介孔材料-氧化石墨烯复合纳米粒子协同增强改性不饱和聚酯复合材料的研究

Using various inorganic nanomaterials to reinforce polymer matrix composites is becoming a research hot spot all over the world. The key scientific problem needed to be solved in this field is the interfacial interaction between the inorganic particles and the polymer matrix. In this proposal, grafting reactions of the surface hydroxyl groups of mesoporous nanomaterials(MC) and graphene oxide (GO) are carried out with organic silicon compounds, to synthesis composite nanoparticles (named as MC-g-GO), which are employed to parepare MC-g-GO/UP composites by in situ polymerization, in order to enhance the adhesion between inorganic particles and polymer matrix. The MC-g-GO/UP nanocomposite materials are fabricated by blending, extruding and palletizing in sequence. Investigations will focus on:(1)the effects of the morphology of mesoporous silica and grafting reaction process on the structure and properties of grafting products;(2)the influences of the surface dispersion and in situ polymerization conditions on the the structure and properties of MC-g-GO/UP composite resin;(3)the influences of the blending methods, processing conditions and curing process on the performances of MC-g-GO/UP nanocomposite materials.More efforts will be paid to solve the problem occurred in the grafting reaction between mesoporous silica and graphene oxide, the in situ polymerization with UP, the control on the structure of the reaction products, as well as the fabrication and molding technology of MC-g-GO/UP nanocomposite materials,in order to achieve a good interfacial interaction between mesoporous silicon-GO and UP, to form a organic- inorganic interpenetrating.Through our research,the mechanism on the synergetic enhancement of composite nanostructures in the polymer matrix will be clarified, which offers the fundamental theory for the fabrication of high performance UP composites for electric purposes.

采用无机纳米材料增强聚合物基复合材料是目前国内外的研究热点。纳米粒子与聚合物基体之间的界面作用始终是该领域有待解决的关键科学问题。本课题提出利用介孔材料(MC)和氧化石墨烯(GO)与有机硅化合物进行接枝化学反应，制备复合纳米粒子(MC-g-GO)，将其与UP单体进行原位聚合，合成UP复合树脂（MC-g-GO/UP）。再经熔融辊炼、挤出造粒，制备MC-g-GO/UP复合材料。重点研究：不同结构形态介孔硅、反应工艺对接枝产物结构和性能的影响；分散方法、原位聚合反应条件对UP复合树脂结构和性能的影响；共混加工方法、成型条件、固化工艺等对UP复合材料性能的影响。重点解决：MC-g-GO的接枝及与UP的原位聚合、结构控制，UP复合材料制备与成型工艺技术。形成互穿的有机-无机杂化网络结构，实现MC-g-GO与UP之间良好的界面作用。阐明复合纳米结构协同增强机理，为电工用不饱和聚酯高性能化奠定基础。

采用无机纳米材料增强聚合物基复合材料是目前国内外的研究热点。纳米粒子与聚合物基体之间的界面作用始终是该领域有待解决的关键科学问题。本课题利用介孔材料(MC)和氧化石墨烯(GO)经表面改性，制备介孔硅-石墨烯杂化体(MC-g-GO)，将其与UP单体进行原位聚合成UP复合树脂，再配以固化阻燃等助剂，经熔融辊炼、挤出造粒，制备介孔-石墨烯/不饱和聚酯（MC-g-GO/UP）复合材料。研究了不同的介孔硅、石墨烯的制备与改性、分散方法、原位聚合反应、复合材料的加工方法、成型条件、固化工艺等对UP复合材料性能的影响。解决了MC-g-GO的接枝及与UP树脂合成、UP复合材料制备及成型工艺技术难点。.本课题主要成果：（1）介孔硅-氧化石墨烯杂化体（MC-g-MGO）的制备，比较选定了石墨烯和介孔材料，研究了不同反应条件对接枝反应产物接枝率、产物的结构和性能的影响。确定了可行的介孔硅/氧化石墨烯杂化体的制备工艺。（2）研究确定了MC-g-GO/UP树脂的合成技术：将配方量的介孔-氧化石墨烯杂化粉体与液态单体球磨、超声预分散后，采用本体熔融聚会工艺于180～230℃下聚合反应；当达到反应终点，加入配方量的扩链剂和稳定剂混溶均匀后出料，经冷却、粉碎包装即得介孔-氧化石墨烯/不饱和聚酯树脂。该树脂的技术指标：介孔-氧化石墨烯粉体含量1-3%；酸值≤8 mgKOH/g；最大固化放热温度≥200℃；固化时间（160℃）≤60s；软化温度≥110℃；热失重温度（5%）≥400℃；体积磨损率（160℃）≤0.2×10-8cm3/N•m。（3）以MC-g-GO/UP树脂为基体，通过固化交联体系、填料助剂等的选择与配合，采用混炼挤出工艺制备复合材料。研究不同配方和混炼挤出工艺条件等因素对复合材料性能的影响。确定了MC-g-GO/UP复合材料的制备技术。得到的MC-g-GO/UP复合材料具有更好的耐磨性和耐热性，在100℃、150℃、200℃下该复合材料的体积磨损率分别比纯UP复合材料降低了38.5%、28.6%、25.4%。且蠕变程度更小，松弛模量更高。与纯UP复合材料相比，MC-g-GO的加入也使复合材料的冲击强度、弯曲强度分别提高17.4%、8.2%，电气绝缘性能保持良好。（4）经小批量试制和应用表明：MC-g-GO/UP复合材料具有较好的注射成型加工工艺性：塑化，注塑，固化，脱模，毛刺和飞边清理