Nickel-Based Heterometallic Catalysts for Ethylene-Acrylate Copolymerization: Interrogating Effects of Secondary Metal Additives
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1.
California Institute of Technology
Abstract
A class of in situ-generated Ni-based multimetallic complexes based on a bisphosphine phenoxide ligand (POP) was studied for ethylene-acrylate copolymerization. Starting from a previously prepared Ni-POP complex, addition of several metal precursors results in coordination involving the second phosphine not bound to Ni. These isolated complexes show lower copolymerization activity compared to Ni-POP. Structural characterization of relevant bimetallic complexes shows ancillary ligand binding in a PO-bidentate fashion to each metal with phenoxide bridging. Additionally, halide bridges are observed in several complexes, highlighting a potential inhibition mechanism by binding to Ni. In contrast, in situ addition of Al(OᶦPr)₃ as a secondary metal results in an increase in activity for ethylene/acrylate copolymerization while maintaining high levels of acrylate incorporation. Overall, these results demonstrate various effects in bimetallic systems for polymerization catalysis relevant to future catalyst design.
Copyright and License
© 2023 American Chemical Society.
Acknowledgement
We are grateful to Dow (TA) for funding. We thank Brad C. Bailey and Todd D. Senecal for insightful discussions. We thank Michael K. Takase and Lawrence Henling for assistance with X-ray crystallography and David VanderVelde for assistance with NMR spectroscopy. We thank Hannah Bailey and Heidi Clements for assistance in collecting polymer characterization data (GPC, DSC, and FT-IR). Support has been provided for the X-ray diffraction and NMR instrumentation via the Dow Next Generation Educator Fund.
Conflict of Interest
The authors declare no competing financial interest.
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Additional details
- ISSN
- 1520-6041
- Dow Chemical (United States)