CN102869257B - 丙烯酸锌共聚物的合成方法 - Google Patents
丙烯酸锌共聚物的合成方法 Download PDFInfo
- Publication number
- CN102869257B CN102869257B CN201180016521.0A CN201180016521A CN102869257B CN 102869257 B CN102869257 B CN 102869257B CN 201180016521 A CN201180016521 A CN 201180016521A CN 102869257 B CN102869257 B CN 102869257B
- Authority
- CN
- China
- Prior art keywords
- copper
- composition
- acid
- polymer
- energy
- 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.)
- Expired - Fee Related
Links
- 229920001577 copolymer Polymers 0.000 title description 12
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 238000003786 synthesis reaction Methods 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 54
- QHNCWVQDOPICKC-UHFFFAOYSA-N copper;1-hydroxypyridine-2-thione Chemical compound [Cu].ON1C=CC=CC1=S.ON1C=CC=CC1=S QHNCWVQDOPICKC-UHFFFAOYSA-N 0.000 claims abstract description 51
- -1 zinc ester Chemical class 0.000 claims abstract description 39
- 229910052802 copper Inorganic materials 0.000 claims abstract description 34
- 239000010949 copper Substances 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 34
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 24
- 239000011701 zinc Substances 0.000 claims abstract description 24
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims description 53
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 230000003373 anti-fouling effect Effects 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 19
- 239000008199 coating composition Substances 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 150000007524 organic acids Chemical class 0.000 claims description 15
- 239000005749 Copper compound Substances 0.000 claims description 13
- 150000001880 copper compounds Chemical class 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000004925 Acrylic resin Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical group [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 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 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 4
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 claims description 4
- 229940120693 copper naphthenate Drugs 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical group [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 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 2
- BWHJGKGBLUSGIC-UHFFFAOYSA-N 2-n-cyclopropyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(NC2CC2)=N1 BWHJGKGBLUSGIC-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 239000005870 Ziram Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000011717 all-trans-retinol Substances 0.000 claims description 2
- 235000019169 all-trans-retinol Nutrition 0.000 claims description 2
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- BQVVSSAWECGTRN-UHFFFAOYSA-L copper;dithiocyanate Chemical compound [Cu+2].[S-]C#N.[S-]C#N BQVVSSAWECGTRN-UHFFFAOYSA-L 0.000 claims description 2
- WURGXGVFSMYFCG-UHFFFAOYSA-N dichlofluanid Chemical compound CN(C)S(=O)(=O)N(SC(F)(Cl)Cl)C1=CC=CC=C1 WURGXGVFSMYFCG-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- YKSNLCVSTHTHJA-UHFFFAOYSA-L maneb Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S YKSNLCVSTHTHJA-UHFFFAOYSA-L 0.000 claims description 2
- 229920000940 maneb Polymers 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 235000021313 oleic acid Nutrition 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 229920001289 polyvinyl ether Polymers 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- HYVWIQDYBVKITD-UHFFFAOYSA-N tolylfluanid Chemical compound CN(C)S(=O)(=O)N(SC(F)(Cl)Cl)C1=CC=C(C)C=C1 HYVWIQDYBVKITD-UHFFFAOYSA-N 0.000 claims description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 2
- DDVNRFNDOPPVQJ-HQJQHLMTSA-N transfluthrin Chemical compound CC1(C)[C@H](C=C(Cl)Cl)[C@H]1C(=O)OCC1=C(F)C(F)=CC(F)=C1F DDVNRFNDOPPVQJ-HQJQHLMTSA-N 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 claims description 2
- 229920006243 acrylic copolymer Polymers 0.000 claims 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims 1
- 239000005751 Copper oxide Substances 0.000 claims 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims 1
- 229910000431 copper oxide Inorganic materials 0.000 claims 1
- JLOULEJYJNBUMX-UHFFFAOYSA-L copper;quinoline-2-carboxylate Chemical compound [Cu+2].C1=CC=CC2=NC(C(=O)[O-])=CC=C21.C1=CC=CC2=NC(C(=O)[O-])=CC=C21 JLOULEJYJNBUMX-UHFFFAOYSA-L 0.000 claims 1
- 229920001002 functional polymer Polymers 0.000 abstract description 8
- 150000001879 copper Chemical class 0.000 abstract 1
- 229940043810 zinc pyrithione Drugs 0.000 abstract 1
- 238000000034 method Methods 0.000 description 21
- 238000005498 polishing Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000523 sample Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical group CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
- 238000000227 grinding Methods 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003139 biocide Substances 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003053 toxin Substances 0.000 description 3
- 231100000765 toxin Toxicity 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 241000238586 Cirripedia Species 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- UTOVMEACOLCUCK-SNAWJCMRSA-N (e)-4-butoxy-4-oxobut-2-enoic acid Chemical compound CCCCOC(=O)\C=C\C(O)=O UTOVMEACOLCUCK-SNAWJCMRSA-N 0.000 description 1
- IQBLWPLYPNOTJC-FPLPWBNLSA-N (z)-4-(2-ethylhexoxy)-4-oxobut-2-enoic acid Chemical compound CCCCC(CC)COC(=O)\C=C/C(O)=O IQBLWPLYPNOTJC-FPLPWBNLSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical group CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- DGZIMLVEXGVYDW-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(O)COC(=O)C=C DGZIMLVEXGVYDW-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical group C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical group COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- GHUXAYLZEGLXDA-UHFFFAOYSA-N 8-azido-5-ethyl-6-phenylphenanthridin-5-ium-3-amine;bromide Chemical compound [Br-].C12=CC(N=[N+]=[N-])=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 GHUXAYLZEGLXDA-UHFFFAOYSA-N 0.000 description 1
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 235000005018 Pinus echinata Nutrition 0.000 description 1
- 241001236219 Pinus echinata Species 0.000 description 1
- 235000011334 Pinus elliottii Nutrition 0.000 description 1
- 235000017339 Pinus palustris Nutrition 0.000 description 1
- 235000008566 Pinus taeda Nutrition 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KOBKUSXTVUSJEU-UHFFFAOYSA-N copper;prop-2-enoic acid Chemical compound [Cu].OC(=O)C=C KOBKUSXTVUSJEU-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical group COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 238000007415 particle size distribution analysis Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical class CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 description 1
- GQKJONISYVOIGJ-UHFFFAOYSA-N prop-2-enoic acid;tributyltin Chemical compound OC(=O)C=C.CCCC[Sn](CCCC)CCCC GQKJONISYVOIGJ-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C09D5/1612—Non-macromolecular compounds
- C09D5/1625—Non-macromolecular compounds organic
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
- A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
-
- 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
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/69—Particle size larger than 1000 nm
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Nanotechnology (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明公开了含锌酯官能的聚合物和粒状巯氧吡啶铜的组合物,其中该颗粒的平均长径比范围为约8-约15,其中通过使酸官能的聚合物与巯氧吡啶锌和铜盐或羧酸铜反应,获得锌酯官能的聚合物和巯氧吡啶铜。
Description
发明领域
本发明涉及含金属酯官能聚合物和巯氧吡啶铜的组合物,生产这一组合物的方法,和含有这一组合物的油漆。
发明背景
轮船、渔网或其他水下结构体或设备倾向于受到水生生物,例如藤壶,蚌类和藻类等的进攻。生物体可生长并繁殖,和最终引起严重的问题。例如,在轮船外壳的情况下,海洋生物体在外壳上的生长可增加外壳与水之间的摩擦阻力,从而增加燃耗并降低船速。
解决该问题的一种方法是用在其内存在含金属的聚合物的防垢涂料涂布结构体的表面。这些聚合物通常具有连接到聚合物主链上的可水解基团。随着时间流逝,在涂层的最外层处的聚合物水解并成为水可侵蚀的残渣。随后这一残渣被水除去,提供光滑的不含污垢的表面。这一作用通常称为“自抛光”效应。
多年来含金属的自抛光共聚物在商业中使用。由于IMO禁止自抛光的丙烯酸三丁锡,因此,丙烯酸的铜和锌盐成为了在自抛光的防垢涂料中使用的常见聚合物。
在文献中公开了金属丙烯酸盐及其制备方法。
作为例举,美国专利No.4,774,080公开了通过使共聚物与单价有机酸和金属氧化物、氯化物或氢氧化物反应获得的金属丙烯酸盐自抛光聚合物。或者,可用金属砷酸盐替代有机酸和金属盐。可由共聚不饱和有机酸单体和其他可共聚的不饱和单体,获得在该反应中所使用的共聚物。专利‘080还公开了在与其他不饱和的可聚合单体共聚制备金属丙烯酸盐聚合物之前,可首先制备不饱和金属酯。
美国专利No.6,177,530公开了由共聚具有两个不饱和基团的含金属的可聚合单体和含金属的可聚合单体获得的含金属的可水解共聚物。也可存在其他可聚合的单体。
单独或与其他杀生物剂结合使用自抛光聚合物,进一步提高防垢性能。当与其他杀生物剂一起使用该聚合物时,目前的实践是独立地制备聚合物以及主要和辅助的杀生物剂,然后将它们单独地添加到防垢油漆组合物中。
防垢油漆协会需要可生产同时含金属的自抛光聚合物和辅助杀生物剂(booster biocide)的混合物的成本有效的方法。本发明提供对该需求的一种应答。
发明概述
在一个方面中,本发明提供含有锌酯官能聚合物和巯氧吡啶铜颗粒的组合物,其中该颗粒的平均长径比范围为约8-约15。通过使酸官能的聚合物与巯氧吡啶锌和选自铜盐、羧酸铜、氢氧化铜、元素铜及其组合的铜化合物反应,获得锌酯官能的聚合物和巯氧吡啶铜。
在另一个方面中,本发明提供防垢涂料组合物,它包括锌酯官能聚合物和巯氧吡啶铜颗粒,其中该颗粒的平均长径比范围为约8-约15。通过使酸官能的聚合物与巯氧吡啶锌和选自铜盐、羧酸铜、氢氧化铜、元素铜及其组合的铜化合物反应,获得锌酯官能的聚合物和巯氧吡啶铜。该防垢组合物可进一步含有水溶性或微水溶性树脂。
在再一方面中,本发明涉及制造含锌酯官能的聚合物和巯氧吡啶铜颗粒的组合物的方法,其中该颗粒的平均长径比范围为约8-约15。该方法包括下述步骤:在溶剂中,使酸官能的聚合物与巯氧吡啶锌和选自铜盐、羧酸铜、氢氧化铜、元素铜及其组合的铜化合物反应。
附图简述
本专利或申请包含彩色完成的至少一副附图。当请求并支付必须的费用时,专利局将提供具有彩色附图的本专利或专利申请公布的副本。
图1和2是根据本发明的方法制备的巯氧吡啶铜,样品507C和508D的扫描电镜(SEM)图。
图3是可商购的巯氧吡啶铜,样品513的SEM图。
图4是在样品制备之后1小时拍摄的样品A,C和D的照片。
图5是在样品制备之后1天拍摄的样品A,C和D的照片。
图6是显示面板测试结果的照片。
优选实施方案的详细说明
申请人令人惊奇地发现,由酸官能的聚合物,巯氧吡啶锌和选自铜盐、羧酸铜、氢氧化铜、元素铜及其组合的铜化合物的反应,可同时生产含锌的自抛光聚合物和巯氧吡啶铜。与牵涉单独生产自抛光的含锌聚合物和单独地添加汞杀生物剂的方法相比,本发明的方法有效且性价比合适。而且,通过本发明方法生产的巯氧吡啶铜为微粒形式,甚至当未研磨的巯氧吡啶锌湿饼用作反应的起始材料时。通过避免在其他情况下根据生产油漆等级的巯氧吡啶铜的常规方法所要求的干燥和粉碎或研磨巯氧吡啶铜的需求,这一特征节约了成本。
申请人还令人惊奇地发现,通过本发明方法生产的巯氧吡啶铜颗粒落在独特的平均长径比范围内,所述范围不同于通过研磨巯氧吡啶铜可获得的比值范围。与可商购的研磨过的巯氧吡啶铜相比,在平均长径比的独特范围内的巯氧吡啶铜颗粒不那么可能聚集和/或从含有它们的组合物中沉降出来。
通过本发明方法生产的组合物可掺入到防垢涂料组合物中。与含有可商购的自抛光聚合物和研磨过的巯氧吡啶铜的结合物的防垢涂料相比,这一防垢涂料组合物显示出较好的效果。
因此,在一个实施方案中,本发明提供含有锌酯官能聚合物和巯氧吡啶铜颗粒的组合物,其中该颗粒的平均长径比范围为约8-约15。没有特别限制锌酯官能的聚合物,且可以是丙烯酸锌,聚酯锌,醇酸树脂锌,或其结合物。优选的锌酯官能的聚合物是丙烯酸锌。本发明的锌酯官能的聚合物具有自抛光效果。合适的锌酯官能的聚合物公开于例如US4,774,080中。
优选地,包含在本发明组合物内的巯氧吡啶铜是D50为约3-5微米的微粒。此处所使用的D50是下述直径,其中50wt%巯氧吡啶铜颗粒的直径等于或小于D50值,同时恰好小于50wt%的巯氧吡啶铜存在于直径大于该D50值的颗粒内。优选使用Horiba LA-910粒度分布分析仪,通过激光散射,测定颗粒直径。
有利的是,本发明的巯氧吡啶铜颗粒的平均长径比范围为约8-约15,优选约9-约12。在一个实施方案中,至少5%的颗粒的平均长径比等于或大于20。此处所使用的长径比是指最长与最短的颗粒尺寸之比。与可商购的研磨过的巯氧吡啶铜相比,本发明的巯氧吡啶铜具有较低程度的聚集,或者沉降。在没有束缚于任何理论的情况下,认为当巯氧吡啶铜颗粒在本发明的方法中形成时,它们被聚合物浸湿,从而最小化颗粒因范德华力导致的结块和/或聚集的危险。
在另一实施方案中,本发明提供生产含有锌酯官能的聚合物和巯氧吡啶铜颗粒的组合物的方法,其中该颗粒的平均长径比为约8-约15。该方法包括下述步骤:在溶剂中使酸官能的聚合物与巯氧吡啶锌和选自铜盐、羧酸铜、氢氧化铜、元素铜及其组合的铜化合物反应。
没有特别限制适合于本发明的酸侧挂的聚合物。在优选的实施方案中,它们是数均分子量(Mn)在10,000以下,优选2,000-6,000的酸官能的丙烯酸酯聚合物。可通过本领域技术人员已知的任何方法,制备丙烯酸酯共聚物。典型地,可通过使不饱和有机酸单体与其他不饱和单体聚合,获得这些共聚物。不饱和有机酸单体包括具有至少一个羧基的那些化合物,例如丙烯酸或甲基丙烯酸,以提供酸官能度。合适的其他不饱和单体的实例包括,但不限于,丙烯酸甲酯,甲基丙烯酸甲酯,丙烯酸乙酯,甲基丙烯酸乙酯,丙烯酸丁酯,甲基丙烯酸丁酯,丙烯酸2-乙基己酯,甲基丙烯酸2-乙基己酯,丙烯酸2-甲氧基乙酯,丙烯酸2-乙氧基乙酯,丙烯酸乙氧基乙氧基乙酯,丙烯酸2-苯氧基乙酯,丙烯酸2-羟乙酯,丙烯酸2-羟丙酯,丙烯酸4-羟丁酯,甲基丙烯酸异丁酯,甲基丙烯酸叔丁酯,丙烯腈,丙烯酸异丁酯,丙烯酸叔丁酯及其组合。
也可共聚的其他非丙烯酸酯单体包括,但不限于,乙酸乙烯酯,丙酸乙烯酯,苯乙烯,富马酸丁酯,富马酸锌酯,氯乙烯,偏氯乙烯,氟乙烯,偏氟乙烯,四氟乙烯,乙烯,丙烯,丁二烯,氯丁二烯,异戊二烯,丙烯酰胺,马来酸丁酯,马来酸辛酯,马来酸酐,丁酸乙烯酯,乙烯基甲醚,乙烯醇,乙烯基吡啶,乙烯基甲苯,及其组合。
典型地选择单体,以提供具有适合于其中使用防垢油漆的条件所要求的挠性、硬度、亲水性和Tg的无定形聚合物。通过控制共聚的丙烯酸或甲基丙烯酸单体的用量,控制抛光速度。酸单体越多,金属丙烯酸盐聚合物具有的潜在的酯官能度越多。金属酯官能度越多,水解越高,和因此在所有别的条件一样的情况下,抛光速度将相等。以酸值(也称为酸的数值)形式测量基础聚合物的酸官能度。酸值范围为约60-约140的金属酯官能的聚合物是在防垢油漆中使用的自抛光共聚物的典型。
没有特别限制在反应中所使用的巯氧吡啶锌的形式。它可以是未研磨的湿饼形式。生产巯氧吡啶锌的方法是本领域技术人员已知的且公开于例如美国专利4,396,766中,其公开内容在此通过参考全文引入。
在反应中所使用的例举的铜盐包括,但不限于,碳酸铜,硝酸铜,硫酸铜,氯化铜及其组合。
当所使用的铜化合物是铜盐,铜的氢氧化物,或元素铜时,任选地可添加有机酸到该反应混合物中,控制交联度。使用较多的有机酸是指更多的金属酯基将侧挂,而不是交联,这反过来要求更多的巯氧吡啶锌和铜化合物以供反应。
例举的有机酸包括,但不限于,乙酸,氯乙酸,丙酸,辛酸,叔羧酸(versatic acid),乙基己酸,苯甲酸,环烷酸,棕榈酸,硬脂酸,油酸,或任何脂肪酸,松香酸(rosin acid),例如松香酸(abietic acid)及其组合。优选的有机酸是乙酸,环烷酸及其组合。
或者,可使用羧酸铜替代铜盐、铜的氢氧化物或元素铜加上有机酸的结合物。羧酸铜的代表性且非限定性实例包括乙酸铜,环烷酸铜,羟基喹啉(quinol inolate)铜,硬脂酸铜,苯甲酸铜,乙基己酸铜,松香酸铜,及其组合。在优选的实施方案中,所使用的羧酸铜选自乙酸铜,环烷酸铜及其组合。
典型地,在溶剂存在下进行反应。优选地,溶剂含有至少与水混溶的组分,以便来自反应和/或来自巯氧吡啶锌湿饼的水与聚合物溶液混溶。在一些实施方案中,溶剂含有与水混溶的组分和与水不混溶的组分。有利的是,约25%-约50%的溶剂是与水混溶的,这取决于形成侧挂的金属酯所使用的有机酸。例举的与水混溶的组分包括,但不限于,甲氧基丙醇,甲氧基丁醇,甲氧基-甲基乙氧基丙醇,丁氧基乙醇,乙氧基乙醇,和丙醇。例举的与水不混溶的组分包括,但不限于,二甲苯,甲苯,乙苯,石脑油,甲基异丁基酮,和枯烯。也可使用部分与水混溶的溶剂,例如甲乙酮或丁醇。适合于在本发明的方法中使用的例举的溶剂是甲氧基丙醇和二甲苯的结合物。
可在室温下或者在升高的温度下,和在标准大气压下进行反应。在该反应中,并不总是需要使用化学计量用量的反应物以获得所需产物。在一些实施方案中,合适的是,就摩尔当量比为单位,使用巯氧吡啶锌:在酸官能的聚合物内的酸官能的单体:铜化合物=1:1.8-3.0:0.8-1.5,优选1:2.0-2.5:1.0-1.2,更优选1:2:1。若在反应中使用有机酸,则巯氧吡啶锌:有机酸加上在酸官能的聚合物内的酸官能单体之和:铜化合物为1:1.8-3.0:0.8-1.5,优选1:2.0-2.5:1.0-1.2,更优选1:2:1。
在再一实施方案中,本发明提供含有锌酯官能聚合物和巯氧吡啶铜颗粒的防垢涂料组合物,其中该颗粒的平均长径比为约8-约15。通过使酸官能的聚合物与巯氧吡啶锌和选自铜盐、羧酸铜、铜的氢氧化物及其组合的铜化合物反应,获得锌酯官能的聚合物和巯氧吡啶铜。优选地,锌酯官能的聚合物和巯氧吡啶铜结合的存在量为约5-约30,更优选约10-约25,基于涂料组合物的总重量。
本发明的防垢涂料组合物可另外含有一种或更多种水溶性树脂或微水溶性树脂,例如松香,聚乙烯醚,壳聚糖,或其结合物。这些树脂的配制量范围优选为约1-约20%,更优选约4-约15%,基于涂料组合物的总重量。
防垢涂料组合物也可包括一些其他的添加剂。例如,防止硬污垢的毒素,例如铜金属,氧化亚铜,硫氰酸铜,氧化锌,硼酸锌,偏硼酸钡,吡啶三苯基硼,三苯基硼十八烷基(octidecyl)胺,四氟苯菊酯,虫螨腈,甲苯氟磺胺,或抑菌灵;和控制软污垢的毒素,例如巯氧吡啶锌,巯氧吡啶铜,4,5-二氯-2-正辛基-4-异噻唑啉-3-酮,2-甲硫基-4-叔丁基氨基-6-环丙基氨基-s-三嗪,代森锌,福美锌,代森福美锌,代森锰,百菌清及其任何混合物。
可例如通过添加树脂和/或其他毒素到含锌酯官能的聚合物和巯氧吡啶铜颗粒的组合物中,并通过任何常规的方式混合它们,从而制备本发明的防垢涂料,其中该颗粒的平均长径比范围为约8-约15。
防垢涂料当通过常规技术涂布在基底表面上并在室温或者升高的温度下蒸发掉溶剂时,形成干燥的薄膜。
通过下述实施例,进一步详细地描述本发明。所有份和百分数以重量计且所有温度为摄氏度,除非另外特别说明。
实验
实施例1制备含自抛光聚合物和巯氧吡啶铜的组合物
A.制备酸官能的聚合物
向配有滴液漏斗、回流冷凝器、搅拌器和温度计的1升反应烧瓶中添加89.0g甲氧基丙醇,100.0g二甲苯和16.0g丙烯酸乙酯。在搅拌的同时,在低速下,在氮气覆盖下,使反应混合物升温到95±5℃。
在单独的烧瓶中彻底预混下述单体和引发剂:40.0g甲基丙烯酸甲酯,244.0g丙烯酸乙酯,40.0g丙烯酸2-甲氧基乙酯,60.0g甲基丙烯酸,10.0g2,2’-偶氮双(2-甲基丙腈),28.0g2,2-偶氮双(2-甲基丁腈),4.0g甲基苯乙烯二聚体和40.0g甲氧基丙醇。将单体/引发剂混合物转移到安装在反应烧瓶上的滴液漏斗中;并在恒定的速度下,在6小时内,在95±5℃下,在连续搅拌的同时,添加到反应烧瓶内。
接下来,向滴液漏斗中引入预混的甲氧基丙醇(40.0g)和过氧叔丁基2-乙基己基碳酸酯(2.0g)。在0.5小时的期间内,在95±5℃下,将这一碾碎(chaser)混合物加入到反应烧瓶内。在95±5℃下,将反应混合物再搅拌1.5小时。添加甲氧基丙醇(32.0g),并在连续搅拌的同时,允许反应混合物冷却到室温。
使用凝胶渗透色谱法,测量聚合物的分子量。测量到数均分子量(Mn)为约3,000和测量到重均分子量(Mw)为约7,000。计算酸值为约90。
B.制备含丙烯酸锌共聚物和巯氧吡啶铜的组合物
向1/2品脱的混合容器中添加93.0g以上制备的酸官能的丙烯酸聚合物溶液。在具有1′刀片的高速cowles型分配器下方放置混合容器。混合器变为1000rpm。向这一混合容器中添加25.9g60%固体巯氧吡啶锌湿饼,26.3g甲氧基丙醇,和3.0g乙酸。混合器的速度增加到2000rpm。向混合容器中添加1.45g氢氧化铜(58%铜),接着10分钟混合和连续添加另外3批次氢氧化铜(1.45g每批次)。一旦反应混合物变为暗绿色,则添加2.50gNH4OH(29.6%)到混合容器中,并继续搅拌30分钟,提供含丙烯酸锌共聚物和巯氧吡啶铜的组合物。
对比例1使用美国专利4,774,080的技术,制备丙烯酸锌聚合物
使用美国专利4,774,080的技术,制造用于与本发明比较所使用的丙烯酸锌聚合物。始于实施例1的制备中所述的酸官能的聚合物,在配有回流冷凝器、氮气入口、滴液漏斗和温度探针的反应烧瓶中,通过添加14.6g氧化锌到100.0g酸官能的聚合物(53.0%不挥发物),80.0g甲氧基丙醇,3.3g水和5.05g环烷酸中,制造丙烯酸锌。使混合物升温到100±5℃。独立地混合15.0g环烷酸与300.0g酸官能的聚合物并倾倒在滴液漏斗内。在6小时的期间内,在氮气覆盖下,将这一混合物逐滴添加到反应烧瓶中,并反应额外2小时,得到46.3%的固体丙烯酸锌共聚物。
实施例2分析由本发明的方法形成的巯氧吡啶铜
制样
如下所述制备三个样品:
样品:507C,根据实施例1,步骤B制备的巯氧吡啶铜,甲氧基丙醇用作溶剂;
508D,根据实施例1,步骤B制备的巯氧吡啶铜,甲氧基丙醇/二甲苯用作溶剂;
513,ACM巯氧吡啶铜,商购于Arch Chemicals,Inc。
B.显微图像
图1-3中示出了样品507C,508D和513的显微图像。使用HitachiS-300N扫描电镜,获得所有图像。
B.长径比分析
工序:通过在颗粒图像上叠加微米尺,并按规定比例,视觉比较颗粒的长度与宽度,从而测定长径比。长度除以宽度确定长径比。使用Hitachi S-300N扫描电镜,获得图像。
结果:表1中所示的结果证明,与可商购的研磨过的巯氧吡啶铜相比,由本发明方法制备的粒状巯氧吡啶铜具有高得多的长径比(12.2和9.1vs4.3)。另外,对于本发明的两种巯氧吡啶铜样品来说,存在至少5%长径比大于或等于20的颗粒,而在可商购的研磨过的巯氧吡啶铜中,无一颗粒的长径比大于15。
C.聚集-沉降数据
在等重量的二甲苯中混合等重量实施例2的B部分中所述的样品507C,508D和513,提供样品C,D和A。在1小时之后(图4)和在24小时之后(图5),测量样品的沉降。就地形成的颗粒的两个样品(C和D)沉降小于常规方法的巯氧吡啶铜(A)。具有较高长径比的样品(C)沉降最小。
实施例3防垢涂料组合物
使用高速混合器,通过一起共混实施例1获得的组合物与表2中详述的其他物质,制备本发明的涂料组合物(P)。
使用高速混合器,通过共混对比例1制备的丙烯酸锌,可商购的巯氧吡啶铜和表2所示的其他物质,获得对比涂料组合物(J)。
表2
接下来,通过辊,在事先用2份环氧树脂打底过的两个玻璃增强的聚酯(GRP)面板上两次施加以上每一种涂料组合物J和F总计两层防垢涂层。以下示出了每一面板的干燥防垢涂层的总重量:
J-1 J-2 P-1 P-2
35.85 36.36 33.86 35.41
然后将上述试验面板紧固到2′X6″X8″压力处理过的南方黄松木板上并垂直悬挂在海水中1年。在West Palm Beach,FL的RybovichMarina处进行试验,并在图6中示出了结果。
结果表明,含有丙烯酸锌聚合物和就地生成的巯氧吡啶铜的本发明涂料组合物就防垢效率来说的性能好于通过常规方法制备的含丙烯酸锌聚合物和研磨过的巯氧吡啶铜的涂料组合物。
Claims (20)
1.一种组合物,它包括锌酯官能的聚合物和巯氧吡啶铜颗粒,其中所述颗粒的平均长径比范围为8-15。
2.权利要求1的组合物,其中所述锌酯官能的聚合物是丙烯酸锌聚合物。
3.权利要求1的组合物,其中通过使酸官能的聚合物与巯氧吡啶锌和选自铜盐、羧酸铜、氢氧化铜、元素铜及其组合的铜化合物反应,获得所述锌酯官能的聚合物和所述巯氧吡啶铜。
4.权利要求3的组合物,其中所述酸官能的聚合物是酸官能的丙烯酸类共聚物。
5.权利要求4的组合物,其中所述酸官能的丙烯酸类共聚物的数均分子量在10,000以下。
6.权利要求4的组合物,其中所述酸官能的丙烯酸类共聚物衍生于选自丙烯酸、甲基丙烯酸及其组合的不饱和有机酸单体。
7.权利要求4的组合物,其中所述铜盐选自碳酸铜、硝酸铜、硫酸铜、氯化铜及其组合。
8.权利要求4的组合物,其中所述铜化合物是氢氧化铜。
9.权利要求7或8的组合物,进一步包括选自乙酸、氯乙酸、丙酸、辛酸、叔羧酸,乙基己酸,苯甲酸,环烷酸,棕榈酸,硬脂酸,油酸,脂肪酸,松香酸,及其组合的有机酸。
10.权利要求9的组合物,其中所述有机酸是乙酸或环烷酸。
11.权利要求3的组合物,其中所述羧酸铜选自乙酸铜,环烷酸铜,羟基喹啉铜,硬脂酸铜,苯甲酸铜,乙基己酸铜,松香酸铜,及其组合。
12.权利要求11的组合物,其中所述羧酸铜是乙酸铜或环烷酸铜。
13.权利要求3的组合物,其中所述巯氧吡啶铜的颗粒的D50为3-5微米。
14.权利要求1的组合物,其中所述巯氧吡啶铜的颗粒的平均长径比范围为9-12。
15.权利要求4的组合物,其中所述酸官能的丙烯酸类共聚物的数均分子量为2000-6000。
16.一种防垢涂料组合物,它包括权利要求1-15中任一项的组合物。
17.权利要求16的防垢涂料组合物,进一步包括水溶性或微水溶性的树脂,其中所述树脂的存在量为4-15%,基于涂料组合物的总重量。
18.权利要求17的防垢涂料组合物,其中树脂选自松香,聚乙烯醚,壳聚糖及其组合。
19.权利要求16的防垢涂料组合物,进一步包括选自铜金属,氧化铜,硫氰酸铜,氧化锌,硼酸锌,偏硼酸钡,吡啶三苯基硼,三苯基硼十八烷基胺,四氟苯菊酯,虫螨腈,甲苯氟磺胺,苯氟磺胺,巯氧吡啶锌,4,5-二氯-2-正辛基-4-异噻唑啉-3-酮,2-甲硫基-4-叔丁基氨基-6-环丙基氨基-s-三嗪,代森锌,福美锌,代森福美锌,代森锰,百菌清及其组合的添加剂。
20.权利要求1的组合物的制备方法,包括下述步骤:使酸官能的聚合物与巯氧吡啶锌和选自铜盐、羧酸铜、氢氧化铜、元素铜及其组合的铜化合物在溶剂中反应。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/660,053 | 2010-02-19 | ||
US12/660,053 US8541493B2 (en) | 2010-02-19 | 2010-02-19 | Synthesis of zinc acrylate copolymer from acid functional copolymer, zinc pyrithione, and copper compound |
PCT/US2011/023865 WO2011102983A1 (en) | 2010-02-19 | 2011-02-07 | Synthesis of zinc acrylate copolymer |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102869257A CN102869257A (zh) | 2013-01-09 |
CN102869257B true CN102869257B (zh) | 2014-06-25 |
Family
ID=44476661
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201180016521.0A Expired - Fee Related CN102869257B (zh) | 2010-02-19 | 2011-02-07 | 丙烯酸锌共聚物的合成方法 |
Country Status (17)
Country | Link |
---|---|
US (2) | US8541493B2 (zh) |
EP (1) | EP2536281B1 (zh) |
JP (1) | JP5722919B2 (zh) |
KR (1) | KR20130054228A (zh) |
CN (1) | CN102869257B (zh) |
AU (1) | AU2011218367B2 (zh) |
BR (1) | BR112012020841A2 (zh) |
CL (1) | CL2012002277A1 (zh) |
DK (1) | DK2536281T3 (zh) |
ES (1) | ES2585877T3 (zh) |
HR (1) | HRP20161028T1 (zh) |
MY (1) | MY156570A (zh) |
PL (1) | PL2536281T3 (zh) |
PT (1) | PT2536281T (zh) |
RU (1) | RU2573466C2 (zh) |
SG (1) | SG183339A1 (zh) |
WO (1) | WO2011102983A1 (zh) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8541493B2 (en) | 2010-02-19 | 2013-09-24 | Arch Chemicals, Inc. | Synthesis of zinc acrylate copolymer from acid functional copolymer, zinc pyrithione, and copper compound |
KR20140057609A (ko) | 2011-08-17 | 2014-05-13 | 아크 캐미컬스 인크 | 아연 피리티온 및 구리 화합물로부터의 구리 피리티온의 합성 |
WO2015048266A1 (en) | 2013-09-27 | 2015-04-02 | Rohm And Haas Chemicals Llc | Water dispersible films for packaging high water containing formulations |
CN105518068B (zh) * | 2013-09-27 | 2018-09-14 | 罗门哈斯公司 | 膜与颗粒的离子强度触发的崩解 |
US10721934B2 (en) | 2013-11-19 | 2020-07-28 | Arch Chemicals, Inc. | Enhanced preservative |
SG11201704006SA (en) * | 2014-11-26 | 2017-06-29 | Chugoku Marine Paints | Antifouling coating composition, antifouling coating film, substrate with an antifouling coating film, antifouling substrate, methods for producing substrate with an antifouling coating film, and method for preventing substrates from fouling |
CN104530986B (zh) * | 2014-12-23 | 2017-11-14 | 中国海洋大学 | 具有丙烯酸金属盐树脂化学结构特征和性能的松香有机酸金属盐树脂及其制备方法与用途 |
CN104559579B (zh) * | 2014-12-25 | 2017-02-22 | 上海海隆石油化工研究所 | 环保型高附着力自抛光防污漆 |
CN104629567B (zh) * | 2015-01-30 | 2017-01-11 | 厦门双瑞船舶涂料有限公司 | 一种抗龟裂丙烯酸锌防污涂料的制备方法 |
CN104911904A (zh) * | 2015-05-14 | 2015-09-16 | 巢湖市大江渔具有限公司 | 一种渔网的防污涂料 |
CN107337974A (zh) * | 2017-07-11 | 2017-11-10 | 苏州市阳澄湖蟹王水产有限公司 | 一种抑制大闸蟹养殖池中藻类生长的涂料 |
CN108690447A (zh) * | 2017-07-25 | 2018-10-23 | 山东科耀化工有限公司 | 松香酸改性聚丙烯酸树脂锌盐防污涂料的制备方法 |
CN109803309B (zh) * | 2017-11-17 | 2021-06-29 | 华为技术有限公司 | 通信方法及装置 |
CN111978799B (zh) * | 2020-09-08 | 2022-04-12 | 安徽省金盾涂料有限责任公司 | 一种无铜环保水解型防污漆 |
WO2024006517A1 (en) * | 2022-07-01 | 2024-01-04 | Arxada, LLC | Copper containing compounds and compositions for antimicrobial paint and coating |
CN115850559A (zh) * | 2022-11-18 | 2023-03-28 | 湘潭大学 | 丙烯酸锌/类辣椒素共聚物及其制备方法与应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1225660A (zh) * | 1996-05-22 | 1999-08-11 | J·C·亨普尔斯基布斯法夫工厂股份公司 | 防污涂料 |
CN1342099A (zh) * | 1999-03-05 | 2002-03-27 | 阿奇化工公司 | 用于制备巯氧吡啶颗粒分散液的化学方法 |
WO2008038967A1 (en) * | 2006-09-25 | 2008-04-03 | Sang-Ki Ahn | Anti-fouling paint composition |
CN101558112A (zh) * | 2005-11-23 | 2009-10-14 | 阿奇化工公司 | 含巯氧吡啶的金属盐和氧化亚铜的油漆 |
Family Cites Families (56)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NO128713B (zh) * | 1967-07-03 | 1974-01-02 | Takeda Chemical Industries Ltd | |
US4396766A (en) * | 1982-04-28 | 1983-08-02 | Olin Corporation | Process for producing sodium and zinc pyrithione |
NO168116C (no) * | 1985-05-17 | 1992-01-15 | Nippon Paint Co Ltd | Hydrolyserbart harpikspreparat og dets anvendelse |
JPH0667975B2 (ja) * | 1986-11-17 | 1994-08-31 | 日本ペイント株式会社 | 金属含有塗料用樹脂の製造方法 |
US5057153A (en) * | 1990-05-03 | 1991-10-15 | Olin Corporation | Paint containing high levels of a pyrithione salt plus a copper salt |
US5112397A (en) * | 1991-06-17 | 1992-05-12 | Olin Corporation | Process for stabilizing zinc pyrithione plus cuprous oxide in paint |
US5098473A (en) * | 1991-03-04 | 1992-03-24 | Olin Corporation | Process for stabilizing zinc pyrithione plus cuprous oxide in paint |
US5137569A (en) * | 1991-10-10 | 1992-08-11 | Olin Corporation | Process for stabilizing zinc pyrithione plus cuprous oxide in paint |
US5601785A (en) * | 1991-12-23 | 1997-02-11 | Microsensor Technology, Inc. | Connector for detachable column cartridge for gas chromatograph |
US5185033A (en) * | 1992-09-01 | 1993-02-09 | Olin Corporation | Gel-free paint containing copper pyrithione or pyrithione disulfide plus cuprous oxide |
US5232493A (en) * | 1992-09-01 | 1993-08-03 | Olin Corporation | Process for stabilizing zinc pyrithione plus cuprous oxide in paint |
US5238490A (en) * | 1992-09-04 | 1993-08-24 | Olin Corporation | Process for generating copper pyrithione in-situ in a paint formulation |
US5246489A (en) * | 1992-09-04 | 1993-09-21 | Olin Corporation | Process for generating copper pyrithione in-situ in a paint formulation |
US5298061A (en) * | 1993-05-14 | 1994-03-29 | Olin Corporation | Gel-free paint containing zinc pyrithione, cuprous oxide, and amine treated rosin |
US5730943A (en) * | 1993-08-12 | 1998-03-24 | Optimize Technologies, Inc. | Integral fitting and filter of an analytical chemical instrument |
DE69417240T2 (de) * | 1993-08-12 | 1999-07-29 | Optimize Tech Inc | Integriertes verbindungsstück und filter |
US5342437A (en) * | 1993-10-15 | 1994-08-30 | Olin Corporation | Gel-free paint containing zinc pyrithione cuprous oxide and carboxylic acid |
US5540860A (en) * | 1994-02-28 | 1996-07-30 | Olin Corporation | Process for preparing copper pyrithione |
US5472598A (en) * | 1994-04-15 | 1995-12-05 | Upchurch Scientific, Inc. | Connection assembly for liquid chromatography columns |
US5651885A (en) * | 1994-04-15 | 1997-07-29 | Schick; Hans G. | Column for liquid chromatography |
JP3062917B2 (ja) * | 1994-09-01 | 2000-07-12 | 日本ペイント株式会社 | 加水分解型金属含有樹脂および防汚塗料組成物 |
AU6889398A (en) | 1997-04-18 | 1998-11-13 | Arch Chemicals, Inc. | In-situ generation of zinc pyrithione |
US6162446A (en) * | 1998-03-11 | 2000-12-19 | Arch Chemicals, Inc. | In-situ generation of zinc pyrithione in personal care compositions |
US6017562A (en) * | 1997-04-28 | 2000-01-25 | Arch Chemicals, Inc. | Non-spherical and non-platelet crystalline forms of pyrithione salts |
US6242007B1 (en) * | 1997-04-28 | 2001-06-05 | Arch Chemicals, Inc. | Non-spherical and non-platelet forms of pyrithione salts and methods of making same |
EP1707602B1 (en) | 1997-05-20 | 2009-12-30 | Mitsubishi Rayon Co., Ltd. | Antifouling paint composition |
US6095572A (en) * | 1998-01-20 | 2000-08-01 | Optimize Technologies, Inc. | Quarter turn quick connect fitting |
US7942958B1 (en) * | 1998-07-22 | 2011-05-17 | Arch Chemicals, Inc. | Composite biocidal particles |
PL200670B1 (pl) | 1998-12-28 | 2009-01-30 | Chugoku Marine Paints | Kopolimer sililo(met)akrylanowy, sposób jego wytwarzania, przeciwporostowa kompozycja do malowania zawierająca kopolimer sililo(met)akrylanowy oraz jej zastosowanie |
US7455851B1 (en) * | 1999-06-25 | 2008-11-25 | Arch Chemicals, Inc. | Pyrithione biocides enhanced by silver, copper, or zinc ions |
ES2247136T3 (es) * | 2000-07-06 | 2006-03-01 | Akzo Nobel Coatings International B.V. | Pintura anti-incrustaciones. |
US6712587B2 (en) * | 2001-12-21 | 2004-03-30 | Waters Investments Limited | Hydraulic amplifier pump for use in ultrahigh pressure liquid chromatography |
ES2601463T3 (es) * | 2002-04-22 | 2017-02-15 | The Procter & Gamble Company | Composiciones para la higiene personal que comprenden un material que contiene cinc en una composición tensioactiva acuosa |
MXPA04009515A (es) * | 2002-04-22 | 2005-07-26 | Procter & Gamble | Uso de materiales con comportamiento de ionoforos de zinc. |
US8367048B2 (en) * | 2002-06-04 | 2013-02-05 | The Procter & Gamble Company | Shampoo containing a gel network |
WO2004037932A1 (ja) | 2002-10-23 | 2004-05-06 | Chugoku Marine Paints, Ltd. | 防汚塗料組成物、防汚塗膜、該防汚塗膜で被覆された船舶、水中構造物、漁具または漁網 |
US6821326B2 (en) * | 2002-12-20 | 2004-11-23 | Arch Chemicals, Inc. | Small particle copper pyrithione |
US7481873B2 (en) * | 2002-12-20 | 2009-01-27 | Arch Chemicals, Inc. | Small particle copper pyrithione |
US20040191331A1 (en) * | 2003-03-18 | 2004-09-30 | The Procter & Gamble Company | Composition comprising particulate zinc materials having a defined crystallite size |
US7022750B2 (en) * | 2003-04-04 | 2006-04-04 | Ppg Industries Ohio, Inc. | Anti-fouling coating containing copper and graphite |
DK1641862T3 (da) * | 2003-07-07 | 2007-02-26 | Akzo Nobel Coatings Int Bv | Silylesterpolymersammensætninger |
CN100455569C (zh) * | 2003-10-24 | 2009-01-28 | 有限会社Yhs | 新型巯氧吡啶复合化合物、其生产方法及其用途 |
JP4782701B2 (ja) * | 2004-01-23 | 2011-09-28 | ウオーターズ・テクノロジーズ・コーポレイシヨン | 液体クロマトグラフィーのための試料注入システム |
CA2555057C (en) * | 2004-02-03 | 2013-12-31 | Akzo Nobel Coatings International B.V. | Antifouling coating composition and its use on man made structures |
US20050252408A1 (en) * | 2004-05-17 | 2005-11-17 | Richardson H W | Particulate wood preservative and method for producing same |
US7144502B2 (en) * | 2004-06-04 | 2006-12-05 | Johnson & Johnson | Chromatography system with gradient storage and method for operating the same |
WO2006137577A2 (en) * | 2005-06-21 | 2006-12-28 | Dow Corning Toray Co., Ltd. | Cosmetics comprising a modified organopolysiloxane |
WO2007026692A1 (ja) * | 2005-09-01 | 2007-03-08 | Chugoku Marine Paints, Ltd. | 防汚塗料組成物、防汚塗膜、塗膜付き基材、防汚性基材、基材表面への塗膜の形成方法および基材の防汚方法 |
US7335248B2 (en) * | 2005-09-06 | 2008-02-26 | Novus International, Inc. | Marine antifouling coating compositions |
US20100278876A1 (en) * | 2005-12-28 | 2010-11-04 | Chugoku Marine Paints, Ltd. | High-solid antifouling paint composition, antifouling coating film, base material with coating film, antifouling base material, method for forming coating film on surface of base material, antifouling method for base material, and high-solid multi-package antifouling paint composition set |
CN101355877B (zh) * | 2006-02-01 | 2012-11-14 | 詹森药业有限公司 | 4-溴-2-(4-氯苯基)-5-(三氟甲基)-1h-吡咯-3-腈和金属化合物的组合物 |
US7893047B2 (en) | 2006-03-03 | 2011-02-22 | Arch Chemicals, Inc. | Biocide composition comprising pyrithione and pyrrole derivatives |
WO2009031509A1 (ja) | 2007-09-07 | 2009-03-12 | Chugoku Marine Paints, Ltd. | 防汚塗料組成物、防汚塗膜、塗膜付き基材、防汚性基材、基材表面への塗膜の形成方法および基材の防汚方法 |
US8201854B2 (en) * | 2008-06-02 | 2012-06-19 | Optimize Technologies, Inc. | Hybrid ferrule |
US20100021530A1 (en) * | 2008-07-25 | 2010-01-28 | Innovation Biomedical Devices, Inc. | Enhanced trans-keratin drug delivery |
US8541493B2 (en) | 2010-02-19 | 2013-09-24 | Arch Chemicals, Inc. | Synthesis of zinc acrylate copolymer from acid functional copolymer, zinc pyrithione, and copper compound |
-
2010
- 2010-02-19 US US12/660,053 patent/US8541493B2/en not_active Expired - Fee Related
-
2011
- 2011-02-07 RU RU2012140024/05A patent/RU2573466C2/ru not_active IP Right Cessation
- 2011-02-07 CN CN201180016521.0A patent/CN102869257B/zh not_active Expired - Fee Related
- 2011-02-07 MY MYPI2012003742A patent/MY156570A/en unknown
- 2011-02-07 SG SG2012060661A patent/SG183339A1/en unknown
- 2011-02-07 PT PT117450445T patent/PT2536281T/pt unknown
- 2011-02-07 EP EP11745044.5A patent/EP2536281B1/en not_active Not-in-force
- 2011-02-07 BR BR112012020841-1A patent/BR112012020841A2/pt not_active Application Discontinuation
- 2011-02-07 PL PL11745044.5T patent/PL2536281T3/pl unknown
- 2011-02-07 DK DK11745044.5T patent/DK2536281T3/en active
- 2011-02-07 ES ES11745044.5T patent/ES2585877T3/es active Active
- 2011-02-07 AU AU2011218367A patent/AU2011218367B2/en not_active Ceased
- 2011-02-07 WO PCT/US2011/023865 patent/WO2011102983A1/en active Application Filing
- 2011-02-07 KR KR1020127023351A patent/KR20130054228A/ko active IP Right Grant
- 2011-02-07 JP JP2012553932A patent/JP5722919B2/ja not_active Expired - Fee Related
-
2012
- 2012-08-17 CL CL2012002277A patent/CL2012002277A1/es unknown
-
2013
- 2013-03-05 US US13/785,958 patent/US9156997B2/en not_active Expired - Fee Related
-
2016
- 2016-08-17 HR HRP20161028TT patent/HRP20161028T1/hr unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1225660A (zh) * | 1996-05-22 | 1999-08-11 | J·C·亨普尔斯基布斯法夫工厂股份公司 | 防污涂料 |
CN1342099A (zh) * | 1999-03-05 | 2002-03-27 | 阿奇化工公司 | 用于制备巯氧吡啶颗粒分散液的化学方法 |
CN101558112A (zh) * | 2005-11-23 | 2009-10-14 | 阿奇化工公司 | 含巯氧吡啶的金属盐和氧化亚铜的油漆 |
WO2008038967A1 (en) * | 2006-09-25 | 2008-04-03 | Sang-Ki Ahn | Anti-fouling paint composition |
Also Published As
Publication number | Publication date |
---|---|
AU2011218367B2 (en) | 2014-03-20 |
KR20130054228A (ko) | 2013-05-24 |
HRP20161028T1 (hr) | 2016-11-04 |
DK2536281T3 (en) | 2016-09-05 |
JP2013520417A (ja) | 2013-06-06 |
RU2012140024A (ru) | 2014-03-27 |
RU2573466C2 (ru) | 2016-01-20 |
US20110206632A1 (en) | 2011-08-25 |
JP5722919B2 (ja) | 2015-05-27 |
AU2011218367A1 (en) | 2012-09-13 |
PT2536281T (pt) | 2016-08-19 |
US9156997B2 (en) | 2015-10-13 |
CN102869257A (zh) | 2013-01-09 |
MY156570A (en) | 2016-03-15 |
US20130183362A1 (en) | 2013-07-18 |
SG183339A1 (en) | 2012-09-27 |
US8541493B2 (en) | 2013-09-24 |
EP2536281B1 (en) | 2016-05-18 |
PL2536281T3 (pl) | 2016-12-30 |
BR112012020841A2 (pt) | 2020-09-29 |
ES2585877T3 (es) | 2016-10-10 |
EP2536281A4 (en) | 2013-09-11 |
CL2012002277A1 (es) | 2012-09-28 |
WO2011102983A1 (en) | 2011-08-25 |
EP2536281A1 (en) | 2012-12-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102869257B (zh) | 丙烯酸锌共聚物的合成方法 | |
JP5661766B2 (ja) | 防汚塗料組成物、防汚塗膜および基材の防汚方法 | |
TWI335930B (en) | Acid-capped quaternised polymer and compositions comprising such polymer | |
JPH0764985B2 (ja) | 金属含有樹脂組成物 | |
KR20140023436A (ko) | 이액형 가수분해형 방오도료 조성물, 방오도막 및 방오기재의 제조방법 | |
WO2014010702A1 (ja) | 防汚塗料用ポリエステル樹脂、その製造方法、防汚塗料組成物、防汚塗膜、防汚基材 | |
JP5949549B2 (ja) | 金属含有共重合体、その製造方法、防汚塗料用組成物、防汚塗料およびその塗膜を有する物品 | |
JP4154344B2 (ja) | 塗料組成物及び共重合体 | |
JP2006232808A (ja) | 特定の粒度分布を有するピリチオン金属塩、及び、塗料組成物 | |
JPH0545632B2 (zh) | ||
JP2004196957A (ja) | 防汚塗料組成物、防汚塗膜、該防汚塗膜で被覆された船舶、水中構造物、漁具または漁網並びにこれらの防汚方法 | |
JP5497351B2 (ja) | 防汚塗料用金属含有共重合体の製造方法および防汚塗料組成物 | |
JP2017014490A (ja) | 防汚塗料組成物 | |
JP5608301B1 (ja) | 2価金属含有樹脂の製造方法及び2価金属含有樹脂 | |
JP6354825B2 (ja) | 防汚塗料用金属含有共重合体および防汚塗料組成物 | |
JP2015178640A (ja) | 防汚塗料用金属含有共重合体および防汚塗料組成物 | |
JP2013234329A (ja) | 防汚塗料用金属含有共重合体および防汚塗料組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140625 Termination date: 20190207 |