Yu Shuyuan, Zhang Chenggen, Wang Fei, Liang Xinru, Yang Mengyao, An Mengyu
College of Chemistry and Material Science, Langfang Normal University, Langfang 065000, China.
Polymers (Basel). 2023 May 24;15(11):2435. doi: 10.3390/polym15112435.
Density functional theory (DFT) is employed to investigate the promotion of B(CF) as a ligand for titanium (or vanadium) catalysts in ethylene/1-hexene copolymerization reactions. The results reveal that (I) Ethylene insertion into (with B(CF) as a ligand ) is preferred over both thermodynamically and kinetically. (II) In and catalysts, the 2,1 insertion reaction ( and ) is the primary pathway for 1-hexene insertion. Furthermore, the 1-hexene insertion reaction for is favored over and is easier to perform. Consequently, the entire ethylene and 1-hexene insertion reaction proceeds smoothly using the catalyst to yield the final product. (III) Analogous to the catalyst case, (with B(CF) as a ligand) is preferred over for the entire ethylene/1-hexene copolymerization reaction. Moreover, exhibits higher reaction activity than , thus agreeing with experimental results. Additionally, the electron localization function and global reactivity index analysis indicate that titanium (or vanadium) catalysts with B(CF) as a ligand exhibit higher reactivity. Investigating the promotion of B(CF) as a ligand for titanium (or vanadium) catalysts in ethylene/1-hexene copolymerization reactions will aid in designing novel catalysts and lead to more cost-effective polymerization production methods.
采用密度泛函理论（DFT）研究了B（CF）作为乙烯/1-己烯共聚反应中钛（或钒）催化剂配体的促进作用。结果表明：（I）在热力学和动力学上，乙烯插入（以B（CF）作为配体）比插入更有利。（II）在和催化剂中，2,1插入反应（和）是1-己烯插入的主要途径。此外，的1-己烯插入反应比更有利，且更容易进行。因此，使用催化剂时，整个乙烯和1-己烯插入反应顺利进行，生成最终产物。（III）与催化剂情况类似，对于整个乙烯/1-己烯共聚反应，（以B（CF）作为配体）比更有利。此外，的反应活性高于，这与实验结果一致。此外，电子定域函数和全局反应性指数分析表明，以B（CF）作为配体的钛（或钒）催化剂具有更高的反应活性。研究B（CF）作为乙烯/1-己烯共聚反应中钛（或钒）催化剂配体的促进作用将有助于设计新型催化剂，并导致更具成本效益的聚合生产方法。
