WO2023062931A1 - 化合物及び当該化合物の製造方法 - Google Patents
化合物及び当該化合物の製造方法 Download PDFInfo
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- WO2023062931A1 WO2023062931A1 PCT/JP2022/030810 JP2022030810W WO2023062931A1 WO 2023062931 A1 WO2023062931 A1 WO 2023062931A1 JP 2022030810 W JP2022030810 W JP 2022030810W WO 2023062931 A1 WO2023062931 A1 WO 2023062931A1
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- Prior art keywords
- compound
- group
- polymerization
- monomer unit
- methacrylate
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 52
- 125000001425 triazolyl group Chemical group 0.000 claims abstract 4
- 239000000178 monomer Substances 0.000 claims description 58
- 238000006116 polymerization reaction Methods 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 35
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 claims description 27
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 239000003505 polymerization initiator Substances 0.000 claims description 18
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 17
- 229910052740 iodine Inorganic materials 0.000 claims description 17
- 239000011630 iodine Substances 0.000 claims description 17
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims description 15
- 239000007870 radical polymerization initiator Substances 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 150000001540 azides Chemical group 0.000 claims description 9
- 150000001993 dienes Chemical class 0.000 claims description 8
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 7
- 150000002825 nitriles Chemical class 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 238000001308 synthesis method Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 30
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 18
- 238000005227 gel permeation chromatography Methods 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 12
- 239000003999 initiator Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 150000003852 triazoles Chemical group 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 8
- 238000005873 Huisgen reaction Methods 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 238000007872 degassing Methods 0.000 description 7
- IOLQWGVDEFWYNP-UHFFFAOYSA-N ethyl 2-bromo-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)Br IOLQWGVDEFWYNP-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 7
- 235000010378 sodium ascorbate Nutrition 0.000 description 7
- 229960005055 sodium ascorbate Drugs 0.000 description 7
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 7
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 5
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 5
- 229920000578 graft copolymer Polymers 0.000 description 5
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 4
- HLWROINQOSYBAM-UHFFFAOYSA-N 4-ethenyl-5-methyl-2h-triazole Chemical compound CC=1NN=NC=1C=C HLWROINQOSYBAM-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 150000002896 organic halogen compounds Chemical class 0.000 description 4
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- -1 temperature Polymers 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Chemical group 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 150000005527 organic iodine compounds Chemical class 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 2
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- PYNYHMRMZOGVML-UHFFFAOYSA-N 2-bromopropanenitrile Chemical compound CC(Br)C#N PYNYHMRMZOGVML-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical group CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- RLFXJQPKMZNLMP-UHFFFAOYSA-N 2-phenylprop-2-enenitrile Chemical compound N#CC(=C)C1=CC=CC=C1 RLFXJQPKMZNLMP-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 2
- XFZOHDFQOOTHRH-UHFFFAOYSA-N 7-methyloctyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C(C)=C XFZOHDFQOOTHRH-UHFFFAOYSA-N 0.000 description 2
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
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- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
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- 238000011088 calibration curve Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
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- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- AVMMXNKUHBWIMU-UHFFFAOYSA-N ethyl 2-iodopropanoate Chemical compound CCOC(=O)C(C)I AVMMXNKUHBWIMU-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
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- YDCHPLOFQATIDS-UHFFFAOYSA-N methyl 2-bromoacetate Chemical compound COC(=O)CBr YDCHPLOFQATIDS-UHFFFAOYSA-N 0.000 description 2
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
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- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
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- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 2
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- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 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
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- OUNGCXOSNIXVIL-UHFFFAOYSA-N 1,3,5-tris(1-iodoethyl)benzene Chemical compound IC(C)C1=CC(=CC(=C1)C(C)I)C(C)I OUNGCXOSNIXVIL-UHFFFAOYSA-N 0.000 description 1
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- RJZCPVOAAXABEZ-UHFFFAOYSA-N 1,4-bis(iodomethyl)benzene Chemical compound ICC1=CC=C(CI)C=C1 RJZCPVOAAXABEZ-UHFFFAOYSA-N 0.000 description 1
- INKNHBKFSPIMKS-UHFFFAOYSA-N 1-(iodomethyl)-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(CI)C=C1 INKNHBKFSPIMKS-UHFFFAOYSA-N 0.000 description 1
- CRRUGYDDEMGVDY-UHFFFAOYSA-N 1-bromoethylbenzene Chemical compound CC(Br)C1=CC=CC=C1 CRRUGYDDEMGVDY-UHFFFAOYSA-N 0.000 description 1
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- OBNIRVVPHSLTEP-UHFFFAOYSA-N 1-ethoxy-2-(2-hydroxyethoxy)ethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(O)COCCO OBNIRVVPHSLTEP-UHFFFAOYSA-N 0.000 description 1
- HOVGFTKZAOQJEF-UHFFFAOYSA-N 1-iodoethylbenzene Chemical compound CC(I)C1=CC=CC=C1 HOVGFTKZAOQJEF-UHFFFAOYSA-N 0.000 description 1
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- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-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
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 1
- WULAHPYSGCVQHM-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethanol Chemical compound OCCOCCOC=C WULAHPYSGCVQHM-UHFFFAOYSA-N 0.000 description 1
- XOYBOVVEAZCGEU-UHFFFAOYSA-N 2-(2-hydroxyethyldisulfanyl)ethyl 2-bromo-2-methylpropanoate Chemical compound CC(C)(Br)C(=O)OCCSSCCO XOYBOVVEAZCGEU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 description 1
- REXUYBKPWIPONM-UHFFFAOYSA-N 2-bromoacetonitrile Chemical compound BrCC#N REXUYBKPWIPONM-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- DADRTBXENQOJNW-UHFFFAOYSA-N 2-hydroxyethyl 2-iodo-2-methylpropanoate Chemical compound CC(C)(I)C(=O)OCCO DADRTBXENQOJNW-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- CREOHKRPSSUXCW-UHFFFAOYSA-N 2-iodo-1-phenylethanone Chemical compound ICC(=O)C1=CC=CC=C1 CREOHKRPSSUXCW-UHFFFAOYSA-N 0.000 description 1
- DBESYUOJKJZGLV-UHFFFAOYSA-N 2-iodo-2-methylpropanenitrile Chemical compound CC(C)(I)C#N DBESYUOJKJZGLV-UHFFFAOYSA-N 0.000 description 1
- ZGPRANYVOMBLFL-UHFFFAOYSA-N 2-iodo-2-phenylacetic acid Chemical compound OC(=O)C(I)C1=CC=CC=C1 ZGPRANYVOMBLFL-UHFFFAOYSA-N 0.000 description 1
- WKZUKIUUBDORKH-UHFFFAOYSA-N 2-iodo-2-phenylacetonitrile Chemical compound N#CC(I)C1=CC=CC=C1 WKZUKIUUBDORKH-UHFFFAOYSA-N 0.000 description 1
- VODKOOOHHCAWFR-UHFFFAOYSA-N 2-iodoacetonitrile Chemical compound ICC#N VODKOOOHHCAWFR-UHFFFAOYSA-N 0.000 description 1
- QKSBEDINHRIOJR-UHFFFAOYSA-N 2-iodopropanamide Chemical compound CC(I)C(N)=O QKSBEDINHRIOJR-UHFFFAOYSA-N 0.000 description 1
- MEKNBSXCEMCLHJ-UHFFFAOYSA-N 2-iodopropanenitrile Chemical compound CC(I)C#N MEKNBSXCEMCLHJ-UHFFFAOYSA-N 0.000 description 1
- KZLYQYPURWXOEW-UHFFFAOYSA-N 2-iodopropanoic acid Chemical compound CC(I)C(O)=O KZLYQYPURWXOEW-UHFFFAOYSA-N 0.000 description 1
- CXFBCWNSRKBIJU-UHFFFAOYSA-N 3-iodooxolan-2-one Chemical compound IC1CCOC1=O CXFBCWNSRKBIJU-UHFFFAOYSA-N 0.000 description 1
- GEVOCWHKMYIZGM-UHFFFAOYSA-N 3-trichlorosilylpropyl 2-bromo-2-methylpropanoate Chemical compound CC(C)(Br)C(=O)OCCC[Si](Cl)(Cl)Cl GEVOCWHKMYIZGM-UHFFFAOYSA-N 0.000 description 1
- PBHIWZGFSZBQJV-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-bromo-2-methylpropanoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)(C)Br PBHIWZGFSZBQJV-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- IJIBRSFAXRFPPN-UHFFFAOYSA-N 5-bromo-2-methoxybenzaldehyde Chemical compound COC1=CC=C(Br)C=C1C=O IJIBRSFAXRFPPN-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- YPZMUXQQEWJJSD-UHFFFAOYSA-N 9-iodo-9h-fluorene Chemical compound C1=CC=C2C(I)C3=CC=CC=C3C2=C1 YPZMUXQQEWJJSD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- ZWLNOMIBMMWIII-UHFFFAOYSA-N C1=CC=C(C=C1)C(C(=O)O)I.C1=CC=C(C=C1)C(C(=O)O)I.C(CO)O Chemical compound C1=CC=C(C=C1)C(C(=O)O)I.C1=CC=C(C=C1)C(C(=O)O)I.C(CO)O ZWLNOMIBMMWIII-UHFFFAOYSA-N 0.000 description 1
- 241001264766 Callistemon Species 0.000 description 1
- RENMDAKOXSCIGH-UHFFFAOYSA-N Chloroacetonitrile Chemical compound ClCC#N RENMDAKOXSCIGH-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BLYDPGKPVALUGA-UHFFFAOYSA-N OCC(O)CO.CC(C(=O)O)(C)I.CC(C(=O)O)(C)I.CC(C(=O)O)(C)I Chemical compound OCC(O)CO.CC(C(=O)O)(C)I.CC(C(=O)O)(C)I.CC(C(=O)O)(C)I BLYDPGKPVALUGA-UHFFFAOYSA-N 0.000 description 1
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- DKWYZBFGYJOCJX-UHFFFAOYSA-N [iodo(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(I)C1=CC=CC=C1 DKWYZBFGYJOCJX-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- KIMUBWCCUQTWEW-UHFFFAOYSA-N benzyl 2-iodo-2-methylpropanoate Chemical compound O=C(OCC1=CC=CC=C1)C(C)(C)I KIMUBWCCUQTWEW-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- QEAHGOUBRPCBNV-UHFFFAOYSA-N diethyl 2,5-diiodohexanedioate Chemical compound CCOC(=O)C(I)CCC(I)C(=O)OCC QEAHGOUBRPCBNV-UHFFFAOYSA-N 0.000 description 1
- WHVKBVFJYRWJHM-UHFFFAOYSA-N diethyl 2-iodo-2-methylpropanedioate Chemical compound CCOC(=O)C(C)(I)C(=O)OCC WHVKBVFJYRWJHM-UHFFFAOYSA-N 0.000 description 1
- JMQGGPRJQOQKRT-UHFFFAOYSA-N diphenyl hydrogen phosphate;azide Chemical compound [N-]=[N+]=[N-].C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 JMQGGPRJQOQKRT-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- JGNSTLRRCFVAEI-UHFFFAOYSA-N ethane-1,2-diol 2-iodo-2-methylpropanoic acid Chemical compound OCCO.CC(C)(I)C(O)=O.CC(C)(I)C(O)=O JGNSTLRRCFVAEI-UHFFFAOYSA-N 0.000 description 1
- VOSLESJOKKAPMJ-UHFFFAOYSA-N ethyl 2-iodo-2-(4-methylphenyl)acetate Chemical compound IC(C(=O)OCC)C1=CC=C(C=C1)C VOSLESJOKKAPMJ-UHFFFAOYSA-N 0.000 description 1
- XHHOWVHYQVFMST-UHFFFAOYSA-N ethyl 2-iodo-2-methyl-3-oxobutanoate Chemical compound C(C)OC(C(C(=O)C)(C)I)=O XHHOWVHYQVFMST-UHFFFAOYSA-N 0.000 description 1
- AYVTVRNTNCEPSH-UHFFFAOYSA-N ethyl 2-iodo-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)I AYVTVRNTNCEPSH-UHFFFAOYSA-N 0.000 description 1
- GFYUBPKXVMWINH-UHFFFAOYSA-N ethyl 2-iodo-2-phenylacetate Chemical compound CCOC(=O)C(I)C1=CC=CC=C1 GFYUBPKXVMWINH-UHFFFAOYSA-N 0.000 description 1
- BEKQSWCOHDSDPD-UHFFFAOYSA-N ethyl 2-iodobutanoate Chemical compound CCOC(=O)C(I)CC BEKQSWCOHDSDPD-UHFFFAOYSA-N 0.000 description 1
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 description 1
- MFFXVVHUKRKXCI-UHFFFAOYSA-N ethyl iodoacetate Chemical compound CCOC(=O)CI MFFXVVHUKRKXCI-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration 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
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- JDNTWHVOXJZDSN-UHFFFAOYSA-N iodoacetic acid Chemical compound OC(=O)CI JDNTWHVOXJZDSN-UHFFFAOYSA-N 0.000 description 1
- XJTQJERLRPWUGL-UHFFFAOYSA-N iodomethylbenzene Chemical compound ICC1=CC=CC=C1 XJTQJERLRPWUGL-UHFFFAOYSA-N 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- ACEONLNNWKIPTM-UHFFFAOYSA-N methyl 2-bromopropanoate Chemical compound COC(=O)C(C)Br ACEONLNNWKIPTM-UHFFFAOYSA-N 0.000 description 1
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 description 1
- CYIPOXZPELQRJS-UHFFFAOYSA-N methyl 2-iodo-2-methylpropanoate Chemical compound COC(=O)C(C)(C)I CYIPOXZPELQRJS-UHFFFAOYSA-N 0.000 description 1
- YDGMIJCIBXSCQR-UHFFFAOYSA-N methyl 2-iodoacetate Chemical compound COC(=O)CI YDGMIJCIBXSCQR-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- IGVNJALYNQVQIT-UHFFFAOYSA-N tert-butyl 2-bromo-2-methylpropanoate Chemical compound CC(C)(C)OC(=O)C(C)(C)Br IGVNJALYNQVQIT-UHFFFAOYSA-N 0.000 description 1
- SEDZOYHHAIAQIW-UHFFFAOYSA-N trimethylsilyl azide Chemical compound C[Si](C)(C)N=[N+]=[N-] SEDZOYHHAIAQIW-UHFFFAOYSA-N 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- 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
- C08F8/48—Isomerisation; Cyclisation
Definitions
- the present invention relates to a compound and a method for producing the compound.
- Comb-shaped polymers such as bottlebrush polymers are graft polymers that are expected to be developed as stimuli-responsive polymers such as temperature, polymer templates, or polymers for drug delivery systems.
- Such graft polymers can be obtained by various graft polymerizations, and a grafting-through method using a macromonomer is expected as a new technique (Non-Patent Document 1).
- the macromonomer that can be used in the grafting-through method is required to be a compound that has a polymer portion that can become a side chain in the graft polymer and a polymerizable group that can constitute the main chain.
- the number of types of compounds provided as such macromonomers is still small, and methods for synthesizing them are also limited.
- the present invention has been made in view of such problems, and provides a novel compound having a polymer portion and a polymerizable group, and a method for synthesizing the same.
- the present invention comprises a first portion and a second portion, wherein the first portion has a polymer chain, and the second portion comprises a triazole skeleton and a polymerizable group attached to the triazole skeleton. having a compound provided
- a compound comprising a first portion and a second portion, wherein the first portion has a polymer chain, and the second portion has a triazole skeleton and a polymerizable group bonded to the triazole skeleton.
- the polymer chain has radically polymerizable monomer units, and the radically polymerizable monomer units are styrene monomer units, (meth)acrylic monomer units, and diene monomer units.
- the compound according to [1] which is at least one monomer unit selected from the group consisting of a body unit, a vinyl ether-based monomer unit, and an unsaturated nitrile-based monomer unit.
- [3] The compound according to [1] or [2], wherein the polymerizable group is a vinyl group.
- [4] The compound according to any one of [1] to [3], wherein the first portion has a terminal group derived from an atom transfer radical polymerization initiator or an iodine transfer polymerization initiator.
- a polymerization step, an azide group introduction step, and a polymerizable group introduction step wherein in the polymerization step, the radically polymerizable monomer is polymerized to produce a first intermediate, and the azide group is introduced.
- the first intermediate is subjected to an azidation reaction to produce a second intermediate, and in the step of introducing a polymerizable group, the second intermediate is reacted with monovinylacetylene or a monovinylacetylene derivative, [1] A method for producing the compound according to any one of [4].
- Compound A compound according to one embodiment of the present invention comprises a first portion and a second portion.
- the first portion and the second portion are covalently attached to each other.
- the first portion has a polymer chain. Also, the first portion may have a terminal group derived from an atom transfer radical polymerization initiator or an iodine transfer polymerization initiator. The polymer chains and the terminal groups derived from the atom transfer radical polymerization initiator or the iodine transfer polymerization initiator are covalently bonded to each other.
- the polymer chain has radically polymerizable monomer units.
- a radically polymerizable monomer unit is a structural unit of a polymer chain derived from a radically polymerizable monomer. Radically polymerizable monomer units include, for example, styrene-based monomer units, (meth)acrylic-based monomer units, diene-based monomer units, vinyl ether-based monomer units, and unsaturated nitrile-based monomer units. etc. These can be used singly or in combination.
- Styrenic monomer units include, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, ⁇ -methylstyrene, and It is a unit derived from a styrenic monomer such as ⁇ -methyl-p-methylstyrene.
- (Meth)acrylic monomer units include, for example, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, normal propyl acrylate, normal propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, normal butyl acrylate, normal Butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, secondary butyl acrylate, secondary butyl methacrylate, tertiary butyl acrylate, tertiary butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, normal octyl acrylate, normal octyl methacrylate, isooctyl methacrylate, normal nonyl acrylate, normal nonyl acrylate, normal nonyl
- the diene-based monomer unit is, for example, a unit derived from a conjugated diene monomer such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and chloroprene. .
- Vinyl ether monomer units include, for example, vinyl ether monomers such as vinyl acetate, vinyl propionate, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, vinyl methyl ether, vinyl butyl ether and vinyl octyl ether. is a unit derived from
- the unsaturated nitrile-based monomer units are units derived from unsaturated nitrile-based monomers such as acrylonitrile, methacrylonitrile, ethacrylonitrile, and phenylacrylonitrile.
- the polymer chain may be a homopolymer composed of monomer units derived from a single monomer, or a copolymer composed of monomer units derived from a plurality of types of monomers. may be When the polymer chain is a copolymer, it may be a random copolymer, alternating copolymer, block copolymer, graft copolymer, or the like.
- Terminal Group Derived from Atom Transfer Radical Polymerization Initiator is a site derived from the polymerization initiator used for atom transfer radical polymerization (ATRP).
- ATRP initiators are organohalogen compounds.
- Organic halogen compounds as ATRP initiators include, for example, methyl 2-chloropropionate, 2,2-dichloroacetophenone, 3-(trimethoxysilyl)propyl 2-bromo-2-methylpropanoate, chloroacetonitrile, and methyl chloroacetate.
- tert-butyl 2-bromoisobutyrate (1-bromoethyl)benzene, methyl 2-bromopropionate, methyl 2-chloropropionate, 3-(trichlorosilyl)propyl 2-bromo-2-methylpropanoate, 2-bromo -3-(triethoxysilyl)propyl 2-methylpropanoate, 2-[(2-hydroxyethyl)disulfanyl]ethyl 2-bromo-2-methylpropionate, 11-mercapto 2-bromo-2-methylpropanoate undecyl, bromoacetonitrile, (1-chloroethyl)benzene, ethyl 2-bromoisobutyrate, [11-[(2-bromo-2-methylpropanoyl)oxy]undecyl]phosphonic acid, 2-bromo-2-methylpropanoic acid 2-hydroxyethyl, ethyl bromoacetate, ally
- YX (Y is an organic group and X is a halogen group) is used as the organic halogen compound
- Y is the terminal group derived from the atom transfer radical polymerization initiator.
- Y is bonded to the polymer chain through the carbon atom or the like in Y to which the halogen group was bonded.
- Y preferably has a substituent capable of delocalizing an unpaired electron such as a carbonyl group, a cyano group, a nitro group, or a phenyl group.
- the carbon atom to which the halogen group X is bonded is preferably adjacent to the electron-withdrawing group.
- the terminal group derived from the atom transfer radical polymerization initiator has a structure represented by the following general formula (1).
- A1 represents a bond with a polymer chain.
- Terminal Groups Derived from Iodine Transfer Polymerization Initiator are moieties derived from the polymerization initiator used for iodine transfer polymerization. ITP initiators are organoiodine compounds.
- Organic iodine compounds as ITP initiators include, for example, 2-iodoacetic acid, methyl 2-iodoacetate, ethyl 2-iodoacetate, 2-iodopropionic acid, ethyl 2-iodopropionate, ethyl 2-iodobutyrate, 2-iodo Ethyl valerate, methyl 2-iodoisobutyrate, ethyl 2-iodoisobutyrate, benzyl 2-iodoisobutyrate, ⁇ -iodo- ⁇ -butyrolactone, 2-hydroxyethyl 2-iodoisobutyrate, diethyl 2-iodo-2-methylmalonate , ethyl 2-iodo-2-methylacetoacetate, 2-iodo-2-phenylacetic acid, ethyl 2-iodo-2-phenylacetate, ethyl 2-iodo-2-(4′-
- YI (Y is an organic group and I is iodine) is used as the organic iodine compound
- Y is the terminal group derived from the iodine transfer polymerization initiator.
- Y is bonded to the polymer chain through the carbon atom in Y to which iodine was bonded.
- Y preferably has a substituent capable of delocalizing an unpaired electron such as a carbonyl group, a cyano group, a nitro group, or a phenyl group.
- the carbon atom to which iodine I is bound is preferably adjacent to the electron-withdrawing group.
- Second Part has a triazole skeleton and a polymerizable group attached to the triazole skeleton.
- a nitrogen atom contained in the ring structure of the triazole skeleton is covalently bonded to the polymer chain of the first portion.
- the carbon atoms contained in the cyclic structure of the triazole skeleton are covalently bonded to the polymerizable group.
- a polymerizable group is a functional group that can be polymerized by itself or copolymerized with other monomers (for example, radical polymerization, anionic polymerization, cationic polymerization, etc.).
- the polymerizable group is, for example, a group having a carbon-carbon double bond such as a vinyl group.
- a vinyl group is preferable as the polymerizable group from the viewpoint of ease of introduction as a polymerizable group bonded to the triazole skeleton.
- the second portion may have a structure represented by the following general formula (2).
- R 1 is hydrogen, chlorine, bromine, iodine, substituted or unsubstituted alkyl group, alkenyl group, aryl group, mercapto group, heterocyclyl group, substituted or unsubstituted silyl group, substituted or unsubstituted ether group, and substituted Or any one selected from the group consisting of unsubstituted amino groups.
- R 2 , R 3 and R 4 are each independently hydrogen, chlorine, bromine, iodine, substituted or unsubstituted alkyl group, alkenyl group, aryl group, mercapto group, heterocyclyl group, substituted or unsubstituted silyl is any one selected from the group consisting of a group, a substituted or unsubstituted ether group, and a substituted or unsubstituted amino group.
- a specific example of the second moiety is a structure represented by the following general formula (3) in which R 1 , R 2 , R 3 and R 4 are hydrogen atoms.
- A2 represents a bond with the first portion.
- the number average molecular weight (Mn) of the compound according to one embodiment of the present invention is preferably 1,000 to 100,000, more preferably 2,000 to 50,000.
- a compound according to one embodiment of the present invention for example, specifically has a structure represented by the following formula (6).
- R 1 , R 2 , R 3 and R 4 in formula (6) above are the same as in formula (2) above.
- W is the aforementioned polymer chain contained in the first portion.
- Y is an organic group, and is a terminal group derived from the above atom transfer radical polymerization initiator or iodine transfer polymerization initiator.
- Method for Producing Compound includes a polymerization step, an azide group introduction step, and a polymerizable group introduction step.
- radically polymerizable monomers examples include styrene-based monomers, (meth)acrylic-based monomers, diene-based monomers, vinyl ether-based monomers, and unsaturated nitrile-based monomers. These can be used singly or in combination.
- Styrenic monomers include, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p-tert-butylstyrene, ⁇ -methylstyrene, and ⁇ -methyl-p-methylstyrene and the like.
- (Meth)acrylic monomers include, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, normal propyl acrylate, normal propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, normal butyl acrylate, normal butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, secondary butyl acrylate, secondary butyl methacrylate, tertiary butyl acrylate, tertiary butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, normal octyl acrylate, normal octyl methacrylate, isooctyl methacrylate, normal nonyl acrylate, Normal nonyl methacrylate, isononyl
- diene-based monomers include conjugated diene monomers such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and chloroprene.
- vinyl ether monomers examples include vinyl acetate, vinyl propionate, vinyl methyl ether, vinyl butyl ether and vinyl octyl ether.
- Unsaturated nitrile-based monomers include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, and the like.
- the polymerization reaction in the polymerization step is carried out by polymerizing radically polymerizable monomers in the presence of a polymerization initiator.
- a polymerization initiator for example, the above ATRP initiator or ITP initiator is used.
- a catalyst such as a transition metal complex such as copper is added.
- a catalyst such as sodium azide or a salt containing iodine is added.
- the first intermediate is a polymer (homopolymer or copolymer) of radically polymerizable monomers.
- a polymer has a structure that becomes the polymer chain of Part 1 above.
- the first intermediate preferably has a terminal structure that can be azidated.
- Azidizable terminal structures are, for example, carbons such as methylene groups substituted by halogens such as fluorine, chlorine, bromine or iodine.
- the first intermediate has a terminal group derived from the atom transfer radical polymerization initiator.
- the first intermediate has a terminal group derived from the iodine transfer polymerization initiator.
- the first intermediate is subjected to an azidation reaction to produce a second intermediate.
- the azidation reaction can be carried out by reacting the first intermediate with an azidating agent.
- Azidation reactions include nucleophilic substitution reactions, reactions using organometallic reagents (organolithium reagents and Grignard reagents), coupling reactions using transition metal catalysts (eg, copper catalysts), and the like.
- azidating agents examples include sodium azide, trimethylsilyl azide, diphenyl phosphate azide, tributyltin azide, tetramethylguanidinium azide and the like. Any other azidation agent can be selected depending on the azidation reaction to be used.
- the second intermediate has a polymer of radically polymerizable monomers and an azide group. Moreover, the second intermediate may further have a terminal group derived from the atom transfer radical polymerization initiator.
- polymerizable Group-introducing step the second intermediate is reacted with monovinylacetylene or a monovinylacetylene derivative (monovinylacetylene-based compound) to obtain a compound containing the above first portion and second portion.
- the azide group of the second intermediate reacts with monovinylacetylene or a monovinylacetylene derivative to form a triazole skeleton.
- Monovinylacetylene or a monovinylacetylene derivative is, for example, a structure represented by the following general formula (4).
- R 1 , R 2 , R 3 and R 4 in formula (4) above are the same as in formula (2) above.
- R 1 , R 2 , R 3 and R 4 in the above formula (4) are hydrogen atoms.
- Example 1 (Styrene polymerization step) The polymerization reaction was carried out according to reference 1 (J Polym Sci Part A: Polym Chem 2006, 44, 1667-1675.).
- Intermediate 2-1 was also analyzed by an infrared spectrophotometer. A peak was confirmed near 2100 cm ⁇ 1 , confirming the introduction of an azide group.
- the measurement conditions for the infrared spectrophotometer are as follows. Apparatus name: Frontier (manufactured by PerkinElmer Co., Ltd.) Start Range: 4000 cm -1 End Range: 400 cm -1 Number of times of accumulation: 16 times Resolution: 4.0 cm -1 Spacing: 1.0 cm -1 Measurement method: ATR method (Durascope)
- the resulting compound 1 was dissolved in tetrahydrofuran, precipitated by adding methanol, and then filtered. The residue was dried under reduced pressure to obtain a sample. After dissolving the sample in deuterated chloroform, the 1H-NMR spectrum was measured. The measurement data were corrected based on the chloroform peak (7.24 ppm) in the deuterated chloroform used as the solvent.
- the number average molecular weight of compound 1 was measured by gel permeation chromatography (GPC).
- the number average molecular weight of compound 1 was 5,000.
- the GPC measurement conditions are as follows.
- Example 2 (Styrene polymerization step) Polymerization reactions were carried out according to reference 1.
- the resulting compound 2 was dissolved in tetrahydrofuran, precipitated by adding methanol, and then filtered. The residue was dried under reduced pressure to obtain a sample. After dissolving the sample in deuterated chloroform, the 1H-NMR spectrum was measured. The measurement data were corrected based on the chloroform peak (7.24 ppm) in the deuterated chloroform used as the solvent.
- Example 3 Metal methacrylate polymerization step
- the polymerization reaction was carried out according to reference 2 (Macromolecules 1997, 30, 2216-2218.).
- a 200 ml eggplant-shaped flask was charged with 50 ml of acetone, 50 g of methyl methacrylate, 2.2 g of pentamethyldiethylenetriamine, and 0.90 g of copper (I) bromide, and freeze degassing was performed three times under a nitrogen atmosphere. After heating the reaction solution to 50° C., it was stirred with a magnetic stirrer. Polymerization was initiated by adding 2.4 g of ethyl 2-bromoisobutyrate as a polymerization initiator. When the polymerization rate reached 80%, the temperature of the reaction solution was lowered to 20° C. to terminate the reaction. Toluene was added to the reaction solution to precipitate polymethyl methacrylate, and the intermediate 1-3 polymer was recovered. A portion of the polymer was sampled for analysis and the remainder was used for azidation.
- the obtained compound 3 was dissolved in tetrahydrofuran, precipitated by adding methanol, and then filtered. The residue was dried under reduced pressure to obtain a sample. After dissolving the sample in deuterated chloroform, the 1H-NMR spectrum was measured. The measurement data were corrected based on the chloroform peak (7.24 ppm) in the deuterated chloroform used as the solvent.
- Example 4 Metal methacrylate polymerization step, azidation step
- Polymerization and azidation reactions were carried out according to Reference 6 (J.Am.Chem.Soc., 2017, 139, 10551-10560).
- Example 2 the number average molecular weight of Intermediate 2-4 measured by GPC in the same manner as in Example 1 was 5,500.
- Intermediate 2-4 was also analyzed by an infrared spectrophotometer in the same manner as in Example 1. A peak was confirmed near 2100 cm ⁇ 1 , confirming the introduction of an azide group.
- the obtained compound 3 was dissolved in tetrahydrofuran, precipitated by adding methanol, and then filtered. The residue was dried under reduced pressure to obtain a sample. After dissolving the sample in deuterated chloroform, the 1H-NMR spectrum was measured. The measurement data were corrected based on the chloroform peak (7.24 ppm) in the deuterated chloroform used as the solvent.
- Example 5 butadiene polymerization step
- the polymerization reaction was carried out according to reference 3 (ACS Catal. 2020, 10, 12, 6645-6663).
- the obtained compound 5 was dissolved in tetrahydrofuran, precipitated by adding methanol, and then filtered. The residue was dried under reduced pressure to obtain a sample. After dissolving the sample in deuterated chloroform, the 1H-NMR spectrum was measured. The measurement data were corrected based on the chloroform peak (7.24 ppm) in the deuterated chloroform used as the solvent.
- Example 6 (Vinyl acetate polymerization step) The polymerization reaction was carried out according to reference 4 (AIChE J. 55 (2009) 737-746.).
- Example 7 (Acrylonitrile polymerization step) Polymerization reactions were carried out according to reference 5 (Macromolecules 1997, 30, 6398-6400).
- the resulting compound 7 was dissolved in dimethylsulfoxide, added with methanol to precipitate, and then filtered. The residue was dried under reduced pressure to obtain a sample. After dissolving the sample in deuterated dimethylsulfoxide, the 1H-NMR spectrum was measured. The measurement data were corrected based on the heavy dimethylsulfoxide peak (2.50 ppm) in the heavy dimethylsulfoxide used as the solvent.
- the number average molecular weight of compound 7 measured by GPC in the same manner as in Example 1 was 5,000. However, dimethylformamide was used as a solvent.
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Abstract
Description
[1]第1部分と、第2部分と、を含み、前記第1部分は、ポリマー鎖を有し、前記第2部分は、トリアゾール骨格及び前記トリアゾール骨格に結合した重合性基を有する、化合物。
[2]前記ポリマー鎖は、ラジカル重合性単量体単位を有し、前記ラジカル重合性単量体単位は、スチレン系単量体単位、(メタ)アクリル系単量体単位、ジエン系単量体単位、ビニルエーテル系単量体単位、不飽和ニトリル系単量体単位からなる群から選択される1種以上の単量体単位である、[1]に記載の化合物。
[3]前記重合性基は、ビニル基である、[1]又は[2]に記載の化合物。
[4]前記第1部分は、原子移動ラジカル重合開始剤あるいはヨウ素移動重合開始剤由来の末端基を有する、[1]~[3]の何れか1項に記載の化合物。
[5]重合工程と、アジド基導入工程と、重合性基導入工程と、を備え、前記重合工程では、前記ラジカル重合性単量体の重合により第1中間体を生成し、前記アジド基導入工程では、前記第1中間体に対するアジド化反応により第2中間体を生成し、前記重合性基導入工程では、前記第2中間体と、モノビニルアセチレン又はモノビニルアセチレン誘導体とを反応させる、[1]~[4]の何れか1項に記載の化合物の製造方法。
本発明の一実施形態に係る化合物は、第1部分と、第2部分と、を含む。第1部分と第2部分は互いに共有結合により結合されている。
第1部分は、ポリマー鎖を有する。また、第1部分は、原子移動ラジカル重合開始剤あるいはヨウ素移動重合開始剤由来の末端基を有していてもよい。ポリマー鎖と原子移動ラジカル重合開始剤あるいはヨウ素移動重合開始剤由来の末端基は、互いに共有結合で結合されている。
ポリマー鎖は、ラジカル重合性単量体単位を有する。ラジカル重合性単量体単位は、ラジカル重合性の単量体に由来するポリマー鎖の構成単位である。ラジカル重合性単量体単位は、例えば、スチレン系単量体単位、(メタ)アクリル系単量体単位、ジエン系単量体単位、ビニルエーテル系単量体単位、不飽和ニトリル系単量体単位等である。これらは単独又は複数を組み合わせて用いることができる。
原子移動ラジカル重合開始剤由来の末端基は、原子移動ラジカル重合(ATRP)に用いられる重合開始剤に由来する部位である。ATRP開始剤は、有機ハロゲン化合物である。
ヨウ素移動重合(ITP)開始剤由来の末端基は、ヨウ素移動重合に用いられる重合開始剤に由来する部位である。ITP開始剤は、有機ヨウ素化合物である。
第2部分は、トリアゾール骨格及び当該トリアゾール骨格に結合した重合性基を有する。トリアゾール骨格の環状構造に含まれる窒素原子が第1部分のポリマー鎖と共有結合している。また、トリアゾール骨格の環状構造に含まれる炭素原子が重合性基と共有結合している。
本発明の一実施形態に係る化合物の数平均分子量(Mn)は、好ましくは1000~100000であり、より好ましくは2000~50000である。
本発明の一実施形態に係る化合物の製造方法は、重合工程と、アジド基導入工程と、重合性基導入工程と、を備える。
重合工程では、ラジカル重合性単量体の重合により第1中間体を生成する。
アジド基導入工程では、第1中間体に対するアジド化反応により第2中間体を生成する。
重合性基導入工程では、第2中間体と、モノビニルアセチレン又はモノビニルアセチレン誘導体(モノビニルアセチレン系化合物)とを反応させ、上述の第1部分と第2部分を含む化合物を得る。
(スチレン重合工程)
重合反応は参考文献1(J Polym Sci Part A: Polym Chem 2006, 44, 1667-1675.)に従って実施した。
装置名:HLC-8320(東ソー株式会社製)
カラム:TSKgel GMHHR-Hを3本直列
温度:40℃
検出:示差屈折率
溶媒:テトラヒドロフラン
検量線:標準ポリスチレン(PS)を用いて作成
重合で得たポリスチレン(中間体1-1)をジメチルホルムアミド50mlに溶解し、室温でアジ化ナトリウム0.89g添加をしてポリマー末端をアジド化し、中間体2-1を得た。
装置名:Frontier(パーキンエルマー株式会社製)
Start Range:4000cm-1
End Range:400cm-1
積算回数:16回
分解能:4.0cm-1
間隔:1.0cm-1
測定手法:ATR法(デュラスコープ)
アジド化工程の後、モノビニルアセチレン(MVA)0.78g、酢酸銅(II)1.1g、アスコルビン酸ナトリウム1.5gを添加して中間体2-1のアジド末端とMVAを反応させ、1-ポリスチレン-4-ビニル-1,2,3-トリアゾール(化合物1)を得た。
装置名:HLC-8320(東ソー株式会社製)
カラム:TSKgel GMHHR-Hを3本直列
温度:40℃
検出:示差屈折率
溶媒:テトラヒドロフラン
検量線:標準ポリスチレン(PS)を用いて作成
(スチレン重合工程)
重合反応は参考文献1に従って実施した。
重合で得たポリスチレン(中間体1-2)をジメチルホルムアミド50mlに溶解し、室温でアジ化ナトリウム0.45g添加をしてポリマー末端をアジド化し、中間体2-2を得た。
アジド化工程の後、モノビニルアセチレン0.39g、酢酸銅(II)0.57g、アスコルビン酸ナトリウム0.74gを添加して中間体2-2のアジド末端とMVAを反応させ、1-ポリスチレン-4-ビニル-1,2,3-トリアゾール(化合物2)を得た。
(メタクリル酸メチル重合工程)
重合反応は参考文献2(Macromolecules 1997, 30, 2216-2218.)に従って実施した。
重合で得たポリメタクリル酸メチル(中間体1-3)をジメチルホルムアミド50mlに溶解し、室温でアジ化ナトリウム0.89g添加をしてポリマー末端をアジド化し、中間体2-3を得た。
アジド化工程の後、モノビニルアセチレン0.78g、酢酸銅(II)1.1g、アスコルビン酸ナトリウム1.5gを添加して中間体2-3のアジド末端とMVAを反応させ、1-ポリメタクリル酸メチル-4-ビニル-1,2,3-トリアゾール(化合物3)を得た。
(メタクリル酸メチル重合工程、アジド化工程)
重合反応及びアジド化反応は参考文献6(J.Am.Chem.Soc.,2017, 139, 10551-10560)に従って実施した。
アジド化工程の後、モノビニルアセチレン0.78g、酢酸銅(II)1.1g、アスコルビン酸ナトリウム1.5gを添加して中間体2-4のアジド末端とMVAを反応させ、1-ポリメタクリル酸メチル-4-ビニル-1,2,3-トリアゾール(化合物4)を得た。
(ブタジエン重合工程)
重合反応は参考文献3(ACS Catal. 2020, 10, 12, 6645-6663)に従って実施した。
重合で得たポリブタジエン(中間体1-5)をジメチルホルムアミド50mlに溶解し、室温でアジ化ナトリウム0.89g添加をしてポリマー末端をアジド化し、中間体2-5を得た。
アジド化工程の後、モノビニルアセチレン0.78g、酢酸銅(II)1.1g、アスコルビン酸ナトリウム1.5gを添加して中間体2-4のアジド末端とMVAを反応させ、1-ポリブタジエン-4-ビニル-1,2,3-トリアゾール(化合物5)を得た。
(酢酸ビニル重合工程)
重合反応は参考文献4(AIChE J. 55 (2009) 737-746.)に従って実施した。
重合で得たポリ酢酸ビニル(中間体1-6)をジメチルホルムアミド50mlに溶解し、室温でアジ化ナトリウム0.89g添加をしてポリマー末端をアジド化し、中間体2-6を得た。
アジド化工程の後、モノビニルアセチレン0.78g、酢酸銅(II)1.1g、アスコルビン酸ナトリウム1.5gを添加して中間体2-6のアジド末端とMVAを反応させ、1-ポリ酢酸ビニル-4-ビニル-1,2,3-トリアゾール(化合物6)を得た。
(アクリロニトリル重合工程)
重合反応は参考文献5(Macromolecules 1997, 30, 6398-6400)に従って実施した。
重合で得たポリアクリロニトリル(中間体1-7)のジメチルホルムアミド溶液に対し、室温でアジ化ナトリウム0.89g添加をしてポリマー末端をアジド化し、中間体2-7を得た。
アジド化工程の後、モノビニルアセチレン0.78g、アスコルビン酸ナトリウム1.5gを添加して中間体2-6のアジド末端とMVAを反応させ、1-ポリアクリロニトリル-4-ビニル-1,2,3-トリアゾール(化合物7)を得た。
Claims (5)
- 第1部分と、第2部分と、を含み、
前記第1部分は、ポリマー鎖を有し、
前記第2部分は、トリアゾール骨格及び前記トリアゾール骨格に結合した重合性基を有する、
化合物。 - 前記ポリマー鎖は、ラジカル重合性単量体単位を有し、
前記ラジカル重合性単量体単位は、スチレン系単量体単位、(メタ)アクリル系単量体単位、ジエン系単量体単位、ビニルエーテル系単量体単位、不飽和ニトリル系単量体単位からなる群から選択される1種以上の単量体単位である、請求項1に記載の化合物。 - 前記重合性基は、ビニル基である、請求項1に記載の化合物。
- 前記第1部分は、原子移動ラジカル重合開始剤あるいはヨウ素移動重合開始剤由来の末端基を有する、請求項1に記載の化合物。
- 重合工程と、アジド基導入工程と、重合性基導入工程と、を備え、
前記重合工程では、前記ラジカル重合性単量体の重合により第1中間体を生成し、
前記アジド基導入工程では、前記第1中間体に対するアジド化反応により第2中間体を生成し、
前記重合性基導入工程では、前記第2中間体と、モノビニルアセチレン又はモノビニルアセチレン誘導体とを反応させる、
請求項1~請求項4の何れか1項に記載の化合物の製造方法。
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