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.