Sulfur Chemistry in Polymer and Materials Science

Abstract

The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/marc.201800650. ChemistryBefore moving to the recent advances within the last 5 years in the diverse applications of sulfur chemistry in polymer and Sulfur-Containing PolymersSulfur and its functional groups are major players in an area of exciting research taking place in modern polymer and materials science, both in academia and industry. In fact, manifold sulfur-based reactions that are both exceptionally versatile as well as tremendously useful have been implemented, and further utilized for the design and preparation of polymeric materials that lead to a plethora of applications ranging from medicine to optics and nanotechnology to separation science. Hence, within this review, an overview of strategies and developments used over the last 5 years to reinforce the importance of the sulfur functional group in modern polymer and materials science is presented. In particular, many important references in the primary literature of sulfur chemistry are referred to, including thiol-ene, thiol-yne, thiol-Michael addition, disulfide cross-linking, and thiol-disulfide exchange, among others, by explaining and illustrating the important principles. Last but not least, the grand aim to underpin the importance of sulfur in modern polymer and materials science is achieved by presenting selected examples in diverse fields and postulating the respective potential for real-world applications. he is now a full professor at KIT.sulfur atoms, and tetraphenylethene-bearing di(alkyl bromide) (Scheme 3). The yield of the polymerization was dependent on the di(alkyl bromide) monomer; the longer spacer between the aromatic moiety and the reactive bromide end groups Scheme 1. The discussion henceforth focuses on the synthesis of polymers possessing the depicted sulfur functional groups. Scheme 2.Representative examples of polythioethers prepared via A) the nucleophilic substitution reaction between an electrophilic dihalide with nucleophilic derivatives of dithiols under alkaline conditions; B) the thiol-ene/yne addition reaction between AA and BB type monomers (i.e., dithiols and dienes/diynes); and C) radical or ionic ring-opening of sulfurcontaining strained rings.Scheme 3. The thiol-bromo polymerization of conformationally fixed monomers to provide multifunctional polymers. [19] Macromol. Rapid Commun. 2019, 40, 1800650 Scheme 4. The regioselective selective nucleophilic aromatic substitution between thiol and fluorinated aromatic compounds, the para-fluorothiol reaction (PFTR).Scheme 5. Synthesis of a linear polymer via PFTR-reaction. [21]

Sequential crosslinking for mechanical property development in high sulfur content composites

“…High sulfur-content materials (HSMs) can be conveniently prepared by the reaction of elemental sulfur with olefins by inverse vulcanization (InV) [1][2][3] or from aryl halides by radical-induced aryl halide-sulfur polymerization (RASP, Scheme 1). [4][5][6] HSMs produced by these routes have been proposed for applications such as electrode materials, [7][8][9][10][11][12] lenses for thermal imaging, [13] fertilizers [14,15] absorbents for removing toxins from water, [16][17][18][19][20][21] or as structural materials [22][23][24][25][26][27][28][29] and thermal insulators. [30,31] The InV mechanism proceeds when olefins are crosslinked by their reaction with sulfur radicals produced by heating elemental sulfur to >159 C. RASP involves thermal reaction of aryl halides with elemental sulfur whereby S C aryl bonds are formed, a process requiring slightly higher temperatures of 220-250 C.…”

Atomic and electronic structure of solids of Ge2Br2PN, Ge2I2PN, Sn2Cl2PN, Sn2Br2PN and Sn2I2PN inorganic double helices: a first principles study

“…It is to be noted that a double helical structure of selenium, an element just below S in the periodic table, has been reported 12 to occur in a double wall carbon nanotube. Also, sulphur favours polymeric chains 13 and a one-dimensional helical structure of phosphorous has also been reported. 14,15 Some of the earlier reported inorganic double helices, such as, [(CH 3 ) 2 NH 2 ]K 4 [V 10 O 10 (H 2 O) 2 (OH) 4 (-PO 4 ) 7 ]$4H 2 O and the combination of cadmium sulphide and cadmium tellurium forms very complicated double helical geometry.…”

Density-Adjustable Bio-Based Polysulfide Composite Prepared by Inverse Vulcanization and Bio-Based Fillers

“…The reaction between sulfur and unsaturated compound is known as “inverse vulcanization” [ 5 ]. Polysulfides usually exhibit excellent properties preferring them suitable for direct use or as intermediates for further functionalization for various applications [ 15 , 16 ] such as solar cell [ 17 ], hydrogen fuel cell [ 18 ], lithium-ion batteries [ 11 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 ], high refractive index and IR transmitting optical devices [ 27 , 28 , 29 , 30 ], sulfur-doped carbon materials [ 31 ], heavy metal remediation [ 14 , 31 , 32 , 33 , 34 , 35 ], rubber [ 10 ], fertilizer [ 36 , 37 ], and other advanced materials [ 38 , 39 , 40 ].…”