NOVEL POLYMER SYNTHESIS ON THE BASIS OF FUNCTIONAL MACROMONOMERS.

聚（2-烷基-2-恶唑啉）s （PROZO）的大单体具有亲水性（如R=Me）或疏水性（如R=n-Bu），具有较长烷基的规则支链结构。因此，我们将这些大单体命名为功能性大单体。研究了端基为甲基丙烯酸酯（MA-PROZO）和端基为乙烯基苯基（VB-PROZO）的PROZO大单体（R=Me, n-Bu, n-Oc）的聚合性。CD_3CN、CDCI_3和D_2O在60℃的自由基均聚反应中，聚合速率普遍随着PROZO链长度和烷基的增加而增加。而MA-POcOZO的聚合则呈现相反的趋势。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单体自由基共聚时，短链长度的VB-PMeOZO （PROZO-3的DP）的活性优于共聚物，但随着DP的增加而降低。用一般的正离子和阴离子聚合方法处理高分子单体，没有得到聚合物。以硅酮缩醛为引发剂，在24-50℃的温度下进行MA-PROZO基团转移聚合，得到活性高分子，活性高分子可以被活性PROZO终止，得到AB嵌段共聚物。以乙烯苄基醇氧基和乙烯苄基硫化物为阴离子，终止活PROZO，合成了新型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.