Synthesis, Characterization, and Functions of Novel Silicon-Containing Polyacetylenes

新型含硅聚乙炔的合成、表征及功能

• 批准号: 61550676
• 负责人: MASUDA Toshio
• 金额: $ 1.15万
• 依托单位: Kyoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1986
• 资助国家: 日本
• 起止时间: 1986 至 1987
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-61550676/
• 关键词: 3-(Trimethylsilyl)-1-alkyne; Silylacetylene; 3-Silyl-1-hexyne; Polymerization; Transition Metal Catalyst; Substituted Polyacetylene; Polyene Structure; 成膜性; シリルアセチレン; ポリアセチレン; ポリエレン構造

The present project has dealt with the synthesis of novel, high-molecular-weight polymers form Si-containing acetylenes, elucidation of unique properties of the polymers, and exploitation of their functions. The results are summarized as follows:1. Synthesis and Characterization of Polymers from 3-(Trimethylsilyl)-1-alkyne Polymerization of four kinds of 3-(trimethylsilyl)-1-alkynes [HC<congruent>CCH(SiMe_3)R; R= CH_3, n-C_3H_7,n-C_5H_<11>, and n-C_7H_<15>) was examined. New polymers were obtained in high yields from these monomers in the pressence of Mo, W, and Nb catalysts. Every polymer was a yellow solid, whose structure could be expressed by [CH=CCH(SiMe_3)R_n]. Thepolymer with R = n-C_5H_<11> had high molecular weights up to 45x10^4, dissolved in many common organic solvents such as toluene and chloroform, and afforded a membrane by solution casting. The electrical conductivity of this polymer was 10^<-18> S.cm^<-1>, and its unpaired-electron density was <1x10^<15> spin/g. Further, the gas permeability ofthe polymer was investigated.2. Polymerization of Silylacetylenes and Polymer Properties Polymerization of five kinds of trimethylsilylacetylene homologues (HC<congruent>CSiMe_2R; R = n-C_6H_<13>, CH_2CH_2Ph, CH_2Ph, Ph, and t-Bu) was examined. Every monomer produced a polymer in the presence of suitable W catalysts. The polymers were yellow solids or rubbers. The polymers with flexible groups (R = n-C_6H_<13>, CH_2CH_2Ph, and CH_2Ph) were totally soluble in organic solvents, and their molecular weights were around 1x10^4.3. Polymerization of 3-Silyl-1-hexyne and Polymer Properties Two kinds of novel Si-containing monosubstituted acetylenes [HC<congruent>CCH(SiMe_<>R)-n-C_3H_7; R = n-C_6H^3 and Ph) produced polymers (MW 1x10^5 - 4x10^5) in good yields in the presence of Mo, W, and Nb catalysts. Both polymers were yellow solids and soluble in many solvents. Thermal, mechanical, electrical, and magnetic properties of these polymers have been elucidated.

本项目涉及由含硅乙炔合成新型高分子量聚合物，阐明聚合物的独特性质，并开发其功能。主要研究结果如下：1. 3-（三甲基硅基）-1-炔聚合物的合成与表征研究了四种3-（三甲基硅基）-1-炔[HC <congruent>CCH（SiMe_3）R; R= CH_3，n-C_3 H_7，n-C_5 H_<11>，n-C_7 H_<15>]的聚合。在Mo、W和Nb催化剂存在下，由这些单体以高产率得到新的聚合物。聚合物均为黄色固体，其结构可用[CH=CCH（SiMe_3）R_n]表示。R = n-C_5 H_4的聚合物<11>分子量高达45 × 10^4，可溶于甲苯、氯仿等多种常见有机溶剂中，通过溶液浇铸法可制得膜。该聚合物的电导率为10 μ<-18>S.cm g/g<-1>，并且其未配对电子密度为&lt;1 × 10 - 6<15>自旋/g。进一步研究了聚合物的透气性.研究了五种三甲基硅基乙炔同系物（HC <congruent>CSiMe_2R; R = n-C_6 H_<13>，CH_2CH_2Ph，CH_2Ph，Ph，t-Bu）的聚合反应。在合适的W催化剂存在下，每个单体都生成聚合物。聚合物是黄色固体或橡胶。含柔性基团的聚合物（R = n-C_6 H_<13>、CH_2CH_2Ph和CH_2Ph）完全溶于有机溶剂，分子量约为1 × 10^4.3。3-甲硅烷基-1-己炔的聚合及聚合物性质两种新型含硅单取代乙炔[HC <congruent>CCH（SiMe_&lt;&gt;R）-n-C_3 H_7; R = n-C_6 H ^3和Ph）在Mo、W和Nb催化剂的存在下以良好的产率产生了聚合物（MW 1x 10^5 - 4x 10^5）。两种聚合物均为黄色固体，可溶于多种溶剂。这些聚合物的热，机械，电气和磁性能已经阐明。

项目成果

H.Tajima: J.Polym.Sci.,Part A,Polym.Chem.25. 2033-2042 (1987)

H.Tajima：J.Polym.Sci.，A 部分，Polym.Chem.25。

T.Masuda: Macromolecules. 20. 1467-1472 (1987)

T.增田：高分子。

T.Masuda: Macromolecules.

T.增田：高分子。

H.Tajima: J.Polym.Sci.,Part A,Polym.Chem.

H.Tajima：《高分子科学杂志》，A 部分，《高分子化学》。

H. Tajima et al.: "Polymerization of Silylacetylenes by W and Mo Catalysts" J. Polym. Sci., Part A, Polym. Chem.25. 2033-2042 (1987)

H. Tajima 等人：“W 和 Mo 催化剂对甲硅烷基乙炔的聚合”J. Polym。