Synthesis and Characterization of Ethylene-Bridged Copolycarbosilazane as Precursors for Silicon Carbonitride Ceramics
Synthesis and Characterization of Ethylene-Bridged Copolycarbosilazane as Precursors for Silicon Carbonitride Ceramics
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DOI：
10.1111/jace.12770
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发表时间：
2014-04
影响因子：
3.9
通讯作者：
Dong Su;Ya-li Li;F. Hou;Xiao-xia Yan
中科院分区：
文献类型：
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作者：
Dong Su;Ya-li Li;F. Hou;Xiao-xia Yan
以乙烯基甲基二氯硅烷和甲基二氯硅烷的混合物为原料，以三乙胺为吸酸剂，以乙二胺为缩聚反应合成了共聚乙基乙二胺（co-PSDA）的乙烯桥共聚碳硅烷前驱体。傅里叶变换红外（FTIR）和核磁共振（NMR， 1H NMR和13C NMR）光谱分析表明，合成的co-PSDA为乙烯桥接的聚碳硅烷结构，主链为- Si - n - c - c - n -，侧基为- ch =CH2， - h和- ch3。Co-PSDA可以在80℃下以2,2 -偶氮二异丁腈为引发剂，通过乙烯基的聚加成和Si-H和N-H的脱氢/脱氨反应进行交联。然后将交联co-PSDA前驱体在1000℃氩气中热解，得到非晶态氮化硅碳（SiCN）陶瓷，陶瓷收率高达76%。所制得的SiCN陶瓷由以SiN4为主要成分的富氮硅位和部分SiCN3位组成，这可能是由于600℃以下N-C键断裂和活性N-Si键形成所致。
An ethylene-bridged copolycarbosilazane precursor of copolysilylethylenediamine (co-PSDA) is synthesized by polycondensation of ethylenediamine with the mixture of vinylmethyldichlorosilane and methyldichlorosilane in the presence of triethylamine as acid absorbing agent. Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR, 1H NMR and 13C NMR) spectral analysis of the as-synthesized co-PSDA suggests a structure of ethylene-bridged polycarbosilazane having –Si–N–C–C–N– as backbone chain with –CH=CH2, –H and –CH3 attached to Si as side groups. Co-PSDA can be cross-linked at 80°C using 2, 2-azobisisobutyronitrile as initiator through the polyaddition of the vinyl group and dehydrogenation/deamination of Si–H and N–H. Then the cross-linked co-PSDA precursor is pyrolyzed at 1000°C in argon, giving out amorphous silicon carbon nitride (SiCN) ceramics with a high ceramic yield of 76 wt%. The obtained SiCN ceramics consist of nitrogen-rich silicon sites of SiN4 as predominant component and some SiCN3 sites, which should arise from the breaking of N–C bonds below 600°C and the formation of active N–Si bonds.