Search Results (33)

Sulfur-containing polymers are unique sustainable materials with promise for the development of various adsorbents for environmental remediation. However, they have not been explored for CO₂ capture despite reports on its ability to decontaminate various aqueous pollutants. This study reports on the single-step synthesis of a diamine-functionalized sulfur-containing copolymer by the thermally induced radical copolymerization of N2,N2-Diallylmelamine (NDAM), a difunctional monomer, with sulfur and explores its use for CO₂ capture. The influence of reaction parameters such as the weight ratios of sulfur to NDAM, reaction temperature, time, and the addition of a porogen on the properties of aminated copolymer was investigated. The resulting copolymers were characterized using FTIR, TGA, DSC, SEM, XRD, and BET surface area analyses. The incorporation of NDAM directly imparted amine functionality while stabilizing the polysulfide chains by crosslinking, leading to a thermoset copolymer with an amorphous structure. The addition of a NaCl particle porogen to the S/NDAM mixture generated a mesoporous structure, enabling the resulting copolymer to be tested for CO₂ adsorption under varying pressures, leading to an adsorption capacity as high as 517 mg/g at 25 bar. This work not only promotes sustainable hybrid materials that advance green chemistry while aiding CO₂ mitigation efforts but also adds value to the abundant amount of sulfur by-products from petroleum refineries. Full article

Recently, polyacetylene (PA) has been receiving renewed scientific attention due to its electrical properties, potentially useful for energy applications (e.g., fabrication of electrodes for rechargeable batteries and supercapacitors), and unique functional characteristics (e.g., gas trap, oxygen scavenger, EMI shielding, etc.). This chemical compound can be obtained in the form of polyacetylene–PVOH copolymers simply through the chemical dehydration of poly(vinyl alcohol) (PVOH), which is a very common type of polymer, widely used in packaging and other technological areas. This very inexpensive chemical reaction for the large-scale synthesis of PA/polyvinylenes is investigated by reacting PVOH with sulfuric acid at room temperature. In this process, PVOH, shaped in the form of a film, is dipped in sulfuric acid (i.e., H₂SO₄ at 95%–97%) and, after complete chemical dehydration, it is mechanically removed from the liquid phase by using a nylon sieve. The reduction process leads to a substantial PVOH film conversion into PA, as demonstrated by infrared spectroscopy (ATR mode). Indeed, the ATR spectrum of the reaction product includes all the characteristic absorption bands of PA. The reaction product is also characterized through the use of UV–Vis spectroscopy in order to evidence the presence in the structure of conjugated carbon–carbon double bonds of various lengths. Differential scanning calorimetry (DSC) and thermogravimetric analysis are used to investigate the PA solid-state cis–trans isomerization and thermal stability in air and nitrogen, respectively. XRD is used to verify the polymer amorphous nature. Full article

Gel electrolytes for lithium-ion batteries continue to replace the organic liquid electrolytes in conventional batteries due to their advantages of being less prone to leakage and non-explosive and possessing a high modulus of elasticity. However, the development of gel electrolytes has been hindered by their generally low ionic conductivity at room temperature and high interfacial impedance with electrodes. In this paper, a poly (vinylidene fluoride)-hexafluoropropylene copolymer (PVdF-HFP) with a flexible structure, Li₆PS₅Cl (LPSCl) powder of the sulfur–silver–germanium ore type, and lithium perchlorate salt (LiClO₄) were prepared into sulfide gel composite electrolyte films (GCEs) via a thermosetting process. The experimental results showed that the gel composite electrolyte with 1% LPSCl in the PVdF-HFP matrix exhibited an ionic conductivity as high as 1.27 × 10⁻³ S·cm⁻¹ at 25 °C and a lithium ion transference number of 0.63. The assembled LiFePO₄||GCEs||Li batteries have excellent rate (130 mAh·g⁻¹ at 1 C and 54 mAh·g⁻¹ at 5 C) and cycling (capacity retention was 93% after 100 cycles at 0.1 C and 80% after 150 cycles at 0.2 C) performance. This work provides new methods and strategies for the design and fabrication of solid-state batteries with high ionic conductivity and high specific energy. Full article

A series of polyacrylonitrile (PAN)-based block copolymers with poly(methyl methacrylate) (PMMA) as sacrificial bock were synthesized by atom transfer radical polymerization and used as precursors for the synthesis of porous carbons. The carbons enriched with O- and S-containing groups, introduced by controlled oxidation and sulfuration, respectively, were characterized by Raman spectroscopy, scanning electron microscopy, and X-ray photoelectron spectrometry, and their surface textural properties were measured by a volumetric analyzer. We observed that the presence of sulfur tends to modify the structure of the carbons, from microporous to mesoporous, while the use of copolymers with a range of molar composition PAN/PMMA between 10/90 and 47/53 allows the obtainment of carbons with different degrees of porosity. The amount of sacrificial block only affects the morphology of carbons stabilized in oxygen, inducing their nanostructuration, but has no effect on their chemical composition. We also demonstrated their suitability for separating a typical N₂/CO₂ post-combustion stream. Full article

All-solid-state lithium-sulfur batteries (ASSLSBs) are a promising next-generation battery technology. They exhibit high energy density, while mitigating intrinsic problems such as polysulfide shuttling and lithium dendrite growth that are common to liquid electrolyte-based batteries. Among the various types of solid electrolytes, solid polymer electrolytes (SPE) are attractive due to their superior flexibility and high safety. In this work, cross-linkable polymers composed of pentaerythritol tetraacrylate (PETEA) and tri(ethylene glycol) divinyl ether (PEG), are incorporated into sulfur–carbon composite cathodes to serve a dual function as both a binder and electrolyte, as a so-called catholyte. The influence of key parameters, including the sulfur–carbon ratio, catholyte content, and ionic conductivity of the electrolyte within the cathode on the electrochemical performance, was investigated. Notably, the sulfur composite cathode containing 30 wt% of the PETEA-PEG copolymer catholyte achieved a high initial discharge capacity of 1236 mAh g${}_{\mathrm{S}}{}^{-1}$ at a C-rate of 0.1 and 80 ${}^{°}$C. Full article

In this work, ground tire rubber and styrene–butadiene block copolymer (GTR/SBS) blends at the ratio of 50/50 wt%, with the application of four different SBS copolymer grades (linear and radial) and two types of cross-linking agent (a sulfur-based system and dicumyl peroxide), were prepared by melt compounding. The rheological and cross-linking behavior, physico-mechanical parameters (i.e., tensile properties, abrasion resistance, hardness, swelling degree, and density), thermal stability, and morphology of the prepared materials were characterized. The results showed that the selected SBS copolymers improved the processability of the GTR/SBS blends without any noticeable effects on their cross-linking behavior—which, in turn, was influenced by the type of cross-linking agent used. On the other hand, it was observed that the tensile strength, elongation at break, and abrasion resistance of the GTR/SBS blends cured with the sulfur system (6.1–8.4 MPa, 184–283%, and 235–303 mm³, respectively) were better than those cross-linked by dicumyl peroxide (4.0–7.8 MPa, 80–165%, and 351–414 mm³, respectively). Furthermore, it was found that the SBS copolymers improved the thermal stability of GTR, while the increasing viscosity of the used SBS copolymer also enhanced the interfacial adhesion between the GTR and SBS copolymers, as confirmed by microstructure evaluation. Full article

In this work, ground tire rubber (GTR) was thermo-mechanically treated in the presence of styrene-butadiene-styrene (SBS) copolymers. During preliminary investigation, the effects of different SBS copolymer grades, the variable content of SBS copolymer on the Mooney viscosity, and the thermal and mechanical properties of modified GTR were determined. Subsequently, GTR modified by SBS copolymer and cross-linking agents (sulfur-based system and dicumyl peroxide) was characterized by assessment of rheological, physico-mechanical, and morphological properties. Rheological investigations showed that linear SBS copolymer, with the highest melt flow rate among studied SBS grades, was the most promising modifier of GTR, considering processing behavior. It was also observed that an SBS improves the thermal stability of the modified GTR. However, it was found that higher content of SBS copolymer (above 30 wt%) does not bring any effective changes and, for economic reasons, is inefficient. The results showed that samples based on GTR modified by SBS and dicumyl peroxide have better processability and slightly higher mechanical properties compared to samples cross-linked by a sulfur-based system. This is due to the affinity of dicumyl peroxide to the co-cross-linking of GTR and SBS phases. Full article

The study addresses the growth of the wild-type strain Cupriavidus necator B-10646 and the synthesis of sulfur-containing polyhydroxyalkanoates (PHA) by this strain on media containing fructose and three different precursors (3-mercaptopropionic acid, 3′,3′-dithiodipropionic acid and 3′,3′-thiodipropionic acid). By varying the concentration and number of doses of the precursors added into the bacterial culture, it was possible to find conditions that ensure the formation of 3-mercaptopropionate (3MP) monomers from the precursors and their incorporation into the C-chain of poly(3-hydroxybutyrate). A series of P(3HB-co-3MP) copolymer samples with different content of 3MP monomers (from 2.04 to 39.0 mol.%) were synthesized and the physicochemical properties were studied. The effect of 3MP monomers is manifested in a certain decrease in the molecular weight of the samples and an increase in polydispersity. Temperature changes are manifested in the appearance of two peaks in the melting region with different intervals regardless of the 3MP content. The studied P(3HB-co-3MP) samples, regardless of the content of 3MP monomers, are characterized by equalization of the ratio of the amorphous and crystalline phases and have a close degree of crystallinity with a minimum of 42%, = and a maximum of 54%. Full article

A simple, efficient procedure has been employed to effect intra- and inter-chain crosslinking of two commercially available thiolated poly(dimethylsiloxane) copolymers (T-PDMS) with 4–6% or 13–17% of mercaptopropyl side-chains. The thiol functional groups were converted to disulfides (D-PDMS) in chloroform solutions of I₂. Importantly, the conditions employed avoid over-oxidation to other types of sulfur-containing species, and the concentration of T-PDMS during the crosslinking reaction dictated the rheological properties and liquid or solid nature of the D-PDMS. The procedure for obtaining the crosslinked copolymers is simpler than other approaches in the literature used to crosslink polysiloxane backbones and to modulate their properties. By changing the concentration of T-PDMS during the treatment with I₂, the degree of intra- and inter-chain crosslinking can be controlled (as assessed qualitatively by the solid or liquid nature of the products and their viscoelastic properties). For each of the T-PDMS materials, there is a concentration threshold, above which products are solids, and below which they are oils. Liquid and solid materials were characterized using ¹H and ¹³C solution-state and ¹³C solid-state NMR spectroscopy, respectively. They indicate greater than 90% conversion of thiols to disulfides in the presence of excess I₂. The rheological behavior of the liquid products, solvent swelling ability of solid products, and the thermal stability of the reactants and products are described. Furthermore, the solid products exhibit some of the highest swelling values reported in the literature for poly(dimethylsiloxane) (PDMS) materials. As assessed by thermal gravimetric analyses, the disulfide-crosslinked materials are more stable thermally than the corresponding thiols. Full article

Aromatic polyamides are well-known as high-performance materials due to their outstanding properties making them useful in a wide range of applications. However, their limited solubility in common organic solvents restricts their processability and becomes a hurdle in their applicability. This study is focused on the synthesis of processable ferrocene-based terpolyamides and their polydimethylsiloxane (PDMS)-containing block copolymers, using low-temperature solution polycondensation methodology. All the synthesized materials were structurally characterized using FTIR and ¹H NMR spectroscopic techniques. The ferrocene-based terpolymers and block copolymers were soluble in common organic solvents, while the organic analogs were found only soluble in sulfuric acid. WXRD analysis showed the amorphous nature of the materials, while the SEM analysis exposed the modified surface of the ferrocene-based block copolymers. The structure–property relationship of the materials was further elucidated by their water absorption and thermal behavior. These materials showed low to no water absorption along with their high limiting oxygen index (LOI) values depicting their good flame-retardant behavior. DFT studies also supported the role of various monomers in the polycondensation reaction where the electron pair donation from HOMO of diamine monomer to the LUMO of acyl chloride was predicted, along with the calculation of various other parameters of the representative terpolymers and block copolymers. Full article

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). Full article

The aim of the study is to search for a reaction that provides the possibility of tandem “one-pot” formation of polymer networks during radical copolymerization of N-vinyl-2-pyrrolidone and glycidyl methacrylate. It was shown that the addition of recently synthesized 1,3-dimethylimidazolium (phosphonooxy-)oligosulfanide makes it possible to obtain a cross-linked copolymer in one stage as a result of radical copolymerization of N-vinyl-2-pyrrolidone and glycidyl methacrylate with a molar ratio of monomers less than 1.4. The structure of the copolymerization products of N-vinyl-2-pyrroldione and glycidyl methacrylate formed in the presence of 1,3-dimethylimidazolium (phosphonooxy-)oligosulfanide was characterized by ¹H NMR, FTIR and MALDI spectroscopy. ¹H NMR spectroscopy revealed an interaction under moderate heating between glycidyl methacrylate and 1,3-dimethylimidazolium (phosphonooxy-)oligosulfanide, accompanied by the formation of a mixture of unsaturated products of complex structure, presumably acting as crosslinking agents. It is shown that when the molar ratio of N-vinyl-2-pyrroldione/glycidyl methacrylate comonomers is 0.89, a densely crosslinked copolymer is formed, capable of limited swelling in water with a velocity constant of 5.06 × 10⁻² min⁻¹ and an equilibrium degree of swelling of about 227%. Full article

To improve the crop yield and nitrogen uptake efficacy, a novel slow-release urea composite fertilizer (SUCF) was developed using inverse vulcanized copolymer with better biodegradation and nutrient release longevity. Copolymers were synthesized via inverse vulcanization of jatropha oil, and their properties were evaluated using thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), powdered-X-ray diffractometry (p-XRD), and scanning electron microscopy (SEM). SUCFs were developed by ex situ mixing of inverse vulcanized copolymer with urea powder using mechanical mixer, and their properties were evaluated using Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). FTIR spectra of developed fertilizer possesses the urea characteristics peaks along with the undisturbed peaks representing copolymer, confirming the mechanical mixing and that no reaction took place. SEM images of the SUCFs compared with images of copolymer revealed the appearance of new isolated particles with different morphology; EDX mapping showed that these particles represent the urea added to the copolymer. Nitrogen release longevity of developed fertilizers was evaluated in both soil and distilled water. The leaching test revealed that only 70% of the total nitrogen of SUCF prepared from 50 wt% sulfur copolymer was released after 16 days of incubation in distilled water, whereas it released only 35% nitrogen after 20 days in soil. The biodegradability of all copolymers developed was investigated by burying in soil and it revealed their biodegradable nature as weight loss was observed, which increased with the increase of incubation period. Full article

In order to improve the thermal and mechanical properties of poly(styrene-co-butadiene) (SBR) to use it as a pervaporation membrane in the separation of the azeotropic mixture toluene/methanol, poly(styrene-co-butadiene) crosslinked Maghnia-organo-montmonrillonite (CSBR/OMMT), a nanocomposite of different compositions was first prepared by a solvent casting method. SBR was crosslinked in situ in the presence of OMMT nanoparticles by an efficient vulcanization technique using sulfur as a crosslinking agent and zinc diethyldithiocarbamate as a catalyst. The structure and morphology of the hybrid materials obtained were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscope analysis. The thermal properties of these hybrid materials were studied by differential scanning calorimetry and thermogravimetric analysis/thermal differential analysis. The mechanical properties were studied by strength measurements. The results obtained occurred when the OMMT was incorporated in the CSBR matrix; a significant increase in the glass transition temperature of the SBR was observed which passed from −27 °C for virgin SBR to −21.5 °C for that containing 12 wt% of OMMT. The addition of OMMT nanoparticles to CSBR also improved the mechanical properties of this copolymer. When the OMMT content in the CSBR varied from 0 to 15% by weight, the tensile strength, the elongation at the nose and the modulus at 100% elongation increased from 3.45 to 6.25 MPa, from 162, 17 to 347.20% and 1.75 to 3.0 MPa, respectively. The results of pervaporation revealed that when the OMMT content varied between 3% and 12%, a significant increase in the total flux, the separation factor and the separation index by pervaporation increased from 260.67 to g m⁻² h⁻¹, 0.31 to 1.43, and 0.47 to 113.81 g m⁻² h⁻¹, respectively. Full article

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. Full article