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

开发了一种新的制备方法--缠绕聚合法来制备直链淀粉-聚合物包合物。聚合方法的第一个例子是通过在聚四氢呋喃作为客体聚合物的存在下，由磷酸化酶催化葡萄糖1-磷酸单体的酶聚合实现的。X-射线粉末衍射法和核磁共振法确定产物为包合物。用不同相对分子质量和端基的聚四氢呋喃和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情况。在此基础上，以聚酯为客体形成了相应的包合物，考察了直链淀粉与疏水性强的聚酯在平行聚合体系中形成包合物的情况。包合物的制备是通过两种酶催化聚合反应实现的。产物分析数据表明产物中含有包合物。以阳离子甲基丙烯酸酯单体2-氨基乙基甲基丙烯酸酯盐酸盐为原料，在海藻酸钠存在下进行自由基聚合，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，形成了不溶物质。产物的结构经红外光谱、元素分析和酸解实验确定为由海藻酸盐和聚甲基丙烯酸甲酯组成。产物的TG和DSC数据与海藻酸钠和聚甲基丙烯酸2-氨基乙酯盐酸盐的混合物不同。此外，甲基丙烯酸酯单体在海藻酸钠存在下聚合，然后挥发溶剂，即可形成杂化材料的薄膜。

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.