The control of polymer microstructure is of paramount importance. In Nature, the sequence of monomers within copolymers such as DNA, proteins, etc..., directly impacts the architecture of the macromolecules, and induces specific properties. Synthetic alternating copolymers are thus of great interest, allowing optimal repartition of functional substituent all along the polymer chain, over copolymers with lower periodicity (block, random copolymers). Our team has developed over the past decade several classes of rare-earth based catalysts for the ROP of β-lactones, such as the functional alkyl malolactonates (MLAR) or 4-alkoxymethylene-β-propiolactones (BPLOR). Those different catalysts, depending on the nature of the ortho-substituent on the bisphenolate platform, enable the preparation of syndiotactic or, quite uniquely, isotactic polymers starting from racemic mixtures of the β-lactones. On the other hand, starting from mixtures of chemically different enantiopure MLAR or BPLOR with opposite absolute configuration, original highly alternated copolymers can be accessed.

Rare-earth promoted stereoselective ROP of β-lactones: Syndiotactic, isotactic or chemically tunable alternating polymers

256th National Meeting (2018)

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