聚己内酯基生物降解高分子的合成与抗污性能的研究

发布时间：2018-01-15 21:05

本文关键词：聚己内酯基生物降解高分子的合成与抗污性能的研究　出处：《华南理工大学》2015年博士论文　论文类型：学位论文

【摘要】：本论文主要研究聚己内酯基可生物降解高分子的合成及其性质。我们利用阳离子开环聚合和自由基开环聚合,合成了聚己内酯均聚物和其共聚物;在此基础上,研究了其海洋抗污等性质。本论文的主要成果如下:1、用有机酸联萘酚磷酸酯(BPA)为催化剂、正辛醇为引发剂、甲苯为溶剂、85°C下开环聚合己内酯(?-CL),得到分子量可控且窄分布的聚己内酯(PCL)。反应动力学实验以及扩链实验证明该开环聚合是活性/可控的。我们发现仅用微量(ppm级)的BPA足以有效地催化该聚合反应,及其与乙交酯或丙交酯的共聚反应。2、2-亚甲基-1,3-二氧杂环庚烷(MDO)可以通过自由基开环聚合形成PCL结构。以AIBN为引发剂、70°C本体条件下,MDO、甲基丙烯酸甲酯(MMA)和三丁基硅基甲基丙烯酸酯(TBSM)发生自由基共聚合,形成可降解的聚(己内酯-co-甲基丙烯酸甲酯-co-三丁基硅基甲基丙烯酸酯)(PMSM)。从核磁共振氢谱(1H-NMR)得知:酯键结构被成功地引入到甲基丙烯酸硅共聚物碳-碳结构的主链中。我们发现:主链上酯键的引入提高了甲基丙烯酸硅共聚物的成膜性和热稳定性;在增加了共聚物膜的侵蚀速度的同时降低其溶胀性;此外,共聚物膜表面自抛光性能得以提高,防污剂的释放也得到适度的控制。实海挂板测试的结果说明主链酯键的引入能够提高甲基丙烯酸硅共聚物涂层的力学性能和抗海洋生物污损附着的能力。3、以AIBN为引发剂,80°C二氧六环溶液中,MDO、N,N-二甲氨基乙基甲基丙烯酸酯(DMAEMA)和γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)共聚,可一步合成自交联型可降解抗蛋白聚合物聚(己内酯-co-N,N-二甲氨基乙基甲基丙烯酸酯-co-γ-甲基丙烯酰氧基丙基三甲氧基硅烷)(MDK)。我们发现:DMAEMA的引入能改善聚合物的成膜性能,只是膜的热稳定性稍有降低;随着DMAEMA含量的增加,MDK膜的抗蛋白非特异性吸附性能和抗细菌粘附能力增加;MDK膜的降解速度降低;膜的溶胀性会有不同程度的增加。
[Abstract]:In this paper, the synthesis and properties of polycaprolactone biodegradable polymers were studied. The homopolymers and copolymers of polycaprolactone were synthesized by cationic ring-opening polymerization and free radical ring-opening polymerization. The main results of this paper are as follows: 1, using organic acid binaphthol phosphate as catalyst, n-octanol as initiator, toluene as solvent. Ring-opening polymerization of caprolactone at 85 掳C? -CL. The molecular weight controlled and narrow distribution of polycaprolactone (PCL) were obtained. The reaction kinetics and chain extension experiments proved that the ring-opening polymerization was active / controllable. BPA is sufficient to catalyze the polymerization effectively. The copolymerization of AIBN with glycolide or lactide. The structure of PCL can be formed by free radical ring-opening polymerization. AIBN is used as initiator. Free radical copolymerization of MDO, methyl methacrylate (MMA) and tributylsilyl methacrylate (TBSM) was carried out under 70 掳C bulk condition. Formation of degradable poly (caprolactone-methyl methacrylate-co-tributylsilyl methacrylate) PMSM. 1H-NMRs from 1H-NMRs. It was found that the ester bond structure was successfully introduced into the main chain of the carbon-carbon structure of silicon methacrylate copolymers. We found that the introduction of ester bonds in the main chain improved the film forming and thermal stability of the silicon methacrylate copolymers. The corrosion rate of copolymers was increased and the swelling property was decreased at the same time. In addition, the self-polishing properties of the copolymers were improved. The release of antifouling agent is also controlled moderately. The results of real sea board test show that the introduction of the main chain ester bond can improve the mechanical properties of silicone methacrylate copolymer coating and the ability to resist marine fouling and adhesion. 3. AIBN was used as initiator in 80 掳C dioxane solution. N-dimethylaminoethyl methacrylate (DMAEMA) and 纬 -methacryloxy propyl trimethoxysilane (KH570) were copolymerized. Poly (caprolactone-co-N), a self-crosslinking type of protein-resistant polymer, can be synthesized in one step. N-dimethylaminoethyl methacrylate (-co- 纬 -methacryloxypropyltrimethoxysilane) has been found to improve the film forming properties of the polymer. Only the thermal stability of the membrane decreased slightly; With the increase of DMAEMA content, the anti-protein nonspecific adsorption and anti-bacterial adhesion of the membrane increased. The degradation rate of MDK film was decreased. The swelling property of the membrane will increase in varying degrees.
【学位授予单位】：华南理工大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TQ317

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