Cascading Retro-Diels-Alder Cycloreversion and Sydnone-Maleimide Based Double 1,3-Dipolar Cycloaddition for Quantitative Thermal Cross-Linking of an Amorphous Polymer Solid

Jeremy J Intemann; Wei Huang; Zhian Jin; Zhengwei Shi; Xi Yang; Jeffrey Yang; Jingdong Luo; Alex K-Y Jen

doi:10.1021/mz4000267

Cascading Retro-Diels-Alder Cycloreversion and Sydnone-Maleimide Based Double 1,3-Dipolar Cycloaddition for Quantitative Thermal Cross-Linking of an Amorphous Polymer Solid

ACS Macro Lett. 2013 Mar 19;2(3):256-259. doi: 10.1021/mz4000267. Epub 2013 Mar 5.

Authors

Jeremy J Intemann¹, Wei Huang^{1

2}, Zhian Jin¹, Zhengwei Shi¹, Xi Yang¹, Jeffrey Yang¹, Jingdong Luo¹, Alex K-Y Jen¹

Affiliations

¹ Department of Materials Science and Engineering, University of Washington, Seattle, Washington, 98195-2120, United States.
² Department of Chemistry, East China Normal University, 500 Dongchuan Road, Shanghai 200241, China.

PMID: 35581892
DOI: 10.1021/mz4000267

Abstract

A new approach to polymer cross-linking is investigated using a cascading cycloreversion of a maleimide-furan adduct and a double 1,3-dipolar cycloaddition between a sydnone and maleimide. The cross-linking proceeds quantitatively above 63 °C, despite the polymer possessing no observable glass transition temperature. The resulting polymer network possesses a high thermal stability (>300 °C) due to the irreversibility of the sydnone-maleimide cycloaddition, which releases CO₂ during the cross-linking, driving the reaction. The rigid three-dimensional structure of the bis-maleimide-sydnone cycloadduct produced local free volumes in films, decreasing the dielectric constant of the material.