Synthesis of Poly(Ester-Ether) Polymers via Hydroesterificative Polymerization of α,ω-Enol Ethers
The Pd-catalyzed carbonylative polymerization of α,ω-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. Here, by varying the length of the aliphatic diol fragment in the α,ω-enol ether monomers the T m and T d of the polymers could be modified, ranging from 53 to 62 °C and 247 to 277 °C. Additionally, polymerization of α,ω-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 α,ω-enol ether monomers resulted in further tuning of the polymer physical properties, with T m values ranging from 54 to 68 °C and T g values increasing up to –17 °C.