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.

Random Terpolymer of Carbon Dioxide, Butadiene and Epoxides: Synthesis, Functionalization and Degradability

“…[ 29 ] EVL derivatives such as oligomerized and hydrogenated ones generally had higher reactivity for anionic ROP. [ 30‐35 ] Furthermore, various functional groups were introduced to the obtained polyesters via thiol‐ene click reactions, demonstrating the potential of functionalization. [ 29,32,34 ]…”

Bifunctional and Recyclable Polyesters by Chemoselective Ring-Opening Polymerization of a δ-Lactone Derived from CO2 and Butadiene

“…33 Another strategy was developed by Ni and coworkers consisting in the copolymerization of EVP with comonomers such as -butyrolactone (BBL) and εcaprolactone (ε-CL) (Figures 1f and 1g, respectively). [34][35] Recently, Eagan and coworkers achieved the polymerization of EVP by ring-opening and 1, 4-conjugate reactions (Figure 1h). The dimer (Di-EVP) was first formed by vinylogous 1,4conjugate addition and then polymerized to degradable polyesters.…”

Ring-Opening Copolymerizations of a CO2-derived δ-Valerolactone with ε-Caprolactone and L-Lactide

“…However, there have been a few recent copolymer syntheses with EVP (Figure 1), which were developed because EVP is reticent to homopolymerize. [29][30][31][32] The Ni group has reported the use of b-butyrolactone (Figure 1, reaction A), 29 ε-CL (Figure 1, reaction B), 30 and cyclohexene oxide (Figure 1, reaction C) 31 as comonomers for the ROP of EVP to synthesize random copolymers; similarly, the Tang group has used propylene oxide (Figure 1, reaction D). 32 In all cases, low molar mass polymers with high dispersities were obtained, especially at high feed ratios of EVP.…”