Acrylic Monomers Research Articles

Optical Interaction of CdTe/ZnS Quantum Dots with Sodium Alginate Biopolymer PAA-Modified for Glucose Detection

In this paper, a novel and efficient method for glucose detection is designed and synthesized using a biopolymer-based nanocomposite covering zinc sulfide-coated cadmium telluride quantum dots. The obtained quantum dot is modified with polyacrylic acid (PAA) polymer attached to sodium alginate so that it can be used as a biosensor based on nanotechnology to detect glucose with a new method while taking advantage of the characteristics of fluorescent cadmium telluride-sulfide. The used method has advantages such as a safe preparation method and the use of cheap materials. The Fluorescence quenching method is used to systematically investigate the effect of quantum dots of cadmium telluride-zinc sulfide modified with biopolymer on glucose. One of the important advantages is the possibility of evaluating several parameters at the same time according to the multiple wavelengths of radiation of quantum dots of the sensor. The resulted experiments shows that quantum dots prepared from acrylic acid monomer with a concentration of 50 microliters and measured at temperatures lower than 25 °C at which the sensitivity is measured as 6.36 μg ml−1 at the lowest detection range whose characteristics can be evident from the glucose and absorption curve studies.

Functional Thermoplastic Polyurethane Elastomers with α, ω-Hydroxyl End-Functionalized Polyacrylates.

Thermoplastic polyurethane (TPU) is an essential class of materials for demanding applications, from soft robotics and electronics to medical devices and batteries. However, traditional TPU development is primarily relied on specific soft segments, such as polyether, polyester, and polycarbonate polyols. Here, a novel method is introduced for developing TPU elastomers with enhanced performance and superior functionalities compared to conventional TPUs, achieved through the use of α,ω-hydroxyl end-functionalized polyacrylates. This approach involves a defect-free synthesis of α,ω-hydroxyl end-functionalized polyacrylates through visible-light-driven photoiniferter polymerization. By strategically blending these functionalized polyacrylates with conventional polyols, TPUs that exhibit exceptional toughness and notable self-healing capabilities, traits rarely found in existing TPUs are engineered. Furthermore, incorporating photo-crosslinkable acrylic monomers has enabled the creation of the first TPU with superior elastomeric properties and photopatterning capabilities. This approach paves the way for a new direction in polyurethane engineering, introducing a novel class of soft segments and unlocking the potential for a wide range of advanced applications.

Solvent-free Acrylate/BCB drop-on-demand (DOD) inkjet dielectric ink for 3D printing

Currently, drop-on-demand (DOD) inkjet-printed dielectric inks used to produce next-generation high-frequency electronic devices fail to meet the requirements of circuit board substrates in terms of thermal, mechanical, and dielectric properties. To address this gap, we synthesized a low-viscosity acrylate monomer featuring an intrinsically low dielectric structure (hexafluorobisphenol A) and multiple cross-linking sites, and a benzocyclobutene monomer with low curing shrinkage and excellent thermomechanical properties. By mixing these monomers with other reactive diluents and verifying them through theoretical calculations and printing, we have developed a range of dielectric inks suitable for inkjet 3D printing. To enhance the overall performance of the cured inks, a sequential UV/thermal curing strategy was employed to form interpenetrating networks (IPNs). The optimal ink formulations met the requirements of circuit board substrates, demonstrating excellent heat resistance (Td5% = 334 °C, Tg = 181 °C), mechanical properties (tensile strength = 85 MPa, elongation at break = 13.5 %), and dielectric properties (Dk = 2.526 and Df = 0.113 at 15 GHz). These formulations meet the performance requirements for circuit board substrates and lead the industry in mechanical and dielectric properties. Furthermore, the feasibility of inkjet printing heterogeneous integrated electronic devices was verified, showing excellent print resolution and continuity of the conductive network. This work provides new insights into the future development of dielectric materials for inkjet 3D printing.

Spectroscopic and Thermal Characterisation of Interpenetrating Hydrogel Networks (IHNs) Based on Polymethacrylates and Pluronics, and Their Physicochemical Stability under Aqueous Conditions

This study describes the physicochemical characterisation of interpenetrating hydrogel networks (IHNs) composed of either poly(hydroxyethylmethacrylate, p(HEMA)) or poly(methacrylic acid, p(MAA)), and Pluronic block copolymers (grades F127, P123 and L121). IHNs were prepared by mixing the acrylate monomer with Pluronic block copolymers followed by free radical polymerisation. p(HEMA)–Pluronic blends were immiscible, evident from a lack of interaction between the two components (Raman spectroscopy) and the presence of the glass transitions (differential scanning calorimetry, DSC) of the two components. Conversely, IHNs of p(MAA) and each Pluronic were miscible, displaying a single glass transition and secondary bonding between the carbonyl group of p(MAA) and the ether groups in the Pluronic block copolymers (Raman and ATR-FTIR spectroscopy). The effect of storage of the IHNs in Tris buffer on the physical state of each Pluronic and on the loss of Pluronic from the IHNs were studied using DSC and gravimetric analysis, respectively. Pluronic loss from the IHNs was dependent on the grade of Pluronic, time of immersion in Tris buffer, and the nature of the IHN (p(HEMA) or p(MAA)). At equilibrium, the loss was greater from p(HEMA) than from p(MAA) IHNs, whereas increasing ratio of poly(propylene oxide) to poly(ethylene oxide) decreased Pluronic loss. The retention of each Pluronic grade was shown to be primarily due to its micellization; however, hydrogen bonding between Pluronic and p(MAA) (but not p(HEMA)) IHNs contributed to their retention.

Synthesis of Amphiphilic Polyacrylates as Peelable Coatings for Optical Surface Cleaning

Optical instruments require extremely high precision, and even minor surface contamination can severely impact their performance. Peelable coatings offer an effective and non-damaging method for removing contaminants from optical surfaces. In this study, an amphiphilic polyacrylate copolymer (PMLEA) was synthesized via solution radical copolymerization using the lipophilic monomer lauryl acrylate (LA) and hydrophilic monomers ER-10, methyl methacrylate (MMA), and butyl acrylate (BA). The structure and molecular weight of the copolymer were characterized using Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC). The hydrophilic–lipophilic balance, surface tension, and wettability of the copolymer were analyzed through water titration, the platinum plate method, and liquid contact angle tests. The cleaning performance of the copolymer coating on quartz glass surface contaminants was evaluated using optical microscopy and Ultraviolet-Visible Near-Infrared (UV-Vis-NIR) spectroscopy. The study examined the effect of varying the ratio of LA to ER-10 on the hydrophilicity, lipophilicity, cleaning efficiency, and mechanical properties of the copolymer coating. The results showed that when the mass ratio of LA to ER-10 was 1:2, the synthesized copolymer exhibited optimal performance in removing dust, grease, and fingerprints from quartz glass surfaces. The coating had a tensile strength of 2.57 MPa, an elongation at break of 183%, and a peeling force of 2.07 N m−1.

Модификация твердофазной полимерной поверхности путём прививки акриловых мономеров

Graft copolymerization onto a solid polymer surface is an effective tool for its modification. A large number of works have been published and require systematization. A search and review of English-language scientific literature devoted to the graft copolymerization of acrylic monomers onto a polymeric solid-phase surface have been carried out. Grafting onto plates and films, as well as fibers and colloidal particles, is considered. It has been revealed that the most popular substrates for graft copolymerization are, besides polyethylene, propylene and polyethylene terephthalate; polyurethanes, polyfluoroethylenes, rubbers, etc. Graft polymerization mainly proceeds on amorphous areas of the substrate and does not destroy the crystalline phase. It is possible to use the methods of controlled radical polymerization (ATRP, RAFT). Of the acrylic monomers, acrylic and methacrylic acids, glycidyl acrylate and glycidyl methacrylate, and others have been used, while the main method has been UV photopolymerization with an initiator–benzophenone. Of the three aliphatic ketones (acetone, methyl ethyl ketone and methyl propyl ketone), acetone has been the best solvent. Cophotoinitiators have been also used (a synergistic effect was observed), corona discharge, gamma radiation (60Co), ozone and plasma treatment, and a supercritical CO2 medium. The degree of grafting has been controlled by changing the soaking time in the monomer, pressure, concentration of monomer and initiator in the liquid phase, reaction temperature and reaction time. A new technology of graft polymerization with photopatterning has also been proposed. Problems of graft polymerization in terms of surface modification of polymer materials (hydrophilization of the surface, improving paintability and wettability, enhancing adhesion to certain surfaces, biocompatibility) are touched upon, and possible areas of their application are outlined.

Study on UV-Curable Acrylic Clear Viscoelastic Materials with Grafted Structures

Flexible substrates are crucial for wearable electronic strain sensors, but achieving biocompatibility, low cost, and aesthetic appeal alongside good mechanical performance remains challenging. Acrylic-based clear viscoelastic films (CVFs) are gaining attention due to their excellent transparency and potential for enhanced mechanical properties. This study synthesized copolymers CVF1-4 with varying branch content using soft monomers 2-ethylhexyl acrylate (2-EHA), butyl acrylate (n-BA), and functional monomer acrylic acid (AA). Employing a "grafting-through" strategy, small molecule monomers, ATRP-synthesized oligomer pBA25, and photoinitiator 1,6-hexanediol diacrylate (HDDA) were in-situ polymerized under UV light to form transparent, flexible elastic films CVF1-4. Between -20 to 80 C, CVF1-4 demonstrated excellent mechanical properties such as low modulus (in the kPa range), low glass transition temperature (below -20 C), large deformation (500-600%), and high strain recovery rate (>95%). Among them, CVF3 with 15% branching showed a balanced comprehensive performance, exhibiting primarily elastic behavior at room temperature. Therefore, selecting appropriate molecular composition and grafting structure provides a simple and customizable solution for optimizing CVF properties.

Silver-Mediated ARGET-ATRP of Reactive Acrylates Using TPMANMe2 Ligand: A Universal Strategy for Controlled Copolymerization.

A controlled polymerization using activated acrylate monomers via ARGET-ATRP is developed with a tris[(4-dimethylamino pyridyl)methyl]amine ligand to address issues with weaker ligands and monomers that can undergo postpolymerization functionalization. This catalyst system enables the polymerization of N-acryloxy succinimide, fluorinated monomers, and isocyanato ethyl acrylate under controlled homogeneous conditions, ensuring linear molecular-weight growth and low polydispersity. Two block copolymerization strategies produce amphiphilic copolymers with narrow molecular-weight distributions and customizable compositions, allowing for various postpolymerization functionalizations.

Direct Synthesis of Perovskite Quantum Dot Photoresist for Direct Photolithography.

Perovskite quantum dots (PQDs) photoresists are promising building blocks for photolithographically patterned devices. However, their complex synthesis and combination processes limit their optical properties and potential patterning applications. Here, we present an exceptionally simple strategy for the synthesis of PQDs photoresist. Unlike traditional approaches that involve centrifugation, separation, and combination processes, our direct synthesis technique using polymerizable acrylic monomer as solvent to fabricate PQDs photoresists without complex post-synthesis process. We demonstrate that the change in solubility of the precursors is the main reason for the formation of PQDs in the polymerizable monomer. By direct photolithography, colorful PQD patterns with high photoluminescence quantum yields and excellent fluorescence uniformity are successfully demonstrated. This work opens a new avenue for the direct synthesis of PQDs photoresist, expanding their applications in various integrated applications, such as photonic, energy harvesting, and optoelectronic devices.

Direct Synthesis of Perovskite Quantum Dot Photoresist for Direct Photolithography

Perovskite quantum dots (PQDs) photoresists are promising building blocks for photolithographically patterned devices. However, their complex synthesis and combination processes limit their optical properties and potential patterning applications. Here, we present an exceptionally simple strategy for the synthesis of PQDs photoresist. Unlike traditional approaches that involve centrifugation, separation, and combination processes, our direct synthesis technique using polymerizable acrylic monomer as solvent to fabricate PQDs photoresists without complex post‐synthesis process. We demonstrate that the change in solubility of the precursors is the main reason for the formation of PQDs in the polymerizable monomer. By direct photolithography, colorful PQD patterns with high photoluminescence quantum yields and excellent fluorescence uniformity are successfully demonstrated. This work opens a new avenue for the direct synthesis of PQDs photoresist, expanding their applications in various integrated applications, such as photonic, energy harvesting, and optoelectronic devices.

Characterization and comparability study of a series of novel fluorinated polyacrylates with a rigid cyclohexane mesogenic core

Surface reconstruction has always been a pain point in the study of short-chain perfluoroalkyl acrylate polymers, and how to maintain the balance between environmental protection and good performance is the key issue. We exploited the high efficiency and selectivity of the reaction between the isophorone di-isocyanate group and the hydroxyl group, and the rigid cyclohexane structure contained in their molecule to efficiently prepare a series of novel fluoro acrylate monomers (IFAM) containing rigid cyclohexane as mesogenic core and their homopolymers (PIFAM) with different lengths of short-chain perfluoroalkyl side chains. Their structures, liquid crystal behavior, thermal properties, surface chemical compositions, surface morphologies, and hydrophobicity were characterized and comparatively studied by FTIR, NMR, XRD, POM, DSC, TGA, XPS, AFM, and static/dynamic contact angle tester and dodecafluoroheptyl methacrylate (DFMA) and its homopolymer as a contrast. The results demonstrated that both the synthesized monomers and homopolymers possessed the expected chemical structures with thermotropic liquid crystalline behavior. Furthermore, the thermal stability and hydrophobicity of the polymers increased with the extension of the fluorocarbon chain length. The incorporation of the mesocrystalline motif and appropriate length of fluoroalkyl tails in the PIFAM polymers would enhance hydrophobic stability, as it promoted the crystallinity of the side chains and limited the structural rearrangement of the fluorocarbon chains. This study offers a straightforward method for synthesizing fluoro acrylate polymers with stable surface properties, highlighting their potential application in hydrophobic coatings.

POSS based poly (zwitterionic liquids) electrolytes with 3D crosslinked networks for lithium metal batteries

Polymer electrolyte is a potential candidate for the next-generation lithium metal batteries. However, its low room temperature ionic conductivity limited its practical application. Here, a novel POSS-based poly (zwitterionic liquids) organic–inorganic hybrid electrolyte with 3D crosslinked networks was proposed for enabling lithium-ion fast transport by photoinitiated radical polymerization of vinyl zwitterionic monomers and acrylate monomers containing rich EO units and POSS. The synergistic effect of unique structures of 3D organic–inorganic hybrids gel electrolytes such as zwitterionic, rich EO segments and POSS cages facilitate Li+ conduction, resulting in high room temperature ionic conductivity (1.03 × 10-3 S cm-1) and a satisfactory Li+ transference number (0.45). The lithium-symmetric batteries assembled with the novel POSS-based poly (zwitterionic liquids) gel hybrid electrolytes can operate continuously at 0.1 mA cm-2 for 2300 h without any obvious short circuit, indicating good interfacial compatibility between the electrolytes and lithium electrodes. The Li/LiFePO4 batteries assembled with the novel POSS-based poly (zwitterionic liquids) gel hybrid electrolytes exhibit long-term stability.

FEATURES FOR OPTIMISING THE PROPERTIES OF COMPOSITE MATERIALS BASED ON ACRYLIC MONOMERS

Further development of research in the field of acrylic composites is aimed at creating modifiers with specified properties that will improve the characteristics of composites in specific application conditions; developing optimal ratios of composite components to ensure the required properties; developing universal mathematical models that will predict the properties of composites depending on the composition and curing conditions; searching for new applications for acrylic composites, such as industrial and civil engineering. Among all organic compounds, acrylic compounds demonstrate the highest rate of strength gain over a wide temperature range. This is due to the low activation energy of the polymerisation process of acrylic monomers, which is triggered by special initiators. Due to this feature, acrylic composites can cure even at low temperatures and gain high strength in a short time. However, despite the obvious advantages, there are a number of questions that require further research: how does the rate of strength gain and other properties of acrylic composites change at different temperatures? How does changing the ratio of composite components (pliable, filler, initiator) affect its properties? How does the curing process of acrylic composites work at the molecular level? Determining the answers to these questions will make it possible to select the optimal ratio of components to obtain a material with the required properties, control the rate of strength gain of the composite by changing the temperature and composition, and use acrylic composites in a wider range of temperature conditions. Thus, a deep understanding of the processes that occur during the curing of acrylic composites is a prerequisite for their effective use in various industries and construction. The aim of the study is to comprehensively study the properties of composite materials based on methyl methacrylate (MMA) for the purpose of their effective use. Research objectives: determination of the optimal temperature regime to achieve maximum composite strength in the shortest possible time (1.5-2 hours). Study the effect of various fillers and other components on the strength, durability and other properties of the material. Identification of effective ways to modify MMA to increase the strength of the composite. Development of methods for controlling the rate of strength gain to ensure optimal operation. Assessment of the durability of the adhesive bond under various operating conditions. Comparison of the properties of the developed composites with existing materials. The results of the study will make it possible to develop new, more efficient composite materials for repair work that will be widely used in construction, industry and other sectors. Keywords: acrylic composites, modification, methyl methacrylate, strength, temperature, curing, repair.

Non‐Isocyanate Synthesis of Covalent Adaptable Networks Based on Dynamic Hindered Urea Bonds: Sequential Polymerization and Chemical Recycling

AbstractThe development of environmentally sustainable processes for polymer recycling is of paramount importance in the polymer industry. In particular, the implementation of chemical recycling for thermoset polymers via covalent adaptable networks (CANs), particularly those based on the dynamic hindered urea bond (HUB), has garnered intensive attention from both the academic and industrial sectors. This interest stems from its straightforward chemical structure and reaction mechanism, which are well‐suited for commercial polyurethane and polyurea applications. However, a substantial drawback of these CANs is the requisite use of toxic isocyanate curing agents for their synthesis. Herein, we propose a new HUB synthesis pathway involving thiazolidin‐2‐one and a hindered amine. This ring‐opening reaction facilitates the isocyanate‐free formation of a HUB and enables sequential reactions with acrylate and epoxide monomers via thiol–Michael and thiol–epoxy click chemistry. The CANs synthesized using this methodology exhibit superior reprocessability, chemical recyclability, and reutilizability, facilitated by specific catalytic and solvent conditions, through the reversible HUB, thiol–Michael addition, and transesterification processes.

Stereolithographic 3D Printing of Intrinsically Flame‐Retardant Shape‐Memory Polymers

AbstractThis study presents a novel approach to fabricate 3D‐printed phosphorous‐based acrylate monomers using stereolithographic 3D printing technology, aiming to create demonstrators with exceptional shape‐memory characteristics and robust flame retardant properties. The synthesized materials combine the advantages of 3D printing precision with the intrinsic flame retardancy of phosphorous‐based monomers, offering a versatile solution for applications requiring both shape memory functionality and fire resistance. The limiting oxygen index (LOI) value of the intrinsically flame‐retardant shape‐memory polymer (IFR‐SMP) can reach 34%, and the vertical combustion rating after UL 94 can obtain V‐0. The mechanism of the IFR‐SMP flame retardant mainly includes terminating a free‐radical chain reaction and gas phase dilution, which indicates that the gas‐phase mechanism plays an important role in the flame retardancy. This work advances the frontiers of 3D printing technology by demonstrating the synergistic potential of shape memory and flame retardancy within a single material system, providing a pathway toward the development of innovative and resilient materials for the future.

Direct Acrylation of Soybean Oil and the Influence of the Acrylation Degree on Waterborne Acrylic Systems.

The direct acrylation of soybean oil was investigated by the activation of soybean oil's (SO's) internal fatty unsaturation with acidic catalysts. The effect of the catalyst and the reactant ratio with respect to the unsaturation and reaction time on the direct acrylation process were explored. ASO (acrylated soybean oil) with acrylation degrees (the number of acrylate molecules introduced in a triglyceride molecule) between 1.6 and 2.55 were obtained. The effect of the ASO acrylation degree on copolymerization processes was investigated. The resulting monomers were successfully copolymerized with meth(acrylate) monomers by the miniemulsion polymerization process, favoring the droplet nucleation mechanism and showing conversions higher than 97%. The acrylic-ASO copolymers presented lower Tg and higher hydrophobicity and oleophobicity than the acrylic copolymer.

Developing Catalysts for the Hydrolysis of Glycosidic Bonds in Oligosaccharides Using a Spectrophotometric Screening Assay.

In a proof-of-concept study, a method for the empirical design of polyacrylate gel catalysts with the ability to cleave 1→4 α-glycosidic bonds in di- and trisaccharides was elaborated. The study included the synthesis of a 300-gel member library based on two different cross-linkers and 10 acrylate monomers, identification of monomodal gels by dynamic light scattering, and a 96-well plate spectrophotometric screening assay to monitor the hydrolysis of chromophore-free maltose into glucose units. The composition of the matrix of the most efficient catalysts in the library was found to enable CH-π, hydrophobic, and H-bond accepting interactions during the hydrolysis as typically seen in glycosylases. The same gel catalysts allowed the hydrolysis of the trisaccharide maltotriose with a catalytic proficiency of 2 × 106 indicating transition state stabilization during the hydrolysis of 5 × 10-7. The results place the developed gels among the most efficient catalysts developed for the hydrolysis of natural saccharides. The elaborated strategy may lead to catalysts that can transform polysaccharides into valuable synthons in the near future.

Divalent vinyl ketones derived from fluorene: a facile synthesis of bifunctional acrylic monomers with high reactivity in thia-/aza-Michael addition and Morita-Baylis-Hillman reactions

Divalent vinyl ketones derived from fluorene: a facile synthesis of bifunctional acrylic monomers with high reactivity in thia-/aza-Michael addition and Morita-Baylis-Hillman reactions

Tuning the morphology and electro-optical properties of reverse mode PDLCs using multifunctional acrylates

ABSTRACT Reverse-mode Polymer Dispersed Liquid Crystals (rev-PDLCs) are composite materials generally obtained by the phase separation of dispersions of liquid crystal/monomer mixtures and characterised by the possibility to change on-demand their transmittance in a continuous manner from an initial transparent state to an opaque one by application of an electric field. Rev-PDLCs have found applications in many fields, including large-area smart windows, automotive, and bifunctional devices. In this work, acrylate monomers with different functionality (from 3 to 6) and weight ratios (from 5 to 15%) were used to finely adjust the morphology and electro-optical properties of the rev-PDLCs obtained by photo-polymerisation of an aligned LC/LC monomer mixture. The doping of nematic liquid crystalline monomers with acrylate monomers allowed to finely tune the morphology of rev-PDLC films, which were characterised by highly transparent OFF-states (TOFF always larger than 60%), strongly opaque ON-states (TON always around or lower than 1%), but with contrast ratios, transmittance slopes, threshold and switching fields dependent on the amount and functionality of used monomers. Such results could represent a valid method to overcome the drawback of relatively low materials to be used as starting components in the fabrication of reverse mode dimming films.

Development of a quaternary photocurable system for 3D printing based on the addition of acrylate monomers to an epoxy/thiol‐Ene system

AbstractThe exothermic nature of acrylate photopolymerizations enables room temperature 3D printing of a quaternary formulation that incorporates an acrylate monomer, and an epoxy/thiol‐ene system (ETES). The latter comprises an epoxy monomer, a multifunctional thiol and a tetraallyl functionalized ditertiary amine curing agent. Pristine ETES necessitates temperatures of 85–95 °C for curing. Several mechanisms operate simultaneously during this process: homopolymerization of acrylates, thiol‐acrylate photopolymerization, thiol‐ene photopolymerization between the double bonds of curing agent and the multifunctional thiol, the Michael addition between thiolates derived from ETES and the double bonds of acrylates, and the anionic polymerization of the epoxy resin via the tertiary amine groups. To optimize the quaternary formulations for printing, parameters, such as reactivity, exothermicity, and viscosity, was explored. Subsequently, the thermal and viscoelastic properties of the printed cross‐linked polymers derived from these formulations were analyzed using Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA) and Thermogravimetric Analysis (TGA). The polymers derived from quaternary formulations exhibited lower crosslinked density compared to those obtained from the pristine acrylates. This reduction in crosslink density contributes to the improved toughness of the hybrid polymers.