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Gas-Phase Ethylene Polymerization by Single-Site Cr Centers in a Metal–Organic Framework
ACS Catalysis ( IF 11.3 ) Pub Date : 2020-03-10 , DOI: 10.1021/acscatal.9b03282 Hoyoung D. Park 1 , Robert J. Comito 2 , Zhenwei Wu 3 , Guanghui Zhang 4 , Nathan Ricke 5 , Chenyue Sun 5 , Troy Van Voorhis 5 , Jeffrey T. Miller 3 , Yuriy Román-Leshkov 1 , Mircea Dincă 5
ACS Catalysis ( IF 11.3 ) Pub Date : 2020-03-10 , DOI: 10.1021/acscatal.9b03282 Hoyoung D. Park 1 , Robert J. Comito 2 , Zhenwei Wu 3 , Guanghui Zhang 4 , Nathan Ricke 5 , Chenyue Sun 5 , Troy Van Voorhis 5 , Jeffrey T. Miller 3 , Yuriy Román-Leshkov 1 , Mircea Dincă 5
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We report a systematic study on the gas-phase polymerization of ethylene by a metal–organic framework (MOF) catalyst. Cr3+-exchanged MFU-4l (Cr(III)-MFU-4l, MFU-4l = Zn5Cl4(BTDD)3, H2BTDD = bis(1H-1,2,3,-triazolo[4,5-b],[4′,5′-i])dibenzo[1,4]dioxin)) serves as an exemplary system to demonstrate prereaction treatment with alkylaluminum species as a simple method to isolate an active MOF catalyst for liquid-free polymerization of ethylene. AlMe3-treated Cr(III)-MFU-4l subjected to 40 bar of ethylene exhibits a polymerization activity of 52 000 molEthylene·molCr–1·h–1, an order of magnitude higher than that observed in a slurry-phase reaction with Cr(III)-MFU-4l and excess alkylaluminum species. Furthermore, product polyethylene exhibits a low polydispersity index of 1.36 and a free-flowing granular morphology favorable for industrial processing, highlighting the advantages conferred by the single-site MOF catalysts in gas-phase ethylene polymerization.
中文翻译：
金属-有机骨架中单点铬中心的气相乙烯聚合
我们报告了金属-有机骨架（MOF）催化剂对乙烯气相聚合的系统研究。Cr 3+交换的MFU-4 l（Cr（III）-MFU-4 l，MFU-4 l = Zn 5 Cl 4（BTDD）3，H 2 BTDD = bis（1 H -1,2,3，-三唑并[4,5- b ]，[4'，5'- i ]）二苯并[1,4]二恶英））作为示例性系统展示了用烷基铝物质进行预反应处理作为分离活性MOF催化剂的简单方法用于乙烯的无液体聚合。AlMe 3处理的Cr（III）-MFU-4 l乙烯压力为40 bar时，聚合活性为52 000 mol乙烯·mol Cr –1 ·h –1，比在与Cr（III）-MFU-4 l和过量的烷基铝。此外，产物聚乙烯显示出低的1.36的多分散指数和有利于工业加工的自由流动的颗粒形态，突出了单中心MOF催化剂在气相乙烯聚合中所赋予的优点。
更新日期：2020-03-10
中文翻译：
金属-有机骨架中单点铬中心的气相乙烯聚合
我们报告了金属-有机骨架（MOF）催化剂对乙烯气相聚合的系统研究。Cr 3+交换的MFU-4 l（Cr（III）-MFU-4 l，MFU-4 l = Zn 5 Cl 4（BTDD）3，H 2 BTDD = bis（1 H -1,2,3，-三唑并[4,5- b ]，[4'，5'- i ]）二苯并[1,4]二恶英））作为示例性系统展示了用烷基铝物质进行预反应处理作为分离活性MOF催化剂的简单方法用于乙烯的无液体聚合。AlMe 3处理的Cr（III）-MFU-4 l乙烯压力为40 bar时，聚合活性为52 000 mol乙烯·mol Cr –1 ·h –1，比在与Cr（III）-MFU-4 l和过量的烷基铝。此外，产物聚乙烯显示出低的1.36的多分散指数和有利于工业加工的自由流动的颗粒形态，突出了单中心MOF催化剂在气相乙烯聚合中所赋予的优点。
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