Issue 37, 2021

Mg(ii) heterodinuclear catalysts delivering carbon dioxide derived multi-block polymers

Abstract

Carbon dioxide derived polymers are emerging as useful materials for applications spanning packaging, construction, house-hold goods and automotive components. To accelerate and broaden their uptake requires both more active and selective catalysts and greater structural diversity for the carbon dioxide derived polymers. Here, highly active catalysts show controllable selectivity for the enchainment of mixtures of epoxide, anhydride, carbon dioxide and lactone. Firstly, metal dependent selectivity differences are uncovered using a series of dinuclear catalysts, Mg(II)Mg(II), Zn(II)Zn(II), Mg(II)Zn(II), and Mg(II)Co(II), each exposed to mixtures of bio-derived tricyclic anhydride, cyclohexene oxide and carbon dioxide (1 bar). Depending upon the metal combinations, different block structures are possible with Zn(II)Zn(II) yielding poly(ester-b-carbonate); Mg(II)Mg(II) or Mg(II)Co(II) catalysts delivering poly(carbonate-b-ester); and Mg(II)Zn(II) furnishing a random copolymer. These results indicate that carbon dioxide insertion reactions follow the order Co(II) > Mg(II) > Zn(II). Using the most active and selective catalyst, Mg(II)Co(II), and exploiting reversible on/off switches between carbon dioxide/nitrogen at 1 bar delivers precision triblock (ABA), pentablock (BABAB) and heptablock (ABABABA) polymers (where A = poly(cyclohexylene oxide-alt-tricyclic anhydride), PE; B = poly(cyclohexene carbonate), PCHC). The Mg(II)Co(II) catalyst also selectively polymerizes a mixture of anhydride, carbon dioxide, cyclohexene oxide and ε-caprolactone to deliver a CBABC pentablock copolymer (A = PE, B = PCHC C = poly(caprolactone), PCL). The catalysts combine high activity and selectivity to deliver new polymers featuring regularly placed carbon dioxide and biomass derived linkages.

Graphical abstract: Mg(ii) heterodinuclear catalysts delivering carbon dioxide derived multi-block polymers

Supplementary files

Article information

Article type
Edge Article
Submitted
15 iyl 2021
Accepted
29 iyl 2021
First published
26 avq 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2021,12, 12315-12325

Mg(II) heterodinuclear catalysts delivering carbon dioxide derived multi-block polymers

G. Rosetto, A. C. Deacy and C. K. Williams, Chem. Sci., 2021, 12, 12315 DOI: 10.1039/D1SC03856G

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements