Trimethylolpropane Triacrylate Research Articles

Alumina Ceramics for Armor Protection via 3D Printing Using Different Monomers

Alumina ceramic is an ideal candidate for armor protection, but it is limited by the difficult molding or machining process. Three-dimensional printing imparts a superior geometric flexibility and shows good potential in the preparation of ceramics for armor protection. In this work, alumina ceramics were manufactured via 3D printing, and the effects of different monomers on the photosensitive slurry and sintered ceramics were investigated. The photosensitive slurries using dipropylene glycol diacrylate (DPGDA) as a monomer displayed the optimal curing performance, with a low viscosity, small volume shrinkage and low critical exposure energy, and each of the above properties was conducive to a good curing performance in 3D printing, making it a suitable formula for 3D-printed ceramic materials. In the 3D-printed ceramics with DPGDA as a monomer, a dense and uniform microstructure was exhibited after sintering. In comparison, the sample with trimethylolpropane triacrylate (TMPTA) showed an anisotropic microstructure with interlayer gaps and a porosity of about 9.8%. Attributed to the dense uniform microstructure, the sample with DPGDA exhibited superior properties, including a relative density of 97.5 ± 0.5%, a Vickers hardness of 19.4 ± 0.8 GPa, a fracture toughness of 2.6 ± 0.27 MPa·m1/2, a bending strength of 690 ± 54 MPa, and a dynamic strength of 3.7 ± 0.6 GPa at a strain rate of 1200 s−1.

Superhydrophobic/ superoleophilic polystyrene-based porous material with superelasticity for highly efficient and continuous oil/water separation in harsh environments

Three-dimensional separation materials with robust physical/chemical stability have great demand for effective and continuous separation of immiscible oil/water mixtures and water-in-oil emulsions, resulting from chemical leakages and discharge of industrial oily wastewaters. Herein, a superelastic polystyrene-based porous material with superhydrophobicity/superoleophilicity was designed and prepared by high internal phase emulsion polymerization to meet the aforementioned requirements. A flexible and hydrophobic aminopropyl terminated polydimethylsiloxane (NH2-PDMS-NH2) segment was introduced into the rigid styrene-divinylbenzene copolymer through 1, 4-conjugate addition reaction with trimethylolpropane triacrylate. The addition of NH2-PDMS-NH2 simultaneously improved the mechanical and hydrophobic properties of the porous material (the water contact angle from 141.2° to 152.2°). The material exhibited outstanding reversible compressibility (80% strain, even in liquid N2 environments) and superhydrophobic stability, even after being repeatedly compressed 100 times, water contact angle still remained above 150°. Meanwhile, the as-prepared material had outstanding hydrophobic stability in corrosive solutions (strong acidic, alkaline, high-salty, and even strong polar solvent), presence of mechanical interference, strong UV radiations, and high/low temperature environments. More importantly, the material could continuously and efficiently separate immiscible oil/water mixture and water-in-oil emulsions under the above conditions, showing huge potential for the large-scale remediation of complex oily wastewaters.

Chiral Janus emulsions with gold nanocomposite for enantioselective catalysis

Chiral emulsions, with the chiral center of chiral-surfactant as the emulsifier, provide opportunities for selective catalysis and inorganic material synthesis. Janus emulsion draws researcher’s attention due to excellent multiple chambers, advanced structures and diverse interfaces. Chiral Janus emulsions are prepared with two immiscible oils of vegetable oil (VO)/dimethyl phthalate (DMP) and 2-(Perfluorooctyl)ethyl methacrylate (PFOEMA)/Ethoxylated trimethylolpropane triacrylate (ETPTA) as inner phases, by emulsified by chiral-surfactant [H-G-C16]FeCl4, in batch-scale by traditional vortex mixing. AuNPs as functional nanomaterials with peroxidase activity are then applied as active centers, adsorbing at the oil/water interface due to the electrostatic interactions between the positive charge of [H-G-C16]FeCl4 at Janus emulsion interfaces and the negative charge of AuNPs modified by SDS. Chiral Janus emulsion is endowed with catalytic activity and enantioselectivity. Catalytic results show two AuNPs@ Janus emulsions show better affinity to catalyze the oxidation of L-DOPA than D-DOPA. By investigating two AuNPs@ Janus emulsions with different inner phases, chiral Janus emulsion of AuNPs@ETPTA/PFOEMA/[H-G-C16]FeCl4(aq) has better catalytic activity and enantioselectivity than AuNPs@DMP/VO/[H-G-C16]FeCl4 (aq) because of the smaller droplets have larger interface areas could adsorb more [H-G-C16]FeCl4 molecules and AuNPs. The findings open an avenue in the production of chiral Janus emulsions with catalytic effect and enantioselectivity, which would push forward future applications in selective catalysis and inorganic material synthesis.

Evaluation of composites based on virgin rubber/devulcanized rubber reinforced with chemically and radiation activated polyurethane scrap for possible applications

AbstractReusing industrial waste is one of the new tactics being used to fight the dumping of solid waste for environmental protection. In the current work, the waste polyurethane (WPU) was ground to a fine powder and used for reinforcement of devulcanized waste rubber/styrene butadiene rubber (DWR/SBR) blends. DWR/SBR/WPU composites were prepared using (0, 3, 6, 9, 15, 30) phr (parts per hundred of rubber) of WPU. It was hypothesized that the treatment of WPU with trimethylolpropane triacrylate (TMPTMA) and irradiated at 10 kGy would improve its compatibility with the DWR/SBR blend and, consequently, its reinforcement efficacy. The incorporation of 30 phr of treated WPU (TWPU) improved the tensile strength (TS) by 47.7% and 8.6% compared to neat DWR/SBR and composites containing 30 phr of untreated WPU (UWPU). In addition, the incorporation of TWPU improved other mechanical characteristics such as tear strength, hardness, and abrasion resistance. As a result of increasing polarity and cross‐link density within the DWR/SBR blend after the addition of polar WPU, the resistance to motor oil was improved. The outcomes are encouraging from the standpoint of the circular economy and help produce high‐performing, reasonably priced DWR/SBR composites for a range of industrial uses, especially in the floor tiles application.Highlights Waste polyurethane (WPU) was activated using gamma irradiation in the presence of TMPTMA. The treatment of WPU improved its compatibility with DWR/SBR blend. The impact of WPU treatment on the properties of DWR/SBR blend was investigated. TWPU improved the mechanical properties of DWR/SBR blend more than UWPU. TWPU increased the motor oil resistance of DWR/SBR blend more than UWPU.

The role of the terminal benzene derivatives in triphenylamine‐based oxime esters for free radical photopolymerization

In this study, we investigate the effect of terminal benzene derivatives in triphenylamine‐based oxime esters on their photoreactivity. Five novel oxime esters ( Miko series) that containing different benzene derivatives as terminal groups, were synthesized. The electronic properties of the substituents on the benzene ring range from electron‐donating to electron‐withdrawing. Specifically, a methoxy benzene for Miko‐MOB, tert‐butyl benezene for Miko‐t‐Bu, chloro benzene for Miko‐CB, trifluoromethyl benzene for Miko‐TFM, and nitro benzene for Miko‐NB. Additionally, a compound with benzene only as the terminal substituent (TP‐1) was selected for comparision. All the new compounds exhibited higher molar extinction coefficients than TP‐1. Additionally, the steady‐state photolysis and electron spin resonance (ESR) properties would decrease from the electron‐donating substitutes to electron‐withdrawing substitutes. Finally, these oxime esters are utilized in Type I photoinitiating systems for the free radical polymerization of trimethylolpropane triacrylate (TMPTA) under UV or LED@405 nm light irradiation conditions. Among all formulations, Miko‐MOB demonstrated the highest double bond conversion efficiency under both UV and LED@405 nm light irradiation. Thus, terminal benzene derivatives in oxime esters play an important role in tuning the optical and photochemical reaction performance, offering significant value for the design strategy of such photoinitiators.

Fast-curing bio-based thermoset foams produced via the Michael 1,4-addition using fatty acid-based acetoacetate and acrylate

This study introduces an approach for creating bio-based polymer foams exploiting the Michael reaction that could be utilized as thermal insulation. The thermoset foams were developed using a second-generation bio-based feedstock – tall oil. Tall oil is a by-product of wood pulping in paper manufacturing and mainly comprises unsaturated fatty acids like oleic and linoleic acid. The study explores the use of tall oil-based acetoacetates (Michael donor) combined with various acrylates (Michael acceptor), petrochemical-based (bisphenol-A ethoxylate diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate), and bio-based (epoxidized soybean oil acrylate, epoxidized tall oil free fatty acids-based acrylate), to develop polymer foams that meet today's sustainability requirements. The developed polymer foams underwent extensive characterization. Matrix curing parameters were assessed by measuring changes in dielectric polarization during curing. Foaming parameters, including start and rise times, were precisely measured. The chemical composition of the foams was analysed using Fourier-transform infrared spectroscopy. Their thermal, thermo-mechanical, and mechanical properties were evaluated through thermal gravimetric analysis, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and compression tests. Additionally, the content of closed-cell and the coefficient of thermal conductivity were determined, further characterizing the foams as potential thermal insulation materials. Foams from bio-based donors with petrochemical-based acceptors exhibited a range of enhanced properties. They not only achieved high glass transition temperatures (up to 85 °C by DSC and up to 108 °C by DMA) but also displayed a spectrum of mechanical strengths (compression strength ranging from moderate to as high as ∼ 0.40 MPa) and good thermal isolation properties (thermal conductivity coefficient ∼ 31mW/(m·K)). Bio-based foams, derived from renewable resources, were characterized by properties fitting for flexible foam applications, such as low glass transition temperatures (down to −9.7 °C by DSC and down to 9.8 °C by DMA), reduced compression strength (approximately 0.011 MPa), and increased thermal conductivity (up to 46.7mW/(m·K)), indicating their potential utility in applications where flexibility is a key requirement.

Ultrafast Sunlight-Induced Polymerization: Unveiling 2-Phenylnaphtho[2,3-d]Thiazole-4,9-dione as a Unique Scaffold for High-Speed and Precision 3D Printing.

A series of 15 dyes based on the 2-phenylnaphtho[2,3-d]thiazole-4,9-dione scaffold and 1 compound based on the 2,3-diphenyl-1,2,3,4-tetrahydrobenzo[g]quinoxaline-5,10-dione scaffold are studied as photoinitiators. These compounds are used in two- and three-component high-performance photoinitiating systems for the free radical polymerization of trimethylolpropane triacrylate (TMPTA) and polyethylene glycol diacrylate (PEGDA) under sunlight. Remarkably, the conversion of TMPTA can reach ≈60% within 20s, while PEGDA attains a 96% conversion within 90s. To delve into the intricate chemical mechanisms governing the polymerization, an array of analytical techniques is employed. Specifically, UV-vis absorption and fluorescence spectroscopy, steady-state photolysis, stability experiments, fluorescence quenching experiments, cyclic voltammetry, and electron spin resonance spin trapping (ESR-ST) experiments, collectively contribute to a comprehensive understanding of the photochemical mechanisms. Photoinitiation capacities of these systems are determined using real-time Fourier transformed infrared spectroscopy (RT-FTIR). Of particular interest is the revelation that, owing to the superior initiation ability of these dyes, high-resolution 3D patterns can be manufactured by direct laser write (DLW) technology and 3D printing. This underscores the efficient initiation of free radical polymerization processes by the newly developed dyes under both artificial and natural light sources, presenting an avenue for energy-saving, and environmentally friendly polymerization conditions.

Comparing the Kinetic Hydrate Inhibition Performance of Linear versus Branched Polymers.

Kinetic hydrate inhibitors (KHIs) are a chemical method of preventing gas hydrate plugging of oil and gas production flow lines. The main ingredient in a KHI formulation is one or more water-soluble amphiphilic polymers. Poly(N-vinyl caprolactam) (PVCap) is an unbranched polymer and a well-known industrial KHI, often used as a yardstick to compare the performance of new polymers. The effect of branching PVCap on KHI performance has been investigated by polymerizing the VCap monomer in the presence of varying amounts of trimethylolpropane triacrylate, pentaerythritol tetraacrylate, or bis-pentaerythritol hexaacrylate cross-linkers to give PVCap polymers with 3, 4, and 6 branches, respectively. If the ratio of cross-linker to VCap was too high (6:1 to 8:1), gelling and/or poor water solubility was observed, giving short polymer chains and poor KHI efficacy. For higher ratios (30:1 to 60:1), it was found that the concentration of the polymer needed to give total inhibition of structure II tetrahydrofuran hydrate crystal growth could be lowered by using tribranched rather than linear PVCap. Slow constant cooling (1 °C/h) gas hydrate experiments with a synthetic natural gas in steel rocking cells at 76 bar were also carried out. A small improvement in KHI performance was observed for one of the branched PVCaps compared with a linear PVCap. Branched and linear poly(N-isopropylmethacrylamide) (PNIPMAm) polymers were also investigated in the gas hydrate system, but there was no benefit observed when branching this polymer class.

Tough hyperbranched polyaryletherketone-based photosensitive resins bearing excellent dielectric property and thermal resistence

Organic polymer materials with low dielectric properties have garnered significant attention due to their convenient preparation process, low cost, and commendable mechanical properties. Such polymers, especially with heteromorphic structures, exhibited great potential for future electronic devices and antennas, particularly accompanied with rapid manufacturing technologies like three-dimensional (3D) printing. In this study, a series of new allyl ether-ended hyperbranched fluorene-based polyaryletherketone (hb-PFAEK-Allyls) were developed. The content of allyl ether photosensitive groups and molecular weight were controlled by adjusting the molar ratio of OH:F loading. UV-curable resins were then prepared through blending between hb-PFAEK-Allyls with trimethylolpropane triacrylate (TMPTA) and ethylene glycol bis(3-mercaptopropionate) (EGBMP), resulting in thiol-allyl-acrylate ternary UV-cured system. The influence of molecular weight of the hyperbranched polymers on the thermal performance, mechanical properties, and dielectric properties of the UV-cured films was systematically investigated. The results show that due to the introduction of hyperbranched structure with high molecular weight, the Tg of the UV-cured film can reach up to 248 °C. Due to the increased molecular free volume in the hyperbranched structure, the dielectric constant of the UV-cured film can be reduced to as low as 2.74 at 1 GHz. Due to the design of thiol-allyl-acrylate ternary UV-cured system, the cured film has excellent mechanical properties, with the highest tensile strength of 61.0 MPa and the elongation at break of 7.0%. This study represents innovative progress on integrating fully aromatic-based photosensitive hyperbranched polyaryletherketone into UV-curable resin architecture. Overall, the herein hb-PFAEK-Allyls-based photosensitive resins exhibit outstanding comprehensive performance and holds great potential for application in advanced 3D printing technology.

Weak Electrostatic Force on K+ in Gel Polymer Electrolyte Realizes High Ion Transference Number for Quasi Solid-State Potassium Ion Batteries.

Quasi-solid-state potassium-ion batteries (SSPIBs) are of great potential for commercial use due to the abundant reserves and cost-effectiveness of resources, as well as high safety. Gel polymer electrolytes (GPEs) with high ionic conductivity and fast interfacial charge transport are necessary for SSPIBs. Here, the weak electrostatic force between K+ and electronegative functional groups in the ethoxylated trimethylolpropane triacrylate (ETPTA) polymer chains, which can promote fast migration of free K+ , is revealed. To further enhance the interfacial reaction kinetics, a multilayered GPE by in situ growth of poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) on ETPTA (PVDF-HFP|ETPTA|PVDF-HFP) is constructed to improve the interface contact and provide sufficient K+ concentration in PVDF-HFP. A high ion transference number (0.92) and a superior ionic conductivity (5.15 × 10-3 S cm-1 ) are achieved. Consequently, the SSPIBs with both intercalation-type (PB) and conversion-type (PTCDA) cathodes show the best battery performance among all reported SSPIBs of the same cathode. These findings demonstrate that potassium-ion batteries have the potential to surpass Li/Na ion batteries in solid-state systems.

Heterogeneous Brønsted Catalysis in the Solvent-Free and Multigram-Scale Synthesis of Polyalcohol Acrylates: The Case Study of Trimethylolpropane Triacrylate.

This article presents a thorough investigation into the synthesis of trimethylolpropane triacrylate (TMPTA) via the esterification reaction of trimethylolpropane (TMP) with acrylic acid using Amberlite™ 120 IR (H+), Amberlyst® 15, and Dowex™ 50WX8 resins as heterogeneous catalysts. Preliminary comparative tests explored the impact of air flow on water removal during the reaction and different acid-to-alcohol molar ratios (3:1, 6:1, or 9:1 mol:mol). The findings revealed that introducing air significantly enhances TMPTA yield and -OH group conversion, particularly at a 6:1 acid-to-alcohol molar ratio. Based on cost considerations, Amberlite™ 120 IR (H+) was selected as the preferred catalyst for further optimization. This included evaluating the effect of catalyst loading (10%, 5.0%, and 2.5% w/wtot) and assessing the impact of a pre-drying process on resin efficiency. The study concluded that optimal conditions did not necessitate drying, requiring 120 °C, a catalyst loading of 10% w/wtot, a 4 h reaction time, an acid:alcohol ratio of 6:1 mol:mol, the presence of MEHQ (0.1% mol/molAA), and air bubbling at 6 ± 1 Nl/h. Catalyst recycling was effectively implemented with a slight reduction in catalytic activity over consecutive runs. Furthermore, the study explored a scaled-up system with a mechanical stirrer, demonstrating the potential for multi-hundred grams scale-up. Considerations for optimizing the air flow stripping system are also highlighted. In summary, this study provides valuable insights into designing and optimizing the esterification process for TMPTA synthesis, laying the foundation for potential industrial applications.

A Disposable Thermally Triggered Photonic Crystal Anti-Counterfeiting Tag with Irreversible Response and Multi-Step Color Changes.

Thermochromic photonic crystal (PC) is a promising material for anti-counterfeiting applications, but there are still challenges to further improve the anti-counterfeiting performance and the practicability in usage. Here, a disposable thermally triggered PC anti-counterfeiting tag with irreversible response and multi-step color changes is developed based on the thermochromic Silica/(Polyethylene glycol-Ethoxylated trimethylolpropane triacrylate) (SiO2 /(PEG-ETPTA)) double-layer film. The fast and irreversible thermal response come from the quick melting and infiltration of PEG-ETPTA into the PCs upon heating. The multi-step color change at different temperatures originated from the regioselective control of the UV curing degree of the PEG-ETPTA layer and the resulting thermochromic temperature of the double-layer film. Therefore, the invisible PC pattern on the tag can be revealed part by part upon heating and became invisible again after overheating, which offered diversified visual effects and enhanced anti-counterfeiting performances.

Low volume shrinkage, high bio-based, and UV-curable coatings from castor oil-based reactive diluent via a one-step reaction

UV-curing technology possesses the advantages of fast curing, and cured at room temperature, which has been developed rapidly in recent years. However, the volume shrinkage usually occurs during the UV-curing polymerization process, seriously hindering its application. In this paper, a low volume shrinkage, high bio-based contents, and UV-curable resins was fabricated from the raw materials of castor oil, and cardanol. A three functional castor oil-based reactive diluent (COSH) was synthesized using a one-step method of thio-ene click reaction, and the COSH was blended with cardanol-based PUA (CNPUA) oligomer with different content, and prepare bio-based UV-curable materials. The comparative investigation were conducted on the thermal, and mechanical properties with petroleum-based diluents of trimethylolpropane triacrylate (TM), and trimethylolpropane tris (3-mercaptopropionate) (TMSH), respectively. As the content of COSH increased to 40%, the bio-based content of the CNPUA/COSH reached to the highest value of 60.0%, and the viscosity and volume shrinkage of CNPUA/COSH exhibited the lowest data of 1651 mPa·s, and 13.3%, respectively. The COSH not only had good dilution ability, but also possessed excellent anti volume shrinkage ability, and the mechanism of the anti shrinkage COSH was also explored. In addition, the three long carbon chain structures of the COSH endowed the cured coating excellent adhesion of 1 level, and pencil hardness of 3 H-4 H, as well as the flexibility of 2 mm. Lastly, the kinetics of the resulting resins were studied using real-time infrared spectroscopy (RT-IR). This study provides a feasible method for preparation of oil-based reactive diluents, and a new strategy for constructing the sustainable UV-curable materials with high performance.

Highly Reinforced Acrylic Resins for Hard Tissue Engineering and Their Suitability to Be Additively Manufactured through Nozzle-Based Photo-Printing.

Mineralized connective tissues represent the hardest materials of human tissues, and polymer based composite materials are widely used to restore damaged tissues. In particular, light activated resins and composites are generally considered as the most popular choice in the restorative dental practice. The first purpose of this study is to investigate novel highly reinforced light activated particulate dental composites. An innovative additive manufacturing technique, based on the extrusion of particle reinforced photo-polymers, has been recently developed for processing composites with a filler fraction (w/w) only up to 10%. The second purpose of this study is to explore the feasibility of 3D printing highly reinforced composites. A variety of composites based on 2,2-bis(acryloyloxymethyl)butyl acrylate and trimethylolpropane triacrylate reinforced with silica, titanium dioxide, and zirconia nanoparticles were designed and investigated through compression tests. The composite showing the highest mechanical properties was processed through the 3D bioplotter AK12 equipped with the Enfis Uno Air LED Engine. The composite showing the highest stiffness and strength was successfully processed through 3D printing, and a four-layer composite scaffold was realized. Mechanical properties of particulate composites can be tailored by modifying the type and amount of the filler fraction. It is possible to process highly reinforced photopolymerizable composite materials using additive manufacturing technologies consisting of 3D fiber deposition through extrusion in conjunction with photo-polymerization.

Polymer/ceramic gel electrolyte with in-situ interface forming enhances the performance of lithium metal batteries

With the introduction of solid-state electrolytes, solid-state lithium-metal batteries face enormous challenges of low electrolyte ion conductivity and high electrode electrolyte interface impedance. Here, we adopt a strategy of combining rigidity and flexibility to design a polymer/ceramic composite gel electrolyte films (CSEs) with a fiber like structure and local defect channels for rechargeable lithium metal batteries. The CSEs synthesized in situ on LiFePO4 electrode by ultraviolet (UV) curing method, which combines the high ionic conductivity of Li6.5La3Zr1.5Ta0.5O12 (LLZTO) ceramic particles and the flexibility of poly(vinylidene fluoride-co -hexafluoropropylene) (PVDF-HFP) polymer electrolyte. In order to investigate the effect of crosslinker on the performance of electrolytes, 1,6-hexanediol diacrylate (HDDA) and ethoxylated trimethylolpropane triacrylate (ETPTA) were used in the preparation process of ultraviolet (UV) curing method. A comparison was made between gel electrolytes using HDDA and ETPTA crosslinkers, electrolytes containing ETPTA exhibited good overall performance in terms of ion conductivity (7.89 × 10−4 S cm−1), Li+ transference number (0.63), glass transition temperature (−26.2 °C), good flexibility, thermal stability. As a result, the assembled LiFePO4||electrolytes containing ETPTA||Li batteries exhibit excellent the first discharge capacity (151.9 mAh g−1 with 0.1C), good rate performance and its capacity retention rate is 93.1 % after 300 cycles. This study provides a new strategy for the rational design and process method of high-performance CSEs for rechargeable solid lithium metal batteries.

Oxidization and Chain-Branching Reaction for Recycling HDPE and Mixed HDPE/PP with In-situ Compatibilization by Ozone-Induced Reactive Extrusion.

High-density polyethylene(HDPE)and isotactic polypropylene(iPP)are widely used in industrial and residential applications due to theirlow cost and chemical stability, thustheirrecycling process can contributeto a circular economy. However, both polymers are non-polar materials, and the incompatibility with most other materials leadsto substantially inferior properties of blends. In this work, we propose a flexible compatibilization strategy to improve the compatibility of HDPE/iPP blends. Ozone was adopted to induce reactive extrusion for rapid oxidation of HDPE and chain-branching reactions for bothHDPE and HDPE/iPP blends. During extrusion process, ozone oxidizesHDPE effectively in a short time and introducesoxygen-containing groupssuchas carbonyl and ester group, which improvesthe hydrophilicity.The addition of trimethylolpropane triacrylate (TMPTA) could promote branching reaction and facilitate the formation of HDPE-g-iPP copolymers, which improved the compatibility for HDPE/iPP. As a result, the impact strength of ozone-modified HDPE and HDPE/iPP blends increased by 22% and 82%, respectively, and the tensile strength also increased. This strategy would have potential applications in the field of sorting-free and solvent-free recycling of waste polyolefin plastics.

Optimizing rheological performance of unsaturated polyester resin with bio-based reactive diluents: A comprehensive analysis of viscosity and thermomechanical properties

Bio-based reactive diluents (RD) have been explored as alternative to styrene (STY) in unsaturated polyester resin (UPR). Among the different candidates, acrylated epoxidized soybean oil (AESO) and epoxidized linseed oil (ELO) stand out as triglyceride derivatives. Aditionally, methyl methacrylate (MMA), trimethylolpropane triacrylate (TMPTA) with acrylic functionality, limonene (LIM), and cinnamates (CINN), has been tested in different percentages. Firstly, their efficiency in viscosity reduction has been studied. Best results were obtained after the addition of MMA, LIM, and CINN at 5 wt%. These RD achieve a viscosity reduction of 48.9 %, 76.7 %, and 22.9 %, respectively, compared to the reference sample. The industrial utilization of CINN as RD is impeded by its reactivity, as has been evidenced by its prolonged reaction time (24 min) and low reaction enthalpy. The thermo-mechanical properties studied through flexural tests, Shore D hardness, Charpy's Impact test, and heat deflection temperature (HDT), show that the developed UPRs exhibit a decrease in resistant mechanical properties while doubling their ductility by using LIM and MMA as bio-based RD (1.88 and 2.15 kJ m−2, respectively). The HDT study results demonstrate a certain level of thermal stability when MMA is employed (56 °C), which is 15 % lower in the case of LIM. Therefore, it is observed that UPRs with bio-based RD exhibit balanced and improved thermo-mechanical properties in terms of ductility and strength, especially with the use of a 5 wt % of LIM and MMA.

Presence of 2-hydroxyethyl methacrylate (HEMA) and other (meth)acrylates in nail cosmetics, and compliance with EU legislation: An online market survey.

During the last 15-20 years, allergic contact dermatitis from acrylates-containing nail cosmetics (acrylic nails, gel nails, gel nail polish) has been increasingly reported. 2-Hydroxyethyl methacrylate (HEMA) is considered to be the major allergenic culprit; few data on its presence in nail cosmetics are available. To investigate (1) the frequency in which HEMA and di-HEMA trimethylhexyl dicarbamate are present in nail cosmetics; (2) whether nail cosmetics comply with EU regulations; (3) which other (meth)acrylates are present in nail cosmetics and how often. One-line market survey. HEMA was present in nearly 60% of 394 cosmetic nail products and di-HEMA trimethylhexyl dicarbamate in 34%. Mandatory warnings on the packages of products containing HEMA were absent in 35% ('For professional use only') resp. 55% ('Can cause an allergic reaction'). Forty-five other (meth)acrylates were identified, of which the most frequent were hydroxypropyl methacrylate (25%), isobornyl methacrylate (16%) and trimethylolpropane triacrylate (12%). Some ingredient lists mentioned non-INCI names or non-specific names. HEMA was by far the most common ingredient of nail cosmetics, being present in nearly 60% of the products. Violations of EU legislation occurred in >30% (mandatory warnings missing) resp. 10% (mislabelling) of nail cosmetics.

UV-curable Schiff base-containing polymeric adsorbent for selective and efficient removal of Au(III) from aqueous solutions

UV-curable polymeric adsorbent was prepared using a diacrylate-functionalized hydrazone-oxime monomer (DAFHOM), trimethylolpropane triacrylate (TMPTA), and trimethylolpropane tris(3-mercaptopropionate) (TMPTP) through UV-initiated thiol-ene click reaction. Initially, a novel hydrazone-oxime-based Schiff base ligand was synthesized and modified with diacrylate functionality to prepare the UV-curable polymeric adsorbent. The structures of DAFHOM and the resulting polymeric adsorbent were confirmed using Fourier Transform Infrared Spectroscopy (FTIR) analysis. Additionally, the thermal behavior of the UV-cured adsorbent was investigated through thermal gravimetric analysis (TGA), which revealed that the adsorbent exhibited good stability and did not degrade at room temperature. The adsorption performance of the UV-curable polymeric adsorbent for Au(III) from aqueous solutions was studied under various experimental conditions, including pH, contact time, and initial metal concentration. The UV-curable polymeric adsorbent demonstrated effective and selective Au(III) adsorption from aqueous solutions. The findings indicated that removing Au(III) from water solutions positively correlated with pH, particularly within the pH range of 0.5–2.5. However, the efficiency declined when the pH exceeded 1.5. Among the various adsorption isotherm models investigated, the Langmuir model was found to be the most suitable for describing the behavior of the adsorbent. The maximum adsorption capacity of the adsorbent for Au(III) was determined to be 30.06 mg/g. In batch experiments, the UV-curable adsorbent displayed promising selectivity towards Au(III), even in the presence of competitive ions such as Cu(II), Pb(II), and Cd(II).

Antibacterial and angiogenic potential of iron oxide nanoparticles-stabilized acrylate-based scaffolds for bone tissue engineering applications

Pickering emulsion polymerization, stabilized by inorganic nanoparticles such as iron oxide nanoparticles (IONPs), can be used to fabricate scaffolds with the desired porosity and pore size. These nanoparticles create stable emulsions that can be processed under harsh polymerization conditions. IONPs, apart from serving as an emulsifier, impart beneficial bioactivities such as antibacterial and pro-angiogenic activity. Here, we coated IONPs with three different weights of oleic acid (5.0 g, 7.5 g, and 10.0 g) to synthesize oleic acid-IONPs (OA-IONPs) that possess the desired hydrophobicity (contact angle > 100°). Next, glycidyl methacrylate and trimethylolpropane triacrylate were polymerized using the Pickering emulsion polymerization technique stabilized by the OA-IONPs. The physicochemical properties of the resulting porous scaffolds were thoroughly characterized using scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), vibrating sample magnetometry (VSM), and a universal testing machine (UTM). The SEM images confirmed the formation of a porous scaffold. The IONPs content, measured using inductively coupled plasma mass spectrometry (ICP-MS), was in the range of 22–26 µg/mg of the scaffold. The mechanical strengths of the scaffolds were in the range of cancellous bone. The degradation profile of the scaffolds varied between 29% and 41% degradation over 30 days. In vitro cytotoxicity studies conducted using the fibroblast (L929) and osteosarcoma (MG-63) cell lines proved that these scaffolds were non-toxic. SEM images showed that the MG-63 cells adhered firmly to the scaffolds and exhibited a well-spread morphology. The antibacterial activity was confirmed by percentage inhibition studies, SEM analysis of bacterial membrane distortion, and reactive oxygen species (ROS) generation in the bacteria. Chick chorioallantoic membrane assay showed that the total vessel length and branch points were significantly increased in the presence of the scaffolds. These results confirm the pro-angiogenic potential of the fabricated scaffolds. The physicochemical, mechanical, and biological properties of the material suggest that the developed scaffolds would be suitable for bone tissue engineering applications.