CN104449172A - 一种含生物防污剂的防污涂料及其制备方法 - Google Patents

一种含生物防污剂的防污涂料及其制备方法 Download PDF

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CN104449172A
CN104449172A CN201410836582.7A CN201410836582A CN104449172A CN 104449172 A CN104449172 A CN 104449172A CN 201410836582 A CN201410836582 A CN 201410836582A CN 104449172 A CN104449172 A CN 104449172A
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郑纪勇
蔺存国
邱日
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Abstract

本发明属于海洋防污涂料的技术领域，涉及一种含生物防污剂的防污涂料及其制备方法；所含生物防污剂的分子结构由苯环、酚羟基、甲氧基、丙酰基、胺基和R1组成，制备工艺为:先将提取的丹皮酚与三聚甲醛和烷基胺在无水乙醇中混合，再在浓盐酸催化下进行曼尼希反应后，用NaHCO3水溶液中和，再用无水乙醇重结晶得生物防污剂，然后将生物防污剂与三氟丙基-甲基-二甲基丙烯酸酯硅烷、甲基丙烯酸甲酯、甲基丙烯酸和甲基丙烯酸丁酯在甲苯中混合进行自由基聚合反应，得到生物防污剂的液体制品，再在液体制品中加入颜料、填料和涂料助剂进行混合，研磨后得到含生物防污剂的防污涂料；其制备工艺简单，原料易得，应用前景广泛，使用环境友好。

Description

一种含生物防污剂的防污涂料及其制备方法
技术领域：
本发明属于海洋防污涂料的技术领域，涉及一种海洋环境中物体设施表面污损防护用的涂料，特别是一种含生物防污剂的防污涂料及其制备方法，对防除水下设施表面附着污损生物具有明显效果。 
背景技术：
海水中存在着大量污损生物，如藤壶、贻贝、海鞘、苔藓虫、水螅、海绵、绿藻、硅藻等，这些生物可附着在结构物表面，如船舶、船坞、码头、石油平台、海底电缆、浮标、水雷、电厂冷却管道、渔网等，会对海洋环境中的结构物带来危害和经济损失，如造成船舶航行阻力加大，通海管道阻塞，冷却设备导热性降低，渔网渔具堵塞等。目前，解决海洋生物污损的最简便有效的方法是涂刷防污涂料，现有的海洋防污涂料通常是由树脂、防污剂、颜填料、助剂和溶剂组成，其中防污剂和树脂是防污性能的关键。在防污剂方面，有机锡具有良好的防污效果，已得到普遍使用，然而，这种防污剂对其它非目标生物如鱼类、贝类等也有强毒性，并在生物体和海泥中累积，危害海洋生态环境，甚至经食物链传递危及人类健康。世界海事组织已禁止有机锡和DDT等有毒防污剂在防污涂料中的应用，设计和制备新型环保防污剂是未来发展趋势。在现有技术中，各种防污剂很多，如中国专利CN 1189293A公开了一种哒嗪酮类防污剂；中国专利CN1392208A公开了一种海洋大叶藻提取物制成的防污剂；中国专利CN1820603A公开了一种氯氰菊酯防污剂；中国专利CN1651412A公开了一种吲哚的酰胺衍生物防污剂；中国专利CN1499928A公开了烷基胺衍生物防污剂等，现有防污剂的防污性能仍需进一步研发，以期制备一种高性能、环保型海洋防污剂取代现有的技术产品。通常，树脂在涂料中主要起成膜作用，并随着高分子技术的发展，树脂也具备防污性，防污涂料使用树脂的研究从20世纪90年代至今已有大量专利文献公开，其中以基于聚硅氧烷、聚氨酯、丙烯酸酯等的涂料研究较多，如中国专利GB1457590公开了三丁基锡丙烯酸聚合物自抛光 树脂；中国专利CN102402739A公开了一种低表面能氟硅改性丙烯酸防污树脂；中国专利CN101029207A公开了氟硅嵌段聚合物型低表面能树脂；中国专利CN101775144A公开了一种氟硅树脂等；上述这些树脂和防污涂料的合成，均采用硅单体和氟单体，再分别与丙烯酸单体聚合，或者采用硅氧烷聚合链与碳聚合链交联形成聚合物，但开发简单易用，并兼具多种特性的优良树脂的技术和产品仍是有进一步研究和开发的必要。 
发明内容：
本发明的目的在于克服现有技术存在的缺点，提供一种环保型含有生物防污剂防污涂料及其制备方法，利用氟硅丙烯酸脂对生物防污剂进行包裹，以控制防污剂缓慢水解释放，其防污具备防除污损生物附着和生长的功能，采用生物防污剂和水解型低表面能树脂相结合，通过两者的共同作用增加防污效果。 
为了实现上述发明目的，本发明涉及的防污涂料中所含生物防污剂的分子结构为： 
其生物防污剂分子结构由苯环、酚羟基、甲氧基、丙酰基、胺基和R1组成，其中R1为C1-C10的线性或支化的烷基链，优选C4-C8的线性烷基链；该分子结构的部分基团(式中虚线内的分子结构)来源于天然活性成分丹皮酚，由牡丹、芍药和徐长卿植物的根皮或全草中提取，另外含有曼尼希碱结构和烷基胺结构。 
本发明涉及的含生物防污剂的防污涂料的制备工艺包括生物防污剂制备和防污涂料制备两个步骤，其中，生物防污剂的制备是：将 提取的天然分子丹皮酚与三聚甲醛和烷基胺R1NH2在无水乙醇中混合，在浓盐酸催化下进行曼尼希反应，其各成分配置重量比例为丹皮酚：三聚甲醛：烷基胺：无水乙醇：浓盐酸＝1：(1～4)：(1～2)：30：(0.1～1)，反应温度为25～140℃，反应时间为1～48小时，反应完毕后用重量百分比浓度为10％的NaHCO3水溶液中和至pH＝7，分离得到的产物再用无水乙醇重结晶纯化后制得生物防污剂，其中浓盐酸的重量百分比浓度为37％；其氟硅丙烯酸酯包裹生物防污剂的防污涂料制备工艺为：将制备的生物防污剂与三氟丙基-甲基-二甲基丙烯酸酯硅烷、甲基丙烯酸甲酯、甲基丙烯酸、甲基丙烯酸丁酯在甲苯中混合均匀，以偶氮二异丁腈为引发剂进行自由基聚合反应，其各成分的重量配置比例为:生物防污剂：三氟丙基-甲基-二甲基丙烯酸酯硅烷:甲基丙烯酸甲酯:甲基丙烯酸、甲基丙烯酸丁酯:偶氮二异丁腈:甲苯＝1:1:1:1:3:(0.05～0.1):30，在80～90℃下搅拌反应3～8小时，即得到用氟硅丙烯酸酯包裹生物防污剂的液体制品；再在液体制品中按常规工艺加入常规使用的颜料、填料和涂料助剂进行混合，研磨达到80微米细度，即制备得氟硅丙烯酸酯包裹生物防污剂的防污涂料。 
本发明与现有技术相比，其氟硅丙烯酸脂包裹生物防污剂的防污涂料中含有生物防污剂作为污损生物附着生长抑制剂，对硅藻附着的半数抑制浓度达到1ppm；以氟硅丙烯酸树脂作为成膜物，不但可以利用酸根和胺基的作用包裹防污剂，而且可在接触海水后，通过硅氧酯键水解，缓慢释放出防污剂和具有低表面能特性的氟硅氧烷，进一步抑制污损生物的附着；具备防污性好、表面能低和水解抛光效果好等防污特性，其制备工艺简单，原料易得，应用前景广泛，使用环境友好。 
具体实施方式：
下面结合本实施例进一步说明本发明的具体实施方案。 
实施例1：生物防污剂的制备 
将丹皮酚1mol、三聚甲醛3mol、正辛胺1mol、300ml无水乙醇放入反应容器中，使完全溶解搅拌，在回流冷凝条件下缓慢加入37％ 浓盐酸3ml，在80℃温度下反应24小时；反应结束后用重量百分比浓度为10％NaHCO3水溶液中和至pH＝7，产物用无水乙醇重结晶，即得到生物防污剂。 
实施例2：用氟硅丙烯酸脂包裹生物防污剂的防污涂料的制备 
将实施例1所得的生物防污剂10g，氟硅烷基丙烯酸酯10g，甲基丙烯酸甲酯10g、甲基丙烯酸10g、丙烯酸丁酯30g、偶氮二异丁腈0.3g与甲苯200g搅拌混合均匀，在90℃下搅拌反应5小时，得到氟硅丙烯酸酯包裹生物防污剂的液体制品，取该液体制品30g，加入氧化锌15g，氧化铁10g，蒙脱土2g，膨润土1g，二甲苯30g，反复研磨分散均匀后制得防污涂料。 
实施例3：生物防污剂对硅藻的防除性能测试 
取实施例1制备的生物防污剂50mg加入到500ml容量瓶中，加蒸馏水至刻度线，制备100ppm浓度母液100ml；然后将母液稀释成10、5、3、1、0.5、0.1ppm的浓度梯度，然后各取0.9ml分别加入到24孔培养板中,再分别加入1.8ml配制好的f/2培养液，加入硅藻种0.3ml；于20℃、1900lux光照、明暗周期为12h∶12h条件下培养3～7天后对底部附着硅藻计数；根据底部硅藻附着个数，统计计算得到半数抑制浓度为0.8ppm；说明本实施例制备的生物防污剂可抑制硅藻生长，影响污损生物群落的生成，达到防污效果。 
实施例4：用氟硅丙烯酸树脂包裹生物防污剂的防污涂料实海测试 
按照国家标准GB 5370-2007《防污漆样板浅海浸泡试验方法》，取实施例2的用氟硅丙烯酸包裹生物防污剂的防污涂料涂刷在实海测试样板表面，进行实海防污活性测试，结果表明，该防污涂料达到1年以上的防污期效。 

Claims (2)

1.一种含生物防污剂的防污涂料，其特征在于所含生物防污剂的分子结构为：
其生物防污剂分子结构由苯环、酚羟基、甲氧基、丙酰基、胺基和R1组成，其中R1为C1-C10的线性或支化的烷基链；分子结构中的部分基团来源于天然活性成分丹皮酚，由牡丹、芍药和徐长卿植物的根皮或全草中提取，另外含有曼尼希碱结构和烷基胺结构。
2.一种根据权利要求1所述的含生物防污剂的防污涂料的制备方法，其特征在于制备工艺包括生物防污剂制备和防污涂料制备两个步骤，其中，生物防污剂的制备是：将提取的天然分子丹皮酚与三聚甲醛和烷基胺在无水乙醇中混合，在浓盐酸催化下进行曼尼希反应，其各成分配置重量比例为丹皮酚：三聚甲醛：烷基胺：无水乙醇：浓盐酸＝1：(1～4)：(1～2)：30：(0.1～1)，反应温度为25～140℃，反应时间为1～48小时，反应完毕后用重量百分比浓度为10％的NaHCO3水溶液中和至pH＝7，分离得到的产物再用无水乙醇重结晶纯化后制得生物防污剂，其中浓盐酸的重量百分比浓度为37％；其氟硅丙烯酸酯包裹生物防污剂的防污涂料制备工艺为：将制备的生物防污剂与三氟丙基-甲基-二甲基丙烯酸酯硅烷、甲基丙烯酸甲酯、甲基丙烯酸、甲基丙烯酸丁酯在甲苯中混合均匀，以偶氮二异丁腈为引发剂进行自由基聚合反应，其各成分的重量配置比例为:生物防污剂：三氟丙基-甲基-二甲基丙烯酸酯硅烷:甲基丙烯酸甲酯:甲基丙烯酸、甲基丙烯酸丁酯:偶氮二异丁腈:甲苯＝1:1:1:1:3:(0.05～0.1):30，在80～90℃下搅拌反应3～8小时，即得到用氟硅丙烯酸酯包裹生物防污剂的液体制品；再在液体制品中按常规工艺加入常规使用的颜料、填料和涂料助剂进行混合，研磨达到80微米细度，即制备得氟硅丙烯酸酯包裹生物防污剂的防污涂料。
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