Fabrication of oxygen permeable films of polyacetylenes bearing ester group as a side chain and its evaluation.

侧链带有酯基的聚乙炔透氧薄膜的制备及其评价

• 批准号: 07455368
• 负责人: TABATA Masayoshi
• 金额: $ 4.1万
• 依托单位: HOKKAIDO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07455368/
• 关键词: Rh complex catalyst; Polyacetyelene; Stereoregurality; Oxgen permeable film; Oxygen permeable coefficient; Cast; Columnar; Pseudohexagonal; Rh錯体触媒; 酸素富化膜; 立体特異的; 酸素透過係類; キャスト; 擬ヘキサゴナル; ESR; ポリプロピオレート; ヘキサゴナル; シス体

It has been demonstrared that strereoregular polymerization monosubstituted acetylenes were successfully achieved using Rh complex catalysts in the presence of triethylamine or alchohol under fairly mild conditions and the resulting polyacetylenes were carefully characterized using lasr Raman, diffuse reflective UV,NMR,and electron spin resonance (ESR) methods. ^<1-2)> Consequently we found that the Rh complex is a preffered catalyst for formation of cis-transoid polyacetylenes even at room temperature. Acetylene esters bearing n-akllkyl group in the side chain were aslo stereoregularly polymerized to give the corresponding polyacetylene esters' using methanol as the polymerizaion solvent. ^<3)> The ester polymers were found to have a pseudohexagonal structure called columnar as self assembly useful for the oxygen permeable films. ^<4-5,13)> The polyacetylene esters were cast from chloroform and the oxygen permeability was estimated using a so-called GAS PERM,i.e., the separationcoefficient of the ratio, P_<O2>/P_<N2> was ca. alpha=3.4 comparable for other polmers bearing silicon moieties, suggesting that this polymer is promising new materials for oxygen permeable films. Further, the polyacetylenes prepared with Rh complex catalyst was found to be isomerized by compression even at room temperature in order to give the trans isomers involving a large amount of radicals as solitons. ^<4-6)>

已经证明，在三乙胺或醇存在下，在相当温和的条件下，使用Rh配合物催化剂成功实现了立体规整聚合单取代乙炔，并使用激光拉曼、漫反射紫外、核磁共振和电子自旋共振（ESR）方法对所得聚乙炔进行了仔细表征。 ^<1-2)> 因此，我们发现Rh络合物即使在室温下也是形成顺式-反式聚乙炔的优选催化剂。使用甲醇作为聚合溶剂，侧链带有正烷基的乙炔酯也进行有规立构聚合，得到相应的聚乙炔酯。 ^<3)>发现酯聚合物具有称为柱状的假六边形结构作为可用于透氧膜的自组装。 ^<4-5,13)> 聚乙炔酯由氯仿铸造而成，并使用所谓的 GAS PERM 估算透氧性，即 P_<O2>/P_<N2> 比率的分离系数约为 1。 α=3.4 与其他带有硅部分的聚合物相当，表明该聚合物是有前途的透氧薄膜新材料。此外，发现用Rh配合物催化剂制备的聚乙炔即使在室温下也可以通过压缩异构化，从而得到涉及大量作为孤子的自由基的反式异构体。 ^<4-6)>

项目成果

Masayoshi Tabata: "Hexagonal Columnars of Poly(n-alkylpropiolate)Produced with Rhodium Complex Catalyst.X-ray Analysis and Oxygen Permeability"" Macromolecules. 29. 5573-6675 (1996)

Masayoshi Tabata：“用铑络合物催化剂生产的聚（正烷基丙炔酸酯）的六角柱状结构。X射线分析和透氧性””高分子。29。5573-6675（1996）

M.Tabata: "Columnar Formation from Polyethynylbenzene and Poly (rho-methylethynyl benzene) Polymerized Using [Rh (norbornadiene) Cl] 2 as Catalyst. An X-ray and ESR Study" J.Macromoleclar Sci.-Pure Appl.Chem., Pure Appl.Chem.A34. 641-653 (1997)

M.Tabata：“使用 [Rh（降冰片二烯）Cl] 2 作为催化剂聚合聚乙炔基苯和聚（对甲基乙炔基苯）的柱状形成。X 射线和 ESR 研究”J.Macromoleclar Sci.-Pure Appl.Chem.，

Tabata Masayoshi: "Highly Stereoregular Polymerization of Aromatic Acetylenes by [Rh(norbornadiene)Cl]2 Catalyst" Proceeding of Japan Academy. 71. 219-224 (1995)

Tabata Masayoshi：“[Rh(降冰片二烯)Cl]2 催化剂对芳香族乙炔的高度立体规整聚合”日本科学院院刊。

M.Tabata: "Hexagonal Columas of Poly (eta-alkylpropiolate) Produced with Rhodium Complex Catalyst. X-ray Analysis and Oxygen Permeability" Macromolecules. (20). 5573-6675 (1996)

M.Tabata：“用铑络合物催化剂生产的聚(eta-烷基丙炔酸酯)的六角柱。X射线分析和透氧性”大分子。

Masayoshi Tabata: "Columnar Formation from Polyethynylbenzene and Poly(p-methylethynyl benzene)Polymerized Using [Rh(norbornadiene)Cl]2 as Catalyst." J.Macromoleclar Sci.-Pure Appl.Chem.A35. 641-653 (1997)

Masayoshi Tabata：“使用 [Rh(降冰片二烯)Cl]2 作为催化剂，由聚乙炔基苯和聚(对甲基乙炔基苯)聚合形成柱状结构。”