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The aryl diester compound, 2-methyl-1,4-phenyl-ene bis-(3,5-di-bromo-benzoate), C21H12Br4O4, was synthesized by esterification of methyl hydro-quinone with 3,5-di-bromo-benzoic acid. A crystalline sample was obtained by cooling a sample of the melt (m.p. = 502 K/DSC) to room temperature. The mol-ecular structure consists of a central benzene ring with anti-3,5-di-bromo-benzoate groups symmetrically attached at the 1 and 4 positions and a methyl group attached at the 2 position of the central ring. In the crystal structure (space group P), mol-ecules of the title aryl diester are located on inversion centers imposing disorder of the methyl group and H atom across the central benzene ring. The crystal structure is consolidated by a network of C-H⋯Br hydrogen bonds in addition to weaker and offset π-π inter-actions involving the central benzene rings as well as the rings of the attached 3,5-di-bromo-benzoate groups.

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State-of-the-art triboelectric nanogenerators (TENGs) typically employ fluoropolymers, highly negative chargeable materials in triboelectric series. However, many researchers nowadays are concerned about environmental pollution caused by poly-and per-fluoroalkyl substances (PFAS) due to their critical immunotoxicity as fluoropolymers are likely to release PFAS into the ecosystem during their life cycle. Herein, a sulfur-rich polymer (SRP)/MXene composite, offering high-performance yet sustainable TENG is developed. Value-addition of sulfur into SRP-based TENG has huge advantages since sulfur is abundant waste from petroleum refining and possesses the highest electron affinity (-200 kJ mol-1) among polymerizable atoms. MXene segregated structure is introduced into SRP to achieve homogeneous distribution without electrical percolation by utilizing below 0.5 wt% of MXene, resulting in a significantly enhanced dielectric constant without a drastic increase of dielectric loss. Due to homogeneous MXene distribution, SRP/MXene composite-based TENG demonstrates 2.9 times and 19.5 times enhances peak voltage and peak current compared to previous SRP-based TENGs. Additionally, it exhibits reusability without critical reduction of modulus and TENG performance due to dynamically exchangeable disulfide bonds. Finally, after the corona discharging and scaling-up process to a 4-inch wafer size, SRP/MXene composite-based TENG exhibits an 8.4 times improvement in peak power density, reaching 3.80 W m-2 compared to previous SRP-based TENGs.

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Developing non-toxic and sustainable materials with versatile and diverse functions has always been a crucial issue in food preservation packaging. Recently, inverse vulcanization has emerged as a precise and eco-friendly solution, attributed to the versatility of resulting polysulfides. In this study, a polysulfide crosslinked with sorbic acid was prepared by inverse vulcanization, and further combined with bio-macromolecular ethyl cellulose to form composite films via a casting method. Thanks to the ethanol-solubility and good compatibility of ethyl cellulose towards the polysulfide, morphology of the films can be tailored by adjusting the component ratio, thereby achieving favorable water vapor permeability (2.20 × 10-12 gs-1m-1Pa-1), oxygen permeability (4.01 × 10-4 gs-1 m-2), elasticity modulus (~400 MPa), elongation at break (~16 %), etc. Some films demonstrate remarkable antibacterial activity against a broad spectrum of bacteria and fungi, demonstrating their effectiveness in food preservation. The browning and spoilage of preserved Agaricus bisporus were inhibited, with 79.2 % of the initial firmness retained and a 5.6 % weight loss recorded on the 6th day. For the 15-day preservation of grapes, minimal changes in appearance, firmness, or TSS were observed, underscoring the promising potential of this composite for food preservation applications.

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Elemental sulfur has shown to be a promising alternative feedstock for development of novel polymeric materials with high sulfur content. However, the utilization of inverse vulcanized polymers is restricted by the limitation of functional comonomers suitable for an inverse vulcanization. Control over properties and structure of inverse vulcanized polymers still poses a challenge to current research due to the dynamic nature of sulfur-sulfur bonds and high temperature of inverse vulcanization reactions. In here, we report for the first time the inverse vulcanization of norbornenyl pentafluorophenyl ester (NB-PFPE), allowing for post-modification of inverse vulcanized polymers via amidation of reactive PFP esters to yield high sulfur content polymers under mild conditions. Amidation of the precursor material with three functional primary amines (α-amino-ω-methoxy polyethylene glycol, aminopropyl trimethoxy silane, allylamine) was investigated. The resulting materials were applicable as sulfur containing poly(ethylene glycol) nanoparticles in aqueous environment. Cross-linked mercury adsorbents, sulfur surface coatings, and high-sulfur content networks with predictable thermal properties were achievable using aminopropyl trimethoxy silane and allylamine for post-polymerization modification, respectively. With the broad range of different amines available and applicable for post-polymerization modification, the versatility of poly(sulfur-random-NB-PFPE) as a platform precursor polymer for novel specialized sulfur containing materials was showcased.

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Sulfur polymers produced through 'inverse vulcanization' exhibit various attributes, such as photocatalytic activity and a high capacity to adsorb heavy metals. Nevertheless, there is a lack of research investigating the use of sulfur polymers as materials for the removal of organic contaminants. In this work, porous sulfur polymers (PSPs) were synthesized from elemental sulfur and 1,3-diisopropenylbenzene, with porosity introduced via salt templating. The result is a material that can strongly adsorb and chemically neutralize a model organic contaminant (caffeine). PSPs show adsorption up to 5 times higher than a leading adsorption material (activated carbon). Furthermore, either the adsorption or degradation processes can govern the removal efficiency depending on the synthesis parameters of PSPs. This is the first-ever report demonstrating sulfur polymers as effective materials for removing emerging contaminants from water. The versatile synthesis of sulfur polymers offers variation, which means that there is much more to explore in this exciting research area.

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The modification of polymer surfaces using laser light is important for many applications in the nano-, bio- and chemical sciences. Such capabilities have supported advances in biomedical devices, electronics, information storage, microfluidics, and other applications. In most cases, these modifications require high power lasers that are expensive and require specialized equipment and facilities to minimize risk of hazardous radiation. Additionally, polymer systems that can be easily modified by lasers are often complex and costly to prepare. In this report, these challenges are addressed with the discovery of low-cost sulfur copolymers that can be rapidly modified with lasers emitting low-power infrared and visible light. The featured copolymers are made from elemental sulfur and either cyclopentadiene or dicyclopentadiene. Using a suite of lasers with discreet wavelengths (532, 638 and 786 nm) and powers, a variety of surface modifications could be made on the polymers such as controlled swelling or etching via ablation. The facile synthesis and laser modification of these polymer systems were exploited in applications such as direct laser lithography and erasable information storage.

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Three waste plant oils (olive oil, coconut oil, and soybean oil) were utilized as monomer crosslinking agents to synthesize polysulfides by inverse vulcanization with elemental sulfur, for mercury removal from wastewater. NMR analysis showed that 92.1% of the olefins participated in the inverse vulcanization reaction, indicating that the quantity of unsaturated olefins in plant oil mainly affects the ring-opening ratio of sulfur for the formation of sulfur-based polymers. The experimental results showed that olive oil polysulfide (S-r-olive) achieved 100% Hg2+ removal within 2 h at a pH of 6. The S-r-olive, S-r-soybean, and S-r-coconut exhibited adsorption capacities of 130.23, 42.72, and 28.08 mg/g, respectively. The kinetic and adsorption isotherm illustrated that the Hg2+ adsorption by polysulfides conformed to the pseudo-second-order and Freundlich models, showing that the reaction rate constant of S-r-olive is approximately 14 times and 4.6 times greater than that of S-r-soybean and S-r-coconut, respectively. The adsorption mechanism is concluded that Hg2+ first enters the suspended S-r-olive by physical adsorption, then combined with sulfur to form HgS by chemical action and fixed in the S-r-olive adsorbent. This study demonstrates that utilizing waste plant oils as monomer crosslinking agents to synthesize adsorbents for Hg2+ removal is feasible and effective.

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Lithium-sulfur (Li-S) batteries hold a promising position as candidates for next-generation high-energy storage systems. Here, we combine inverse vulcanization of sulfur with multiwalled carbon nanotubes (MWCNTs) to increase the conductivity of cathode materials for Li-S batteries. The mixing process of inversely vulcanized sulfur copolymer networks with MWCNTs is aided by shear in a two-roll mill to take advantage of the soft nature of the copolymer. The high-throughput mixing method demands a source of conductive carbon that can be intimately mixed with the S copolymer, rendering MWCNTs an excellent choice for this purpose. The resulting sulfur copolymer network-MWCNTs composites were thoroughly characterized in terms of structure, chemical composition, thermal, and electronic transport properties, and finally evaluated by electrochemical benchmarking. These promising hybrids yielded electrodes with high sulfur content and demonstrate stable electrochemical performance exhibiting a specific capacity of ca. 550 mAh·gsulfur-1 (380 mAh·gelectrode-1) even after 500 charge-discharge cycles at specific current of 167 mA·g-1 (corresponds to 0.1C discharge rate), and thus are superior to melt-infiltrated reference samples.

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High sulfur content polymers prepared by inverse vulcanization have many reported potential applications, including as novel antimicrobial materials. High sulfur content polymers usually have limited water-solubility and dispersibility due to their hydrophobic nature, which could limit the development of their applications. Herein, we report the formulation of high sulfur content polymeric nanoparticles by a nanoprecipitation and emulsion-based method. High sulfur content polymeric nanoparticles were found to have an inhibitory effect against important bacterial pathogens, including Gram-positive methicillin-resistant Staphylococcus aureus and Gram-negative Pseudomonas aeruginosa. Salt-stable particles were formulated with the addition of a surfactant, which did not inhibit the antibacterial activity of the polymeric particles. Furthermore, the polymeric nanoparticles were found to inhibit S. aureus biofilm formation and exhibited low cytotoxicity against mammalian liver cells. Interaction of the polymeric particles with cellular thiols could be a potential mechanism of action against bacterial cells, as demonstrated by reaction with cysteine as a model thiol. The findings presented demonstrate methods of preparing aqueous dispersions of high sulfur content polymeric nanoparticles that could have useful biological applications.

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Inverse vulcanization utilizes an organic compound as reagent for crosslinking elemental sulfur to result in corresponding polymeric material with a high sulfur content. This work, employing 1,3,5-triisopropylbenzene (TIPB) as the reagent, demonstrates the first attempt on extending the scope of crosslinking agents of inverse vulcanization to saturate compounds. Under nuclear magnetic spectroscopic analysis, the reactions between TIPB and elemental sulfur take places through ring-opening reaction of S8 resulting in sulfur radicals at sulfur chain ends, radicals transferring to isopropyl groups of TIPB, and radical coupling reactions between carbon radicals and sulfur radicals. The obtained products are similar to the sulfur polymers from conventional inverse vulcanization processes and show self-healing property.

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Inverse vulcanization techniques are used to fabricate thermodynamically stable, sulfur polymers. Sulfur-based polymers exhibit higher refractive indices and improved transparency in the mid-wave infrared region compared with most organic polymers. Herein, the postsynthetic modification of sulfur polymers created via inverse vulcanization to generate novel, inorganic/organic photoresists is discussed. Amine-containing sulfur resins are postfunctionalized with cross-linkable alkynes. The sulfur-based materials undergo rapid photo-crosslinking to generate patternable films within 10 min under UV irradiation (365 nm). The development of these resins enables sulfur polymers to be utilized in processes where spatial and hierarchical control is necessary. The generation of this class of materials also expands on sulfur-based organic polymer systems with optical applications.

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Recently, organic polysulfides have been synthesized as cathode active materials exceeding the battery performance of sulfur. However, the conventional organic polysulfides have exhibited capacities lower than the theoretical capacity of sulfur because the π-organic moieties do not conjugate with the sulfur chains. In this work, the organopolysulfides, synthesized via inverse vulcanization using disulfide compounds, exhibited higher capacities equal to the theoretical capacity of sulfur because of enhanced electronic conductivity based on the conjugation between organic moieties and sulfur chains. Furthermore, the organopolysulfide including 1,3-dhitiol-2-thione moiety exhibited the highest capacity because of the enhanced electronic conductivity. This finding will pave the way to develop next-generation rechargeable batteries.

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In recent years, there has been an increasing concern related to the contamination of aqueous ecosystems by heavy metals, highlighting the need to improve the current techniques for remediation. This work intends to address the problem of removing heavy metals from waterbodies by combining two complementary methodologies: adsorption to a copolymer synthesized by inverse vulcanization of sulfur and vegetable oils and phytoremediation by the microalga Chlorella sorokiniana to enhance the metal adsorption. After studying the tolerance and growth of Chlorella sorokiniana in the presence of the copolymer, the adsorption of highly concentrated Cd2+ (50 mg L-1) by the copolymer and microalgae on their own and the combined immobilized system (AlgaPol) was compared. Additionally, adsorption studies have been performed on mixtures of the heavy metals Cd2+ and Cu2+ at a concentration of 8 mg L-1 each. AlgaPol biofilm is able to remove these metals from the growth medium by more than 90%. The excellent metal adsorption capacity of this biofilm can be kinetically described by a pseudo-second-order model.

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Inverse vulcanized polysulfides have been used as low-cost and effective adsorbents to remediate heavy metals in wastewater. Inverse vulcanization introduces sustainable polysulfide synthesis by solving the rapid desulfurization problem of unstable polysulfides, and provides superior performance compared to conventional commercial adsorbents. The review discussed the brief applications of the inverse vulcanized polysulfides to remove heavy metal wastewater and emphasized the modified synthesis processes for enhanced uptake ratios. The characteristics of polysulfide adsorbents, which play a vital role during the removal process are highlighted with a proper discussion of the interaction between metal ions and polysulfides. The review paper concludes with remarks on the future outlook of these low-cost adsorbents with high selectivity to heavy metals. These polysulfide adsorbents can be prepared using a wide variety of crosslinker monomers including organic hydrocarbons, cooking oils, and agro-based waste materials. They have shown good surface area and excellent metal-binding capabilities compared to the commercially available adsorbents. Proper postmodification processes have enabled the benefits of repetitive uses of the polysulfide adsorbents. The improved surface area obtained by appropriate choice of crosslinkers, modified synthesis techniques, and regeneration through post-modification has made inverse vulcanized polysulfides capable of removing.

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Inverse-vulcanized polymeric sulfur has received considerable attention for application in waste-based infrared (IR) polarizers with high polarization sensitivities, owing to its high transmittance in the IR region and thermal processability. However, there have been few reports on highly sensitive polymeric sulfur-based polarizers by replication of pre-simulated dimensions to achieve a high transmission of the transverse magnetic field (TTM ) and extinction ratio (ER). Herein, a 400-nanometer-pitch mid-wavelength infrared bilayer linear polarizer with self-aligned metal gratings is introduced on polymeric sulfur gratings integrated with a spacer layer (SM-polarizer). The dimensions of the SM-polarizer can be closely replicated using pre-simulated dimensions via a systematic investigation of thermal nanoimprinting conditions. Spacer thickness is tailored from 40 to 5100 nm by adjusting the concentration of polymeric sulfur solution during spin-coating. A tailored spacer thickness can maximize TTM in the broadband MWIR region by satisfying Fabry-Pérot resonance. The SM-polarizer yields TTM of 0.65, 0.59, and 0.43 and ER of 3.12 × 103 , 5.19 × 103 , and 5.81 × 103 at 4 µm for spacer thicknesses of 90, 338, and 572 nm, respectively. This demonstration of a highly sensitive and cost-effective SM-polarizer opens up exciting avenues for infrared polarimetric imaging and for applications in polarization manipulation.

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Slow-release fertilizers are developed to enhance the nutrient use efficiency (NUE), by coating urea with less water soluble or hydrophobic material. Diverse range of materials have been utilized to coat urea, however, their inherit non-biodegradability, hydrophilicity, crystallinity, and high synthesis cost limits their scalability. Herein, we reported the preparation of a novel slow-release sulfur enriched urea fertilizers using sustainable hydrophobic, biodegradable, crosslinked copolymer made from sulfur and rubber seed oil (Poly(S-RSO)) through the use of dip coating method. Scanning electron microscopy (SEM) was employed to study the fertilizers morphology and estimate the coating film thickness. A nitrogen release test was carried out in distilled water, which revealed that the coated fertilizers with a coating thickness of 165 µm, 254 µm and 264 µm released only 65 % of its total nutrient content after 2, 19 and 43 days of incubation, respectively: hence, showing an excellent slow-release property. In soil, fertilizer with 264 µm coating thickness released only 17 % nitrogen after 20 days of incubation, in line with the European standard (EN 13266, 2001). The release kinetic data best fits the Ritger-Peppas model with a R2 value of 0.99 and the n value of 0.65 indicated the release was mainly due to diffusion. Submerged cultivation (SmC) demonstrated the potential of poly(S-RSO) to enhance sulfur oxidation; it was observed that the copolymer oxidation was 50 % greater than that of elemental sulfur. A comparison between the newly developed fertilizers and existing coated fertilizers was also presented. On the whole, the results demonstrated outstanding slow-release characteristics and improved sulfur oxidation.

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In this concept review, the fundamental and polymerization chemistry of inverse vulcanization for the preparation of statistical and segmented sulfur copolymers, which have been actively developed and advanced in various applications over the past decade is discussed. This concept review delves into a discussion of step-growth polymerization constructs to describe the inverse vulcanization process and discuss prepolymer approaches for the synthesis of segmented sulfur polyurethanes. Furthermore, this concept review discusses the advantages of inverse vulcanization in conjunction with dynamic covalent polymerization and post-polymerization modifications to prepare segmented block copolymers with enhanced thermomechanical and flame retardant properties of these materials.

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With the continuing growth of waste sulfur production from the petroleum industry processes, its utilization for the production of useful, low-cost, and environmentally beneficial materials is of primary interest. Elemental sulfur has a significant and established history in the modification of bitumen binders, while the sulfur-containing high-molecular compounds are limited in this field. Herein, we report a novel possibility to utilize the sulfur/organic copolymers obtained via the inverse vulcanization process as modifiers for bitumen binders. Synthesis and thermal characterization (TGA-DSC) of polysulfides derived from elemental sulfur (S8) and unsaturated organic species (dicyclopentadiene, styrene, and limonene) have been carried out. The performance of modified bitumen binders has been studied by several mechanical measurements (softening point, ductility, penetration at 25 °C, frass breaking point, adhesion to glass and gravel) and compared to the unmodified bitumen from the perspective of normalized requirements concerning polymer-modified bitumen. The interaction of bitumen binder with sulfur/organic modifier has been studied by means of FTIR spectroscopy and DSC measurements. The impact of the modification on the performance properties of bitumen has been demonstrated. The bitumen binders modified with sulfur/organic copolymers are in general less sensitive to higher temperatures (higher softening point up to 7 °C), more resistant to permanent deformations (lower penetration depth), and more resistant to aging processes without intrusive deterioration of parameters at lower temperatures. What is more, the modification resulted in significantly higher adhesion of bitumen binders to both glass (from 25% up to 87%) and gravel surfaces in combination with a lower tendency to form permanent deformations (more elastic behavior of the modified materials).

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The inverse vulcanization produces high sulfur content polymers from alkenes and elemental sulfur. Control over properties such as the molar mass or the solubility of polymers is not well established, and existing strategies lack predictability or require large variations of the composition. Systematic design principles are sought to allow for a targeted design of materials. Herein, we report on the inverse vulcanization of norbornenylsilanes (NBS), with a different number of hydrolysable groups at the silicon atom. Inverse vulcanization of mixtures of NBS followed by polycondensation yielded soluble high sulfur content copolymers (50 wt % S) with controllable weight average molar mass (MW ), polydispersity (D), glass transition temperature (TG ), or zero-shear viscosity (η0 ). Polycondensation was conducted in the melt with HCl as a catalyst, abolishing the need for a solvent. Purification by precipitation afforded polymers with a greatly reduced amount of low molar mass species.

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Global enhancement of crop yield is achieved using chemical fertilizers; however, agro-economy is affected due to poor nutrient uptake efficacy (NUE), which also causes environmental pollution. Encapsulating urea granules with hydrophobic material can be one solution. Additionally, the inverse vulcanized copolymer obtained from vegetable oils are a new class of green sulfur-enriched polymer with good biodegradation and better sulfur oxidation potential, but they possess unreacted sulfur, which leads to void generations. In this study, inverse vulcanization reaction conditions to minimize the amount of unreacted sulfur through response surface methodology (RSM) is optimized. The copolymer obtained was then characterized using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). FTIR confirmed the formation of the copolymer, TGA demonstrated that copolymer is thermally stable up to 200 °C temperature, and DSC revealed the sulfur conversion of 82.2% (predicted conversion of 82.37%), which shows the goodness of the model developed to predict the sulfur conversion. To further maximize the sulfur conversion, 5 wt% diisopropenyl benzene (DIB) as a crosslinker is added during synthesis to produce terpolymer. The urea granule is then coated using terpolymer, and the nutrient release longevity of the coated urea is tested in distilled water, which revealed that only 65% of its total nutrient is released after 40 days of incubation. The soil burial of the terpolymer demonstrated its biodegradability, as 26% weight loss happens in 52 days of incubation. Thus, inverse vulcanized terpolymer as a coating material for urea demonstrated far better nutrient release longevity compared with other biopolymers with improved biodegradation; moreover, these copolymers also have potential to improve sulfur oxidation.