【作者】 姚志钢；

【导师】 胡艾希；

【作者基本信息】 华南理工大学 ， 应用化学， 2011， 博士

【摘要】 表面活性剂有序聚集体在生命、医药、能源、材料等领域已得到了广泛的应用,由于表面活性剂有序聚集体是靠分子间的作用力形成的,所形成的结构容易随着外界条件的变化（如浓度、盐离子强度、温度等）而不稳定。因此,提高表面活性剂有序聚集体的稳定性研究已成为热点课题。如果使用可聚合表面活性剂形成有序聚集体,然后用聚合的方法固定它们的结构,这将有效地提高有序聚集体的稳定性。设计并合成了结构新型的可聚合表面活性剂——烷基烯丙基琥珀酸双酯磺酸钠系列产物,并对其结构进行了确证,对其表面性能进行了测试,为乳液聚合、微乳液聚合的应用以及聚合囊泡等可聚合有序聚集体的构建提供了新的可聚合表面活性剂品种。以十四烷基烯丙基琥珀酸酯磺酸钠（STASD）和十六烷基三甲基溴化铵（CTAB）配制可聚合囊泡,对囊泡聚合前后的稳定性及影响因素进行了研究。得出采用过硫酸铵（APS）作引发剂,在80℃下聚合1.5小时的样品经过¹HNMR判断囊泡中双键的转化率为3.14%,该样品在常温下可稳定存放8个月,而一般囊泡只能存放3周左右,经聚合后的囊泡稳定性大大提高。在国内,首次利用可聚合表面活性剂制备的聚合囊泡用于药物载体研究,聚合囊泡对阿司匹林的包封率比未聚合囊泡高15²0%。50小时检测期内,在模拟肠液中,未聚合囊泡中阿司匹林释放率达79%左右,聚合囊泡释放率仅为29%左右;在模拟胃液中,未聚合囊泡中阿司匹林释放率达56%左右,聚合囊泡释放率仅为23%左右。相比于未聚合囊泡,聚合囊泡对阿司匹林有非常明显的缓释效果。这些研究开创了自发形成聚合囊泡和取代非自发制备脂质体作为药物载体的先河。采用十二烷基烯丙基琥珀酸酯磺酸钠（SDASD）做乳化剂制备微乳液,并用该体系制备多孔聚合物——高吸油性树脂。利用电导率法确定了微乳液的三种亚结构,同时考察了m（MAA）/m（LMA）和SDASD的质量百分含量对微乳液区域大小的影响。详细探讨了微乳液的双连续区域、单体种类及配比、聚合温度、交联剂用量等工艺因素对合成树脂的吸油率和吸油速率的影响,得出最佳聚合工艺条件,在最优工艺条件下制得的树脂吸油效果为7.9g/g（以汽油计）。可聚合表面活性剂的应用减少了微乳聚合过程中相分离的发生,树脂的孔结构易于调控,为高吸油性树脂的制备提供了一种新的思路。利用SDASD做乳化剂,采用离子液体代替水制备微乳液并用该体系制备透明多孔聚合物,用电导法确定了单相微乳液区存在[bmim] [BF₄] /丙烯酸酯、双连续相、丙烯酸酯/ [bmim][BF₄]三种亚结构。探讨了微乳液亚结构类型、双连续相中水的加入、聚合产物的后处理方法对聚合物的孔结构和透明性的影响。然后在最佳质量配比下进行最佳工艺条件的探究,得出离子液体微乳液聚合制备丙烯酸酯透明多孔聚合物的最佳工艺条件。可聚合表面活性剂和离子液体的引入减少了微乳聚合中相分离的发生和增加了产物的透明性和多孔性。这些研究使微乳液聚合在保持聚合前的理想结构方面取得了进展,丰富了透明多孔聚合物的制备方法。更多还原

【Abstract】 Ordered self-assemblies of surfactants have been widely and successfully used in the fields of life science, medicine, energy, material science, etc. Unfortunately, the self-assemblies are often formed owing to the interactions of surfactants molecules. The microstructures of aggregates are often changed with environment conditions such as consistence, ion intensity, temperature and so on. Thus, improving the stability of self-assemblies has been a hot topic recently. If polymerizable surfactants are employed to fabricat ordered self-assemblies and these structures are fixed by polymerization, then stability of the ordered self-assemblies will be efficiently improved.A series of novel polymerizable surfactants - Sodium Alkyl Allyl Sulfosuccinic Diesters were designed and synthesized in this work. The structures of all products were determined by IR and ¹HNMR. The surface properties were also tested. This provied new polymerizable surfactants for emulsion and microemulsion polymerization and polymerizable ordered self-assemblies such as polymerized vesicles.Polymerized vesicles were prepared spontaneously from aqueous mixtures of polymerizable surfactant - Sodium Tetradecyl Allyl Sulfosuccinic Diester （STASD） and Cetyl Trimethyl Ammonium Bromide （CTAB）. The stability of the vesicles against salts, ethanol, temperature, and staying time was studied before and after polymerization. Adopting APS as initiator, double bond of the vesicles which polymerized for 1.5 h at 80℃had translated 3.14% by ¹HNMR. The polymerized vesicles could be preserved for eight months and the unpolymerized vesicles for three weeks at normal temperature. It was found that stability of the vesicles was markedly enhanced after polymerization. We firstly applied the polymerized vesicles formed from polymerizable surfactants as drug carriers. The encapsulation efficiency of the polymerized vesicles for aspirin was 15²0% higher than the unpolymerized vesicles. During 50 h , the release ratio the polymerized vesicles was about 79% , but the unpolymerized vesicles was about 29% in simulated intestinal fluid , and the release ratio the polymerized vesicles was about 56%, but the unpolymerized vesicles was about 23% in simulated gastric fluid .Compared with unpolymerized vesicles, the polymerized vesicles have higher encapsulation efficiency and distinctly slow release effects for encapsulated aspirin. All the results lead spontaneous forming of polymerized vesivles and replace liposomes from unspontaneous fabrication as drug carriers.The porous polymers-high oil-absorption resins were prepared by microemulsion polymerization, and the microemulsions come from polymerizable surfactant - Sodium Dodecyl Allyl Sulfosuccinic Diester （SDASD） as emulsioner. the three sub-structures of the micromulsion were determined with conductivity. At the same time, the effect of the weight ratios of MAA to LMA and the quality percentage of SDASD aqueous solution on the phase region was also studied. We also studied the influences of the kinds and ratio of monomer, temperature of polymerization and dosage of crosslinker on oil-absorption rate and absorbing speed of the resin, and the optimum cindtions were obtained. The high oil-absorption resins which were prepared at the optimum cindtions had an excellent effect of oil absorption of 7.9g（gasoline）/g（resin）. It is because polymerizable surfactants were used as emulsioner of microemulsion polymerization that phenomenon of phase separation had decreased and the structures of the resins were easy to control and a new idea came into being for preparation of high oil-absorption resin.Taking SDASD as emulsioner, transparent porous polymers were prepared by ionic liquid instead of water, and with conductivity three microstructure of the single-phase microemulsion as well as area of [bmim] [BF₄] / acrylate （methacrylate / n-butyl）, bicontinuous phase and acrylate / [bmim] [BF₄] were further defined. Effects of sub- structures of the micromulsion, enter of water in bicontinuous phase, dispose method of polymer on structures of hole, and transparence of polymers were also discussed. Then the optimum condtions were obtained by ionic liquid microemulsion polymerization to prepare transparent porous polymers at optimum weight ratios. It is because polymerizanle surfactant and ionic liquid were introduced that phenomenon of phase separation had decreased in microemulsion polymerization and the transparence and porosity of polymers were enhanced. We have obtained great progress in keeping microemulsion with ideal structure brfore polymerization and enriched ways and means of preparation of transparent porous polymers.更多还原