【作者】 卢艳；

【导师】 张兴文；

【作者基本信息】 哈尔滨工业大学 ， 物理化学， 2013， 硕士

【摘要】 低聚多面体倍半硅氧烷（POSS）兼具有机材料良好的韧性、透光性，易于加工等特点和无机材料的优异的热稳定性和机械性能，因而广泛的应用于航空航天领域；富勒烯(C₆₀具有三维空间内的离域大π键所表现出的缺电子性而使其具有突出的光电性能；聚甲基丙烯酸甲酯（俗称有机玻璃，PMMA）在低温条件下，具有优异的透光性及机械性能，由于该材料在使用过程容易产生电荷累积和高温条件下各方面的性能出现大幅下降。因此，在很大程度上限制了其应用。本论文采用溶胶-凝胶法，将硅烷偶联剂在甲酸稀溶液的催化下制备了-R基团为氨丙基及环氧基的POSS溶胶；采用相转移氧化法对C₆₀进行表面修饰，在其表面嫁接多个羟基；采用自由基聚合法制备了性能稳定的PMMA。利用FTIR测试表征了反应前后的各物质的化学键、管能团的变化情况。通过亲电取代、环氧基开环、加成的反应使C₆₀（OH）_n表面的羟基与-R基为氨丙基的POSS50和环氧基的POSS60以化学键的方式键合，制备了POSS/C₆₀杂化体系，并将其分散到PMMA中。FTIR测试结果表明POSS与C₆₀（OH）_n是通过化学键的方式键合，而不是简单的物理分散；SEM照片可知， POSS/C₆₀（OH）_n杂化体系可以形成均匀、连续的膜材料，而C₆₀（OH）_n/POSS改性的PMMA没有出现明显的相分离现象，膜层表面均匀。本文针对POSS杂化体系可以形成POSS/C₆₀（OH）_n杂化体系改性PMMA的抗静电性、热稳定性、纳米力学以及光学性能进行了系统的研究。分析结果表明经过10%的杂化C₆₀（OH）_n（1.5%）/POSS掺杂后，PMMA复合膜的表面电阻由10¹⁵Ω/m²下降至108Ω/m²，玻璃化温度由75℃提高至300℃以上，复合膜的硬度达到2.13GPa，与基体的结合强度超过0.49mN；材料表面摩擦系数为0.14，模量为0.64Gpa，使其在具有良好力学性能的同时也具备了自清洁的性能；POSS/C₆₀（OH）_n杂化体系掺杂在不影响PMMA的可见光吸收情况下，赋予了其良好的紫外吸收性能，使其在抗激光打击领域具有广泛的应用前景。更多还原

【Abstract】 Polyhedral oligomeric silsesquioxane （POSS） has a good toughness andtranslucency of the organic material and is easy to process. It also has excellentstable performance characteristics and mechanical properties of inorganic materialsand so is widely used in aerospace fields. With a characteristic of theelectron-deficient shown by the delocalized big π bond in the three-dimensionalspace, fullerene (C₆₀) has outstanding optical and electrical properties. Polymethylmethacrylate （PMMA, commonly known as organic glass） has an excellenttranslucency and mechanical properties. However, the low glass temperature willlead to easy charge accumulation under the condition of high temperature. Thereforeits application is extremely limited.In this paper, we adopt the sol-gel method which includs: under the catalysis ofthe dilute solution of formic acid, use the silane coupling agent to prepare the POSSsol system of epoxy and aminopropyl which contains R group; use phase transferoxidation method to modify the surface of C₆₀and graft many hydroxy on it; useradical polymerization method to prepare the PMMA which has stable performance;use FTIR testing methods to characterize the changes of the chemical substancesand functional groups before and after the response of each system.Prepare the hybrid system of POSS/C₆₀and scattered it into the PMMA, bymaking C₆₀（OH）_ngroup and–R group bond with POSS50of aminopropyl andPOSS60of epoxy respectively through electrophilic substitution, epoxyring-opening and addition reaction. Use FTIR to identify that POSS and C₆₀（OH）_nare bonded in a chemical bond way rather than in a simple physical dispersion way;SEM photos indicate that the hybrid system of C₆₀（OH）_n/POSS can form an uniformand continuous material, and POSS/C₆₀（OH）_nmodified PMMA without significantphase separation phenomenon and the film surface is uniform.In this paper, we carry on a systematic research about the hybrid system ofPOSS/C₆₀（OH）_nmodifying the antistatic properties, thermal stability, mechanicalproperties and optical properties of PMMA. Experimental results shows: through10%of the C₆₀ doped with1.5%of the POSS, the surface resistance of thecomposite membrane of PMMA can decrease from1015Ω/m2to108Ω/m2and theglass temperature of PMMA can increase from75℃to more than300℃; thehardness of the composite membrane can reach2.13GPa and the bonding strengthwith the matrix is more than0.49mN; the friction coefficient of the materialsurface is about0.14and the modulus is0.64GPa and so make it have a good self-cleaning properties; the hybrid system of POSS/C₆₀（OH）_ndoped in the casethat the absorption of visible light of PMMM is not affected, gives its goodultraviolet absorption performance and make it widely used in the field ofresistance of laser attack.更多还原