A Topology‐Defined Polyester Elastomer from CO₂ and 1,3‐Butadiene: A One‐Pot‐One‐Step “Scrambling Polymerizations” Strategy

Abstract

It is significant and challenging to use CO 2 to produce polymeric materials, especially with olefins. Here, a novel strategy named "scrambling polymerizations" is designed and performed for the copolymerization of a CO 2 -and-1,3-butadiene-derived valerolactone, 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one (EVL), with ɛ-caprolactone (CL) to prepare polyesters. Anionic ring-opening polymerization of CL and conjugated addition oligomerization of EVL take place individually to form PCL and EVL oligomers, respectively. Then EVL oligomers insert into PCL by transesterification resulting in polyester P(CL-co-EVL) with a tunable topology and composition. The non-cytotoxic and degradable polyester network with elongation at break of > 600 % can be used as an elastomer. We propose a method to provide polyester elastomers from CO 2 and olefins for the first time, and expand the potential of transformation from sustainable feedstocks to polymeric materials.

Current Challenges and Perspectives in CO2-Based Polymers

“…It yielded CO 2 -based polyester with tunable topologies, featuring high elongation at break (>600%) and almost a complete recovery (>97%) (Figure 17c). 139 Significantly, the hydrogenated products of EVP, one-and diethyl-substituted six-membered lactones (EtVP and DEP), were amenable to ring-opening polymerization catalyzed by a phosphazene base ( t Bu-P 4 ) (Figure 17d). The reaction generated a polyester with an unexpected ultrahigh M n of 613.8 kg mol −1 .…”

How to Open the Ring of a Di‐ene‐Substituted‐δ‐Valerolactone: From Carbon Dioxide and 1,3‐Butadiene to Functional Polyesters

“… [46] The well‐crosslinked P(EVL‐co‐CL) we prepared with degradability, available tensile strength (>1.4 MPa), high elongation at break (>600 %) and excellent recovery (>97 % in 15 min) could be used as degradable polyester elastomers (Figure 12D). [53] …”

“…Very recently, we revealed the ring-opening reactivity of EVL and its derivatives. [53] With strong base, EVL oligomerized to oEVL that contains three kinds of lactone rings. According to DFT calculation, the unconjugated ring A was the most selfactivated one in ring-opening reactions (ΔG ¼ 6 A = + 5.7, ΔG ¼ 6 B = + 16.8, ΔG ¼ 6 C = + 18.1 kcal/mol).…”

“…Very recently, we revealed the ring‐opening reactivity of EVL and its derivatives [53] . With strong base, EVL oligomerized to oEVL that contains three kinds of lactone rings.…”

Highly efficient conversion of CO2intoN-formamides catalyzed by a noble-metal-free aluminum-based MOF under mild conditions

“…In recent years, CO 2 has attracted worldwide attention as a greenhouse gas, and its emission contributes to climate change. 1 Nevertheless, CO 2 is a non-toxic, economical and renewable C1 resource that can be used to synthesize a variety of high value-added chemicals, 2,3 and various pathways have been developed for CO 2 utilization. Through electrochemical or photochemical processes, CO 2 has been reported to be converted into CO, methanol, and carboxylic acids.…”