Glycidyl Methacrylate Research Articles

Monomer in situ polymerization as topological sutures to achieve strong interfacial adhesion and long-term anti-mold of renewable adhesive

Integrated long-term anti-mold and high bonding capacity properties into renewable biomass adhesives hold significant importance for promoting the green and sustainable development of the wood industry, yet it remains an immense challenge. Drawing inspiration from the design of molecular suture materials, we successfully developed a series of innovative quaternary ammonium salt monomers (APM12) that polymerize in situ with glycidyl methacrylate (GMA) at the interface of bonded adherents. This process constructed molecular sutures on the molecular scale, forming a robust topological entanglement network between the adhesive and the wood substrate. Such a rational structure design allowed the modified soybean meal (SM) adhesive to present a boosted bonding strength and water resistance (2.08 and 1.05MPa). The stably riveting high-effect anti-germ platform imparted the protein adhesive with ultra-long mildew resistance of 150 days for liquid SM@GMA-APM12 adhesives, outperforming all the previously reported protein-based bio-adhesives. The implementation of the suture strategy through an in situ sutural interspersed crosslinking network provided a straightforward approach and offered a novel solution for creating renewable adhesives with multiple desirable properties. Moreover, this suture strategy can be applied to other interface strong adhesion and anti-bacterial materials comprised of polymer structure, such as hydrogel, organic coatings, and membrane, broadening its scope of applications.

Solvent Effects in the Synthesis of Highly Charged Foams of Poly(4‐styrenesulfonate‐co‐glycidylmethacrylate) for Efficient Adsorption of Methylene Blue Enhanced by Aromatic–Aromatic Interactions

AbstractWater‐resistant porous solid foams expressing a high amount of benzene sulfonate moieties have been fabricated to enhance the adsorption of cationic aromatic pollutants from wastewaters by aromatic–aromatic interactions. Copolymers of sodium 4‐styrene sulfonate (NaSS) and glycidyl methacrylate (GMA) have been obtained and submitted to thermal treatment at 270 °C for 15 min. The influence of the solvent used in the copolymerization step on foamability and foam stability, when formed, has been studied. The use of water as cosolvent with N,N‐dimethyl formamide (DMF) inhibited foam formation. The use of DMF or DMF/dimethyl sulfoxide (DMSO) = 1:1 as solvents allowed the expansion of copolymers, but the resulting foams are unstable in water, forming hydrogels. However, using DMF/DMSO = 5:1 as solvent, stable water‐resistant foams showing NaSS molar fractions of 43, 57, and 68% are obtained, showing high maximum capacity of 244, 435 and 588 mg g−1 and outstanding pseudo‐second‐order kinetic constants of 1.78, 4.49 and 5.64 g mg−1 min−1 toward adsorption of methylene blue (MB), between 2 and 5 orders‐of‐magnitude higher than referenced adsorbents. This is due to the highly exposed benzene sulfonate active sites / adsorbent mass ratio that induces strong aromatic–aromatic interactions with the cationic aromatic dye.

Flat biofilms extrusion of poly(lactic acid)/poly(butylene adipate‐co‐terephthalate) grafted with glycidyl methacrylate blends: Toward ecological packaging for sustainability

AbstractBlends of poly(lactic acid) (PLA)/poly(butylene adipate‐co‐terephthalate) grafted with glycidyl methacrylate (PBAT‐g‐GMA) were developed to produce flat and flexible biofilms through extrusion. The PLA/PBAT‐g‐GMA (90%/10%, 80%/20%, 70%/30%, and 60%/40% by mass) blends were processed in the internal mixer, injection molded, and manufactured into flat films. The optimal composition to produce flexible biofilms was PLA/PBAT‐g‐GMA (60/40%), as it demonstrated a decrease in elastic modulus of 53.2% and a significant gain in elongation at a break of 4923% about pure PLA. The incorporation of 40% PBAT‐g‐GMA in PLA increased the torque (Z) by 208%, while the melt flow index (MFI) decreased by 51.57%, compared to PLA. Additionally, the degradation rate (Rz) and molar mass loss (Rm) during processing were minimized, indicating that 40% PBAT‐g‐GMA enhanced stability of the PLA matrix. Fourier transform infrared spectroscopy indicated interactions between the GMA of PBAT‐g‐GMA and PLA, justifying the increase in viscosity and elongation at break. The PLA/PBAT‐g‐GMA (60/40%) composition showed a transmittance in the range of 20%–48% (400–800 nm) and an oxygen gas permeability of 1.56 × 10−5 cm3 STP/cm−2 h bar, indicating its potential for applications in packaging with optical barrier properties. Scanning electron microscopy (SEM) revealed ligaments in the interfacial region between PLA and PBAT‐g‐GMA, confirming the good performance in elongation at break. The results presented are essential for the plastics processing sector, aiming to develop eco‐friendly packaging.

Formation of Superhydrophobic Coatings Based on Dispersion Compositions of Hexyl Methacrylate Copolymers with Glycidyl Methacrylate and Silica Nanoparticles.

In the last decade, the task of developing environmentally friendly and cost-effective methods for obtaining stable superhydrophobic coatings has become topical. In this study, we examined the effect of the concentrations of filler and polymer binder on the hydrophobic properties and surface roughness of composite coatings made from organic-aqueous compositions based on hexyl methacrylate (HMA) and glycidyl methacrylate (GMA) copolymers. Silicon dioxide nanoparticles were used as a filler. A single-stage "all-in-one" aerosol application method was used to form the coatings without additional intermediate steps for attaching the adhesive layer or texturing the substrate surface, as well as pre-modification of the surface of filler nanoparticles. As the ratio of the mass fraction of polymer binder (Wn) to filler (Wp) increases, the coatings show the lowest roll-off angles among the whole range of samples studied. Coatings with an optimal mass fraction ratio (Wn/Wp = 1.2 ÷ 1.6) of the filler to polymer binder maintained superhydrophobic properties for 24 h in contact with a drop of water in a chamber saturated with water vapor and exhibited roll-off angles of 6.1° ± 1°.

Arrays of Bowl-Shaped Janus Particle Film with Structured Colors.

Structural colors generated via total internal reflection (TIR) using nanostructure-free micro-concave shapes have garnered increasing attention. However, the application of large micro-concave structures for structural coloration remains limited. Herein, a flexibly tunable structural color film fabricated by casting polydimethylsiloxane (PDMS) on an array of large poly(glycidyl methacrylate) (PGMA) bowl-shaped particles is reported. The resultant film exhibits tunable red to green structural colors with changing observation angles. Moreover, the color can be further tailored by altering the shape of the film itself. The incorporation of the PDMS layer not only facilitates a shift in the locus of TIR from the bottom surface to the top concave surface of the particles, thereby enabling the generation of structural color, but also confers enhanced flexibility to the film. Further decoration with silver nanoparticles imparts antimicrobial properties, yielding a novel antimicrobial coating material with structural colors. The simple and cost-effective strategy for the production of structural color films provides potential applications in antimicrobial coatings, enabling accessible and customizable structural coloration using big-size micro-concave particles.

Evaluation of the Role of [{Cu(PMDETA)}2(O2 2-)]2+ in Open-Air Photo ATRP of Methyl Methacrylate.

Herein, we report an open-air, photo accelerated atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) without employing any deoxygenating agent. Under open-air photo ATRP conditions, oxygen reversibly binds with [{Cu (PMDETA)}2(O2 2-)]2+ (1) to form the required activator, which was demonstrated by simple benchtop oxygen/nitrogen purging experiments. The binding mode of oxygen in (1) (μ(η2-η2) peroxo dicopper(II)) was investigated using UV Visible-NIR, FT-Raman and X-ray photoelectron (XPS) spectroscopic techniques. DFT studies and electrochemical measurements further support the catalytic role of (1) in open-air photo ATRP. With the synergistic involvement of Cu (II)Br2, PMDETA ligand and the intensity of light (365 nm, 4.2 mW cm-2), a well-controlled rapid polymerization of MMA under open-air condition was achieved (1.25< Đ < 1.47, 94% conversion in 200 min). The bromo chain end fidelity was exemplified by chain extension experiment, block copolymerization and MALDI-ToF analysis. Other monomers such as methyl acrylate, glycidyl methacrylate, and benzyl methacrylate were also polymerized under open-air condition with reasonable control over molecular weight and Đ. An open-air photo polymerization methodology would be fruitful for applications like photocurable printing, dental, optoelectronics, stereolithography, and protective coatings where simple but rapid photopolymerizations are desirable.

Biocompatibility and performance of new generation dental composites

Dental composites have undergone significant advancements in recent years, with new-generation materials being developed to improve both biocompatibility and mechanical performance. These innovations have led to the increased use of dental composites in restorative dentistry, particularly in both anterior and posterior restorations. Biocompatibility remains a key concern, as the release of unreacted monomers, such as bisphenol A glycidyl methacrylate (Bis-GMA), can cause local tissue irritation or systemic effects. Modern composites aim to reduce these risks by incorporating alternative resin systems and advanced photo initiators. Nanotechnology has further enhanced the performance of these materials by improving mechanical strength and wear resistance, but questions about the safety of nanoparticles and their long-term biological effects continue to be explored. In addition to biocompatibility, the mechanical properties of new-generation composites have been significantly optimized. The introduction of bulk-fill composites allows for deeper polymerization and faster placement, reducing clinical procedure times while maintaining high mechanical integrity. Polymerization shrinkage, a common issue in traditional composites, has been minimized in newer formulations, reducing the risk of marginal gaps and microleakage. The effectiveness of different light-curing units, such as light-emitting diode (LED) versus halogen lights, plays a crucial role in achieving optimal polymerization depth, especially in posterior restorations where light penetration can be limited. Long-term clinical outcomes depend on several factors, including material choice, placement technique, and patient adherence to oral hygiene. Despite the improvements in composite materials, the longevity of restorations still faces challenges such as wear, fracture, and degradation over time. Continued research into the safety, effectiveness, and clinical performance of new-generation composites is essential to ensuring patient safety and enhancing the durability of restorations in the future. These advancements promise to address many of the limitations seen in earlier dental materials while offering superior performance and patient satisfaction.

Effect of talc modified by poly (glycidyl methacrylate)- block -polybutadiene- block -poly (glycidyl methacrylate) on the properties of nitrile butadiene rubber

Effect of talc modified by poly (glycidyl methacrylate)- block -polybutadiene- block -poly (glycidyl methacrylate) on the properties of nitrile butadiene rubber

Tailoring the Mechanical Properties and Foaming Behaviors of PLA/P4HB Blends by Using P4HB‐g‐GMA as Compatibilizer

ABSTRACTSynthetic poly(4‐hydroxybutyrate) (P4HB), a flexible and biodegradable polymer, shows great promise in improving the toughness of poly(lactic acid) (PLA), but the inherent immiscibility of PLA and P4HB compromises the toughening efficiency. To address this issue, P4HB grafted glycidyl methacrylate (P4HB‐g‐GMA) is synthesized for the purpose of enhancing the compatibility within the PLA/P4HB blend. The epoxy groups on P4HB‐g‐GMA can form strong chemical bonds with PLA chains and remain compatible with P4HB. Rheological data confirm that adding P4HB‐g‐GMA enhances polymer chain entanglement. Therefore, the phase interface of the blend becomes more diffuse, leading to improved mechanical performance. Specifically, a 3D‐printed PLA/P4HB/P4HB‐g‐GMA blend containing 8% P4HB‐g‐GMA (PLA/P4HB/G8) achieves an elongation at break of 161.5%, approximately 22.7 times higher than that of a PLA/P4HB blend without the modifier. Moreover, the PLA/P4HB/G8 blends show a higher volume expansion ratio (VER) and better cell morphology due to the increased melt strength from P4HB‐g‐GMA. This study demonstrates a simple and efficient method to improve the compatibility between PLA and P4HB, resulting in superior mechanical performance of PLA/P4HB blends and broadening their potential applications in foaming.

Self-Healable Hydrogels from Vegetable Oil: Preparation, Mechanism, and Applications.

Hydrogels are indispensable for a variety of applications. Conventional biomaterial-based hydrogels, typically made from proteins or polysaccharides, often suffer from high costs, poor mechanical properties, and limited chemical functionality for modification. In this work, we present a novel hydrogel developed from modified castor oil, which is a renewable and cost-effective resource. Castor oil-based oligomer (CG) was synthesized using glycidyl methacrylate and triethylamine via ring-opening polymerization. The oligomer formed a gel only with Cu2+ ions among the various systematically studied metal ions. Comprehensive density functional theory calculations, atoms in molecules analysis, and steady and dynamic shear rheology were conducted to investigate the metal-binding sites and metal-oligomer interactions as well as the self-healing and viscoelastic properties of the oil-based hydrogels. The hydrogel exhibited 94% self-healing efficiency and performed as a recyclable rhodamine B dye adsorbent (73-90%). This innovative approach offers a novel, cost-effective, and sustainable alternative to traditional hydrogels, paving the way for advanced applications.

Online restricted access molecularly imprinted solid phase extraction coupled with electrospray ionization-tandem mass spectrometry for determination of mebendazole and albendazole in milk samples

Multifunctional materials, such as restricted access molecularly imprinted polymers covered with bovine serum albumin (RAMIP-BSA), are effective alternatives for sample preparation techniques. This material selectively adsorbs analytes while excluding macromolecules, enhancing the analysis's efficiency. Among analytical techniques, ESI-MS/MS (Electrospray Ionization-Tandem Mass Spectrometry) has successfully identified and quantified various molecules, including trace-level drugs. Therefore, we proposed, for the first time, an integrated online extraction/analysis system that combines the benefits of RAMIP-BSA and ESI-MS/MS for analyzing mebendazole (MBZ) and albendazole (ABZ) in milk samples without the need for chromatographic separation. Initially, a RAMIP selective for MBZ was synthesized using the bulk method with methacrylic acid and glycidyl methacrylate. Then, the polymer was covered with bovine serum albumin. Subsequently, this adsorbent was packed in a small column and coupled with an ESI-MS/MS instrument in an online configuration. Milli-Q water was used as the loading and reconditioning mobile phases, and a solution of formic acid in methanol (1:100 v/v) was employed as the elution phase. The system enabled simultaneous extraction and determination of MBZ and ABZ in milk samples. The method exhibited linearity between 15.0 and 125.0 μg L−1 for MBZ and 10.0 and 125.0 μg L−1 for ABZ (with a correlation coefficient exceeding 0.99). The limits of quantification were 15.0 and 10.0 μg L−1 for MBZ and ABZ, respectively. Good precision and accuracy were achieved. The developed method was used to analyze MBZ and ABZ in real milk samples and proved to be a viable alternative to conventional sample preparation and chromatographic techniques.

Effect of radiation-induced graft polymerization onto pineapple nonwoven fabric reinforced polymer composite

Natural fiber-reinforced polymer composites are gaining attention for their environmental benefits, such as biodegradability and reduced carbon footprint, as well as the potential of the natural fibers to replace or partially substitute synthetic fibers in various applications. However, challenges, such as poor interfacial adhesion and moisture absorption, limit the effectiveness of natural fibers, such as pineapple nonwoven fabric (PNWF) as reinforcement materials in polymer composites. To address these challenges, this study aims to enhance the properties of PNWF through glycidyl methacrylate grafting via radiation-induced graft polymerization. A 22 factorial design was employed to assess the effects of absorbed dosage and monomer concentration on the properties of the grafted PNWF. Infrared spectroscopy and electron microscopy analyses confirmed successful grafting. The grafted PNWF exhibited improved thermal stability and mechanical properties. The resulting composites showed significant enhancements in tensile and flexural strength, specifically, with tensile strength increase ranging from 23.32 to 34.49 MPa and flexural strength from 39.14 to 54.59 MPa. Additionally, the tensile modulus ranged from 0.77 to 1.29 GPa, while the flexural modulus varied from 1.17 to 2.06 GPa. These findings highlight the potential of PNWF grafted with polyglycidyl methacrylate (PNWF-g-PGMA) as an effective reinforcement material for various applications.

Visible-light-driven Fe-catalyzed alkylation for synthesizing functionalized polyolefin elastomers as advanced encapsulants in photovoltaic modules

Polyolefin elastomer (POE) has emerged as a promising encapsulant for photovoltaic modules, attributed to its exceptional water vapor barrier properties, robust weather resistance, and enhanced anti-potential induced degradation (anti-PID) capabilities. Despite these advantages, the interfacial adhesion of POE remains a significant challenge, particularly its suboptimal bonding with glass and solar cells, which impedes its broader application within the photovoltaic industry. This study introduced glycidyl methacrylate (GMA) monomers into POE through a photo-induced iron-catalyzed alkylation reaction, developing a novel polyolefin encapsulant for photovoltaic modules. The encapsulant was designed to possess high light transmittance, enhanced adhesion, and elevated resistivity. The modified POE boasts an impressive light transmittance nearing 98% and an adhesive strength of 28.3 N cm−1, both superior to traditional ethylene-vinyl acetate copolymer (EVA) materials. Additionally, this work delves into the correlation between crystallization behavior and light transmittance, elucidating the influence of GMA incorporation on the adhesion and insulation properties of POE through gaussian simulations.

Hybrid Dendrimer Network based on Silsesquioxane and Glycidyl Methacrylate for Enhanced Adsorption of Iodine and Dyes in Environmental Remediation.

A novel hybrid network was synthesized in two steps: the first step involved the attachment of glycidyl methacrylate (GMA) to octa(aminophenyl) silsesquioxane (OAPS) through a ring-opening reaction, forming a hybrid dendrimer structure, and the second step involved the cross-linking of hybrid dendrimer using an azobisisobutyronitrile initiator to create the final hybrid network of OAPS-GMA. The synthesized hybrid material was comprehensively characterized using fourier transform infrared Spectroscopy (FTIR), nuclear magnetic resonance ((1H, 13C, and 29Si NMR) spectroscopy, thermogravimetric Analysis (TGA), and scanning electron microscopy (SEM). The BET surface area was found to be 25.44 m2/g, and significant 2.341 cm3/g of total pore volume was observed. The TGA analysis shows that the material is highly stable up to 450 °C. The synthesized network demonstrated remarkable adsorption capacities for iodine and dyes. It exhibited an iodine adsorption capacity of 3.4 g/g from vapors and 874 mg/g from solution. Additionally, it showed significant adsorption capacities for Rhodamine B and Congo red, with values of 762 mg/g and 517 mg/g, respectively. This study not only provides a novel method for preparing GMA-functionalized silsesquioxane-based porous hybrid polymers but also contributes to advancing solutions for environmental pollution issues.

Effect of Star-like Polymer on Mechanical Properties of Novel Basalt Fibre-Reinforced Composite with Bio-Based Matrix.

This study is aimed at developing a fibre-reinforced polymer composite with a high bio-based content and to investigate its mechanical properties. A novel basalt fibre-reinforced polymer (BFRP) composite with bio-based matrix modified with different contents of star-like n-butyl methacrylate (n-BMA) block glycidyl methacrylate (GMA) copolymer has been developed. n-BMA blocks have flexible butyl units, while the epoxide group of GMA makes it miscible with the epoxy resin and is involved in the crosslinking network. The effect of the star-like polymer on the rheological behaviour of the epoxy was studied. The viscosity of the epoxy increased with increase in star-like polymer content. Tensile tests showed no noteworthy influence of star-like polymer on tensile properties. The addition of 0.5 wt.% star-like polymer increased the glass transition temperature by 8.2 °C. Mode-I interlaminar fracture toughness and low-velocity impact tests were performed on star-like polymer-modified BFRP laminates, where interfacial adhesion and impact energy capabilities were observed. Interlaminar fracture toughness improved by 45% and energy absorption capability increased threefold for BFRP laminates modified with 1 wt.% of star-like polymer when compared to unmodified BFRP laminates. This improvement could be attributed to the increase in ductility of the matrix on the addition of the star-like polymer, increasing resistance to impact and damage. Furthermore, scanning electron microscopy confirmed that with increase in star-like polymer content, the interfacial adhesion between the matrix and fibres improves.

Cover Feature: Hybrid Dendrimer Network based on Silsesquioxane and Glycidyl Methacrylate for Enhanced Adsorption of Iodine and Dyes in Environmental Remediation (Chem. Asian J. 20/2024)

Cover Feature: Hybrid Dendrimer Network based on Silsesquioxane and Glycidyl Methacrylate for Enhanced Adsorption of Iodine and Dyes in Environmental Remediation (Chem. Asian J. 20/2024)

Preparation and Characterization of Photo-Cross-Linkable Methacrylated Silk Fibroin and Methacrylated Hyaluronic Acid Composite Hydrogels.

Composite biomaterials with excellent biocompatibility and biodegradability are crucial in tissue engineering. In this work, a composite protein and polysaccharide photo-cross-linkable hydrogel was prepared using silk fibroin methacrylate (SFMA) and hyaluronic acid methacrylate (HAMA). SFMA was obtained by the methacrylation of degummed SF with glycidyl methacrylate (GMA), while HA was methacrylated by 2-aminoethyl methacrylate hydrochloride (AEMA). We investigated the effect of the addition of 1 wt % HAMA to 5, 10, and 20 wt % SFMA, which resulted in an increase in both static and cycling mechanical strengths. All composite hydrogels gelled under UV light in <30 s, allowing for rapid stabilization and stiffness increases. The biocompatibility of the hydrogels was confirmed by direct and indirect contact methods and by evaluation against the NIH3T3 and MC3T3 cell lines with a live-dead assay by confocal imaging. The range of obtained mechanical properties from developed composite and UV-cross-linkable hydrogels sets the basis as possible future biomaterials for various biomedical applications.

Evaluation of a novel non-ionic graft starch-based antiscalant in reduction of CaSO4 scaling by static and reverse osmosis test

A novel nonionic starch-based antiscalant (St-g-GMA) was designed and obtained by graft copolymerization of starch and glycidyl methacrylate (GMA). St-g-GMA not only achieved an obvious reduction of CaSO4 scaling in static test, but also effectively mitigated the flux decrease in dynamic reverse osmosis (RO) system. This improvement is ascribed to the grafted poly(GMA) chains on St-g-GMA. A suitable grafting ratio of this starch-based antiscalant achieve a high performance cost in control of CaSO4 scaling. Combination of the apparent antiscaling performance, observation under scanning electron microscopy, energy dispersive x-ray spectroscopy unit, x-ray diffraction pattern, conductivity measurement, and dispersion experiment, the scale-inhibition mechanism of St-g-GMA was investigated and mainly attributed to chelation, dispersion and lattice distortion effects. The oxygen-containing groups on poly(GMA) chains such as epoxy groups can chelate with Ca2+, causing the induction time of crystallization prolonged; St-g-GMA with the distinct branched chain configuration can well disperse the formed microcrystal of CaSO4. Moreover, molecular dynamics simulations confirmed that the grafted poly(GMA) chains well bind to the crystal surfaces and the oxygen-containing groups could even enter the crystal lattice to inhibit the crystal growth and change the morphologies. St-g-GMA still mitigated the flux decrease notably in treatment of a synthetic seawater during a 24-h RO measurement. This study provided an efficient, environmentally-friendly and low-cost antiscalant with high application potentials.

Quasi-Hydrogen Bond and Charge-Trapping Effect Originating from Polar Side Group Lead to Significantly Suppressed Charge Transport in Polypropylene.

How to fundamentally suppress charge transport is one of the essential issues in polymer dielectrics. This work reports significant charge transport suppression by glycidyl methacrylate (GMA) side group modification on polypropylene (PP). Experimental and computational investigations discover for the first time a quasi-hydrogen bond effect generated by carbonyl and epoxide of GMA in PP inter/intramolecular structure, while introducing trap energy levels within the HOMO-LUMO gap. These energy levels suppress the leakage current of GMA-modified PP thanks to the charge-trapping effect. The quasi-hydrogen bond originating from the interaction between the high-polar GMA group and flexible PP chain raises the thermostability while averaging the electron distribution between hydrogen and acceptor oxygen, which is conducive to lessening electric weak points, suppressing charge transport, and finally enhancing the electrical breakdown strength. This work provides new thinking on polymer dielectric design and charge transport regulation utilizing electron structure and weak interaction at the molecular scale.

Crystal violet removal from waste water by sulfonated poly (glycidyl methacrylate) nano-adsorbent: optimization by response surface methodology, isotherms, kinetics, and thermodynamics studies

Crystal violet removal from waste water by sulfonated poly (glycidyl methacrylate) nano-adsorbent: optimization by response surface methodology, isotherms, kinetics, and thermodynamics studies