α,ω-Diene Generation from Ethylene and Butadiene by Copolymer Upcycling
Abstract
Linear α-olefins are accessed efficiently from ethylene in the Shell higher olefin process (SHOP), an industrial process practiced on a million-ton scale that generates a statistical mixture of C₄-C₃₀ products. An analogous general process for the preparation of a range of α,ω-dienes is lacking. We herein report a two-step method that generates industrially relevant α,ω-dienes. In the first step, ethylene and butadiene are copolymerized to generate copolymers with a variable butadiene content. A titanium bisphenoxide bisthiolate catalyst activated with methylaluminoxane (MAO) was selected for this step due to the high selectivity for 1,4-butadiene incorporation. Ethenolysis of the copolymers results in a distribution of α,ω-dienes in the C₁₀-C₂₀ range. Depending on the conditions, linear trienes are also generated. The reported protocol provides a strategy for copolymer upcycling to value-added olefin products.
Additional Information
© 2023 American Chemical Society. We are grateful to the Resnick Sustainability Institute at Caltech for financial support. We thank David VanderVelde for assistance with NMR spectroscopy. We thank the Dow Next Generation Educator Fund for support of NMR instrumentation. The authors declare no competing financial interest.Attached Files
Supplemental Material - sc3c02569_si_001.pdf
Files
Name | Size | Download all |
---|---|---|
md5:3b1cd4f264765c4a18171d576deec39a
|
6.0 MB | Preview Download |
Additional details
- Eprint ID
- 122296
- Resolver ID
- CaltechAUTHORS:20230717-49907100.1
- Resnick Sustainability Institute
- Dow Next Generation Educator Fund
- Created
-
2023-08-13Created from EPrint's datestamp field
- Updated
-
2023-08-14Created from EPrint's last_modified field
- Caltech groups
- Resnick Sustainability Institute