双亲聚合物交联网络涂层的制备及其表面特性与海洋防污机理研究

The fouling of underwater structures and ship's hulls in particular, results in increased consumption of fuel, lower obtainable speeds, and higher maintenance costs. The control of fouling by biocidal antifouling paints imposes environmental burdens, and coatings that function solely through the principle of fouling release are generally less effective in protecting the static immersion equipment or slow moving ships with speeds of less than 15 knots. To avoid an approach that requires the use of biocidal agents as well as one that only relies on a fouling-release mechanism, we design a highly complex polymer surface that would be able to resist the settlement of biological organisms and specifically to enhance release of those that do adhere. The amphiphilic network coatings having a hydrophobic fluorinated and hydrophilic poly(ethylene glycol) (PEG) segments crosslinked with hydroxyl group terminated poly(dimethyl siloxane) (PDMS), intended as non-toxic high performance marine coatings with the advantage of lower surface free energy, lower elastic modulus and good protein adhesion-resistance will be prepared. In this study, the influence of the fluorinated and PEG chain length and the kind of terminated-functional group on the composition, topography, wettability of the coating, as well as the effect of the composition and topography of the coating on antifouling properties, and how that may be influenced by nanostructure of coatings, with the goal of developing non-toxic high performance surfaces exhibiting excellent antifouling characteristics for marine antifouling/fouling-release applications will be investigated.

海洋污损生物附着在水下结构（特别是船壳）表面会造成巨大的经济损失。传统的靠释放防污剂来抑制海洋生物附着的防污涂料对海洋环境造成危害，而利用污损释放机理达到防污目的低表面能防污涂料对海洋生物的广谱防污性能不够，且对大多数时间静止或航速小于15节的船只的防污效果极其有限。本申请拟构筑一个多功能的聚合物表面，其可抑制海洋生物附着，而且即使附着也能容易脱除。通过设计新型端基官能化的含氟、聚乙二醇（PEG）链段的前驱物，将其与聚有机硅氧烷在交联剂作用下进行缩聚，制备基于无规双亲共聚物，兼具有机氟的低表面能性、有机硅的低弹性模量、PEG的亲水抗蛋白吸附等优点于一体的交联网络涂层。通过精确调控含氟链段/PEG亲水链段的数量和长度、端基官能团的种类，分析前驱物的结构对涂膜表面化学组成、拓扑、润湿性等的影响，研究双亲无规共聚物交联网络的构筑对防污性能的影响机制，为发展一类高性能的海洋防污材料探索新的途径。

海洋污损生物附着在水下结构表面会造成巨大的经济损失。传统的靠释放防污剂来抑制海洋生物附着的防污涂料对海洋环境造成危害，而利用污损释放机理达到防污目的的低表面能防污涂料对海洋生物的广谱防污性能不够，且对大多数时间静止或航速小于15节的船只的防污效果极其有限。本项目通过设计合成端基官能化的含氟、聚乙二醇（PEG）链段的前驱物，将其与基体树脂进行缩聚，得到了一系列基于无规双亲共聚物，兼具有机氟的低表面能性、有机硅的低弹性模量、PEG的亲水抗蛋白吸附等优点于一体的交联网络涂层。主要内容及结果如下：. （1）采用3-异氰酸酯基丙基三乙氧基硅烷在二月桂酸二丁基锡的催化作用下，与端基为羟基的全氟聚醚发生加成反应，成功合成了α,ω-三乙氧基硅烷封端的全氟聚醚低聚物PFU。与α,ω-三乙氧基硅烷封端的聚二甲基硅氧烷低聚物、羟基丙烯酸酯齐聚物缩聚固化形成交联网络涂层。该涂层具有低表面能、低弹性模量、对基材的附着力好，且抗菌、抗藻附着能力较商品化的有机硅树脂好。在此基础上，在羟基丙烯酸酯齐聚物中引入具有抗蛋白附着的PEG基团，结果发现引入PEG基团能大大提高涂层的防污性能。. （2）以不同分子量的端氢硅油(PDMS)和聚乙二醇二烯丙基醚（PEG）为原料，通过硅氢加成合成了系列双键封端的(PDMS-b-PEG)m多嵌段共聚物，再用三甲氧基氢硅烷进行端基官能化，合成了3种三甲氧基硅烷封端的多嵌段聚合物，即含PEG前驱物。含PEG前驱物、含氟前驱物(FMS-9922)与有机硅基体树脂通过缩合聚合制备了含PEG的氟硅双亲弹性防污涂层。随着PEG前驱物中PDMS链段长度增加，涂层疏水性提高，吸水率减少，在水中较稳定，且表面不易发生重排。而含氟前驱物的加入，使得亲水的PEG链段在疏水链段的推动下，向表面方向迁移形成水化层，并在弹性有机硅基体树脂良好脱附性能的协同作用下，赋予涂层优异的抗蛋白、抗菌、抗藻附着性能及实海防污性能。 . 上述结果不但为获得高性能的海洋防污材料用树脂提供了可靠的方法，而且制备的材料具有诱人的应用前景，有助于提高与国外高档海洋防污涂料产品的竞争力。