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Recent Advances on the Polymerization of Elemental Sulphur, Inverse Vulcanization and Methods to Functional Chalcogenide Hybrid Inorganic/Organic Polymers (Chips)

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Recent Advances on the Polymerization of Elemental Sulphur, Inverse Vulcanization and Methods to Functional Chalcogenide Hybrid Inorganic/Organic Polymers (Chips) Polymer Chemistry Recent Advances on the Polymerization of Elemental Sulphur, Inverse Vulcanization and Methods to Functional Chalcogenide Hybrid Inorganic/Organic Polymers (CHIPs) Journal: Polymer Chemistry Manuscript ID PY-REV-05-2019-000636.R1 Article Type: Review Article Date Submitted by the 11-Jun-2019 Author: Complete List of Authors: Zhang, Yueyan; University of Arizona, Chemistry & Biochemistry Glass, Richard; The University of Arizona, Department of Chemistry and Biochemistry Char, Kookheon; Seoul National University, School of Chemical and Biological Engineering Pyun, Jeff; The University of Arizona, Chemistry Page 1 of 26 PleasePolymer do not Chemistryadjust margins REVIEW Recent Advances on the Polymerization of Elemental Sulphur, In- verse Vulcanization and Methods to Functional Chalcogenide Hy- Received 00th January 20xx, Accepted 00th January 20xx brid Inorganic/Organic Polymers (CHIPs) a a b a,b DOI: 10.1039/x0xx00000x Yueyan Zhang, Richard S. Glass, Kookheon Char and Jeffrey Pyun Recent developments on the polymerization of elemental sulfur and the preparation of functional Chalcogenide Inganic/Organic Polymers (CHIPs) are reviewed. CHIPs represent a class of polymers synthesized from elemental sulfur with the incorporation of inorganic chalcogenide components (S, Se, Te) in the organic polymeric backbones. Novel CHIPs materials exhibit interesting optical, electrochemical and mechanical properties that lead to applications in thermal imaging, energy storage, self-healable materials and separation science. The emphasis of this review is on the key advances in the synthetic approaches to prepare functional polymeric sulfur-rich materials, with recent developments in synthesis, characterization, and application milestones being highlighted. polymeric materials and has grown extensive interest in this 1. Introduction area, as indicated by the numerous studies on the sulfur- containing polymers.10-14 Recent research, both academic and Sulfur is the tenth most abundant element on Earth and has applied, has been focusing on enhancing the properties and been recognized as a valuable chemical agent since antiquity. processing characteristics of these materials by introducing It has been used for medicine, fabric bleaching, construction of sulfur groups in the main-chain to broaden the scope of tech- lamp wicks, gun powder formulation and then more recently, 15 1-2 nological applications of these materials. Different sulfur- in the vulcanization of latex. In modern petroleum refining containing polymers (illustrated in Fig. 1) have been previously processes, the production of elemental sulfur (S8) is achieved summarized in various reviews.9, 15-17 through the removal of highly toxic hydrogen sulfide (H2S) gas Since 2011, Pyun et al. have advanced this field by demon- from crude oil and recovered through a thermal expulsion pro- 3 strating the preparation of sulfur-containing polymers via the cess. With approximately 70 million tons of by-product sulfur direct polymerization of elemental sulfur with organic comon- produced each year, refining of petroleum via hydrodesulfuri- omers. This process was termed inverse vulcanization in 2013 zation is currently the largest source of sulfur production glob- 4 and the materials derived from this methodology were gener- ally. A significant portion of sulfur is used in the industrial 5 ally referred to in the pioneering literature on this work as production of sulfuric acid, rubber, and fertilizer; in addition, “sulfur-containing (co)polymers” or polysulfides. However, modern synthetic chemistry has also benefitted from the ver- 6 since then, there has been numerous attempts to rename this satile chemistry of elemental sulfur. However, there is still a 7 class of polymers derived from elemental sulfur. These include net excess of sulfur that offer few economic utilities, thus, “inverse vulcanized polymers” as first seen in 2014,18 “organi- finding large-scale uses for this sulfur, such as conversion to cally modified chalcogenides” in 201719 and more recently useful materials, would be an important development. “thiopolymers” in 2019.20 The complication and redundancy Numerous advances have been made in the last few dec- are that the aforementioned terms, all refer to the same class ades concerning the synthesis of new types of sulfur- of inorganic/organic hybrid polymers derived from the containing polymers and modification of the properties of polymerization of elemental sulfur. Regardless of the subjec- some important classes of polymers by adding sulfur or poly- 8-9 tive preferences, or biases invoked to name this class of mate- sulfide fragments to the polymer compositions. In many rials, it is important to establish a clear and rational rubric for cases, these new synthetic methods have yielded valuable naming these types of polymers. This confusion is already compounded by the nomenclature similarities and ambiguities a. Department of Chemistry and Biochemistry, University of Arizona, 1306 East of organo-polysulfides, inorganic polysulfides, or sulfur allo- University Boulevard, Tucson, AZ, 85721. Email: [email protected] tropes. For the purposes of distinguishing how polymers de- b. School of Chemical and Biological Engineering, Program for Chemical Conver- gence for Energy & Environment, The National Creative Research Initiative Center rived from the polymerization of elemental sulphur are struc- for Intelligent Hybrids, Seoul 151-744, Korea. Email: [email protected]. turally distinctive from other sulfur containing polymers, we † Footnotes relating to the title and/or authors should appear here. Electronic Supplementary Information (ESI) available: [details of any supplemen- briefly summarize the classical terms used to describe these tary information available should be included here]. See DOI: 10.1039/x0xx00000x types of materials. Please do not adjust margins PleasePolymer do not Chemistryadjust margins Page 2 of 26 ARTICLE Journal Name Historically, the term “polysulfide” referred to both inor- structure perspective, CHIPs derived from the polymerization ganic forms of sulfur-containing covalent solids of sulfur chains of elemental sulfur will contain a statistical/random sequence 2- (-Sn-), ionic compounds (Sn , n>2) and organosulfur com- & composition of –Sx- units bonded to organic comonomer pounds in which the sulfur chain was terminated by organic units. These sulphur units may be mono, di-, or multiple S-S substituents R (R-Sn-R). To address this issue, a nomenclature bonds in the (co)polymer backbone, which is the distinctive based on sulfanes and polysulfanes was provided in a compre- structural feature of CHIPs made from S8 polymerization (Fig. hensive review by Steudel in 2002.21 According to this nomen- 1). To date, either free radical inverse vulcanization, or anionic clature, the name polysulfide was invoked to describe inorgan- polymerization processes have been the primary methods ic ionic compounds.22-23 The term organic polysulfanes were used to prepare polymeric materials from elemental sulfur. used to describe compounds of the type R-Sn-R with n > 2 in We propose that sulfur-containing polysulfides prepared from which the organic residues (alkyl or aryl) are linked to the sul- the polymerization of elemental sulfur with organic comono- fur chain via carbon atoms. The polymeric materials containing mers be generally referred to as CHIPs and appropriately cate- multiple sulfur units and hydrocarbons in the backbones were gorized as a class of organo-polysulfides consistent with the often referred as polysulfide polymers.8, 21, 24-30 Penczek et al. original Penczek formalism.9 However, regardless of whether was among the first to comprehensively review organosulfur CHIPs, or the other variations referred to previously are used, based polymers, the most common of which include poly- we recommend that a consistent rubric be used to distinguish alkylene sulphides, polyarylene sulphides, polythioureas, poly- these polymers from other sulfur-containing polymers. sulfoxides and polysulfones.9 From a chemical structural per- The focus of this review is to discuss the recent advances spective, all of these aforementioned sulphur containing pol- on the polymerization of elemental sulfur to prepare CHIPs, ymers in Fig.1 are comprised of single C-S moiety per repeating with an emphasis on new synthetic advances since our original unit. Organo-disulphide copolymers have also been widely comprehensive review on this subject in 2016.12 In particular, explored and contain an S-S moiety per repeating unit.24, 31-32 we discuss recent work on free radical and inverse vulcaniza- In a recent review, Theato et al. has elegantly discussed recent tion processes, along with new anionic polymerization meth- advances on the preparation of polymers containing thioe- ods to prepare CHIPs materials. Furthermore, we review for sters, thiocarbonates, thiocarbamates and thioamides, which the first time synthetic methods to introduce functionality contain multiple C-S moieties per repeating unit as incorpo- onto monomers and polymers derived from elemental sul- rated thru thiocarbonyl-based functional groups.15 phur. With the advent of inverse vulcanization and other meth- ods for the polymerization of elemental sulfur, it is apparent that a new subset of sulfur-containing polymers, or polysul- 2. Direct polymerization with elemental sulfur fides have been created that warrants classification in compar- 2.1 Inverse vulcanization with elemental sulfur. ison to these known
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