自组装论文受限空间内制备单分散聚苯乙烯微粒.docVIP

自组装论文：受限空间内制备单分散聚苯乙烯微粒 【中文摘要】为了制备单分散纳米尺度的功能颗粒,采用了受限空间反应体系(纳米反应器),包括够通过两亲大分子自组装构建的纳米反应器体系、无皂乳液聚合体系以及Pickering乳液聚合体系进行制备,并对制备的颗粒进行表征。以五氰基氨合铁(Ⅱ)酸(N,N-二甲氨基-4-吡啶)封端的聚氧丙烯聚氧乙烯共聚物(EPE-Fe)与苯乙烯在水中自组装形成纳米体系(EPE-Fe-St),在纳米尺度受限空间内进行了苯乙烯自由基聚合,制备了聚苯乙烯微球(EPE-Fe-PS)。用Fe3+对自组装体系的纳米球壳进行固化后形成Fe-EPE-Fe-St体系,聚合后也制备了聚苯乙烯微球(Fe-EPE-Fe-PS)。研究结果表明,制备了粒径为80-200nm的不同粒径聚苯乙烯微球,聚合温度对纳米Fe-EPE-Fe-St体系粒径影响较小,而对EPE-Fe-St体系较大。在受限空间内苯乙烯的自由基聚合可得到数均分子量超过70万的聚苯乙烯；自组装体系中引发剂量增多使聚苯乙烯分子量下降,聚合温度上升也使分子量下降,而增加自组装的EPE-Fe用量可增加聚苯乙烯的分子量。两种受限条件下的聚苯乙烯微球的玻璃化转变温度(Tg)在90-135℃之间,纳米反应器壳层的硬化提高了聚苯乙烯微球的Tg。以对苯乙烯磺酸钠(SSS)与苯乙烯组成无皂乳液聚合体系(SSS-PS)制备了粒度不等的窄分布聚苯乙烯微球。在SSS-PS体系中引入纳米二氧化硅溶胶(NanoSiO2)组成NanoSiO2-SSS-PS体系对聚苯乙烯微球粒度进行了调制。研究结果表明制备了粒径70-700nm的单分散窄分布的聚苯乙烯微球。在SSS-PS体系中改变SSS用量能够调节微球的粒径,SSS用量增多会使微球的尺寸下降,但对粒径分散性没有影响,而PS的分子量会随着SSS用量增多而略有下降；改变引发剂用量也会对微球的粒径产生影响,随着引发剂用量的增多,微球粒径会下降。在NanoSiO2-SSS-PS体系中,NanoSiO2量的增多会导致制备的微球粒径下降,可以通过调节其用量而调节微球粒径。引入SSS后会对制备的聚苯乙烯的玻璃化转变温度造成影响,增加SSS用量会使PS的Tg有明显升高。 【英文摘要】By taking the advantage of confined space to prepare the monodisperse polystyrene (PS) nanospheres. The confined space involve the nanoreactor developed from the selfassembly of amphiphilic copolymer, the soap-free emulsion polymerization system and Pickering emulsion polymerization. The products were characterized and the results were discussed.The poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol) terminated with pentacyano(4-(dimethylamino)-pyridine) ferrate (EPE-Fe) complex surfactant was synthesized and self-assembled with styrene (St) in water to form a nano-reactor (EPE-Fe-St). And the polystyrene nanospheres (EPE-Fe-PS) were prepared through free radical polymerization in the nano-reactor. Furthermore, ferric ion was used to cure the shell of the EFE-Fe-St to form a hardened nano-reactor (Fe-EPE-Fe-St). The styrene polymerization was also arisen in the nano-reactor to form polystyrene nanospheres (Fe-EPE-Fe-PS) with a hardened shell. The results of molecular