自组装论文：受限空间内制备单分散聚苯乙烯微粒.doc

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()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 weight and morphology of polystyrene nanospheres show that the various size of monodispersed polystyrene nanospheres in 80-120 nm have been obtained. The effect of polymerization temperature on the size of self-assembled EPE-Fe-St is remarkable, and on the size of the Fe-EPE-Fe-St is slight. The higher molecular weight of the polystyrene has achieved more than 700,000 in the confine space. In the self-assembled nano-reactor, the molecular weight of PS decreases with increase of initiator content in St and enhancement of polymerization temperature, and increases with augment of EFE-Fe content in water. The glass transition temperature (Tg) of the polystyrene nanospheres prepared in two kinds of the confined space are in the range of 90-135. The Tg of polystyrene nanosphere is enhanced after hardening the shell of nano-reactor whether St was polymerized in the confined space with harden shere or not.Sodium p-styrenesulfonate(SSS) was used to get the soap-free emulsion system for the production of polystyrene spheres, and this system was named with SSS-PS system. The results show that monodisperse polystyrene spheres have been produced and the size of the spheres ranges from 70nm to 700nm. To modulate the size of the polystyrene nanospheres developed from SSS-PS system, the nanosize silica sol (NanoSiO2) was introduced into the former SSS-PS system to get another hybrid system:NanoSiO2-SSS-PS system. Both of these two systems could get monodisperse polystyrene spheres with various sizes for changes of the parameters. In the SSS-PS system, the diameter of spheresdecrease with the increase of the amount of SSS without change of the dispersibility. At the same time, the molecular weight of polystyrene decreases with the increase of the amount of SSS as well, and the diameter of polystyrene spheres decrease with the increase of amount of initiator. However, the effect of initiator on the spheres is not as evident as SSS.After the introduction of nanosize silica sol, the sizes of products decrease with the increase of the amount of nanosize silica sol, that means the size of polystyrene could be modulated through the change of amount of nanosize silica sol. DSC results show that the introduction of SSS into the polystyrene increases the glass transition temperature (Tg), and with the increase of the amount of SSS, the glass transition temperature (Tg) could even get to 120.【关键词】自组装 纳米反应器 受限空间 聚苯乙烯微球 形貌【英文关键词】Self-assembly nano-reactor confined space polystyrene nanosphere morphology【备注】在线加我索购全文 ：13993捌捌肆捌同时提供论文辅导写作和论文发表委托服务。【目录】受限空间内制备单分散聚苯乙烯微粒摘要5-6Abstract6-7第1章 绪论10-191.1 引言101.2 纳米微粒种类10-111.3 高分子纳米颗粒的制备11-151.3.1 乳液聚合法111.3.2 微乳液聚合111.3.3 星形聚合物11-121.3.4 模板法121.3.5 自组装法12-131.3.6 受限空间制备纳米微米超细颗粒13-151.3.6.1 基于氢键的受限空间13-141.3.6.2 金属配体相互作用形成的受限空间141.3.6.3 疏水效应形成的受限空间141.3.6.4 活性位点受限空间141.3.6.5 高分子胶束14-151.4 微纳米颗粒的应用15-171.4.1 纳米粒子在生物医药领域里的应用15-161.4.2 纳米光材料161.4.3 纳米磁性材料161.4.4 航天领域161.4.5 能源领域16-171.4.6 催化方面应用171.5 本文的设计思路和研究内容17-19第2章 纳米反应器的制备及其苯乙烯微球合成19-402.1 引言192.2 实验部分19-232.2.1 实验试剂19-202.2.2 药品处理202.2.3 构造纳米反应器的双亲分子EPE-Fe的合成20-222.2.4 自组装和苯乙烯聚合22-232.2.4.1 EPE-Fe体系制备聚苯乙烯微粒222.2.4.2 Fe-EPE-Fe体系制备聚苯乙烯微粒22-232.2.5 分析与表征232.3 结果与讨论23-342.3.1 构造纳米反应器的双亲分子EPE-Fe的表征242.3.2 EPE-Fe-PS和Fe-EPE-Fe-PS制备24-262.3.3 纳米反应器内聚苯乙烯的粒度及分散性26-342.3.3.1 EPE-Fe体系的粒径与EPE-Fe和St用量以及温度相关性27-292.3.3.2 EPE-Fe体系的粒径与St用量相关性29-302.3.3.3 温度对于EPE-Fe体系纳米微粒尺寸稳定性的影响30-322.3.3.4 温度对于Fe-EPE-Fe体系纳米微粒尺寸稳定性的影响32-342.4 分子量及聚合影响因素34-372.4.1 不同体系对于分子量的影响34-362.4.2 温度对于Fe-EPE-Fe体系中聚苯乙烯分子量以及分子量分散度的影响362.4.3 引发剂用量对于Fe-EPE-Fe体系中聚苯乙烯分子量以及分子量分散度的影响36-372.4.4 苯乙烯用量对于Fe-EPE-Fe体系中聚苯乙烯分子量以及分子量分散度的影响372.5 纳米反应器制备聚苯乙烯微粒的时间与转化率关系37-382.6 聚苯乙烯的热性能38-40第3章 无皂乳液聚合制备聚苯乙烯微球40-623.1 引言403.2 实验部分40-423.2.1 实验试剂40-413.2.2 药品处理413.2.3 聚苯乙烯单分散微粒制备41-423.2.3.1 苯乙烯磺酸