CN86103128A - 船舶防污涂料 - Google Patents
船舶防污涂料 Download PDFInfo
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- CN86103128A CN86103128A CN86103128.8A CN86103128A CN86103128A CN 86103128 A CN86103128 A CN 86103128A CN 86103128 A CN86103128 A CN 86103128A CN 86103128 A CN86103128 A CN 86103128A
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- 239000003973 paint Substances 0.000 title claims abstract description 16
- 230000003373 anti-fouling effect Effects 0.000 title claims abstract description 15
- 239000000049 pigment Substances 0.000 claims abstract description 38
- 238000000576 coating method Methods 0.000 claims abstract description 35
- 239000011248 coating agent Substances 0.000 claims abstract description 34
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
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- 239000011347 resin Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 8
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims abstract 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract 2
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- 125000000217 alkyl group Chemical group 0.000 claims description 2
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
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- 239000003139 biocide Substances 0.000 description 4
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
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- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- LDVVMCZRFWMZSG-OLQVQODUSA-N (3ar,7as)-2-(trichloromethylsulfanyl)-3a,4,7,7a-tetrahydroisoindole-1,3-dione Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)Cl)C(=O)[C@H]21 LDVVMCZRFWMZSG-OLQVQODUSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920006387 Vinylite Polymers 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- YYNNRJWNBXEQTP-UHFFFAOYSA-N 2-[(4-bromophenyl)sulfonylamino]-3-phenylpropanoic acid Chemical compound C=1C=C(Br)C=CC=1S(=O)(=O)NC(C(=O)O)CC1=CC=CC=C1 YYNNRJWNBXEQTP-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- LAVPWYRENKSWJM-UHFFFAOYSA-N 4-butylbenzene-1,2-diol Chemical compound CCCCC1=CC=C(O)C(O)=C1 LAVPWYRENKSWJM-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000005745 Captan Substances 0.000 description 1
- 241000238586 Cirripedia Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 description 1
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000005870 Ziram Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- QQWGVQWAEANRTK-UHFFFAOYSA-N bromosuccinic acid Chemical compound OC(=O)CC(Br)C(O)=O QQWGVQWAEANRTK-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 229940117949 captan Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- NJVOZLGKTAPUTQ-UHFFFAOYSA-M fentin chloride Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 NJVOZLGKTAPUTQ-UHFFFAOYSA-M 0.000 description 1
- BFWMWWXRWVJXSE-UHFFFAOYSA-M fentin hydroxide Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(O)C1=CC=CC=C1 BFWMWWXRWVJXSE-UHFFFAOYSA-M 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100000636 lethal dose Toxicity 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
-
- 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
- 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
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Paints Or Removers (AREA)
Abstract
逐渐溶解于海水中的船舶用防污涂料，其中包含由松与至少含有一个伯胺或仲胺基团的脂族多胺反应生成的树脂做基料。所述树脂含有酰氨基胺或咪唑啉基团。所述防污涂料包含该基料、海洋生物杀伤剂和在海水中溶解度按重量计不超过10ppm的颜料。所述颜料本身亦可以是涂料中的海洋生物杀伤剂。
Description
本发明涉及通常用作船壳表面层油漆的船用防污涂料。
海洋生物在船壳浸没在水中部分上的生长会增加船壳对水的摩擦阻力，以至造成燃料消耗增加、航速降低。由于海洋生物如藤壶和藻类在船舶底壳上聚积速度甚快，因而，以清理或重新涂敷涂料作为补救，实属不切实际。通常，为了降低海洋生物造成的污损，需在船壳上涂上一层能释放出海洋生物杀伤剂的表层涂料。传统上，这种包含相对惰性的基料及从涂料中渗出的杀生物药性颜料。主要的基料，通常乙烯基树脂、特别是氯乙烯/醋酸乙烯共聚合物以及松香。乙烯基树脂不溶于海水，因而，以它为基料的涂料常用高浓度颜料，以使颜料粒子间有接触，从而确保颜料可以渗出。松香是一种硬而脆的树脂，微溶于海水。杀生物药性颜料可逐渐由使用中的松香基料的间质中渗出，留下松香基料的间质的骨架，经海水冲洗，以雪花状薄片由船壳表面剥落下来，从而使涂料膜中深层的杀生物药性颜料能继续渗出。松香防污涂料的实例在英国船舶研究协会1973年出版的“船舶的保护和涂漆实用技术”（Recommended Practice tor Proteetion and Painting of ships）一书第261及262页中已有叙述。由于杀生物药性颜料的渗出，已渗出颜料的基料就成为不规则的层面，这就使得船舶壳表面的粗糙度在使用中逐渐增加。
近年来最成功的涂料，例如英国专利第1，457，590号中所叙述的，是一种基于聚合物基料的“自动抛光共聚物”涂料，在其中杀生物药性的三有机锡部分是以化学键形式与之相连的，且能逐渐被水所水解下来。这就产生了一种水溶性树脂，当船舶航行时，这种树脂会从船壳表面上逐渐溶解。这种逐渐溶解作用能使涂敷过涂料的船壳在航行中至少能保持如初始时一样光洁，甚至越来越光洁。此外，逐渐溶解还意味着不断更新防污涂敷层，延长从涂料表面释放的杀生物性药维持在致死浓度之上的时间。然而，近来对具体来说游艇释放的三有机锡生物杀伤剂对环境的影响引起人们的关注，因而需要一种既能平滑地溶解在水中，又不会释放出三有机锡部分的船舶用涂料。
本发明所述的船舶用防污涂料，包括在海水中能逐渐溶解的能成膜的基料，海洋生物杀伤剂以及颜料，这种颜料在海水中的溶解度为按重量计不超过百万分之十（10ppm）。这种防污涂料的特征在于涂料的基料是由松香与脂肪族多胺反应而制成得的树脂。其中的脂肪族多胺至少含有一个伯胺或者仲胺的基团。使用的颜料本身可以是涂料中海洋生物杀伤剂。
松香是一种有羧基萜烯类化合物的混合物。它的主要成份是化学式为C19H29COOH的松香酸，松香酸含量高的松香比较好，市售的WW松香即为其例。另外，马来酸化松香或者富马酸化松香亦可使用。马来酸化或富马酸化松香较萜烯衍生出的松香每个萜烯分子多了两个羧基。中等酸值的松香可用醇类对马来酸化或富马酸化的松香进行部分酯化的方法来制备，如在每个分子中酯化一个羧基。
脂肪族多胺具有化学式H2N（RNH）nR′的化合物为比较好，其中R为含2至4个碳原子的亚烷基如亚乙基、1，2-亚丙基、1，3-亚丙基、1，2亚丁基或1，4亚丁基，R′为氢或含1至3个碳原子的烷基或羟烷基如甲基或乙基，而n为1至6的整数。比较好的多胺实例为1，2-乙二胺、二亚乙基三胺、三亚乙基四胺、四亚乙基胺、五亚乙基六胺、N-甲基乙二胺及N-羟乙基二胺。另外，多胺中可含有一个或多个醚键，如聚氧乙烯二胺一种商名为“杰佛明”（Jeffamine）的多胺也可使用。
按照下述松香与多胺的反应，反应产物主要为酰氨基胺，ZCOOH+H2N（RNH）nR′→
（RNH）nR′+H2O
其中Z为大体上满足经验式C19H29的萜烯残基;或，当R为亚乙基或1，2-亚烷基基团时，按照下述反应，其产物咪唑啉ZCOOH+H2NRNHR″→ 
+2H2O其中R″为式（RNH）mR′，m为0至5，或反应产物为酰氨基胺与咪唑啉的化合物。
松香与多胺的反应择优在60～150℃温度下进行。反应可在过量的多胺中或在有机溶剂例如芳烃（如二甲苯或甲苯）、脂族烃（如石油溶剂）、酯类（如乙酸丁酯或乙氧乙酸基乙酯）、醇类（如丁醇或丁氧基乙醇）或酮类（如甲基异丁基酮或甲基异戊基酮）中进行。反应温度，如需要生成咪唑啉时最好至少为100℃，反应时最好用如共沸蒸馏法除去水分。酰氯基胺的产量，在反应达到对加入的每摩尔多胺除去大约1摩尔水后终止反应，则其产量可达最佳值。而咪唑啉的产量，则适当情况下，继续维持进行反应，直至对加入的每摩尔多胺除去大约2摩尔水时，则其产量可达最佳值。
松香与多胺的反应产物是比松香本身更具挠性的聚合物，与松香比较其海水溶解性则稍有增大。基于此反应产物的涂料，会从船壳表面平滑地溶解，从而稳定地从涂料中释放出生物杀伤剂。
涂料的基料与所用的生物杀伤剂组分和一种或多种颜料是一起混合在涂料之中的。可采用常规的混合方法。所用的颜料最好是微溶颜料，在海水中的溶解度按重量计从0.5至10ppm。这类颜料有氧化亚铜、硫氰酸亚铜、氧化锌、铬酸锌、亚乙基双二硫代氨基甲酸锌、二甲基二硫代氨基甲酸锌或二乙基二硫代氨基甲酸锌。这类微溶的铜与锌的化合物通常是海洋生物杀伤剂。这类颜料与海水反应时生成水溶性金属化合物。因此，颜料中的粒子不会残留在涂料表面。可应用混合的微溶颜料、如氧化亚铜、硫氰酸亚铜或亚乙基双二硫代氨基甲酸锌这类最有效的杀生物颜料与在海水中溶解稍快的氧化锌混合使用。
涂料组合物，可另加或者更换其中一种与海水不反应的颜料，这种颜料在海水中是极不易溶（溶解度按重量计低于0.5ppm）的如二氧化钛或三氧化二铁。这种极不易溶的颜料的用量，按重量计算，其比例可以高到占涂料中总颜料组分的40%为好，而以少于20%（按重量）为最好。
颜料与树脂基料的比例，以于涂料膜中含有25%以上体积浓度的颜料，但低于临界颜料体积浓度为好，而以颜料体积浓度为35～50%最好。
涂料组合物可含有增塑剂，如聚（乙烯基甲基醚）、或取代磺酰胺如N-乙基-对-甲苯磺酰胺。
微溶于海水的颜料的杀生物效果特别是氧化亚铜、硫氰酸亚铜及亚乙基双二硫代氨基甲酸锌等颜料的杀生物效果已是足够，因此涂料中不需另加其它生物杀伤剂。但如遇到严重污损情况，可于涂料中另加生物杀伤剂。三有机锡盐及氧化物如氟化三苯基锡、氟化三丁基锡、二溴代丁二酸三丁基锡、氯化三苯锡、氢氧化三苯基锡及氧化三丁基锡均为有效的海洋生物杀伤剂，并可按本发明所述，用于配制船舶用涂料。按本发明所述的涂料含有三有机锡盐（按体积占颜料的25%以上）并具有与三有机锡含量高得多的三有机锡共聚合物涂料相同的防污和平滑性能。在某些情况下，需要完全避免释放三有机锡离子。其它有效的船舶用涂料的防污剂的实例有：二硫代氨基甲酸酯的衍生物如亚乙基双硫代氨基甲酸亚铜或二硫化四甲基秋兰姆、亚甲基双硫脲、4-丁基-邻苯二酚及克菌丹（Captan.）
本发明可用下列实例来说明，除另有说明外各成份均按重量计算。
实例1
WW级松香（假定所用松香为松香酸）与摩摩尔量的N-羟乙基二胺在二甲苯中、100℃温度下反应，并用共沸蒸馏法除去水分，40分钟后，当除去水分的量大约相当于每摩尔二胺为1摩尔水时，停止加热。所对应反应生成的产物主要包含酰氯基胺。
将包含20.0份松香/多胺反应产物在13.0份二甲苯中的树脂溶液与52.0份氧化亚铜、1.55份抗沉降剂及13.45份石油溶剂一起研磨，生成船舶用防污涂料，其颜料的体积浓度为35%。
实例2
WW级松香与N-羟乙基乙二胺按与实例1相同的比例，在二甲苯及120℃温度下反应1小时，除去水分的量接近相当于每摩尔二胺为2摩尔，所对应的反应的产物主要包含咪唑啉-取代松香。
用实例1的配方制备船舶用防污涂料，不过此时是用实例2中的反应咪唑产物代替实例1中的反应产物酰氨基胺。
实例3及4
重复实例1的方法，但用等摩尔的五亚乙基六胺（实例3）或三亚乙基四胺（实例4）代替N-羟乙基乙二胺，制备酰氨基胺反应产物;各实例中船舶用防污涂料按实例1所描述的方法由上述各反应产物制备。
Claims (8)
1、一种船舶用防污涂料，其组成包括：能逐渐溶解于海水中的基料，海洋生物杀伤剂以及在海水中的溶解度按重量计不大于百万分之十的颜料，该涂料特征在于，其中的基料是由松香与至少含有一个伯胺或仲胺基团的脂族多胺反应而生成的树脂。
2、按权利要求1所述的涂料，其特征在于，其中的脂族多胺具有如下通式：
式中R为含有2至4个碳原子的，R′为氢或含有1至3个碳原子的烷基或羟烷基，n为1至6。
3、按权利要求2所述的涂料，其特征在于，其中脂族多胺通式中的R为-CH2CH2-基团。
4、一种船舶用涂料，其组成包括：能逐渐溶解于海水中的基料，海洋生物杀伤剂及在海水中的溶解度按重量计不大于百万分之十的颜料，该涂料的特征在于，其中的基料是由松香衍生来的酰氨基胺而且该基料至少主要是由下式所示物质组成：
式中Z为大体上是经验式C19H29-的萜烯残基，R，R′及n的定义如权利要求2中所述。
5、一种船舶防污涂料，其组成包括：能逐渐溶解于海水中的基料，海洋生物杀伤剂及在海水中的溶解度按重量计不大于百万分之十的颜料，该涂料的特征在于，其中的基料是由松香衍生来的咪唑啉而且该涂料至少主要是由下式所示物质组成：
式中Z为大体上是经验式C19H29-的萜烯残基，而R″为式-（CH2CH2NH）mR′所示的基团，其中R′如权利要求2所定义的，m为0至5。
6、按权利要求1至3中任何一项所述的涂料，其特征在于，其中与多胺进行反应的松香是来酸化或富马酸化的松香或部分酯化的马来酸化或富马酸化的松香。
7、按权利要求1至6中任何一项所述的涂料，其特征在于，其中所述的颜料为一种在海水中的溶解度按重量计为0.5至10ppm的微溶的铜或锌的化合物，同时也是涂料中的海洋生物杀伤剂。
8、按权利要求7所述的涂料，其特征在于，其中的颜料包括氧化亚铜、硫氰酸亚铜或亚乙基双二硫代氨基甲酸锌。
Applications Claiming Priority (2)
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| GB8511144 | 1985-05-02 | ||
| GB858511144A GB8511144D0 (en) | 1985-05-02 | 1985-05-02 | Marine anti-fouling paint |
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| Publication Number | Publication Date |
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| CN86103128A true CN86103128A (zh) | 1986-10-29 |
| CN1005727B CN1005727B (zh) | 1989-11-08 |
Family
ID=10578539
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| Application Number | Title | Priority Date | Filing Date |
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| CN86103128.8A Expired CN1005727B (zh) | 1985-05-02 | 1986-04-30 | 船舶防污涂料 |
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| US (1) | US4675051A (zh) |
| EP (1) | EP0201279B1 (zh) |
| JP (1) | JPS61258873A (zh) |
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| AU (1) | AU578150B2 (zh) |
| BR (1) | BR8601916A (zh) |
| CA (1) | CA1264503A (zh) |
| DE (1) | DE3683533D1 (zh) |
| DK (1) | DK199586A (zh) |
| ES (1) | ES8801349A1 (zh) |
| FI (1) | FI81598C (zh) |
| GB (1) | GB8511144D0 (zh) |
| GR (1) | GR861134B (zh) |
| HK (1) | HK49092A (zh) |
| IN (1) | IN167831B (zh) |
| MX (1) | MX167463B (zh) |
| NO (1) | NO168835C (zh) |
| PT (1) | PT82475B (zh) |
| SG (1) | SG22092G (zh) |
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| US4690712A (en) * | 1985-04-01 | 1987-09-01 | Sun Chemical Corporation | Polyamide-modified metal resinates and their use in publication gravure printing inks |
| FR2606021B1 (fr) * | 1986-10-30 | 1989-08-25 | Provence Universite | Liants pour peintures resistant aux salissures marines et leur procede de preparation |
| DE3885146T2 (de) * | 1987-04-28 | 1994-03-24 | Fina Research | Selbstpolierende Anwuchsverhindernde Anstrichfarben. |
| US4881976A (en) * | 1987-11-17 | 1989-11-21 | Rhone-Poulenc Inc. | Antifouling paints containing matrices cross-linked with lanthanides and methods of making and use |
| US4866106A (en) * | 1988-02-08 | 1989-09-12 | Waitomo Industrial Investments Ltd. | Antifouling composition |
| US5173110A (en) * | 1988-02-08 | 1992-12-22 | Waitomo Industrial Investments Ltd. | Antifouling composition |
| US5096488A (en) * | 1988-02-08 | 1992-03-17 | Waitomo Industrial Investments Ltd. | Antifouling composition |
| US4990547A (en) * | 1988-02-08 | 1991-02-05 | Waitomo Industrial Investments Ltd. | Antifouling composition |
| US5116407A (en) * | 1988-10-13 | 1992-05-26 | Courtaulds Coatings Limited | Antifouling coatings |
| US5236493A (en) * | 1988-10-13 | 1993-08-17 | Courtaulds Coatings (Holdings) Limited | Antifouling coating |
| EP0549714A1 (en) * | 1990-09-06 | 1993-07-07 | Electric Power Research Institute, Inc | Methods for control and mitigation of molluscs |
| US5143545A (en) * | 1991-09-20 | 1992-09-01 | The United States Of America As Represented By The Secretary Of The Navy | Antifouling marine coatings |
| CA2345231C (en) * | 1998-09-23 | 2009-12-22 | Phycogen, Inc. | Pharmaceutical compositions comprising derivatives of sulphur acids |
| CN1202178C (zh) | 1999-01-20 | 2005-05-18 | 阿克佐诺贝尔公司 | 防污油漆 |
| BR0112197B1 (pt) | 2000-07-06 | 2011-07-12 | tinta antiincrustação. | |
| JP4695390B2 (ja) | 2002-08-09 | 2011-06-08 | アクゾ ノーベル コーティングス インターナショナル ビー ヴィ | 酸キャップされた四級化ポリマー及びそのようなポリマーを含む組成物 |
| US7598299B2 (en) * | 2004-02-03 | 2009-10-06 | Akzo Nobel Coatings International B.V. | Anti-fouling compositions comprising a polymer with salt groups |
| US20070254109A1 (en) * | 2006-04-28 | 2007-11-01 | Albemarle Corporation | Coatings, coating formulations, and compositions containing quaternary ammonium compounds |
| JP5823692B2 (ja) | 2007-09-20 | 2015-11-25 | テル ハショメール メディカル リサーチ インフラストラクチャ アンド サービシーズ リミテッド | 細胞接着の予防のための水生生物起源の組成物、及びこれを使用する方法 |
| JP5676451B2 (ja) | 2008-09-24 | 2015-02-25 | テル ハショメール メディカル リサーチ，インフラストラクチャ アンド サービシーズ リミテッド | ペプチド |
| SG10201401054YA (en) | 2008-12-29 | 2014-07-30 | Tel Hashomer Medical Res Infrastructure & Services Ltd | Peptides and compositions for prevention of cell adhesion and methods of using same |
| US8356959B2 (en) * | 2009-10-01 | 2013-01-22 | Teledyne Scientific & Imaging Llc | System for mitigating marine bio-fouling of an underwater structure |
| CN102250499B (zh) * | 2011-05-16 | 2013-11-06 | 大连海事大学 | 一种松香包覆处理氧化亚铜的制备方法 |
| WO2012164380A2 (en) | 2011-05-31 | 2012-12-06 | Hutchison Biofilm Medical Solutions Limited | Dispersion and detachment of cell aggregates |
| CA2928905A1 (en) | 2013-10-31 | 2015-05-07 | Hutchison Biofilm Medical Solutions Limited | Use of peptides in antibiotic resistance |
| US10077870B2 (en) | 2015-09-11 | 2018-09-18 | Donald Gross | Nuisance marine growth preventing compound and valve system |
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| US2750366A (en) * | 1952-02-16 | 1956-06-12 | Armour & Co | Mono-acyl derivatives of alkylene diamines and process for preparing same |
| US2738283A (en) * | 1952-08-20 | 1956-03-13 | Copper Res | Copper bearing antifouling shipbottom paints |
| US3778394A (en) * | 1972-08-24 | 1973-12-11 | Gen Mills Chem Inc | Polymeric fatty acid polyamide modified with a rosin adduct |
| US3898190A (en) * | 1974-03-11 | 1975-08-05 | Du Pont | Antifouling marine coating composition |
| US4219382A (en) * | 1976-02-19 | 1980-08-26 | American Cyanamid Company | Cationic fortified rosin size |
| US4270953A (en) * | 1978-03-09 | 1981-06-02 | Kansai Paint Co., Ltd. | Two component antifouling paint |
| DK149187B (da) * | 1979-05-10 | 1986-03-10 | M & T Chemicals Inc | Begroningshaemmende overtraeksmateriale indeholdende en phenyltinforbindelse |
-
1985
- 1985-05-02 GB GB858511144A patent/GB8511144D0/en active Pending
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1986
- 1986-04-15 NO NO861467A patent/NO168835C/no unknown
- 1986-04-18 KR KR1019860003032A patent/KR860009086A/ko not_active Application Discontinuation
- 1986-04-23 IN IN359/DEL/86A patent/IN167831B/en unknown
- 1986-04-24 FI FI861726A patent/FI81598C/fi not_active IP Right Cessation
- 1986-04-29 GR GR861134A patent/GR861134B/el unknown
- 1986-04-29 PT PT82475A patent/PT82475B/pt not_active IP Right Cessation
- 1986-04-29 BR BR8601916A patent/BR8601916A/pt unknown
- 1986-04-29 US US06/857,126 patent/US4675051A/en not_active Expired - Fee Related
- 1986-04-30 CN CN86103128.8A patent/CN1005727B/zh not_active Expired
- 1986-04-30 MX MX002358A patent/MX167463B/es unknown
- 1986-04-30 CA CA000507977A patent/CA1264503A/en not_active Expired - Fee Related
- 1986-04-30 ES ES554596A patent/ES8801349A1/es not_active Expired
- 1986-05-01 DE DE8686303304T patent/DE3683533D1/de not_active Expired - Fee Related
- 1986-05-01 EP EP86303304A patent/EP0201279B1/en not_active Expired - Lifetime
- 1986-05-01 AU AU57015/86A patent/AU578150B2/en not_active Ceased
- 1986-05-01 JP JP61099498A patent/JPS61258873A/ja active Pending
- 1986-05-01 DK DK199586A patent/DK199586A/da not_active Application Discontinuation
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1992
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Also Published As
| Publication number | Publication date |
|---|---|
| FI861726A0 (fi) | 1986-04-24 |
| DE3683533D1 (de) | 1992-03-05 |
| HK49092A (en) | 1992-07-10 |
| FI81598B (fi) | 1990-07-31 |
| NO168835B (no) | 1991-12-30 |
| GB8511144D0 (en) | 1985-06-12 |
| CN1005727B (zh) | 1989-11-08 |
| DK199586A (da) | 1986-11-03 |
| SG22092G (en) | 1992-04-16 |
| AU5701586A (en) | 1986-11-06 |
| JPS61258873A (ja) | 1986-11-17 |
| US4675051A (en) | 1987-06-23 |
| DK199586D0 (da) | 1986-05-01 |
| FI861726A (fi) | 1986-11-03 |
| NO168835C (no) | 1992-04-08 |
| BR8601916A (pt) | 1987-11-10 |
| GR861134B (en) | 1986-08-26 |
| IN167831B (zh) | 1990-12-29 |
| ES554596A0 (es) | 1988-01-01 |
| EP0201279A2 (en) | 1986-11-12 |
| MX167463B (es) | 1993-03-22 |
| ES8801349A1 (es) | 1988-01-01 |
| NO861467L (no) | 1986-11-03 |
| PT82475B (pt) | 1988-05-27 |
| EP0201279A3 (en) | 1987-12-16 |
| FI81598C (fi) | 1990-11-12 |
| AU578150B2 (en) | 1988-10-13 |
| PT82475A (en) | 1986-05-01 |
| KR860009086A (ko) | 1986-12-20 |
| CA1264503A (en) | 1990-01-23 |
| EP0201279B1 (en) | 1992-01-22 |
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