量体を原子移動ラジカル重合法によるリビングラジカル重合で製造する方法において、カルボキシル基を有するビニル単量体を塩基性物質で中和した後、重合することにより、分子量分布の狭い重合体を安価かつ容易に得ることができることを見出し、本発明を完成させるに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that in a method for producing a vinyl monomer having a carboxyl group by living radical polymerization by an atom transfer radical polymerization method, a vinyl monomer having a carboxyl group is produced. It was found that a polymer having a narrow molecular weight distribution can be obtained inexpensively and easily by neutralizing the polymer with a basic substance and then polymerizing, thereby completing the present invention.
すなわち、本発明は以下の通りである。
１．カルボキシル基を有するビニル単量体を原子移動ラジカル重合法によるリビングラジカル重合で製造する方法において、前記カルボキシル基を有するビニル単量体を塩基性物質で中和した後、有機溶剤中で重合することを特徴とするカルボキシル基含有重合体の製造方法。
２．上記ビニル単量体中のカルボキシル基と、中和する塩基性物質との当量比は、１：０．３〜３であることを特徴とする上記１に記載のカルボキシル基含有重合体の製造方法。
３．上記塩基性物質が、有機アミンであることを特徴とする上記１又は２に記載のカルボキシル基含有重合体の製造方法。
４．上記カルボキシル基を有するビニル単量体の含有量が、ビニル単量体の全量に対して７０質量％以上であることを特徴とする上記１〜３のいずれかに記載のカルボキシル基含有重合体の製造方法。
５．上記原子移動ラジカル重合法は、重合開始剤として有機ハロゲン化物又はハロゲン化スルホニル化合物を用い、触媒として遷移金属錯体を用いることを特徴とする上記１〜４のいずれかに記載のカルボキシル基含有重合体の製造方法。
６．上記遷移金属錯体が、銅、ニッケル、ルテニウム又は鉄の錯体より選ばれることを特徴とする上記５に記載のカルボキシル基含有重合体の製造方法。
７．上記遷移金属錯体が、銅の錯体であることを特徴とする上記６に記載のカルボキシル基含有重合体の製造方法。
８．上記リビングラジカル重合終了後に、陽イオン交換樹脂を用いて前記塩基性物質を除去する工程を含むことを特徴とする上記１〜７のいずれかに記載のカルボキシル基含有重合体の製造方法。
９．上記１〜８のいずれかに記載の製造方法により得ることができる、数平均分子量が５００〜１０００００であることを特徴とするビニル系重合体。
１０．ゲルパーミエーションクロマトグラフィーで測定した重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）が、１．８未満であることを特徴とする上記９に記載のビニル系重合体。
１１．上記ビニル系重合体が、アクリル酸とアクリル酸エステルとの共重合体であることを特徴とする請求項９又は１０に記載のビニル系重合体。That is, the present invention is as follows.
1. In a method for producing a vinyl monomer having a carboxyl group by living radical polymerization by an atom transfer radical polymerization method, the vinyl monomer having a carboxyl group is neutralized with a basic substance and then polymerized in an organic solvent. A process for producing a carboxyl group-containing polymer.
2. 2. The method for producing a carboxyl group-containing polymer according to 1 above, wherein the equivalent ratio of the carboxyl group in the vinyl monomer to the basic substance to be neutralized is 1: 0.3-3. .
3. 3. The method for producing a carboxyl group-containing polymer as described in 1 or 2 above, wherein the basic substance is an organic amine.
4). Content of the vinyl monomer which has the said carboxyl group is 70 mass% or more with respect to the whole quantity of a vinyl monomer, The carboxyl group-containing polymer in any one of said 1-3 characterized by the above-mentioned. Production method.
5. 5. The carboxyl group-containing polymer as described in any one of 1 to 4 above, wherein the atom transfer radical polymerization method uses an organic halide or a sulfonyl halide compound as a polymerization initiator and a transition metal complex as a catalyst. Manufacturing method.
6). 6. The method for producing a carboxyl group-containing polymer as described in 5 above, wherein the transition metal complex is selected from a complex of copper, nickel, ruthenium or iron.
7). 7. The method for producing a carboxyl group-containing polymer as described in 6 above, wherein the transition metal complex is a copper complex.
8). 8. The method for producing a carboxyl group-containing polymer according to any one of 1 to 7, further comprising a step of removing the basic substance using a cation exchange resin after the living radical polymerization is completed.
9. A vinyl polymer having a number average molecular weight of 500 to 100,000 which can be obtained by the production method according to any one of 1 to 8 above.
10. 10. The vinyl polymer as described in 9 above, wherein the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography is less than 1.8. .
11. The vinyl polymer according to claim 9 or 10, wherein the vinyl polymer is a copolymer of acrylic acid and an acrylic ester.
本発明に係るカルボキシル基含有重合体の製造方法は、以上のように、カルボキシル基を有するビニル単量体を塩基性物質で中和した後、有機溶剤中で原子移動ラジカル重合法によるリビングラジカル重合を行う。そのため、触媒である遷移金属錯体がカルボキシル基と反応することなくリビングラジカル重合が進むため、分子量分布の狭いビニル系重合体を得ることができる。また、本発明の製造方法によれば、任意の末端を有する重合体を、安価かつ容易に製造することができる。更に、重合液を陽イオン交換樹脂を用いて処理する工程を含むことにより、容易に塩基性物質を除去することができる。 As described above, the method for producing a carboxyl group-containing polymer according to the present invention comprises neutralizing a vinyl monomer having a carboxyl group with a basic substance, and then living radical polymerization by an atom transfer radical polymerization method in an organic solvent. I do. Therefore, since the living radical polymerization proceeds without the transition metal complex as a catalyst reacting with the carboxyl group, a vinyl polymer having a narrow molecular weight distribution can be obtained. Moreover, according to the production method of the present invention, a polymer having an arbitrary terminal can be produced inexpensively and easily. Furthermore, a basic substance can be easily removed by including the process of processing a polymerization liquid using a cation exchange resin.
本発明の一実施形態について説明すると以下の通りであるが、本発明はこれに限定されるものではない。
１．カルボキシル基含有重合体の製造方法
本発明に係るカルボキシル基含有重合体の製造方法は、カルボキシル基を有するビニル単量体を塩基性物質で中和した後、有機溶剤中で原子移動ラジカル重合法によるリビングラジカル重合を行う。この原子移動ラジカル重合法は、重合開始剤として有機ハロゲン化物又はハロゲン化スルホニル化合物を用い、触媒として遷移金属錯体を用いるリビングラジカル重合である。An embodiment of the present invention will be described as follows, but the present invention is not limited to this.
1. Method for Producing Carboxyl Group-Containing Polymer The method for producing a carboxyl group-containing polymer according to the present invention is based on an atom transfer radical polymerization method in an organic solvent after neutralizing a vinyl monomer having a carboxyl group with a basic substance. Living radical polymerization is performed. This atom transfer radical polymerization method is living radical polymerization using an organic halide or a sulfonyl halide compound as a polymerization initiator and a transition metal complex as a catalyst.
（１）重合開始剤
原子移動ラジカル重合法に用いる重合開始剤は、有機ハロゲン化物又はハロゲン化スルホニル化合物である。有機ハロゲン化物としては、分子内に１個以上の炭素−ハロゲン結合（但しハロゲンはフッ素以外とする）を有する種々の有機化合物を使用でき、脂肪族炭化水素系ハロゲン化合物、脂環族炭化水素系ハロゲン化合物、芳香族炭化水素系ハロゲン化合物、及び複素環系ハロゲン化合物などがある。(1) Polymerization initiator The polymerization initiator used in the atom transfer radical polymerization method is an organic halide or a sulfonyl halide compound. As the organic halide, various organic compounds having one or more carbon-halogen bonds in the molecule (where halogen is other than fluorine) can be used, including aliphatic hydrocarbon-based halogen compounds and alicyclic hydrocarbon-based compounds. Examples include halogen compounds, aromatic hydrocarbon halogen compounds, and heterocyclic halogen compounds.
脂肪族炭化水素系ハロゲン化合物の具体例としては、２−ブロモプロピオン酸メチル、２−ブロモプロピオン酸エチル、２−ブロモプロピオン酸ブチル、２−ブロモイソ酪酸メチル、２−ブロモイソ酪酸エチル、２−ブロモイソ酪酸ブチル、２−ブロモイソブチル酸メチル、２−ブロモイソブチル酸エチル、２−ブロモイソブチル酸ブチル、２，３−ジブロモコハク酸ジメチル、２，３−ジブロモコハク酸ジエチル、２，３−ジブロモコハク酸ジブチル、２，４−ジブロモグルタル酸ジメチル、２，４−ジブロモグルタル酸ジエチル、２，４−ジブロモグルタル酸ジブチル、２，５−ジブロモアジピン酸ジメチル、２，５−ジブロモアジピン酸ジエチル、２，５−ジブロモアジピン酸ジブチル、２，６−ジブロモピメリン酸ジメチル、２，６−ジブロモピメリン酸ジエチル、２，６−ジブロモピメリン酸ジブチル、２，７−ジブロモスベリン酸ジメチル、２，７−ジブロモスベリン酸ジエチル、２，７−ジブロモスベリン酸ジブチルなどが挙げられる。これらの中では、分子量分布の制御の点から、２−ブロモイソ酪酸エチルが好ましい。 Specific examples of the aliphatic hydrocarbon halogen compound include methyl 2-bromopropionate, ethyl 2-bromopropionate, butyl 2-bromopropionate, methyl 2-bromoisobutyrate, ethyl 2-bromoisobutyrate, and 2-bromoisobutyric acid. Butyl, methyl 2-bromoisobutyrate, ethyl 2-bromoisobutyrate, butyl 2-bromoisobutyrate, dimethyl 2,3-dibromosuccinate, diethyl 2,3-dibromosuccinate, dibutyl 2,3-dibromosuccinate, Dimethyl 2,4-dibromoglutarate, diethyl 2,4-dibromoglutarate, dibutyl 2,4-dibromoglutarate, dimethyl 2,5-dibromoadipate, diethyl 2,5-dibromoadipate, 2,5-dibromo Dibutyl adipate, dimethyl 2,6-dibromopimelate, 2,6 Jiburomopimerin diethyl, 2,6 Jiburomopimerin dibutyl, 2,7-dibromo-slip phosphate dimethyl, 2,7-dibromo-slip phosphate diethyl, such as 2,7-dibromo-slip phosphate dibutyl. Among these, ethyl 2-bromoisobutyrate is preferable from the viewpoint of controlling the molecular weight distribution.
芳香族炭化水素系ハロゲン化合物の具体例としては、ビス（ブロモメチル）ベンゼン、ビス（１−ブロモエチル）ベンゼン、ビス（１−ブロモイソプロピル）ベンゼン、トリス（ブロモメチル）ベンゼン、トリス（１−ブロモエチル）ベンゼン、トリス（１−ブロモイソプロピル）ベンゼンなどが挙げられる。 Specific examples of the aromatic hydrocarbon halogen compound include bis (bromomethyl) benzene, bis (1-bromoethyl) benzene, bis (1-bromoisopropyl) benzene, tris (bromomethyl) benzene, tris (1-bromoethyl) benzene, And tris (1-bromoisopropyl) benzene.
また、ハロゲン化スルホニル化合物としては、例えば、
Ｒ1−Ｃ6Ｈ4−ＳＯ2Ｘ
Ｘ−ＳＯ2−Ｃ6Ｈ4−ＳＯ2−Ｘ
Ｃ6Ｈ3−（ＳＯ2−Ｘ）3
で示される化合物などが挙げられる。
｛式中、Ｒ1は、水素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、又は炭素数７〜２０のアラルキル基を表わす。Ｘは、塩素、臭素又はヨウ素を表わす。｝Examples of the halogenated sulfonyl compound include:
R 1 —C 6 H 4 —SO 2 X
X-SO 2 -C 6 H 4 -SO 2 -X
C 6 H 3 - (SO 2 -X) 3
And the like.
{In the formula, R 1 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. X represents chlorine, bromine or iodine. }
単量体に対する重合開始剤の使用量は、リビングアニオン重合の場合と同様に目的とする重合体の分子量に応じて選択される。該使用量を算出するには、以下の計算式を用いることができる。すなわち、重合過程での数平均分子量は、以下の式で表される。
（ΔＭ／ＲＸ）×ｍｗ
｛式中、ΔＭ：重合した単量体のモル数、ＲＸ：有機ハロゲン化物（ｍ＝１）のモル数（ｍは有機ハロゲン化物におけるハロゲン原子の個数）、ｍｗ：単量体の分子量｝
従って、全単量体の重合が終了した場合の得られる重合体の分子量（Ｍｎ）は下記の式で表される。この式から目的とするＭｎに対応する有機ハロゲン化合物の使用量を決定できる。
Ｍｎ＝（Ｍ／ＲＸ）×ｍｗ
｛式中、Ｍ：仕込んだ単量体の量（モル数）｝The amount of the polymerization initiator used with respect to the monomer is selected according to the molecular weight of the target polymer as in the case of living anion polymerization. In order to calculate the usage amount, the following calculation formula can be used. That is, the number average molecular weight in the polymerization process is represented by the following formula.
(ΔM / RX) × mw
{In the formula, ΔM: number of moles of polymerized monomer, RX: number of moles of organic halide (m = 1) (m is the number of halogen atoms in the organic halide), mw: molecular weight of monomer}
Therefore, the molecular weight (Mn) of the polymer obtained when the polymerization of all the monomers is completed is represented by the following formula. From this formula, the amount of the organic halogen compound corresponding to the target Mn can be determined.
Mn = (M / RX) × mw
{In the formula, M: amount of monomer charged (number of moles)}
（２）触媒
原子移動ラジカル重合法の触媒として用いられる遷移金属錯体は、周期表第８族〜第１１族から選ばれる金属元素の錯体である。遷移金属錯体は、遷移金属及び配位子からなる。遷移金属の具体例としては、銅、ニッケル、ルテニウム又は鉄である。これらの中でも、反応制御やコストの観点から銅の錯体が好ましい。１価の銅化合物としては、例えば、塩化第一銅、臭化第一銅、ヨウ化第一銅、シアン化第一銅、酸化第一銅、過塩素酸第一銅などが挙げられる。その中でも塩化第一銅、臭化第一銅が、重合の制御の観点から好ましい。また、より安定で取り扱いの容易な塩化第二銅、臭化第二銅に還元剤を加え、系中で塩化第一銅、臭化第一銅を発生させ、重合を行うこともできる。また、前記遷移金属とともに錯体を形成する配位子としては、２座以上の窒素配位子が好ましく、例えば、２，２'−ビピリジル、４，４'−ビピリジル、エチレンジアミン、トリス（２−（ジメチルアミノ）エチル）アミン、及びトリス（２−（ピリジル）メチル）アミンなどが挙げられる。(2) Catalyst The transition metal complex used as a catalyst for the atom transfer radical polymerization method is a complex of a metal element selected from Groups 8 to 11 of the periodic table. The transition metal complex consists of a transition metal and a ligand. Specific examples of the transition metal are copper, nickel, ruthenium or iron. Among these, a copper complex is preferable from the viewpoint of reaction control and cost. Examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, and cuprous perchlorate. Of these, cuprous chloride and cuprous bromide are preferred from the viewpoint of polymerization control. In addition, it is possible to carry out polymerization by adding a reducing agent to cupric chloride and cupric bromide which are more stable and easy to handle, to generate cuprous chloride and cuprous bromide in the system. Moreover, as a ligand which forms a complex with the said transition metal, a bidentate or more nitrogen ligand is preferable, for example, 2,2'-bipyridyl, 4,4'-bipyridyl, ethylenediamine, tris (2- ( And dimethylamino) ethyl) amine and tris (2- (pyridyl) methyl) amine.
上記重合開始剤と、触媒の量は、使用する単量体の種類、及び溶媒の量と必要とする反応速度の関係から決定すればよい。一般的には、重合開始剤１モル当たり、触媒０．１〜１．５モルであり、より好ましくは、重合開始剤１モル当たり、触媒０．５〜１．０モルである。 The amount of the polymerization initiator and the catalyst may be determined from the relationship between the type of monomer used and the amount of solvent and the required reaction rate. In general, the amount is 0.1 to 1.5 moles of catalyst per mole of polymerization initiator, and more preferably 0.5 to 1.0 mole of catalyst per mole of polymerization initiator.
（３）ビニル単量体
本発明において用いられる分子内にカルボキシル基を有するビニル単量体としては、例えば、アクリル酸、メタクリル酸、クロトン酸、ビニル酢酸、アクリロキシプロピオン酸等の不飽和一塩基酸、マレイン酸、イタコン酸、フマル酸、メサコン酸、シトラコン酸、シクロヘキサンジカルボン酸等の不飽和二塩基酸、無水マレイン酸、無水イタコン酸、無水シトラコン酸、無水テトラヒドロフタル酸等の不飽和酸無水物等が挙げられる。これらは、単独で用いてよいし２つ以上を組み合わせて用いてもよい。これらの中でも（メタ）アクリル酸は安価であり、他の各種単量体と共重合反応を起こしやすいので好ましい。また、本発明においては、前記カルボキシル基含有ビニル単量体以外に、他の共重合単量体を併用しても良い。併用割合は、特に限定されないが、本発明においては仕込み単量体におけるカルボキシル基含有ビニル単量体の割合が７０質量％以上であることが好ましい。カルボキシル基含有ビニル単量体単位を７０質量％以上の含有するような重合体をリビングラジカル重合により狭い分子量分布で得ることは、従来技術的に困難であった。(3) Vinyl monomer Examples of the vinyl monomer having a carboxyl group in the molecule used in the present invention include unsaturated monobases such as acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, and acryloxypropionic acid. Unsaturated dibasic acids such as acid, maleic acid, itaconic acid, fumaric acid, mesaconic acid, citraconic acid and cyclohexanedicarboxylic acid, and unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride and tetrahydrophthalic anhydride Thing etc. are mentioned. These may be used alone or in combination of two or more. Among these, (meth) acrylic acid is preferable because it is inexpensive and easily causes a copolymerization reaction with other various monomers. In the present invention, in addition to the carboxyl group-containing vinyl monomer, other copolymer monomers may be used in combination. The combined proportion is not particularly limited, but in the present invention, the proportion of the carboxyl group-containing vinyl monomer in the charged monomer is preferably 70% by mass or more. It has been difficult in the prior art to obtain a polymer containing 70% by mass or more of a carboxyl group-containing vinyl monomer unit by living radical polymerization with a narrow molecular weight distribution.
本発明に係るカルボキシル基含有ビニル単量体と、共重合可能な他の単量体は、ラジカル重合性を有する不飽和化合物であれば、特に限定されない。この不飽和化合物としては、（メタ）アクリル酸アルキル、シアノ基を有するビニル単量体、ヒドロキシル基を有するビニル単量体、芳香族ビニル単量体、アミノ基を有するビニル単量体、アミド基を有するビニル単量体、アルコキシル基を有するビニル単量体、共役ジエン系単量体、マレイミド系単量体、ビニルエステル単量体、ビニルエーテル単量体、グリシジル基を有するビニル単量体、不飽和ジカルボン酸のモノアルキルエステル、不飽和ジカルボン酸のジアルキルエステル、珪素含有基を有する単量体等が挙げられる。これらは、１種単独であるいは２種以上を組み合わせて用いることができる。 The carboxyl group-containing vinyl monomer according to the present invention and the other copolymerizable monomer are not particularly limited as long as they are unsaturated compounds having radical polymerizability. This unsaturated compound includes alkyl (meth) acrylate, vinyl monomer having cyano group, vinyl monomer having hydroxyl group, aromatic vinyl monomer, vinyl monomer having amino group, amide group Vinyl monomers having an alkoxyl group, vinyl monomers having an alkoxyl group, conjugated diene monomers, maleimide monomers, vinyl ester monomers, vinyl ether monomers, vinyl monomers having a glycidyl group, Examples thereof include monoalkyl esters of saturated dicarboxylic acids, dialkyl esters of unsaturated dicarboxylic acids, and monomers having silicon-containing groups. These can be used alone or in combination of two or more.
（メタ）アクリル酸アルキルとしては、（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ｎ−プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓｅｃ−ブチル、（メタ）アクリル酸ｔｅｒｔ−ブチル、（メタ）アクリル酸ｎ−ペンチル、（メタ）アクリル酸イソアミル、（メタ）アクリル酸ｎ−ヘキシル、（メタ）アクリル酸２−メチルペンチル、（メタ）アクリル酸ｎ−オクチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ｎ−オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ｎ−ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸２−メチルオクチル、（メタ）アクリル酸デシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸トリデシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリ酸イソボルニル等が挙げられる。これらは、単独で用いてよいし２つ以上を組み合わせて用いてもよい。 Examples of alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, (meth ) 2-methylpentyl acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate , Isononyl (meth) acrylate, 2-methyloctyl (meth) acrylate, (meth) acrylic acid de Le, (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl and (meth) acrylate isobornyl like. These may be used alone or in combination of two or more.
シアノ基を有するビニル単量体としては、例えば、アクリロニトリル、メタクリロニトリル、α−エチルアクリロニトリル、α−イソプロピルアクリロニトリル、α−クロロアクリロニトリル、α−フルオロアクリロニトリル等が挙げられる。これらは、単独で用いてよいし２つ以上を組み合わせて用いてもよい。 Examples of the vinyl monomer having a cyano group include acrylonitrile, methacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile and the like. These may be used alone or in combination of two or more.
ヒドロキシル基を有する単量体としては、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸２−ヒドロキシプロピル、（メタ）アクリル酸３−ヒドロキシプロピル、（メタ）アクリル酸２−ヒドロキシブチル、（メタ）アクリル酸３−ヒドロキシブチル、（メタ）アクリル酸４−ヒドロキシブチル、（メタ）アクリル酸６−ヒドロキシヘキシル、（メタ）アクリル酸８−ヒドロキシオクチル、（メタ）アクリル酸１２−ヒドロキシラウリル、ポリエチレングリコール、ポリプロピレングリコール等のポリアルキレングリコールのモノ（メタ）アクリル酸エステルや、ｐ−ヒドロキシスチレン、ｍ−ヒドロキシスチレン、ｏ−ヒドロキシスチレン、ｐ−イソプロペニルフェノール、ｍ−イソプロペニルフェノール、ｏ−イソプロペニルフェノール等が挙げられる。これらは、単独であるいは２つ以上を組み合わせて用いることができる。 Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, Mono (meth) acrylic acid ester of polyalkylene glycol such as polyethylene glycol, polypropylene glycol, p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isoprop Alkenyl phenols and the like. These can be used alone or in combination of two or more.
芳香族ビニル単量体としては、スチレン、２−メチルスチレン、３−メチルスチレン、４−メチルスチレン、α−メチルスチレン、２，４−ジメチルスチレン、２，４−ジイソプロピルスチレン、４−ｔｅｒｔ−ブチルスチレン、ｔｅｒｔ−ブトキシスチレン、ビニルトルエン、ジビニルトルエン、ベンジル（メタ）アクリレート、ビニルナフタレン、モノクロロスチレン、ジクロロスチレン、モノブロモスチレン、ジブロモスチレン、トリブロモスチレン、フルオロスチレン、スチレンスルホン酸及びその塩、α−メチルスチレンスルホン酸及びその塩等が挙げられる。これらは、単独であるいは２つ以上を組み合わせて用いることができる。 Examples of aromatic vinyl monomers include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, and 4-tert-butyl. Styrene, tert-butoxystyrene, vinyl toluene, divinyl toluene, benzyl (meth) acrylate, vinyl naphthalene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, fluorostyrene, styrenesulfonic acid and salts thereof, α -Methyl styrene sulfonic acid, its salt, etc. are mentioned. These can be used alone or in combination of two or more.
アミノ基を有するビニル単量体としては、（メタ）アクリル酸アミノエチル、（メタ）アクリル酸ジメチルアミノメチル、（メタ）アクリル酸ジエチルアミノメチル、（メタ）アクリル酸２−ジメチルアミノエチル、（メタ）アクリル酸２−ジエチルアミノエチル、（メタ）アクリル酸２−（ジ−ｎ−プロピルアミノ）エチル、（メタ）アクリル酸２−ジメチルアミノプロピル、（メタ）アクリル酸２−ジエチルアミノプロピル、（メタ）アクリル酸２−（ジ−ｎ−プロピルアミノ）プロピル、（メタ）アクリル酸３−ジメチルアミノプロピル、（メタ）アクリル酸３−ジエチルアミノプロピル、（メタ）アクリル酸３−（ジ−ｎ−プロピルアミノ）プロピル等が挙げられる。これらは、単独であるいは２つ以上を組み合わせて用いることができる。 As vinyl monomers having an amino group, aminoethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, (meth) 2-diethylaminoethyl acrylate, 2- (di-n-propylamino) ethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 2-diethylaminopropyl (meth) acrylate, (meth) acrylic acid 2- (di-n-propylamino) propyl, 3-dimethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, 3- (di-n-propylamino) propyl (meth) acrylate, etc. Is mentioned. These can be used alone or in combination of two or more.
アミド基を有するビニル単量体としては、（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ブトキシメチル（メタ）アクリルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−アルコキシメチル（メタ）アクリルアミド等が挙げられる。これらは、単独であるいは２つ以上を組み合わせて用いることができる。 Examples of the vinyl monomer having an amide group include (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N- Examples include butoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, and N-alkoxymethyl (meth) acrylamide. These can be used alone or in combination of two or more.
アルコキシル基を有するビニル単量体としては、（メタ）アクリル酸２−メトキシエチル、（メタ）アクリル酸２−エトキシエチル、（メタ）アクリル酸２−（ｎ−プロポキシ）エチル、（メタ）アクリル酸２−（ｎ−ブトキシ）エチル、（メタ）アクリル酸３−メトキシプロピル、（メタ）アクリル酸３−エトキシプロピル、（メタ）アクリル酸２−（ｎ−プロポキシ）プロピル、（メタ）アクリル酸２−（ｎ−ブトキシ）プロピル等が挙げられる。これらは、単独であるいは２つ以上を組み合わせて用いることができる。 Examples of vinyl monomers having an alkoxyl group include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ethyl (meth) acrylate, and (meth) acrylic acid. 2- (n-butoxy) ethyl, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 2- (n-propoxy) propyl (meth) acrylate, 2- (meth) acrylic acid 2- (N-butoxy) propyl and the like can be mentioned. These can be used alone or in combination of two or more.
共役ジエン系単量体としては、１，３−ブタジエン、イソプレン（２−メチル−１，３−ブタジエン）、２，３−ジメチル−１，３ブタジエン、クロロプレン（２−クロロ−１，３−ブタジエン）等が挙げられる。これらは、単独であるいは２つ以上を組み合わせて用いることができる。 Conjugated diene monomers include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3 butadiene, chloroprene (2-chloro-1,3-butadiene) ) And the like. These can be used alone or in combination of two or more.
上記マレイミド系単量体としては、マレイミド、Ｎ−メチルマレイミド、Ｎ−イソプロピルマレイミド、Ｎ−ブチルマレイミド、Ｎ−ドデシルマレイミド、Ｎ−フェニルマレイミド、Ｎ−（２−メチルフェニル）マレイミド、Ｎ−（４−メチルフェニル）マレイミド、Ｎ−（２、６−ジメチルフェニル）マレイミド、Ｎ−（２、６−ジエチルフェニル）マレイミド、Ｎ−（２−メトキシフェニル）マレイミド、Ｎ−ベンジルマレイミド、Ｎ−（４−ヒドロキシフェニル）マレイミド、Ｎ−ナフチルマレイミド、Ｎ−シクロヘキシルマレイミド等が挙げられる。これらは、単独であるいは２つ以上を組み合わせて用いることができる。 Examples of the maleimide monomer include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4 -Methylphenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N- (4- Hydroxyphenyl) maleimide, N-naphthylmaleimide, N-cyclohexylmaleimide and the like. These can be used alone or in combination of two or more.
上記ビニルエステル単量体としては、メチレン脂肪族モノカルボン酸エステル、酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、酪酸ビニル、安息香酸ビニル、ギ酸ビニル、桂皮酸ビニル、バーサチック酸ビニル等が挙げられる。これらは、単独であるいは２つ以上を組み合わせて用いることができる。 Examples of the vinyl ester monomer include methylene aliphatic monocarboxylic acid ester, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl butyrate, vinyl benzoate, vinyl formate, vinyl cinnamate, vinyl versatate, and the like. These can be used alone or in combination of two or more.
上記ビニルエーテル単量体としては、ビニルメチルエーテル、ビニルエチルエーテル、ビニル−ｎ−ブチルエーテル、ビニルイソブチルエーテル、ビニルフェニルエーテル、ビニルシクロヘキシルエーテル等が挙げられる。これらは、単独であるいは２つ以上を組み合わせて用いることができる。 Examples of the vinyl ether monomer include vinyl methyl ether, vinyl ethyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl phenyl ether, vinyl cyclohexyl ether and the like. These can be used alone or in combination of two or more.
グリシジル基を有するビニル単量体としては、（メタ）アクリル酸グリシジル、（メタ）アリルグリシジルテーテル、（メタ）アクリル酸β−メチルグリシジル、４−ヒドロキシブチル（メタ）アクリル酸グリシジル、３，４−エポキシシクロヘキシルメチル（メタ）アクリルレート、３，４−エポキシシクロヘキシルエチル（メタ）アクリルレート、３，４−エポキシシクロヘキシルプロピル（メタ）アクリルレート等が挙げられる。これらは、単独であるいは２つ以上を組み合わせて用いることができる。 Examples of the vinyl monomer having a glycidyl group include glycidyl (meth) acrylate, (meth) allyl glycidyl tether, (meth) acrylate β-methylglycidyl, 4-hydroxybutyl (meth) acrylate glycidyl, 3,4- Examples thereof include epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.
不飽和ジカルボン酸のモノアルキルエステルとしては、マレイン酸、フマル酸、イタコン酸、シトラコン酸、メサコン酸、無水マレイン酸、無水イタコン酸、無水シトラコン酸、無水テトラヒドロフタル酸等のモノアルキルエステルが挙げられる。これらは、単独であるいは２つ以上を組み合わせて用いることができる。
不飽和ジカルボン酸のジアルキルエステルとしては、マレイン酸、フマル酸、イタコン酸、シトラコン酸、メサコン酸、無水マレイン酸、無水イタコン酸、無水シトラコン酸、無水テトラヒドロフタル酸等のジアルキルエステルが挙げられる。これらは、単独であるいは２つ以上を組み合わせて用いることができる。Examples of monoalkyl esters of unsaturated dicarboxylic acids include monoalkyl esters such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, and tetrahydrophthalic anhydride. . These can be used alone or in combination of two or more.
Examples of the dialkyl ester of unsaturated dicarboxylic acid include dialkyl esters such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, and tetrahydrophthalic anhydride. These can be used alone or in combination of two or more.
珪素含有基を有する単量体としては、ビニルトリクロロシラン、ビニルトリブロモシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリ−ｎ−プロポキシシラン、ビニルトリ−ｉ−プロポキシシラン、ビニルトリ−ｎ−ブトキシシラン、ビニルトリス（２−ヒドロキシメトキシエトキシ）シラン、ビニルトリアセトキシシラン、ビニルジエトキシシラノール、ビニルエトキシシラジオール、ビニルメチルジエトキシシラン、ビニルジメチツエトキシシラン、ビニルメチルジアセトキシシラン、アリルトリメトキシシラン、アリルトリエトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−アクリロキシプロピルトリエトキシシラン、３−メタクリロキシプロピルトリス（２−メトキシエトキシ）シラン、３−メタクリロキシプロピルメチルジエトキシシラン、３−メタクリロキシプロピルジメチルエトキシシラン、３−アクリロキシプロピルジメトキシシラン、２−アクリルアミドエチルトリエトキシシラン等が挙げられる。これらは、単独であるいは２つ以上を組み合わせて用いることができる。 Examples of the monomer having a silicon-containing group include vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-i-propoxysilane, and vinyltri-n-butoxysilane. , Vinyltris (2-hydroxymethoxyethoxy) silane, vinyltriacetoxysilane, vinyldiethoxysilanol, vinylethoxysiladiol, vinylmethyldiethoxysilane, vinyldimethiethoxysilane, vinylmethyldiacetoxysilane, allyltrimethoxysilane Triethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltris (2-methoxyethoxy) sila , 3-methacryloxypropyl methyl diethoxy silane, 3-methacryloxypropyl dimethyl ethoxysilane, 3-acryloxy propyl dimethoxysilane, and 2-acrylamide-ethyl triethoxysilane and the like. These can be used alone or in combination of two or more.
これらの他の単量体のうち、好ましくは、（メタ）アクリル酸アルキル、ヒドロキシル基を有する単量体及び芳香族ビニル単量体であり、より好ましくはアクリル酸エステルである。これらの単量体を用いることにより、安価にカルボキシル基含有重合体を製造することができる。 Among these other monomers, alkyl (meth) acrylate, a monomer having a hydroxyl group, and an aromatic vinyl monomer are preferable, and an acrylate ester is more preferable. By using these monomers, a carboxyl group-containing polymer can be produced at a low cost.
また、カルボキシル基を有するビニル単量体を本発明の方法で重合した後、上記したラジカル重合性を有する不飽和化合物を添加し、重合を継続することにより、ブロック共重合体を合成することもできる。その際、ラジカル重合性を有する不飽和化合物を、先に重合し、カルボキシル基を有するビニル単量体を添加し、ブロック重合させることも可能である。 In addition, after the vinyl monomer having a carboxyl group is polymerized by the method of the present invention, the above-mentioned unsaturated compound having radical polymerizability is added and the polymerization is continued to synthesize a block copolymer. it can. At that time, it is also possible to polymerize an unsaturated compound having radical polymerizability first, add a vinyl monomer having a carboxyl group, and perform block polymerization.
（４）塩基性物質
ビニル単量体のカルボキシル基を中和する塩基性物質としては、例えば、アンモニア、水酸化アンモニウム、ヒドラジン、ヒドラジン水和物、各種有機アミン等のアミン化合物；酸化ナトリウム、過酸化ナトリウム、酸化カリウム、過酸化カリウム、酸化カルシウム、酸化ストロンチウム、酸化バリウム等の金属酸化物；水酸化バリウム、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、水酸化ストロンチウム等の金属水酸化物；水素化ナトリウム、水素化カリウム、水素化カルシウム等の金属水素化物；炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、炭酸水素カルシウム等の炭酸塩；酢酸ナトリウム、酢酸カリウム、酢酸カルシウム等の酢酸塩などが挙げられる。これらの中でも、リビングラジカル重合後の除去のし易さの観点から、有機アミンが好ましい。(4) Basic substance Examples of basic substances that neutralize the carboxyl groups of vinyl monomers include amine compounds such as ammonia, ammonium hydroxide, hydrazine, hydrazine hydrate, and various organic amines; Metal oxides such as sodium oxide, potassium oxide, potassium peroxide, calcium oxide, strontium oxide and barium oxide; metal hydroxides such as barium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and strontium hydroxide; Metal hydrides such as sodium hydride, potassium hydride, calcium hydride; carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydrogen carbonate; acetic acid such as sodium acetate, potassium acetate, calcium acetate Examples include salt. Among these, an organic amine is preferable from the viewpoint of easy removal after living radical polymerization.
有機アミンとしては、例えば、メチルアミン、エチルアミン、プロピルアミン、イソプロピルアミン、ｎ−ブチルアミン、２−エチルヘキシルアミン、３−（２−エチルヘキシルオキシ）プロピルアミン、３−メトキシプロピルアミン、３−エトキシプロピルアミン等の脂肪族第１級アミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジイソプロピルアミン、ジブチルアミン、ジイソブチルアミン、ジ−２−エチルヘキシルアミン、ジ−ｎ−オクチルアミン等の脂肪族第２級アミン、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリイソプロピルアミン、トリブチルアミン、テトラメチルエチレンジアミン、トリ−ｎ−オクチルアミン等の脂肪族第３級アミン等の脂肪族アミン；Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’’，Ｎ’’−ペンタメチルジエチレントリアミン、１，１，４，７，１０，１０−ヘキサメチルトリエチレンテトラアミン等の脂肪族ポリアミン；アニリン、トルイジン、ｍ−トルイレンジアミン、フェニレンジアミン、フェネチルアミン、ベンジルアミンなどの芳香族第１級アミン、ジベンジルアミン、ジフェニルアミンなどの芳香族第２級アミン、Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジメチル−ｐ−トルイジン、トリフェニルアミンなどの芳香族第３級アミン等の芳香族アミン；ピロール、イミダゾール、ピラゾール、ピリジン、ピペリジン、ピペラジン、モルホリン等の複素環式アミンなどを挙げることができる。 Examples of the organic amine include methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, 2-ethylhexylamine, 3- (2-ethylhexyloxy) propylamine, 3-methoxypropylamine, and 3-ethoxypropylamine. Aliphatic secondary amines such as aliphatic primary amines, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, di-2-ethylhexylamine, di-n-octylamine, trimethylamine, Aliphatic amines such as aliphatic tertiary amines such as triethylamine, tripropylamine, triisopropylamine, tributylamine, tetramethylethylenediamine, tri-n-octylamine; N, N, N ′, N′-tetramethyl Aliphatic polyamines such as ruethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetraamine; aniline, toluidine, Aromatic primary amines such as m-toluylenediamine, phenylenediamine, phenethylamine and benzylamine, aromatic secondary amines such as dibenzylamine and diphenylamine, N, N-dimethylaniline, N, N-dimethyl-p -Aromatic amines such as aromatic tertiary amines such as toluidine and triphenylamine; heterocyclic amines such as pyrrole, imidazole, pyrazole, pyridine, piperidine, piperazine and morpholine.
ビニル単量体中のカルボキシル基（ａ）と、中和する塩基性物質（ｂ）との当量比（ａ：ｂ）は、１：０．３〜３であることが好ましく、１：０．５〜２であることがより好ましく、１：０．７〜１．５であることが更に好ましい。塩基性物質（ｂ）の当量比が０．３に満たない場合は、重合が進行しない場合がある。一方、塩基性物質（ｂ）の当量比が３を超える場合は、分子量分布の制御が十分できない場合がある。 The equivalent ratio (a: b) between the carboxyl group (a) in the vinyl monomer and the basic substance (b) to be neutralized is preferably 1: 0.3-3, and 1: 0. More preferably, it is 5-2, and it is still more preferable that it is 1: 0.7-1.5. When the equivalent ratio of the basic substance (b) is less than 0.3, the polymerization may not proceed. On the other hand, when the equivalent ratio of the basic substance (b) exceeds 3, the molecular weight distribution may not be sufficiently controlled.
中和に使用した塩基性物質は、長時間経過後にポリマーが着色及び劣化する原因となりえるため、リビングラジカル重合終了後に除去することが好ましい。除去方法は特に限定されないが、工程が簡便であることから、陽イオン交換樹脂を用いて除去することが好ましい。陽イオン交換樹脂の交換基としては、スルホン酸基、カルボン酸基、ホスホン酸基、フェノール基等が挙げられる。このような陽イオン交換樹脂は市販されており、例えば、三菱化学社製 商品名「ダイヤイオン」、ダウ・ケミカル社製 商品名「アンバーライト」等がある。また、イオン交換樹脂量としては、バッチ法においては、ポリマー １ｇあたり２０ｇ以上用いて処理することが好ましい。 Since the basic substance used for neutralization may cause the polymer to be colored and deteriorated after a long time, it is preferably removed after the living radical polymerization is completed. Although the removal method is not particularly limited, it is preferable to remove using a cation exchange resin because the process is simple. Examples of the exchange group of the cation exchange resin include a sulfonic acid group, a carboxylic acid group, a phosphonic acid group, and a phenol group. Such cation exchange resins are commercially available, for example, trade name “Diaion” manufactured by Mitsubishi Chemical Co., Ltd. and trade name “Amberlite” manufactured by Dow Chemical Co., Ltd. In addition, as the amount of ion exchange resin, in the batch method, it is preferable to use 20 g or more per 1 g of polymer.
本発明におけるリビングラジカル重合は、有機溶剤中で行う。好ましい有機溶剤としては、ジオキサン、ジメチルホルムアミド、ジメチルスルホキシド、メタノール、エタノール又は２−プロパノール等が挙げられる。これらの中でも、溶解性の点から、ジオキサン、ジメチルホルムアミド、ジメチルスルホキシドが好ましく、ジメチルホルムアミドがより好ましい。混合溶剤とする場合は、ジメチルホルムアミドの混合割合を５０質量％以上とすることが好ましい。 The living radical polymerization in the present invention is performed in an organic solvent. Preferred organic solvents include dioxane, dimethylformamide, dimethyl sulfoxide, methanol, ethanol or 2-propanol. Among these, from the viewpoint of solubility, dioxane, dimethylformamide and dimethylsulfoxide are preferable, and dimethylformamide is more preferable. When the mixed solvent is used, the mixing ratio of dimethylformamide is preferably 50% by mass or more.
重合温度は、５０〜１３０℃であることが好ましく、８０〜１００℃であることがより好ましい。重合温度が５０℃未満であると、重合速度が非常に遅くなり、重合がほとんど進行しなくなる場合がある。一方、重合温度が１３０℃を超えると、ラジカル濃度の増加に伴い、成長ラジカル同士の停止反応が起こり、重合の制御が困難となる場合がある。 The polymerization temperature is preferably 50 to 130 ° C, and more preferably 80 to 100 ° C. When the polymerization temperature is less than 50 ° C., the polymerization rate becomes very slow, and the polymerization may hardly proceed. On the other hand, when the polymerization temperature exceeds 130 ° C., the growth radicals may stop with each other as the radical concentration increases, making it difficult to control the polymerization.
２．カルボキシル基含有ビニル系重合体
本発明に係る製造方法で得られるビニル系重合体の数平均分子量は、ゲルパーミエーションクロマトグラフィー（以下「ＧＰＣ」ともいう）によるポリスチレン換算分子量で５００〜１０００００であることが好ましい。数平均分子量が５００未満では、ビニル系重合体の本来の性能が発現されない場合がある。一方、数平均分子量が１０００００を超えると、重合制御が困難になる場合がある。2. Carboxyl group-containing vinyl polymer The vinyl polymer obtained by the production method according to the present invention has a number average molecular weight of 500 to 100,000 in terms of polystyrene by gel permeation chromatography (hereinafter also referred to as “GPC”). Is preferred. If the number average molecular weight is less than 500, the original performance of the vinyl polymer may not be expressed. On the other hand, when the number average molecular weight exceeds 100,000, polymerization control may be difficult.
ＧＰＣで測定した重量平均分子量（Ｍｗ）と、数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）は、１．８未満であることが好ましく、１．６未満であることがより好ましい。 The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC is preferably less than 1.8, and more preferably less than 1.6.
本発明について、実施例及び比較例に基づいて具体的に説明するが、本発明はこれに限定されるものではない。尚、本発明において、重合率及び平均分子量は、以下のようにして評価した
１．評価方法
（１）重合率
重合溶液をサンプリングして、1Ｈ ＮＭＲ測定を行い、単量体及び重合体の積分比により求めた。測定溶媒：重ジメチルスルホキシド
（２）重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）
ゲル浸透クロマトグラフ装置（型式名「ｗａｔｅｒｓ２６９５」、ｗａｔｅｒｓ社製）を用いて、下記の条件によりＭｗ及びＭｎを測定し、標準ポリスチレンにより換算した。
＜測定条件＞
カラム：ＴＳＫｇｅｌ Ｓｕｐｅｒ ＨＺＭ−Ｎ ２本（東ソー社製）
カラム温度：４０℃
溶離液：テトラヒドロフラン
流速：０．５ｍｌ／分
検出器：ＲＩThe present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited thereto. In the present invention, the polymerization rate and average molecular weight were evaluated as follows. Evaluation method (1) Polymerization rate The polymerization solution was sampled, 1 H NMR measurement was performed, and the integral ratio of the monomer and the polymer was obtained. Measurement solvent: heavy dimethyl sulfoxide (2) weight average molecular weight (Mw) and number average molecular weight (Mn)
Using a gel permeation chromatograph (model name “waters2695”, manufactured by Waters), Mw and Mn were measured under the following conditions and converted to standard polystyrene.
<Measurement conditions>
Column: 2 TSKgel Super HZM-N (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Flow rate: 0.5 ml / min Detector: RI
２．カルボキシル基含有重合体の製造
（１）実施例１
１００ｍｌのガラス製反応容器に、塩化銅（２価）４６ｍｇ、トリス（２−（ジメチルアミノ）エチル）アミン４００ｍｇ、 ジメチルホルムアミド３．５ｇを仕込み、室温下で１０分間撹拌した後に、アクリル酸５ｇ及びトリエチルアミン７ｇ（当量比１：１）を加え、窒素で３０分間バブリングを行い、脱酸素を行った。次に、重合開始剤として２−ブロモイソブチル酸ブチル７７ｍｇ、及び２−エチルヘキサン酸錫１．４ｇを添加し、９０℃で重合を行った。一定時間経過後に、重合溶液をサンプリングして評価を行った。重合開始後、５時間後の重合溶液１７．５ｇを陽イオン交換樹脂（オルガノ社製 商品名「アンバーライトＩＲ１２０Ｂ 」）１５０ｇと撹拌して、前記アミンを除去した。次に、この重合溶液をろ過し、脱溶して、カルボキシル基含有重合体２．３ｇを得た。重合結果を表１に示す。2. Production of carboxyl group-containing polymer (1) Example 1
A 100 ml glass reaction vessel was charged with 46 mg of copper chloride (divalent), 400 mg of tris (2- (dimethylamino) ethyl) amine, and 3.5 g of dimethylformamide. After stirring at room temperature for 10 minutes, 5 g of acrylic acid and 7 g of triethylamine (equivalent ratio 1: 1) was added, and deoxygenation was performed by bubbling with nitrogen for 30 minutes. Next, 77 mg of butyl 2-bromoisobutyrate and 1.4 g of tin 2-ethylhexanoate were added as polymerization initiators, and polymerization was performed at 90 ° C. After a certain period of time, the polymerization solution was sampled and evaluated. After the start of polymerization, 17.5 g of the polymerization solution 5 hours later was stirred with 150 g of a cation exchange resin (trade name “Amberlite IR120B” manufactured by Organo Corporation) to remove the amine. Next, this polymerization solution was filtered and dissolved, to obtain 2.3 g of a carboxyl group-containing polymer. The polymerization results are shown in Table 1.
（２）実施例２〜１０、比較例１
重合開始剤の添加量、塩基性化合物の種類及び量を表２の通りとした以外は、実施例１と同様にカルボキシル基含有重合体を製造した。重合時間は５時間とした。(2) Examples 2 to 10 and Comparative Example 1
A carboxyl group-containing polymer was produced in the same manner as in Example 1 except that the addition amount of the polymerization initiator and the kind and amount of the basic compound were as shown in Table 2. The polymerization time was 5 hours.
（３）実施例１１
１００ｍｌのガラス製反応容器に、塩化銅（２価）４６ｍｇ、トリス（２−（ジメチルアミノ）エチル）アミン４００ｍｇ、ジメチルホルムアミド３．５ｇを仕込み、室温下で１０分間撹拌した後に、メタクリル酸６ｇ及びトリエチルアミン７ｇを加え、窒素で３０分間バブリングを行い、脱酸素を行った。次に、重合開始剤として２−ブロモイソブチル酸ブチル７７ｍｇ、及び２−エチルヘキサン酸錫１．４ｇを添加し、９０℃で重合を行った。重合結果を表３に示す。(3) Example 11
A 100 ml glass reaction vessel was charged with 46 mg of copper chloride (divalent), 400 mg of tris (2- (dimethylamino) ethyl) amine, and 3.5 g of dimethylformamide. After stirring at room temperature for 10 minutes, 6 g of methacrylic acid and 7 g of triethylamine was added, and deoxygenation was performed by bubbling with nitrogen for 30 minutes. Next, 77 mg of butyl 2-bromoisobutyrate and 1.4 g of tin 2-ethylhexanoate were added as polymerization initiators, and polymerization was performed at 90 ° C. The polymerization results are shown in Table 3.
（４）実施例１２
１００ｍｌのガラス製反応容器に、塩化銅（２価）４６ｍｇ、トリス（２−（ジメチルアミノ）エチル）アミン４００ｍｇ、ジメチルホルムアミド３．５ｇを仕込み、室温下で１０分間撹拌した後に、アクリル酸５ｇ及びトリエチルアミン７ｇを加え、窒素で３０分間バブリングを行い、脱酸素を行った。次に、重合開始剤として２−ブロモイソブチル酸ブチル７７ｍｇ、及び２−エチルヘキサン酸錫１．４ｇを添加し、９０℃で重合を行った。８時間経過後、アクリル酸ｎ−ブチルを９ｇ添加し、その後２時間重合をした（計１０時間）。重合開始後、１０時間後の重合溶液２６．５ｇを陽イオン交換樹脂（オルガノ社製 商品名「アンバーライトＩＲ１２０Ｂ」）２００ｇと撹拌して、前記アミンを除去した。次に、この重合溶液をろ過し、脱溶して、カルボキシル基含有共重合体１０．５ｇを得た。重合結果を表４に示す。(4) Example 12
A 100 ml glass reaction vessel was charged with 46 mg of copper chloride (divalent), 400 mg of tris (2- (dimethylamino) ethyl) amine, and 3.5 g of dimethylformamide. After stirring at room temperature for 10 minutes, 5 g of acrylic acid and 7 g of triethylamine was added, and deoxygenation was performed by bubbling with nitrogen for 30 minutes. Next, 77 mg of butyl 2-bromoisobutyrate and 1.4 g of tin 2-ethylhexanoate were added as polymerization initiators, and polymerization was performed at 90 ° C. After 8 hours, 9 g of n-butyl acrylate was added, followed by polymerization for 2 hours (10 hours in total). After the initiation of polymerization, 26.5 g of the polymer solution 10 hours later was stirred with 200 g of a cation exchange resin (trade name “Amberlite IR120B” manufactured by Organo Corporation) to remove the amine. Next, this polymerization solution was filtered and dissolved to obtain 10.5 g of a carboxyl group-containing copolymer. The polymerization results are shown in Table 4.
本発明に係る製造方法は、重合後に脱保護反応をすることなく、直接カルボキシル基含有重合体を製造することができる。得られた重合体は、分子量分布が狭く、水溶性重合体又は両親媒性共重合体として有用である。 The production method according to the present invention can produce a carboxyl group-containing polymer directly without deprotection after polymerization. The obtained polymer has a narrow molecular weight distribution and is useful as a water-soluble polymer or amphiphilic copolymer.
Claims (8)
有機溶剤と遷移金属錯体とを混合する工程、この混合液にカルボキシル基を有するビニル単量体及び有機アミンを添加し、当該ビニル単量体を中和する工程、次いで、重合開始剤を添加してリビングラジカル重合を行う工程とを備えることを特徴とするカルボキシル基含有重合体の製造方法。 In a method for producing a vinyl monomer having a carboxyl group by living radical polymerization by an atom transfer radical polymerization method,
A step of mixing an organic solvent and a transition metal complex, a step of adding a vinyl monomer having a carboxyl group and an organic amine to the mixed solution, neutralizing the vinyl monomer, and then adding a polymerization initiator And a step of conducting living radical polymerization. A method for producing a carboxyl group-containing polymer.
The method for producing a carboxyl group-containing polymer according to any one of claims 1 to 7, further comprising a step of removing the organic amine using a cation exchange resin after the living radical polymerization.
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