Polymerization of Dendritic Macromonomer and Preparation of its membrane for Permseparation

树枝状大分子单体的聚合及其渗透分离膜的制备

• 批准号: 08651048
• 负责人: OIKAWA Eizo
• 金额: $ 0.77万
• 依托单位: Niigata University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08651048/
• 关键词: dendrimer; monodendron; polydendron; poly (phenylacetylene); phenyleneethynylene; rhodium catalyst; palladium catalyst; permselective membrane; デンドリマ-

The well-defined side-chain structure of dendrimers is expected to play an important role on the permselectivity for highly selective membranes. We synthesized dendritic phenylacetylene monomers containing tert-butyl group, trimethylsilyl group, or oligodimethylsiloxane, as the peripheral group using the convergent approach. The monomers were polymerized with rhodium catalyst at the terminal acetylene unit to yield the corresponding poly(phenylacetylene) derivatives as yellow powders with a high degree of polymerization, e.g., DP=2.8 x 10^3, in spite of their steric bulkiness. Some reasons why the monodendrons gave the polydendrons with high molecular weight in spite of their steric bulkiness were probably considered as follows. The terminal acetylene was exposed from dendritic crowd, and the polymerization proceeded stereoregularly to give the reasonable packing of the side-chain dendrons. The polymers were soluble in common organic solvents, such as chloroform and tetrahydrofuran, but insoluble in alcohols, and the solubility of these polydendrons was better than that of the corresponding zero generation poly(phenylacetylene) derivatives. The wide angle X-ray scattering of the polymers suggested the pseudohexagonal lattice of rod-like molecules. The interplanar d spacing increased with increasing generation or size of the peripheral silyl group. The polydendrons indicated good membrane forming ability, and the gas permeability of the membrane was examined. The oxygen permselectivity of the polydendrons showed good performance in comparison with the corresponding zero generation of poly(phenylacetylene) derivatives. It was found that the well-defined dendritic and rod-like structure of the polydendrons was useful for pemselective membrane.

树枝状大分子的侧链结构对高选择性膜的选择透过性能有重要影响。采用收敛法合成了以叔丁基、三甲基硅基或低聚二甲基硅氧烷为外围基团的树枝状苯乙炔单体。单体在末端乙炔单元处用铑催化剂聚合以产生具有高聚合度的黄色粉末状的相应聚（苯乙炔）衍生物，DP=2.8 x 10^3，尽管它们的空间体积很大。尽管它们的空间体积大，但单枝分子产生高分子量的多枝分子的一些原因可能被认为如下。末端乙炔从树枝状群中暴露出来，并且聚合有规立构地进行，以给出侧链树枝状基元的合理堆积。这些聚合物可溶于氯仿和四氢呋喃等常用有机溶剂，但不溶于醇类，其溶解性优于相应的零代聚苯乙炔衍生物。聚合物的广角X射线散射表明，棒状分子的假六方晶格。晶面间距d随着周围甲硅烷基的生成或尺寸的增加而增加。结果表明，该聚合物具有良好的成膜能力，并对膜的透气性进行了测试。与相应的零代聚（苯乙炔）衍生物的氧渗透选择性的聚枝晶表现出良好的性能相比。结果表明，树枝状和棒状结构的多枝晶分子是有效的选择性膜。

项目成果

金子 隆司: "フェニルアセチレンモノデンドロンの合成と重合" 日本化学会第72回春季年会予稿集. 72巻2号. 734-734 (1997)

Takashi Kaneko：“苯乙炔单枝化合物的合成和聚合”日本化学会第 72 届春季年会论文集，第 72 卷，第 2 期，734-734（1997 年）。

金子隆司: "剛直な樹状側鎖を持つポリ(フェニルアセチレン)誘導体の合成" 高分子学会北陸支部第45回研究発表会講演要旨集. 45. 7-7 (1996)

Takashi Kaneko：“具有刚性树枝状侧链的聚(苯乙炔)衍生物的合成”高分子科学技术学会北陆分会第45届研究会议摘要45. 7-7 (1996)。

金子 隆司: "フェニルアセチレンモノデンドロンの合成と重合およびポリマーの特性" 高分子学会予稿集(第47回高分子学会年次大会). 47巻2号. 295-295 (1998)

Takashi Kaneko：“苯乙炔单枝体的合成和聚合以及聚合物的性能”高分子科学技术学会论文集（第 47 届高分子科学技术学会年会）第 47 卷，第 295-295 期。 (1998)

Takashi Kaneko, Hiroyuki Tatsumi, Toshiki Aoki, Eizo Oikawa, Hajime Yoshiki, Naoki Yoshioka, Eishun Tsuchida, Hiroyuki Nishide: ""Polymerization of (p-Vinylphenyl) hydrogalvinoxyl and Formation of a Stable Polyradical Derivative"" Journal of Polymer Scien

Takashi Kaneko、Hiroyuki Tatsumi、Toshiki Aoki、Eizo Oikawa、Hajime Yoshiki、Naoki Yoshioka、Eishun Tsuchida、Hiroyuki Nishide：“（对乙烯基苯基）氢加尔万氧基的聚合和稳定多自由基衍生物的形成”高分子科学杂志

金子 隆司: "フェニルアセチレンモノデンドロンの合成と重合" 日本化学会第72回春季年会予稿集. 72巻1号. 734-734 (1997)

Takashi Kaneko：“苯乙炔单枝化合物的合成和聚合”日本化学会第 72 届春季年会论文集，第 72 卷，第 1. 734-734 期（1997 年）。