三氯环硼氮烷及其衍生物的制备与表征  

Preparation and Characterization of B-Trichloroborazine and Its Derivatives

作　　者：王钰[1] 王希[1] 曹维良[2] 沈志洵[1] 吴言[1] 王长松[3] 张伟刚[1] 

机构地区：[1]中国科学院过程工程研究所多相复杂系统国家重点实验室,北京100080 [2]北京化工大学理学院,北京100029 [3]沈阳化工学院材料科学与工程系,辽宁沈阳110142

出　　处：《过程工程学报》2007年第6期1099-1106,共8页The Chinese Journal of Process Engineering

摘　　要：以三氯化硼和氯化铵为原料,以氯苯为溶剂,采用Schlenk技术合成并提纯出高纯度三氯环硼氮烷(TCB)晶体,利用二甲胺与TCB进行反应,得到TCB的衍生物烷基胺环硼氮烷,为获得高质量BN材料作了原料准备.采用NMR以及单晶衍射方法对合成样品进行了分析,对反应条件、反应装置及反应路线进行了考察.研究结果表明,合成反应为均液相反应,加入催化剂Hg,TCB产率可达89%以上;不加催化剂,适当延长反应时间,TCB产率可达87%以上.在提纯TCB的步骤中,精馏塔理论塔板数为6时较佳.采用B3LYP/6-31G*计算水平对取代反应过程进行模拟计算,结果表明,取代反应过渡态包含Cl-B-N-HCl四元环结构,通过计算推测反应有可能生成几种取代衍生物的混合物.Crystalline B-triehloroborazine （TCB） was synthesized and purified using Sehlenk technique with boron triehloride （BCl3） and ammonium chloride （NH4C1） as raw materials and ehlorobenzene （C6H5C1） as solvent. Further derivatives of TCB were also obtained by substitution reaction of dimethylamine and TCB, from which high quality BN could be prepared. The results were analyzed using NMR and XRD, and the preparation conditions, experimental apparatus and route of reactions were examined. It was found that the TCB synthesis followed a homogeneous liquid phase reaction mechanism. The yield of TCB could reach above 89% when Hg as catalyst or above 87% by proper extending of reaction time without catalyst. The optimum theoretical plate number of rectification column was estimated as 6 for purification of TCB. The substitution reaction of TCB was simulated at the B3LYP/6-31G^＊ level, the results show that there exists a C1-B-N-H-C1 tetratomie ring structure in the intermediate state of the substitution reaction. It can also be postulated from the simulation that a mixture of several different products could be produced in the reaction.

关 键 词：三氯环硼氮烷 二甲胺环硼氮烷 有机前驱体 均液相反应 

分 类 号：O613.81[理学—无机化学]