Precise Synthesis of High Generation Dendrimer-Like Star-Branched Polymers and Their Applications

高世代树枝状星形支化聚合物的精密合成及其应用

基本信息

批准号：
18350060
负责人：
HIRAO Akira
金额：
$ 10.91万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2006
资助国家：
日本
起止时间：
2006 至 2007
项目状态：
已结题

项目摘要

Dendrimer-like star-branched polymers have been synthesized by developing a novel methodology which involves two basic reactions: (1) linking reaction of α-functionalized living anionic polymers with benzyl bromide-functionalized polymers and (2) transformation reaction to benzyl bromides. The two reactions proceeded quantitatively several times, resulting in the formation of high-generation dendrimer-like star-branched polymers up to seventh generation. The resulting polymer (7th generation) is a really huge macromolecule possessing two million in molecular weight and a narrow molecular weight distribution (Mw/Mn =1.02) and comprising 508 polymer segments with 512 termini. Highly dense polymers consisting of four branches at each junction have also succeeded in synthesizing the polymers up to the third generation. The attempt to synthesize the 4th generation polymer was not successful possibly due to the steric hindrance. Other functional polymer segments have been successfully introduced into the outermost layers of dendrimer-like star-branched polymers. They involve poly(2-vinylpyridine), poly(tert-butyl methacrylate), poly(3-perfluorobutylpropyl methacrylate), and poly(2,3-dihydroxypropyl methacrylate), respectively. By introducing such segments, basic, acidic, ionic, hydrophobic and lipophobic, water-soluble characters could be provided to the polymers. Furthermore, the introduction of methacrylate polymers having liquid crystalline, chirality, and thermoresponsive characters were also successful. Their functional polymers have been examined in detail with respect to such functionalities. The shapes of the dendrimer-like star-branched polymers have been measured by SAXS and found to be ellipsoidal shapes rather than spherical ones. AFM structural imaging of the dendrimer-like star-branched polymers has been realized. The structures based on synthetic methodology as well as internal branching points could be clearly observed for the first time.

通过开发一种涉及两种基本反应的新方法，已经合成了类似树状聚合物的星形分支聚合物：（1）将α官能化的活阴离子聚合物与苄基溴化聚合物和（2）转化与苯唑溴的反应的反应。这两种反应进行了数量进行数次进行，导致形成高代树枝状聚合物样的星形分支聚合物，直到第七代。所得聚合物（第七代）是一个非常巨大的大分子，具有200万个分子量和狭窄的分子量分布（MW/MN = 1.02），并完成了508个具有512术语的聚合物段。由每个连接处的四个分支组成的高度致密聚合物也成功地将聚合物合成到第三代。由于空间的阻碍，合成第四代聚合物的尝试是不可能的。其他功能性聚合物片段已成功地引入了类似树状聚合物的星形分支聚合物的最外层。它们涉及聚（2-乙烯基吡啶），聚（二甲基丙烯酸甲酯），聚二氟丁基丙烯酸酯）和聚（2,3-二羟基丙烯酸丙烯酸酯）。通过引入此类片段，碱性，酸性，离子，疏水性和寄生虫，水溶性特征，还引入具有液晶，手性和热响应特征的甲基丙烯酸酯聚合物也成功了。它们的功能聚合物已针对此类功能进行了详细研究。萨克斯州已经测量了类似树状聚合物的星形分支聚合物的形状，发现是椭圆形的形状，而不是球形的形状。已经实现了类似树状聚合物的星形分支聚合物的AFM结构成像。可以首次清楚地观察基于合成方法和内部分支点的结构。