TY - JOUR
T1 - Gas-Phase Ethylene Polymerization by Single-Site Cr Centers in a Metal-Organic Framework
AU - Park, Hoyoung D.
AU - Comito, Robert J.
AU - Wu, Zhenwei
AU - Zhang, Guanghui
AU - Ricke, Nathan
AU - Sun, Chenyue
AU - Van Voorhis, Troy
AU - Miller, Jeffrey T.
AU - Román-Leshkov, Yuriy
AU - Dincǎ, Mircea
N1 - Publisher Copyright:
Copyright © 2020 American Chemical Society.
PY - 2020/3/20
Y1 - 2020/3/20
N2 - 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.
AB - 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.
KW - gas-phase polymerization
KW - heterogeneous catalysis
KW - metal-organic framework
KW - polyethylene
KW - single-site catalyst
UR - http://www.scopus.com/inward/record.url?scp=85082949066&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85082949066&partnerID=8YFLogxK
U2 - 10.1021/acscatal.9b03282
DO - 10.1021/acscatal.9b03282
M3 - Article
AN - SCOPUS:85082949066
SN - 2155-5435
VL - 10
SP - 3864
EP - 3870
JO - ACS Catalysis
JF - ACS Catalysis
IS - 6
ER -