Chemoselective Polymerizations from Mixtures of Epoxide, Lactone, Anhydride, and Carbon Dioxide
Chemoselective Polymerizations from Mixtures of Epoxide, Lactone, Anhydride, and Carbon Dioxide
Authors (7): C. Romain, Y. Zhu, P. Dingwall, S. Paul, H. S. Rzepa, A. Buchard, C. K. Williams
Themes: Transformations
DOI: 10.1021/jacs.5b13070
Citations: 238
Pub type: article-journal
Pub year: 2016

Publisher: American Chemical Society (ACS)

Issue: 12

License: http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html

Publication date(s): 2016/03/30 (print) 2016/03/22 (online)

Pages: 4120-4131

Volume: 138 Issue: 12

Journal: Journal of the American Chemical Society

Link: http://pubs.acs.org/doi/pdf/10.1021/jacs.5b13070

URL: http://dx.doi.org/10.1021/jacs.5b13070

Controlling polymer composition starting from mixtures of monomers is an important, but rarely achieved, target. Here a single switchable catalyst for both ring-opening polymerization (ROP) of lactones and ring-opening copolymerization (ROCOP) of epoxides, anhydrides, and CO2 is investigated, using both experimental and theoretical methods. Different combinations of four model monomers—ε-caprolactone, cyclohexene oxide, phthalic anhydride, and carbon dioxide—are investigated using a single dizinc catalyst. The catalyst switches between the distinct polymerization cycles and shows high monomer selectivity, resulting in block sequence control and predictable compositions (esters and carbonates) in the polymer chain. The understanding gained of the orthogonal reactivity of monomers, specifically controlled by the nature of the metal-chain end group, opens the way to engineer polymer block sequences.

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