多巴胺改性制备复合树脂新型填料及其应用研究

发布时间：2018-01-17 22:06

本文关键词：多巴胺改性制备复合树脂新型填料及其应用研究　出处：《北京化工大学》2015年硕士论文　论文类型：学位论文

【摘要】：生物粘附分子表面改性常常被引入到复合材料界面改性中。多巴胺是一种海洋粘附蛋白,富含儿茶酚基团,能粘附在性质各异的基体表面,甚至包括聚四氟乙烯。基于这种分子的表面改性技术,能够增强复合材料增强体和树脂的界面强度,并且这种生物粘附剂在口腔湿润环境下仍然具有良好的粘结作用。更重要的是,采用这种方法处理齿科修复材料,不会引起生物相容性方面的担忧。因此,本论文采用多巴胺对玻璃纤维以及纳米二氧化硅表面进行处理,并与光固化树脂复合,提高了有机-无机复合材料界面性能,获得了高浸润度纤维增强树脂复合材料,可用于残根残冠的桩核治疗修复。主要工作如下：(1)通过多巴胺氧化聚合改性和聚甲基丙烯酸甲酯(PMMA)吸附这两种表面处理方法,制备了数种(多巴胺改性、PMMA包覆、多巴胺改性/PMMA包覆)玻璃纤维,通过XPS、Raman和SEM表征,证实了证明了目标改性聚合物在玻璃纤维表面的包覆；以原始玻璃纤维为对照,制备了纤维增强光固化树脂(Bis-GMA/TEGDMA)复合材料,通过“三点弯”测试、断面形貌观察、DMTA分析和拔出实验,发现：改性纤维与树脂基的界面粘结均优于未处理的玻璃纤维,其中,经多巴胺改性、然后又吸附PMMA的玻璃纤维增强光固化树脂复合材料的界面性能最佳。解释是,富含儿茶酚等官能团的聚多巴胺与玻璃纤维以及PMMA层,通过螯合、氢键等作用粘附良好,而PMMA分子链与Bis-GMA/TEGDMA树脂具有一定互溶性,树脂经光照固化后,可在界面处半互穿网络,形成良好的界面粘结。将两种改性方法联合应用,可以获得最大的界面粘结强度。(2)采用Stober法制备了二氧化硅纳米粒子,并成功地用多巴胺氧化聚合进行了包覆改性,基于多尺度多维度增强的思路,将多巴胺包覆的二氧化硅纳米粒子预吸附到多巴胺改性玻璃纤维表面,然后一起作为光固化树脂的增强体。发现：与单纯多巴胺改性玻璃纤维增强复合材料比较,表面预吸附了二氧化硅纳米粒子玻璃纤维增强的复合材料,经DMTA测试Tg升高,证实其具有更好的界面粘结。原因是,在玻璃纤维表面的二氧化硅纳米粒子,可能起到了“锚”的连接作用,更能限制分子链的运动,提高界面粘结。本论文在树脂基口腔修复复合材料研究中,引入多巴胺这种高效简单的生物粘附分子表面处理方法,改善了增强体和树脂之间的界面粘接力,提高了复合材料的力学性能。研究结果可为其他应用的有机-无机复合材料界面改性提供参考。
[Abstract]:Surface modification of bioadhesive molecules is often introduced into the interfacial modification of composite materials. Dopamine is a kind of marine adhesion protein rich in catechol-group and can adhere to the matrix surface with different properties. Even PTFE. Surface modification techniques based on this molecule can enhance the interfacial strength of composite reinforcements and resins. And this kind of bioadhesive still has good adhesive effect in the moist environment of oral cavity. More importantly, using this method to deal with dental repair materials will not cause biocompatibility concern. In this paper, the surface of glass fiber and nano-silica was treated with dopamine, and the interface properties of organic-inorganic composites were improved. Fiber reinforced resin composites with high wettability were obtained. It can be used for the treatment of residual root and crown. The main work is as follows: 1) modified by dopamine oxidation polymerization and PMMA adsorption. Several kinds of glass fibers (dopamine modified PMMA and dopamine modified PMMA) were prepared and characterized by SEM and Raman spectra. It is proved that the coating of the target modified polymer on the glass fiber surface. The fiber reinforced light-cured resin Bis-GMA / TEGDMA composite was prepared by using the raw glass fiber as the control. The "three-point bending" test was carried out and the section morphology was observed. DMTA analysis and pull-out experiments showed that the interfacial bond between the modified fiber and the resin base was better than that of the untreated glass fiber, and the modified fiber was modified by dopamine. The interfacial properties of glass fiber reinforced light-cured resin composites adsorbed on PMMA are the best. The explanation is that polydopamine rich in catechol and other functional groups chelate with glass fiber and PMMA layer through chelation. Hydrogen bond adhesion is good, while PMMA molecular chain and Bis-GMA/TEGDMA resin have a certain mutual solubility, the resin can be cured by illumination, the semi-interpenetrating network at the interface can be obtained. When the two modification methods were combined, the maximum interfacial bond strength could be obtained. (2) silica nanoparticles were prepared by Stober method. The dopamine coated silica nanoparticles were preadsorbed on the surface of dopamine modified glass fiber based on the idea of multi-scale and multi-dimensional enhancement. It was found that compared with pure dopamine modified glass fiber reinforced composites, silica nanoparticles were preadsorbed on the surface of glass fiber reinforced composites. The increase of TG by DMTA test shows that it has better interfacial bond, because the silica nanoparticles on the surface of glass fiber may act as "anchor". In this paper, dopamine is introduced into the study of resin based dental repair composites, which is an efficient and simple biological adhesion molecular surface treatment method. The interfacial adhesion between reinforcements and resins was improved and the mechanical properties of composites were improved. The results can be used as reference for the interface modification of organic-inorganic composites.
【学位授予单位】：北京化工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB332

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