Functional Acrylate Monomers Research Articles

Limonene as biobased building block for functional monoterpene acrylate monomers

Abstract Limonene, a widely used natural raw material, provides an excellent basis for the synthesis of functional acrylate monomers. The presence of two double bonds in this monoterpene enables a twofold functionalization, enhancing its versatility for various chemical modifications. By incorporating an acrylate functionality, the polymerization potential of this terpene is significantly increased, allowing for the production of polymers with high conversion rates. The introduction of additional functional groups also makes the synthesized polymers suitable for applications requiring subsequent crosslinking or specialized material properties. Besides the mono- and bifunctional acrylate monomers, variants with additional hydroxyl and epoxide groups were synthesized. These considerably extend the versatility and application possibilities of the compounds. As proof of concept, free radical polymerization of the monomers was demonstrated in this work, and the reaction was determined by differential scanning calorimetry. The resulting polymers exhibit glass transition temperatures between 83 and 96°C, making them suitable for use in, e.g., coating systems.

Molecularly imprinted polymer nanoparticles-based electrochemical chemosensors for selective determination of cilostazol and its pharmacologically active primary metabolite in human plasma

Molecularly imprinted polymer (MIP) nanoparticles-based differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) chemosensors for antiplatelet drug substance, cilostazol (CIL), and its pharmacologically active primary metabolite, 3,4-dehydrocilostazol (dhCIL), selective determination in human plasma were devised, prepared, and tested. Molecular mechanics (MM), molecular dynamics (MD), and density functional theory (DFT) simulations provided the optimum structure and predicted the stability of the pre-polymerization complex of the CIL template with the chosen functional acrylic monomers. Moreover, they accounted for the MIP selectivity manifested by the molecularly imprinted cavity with the CIL molecule complex stability higher than that for each interference. On this basis, a fast and reliable method for determining both compounds was developed to meet an essential requirement concerning the personalized drug dosage adjustment. The limit of detection (LOD) at the signal-to-noise ratio of S/N = 3 in DPV and EIS determinations using the ferrocene redox probe in a “gate effect” mode was 93.5 (±2.2) and 86.5 (±4.6) nM CIL, respectively, and the linear dynamic concentration range extended from 134 nM to 2.58 μM in both techniques. The chemosensor was highly selective to common biological interferences, including cholesterol and glucose, and less selective to structurally similar dehydroaripiprazole. Advantageously, it responded to dhCIL, thus allowing for the determination of CIL and dhCIL together. The EIS chemosensor appeared slightly superior to the DPV chemosensor concerning its selectivity to interferences. The CIL DPV sorption data were fitted with Langmuir, Freundlich, and Langmuir-Freundlich isotherms. The determined sorption parameters indicated that the imprinted cavities were relatively homogeneous and efficiently interacted with the CIL molecule.

Easy-to-Make Polymer Hydrogels by UV-Curing for the Cleaning of Acrylic Emulsion Paint Films.

The cleaning of acrylic emulsion paint surfaces poses a great challenge in the conservation field, due to their high water sensitivity. In this article, we present easy-to-make polymer hydrogels, made by UV-photopolymerization, that show excellent cleaning properties. The formulation of hydrogels obtained by UV-curing and their performance as dry cleaners for acrylic paints was investigated. First, different hydrogel formulations based on functional acrylic monomers were used to formulate a series of UV cross-linked hydrogels by fast UV photopolymerization. Their effectiveness on surface dirt removal was investigated by SEM microscopy and colorimetry. The hydrogels showed excellent cleaning properties and controlled water release, and they still performed satisfactorily after several cleaning uses. The obtained UV-hydrogels were compared to the well-known agar gels, showing benefits in terms of reducing excess water. This article shows that easy-to-make UV-cured hydrogels are an efficient tool for the cleaning of surface dirt from water-sensitive paintings, overcoming the limits of traditional cleaning methods.

Synthesis of Si-containing macro-RAFT agent for the water-borne polyacrylate polyurethane with anti-graffiti coating applications

A new water-borne anti-graffiti polyacrylate (WAPA) was synthesized from the Si-containing macro-RAFT agent and functional acrylate monomers. After the cross-linking of a water-borne isocyanate agent with the WAPA for curing during the film cast, the two-component anti-fouling Si-containing polyacrylate polyurethane (WAPAU) was prepared. The structure and properties of the macro-RAFT agent were characterized by FT-IR, GPC and critical micelle concentration analysis. The integration of silicone in the polymers was confirmed by FT-IR and SEM-EDX analysis. The influence of S,S ' -bis(α, α ' -dimethyl-α '' -acetic acid)-trithiocarbonate (BDATT) dosage, silicone content, crosslinking density on the properties of emulsions and coating films were investigated, which revealed that the properties of emulsion and coating films were optimal when the amount of BDATT was 0.5 w% and the hydroxyl value of polyacrylate was 160. In addition, changes in silicone content greatly affect the performance of coatings.

Preparation of antibacterial polyester–cotton absorbents; the effects of star-shaped functional oligomers

Antibacterial absorbent fabrics were prepared through by the immersion of polyester polyester–cotton fabrics in a soaking media, containing novel functional acrylic monomers and various antibacterial agents. 2-acrylamido 2-methyl propane sulfonic acid (AMPS) and a novel functional star-shaped oligomer (FSO) were used as monomers for inducing the absorbency and compatibility to the fabric. FSO in two steps and employing condensation reaction between glycerol and lactic acid via multi-step microwave irradiation was synthesized. Bio-based materials, such as gallic acid and tannic acid, were used as antibacterial agents to induce antibacterial activity to the cotton fabric. ATR-FTIR, H NMR, SEM, contact angle, as well as antibacterial activity, absorbency in distilled water and saline solution have been employed for further evaluation. The swelling capacity of the modified absorbent fabric H1 (AMPS/FSO: 50:/50 wt%) was up to 21.1 g/g−1 in distilled water, and 6.1 g/g−1 in saline solution. Antibacterial properties tests of these absorbent fabrics showed a good antibacterial behavior, against Staphylococcus aureus.

Study on mussel-inspired tough TA/PANI@CNCs nanocomposite hydrogels with superior self-healing and self-adhesive properties for strain sensors

Tough, self-adhesive and conductive hydrogels have recently attracted considerable interest due to their promising applications in electronic skins, wearable devices and flexible sensors. In this work, we designed a mussel-inspired nanocomposite hydrogel derived from water-soluble tannic acid/polyaniline coated cellulose nanocrystals (TA/PANI@CNCs) and various functional acrylic monomers. The incorporated TA/PANI@CNCs not only endowed the nanocomposite hydrogels with enhanced electrical conductive network and mechanical performance, but also played an important role in repeatable and durable adhesiveness to human skin without additional fixation. By taking the advantage of double networks based on various supramolecular interactions and dynamic borate ester bonds, the hydrogels exhibited a dramatic breaking strain of 974%, fracture stress of 759 kPa and rapid self-healing ability at room temperature without external stimuli. In addition, the as-prepared nanocomposite hydrogels had great strain sensitivity and excellent electrical conductivity, which can be employed as flexible strain sensors for tracking human body motion with a broad range of strain or directly assembled on other materials surfaces as electrical circuits. Compared with previous conductive hydrogels, this work will provide a novel pathway to fabricate nanocomposite hydrogels with self-healing, self-adhesive, strain sensitive and robust mechanical properties for potential applications in wearable strain sensors, flexible electrical interconnection and human motion monitoring.

Preparation and Characterization of New Environmental Functional Polymers Based on Vanillin and N-isopropylacrylamide for Post Polymerization

The study aims to synthetize a new functional acrylate monomer from vanillin in one step reaction. The new monomer has called by vanillin acrylate and abbreviated (VA). It was confirmed by chemical methods 1H NMR, 13C, IR and UV indicated logic results. The homopolymer has been prepared by free radical polymerization and characterized chemically and physically, the 1HNMR and IR have proofed the presence of aldehyde group in the polymer main chain. This monomer was used to synthesize three different molar concentrations of temperature responsive functional polymers with N-isopropylacrylamide via free radical polymerization by AIBN in solution. The 1H NMR was used for determination of actual mole concentration of each monomer. The aldehyde group in polymers were used as a linker for grafting with primary amine compounds by click reactions to form Schiff’s base imine compounds. The grafted copolymers were also investigated by 1H NMR and IR for structure elucidation. Gel permeation chromatography GPC was used for determination the molecular weight and polydispersity; DSC for glass temperature of solid polymers; XRD for crystallinity. UV–Vis Spectroscopy was used for the determination of phase separation or the lower critical solution temperature (Tc) of polymers solution before and after grafting, not only in deionized water but in pH 5 and pH 11. Synthesis of new functional monomer based on vanillin in one step reaction. Monomer has been successfully polymerized by free radical polymerization using AIBN as initiator. Three different mole ratios (10, 15, 20 mol%) of copolymer with NIPAAm were prepared. All monomers and polymers have been chemically elucidated. The aldehyde functional group used as linker for primary amine compounds, the final products have been characteristics as T, pH dual responsive polymers the phase transition temperature of copolymer before and after grafting was determined by UV.vis Spectroscopy.

The use of differential scanning fluorimetry in the rational design of plastic antibodies for protein targets.

The development of molecularly imprinted polymer nanoparticles (MIP-NPs), which specifically bind biomolecules, is of great interest in the area of biosensors, sample purification, therapeutic agents and biotechnology. Polymerisation techniques such as precipitation polymerisation, solid phase synthesis and core shell surface imprinting have allowed for significant improvements to be made in developing MIP-NPs which specifically recognise proteins. However, the development of MIP-NPs for protein templates (targets) still require lengthy optimisation and characterisation using different ratios of monomers in order to control their size, binding affinity and specificity. In this work we successfully demonstrated that differential scanning fluorimetry (DSF) can be used to rapidly determine the optimum imprinting conditions and monomer composition required for MIP-NP design and polymerisation. This is based on the stability of the protein template and shift in apparent melting points (Tm) upon interaction with different functional acrylic monomers. The method allows for the characterisation of molecularly imprinted nanoparticles (MIP-NPs) due to the observed differences in melting point profiles between, protein-MIP-NPs complexes, pre-polymerisation mixtures and non-imprinted nanoparticles (NIP-NPs) without the need for prior purification. The technique is simple, rapid and can be carried out on most quantitative polymerase chain reaction (qPCR) thermal cyclers which have the required filters for SYPRO

Photo-lithographic patterning of biomimetic molecularly imprinted polymer thin films onto silicon wafers

This investigation describes the design and synthesis of molecularly imprinted polymers (MIPs) as patterned thin films, based on molecular modelling of functional monomer-template interactions and validation by NMR-spectroscopy. Several MIP thin films were prepared from a solution containing the template N-boc-l-phenylalanine and functional acrylic monomers at varying ratios with a cross-linker and initiator in a porogenic solvent. This solution was then spin-coated onto 3-(trimethoxysilyl)propyl methacrylate-functionalised silicon wafers and subsequently the film was photo-polymerised. After template extraction, the film thickness and topography of a methacrylic acid MIP was characterised with atomic force microscopy. A 4-vinylpyridine-MIP thin film was then made by depositing the pre-polymerisation solution on top of the methacrylic acid MIP by spin-coating. Photo-lithographic etching through a gold grid and extraction of non-polymerised solution from under the gold mask yielded a grid-patterned surface, in which two different MIPs alternate with dimensionality at the micro- or submicro-meter scale. Selectivity differences between the two MIP surfaces towards fluorescent template analogue N-dansyl-l-phenylalanine were documented using fluorescence microscopy. This side-by-side comparison on the same thin film allows fast and cost-effective assessment of the two very different MIP selectivities towards various biomolecules.

Chemical functional polymers for direct UV assisted nanoimprinting of polymeric photonic microring resonators

AbstractWe report the nanoimprinting of a microring resonator (MRR) and the development of a functional nanoimprint polymer as route toward selective MRR biosensors. A hybrid, residual layer‐free, UV assisted nanoimprint technique was used to pattern freestanding polymer waveguides with a resolution of 300 nm and an aspect ratio of 4:1. A low viscous, functional UV nanoimprint polymer was formulated with a hydroxyl functional acrylate monomer (4‐hydroxyl butyl acrylate, HBA). The functional polymer was characterized by X‐ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The added hydroxyl groups were found on the polymer surface and were accessible for selective binding of a fluorine tag (trifluoroacetic anhydride, TFAA). The density of the hydroxyl groups was tuned by the HBA concentration. A maximum hydroxyl group density of 8.4% was reached for 33.75 wt% HBA. The RMS surface roughness was 1.2–2.2 nm. magnified image Polymeric photonic MRR with superficial chemical functionalities for a subsequent biomolecule binding and application as a biosensor.

Preparation and Adhesion Property of a Low Temperature Cross-Linkable Vinyl Acetate-Acrylate Copolymer Latex

The functional acrylate monomer (FAM) containing an amino group was synthesized by using glycidyl methacrylate (GMA) and ammonia. FAM was then copolymerized with Vinyl acetate and other acrylate monomers by emulsion copolymerization. The cross-linkable latex was obtained by adding a set content of glutaraldehyde to the earlier copolymer emulsion. The FT-IR results show that the cross-linking reaction between amino and aldehyde groups is detected during the curing process of copolymer. The glass transition temperature (Tg) of the copolymer can be evidently increased from −16.2 to −8.7°C as the FAM alters from 0 to 10%. T-peel strength of the polyethylene-polyethylene (PE-PE) packaging films laminated by products was studied. The results show peel strength dramatically increases with the cross-linking density at room temperature, and still reaches 2.5 N·15 mm−1 even at 60°C, which can satisfy the application requirement enough.

Thermoresponsive polyacrylates obtained via a cascade of enzymatic transacylation and FRP or NMP

Following a cascade reaction comprising enzymatic monomer synthesis and radical polymerization, different functional poly(acrylate)s were obtained. Transacylation of methyl acrylate (MA) with diethylene glycol monoethyl ether, 1,2-propanediol or 1,2,6-hexanetriol in the presence of Novozyme 435 led to functional acrylate monomers. In a subsequent step, after filtration of the enzyme, removal of MA by distillation and eventual addition of a hydrophilic co-monomer, (2-hydroxyethyl acrylate, HEA), the mixture was copolymerized via free radical and nitroxide mediated polymerization resulting in poly(acrylate)s with predefined functionalities. Furthermore the thermoresponsive properties of the resulting copolymers are discussed with respect to the polymer composition and the molecular weight distribution.

Hydroxy functional acrylate and methacrylate monomers prepared via lipase—catalyzed transacylation reactions

Candida antarctica lipase B (CAL-B, Novozyme 435) catalyzes the transacylation of methyl acrylate and methyl methacrylate with diols and triols in 2-methyl-2-butanol at 50 °C. Under the experimental conditions, up to 70 mol% of the acyl donor methyl acrylate was converted. Methyl methacrylate is the less efficient acyl donor (up to 60 mol%) due to the higher sterical hindrance in the enzymatic transacylation. Under the reaction conditions high yields of the mono-acylated products are obtained, which contain minor amounts of bis(meth)acrylates. In addition it was observed that Novozyme 435 catalyzes regioselectively the acylation of the primary hydroxyl groups. In comparison with the chemical catalyzed route no selectivity was observed for unsubstituted diols. For substituted diols more mono-acylated product was formed in the lipase-catalyzed reaction than in the chemical catalyzed reaction.

Synthesis of Block Copolymers of Ethylene with Styrene and n-Butyl Acrylate via a Tandem Strategy Combining Ethylene “Living” Polymerization Catalyzed by a Functionalized Pd−Diimine Catalyst with Atom Transfer Radical Polymerization

We report a new two-step tandem strategy combining two versatile “living” polymerization techniques, Pd−diimine catalyzed ethylene “living” polymerization and atom transfer radical polymerization (ATRP), for the synthesis of functionalized polyethylene (PE) diblock copolymers containing an ethylene block and a functional monomer block, such as styrene and n-butyl acrylate. The key to the success of this tandem strategy is the development of a novel functionalized Pd−diimine catalyst, [(ArNC(Me)−(Me)CNAr)Pd(CH2)3C(O)O(CH2)2OC(O)C(CH3)2Br]+SbF6- (Ar = 2,6-(iPr)2C6H3) (3), which uniquely contains a 2-bromoisobutyryl substituting group on its chelate structure. This catalyst was synthesized by convenient equimolar reaction of the acetonitrile Pd−diimine adduct, [(ArNC(Me)−(Me)CNAr)Pd(CH3)(N⋮CMe)]+SbF6- (Ar = 2,6-(iPr)2C6H3) (1), with a functional acrylate monomer, 2-(2-bromoisobutyryloxy) ethyl acrylate (BIEA). The remarkable feature of 3 lies in its unprecedented ability to catalyze ethylene “living” polymer...

Polarizing group attached acrylates and polymers viewing high refractive index

We designed and successfully synthesized UV curable, functional acrylate monomers having a polarizing group, i.e., an electron-withdrawing and/or electron-donating group for the optical materials of high refractive index. Optical polymer films made from the functional methacrylate monomers were achieved with photo crosslinking under UV illumination. A monomer having amino and cyano groups (Dimer-CN) exhibited the highest refractive index (n TE = 1.595 at 850 nm) among the studied methacrylate derivatives, due to the large polarizability of the dipolar monomer structures with electron-donating and withdrawing groups. By controlling the compositions of the functional acrylate monomer of copolymers, the refractive indices of the polymers were readily adjusted within a wide range of 1.498-1.595. The copolymers showed a high glass transition temperature (T g ) and good thermal stability, which are desirable for optical applications.T g andT 10% (10%-weight loss occurred) of the copolymers ranged from 120-140 °C and from 329-387 °C, respectively.

Intrinsically proton conducting polymers and copolymers containing benzimidazole moieties: Glass transition effects

Proton conducting polymers and copolymers containing tethered benzimidazole moieties spanning a wide range of glass transition temperatures (2–113 °C) have been prepared. Conductivity versus temperature plots of the homopolymers display the competing effects of mobility and charge carrier density. Consistent with literature reports, T g values of benzimidazole-containing polymers increased over the parent polymer, however, successful reduction of T g was accomplished by copolymerizing a benzimidazole functional acrylate monomer (B5A) with poly(ethylene glycol) methyl ether acrylate (PEGMEA). The reduction in T g is thought to occur through disruption of intermolecular forces between benzimidazole units. Evaluation of conductivity as a function of temperature by ac impedance methods indicate that decreasing T g through copolymerization results in conductivity increases over the low and intermediate temperature range (40–160 °C). Copolymer T g decreases with increasing PEGMEA content, and conductivity at 40 °C can be increased by nearly 2.5 orders of magnitude over B5A homopolymer. However, conductivity at high temperatures (> 160 °C) decreases due to charge carrier dilution by the addition of PEGMEA.

Ultraviolet curable dry polymer films from emulsion polymers

AbstractLow levels of functional acrylic monomers were incorporated into a core‐shell acrylic copolymer by seeded emulsion polymerization. The increase in glass transition temperature, Tg, from DSC measurement has showed that although certain amount of crosslinking reactions have occurred during the polymerization and isolation of the copolymer, the dried copolymer films could undergo further curing by UV irradiation. The structure and amount of the functional monomer, concentration of photoinitiator, and the extent of UV exposure have exerted significant influence on the Tg of the dry copolymer films. Because of the relatively low level of incorporated unsaturation, there was no significant change in FTIR during the curing of the film. Further, crosslinking of the copolymer film induced by UV irradiation has significantly increased the resistance to swelling in alkaline solution, although the gel content remained the same. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2317–2322, 2006

Graft Polymerisation of Functional Acrylic Monomers onto Cotton Fibres Activated by Continuous Ar Plasma

AbstractSummary: Continuous cold Ar plasmas were used to activate the mercerised cotton fabric towards surface‐initiated graft polymerisation of glycidyl methacrylate, 2‐hydroxyethyl methacrylate (HEMA) and 1,1,2,2‐tetrahydroperfluorodecyl methacrylate (XFDMA). Single and multi‐step processes, carried out either in the plasma chamber (one‐step and two‐step processes) or ex situ after plasma treatment, were explored to optimise the grafting efficiency. The mechanical properties of the grafted cotton were substantially unaffected. Grafting with XFDMA gave good results only when the plasma activation was performed on monomer‐impregnated fabrics, as shown by gravimetry, ATR FT‐IR spectroscopy, and water and oil repellence tests. On the contrary, with HEMA better results were obtained by in situ grafting from monomer vapours.Mercerized cotton fabric before (left) and after (right) graft polymerisation of the fluorinated methacrylate XFDMA from the plasma‐activated surface.magnified imageMercerized cotton fabric before (left) and after (right) graft polymerisation of the fluorinated methacrylate XFDMA from the plasma‐activated surface.

Preparation of functional poly(acrylates and methacrylates) and block copolymers formation based on polystyrene macroinitiator by ATRP

The polymerization by ATRP of hydroxy and amino functional acrylates and methacrylates with tert-butyldimethylsilyl (TBDMS) or tert-butyloxycarbonyl (BOC) protective groups has been studied for the first time achieving high control over molecular weight and polydispersity. Detailed investigation of the ATRP of 2-{[ tert-butyl(dimethyl)silyl]oxy}ethyl acrylate ( M2b) in bulk and 2-[( tert-butoxycarbonyl)amino]ethyl 2-methylacrylate ( M3a) in diphenyl ether (DPE) showed that the type of ligand plays an important role on either the polymerization rate or the degree of control of the polymerization. Among the ligands used, N,N,N,′ N″ N″-pentamethyl diethylenetriamine (PMDETA) was the most suitable ligand for ATRP of all functional acrylates and methacrylates. The kinetics of M2b and M3a polymerization using PMDETA as a ligand was reported and proved the living character of the polymerization. Well-defined block copolymers based on a halogen terminated polystyrene ( Pst) macroinitiator and the functional acrylate and methacrylate monomers were successfully synthesized by ATRP, and subsequent deprotection of the protective groups from the acrylate or methacrylate segment afforded amphiphilic block copolymers with a specific solubility behavior.

The influence of surfactant in reflective HPDLC gratings

The use of highly functional acrylate monomers (large number of reactive bonds) as the precursor to the polymer-rich phase of holographic polymer-dispersed liquid crystals (HPDLC) is well established as providing the best balance between fast polymerization, gelation, and vitrification. Monomers with >3 double bonds (typically between 4 and 5) yield films with the largest diffraction efficiency, all other things being equal. A consequence of this chemistry is that the HPDLC films formed require very high switching fields to dynamically varying their optical properties. These high switching fields are unappealing for many commercial applications. A potential solution has been to add a non-reactive surfactant-like molecule to the reactive syrup. A substantial lowering of the switching field has been attributed to a modification of the anchoring properties of the LC molecules and the polymer host. The dynamics of switching seem to support this supposition as much longer relaxation times are observed. We investigate differences in the polymerization kinetics using differential photocalorimetry (DPC) and relate these results to differences in HPDLC evolution using real-time scattering experiments. Herein, we present large differences in the final morphology of reflection gratings which are supported by optical measurements. We also indirectly show that the surfactant molecules reside near or at the polymer interface by examining contamination of PDLC droplets using polarized optical microscopy and differential scanning calorimetry.