Improved “cure on demand” of aromatic bismaleimide with thiol triggered by retro-Diels-Alder reaction

Abstract

This study focuses on the synthesis of new liquid aromatic bismaleimide monomers in order to improve self-curing on demand (SCOD) systems previously based on aliphatic bismaleimides. These SCOD systems are based on Diels-Alder (DA)/retro-DA reactions. The syntheses of new different aromatic bismaleimides with ester and amide bonds are presented. These maleimides have been protected using DA reaction and characterized by ¹H NMR analysis to determine protection rate and diastereomer ratios. The retro-DA reactions of both aromatic and aliphatic DA adducts in presence of thiol molecules were studied. Kinetic analysis was monitored by ¹H NMR and compared to model study. Finally, both aromatic and aliphatic bismaleimides-based polymers were synthesized with 2-mercaptoethyl ether and thermal properties of polymers were compared. The glass transition temperature values ranged from –20 °C to 14 °C and very good thermal stabilities were observed (up to 300 °C).

Graphical abstract

Keywords

thiol-ene polymerization / self-curing on demand / thia-michael addition / Diels-Alder / maleimide

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Acknowledgments

The authors thank the Hutchinson Company for its financial support, Biobased Polymer Company for reactants supply.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-020-1929-6 and is accessible for authorized users.

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