陶瓷学报2024,Vol.45Issue(1) :109-116.DOI:10.13957/j.cnki.tcxb.2024.01.010

含氰基聚碳硅烷的合成及影响因素研究

Synthesis and Influence Factors of Cyano-polycarbosilane

谢富成 陈豆 莫高明 何流 黄庆
陶瓷学报2024,Vol.45Issue(1) :109-116.DOI:10.13957/j.cnki.tcxb.2024.01.010

含氰基聚碳硅烷的合成及影响因素研究

Synthesis and Influence Factors of Cyano-polycarbosilane

谢富成 1陈豆 2莫高明 2何流 2黄庆2
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作者信息

  • 1. 中国科学院宁波材料技术与工程研究所先进能源材料工程实验室,浙江宁波 315201;浙江工业大学化学工程学院,浙江杭州 310014
  • 2. 中国科学院宁波材料技术与工程研究所先进能源材料工程实验室,浙江宁波 315201
  • 折叠

摘要

聚碳硅烷(PCS)是碳化硅(SiC)纤维和陶瓷的重要先驱体之一.以PCS作为先驱体制备SiC纤维和陶瓷时,通常存在陶瓷产率低的问题,进而影响最终产品质量.利用含铑催化剂以及偶氮二异丁腈,使通常不易进行硅氢化反应的丙烯腈和PCS发生反应,将氰基引入PCS分子中,合成出新型含氰基聚碳硅烷(PCSCN)先驱体.与PCS相比,以含铑催化剂合成的PCSCN的陶瓷产率可大幅提高至80%以上.用红外、核磁分析了 PCSCN的分子结构,结果表明两种催化剂引发的硅氢化反应均是以α加成方式为主.此外,以含铑催化剂催化硅氢化反应时,反应程度初期随着反应时间延长、反应温度升高而加深,但反应5 h后或60 ℃以上基本不变;增加丙烯腈的量有利于增加反应程度,从而引入较多的氰基,但增加幅度不明显.

Abstract

Polycarbosilane(PCS)is an important precursor of silicon carbide(SiC)fibers and ceramics.As a precursor for preparing SiC fibers and ceramics,it has several deficiencies,such as low ceramic yield,which affect the properties of final products.Cyano-polycarbosilane,a new SiC precursor,was synthesized by using hydrosilylation addition reaction of PCS and acrylonitrile,which is not easy for hydrosilylation generally.During the synthetic process,rhodium-containing catalyst and 2-methylpropionitrile were used.The ceramic yield of PCSCN would be significantly increased to over 80%,as compared with that of PCS,especially as the rhodium-containing catalyst was used.The molecular structure of PCSCN was analyzed by using IR and NMR,showing that the hydrosilylation reaction was mainly α-addition.In addition,the degree of hydrosilylation increased with increasing reaction time and reaction temperature at the initial stage,but remained almost unchanged when the time was longer than 5 h or the temperature was higher than 60 ℃.Increasing the content of acrylonitrile would lead to increase in the degree of reaction and thus more cyano groups were introduced in PCSCN,but the magnitude was low.

关键词

丙烯腈/聚碳硅烷/硅氢化/陶瓷产率

Key words

acrylonitrile/polycarbosilane/hydrosilylation/ceramic yield

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基金项目

浙江省自然科学基金(LY21B040003)

宁波市"3315"创新计划(2018A-03-A)

出版年

2024
陶瓷学报
景德镇陶瓷学院

陶瓷学报

CSTPCD北大核心
影响因子:0.7
ISSN:1000-2278
参考文献量24
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