Search Results (238)

The copolymerization of biologically active N-(carboxyphenyl)maleimides with styrene was systematically investigated to elucidate the effect of positional isomerism (ortho-, meta-, and para-) on monomer reactivity and copolymer properties. Reactivity ratios (r₁, r₂) were determined using the Fineman–Ross method, and Q–e parameters were evaluated within the Alfrey–Price framework, revealing distinct electronic effects governing copolymerization behavior. Increasing the maleimide fraction in the feed resulted in decreased copolymer yield, intrinsic viscosity, molecular weight, and glass transition temperature, while all copolymers remained styrene-rich, indicating preferential styrene propagation. Comprehensive structural characterization (NMR, FTIR, and UV–Vis) confirmed successful incorporation of both monomer units. Rheological analysis demonstrated a clear viscosity trend (ortho > meta > para), highlighting the influence of substituent position on chain interactions and macromolecular architecture. Thermal analysis (TGA/DTA) showed good thermal stability up to 250–300 °C. Notably, the copolymers exhibited significant antibacterial and antifungal activity, with maximum inhibition observed against Candida albicans. This study establishes a direct correlation between substituent position and structure–property relationships, providing new insights for the rational design of functional styrenic copolymers with potential applications in antimicrobial and biomedical materials. Full article

Gel plugging agents are key drilling fluid additives for maintaining wellbore stability. However, the downhole ultra-high-temperature, high-salinity environments, and developed micro-fractures in deep and ultra-deep wells pose severe challenges to the performance of gel plugging agents. To address this problem, this paper presents the preparation of a nano-micron gel plugging agent with a core–shell structure, denoted as LMS, suitable for high-temperature and high-salinity water-based drilling fluids. LMS was synthesized via emulsion polymerization, using a styrene–sodium p-styrenesulfonate copolymer as the core and 2-acrylamido-2-methylpropanesulfonic acid and methacryloyloxyethyltrimethyl ammonium chloride as the shell-modifying monomers. LMS was characterized by infrared spectroscopy, thermogravimetric analysis, transmission electron microscopy, and particle size analysis, confirming that LMS met the design expectations. Experimental results showed that after aging at 220 °C for 16 h under saturated-salt conditions, the filtration loss of the drilling fluid with 3 wt% LMS was 10.4 mL, a reduction of 57.4% compared to the base mud. Meanwhile, LMS exhibited good plugging performance in microporous membrane tests and sand bed tests. After aging at 220 °C for 16 h under saturated-salt conditions, the core plugging rate reached 95.4%. LMS can not only adsorb onto clay surfaces to increase the thickness of the hydration film, enhancing drilling fluid stability, but can also synergistically build a filter cake with clay particles to plug nano-micron pores, preventing drilling fluid infiltration into the formation. This paper provides a preparation method for a high-temperature- and high-salinity-resistant gel plugging agent with excellent plugging effects, which is expected to support safe and efficient drilling in deep and ultra-deep formations. Full article

This paper systematically investigates the failure characteristics and mechanisms of insulating materials in DC voltage dividers under combined high-frequency voltage and high-temperature conditions via simulations and experiments. The results showed that high-frequency harmonics severely degrade the insulation strength of polypropylene/paper/polypropylene (PPLP) at 10 kHz, in which the bulk breakdown strength of PPLP decreases by over 50%. Furthermore, the surface flashover voltage in oil is reduced by 17.7% under high-frequency voltage alone, and by as much as 51% when white flocculent substances are present in the oil. The dielectric properties of PPLP strongly depend on frequency and temperature, which aggravate the heat accumulation of the divider under high-frequency voltage. Furthermore, the multilayer structure of PPLP introduces deeper trap levels due to interfacial states, which reduce the breakdown strength and flashover voltage of PPLP. Electro-thermal coupling induces a rapid temperature rising to 98 °C at 25 kHz caused by dielectric loss, leading to oil turbidity and white precipitation, consistent with finite element simulations. Consequently, a failure mechanism is proposed as follows: prolonged electro-thermal stress causes chain scission in styrene-containing materials, releasing monomers that repolymerize into white polystyrene deposits. Their porous structure and dielectric mismatch distort the interfacial field, trigger partial discharge, and aggravate surface flashover. Full article

This study evaluates the non-catalytic thermal pyrolysis of post-consumer polystyrene (PS) in a laboratory-scale batch fixed-bed reactor to recover aromatic-rich liquid products. The PS feedstock was characterized by thermogravimetric analysis (TGA) and micro-Raman spectroscopy to assess its thermal behavior and chemical homogeneity. In addition, the main TGA degradation region was analyzed using Coats–Redfern, Horowitz–Metzger, and Broido kinetic models, yielding apparent activation energies of 269.18, 288.83, and 280.69 kJ mol⁻¹, respectively. Pyrolysis experiments were performed at final temperatures of 400, 450, and 500 °C and heating rates of 10 and 20 °C min⁻¹ under continuous N₂ flow. The maximum liquid yield reached 95.2 wt% at 500 °C and 20 °C min⁻¹, while the estimated gaseous fraction decreased to approximately 2.0 wt%. ANOVA confirmed that final temperature was the dominant factor controlling liquid recovery, contributing approximately 83% of the model variability, whereas heating rate had a secondary but significant effect. GC–MS analysis showed that the pyrolysis oil was mainly composed of aromatic hydrocarbons, including styrene, toluene, and ethylbenzene, with increasing temperature promoting the redistribution of the liquid fraction toward lighter monoaromatic compounds. These results indicate that non-catalytic fixed-bed pyrolysis is a promising route for converting post-consumer PS into aromatic-rich liquid products. However, the recovered oil should be considered a complex mixture rather than a purified monomer stream, and further gas-phase characterization, downstream purification, energy-balance evaluation, life-cycle assessment, and techno-economic analysis are required before definitive claims regarding industrial circularity or environmental performance can be established. Full article

This study develops a quantitative kinetic framework for graft copolymerization of methyl methacrylate (MMA) and styrene (ST) onto natural rubber latex (NRL), with emphasis on Redox initiation and Interfacial polymerization in a multiphase system. Experiments were conducted using a cumene hydroperoxide/tetraethylenepentamine (CHPO/TEPA) system. Core–shell particles, consisting of a soft NR core and a rigid poly(vinyl monomer) shell, were obtained at 40–60 °C with initiator concentrations of 0.0051–0.0205 mol L⁻¹ and monomer concentrations of 0.39–0.83 mol L⁻¹. Radical generation occurs predominantly at the aqueous rubber interface, where monomer partitioning takes place between phases. This leads to simultaneous homopolymerization in the aqueous phase, while grafting occurs on the rubber backbone. Overall conversion (x_p), graft conversion (x_g), and grafting efficiency were determined gravimetrically, while morphology was confirmed by FTIR and TEM. The conversion profiles show nonlinear behavior consistent with power-law kinetics, allowing formulation of rate expressions for overall polymerization rate (R_p) and grafting rate (R_g). Reaction order and Arrhenius analyses indicate fractional, heterogeneous behavior characteristic of multiphase reaction kinetics. Styrene shows lower activation energy, whereas MMA exhibits higher collision frequency. The model reproduces experimental trends well (R² up to 0.95) and provides insight into propagation–grafting competition in natural rubber latex systems. Full article

The Activators Regenerated by Electron Transfer Atom Transfer Radical Polymerization (ARGET-ATRP) of vanillin methacrylate (VMA), a bio-based methacrylic monomer derived from vanillin, was systematically studied for the first time. The reaction conditions were optimized aiming at achieving good monomer conversions while preserving the antimicrobial aldehyde functionality. Bipyridine-based catalysts showed limited effectiveness, whereas polydentate aliphatic amines displayed higher activity. Kinetic studies showed linear profiles during the early stages of the polymerization before reaching a conversion plateau accountable to the depletion of the reducing agent, as confirmed by reactivation experiments. The resulting polymer (PVMA) exhibited a glass transition temperature comparable to that of poly(styrene), emerging as a potential bio-derived alternative to fossil-based thermoplastic materials. Furthermore, preliminary in vitro tests demonstrated that PVMA has potential antimicrobial activity against both Escherichia coli (Gram-negative) and Bacillus subtilis (Gram-positive). Full article

As global oil and gas exploration extends to deep and ultra-deep formations, high-temperature and high-salt environments have become major challenges for drilling fluid viscosifiers. In this study, a hydrophobic associative polymer viscosifier, HATA, was synthesized via free-radical copolymerization using acrylamide (AM), 2-acrylamido-2-methylpropanesulfonic acid (AMPS), sodium styrene sulfonate (SSS), and stearyl methacrylate (SMA) as monomers, and its structure was systematically characterized, while its performance and action mechanism in a 4 wt% bentonite base slurry were evaluated. The results show that the base slurry modified with 3 wt% HATA maintains an apparent viscosity retention ratio of 69.20% following 16 h of hot rolling at 180 °C, with an API filtration loss of only 7.2 mL, and its HTHP filtration loss is 73.72% lower than that of the blank bentonite slurry system; this viscosifier sustains effective viscosity and yield point of the drilling fluid system at 200 °C and in 36 wt% NaCl brine. HATA achieves viscosity enhancement and filtration control by regulating surface charges of bentonite particles, constructing stable three-dimensional networks, and stabilizing clay hydration layers, thus presenting a high-performance viscosifier formulation for high-temperature and high-salinity water-based drilling fluids with important theoretical and engineering application values. Full article

The current paper aims to study the thermal stability of ethylene–propylene–diene monomer (EPDM) and styrene–ethylene–butylene–styrene (SEBS) block copolymer attained by radiation processing and evaluated by chemiluminescence (CL). Three blends with different weight ratios (1:3, 1:1 and 3:1), as well as individual rubbers, are γ-irradiated at 25, 50, 100 and 150 kGy. Their thermal stabilities are intercompared, and the activation energies required for oxidative degradation are calculated by using the values of oxidation induction times. Another investigation concerning the development of gel is in good agreement with the CL results. The aspects related to the mechanisms of the radiation fragmentation of blended components are discussed. The contributions of the blending components are evaluated based on the peculiar kinetic parameters, namely oxidation induction time (OIT) and onset oxidation temperatures (OOTs). It is clearly demonstrated that the EPDM component serves as the main source of radicals required for crosslinking, while the SEBS skeletons become the structural frames for the new crosslinked branches. The activation energies increase from 50 kJ mol⁻¹ to 59 kJ mol⁻¹ for unirradiated materials, but the increase for the blends exposed to 100 kGy is significantly larger from 41 kJ mol⁻¹ to 54 KJ mol⁻¹. The growth in the blending proportion of SEBS improves the thermal stability of the resulting materials. It is observed that the largest differences in the thermal resistances of γ-irradiated compounds are obtained for the samples exposed at 150 kGy, when the participation of each of the components is taken into account. This study highlights the research on and the productive methods of polymer processing, and the study of the irradiation of blends generates high-performance technical articles by the appropriate selection of technological parameters. Full article

The ultraviolet (UV) copolymers of two monomers, one methacrylic and the other vinyl monomer (styrene, S) were prepared. As methacrylic monomers, citronellyl methacrylate (CM) or geranyl methacrylate (GM) were used. The preparation was proven to contain high solvent- and chemical-resistant copolymers due to their cross-linked structure with the conversion degree of the double bonds above 0.92 for poly(citronellyl methacrylate)/polystyrene (PCM/PS) and above 0.85 for poly(geranyl methacrylate)/polystyrene (PGM/PS) copolymers. The obtained copolymers showed only one glass transition temperature (T_g). Depending on the structure and amount of the used methacrylic monomer, the T_g values were from 0.4 °C to −15.2 °C for PCM/PS copolymers and from −23.2 °C to −50.5 °C for PGM/PS copolymers. The thermogravimetric analysis (TG/DTG) showed a higher thermal stability for PCM/PS (148–187 °C) than for PGM/PS copolymers (119–159 °C) in inert and oxidative atmospheres. The simultaneous thermogravimetric analysis coupled with Fourier Transform Infrared spectroscopy (TG/FTIR) showed that the pyrolysis and oxidative decomposition of the tested copolymers took place according to the radical mechanism. This led to receiving a mixture of low molecular mass organic molecules containing saturated and unsaturated fragments, carbonyl groups, aromatic fragments as well as to CO, CO₂ and H₂O. This indicated the depolymerization process (inert) and further oxidation processes of the initially formed volatiles and/or residues in oxidative conditions. Full article

Plastics are highly persistent materials, and their environmental degradation can potentially exacerbate, rather than alleviate, pollution. The degradation of plastic materials releases toxic monomers and additives, such as bisphenol A (BPA), styrene, and dioxins, which are more reactive, harmful, and persistent than intact plastics. With half-lives ranging from weeks to decades, they bioaccumulate in food chains, disrupt ecosystems, and contribute to endocrine disruption and mutagenicity. Natural degradation pathways, like microbial metabolism and photodegradation, are slow and incomplete, often leaving toxic intermediates such as microplastics. Artificial strategies, including bioremediation and advanced oxidation processes (AOPs), show potential to address the problems of plastic pollution but face additional challenges like secondary pollution and scalability. Sustainable alternatives, including bioplastics and renewable non-plastic substitutes, present promising solutions. However, their widespread adoption is hindered by challenges such as high production costs and the need for specific conditions to facilitate degradation, necessitating further research and development. A combined approach of reducing plastic production, advancing recycling, and implementing effective remediation strategies is critical to mitigating plastic pollution’s long-term impacts on ecosystems, biodiversity, and human health. This review provides a critical analysis of the current understanding of plastic degradation processes and the toxic byproducts they generate. It highlights the paradox wherein increased degradability may exacerbate environmental hazards. Additionally, the review assesses innovative, eco-friendly alternatives designed to mitigate plastic pollution. Full article

Reversible addition-fragmentation chain transfer mediated polymerization-induced self-assembly (RAFT-PISA) offers an efficient approach for the preparation of polymeric nanomaterials, giving access not only to common structures such as spheres, worm-like micelles and vesicles, but also to much more complex meso-objects. However, when the core forming block polymer possesses a high glass transition temperature (Tg), like poly(methyl methacrylate) or polystyrene (PS), high-order morphologies are particularly difficult to achieve since the glassy core can prevent polymer chain reorganization during PISA. To overcome this issue, we chose to perform visible light-initiated RAFT-PISA of poly(tert-butyl acrylate)-block-polystyrene (PtBA-b-PS) in solvent systems with varying degrees of polarity. More specifically, we prepared different mixtures of diisopropyl ether and ethanol and chose PtBA as macro-CTA due to its broad range of solubility. By varying the ratio between ethanol and diisopropyl ether, we could observe a transition from spherical micelles to vesicles via intermediate structures (e.g., necklace-like micelles, network-like micellar aggregates and wedding rings). This result was particularly remarkable since the experiments were performed near room temperature. We believe that these multiple morphologies were induced by the interactions between the solvent and the corona and the change in swelling of the polystyrene core with styrene monomer that facilitated its rearrangement. We anticipate that this approach could be applied to other polymeric systems with high Tgs. Full article

Polyelectrolyte microspheres based on a polymer containing sulfonate groups are considered promising drug delivery systems for encapsulating drugs and ensuring their prolonged release. In this study, gel microparticles based on various sulfonate-containing polymers were formed, and their potential as drug delivery systems was evaluated, particularly for the controlled administration of the cytotoxic anthracycline antibiotic doxorubicin and the antifungal drug fuchsine. An undeniable advantage of such gel microspheres is the presence in their structure of sulfonate groups localized both in the surface layer and in the volume. The main monomers used were styrene-4-sulfonic acid sodium salt and 3-sulfopropyl methacrylate potassium salt; spherical, porous microparticles were obtained via free-radical reverse suspension polymerization. Microsphere properties (size, porosity, pore structure, electrical surface properties, and swelling) were tailored by changing the nature of the sulfonate, using a comonomer (vinyl acetate or ethyl acrylate), adding a co-solvent, or modulating the crosslinker composition, which influenced drug loading efficiency (doxorubicin, fuchsine). The gel-like structure of the microspheres was confirmed, and the sulfonate groups were found to be distributed throughout both the surface layer and the internal volume of the microspheres. A comparison was also made with non-porous polymer particles containing sulfonate groups. The sorption capacity of the gel microspheres for doxorubicin was 2.2 mmol/g, significantly higher than the 0.4 mmol/g observed for the non-porous reference particles. The obtained values of doxorubicin sorption on gel microspheres are over 60 times higher than the values reported in the literature. Full article

Vitamin D₃ (VD3) is an essential micronutrient, but its analytical determination in biological matrices is often hindered by structurally related metabolites and the limited selectivity of conventional analytical sorbents. The preparation of a molecularly imprinted polymer (MIP) using VD3 as a template is challenging due to its hydrophobic structure and lack of polar groups. Therefore, in this work, MIPs were prepared using the closely related structure hyodeoxycholic acid methyl ester as a template and tested for their adsorption capacity toward VD3. Several MIPs were first prepared using different functional monomers, and the results showed that 4-vinylpyridine (4VP) monomer in combination with divinylbenzene (DVB) as a crosslinker exhibited a relatively high binding capacity and imprinting factor. UV spectroscopy indicated an optimal VD3–monomer ratio of 1:4, while computational modeling further confirmed favorable interactions between VD3 and 4VP. The effect of incorporating styrene as a co-monomer with 4VP was also investigated, showing an enhancement in adsorption capacity with a slight increase in the imprinting factor. However, TGA analysis revealed that the thermal stability of the MIPs decreased with higher styrene content. Overall, the prepared MIPs demonstrated improved selectivity and recognition of VD3 compared to the non-imprinted polymers, offering a promising approach for its selective extraction and quantification. Full article

Bacterial biofilms on different types of microplastics in aquatic environments have become an increasing ecological and public health concern. In this context, this study investigated biofilm formation on virgin and aged microplastics under marine conditions. Serratia marcescens biofilm formation was observed on both virgin and aged polyethylene particles after 7 days, with no significant changes by day 14. Concerning polypropylene microplastics, biofilms developed on aged particles but were not detectable on virgin particles, likely due to interference from the polypropylene red color matching S. marcescens cells. In contrast, expanded polystyrene spheres showed an initial biofilm formation that dissipated by day 14, potentially due to toxic residues from photooxidation, including potential styrene monomers and other chemical additives, inhibiting biofilm persistence. These findings indicate differences in biofilm formation across microplastics types, which may influence microplastic buoyancy and ecological impacts. Thus, microplastic color and additives should be considered in future studies on microplastics biofilm formation and biofouling. Full article

In this contribution, two silsesquioxane–cyclopentadienyl titanium complexes featuring one or two chloride ancillary ligands, [Ti(η⁵-C₅H₄SiMeO₂Ph₇Si₇O₁₀-κO)Cl₂] (1) and [Ti(η⁵-C₅H₄SiMe₂OPh₇Si₇O₁₁-κ²O₂)Cl] (2), were synthesized and evaluated in the Ziegler–Natta polymerization of styrene and the ring-opening polymerization (ROP) of L-lactide, respectively. Complex 1, activated with methylaluminoxane (MAO), catalyzed the syndiotactic polymerization of styrene with turnover frequencies up to 28 h⁻¹, affording polymers with narrow dispersity, low number-average molecular weights (M_n = 5.2–8.2 kDa), and high stereoregularity, as confirmed by ¹³C NMR. Complex 2, in combination with benzyl alcohol, promoted the ring-opening polymerization of L-lactide in solution at 100 °C, achieving conversions up to 95% with good molecular weight control (M_n close to theoretical, Đ = 1.19–1.32). Under melt conditions at 175 °C, it converted up to 3000 equiv. of monomer within 1 h. Kinetic analysis revealed first-order dependence on monomer concentration. The results highlight the ability of these complexes to produce syndiotactic polystyrene with narrow molecular weight distributions and to catalyze controlled ROP of L-lactide under both solution and melt conditions. Computational studies provided insight into key structural and energetic features influencing reactivity, offering a framework for further catalyst optimization. This work broadens the application scope of silsesquioxane–cyclopentadienyl titanium complexes and supports their potential as sustainable and versatile catalysts for both commodity and biodegradable polymer synthesis. Full article