CAJ | 학술논문

利用分子模拟方法,对异丁烷-丁烯烷基化反应体系中C_4和C_8碳正离子可能进行的各类基元反应进行了研究.结果表明,对于C_4碳正离子而言,2种伯丁基碳正离子的能量明显较高,而仲丁基碳正离子和叔丁基碳正离子的能量分别比伯正丁基碳正离子低71.94 kJ/mol和125.99 kJ/mol;对于C_8碳正离子而言,所有的伯碳正离子在结构优化时,均自发地异构成了相应的C_8仲碳正离子或叔碳正离子.这表明异丁烷-丁烯烷基化反应体系中C_4和C_8伯碳正离子不可能存在,或者说存在几率很低.依据量子化学计算结果,确定了异丁烷-丁烯烷基化反应体系中可能存在的碳正离子中间体,依据碳正离子反应假设,确定了12种烯烃质子化反应、29种碳正离子异构化反应、32种碳正离子与丁烯的加成反应、30种碳正离子与异丁烷之间的负氢离子转移反应和18种碳正离子脱附反应.在此基础之上,构建了涉及60个物种和121个基元反应的具有较强预测能力的基元反应网络.
이용분자모의방법,대이정완-정희완기화반응체계중C_4화C_8탄정리자가능진행적각류기원반응진행료연구.결과표명,대우C_4탄정리자이언,2충백정기탄정리자적능량명현교고,이중정기탄정리자화숙정기탄정리자적능량분별비백정정기탄정리자저71.94 kJ/mol화125.99 kJ/mol;대우C_8탄정리자이언,소유적백탄정리자재결구우화시,균자발지이구성료상응적C_8중탄정리자혹숙탄정리자.저표명이정완-정희완기화반응체계중C_4화C_8백탄정리자불가능존재,혹자설존재궤솔흔저.의거양자화학계산결과,학정료이정완-정희완기화반응체계중가능존재적탄정리자중간체,의거탄정리자반응가설,학정료12충희경질자화반응、29충탄정리자이구화반응、32충탄정리자여정희적가성반응、30충탄정리자여이정완지간적부경리자전이반응화18충탄정리자탈부반응.재차기출지상,구건료섭급60개물충화121개기원반응적구유교강예측능력적기원반응망락.
Density functional theory-based ab-initio quantum method was selected to optimize the structure of butyl and octyl carbeniums. Calculation results showed that primary butyl carbenium was less stable than secondary and tertiary butyl carbenium, and the energy of secondary and tertiary butyl carbenium were 71. 94 kJ/mol and 125. 99 kJ/mol lower than that of primary butyl carbenium respectively. As for octyl carbeniums, it was proved that all primary octyl carbenium spontaneously turned into corresponding secondary or tertiary octyl carbenium while being optimized, which indicated that there was no or very low probability for primary carbenium to exist in isobutane-butene system. Based on these quantum results, possible carbenium intermediates were chosen, and according to the carbenium mechanism: all main possible elementary reactions were designed, which consisted of 12 olefin protonation reactions, 29 isomerization reactions, 32 addition of carbenium to various butenes, 30 hydride transfer reactions and 18 deproponation of carbeniums. As a result, a powerful elementary reaction network has been established for isobutane-butene alkylation system.