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Electron Paramagnetic Resonance Study of the Interaction of Surface Titanium Species with AlR3 Cocatalyst in Supported Ziegler–Natta Catalysts with a Low Titanium Content
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2016-01-08 00:00:00 , DOI: 10.1021/acs.jpcc.5b11286
Evgeny I. Koshevoy 1 , Tatiana B. Mikenas 1 , Vladimir A. Zakharov 1, 2 , Aleksandr A. Shubin 1, 2 , Artem A. Barabanov 1
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2016-01-08 00:00:00 , DOI: 10.1021/acs.jpcc.5b11286
Evgeny I. Koshevoy 1 , Tatiana B. Mikenas 1 , Vladimir A. Zakharov 1, 2 , Aleksandr A. Shubin 1, 2 , Artem A. Barabanov 1
Affiliation
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The electron paramagnetic resonance (EPR) method was used to investigate the formation of alkylated Ti(III) species in superactive titanium–magnesium catalysts with a low titanium content during their interaction with an organoaluminum activator (AlMe3), as well as the interaction of alkylated Ti(III) surface species with carbon monoxide. EPR data on the content of alkylated Ti(III) species in these catalysts agree well with the number of Ti–R bonds that are determined after the interaction of radioactive carbon monoxide (14CO) with catalyst activated by triethylaluminum in the absence of monomer. Parameters of EPR spectra of the Ti(III) species having different structure and composition on the surface of titanium–magnesium catalysts were calculated by quantum-chemical simulations. The calculated g-values are consistent with the g-values observed in EPR spectra of the catalysts. Analysis of the literature data and results of our study made it possible to propose the parameters of EPR spectra characterizing the alkylated Ti(III) species that can serve as precursors of the active sites in supported Ziegler–Natta catalysts.
中文翻译：
低钛含量的负载齐格勒-纳塔催化剂中表面钛物种与AlR 3助催化剂相互作用的电子顺磁共振研究
电子顺磁共振（EPR）方法用于研究低钛含量的超活性钛-镁催化剂与有机铝活化剂（AlMe 3）相互作用过程中烷基化Ti（III）物种的形成。用一氧化碳将Ti（III）表面烷基化。这些催化剂中烷基化Ti（III）种类的含量的EPR数据与放射性一氧化碳相互作用后确定的Ti-R键数非常吻合（14在不存在单体的情况下用三乙基铝活化的催化剂。通过量子化学模拟计算了钛镁催化剂表面具有不同结构和组成的Ti（III）物种的EPR光谱参数。计算出的g值与在催化剂的EPR光谱中观察到的g值一致。通过对文献数据和我们研究结果的分析，有可能提出表征烷基化Ti（III）物种的EPR光谱参数，这些烷基化Ti-III可以作为负载型Ziegler-Natta催化剂中活性位点的前体。
更新日期：2016-01-08
中文翻译：
低钛含量的负载齐格勒-纳塔催化剂中表面钛物种与AlR 3助催化剂相互作用的电子顺磁共振研究
电子顺磁共振（EPR）方法用于研究低钛含量的超活性钛-镁催化剂与有机铝活化剂（AlMe 3）相互作用过程中烷基化Ti（III）物种的形成。用一氧化碳将Ti（III）表面烷基化。这些催化剂中烷基化Ti（III）种类的含量的EPR数据与放射性一氧化碳相互作用后确定的Ti-R键数非常吻合（14在不存在单体的情况下用三乙基铝活化的催化剂。通过量子化学模拟计算了钛镁催化剂表面具有不同结构和组成的Ti（III）物种的EPR光谱参数。计算出的g值与在催化剂的EPR光谱中观察到的g值一致。通过对文献数据和我们研究结果的分析，有可能提出表征烷基化Ti（III）物种的EPR光谱参数，这些烷基化Ti-III可以作为负载型Ziegler-Natta催化剂中活性位点的前体。
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