高分子孪生表面活性剂合成及表征
于二雷
学位类型博士
导师吾满江·艾力
2015-05-22
学位授予单位中国科学院大学
学位授予地点北京
学位专业物理化学
关键词甲氧基聚乙二醇 酯化反应 Raft聚合 高分子表面活性剂 孪生表面活性剂
摘要

孪生表面活性剂与高分子表面活性剂相结合而产生的新型高分子孪生表面活性剂可以提高高分子表面活性剂的表面活性, 从而具有广阔的应用前景。基于此, 本文设计合成了几种不同类型的新的高分子孪生表面活性剂及其单体, 即采用RAFT聚合合成得到以RAFT试剂为链接基团的新的高分子孪生表面活性剂以及以脂肪酸为原料合成的不对称孪生表面活性剂,并对其结构性质进行了表征。首先, 减压条件下合成了孪生表面活性剂单体甲氧基聚乙二醇400丙烯酸酯并考察了反应温度及压力,反应时间,催化剂,阻聚剂等的影响,确定了最佳反应条件,并用红外及高效液相色谱进行了表征,酯化率达到了92.6%。其次, 采用RAFT聚合合成了一系列聚丙烯酸甲酯丙烯酸型高分子孪生表面活性剂,以RAFT试剂为链接基团,设计合成了一种合成高分子孪生表面活性剂的新方法,通过红外,核磁,热重,凝胶渗透色谱,透射电镜,光散射仪进行了分析,结果表明,聚丙烯酸甲酯丙烯酸嵌段共聚物成功合成,当摩尔比增加时分子量分布降低,最低在RAFT=5.23 wt%得到。RAFT试剂量变化时,理论分子量与实际分子量相近。透射电镜发现由于其孪生表面活性剂结构,得到了一种较为特殊的具有较大孔径的胶束结构,可能是形成低的临界胶束浓度和表面张力的原因。同时, 采用RAFT聚合合成了一系列聚丙烯酸酯丙烯酸型高分子孪生表面活性剂,研究了不同丙烯酸酯对聚合及表面活性的影响,研究表明分子量分布对表面性质影响很大,分子量分布越小,临界胶束浓度越低。最后, 以脂肪酸和环氧氯丙烷等为原料,合成了非离子-阳离子非对称孪生表面活性剂,用核磁氢谱,红外,元素分析,表面张力和电导率对产物的结构和性质进行了表征。结果表明,成功合成了目标化合物,得到了低的临界胶束浓度和表面张力,酯基对于表面活性剂的影响很大,叔胺的碳链对于CMC和γcmc的影响较小。

其他摘要

Gemini polymer surfactants have broad application in various aspects. In the work reported here, we focus on synthesizing several different types of gemini polymer surfactants and monomers. Gemini polymer surfactants monomer methoxy polyethylene glycol acrylate was synthesized under reduced pressure. Effects of reaction temperature and pressure, reaction time, catalyst and polymerization inhibitor were investigated to determine the optimal reaction conditions. The synthesized products were characterized by IR and HPLC. Secondly, a series of acrylic-methyl acrylate copolymer gemini surfactants were also synthesized by RAFT polymerization. They are characterized by IR, NMR, TGA, gel permeation chromatography, transmission electron microscopy and light scattering. The results showed that the synthesis of acrylic-methyl acrylate copolymers was successful. PDIs decreased as the molar ratio increased, the lowest PDI was obatained at RAFT = 5.23 wt%. Actual molecular weight was found to be similar to the theoretica molecular weight. TEM results implied a special vesicle structure was formed, which may be the reason for the formation of low critical micelle concentration and surface tension. Furthermore, a series of acrylic-acrylate copolymer gemini surfactants were synthesized by RAFT polymerization. The effect of different acrylate was studied. PDI was found to have great influence on surfactant property. Critical micelle concentration decreased as the PDIs decreased. Finally, a series of novel anionic–non-ionic heterogemini surfactants are synthesized from fatty acid, epichlorohydrin and aldciphatic amine. The chemical structures of the surfactants were confirmed by IR spectra, NMR and elemental analysis. Their critical micelle concentrations (CMC) in aqueous solutions were determined by surface-tension at 25 ℃. A relationship between surface tension and hydrophobic chain length showed a large increase upon increasing of chain length with ester.

文献类型学位论文
条目标识符http://ir.xjipc.cas.cn/handle/365002/4250
专题新疆维吾尔自治区精细化工工程技术研究中心
作者单位中国科学院新疆理化技术研究所
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于二雷. 高分子孪生表面活性剂合成及表征[D]. 北京. 中国科学院大学,2015.
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