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.

本项目涉及以含硅乙炔为原料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。1.考察了四种3-(三甲基硅基)-1-炔[HC&lt；同分和GT；CCH(SiMe_3)R；R=CH_3，n-C_3H_7，n-C_5H&lt；11&gt；n-C_7H&lt；15&gt；]的3-(三甲基硅基)-1-炔聚合产物的合成和表征。在Mo、W和Nb催化剂的存在下，这些单体高产率地合成了新的聚合物。每种聚合物均为黄色固体，其结构可用[CH=CCH(SiMe_3)R_n]表示。该聚合物的R=n-C_5H_&lt；11&gt；高相对分子质量可达45×10~(-4)，可溶于甲苯、氯仿等多种常见有机溶剂，并可通过溶液浇铸制得膜。该聚合物的电导率为10~(-18)cm~(-1)，未成对电子密度为~lt；1x10；~(15)自旋/g，并对其气体渗透性进行了研究。考察了5种三甲基硅基乙炔同系物(Hc&lt；同分&gt；CSiMe_2R；R=n-C_6H&lt；13&gt；CH2CH2Ph，CH2Ph，t-Bu)的聚合反应。在合适的W催化剂存在下，每个单体产生一种聚合物。聚合物是黄色固体或橡胶。具有柔性基团的聚合物(R=n-C6H&lt；13&gt；CH2CH2Ph和CH2Ph)在有机溶剂中完全溶解，其相对分子质量约为1×10？4.3。3-硅基-1-己炔的聚合及聚合物性质在Mo、W和Nb催化剂存在下，两种新型含硅单取代乙炔[HC&lt；congruent&gt；CCH(SiMe_&lt；&gt；R)-n-C_3H_7；R=n-C_6H^3和Ph)以较高的产率合成了聚合物(MW 1×10~(-5)-4×10~(10^5))。这两种聚合物都是黄色固体，可溶于多种溶剂。这些聚合物的热、机械、电和磁性能已被阐明。

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。