摘要
本文介绍了溶致液晶的组装及其研究进展,研究了可聚合型溶致液晶的制备、自组装及其光固化行为,并对其在膜材料上的应用可能性提出了探索。
文中首先合成一种可聚合型溶致液晶单体,研究了其在一定条件下的组装行为,在此组装的基础上对其光固化程度及固化后组装体结构的保留行为进行了研究,最后将其涂布在聚酯膜上形成了复合功能膜材料,并对其在膜材料上的应用性提出了展望。首先可聚合型溶致液晶单体的合成以没食子酸为原材料,依次经过酯化、醚化、酰氯化和钠盐化四步反应,生成一种含有三条支链的三官能团单体,通过IR与1H NMR对其结构及其纯度进行了表征。其次在临界堆积参数理论计算的基础上,研究了单体与水的组装行为,结果发现单体/水等于8/2(甲醇占总量的90%),室温时先磁力搅拌24h,再静置至少48h即可得到组装比较完善的L相,并通过PLM和XRD对其结构进行了表征;发现HII相的制备工艺与L相相似,目前得到的最佳配比为单体/水等于92/8,随后再在上述体系中加入不同种类的光引发剂并进行紫外光固化,结果发现在强度为30mW/cm2的紫外光下曝光30min,含光引发剂Darocur2959的体系双键转化率最高,为78%,在此条件下经XRD与PLM证实,L和HII相都可得到一定程度的保留。最后将含有光引发剂Darocur2959的溶致液晶体系涂布在聚酯膜上并进行固化,通过SEM表征,得到表面形貌比较均一、孔径约为1μm的复合材料。该方法得到的复合膜材料孔径均匀、可控性较强且上下层之间可以很好的复合。通过对其制备工艺的改善使其具有更好的机械性能有望在水处理方面作进一步的应用。
In this paper, the assembly and research development of lyotropicliquid crystals (LLCs) are introduced. Then, the synthesis, self-assemblyand UV-curing behavior of the polymerizable LLCs are also studied. Andin the end we make a prospect of the application probability in membranematerials.
In this thesis, a polymerizable LLC monomer was preparaed first, andthe self-assembly behavior of the monomer with water in methanol wasdiscussed, followed by UV-curing and nanostructure retention. Finally, theLLC was coated on a PET membrane to form composite membranematerials and the application in membrane materials was proposed. Apolymerizable LLC monomer was synthesized by a convenient routestarting from3,4,5-trihydroxybenzoic acid via esterification followed byetherification, acrylation and finally neutralization and generated atrifunctional group monomer with three branches, and the chemicalstructure and purity were confirmed by IR and1H NMR spectral analysis.We demonstrated the self-organization behavior of monomer1with deionized water in methanol at room temperature based on the theoreticalcalculation of critical packing parameter. And the results revealed that, thefine lamellar (L) phase could be formed when the solution of monomer1/water (8/2) was allowed to equilibrate for at least48h after stirred24h atambient temperature in the presence of methanol (90%of the total amount)as a cosolvent, and the assemblies were confirmed by PLM and XRDanalysis. The preparation of inverted hexagonal (HII) phase was similar tothat of L phase, and the best ratio of monomer1/water we found until nowwas92/8. After that, we added different kind of photoinitiators to the LLCsystem and polymerized by UV-curing. The results show that, the acrylateconversion could reach up to78%when the LLC system containingphotoinitiator Darocur2959was exposed to30mW/cm2365nm UV lightfor30min, under which circumstances both L and HIIphases got retentionto some extent confirmed by XRD and PLM. Finally, the LLC containingphotoinitiator Darocur2959was coated on a nanofibrous PET membraneand polymerized, we could get composite membrane materials withsmooth surface morphology and pore diameter of1μm characterized bySEM images. The composite membrane materials obtained in this wayhave the advantage of uniform pore size, strong controllability, and goodcompatibity between the two layers, which makes it hopeful to exhibit afurther application in water filtration if the mechanical behavior could beimproved by optimizing the preparation technology.
引文
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