Acrylic Monomers Research Articles

Using the Polymerization of Acrylic Monomers for the Treatment and Conservation of a Historical Piece in the Agricultural Museum, Dokki “An Applied Study”

Using the Polymerization of Acrylic Monomers for the Treatment and Conservation of a Historical Piece in the Agricultural Museum, Dokki “An Applied Study”

Acrylate-Induced β-H Elimination in Coordination Insertion Copolymerizaton Catalyzed by Nickel.

Polar monomer-induced β-H elimination is a key elementary step in polar polyolefin synthesis by coordination polymerization but remains underexplored. Herein, we show that a bulky neutral Ni catalyst, 1Ph, is not only a high-performance catalyst in ethylene/acrylate copolymerization (activity up to ∼37,000 kg/(mol·h) at 130 °C in a batch reactor, mol % tBA ∼ 0.3) but also a suitable platform for investigation of acrylate-induced β-H elimination. 4Ph-tBu, a novel Ni alkyl complex generated after acrylate-induced β-H elimination and subsequent acrylate insertion, was identified and characterized by crystallography. A combination of catalysis and mechanistic studies reveals effects of the acrylate monomer, bidentate ligand, and the labile ligand (e.g., pyridine) on the kinetics of β-H elimination, the role of β-H elimination in copolymerization catalysis as a chain-termination pathway, and its potential in controlling the polymer microstructure in polar polyolefin synthesis.

Graft copolymer of tannin and polyvinyl alcohol with acrylic acid for the preparation of hydrophobic biodegradable film

Using CaCl2-H2O2 as the initiator, hydrophobic tannin-acrylic resin (TA) was prepared by grafting acrylic monomers onto tannins through redox reaction. Subsequently, biodegradable TA-polyvinyl alcohol (PVOH) hydrophobic film (TAP) was prepared by blending TA with PVOH at room temperature. The results of Fourier transform infrared spectroscopy (FT-IR) and Electro Spray Ionization Mass Spectroscopy (ESI-MS) showed that polypropylene undergoes graft copolymerization at position 8 of the A-ring in tannin and acrylic monomers. The results of Gel Permeation Chromatography (GPC) showed that the blending of TA resin with PVOH resulted in a higher molecular weight and denser network structure of the film. The preparation process of TAP film is simple, with room temperature curing and no surface pores and cracks. Moreover, the addition of TA transforms hydrophilic PVOH films into hydrophobic films, with a water contact angle of up to 110°. At the same time, TAP films have higher Brinell hardness and elongation at break compared to PVOH film. In addition, thermogravimetric analyzer (TG) and ultraviolet visible light (UV–Vis) measurements showed that the TAP film has good thermal stability and excellent resistance to UV–Vis. More importantly, the TAP film was found to have good biodegradability against Penicillium sp. Scanning electron microscopy (SEM) observed that the TAP film was degraded by Penicillium sp. after 15-days exposure.

Photoinitiators with low migration capability based on benzophenone

Due to the increasing safety concerns caused by migration of photoinitiators, the development of low migration photoinitiators has become a priority in the current stage. As a widely used Type II photoinitiator, benzophenone is known to cause the migration of residual small molecule initiators and co-initiators after photopolymerization, leading to safety issues and severely limiting its applications. In this work, a polymerizable photoinitiator (VBP) was synthesized by directly introducing an ethylene group into benzophenone, three different molecular weight single-component photoinitiators PVBN1-3 were synthesized based on VBP. The characterization was conducted by using spectroscopic techniques, revealing stronger absorption ability in the range of 200–330 nm compared to benzophenone. The initiation efficiency of the acrylic monomer by PVBN1-3 was evaluated by using real-time FT-IR technique. The migration stability of the cured system was investigated through immersion extraction. The results demonstrate that VBP and PVBN1-3 are a series of high-performance, low-migration photoinitiators.

Synthesis and performance of novel fluoro acrylate polymer containing rigid cyclohexane group as a mesogenic core

Fluorine-containing liquid crystal polymers have excellent hydrophobic stability, making them attractive for use in the field of stable hydrophobic coatings. To improve the hydrophobic stability of fluoropolymers, a novel fluoro acrylate monomer (FAM) containing a rigid cyclohexane structure was simply synthesized using isophorone diisocyanate (IPDI), hydroxyethyl methacrylate (HEMA), and perfluorohexylethanol (S104) as raw materials and its homopolymer (PFAM) was prepared by radical solution polymerization. The structure, liquid crystal behavior, thermal properties, hydrophobic properties, and surface properties of FAM or PFAM and a reference substance, dodecafluoroheptyl methacrylate (DFMA) and its homopolymer (PDFMA), were studied using various techniques including FT-IR, NMR, GPC, XRD, POM, DSC, TGA, XPS, AFM, and static/dynamic contact angle measurements. The results indicate that FAM and PFAM are thermally liquid crystalline. PFAM's thermal stability is higher than that of PDFMA. The presence of a rigid cyclohexane structure facilitates the dense distribution of fluorocarbon chain tails of the homopolymer and also prevents surface reconstruction when the homopolymer comes into contact with polar liquids, resulting in improved hydrophobicity and hydrophobic stability. Thus, this study provides a straightforward method for the synthesis of fluoro acrylates with surface stability, highlighting their potential application in hydrophobic coatings.

Nonflammable Polyfluorides-Anchored Quasi-Solid Electrolytes for Ultra-Safe Anode-Free Lithium Pouch Cells without Thermal Runaway.

The safe operation of rechargeable batteries is crucial because of numerous instances of fire and explosion mishaps. However, battery chemistry involving metallic lithium (Li) as the anode is prone to thermal runaway in flammable organic electrolytes under abusive conditions. Herein, an in situ encapsulation strategy is proposed to construct nonflammable quasi-solid electrolytes through the radical polymerization of a hexafluorobutyl acrylate (HFBA) monomer and a pentaerythritol tetraacrylate (PETEA) crosslinker. The quasi-solid system eliminates the inherent flammability of ether electrolytes with zero self-extinguishing time owing to the gas-phase radical capturing ability of HFBA. Additionally, the graphitized carbon layer generated during the decomposition of PETEA at high temperatures obstructs the heat and oxygen required for combustion. When coupled with Au-modified reduced graphene oxide anodic current collectors and lithium sulfide cathodes, the assembled anode-free Li-metal cell based on the quasi-solid electrolyte exhibits no signs of cell expansion or gas generation during cycling, and thermal runaway is eliminated under multiple mechanical, electrical, and thermal abuse scenarios and even rigorous strikes. This nonflammable quasi-solid configuration with gas- and condensed-phase flame-retardant mechanisms can drive a technological leap in anode-free Li-metal pouch cells and secure the practical applications necessary to power this society in a safe manner.

Polyurethane/acrylic coatings for wood made hydrophobic by melamine addition

Hydrophobic polyurethane/acrylic hybrid dispersions were obtained for exterior wood coatings. Thus, polyurethane was synthesised using as solvent methyl methacrylate, and after phase inversion provoked by water addition, the acrylic monomer radically polymerised giving rise to the polyurethane/acrylic hybrid dispersion. Melamine was added as a hydrophobic and fire retardant additive by two different approaches: in the phase inversion (A) and the beginning of the synthesis (B). FTIR-ATR, 1H NMR, and molar mass measurements (AF4/MALS/RI) showed that in the B method, the melamine reacted with isocyanate. However, the addition of melamine in the phase inversion provoked a reduction of the molecular weight of the acrylic part because of the interaction with the radical initiator. According to TGA, Pyrolysis Combustion Flow Calorimetry (PCFC), and water permeation experiments, melamine induced the formation of a carbonaceous char when heating and reduced the water vapour transmission rate of the hybrid films. Moreover, wood application tests showed that the incorporation of melamine improved the transparency, adhesion, and water resistance of the coatings but the employed amount was not enough to produce significant changes in the fire behaviour of the coatings measured in the cone calorimetry.

On-line extraction and determination of coumarins compounds from mouse plasma based on a homemade phenyl-hybrid monolithic adsorbent

A phenyl-hybrid monolithic adsorbent was prepared using an organic monomer of ethylene glycol phenyl ether acrylate and inorganic monomers of tetramethoxysilane and vinyltrimethoxysilane, via polycondensation and polymerization in a stainless-steel column, which shows porous structure and multiple functional groups, according to the measurements of scanning electron microscopy, nitrogen adsorption-desorption method and infrared spectroscopy. The resulting hybrid phenyl-based monolith was used as a solid-phase extraction column, combining with an analytical column in conjunction with high-performance liquid chromatography system for the on-line extraction and determination of coumarins (praeruptorin A and praeruptorin B) in Peucedani Radix from mouse plasma. The homemade hybrid monolithic solid-phase extraction column exhibits good removal ability for the sample matrices, as well as unique selectivity for the two praeruptorins. Methodology validation results indicate that the present method is applicable for the on-line extraction and quantitative analysis of praeruptorin A and praeruptorin B in Peucedani Radix from mouse plasma with a limit of quantitation 0.06 μg/mL and a linear range 0.06–5 μg/mL (r＞0.999), thus indicating the present method is a promising and alternative method for the quantitative determination of similar target components with micro or trace concentration from complex extract solution and plasma.

A crosslinked waterborne poly(urethane‐urea) oligomer enables mechanically strong waterborne polyacrylate–poly(urethane‐urea) hybrid films with superior film‐forming ability

AbstractIn this article, a crosslinked waterborne poly(urethane‐urea) (WPUU) is synthesized based on the terminal aromatic amine polyether (DP‐1000) and aliphatic isophorone diisocyanate. Then WPUU is compound with acrylate monomer by emulsion polymerization to produce waterborne polyacrylate–poly(urethane‐urea) (WPUUA) hybrid emulsions. Compared with waterborne polyacrylate (WPA) film, the film‐forming ability of WPUUA film is improved and the surface roughness Ra and Rq of WPUUA film decreases from 47.5 and 36.4 nm to 35.2 and 18.8 nm, respectively. Meanwhile, the mechanical properties of WPUUA films are significantly improved compared to WPA film. In addition, the performances of WPUUA hybrid films can be modified according to requirements by adjusting the molar ratio between DP‐1000 and polyisocyanate. As a result, these WPUUA hybrid emulsions have great application potential in waterborne coatings and other fields.

Properties of dispersions and films made of copolymers obtained from acrylic, methacrylic and vinyl monomers

AbstractThe following paper presents a study of water dispersion obtained by emulsion co-polymerization of acrylic, methacrylic and vinyl monomers with the use of surfactants. Water dispersions of copolymers used in the production of paints intended for painting surfaces of steel metals and aluminum and its alloys were selected. They were synthesized by ethyl acrylate, butyl acrylate, acrylic acid, methyl methacrylate, methacrylic acid, acrylic acid amide, 2-hydroxyethylacrylate, glycidyl methacrylate, vinyl acetate and 1-ethyl-1-ethylpropylcarbamate (VeoVa 10). The investigated dispersion properties were considered in three groups. It turned out that the dispersions in which the copolymer had the lowest crystallinity temperature and were built of units having hydroxyl, carboxyl or amide groups were characterized by the most favorable properties. The hardness and weight of the membranes changed the least in the case of copolymers consisting of many units with functional groups. Graphical abstract

Unique Polymer-Stabilized Liquid Crystal Structure Prepared by Addition of a Reversible Addition-Fragmentation Chain Transfer Agent.

Polymer-stabilized liquid crystals (PSLCs) are important electrically switchable materials due to their superior electro-optical properties. Nevertheless, it remains a formidable challenge to balance PSLCs' instant electro-optical performance and long-term durability due to their relatively low polymer content and the related sensitivity to external force. Herein, we demonstrate the possibility of regulating the polymer network structure in PSLCs via reversible addition-fragmentation chain transfer (RAFT) polymerization reactions of acrylate monomers with a chain transfer agent (CTA). By controlling the concentration of CTA and conditions of photopolymerization, the kinetics of the polymerization reaction can be modified. Compared to conventional free-radical (FR) polymerization, the reduced chain growth rate leads to sufficient chain relaxation, reorientation of liquid crystal (LC) directors, and alleviation of shrinkage stresses in the RAFT polymerization process. This in turn produces an ordered polymer network structure in the vertical direction and a uniform distribution in the horizontal plane. As a result, the PSLC network presents increased elasticity with a lower hysteresis effect and greatly improved durability. Our research offers insightful guidance for the fine-tuning of polymer network structures to prepare advanced LC/polymer composite structures with outstanding performances.

A Methodology for Multivariate Investigation on the Effect of Acrylate Molecular Structure on the Mechanical Properties and Delivery Efficiency of Microcapsules via In Situ Polymerization.

In the field of encapsulation, microcapsules containing perfume have emerged as effective vehicles for delivering active ingredients across various applications. The present study employed a multivariate analysis framework to examine polyacrylate microcapsules for household products synthesized using different acrylate monomers. The advanced multivariate approach allowed us to quantify critical properties such as the Molecular Weight between Cross-links (MWc), mechanical attributes, Encapsulation Efficiency (EE), and On-Fabric delivery. It is worth noting that the mechanical properties were gauged using a novel nanoindentation technique, which measures the Rupture Force per unit diameter (RFD). Both Encapsulation Efficiency and On-Fabric delivery were assessed using GC-MS. Our findings identified the optimal microcapsule system as one synthesized with 100% aromatic hexafunctional urethane acrylate, showcasing a 94.3% Encapsulation Efficiency and an optimal RFD of 85 N/mm. This system achieved an exemplary On-Fabric delivery rate of 307.5 nmol/L. In summary, this research provides crucial insights for customizing microcapsule design to achieve peak delivery efficiency. Furthermore, by designing acrylic monomers appropriately, there is potential to reduce the amount of active ingredients used, owing to enhanced delivery efficiency and the optimization of other microcapsule properties. Such advancements pave the way for more environmentally friendly and sustainable production processes in the fast-moving consumer goods industry.

Biomass RNA for the Controlled Synthesis of Degradable Networks by Radical Polymerization.

Nucleic acids extracted from biomass have emerged as sustainable and environmentally friendly building blocks for the fabrication of multifunctional materials. Until recently, the fabrication of biomass nucleic acid-based structures has been facilitated through simple crosslinking of biomass nucleic acids, which limits the possibility of material properties engineering. This study presents an approach to convert biomass RNA into an acrylic crosslinker through acyl imidazole chemistry. The number of acrylic moieties on RNA was engineered by varying the acylation conditions. The resulting RNA crosslinker can undergo radical copolymerization with various acrylic monomers, thereby offering a versatile route for creating materials with tunable properties (e.g., stiffness and hydrophobic characteristics). Further, reversible-deactivation radical polymerization methods, such as atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT), were also explored as additional approaches to engineer the hydrogel properties. The study also demonstrated the metallization of the biomass RNA-based material, thereby offering potential applications in enhancing electrical conductivity. Overall, this research expands the opportunities in biomass-based biomaterial fabrication, which allows tailored properties for diverse applications.

Membrane-Active Thermoresponsive Block Copolymers Containing a Diacylglycerol-Based Segment: RAFT Synthesis, Doxorubicin Encapsulation, and Evaluation of Cytotoxicity against Breast Cancer Cells.

Herein, we report the formation of drug delivery systems from original thermoresponsive block copolymers containing lipid-based segments. Two acrylate monomers derived from palmitic- or oleic-acid-based diacylglycerols (DAGs) were synthesized and polymerized by the reversible addition-fragmentation chain transfer (RAFT) method. Well-defined DAG-based polymers with targeted molar masses and narrow molar mass distributions were next used as macro-chain transfer agents (macro-CTAs) for the polymerization of N-isopropylacrylamide (NIPAAm) or N-vinylcaprolactam (NVCL). The obtained amphiphilic block copolymers were formed into polymeric nanoparticles (PNPs) with and without encapsulated doxorubicin and characterized. Their biological assessment indicated appropriate cytocompatibility with the representatives of normal cells. Furthermore, compared to the free drug, increased cytotoxicity and apoptosis or necrosis induction in breast cancer cells was documented, including a highly aggressive and invasive triple-negative MDA-MB-231 cell line.

Synthesis, Characterization, and Energetic Properties of Nitrate Ester Acrylate Polymer.

An energetic nitrate ester acrylate monomer (4) was synthesized in a total yield of 68% and polymerized to form the energetic nitrate ester acrylate polymer (NEAP). Compound 4 is a liquid at room temperature with a melting point of -8.6 °C and NEAP is a solid with a glass-transition temperature of -8.8 °C. Intermediates leading to 4 and NEAP were characterized by high-resolution mass spectrometry, elemental analysis, Fourier transform infrared spectroscopy, and proton and carbon nuclear magnetic resonance spectroscopies (1H and 13C{1H} NMR). Both 4 and NEAP have electrostatic discharge, friction, and impact sensitivities comparable to those of trinitrotoluene, making NEAP a potential candidate for advanced energetic formulations.

Hydrogels and their composites based on sulfo-containing acrylates: preparation, properties, and proton conductivity

This work presents a method for the synthesis of multifunctional hydrogels based on polymer framework obtained by UV-initiated polymerization of the acrylic monomers (acrylamide, acrylonitrile, and sulfo-group-containing monomer (3-sulfopropyl acrylate potassium salt, 2-acrylamido-2-methylpropane sulfonic acid, and sodium styrene sulfonate)) in the presence of N,N′-methylenebisacrylamide as a cross-linking agent. Composite polymer/silica nanogels have been created in situ using a TEOS-based sol–gel system and the above-mentioned polymeric matrices. The synthesized material characteristics such as composition, morphology, and thermal stability were explored with FTIR, SEM, and DCS. In addition, the effect of temperature, inorganic component content, sulfo-group-containing monomer to proton conductivity and water uptake have been explored. The obtained hydrogels possess proton conductivity up to 19 mSm/cm with potential implying for application in electrochemical devices and superabsorbent material. This method is user-friendly and cost-efficient, and proceeds in an aqueous environment under atmospheric conditions without the use of heavy metal catalysts.

Influencing ionic conductivity and mechanical properties of ionic liquid polymer electrolytes by designing the chemical monomer structure

ABSTRACTPolymeric single chloride-ion conductor networks based on acrylic imidazolium chloride ionic liquid monomers AACXImCYCl as reported previously are prepared. The chemical structure of the polymers is varied with respect to the acrylic substituents (alkyl spacer and alkyl substituent in the imidazolium ring). The networks are examined in detail with respect to the influence of the chemical structure on the resulting properties including thermal behavior, rheological behavior, swelling behavior, and ionic conductivity. The ionic conductivities increase (by two orders of magnitude from 10−6 to 10−4 S·cm−1 with increasing temperature), while the complex viscosities of the polymer networks decrease simultaneously. After swelling in water for 1 week the ionic conductivity reaches values of 10−2 S·cm−1. A clear influence of the spacer and the crosslinker content on the glass transition temperature was shown for the first time in these investigations. With increasing crosslinker content, the Tg values and the viscosities of the networks increase. With increasing spacer length, the Tg values decrease, but the viscosities increase with increasing temperature. The results reveal that the materials represent promising electrolytes for batteries, as proven by successful charging/discharging of a p(TEMPO-MA)/zinc battery over 350 cycles.

Pseudoplastic liquid mulch film incorporating waste lignin and starch to improve its sprayability and available soil nitrogen

Because traditional slow-release fertilizers cannot effectively retain soil heat and moisture, their ability to increase crop yields is limited. To solve this problem, novel sprayable liquid mulch films (lignin-starch-acrylate, LSA) were prepared with a slow-release urea function, created by emulsion polymerization between lignin (extracted from papermaking waste liquor), starch, and acrylate monomers. The introduction of lignin transformed the LSA emulsion into a pseudoplastic fluid with enhanced sprayability. The presence of lignin in LSA film increased the elongation at break and lowered the Young's modulus, resulting in a film that is more easily pierced by crop seedlings and preserves the heat and moisture of the soil after seedling piercing. Experimental results showed that at a mass ratio of lignin to acrylate monomers of 3/7, the LSA mulch film had good sprayability and film-forming properties, suitable mechanical properties, and the lowest urea release rate. This optimized LSA film exhibited better soil insulation and water retention performance than other slow-release fertilizers. The contents of available soil nitrogen, including NH4+-N and NO3−-N, in soil covered with LSA film were 44.82 and 45.49% higher than those in soil covered with urea, respectively, and the corresponding cabbage yields increased by 33.73%. The results of this study provide a new method for preparing agricultural materials with urea slow-release as well as soil moisture and heat preservation functions.

Synthesis of water-soluble tetrafunctional urethane acrylate bearing a pentaerythritol core and its radical polymerization behaviors in an aqueous solution

A novel water-soluble tetrafunctional urethane acrylate (TUA) was successfully synthesized by addition reaction of pentaerythritol to 2-isocyanatoethyl acrylate. TUA efficiently underwent radical polymerization and its copolymerization with monofunctional acrylate monomers exhibiting hydrophilicity in an ethanol aqueous solution, affording corresponding networked polymers in high yields. Notably, TUA exhibited much lower volume shrinkage during the radical polymerization compared to a comparative pentaerythritol core based tetrafunctional acrylate containing no urethane bonds. The thermal decomposition temperature of the networked homopolymer, synthesized from TUA, was much higher than those of the linear polymers, synthesized from monofunctional urethane acrylate monomers. TUA is expected to be applied to the development of environmentally sustainable polymer materials.

Effect of novel furan‐based ester reactive diluent on structure and properties of UV‐crosslinked acrylated rapeseed oil

AbstractUnsaturated furan‐based ester (UES) was prepared by green electrosynthesis using a single‐cell setup and inexpensive graphite electrodes. The UES was validated as a reactive diluent for a bio‐based acrylated rapeseed oil (ARO). UV‐light photopolymerization of the bio‐based resin was initiated using a diphenyl (2,4,6‐trimethylbenzoyl)phosphine oxide (TPO) radical photoinitiator. The addition of 20 wt% UES to ARO dropped the resin viscosity by 1.6‐fold. Incorporating 5 wt% UES into the ARO resin increased crosslinking density νe from 1.07 to 1.65 mol/m3. Fourier‐transform infrared spectroscopy (FT‐IR) spectra revealed that ARO has been grafted with UES. The UES functional moieties promote the formation of soft mobile dangling chain end segments in the developed macromolecular network. UV‐cured thermoset polymer reveals distinct morphologies in SEM micrographs, indicating notable structural changes with the addition of UES. A total of 5 wt% UES increased tensile strength from 0.49 to 0.55 MPa and storage modulus from 7.9 to 12.0 MPa at room temperature (22 ± 1 °C). The biodegradability in composting conditions was investigated, and up to 28% of the initial mass was lost after 60 days. UES was shown as to be efficient reactive diluent that can successfully replace fossil‐based acrylate monomers in vegetable oil‐based thermoset polymer synthesis.