A sulfur copolymer with a pyrrole compound for the crosslinking of unsaturated elastomers

Abstract

Effective applications must be found for sulfur, a widely available and inexpensive element. Over the last decade, copolymers with unsaturated comonomers have been prepared via so-called inverse vulcanization. In this work, a sulfur copolymer with a circular and biosourced di-pyrrole compound was obtained for the first time and was used as the sole crosslinking agent of an unsaturated elastomer. Pyrrole compounds (PyCs) were synthesized via the Paal-Knorr reaction of 2,5-hexanedione (HD) and hexamethylenediamine (HMD) or ethylenediamine (EDM). The PyCs were obtained without using solvents or catalysts in high yield and with water as the only co-product. Poly(S-co-HMDP) and poly(S-co-EDP) copolymers were prepared under the typical conditions of inverse vulcanization. Throughout the entire synthetic pathway, the overall yield was up to 92% and the atom efficiency was up to 73%. The E-factor evaluated for organic compounds was almost null. The sulfur weight content in the copolymers ranged from 40% to 80% and the average number of sulfur atoms in the sequences ranged from 3 to 17. The copolymers were found to be amorphous with a glass transition temperature ranging from −2 to 38 °C, increasing with the content of the pyrrole ring. The number average molecular weight was found to be in the range from 1500 to 9000 g mol−1. The molecular weight distribution was pretty narrow, with values lower than 2. NMR investigation suggested that the β position of the pyrrole ring reacted with sulfur atoms. A poly(S-co-HMDP) copolymer with an average sequence of 3 sulfur atoms was used as the sole crosslinking agent in a composite based on an unsaturated elastomer such as poly(styrene-co-butadiene) from anionic polymerization. More efficient crosslinking was obtained by promoting the ionic reaction of sulfur with elastomer chains by using 1,5-diazabicyclo(5.4.0)undec-7-ene. These results pave the way for the synthesis of a wide variety of sulfur copolymers with comonomers containing pyrrole rings for the sustainable crosslinking of elastomers, avoiding the use of oil-based accelerators.