ma7b01107_si_001.pdf (3.61 MB)
Polymerization Mechanism and Cross-Link Structure of Nadic End-Capped Polymers: A Quantum Mechanical and Microkinetic Investigation
journal contribution
posted on 2017-08-11, 18:04 authored by Sooraj Kunnikuruvan, Priya V. Parandekar, Om Prakash, Thomas K. Tsotsis, Nisanth N. NairThe
applications of norbornene or nadic end-capped high performance
polymers (HPPs) are manifold and have been discussed in the literature
for more than two decades. The cross-links formed from nadic end-cap
determine the mechanical and thermal properties of these polymers.
In spite of extensive studies, the cross-link structure and the cross-linking
mechanism of nadic end-capped polymers remain elusive. Quantum chemical
computations together with microkinetic modeling are used here to
elucidate these aspects. Various possible polymerization pathways
that contribute to the final cross-link structure of nadic end-capped
polymers are proposed, and the distribution of cross-link structures
is computed. The cross-linking mechanisms are modeled considering
radical initialization, chain propagation, and termination, and our
computations identify the most active cross-linking mechanism. The
results of our study are then compared with the available experimental
data.