Gas-Phase Ethylene Polymerization by Single-Site Cr Centers in a Metal-Organic Framework

Hoyoung D. Park; Robert J. Comito; Zhenwei Wu; Guanghui Zhang; Nathan Ricke; Chenyue Sun; Troy Van Voorhis; Jeffrey T. Miller; Yuriy Román-Leshkov; Mircea Dincǎ

doi:10.1021/acscatal.9b03282

Gas-Phase Ethylene Polymerization by Single-Site Cr Centers in a Metal-Organic Framework

Hoyoung D. Park
, Robert J. Comito
, Zhenwei Wu
, Guanghui Zhang
, Nathan Ricke
, Chenyue Sun
, Troy Van Voorhis
, Jeffrey T. Miller
, Yuriy Román-Leshkov
, Mircea Dincǎ

Research output: Contribution to journal › Article › peer-review

27 Scopus citations

Abstract

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 mol_Ethylene·mol_Cr ^-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.

Original language	English (US)
Pages (from-to)	3864-3870
Number of pages	7
Journal	ACS Catalysis
Volume	10
Issue number	6
DOIs	https://doi.org/10.1021/acscatal.9b03282
State	Published - Mar 20 2020
Externally published	Yes

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry

Keywords

gas-phase polymerization
heterogeneous catalysis
metal-organic framework
polyethylene
single-site catalyst

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10.1021/acscatal.9b03282

Cite this

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title = "Gas-Phase Ethylene Polymerization by Single-Site Cr Centers in a Metal-Organic Framework",

abstract = "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.",

keywords = "gas-phase polymerization, heterogeneous catalysis, metal-organic framework, polyethylene, single-site catalyst",

author = "Park, \{Hoyoung D.\} and Comito, \{Robert J.\} and Zhenwei Wu and Guanghui Zhang and Nathan Ricke and Chenyue Sun and \{Van Voorhis\}, Troy and Miller, \{Jeffrey T.\} and Yuriy Rom{\'a}n-Leshkov and Mircea Dincǎ",

note = "Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

year = "2020",

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doi = "10.1021/acscatal.9b03282",

language = "English (US)",

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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

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

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JF - ACS Catalysis

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Gas-Phase Ethylene Polymerization by Single-Site Cr Centers in a Metal-Organic Framework

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