Search Results (141)

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 reaction of the pyridylalcohol Ph₂C(OH)CH₂-2-py-6-Me (IH) with Me₃Al in refluxing toluene led to the isolation of the dimer [AlMe₂(μ-OC(Me)Ph₂)]₂ (1), whilst at ambient temperature the complex [(I)AlMe₂]·MeCN (2·MeCN) was isolated. Complex 1 is also readily available via the interaction of diphenylethanol and Me₃Al. Similar treatment of iPr₂C(OH)CH₂-2-py-6-Me (IIH) at ambient temperature afforded [(II)AlMe₂] (3). Treatment of IH and IIH with [VO(OiPr)₃] led to oxo-bridged complexes of the type [(VO)(μ₂-O)(I/II)]₂ (I (4·0.67MeCN), II (5)). The molecular structures of 1–5 are reported. These complexes have been employed as catalysts for the ring-opening polymerization (ROP) of the cyclic esters ε-caprolactone (ε-CL) and δ-valerolactone (δ-VL). For aluminium, complex 1/BnOH produced medium- to high-molecular-weight (M_n) PCL at 20 to 110 °C in solution, though some bi-/multi-modal behaviour was observed; for melts the M_n values were toward the lower end. For complexes 2 and 3, far lower M_n values for PCL were observed at 20 °C in solution and as melts, whilst in solution at 110 °C higher M_n values were achieved, though with less control. In general, M_n values for the PCL obtained using the vanadium complexes were low (≤8560 Da for 4, ≤2920 Da for 5). In the case of PVL, 1/BnOH in solution exhibited higher M_n values at lower temperatures with good control, and when employed as a melt, the M_n was toward the higher end (30,830 Da) observed. For 2/BnOH, much lower M_n values (≤2740 Da) were recorded both in solution and as a melt, whilst for 3, high M_n values were only observed in the absence of BnOH. Low M_n values (≤2920 Da) were also observed for the vanadium complexes 4 and 5. Kinetic results (both ε-CL and δ-VL) revealed that the vanadium complexes, particularly 4, outperformed the aluminium complexes. MALDI-ToF spectra revealed the formation of linear PCL polymers with BnO/H end groups for the aluminium/BnOH complexes in solution, and cyclic polymers when employed as melts. For vanadium, cyclic PCL polymers were the major family present. In the case of PVL, linear (BnO/H end groups) and cyclic polymers were observed when employing the Al/BnOH systems, whilst cyclic polymers were observed for vanadium. Copolymerization of ε-CL and δ-VL using 4/BnOH at 110 °C over 24 h led to incomplete conversion and formation of a random-type copolymer. Full article

Composite superabsorbents (C-SAPs) that combine synthetic and polysaccharide components hold great promise for sustainable agriculture. They improve water management and enable the controlled release of agrochemicals. However, increasing the polysaccharide content to enhance biodegradability often reduces water absorption capacity. In this study, we explore plasticization with succinic acid esters as a strategy to overcome this limitation. Our goal is to establish structure–property relationships between plasticizer architecture and C-SAP performance. A series of carboxymethyl cellulose-based superabsorbents was synthesized via radical copolymerization. They were then plasticized with 5 wt.% of dibutyl succinate, di-sec-butyl succinate, or di-iso-butyl succinate. The resulting materials were characterized using FTIR spectroscopy, differential scanning calorimetry, rheological tests, swelling kinetics, and phytotoxicity assays against oilseed radish and common oat. Increased plasticizer branching and molecular volume enhanced polymer network elasticity, lowered the glass transition temperature (by up to 6 °C), and increased the equilibrium swelling ratio by up to 64% compared to the unplasticized C-SAP (661 ± 17 vs. 402 ± 10 g/g). All plasticized C-SAPs retained more than 80% of their initial swelling capacity over five swelling–deswelling cycles across pH 3.0–9.2. They also showed no phytotoxicity at agriculturally relevant concentrations. These findings demonstrate that molecular engineering of plasticizer architecture enables simultaneous optimization of water absorption and environmental safety in C-SAPs for agricultural use. Full article

The industrial preparation via solid-state polymerization (SSP) of high-viscosity copolyamides 6/66 (PA6/66) addresses the challenges, including prolonged reaction times, high energy consumption, and uneven viscosity distribution. In this study, sodium hypophosphite was introduced into the PA6/66 copolymerization system as a solid-state polymerization catalyst. The effects of this catalyst on the solid-state viscosity-increasing rate and relative viscosity were systematically investigated, and the extraction process was optimized to solve the loss of catalyst and controllable extractable content. The results showed that the relative viscosity of PA6/66 increased linearly with the SSP time, and the apparent viscosity increase rate could be stably maintained at 0.14 h⁻¹ at 160 °C due to the catalytic action. Based on the phosphorus (P) content in the chips, the viscosity increase rate is not further large when the P content is 25 ppm at 150 °C and 30 ppm at 160 °C, which can be added as a “control concentration” as a catalyst. The extraction kinetics showed that the catalyst concentration of the chip could be kept higher than the control concentration, and the extractable content can satisfy the requirements for processing. The catalyst of sodium hypophosphite was utilized on the 4500 tons/year PA6/66 continuous polymerization test line, and the high-viscosity PA6/66 chips with uniform viscosity were stably prepared. This study provides a reliable theoretical basis and process route for the large-scale continuous preparation of high-quality and high-viscosity PA6/66 resin. Full article

Poly(L-lactide-co-ε-caprolactones) (PLCL) are promising biodegradable polymers with tunable properties for various biomedical applications. Along with the composition, the microstructure of PLCL chain is an important factor affecting its properties, crystallinity, and degradation profile. In this study, to find effective ways for tailoring the microstructure of PLCL chain, kinetic patterns of L-lactide/ε-caprolactone (75:25) ring-opening copolymerization in the presence of two different catalysts were evaluated. The kinetic studies, accompanied by the assessment of the evolution of PLCL microstructure over the reaction course, provided the optimal regimes for synthesis of PLCL with a fixed composition (LA:CL = 75:25) and different chain microstructure. This was achieved by employing two types of catalysts (tin(II) 2-ethylhexanoate and zirconium(IV) acetylacetonate) and delayed co-monomer addition approach. The control of average LA block length (l_LA) was achieved in a wide range from 4 to 14 monomeric units. Differential scanning calorimetry and wide-angle X-ray scattering revealed a pronounced effect of l_LA on glass transition temperature, melting temperature, and crystallinity. Full article

Conventional synthesis of polycarboxylate superplasticizers (PCEs) typically relies on high-temperature processes, posing challenges for sustainable production. Ethylene glycol monovinyl polyethylene glycol ether (EPEG), characterized by the high reactivity of its vinyloxy double bond, offers a promising sustainable alternative for low-temperature synthesis. This study systematically investigates the aqueous free radical copolymerization of EPEG and acrylic acid, identifying a reaction temperature of 20 °C as the kinetic optimum that achieves a macromonomer conversion rate exceeding 95% under ambient conditions. Through the variation in five key process parameters, a clear “synthesis–structure–property” relationship was established, revealing that the weight-average molecular weight (M_w) acts as the pivotal regulator of performance. High-M_w PCEs exhibited superior initial dispersion driven by strong electrostatic repulsion and high adsorption but suffered from poor slump retention due to the rapid depletion of free polymers. Conversely, low-M_w variants, regulated by chain transfer agent dosage, significantly reduced the pore solution surface tension, thereby enhancing wetting ability and workability retention. The optimal synthesis conditions (20 °C, 4:1 acid-to-ether ratio, 2.5% initiator, 1.5% chain transfer agent) yielded PCEs with an ideal balance between initial dispersion and retention. Furthermore, the synthesis demonstrated excellent process robustness with a broad dosing window (>60 min). These findings provide a vital theoretical basis for the robust and low-temperature industrial production of EPEG-based PCEs for sustainable infrastructure materials. Full article

A novel mesoporous spherical chelating lignin-based adsorbent was successfully synthesized via inverse suspension polymerization using sulfate pine pulping black liquor as raw material, followed by graft copolymerization with acrylonitrile and subsequent amination. The obtained aminated cyanoethyl spherical lignin resin (ACSLR) exhibited a well-defined porous morphology and abundant active sites, as confirmed by SEM and FT-IR. Adsorption experiments demonstrated high Pb²⁺ uptake capacity (63.98 mg·g⁻¹) under optimal conditions (pH = 5.5, 2.0 g·L⁻¹ adsorbent dosage, and 150 mg·L⁻¹ initial concentration of Pb²⁺ solution). The adsorption process followed the Langmuir isotherm and pseudo-second-order kinetics, indicating monolayer chemisorption dominated by amino and cyano groups. This work provides a sustainable strategy for valorizing industrial lignin waste into efficient adsorbents for heavy metal removal, highlighting its potential for practical wastewater treatment applications. Full article

Readily degradable low-dose hydrate inhibitors are of great significance for flow assurance in the petroleum industry. Recently, α-lipoic acid (LA) was shown to undergo ring-opening reaction via reversible addition–fragmentation chain-transfer copolymerization with acrylamides to introduce labile disulfide bonds into the stable vinyl polymer backbone. Here, LA was copolymerized with acryloyl morpholine (AM) to evaluate their performance as kinetic hydrate inhibitors. Degradability was confirmed for the copolymers with 20 mol.% LA (AM/LA20, M_n = 19 → 9 kDa) after disulfide reduction. Thermogravimetric analysis also indicated faster thermal degradation of AM/LA due to the incorporation of weaker S-S and S-C linkages. Increasing LA content reduced hydrophilicity, and the copolymers were treated with NaOH to ensure water solubility. However, at 700 ppm, poly(AM) homopolymer reduced methane consumption during hydrate growth to 54% with respect to the uninhibited system, while gas consumption for the carboxylate AM/LA20 reached 78%. An advantageous feature of LA is its carboxylic acid, allowing desired functionalities to be grafted onto the degradable copolymer. Isopropyl amine (IPAm) was coupled with LA to form an amide known to be effective during hydrate inhibition (LA(IPAm)). The copolymer AM/LA(IPAm)20 demonstrated better water solubility compared to the original AM/LA20. Furthermore, the desirable IPAm functionality allowed the hydrate inhibition to be re-established at 54%, nearly recovering the performance of the poly(AM) homopolymer. This article assesses the application of LA and LA derivatives as building blocks for degradable amide-based kinetic hydrate inhibitors by validating their degradability with material characterizations and their inhibition performance during structure I hydrate growth. Full article

Sodium ions are the main harmful ions in coastal saline–alkali soils, and they seriously affect crop growth and soil structure. A bentonite/humic acid composite hydrogel, synthesized via graft copolymerization as a new type of water-retaining agent, can adsorb excessive Na⁺ in soil, thereby slowing down its adverse effects. This study used batch adsorption experiments to systematically investigate the effects of contact time, initial concentration, pH, temperature, and repeated cyclic adsorption on Na⁺ adsorption performance of the hydrogel material. The results indicated that Na⁺ equilibrium was achieved in 25 min, and the maximum adsorption capacity was 91.29 mg/g. Optimal adsorption occurred at pH 6–8.5, particularly in neutral to weakly alkaline conditions. At 30–50 °C, the bentonite substrate maintained excellent adsorption performance despite structural damage to the grafted copolymer. Mechanistic analysis revealed that adsorption followed pseudo-second-order kinetics and the Langmuir isotherm model, indicating chemisorption-dominated monolayer adsorption controlled by both intra-particle and liquid film diffusion. These findings demonstrate the potential of bentonite-based hydrogels for remediating coastal saline–alkali soils by mitigating Na⁺ toxicity. Full article

Graft copolymers of polysaccharides with side chains of carbon-chain monomers have significant potential for a variety of practical applications. In this work, the effect of the N,N-methylenebisacrylamide (MBA) introduction stage and acrylamide concentration in microwave-assisted radical copolymerization with xanthan gum on the structure and sorption properties of the cross-linked graft copolymer was studied. It has been found that the spatial network density and average molecular weight of interstitial fragments can be controlled by varying these factors. Moderate crystallinity (<50%) and a highly developed surface of our synthesized samples were revealed using XRD and SEM. The graft copolymer exhibits the Schroeder effect; its liquid water sorption obeys Fick’s law and increases with MBA introduction at later stages and with increasing grafting degree, reaching 17.2 g/g. Studying the methylene blue sorption kinetics using pseudo-first/pseudo-second order models, a combined model and an average pseudo-order model have shown that the lower the monomer concentration in the reaction mixture and the earlier (from the onset of the reaction) the cross-linking agent is introduced, the higher the equilibrium sorption. The observed “equilibrium degree of sorption on xanthan gum vs. pseudo-order” relationship, which passes through a minimum, is explained by chemisorption and the sorbate consumption effect. An assumption is made about the prospects of using our synthesized copolymers for designing selective sorbents and ion-exchange membranes. Full article

This work aims to design versatile hybrids fabricated by poly(hydroxypropyl methacrylate-co-glycidyl methacrylate) gels loaded with pristine montmorillonite, P(HPMA-co-GMA)/Mmt, by varying the clay content. Insights into design of epoxy-functional hybrids were provided by combining in situ copolymerization reactions with solution mixing to evaluate the effect of aluminosilicate addition on structure–property changes in (alkyl)methacrylate-based gels. Comprehensive analyses were conducted regarding the composition and structural properties of hybrids in the presence of Mmt. The hybrids exhibited excellent swelling, salt surfactant tolerance, and pH sensitivity depending on the composition. The higher the Mmt concentration, the lower the swelling ratio; however, the compressive moduli did not change monotonically with increasing Mmt from 0.80 to 2.20% (w/v). Dye adsorption revealed the effects of variables (dye type, pH, contact time, concentration) on adsorptive properties of hybrids towards cationic methylene blue (MB) and anionic sunset yellow, allura red, blue brilliant, carmoisine, and tartrazine dyes. Adsorption kinetics of MB obeyed pseudo-second-order model, and the maximum dye adsorption capacity for hybrids increased from 5.01 mg g⁻¹ to 16.42 mg g⁻¹, while adsorption isotherms were defined by the Freundlich model. The proposed hybrids have emerged as alternative materials that enable multiple uses of same adsorbent for the removal of different types of pollutants. 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

Linear Low-Density Polyethylene (LLDPE) is a versatile polyolefin made by copolymerizing ethene with minor amounts of a 1-alkene. The short side chain branches in the comonomer units partly hinder the ability of the polyethylene main chain to crystallize, thus providing a way to fine-tune material properties between the extremes of a thermoplastic and a moderate elastomer. In this function, higher 1-alkenes such as 1-hexene or 1-octene are more effective than shorter homologs like propene or 1-butene, because their alkyl substituents are fully incompatible with the polyethylene lattice. On the other hand, the former comonomers are also more expensive and, above all, poorly reactive with heterogeneous Ziegler–Natta (ZN) catalysts, the workhorses of the polyolefin industry; as a matter of fact, they can only be used with technologically more demanding molecular catalysts. The molecular kinetic factors governing this important and complicated catalytic reactivity are still poorly understood, and perusal of the literature led us to conclude that data reliability is often questionable due to experimental limitations in reaction equipment and protocols, particularly in academic laboratories. In this study, we made use of a state-of-the-art High-Throughput Experimentation workflow to measure the reactivity ratios with ethene of two representative higher 1-alkenes, namely 1-hexene and 1-decene, in the presence of a variety of well-defined molecular catalysts of metallocene and post-metallocene nature comparatively with a typical MgCl₂/TiCl₄ ZN catalyst for polyethylene application. We found that the two comonomers react almost identically with molecular catalysts, whereas a major decrease in reactivity for 1-decene compared with 1-hexene was observed idiosyncratically for the ZN catalyst. In our opinion, the overall results suggest that in the latter case, surface effects can be dominant over direct comonomer interactions with the coordination sphere of the active metal in dictating the observed molecular kinetic behavior. Full article

The oxygen inhibition and migration of micromolecules which stem from photoinitiators (PIs) remain two critical challenges to address in radical photocuring. In this work, we reported a one-step ternary copolymerization strategy to construct a one-component macromolecular photoinitiator (PPI) using polymerizable thioxanthone (TX), amine (N), and fluorinated alkane (F) as monomers. Then, we utilize the low surface energy of F unit and macromolecular skeleton to reduce oxygen inhibition and migration. Compared to micromolecule TX, PPI also exhibits a broad absorption in the 250–430 nm range, and a higher molar extinction coefficient. The effects of the TX, N, and F component ratios on the photoinitiation efficiency of PPI were systematically investigated, and the photopolymerization kinetics revealed that the increased content of F unit can eliminate the oxygen inhibition of PPI. As a result, PPI demonstrates the more superior photoinitiation efficiency compared to the traditional TX/N two-component macromolecule photoinitiation system. Migration experiments indicated that there is a 60% reduction in the migration rate for PPI compared to the TX/N photoinitiation system. This work provides an effective strategy to address oxygen inhibition and micromolecule migration issues in radical photocuring, showing potential applications in food and pharmaceutical packaging fields. 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