Synthesis of Poly(Ester-Ether) Polymers via Hydroesterificative Polymerization of alpha,omega-Enol Ethers

The Pd-catalyzed carbonylative polymerization of alpha,omega-enol ethers derived from etherification of 10-undecenol with diols is reported, extending the scope of this relatively new polymerization strategy beyond simple 10-undecenol. By varying the length of the aliphatic diol fragment in the alpha,omega-enol ether monomers the T-m and T-d of the polymers could be modified, ranging from 53 to 62 degrees C and 247 to 277 degrees C. Additionally, polymerization of alpha,omega-enol ethers containing rigid and bioderived diol moieties has been achieved, expanding the range of structures and polymer properties accessible via hydroesterificative polymerization. These more rigid alpha,omega-enol ether monomers resulted in further tuning of the polymer physical properties, with T-m values ranging from 54 to 68 degrees C and T-g values increasing up to -17 degrees C.