Polyether Synthesis by Bulk Self-Condensation of Diols Catalyzed by Non-Eutectic Acid-Base Organocatalysts

Polyethers constitute a well-established class of polymers covering a wide range of applications from industrial manufacturing to nanomedicine. Nevertheless, their industrial implementation is limited to short chain aliphatic polyethers such as polyethylene glycol (PEO or PEG), polypropylene glycol (PPG), or polytetramethylene glycol (PTMG) produced by the ring-opening polymerization of the corresponding cyclic ethers. Herein, we report a sustainable and scalable approach for the preparation of medium and long chain aliphatic polyethers by the melt self-polycondensation of aliphatic diols in the presence of non-eutectic acid-base mixtures as organocatalyst. These organocatalysts were prepared by forming stoichiometric and non-stoichiometric complexes of methanesulfonic acid (MSA) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as confirmed by NMR spectroscopy and DFT calculations. The non-stoichiometric 2:1 and 3:1 MSA:TBD molar complexes showed superior thermal stability. These non-eutectic acid-base mixtures were tested in the bulk-self-condensation of 1,6-hexanediol leading to telechelic alpha,omega-hydroxy-poly(oxyhexane). The optimized polymerization conditions involved the use of MSA:TBD (3:1) catalyst in a three-step polycondensation process at 130-180 and 200 degrees C, respectively. These conditions were applied to the synthesis of a wide range of aliphatic polyethers with a number of methylene units ranging from 6 to 12 units and molecular weights between 5000 and 22 000 g mol(-1). The aliphatic polyethers were highly semicrystalline with melting temperatures ranging from 55 to 85 degrees C. The synthesis approach was extended to the preparation of value-added copolymers from different length chain diols and different functionality, giving rise to different copolymer architectures from linear copolyethers to polyether thermosets. Altogether, this straightforward polymerization strategy enables access to medium-long chain and cross-linked aliphatic polyethers using easily prepared and recyclable organocatalysts.