A systematic investigation of the ring size effects on the free radical ring-opening polymerization (rROP) of cyclic ketene acetal (CKA) using both experimental and theoretical approach

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A systematic investigation of the ring size effects on the free radical ring-opening polymerization (rROP) of cyclic ketene acetal (CKA) using both experimental and theoretical approach
Title:
A systematic investigation of the ring size effects on the free radical ring-opening polymerization (rROP) of cyclic ketene acetal (CKA) using both experimental and theoretical approach
Journal Title:
Journal of Polymer Science
Publication Date:
21 May 2020
Citation:
Mothe, S. R.; Tan, J. S. J.; Chennamaneni, L. R.; Aidil, F.; Su, Y.; Kang, H. C.; Lim, F. C. H.; Thoniyot, P., A systematic investigation of the ring size effects on the free radical ring-opening polymerization (rROP) of cyclic ketene acetal (CKA) using both experimental and theoretical approach. Journal of Polymer Science DOI: 10.1002/pol.20200210.
Abstract:
Radical ring‐opening polymerization (rROP) reaction of cyclic ketene acetals (CKA) is an interesting route to biodegradable polymers. Contrary to their tremendous potential, fundamental understanding of their reaction kinetics and thermodynamics is still limited. We present experimental and theoretical investigations for rROP reactions of CKA to systematically elucidate the effects of monomer ring sizes on the homopolymerization. We aim to provide insights on the structural‐reactivity relationship of CKA by studying the thermodynamics and kinetics of the forward ring‐opening propagation reactions and key side reactions, namely ring‐retained propagation and radical back‐biting reaction leading to branching. Experimental results show that for the CKA with smaller ring sizes, significant amount of ring‐retained side products are formed when up to 90% of the monomers are converted. However, for the larger ring sizes (7 and 8 membered), almost complete ring‐opening polymerization with <1% of ring‐retained products are formed. Density functional theory (DFT) calculations show that kinetic effects from the collision frequency dominate in differentiating between ring‐opening propagation, ring‐retained propagation, and backbiting. The results corroborate well with experiments and reports in the literature. Our systematic study from the first principle and experimental validation provide insights into CKA rROP to apply radical polymerization to generate biodegradable polymers.
License type:
PublisherCopyrights
Funding Info:
This work was supported by the Industry Alignment Fund - Pre-Positioning Programme (IAF-PP) of Agency for Science, Technology and Research (A*STAR) (A1786a0025).
Description:
This is the peer reviewed version of the following article: Mothe, S. R.; Tan, J. S. J.; Chennamaneni, L. R.; Aidil, F.; Su, Y.; Kang, H. C.; Lim, F. C. H.; Thoniyot, P., A systematic investigation of the ring size effects on the free radical ring-opening polymerization (rROP) of cyclic ketene acetal (CKA) using both experimental and theoretical approach. Journal of Polymer Science DOI: 10.1002/pol.20200210., which has been published in final form at https://doi.org/10.1002/pol.20200210. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
ISSN:
0887-624X
1099-0518
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