Direct Synthesis of Polyesterether from Ethylene Glycol

We report here a method for making polyesterether from ethylene glycol. The reaction is catalyzed by a ruthenium complex and liberates H₂ gas and H₂O as byproducts. Mechanistic studies conducted through experiments and DFT computations suggest that the chain growth of the polymerization process involves both dehydrogenation and dehydration pathways stemming from a hemiacetal intermediate, leading to the formation of esters and ethers, respectively. Investigations into the polymerization of other diols have also been conducted, showing that diols with a lower number of carbons between the alcohol groups (propylene glycol, glycerol, and 1,3-propanediol) lead to the formation of polyesterether whereas α,ω-diols containing a higher number of carbons (1,6-hexanediol and 1,10-decanediol) lead to the formation of polyester.