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Formation of Gas Permeable Channel through the Phase Separation of Polydimethylsiloxane Graft Copolymers.

通过聚二甲基硅氧烷接枝共聚物的相分离形成透气通道。

基本信息

批准号：
62470104
负责人：
KAWAKAMI Yuhsuke
金额：
$ 2.88万
依托单位：
Nagoya University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1987
资助国家：
日本
起止时间：
1987 至 1988
项目状态：
已结题

项目摘要

In order to establish the principle to precisely control the gas permeability and permselectivity, by designing the structure of polymers in the solid state, three approaches were attempted.Gas permeation channnel could be prepared by taking advantage of micto-phase sparation ofhydrophilic and hydrophobic graft copolyners prepared from macromers. Cocomplexes were introduced by reacting with bromomathyl groups in polymer side chain to enhance the selectivity in permeation. It was also found that surface accumulation of polydimethylsiloxane based graft copolymers could effectvely enhance both permeability and permselectivity of oxygen gas over nitrogen gas. This principle was applied to enhance the permeability and permselectivity of oxygen permeation through the commercialized polydimethylsiloxane-b-polycarbonate oxygen separation film.Meanwhile, factors controlling the permeation of gases through polymer films were investigated. It was elucidated, by invesitigating the glass transition temperature, diffusion coefficient and relaxation phenomena in the permeation, that mobility of side chains of polymer is playing essential roles in permeation. The mobility of side chains can be precisely controlled by introducing siloxane spacers between polymer main chain and side chains. The number and the type of siloxane linkage have big effect on the property of the polymers. For instance, one siloxane linkage reduce the glass transition temperature by 100゜C and permeability coefficient was increased by 30 times. According to this principle, it could be shown that polynorbornenes with oligodimethylsiloxane side chains were quite good materials for oxygen selectively permeable membrane materials.

为了建立精确控制气体渗透性和渗透选择性的原理，通过设计固态聚合物的结构，尝试了三种方法：利用大分子单体制备的亲水性和疏水性接枝共聚体的微相分离，制备气体渗透通道。通过与聚合物侧链上的溴代甲基反应，引入了络合物，以提高渗透选择性。研究还发现，聚二甲基硅氧烷接枝共聚物的表面积累可以有效地提高氧气对氮气的渗透性和选择性。应用这一原理，通过商品化的聚二甲基硅氧烷-聚碳酸酯氧分离膜来提高氧气的渗透性和选择性，同时研究了控制气体透过聚合物膜的因素。通过对渗透过程中的玻璃化转变温度、扩散系数和松弛现象的研究，阐明了聚合物侧链的流动性对渗透起着至关重要的作用。通过在聚合物主链和侧链之间引入硅氧烷间隔物，可以精确控制侧链的迁移率。硅氧烷键的数目和类型对聚合物的性能有很大的影响。例如，一个硅氧烷键可使玻璃化转变温度降低100゜C，渗透系数提高30倍。根据这一原理，含低聚二甲基硅氧烷侧链的聚降冰片烯是一种很好的氧选择透膜材料。