High‐Tg Thiol‐Click Thermoset Networks via the Thiol‐Maleimide Michael Addition. Issue 13 (11th May 2016)

• Record Type: Journal Article
• Authors: Parker, Shelbi; Reit, Radu; Abitz, Haley; Ellson, Gregory; Yang, Kejia; Lund, Benjamin; Voit, Walter E.
• Is Part Of: Macromolecular rapid communications. Volume 37:Issue 13(2016)
• Page Start: 1027
• Page End: 1032
• Publication Date: 2016-05-11
• Subjects: click chemistry -- high Tg -- Michael addition -- thermoset -- thiol‐maleimide; Macromolecules -- Periodicals; Polymers -- Periodicals; Chemistry -- Periodicals; 547.705
• DOI: 10.1002/marc.201600033
• Languages: English
• ISSNs: 1022-1336

Abstract

Abstract : Thiol‐click reactions lead to polymeric materials with a wide range of interesting mechanical, electrical, and optical properties. However, this reaction mechanism typically results in bulk materials with a low glass transition temperature ( T g ) due to rotational flexibility around the thioether linkages found in networks such as thiol‐ene, thiol‐epoxy, and thiol‐acrylate systems. This report explores the thiol‐maleimide reaction utilized for the first time as a solvent‐free reaction system to synthesize high‐ T g thermosetting networks. Through thermomechanical characterization via dynamic mechanical analysis, the homogeneity and T g s of thiol‐maleimide networks are compared to similarly structured thiol‐ene and thiol‐epoxy networks. While preliminary data show more heterogeneous networks for thiol‐maleimide systems, bulk materials exhibit T g s 80 °C higher than other thiol‐click systems explored herein. Finally, hollow tubes are synthesized using each thiol‐click reaction mechanism and employed in low‐ and high‐temperature environments, demonstrating the ability to withstand a compressive radial 100 N deformation at 100 °C wherein other thiol‐click systems fail mechanically. Abstract : The thiol‐maleimide Michael addition is demonstrated as a reaction mechanism used to synthesize high‐ T g thiol‐click thermosetting networks that exhibit T g s 80 °C higher than similarly structured thiol‐click systems. Hollow cylindrical samples of each composition are fabricated and loaded radially, showing the thiol‐maleimide thermosets withstanding a 100 N load at elevated temperatures.