【作者】 何腾云；

【导师】 戴李宗； 罗正鸿；

【作者基本信息】 厦门大学 ， 高分子化学与物理， 2008， 硕士

【摘要】 生物污损给人们带来了巨大的经济损失,防止海洋生物污损具有重要的现实意义。最简单,最有效的海洋防污方法当属海洋防污涂料技术,其中,防污效果最好,防污寿命最长的当属有机锡自抛光海洋防污涂料(TBT)。但是TBT对海洋环境造成了巨大的影响而逐渐被国际海事组织所禁用,正因为如此,国际上无毒环保型海洋防污涂层的研究日益热门起来。其中,低表面能无毒防污涂层由于其特殊的性能以及优异的环保性能而倍受人们关注。低表面能高分子涂层构造、降低成本与提高性价比研究是当前的重点。可用于制备低表面能防污涂料的树脂主要有氟碳树脂,有机硅树脂以及氟硅树脂三大类。其中,氟碳涂料和有机硅涂料都有工业化产品问世,但是,两者的性价比都很难令人满意。氟硅涂料并没有工业化产品出现,但是其性能更加优异,价格也比氟碳涂料低,因此,发展氟硅涂料具有更好的应用前景。在过去的文献报道中,氟硅低表面能聚合物一般由两种方法制备,一种方法是将聚硅氧烷氟化,另一种方法是将含有氟的乙烯基单体和含有硅氧烷成分的乙烯基单体进行共聚;通过这两种方法得到的聚合物存在一定的缺欠,比如结构不明确、分子量较低、表面能较高等等。本论文采用新型的合成方法,通过聚二甲基硅氧烷大分子引发剂直接引发含氟丙烯酸酯类单体的原子转移自由基聚合,得到了结构明确、分子量较高和较低表面能的新型氟硅嵌段共聚物;最终,我们合成了表面能很低的新型氟硅共聚物聚二甲基硅氧烷-b-聚甲基丙烯酸甲酯-b-聚七氟丁基甲基丙烯酸酯(PDMS-b-PMMA-b-PHFB-MA),其表面能可低至3.03 mN/m。其中,PMMA嵌段的加入不仅降低了含氟单体的使用量而且还降低了聚合物的表面能,我们认为三嵌段共聚物的微相分离是产生这一现象的重要原因,微相分离使得低表面能成分更容易迁移到聚合物表面,从而产生了更低表面能。更多还原

【Abstract】 The prevention of biofouling is of significance due to the great economic lost caused by biofouling. Among many marine antifouling technologies, marine antifouling coating is the easiest and most effective. Of many marine antifouling coatings, tetra-n-butyltin(TBT) self-polish marine antifouling coating is famous for the best effect and the longest life. International Maritime Organization has been gradually inhibiting the use of TBT on the basis of it’s bad effect on marine environment, so environmental friendly antifouling coatings become popular as the environment protection appeal from all over the word. People are paying more attention to antifouling coating with a low surface energy due to its particular merits and environmental friendly character. At present, the points are constructing polymer, cutting down cost, and improving Performance-price ratios.Siloxane polymers, fluorinated polymers, and fluorosilicone polymers can be used as antifouling coating with a low surface energy. Siloxane coating and fluorocarbon coating have been industrialized, but people are not satisfied with their Performance-price ratios. Although there is no fluorosilicone coating industrialized, with the better property and lower price, the application of fluorosilicone coating as antifouling coating is very promising. In previous literature, fluorosilicone polymers have been achieved mainly by two approaches: by fluorinating siloxanes, or by copolymerizing vinyl monomers containing fluorinated alkyl side groups and siloxane moieties. Polymers prepared by these methods exist some defects, such as random structure, low molecular weight, high surface energy, and so on.In this paper, we use a polydimethylsiloxane macroinitiator to initiate polymerization of methacrylate monomers with fluorinated side groups to prepare fluorosilicone copolymers which have well-defined structure, higher molecular weight, lower surface energy. Finally, poly(dimethylsiloxane)-block-poly(methyl methacrylate)-block-poly(2, 2,3,3,4,4,4-heptafluorobutyl methacrylate) (PDMS-b-PMMA-b-PHFBMA) triblock copolymers are synthesized, with a very low surface energy of 3.03 mN/m. The addition of PMMA block not only diminishes fluorine content but also decreases surface energy. In our opinion, microphase separation makes the low surface energy parts in the bulk easierly tend to segregate to the surface, results in more fluorine enrichment, and gives stronger hydrophobicity.更多还原