【作者】 强婧；

【导师】 江金强； 刘晓亚；

【作者基本信息】 江南大学 ， 材料学， 2011， 硕士

【摘要】 本文通过自由基聚合方法,合成了1)光敏感遥爪聚合物聚乙烯基吡啶(C-P4VP)、2)双亲性4-乙烯基吡啶系列聚合物(P4VP-PEO和P4VP-OPD)、3)双亲性交替聚合物P(CMS-alt-OPD)和P(VBDBA-alt-OPD)。用傅立叶变换红外光谱(FTIR)、凝胶渗透色谱(GPC)、核磁共振(1H-NMR)等方法表征了聚合物的结构,并研究了聚合物的自组装行为,讨论了C-P4VP胶束光敏感性和pH敏感性、P4VP-PEO,P4VP-OPD胶束的pH敏感性、P(CMS-alt-OPD)和P(VBDBA-alt-OPD)胶束的反离子影响及其乳化性能。1)以香豆素二硫化物(C-S-S-C)/三丁基膦/H2O复合体系为链转移剂、偶氮二异丁腈(AIBN)为引发剂、4-乙烯基吡啶为单体制备了末端含有疏水性香豆素光响应基元的光敏感遥爪聚合物聚乙烯基吡啶(C-P4VP)。研究显示该遥爪聚合物可在不同pH值的酸性水溶液中自组装成胶束,且随体系酸值的降低,聚合物胶束结构由松散变为紧密,同时香豆素端基的光二聚反应程度也随之上升。2)通过含有S-S二硫键的苯乙烯单体(St-S-S-St)与4-乙烯基吡啶自由基共聚合反应制备了P4VP交联聚合物,然后在Bu3P/H2O催化下使交联聚合物S-S键打开并分别与聚乙二醇甲基丙烯酸酯(PEO)和N-正辛基马来酰亚胺(OPD)发生“巯基-乙烯基”加成反应,合成了双亲性聚4-乙烯基吡啶系列聚合物(P4VP-PEO和P4VP-OPD)。研究显示通过调节体系pH可使两种聚合物在水中自组装成胶束,且随体系pH上升,P4VP-PEO胶束粒径逐渐增大,胶束形态由松散变得紧密;而P4VP-OPD则在pH = 4.77时可形成表面弥散型球形结构。3)以N-正辛基马来酰亚胺(OPD)与对氯甲基苯乙烯(CMS)为聚合单体,自由基聚合法制备了交替聚合物P(CMS-alt-OPD),并分别利用三甲胺和三正丁胺将聚合物中的苄氯进行季铵化反应得到新型季铵盐型双亲性交替聚合物P(TMVPMA-alt-OPD)和P(VBDBA-alt-OPD),且可以通过改变反离子类型改变聚合物的亲疏水性能。研究了不同反离子条件下该系列聚合物的自组装行为与乳化性能。研究表明,P(TMVPMA-alt-OPD)和P(VBDBA-alt-OPD)系列聚合物均可在水溶液中自组装成胶束,且所得胶束的粒径随聚合物的疏水性增加而降低;聚合物胶束的乳化性能研究表明,疏水性大的聚合物所制得的乳液具有更好的稳定性。更多还原

【Abstract】 In this paper, 1) the photo-sensitive telechelic poly(4-vinylpyridine) (C-P4VP), 2) modified poly(4-vinylpyridine) polymers (P4VP-PEO, P4VP-OPD), 3) the ammonium salt containing amphiphilic alternating polymers P(TMVPMA-alt-OPD) and P(VBDBA-alt-OPD) were synthesized by free radical polymerization. All polymers were characterized with 1H-NMR, GPC and FTIR, and the self-assembly of them were respectively researched.1) The novel photo-sensitive telechelic polymer (C-P4VP) was prepared with 4-vinylpyridine, using coumarin-containing disulfides (C-S-S-C) as a chain transfer agent in the presence of tributylphosphine and water. It was found that the telechelic polymer can form the micelles in the aqueous solutions at various pH values (pH = 3-6). Moreover, lowering the pH of the aqueous polymer solution, the polymer micelles gradually transferred into the compact morphology, and the photo-dimerization of coumarin group increased relatively within the same irradiation time.2) The crosslinked poly(4-vinylpyridine) (P4VP) was prepared by the copolymerization a styrene monomer containing disulfide bond (St-S-S-St) and 4-vinylpyridine. Then the internal disulfide bond was cleaved to thiol by reduction with tributylphosphine/water, and the“Thiol-ene”reaction happened between the thiol and the monomer of PEO or OPD, resulting in the P4VP-PEO and P4VP-OPD, respectively. It was found that both polymers can form the micelles in the aqueous solutions at various pH values. Moreover, as the pH of the aqueous solution got higher, the micelles of P4VP-PEO became bigger with the more compact morphology; while P4VP-OPD formed micelles at pH = 4.77, with a dispersion structure on the surface.3) The alternating polymer P(CMS-alt-OPD) was prepared by N-(n-Octyl) maleimide (OPD) and p-(chloromethyl) styrene (CMS) through free-radical polymerization. Then the P(CMS-alt-OPD) was used to prepare ammonium salt amphiphilic P(TMVPMA-alt-OPD) and P(VBDBA-alt-OPD) with trimethylamine and tri-n-butylamine, respectively, and the amphiphilic properties of these polymers can also be adjusted by the change of counter ions. Their self-assembly and emulsification were characterized by Malvern Nano ZS ZEN3600 instrument or dynamic laser scattering (DLS) and transmission electron microscopy (TEM). It was found that all the polymers can form micelles in aqueous solutions, and the average diameter decreased along with the hydrophobic enhancement of polymers. And the emulsion experiment showed that the more hydrophobic the polymer, the more stable the emulsion solution.更多还原