【作者】 冯泽峰；

【导师】 王明刚；

【作者基本信息】 山东大学 ， 应用化学， 2011， 硕士

【摘要】 含氟丙烯酸树脂是指传统丙烯酸树脂的主链或者侧链上的氢原子被氟原子取代后的聚合物。含氟丙烯酸树脂具有良好的成膜性、强憎水性、化学稳定性、热稳定性、抗氧化性、生物相容性以及良好的气体渗透性,这些性质使其在许多领域都得到了很好的应用,有效地改善了传统丙烯酸树脂所存在的耐水性差、低温变脆、高温易发黏等弱点。目前开发的含氟丙烯酸树脂主要是以全氟辛烷磺酸基化合物(PFOS)和全氟辛酸(PFOA)为原料制备的,但在降解过程中会生成难降解的全氟烷基羧酸和磺酸类化合物,对环境和人体具有较大的危害。欧洲议会于2006年12月2日发布了关于限制PFOS的2006/122/ECOF法令,严格限制PFOS及其相关产品的销售和使用。另外,这类树脂的难降解性与氟碳链长度成正比,因此含短氟碳链的高性能树脂的研究成为一个重要的课题。本课题从3-(全氟正己基)环氧丙烷(PFOP)出发合成了多种含全氟己基侧链的甲基丙烯酸酯单体；通过1HNMR、13CNMR、19FNMR及元素分析法对其进行了表征。选取其中两种含氟单体(FMA)与甲基丙烯酸丁酯(BMA)、丙烯酸丁酯(EA)聚合得到了三元共聚物,通过IR、DSC、SEM等对其涂膜性能进行了初步研究。结果表明,全氟己基侧链的引入能有效提高涂膜的拒水能力和耐高温性能；芳香环的引入提高了涂膜的硬度；利用热场发射扫描电镜对聚合物薄膜截面的氟元素含量进行了分析,结果表明,退火工艺有助于含氟基团更好的向表面迁移,氟元素沿截面呈梯度分布。本课题采用了PFOP开环制备含氟醇,合成方法简单,为今后实验室单体制备提供了一种较为简便的方法。本课题合成的聚合物在具有已知含氟丙烯酸酯聚合物特点的基础上,同时具有易降解、对环境污染小、对颜料、填料的附着力好的优点,综合性能良好,预期可作为防水涂料,具有较好的应用前景。更多还原

【Abstract】 Fluorine-containing acrylic resins are the acrylic resins whose hydrogen atoms on the main or chain are replaced by the fluorine atoms. They have been widely used for their excellent properties of film forming, hydrophobic property, chemical stability, thermal stability, oxidation resistance, biocompatibility and gas permeability. Thus effectively improve the weakness such as poor water resistance, low temperature brittle and prone to high temperature of the traditional acrylic resins.The degradation process of the current fluorine-containing acrylic resins would produce persistent organic pollutants:perfluoroalkyl carboxylic acids and sulfonic acids, which result environmental pollution and illness. European Parliament issued a decree (2006/122/ECOF) on the restriction of PFOS on December 2,2006:PFOS and the related products must be strictly limited both in business and application. In addition, the recalcitrance of the resins is directly proportional to the length of the fluorocarbon chains.Starting from 3-perfluorohexyl-1,2-epoxypropane (FHOP), several fluorinated acrylate monomers containing tridecafluorohexane were obtained in this paper; The monomers were characterized by 1H NMR,13C NMR and 19F NMR. Fluoroacrylate copolymers P(FA-BMA-EA) were successfully synthesized by solution polymerization. IR, DSC, GPC, and SEM were used in investigating the copolymer films. The results show:The addition of tridecafluorohexane can increase the water and heat resistance; while the aromatic ring increase the heat resistance and the rigidity of the films. The Thermal Field Emission SEM was used in analyzing the distribution of fluorine on the cross-section of the films. The results show that the annealing process helps the fluoride groups migrate to the surface better, and fluorine distributes graded along the cross-section.Fluorinated alcohols were obtained by the ring opening reaction of PFOP in this paper. The synthesis process is simple for preparing fluorinated acrylate monomers.Besides the features of the traditional acrylic resins, the copolymers prepared in this paper also had good performance as easy-degradation, low-pollution, excellent-adhesion, and is expected to be used as waterproof coating.更多还原