Two-in-One: Photothermal Ring-Opening Copolymerization of CO₂ and Epoxides

Abstract

A two-in-one strategy for the photothermal ring-opening copolymerization (PROCOP) of carbon dioxide (CO2) and epoxides was developed by using visible light as an external stimulus. This strategy bridges two processes involving light-to-heat conversion and the alternating copolymerization of CO2 and epoxides. As a proof-of-concept, aluminum porphyrin complexes were explored as photothermal catalysts to afford the copolymerization of CO2/epoxides under a 635 nm laser irradiation. We demonstrated photothermally enhanced polymerization activity, in which the polymerization initiated by the photothermal effect showed a much higher turnover frequency than in the thermal system. Moreover, the PROCOP demonstrated a spatial–temporal control by a light on/off switch. This study provides a fascinating photothermal strategy not only for the CO2/epoxides copolymerization but also for the ring-opening (co)­polymerization of other cyclic monomers.

Cd(ii) and Zn(ii) coordination polymer-assisted CO2/cyclohexene oxide copolymerization with a double metal cyanide catalyst

“…3 As a result, it is attractive to create effective catalysts and explore valid methods to control the selectivity of products. 4 In 2020, Hu and Zhang's group synthesized an Al-salen catalyst in cooperation with an ionic liquid to convert CO 2 into cyclic carbonate. 5 The highest yield is 92% with a wide scope of substrates at 25 °C and 1 MPa CO 2 .…”

“…3 As a result, it is attractive to create effective catalysts and explore valid methods to control the selectivity of products. 4…”

Phosphine-Borane Frustrated Lewis Pairs for Metal-Free CO2/Epoxide Copolymerization

“…Subsequent studies focused on the design of catalysts to improve the activity, selectivity, and controllability of copolymerization. Metal catalysts involving Zn, − Al, − Cr, − Co, − and Mg , as metal centers complexed with well-designed ligands have been developed. Particularly, bifunctional − , and di- or tri-nuclear , catalysts including homonuclear − ,,− , and heteronuclear − catalysts have become research highlights.…”

Reversibly photoswitchable catalysts for high regioselectivity and enantioselectivity in polymerization of allenes

“…22 Besides the above-mentioned strategies, light is an attractive stimulus because of its noninvasiveness, highly versatility, ready availability, and high temporal, and spatial resolution. [23][24][25][26] Therefore, a series of photoswitchable catalysts have been demonstrated in the field of synthesizing artificial polymers. [27][28][29] Azobenzene, a kind of photosensitive functional group, has attracted a lot attention owing to its photoisomerized reversible structures between trans and cis via alternate irradiation with visible light (420 nm) and dark conditions.…”