Anionic Hybrid Copolymerization of Sulfur with Acrylate: Strategy for Synthesis of High-Performance Sulfur-Based Polymers

Abstract

Copolymerization of elemental sulfur (S8) with vinyl monomers to develop new polymer materials is significant. Here, for the first time, we report the anionic hybrid copolymerization of S8 with acrylate at 25 °C, yielding a copolymer with short polysulfide segments; i.e., each of them consists of only one to four sulfur atoms. The formation of a longer polysulfide segment would be ceaselessly disrupted by carbon anions through the chain-transfer reaction. The copolymer of S8 with diacrylate was cross-linked and exhibited excellent mechanical properties, with an ultimate tensile strength as high as 10.7 MPa and a breaking strain of 22%. Furthermore, the introduction of tertiary amide groups to the copolymer enabled it not only to be reprocessed via press molding at room temperature but also to exhibit self-healing properties without external intervention. This study provides a facile strategy to synthesize high-performance sulfur-based copolymers under mild conditions.

Nonconjugated Organic Room-Temperature Phosphorescent Vitrimers with Multicolor Afterglow via Multicomponent Hybrid Copolymerization

“…The signals in the range of 3000–3600 and 1000–1170 cm –1 were due to the vibration absorption signals of −OH/–NH 2 groups and the stretching vibration signals of −C–O– bonds in PBEHA, respectively . The signals in the ranges of 980–1000, 860–920, and 770–840 cm –1 corresponded to in-plane B–N, B–O–C, and N–B–N bonds. ,,, These signals cannot be found for PEHA. No CC bond (1610 cm –1 ) or plane B–O–H bending (1190 cm –1 ) signals were observed for all copolymers, illustrating high comonomer conversions.…”

“…RTP vitrimers were readily synthesized via one-step multicomponent hybrid copolymerization, 6-hexanediamine (HDA), ethylene glycol diglycidyl ether (EGDE), AM, and BA. , During the copolymerization, the reaction between HDA and EGDE has been widely studied for the preparation of epoxide resin (Figure A) . AM was incorporated into the copolymer system via the aze-Michael addition with HDA as well as the oxa-Michael addition reaction with the negative oxygen-ion formed by the ring opening reaction of EGDE .…”

Step‐growth Polymerization of Aziridines with Elemental Sulfur: Easy Access to Linear Polysulfides and Their Use as Recyclable Adhesives

“…Very recently, anionic inverse vulcanization of diacrylate has been developed for the easy synthesis of cross-linked polysulfides. [22,28] Additionally, elemental sulfur can react with acrylamides to produce small molecular polysulfides in the presence of an organobase. [29] It is important to note that such anionic step-growth reactions with sulfur have so far been limited to electron-deficient alkenes.…”

“…[21] Another notable advancement was made by Zhang et al, who reported an anionic hybrid copolymerization of sulfur with diacrylate at 25 °C, yielding a copolymer with short polysulfide segments. [22] Despite the significant progress that has been achieved, exploring non-vinyl copolymers remains a big challenge, as does the direct transformation of elemental sulfur into polysulfides with a controlled linear structure.…”

Biobased Inverse Vulcanized Polymer from Magnolol as a Multifunctional Ingredient for Carbon-Black-Reinforced Rubber Composites

“…Inverse vulcanization reported by Pyun and coworkers is a facile and powerful methodology to convert the abundant byproduct sulfur from petroleum industry into sulfur-rich polymers. − In addition to petrobased feedstocks, biobased monomers have also been utilized to prepare inverse vulcanized polymers. − Owing to the unique chemophysical properties arising from the high sulfur content, these materials show great potential for various applications, including the refractive index, Li–S battery cathodes, , self-healing materials, , heavy metal capture, , infrared imaging, and also injecting new vitality into rubber composites. Guo et al reported that the sulfur and styrene copolymers through inverse vulcanization as an efficient vulcanizing agent could cross-link diene rubbers in a green manner .…”