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首页> 外文期刊>Journal of Applied Polymer Science >ESR Studies on Vanadocene/Cocatalyst Systems for Ethylene Polymerization
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ESR Studies on Vanadocene/Cocatalyst Systems for Ethylene Polymerization

机译：Vanadocene /助催化剂乙烯聚合反应的ESR研究

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摘要

Three vanadocene-cocatalyst catalytic systems for ethylene polymeriza- tion-Cp_2ZrC1J Al_2Et_3C1_3 [ dichlorobis( #eta#-cyclopentadienyl)vanadi umlethylal umin um - sesquichloride] , Cp_2ZrC1JMAO [dichlorobis( #eta#-cyclopentadienyl)vanadiumlmethylalu- minoxane] and Cp_2ZrC1JAlEt_3 [dichlorobis( #eta#-cyclopentadienyl)vanadiumltriethylalu- minum]-were monitored by electron spin resonance (ESR) spectroscopy. It was found that at least a certain kind of vanadium complex is formed after mixing dichlorobis( 1}- cyclopentadienyl)vanadium with ethylaluminumsesquichloride. After introducing eth- ylene, a new kind of vanadium complex is detected by ESR. Ethylene can be polymer- ized by using a dichlorobis(#eta#-cyclopentadienyl)vanadiumlethylaluminumsesquichloride catalytic system. These results possibly indicate that the vanadium complex exists in the forms C1Cp_2 VC1EtAlC1_2 and C1Cp_2 VC1EtAlC1Et, which are responsible for forming active centers. The Dichlorobis( #eta#-cyclopentadieny1)vanadiumlmethylaluminoxane and dichlorobis( #eta#-cyclopentadienyl)vanadiumltriethylaluminum systems also were moni- tored by ESR. Completely different spectra were recorded compared to those of the dichlorobis( #eta#-cyclopentadienyl) vanadiumlethylaluminumsesquichloride system. Eth- ylene almost cannot be polymerized by the dichlorobis(#eta#-cyclopentadienyl)vanadiuml methylaluminoxane and dichlorobis(#eta#-cyclopentadienyl)vanadiumltriethylaluminum catalytic systems, showing that resultant vanadium complexes of dichlorobis( #eta#-cyclo- pentadienyl)vanadiumlmethylaluminoxane and dichlorobis( #eta#-cyclopentadienyl)vana- diumltriethylaluminum catalytic systems are different from that arising from the dichlorobis( #eta#-cyclopentadienyl)vanadiumlethylaluminumsesquichloride system. Plau- sible mechanisms are suggested for this.
机译：乙烯聚合的三个钒氧烯助催化剂-Cp_2ZrC1J Al_2Et_3C1_3 [二氯双（＃eta＃-环戊二烯基）钒基乙基乙基um um-倍半氯化物]，Cp_2ZrC1JMAO [二氯双（二乙基J铝[ZeC] [ZuC1Z [Z] C] [Z-C1Z [C] Z] [Z-C1Z [C] Z [A] -Z] [Z-C1Z] [Z] C]通过电子自旋共振（ESR）光谱监测＃η--环戊二烯基）钒三乙基铝。发现在将二氯双（1}-环戊二烯基）钒与乙基铝倍半氯化物混合后形成至少某种钒络合物。引入乙烯后，ESR可检测出一种新型的钒配合物。可以使用二氯双（＃eta＃-环戊二烯基）钒乙基铝倍半氯化物催化系统聚合乙烯。这些结果可能表明钒络合物以C1Cp_2 VC1EtAlC1_2和C1Cp_2 VC1EtAlC1Et的形式存在，它们负责形成活性中心。 ESR监测了二氯双（＃η--环戊二烯基）钒基甲基铝氧烷和二氯双（＃η--环戊二烯基）钒基三乙基铝体系。与二氯双（＃eta＃-环戊二烯基）钒乙基乙基铝倍半氯化物体系的光谱相比，记录了完全不同的光谱。乙烯几乎不能通过二氯双（＃eta＃-环戊二烯基）钒甲基铝氧烷和二氯双（＃eta＃-环戊二烯基）钒三乙基铝催化体系进行聚合，这表明二氯双（＃eta＃-环戊二烯基）钒的甲基钒铝与五氯合钒的钒配合物。二氯双（＃η--环戊二烯基）钒-三乙基铝的催化体系不同于二氯双（＃η--环戊二烯基）钒-乙基铝倍半氯化物体系。建议采用可行的机制。

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