Synthesis of novel amphihilic branched polymers with well-controlled architectures with respect to position, number, and molecular weight

合成新型两亲性支化聚合物，在位置、数量和分子量方面具有良好控制的结构

• 批准号: 09650974
• 负责人: HIRAO Akira
• 金额: $ 2.24万
• 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 (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09650974/
• 关键词: Anionic living polymer; Chloromethylphenyl group; Star polymer; Multifunctionalized polymer; Glucose end-functionalized polystyrene; Rf end-functionalized polystyrene; Surface enrichment; Reversed micelle; 分枝ポリマー; H型ポリマー; グラフトポリマー; クロロメチル基; 構造

We have successfully introduced a definite number of methoxymethyl-phenyl groups either at the chain ends or in the chains by reacting anionic living polymers with methoxymethyl substituted 1,1-diphenylethylene and/or the derivatives. The numbers introduced range from 2 to 16. These methoxymethylphenyl groups were quantitatively transformed into chloromethylphenyl groups by the treatment with boron trichloride. The chloromethylphenyl functionalized polymers thus prepared were reacted with another anionic living polymers to result in the formation of well-defined heteroarm star polymers. The arm segments used were polystyrene, polyisoprene, poly(ethylene oxide), and poly(methacrylic acid), respectively. Furthermore, it was found that these functionalized polymers could be reacted quantitatively with functionalized anions derived from the corresponding 1,1-diphenylethylene derivatives. As the result, new functionalized polymers having a definite number of functional groups (phenol, glucose, perfluoroalkyl etc) at the chain ends or in the chains were obtained. Such functionalized polymers were observed to behave characteristically in solutions and in solid state (especially at the film surfaces).

我们通过与甲氧基甲基替代的1,1-二苯基乙烯和/或衍生物反应，通过反应阴离子活性聚合物和/或衍生物，成功地在链端或链中成功地引入了确定的甲氧甲基苯基基团。引入的数字范围为2至16。这些甲氧基苯基基团通过三氯化硼的处理将这些甲氧基苯基基团定量转化为氯甲基苯基。这样制备的氯甲基苯基官能化聚合物与另一种阴离子活性聚合物反应，从而形成明确定义的杂臂星形聚合物。所使用的手臂段分别是聚苯乙烯，聚异丙烯，聚乙烷氧化物和聚（甲基丙烯酸）。此外，发现这些功能化的聚合物可以与源自相应的1,1-二苯基乙烯衍生物的功能化阴离子进行定量反应。结果，获得了链末端或链中具有确定数量的官能团（苯酚，葡萄糖，全烷基等）的新功能化聚合物。观察到这种功能化的聚合物在溶液和固态（尤其是在膜表面）中具有特征性的特征。

项目成果

A.Hirao,M.Hayashi: "Recent advance in synthesis and applications of well-defined end-functionalized polymers by means of anionic Living polymerization"Acta Polymerica. 50. 219-231 (1999)

A.Hirao、M.Hayashi：“通过阴离子活性聚合方法合成和应用明确的末端官能化聚合物的最新进展”Acta Polymerica。

A.Hirao,S.Nakahama: "Anionic living polymerization of functionalized monomers" Acta Polymerica. 49. 133-144 (1998)

A.Hirao，S.Nakahama：“官能化单体的阴离子活性聚合”Acta Polymerica。

Akira Hirao and Mayumi Hayashi: "Recent advance in syntheses and applications fo well-defined end-functionalized polymers by means of anionic living polymerization"Acta polymerica. 50. 219-231 (1999)

Akira Hirao 和 Mayumi Hayashi：“通过阴离子活性聚合来合成和应用明确的末端官能化聚合物的最新进展”《聚合学报》。

M. Hayashi, Y. Negishi, A. Hirao: "Synthesis of heteroarm star-branched polymers by means of anionic living polymerization in conjunction with functional group transformation"Proc. Japan Acad.. 75. 93-96 (1999)

M. Hayashi、Y. Negishi、A. Hirao：“通过阴离子活性聚合与官能团转化合成杂臂星形支化聚合物”Proc。

M.Hayashi,S.Nakahawa,A.Hirao: "Synthesis of End-Functionalizes Polymers by Meaus of Living Anionic Polymerization.10"Macromolecules. 32,5. 1325-1331 (1999)

M.Hayashi、S.Nakahawa、A.Hirao：“通过活性阴离子聚合方法合成末端官能化聚合物。10”大分子。