Sulfenyl Chlorides: An Alternative Monomer Feedstock from Elemental Sulfur for Polymer Synthesis

Abstract

A polymerization methodology is reported using sulfur monochloride (S 2 Cl 2 ) as an alternative feedstock for polymeric materials. S 2 Cl 2 is an inexpensive petrochemical derived from elemental sulfur (S 8 ) but has numerous advantages as a reactive monomer for polymerization vs S 8 . This new process, termed sulfenyl chloride inverse vulcanization, exploits the high reactivity and miscibility of S 2 Cl 2 with a broad range of allylic monomers to prepare soluble, high molar-mass linear polymers, segmented block copolymers, and crosslinked thermosets with greater synthetic precision than achieved using classical inverse vulcanization. This step-growth addition polymerization also allows for preparation of a new class of thiol-free, inexpensive, highly optically transparent thermosets (α = 0.045 cm −1 at 1310 nm), which exhibit among the best optical transparency and low birefringence relative to commodity optical polymers, while possessing a higher refractive index (n > 1.6) in the visible and near-infrared spectra. The fabrication of large-sized optical components is also demonstrated.

Inverse Vulcanized Polymers for Sustainable Metal Remediation

“…Some recent progress in alternative sulfur sources is promising in this regard. [56] In the case of inverse vulcanized polymers with binding sites other than sulfur, it would be possible to trap other toxic metals such as arsenic or chromium, which are also environmentally threatening pollutants, or even low-toxic precious metals such as silver or platinum that could reduce the need for mining ore and facilitate recycling of various electronic waste.…”

Electrochemical synthesis of poly(trisulfides)

“…32 Regarding control of sulfur rank and structure, Pyun and associates have recently reported alternative sulfur-derived monomers such as sulfur monochloride (S2Cl2) that can react with alkene-containing comonomers through a step-growth mechanism, providing polymers with disulfide linkages throughout the backbone. 33 In this study, we report a new and complementary electrochemical polymerization method that provides poly(trisulfides) with precise control of sulfur rank (Fig. 1B).…”

Cooperative taming of CS2/oxetane copolymerisation: Consequences of main-chain sulfuration on polymer properties and catalysis

“…8-10 Furthermore, using monomers which can be directly sourced from elemental sulfur (such as CS2 from S8 and methane) is also relevant in the context of S8 utilization, a waste product of the petrochemical industry being produced at an annual megaton surplus. [11][12][13][14][15] Sulfur containing polymers are often synthesized by condensation or ring-opening polymerisation (ROP) methods, which can require multi-step monomer synthesis and do not give easy access to many polymer structures. 16,17 An increasingly popular method for the synthesis of heteroatom containing polymers is the ring-opening copolymerisation (ROCOP) of a strained heterocycle with heteroallenes.…”