title: High-Tg Thiol-Click Thermoset Networks via the Thiol-Maleimide Michael Addition.
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 (Tg ) 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-Tg thermosetting networks. Through thermomechanical characterization via dynamic mechanical analysis, the homogeneity and Tg 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 Tg 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.
authors.affiliation: Department of Bioengineering, The University of Texas at Dallas, 800 West Campbell Road, Mailstop RL 10, Richardson, TX, 75080, USA.
authors.forename: Shelbi
authors.initials: S
authors.lastname: Parker
authors.affiliation: Department of Bioengineering, The University of Texas at Dallas, 800 West Campbell Road, Mailstop RL 10, Richardson, TX, 75080, USA.
authors.forename: Radu
authors.initials: R
authors.lastname: Reit
authors.affiliation: Department of Mechanical Engineering, The University of Texas at Dallas, 800 West Campbell Road, Mailstop RL 10, Richardson, TX, 75080, USA.
authors.forename: Haley
authors.initials: H
authors.lastname: Abitz
authors.affiliation: Department of Materials Science and Engineering, The University of Texas at Dallas, 800 West Campbell Road, Mailstop RL 10, Richardson, TX, 75080, USA.
authors.forename: Gregory
authors.initials: G
authors.lastname: Ellson
authors.affiliation: Department of Chemistry, The University of Texas at Dallas, 800 West Campbell Road, Mailstop RL 10, Richardson, TX, 75080, USA.
authors.forename: Kejia
authors.initials: K
authors.lastname: Yang
authors.affiliation: Department of Materials Science and Engineering, The University of Texas at Dallas, 800 West Campbell Road, Mailstop RL 10, Richardson, TX, 75080, USA.
authors.forename: Benjamin
authors.initials: B
authors.lastname: Lund
authors.affiliation: Department of Bioengineering, The University of Texas at Dallas, 800 West Campbell Road, Mailstop RL 10, Richardson, TX, 75080, USA.|Department of Mechanical Engineering, The University of Texas at Dallas, 800 West Campbell Road, Mailstop RL 10, Richardson, TX, 75080, USA.|Department of Materials Science and Engineering, The University of Texas at Dallas, 800 West Campbell Road, Mailstop RL 10, Richardson, TX, 75080, USA.|Department of Chemistry, The University of Texas at Dallas, 800 West Campbell Road, Mailstop RL 10, Richardson, TX, 75080, USA.
authors.forename: Walter E
authors.initials: WE
authors.lastname: Voit
mesh_terms: D057930:Click Chemistry; D005898:Glass; D008301:Maleimides / Q000737:chemistry*; D015394:Molecular Structure; D011108:Polymers / Q000138:chemical synthesis* / Q000737:chemistry; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D044366:Transition Temperature
chemical_list: D008301:Maleimides; D011108:Polymers; D013438:Sulfhydryl Compounds; C043592:maleimide
keywords: Michael addition; click chemistry; high Tg; thermoset; thiol-maleimide