Single-Site Heterogeneous Catalysts for Olefin Polymerization Enabled by Cation Exchange in a Metal-Organic Framework
The manufacture of advanced polyolefins has been critically enabled by the development of single-site heterogeneous catalysts. Metal-organic frameworks (MOFs) show great potential as heterogeneous catalysts that may be designed and tuned on the molecular level. In this work, exchange of zinc ions in...
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| Published in | Journal of the American Chemical Society Vol. 138; no. 32; pp. 10232 - 10237 |
|---|---|
| Main Authors | , , , , |
| Format | Journal Article |
| Language | English |
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United States
American Chemical Society
17.08.2016
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| Abstract | The manufacture of advanced polyolefins has been critically enabled by the development of single-site heterogeneous catalysts. Metal-organic frameworks (MOFs) show great potential as heterogeneous catalysts that may be designed and tuned on the molecular level. In this work, exchange of zinc ions in Zn5Cl4(BTDD)3, H2BTDD = bis(1H-1,2,3-triazolo[4,5-b],[4′,5′-i])dibenzo[1,4]dioxin) (MFU-4l) with reactive metals serves to establish a general platform for selective olefin polymerization in a high surface area solid promising for industrial catalysis. Characterization of polyethylene produced by these materials demonstrates both molecular and morphological control. Notably, reactivity approaches single-site catalysis, as evidenced by low polydispersity indices, and good molecular weight control. We further show that these new catalysts copolymerize ethylene and propylene. Uniform growth of the polymer around the catalyst particles provides a mechanism for controlling the polymer morphology, a relevant metric for continuous flow processes. |
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| AbstractList | The manufacture of advanced polyolefins has been critically enabled by the development of single-site heterogeneous catalysts. Metal-organic frameworks (MOFs) show great potential as heterogeneous catalysts that may be designed and tuned on the molecular level. In this work, exchange of zinc ions in Zn5Cl4(BTDD)3, H2BTDD = bis(1H-1,2,3-triazolo[4,5-b],[4′,5′-i])dibenzo[1,4]dioxin) (MFU-4l) with reactive metals serves to establish a general platform for selective olefin polymerization in a high surface area solid promising for industrial catalysis. Characterization of polyethylene produced by these materials demonstrates both molecular and morphological control. Notably, reactivity approaches single-site catalysis, as evidenced by low polydispersity indices, and good molecular weight control. We further show that these new catalysts copolymerize ethylene and propylene. Uniform growth of the polymer around the catalyst particles provides a mechanism for controlling the polymer morphology, a relevant metric for continuous flow processes. The manufacture of advanced polyolefins has been critically enabled by the development of single-site heterogeneous catalysts. Metal-organic frameworks (MOFs) show great potential as heterogeneous catalysts that may be designed and tuned on the molecular level. In this work, exchange of zinc ions in Zn5Cl4(BTDD)3, H2BTDD = bis(1H-1,2,3-triazolo[4,5-b],[4',5'-i])dibenzo[1,4]dioxin) (MFU-4l) with reactive metals serves to establish a general platform for selective olefin polymerization in a high surface area solid promising for industrial catalysis. Characterization of polyethylene produced by these materials demonstrates both molecular and morphological control. Notably, reactivity approaches single-site catalysis, as evidenced by low polydispersity indices, and good molecular weight control. We further show that these new catalysts copolymerize ethylene and propylene. Uniform growth of the polymer around the catalyst particles provides a mechanism for controlling the polymer morphology, a relevant metric for continuous flow processes. The manufacture of advanced polyolefins has been critically enabled by the development of single-site heterogeneous catalysts. Metal-organic frameworks (MOFs) show great potential as heterogeneous catalysts that may be designed and tuned on the molecular level. In this work, exchange of zinc ions in Zn₅Cl₄(BTDD)₃, H₂BTDD = bis(1H-1,2,3-triazolo[4,5-b],[4′,5′-i])dibenzo[1,4]dioxin) (MFU-4l) with reactive metals serves to establish a general platform for selective olefin polymerization in a high surface area solid promising for industrial catalysis. Characterization of polyethylene produced by these materials demonstrates both molecular and morphological control. Notably, reactivity approaches single-site catalysis, as evidenced by low polydispersity indices, and good molecular weight control. We further show that these new catalysts copolymerize ethylene and propylene. Uniform growth of the polymer around the catalyst particles provides a mechanism for controlling the polymer morphology, a relevant metric for continuous flow processes. |
| Author | Fritzsching, Keith J Dincă, Mircea Comito, Robert J Sundell, Benjamin J Schmidt-Rohr, Klaus |
| AuthorAffiliation | Department of Chemistry Massachusetts Institute of Technology Aramco Research Center, Aramco Services Company Brandeis University |
| AuthorAffiliation_xml | – name: Department of Chemistry – name: Aramco Research Center, Aramco Services Company – name: Massachusetts Institute of Technology – name: Brandeis University |
| Author_xml | – sequence: 1 givenname: Robert J surname: Comito fullname: Comito, Robert J – sequence: 2 givenname: Keith J surname: Fritzsching fullname: Fritzsching, Keith J – sequence: 3 givenname: Benjamin J surname: Sundell fullname: Sundell, Benjamin J – sequence: 4 givenname: Klaus surname: Schmidt-Rohr fullname: Schmidt-Rohr, Klaus – sequence: 5 givenname: Mircea surname: Dincă fullname: Dincă, Mircea email: mdinca@mit.edu |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/27443860$$D View this record in MEDLINE/PubMed |
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| Snippet | The manufacture of advanced polyolefins has been critically enabled by the development of single-site heterogeneous catalysts. Metal-organic frameworks (MOFs)... |
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| SubjectTerms | catalysts catalytic activity cation exchange coordination polymers dioxins ethylene ions molecular weight olefin polyethylene polymerization propylene surface area weight control zinc |
| Title | Single-Site Heterogeneous Catalysts for Olefin Polymerization Enabled by Cation Exchange in a Metal-Organic Framework |
| URI | http://dx.doi.org/10.1021/jacs.6b05200 https://www.ncbi.nlm.nih.gov/pubmed/27443860 https://www.proquest.com/docview/1812439281 https://www.proquest.com/docview/2000403955 |
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