不同钛含量的陶瓷前驱体聚钛硅氮烷的制备与性能  

Preparation and Characterization of Precursor Polytitasilazanes with Different Titanium Contents

作　　者：杨方兴 崔秀琪 滕雅娣[1] Fangxing Yang;Xiuqi Cui;Yadi Teng(Organic-Silicon Chemistry Laboratory,College of Science,Shenyang University of Chemical Technology,Shenyang 110142,China)

机构地区：[1]沈阳化工大学理学院有机硅化学研究室,辽宁沈阳110142

出　　处：《高分子材料科学与工程》2022年第7期23-30,共8页Polymer Materials Science & Engineering

基　　金：辽宁省自然科学基金资助项目(2020031815)。

摘　　要：采用硅氮烷低聚物(OSZ)与TiCl_(4)反应,设计Si:Ti的摩尔比分别为5:1,10:1,15:1,20:1和25:1,合成并分离出一系列聚钛硅氮烷(PTiSZ-x,x=5~25),利用马尔文粒度仪测得其重均分子量(M_(W))为(1.51~9.97)×10~4。利用波长色散X射线荧光光谱仪测得聚钛硅氮烷的实际钛质量分数为2.34%~7.48%。钛比例高或低的PTiSZ相对分子质量都较小,而钛比例适中的PTiSZ相对分子质量则较大。采用红外光谱和核磁共振氢谱对PTiSZ-x进行结构表征,推测出聚钛硅氮烷的结构式为钛原子在低聚物分子间形成钛桥将低聚小分子连接成为线型大分子。PTiSZ-x为线型结构,可溶解于正己烷、二氯甲烷、乙酸乙酯、二甲苯、丙酮等常用有机溶剂。通过热重分析对系列PTiSZ-x及OSZ的耐热性能进行测试,PTiSZ-x的陶瓷收率为71%~78%,发现其相对分子质量影响不大,说明热处理期间形成了新的交联;而OSZ的陶瓷收率为56%,与其低分子量相对应。Using silazane oligomer(OSZ) to react with TiCl_(4),a series of polytitasilazanes(PTiSZ-x,x=5~25) with n(Si):n(Ti) of 5:1,10:1,15:1,20:1,25:1 were synthesized and separated,the weight average molecular weight(MW)measured by Malvern particle size analyzer is(1.51~9.97) × 10~4.The actual titanium mass fraction measured by wavelength dispersive X-ray fluorescence spectrometer is 2.34% ~7.48%.The molecular weight of PTiSZ obtained with a high or low titanium ratio is small,and the molecular weight of PTi SZ with the moderate titanium ratio is large.Using FT-IR and1H-NMR was applied to characterize the structure of PTiSZ,it is speculated that the structural formula of polytitasilazanes is that titanium atoms form titanium bridges between oligomer molecules and connect oligomers to be linear macromolecules.PTiSZ can be dissolved in common organic solvents such as n-hexane,dichloromethane,ethyl acetate,xylene,tetrahydrofuran,acetone,etc.,which proves that this series of PTiSZ have linear structure.The heat resistance of this series of PTiSZ and OSZ measured by TGA results show that the ceramic yield of PTiSZ-x is 71%~78%,and its molecular weight has little effect,indicating that new crosslinks are formed during the heat treatment;the ceramic yield of OSZ is 56%,which corresponds to its low molecular weight.

关 键 词：陶瓷前驱体 聚钛硅氮烷 SiTiCN陶瓷 钛元素含量 

分 类 号：TQ174.1[化学工程—陶瓷工业]