NOVEL POLYMER SYNTHESIS ON THE BASIS OF FUNCTIONAL MACROMONOMERS.

基于功能性大分子单体的新型聚合物合成。

• 批准号: 06651037
• 负责人: SHIMANO Yasuo
• 金额: $ 0.64万
• 依托单位: HACHINOHE NATIONAL COLLEGE OF TECHNOLOGY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06651037/
• 关键词: 2-oxazoline; macromonomer; polymerizability; reactivity; radical polymerization; copolymerization; iomic polymerization; group trasfer polymerization; ポリオキサゾリン; リビング重合; シリルケテンアセタール; 機能性; 共重合; 反応性比; ポリ(2-オキサゾリン); ポリ(N-アシルエチレンイミン)

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.

聚（2-烷基-2-恶唑啉）（PROZO）的大分子单体具有亲水性（例如，例如，在一个实施例中，R=Me）或疏水性（e.例如，在一个实施例中，R=n-Bu）性质，以及具有较长烷基的规则支化结构。研究了带有甲基丙烯酸酯端基（MA-PROZO）和乙烯基苄基端基（VB-PROZO）的PROZO大分子单体（R=Me，n-Bu，n-Oc）的聚合性能。在CD_3CN、CDCl_3和D_2O中，60 ℃自由基均聚时，聚合速率随PROZO链长和烷基长度的增加而增加。而MA-POcOZO的聚合则表现出相反的趋势。在D_2O中，PMeOZO大分子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。在与甲基丙烯酸甲酯等小单体的自由基共聚合中，短链VB-PMeOZO（DP为PROZO-3）的反应活性高于单体，但随DP的增加而降低。在24-50 ℃下，以甲硅烷基乙烯酮缩醛为引发剂，进行MA-PROZO基团转移聚合，得到活性大分子单体，该活性大分子单体可被活性PROZO封端，得到AB嵌段共聚物。以乙烯基苄醇盐和乙烯基苄硫醚为阴离子，对活性PROZO进行封端，合成了新型的VB-PROZO。

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