Chemically recyclable polyesters from CO2, H2, and 1,3-butadiene

Abstract

•CO2-based recyclable polymers are promising in reducing CO2 emission and pollution•Disubstituted δ-lactone, a previously non-polymerizable monomer, was polymerized•Complete monomer recovery was successfully achieved via chemical recycling process•CO2 constitutes 28% of the weight of newly designed chemically recyclable polymers•The polymers show pressure-sensitive adhesive property comparable to commercial tapes Chemically recyclable solid polymeric materials with commercializable properties only using CO2 and inexpensive bulk chemicals as chemical feedstock can open a brand-new avenue to economically viable, large-scale fixation of CO2 over a long period of time. Despite previous great advancements, development of such a kind of CO2-based polymers remains a long-term unsolved research challenge of great significance. Herein, we reported the first methodology to polymerize six-membered lactone with two substituents vicinal to the ester group (HL), a compound previously found to be non-polymerizable. The present methodology enables the first synthesis of chemically recyclable solid polyesters (polyHL) with a high CO2 content (28 wt %) and large molecular weights (Mn up to 613.8 kg mol−1). Transparent membranes with promising pressure-sensitive adhesive (PSA) properties comparable with their commercial counterparts can be conveniently fabricated from the polyesters. Mechanistic studies indicate that rigorous removal of water impurity is the key to the successful polymerization of the relatively inert disubstituted six-membered lactone. A complete monomer recovery from polyHL was also successfully achieved under mild catalytic conditions. The synthesis of polyHL only requires CO2 and two inexpensive bulk chemicals, H2 and 1,3-butadiene, as the starting materials, thus providing a new strategy for potential scalable chemical utilization of CO2 with desirable economic values and concomitant mitigation of CO2 emissions. This work should inspire future research to make useful new solid CO2-based polymers that can meaningfully increase the scale of chemical utilization of CO2 and promote the contribution of chemical utilization of CO2 to global mitigation of CO2 emissions. Chemically recyclable solid polymeric materials with commercializable properties only using CO2 and inexpensive bulk chemicals as chemical feedstock can open a brand-new avenue to economically viable, large-scale fixation of CO2 over a long period of time. Despite previous great advancements, development of such a kind of CO2-based polymers remains a long-term unsolved research challenge of great significance. Herein, we reported the first methodology to polymerize six-membered lactone with two substituents vicinal to the ester group (HL), a compound previously found to be non-polymerizable. The present methodology enables the first synthesis of chemically recyclable solid polyesters (polyHL) with a high CO2 content (28 wt %) and large molecular weights (Mn up to 613.8 kg mol−1). Transparent membranes with promising pressure-sensitive adhesive (PSA) properties comparable with their commercial counterparts can be conveniently fabricated from the polyesters. Mechanistic studies indicate that rigorous removal of water impurity is the key to the successful polymerization of the relatively inert disubstituted six-membered lactone. A complete monomer recovery from polyHL was also successfully achieved under mild catalytic conditions. The synthesis of polyHL only requires CO2 and two inexpensive bulk chemicals, H2 and 1,3-butadiene, as the starting materials, thus providing a new strategy for potential scalable chemical utilization of CO2 with desirable economic values and concomitant mitigation of CO2 emissions. This work should inspire future research to make useful new solid CO2-based polymers that can meaningfully increase the scale of chemical utilization of CO2 and promote the contribution of chemical utilization of CO2 to global mitigation of CO2 emissions.

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