Search Results (68)

The coordination polymerization of 1,3-butadiene with half-metallocenes/MAO catalysts is a versatile route to polybutadiene, yet the kinetic impact of catalyst preparation remains poorly understood. This work compares CpTiCl₃/MAO systems prepared either in situ or by aging as a function of [MAO]/[Ti], temperature, and the presence of residual trimethylaluminum (TMA) in MAO. Aged catalysts display markedly higher activity than in-situ systems, achieving up to 99% conversion at [MAO]/[Ti] = 250 (vs. 34% in situ) while maintaining similar molecular weights and cis-1,4 microstructure (76–77%). Because the in-situ and aged systems were evaluated at different titanium concentrations, this activity difference should be interpreted as arising from both catalyst pre-conditioning and differences in effective Ti concentration. Time-resolved GPC coupled with chromatogram deconvolution reveals two coexisting macromolecular populations, associated with kinetically distinct chain-growth contributions. For aged systems, the corresponding apparent propagation rate constants remain of the same order of magnitude throughout the reaction, consistent with persistent catalytic heterogeneity rather than progressive site deactivation. The role of residual trimethylaluminum (TMA) in commercial MAO is clarified: TMA accelerates initial activation and enhances chain transfer processes, lowering molecular weight and broadening dispersity, but does not measurably affect cis-1,4 selectivity, which is governed by the ligand environment of CpTiCl₃. Overall, thermal aging and MAO conditioning emerge as effective tools to tune the kinetic behavior of CpTiCl₃/MAO catalysts without compromising microstructural control in polybutadiene synthesis. Full article

The harvesting of energy from movements is one of the purposes of triboelectric nanogenerators (TENGs). Among the various devices designed to perform this function, floors are one of the primary ones, as they do not need to be individually fitted to each subject and can be manufactured and installed on a large scale. This work classifies previously published TENG-based floors based on their materials, electrical performance in terms of the voltage, current, and power they produce, and their application in different fields. The materials used have been correlated with other important aspects for floors, such as weather or flame resistance, sustainability, recyclability or biodegradability of materials, and price. The synthesis of the variety of TENG-based floor models, which incorporate novel materials, hybrid technologies, or various functionalities, among other characteristics, can enrich and inspire the reader to enhance the performance of future floor designs based on the triboelectric effect. In addition, a novel triboelectric floor design made of nitrile butadiene rubber (NBR) and fluorine kautschuk material is presented, along with the electrical power generated when tribolayers are in contact. For the three floor strips measuring 40 cm long × 4 cm wide and 1 mm thick, electrical current and voltage output was measured, achieving nearly 0.1 W (20 V & 4.5 mA) of electrical power generation. Full article

Traditional oxidative dehydrogenation of n-butene has typically required relatively high operating temperatures (400–500 °C), which has driven increasing interest in the development of catalysts capable of delivering high activity at lower temperatures. In this study, zinc ferrite (ZnFe₂O₄-ST) was successfully synthesized via hydrothermal hydrolysis of Zn–Fe oleate and demonstrated remarkable catalytic performance for the oxidative dehydrogenation of n-butene under mild conditions. At 300 °C, ZnFe₂O₄-ST achieved a conversion of 72.9% with 92.1% selectivity toward 1,3-butadiene, a result that, to the best of our knowledge, ranks among the best reported in the literature. By contrast, ZnFe₂O₄ prepared by conventional coprecipitation (17.2% conversion with 91.3% selectivity) and sol-gel (10.1% conversion with 86.4% selectivity) methods showed much lower activities, highlighting the critical influence of synthesis strategy on catalytic performance. To better understand the origin of these differences, a detailed structural and physicochemical characterization was undertaken using X-ray diffraction (XRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), N₂ adsorption–desorption, X-ray photoelectron spectroscopy (XPS), H₂-temperature-programmed reduction (H₂-TPR), temperature-programmed re-oxidation (TPRO), and NH₃-temperature-programmed desorption (NH₃-TPD). These analyses revealed that the as-synthesized ZnFe₂O₄-ST possessed a significantly smaller average particle size, a larger specific surface area, and superior reducibility compared with the other samples. These properties are believed to be the key factors underpinning its outstanding catalytic behavior and provide important insights into the design of efficient low-temperature catalysts for selective oxidative dehydrogenation. Full article

This work presents the results of the synthesis and investigation of new antibacterial composite materials based on acrylonitrile–butadiene–styrene (ABS) copolymer and o-, m-, p-carboxyphenylmaleimides (CPhMI). The composites were obtained by thermal mixing with varying contents of different CPhMI isomers in the polymer matrix. The structural and thermal characteristics of the synthesized materials were investigated using IR and UV spectroscopy, as well as thermogravimetric (TGA) and differential thermal analysis (DTA). The results indicate that the o-isomer imparts the highest thermal stability, while the p-isomer shows slightly lower stability. In terms of processability, the m-isomer exhibits the highest melt flow, the p-isomer an intermediate level, and the o-isomer the lowest. The antibacterial activity of the composites was evaluated by the agar diffusion method against Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) microorganisms. All synthesized samples exhibited strong antibacterial activity against S. aureus and E. coli at a concentration of 0.5 wt%, confirming their potential for application in medical devices, as well as in sanitary polymer coatings and packaging. Full article

This study investigates the synthesis and photochemical behavior of a series of (E)-1-aryl-1,3-butadienes with different aromatic substituents. Despite their simple structure and straightforward preparation, detailed studies of their photochemical properties, especially UV light-induced (E) to (Z) isomerization, are scarce. Our results demonstrate that these compounds can efficiently undergo photo-triggered geometric changes, highlighting their potential as functional units in photochemical applications. The findings underline the significance of extended conjugation in managing excited-state processes, providing new insights into the dynamics of photoinduced transformations in conjugated diene systems. Additional computational analyses show how geometric modifications influence conformational energies in the synthesized compounds. Overall, these results improve understanding of structure–reactivity relationships and lay the foundation for designing photoresponsive materials based on (E) and (Z)-1-aryl-1,3-butadiene frameworks, with promising applications in photochemistry and materials science. Full article

The global production of electronic waste (e-waste) has increased due to the quick turnover of electronic devices, creating urgent problems for resource management and environmental sustainability. As a result, e-waste-derived materials (EWDMs) are being explored in pavement engineering research as sustainable substitutes in line with Sustainable Development Goals (SDGs), specifically SDG 9 (Industry, Innovation, and Infrastructure), 11 (Sustainable Cities and Communities), 12 (Responsible Consumption and Production), and 13 (Climate Action). Therefore, to assess global research production and the effectiveness of EWDMs in asphalt applications, this review combines scientometric mapping and systematic evidence synthesis. A total of 276 relevant publications were identified via a thorough search of Web of Science, Scopus, and ScienceDirect (2010–2025). These were examined via coauthorship structures, keyword networks, and contributions at the national level. The review revealed that China, India, and the United States are prominent research hubs. Additionally, experimental studies have shown that EWDMs, such as printed circuit board powder, fluorescent lamp waste glass, high-impact polystyrene, and acrylonitrile–butadiene–styrene, improve the fatigue life, Marshall stability, rutting resistance (up to 35%), and stiffness (up to 28%). However, issues with long-term field durability, microplastic release, heavy metal leaching, and chemical compatibility still exist. These restrictions highlight the necessity for standardised toxicity testing, harmonised mixed-design frameworks, and performance standards unique to EWDMs. Overall, the review shows that e-waste valorisation can lower carbon emissions, landfill build-up, and virgin material extraction, highlighting its potential in the circular pavement industry and promoting sustainable paving practices in accordance with SDGs 9, 11, 12, and 13. This review suggests that further studies on large-scale field trials, life cycles, and technoeconomic assessments are needed to guarantee the safe, long-lasting integration of EWDMs in pavements. It also advocates for coordinated research, supportive policies, and standardised methods. Full article

Several nickel dichloride phosphine complexes have been synthesized, their crystalline structure determined, and their behavior, in combination with methylaluminoxane, in the polymerization of butadiene has been examined. High-cis polybutadienes were consistently obtained, regardless of the nature of the phosphine coordinated to the metal and the methylaluminoxane/Ni molar ratio used, contrary to what was previously observed in the polymerization of butadiene with analogous cobalt phosphine complexes, in which catalytic selectivity was found to be strongly influenced by these two factors. An interpretation for such different behavior is provided. Full article

An analysis was conducted to investigate how reaction system turbulence affects the butadiene-isoprene copolymerization in the presence of the TiCl₄ + Al(i-Bu)₃ catalytic system. A model was developed, which integrates CFD simulations of TiCl₄ + Al(i-Bu)₃ particle breakage based on population balance equations with the kinetic modeling of the butadiene-isoprene copolymerization. It was established that an increase in turbulent kinetic energy leads to a reduction in catalyst particle size, an increase in active site concentration, an acceleration of the copolymerization process, and a decrease in the average molecular weights of the copolymer. Furthermore, catalytic activity correlates with both the average and maximum values of turbulent kinetic energy in the reaction system, whereas the effect of the average residence time of catalytic particles under turbulent conditions is insignificant. Based on these results, recommendations were provided for optimizing the impact of reaction system turbulence on TiCl₄ + Al(i-Bu)₃ particles to enhance the butadiene-isoprene copolymerization rate and achieve precise control over the molecular weight characteristics of the copolymer. The findings of this study can be applied to optimize the synthesis technology of the cis-1,4 butadiene-isoprene copolymer, which is used in the production of frost-resistant rubber. Full article

The increasing demand for sustainable materials has propelled the development of bio-based elastomers derived from renewable terpenes. This study presents the synthesis of high-cis poly(butadiene-co-terpene) copolymers using coordination chain transfer polymerization with neodymium-based catalysts, enabling precise control of molecular weight and microstructure. Two terpene monomers, β-myrcene and trans-β-farnesene, were incorporated up to 45 wt% without compromising the elastomeric 1,4-cis polybutadiene segments. The copolymers were evaluated as impact modifiers in acrylonitrile–butadiene–styrene (ABS) and as vulcanizable rubber formulations. ABS containing bio-based copolymers exhibited distinct rubber morphologies, including elongated and rod-like particles with average particle diameters greater than 1042 nm and rubber phase volume fraction values ≥ 0.49, resulting in improved impact resistance exceeding 580 J/m and elongation at break higher than 12%. Vulcanized rubbers incorporating terpene segments displayed tunable curing kinetics, mechanical properties, and dynamic mechanical behavior, with notable increases in elongation (up to ~520%) and elasticity attributed to lower crosslink density (<1.20 × 10⁻⁴ mol/mL). Additionally, its energy dissipation capacity has been enhanced compared to the high-cis polybutadiene. These findings highlight the potential of terpene-derived bioelastomers as sustainable alternatives to fossil-based rubbers, offering comparable or enhanced performance for engineering polymer applications. The study underscores important structure–property relationships, providing a foundation for further optimization toward industrial adoption. Full article

1,3-Butadiene and its analogues constitute an important raw material in the petrochemical industry. What is more, due to their specific structure, these compounds are attractive components in the synthesis of heterocyclic compounds. Modification of the 1,3-butadiene structure allows obtaining compounds characterized by different reactivity and possessing various biological properties. In order to thoroughly investigate this phenomenon, an analysis of 20 compounds, including 1,3-butadiene and its analogues, was carried out. For this purpose, a study based on MEDT, ADME, and PASS was performed. In this research, changes in electronic properties and basic physicochemical parameters under the presence of various substituents at various positions in the structure of 1,3-butadiene were studied. At the end, the influence of modifications on biological activities for the tested compounds was evaluated. Based on the presented results, it was found that substituent modifications cause significant changes in both electronic structures and in physicochemical properties of all the compounds. This fact is probably caused by the small size of the considered compounds. On the other hand, the main preferences for the most important active sites in the tested molecules remain the same due to the presence of a strongly conjugated system of double bonds. Full article

Sulfur-containing heterocyclic structures play an important role in modern biotechnology. Their synthesis is made possible by means of the hetero Diels–Alder reaction involving unsaturated sulfur compounds. In the framework of this paper, the molecular mechanism of the cycloaddition reactions between tioanalogs of the butadiene generated in situ with the participation of the Lawesson reagent and the E-2-phenyl-1-nitroethene was evaluated on the basis of the DFT quantum chemical calculations. It was found that the most favored reaction path is realized according to a stepwise mechanism with the participation of the zwitterionic intermediate. To study this further, the molecular mechanism of the deamination process of the primary cycloadducts was also analyzed. It was found that this mechanism is substantially different to the case of other known β-elimination processes and is achieved via a stepwise scheme. In addition to these investigations, the LA catalysis of the deamination process was also explored. Full article

Under elevated loading conditions, the aggregation of fillers emerges as a pivotal factor driving the degradation of separation performance in mixed matrix membranes. The two-dimensional (2D) modification of fillers, aimed at enhancing interfacial contact with polymers, has been recognized as an effective strategy to improve interphase compatibility and increase filler loading capacity. However, it is worth noting that the BET surface area of 2D fillers is typically relatively low. In this study, a two-step approach was developed. First, a “diffusion-mediated” process was combined with a solvent optimization strategy based on first-principles (DFT) calculations, achieving a 20-fold suppression in ZIF-67 nucleation-crystallization rate. This enabled the successful synthesis of a 2D amorphous nanoflower structure. Subsequently, the processing parameters were fine-tuned to enhance the specific surface area of ZIF-67 to 403 m²/g while preserving its 2D structural integrity. Ultimately, the as-prepared 2D ZIF-67 was incorporated into a hydrogenated styrene-butadiene block copolymer (SEBS) matrix to fabricate a mixed matrix membrane. Remarkably, at a filler loading of 20 wt%, the CH₄ permeability coefficient increased significantly from 11.7 barrer to 35.3 barrer, while the CH₄/N₂ selectivity was maintained at 3.21, indicating minimal interfacial defects and demonstrating the feasibility and effectiveness of the proposed methodology. Full article

Divinylisoprene rubber, a copolymer of butadiene and isoprene, is used as raw material for rubber technical products, combining isoprene rubber’s elasticity and butadiene rubber’s wear resistance. These properties depend quantitatively on the copolymer composition, which depends on the kinetics of its synthesis. This work aims to theoretically describe how the monomer mixture composition in the butadiene–isoprene copolymerization affects the activity of the TiCl₄-Al(i-C₄H₉)₃ catalytic system (expressed by active sites concentration) via kinetic modeling. This enables development of a reliable kinetic model for divinylisoprene rubber synthesis, predicting reaction rate, molecular weight, and composition, applicable to reactor design and process intensification. Active sites concentrations were calculated from experimental copolymerization rates and known chain propagation constants for various monomer compositions. Kinetic equations for active sites formation were based on mass-action law and Langmuir monomolecular adsorption theory. An analytical equation relating active sites concentration to monomer composition was derived, analyzed, and optimized with experimental data. The results show that monomer composition’s influence on active sites concentration is well described by a two-step kinetic model (physical adsorption followed by Ti–C bond formation), accounting for competitive adsorption: isoprene adsorbs more readily, while butadiene forms more stable active sites. Full article

ZSM-22 zeolites with different Si/Al ratios (38, 50, 80) were prepared via a hydrothermal synthesis method, investigated for the catalytic dehydration of 1,3-butanediol (1,3-BDO) to butadiene (BD) at 300 °C. The catalytic performance of the synthesized materials was related to their properties and compared to a commercial ZSM-22 zeolite (Si/Al = 30). ZSM-22 (50) exhibited a quick decline in conversion, a lower BD selectivity, and higher propylene selectivity compared to the other materials, which could be attributed to the presence of strong Lewis acid sites and silanol nests. The Lewis sites favor the cracking of the intermediate 3-buten-1-ol (3B1OL) into propylene, while the silanol nests interact with the free hydroxyl group of 3B1OL, potentially inhibiting further dehydration towards BD. The highest initial BD yield of 74% was observed over ZSM-22 (80), while the highest initial BD productivity of 2.7 g_BD·g⁻¹_cata·h⁻¹ was achieved over ZSM-22 (38). After 22 h time on stream (TOS), c-ZSM-22 and ZSM-22 (38) outperformed previously reported catalysts from the literature, with productivities amounting to 1.3 g_BD·g⁻¹_cata·h⁻¹ and 1.2 g_BD·g⁻¹_cata·h⁻¹, respectively, at a site time of 6.6 mol_H+·s·mol⁻¹_1,3-BDO. Full article

Heavier element analogues of a ketone, a C=O double-bond compound, have been fascinating compounds from the viewpoint of main-group element chemistry because of their unique structural features and reactivity as compared with those of a ketone, which plays an important role in organic chemistry. We will report here the synthesis of diorgano-stannanethione and stannaneselone featuring tin–chalcogen double bonds, which are the heavy-element analogues of a ketone. The newly obtained stannaneselone has been structurally characterized by spectroscopic analyses and single-crystal X-ray diffraction (SC-XRD) analysis, showing the short Sn–Se bond length featuring π-bond character. The obtained bis(ferrocenyl)stannanechalcogenones were found to undergo [2+4]cycloaddition reactions with 2,3-dimethyl-1,3-butadiene, affording the corresponding six-membered ring compound. Notably, thermolysis of the [2+4]cycloadduct of the stannaneselone regenerated the stannaneselone via the retro[2+4]cycloaddition, whereas the sulfur analogue was thermally very stable. Full article