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.

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.