Exploitation of New Tamplate Polymerization Systems by Using the Interaction between Polymers and Monomers Based on Hydrogen Bondings

在侧链上有羰基的聚甲基丙烯酸甲酯（PMMA）作为模板聚合物的情况下，丙烯酰胺（Aam）的模板聚合可以进行。特别是在合适的引发剂条件下，采用阴离子聚合法制备了富顺规或等规的立体规整PMMA。用制备的PMMA在四氢呋喃中进行了AAm的聚合，并通过核磁共振（NMR）测定了所制聚丙烯酰胺（PAAm）的三征性。在聚合开始时（转化率<10%），富同规（n>73.8%）和富等规（mm>98.6%）的PMMA模板聚合物分别具有较高的rr和mm序列含量。但随着聚合的进行，聚合物的立体规整性有降低的趋势。此外，发现AAm在富等规PMMA存在下的聚合性远低于富同规PMMA。在侧链上有酰胺基团的聚n -异丙基丙烯酰胺（PNIPAAm）存在的情况下，以形成更强的相互作用为目标，进行了AAm的聚合。结果发现模板聚合物的转录效果比PMMA增强。此外，通过自由基聚合和分馏制备了不同分子量的PNIPAAm模板，并在得到的PNIPAAm模板存在的情况下在THF溶剂中进行了AAm的聚合。模板分子量对聚合性有显著影响，即PNIPAAm分子量的增加导致聚合性明显降低。由于聚合体系具有高极性和高粘度等特点，我们也对其进行了研究。我们研究了温度对聚合的影响，发现PNIPAAm作为模板聚合物的LCST （Lower Critical Solution temperature）与AAm的可聚合性有关。特别是，当聚合温度低于最低温度时，发现PNIPAAm存在时AAm的聚合性较低。少

Template polymerization of acrylamide (Aam) was found to proceed in the presence of poly(methyl methacrylate) (PMMA) as a template polymer which have carbonyl groups in its side chains. Especially, the stereoregular PMMA which was syndiotactic or isotactic rich was prepared by the anionic polymerization using an adequate initiator., Using the prepared PMMA the polymerization of AAm was performed in THF, and the triad tacticlty of the resulting poly(acrylamide) (PAAm) was determined by NMR. At the beginning of the polymerization (conversion<10%), both of the syndiotactic rich (n>73.8%) and isotactic rich (mm>98.6%) PMMA as template polymers were found to afford relatively high content of rr and mm sequences respectively. However, the stereoregularity of the resulting polymers tended to decrease with the progress of polymerization. Furthermore, the polymerizability of AAm in the presence of isotactic rich PMMA was found to be much lower than syndiotactic rich PMMA. Aiming the formation o … More f the strong interaction, the polymerization of AAm was carried out in the presence of poly (N-isopropylacrylamide) (PNIPAAm) which has amide groups in its side chains. Resultingly the transcription effect of the template polymer was found to increase in comparison with PMMA. Furthermore, several PNIPAAm templates having various molecular weights were prepared by the radical polymerization and subsequent fractionation, and the polymerization of AAm was also carried out in the presence of the resulting PNIPAAm templates in THF solvent. The polymerizability was remarkably affected by the molecular weight of the templates, that is, the increase of the molecular weight of PNIPAAm resulted in considerable decrease of the polymerizability. We have also investigated polymerization system because of its distinctive characters such as high polarity and viscosity. We have investigated the temperature effects in this polymerization and found that the LCST (Lower Critical Solution Temperature) of PNIPAAm as a template polymer concerns the polymeriability of AAm. Expecially, the polymerizability of AAm in the presence of PNIPAAm was found to be lower at the polymerization temperature below the LCST. Less