CN115595029A - 一种两性离子基环境友好型海洋防污涂料及其制备方法 - Google Patents
一种两性离子基环境友好型海洋防污涂料及其制备方法 Download PDFInfo
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- 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
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Abstract
本发明属于精细化工技术领域,具体为一种两性离子基环境友好型海洋防污涂料。本发明涂料组成按重量份计为:可湿固化丙烯酸树脂40‑80份,两性离子前驱体硅氧烷5‑30份,防污抗菌硅氧烷2‑20份,无机纳米杀菌剂2‑50份,氨基硅烷0‑8份,溶剂5‑20份,助剂0‑5份。该涂料中的有机防污剂在固化过程中化学键合在涂层聚合物链中,成为成膜物质的一部分,延长了防污剂的使用寿命;两性离子前驱体硅氧烷通过原位生成两性离子,与有机防污剂和/或无机纳米抗菌剂协同作用提高涂层防污性能。该涂料可大规模室温喷涂固化,水下力学强度高,可适合于船舶、海水管道等多种场合的防污涂层,尤其适合用作水下智能机器人清洗的硬质防污涂层。
Description
技术领域
本发明属于精细化工技术领域,具体涉及一种海洋防污涂料及其制备方法。
背景技术
当前,商业化的海洋防污涂层的成膜树脂主要有两类:自抛光树脂(主要为丙烯酸硅氧烷树脂)和有机硅树脂。丙烯酸硅氧烷树脂通过海水弱碱条件下三烷氧基硅基的水解生成羧基,增加了聚合物分子的亲水性,在水流的冲刷下进入海水中,缩短了涂层中防污剂向涂层/海水界面的扩散距离,确保涂层近表面较长时间保持一定的杀菌剂浓度,从而起到防污效果。但此类涂料中常用的Cu2O防污剂含量高,环境友好型差,而且自抛光树脂在使用过程中会逐渐损失,在不同服役环境下寿命相差巨大。基于有机硅树脂的海洋防污涂层是一类污损释放型涂层,由于涂层表面能低,污损生物在涂层表面的附着力低,可在一定航速下自动脱除宏观污损生物。有机硅树脂防污涂层虽然环境友好型佳,但其静态防污性能差,力学性能弱,重涂性不佳,限制了其使用范围。因此,新型的环境友好型海洋防污涂料亟待进一步发展。
目前,环境友好型海洋防污涂料的主要方向包括:(1)亲水化方向,在涂层引入亲水聚合物、两性离子等亲水组分,主要通过抑制条件膜和生物膜的形成来减少宏观生物的附着,但亲水基团引入过多导致涂层水下力学性能严重恶化,亲水基团过少,则无法有效抑制件膜和生物膜的生成;(2) 无毒防污剂方向,包括天然防污剂和人工合成无毒防污剂的应用,但这些防污剂在海水中释放快,易降解,防污寿命短;(3) 仿生微纳结构表面防污,但此类防污表面不易大规模制备,而且易磨损,难于再生。因此,现有报道的环境友好海洋防污涂料面临实际应用的困难。
在环境友好型海洋防污涂料的发展方向中,两性离子的引入受到关注,其亲水能力强,易在表面形成高亲水性或与疏水链段组成两亲性表面,防蛋白粘附性能好,是一种仿生型的防污基团。采用两性离子制备海洋防污涂料的报道有:如中国发明专利CN2015108299158报道了一种含甜菜碱型两性离子改性的丙烯酸酯自抛光防污涂料及其制备方法,其组成包括甜菜碱型两性离子功能化的丙烯酸酸自抛光树脂、复合防污剂、颜填料、助剂等。中国发明专利201711477882 .0中先合成含四乙烯基吡啶的共聚物,再与丙磺酸内酯反应得到了一种两性离子防污涂料树脂。中国发明专利201410680546.6将甲氧基聚乙二醇-b-聚甲基丙烯酸乙酯二甲基磺丙基甜菜碱-b-聚甲基丙烯酸二甲氨基乙酯与3-氯丙基三乙氧基硅烷进行季铵化反应,制得了含有两性离子的防污抗菌涂层材料。中国发明专利202080005838.3采用双[3-(三乙氧基硅)丙基]胺与两性离子单体反应生成具有两性离子性的硅烷偶联剂,再与聚乙二醇双封端PDMS和羟基封端PDMS反应,制备了含两性离子的硅凝胶防污涂料。上述防污涂料中的两性离子大多由预先合成的含两性离子共聚物引入,其含量固定,相应的涂层吸水量高,水下力学性能不佳;或者两性离子与其它防污剂配合不够,在实际海洋中防污性能不能满足使用要求。通过与无毒有机或无机防污剂的复配协同作用,是提高环境友好海洋防污涂料防污性能的有效途径,但防污寿命仍然不能满足实际应用。将环境友好海洋防污涂料与水下智能机器人清洗相结合是解决其实际海洋应用的理想方法。但适合水下机器人清洗的涂层通常需要较高的力学强度,现有防污涂层用树脂体系不符合使用要求。因此,防污性能优异、水下力学性能突出的两性离子基环境友好海洋防污涂层尚需进一步开发。
发明内容
本发明的目的在于提供一种水下力学性能好、防污功能强和防污寿命长的两性离子基环境友好型海洋防污涂料及其制备方法。
本发明提供的两性离子基环境友好型海洋防污涂料,具体组分按重量份计如下:
可湿固化丙烯酸树脂: 40-80;
两性离子前驱体硅氧烷: 5-30 ;
有机防污抗菌硅氧烷: 2-20;
无机纳米杀菌剂: 2-50;
氨基硅烷: 0-8 ;
溶剂: 5-20 ;
助剂: 0-5。
本发明的两性离子基环境友好海洋防污涂料中,所述湿固化丙烯酸树脂中,用于交联的基团为三烷氧基硅基。该基团通过水解生成硅羟基,然后硅羟基之间缩合形成Si-O-Si键,实现涂层的室温固化交联。
进一步,所述的湿固化丙烯酸树脂的三烷氧基硅基为三甲氧基硅基或三乙氧基硅基。
进一步,所述的湿固化丙烯酸树脂可以来自市售产品,如上海华荣公司的高固体分818A树脂(固含68%、粘度1300mPa.s,溶剂:二甲苯);亦可采用甲基丙烯酸甲酯、丙烯酸丁酯、苯乙烯、甲基丙烯酰氧基丙基三甲氧基硅烷(或乙烯基三甲氧基硅烷)等单体自由基共聚合而成。
本发明的两性离子基环境友好海洋防污涂料中,所述两性离子前驱体硅氧烷为(N-三异丙基硅基酰基丙基)-3-氨基丙基三烷氧基硅烷、(N-甲氧基酰基乙基)-3-氨基丙基三烷氧基硅烷、双(N-甲氧基酰基乙基)-3-氨基丙基三烷氧基硅烷中的一种;其两性离子通过涂层固化或使用过程中原位水解生成,主要局限于涂层表层,避免了涂层内部的高吸水率,从而有助于获得涂层水下高力学性能。同时,该类两性离子前驱体硅氧烷可起催化剂和固化剂的功能,促进涂层固化成膜。
本发明的两性离子基环境友好型海洋防污涂料中,所述有机防污抗菌硅氧烷为2-(2-羟基-3-(3-(三烷氧基甲硅烷基)丙氧基)丙基)苯并异噻唑啉-3-酮和5-氯-2-(2,4-二氯苯氧基)-N-(3-(三烷氧基甲硅烷基)丙基)苯胺中的至少一种。
本发明的两性离子基环境友好海洋防污涂料中,所述两性离子前驱体硅氧烷和有机防污抗菌硅氧烷中的三烷氧基为三甲氧基或三乙氧基中的一种。
进一步,本发明中所述的抗菌防污硅氧烷可采用有机合成的方法合成。典型地,如含有1,2-苯并异噻唑啉-3-酮抗菌基团的硅氧烷,可采用1,2-苯并异噻唑啉-3-酮与3-缩水甘油基氧基丙基三甲氧基硅烷之间进行反应得到,合成条件为:无水环境,温度70 °C,时间40 h。
进一步,本发明中所述的抗菌防污硅氧烷,由于含有三烷氧基硅基,在成膜过程中可与湿固化丙烯酸树脂发生反应,化学键合到成膜物质网络中,避免简单物理共混造成的快速释放问题。
本发明的两性离子基环境友好型海洋防污涂料中,所述无机纳米杀菌剂选自纳米ZnO、纳米Cu2O、纳米TiO2、纳米Ag中的至少一种。
本发明的两性离子基环境友好型海洋防污涂料中,所述助剂包括涂料用流平剂、润湿剂和消泡剂。
本发明的两性离子基环境友好型海洋防污涂料中,所述溶剂选自乙酸丁酯、乙酸乙酯、二甲苯、环己酮、丙二醇甲醚醋酸酯中的一种。
本发明还提供两性离子基环境友好型海洋防污涂料的制备方法,具体过程如下:
首先将无机纳米杀菌剂加入至湿固化丙烯酸树脂中,高速剪切分散,或进行砂磨;当无机纳米杀菌剂分散后,再依次加入有机防污抗菌硅氧烷、两性离子前驱体硅氧烷和溶剂,以及氨基硅烷、助剂,搅拌分散0.5-1.0小时,即得所需涂料。
氨基硅烷和助剂主要用于调节涂层的固化速率和涂膜外观,可根据实际情况加或不加。
本发明涂料组成中,有机防污剂在固化过程中其化学键合在涂层聚合物链中成为成膜物质的一部分,延长了防污剂的使用寿命;同时,两性离子前驱体硅氧烷通过原位生成两性离子,与有机防污剂和/或无机纳米抗菌剂协同作用提高涂层防污性能。该涂料可大规模室温喷涂固化,防污剂种类和用量调控方便,水下力学强度高,在人工海水中浸泡九个月后铅笔硬度仍保持在1 H以上,并具备优异的防污性能。
具体地,涂层在实验室各项防污测试中,细菌量比空白玻璃片降低90%-98%;硅藻量比空白玻璃片降低86%-99%。在实海各项防污测试中,细菌量比空白玻璃片降低84%-97%;硅藻量比空白玻璃片降低72%-92%;稚贝附着量比空白玻璃片降低82%-95%。较优的一组涂层在实验室各项防污测试中,细菌量比空白玻璃片降低98%;硅藻量比空白玻璃片降低99%。在实海各项防污测试中,细菌量比空白玻璃片降低97%;硅藻量比空白玻璃片降低92%;稚贝附着量比空白玻璃片降低95%。
本发明的两性离子基环境友好海洋型防污涂料,可适合于船舶、海水管道等多种场合的防污涂层,尤其适合用作水下智能机器人清洗的硬质防污涂层。
具体实施方式
下面通过具体实施例进一步描述本发明。
实施例1:
将30g纳米ZnO、50g可湿固化丙烯酸树脂818A、5g溶剂二甲苯、加入塑料容器内,以玻璃珠为磨料进行高速剪切分散,得到稳定的纳米粒子分散液。
将纳米粒子分散液、10g (N-甲氧基酰基乙基)-3-氨基丙基三乙氧基硅烷、3g 2-(2-羟基-3-(3-(三甲氧基甲硅烷基)丙氧基)丙基)苯并异噻唑啉-3-酮、2g 氨基硅烷混合,室温下搅拌得到均匀的液体,涂覆后于室温下固化2 d。
涂层在实验室各项防污测试中,细菌量比空白玻璃片降低95%;硅藻量比空白玻璃片降低92%。在实海各项防污测试中,细菌量比空白玻璃片降低86%;硅藻量比空白玻璃片降低88%;稚贝附着量比空白玻璃片降低90%。
实施例2:
将5g 纳米Cu2O、5g 纳米TiO2、42g 可湿固化丙烯酸树脂818A、11g 溶剂二甲苯、加入塑料容器内,以玻璃珠为磨料进行研磨分散,得到稳定的纳米粒子分散液。
将纳米粒子分散液、25g (N-三异丙基硅基酰基丙基)-3-氨基丙基三甲氧基硅烷、10g 5-氯-2-(2,4-二氯苯氧基)-N-(3-(三乙氧基甲硅烷基)丙基)苯胺、1g 流平剂、1g 润湿剂混合,室温下搅拌得到均匀的液体,涂覆后于室温下固化2 d。
涂层在实验室各项防污测试中,细菌量比空白玻璃片降低93%;硅藻量比空白玻璃片降低86%。在实海各项防污测试中,细菌量比空白玻璃片降低90%;硅藻量比空白玻璃片降低76%;稚贝附着量比空白玻璃片降低82%。
实施例3:
将20g 纳米ZnO、10g 纳米Ag、40g 可湿固化丙烯酸树脂818A、6g 溶剂二甲苯、加入塑料容器内,以玻璃珠为磨料进行研磨分散,得到稳定的纳米粒子分散液。
将纳米粒子分散液、12g 双(N-甲氧基酰基乙基)-3-氨基丙基三乙氧基硅烷、5g2-(2-羟基-3-(3-(三乙氧基甲硅烷基)丙氧基)丙基)苯并异噻唑啉-3-酮、3g 5-氯-2-(2,4-二氯苯氧基)-N-(3-(三甲氧基甲硅烷基)丙基)苯胺、2g 氨基硅烷、1g 流平剂、1g 消泡剂混合,室温下搅拌得到均匀的液体,涂覆后于室温下固化2 d。
涂层在实验室各项防污测试中,细菌量比空白玻璃片降低96%;硅藻量比空白玻璃片降低91%。在实海各项防污测试中,细菌量比空白玻璃片降低84%;硅藻量比空白玻璃片降低72%;稚贝附着量比空白玻璃片降低89%。
实施例4:
将10g纳米ZnO、2g纳米Cu2O、2g纳米Ag、60g可湿固化丙烯酸树脂818A、8g溶剂二甲苯、加入塑料容器内,以玻璃珠为磨料进行高速剪切分散,得到稳定的纳米粒子分散液。
将纳米粒子分散液、8g (N-三异丙基硅基酰基丙基)-3-氨基丙基三甲氧基硅烷、5g 2-(2-羟基-3-(3-(三甲氧基甲硅烷基)丙氧基)丙基)苯并异噻唑啉-3-酮、4g 5-氯-2-(2,4-二氯苯氧基)-N-(3-(三乙氧基甲硅烷基)丙基)苯胺、1g润湿剂混合,室温下搅拌得到均匀的液体,涂覆后于室温下固化2 d。
涂层在实验室各项防污测试中,细菌量比空白玻璃片降低95%;硅藻量比空白玻璃片降低91%。在实海各项防污测试中,细菌量比空白玻璃片降低84%;硅藻量比空白玻璃片降低86%;稚贝附着量比空白玻璃片降低91%。
实施例5:
将5g纳米ZnO、5g纳米Cu2O、5g纳米TiO2、5g纳米Ag、50g可湿固化丙烯酸树脂818A、10g溶剂二甲苯、加入塑料容器内,以玻璃珠为磨料进行高速剪切分散,得到稳定的纳米粒子分散液。
将纳米粒子分散液、10g (N-甲氧基酰基乙基)-3-氨基丙基三甲氧基硅烷、3g 2-(2-羟基-3-(3-(三甲氧基甲硅烷基)丙氧基)丙基)苯并异噻唑啉-3-酮、3g 5-氯-2-(2,4-二氯苯氧基)-N-(3-(三乙氧基甲硅烷基)丙基)苯胺、2g氨基硅烷、1g润湿剂、1g流平剂混合,室温下搅拌得到均匀的液体,涂覆后于室温下固化2 d。
涂层在实验室各项防污测试中,细菌量比空白玻璃片降低98%;硅藻量比空白玻璃片降低99%。在实海各项防污测试中,细菌量比空白玻璃片降低97%;硅藻量比空白玻璃片降低92%;稚贝附着量比空白玻璃片降低95%。
Claims (9)
1.一种两性离子基环境友好型海洋防污涂料,其特征终于,按重量份计各组分如下:
可湿固化丙烯酸树脂: 40-80;
两性离子前驱体硅氧烷: 5-30 ;
有机防污抗菌硅氧烷: 2-20;
无机纳米杀菌剂: 2-50;
氨基硅烷: 0-8 ;
溶剂: 5-20 ;
助剂: 0-5。
2.根据权利要求1所述的两性离子基环境友好型海洋防污涂料,其特征在于,所述湿固化丙烯酸树脂中,用于交联的基团为三烷氧基硅基;该基团通过水解生成硅羟基,然后硅羟基之间缩合形成Si-O-Si键,实现涂层的室温固化交联。
3.根据权利要求2所述的两性离子基环境友好型海洋防污涂料,其特征在于,所述湿固化丙烯酸树脂的三烷氧基硅基为三甲氧基硅基或三乙氧基硅基。
4.根据权利要求1所述的两性离子基环境友好型海洋防污涂料,其特征在于,所述两性离子前驱体硅氧烷为(N-三异丙基硅基酰基丙基)-3-氨基丙基三烷氧基硅烷、(N-甲氧基酰基乙基)-3-氨基丙基三烷氧基硅烷、双(N-甲氧基酰基乙基)-3-氨基丙基三烷氧基硅烷中的一种。
5.根据权利要求1所述的两性离子基环境友好型海洋防污涂料,其特征在于,所述有机防污抗菌硅氧烷为2-(2-羟基-3-(3-(三烷氧基甲硅烷基)丙氧基)丙基)苯并异噻唑啉-3-酮和5-氯-2-(2,4-二氯苯氧基)-N-(3-(三烷氧基甲硅烷基)丙基)苯胺中的至少一种。
6.根据权利要求1所述的两性离子基环境友好型海洋防污涂料,其特征在于,所述无机纳米杀菌剂选自纳米ZnO、纳米Cu2O、纳米TiO2、纳米Ag中的至少一种。
7.根据权利要求1所述的两性离子基环境友好型海洋防污涂料,其特征在于,所述助剂包括涂料用流平剂、润湿剂和消泡剂。
8.根据权利要求1所述的两性离子基环境友好型海洋防污涂料,其特征在于,所述溶剂选自乙酸丁酯、乙酸乙酯、二甲苯、环己酮、丙二醇甲醚醋酸酯中的一种。
9.一种如权利要求1-8之一所述的两性离子基环境友好型海洋防污涂料的制备方法,其特征在于,具体过程如下:
首先将无机纳米杀菌剂加入至湿固化丙烯酸树脂中,高速剪切分散,或进行砂磨;当无机纳米杀菌剂分散后,再依次加入有机防污抗菌硅氧烷、两性离子前驱体硅氧烷和溶剂,以及氨基硅烷、助剂,搅拌分散0.5-1.0小时,即得所需涂料。
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