甲醇羰基化制乙酸催化剂的共聚物配体交替结构的理论研究（I）

Theoretical Study on the Alternative Structure of Copolymer Ligands of Catalyst for Methanol Carbonylation to Acetic Acid (I)

采用以ＡＳＥＤ—ＭＯ（合原子对排斥的ＥＨＭＯ法）为基础的结构自动优化的ＥＨＴＯＰＴ法及Ｍｏｎｔｅ—Ｃａｒｌｏ法对甲醇羰基化制乙酸催化剂的共聚物配体交替结构进行了理论研究，计算了ＡＡ，ＡＢ，ＢＢ，ＢＡ二聚反应的反应途径，找出了过渡态，并确定了反应活化势垒，在假设两反应频率因子相同的前提下，求出竞聚率，采用Ｍｏｎｔｅ－Ｃａｒｌｏ法模拟共聚物结构，计算出共聚物配体中起催化活性的ＡＢ交替结构所占比率，比较不同共聚物配体中ＡＢ比率，并研究了改变温度及单体浓度对共聚物配体交替结构的影响．

Theoritical study on the alternative structure of copolymer ligands of catalyst for methanol carbonylation to acetic acid has been investigated by the ASED-MO method and Monte Carlo method. Reaction paths of AA, AB, BB, BA were calculated to determine the energy barriers, respectively. It was assumed that under the premise or frequency factors for bireactions to be equal, reactivity ratios r1 and r2 can be found out. The model of copolymer structure can be simulated and the ratio of AB to the molecular chains can be calculated with changing temperature and the feed ratio.