Sulfur Conversion to Multifunctional Poly(O-thiocarbamate)s through Multicomponent Polymerizations of Sulfur, Diols, and Diisocyanides

Abstract

Sulfur, which is generated from the waste byproducts in the oil and gas refinery industry, is an abundant, cheap, stable, and readily available source in the world. However, the utilization of excessive amounts of sulfur is mostly limited, and developing novel methods for sulfur conversion is still a global concern. Here, we report a facile one-step conversion from elemental sulfur to functional poly(O-thiocarbamate)s through a multicomponent polymerization of sulfur, diols, and diisocyanides, which possesses a series of advantages such as mild condition (55 °C), short reaction time (1 h), 100% atom economy, and transition-metal free in the catalyst system. Seven poly(O-thiocarbamate)s are constructed with high yields (up to 95%), large molecular weight (up to 53100 of M w ), good solubility in organic solvents, and completely new polymer structures. The poly(O-thiocarbamate)s possess a high refractive index above 1.7 from 600 to 1700 nm by adjusting the sulfur content. By incorporating tetraphenylethene (TPE) moieties into the polymer structure, the poly(O-thiocarbamate)s can also be designed as fluorescent sensors to detect harmful metal cation of Hg 2+ in a turn-on mode with high sensitivity (LOD = 32 nM) and excellent selectivity (over interference cations of Pb 2+ , Au 3+ , Ag + ). Different from the previous reports, the exact coordination structure is first identified by single-crystal X-ray diffraction, which is revealed in a tetracoordination fashion (two sulfur and two chloride) using a model coordination compound.

One‐Pot Synthesis of Thiocarbamates

“…Furthermore, only few examples of S-organyl thiocarbamate polymers are known in literature, [49] while Oorganyl thiocarbamate-bearing polymers are mainly synthesized by post-polymerization modification, [50,51] or step-growth polymerization techniques. [52] First experiments featured the synthesis of bisthiocarbamates as the necessary di-N-formamides are easily accessible via their diamines. Afterwards, several pathways for step-growth polymerization were investigated, however, the employed protocols (transesterification/thiol-ene) only led to low yields/molecular weight (Scheme 6), most likely due to solubility challenges.…”

Using conjugated system from natural sources for the synthesis of sulfur copolymers by bi‐function catalysts at mild temperatures

“…On the other hand, it is important to monitor mercury levels in air and water in real‐time, portable, and inexpensive methods. Sulfur‐rich copolymers have found their application as a chemosensor for Hg 2+ 30,31 …”

Segmented Polyurethanes and Thermoplastic Elastomers from Elemental Sulfur with Enhanced Thermomechanical Properties and Flame Retardancy

“…[4][5][6] Due to the large volumes of H 2 S, S 8 and CS 2 that are generated, the conversion of these materials into feedstocks for both commodity and specialty polymers has been identified as an attractive new revenue stream to increase the valorization of these chemicals which would profoundly affect these industrial sectors.T oward this goal, the development of new polymerization and synthetic methods for preparing sulfur containing polymers has been developed which notably include using S 8 for inverse vulcanization, [7][8][9][10] dynamic covalent polymerizations, [11][12] (organo)catalytic CS 2 copolymerizations [13][14][15][16][17][18] and multi-component polymerizations. [19][20][21][22] These new polymerization methods with S 8 have been driven by fundamental interests in polymer chemistry, but also for use in Li-S batteries, [7,9,[23][24][25] high refractive index polymers, [26] infrared optics, [27][28][29][30] environmental remediation [8,[31][32][33][34] and more recently for creation of liquid metal hybrids [35] and new negative electron affinity triboelectronic materials. [36] To date,aremaining challenge for the use of S 8 in polymer synthesis is to improve the thermomechanical properties and solubility of sulfur-based polymers,w hile also retaining ar easonable sulfur utilization yield into the material.…”