%0 Journal Article %A Kunnikuruvan, Sooraj %A Parandekar, Priya V. %A Prakash, Om %A Tsotsis, Thomas K. %A Nair, Nisanth N. %D 2017 %T Polymerization Mechanism and Cross-Link Structure of Nadic End-Capped Polymers: A Quantum Mechanical and Microkinetic Investigation %U https://acs.figshare.com/articles/journal_contribution/Polymerization_Mechanism_and_Cross-Link_Structure_of_Nadic_End-Capped_Polymers_A_Quantum_Mechanical_and_Microkinetic_Investigation/5305336 %R 10.1021/acs.macromol.7b01107.s001 %2 https://acs.figshare.com/ndownloader/files/9090208 %K HPP %K Nadic End-Capped Polymers %K cross-link structure %K cross-linking mechanism %K quantum chemical computations %K nadic end-capped polymers %X The 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. %I ACS Publications