【作者】 俞豪杰；

【导师】 王立；

【作者基本信息】 浙江大学 ， 高分子化学与物理， 2006， 博士

【摘要】 环氧树脂是一种重要的热固性树脂，以其优异的力学、粘结和绝缘等性能被广泛应用于电子、机械、建筑、轻工等领域。本文对各种纳米材料对环氧树脂的改性，新型液晶环氧树脂、有机硅环氧树脂、阻燃环氧树脂和二茂铁基环氧树脂的合成以及环氧树脂在粉末涂料、胶粘剂、生物分子固定等领域的应用等环氧树脂领域的研究热点进行了综述；开展了无机纳米微粒改性环氧树脂的制备和新型功能环氧树脂的合成研究；探索了所得环氧树脂在粉末涂料、修饰电极、自组装等领域的应用；探讨了其无机纳米微粒改性、电化学过程和自组装等的机理，取得了以下主要研究成果：本文建立了1种通过原位及包裹聚合法制备无机纳米微粒改性双酚A型环氧树脂的新工艺，制得了系列无机纳米微粒改性环氧树脂；该工艺由于在单体聚合前加入无机纳米微粒，此时单体可以渗透到无机纳米微粒之间，在聚合过程中环氧树脂在无机纳米微粒之间及周围生成，把已分散的无机纳米微粒包裹其中，所以能够制得无机纳米微粒分散均匀的改性环氧树脂；通过对比实验发现用本工艺制得的无机纳米微粒改性环氧树脂中无机纳米微粒的分散性明显好于通过溶液共混法或熔融共混法制得的同类样品；由于分散良好的无机纳米微粒与环氧树脂分子之间具有相互作用，用原位及包裹聚合法制得的无机纳米微粒改性环氧树脂与未改性环氧树脂相比，nano-CaCO₃含量为15.0 wt％的改性环氧树脂的软化点提高了15℃、nano-CaCO₃的含量为10.0 wt％的固化的改性环氧树脂的断裂伸长率提高了近3倍，拉伸模量在nano-CaCO₃的含量为5.0 wt％时达到最大值，提高了18％；经过中试及工业化试验，实现了无机纳米微粒改性双酚A型环氧树脂的工业化生产；所得无机纳米微粒改性双酚A型环氧树脂可用作粉末涂料的原料。采用通过原位及包裹聚合法制得的无机纳米微粒改性双酚A型环氧树脂为主要原料制得了无机纳米微粒改性环氧粉末涂料；完成了中试和扩试研究，建立了千吨级年生产能力的无机纳米微粒改性环氧粉末涂料示范生产线；所得无机纳米微粒改性环氧粉末涂料的储存稳定性达到1级、耐中性盐雾性能达到1级、反向抗冲击性能超过50 Kg．cm、断裂伸长率达到2.9％、边角覆盖率达到75％、耐阴极剥离性能为6.8 mm，主要性能指标和同类未改性环氧粉末涂料相比有了显著提高。合成了2种不同结构的二茂铁基环氧树脂，通过¹H NMR和FT-IR对所得产物的结构进行了表征；用循环伏安（CV）法研究了所得二茂铁基环氧树脂溶液和膜的电化学行为，峰电流和扫描速率之间的关系表明其电极反应受扩散控制，符合Fick定律；根据Ozawa理论对二茂铁基环氧树脂1，1’-二茂铁二甲酸二缩水甘油酯／双氰胺体系的非等温固化过程进行了研究，发现该固化体系的反应活化能约为531 KJ／mol；二茂铁基环氧树脂在固体火箭推进剂的燃速催化剂和修饰电极等方面表现出了很好的应用前景。合成了带含环氧基侧链和十八烷基侧链的聚（马来酸二缩水甘油酯-co-甲基丙烯酸十八酯）[P（DGMA-co-SMA）]，用¹H NMR对所得的共聚物进行了表征；研究了其在选择性溶剂中的自组装行为，发现P（DGMA-co-SMA）／THF／EtOH体系可以通过自组装形成囊泡形自组装体和支化的管状自组装体，P（DGMA-co-SMA）／THF／H₂O体系最初自组装形成球形自组装体，随着陈化时间的延长，球形自组装体逐渐融合成长条形自组装体和线形自组装体；探讨了自组装过程的机理，建立了可能的自组装过程模型。合成了1种新的二茂铁基树枝状分子4-Fc，用¹H NMR和FT-IR对所得产物的结构进行了表征；用循环伏安法研究了4-Fc在不同溶剂中的电化学行为，发现溶剂的极性和溶剂形成氢键的能力会对其溶液电化学行为产生很大影响，4-Fc和溶剂氢键作用的存在使其电化学行为变得比较复杂；通过CV和UV法研究发现4-Fc对H₂PO₄^-有较好的识别作用；探讨了该体系离子识别的机理。更多还原

【Abstract】 Epoxy resin is an important thermoset. It is widely use in the fields of electron, machine, architecture and so on for its outstanding mechanical, adhesive and insulative properties. In this paper, progress in nano-modification of epoxy resin, synthesis of functional epoxy resin and applications of epoxy resin was reviewed. Inorganic nanoparticle modified epoxy resins and novel functional epoxy resins were prepared and characterized. Applications of the resultant epoxy resins in powder coating, electrode modification and self-assembly were investigated and the mechanisms were discussed.A novel method to prepare inorganic nanoparticle modified bisphenol A epoxy resin through in situ and inclusion polymerization was investigated. In this method, nanoparticles were added and dispersed in the system before polymerization, so the monomers could penetrate into the space among the nanoparticles. Epoxy resin grown both between and around the nanoparticles during polymerization, and nanoparticle modified epoxy resin with uniform dispersed nanoparticles in the matrix was obtained as a result. Compared with the samples prepared by blending or solution blending, the dispersion of nanoparticles in the samples prepared through in situ and inclusion polymerization was better as observed by TEM. As for the nanoparticle modified epoxy resin prepared through in situ and inclusion polymerization, the softening point was increased by 15 ℃ when 15.0 wt% of nano-CaCO₃ was loaded, the stretch strain of the cured sample with 10.0 wt% of nano-CaCO₃ was increased by nearly 3 times and the elastic modulus reached its maximum value when the nano-CaCO₃ content was 5.0 wt% owing to the interactions between the well dispersed nanoparticles and the epoxy resin chains. The industrial production of nanoparticle modified epoxy resin was realized after pilot plant experiments. The obtained nanoparticle modified bisphenol A epoxy resin can be applied in powder coating.Inorganic nanoparticle modified epoxy powder coatings were prepared using the nanoparticle modified epoxy resin obtained through in situ and inclusion polymerization as main component. The industrial production of nanoparticle modified epoxy powder coating was realized after pilot plant experiments. The storage stability and neutral salt spray corrosion resistance of the obtained nanoparticle modified epoxy powder coating were rating 1. The impact resistance was better than 50 Kg.cm. The tensile strain was 2.9 %. The angle coverage was 75 % and the cathodic disbondment resistance was 6.8 mm.Two ferrocene-based epoxy resins with different structures were prepared and characterized.The electrochemical behaviors of their films and solutions were investigated by cyclic voltammetry （CV） measurement. The relationship between the CV peak current values and the scan rate indicated that the charge transport through the films obeyed Fick’s Law and the electrode processes of the films were controlled by diffusion. The curing behavior of GEFDC/ dicyandiamide system was investigated by nonisothermal measurement according to Ozawa’s approach. The ferrocene-based epoxy resins have promising applications in the fields such as burn-rate catalyst for composite solid propellants and electrode modification.A novel polymer of Poly（diglycidyl maleate-co-stearyl methacrylate） [P（DGMA-co-SMA）] was synthesized and its structure was characterized by ¹H NMR. Its self-assembly behavior was studied in different solvents. It was found that vesicles and tubule-liked aggregates can be obtained through self-assembly of P（DGMA-co-SMA）/THF/EtOH system. And spheral aggregates were obtained in P（DGMA-co-SMA）/THF/H₂O system while the spheral aggregates were converted into rod-liked aggregates and line-liked aggregates after aged for different time. The mechanism of the self-assembly behavior was discussed.A dendritic ferrocene derivative （4-Fc） was synthesized and its structure was characterized by ¹H NMR and FT-IR. Its electrochemical behaviors ware investigated by CV measurement. The recognition of H₂PO₄^- by 4-Fc was investigated by CV and UV measurements. The mechanism of the ion recognition was discussed.更多还原