【作者】 冯是军；

【导师】 卿凤翎；

【作者基本信息】 东华大学 ， 纺织化学与染整工程， 2010， 博士

【摘要】 众所周知,含氟聚合物具有极低的表面自由能,优异的光学性能、电学性能、热稳定性和耐化学性,因此在织物整理、光纤涂层、微电子和防污剂等领域具有很好的应用前景。在海洋防污上,自从国际海事组织(IMO)在2003年开始禁用毒性的有机锡防污漆后,世界各国科学家都开始致力于研究和开发新型的环境友好型防污涂料或涂层作为替代品。其中含氟聚合物由于其较低的表面张力和环境友好性而倍受关注,但目前还没有性能很好的商品化的含氟产品出现。因此,找到能够提高海洋防污效果的技术和开发出具有潜在应用价值的含氟聚合物显得特别重要。在本论文中我们设计并合成了几种低表面能含氟共聚物,利用FT-IR、1H NMR、19F NMR、GPC、XPS等方法对聚合物的结构进行了表征,并在玻璃和金属表面制备了相应的涂层,最后对涂层表面进行了海洋防污性能测试。本论文我们先在实验室条件下对含氟涂层的抗菌性能(金黄色葡萄球菌和大肠杆菌)和抗藻性能(污损性硅藻)进行初步评价。之后,筛选出有潜在防污性能的聚合物来作为涂料用的功能性树脂,并将得到的涂料直接用于山东青岛海上的海上挂板实验。全文主要包括以下几个方面的工作。一、从苯乙烯和含氟烷基醇原料出发,通过三步反应合成了两种全氟烷烃取代的苯乙烯单体,再将此重要单体和甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯通过自由基溶液聚合反应得到含全氟烷烃取代的苯乙烯为侧链的预聚物,最后在紫外光照条件下,功能性环氧基团开环得到新型的交联的含全氟烷烃取代的苯乙烯为侧链的功能性聚合物。并采用自然界中普遍存在的金黄色葡萄球菌(革兰氏阳性)进行抑菌性测试和海洋中污损性较强的硅藻进行生物防污测试。二、合成了含全氟聚醚取代的疏水性苯乙烯单体,并设计合成含三乙二醇结构单元的亲水苯乙烯单体,再通过自由基聚合反应,得到一种新型含两亲性的聚合物,并对其性能进行探索性研究。我们采用自然界中普遍存在的大肠杆菌(革兰氏阴性)和金黄色葡萄球菌(革兰氏阳性)进行抑菌性测试。另外,采用室内挂板的方法研究新型功能性树脂的防生物附着性能。三、自组装技术在表面改性中的应用。我们利用自组装技术将含聚乙二醇和短链氟烷基单元的两亲性硫醇嫁接到铜片基底上,以期对金属表面进行改性,实现超薄防污膜的制备。我们用掠角红外反射光谱和X-射线光电子能谱(XPS)对硫醇自组装膜进行了表征,其结果证明两亲性自组装膜已被成功制备。最后用金黄色葡萄球菌和硅藻进行了生物测试,测试结果表明这类自组装膜都有很好的潜在防污性能。四、仿生聚合物的合成。我们结合了具有天然防污性能的磷酰胆碱(PC)和低表面能的全氟聚醚(PFPE)特点,通过乳液聚合合成了一系列新型的仿生聚合物。通过调节亲水性磷酰胆碱(PC)取代的丙烯酸酯单体和疏水性全氟聚醚取代的苯乙烯单体的比例,期望得到一种防污性能优异的仿生聚合物。通过分析常见菌的抑菌圈大小和硅藻吸附的细胞个数得出的结论是：聚合物8c、8d和8e防污性能较好。五、涂料配方的研究。以防污涂料中最核心的两部分：防污剂与成膜树脂为出发点,首先我们通过硫代、还原、酰胺化和氯化反应合成了异噻唑啉酮类化合物MI和CMI,并用它来代替被禁用的有机锡防污剂和有毒的氧化亚铜等无机重金属防污剂。然后在前面章节合成出的各类聚合物基础上,我们筛选出有潜在防污性能的聚合物4a-b以及8c-e作为主要成膜树脂。最后应用涂料知识,设计出以聚合物4a-b以及8c-e作为主要成膜树脂,以异噻唑啉酮类化合物MI和CMI为有机防污剂的涂料。并通过在青岛海上挂板测试,我们发现以聚合物4b为树脂的涂料AF-2和以聚合物8c为树脂的涂料AF-3的防污性能较好,有效期能达2个月以上。更多还原

【Abstract】 Fluorinated polymers have an extremely low surface energy, excellent optical and electrical properties, thermal stability and chemical resistance, so these polymers can be used in the fields of textile finishing, optical fiber claddings, microelectronics as well as antifouling agents. In the area of marine antifouling, scientists around the world have been making their efforts to research and develop novel environmentally benign marine antifouling paints or coatings since antifouling materials containing organotin derivatives have been banned by the International Marine Organization in 2003. Fluorinated polymers have been attracted by researchers due to their low surface tension and environmentally benign property. However, there are not effective fluorinated materials which can be used as marine coatings or paints on the market up to now, so it is very important for us to research and develop some novel promising functional fluorinated polymers capable as antifouling materials.In this dissertation, several classes of low surface energy fluorinated copolymers were designed, synthesized and characterized by FT-IR、1HNMR、19FNMR、GPC and XPS measurements. Then surfaces of slides and metals were coated with these polymers and their marine antifouling properties were evaluated by laboratory assays employing the fouling diatom Nitzschia and bacteria Staphylococcus aurous and Escherichia coli. After the primary biofouling investigation, some promising antifouling polymers were selected to be further used as the functional resins in the paints which were applied directly in the plate assay in the ocean of the coastal city---Qingdao, Shangdong province. Our work in the dissertation includes the following five parts.PartⅠ. Two important monomers---fluorinated styrenes were synthesized through three steps from chloromethylstyrene and fluoroalkylalcohol. And then, the monomers reacted with methyl methacrylate, glycidyl methacrylate through a free radical polymerization reaction to form methyl methacrylate-co-glycidyl methacrylate-co-semifluoroalkyl substituted styrene terpolymers 4a and 4b, finally the prepolymers 4a and 4b were cross-linked under the ultraviolet irradiation from a mercury arc lamp in the presence of an organic photo acid generator WPAG 336. The antifouling properties of the cross-linkable terpolymers containing semifluoroalkyl substituted aromatic side chains were assayed using the fouling diatom Nitzschia and ubiquitous Staphylococcus aureous.PartⅡ. The hydrophobic perfluoropolyether substituted styrene monomer and other styrene containing hydrophilic oligo(ethylene glycol) units were designed and synthesized. And then a novel amphiphilic copolymer was prepared by a free radical polymerization between the two monomers. The bacterial attachment experiments were carried out by using Escherichia coli and Staphylococcus aureous. Additionally, the further investigation of its antifouling property was studied employing the fouling diatom Nitzschia.PartⅢ.The application of assembling technology on surfaces’modification was studied. A series of amphiphilic alkanethiols containing poly(ethylene glycol) and short fluoroalkyl chains were synthesized and grafted on the surface of the copper to form a thin film which was then evaluated as an antifouling coating. From the results of GA-FTIR and XPS measurements on the resultant self-assembled layers, it can be concluded that films were successfully formed on copper substrates. Finally, results of biofouling assays using bacterial Staphylococcus aureous and diatom Nitzschia indicated the good antifouling properties of these self-assembled films.PartⅣ. A class of biomimetic polymers was synthesized and studied. A series of biomimetic polymers containing natural antifouling phosphorylcholine groups (PC) and low surface energy perfluopolyether (PFPE) unit were synthesized by means of emulsion polymerization. By changing the proportion of hydrophilic PC groups grafted acrylate monomer and hydrophobic PFPE substituted styrene, we expect to find some promising biomimetic copolymers. The results of the number of adhesive cells of bacteria and diatom on the substrates indicated that polymers 8c,8d and 8e have the excellent antifouling properties. PartⅤ. Research on coating formula of the paint. It has been known that the most important parts of antifouling paints are antifoulant and the film-forming resin, so based on the knowledge above, we first prepared 2-Methyl-4-isothiazoline-3-one (MI) and 5-chloro-2-methyl-4-isothiazoline-3-one (CMI) via a four-step synthetic protocol including addition, reduction, amidation and chlorination reactions. These organic compounds were designed as non-toxic antifoulants in place of the banned organotin compounds and toxic cuprous oxide. Then we try to select promising antifouling polymers 4a-b and 8c-e which were synthesized on the previous chapters as film-forming resins. Finally, antifouling paints were designed by using CM and CMI as antifoulants and polymers 4a-b,8c-e as film-forming resins. By plate assay in the ocean of Qingdao, it can be found that paints named AF-2 and AF-3 composed of resins 4b and 8c, respectively, have the best antifouling performances and be of effect for at least two months.更多还原