NOVEL POLYMER SYNTHESIS ON THE BASIS OF FUNCTIONAL MACROMONOMERS.

聚(2-烷基-2-恶唑啉)S大单体具有亲水性(如R=Me)或疏水性(如R=n-Bu)，具有规则的支化结构和较长的烷基。研究了具有甲基丙烯酸酯端基(MA-PROZO)和乙烯基苄基端基(VB-PROZO)的PROZO大单体(R=Me，n-Bu，n-Oc)的聚合性能。在60ﾟC下，在Cd_3CN、Cd_3Cl_3和D_2O中进行自由基均聚合时，聚合速率一般随原氮链长度和烷基的增加而增加。而MA-POcOZO的聚合则表现出相反的趋势。在D_2O中，PMeOZO大单体的聚合速度比在有机溶剂中快得多，这可能是由于胶束的形成。在乙醇中与甲基丙烯酸甲酯等小共聚单体的自由基共聚反应中，短链长VB-PMeOZO(PROZO-3的DP)比共聚单体具有更高的活性，但随着DP的增加而降低，一般的阳离子和阴离子处理均不能得到聚合物。以硅烯酮缩醛为引发剂，在24~50ﾟ℃下进行MA-PROZO的基团转移聚合，得到活性大分子单体，活性PROZO可以终止聚合，生成AB嵌段共聚物。用乙烯基苄基烷氧基和乙烯基苄基硫醚阴离子终止活性丙偶氮，合成了新型的VB-PROZO。

Macromonomers of poly (2-alkyl-2-oxazoline)s (PROZO) possess hydrophilic (e. g., R=Me) or hydrophobic (e. g., R=n-Bu) nature, and regularly branched structures with longer alkyl groups. Accordingly, we have named the macromonomers as FUNCTIONAL MACROMONOMER.Polymerizability of the PROZO macromonomers (R=Me, n-Bu, n-Oc) having methacrylate end-group (MA-PROZO) and vinylbenzyl end-group (VB-PROZO) was studied. In radical homopolymerization in CD_3CN, CDCI_3, and D_2O at 60ﾟC, polymerization rate generally increased with increase of length of PROZO chain and the alkyl groups. The polymerization of MA-POcOZO, however, exhibited reverse tendency. In D_2O, PMeOZO macromonomers were polymerized much faster than in organic solvents, probably due to micelle formation. In radical copolymerization with small comonomers such as methyl methacrylate in ethanol, eactivity of VB-PMeOZO of short chain length (DP of PROZO-3) was predominant over that of the comonomers, but decreased with increase of the DP.No polymers were obtained through treating of the macromonomers by general cationic and anionic procedure for polymerization. Group transfer polymerization of MA-PROZO by silyl ketene acetal as initiator at 24-50ﾟC gave living polymacromonomers, which could be terminated by living PROZO giving rise to AB block copolymers. Novel VB-PROZO were synthesized by termination living PROZO with vinulbenzyl alkoxide and vinybenzylsulfide anions.