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有机硅氟低表面能防污涂料的制备和表征

Preparation and Characterization of the Organic Silicone/Fluorine Antifouling Coatings with Low Surface Energy

【作者】 桂泰江

【导师】 王修林;

【作者基本信息】 中国海洋大学 , 海洋化学, 2008, 博士

【摘要】 传统的毒剂型防污涂料在防止海洋生物污损的同时,也给海洋环境带来了严重的污染,随着海洋环境保护呼声的日益高涨,研究开发无毒防污涂料势在必行。本文针对目前国内无毒防污涂料开发相对落后,产品严重缺乏的问题,研制了无毒低表面能有机硅防污涂料,并针对其机械性能差的缺陷,合成了有机氟低表面能防污涂料用基体树脂—含氟丙烯酸酯类共聚物,并对共聚物的结构和涂层的表面性能进行了表征。本文首先制备了不同颜基比以及添加不同种类硅油的低表面能有机硅防污涂料,利用测定水滴在涂层表面的接触角、弹性模量、静态实海挂板、AFM、SEM、EDX等手段对低表面能有机硅防污涂料进行详细的性能表征,在其表征过程中提出了模拟海生物附着力实验室评价方法。同时对其防污机理进行了分析,然后对与之配套的有机硅体系中间连接层进行了研究。结果发现:(1)污损海生物附着强度大致与涂层表面能和弹性模量乘积的二分之一次方成正比,而对表面能以及弹性模量的调控可通过颜基比的改变来实现。合适的颜基比不仅能够赋予有机硅防污涂层足够的机械强度以及合适的弹性模量,而且能够形成与表面化学组成相匹配的微观几何结构,有效降低其表面能,最终使得污损海生物附着力降低、防污性能提高;(2)高苯基含量的PDMDPS硅油能够扩散迁移到涂层的表面,并减弱污损海生物附着强度,进而改善涂层防污性能;(3)低表面能有机硅防污涂料难以阻止海洋生物污损过程的发生,但能够降低污损海生物附着强度,同时硅油的渗出能够协助涂层减弱海洋生物污损过程第一阶段的发生。并且当海洋环境不再适宜污损海生物生长时,海生物会主动从低表面能有机硅涂层表面脱落。经过海水的冲刷作用,涂层仍能保持较好的表面状态;(4)以分子量较大、表面能较高的有机硅树脂为基体树脂,并添加双氨基硅烷偶联剂制备的有机硅中间连接层,与环氧防腐底漆的粘结强度良好,同时有利于表面能较低的有机硅防污面漆的涂覆。针对低表面能有机硅防污涂料机械性能差的缺陷,采用自由基共聚合的方法合成了适用于有机氟低表面能防污涂料的基体树脂—含氟丙烯酸酯类共聚物,利用GPC,IR和H-NMR对得到的共聚物进行了表证,通过测定水滴在漆膜表面的接触角、扫描电子显微镜、XRD散射能谱分析等,研究带有不同全氟烷基丙烯酸酯类单体种类以及含量对漆膜表面性能的影响,结果发现:(1)当含氟丙烯酸酯的用量一定时,具有长烷基侧链更有利于氟原子在漆膜表面的富集,因而具有更低的表面能;(2)对共聚物来说,当含氟单体用量小于3%时,随着含氟单体用量的增加,氟原子自动富集在材料的表面,引起材料表面能显著降低;当含氟单体用量超过3%时,由于氟原子在材料表面基本达到饱和,继续增加含氟单体的用量,材料的表面能没有显著的变化。本文在无毒低表面能防污涂料的研究方面做了大量基础性研究工作,取得了诸多进展,为我国研发具有自主知识产权的无毒有机硅氟低表面能防污涂料做好了理论上的准备,并为其产业化奠定了基础。

【Abstract】 Traditional toxic antifouling coating can prevent the pollution of the marine organisms, at the same time, it also causes serious pollution to the marine environment. As the voice of protection of the marine environment is increasing, the research and development of non-toxic antifouling paint is imperative. However, in china, the development of non-toxic antifouling coatings is low, and the good products is unavailable. In this paper, we prepared the organic silicon non-toxic antifouling coating with the low surface energy, and synthesized the copolymer containing fluorinated acrylic resin in order to improve the mechanism. And, the structure of the copolymer and the property of the coatings were characterized.In this paper, we firstly prepared the organic silicon antifouling coatings with different ratio of the dyes and various kinds of silicon oil. The proprieties of the organic silicon coatings were characterized by measuring the contact angle of the droplet water on the surface of the coating, modulus of elasticity, the simulated biological adhesion, applying static link plate, AFM, SEM and EDAX. We found a new method for measuring the simulated biological adhesion in lab. And the antifouling theory of the organic silicon coatings was analyzed, and a complete set of the organic silicon system for the middle connecting layer was studied. The results showed that: (1) the strength of the defaced marine biology is broadly proportional to the square of the produce of coating’s surface energy and elastic modulus, which can be adjusted by changing the ratio of the dye to the radical polymer. The proper ratio of the dye to the radical polymer not only can give the antifouling films the well mechanism and elastic modulus, but also decrease of the surface energy of the entire system leading to advance of antifouling performance by forming the micro-structure with same the chemical compose.(2)PDMDPS silicone oil with high content of phenyl can diffuse to the surface of the coating, and weaken the adhesive strength of the defaced marine biology, thereby improving the performance of the antifouling coating; (3) the organic silicone antifouling coating with low surface energy can’t prevent defacing process as to marine biology, but it can reduce the adhesive strength of marine biology, and the effusion of the silicone oil can help coating prevent the first stage of the process of the defacement of the marine biology. And when the marine environment is no longer suitable for the growth of the halobios, it will drop from the surface of the organic silicone antifouling coating with low surface energy. After scouring of the sea water, the surface of the coating can still maintain in good condition; (4) When the organic silicone resin with large molecular weight and high surface energy is used as basic resin and organic silicone joining mesosphere made from dual-amino-silane coupling agent is used as the middle layer, it has good bond strength with the anti-corrosion epoxy coating and makes for the coating of organic silicone antifouling paint with low surface energy.In order to improve mechanic properties of the organic silicon antifouling coatings with low surface energy, the various acrylate copolymers with the side-chain containing alkyl full of fluorine was synthesized by the method of radical polymerization, which can be used as the basic resin for make the organic fluorined antifouling coatings with low surface energy. The copolymer is characterized with the technology of GPC, IR and H-NMR, through measuring the contact angle of the droplets on the surface of the coating, scanning electron microscopy, XRD analysis of scattering spectroscopy, the impact of different kinds and the dosage of acrylate monomer with different alkyl full of fluorine to the surface properties of the coating was studied. It is found that: (1) when the amount of acrylate with fluorine is invariable, long alkyl side chains make for the massing of the fluorine atoms on the surface of the paint film, and it leads to lower surface energy; (2) so as to copolymer, when the amount of fluorinated monomers is less than 3%, as the amount of fluorinated monomers increases, fluorine atom assembles on the surface of material, causing that the surface power of the material significantly decreases; when the amount of the fluorinated monomers was in excess of 3%, as fluorine atoms on the material surface basically reaches saturation, even the amount of fluorined containing monomers continues to increase, there is no noticeable change to the surface energy of the material.In this paper, a lot of the basic research work has been made in the non-toxic antifouling coatings with low surface energy and a lot of progress was made. That can make theoretical preparations for the development of non-toxic antifouling coatings in china, and can be helpful for the foundation for the industrialization of the fluorine/ organic silicon low surface energy antifouling coatings which with the independent intellectual property rights.

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