【摘要】：聚合物薄膜的表面性質(zhì)在涂層、密封以及生物相容性材料等領(lǐng)域起著至關(guān)重要的作用。材料的表面性質(zhì)是由其表面最外幾層分子結(jié)構(gòu)所決定,包括最外層基團(tuán)的排列。甲基是聚合物中普遍存在的基團(tuán),且表面能較低。在成膜過程中,往往在表面有較強(qiáng)的富集能力。表面甲基的排列結(jié)構(gòu)會(huì)影響蛋白質(zhì)吸附、血小板粘附以及血栓形成等相關(guān)性質(zhì)。所以研究聚合物中甲基在薄膜表面的有序化排列過程及其影響因素,對(duì)薄膜表面結(jié)構(gòu)的設(shè)計(jì)和調(diào)控有重要的指導(dǎo)意義。本論文以和頻振動(dòng)光譜(SFG)和界面紅外反射吸收光譜(PM-IRRAS)為主要研究手段,研究了側(cè)鏈長(zhǎng)度、與主鏈連接的間隔基團(tuán)及α-甲基對(duì)聚合物單分子膜、Langmuir-Blodgett膜和澆鑄膜表面?zhèn)孺溎┒思谆行蚧^程的影響。得到以下結(jié)論:(1)對(duì)于聚丙烯酸甲酯(PMA)、聚丙烯酸乙酯(PEA)和聚丙烯酸丁酯(PBA),烷基側(cè)鏈越長(zhǎng),酯基側(cè)鏈末端甲基在其單分子膜、LB膜以及澆鑄膜表面的富集能力越強(qiáng),排列有序度增加越快。原因是由于PBA的烷基側(cè)鏈較長(zhǎng),酯基的占比較少,其極性作用相對(duì)較弱。從而使得丁酯基側(cè)鏈有較強(qiáng)的運(yùn)動(dòng)能力,丁酯基側(cè)鏈末端甲基更容易往表面富集,排列有序度快速增大。對(duì)于聚甲基丙烯酸甲酯(PMMA)、聚甲基丙烯酸乙酯(PEMA)和聚甲基丙烯酸丁酯(PBMA),烷基側(cè)鏈越短,酯基側(cè)鏈末端甲基在單分子膜、LB膜以及澆鑄膜表面的富集能力越強(qiáng),排列有序度增加越快。原因是因?yàn)镻BMA的丁酯基側(cè)鏈體積相對(duì)較大,α-甲基的位阻效應(yīng)對(duì)丁酯基側(cè)鏈的限制更加明顯,嚴(yán)重阻礙了丁酯基側(cè)鏈的有序排列。從而導(dǎo)致PBMA的丁酯基側(cè)鏈末端甲基不容易往薄膜表面富集。(2)研究了與主鏈連接的間隔基團(tuán)對(duì)側(cè)甲基在單分子膜、LB膜和澆鑄膜表面富集行為及其有序性排列的影響。以聚乙烯基甲基酮(PVMK)、聚乙烯基甲醚(PVME)、聚丙烯酸甲酯(PMA)和聚醋酸乙烯酯(PVAc)為研究體系。發(fā)現(xiàn)羰基和醚基連接的側(cè)甲基在其單分子膜、LB膜和澆鑄膜表面的富集能力較強(qiáng),排列有序度增加較快。酯基和乙�；B接的側(cè)甲基在單分子膜、LB膜和澆鑄膜表面的富集能力較弱,排列有序度增加較慢。原因可能是因?yàn)橄啾扔隰驶兔鸦?酯基和乙�；臉O性更強(qiáng),它們連接的側(cè)甲基柔性小。因而酯基和乙�；B接的側(cè)甲基運(yùn)動(dòng)能力較弱,不太容易往表面富集。
[Abstract]:The surface properties of polymer films play an important role in coating, sealing and biocompatibility materials. The surface properties of the material are determined by its outermost molecular structure, including the arrangement of the outermost groups. Methyl is a common group in polymers, and the surface energy is low. In the process of film formation, there is a strong enrichment ability on the surface. The structure of surface methylation affects the properties of protein adsorption, platelet adhesion and thrombosis. Therefore, it is of great significance to study the ordered arrangement of methyl in the polymer and its influencing factors for the design and regulation of the surface structure of the film. In this thesis, the sum frequency vibrational spectrum (SFG) and the interface infrared reflectance absorption spectroscopy (PM-IRRAS) were used to study the length of side chain, the spacer groups connected to the main chain and the 偽 -methyl-pair polymer monolayers. Effects of side chain end Methyl ordering on the Surface of Langmuir-Blodgett Film and cast Film. The following conclusions are obtained: (1) the longer the alkyl side chain of polymethyl acrylate (PMA),) ethyl acrylate (PEA) and polybutyl acrylate (PBA), the end methyl group of the ester side chain is in its monolayer membrane. The stronger the enrichment ability of LB film and casting film is, the faster the order of arrangement increases. The reason is that the alkyl side chain of PBA is longer, the proportion of ester group is less, and the polarity of PBA is relatively weak. Therefore, the butylated side chain has a strong mobility, and the methyl group at the end of the butyl side chain is easier to enrich to the surface, and the ordering degree increases rapidly. The shorter the alkyl chain of poly (methyl methacrylate) (PMMA), polyethyl methacrylate (PEMA) and polybutyl methacrylate (PBMA), the stronger the enrichment ability of methyl ester on the surface of monolayer, LB film and cast film. The faster the order of arrangement increases. The reason is that the volume of butyl side chain of PBMA is relatively large, and the steric resistance effect of 偽 -methyl has more obvious limitation on butyl side chain, which seriously hinders the ordered arrangement of butyl side chain. As a result, the butylated side chain end methyl of PBMA is not easy to enrich on the surface of the film. (2) the effect of the opposite side methyl groups connected with the main chain on the surface enrichment behavior and ordered arrangement of monolayer, LB film and cast film are studied. Polyethylene methyl ketone (PVMK),) polyethylene methyl ether (PVME),) polymethyl acrylate (PMA) and poly (vinyl acetate) (PVAc) were used as study systems. It was found that the side methyl group connected with carbonyl group and ether group had strong enrichment ability on the surface of monolayer, LB film and casting film, and the order degree of arrangement increased rapidly. On the surface of monolayers, LB films and cast films, the side methyl groups connected with ester and acetyl groups have weak enrichment ability, and the order degree of arrangement increases more slowly. The reason may be that the polarity of ester group and acetyl group is stronger than that of carbonyl group and ether group. As a result, the side methyl group connected with ester group and acetyl group has weak mobility and is not easy to enrich on the surface.
【學(xué)位授予單位】：浙江理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O631;TB383.2

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