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. By varying the length of the aliphatic diol fragment in the α,ω-enol ether monomers the Tmand Tdof 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 Tmvalues ranging from 54 to 68 °C and Tgvalues increasing up to -17 °C.
Bibliographical noteFunding Information:
Financial support for this work was provided by the Minnesota Corn Growers’ Association and the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES) under Award DE-SC0020214. Equipment for the Chemistry Department NMR facility was supported through a grant from the National Institutes of Health (S10OD011952) with matching funds from the University of Minnesota.
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