A detailed investigation of the thermodynamics of polymerization is necessary when trying to fully encapsulate the process of producing polyolefins. This investigation yields insight into how to produce isotactic polyolefins outside of a two-carbon branch periodicity, allowing for on insight on the structure-property relationships of tactic polyolefins. In order to probe the thermodynamics and structure-property relationship, ring-opening metathesis polymerization of bulky, allylic cyclopentenes were studied to provide the enthalpies and entropies of polymerization. These values can be advantageously compared to the regioregularity of the polyolefin microstructure to examine the effect of a bulky substituent. While low ring strain monomers have typically been thought to be driven via enthalpy, a complex relationship between the enthalpy and entropy of polymerization has been found. By better understanding the relationships between the thermodynamic parameters and regioregularity of the polymerization, a unique portion of the polymer genome can be better understood. Synthesis and the preliminary investigation of these properties will be discussed.

Thermodynamics and structural properties for ROMP of allylic cyclopentene to produce precision, isotactic polyolefins

ACS Spring Meeting 2021

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