Copolymerization Of Methyl Methacrylate Research Articles

Preparation of high transparency, thermal stability, flame retardant polymethyl methacrylate nanocomposite via gamma-radiation polymerization

Achieving flame retardancy and thermal stability in poly(methyl methacrylate) (PMMA) while maintaining its inherent high transparency presents a significant challenge. In this work, we successfully fabricated an exceptional composite (P-SiO2-PMMA) with high transparency, flame retardancy, and thermal stability using 60Co γ-ray irradiation-induced copolymerization of methyl methacrylate (MMA), 2-hydroxyethyl 2-methyl-2-propenoate phosphate (HEMAP), and nano-silica (SiO2). The impact of the HEMAP on the crystal, optical, thermal stability, and combustion behavior properties of P-SiO2-PMMA has been investigated. P-SiO2/PMMA forms a three-dimensional network cross-linked molecular chain structure, enhancing the thermal decomposition temperature (Tdi), maximum thermal decomposition temperature (Tmax), glass transition temperature (Tg), and reducing the coefficient of thermal expansion (CTE). HEMAP and SiO2 significantly enhance the flame retardancy of the material. The limiting oxygen index (LOI) value of transparent flame-retardant 20-P-SiO2/PMMA composite material increased from 17.5% for PMMA to 23.2%, with a 47.3% decrease in peak heat release rate (PHRR). The flame retardant mechanism was also investigated. This study offers a novel approach for the industrial application of high transparency, thermal stability, and halogen-free flame-retardant PMMA composite.

Magnetic Phase-Change Microcapsules with High Encapsulation Efficiency, Enhancement of Infrared Stealth, and Thermal Stability

Due to energy shortages and the greenhouse effect, the efficient use of energy through phase-change materials (PCMs) is gaining increased attention. In this study, magnetic phase-change microcapsules (Mag-mc) were prepared by suspension polymerization. The shell layer of the microcapsules was formed by copolymerizing methyl methacrylate and triethoxyethylene silane, with the latter enhancing the compatibility of the shell layer with the magnetic additive. Ferric ferrous oxide modified by oleic acid (Fe3O4(m)) was added as the magnetic additive. Differential scanning calorimetry (DSC) testing revealed that the content of phase-change materials in microcapsules without and with ferric ferrous oxide were 79.77% and 96.63%, respectively, demonstrating that the addition of Fe3O4(m) improved the encapsulation efficiency and enhanced the energy storage ability of the microcapsules. Laser particle size analysis showed that the overall average particle sizes for the microcapsules without and with ferric ferrous oxide were 3.48 μm and 2.09 μm, respectively, indicating that the incorporation of magnetic materials reduced the size and distribution of the microcapsules. Thermogravimetric analysis indicated that the thermal stability of the microcapsules was enhanced by the addition of Fe3O4(m). Moreover, the infrared emissivity of the microcapsule-containing film decreased from 0.77 to 0.72 with the addition of Fe3O4(m) to the shell of microcapsules.

Increased stability of polymer dispersions obtained by heterophase radical polymerization of styrene and MMA in the presence of water-insoluble organosilicon macromeres

It is shown that during the copolymerization of methyl methacrylate with the surfactant comonomer α,ω-dipropylmethacrylatep olidimethylsiloxane with the number of repeating dimethylsiloxane units n = 20 (DPMPDMS), strong interfacial adsorption layers are formed on the surface of polymer–monomer particles formed from microdrops, ensuring the stability of particles to various types of influences.

Phase equilibrium and mixing thermodynamics of polystyrene with copolymers of styrene and methyl methacrylate

AbstractData on the solubility of oligomer polystyrene and random copolymers of styrene and methyl methacrylate with different styrene contents have been obtained. Phase diagrams were constructed and the values of critical points were determined. The upper critical solution temperature is localized in the temperature range above 420 K and grows with increasing molecular weight of PS and decreasing styrene content in the copolymer. Based on the compositions of the coexisting phases, paired interaction parameters were calculated and their temperature dependences were plotted. The dependence of the interaction parameter on the copolymer composition and the correlation dependence between its enthalpy and entropy components were constructed. A method for simulation phase equilibrium for copolymers of arbitrary composition and molecular weight is proposed.

Methyl Methacrylate Copolymer with Pendant Thioxanthenone Groups as Active Layer for Resistive Memory Devices.

An electro-active copolymer of methyl methacrylate and 2-((4-acroylpiperazine-1-yl)methyl)-9H-thioxanthene-9-one (poly(MMA-co-ThS)) was synthesized by radical polymerization. The copolymer has good solubility in most organic solvents, thermal stability up to 282 °C and excellent ability to form thin films on silicon wafers. Poly(MMA-co-ThS) films exhibited an electrochemical and electrochromic activity resulting in the formation of long-lived radical anion states of pendant thioxanthone groups inside the film. These states exhibit optical transitions in the visible region as a broad optical absorption band, 500<λ<900 nm (1.38<Wopt(ThS)<2.48 eV) with a maximum at λmax=675 nm (1.84 eV). Using temperature measurements of the current-voltage characteristics of p-Si(100)/poly(MMA-co-ThS)/Al devices, it was shown that the charge transport in the film occurs by a multiphonon mechanism, which is quantitatively described by the Nasyrov-Gritsenko model of phonon-assisted tunneling between traps. The value of the optical transition energy of the trap, determined by the Nasyrov-Gritsenko model, Wopt=1.8 eV, is in a good agreement with Wopt(ThS), confirming the nature of the traps as 9H-thioxanthen-9-one structures. The n++Si(100)/poly(MMA-co-ThS)/Al memory device exhibited a memristive effect (reversible ON/OFF switching of the device) with an initial "forming" cycle followed by repetitive memory cycles characterized by bipolar switching.

Synthesis and properties of AM/AMPS/MMA and cationic monomer copolymer flooding agent

Abstract A novel hydrophobic association copolymer (PAMA) was synthesized by incorporating acrylamide (AM), 2-acrylamide-2-methylpropanesulfonic acid (AMPS), cationic monomer (MEDDA), and methyl methacrylate (MMA). The properties of MMA copolymers with varying contents were analyzed using infrared spectroscopy, nuclear magnetic resonance spectroscopy, and scanning electron microscopy. Optimal overall performance of the solution was achieved when the MMA content reached 1.4 % w/w. Compared to pure PAAM (without MMA), the PAMA-1.4 % polymer exhibited superior viscoelasticity, temperature resistance, and shear resistance. This enhancement in PAMA performance can be attributed to the significant inhibition of intermolecular water film formation within the polymer matrix by MMA, effectively improving and regulating solution solubility while strengthening molecular chain interactions and enhancing the structural network strength of PAMA polymers. Additionally, the inclusion of MMA transformed rock surfaces from non-wetting to wetting conditions, thereby greatly improving oil displacement efficiency. In displacement experiments, PAMA-1.4 % performed better in terms of enhanced oil recovery, the recovery rate of 0.1 % w/w PAMA-2.4 % solution is only 7.78 %, while the recovery rate of 0.1 % w/w PAMA-1.4 % solution is 13.06 %.

Effect of polybutadiene grafted methyl methacrylate copolymer on the mechanical performance of PC/ABS composites

AbstractPolybutadiene grafted methyl methacrylate copolymer (PBL‐g‐MMA, MB) with core‐shell structure was prepared by emulsion polymerization. Without adding compatibilizers, PC/ABS composites were blended with polycarbonate (PC) and SAN. The effects of methacrylate butadiene (MB) on mechanical properties, flow properties, and thermal properties of PC/ABS composites were investigated. The results show that the addition of MB has obvious toughening effect on PC/ABS, effectively improving the mechanical properties and melt flow rate (MFR) of PC/ABS composites, and hence significantly improving the processability of PC/ABS composites. When the amount of MB is 12 phr, the notched impact strength of PC/ABS blend can reach up to 430 J/m. This is several times more than pure PC resin. The scanning electron microscope (SEM) analysis results show that the compatibility of PC/ABS and the impact strength of PC/ABS blend are improved with the increase of MB dosage. With the increase of MB content, the softening temperature of Vicat first decreased and then increased. It increased with the increase of PC content.

RAFT copolymerization of methyl methacrylate and di(ethylene glycol) methyl ether methacrylate in a hexylpyridinium ionic liquid

AbstractSmart polymers undergo significant physical or chemical changes in response to stimuli like temperature and pH. Achieving a narrow molecular weight distribution is crucial for their sensitivity. Reversible addition–fragmentation chain transfer (RAFT) in ionic liquids is an effective method for synthesizing such polymers due to its favorable kinetics and environmental benefits. Most studies use imidazolium ionic liquids, while pyridinium ionic liquids are less common despite their easy synthesis. This study reports the first successful RAFT copolymerization of di(ethylene glycol) methyl ether methacrylate (DEGMEMA) and methyl methacrylate in N‐hexylpyridinium hexafluorophosphate ([HPY][PF6]). Both linear and hyperbranched copolymers (Mn &gt; 25,000) with narrow molecular weight distribution were synthesized, showing observable temperature responses and biocompatibility. The linear copolymers had a desirable dispersity (Ð) of less than 1.10, while the hyperbranched copolymer had a Ð of 2.034. The lower critical solution temperatures (LCSTs) of the copolymers were close to or below the LCST of PDEGMEMA (26°C). This study indicates that pyridinium ionic liquids can be explored as a suitable solvent for synthesizing methacrylate‐based smart polymers.

Triple passivation strategy for ultra-stable luminous CsPbBr3 NCs-Acrylate based films as backlight display

To improve the stability of CsPbBr3 nanocrystals (NCs), triple protection strategies were performed to obtain the ultra-stable films, including fluorinated hydrophobic film surface, polymer coating and silica encapsulation. CsPbBr3 QDs@SiO2 nanoparticles (SiPNCs) were prepared with well-dispersed NCs (8 nm) within acrylate-modified silica-shell. Polymer@SiPNCs (poly@SiPNCs) films were prepared by copolymerization of methyl methacrylate (MMA), 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl methacrylate (DFHM) and SiPNCs under ultraviolet (UV) light. Compared to CsPbBr3 NCs solution, SiPNCs solution had well maintained light absorption and emission wavelengths of ∼509 nm and ∼522 nm respectively. High SiPNCs content resulted in enhanced micro/nano structure and increased roughness on the surface of poly@SiPNCs film. With increasing SiPNCs content, water contact angles (WCAs) of poly@SiPNCs films reached 126 ± 2.4°, 137.3 ± 1.3° and 141.5 ± 1.9° respectively. This fabricated poly@SiPNCs film exhibited much improved stabilities to water and UV light, even after 90 days of water immersion and 120 h of UV irradiation. White light-emitting-diode (LED) device emitted bright pure white light. This work will boost a large-scale preparation of stable QDs films as backlight display.

Carbon microspheres/carbon sheets as efficient electromagnetic wave absorbers

To address the issue of weak absorption intensity and narrow frequency band in pure dielectric electromagnetic wave (EMW) absorbing materials, this study adopts a simple method to successfully prepare a pure dielectric EMW absorption material by modifying acrylonitrile–methylmethacrylate copolymer carbon microspheres (co-AN-MMA@CS) with capsaicin-like 3,5-dimethylphenol derivative (DMPD). The introduction of DMPD into the carbon microspheres increases the heteroatoms (N, O) in the carbon material, thus resulting in functional groups (-C-N, –NO, and C–O) that enable energy loss through dipole polarization. Additionally, the special morphology of carbon microspheres attached or embedded in carbon sheets derived from DMPD increases the inhomogeneous interfaces, thereby increasing the interface polarization relaxation and further attenuating EMWs. The resulting carbon material with the optimal structure (denoted as CNO-2) exhibits superior EMW absorption properties. At a thickness of 2.50 mm, the minimum reflection loss (RLmin) reaches −63.10 dB at 13.14 GHz, whereas the maximum effective absorption bandwidth (EABmax) reaches 6.81 GHz (8.95–15.76 GHz). CNO-2 has excellent EMW absorption capabilities due to the controllable complex dielectric constant and multiple attenuation mechanisms, including interfacial polarization, dipole polarization, and conduction loss. The CNO absorbers prepared in this study can be used as efficient microwave absorbers for electromagnetic protection applications.

Adaptable intelligent filters based on nanotextured nonwoven membranes containing water-insoluble hydrogels

The work demonstrates, for the first time, thermo-responsive, water-insoluble, hydrogel-based, nano-fibrous filter media comprised of copolymers of N-isopropylacrylamide (NIPAM) and methyl methacrylate formed by electrospinning. Moreover, a comprehensive novel physical explanation of all aspects responsible for the physical mechanisms resulting in the thermo-responsive regulation of the water flow rate and an enhanced interception of nanoparticles by such filter membranes is given. They are the wettable-non-wettable transition, pore, and fiber-size changes, as well as a diminishing filter thickness at the lower critical solution temperature (LCST) of the copolymers developed here, which interplay with a significant reduction in the water viscosity with temperature. Poly(N-isopropylacrylamide) (PNIPAM) hydrogel is an attractive material because of its thermo-responsive properties. Its wettability changes with water temperature. This characteristic holds great promise for the development of advanced filter media and related responsive materials. In this study, PNIPAM hydrogels were designed and transformed into filter membranes for applications in water filtration in biomedical and other related systems. These thermo-responsive filter membranes offer the potential for enhanced filtration efficiency, selectivity, and the overall system performance. Here, two different procedures were adopted to form water-insoluble thermo-responsive filter media based on PNIPAM hydrogels. The PNIPAM-based hydrogels were electrospun, resulting in the formation of thermo-responsive water-insoluble nanofiber membranes. These membranes underwent a series of comprehensive experiments to assess their performance and characteristics, including mass loss, water droplets for the wettability assessment, filtration tests, shrinkage measurements, and microscopic observations. These diverse experiments yield a full understanding of the PNIPAM-based nanofiber membranes’ properties and their potential applications.

Bulk Depolymerization of Methacrylate Polymers via Pendent Group Activation.

In this study, we present an efficient approach for the depolymerization of poly(methyl methacrylate) (PMMA) copolymers synthesized via conventional radical polymerization. By incorporating low mol % phthalimide ester-containing monomers during the polymerization process, colorless and transparent polymers closely resembling unfunctionalized PMMA are obtained, which can achieve >95% reversion to methyl methacrylate (MMA). Notably, our catalyst-free bulk depolymerization method exhibits exceptional efficiency, even for high-molecular-weight polymers, including ultrahigh-molecular-weight (106-107 g/mol) PMMA, where near-quantitative depolymerization is achieved. Moreover, this approach yields polymer byproducts of significantly lower molecular weight, distinguishing it from bulk depolymerization methods initiated from chain ends. Furthermore, we extend our investigation to polymethacrylate networks, demonstrating high extents of depolymerization. This innovative depolymerization strategy offers promising opportunities for the development of sustainable polymethacrylate materials, holding great potential for various applications in polymer science.

Charge transport mechanism and trap origin in methyl methacrylate copolymer with thioxanthenone side groups

The transverse charge transport mechanism in a specially synthesized novel methyl methacrylate copolymer containing 2 % electron-accepting 9H-thioxanthene-9-one side groups (poly(MMA-co-ThS)) has been studied experimentally and theoretically. These side groups are shown to be deep electron traps. The charge transport in poly(MMA-co-ThS) is governed by the model of phonon-assisted tunneling between traps. The optical ionization trap energy (Wopt = 1.8 eV), independently determined by a reduction spectroelectrochemical method, confirms the validity of the phonon-assisted tunneling model used to describe charge transport in organic dielectrics with high content of electron traps.

Enhanced flame retardancy and thermal stability in flexible polyurethane foam through synergistic core-shell structured DBDPE@PMA particles

This research presents the synthesis of core–shell structured flame retardant particles, DBDPE@PMA, which combines the flame-retardant and toughening functions. These particles utilize decabromodiphenyl ethane (DBDPE) as the core and a copolymer of methyl methacrylate and acrylic acid (MMA-AA) as the shell, which are created via emulsion polymerization. The process involved an initial reaction of DBDPE@PMA with isocyanate, followed by foaming with polyether polyol to fabricate flame retardant, and the flexible polyurethane foam (P/D-FPUF) was thermally insulated. The study examined the influence of DBDPE@PMA on the flame retardancy properties of flexible polyurethane foam. Scanning electron microscopy confirmed the encapsulation of DBDPE by the polymer, resulting in a core–shell composite particle. The interaction between the carboxylic groups (–COOH) on the DBDPE@PMA shell and isocyanate enhanced the interfacial bonding, thereby increasing the foam's apparent density and ensuring better integration with the polyurethane matrix. However, DBDPE@PMA had aggregates on the foam matrix bubble holes, resulting in uneven bubble holes. DBDPE@PMA markedly improved the flame retardancy and thermal stability of the foam, compared to both pure polyurethane and foam containing solely DBDPE (10D-FPUF). The oxygen index value of the foam with 20% DBDPE@PMA (20P/D-FPUF) reached 33.6%, with UL-94 horizontal and Vertical burning level tests achieving the highest classifications. The char residue after thermal degradation increased significantly from 1.93% in pure foam to 5.06%. While the smoke density level rose, the duration to peak smoke density was prolonged to 78 s, offering an enhanced margin for evacuation during the initial stages of a fire.

Preparation and Characterization of Chloroprene Latexes Modified with Vinyl-POSS.

Water-based chloroprene latex is a solvent-free, environmentally friendly adhesive. Currently, its market demand is growing rapidly. However, there are problems such as a lack of heat resistance and poor mechanical properties, which limit its application. The introduction of vinyl-POSS (OVS) into the resin structure can effectively improve the thermal stability of chloroprene adhesives. In this paper, modified waterborne chloroprene latex was prepared by copolymerization of methyl methacrylate and OVS with chloroprene latex. The results showed that vinyl-POSS was successfully grafted onto the main chain of the waterborne chloroprene latex, and the modified waterborne chloroprene latex had good storage stability. With the increase in vinyl-POSS, the tensile strength of the chloroprene latex firstly increased and then decreased, the tensile property (peel strength of 20.2 kgf) was maintained well at a high temperature (100 °C), and the thermal stability of the chloroprene latex was improved. When the addition amount was 4%, the comprehensive mechanical properties were their best. This study provides a new idea for the construction of a new and efficient waterborne chloroprene latex system and provides more fields for the practical application of waterborne chloroprene latex. This newly developed vinyl-POSS modified chloroprene latex has great application potential for use in home furniture, bags, and seat cushions.

Preparation of reed fibers reinforced graft-modified starch-based adhesives based on quantum mechanical simulation and molecular dynamics simulation

Starch is a biomass polymer material with a high yield and comprehensive source. It is used as a raw material for preparing adhesives because of its highly active hydroxyl group. However, poor adhesion and water resistance hinder the application of starch-based adhesives (SBAs). Based on this, the starch was modified through graft copolymerization with itaconic acid as a cross-linking agent, methyl methacrylate and methyl acrylate as copolymers. Additionally, reed fibers were synergistically modified with polydopamine deposition to prepare an environmentally friendly SBA used in plywood production. Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (1H NMR), X-ray diffraction (XRD), and thermogravimetric analysis (TG) demonstrate that copolymerization of methyl methacrylate and methyl acrylate with starch improves the shear strength, water resistance, and thermal stability of the SBA. Compared to unmodified starch, the modified SBA exhibits a 129 % increase in dry strength and achieves a wet strength of 1.36 MPa. Fukui function, Frontier orbit theory, and molecular dynamics simulation have shown that itaconic acid promotes the copolymerization of starch and acrylate monomers. The modified starch has fewer hydrogen bonds, less order, and a denser macromolecular network structure, which provides a reference for studying the molecular interaction mechanisms of SBAs.

Fabrication of pH-Responsive Amphiphilic Poly(Vinyl Alcohol–Methyl Methacrylate) Copolymer Nanoparticles for Application in Cancer Drug Delivery Systems

Fabrication of pH-Responsive Amphiphilic Poly(Vinyl Alcohol–Methyl Methacrylate) Copolymer Nanoparticles for Application in Cancer Drug Delivery Systems

Printable Single‐Ion Polymer Nanoparticle Electrolytes for Lithium Batteries

New material solutions are searched for the manufacturing and safety of current batteries. Herein, an extrusion printable polymer separator for lithium batteries based on single‐ion polymer electrolytes is presented. The polymer electrolytes are based on methacrylic polymeric nanoparticles (NPs) functionalized with a lithium sulfonamide group combined with different organic plasticizers such as sulfolane and carbonates. The synthesis of the polymer NPs is carried out by emulsion copolymerization of methyl methacrylate and lithium sulfonamide methacrylate in the presence of a crosslinker, resulting in particle sizes of less than 30 nm, as shown by electron microscopy. Then polymer electrolytes are prepared by mixing polymer NPs with varying lithium sulfonamide content and different plasticizers such as carbonates and sulfolane. The polymer electrolytes show ionic conductivities between 2.9 × 10−4 and 2.3 × 10−5 S cm−1 at 85 °C with the highest values for the small‐sized NPs with the highest lithium content. As a proof‐of‐concept application, layer‐by‐layer printing of a sulfolane‐based polymer electrolyte is evaluated via direct ink writing directly onto classic battery electrodes. The electrochemical characterization of the printed solid electrolyte indicates favorable properties, ionic conductivity, lithium transfer number, electrochemical stability window, and cyclability in lithium symmetrical cells, to be used in lithium batteries.

2D ZIF-L(Zn) for Hybrid Copolymerization of Methyl Methacrylate and ε-Caprolactone under Solvent-free Medium

Herein, we report the hybrid copolymerization of methyl methacrylate (MMA) and ε-caprolactone (CL). 2D metal-organic frameworks, ZIF-L as a robust polymerization catalyst, can catalyze this hybrid copolymerization. Though these monomers differ from each other in structure and activity, different characterization techniques (1H-NMR, 13C-NMR, GPC, DSC, fractional precipitation techniques) confirm that they form biodegradable block copolymer PMMA-b-PCL with high molecular weight (1190 kg/mol). Also, PXRD and SEM results of the recovered ZIF-L reveal that the catalyst ZIF-L is remarkably stable even after a long-time polymerization reaction with no significant loss in activity.

PH-Sensitive Acrylic Terpolymers for the Coating of Orally Administered Drugs Used for Colonic Release.

Polymeric coatings are a promising option for the development of delivery systems for orally administered drugs. However, the gastrointestinal conditions to which they are subjected, which include low pH and solubility as well as peristaltic movements, can limit their applications. In this work, different formulations of polymeric coatings were produced using pH-sensitive materials consisting of copolymers of methyl acrylate, methyl methacrylate, and methacrylic acid. The polymers were synthesized by the emulsion polymerization technique, obtaining small average particle sizes (56-190 nm), molecular weights between 200,000 and 400,000 g/mol, and a glass transition temperature above 35 °C, which are suitable for film formation at room temperature. Thus, they were assessed as coatings for hydroxypropyl methylcellulose capsules (HPMC) using the immersion method, showing adequate capacity to protect the capsule at gastric pH (pH 1.2) and dissolve at the simulated intestinal pH (pH= 7.2). In particular, the higher the content of the acidic monomer, the higher the release time of the test molecule contained in the acrylic terpolymer-coated HPMC capsules proposed, which was a curcuminoid derivative due to their bright color and potential medical benefits. In addition, a minimum number of immersions was required for coating the HPMC capsules at high acidic concentrations, which further facilitates the delayed release needed for colonic treatment. However, too high proportions of methacrylic acid may result in cytotoxicity issues. Consequently, a biocompatible formulation containing a proportion of methyl acrylate, methyl methacrylate, and methacrylic acid of 7:3:3 is proposed as the most adequate for colonic release. Thus, by chemically modulating the molar percentages of the acrylic monomers, it was possible to obtain tailored acrylic terpolymer coatings with different characteristics and desired properties in order to modulate the release kinetics of an active substance in a colonic environment.