CN113226039B - 用于防污保护的铜螯合物复合物 - Google Patents
用于防污保护的铜螯合物复合物 Download PDFInfo
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- CN113226039B CN113226039B CN201980080752.4A CN201980080752A CN113226039B CN 113226039 B CN113226039 B CN 113226039B CN 201980080752 A CN201980080752 A CN 201980080752A CN 113226039 B CN113226039 B CN 113226039B
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- Prior art keywords
- etfaa
- antifouling
- cupt
- ratio
- acrylate
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Abstract
本发明涉及包含二(乙基4,4,4‑三氟乙酰乙酸酯)铜(Cu(ETFAA)2)的防污组合物,其对船舶和海洋结构物表面的海洋生物污损非常有效,它们用于抑制海洋生物污损的用途,以及包含所述组合物的防污涂料。
Description
技术领域
本发明涉及包含二(乙基4,4,4-三氟乙酰乙酸酯)铜(Cu(ETFAA)2)的防污组合物,其对船舶和海洋结构物表面的海洋生物污损非常有效,其用于抑制海洋生物污损的用途,以及包含所述组合物的防污涂料。
背景技术
船舶、水产养殖渔网、水下结构和设备容易受到诸如藤壶、苔藓虫、水螅、贻贝、藻类等海洋生物的侵蚀。生物可以生长和繁殖,并最终导致重大问题。例如,对于船体,船体上海洋生物的生长会增加船体与水体之间的摩擦阻力,从而增加油耗,降低船速。需要保护船体以防止海洋生物的生长,从而保持它们的清洁和光滑,以最大限度地提高燃油效率。还有一个问题是将海洋生物从世界的一个地方运送到另一个地方,外来生物有可能破坏本地生态。因此,水下部件需要充分保护以防止海洋生物污损,这通常是通过防污涂料来实现的。
用于此类防污涂料的粘合剂体系通常由易腐蚀粘合剂组成。涂料膜的腐蚀通过随时间推移从涂层中释放防污剂(杀生物剂)从而阻止污损生物体的附着来帮助防止污损。侵蚀性防污涂层有两种主要类型,业界将其描述为“自抛光”和“烧蚀”。
烧蚀涂层的粘合剂体系主要由松香组成,松香会与海水反应变成水溶性并被侵蚀掉。替代地,松香或松香衍生物也与诸如聚酯树脂、丙烯酸树脂、环氧树脂、氯乙烯树脂、氯化橡胶树脂、氯化聚乙烯树脂、氯化聚丙烯树脂、苯乙烯-丁二烯树脂或聚酰胺等非侵蚀性粘合剂混合使用。
在“自抛光防污涂料”中,粘合剂体系基于可水解的丙烯酸酯聚合物。可水解官能团通常由金属羧酸盐丙烯酸酯单体或丙烯酸甲硅烷基酯单体提供给聚合物。也使用易腐蚀的聚酯粘合剂,从而导致低成本的防污涂料。烧蚀涂层和自抛光涂层之间的区别主要在于浸出层的厚度和自抛光涂层随时间推移的更线性的侵蚀率。
“混合涂料”也存在,其粘合剂系统由易腐蚀的丙烯酸酯组成,例如自抛光涂料和松香。浸出层的厚度比烧蚀涂层薄,但比真正的自抛光涂层厚。
由于其中用作杀生物剂的氧化亚铜(Cu2O)的浓度高,即通常约40wt%,这是适当的防污保护所需要的,因此大多数市售防污涂料含有高金属含量。氧化亚铜可能对许多生物有害。防污涂料中的浸出会导致水中、沉积物和周围环境中的铜含量升高。人为的高铜含量可能会对生态产生重大影响。虽然Cu2O在防污涂料中被广泛用作防污剂,但防污涂料还可以包含额外的杀生物剂,因为单独的Cu2O仅对诸如藤壶之类的坚硬污损生物有效。
作为另一个缺点,氧化亚铜通常会赋予防污涂料膜强烈的红褐色,并且还可能与大气中的二氧化碳和海水中的氯化物发生反应,从而在涂层表面形成不均匀的条纹。这是一种不吸引人的外观并且可能发生,例如,在船舶下水后不久发生。一些游艇所有者和游轮运营商更喜欢明亮的颜色和均匀的外观,这是含有氧化亚铜的涂料无法实现的。
在市售防污涂料中取代氧化亚铜的尝试导致开发了氧化亚铜的替代品,例如白色的硫氰酸铜和对藤壶有效的农用杀虫剂溴代吡咯腈(tralopyril)。但是这些替代品的成本更高,而且它们不如基于氧化亚铜的防污涂料有效。
因此,需要在生态和经济上改进的具有降低铜含量的船用防污涂料,或者甚至完全替代常规使用的防污涂料中的氧化亚铜。
本发明的包含Cu(ETFAA)2的防污组合物满足了这种需要。发明人惊奇地发现,Cu(ETFAA)2是一种高效、通用的试剂,其可增强所有类型的防污涂料(如烧蚀涂料或自抛光涂料)的防污性能,并且也可用于简单的接触浸出涂料。
因此,现在可以部分或完全替代防污涂料中的Cu2O,从而大幅降低其中的金属含量,同时保持适当的防污性能。此外,本发明的包含Cu(ETFAA)2的防污组合物基本上是无色的,因此不会干扰船体通常需要的亮色。
附图说明
图1描绘了用表1的实施例2的防污涂料涂覆的面板,并且显示了在未漂洗状态下在海水中放置24个月之后以及漂洗之后的面板外观。
具体实施方式
除非另有定义,否则本文使用的所有技术和科学术语与本发明相关领域的普通技术人员通常理解的含义相同。本文使用了以下缩写词和术语:
AIBN:偶氮二(异丁腈)
AMBN:偶氮二-(2-甲基丁腈)
A630-20X:脂肪酸酰胺
BA:丙烯酸丁酯
百菌清:2,4,5,6-四氯苯-1,3-二甲腈
Cu2O:氧化亚铜
Cu(ETFAA)2:二(4,4,4-三氟乙酰乙酸乙酯)铜
CuSCN:硫氰酸铜(I)
DCOIT:4,5-二氯-2-正辛基-4-异噻唑啉-3-酮
敌草隆:3-(3,4-二氯苯基)-1,1-二甲基脲
ETFAA:4,4,4-三氟乙酰乙酸乙酯
2MEA:丙烯酸2-甲氧基乙酯单体
美托咪定(Medetomidine):4-[1-(2,3-二甲基苯基)乙基]-1H-咪唑
MMA:甲基丙烯酸甲酯单体
MIBK:甲基异丁基酮
MPM:甲氧基丙烯单体
PGM:丙二醇单甲醚
TIPX:丙烯酸三异丙基甲硅烷酯单体
溴代吡咯腈(Tralopyril):4-溴-2-(4-氯苯基)-5-(三氟甲基)-1H-吡咯-3-甲腈
VAGH:氯乙烯/醋酸乙烯/乙烯醇共聚物(商品)
Zineb:乙烷-1,2-二基双(二硫代氨基甲酸)锌
Ziram:N,N-二甲基氨基二硫代锌
ZnO:氧化锌
ZnPT,吡啶硫酮锌:2-吡啶硫醇-1-氧化锌
术语“(甲基)丙烯酸酯”是表示丙烯酸酯和甲基丙烯酸酯单体的统称。
术语“甲基丙烯酸酯”或“甲基-丙烯酸酯”仅表示甲基丙烯酸酯单体。
Bentone SD2是一种为了抗沉降性能而添加的有机粘土;Bentone#38是季铵盐18-锂蒙脱石粘土;Minex 4是霞石正长岩粘土。Disparlon 6900-20x(A630-20X聚酰胺蜡)是聚酰胺蜡在二甲苯中的20%分散体,其用作流变改性剂;Disperbyk 161是一种分散添加剂。树脂是指可以用作本发明的防污涂料中使用的粘合剂的原料的所有预聚物或聚合物。松香(Rosin)或脂松香(gum rosin)是指松脂(colophony)(CAS:8050-09-7,另见https:// www.megaglori.com/what-is-gum-rosin/)。
“杀生物剂”是指防止海洋生物在表面上沉降和/或防止海洋生物在表面上生长和/或促使海洋生物从表面脱落的任何化合物。
术语“防污涂料”、“防污涂层”和“防污制剂”在本文中可互换使用。
本发明提供了一种新的方法来抑制水下物体(例如船体或任何其他海洋结构)的表面污损。具体而言,本发明提供了包含Cu(ETFAA)2的防污组合物。令人惊讶地发现,Cu(ETFAA)2显著增强防污组合物防止海洋生物(例如藤壶、苔藓虫、水螅、贻贝、藻类等)的沉降的防污功效。
ETFAA是一种化合物,其被称为生产在农业和制药中使用的化合物的中间体。ETFAA的铜螯合物可以通过按1:2的摩尔比将氢氧化铜(Cu(OH)2)加入ETFAA形成。复合物在室温下快速形成,产率高:
2ETFAA+Cu(OH)2→Cu(ETFAA)2+2H2O。
本发明的防污组合物还可以包含一种或多种能够防止物体表面污损的杀生物剂。
这种杀生物剂可以是无机杀生物剂、有机金属杀生物剂或有机杀生物剂。
无机杀生物剂的实例是铜和铜化合物,例如铜氧化物,例如氧化亚铜和氧化铜;铜合金,例如铜镍合金;铜盐,例如硫氰酸铜(CuSCN),硫化铜;或偏硼酸钡(bariummetaborate)。
有机金属杀生物剂的实例是2-吡啶硫醇-1-氧化锌[ZnPT,吡啶硫酮锌];有机铜化合物,例如2-吡啶硫醇-1-氧化铜[CuPT,吡啶硫酮铜]、乙酸铜、环烷酸铜、8-氨基脲酸铜[喹啉铜(oxine-copper)]、壬基酚磺酸铜、双(乙二胺)双(十二烷基苯磺酸)铜和双(五氯苯酚)铜;二硫代氨基甲酸酯化合物,例如N,N-二甲基氨基甲二硫代酸锌[ziram]、乙烷-1,2-二基双(二硫代氨基甲酸)锌[zineb]、亚乙基双(二硫代氨基甲酸)锰[maneb]或亚乙基双(二硫代氨基甲酸)锰与锌盐[代森锰锌(mancozeb)].
有机杀生物剂的实例是杂环化合物,例如2-(叔丁基氨基)-4-(环丙胺)-6-(甲硫基)-1,3,5-三嗪[cybutryne]、4,5-二氯-2-正辛基-4-异噻唑啉-3-酮[DCOIT]、1,2-苯并异噻唑啉-3-酮[BIT]、2-(硫氰酸根合甲硫基)-1,3-苯并噻唑[苯噻唑(benthiazole)]、3-苯并[b]噻吩-2-基-5,6-二氢-1,4,2-恶噻嗪-4-氧化物[bethoxazin]和2,3,5,6-四氯-4-(甲基磺酰基)吡啶;脲衍生物,例如3-(3,4-二氯苯基)-1,1-二甲基脲[敌草隆];羧酸、磺酸和次磺酸的酰胺和酰亚胺,例如N-(二氯氟甲硫基)邻苯二甲酰亚胺、N-二氯氟甲硫基-N',N'-二甲基-N-苯基磺酰胺[dichlofluanid]、N-二氯氟甲硫基-N',N'-二甲基-N-p-甲苯磺酰胺[甲苯氟磺胺]和N-(2,4,6-三氯苯基)马来酰亚胺;其他有机化合物,例如吡啶三苯基硼烷、胺三苯基硼烷、3-碘-2-丙炔基-N-丁基氨基甲酸酯[iodocarb]、2,4,5,6-四氯间苯二甲腈[百菌清]、对((二碘甲基)磺酰基)甲苯或4-溴-2-(4-氯苯基)-5-(三氟甲基)-1H-吡咯-3-甲腈[tralopyril]。
杀生物剂的其他实例是四烷基鏻卤化物,胍衍生物,含咪唑的化合物,例如4-[1-(2,3-二甲基苯基)乙基]-1H-咪唑[美托咪定]及其衍生物,大环内酯,其包括阿维菌素及其衍生物,例如伊维菌素,或多杀菌素及其衍生物,例如多杀菌素,或酶,例如氧化酶,或具有蛋白水解、半纤维素分解、纤维素分解、脂肪分解或淀粉分解活性的酶。
在一实施方案中,本发明的防污组合物包含Cu(ETFAA)2和另外一种或多种杀生物剂,所述杀生物剂选自2-吡啶硫醇-1-氧化铜(羟基吡啶硫酮铜,CuPT)、2-吡啶硫醇-1-氧化锌(羟基吡啶硫酮锌,ZnPT)、4,5-二氯-2-正辛基-4-异噻唑啉-3-酮(DCOIT)、氧化亚铜(Cu2O)、氧化锌(ZnO)、4-溴-2-(4-氯苯基)-5-(三氟甲基)-1H-吡咯-3-甲腈(溴代吡咯腈)、乙烷-1,2-二基双(二硫代氨基甲酸酯)锌(zineb),N,N-二甲基氨基二硫代锌(ziram)、3-(3,4-二氯苯基)-1,1-二甲基脲(敌草隆)、硫氰酸铜(I)(CuSCN)、4-[1-(2,3-二甲基苯基)乙基]-1H-咪唑(美托咪定)、三嗪、氟烷和2,4,5,6-四氯间苯二甲腈(百菌清)。
在一优选的实施方案中,本发明的防污组合物包含Cu(ETFAA)2和一种或多种杀生物剂,所述一种或多种杀生物剂选自CuPT、ZnPT、DCOIT、Cu2O和溴代吡咯腈。
在更优选的实施方案中,本发明的防污组合物包含Cu(ETFAA)2和选自CuPT和Cu2O的一种或多种杀生物剂。Cu(ETFAA)2(wt%)比CuPT(wt%)的比率和/或Cu(ETFAA)2(wt%)比Cu2O(wt%)的比率有利地为100:1至1:100,优选10:1至1:10,最优选为5:1至1:5。
在一具体的实施方案中,本发明的防污组合物包含Cu(ETFAA)2和CuPT。Cu(ETFAA)2(wt%)比CuPT(wt%)的比率有利地为100:1至1:100,优选10:1至1:10,最优选5:1至1:5。
在另一具体实施方案中,本发明的防污组合物包含Cu(ETFAA)2和Cu2O。Cu(ETFAA)2(wt%)比Cu2O(wt%)的比率有利地为100:1至1:100,优选10:1至1:10,最优选5:1至1:5。
在更具体的实施方案中,本发明的防污组合物包含Cu(ETFAA)2、CuPT和Cu2O,其中Cu(ETFAA)2(wt%)比CuPT(wt%)的比率为5:1至2:1,其中Cu(ETFAA)2(wt%)比Cu2O(wt%)的比率为5:1至1:5。
在另一具体实施方案中,本发明的防污组合物包含Cu(ETFAA)2和CuPT且不含Cu2O,其中Cu(ETFAA)2(wt%)比CuPT(wt%)的比率为5:1至2:1。
本发明的包含Cu(ETFAA)2的防污组合物不仅提供优异的防污性能,而且基本上是无色的,因此不会干扰船体通常需要的亮色。
本发明进一步提供了本发明的防污组合物用于抑制固体表面上的海洋生物污损的用途。固体表面可以是任何水下物体的固体表面,例如船舶、水产养殖渔网、水下结构和设备、罐、海上建筑、管道、网、码头、桩或柱等的固体表面。
本发明的防污组合物可以进一步与聚合物和/或共聚物组合使用,所述聚合物和/或共聚物使得Cu(ETFAA)2能受控释放,并且如果存在的话,还使得其中包含的所述一种或多种杀生物剂能受控释放,例如通过这些试剂随着时间的推移从防污涂层中释放出来(就像自抛光或烧蚀涂层的情况一样)来实现。
本发明人惊奇地发现,Cu(ETFAA)2是一种通用试剂,其可用于所有类型的防污涂层,即用于基于各种不同聚合物和/或共聚物的防污涂层,这些聚合物和/或共聚物通常用作防污涂料组合物的粘合剂。因此,使得Cu(ETFAA)2能受控释放并且如果存在的话也使得包含在其中的所述一种或多种杀生物剂能受控释放的聚合物和/或共聚物可以是通常用作防污涂层中的粘合剂的任何聚合物和/或共聚物。用于该目的的合适的聚合物和/或共聚物是本领域技术人员已知的。根据所使用的粘合剂的量和种类,Cu(ETFAA)2和一种或多种杀生物剂将以预定的期望速率以受控方式释放,例如,适合于船舶的航行模式。
例如,在使得Cu(ETFAA)2和所述一种或多种杀生物剂能受控释放的“自抛光防污涂料”中用作粘合剂的聚合物和/或共聚物可以是可水解的丙烯酸酯聚合物,例如(甲基)丙烯酸酯基聚合物和/或共聚物。(甲基)丙烯酸酯聚合物和/或共聚物中的(甲基)丙烯酸酯单体部分可以是(甲基)丙烯酸烷基酯,例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸3,5,5-三甲基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十六烷基酯和(甲基)丙烯酸硬脂酯;还有(甲基)丙烯酸苯酯;(甲基)丙烯酸苄酯;或者(甲基)丙烯酸烷氧基烷基酯,例如(甲基)丙烯酸甲氧基甲酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸乙氧基甲酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸4-甲氧基丁酯、(甲基)丙烯酸甲氧基丙酯、(甲基)丙烯酸乙氧基丙酯、(甲基)丙烯酸丙氧基乙酯、(甲基)丙烯酸2-丁氧基乙酯、(甲基)丙烯酸异丁氧基丁基二甘醇酯;以及(甲基)丙烯酸苯氧基乙酯;或(甲基)丙烯酸羟烷基酯,例如(甲基)丙烯酸羟甲酯、(甲基)丙烯酸2-羟乙酯、(甲基)丙烯酸2-羟丙酯、(甲基)丙烯酸4-羟丁酯或(甲基)丙烯酸2-羟基-3-苯氧基丙酯;
(甲基)丙烯酸酯聚合物和/或共聚物中的(甲基)丙烯酸酯单体部分可以进一步是(甲基)丙烯酸甲硅烷基酯,例如(甲基)丙烯酸三苄基甲硅烷基酯、(甲基)丙烯酸三甲基甲硅烷基酯、(甲基)丙烯酸三乙基甲硅烷基酯、(甲基)丙烯酸三异丙基甲硅烷基酯、(甲基)丙烯酸三正丁基甲硅烷基酯、(甲基)丙烯酸三异丁基甲硅烷基酯、(甲基)丙烯酸三叔丁基甲硅烷基酯、(甲基)丙烯酸三正戊基甲硅烷基酯、(甲基)丙烯酸三正十二烷基甲硅烷基酯、(甲基)丙烯酸三正己基甲硅烷基酯、(甲基)丙烯酸三正辛基甲硅烷基酯、(甲基)丙烯酸三正丙基甲硅烷基酯或(甲基)丙烯酸三苯基甲硅烷基酯;
(甲基)丙烯酸酯聚合物和/或共聚物还可包含丙烯酸或甲基丙烯酸的金属盐部分,本文称为“(甲基)丙烯酸金属盐”。金属可以是本领域技术人员已知的任何合适的金属,例如锌、钙、镁、锂、铁、锆、铝、钴、锆、钡和铋。
使得Cu(ETFAA)2能受控释放并且如果存在的话也使得所述一种或多种杀生物剂能受控释放的聚合物和/或共聚物也可以是VAGH共聚物。VAGH共聚物可以溶解在2:3的二甲苯:MIBK中。
因此,在一实施方案中,使得Cu(ETFAA)2能受控释放且如果存在的话也使得所述一种或多种杀生物剂能受控释放的聚合物和/或共聚物包含(甲基)丙烯酸酯聚合物和/或共聚物,或VAGH共聚物。(甲基)丙烯酸酯聚合物和/或共聚物可以是选自(甲基)丙烯酸烷基酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸烷氧基烷基酯、(甲基)丙烯酸羟烷基酯、(甲基)丙烯酸锌和(甲基)丙烯酸甲硅烷酯中的单体部分的聚合物或共聚物;或者(甲基)丙烯酸酯聚合物和/或共聚物可以是选自丙烯酸乙酯、甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸2-甲氧基乙酯、甲基丙烯酸锌和丙烯酸三异丙基甲硅烷酯中的单体部分的聚合物或共聚物,优选地,(甲基)丙烯酸酯聚合物和/或共聚物是选自丙烯酸乙酯、甲基丙烯酸甲酯和甲基丙烯酸锌中的单体部分的共聚物,更优选地,(甲基)丙烯酸酯聚合物和/或共聚物是选自丙烯酸乙酯、甲基丙烯酸甲酯、丙烯酸2-甲氧基乙酯和甲基丙烯酸锌中的单体部分的共聚物,最优选地,(甲基)丙烯酸酯聚合物聚合物和/或共聚物是选自甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸2-甲氧基乙酯和丙烯酸三异丙基甲硅烷基酯中的单体部分的共聚物。
因此,本发明进一步提供了一种防污涂料,其包含本发明的防污组合物和使得Cu(ETFAA)2能受控释放并且如果存在的话也使得所述一种或多种杀生物剂能受控释放的聚合物和/或共聚物。
本发明的防污涂料中的Cu(ETFAA)2的含量为约1至约25wt%,优选约3至约20wt%,更优选约4至约18wt%,最优选约5至约15wt%。
由于Cu(ETFAA)2的优异增强性能,因此在本发明的防污涂料中仅需要少量的所述一种或多种杀生物剂。本发明的防污涂料中的一种或多种杀生物剂的总含量小于约30wt%,优选小于约25wt%,更优选小于约20wt%,最优选小于约18wt%。
本发明的防污涂料中的CuPT的总含量小于约10wt%,更优选小于约8wt%,最优选小于约7wt%。
本发明的防污涂料中Cu2O的总含量小于约20wt%,更优选小于约15wt%,最优选小于约12wt%。
因此,有毒金属化合物,特别是Cu2O的含量保持在非常低的水平,甚至可以避免。
本发明还提供了一种抑制固体表面上的海洋生物污损的方法,其特征在于将包含本发明的防污组合物的防污涂料施涂在所述表面上。固体表面可以是任何水下物体的固体表面,例如船舶、水产养殖渔网、水下结构和设备、罐、海上建筑、管道、网、码头、桩或柱等。
下面结合实施例对本发明作进一步的说明,但应当解释为本发明并不限于这些实施例。
实施例
实施例1:用于防污涂料的示例性的聚合物基粘合剂的制备
可用于自抛光防污涂料或混合涂层的不同示例性聚合物基粘合剂已按如下所述的制备。
实施例1A:合成丙烯酸酯聚合物“丙烯酸酯低酸值”,其在本文中称为“Ac(AV=100-)”
实施例1B:合成丙烯酸酯聚合物“丙烯酸酯100酸值”,其在本文中称为“Ac(AV=100)”
实施例1C:使用丙烯酸酯聚合物“Ac(AV=100-)”合成粘合剂组分以得到本文称为“Zn-Ac(AV=100-)”的丙烯酸锌聚合物
实施例1D:使用丙烯酸酯聚合物“Ac(AV=100)”合成粘合剂组分以得到本文称为“Zn-Ac(AV=100)”的丙烯酸锌聚合物
实施例1E:合成丙烯酸甲硅烷酯聚合物标准TIPX粘合剂组分,其在本文中称为“Si-Ac”
实施例1F:合成丙烯酸甲硅烷酯聚合物低级TIPX粘合剂组分,其在本文中称为“Si-Ac(TIPX-L)”
实施例2:Cu2O和Cu(ETFAA)2在防污涂料中的功效比较
为了确认如果防污涂料中存在Cu(ETFAA)2可以显著减少甚至避免Cu2O的含量,在试验筏上通过将实验涂料面板浸入海水中,评估一组自抛光防污涂料的功效。已经为此目的制备了两种含有丙烯酸甲硅烷酯聚合物作为粘合剂组分以及Cu(ETFAA)2和CuPT(“实验涂料”)或Cu2O和CuPT(“对照涂料”)的自抛光防污涂料(参见表1)。用于这些涂料的丙烯酸甲硅烷基酯聚合物组分的合成在以上实施例1E中提供。
表1:实验涂料和对照涂料的组成:
因为氧化亚铜的密度是Cu(ETFAA)2的大约3倍,所以加入2.5克滑石使滑石和Cu(ETFAA)2的体积达到大致为涂料中氧化亚铜的体积。添加更多滑石以完全弥补氧化亚铜的体积会影响游离粘合剂的量,因为滑石比氧化亚铜具有更高的粘合剂需求(表面积/克)。
结果:图1中显示了从2015年9月到2017年9月在海水中浸泡24个月后的结果,图1显示了未冲洗状态和冲洗后的面板图片。用低压水流冲洗面板模拟船的缓慢运动。船的运动会松开并去除任何松散附着的污垢。含有Cu(ETFAA)2和吡啶硫酮铜的“实验涂料”有效抑制了海洋生物的生长,并且在这方面比含有40wt%的氧化亚铜和吡啶硫酮铜的对照涂料更有效。实验涂料的侵蚀速度比对照涂料略快。由于氧化亚铜降低丙烯酸甲硅烷酯聚合物的侵蚀速率的已知特性,这是预料中的。
实施例3:防污涂料的制备
根据不同类型船用防污涂料所采用的粘合剂技术,制备了三套防污涂料。制备示例性涂料,其包括:自抛光粘合剂类型,即其基于两种不同量的功能单体(丙烯酸锌单体或丙烯酸甲硅烷基酯单体)的丙烯酸锌聚合物和丙烯酸甲硅烷基聚合物;或烧蚀粘合剂类型,其基于松香和非侵蚀性VAGH聚合物。由于用于制造涂料的材料的体积会影响涂料的性能,例如干膜厚度和干膜中防污剂的数量,因此配方中材料的固体体积(volume solids)在每一类涂料中基本保持不变,除非故意改变它们以观察材料对防污性能的影响。
基于“丙烯酸锌聚合物基粘合剂”的自抛光防污涂料
实验涂料No.4、11、12和对照涂料69,均使用根据实施例1D的在本文中称为“Zn-Ac(AV=100)”的丙烯酸锌聚合物作为粘合剂组分
实验涂料No.22、25、20、23和26都使用根据实施例1C的本文称为“Zn-Ac(AV=100-)”的丙烯酸锌聚合物作为粘合剂组分
烧蚀防污涂料
实验涂料No.32、36、37、108A、108B和108C以及对照涂料70,均使用商业VAGH聚合物作为粘合剂组分
实验涂料108A:实验涂料101和104的1:1的混合物
实验涂料108B:实验涂料101和104的5:3的混合物
实验涂料108C:实验涂料101和104的3:5的混合物
基于“丙烯酸甲硅烷酯”聚合物基粘合剂的自抛光防污涂料
实验涂料No.53、60、61、63、64、66、67和111,均使用根据实施例1E和1F的被称为“Si-Ac”或“Si-Ac(TIPX-L)”的丙烯酸甲硅烷基酯聚合物作为粘合剂组件
由于材料相互作用和影响性能(如适用性和粘度)的方式不同,因此每类防污涂料(即,基于不同的粘合剂类型)在所用特定材料的比率上可能会有所不同。本领域技术人员应理解,由于材料对涂层的涂敷和粘度的影响,有时需要在不同类别的涂层(例如固体体积)之间不具有等效特性。
还允许(并保证)组合物的可变性来应对防污剂的预期浸出率。例如,防污剂从基于丙烯酸甲硅烷基粘合剂的涂料中浸出的速度比从基于烧蚀粘合剂或丙烯酸锌基粘合剂的涂料中浸出的速率要慢。因此,在基于丙烯酸甲硅烷基酯基粘合剂(silyl acrylatebased binders)的涂料中使用防污剂的量更多,因为静态筏测试需要相对较高的防污剂浸出率以防止污损。
示例5:防污实验
就防污性能评价上述实施例4的防污涂料。玻璃纤维(FRP)面板已涂有这些涂料。由于干膜厚度会影响防污性能,因此这可以通过以下方式仔细控制:在每层涂料干燥后称重FRP板并针对干涂料的密度调整所施加的涂料的重量以得到150μm的目标干膜厚度。所有涂漆面板的目标干膜厚度均与150μm的目标干膜厚度相差在10μm以内。
测试面板尺寸为457mm×102mm×3.33mm。因此,150μm的干膜厚度所需的面板正面的干涂层体积为6.992ml。背面和边缘所需的体积为6.992+0.533=7.525ml。所涂敷的涂料的体积不是测得的,而是通过所涂敷的干涂料的密度和干涂料的重量来计算出的。
a)涂敷在面板前面的干涂料的重量=6.992ml×涂料固体的密度(g/ml)
b)涂敷在面板背面和边缘的干涂料的重量=7.525ml×涂料固体的密度
测试板暴露于海水中。浸入2、4、6和8个月后的结果示于下表2。所有根据本发明的防污涂料均显示出优异的防污性能。
表2:防污涂料的防污性能
应用于结果的类别的详细信息如下所述。
对于藻类的防污性能:
优异(4):没有藻类。
好(3):其是薄的并且被粘液覆盖。
一般(2):其是厚的并且被粘液覆盖。
较差(1):其是厚的并且被粘液和/或很少的藻类覆盖。
低劣(0):其是厚的并且被粘液和/或许多藻类覆盖。
对于诸如藤壶、苔藓虫、水螅、贻贝等动物的防污性能
优异(4):没有动物。
好(3):其被小动物和很少的动物覆盖。
一般(2):其被小的且少量的动物覆盖。
较差(1):其被小/大的且少量的动物覆盖。
低劣(0):它被小/大的且许多的动物覆盖。
Claims (30)
1.防污组合物用于抑制固体表面上的海洋生物污损的用途,其中所述防污组合物包含Cu(ETFAA)2。
2.根据权利要求1所述的用途,其中所述防污组合物包含Cu(ETFAA)2和一种或多种杀生物剂。
3.根据权利要求2所述的用途,其中所述一种或多种杀生物剂选自2-吡啶硫醇-1-氧化铜(羟基吡啶硫酮铜,CuPT)、2-吡啶硫醇-1-氧化锌(羟基吡啶硫酮锌,ZnPT)、4,5-二氯-2-正辛基-4-异噻唑啉-3-酮(DCOIT)、氧化亚铜(Cu2O)、氧化锌(ZnO)、4-溴-2-(4-氯苯基)-5-(三氟甲基)-1H-吡咯-3-甲腈(溴代吡咯腈)、乙烷-1,2-二基双(二硫代氨基甲酸酯)锌(zineb),N,N-二甲基氨基二硫代锌(ziram)、3-(3,4-二氯苯基)-1,1-二甲基脲(敌草隆)、硫氰酸铜(I)(CuSCN)、4-[1-(2,3-二甲基苯基)乙基]-1H-咪唑(美托咪定)、三嗪、氟烷和2,4,5,6-四氯间苯二甲腈(百菌清)。
4.根据权利要求3所述的用途,其中所述一种或多种杀生物剂选自CuPT和Cu2O。
5.根据权利要求4所述的用途,其中Cu(ETFAA)2(wt%)比CuPT(wt%)的比率和/或Cu(ETFAA)2(wt%)比Cu2O(wt%)的比率为100:1至1:100。
6.根据权利要求5所述的用途,其中Cu(ETFAA)2(wt%)比CuPT(wt%)的比率和/或Cu(ETFAA)2(wt%)比Cu2O(wt%)的比率为10:1至1:10。
7.根据权利要求6所述的用途,其中Cu(ETFAA)2(wt%)比CuPT(wt%)的比率和/或Cu(ETFAA)2(wt%)比Cu2O(wt%)的比率为5:1至1:5。
8.根据权利要求1至7中任一项所述的用途,其中所述防污组合物与使得Cu(ETFAA)2能受控释放的聚合物和/或共聚物组合使用。
9.一种防污组合物,其包含Cu(ETFAA)2和一种或多种杀生物剂,所述杀生物剂选自2-吡啶硫醇-1-氧化铜(羟基吡啶硫酮铜,CuPT)、2-吡啶硫醇-1-氧化锌(羟基吡啶硫酮锌,ZnPT)、4,5-二氯-2-正辛基-4-异噻唑啉-3-酮(DCOIT)、氧化亚铜(Cu2O)、氧化锌(ZnO)、4-溴-2-(4-氯苯基)-5-(三氟甲基)-1H-吡咯-3-甲腈(溴代吡咯腈)、乙烷-1,2-二基双(二硫代氨基甲酸酯)锌(zineb),N,N-二甲基氨基二硫代锌(ziram)、3-(3,4-二氯苯基)-1,1-二甲基脲(敌草隆)、硫氰酸铜(I)(CuSCN)、4-[1-(2,3-二甲基苯基)乙基]-1H-咪唑(美托咪定)、三嗪、氟烷和2,4,5,6-四氯间苯二甲腈(百菌清)。
10.根据权利要求9所述的防污组合物,其中所述一种或多种杀生物剂选自CuPT、ZnPT、DCOIT、Cu2O和溴代吡咯腈。
11.根据权利要求10所述的防污组合物,其中所述一种或多种杀生物剂选自CuPT和Cu2O。
12.根据权利要求11所述的防污组合物,其中所述杀生物剂是CuPT。
13.根据权利要求11所述的防污组合物,其中所述杀生物剂是Cu2O。
14.根据权利要求11所述的防污组合物,其中所述杀生物剂是CuPT和Cu2O。
15.根据权利要求11所述的防污组合物,其中Cu(ETFAA)2(wt%)比CuPT(wt%)的比率和/或Cu(ETFAA)2(wt%)比Cu2O(wt%)的比率为100:1至1:100。
16.根据权利要求15所述的防污组合物,其中Cu(ETFAA)2(wt%)比CuPT(wt%)的比率和/或Cu(ETFAA)2(wt%)比Cu2O(wt%)的比率为10:1至1:10。
17.根据权利要求16所述的防污组合物,其中Cu(ETFAA)2(wt%)比CuPT(wt%)的比率和/或Cu(ETFAA)2(wt%)比Cu2O(wt%)的比率为5:1至1:5。
18.一种防污涂料,其包含权利要求9至17中任一项所述的防污组合物和使得Cu(ETFAA)2能受控释放的聚合物和/或共聚物。
19.根据权利要求18所述的防污涂料,其中Cu(ETFAA)2的含量为1wt%至25wt%。
20.根据权利要求19所述的防污涂料,其中Cu(ETFAA)2的含量为3wt%至20wt%。
21.根据权利要求20所述的防污涂料,其中Cu(ETFAA)2的含量为4wt%至18wt%。
22.根据权利要求21所述的防污涂料,其中Cu(ETFAA)2的含量为5wt%至15wt%。
23.根据权利要求18至22中任一项所述的防污涂料,其中所述一种或多种杀生物剂的总含量小于30wt%。
24.根据权利要求23所述的防污涂料,其中所述一种或多种杀生物剂的总含量小于25wt%。
25.根据权利要求24所述的防污涂料,其中所述一种或多种杀生物剂的总含量小于20wt%。
26.根据权利要求25所述的防污涂料,其中所述一种或多种杀生物剂的总含量小于18wt%。
27.根据权利要求18至22中任一项所述的防污涂料,其中CuPT的总含量小于10wt%和/或Cu2O的总含量小于20wt%。
28.根据权利要求27所述的防污涂料,其中CuPT的总含量小于8wt%和/或Cu2O的总含量小于15wt%。
29.根据权利要求28所述的防污涂料,其中CuPT的总含量小于7wt%和/或Cu2O的总含量小于12wt%。
30.一种抑制固体表面上海洋生物污损的方法,其包括将权利要求18至29中任一项所述的防污涂料施加到所述固体表面上。
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104046108A (zh) * | 2014-05-29 | 2014-09-17 | 青岛辰青信息技术有限公司 | 一种船舶涂料 |
CN106470550A (zh) * | 2014-09-19 | 2017-03-01 | 昭和电工株式会社 | 抗菌抗病毒组合物、抗菌抗病毒剂、光催化剂以及细菌病毒灭活方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2000248207A (ja) | 1999-03-02 | 2000-09-12 | Kansai Paint Co Ltd | 防汚塗料組成物 |
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JP5994725B2 (ja) | 2013-05-16 | 2016-09-21 | 信越化学工業株式会社 | 新規アルミニウムキレート化合物 |
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-
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104046108A (zh) * | 2014-05-29 | 2014-09-17 | 青岛辰青信息技术有限公司 | 一种船舶涂料 |
CN106470550A (zh) * | 2014-09-19 | 2017-03-01 | 昭和电工株式会社 | 抗菌抗病毒组合物、抗菌抗病毒剂、光催化剂以及细菌病毒灭活方法 |
Non-Patent Citations (2)
Title |
---|
Synthesis, Characterisation and Biological Evaluation of Copper and Silver Complexes based on Acetylsalicylic Acid;Rubner,Gerhard;et al.;《Arch.Pharm.Chemistry in Life Science》;20110829;第344卷(第10期);685 * |
β-二酮类金属螯合物的毛细管气相色谱行为研究;王顺荣,徐福正,李从,金秀兰,吴晓军;《化学学报》;19850630;518 * |
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