超支化环氧的合成及其对DGEBA的改性研究

发布时间：2018-03-20 15:47

  本文选题：环氧　切入点：超支化聚合物　出处：《北京化工大学》2016年硕士论文　论文类型：学位论文

【摘要】：环氧材料具有优异的力学、热学和电学性能,因而被广泛用于各个领域；但其不足的冲击韧性限制了其应用。它在涂料中用量很大,但在耐酸碱性和固化收缩方面还有待进一步提高。为了改善以上不足,设计合成了三种超支化聚合物,并将其应用于改性双酚A型环氧树脂,制备高性能环氧结构材料和功能防腐材料。以1,4-丁二醇二缩水甘油醚(A2)、三酚基甲烷(B3)和高活性端酚羟基四官能度单体(B4)为原料,分别用A2+B3和A2+B4法合成了两种超支化分子(HBP3和HBP4),研究了反应条件(如溶剂种类、单体投料比、反应温度和反应时间)对产物相对分子量及其分布的影响,并对其结构进行表征。把超支化环氧HBP4添加到E51/甲基纳迪克酸酐体系中进行增韧改性。当添加量为5%时,力学和热学性能达到最优,使得拉伸性能和冲击性能分别提高了26.3%和36.4%,Tg提高9.1℃。用几种无模型动力学方法分析了升温固化数据,发现添加HBP4可降低体系的活化能。将HBP4引入到E51/NX-2007涂料体系中,在未影响喷涂工艺的条件下制备出了高固含涂层,使得漆膜的硬度、附着力、冲击强度和耐介质性均有大幅度提高。以4,4’-二氟二苯砜(A2)、三羟甲基丙烷(B3)和3-甲基-3-羟甲基氧杂环丁烷制备超支化氧杂环丁烷POXEM,并对其结构进行表征。将POXEM作为改性剂,添加到E51/三氟化硼乙胺固化体系中,材料的Tg提高12℃,冲击性能提高22.8%。
[Abstract]:Epoxy materials are widely used in various fields because of their excellent mechanical, thermal and electrical properties, but their low impact toughness limits their application. In order to improve the acid-alkali resistance and curing shrinkage, three kinds of hyperbranched polymers were designed and synthesized and applied to the modified bisphenol A epoxy resin. High performance epoxy structural materials and functional anticorrosive materials were prepared. Two hyperbranched molecules, HBP3 and HBP4, were synthesized by A2B 3 and A2 B 4 methods respectively. The effects of reaction conditions (such as solvent type, monomer feed ratio, reaction temperature and reaction time) on the relative molecular weight and distribution of the product were studied. The hyperbranched epoxide HBP4 was added to the E51 / methyl-Nadidic anhydride system for toughening and modification. When the addition amount was 5, the mechanical and thermal properties were optimized. The tensile and impact properties were increased by 26.3% and 36.4Tg, respectively. The curing data were analyzed by several model-free kinetic methods. It was found that the activation energy of the system could be reduced by adding HBP4. HBP4 was introduced into the E51 / NX-2007 coating system. The high solid coating was prepared without affecting the spraying process, which made the film hardness and adhesion. The impact strength and dielectric resistance of hyperbranched oxybutane POXEMs were characterized by the preparation of hyperbranched oxybutane POXEMs using 4H4 (4-difluorodiphenylsulfone), trihydroxymethylpropane (B3) and 3-methyl-3-hydroxymethyl oxyoxyoxyoxybutane (3methyl-3-hydroxymethyl oxyoxybutane) as modifiers, and the structure of POXEMs was characterized by using POXEM as modifier. The TG of E51 / E3F3 curing system was increased by 12 鈩，

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