High Refractive Index Copolymers with Improved Thermomechanical Properties via the Inverse Vulcanization of Sulfur and 1,3,5-Triisopropenylbenzene

Tristan S Kleine; Ngoc A Nguyen; Laura E Anderson; Soha Namnabat; Edward A LaVilla; Sasaan A Showghi; Philip T Dirlam; Clay B Arrington; Michael S Manchester; Jim Schwiegerling; Richard S Glass; Kookheon Char; Robert A Norwood; Michael E Mackay; Jeffrey Pyun

doi:10.1021/acsmacrolett.6b00602

High Refractive Index Copolymers with Improved Thermomechanical Properties via the Inverse Vulcanization of Sulfur and 1,3,5-Triisopropenylbenzene

ACS Macro Lett. 2016 Oct 18;5(10):1152-1156. doi: 10.1021/acsmacrolett.6b00602. Epub 2016 Sep 23.

Authors

Tristan S Kleine¹, Ngoc A Nguyen², Laura E Anderson¹, Soha Namnabat³, Edward A LaVilla³, Sasaan A Showghi³, Philip T Dirlam¹, Clay B Arrington¹, Michael S Manchester¹, Jim Schwiegerling³, Richard S Glass¹, Kookheon Char⁴, Robert A Norwood³, Michael E Mackay^{2

5}, Jeffrey Pyun^{1

4}

Affiliations

¹ Department of Chemistry and Biochemistry, University of Arizona, 1306 East University Boulevard, Tucson, Arizona 85721, United States.
² Department of Materials Science and Engineering, University of Delaware, 201 Dupont Hall, Newark, Delaware 19716, United States.
³ College of Optical Sciences, University of Arizona, Tucson, Arizona 85721, United States.
⁴ School of Chemical and Biological Engineering, Program of Chemical Convergence of Energy and Environment, The National Creative Research Initiative Center for Intelligent Hybrids, Seoul National University, Seoul 151-744, Korea.
⁵ Department of Chemical and Biomolecular Engineering, University of Delaware, 150 Academy Street, Newark, Delaware 19716, United States.

PMID: 35658175
DOI: 10.1021/acsmacrolett.6b00602

Abstract

The synthesis of a novel high sulfur content material possessing improved thermomechanical properties is reported via the inverse vulcanization of elemental sulfur (S₈) and 1,3,5-triisopropenylbenzene (TIB). A key feature of this system was the ability to afford highly cross-linked, thermosetting materials, where the use of TIB as a comonomer enabled facile control of the network structure and dramatically improved the glass transition temperature (relative to our earlier sulfur copolymers) of poly(sulfur-random-(1,3,5-triisopropenylbenzene)) (poly(S-r-TIB)) materials over a range from T = 68 to 130 °C. This approach allowed for the incorporation of a high content of sulfur-sulfur (S-S) units in the copolymer that enabled thermomechanical scission of these dynamic covalent bonds and thermal reprocessing of the material, which we confirmed via dynamic rheological characterization. Furthermore, the high sulfur content also imparted high refractive index (n > 1.75) and IR transparency to poly(S-r-TIB) copolymers, which offered a route to enhanced optical transmitting materials for IR thermal imaging applications with improved thermomechanical properties.