Development of New Preparation Method for Supramolecules by Control of Higher-Ordered Structures of Produced Polymers in Polymerization System

提出了一种新的制备方法，即“藤蔓缠绕聚合”，以制备直链淀粉-聚合物包合物。聚合方法的第一个实例是在聚四氢呋喃作为客体聚合物存在的情况下，通过磷酸化酶催化葡萄糖-磷酸单体的酶促聚合实现的。产物的结构经x射线粉末衍射和核磁共振测定确定为包合物。用不同分子量和端基的聚四氢呋喃以及其他聚醚作为客体聚合物，考察了这种聚合方法形成包合物的过程。此外，以聚酯为客体聚合物形成相应的包合物。研究了在平行聚合体系中直链淀粉与强疏水聚酯包合物的形成。包合物的制备是在两次酶催化聚合中完成的。产品的分析数据表明该产品含有包合物。在海藻酸钠存在的条件下，以阳离子甲基丙烯酸单体2-氨基乙基甲基丙烯酸盐酸盐为原料，通过自由基聚合制备了海藻酸盐-聚甲基丙烯酸酯杂化材料。随着聚合反应的进行，形成了不溶性物质。产物的结构经红外光谱、元素分析和酸水解实验证实为海藻酸盐和聚甲基丙烯酸酯组成。产物的TG和DSC数据不同于海藻酸钠与聚2-氨基乙基甲基丙烯酸酯盐酸盐的混合物。此外，混合材料的薄膜可以通过甲基丙烯酸酯单体在海藻酸钠存在下聚合，然后蒸发溶剂来形成。

A new preparation manner termed as "vine-twining Polymerization" was developed to produce amylose-polymer inclusion complexes. A first example of the polymerization method was achieved by an enzymatic polymerization of glucose 1-phosphate monomer catalyzed by phosphorylase in the presence of polyTHF as a guest polymer. The structure of the product was determined by the X-ray powder diffraction and NMR measurements to be the inclusion complex. The formation of the inclusion complexes by this polymerization method using polyTHFs with various molecular weights and end groups, as well as other polyethers as the guest polymers was also examined. Furthermore, polyesters were taken as guest polymers to form the corresponding inclusion complexes.Formation of inclusion complex of amylose with a strong hydrophobic polyester was examined in parallel polymerization system. The preparation of the inclusion complex was achieved in two enzyme-catalyzed polymerizations. The analytical data of the product indicated that the product contained the inclusion complex.An alginate-polymethacrylate hybrid material was prepared by radical polymerization of a cationic methacrylate monomer, i.e., 2-aminoethyl methacrylate hydrochloride in the presence of sodium alginate in water. The insoluble material was formed with progress of the polymerization. The structure of the product was confirmed by the IR spectrum and elemental analysis, as well as the acid hydrolysis experiment to be composed of alginate and polymethacrylate. The TG and DSC data of product were different from those of a mixture of sodium alginate with poly(2-aminoethyl methacrylate hydrochloride). Furthermore, the films of the hybrid materials could be formed by means of the polymerization of the methacrylate monomer in the presence of sodium alginate, followed by the evaporation of the solvent.