JP6797442B2 - Method for preparing main chain decomposition type zinc polyacrylate resin prepared by the monomer method - Google Patents
Method for preparing main chain decomposition type zinc polyacrylate resin prepared by the monomer method Download PDFInfo
- Publication number
- JP6797442B2 JP6797442B2 JP2019557837A JP2019557837A JP6797442B2 JP 6797442 B2 JP6797442 B2 JP 6797442B2 JP 2019557837 A JP2019557837 A JP 2019557837A JP 2019557837 A JP2019557837 A JP 2019557837A JP 6797442 B2 JP6797442 B2 JP 6797442B2
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- JP
- Japan
- Prior art keywords
- zinc
- acid
- acrylate
- parts
- weight
- 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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- 239000011701 zinc Substances 0.000 title claims description 83
- 229910052725 zinc Inorganic materials 0.000 title claims description 83
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 79
- 239000000178 monomer Substances 0.000 title claims description 57
- 239000004925 Acrylic resin Substances 0.000 title claims description 54
- 238000000354 decomposition reaction Methods 0.000 title claims description 48
- 238000000034 method Methods 0.000 title claims description 22
- -1 vinyl zinc ester Chemical class 0.000 claims description 57
- 239000002904 solvent Substances 0.000 claims description 39
- 239000011347 resin Substances 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 37
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 25
- 239000003999 initiator Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 15
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 13
- 230000003797 telogen phase Effects 0.000 claims description 13
- 239000008096 xylene Substances 0.000 claims description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 125000004122 cyclic group Chemical group 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 8
- 229920000058 polyacrylate Polymers 0.000 claims description 8
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 6
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 claims description 6
- 239000012429 reaction media Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 claims description 4
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims description 4
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 4
- 229940007718 zinc hydroxide Drugs 0.000 claims description 4
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 4
- IWVNGOKOJNZZKX-UHFFFAOYSA-N (4-methylcyclohexyl) 2-methylprop-2-enoate Chemical compound CC1CCC(OC(=O)C(C)=C)CC1 IWVNGOKOJNZZKX-UHFFFAOYSA-N 0.000 claims description 3
- RXOMMEFYXLIGTD-UHFFFAOYSA-N (4-methylcyclohexyl) prop-2-enoate Chemical compound CC1CCC(OC(=O)C=C)CC1 RXOMMEFYXLIGTD-UHFFFAOYSA-N 0.000 claims description 3
- PILKNUBLAZTESB-UHFFFAOYSA-N (4-tert-butylcyclohexyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCC(C(C)(C)C)CC1 PILKNUBLAZTESB-UHFFFAOYSA-N 0.000 claims description 3
- LAIJAUHBAWLPCO-UHFFFAOYSA-N (4-tert-butylcyclohexyl) prop-2-enoate Chemical compound CC(C)(C)C1CCC(OC(=O)C=C)CC1 LAIJAUHBAWLPCO-UHFFFAOYSA-N 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 claims description 3
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 3
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 3
- ZHUWXKIPGGZNJW-UHFFFAOYSA-N 6-methylheptyl 3-sulfanylpropanoate Chemical compound CC(C)CCCCCOC(=O)CCS ZHUWXKIPGGZNJW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- BCCNDAWKXLODGN-UHFFFAOYSA-N octan-3-yl 3-sulfanylpropanoate Chemical compound CCCCCC(CC)OC(=O)CCS BCCNDAWKXLODGN-UHFFFAOYSA-N 0.000 claims description 3
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 3
- 229940065472 octyl acrylate Drugs 0.000 claims description 3
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 claims description 3
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 claims description 3
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 claims description 3
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 230000003373 anti-fouling effect Effects 0.000 description 17
- 239000003973 paint Substances 0.000 description 13
- 238000005498 polishing Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229920000098 polyolefin Polymers 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 6
- 239000013535 sea water Substances 0.000 description 6
- 230000012010 growth Effects 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920000426 Microplastic Polymers 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 3
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- 229940125773 compound 10 Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 2
- OEDAJYOQELMMFC-UHFFFAOYSA-N octadecanoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCCCCCCCCCCCCCCC(O)=O OEDAJYOQELMMFC-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- QRIGFEIETDNHKR-UHFFFAOYSA-N 2,4-dimethylidenecyclopentane-1,3-dione Chemical compound C=C1C(CC(C1=O)=C)=O QRIGFEIETDNHKR-UHFFFAOYSA-N 0.000 description 1
- HVYJJTRRPRXKEP-UHFFFAOYSA-N 2,5-dimethylidene-1,3-dioxane Chemical compound C=C1COC(=C)OC1 HVYJJTRRPRXKEP-UHFFFAOYSA-N 0.000 description 1
- NYEZZYQZRQDLEH-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1,3-oxazole Chemical compound CCC1=NCCO1 NYEZZYQZRQDLEH-UHFFFAOYSA-N 0.000 description 1
- OMOATNXZPGTFGO-UHFFFAOYSA-N 2-ethylidene-1,3-dioxane Chemical compound CC=C1OCCCO1 OMOATNXZPGTFGO-UHFFFAOYSA-N 0.000 description 1
- RBHUQXMAWASDAL-UHFFFAOYSA-N 2-ethylidenecycloheptane-1,3-dione Chemical compound C(C)=C1C(CCCCC1=O)=O RBHUQXMAWASDAL-UHFFFAOYSA-N 0.000 description 1
- GUXJXWKCUUWCLX-UHFFFAOYSA-N 2-methyl-2-oxazoline Chemical compound CC1=NCCO1 GUXJXWKCUUWCLX-UHFFFAOYSA-N 0.000 description 1
- IYBOGQYZTIIPNI-UHFFFAOYSA-N 2-methylhexano-6-lactone Chemical compound CC1CCCCOC1=O IYBOGQYZTIIPNI-UHFFFAOYSA-N 0.000 description 1
- PWKDHWCKSUMJID-UHFFFAOYSA-N 2-methylidene-1,3-dioxane Chemical compound C=C1OCCCO1 PWKDHWCKSUMJID-UHFFFAOYSA-N 0.000 description 1
- WPKPNMPVCHNBCO-UHFFFAOYSA-N 2-methylidene-4-phenylcyclopentane-1,3-dione Chemical compound C=C1C(CC(C1=O)C1=CC=CC=C1)=O WPKPNMPVCHNBCO-UHFFFAOYSA-N 0.000 description 1
- RMXSPVFNDDZVLE-UHFFFAOYSA-N 2-methylidene-5-phenyl-1,3-dioxane Chemical compound C1OC(=C)OCC1C1=CC=CC=C1 RMXSPVFNDDZVLE-UHFFFAOYSA-N 0.000 description 1
- QCJCEHFWICFNMI-UHFFFAOYSA-N 2-methylidene-5-phenylcycloheptane-1,3-dione Chemical compound C=C1C(CCC(CC1=O)C1=CC=CC=C1)=O QCJCEHFWICFNMI-UHFFFAOYSA-N 0.000 description 1
- CJWFHEXHTHSGOB-UHFFFAOYSA-N 2-methylidenecycloheptane-1,3-dione Chemical compound C=C1C(CCCCC1=O)=O CJWFHEXHTHSGOB-UHFFFAOYSA-N 0.000 description 1
- MLKBDUKURHYFKP-UHFFFAOYSA-N 2-methylidenecyclopentane-1,3-dione Chemical compound C=C1C(=O)CCC1=O MLKBDUKURHYFKP-UHFFFAOYSA-N 0.000 description 1
- XEWQXJJJOIKGTP-UHFFFAOYSA-N 2-methylprop-2-enoic acid;octadecanoic acid Chemical class CC(=C)C(O)=O.CCCCCCCCCCCCCCCCCC(O)=O XEWQXJJJOIKGTP-UHFFFAOYSA-N 0.000 description 1
- XJOZVHUKILXBEV-UHFFFAOYSA-N 3-chlorooxepan-2-one Chemical compound ClC1CCCCOC1=O XJOZVHUKILXBEV-UHFFFAOYSA-N 0.000 description 1
- HAPFVJSPEDZQEI-UHFFFAOYSA-N 4,7-dimethyl-2-methylidenecycloheptane-1,3-dione Chemical compound C=C1C(C(CCC(C1=O)C)C)=O HAPFVJSPEDZQEI-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- CGKQZIULZRXRRJ-UHFFFAOYSA-N Butylone Chemical compound CCC(NC)C(=O)C1=CC=C2OCOC2=C1 CGKQZIULZRXRRJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000005791 algae growth Effects 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- DBOVMTXPZWVYAQ-UHFFFAOYSA-N cycloheptane-1,3-dione Chemical compound O=C1CCCCC(=O)C1 DBOVMTXPZWVYAQ-UHFFFAOYSA-N 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1637—Macromolecular compounds
- C09D5/165—Macromolecular compounds containing hydrolysable groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、海洋防汚材料の技術分野に属し、海洋防汚塗料用のポリアクリル酸亜鉛樹脂、特にモノマー法によって調製された主鎖分解型ポリアクリル酸亜鉛樹脂、ならびにその方法および使用に関する。前記樹脂は、海洋防汚塗料の製造に使用される。 The present invention belongs to the technical field of marine antifouling materials, and relates to zinc polyacrylate resins for marine antifouling paints, particularly main chain decomposition type zinc polyacrylate resins prepared by the monomer method, and methods and uses thereof. The resin is used in the production of marine antifouling paints.
海洋生物汚損は、海水に浸された表面への海の生き物の付着と成長によって形成された生体垢を指す。それは海洋水産養殖、輸送および海洋工学に計り知れない危険をもたらし、そして巨大な経済的損失に直接反映されている。例えば、海洋生物汚損はケージの穴を塞ぎ、魚を酸素欠乏で死亡させ、生産量を減らし、船の自重と航行抵抗を増加させ、間接的に操縦性と戦闘能力の低下、燃料消費と温室効果ガス排出の増加を招く。また、原子力発電所の熱交換パイプラインを塞ぐと、冷熱交換の効率が大幅に低下し、さらに、石油生産プラットフォームなどの舶用機器鋼構造物の腐食も悪化する。したがって、海洋汚染の問題を解決することは、中国の経済、エネルギー、軍事にとって重要な戦略的意義を持つ。 Marine biological pollution refers to biological dirt formed by the attachment and growth of marine organisms on surfaces submerged in seawater. It poses immeasurable dangers to marine aquaculture, transportation and marine engineering, and is directly reflected in the enormous economic losses. For example, marine life pollution closes cage holes, kills fish from oxygen deficiency, reduces production, increases ship weight and navigation resistance, indirectly reduces maneuverability and combat capability, fuel consumption and greenhouses. It causes an increase in greenhouse gas emissions. In addition, blocking the heat exchange pipeline of a nuclear power plant significantly reduces the efficiency of cold heat exchange and further exacerbates the corrosion of marine equipment steel structures such as oil production platforms. Therefore, solving the problem of marine pollution has important strategic significance for China's economy, energy and military.
海洋防汚塗料の塗装は、現在、海洋生物付着の問題を解決するための最も経済的で便利で最も一般的に使用されている方法であり、その中で自己研磨型防汚塗料が最も広く使用されている。塗料の多くの成分の中で、樹脂は決定的な役割を果たす。樹脂の構造、分子量、酸価および他のパラメータは、塗料の性能および耐用年数を決定する。２００３年に国際海事機関（ＩＭＯ）が有機錫を含む防汚塗料の製造を完全に禁止することを決定して以来、自己研磨技術は更新され、現在主流の自己研磨技術はポリアクリル酸シランエステル樹脂、ポリアクリル酸亜鉛樹脂およびポリアクリル酸銅樹脂３種類を含む。しかしながら、既存の自己研磨技術は主に側鎖加水分解型であり、その性能は帆走期間および速度に関して一定の要件を有する。静止期では、海水のフラッシングだけでは所望の自己研磨効果を達成することは困難であるため、静的な防汚効果は良くない。それだけでなく、側鎖が加水分解された後、ポリマーの主鎖がコーティング層の表面を離れて海洋に入り、海洋のマイクロプラスチック汚染を引き起こし、それが海洋の生態系を深刻に脅かす。 Painting marine antifouling paints is currently the most economical, convenient and most commonly used method for solving marine biofouling problems, of which self-polishing antifouling paints are the most widespread. in use. Of the many components of paint, resins play a decisive role. The structure, molecular weight, acid value and other parameters of the resin determine the performance and service life of the paint. Since the International Maritime Organization (IMO) decided in 2003 to completely ban the production of antifouling paints containing organotin, self-polishing technology has been updated and the current mainstream self-polishing technology is sodium polyacrylate silane ester. Includes three types of resin, zinc polyacrylate resin and copper polyacrylate resin. However, existing self-polishing techniques are primarily side chain hydrolyzed and their performance has certain requirements regarding sailing duration and speed. In the stationary period, it is difficult to achieve the desired self-polishing effect only by flushing seawater, so the static antifouling effect is not good. Not only that, but after the side chains are hydrolyzed, the polymer backbone leaves the surface of the coating layer and enters the ocean, causing microplastic pollution in the ocean, which seriously threatens the marine ecosystem.
従来の自己研磨性樹脂の主鎖への分解性構造の導入は、防汚塗料にとって非常に効率的で長期的で環境に優しい樹脂を製造することが期待される。特にポリアクリル酸亜鉛樹脂については、コストが低く、加水分解速度は中程度であり、そして亜鉛エステル結合の加水分解後に生成される亜鉛イオンもまたある種の藻類成長阻害機能を有する。 The introduction of a degradable structure into the main chain of a conventional self-polishing resin is expected to produce a resin that is very efficient, long-term and environmentally friendly for antifouling paints. Particularly for zinc polyacrylate resins, the cost is low, the rate of hydrolysis is moderate, and the zinc ions produced after hydrolysis of the zinc ester bond also have certain algal growth inhibitory functions.
本発明の目的は、既存の海洋防汚塗料における自己研磨性樹脂技術の欠点を考慮して、主鎖にポリエステル構造を有し、側鎖に亜鉛鎖エステル結合を有する主鎖分解型ポリアクリル酸亜鉛樹脂を提供することにある。前記樹脂は、主鎖分解型ポリアクリル酸亜鉛樹脂であり、海洋の静的な防汚需要を満たすだけでなく、同時に海洋のミクロプラスチック汚染の問題を解決することができる。 An object of the present invention is a main chain decomposition type polyacrylic acid having a polyester structure in the main chain and a zinc chain ester bond in the side chain in consideration of the drawbacks of the self-polishing resin technology in the existing marine antifouling paint. The purpose is to provide zinc resin. The resin is a main chain decomposition type zinc polyacrylate resin, which can not only satisfy the static antifouling demand of the ocean but also solve the problem of microplastic pollution in the ocean.
本発明の他の目的は、上記主鎖分解型ポリアクリル酸亜鉛樹脂の調製方法を提供することにある。 Another object of the present invention is to provide a method for preparing the main chain decomposition type zinc polyacrylate resin.
本発明の他の目的は、上記主鎖分解型ポリアクリル酸亜鉛樹脂の応用を提供することにある。前記主鎖分解型ポリアクリル酸亜鉛樹脂は海洋防汚塗料を調製するために使用される。 Another object of the present invention is to provide an application of the main chain decomposition type zinc polyacrylate resin. The main chain decomposition type zinc polyacrylate resin is used for preparing a marine antifouling paint.
本発明の目的は、以下の技術案によって達成される。 The object of the present invention is achieved by the following technical proposals.
主鎖分解型ポリアクリル酸亜鉛樹脂は、主に以下の成分からなり、
ビニル亜鉛エステルの機能性モノマー ５〜８０部
環状モノマー ５ 〜９５部
ビニルモノマー ０ 〜９５部
開始剤 ０.０１〜１０部
有機溶媒 ５０〜１００部、
前記ビニル亜鉛エステルの機能性モノマーは、以下の成分の重量部で調製され、
亜鉛含有化合物 １０〜４０部
（メタ）アクリル酸 １５〜３０部
モノカルボン酸 ２０〜７５部
溶媒 ５０〜１０５部、
前記（メタ）アクリル酸とはアクリル酸またはメタクリル酸を指す。
Main chain decomposition type zinc polyacrylate resin mainly consists of the following components.
Functional monomer of vinyl zinc ester 5 to 80 parts Cyclic monomer 5 to 95 parts Vinyl monomer 0 to 95 parts Initiator 0.01 to 10 parts Organic solvent 50 to 100 parts,
The functional monomer of the vinyl zinc ester is prepared by weight parts of the following components.
Zinc-containing compound 10 to 40 parts (meth) Acrylic acid 15 to 30 parts Monocarboxylic acid 20 to 75 parts Solvent 50 to 105 parts,
The (meth) acrylic acid refers to acrylic acid or methacrylic acid.
前記亜鉛含有化合物は、酸化亜鉛、水酸化亜鉛、塩化亜鉛、酢酸亜鉛、およびプロピオン酸亜鉛のうちの１つまたは複数である。亜鉛含有化合物が酸化亜鉛であるとき、反応中脱イオン水が添加される必要がある。 The zinc-containing compound is one or more of zinc oxide, zinc hydroxide, zinc chloride, zinc acetate, and zinc propionate. When the zinc-containing compound is zinc oxide, deionized water needs to be added during the reaction.
前記モノカルボン酸は、アクリル酸、メタクリル酸、ギ酸、酢酸、プロピオン酸、安息香酸、ｎ−オクタン酸、イソオクタン酸、ステアリン酸、イソステアリン酸、ナフテン酸、イタコン酸、マレイン酸、オレイン酸、パルミチン酸およびロジン酸のうちの１つまたは複数である。 The monocarboxylic acid includes acrylic acid, methacrylic acid, formic acid, acetic acid, propionic acid, benzoic acid, n-octanoic acid, isooctanoic acid, stearic acid, isostearic acid, naphthenic acid, itaconic acid, maleic acid, oleic acid, and palmitic acid. And one or more of logonic acids.
前記溶媒は、炭化水素系溶媒、アルコール系溶媒および脱イオン水のうちの１つ以上であり、前記炭化水素系溶媒は、トルエン、キシレンのうちの１つ以上であり、前記アルコール系溶媒は、イソプロパノール、ｎ−ブタノール、イソブタノールおよびプロピレングリコールメチルエーテルのうちの１つ以上である。 The solvent is one or more of a hydrocarbon solvent, an alcohol solvent and deionized water, the hydrocarbon solvent is one or more of toluene and xylene, and the alcohol solvent is One or more of isopropanol, n-butanol, isobutanol and propylene glycol methyl ether.
前記環状モノマーは、次の１〜３８個の化合物のうちの１つ以上である。（１）グリコリド、（２）ラクチド、（３）ε−カプロラクトン、（４）２−メチル−ε−カプロラクトン、（５）２−クロロ−ε−カプロラクトン、（６）γ−ブチロラクトン、（７）δ−バレロラクトン、（８）γ−バレロラクトン、（９）エチレンカーボネート、（１０）プロピレンカーボネート、（１１）トリメチレン環カーボネート、（１２）２，２−ジメチルトリメチレン環状カーボネート、（１３）２−メチル−２−オキサゾリン、（１４）２−エチル−２−オキサゾリン、（１５）環オキシエタン、（１６）プロピレンオキシド、（１７）エピクロロヒドリン、（１８）γ−グリシドキシプロピルトリメトキシシラン、（１９）２−メチレン−１,３−ジオキソシクロペンタン、（２０）２−メチレン−４−フェニル−１,３−ジオキソシクロペンタン、（２１）２−メチレン−４−アルキル−１,３−ジオキソシクロペンタンアルカン、（２２）２，４−ジメチレン−１，３−ジオキソシクロペンタン、（２３）２−メチレン−１，３−ジオキソ−４，５−ベンゾシクロペンタン、（２４）２−メチレン−１，３−ジオキサン、（２５）２，５−ジメチレン−１，３−ジオキサン、（２６）２−メチレン-５−フェニル−１，３−ジオキサン、（２７）２−メチレン−４−アルキル−１，３−ジオキサン、（２８）２−メチレン−１、３−ジオキソシクロヘプタン、（２ ９）２−メチレン−５−アルキル−１，３−ジオキソシクロヘプタン、（３０）２−メチレン−４，７−ジメチル−１，３−ジオキソシクロヘプタン、（３１）２−メチレン−１，３−ジオキソ−５，６−ベンゾシクロヘプタン、（３２）２−メチレン−５−フェニル−１，３−ジオキソシクロヘプタン、（３３）２−エチリデン−１，３−ジオキソシクロヘプタン、（３４）２−メチレン−１，３−ジオキソ−５−シクロヘプテン、（３５）２−エチリデン−４−アルキル−１，３−ジオキソラン、（３６）２−エチリデン−１，３−ジオキサン、（３７）２−アリル−４−フェニル−１，３−ジオキシシクロペンタン、（３８）２−エチリデン−１，３−ジオキソ−５，６−ベンゾシクロヘプタン。 The cyclic monomer is one or more of the following 1 to 38 compounds. (1) Glycolide, (2) Lactide, (3) ε-caprolactone, (4) 2-methyl-ε-caprolactone, (5) 2-chloro-ε-caprolactone, (6) γ-butyrolactone, (7) δ -Valerolactone, (8) γ-Valerolactone, (9) ethylene carbonate, (10) propylene carbonate, (11) trimethylene ring carbonate, (12) 2,2-dimethyltrimethylene cyclic carbonate, (13) 2-methyl -2-oxazoline, (14) 2-ethyl-2-oxazoline, (15) ring oxyheptane, (16) propylene oxide, (17) epichlorohydrin, (18) γ-glycidoxypropyltrimethoxysilane, ( 19) 2-Methylene-1,3-dioxocyclopentane, (20) 2-methylene-4-phenyl-1,3-dioxocyclopentane, (21) 2-methylene-4-alkyl-1,3- Dioxocyclopentane Alcan, (22) 2,4-dimethylene-1,3-dioxocyclopentane, (23) 2-methylene-1,3-dioxo-4,5-benzocycloheptane, (24) 2- Methylene-1,3-dioxane, (25) 2,5-dimethylene-1,3-dioxane, (26) 2-methylene-5-phenyl-1,3-dioxane, (27) 2-methylene-4-alkyl -1,3-dioxane, (28) 2-methylene-1,3-dioxocycloheptane, (29) 2-methylene-5-alkyl-1,3-dioxocycloheptane, (30) 2-methylene -4,7-dimethyl-1,3-dioxocycloheptane, (31) 2-methylene-1,3-dioxo-5,6-benzocycloheptane, (32) 2-methylene-5-phenyl-1, 3-Dioxocycloheptane, (33) 2-ethylidene-1,3-dioxocycloheptane, (34) 2-methylene-1,3-dioxo-5-cycloheptane, (35) 2-ethylidene-4-alkyl -1,3-dioxolane, (36) 2-ethylidene-1,3-dioxane, (37) 2-allyl-4-phenyl-1,3-dioxycyclopentane, (38) 2-ethylidene-1,3 -Dioxo-5,6-benzocycloheptane.
１〜３８個の化合物の環状モノマーの構造式は以下の通りである。 The structural formulas of the cyclic monomers of 1 to 38 compounds are as follows.
ここで、ｍ＝１−１２は、ｍが１−１２の整数であることを意味する。 Here, m = 1-12 means that m is an integer of 1-12.
前記ビニルモノマーは、アクリレート，メタクリレート、末端水酸基のアクリレート、末端水酸基のメタクリレート、アクリル酸の環状炭化水素エステル、メタクリル酸の環状炭化水素エステル、アクリル酸のポリオレフィンジオールエステルおよびメタクリル酸ポリオレフィンジオールエステルのうちの１つ以上であり、
アクリレートは、メチルアクリレート、エチルアクリレート、２−メトキシエチルアクリレート、プロピルアクリレート、イソプロピルアクリレート、ｎ−ブチルアクリレート、イソブチルアクリレート、ｔｅｒｔ−ブチルアクリレート、オクチルアクリレート、イソオクチルアクリレート、ラウリルアクリレートおよびステアリン酸アクリレートのうちの１つ以上であり、
メタクリレートは、メチルメタクリレート、エチルメタクリレート、２−メトキシエチルメタクリレート、プロピルメタクリレート、イソプロピルメタクリレート、ｎ−ブチルメタクリレート、イソブチルメタクリレート、ｔ−ブチルメタクリレート、オクチルメタクリレート、イソオクチルメタクリレート、ラウリルメタクリレート、およびメタクリル酸ステアリン酸エステルのうちの１つ以上であり、
末端水酸基のアクリレートは、ヒドロキシエチルアクリレートおよびヒドロキシプロピルアクリレートのうちの１つ以上であり、
末端水酸基のメタクリレートは、ヒドロキシエチルメタクリレートおよびヒドロキシプロピルメタクリレートのうちの１つ以上であり、
アクリル酸の環状炭化水素エステルは、フェニルアクリレート、シクロヘキシルアクリレート、４−メチルシクロヘキシルアクリレート、および４−ｔｅｒｔ−ブチルシクロヘキシルアクリレートのうちの１つ以上であり、
メタクリル酸の環状炭化水素エステルは、フェニルメタクリレート、シクロヘキシルメタクリレート、４−メチルシクロヘキシルメタクリレート、および４−ｔｅｒｔ−ブチルシクロヘキシルメタクリレートのうちの１つ以上であり、
アクリル酸のポリオレフィンジオールエステルは、ポリエチレングリコールアクリレート（好ましくは１〜１０の重合度を有する）であり、
メタクリル酸ポリオレフィンジオールエステルは、ポリエチレングリコールメタクリレート（好ましくは１〜１０の重合度を有する）である。
The vinyl monomer includes acrylate, methacrylate, terminal hydroxyl group acrylate, terminal hydroxyl group methacrylate, acrylic acid cyclic hydrocarbon ester, methacrylic acid cyclic hydrocarbon ester, acrylic acid polyolefin diol ester and methacrylic acid polyolefin diol ester. One or more
The acrylate includes methyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, octyl acrylate, isooctyl acrylate, lauryl acrylate and stearate acrylate. One or more
Methacrylates include methyl methacrylate, ethyl methacrylate, 2-methoxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, octyl methacrylate, isooctyl methacrylate, lauryl methacrylate, and stearic acid methacrylate esters. One or more of
The acrylate of the terminal hydroxyl group is one or more of hydroxyethyl acrylate and hydroxypropyl acrylate.
The methacrylate of the terminal hydroxyl group is one or more of hydroxyethyl methacrylate and hydroxypropyl methacrylate.
The cyclic hydrocarbon ester of acrylic acid is one or more of phenyl acrylate, cyclohexyl acrylate, 4-methylcyclohexyl acrylate, and 4-tert-butylcyclohexyl acrylate.
The cyclic hydrocarbon ester of methacrylic acid is one or more of phenyl methacrylate, cyclohexyl methacrylate, 4-methylcyclohexylmethacrylate, and 4-tert-butylcyclohexylmethacrylate.
The polyolefin diol ester of acrylic acid is a polyethylene glycol acrylate (preferably having a degree of polymerization of 1-10).
The methacrylic acid polyolefin diol ester is polyethylene glycol methacrylate (preferably having a degree of polymerization of 1 to 10).
前記開始剤は、リンシアノ、ホスファゼン塩、ホスファゼンオキシド、アゾビスイソブチロニトリル、アゾビスイソバレロニトリル、過酸化ベンゾイル、ジ−ｔｅｒｔ−ブチルペルオキシドおよびｔｅｒｔ−ブチルペルオキシ−２−エチルヘキサノエートのうちの１つ以上であり、
前記主鎖分解型ポリアクリル酸亜鉛樹脂において、前記成分は、低分子アルコールまたは低分子アミンおよび／またはテロゲンを含み、低分子アルコールまたは低分子アミンは開始剤と配合され、テロゲンは開始剤と配合され、
前記低分子アルコールは、１〜１２個の炭素原子を有する脂肪族または芳香族アルコールのうちの１つ以上である。
The initiator is among phosphocyan, phosphazene salt, phosphazene oxide, azobisisobutyronitrile, azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide and tert-butyl peroxy-2-ethylhexanoate. Is one or more of
In the main chain decomposition type zinc polyacrylate resin, the component contains a low molecular weight alcohol or a low molecular weight amine and / or a telogen, the low molecular weight alcohol or a low molecular weight amine is compounded with an initiator, and the telogen is compounded with an initiator. Being done
The low molecular weight alcohol is one or more of aliphatic or aromatic alcohols having 1 to 12 carbon atoms.
前記低分子アミンは、１〜１２個の炭素原子を有する脂肪族または芳香族アミンのうちの１つ以上である。 The low molecular weight amine is one or more of aliphatic or aromatic amines having 1 to 12 carbon atoms.
前記低分子アルコールまたは低分子アミンが開始剤と配合されるとき、開始剤と低分子アルコールまたは低分子アミンとの合計の重量部は０.０１〜１０部であり、配合される開始剤と低分子アルコールまたは低分子アミンとの質量比は１：（０.１〜４）が好ましい。 When the low molecular weight alcohol or low molecular weight amine is blended with the initiator, the total weight portion of the initiator and the low molecular weight alcohol or low molecular weight amine is 0.01 to 10 parts, and the blended initiator and low molecular weight are low. The mass ratio with the molecular alcohol or the low molecular weight amine is preferably 1: (0.1 to 4).
前記テロゲンは、ｎ−ドデシルメルカプタン、ｔｅｒｔ−ドデシルメルカプタン、３−メルカプトプロピオン酸イソオクチル、３−メルカプトプロピオン酸エチルヘキシル、テトラキス（３−メルカプトプロピオン酸）４級テトラオールエステル、α−メチルスチレン二量体のうちの１つ以上であり、α−メチルスチレン二量体およびｎ−ドデシルメルカプタンのうちの１つ以上であることが好ましい。 The telogen is n-dodecyl mercaptan, tert-dodecyl mercaptan, isooctyl 3-mercaptopropionate, ethylhexyl 3-mercaptopropionate, tetrakis (3-mercaptopropionic acid) quaternary tetraol ester, α-methylstyrene dimer. It is preferably one or more of them, and preferably one or more of α-methylstyrene dimer and n-dodecyl mercapto.
前記テロゲンが開始剤と配合されるとき、前記テロゲンの重量部は０.５〜５部であり、テロゲンと開始剤の重量比は（０.５〜５）：（０.０１〜１０）である。 When the telogen is compounded with the initiator, the weight parts of the telogen are 0.5-5 parts and the weight ratio of the telogen to the initiator is (0.5-5) :( 0.01-10). is there.
前記主鎖分解型ポリアクリル酸亜鉛樹脂の成分には、開始させるものが含まれ、前記開始させるものは、開始剤で、開始剤と低分子アルコールまたは低分子アミンとの配合物、テロゲンと開始剤との配合物のうちの１つ以上である。前記開始させるもの内の開始剤の重量部は０.０１〜１０部である。 The components of the main chain decomposition type zinc polyacrylate resin include an initiator, which is an initiator, a combination of an initiator and a low molecular weight alcohol or a low molecular weight amine, and a telogen. One or more of the formulations with the agent. The weight portion of the initiator in the initiator is 0.01 to 10 parts.
前記有機溶媒は、炭化水素系溶媒、アルコール系溶媒、ケトン系溶媒およびエステル系溶媒のうちの１つ以上であり、
前記炭化水素系溶媒は、トルエンおよびキシレンのうちの１種以上であり、前記アルコール系溶媒は、イソプロパノール、ｎ−ブタノール、イソブタノールおよびプロピレングリコールメチルエーテルのうちの１つ以上であり、前記ケトン系溶媒は、メチルエチルケトン、メチルイソブチルケトン、アセトン、ブタノンおよびシクロヘキサノンのうちの１つ以上であり、前記エステル系溶媒は酢酸エチルおよび酢酸ブチルのうちの１つ以上である。
The organic solvent is one or more of a hydrocarbon solvent, an alcohol solvent, a ketone solvent and an ester solvent.
The hydrocarbon solvent is one or more of toluene and xylene, and the alcohol solvent is one or more of isopropanol, n-butanol, isobutanol and propylene glycol methyl ether, and the ketone solvent. The solvent is one or more of methyl ethyl ketone, methyl isobutyl ketone, acetone, butanone and cyclohexanone, and the ester solvent is one or more of ethyl acetate and butyl acetate.
前記主鎖分解型ポリアクリル酸亜鉛樹脂において、ビニル亜鉛エステルの機能性モノマーの重量部は、ビニル亜鉛エステルの機能性モノマーを調製した後の反応液の総重量に基づいてもよく、ビニル亜鉛エステルの機能性モノマー内の反応物（亜鉛含有化合物、（メタ）アクリル酸和モノカルボン酸）の総重量に基づいてもよい。 In the main chain decomposition type zinc acrylate resin, the weight part of the functional monomer of the vinyl zinc ester may be based on the total weight of the reaction solution after preparing the functional monomer of the vinyl zinc ester, and the vinyl zinc ester may be used. It may be based on the total weight of the reactants (zinc-containing compound, (meth) acrylic acid sum monocarboxylic acid) in the functional monomer of.
前記主鎖分解型ポリアクリル酸亜鉛樹脂の調製方法は、
５０〜１０５重量部の溶媒を反応媒体とし、亜鉛含有化合物１０〜４０重量部、（メタ）アクリル酸１５〜３０重量部およびモノカルボン酸２０〜７５重量部を、５０〜１４０ ℃で３〜８時間反応させ、ビニル亜鉛エステルの機能性モノマーを得る、ビニル亜鉛エステルの機能性モノマーの合成工程（１）と、
不活性雰囲気で５０〜１００重量部の有機溶媒を反応媒体とし、０.０１〜１０重量部の開始剤の作用で、環状モノマー５〜９５重量部、ビニルモノマー０〜９５重量部およびビニル亜鉛エステルの機能性モノマー５〜８０重量部を反応させ、７０〜１２０℃で８〜１８時間の反応条件下で、ポリアクリル酸亜鉛ポリマーを得る、ポリアクリル酸亜鉛樹脂の合成工程（２）とを備える。
The method for preparing the main chain decomposition type zinc polyacrylate resin is as follows.
Using 50 to 105 parts by weight of a solvent as a reaction medium, 10 to 40 parts by weight of the zinc-containing compound, 15 to 30 parts by weight of (meth) acrylic acid and 20 to 75 parts by weight of monocarboxylic acid were added at 50 to 140 ° C. at 3 to 8 parts. The step (1) of synthesizing the functional monomer of vinyl zinc ester, which is reacted for a time to obtain the functional monomer of vinyl zinc ester, and
Using 50 to 100 parts by weight of an organic solvent as a reaction medium in an inert atmosphere, and by the action of 0.01 to 10 parts by weight of the initiator, 5 to 95 parts by weight of the cyclic monomer, 0 to 95 parts by weight of the vinyl monomer, and vinyl zinc ester The step (2) for synthesizing a zinc polyacrylate resin is provided, wherein 5 to 80 parts by weight of the functional monomer of the above is reacted to obtain a zinc polyacrylate polymer under reaction conditions of 70 to 120 ° C. for 8 to 18 hours. ..
前記主鎖分解型ポリアクリル酸亜鉛樹脂の亜鉛元素の含有量が０.５〜２０％、好ましくは３〜１０％である。 The zinc element content of the main chain decomposition type zinc polyacrylate resin is 0.5 to 20%, preferably 3 to 10%.
前記主鎖分解型ポリアクリル酸亜鉛樹脂の数平均分子量Ｍｎ（ポリスチレンを標準としてＧＰＣにより測定）は、１０００〜８００００、好ましくは１０００〜５００００である。 The number average molecular weight Mn (measured by GPC using polystyrene as a standard) of the main chain decomposition type zinc polyacrylate resin is 1000 to 80,000, preferably 1000 to 50,000.
前記主鎖分解型ポリアクリル酸亜鉛樹脂は、酸価が３０〜３００ｍｇＫＯＨ／ｇ、好ましくは５０〜２３０ｍｇＫＯＨ／ｇである。 The main chain decomposition type zinc polyacrylate resin has an acid value of 30 to 300 mgKOH / g, preferably 50 to 230 mgKOH / g.
前記主鎖分解性ポリアクリル酸亜鉛樹脂は、海洋防汚塗料の調製に用いられる。 The main chain degradable zinc polyacrylate resin is used for preparing a marine antifouling paint.
本発明は、モノマー法により製造された、ポリエステルセグメント、ビニルモノマーおよびビニル亜鉛エステル単位からなるランダムコポリマーである構造を有する主鎖分解性ポリアクリル酸亜鉛樹脂を提供する。本発明は、分解性ポリエステルセグメントをポリアクリル酸亜鉛樹脂の主鎖に導入するので、関与する材料において、海水の存在下で側鎖亜鉛エステル結合を分解することができ、主鎖ポリエステル構造も分解することができる。亜鉛含有量および環状モノマーの含有量を調整することによって、加水分解および分解速度を協同する目的が達成され、そして静的な防汚の需要が満たされる。同時に、加水分解と分解が続くにつれて、物質は最終的に小さな分子に分解され、海洋のマイクロプラスチック汚染の問題を解決する。 The present invention provides a main chain degradable zinc polyacrylate resin having a structure which is a random copolymer composed of a polyester segment, a vinyl monomer and a vinyl zinc ester unit produced by the monomer method. In the present invention, since the degradable polyester segment is introduced into the main chain of the zinc polyacrylate resin, the side chain zinc ester bond can be decomposed in the presence of seawater in the material involved, and the main chain polyester structure is also decomposed. can do. By adjusting the zinc content and the content of the cyclic monomer, the purpose of coordinating hydrolysis and decomposition rates is achieved, and the demand for static antifouling is met. At the same time, as hydrolysis and decomposition continue, the substance is eventually broken down into smaller molecules, solving the problem of marine microplastic pollution.
従来技術と比較して、本発明は以下の利点および顕著な効果を有する。 Compared with the prior art, the present invention has the following advantages and significant effects.
（１）本発明においては、ポリアクリル酸亜鉛樹脂に環状モノマーとビニル亜鉛エステルの機能性モノマーとの共重合が導入されることにより、主鎖にポリエステルセグメントが含有され、側鎖に亜鉛エステル結合が含有される主鎖分解性自己研磨防汚樹脂を調製した。得られた樹脂は、海水の存在の下で、側鎖亜鉛エステル結合が加水分解される以外に、主鎖ポリエステルセグメントも分解されるので、従来の自己研磨材料の船速への依存性を解消し、そして静的な海水で加水分解によりコーティング層の表面は自己再生でき、それによって防汚剤の定速での放出を効果的に調節し、船舶または海洋機器の表面上の活物質の維持を確実にし、低速船舶および沖合石油プラットフォームなどの施設の防汚需要を十分に満たす。
（２）本発明により提供される材料は、海水の存在の下で主鎖および側鎖が破損するために等速かつ徹底的に研磨することができ、航行中に船はコーティング層の表面に低い粗さを維持し、航行抵抗を低減し、優れた材料に抗力低減性能を与える。
（３）本発明は、共重合に、異なる種類および異なる含有量のビニルモノマーを添加して、材料のガラス転移温度および機械的性質を調整し、そして船舶塗料の常用溶媒中の材料の溶解性を改善することができる。
（４）本発明の製造方法は簡便であり、安価であり、工業生産に適しており、調製されたポリアクリル酸亜鉛樹脂は海洋防汚コーティング層の分野で開発の見込みが高い。
(1) In the present invention, a polyester segment is contained in the main chain and a zinc ester bond is formed in the side chain by introducing a copolymerization of a cyclic monomer and a functional monomer of vinyl zinc ester into a zinc polyacrylate resin. A main chain decomposable self-polishing antifouling resin containing the above was prepared. In the obtained resin, in the presence of seawater, not only the side chain zinc ester bond is hydrolyzed, but also the main chain polyester segment is decomposed, so that the dependence of the conventional self-polishing material on the ship speed is eliminated. And by hydrolysis in static seawater, the surface of the coating layer can self-regenerate, thereby effectively regulating the constant velocity release of the antifouling agent and maintaining the active material on the surface of the ship or marine equipment. And fully meet the antifouling demand of facilities such as low speed vessels and offshore oil platforms.
(2) The material provided by the present invention can be polished at a constant speed and thoroughly due to the breakage of the main chain and side chains in the presence of seawater, and the ship can be applied to the surface of the coating layer during navigation. Maintains low roughness, reduces navigation resistance and gives superior materials drag reduction performance.
(3) The present invention adds different types and different contents of vinyl monomers to the copolymer to adjust the glass transition temperature and mechanical properties of the material, and the solubility of the material in the common solvent of marine paints. Can be improved.
(4) The production method of the present invention is simple, inexpensive, and suitable for industrial production, and the prepared zinc polyacrylate resin is highly expected to be developed in the field of marine antifouling coating layer.
以下、具体的な実施例を参照して本発明をさらに詳細に説明するが、本発明の実施形態はこれらに限定されない。 Hereinafter, the present invention will be described in more detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
（実施例１）
主鎖分解型ポリアクリル酸亜鉛樹脂の調製方法は、以下の工程を備える。
(Example 1)
The method for preparing the main chain decomposition type zinc polyacrylate resin includes the following steps.
工程（１）ビニル亜鉛エステルの機能性モノマーの合成
反応容器に酸化亜鉛８１．４ｇ、プロピレングリコールメチルエーテル２００ｇ、キシレン４０ｇを加え、６５℃に昇温し、アクリル酸７２．１ｇ、メタクリル酸８６．１ｇ、脱イオン水１０ｇの混合物を３時間かけて滴下した。滴下完了後、保温反応を２時間続けて、無色透明のビニル亜鉛エステルの機能性モノマー溶液を得た。
Step (1) Synthesis of functional monomer of vinyl zinc ester 81.4 g of zinc oxide, 200 g of propylene glycol methyl ether and 40 g of xylene were added to a reaction vessel, and the temperature was raised to 65 ° C., and 72.1 g of acrylic acid and 86 g of methacrylic acid. A mixture of 1 g and 10 g of deionized water was added dropwise over 3 hours. After the dropping was completed, the heat retention reaction was continued for 2 hours to obtain a colorless and transparent vinyl zinc ester functional monomer solution.
工程（２）ポリアクリル酸亜鉛樹脂の合成
攪拌条件の下で、反応容器にキシレン５００ｇ、プロピレングリコールメチルエーテル１００ｇ、エチルアクリレート２４ｇを加え、窒素雰囲気下で９０℃に昇温し、２−メチレン−１,３−ジオキソシクロヘプタン４４ｇ、２−メトキシエチルメタクリレート４４ｇ、メチルメタクリレート１７６ｇ、メチルメタクリレート３９６ｇ、工程（１）のビニル亜鉛エステルの機能性モノマー溶液４４９．６ｇ、アゾビスイソブチロニトリル２２ｇおよびα−メチルスチレン二量体８ｇの混合物を６時間かけて滴下した。そして、ジ−ｔｅｒｔ−ブチルペルオキシド８ｇとキシレン９０ｇの混合物を３０分かけて滴下した。１．５時間攪拌した後、主鎖分解型ポリアクリル酸亜鉛樹脂（無色または黄色の透明な樹脂溶液）を得た。
Step (2) Synthesis of zinc polyacrylate resin Under stirring conditions, 500 g of xylene, 100 g of propylene glycol methyl ether, and 24 g of ethyl acrylate were added to the reaction vessel, the temperature was raised to 90 ° C. under a nitrogen atmosphere, and 2-methylene- 44 g of 1,3-dioxocycloheptane, 44 g of 2-methoxyethyl methacrylate, 176 g of methyl methacrylate, 396 g of methyl methacrylate, 449.6 g of a functional monomer solution of the vinyl zinc ester of step (1), 22 g of azobisisobutyronitrile and A mixture of 8 g of α-methylstyrene dimer was added dropwise over 6 hours. Then, a mixture of 8 g of di-tert-butyl peroxide and 90 g of xylene was added dropwise over 30 minutes. After stirring for 1.5 hours, a main chain decomposition type zinc polyacrylate resin (colorless or yellow transparent resin solution) was obtained.
本実施例では、樹脂の数平均分子量Ｍｎは２．５×１０４ｇ／ｍｏｌ、亜鉛含有量は７．２％、酸価は１２４ｍｇＫＯＨ／ｇである。浅海懸垂板実験によれば、１４ヶ月で海の生き物の成長はない。 In this example, the resin has a number average molecular weight Mn of 2.5 × 10 4 g / mol, a zinc content of 7.2%, and an acid value of 124 mgKOH / g. According to the shallow sea suspension plate experiment, there is no growth of sea creatures in 14 months.
（実施例２）
主鎖分解型ポリアクリル酸亜鉛樹脂の調製方法は、以下の工程を備える。
(Example 2)
The method for preparing the main chain decomposition type zinc polyacrylate resin includes the following steps.
工程（１）ビニル亜鉛エステルの機能性モノマーの合成
反応容器に酸化亜鉛８１．４ｇ、キシレン４００ｇ、イソプロパノール１００ｇを加え、８０℃に昇温し、アクリル酸７２．１ｇとナフテン酸３４０ｇ（酸価１６５）の混合物を３時間かけて定速で滴下した。滴下完了後、保温反応を２時間続けて、褐色透明なビニル亜鉛エステルの機能性モノマー溶液を得た。
Step (1) Synthesis of functional monomer of vinyl zinc ester 81.4 g of zinc oxide, 400 g of xylene and 100 g of isopropanol were added to a reaction vessel, the temperature was raised to 80 ° C., and 72.1 g of acrylic acid and 340 g of naphthenic acid (acid value 165) were added. ) Was added dropwise at a constant speed over 3 hours. After the dropping was completed, the heat retention reaction was continued for 2 hours to obtain a brown transparent vinyl zinc ester functional monomer solution.
工程（２）ポリアクリル酸亜鉛樹脂の合成
攪拌条件の下で、反応容器にキシレン３５０ｇとメチルイソブチルケトン１００ｇを加え、窒素雰囲気下で９５℃に昇温し、カプロラクトン１００ｇ、メチルアクリレート１００ｇ、ブチルアクリレート１００ｇ、シクロヘキシルアクリレート２００ｇ、工程（１）のビニル亜鉛エステルの機能性モノマー溶液８９３．５ｇ、メタノール１ｇおよびホスファゼン（ｔ−ＢｕＰ４）のｎ−ヘキサン溶液（０．５ｇのｔ−ＢｕＰ４）１ｍＬからなる混合物を、４時間かけて等速に滴下した。滴下完了後、２時間保温した後、アゾビスイソブチロニトリル５ｇとキシレン５０ｇを３０分間で等速滴下し、さらに４時間攪拌して、主鎖分解型ポリアクリル酸亜鉛樹脂（褐色透明樹脂溶液）を得た。
Step (2) Synthesis of zinc polyacrylate resin Under stirring conditions, 350 g of xylene and 100 g of methylisobutylketone are added to a reaction vessel, the temperature is raised to 95 ° C. under a nitrogen atmosphere, and 100 g of caprolactone, 100 g of methyl acrylate and butyl acrylate From 100 g, 200 g of cyclohexyl acrylate, 893.5 g of functional monomer solution of vinyl zinc ester of step (1), 1 g of methanol and 1 mL of n-hexane solution of phosphazene (t-BuP 4 ) (0.5 g of t-BuP 4 ). The mixture was added dropwise at a constant velocity over 4 hours. After the dropping is completed, after keeping warm for 2 hours, 5 g of azobisisobutyronitrile and 50 g of xylene are dropped at a constant velocity for 30 minutes, and further stirred for 4 hours to decompose the main chain of zinc polyacrylate (brown transparent resin solution). ) Was obtained.
本実施例では、樹脂の数平均分子量Ｍｎは３.０×１０４ ｇ／ｍｏｌであり、亜鉛含有量は６.７ ％、酸価は１１５ ｍｇＫＯＨ／ｇである。浅海懸垂板実験によれば、１２ヶ月で海の生き物の成長はない。 In this example, the number average molecular weight Mn of the resin is 3.0 × 10 4 g / mol, the zinc content is 6.7%, and the acid value is 115 mgKOH / g. According to the shallow sea suspension plate experiment, there is no growth of sea creatures in 12 months.
（実施例３）
主鎖分解型ポリアクリル酸亜鉛樹脂の調製方法は、以下の工程を備える。
(Example 3)
The method for preparing the main chain decomposition type zinc polyacrylate resin includes the following steps.
工程（１）ビニル亜鉛エステルの機能性モノマーの合成
反応容器に水酸化亜鉛９９．４ｇ、トルエン４００ｇ、イソブタノール７４ｇを加えて７５℃に昇温し、アクリル酸７２．１ｇとロジン酸３０２．５ｇの混合物を３時間かけて等速で滴下した後、２時間保温反応を続けた。そして、黄色透明のビニル亜鉛エステルの機能性モノマー溶液を得た。
Step (1) Synthesis of functional monomer of vinyl zinc ester 99.4 g of zinc hydroxide, 400 g of toluene and 74 g of isobutanol were added to the reaction vessel and the temperature was raised to 75 ° C., and 72.1 g of acrylic acid and 302.5 g of logonic acid were added. The mixture was added dropwise at a constant velocity over 3 hours, and then the heat retention reaction was continued for 2 hours. Then, a functional monomer solution of a yellow transparent vinyl zinc ester was obtained.
工程（２）ポリアクリル酸亜鉛樹脂の合成
反応容器にキシレン５００ｇ、酢酸ブチル４００ｇを加え、窒素雰囲気下で１００℃に昇温し、ラクチド１５０ｇ、イソオクチルアクリレート５８４ｇ、エチルメタクリレート２９２ｇ、工程（１）のビニル亜鉛エステルの機能性モノマー溶液９４８ｇ、ジエチレングリコール０．１５ｇおよびｔ−ＢｕＰ４のｎ−ヘキサン溶液（０．５ｇのｔ−ＢｕＰ４）１ｍＬの混合物を４時間かけて等速で滴下した。滴下完了後、２時間保温した。そして、過酸化ベンゾイル８ｇ、キシレン１００ｇを３０分間で等速滴下し、さらに４時間攪拌して、主鎖分解型ポリアクリル酸亜鉛樹脂（黄色透明樹脂溶液）を得た。
Step (2) Synthesis of zinc polyacrylate resin 500 g of xylene and 400 g of butyl acetate are added to the reaction vessel, the temperature is raised to 100 ° C. under a nitrogen atmosphere, lactide 150 g, isooctyl acrylate 584 g, ethyl methacrylate 292 g, step (1). functional monomer solution 948g of vinyl zinc ester was added dropwise at a constant rate over a mixture of diethylene glycol 0.15g and t-BuP 4 of n- hexane solution (0.5g t-BuP 4 of) 1 mL 4 hours. After the dropping was completed, the mixture was kept warm for 2 hours. Then, 8 g of benzoyl peroxide and 100 g of xylene were added dropwise over 30 minutes at a constant velocity, and the mixture was further stirred for 4 hours to obtain a main chain decomposition type zinc polyacrylate resin (yellow transparent resin solution).
本実施例では、樹脂の数平均分子量Ｍｎは１.２×１０４ ｇ／ｍｏｌ、亜鉛含有量は４.５ ％、酸価は７７ｍｇＫＯＨ／ｇである。浅海懸垂板実験によれば、８ヶ月で海の生き物の成長はない。 In this example, the resin has a number average molecular weight Mn of 1.2 × 10 4 g / mol, a zinc content of 4.5%, and an acid value of 77 mgKOH / g. According to the shallow sea suspension plate experiment, there is no growth of sea creatures in 8 months.
（実施例４）
主鎖分解型ポリアクリル酸亜鉛樹脂の調製方法は、以下の工程を備える。
(Example 4)
The method for preparing the main chain decomposition type zinc polyacrylate resin includes the following steps.
工程（１）ビニル亜鉛エステルの機能性モノマーの合成
反応容器に酢酸亜鉛１８３．５ｇ、トルエン１１４ｇ、ｎ−ブタノール３００ｇを加えて１３０℃に昇温し、メタクリル酸８６．１ｇとイソオクタン酸１４４．２ｇの混合物を３時間かけて等速で滴下した。滴下完了後、保温反応を２時間続けて無色透明のビニル亜鉛エステルの機能性モノマー溶液を得た。
Step (1) Synthesis of functional monomer of vinyl zinc ester 183.5 g of zinc acetate, 114 g of toluene and 300 g of n-butanol were added to a reaction vessel and the temperature was raised to 130 ° C., and 86.1 g of methacrylic acid and 144.2 g of isooctanoic acid were added. The mixture was added dropwise at a constant velocity over 3 hours. After the dropping was completed, the heat retention reaction was continued for 2 hours to obtain a colorless and transparent vinyl zinc ester functional monomer solution.
工程（２）ポリアクリル酸亜鉛樹脂の合成
攪拌条件の下で、反応容器にプロピレングリコールメチルエーテル１８００ｇ、酢酸エチル４００ｇを加え、窒素雰囲気下で１００℃に昇温し、２−メチレン−１，３−ジオキソシクロペンタン１１７２ｇ、ヒドロキシエチルアクリレート２９３ｇ、フェニルアクリレート５８６ｇ、ｔｅｒｔ−ブチルメタクリレート５８６ｇ、工程（１）のビニル亜鉛エステルの機能性モノマー溶液８２７．８ｇ、ｔ−ブチルペルオキシ−２−エチルヘキサノエート８８ｇおよびα−メチルスチレンダイマー２９ｇの混合物を、４時間かけて均一に滴下した。滴下完了後、２時間保温した。そして、ｔｅｒｔ−ブチルペルオキシ−２−エチルヘキサノエート１５ｇとキシレン３００ｇを３０分間かけて等速で滴下した後、さらに４時間攪拌して、主鎖分解ポリアクリル酸亜鉛樹脂（無色透明樹脂溶液）を得た。
Step (2) Synthesis of zinc polyacrylate resin Under stirring conditions, 1800 g of propylene glycol methyl ether and 400 g of ethyl acetate were added to the reaction vessel, and the temperature was raised to 100 ° C. under a nitrogen atmosphere to 2-methylene-1,3. -Dioxocyclopentane 1172 g, hydroxyethyl acrylate 293 g, phenyl acrylate 586 g, tert-butyl methacrylate 586 g, functional monomer solution of vinyl zinc ester in step (1) 827.8 g, t-butylperoxy-2-ethylhexanoate A mixture of 88 g and 29 g of α-methylstyrene dimer was uniformly added dropwise over 4 hours. After the dropping was completed, the mixture was kept warm for 2 hours. Then, 15 g of tert-butylperoxy-2-ethylhexanoate and 300 g of xylene were added dropwise over 30 minutes at a constant velocity, and then the mixture was further stirred for 4 hours to decompose the main chain of zinc polyacrylate (colorless transparent resin solution). Got
本実施例では、樹脂の数平均分子量Ｍｎは２.６×１０４ ｇ／ｍｏｌ、亜鉛含有量は２.３ ％、酸価は３８ｍｇＫＯＨ／ｇである。浅海懸垂板実験によれば、６ヶ月で海の生き物の成長はない。 In this example, the resin has a number average molecular weight Mn of 2.6 × 10 4 g / mol, a zinc content of 2.3%, and an acid value of 38 mgKOH / g. According to the shallow sea suspension plate experiment, there is no growth of sea creatures in 6 months.
（付記）
（付記１）
主鎖分解型ポリアクリル酸亜鉛樹脂であって、
主鎖分解型ポリアクリル酸亜鉛樹脂は、主に以下の成分からなり、
ビニル亜鉛エステルの機能性モノマー ５〜８０部
環状モノマー ５ 〜 ９５部
ビニルモノマー ０ 〜 ９５部
開始剤 ０.０１〜１０部
有機溶媒 ５０〜１００部、
前記ビニル亜鉛エステルの機能性モノマーは、以下の成分の重量部で調製され、
亜鉛含有化合物 １０〜４０部
（メタ）アクリル酸 １５〜３０部
モノカルボン酸 ２０〜７５部
溶媒 ５０〜１０５部、
前記（メタ）アクリル酸とは、アクリル酸またはメタクリル酸を指す、
ことを特徴とする、主鎖分解型ポリアクリル酸亜鉛樹脂。
(Additional note)
(Appendix 1)
Main chain decomposition type zinc polyacrylate resin,
Main chain decomposition type zinc polyacrylate resin mainly consists of the following components.
Functional monomer of vinyl zinc ester 5 to 80 parts Cyclic monomer 5 to 95 parts Vinyl monomer 0 to 95 parts Initiator 0.01 to 10 parts Organic solvent 50 to 100 parts,
The functional monomer of the vinyl zinc ester is prepared by weight parts of the following components.
Zinc-containing compound 10 to 40 parts (meth) Acrylic acid 15 to 30 parts Monocarboxylic acid 20 to 75 parts Solvent 50 to 105 parts,
The (meth) acrylic acid refers to acrylic acid or methacrylic acid.
A main chain decomposition type zinc polyacrylate resin, which is characterized by this.
（付記２）
前記環状モノマーは、以下の１〜３８の構造のうちの１つ以上であり、
前記ビニルモノマーは、アクリレート、メタクリレート、末端水酸基のアクリレート、末端水酸基のメタクリレート、アクリル酸の環状炭化水素エステル、メタクリル酸の環状炭化水素エステル、アクリル酸のポリオレフィンジオールエステルおよびメタクリル酸ポリオレフィンジオールエステルのうちの１つ以上である、
ことを特徴とする、付記１に記載の主鎖分解型ポリアクリル酸亜鉛樹脂。
(Appendix 2)
The cyclic monomer is one or more of the following structures 1 to 38.
The vinyl monomer is one of acrylate, methacrylate, terminal hydroxyl group acrylate, terminal hydroxyl group methacrylate, acrylic acid cyclic hydrocarbon ester, methacrylic acid cyclic hydrocarbon ester, acrylic acid polyolefin diol ester and methacrylic acid polyolefin diol ester. One or more,
The main chain decomposition type zinc polyacrylate resin according to Appendix 1, wherein the resin is characterized by the above.
（付記３）
アクリレートは、メチルアクリレート、エチルアクリレート、２−メトキシエチルアクリレート、プロピルアクリレート、イソプロピルアクリレート、ｎ−ブチルアクリレート、イソブチルアクリレート、ｔｅｒｔ−ブチルアクリレート、オクチルアクリレート、イソオクチルアクリレート、ラウリルアクリレートおよびステアリン酸アクリレートのうちの１つ以上であり、
メタクリレートは、メチルメタクリレート、エチルメタクリレート、２−メトキシエチルメタクリレート、プロピルメタクリレート、イソプロピルメタクリレート、ｎ−ブチルメタクリレート、イソブチルメタクリレート、ｔ−ブチルメタクリレート、オクチルメタクリレート、イソオクチルメタクリレート、ラウリルメタクリレート、メタクリル酸ステアリン酸エステルのうちの１つ以上であり、
末端水酸基のアクリレートは、ヒドロキシエチルアクリレートまたはヒドロキシプロピルアクリレートのうちの１つ以上であり、
末端水酸基のメタクリレートは、ヒドロキシエチルメタクリレートおよびヒドロキシプロピルメタクリレートのうちの１つ以上であり、
アクリル酸の環状炭化水素エステルは、フェニルアクリレート、シクロヘキシルアクリレート、４−メチルシクロヘキシルアクリレート、および４−ｔｅｒｔ−ブチルシクロヘキシルアクリレートのうちの１つ以上であり、
メタクリル酸の環状炭化水素エステルは、フェニルメタクリレート、シクロヘキシルメタクリレート、４−メチルシクロヘキシルメタクリレート、および４−ｔｅｒｔ−ブチルシクロヘキシルメタクリレートのうちの１つ以上であり、
アクリル酸のポリオレフィンジオールエステルは、ポリエチレングリコールアクリレートであり、
メタクリル酸ポリオレフィンジオールエステルは、ポリエチレングリコールメタクリレートである、
ことを特徴とする、付記２に記載の主鎖分解型ポリアクリル酸亜鉛樹脂。
(Appendix 3)
The acrylate includes methyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, octyl acrylate, isooctyl acrylate, lauryl acrylate and stearate acrylate. One or more
Methacrylate includes methyl methacrylate, ethyl methacrylate, 2-methoxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, octyl methacrylate, isooctyl methacrylate, lauryl methacrylate, and stearic acid methacrylate ester. One or more of them
The acrylate of the terminal hydroxyl group is one or more of hydroxyethyl acrylate and hydroxypropyl acrylate.
The methacrylate of the terminal hydroxyl group is one or more of hydroxyethyl methacrylate and hydroxypropyl methacrylate.
The cyclic hydrocarbon ester of acrylic acid is one or more of phenyl acrylate, cyclohexyl acrylate, 4-methylcyclohexyl acrylate, and 4-tert-butylcyclohexyl acrylate.
The cyclic hydrocarbon ester of methacrylic acid is one or more of phenyl methacrylate, cyclohexyl methacrylate, 4-methylcyclohexylmethacrylate, and 4-tert-butylcyclohexylmethacrylate.
The polyolefin diol ester of acrylic acid is polyethylene glycol acrylate,
The methacrylic acid polyolefin diol ester is polyethylene glycol methacrylate,
The main chain decomposition type zinc polyacrylate resin according to Appendix 2, wherein the resin is characterized by the above.
（付記４）
前記亜鉛含有化合物は、酸化亜鉛、水酸化亜鉛、塩化亜鉛、酢酸亜鉛、およびプロピオン酸亜鉛のうちの１つまたは複数であり、
前記モノカルボン酸は、アクリル酸、メタクリル酸、ギ酸、酢酸、プロピオン酸、安息香酸、ｎ−オクタン酸、イソオクタン酸、ステアリン酸、イソステアリン酸、ナフテン酸、イタコン酸、マレイン酸、オレイン酸、パルミチン酸およびロジン酸のうちの１つまたは複数である、
ことを特徴とする、付記１に記載の主鎖分解型ポリアクリル酸亜鉛樹脂。
(Appendix 4)
The zinc-containing compound is one or more of zinc oxide, zinc hydroxide, zinc chloride, zinc acetate, and zinc propionate.
The monocarboxylic acids include acrylic acid, methacrylic acid, formic acid, acetic acid, propionic acid, benzoic acid, n-octanoic acid, isooctanoic acid, stearic acid, isostearic acid, naphthenic acid, itaconic acid, maleic acid, oleic acid, and palmitic acid. And one or more of logic acids,
The main chain decomposition type zinc polyacrylate resin according to Appendix 1, wherein the resin is characterized by the above.
（付記５）
前記溶媒は、炭化水素系溶媒、アルコール系溶媒および脱イオン水のうちの１つ以上である、
ことを特徴とする、付記１に記載の主鎖分解型ポリアクリル酸亜鉛樹脂。
(Appendix 5)
The solvent is one or more of a hydrocarbon solvent, an alcohol solvent and deionized water.
The main chain decomposition type zinc polyacrylate resin according to Appendix 1, wherein the resin is characterized by the above.
（付記６）
前記有機溶媒は、炭化水素系溶媒、アルコール系溶媒、ケトン系溶媒およびエステル系溶媒のうちの１つ以上であり、前記開始剤は、リンシアノ、ホスファゼン塩、ホスファゼンオキシド、アゾビスイソブチロニトリル、アゾビスイソバレロニトリル、過酸化ベンゾイル、ジ−ｔｅｒｔ−ブチルペルオキシドおよびｔｅｒｔ−ブチルペルオキシ−２−エチルヘキサノエートのうちの１つ以上である、
ことを特徴とする、付記１に記載の主鎖分解型ポリアクリル酸亜鉛樹脂。
(Appendix 6)
The organic solvent is one or more of a hydrocarbon solvent, an alcohol solvent, a ketone solvent and an ester solvent, and the initiators are phosphocyano, phosphazene salt, phosphazenide oxide, azobisisobutyronitrile, and the like. Azobisisobutaleronitrile, benzoyl peroxide, di-tert-butyl peroxide and one or more of tert-butyl peroxy-2-ethylhexanoate.
The main chain decomposition type zinc polyacrylate resin according to Appendix 1, wherein the resin is characterized by the above.
（付記７）
前記炭化水素系溶媒は、トルエンおよびキシレンのうちの１種以上であり、前記アルコール系溶媒は、イソプロパノール、ｎ−ブタノール、イソブタノールおよびプロピレングリコールメチルエーテルのうちの１つ以上であり、前記ケトン系溶媒は、メチルエチルケトン、メチルイソブチルケトン、アセトン、ブタノンおよびシクロヘキサノンのうちの１つ以上であり、前記エステル系溶媒は酢酸エチルおよび酢酸ブチルのうちの１つ以上である、
ことを特徴とする、付記６に記載の主鎖分解型ポリアクリル酸亜鉛樹脂。
(Appendix 7)
The hydrocarbon solvent is one or more of toluene and xylene, and the alcohol solvent is one or more of isopropanol, n-butanol, isobutanol and propylene glycol methyl ether, and the ketone solvent. The solvent is one or more of methyl ethyl ketone, methyl isobutyl ketone, acetone, butanone and cyclohexanone, and the ester solvent is one or more of ethyl acetate and butyl acetate.
The main chain decomposition type zinc polyacrylate resin according to Appendix 6, wherein the resin is characterized by the above.
（付記８）
前記主鎖分解型ポリアクリル酸亜鉛樹脂において、前記成分は、低分子アルコールまたは低分子アミンおよび／またはテロゲンをさらに含み、低分子アルコールまたは低分子アミンは開始剤と配合され、テロゲンは開始剤と配合され、
前記低分子アルコールは、１〜１２個の炭素原子を有する脂肪族または芳香族アルコールのうちの１つ以上であり、
前記低分子アミンは１〜１２個の炭素原子を有する脂肪族または芳香族アミンのうちの１つ以上であり、
前記テロゲンは、ｎ−ドデシルメルカプタン、ｔｅｒｔ−ドデシルメルカプタン、３−メルカプトプロピオン酸イソオクチル、３−メルカプトプロピオン酸エチルヘキシル、テトラキス（３−メルカプトプロピオン酸）４級テトラオールエステル、α−メチルスチレン二量体のうちの１種以上である、
ことを特徴とする、付記１に記載の主鎖分解型ポリアクリル酸亜鉛樹脂。
(Appendix 8)
In the main chain decomposition type zinc polyacrylate resin, the component further contains a low molecular weight alcohol or a low molecular weight amine and / or a telogen, the low molecular weight alcohol or the low molecular weight amine is compounded with an initiator, and the telogen is an initiator. Formulated,
The low molecular weight alcohol is one or more of aliphatic or aromatic alcohols having 1 to 12 carbon atoms.
The low molecular weight amine is one or more of aliphatic or aromatic amines having 1 to 12 carbon atoms.
The telogens are n-dodecyl mercaptan, tert-dodecyl mercaptan, isooctyl 3-mercaptopropionate, ethylhexyl 3-mercaptopropionate, tetrakis (3-mercaptopropionic acid) quaternary tetraol ester, α-methylstyrene dimer. One or more of them,
The main chain decomposition type zinc polyacrylate resin according to Appendix 1, wherein the resin is characterized by the above.
（付記９）
付記１ないし付記８のいずれか１つに記載の主鎖分解型ポリアクリル酸亜鉛樹脂を調製する方法であって、
５０〜１０５重量部の溶媒を反応媒体とし、亜鉛含有化合物１０〜４０重量部、（メタ）アクリル酸１５〜３０重量部およびモノカルボン酸２０〜７５重量部を５０〜１４０ ℃で３〜８時間反応させ、ビニル亜鉛エステルの機能性モノマーを得る、ビニル亜鉛エステルの機能性モノマーの合成工程（１）と、
不活性雰囲気で５０ー１００重量部の有機溶媒を反応媒体とし、０.０１〜１０重量部の開始剤の作用で、環状モノマー５〜９５重量部、ビニルモノマー０〜９５重量部およびビニル亜鉛エステルの機能性モノマー５〜８０重量部を反応させ、７０〜１２０℃で８〜１８時間の反応条件下で、アクリル酸亜鉛ポリマーを得る、アクリル酸亜鉛樹脂の合成工程（２）と、
を備えることを特徴とする、主鎖分解型ポリアクリル酸亜鉛樹脂の調製方法。
(Appendix 9)
The method for preparing a main chain decomposition type zinc polyacrylate resin according to any one of Supplementary note 1 to Supplementary note 8.
Using a solvent of 50 to 105 parts by weight as a reaction medium, 10 to 40 parts by weight of the zinc-containing compound, 15 to 30 parts by weight of (meth) acrylic acid and 20 to 75 parts by weight of the monocarboxylic acid were used at 50 to 140 ° C. for 3 to 8 hours. The step (1) of synthesizing the functional monomer of vinyl zinc ester, which is reacted to obtain the functional monomer of vinyl zinc ester, and
Using 50-100 parts by weight of an organic solvent as a reaction medium in an inert atmosphere, the action of an initiator of 0.01 to 10 parts by weight causes 5 to 95 parts by weight of a cyclic monomer, 0 to 95 parts by weight of a vinyl monomer, and a vinyl zinc ester. To obtain a zinc acrylate polymer under reaction conditions of 70 to 120 ° C. for 8 to 18 hours by reacting 5 to 80 parts by weight of the functional monomer of
A method for preparing a main chain decomposition type zinc polyacrylate resin, which comprises the above.
（付記１０）
前記主鎖分解性ポリアクリル酸亜鉛樹脂は、海洋防汚塗料の調製に用いられる、
ことを特徴とする、付記１ないし付記８のいずれか１つに記載の主鎖分解型ポリアクリル酸亜鉛樹脂の使用。
(Appendix 10)
The main chain degradable zinc polyacrylate resin is used in the preparation of marine antifouling paints.
Use of the main chain decomposition type zinc polyacrylate resin according to any one of Supplementary note 1 to Supplementary note 8, which is characterized by the above.
Claims (7)
主鎖分解型ポリアクリル酸亜鉛樹脂は、以下の成分の重量部で調製され、
ビニル亜鉛エステルの機能性モノマー ５〜８０重量部
環状モノマー ５ 〜 ９５重量部
ビニルモノマー ０ 〜 ９５重量部
開始剤 ０.０１〜１０重量部
有機溶媒 ５０〜１００重量部、
前記ビニル亜鉛エステルの機能性モノマーは、以下の成分の重量部で調製され、
亜鉛含有化合物 １０〜４０重量部
（メタ）アクリル酸 １５〜３０重量部
モノカルボン酸 ２０〜７５重量部
溶媒 ５０〜１０５重量部、
前記（メタ）アクリル酸とはアクリル酸またはメタクリル酸を指す、主鎖分解型ポリアクリル酸亜鉛樹脂を、調製する方法であって、
５０〜１０５重量部の溶媒を反応媒体とし、亜鉛含有化合物１０〜４０重量部、（メタ）アクリル酸１５〜３０重量部およびモノカルボン酸２０〜７５重量部を５０〜１４０℃で３〜８時間反応させ、ビニル亜鉛エステルの機能性モノマーを得る、ビニル亜鉛エステルの機能性モノマーの合成工程（１）と、
不活性雰囲気で５０〜１００重量部の有機溶媒を反応媒体とし、０.０１〜１０重量部の開始剤の作用で、環状モノマー５〜９５重量部、ビニルモノマー０〜９５重量部およびビニル亜鉛エステルの機能性モノマー５〜８０重量部を反応させ、７０〜１２０℃で８〜１８時間の反応条件下で、アクリル酸亜鉛ポリマーを得る、アクリル酸亜鉛樹脂の合成工程（２）と、
を備え、
前記環状モノマーは、以下の２〜５の構造のうちの１つ以上であり、
ことを特徴とする、主鎖分解型ポリアクリル酸亜鉛樹脂の調製方法。 Main chain decomposition type zinc polyacrylate resin,
The main chain decomposition type zinc polyacrylate resin is prepared by weight parts of the following components.
Functional monomer of vinyl zinc ester 5 to 80 parts by weight
Cyclic monomer 5 to 95 parts by weight
Vinyl monomer 0 to 95 parts by weight
Initiator 0.01-10 parts by weight
Organic solvent 50-100 parts by weight,
The functional monomer of the vinyl zinc ester is prepared by weight parts of the following components.
Zinc-containing compound 10-40 parts by weight
(Meta) Acrylic acid 15 to 30 parts by weight
20-75 parts by weight of monocarboxylic acid
Solvent 50-105 parts by weight,
The (meth) acrylic acid refers to acrylic acid or methacrylic acid, the main chain decomposition type polyacrylic acid zinc resin, a process for preparing,
Using a solvent of 50 to 105 parts by weight as a reaction medium, 10 to 40 parts by weight of the zinc-containing compound, 15 to 30 parts by weight of (meth) acrylic acid and 20 to 75 parts by weight of the monocarboxylic acid were added at 50 to 140 ° C. at 3 to 8 parts. The step (1) of synthesizing the functional monomer of vinyl zinc ester, which is reacted for a time to obtain the functional monomer of vinyl zinc ester,
Using 50 to 100 parts by weight of an organic solvent as a reaction medium in an inert atmosphere, and by the action of 0.01 to 10 parts by weight of the initiator, 5 to 95 parts by weight of the cyclic monomer, 0 to 95 parts by weight of the vinyl monomer, and vinyl zinc ester To obtain a zinc acrylate polymer under reaction conditions of 70 to 120 ° C. for 8 to 18 hours by reacting 5 to 80 parts by weight of the functional monomer of
Equipped with a,
The cyclic monomer is one or more of the following 2 to 5 structures.
A method for preparing a main chain decomposition type zinc polyacrylate resin, which is characterized by the above.
アクリレートは、メチルアクリレート、エチルアクリレート、２−メトキシエチルアクリレート、プロピルアクリレート、イソプロピルアクリレート、ｎ−ブチルアクリレート、イソブチルアクリレート、ｔｅｒｔ−ブチルアクリレート、オクチルアクリレート、イソオクチルアクリレート、およびラウリルアクリレートのうちの１つ以上であり、
メタクリレートは、メチルメタクリレート、エチルメタクリレート、２−メトキシエチルメタクリレート、プロピルメタクリレート、イソプロピルメタクリレート、ｎ−ブチルメタクリレート、イソブチルメタクリレート、ｔ−ブチルメタクリレート、オクチルメタクリレート、イソオクチルメタクリレート、およびラウリルメタクリレートのうちの１つ以上であり、
末端水酸基のアクリレートは、ヒドロキシエチルアクリレートまたはヒドロキシプロピルアクリレートのうちの１つ以上であり、
末端水酸基のメタクリレートは、ヒドロキシエチルメタクリレートおよびヒドロキシプロピルメタクリレートのうちの１つ以上であり、
アクリル酸の環状炭化水素エステルは、フェニルアクリレート、シクロヘキシルアクリレート、４−メチルシクロヘキシルアクリレート、および４−ｔｅｒｔ−ブチルシクロヘキシルアクリレートのうちの１つ以上であり、
メタクリル酸の環状炭化水素エステルは、フェニルメタクリレート、シクロヘキシルメタクリレート、４−メチルシクロヘキシルメタクリレート、および４−ｔｅｒｔ−ブチルシクロヘキシルメタクリレートのうちの１つ以上である、
ことを特徴とする、請求項１に記載の主鎖分解型ポリアクリル酸亜鉛樹脂の調製方法。 Before Symbol vinyl monomers, acrylates, methacrylates, terminal hydroxyl groups of acrylates, terminal hydroxyl groups methacrylate, Ri one or more der of the cyclic hydrocarbon ester le cyclic hydrocarbon esters and methacrylic acid, acrylic acid,
The acrylate is one or more of methyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, octyl acrylate, isooctyl acrylate, and lauryl acrylate. And
The methacrylate is one or more of methyl methacrylate, ethyl methacrylate, 2-methoxyethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, octyl methacrylate, isooctyl methacrylate, and lauryl methacrylate. And
The acrylate of the terminal hydroxyl group is one or more of hydroxyethyl acrylate and hydroxypropyl acrylate.
The methacrylate of the terminal hydroxyl group is one or more of hydroxyethyl methacrylate and hydroxypropyl methacrylate.
The cyclic hydrocarbon ester of acrylic acid is one or more of phenyl acrylate, cyclohexyl acrylate, 4-methylcyclohexyl acrylate, and 4-tert-butylcyclohexyl acrylate.
The cyclic hydrocarbon ester of methacrylic acid is one or more of phenyl methacrylate, cyclohexyl methacrylate, 4-methylcyclohexylmethacrylate, and 4-tert-butylcyclohexylmethacrylate.
The method for preparing a main chain decomposition type zinc polyacrylate resin according to claim 1, wherein the resin is characterized by the above.
前記モノカルボン酸は、アクリル酸、メタクリル酸、ギ酸、酢酸、プロピオン酸、安息香酸、ｎ−オクタン酸、イソオクタン酸、ステアリン酸、イソステアリン酸、ナフテン酸、イタコン酸、マレイン酸、オレイン酸、パルミチン酸およびロジン酸のうちの１つまたは複数である、
ことを特徴とする、請求項１に記載の主鎖分解型ポリアクリル酸亜鉛樹脂の調製方法。 The zinc-containing compound is one or more of zinc oxide, zinc hydroxide, zinc chloride, zinc acetate, and zinc propionate.
The monocarboxylic acids include acrylic acid, methacrylic acid, formic acid, acetic acid, propionic acid, benzoic acid, n-octanoic acid, isooctanoic acid, stearic acid, isostearic acid, naphthenic acid, itaconic acid, maleic acid, oleic acid, and palmitic acid. And one or more of logic acids,
The method for preparing a main chain decomposition type zinc polyacrylate resin according to claim 1, wherein the resin is characterized by the above.
ことを特徴とする、請求項１に記載の主鎖分解型ポリアクリル酸亜鉛樹脂の調製方法。 The solvent is one or more of a hydrocarbon solvent, an alcohol solvent and deionized water.
The method for preparing a main chain decomposition type zinc polyacrylate resin according to claim 1, wherein the resin is characterized by the above.
ことを特徴とする、請求項１に記載の主鎖分解型ポリアクリル酸亜鉛樹脂の調製方法。 The organic solvent, hydrocarbon solvent, alcoholic solvent, Ru one or more der of the ketone solvent and ester solvent,
Characterized the this method the preparation of the main chain decomposition type polyacrylic acid zinc resin according to claim 1.
ことを特徴とする、請求項５に記載の主鎖分解型ポリアクリル酸亜鉛樹脂の調製方法。 The hydrocarbon solvent is one or more of toluene and xylene, and the alcohol solvent is one or more of isopropanol, n-butanol, isobutanol and propylene glycol methyl ether, and the ketone solvent. The solvent is one or more of methyl ethyl ketone, methyl isobutyl ketone, acetone, butanone and cyclohexanone, and the ester solvent is one or more of ethyl acetate and butyl acetate.
The method for preparing a main chain decomposition type zinc polyacrylate resin according to claim 5 , wherein the resin is characterized by the above.
前記低分子アルコールは、１〜１２個の炭素原子を有する脂肪族または芳香族アルコールのうちの１つ以上であり、
前記低分子アミンは１〜１２個の炭素原子を有する脂肪族または芳香族アミンのうちの１つ以上であり、
前記テロゲンは、ｎ−ドデシルメルカプタン、ｔｅｒｔ−ドデシルメルカプタン、３−メルカプトプロピオン酸イソオクチル、３−メルカプトプロピオン酸エチルヘキシル、テトラキス（３−メルカプトプロピオン酸）４級テトラオールエステル、α−メチルスチレン二量体のうちの１種以上である、
ことを特徴とする、請求項１に記載の主鎖分解型ポリアクリル酸亜鉛樹脂の調製方法。 The components of the main chain decomposition type polyacrylic acid zinc resin further comprises a low molecular alcohol or low molecular amines and / or telogen, low molecular alcohol or low molecular amine is combined with an initiator, telogen and initiator formulations Being done
The low molecular weight alcohol is one or more of aliphatic or aromatic alcohols having 1 to 12 carbon atoms.
The low molecular weight amine is one or more of aliphatic or aromatic amines having 1 to 12 carbon atoms.
The telogens are n-dodecyl mercaptan, tert-dodecyl mercaptan, isooctyl 3-mercaptopropionate, ethylhexyl 3-mercaptopropionate, tetrakis (3-mercaptopropionic acid) quaternary tetraol ester, α-methylstyrene dimer. One or more of them,
The method for preparing a main chain decomposition type zinc polyacrylate resin according to claim 1, wherein the resin is characterized by the above.
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| CN113880972A (en) * | 2021-10-15 | 2022-01-04 | 国能粤电台山发电有限公司 | Zinc polyacrylate/capsaicinoid copolymer, preparation method thereof and antifouling paint |
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| AU584199B2 (en) * | 1985-05-17 | 1986-11-20 | Nippon Paint Co., Ltd. | A hydrolyzable resin composition and an antifouling coating composition containing the same |
| EP1167398B1 (en) * | 2000-06-28 | 2005-11-09 | Mitsubishi Rayon Co., Ltd. | Metal-containing monomer dissolved mixture, metal-containing resin and antifouling paint composition |
| CN102167775A (en) * | 2011-03-02 | 2011-08-31 | 上海大学 | Synthesis technology of zinc acrylate or copper acrylate self-polishing anti-fouling resin |
| CN102731745A (en) * | 2012-06-29 | 2012-10-17 | 华南理工大学 | Degradation type marine anti-fouling material, preparation method and application thereof |
| CN103396513B (en) * | 2013-07-24 | 2016-03-02 | 华南理工大学 | A kind of preparation method of main chain fracture type polyacrylic acid silane ester resin and application |
| CN107056990A (en) * | 2017-04-28 | 2017-08-18 | 华南理工大学 | Main chain degradation-type polyacrylic acid zinc resin and its method and application prepared by a kind of simplex method |
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