Phenyl Methacrylate Research Articles

Hyperbranching-Enhanced-Emission Effect Discovered in Hyperbranched Poly(4-(cyanomethyl)phenyl methacrylate).

To disclose the effect of architecture over fluorescence behaviors of polymers, linear and hyperbranched poly(4-(cyanomethyl)phenyl methacrylate)s (PCPMAs) were synthesized by using atom transfer radical polymerization (ATRP). Compared to linear PCPMAs with weakly AIE (AIE: aggregation-induced-emission) characteristics and small-molecule analogues of 4-(cyanomethyl)phenyl isobutyrate (CPB) with ACQ (ACQ: aggregation-caused-quenching) behaviors, hyperbranched PCPMA showed dramatically stronger fluorescence at both solution and solid states and more significant AIE characteristics, which were further enhanced by increasing the branching degree, indicating a significant hyperbranching-enhanced-emission effect (HEE). The HEE effect was attributed to the strong promotion of hyperbranched architecture over the formation of a nitrile group cluster with through-space conjugation (TSC). The HEE effect provided a promising methodology to construct efficient nontraditional fluorescent polymers without large-conjugated, rigid, and planar emitter groups.

Light-Triggered Reversible Slimming of Azobenzene-Containing Wormlike Nanoparticles Synthesized by Polymerization-Induced Self-Assembly for Nanofiltration Switches.

Photoresponsive wormlike block copolymer nanoparticles (NPs) have potential applications in versatile fields, but their preparation suffers from narrow worm phase region and tedious approaches. In this work, azobenzene-containing wormlike NPs based on poly(methylacrylic acid)-b-poly(4-((4-butylphenyl)diazenyl)phenyl methacrylate) are prepared via polymerization-induced self-assembly at high solids concentration in ethanol. The pure wormlike NPs occupy a remarkably broad region in the morphological phase diagram because of the rigid nature of the core-forming block. These wormlike NPs expand resulting from trans-cis transformation upon UV irradiation, and slim near to the original state via visible light irradiation. The diameter and its variation amplitude of worms increase with the chain length of core-forming block. Moreover, a nanofiltration switch for rhodamine B is assembled to illustrate one of its potential applications by remote trigger using light.

Recording Polarization Holograms in Films of 4-((2-Bromo-4-nitrophenyl)diazenyl)phenyl Methacrylate Copolymers

Recording media for polarization holography have been created on the basis of 4-((2-bromo-4-nitrophenyl)diazenyl)phenyl methacrylate copolymers, and the properties during that they manifest during recording of holograms of a plane wavefront have been studied. It has been found that the hologram recording rate at room temperature is the same for the perpendicular and parallel polarization of recording rays and the hologram relaxation rate is higher in the case of perpendicular polarization orientation of recording rays. It has been shown that the diffraction efficiency of holograms does not exhibit a monotonic relation with the film softening temperature.

Запись поляризационных голограмм в пленках сополимеров 4-((2-бром-4-нитрофенил)диазенил)фенилметакрилата

AbstractRecording media for polarization holography have been created on the basis of 4-((2-bromo-4-nitrophenyl)diazenyl)phenyl methacrylate copolymers, and the properties during that they manifest during recording of holograms of a plane wavefront have been studied. It has been found that the hologram recording rate at room temperature is the same for the perpendicular and parallel polarization of recording rays and the hologram relaxation rate is higher in the case of perpendicular polarization orientation of recording rays. It has been shown that the diffraction efficiency of holograms does not exhibit a monotonic relation with the film softening temperature.

Ferrocene Bearing Non-ionic Poly-aryl Tosylates: Synthesis, Characterization and Electron Beam Lithography Applications

The development of new organic-inorganic hybrid photoresists with optimal lithographic performances is an extremely important but challenging task. In this regard, we have synthesized a new family of homo- and hybrid-polymer resists based on 4-(tosyloxy)phenyl methacrylate (TPMA) and ferrocene methacrylate (FEMA) monomers for micro-/nano-lithography applications. The homo polymer resist, poly(TPMA), was synthesized by a free radical polymerization of TPMA monomer in ACN/THF (2:1, v/v) solvent system using azobisisobutyronitrile (AIBN) as the radical initiator. The hybrid copolymer resists, 2.0%-&4.0%-poly(FEMA-co-TPMA), containing 2.0 and 4.0 weight percentages of FEMA respectively, were synthesized by reacting FEMA (10 and 20% initial feed ratios respectively) and TPMA (90 and 80% initial feed ratios respectively) under similar reaction conditions. The ferrocene contents of the hybrid copolymers were calculated by proton NMR analysis. The potential of these polymer resists to pattern micro- and nano-features were tested under deep ultraviolet (DUV) and electron beam (e-beam) lithography tools respectively. The thin films formed by 4.0%-poly(FEMA-co-TPMA) exhibited high surface roughness in comparison to those of poly(TPMA) and 2.0%-poly(FEMA-co-TPMA) resists, probably due to the high ferrocene content of the former. The scanning electron microscopy (SEM) analysis of the e-beam exposed (dose 950 µC/cm2) thin films of poly(TPMA) revealed patterning of 40 nm (L/10S to L/4S), 30 nm (L/10S & L/5S) and 22 nm (L/10S) line features. Similarly, 2.0%-poly(FEMA-co-TPMA) patterned 40 nm (L/5S to L/S), 30 (L/5S to L/S) and 20 nm (L/5S & L/4S) line features under the e-beam exposure (dose 500 µC/cm2). The sensitivity and contrast values were calculated from the normalized remaining thickness (NRT) curve analysis as 270 µC/cm2; 5.2 and 153 µC/cm2; 1.98 respectively for poly(TPMA) and 2.0%-poly(FEMA-co-TPMA) resists. The present study therefore reveals that the incorporation of small amounts of ferrocene into the poly-aryl tosylate based resist formulations helps to enhance its sensitivity and resolution.

Single-Domain Antibody-Functionalized pH-Responsive Amphiphilic Block Copolymer Nanoparticles for Epidermal Growth Factor Receptor Targeted Cancer Therapy.

Biocompatible antibody-nanoparticle conjugates have attracted interest as anticancer agents due to their potential to selectively target therapeutic agents at disease sites. However, new formulation and conjugation approaches are urgently needed to improve their uniformity for clinical applications. Here, a pH-responsive benzaldehyde-functionalized poly[oligo(ethylene glycol) methacrylate-st-para-formyl phenyl methacrylate]-b-poly[2-(diisopropyl)aminoethyl methacrylate] [P(OEGMA-st-pFPMA)-b-PDPA] block copolymer, prepared by reversible addition-fragmentation chain transfer polymerization, produced PEGylated nanoparticles (pH ∼ 7.4) by a single emulsion-solvent evaporation formulation approach. Efficient site-specific attachment of an aminooxy-functionalized anti-EGFR single-domain antibody (sdAb) on these benzaldehyde-decorated nanoparticles is achieved by oxime bond formation. These nanoconjugates can specifically bind EGFR (modified ELISA) and have enhanced uptake over nonfunctionalized controls in EGFR-positive HeLa cells. Encapsulation of rhodamine 6G dye and its dispersion upon cellular uptake, consistent with nanoparticle stability loss at pH < 5.7, prove their ability to facilitate triggered release in endosomal compartments and highlight their potential for use as next-generation antibody-drug nanoconjugates for therapeutic drug delivery.

A Recording Medium Based on Copolymer of 4-((1,5-Dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)diazenyl)phenyl Methacrylate with Nonyl Methacrylate for Polarization Holography

A recording medium based on a novel copolymer of 4-((4-hydroxyphenyl)diazenyl)-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one with nonyl methacrylate is created, and the possibility of its use for polarization holography is investigated. It is shown that, for films based on this copolymer, holograms can be recorded without special heating due to a fairly low softening temperature. The recorded holograms are characterized by low noisiness.

Identification of the reaction mechanism between phenyl methacrylate and epoxy and its application in preparing low-dielectric epoxy thermosets with flexibility

NORYL™ SA9000 resin is a commercialized telechelic PPO oligomer with phenyl methacrylate end groups. However, neat SA9000 thermoset is brittle after thermally curing. To find a method to enhance the toughness of neat SA9000 thermoset, three model reactions are designed. The first one is the 4-dimethylaminopyridine (DMAP)-catalyzed homopolymerization of glycidyl phenyl ether. The second one is the reaction of glycidyl phenyl ether and phenyl acetate in the presence of DMAP. The third one is the reaction of glycidyl phenyl ether and phenyl methacrylate in the presence DMAP. Through 1H NMR analysis, the product is 1,3-diphenoxy-2-acetoxypropane and 1,3-diphenoxy-2-methacryalatepropane, respectively, for model reactions 2 and 3. According to the structure of products, we identify the reaction mechanisms between the phenyl acetate and epoxy, and between the phenyl methacrylate and epoxy. Based on the knowledge, we used two commercialized epoxy resin (DGEBA and HP7200) to copolymerize with SA9000 in the presence of DMAP and tert-butyl cumyl peroxide (TBCP). The toughness of the thermosets are significantly improved, which means the brittle drawback of neat SA9000 thermoset has been solved. Homogeneous, flexible thermosetting films with high glass transition temperatures, low dielectric constants, and extremely low dissipation factors are obtained.

Synthesis and characterization of poly(N-isopropyl methacrylamide) core/shell nanogels for controlled release of chemotherapeutics

A method is presented for synthesizing and characterizing core/shell nanogels based around poly(N-isopropyl methacrylamide) (PNIPMAAm). The effectiveness of the sequential addition reaction scheme was determined for its impact on temperature response, glass transition temperature, and details of polymer structure as revealed by 1H NMR spectra. PNIPMAAm cores coated with poly(tert-butyl methacrylate) (PTBMA), poly(ethylene glycol phenyl acrylate) (PEGPhA), and poly(phenyl methacrylate) (PPhMA) were characterized for structure and effectiveness as carriers for the model chemotherapeutic Doxorubicin (DOX). Swelling studies showed that the core/shell polymerization significantly decreases the collapse, though had limited impact on the lower critical solution temperature (LCST) of PNIPMAAm. Coating with PEGPhA did impart large variability in the particle size. Proton NMR and DSC confirmed the core/shell structure for all samples; however it proved that PPhMA was less effective at coating the PNIPMAAm nanogel. The core/shell nanogels were then characterized for their application as drug delivery vehicles using DSC, partition coefficient, and drug release studies with DOX. These studies showed that coating PNIPMAAm with PTBMA developed a more effective drug delivery vehicle for hydrophobic drugs like DOX.

Adjustment of diffraction efficiency of polarization holograms in azobenzene polymers films using electric field

There have been two effects of the external electric field influence on the diffraction efficiency of reconstructed holograms observed in the films of copolymers 4-[(2-nitrophenyl)diazenyl]phenyl methacrylate with octylmethacrylate, when holographic recording of the plane wave front for parallel and orthogonal orientation of polarization vectors of light beams was performed at room temperature. After recording at exposure with small energies, diffraction efficiency in the electric field formed by corona discharge decreases, while with large exposure energies, it increases. Diffraction efficiency and recording velocity are higher in copolymer with lower softening temperature. The first effect is caused by reorientation of the dipole moments of azobenzene isomer fragments in the electric field, while the growth of diffraction efficiency is explained by the increase in the amplitude of regular geometric relief of the film surface, which appears during formation of the polarization hologram.

Phase Behavior for the Poly(phenyl methacrylate) and Phenyl Methacrylate in Supercritical Carbon Dioxide and Dimethyl Ether

Experimental data up to 463.1 K and 269.14 MPa are revealed for binary and ternary mixtures of poly(phenyl methacrylate) [P(PhMA)] + carbon dioxide (CO2) + phenyl methacrylate (PhMA) and P(PhMA) + CO2 + dimethyl ether (DME) systems. The cloud-point pressure for the P(PhMA) + CO2 + PhMA system is measured with the variations of temperature, and PhMA weight fraction of 39.4, 45.8, 54.2, 59.9, and 62.1 wt %. In 62.1 wt % PhMA to the solution of P(PhMA) + carbon dioxide, the cloud-point phase behaviors are shown the typical lower critical solution temperature (LCST). In addition, the effect by cosolvents concentration for the P(PhMA) + CO2 + DME system is investigated at temperature to 453.9 K and pressure range from 52.24 to 80.86 MPa. The cloud point curve for P(PhMA) + CO2 + DME systems is shifted from LCST region to upper critical solution temperature (UCST) region according to the increase of DME concentration. We report experimental data of the PhMA + CO2 system at high pressures range from 6.24 to 24.9...

Синтез и применение сополимеров 4-((2-нитрофенил)диазенил)фенилметакрилата с октилметакрилатом для создания поляризационно-чувствительных голографических сред

Синтез и применение сополимеров 4-((2-нитрофенил)диазенил)фенилметакрилата с октилметакрилатом для создания поляризационно-чувствительных голографических сред

Perfluorocyclobutyl Aryl Ether-Based ABC Amphiphilic Triblock Copolymer.

A series of fluorine-containing amphiphilic ABC triblock copolymers comprising hydrophilic poly(ethylene glycol) (PEG) and poly(methacrylic acid) (PMAA), and hydrophobic poly(p-(2-(4-biphenyl)perfluorocyclobutoxy)phenyl methacrylate) (PBPFCBPMA) segments were synthesized by successive atom transfer radical polymerization (ATRP). First, PEG-Br macroinitiators bearing one terminal ATRP initiating group were prepared by chain-end modification of monohydroxy-terminated PEG via esterification reaction. PEG-b-PBPFCBPMA-Br diblock copolymers were then synthesized via ATRP of BPFCBPMA monomer initiated by PEG-Br macroinitiator. ATRP polymerization of tert-butyl methacrylate (tBMA) was directly initiated by PEG-b-PBPFCBPMA-Br to provide PEG-b-PBPFCBPMA-b-PtBMA triblock copolymers with relatively narrow molecular weight distributions (Mw/Mn ≤ 1.43). The pendant tert-butyoxycarbonyls were hydrolyzed to carboxyls in acidic environment without affecting other functional groups for affording PEG-b-PBPFCBPMA-b-PMAA amphiphilic triblock copolymers. The critical micelle concentrations (cmc) were determined by fluorescence spectroscopy using N-phenyl-1-naphthylamine as probe and the self-assembly behavior in aqueous media were investigated by transmission electron microscopy. Large compound micelles and bowl-shaped micelles were formed in neutral aqueous solution. Interestingly, large compound micelles formed by triblock copolymers can separately or simultaneously encapsulate hydrophilic Rhodamine 6G and hydrophobic pyrene agents.

Effect of External Electric Field on Diffraction Efficiency of Polarized Holograms in Films of 4-[(2-Nitrophenyl)Diazenyl]Phenyl Methacrylate Copolymer With Octyl Methacrylate

Holograms with a plane wavefront for parallel and orthogonal orientation of polarization of the light beams were obtained in films of the 4-[(2-nitrophenyl)diazenyl]phenyl methacrylate copolymer with octyl methacrylate, and the effect of an external electric field on their diffraction efficiency was investigated. Two effects from the electric field on the diffraction efficiency of the reconstructed holograms were observed: a fast effect leading to decrease of the diffraction efficiency and a slow effect leading to increase of the diffraction efficiency in the reconstructed holograms. The mechanism of formation of the latent holographic image and the effect of the external electric field on it are due not to the photosemiconducting properties of the films but to optical anisotropy in the isomers of the azobenzene groups and the formation of regular surface relief in the films.

The effect of impurities in reactive diluents prepared from lignin model compounds on the properties of vinyl ester resins

ABSTRACTVinyl ester resins (VERs) often contain high concentrations of a petroleum‐based reactive diluent, such as styrene. Reactive diluents that can be derived from lignin, including phenyl methacrylate (PM), 2‐methoxyphenyl methacrylate (MG), and 4‐propyl‐2‐methoxyphenyl methacrylate (M4PG), were synthesized and investigated as potential styrene replacements. A commercial VER was blended with each lignin‐derived reactive diluent, and styrene, in 7:3 and 1:1 weight ratios and cured to ≥ 94%, based on near‐IR spectral analysis. The substituents on the aromatic ring of the lignin‐derived reactive diluent are shown to have small effects on viscosity, thermogravimetric, and thermomechanical properties of the cured resins, where, in general, the smaller the reactive diluent, the greater the glass‐transition temperature (Tg) and the lower the viscosity. Increasing purity of the reactive diluents through chromatographic separations substantially increases the Tg and degradation temperatures of the resins. The results suggest that PM, MG, and M4PG are effective bio‐based reactive diluent replacements for styrene. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43817.

Temperature-independent zero-birefringence polymer for liquid crystal displays

A polymer film that shows almost no orientational birefringence even when the polymer main chain is in an oriented state and almost no temperature dependence of orientational birefringence in the temperature range from around −40 to 85 °C was prepared. This temperature range is important because it is where in-car liquid crystal displays (LCDs) are generally used; therefore, it is desirable to have constant orientational birefringence over this range. We suggest a method to compensate for the intrinsic birefringence and temperature coefficient of intrinsic birefringence of individual polymers by copolymerizing monomers of homopolymers that display opposite signs of the two parameters described above. Analysis of four types of polymers, methyl methacrylate (MMA), 2,2,2-trifluoroethyl methacrylate, benzyl methacrylate (BzMA), and phenyl methacrylate (PhMA), reveal that they possess both positive and negative signs of their temperature coefficient of intrinsic birefringence. Using this approach, we prepare P(MMA/PhMA/BzMA) (39:23:38 wt. %), which exhibits almost no intrinsic birefringence and almost no temperature dependence of intrinsic birefringence. The retardation of this polymer film when drawn uniaxially scarcely changed (between 0.3 and 0.8 nm) between 12 and 70 °C, which is small enough not to cause image degradation in LCDs.

Electrospun nanofibers of poly(NPEMA-co.-CMPMA): Used as Heavy metal ion remover and water sanitizer

Homo and copolymers of monomers 2-(N-phthalimido) ethylmethacrylate (NPEMA) and 4-Chloro-3-methyl phenyl methacrylate (CMPMA) were prepared in N,N-dimethyl formamide (DMF) solution at 70 °C using 2,2-azobisisobutyronitrile (AIBN) as initiator. The solution of poly(NPEMA-co.-CMPMA) in 20 % DMF was used to fabrication electrospun nanofiber by electrospinning technique. IR data were primarily employed to characterize polymers. The formation of nanofibers was identified by SEM study. The metal ion uptake capacity of copolymers and nanofibers were obtain by batch equilibrium method using different metal ion solution. The antimicrobial activity of the copolymers, Polymer nanocomposites and their nanofibers were tested against different microbial organisms by using quantitative method. The main objective of this investigation was to find whether nanofiber are better remover of metal ions compared to copolymers. It was also aimed to study the efficacy of nanofibers of copolymers and copolymer composite with nano Ag as water sanitizer.

ChemInform Abstract: Acid‐Catalyzed Cascade Radical Addition/Cyclization of Arylacrylamides with Ketones.

AbstractN‐arylacrylamides, phenyl methacrylate as well as pentane‐2,4‐dione and ethyl acetoacetate do not react.

Degradation kinetics of starch-g-poly(phenyl methacrylate) copolymers

Both the thermal behavior and kinetic decomposition of starch-g-poly(phenyl methacrylate) copolymers were studied by the TG/DSC/FTIR/QMS coupled technique under inert conditions. In order to compare the results, potato starch was used as a reference material. The results indicate that the thermal degradation takes place in two large stages: (i) destruction of the molecular polysaccharide blocks at temperatures ≤300°C and (ii) structural graft depolymerization from 320 to 440°C. The kinetic analysis in terms of E(α) on α indicates that during the initial stage, with activation energies ranging from 140 to 205kJmol−1, a two-step reaction mechanism involving two consecutive reactions takes place, an initial endothermic reversible reaction followed by an irreversible one, which is related to the cracking of the starch glycosidic bonds. Meanwhile the degradation analysis of the graft polymer reveals that the stage involves several overlapping steps with average activation energies between 120 and 180kJmol−1.

Synthesis of chalcone‐containing methacrylate‐based hydrogen bonded side chain liquid crystalline polymer and its dielectric properties

In this work, a new methacrylate‐based hydrogen bonded side chain liquid crystalline polymer having chalcone moieties (HBCP) was prepared from poly(4‐(3‐(pyridin‐4‐yl)acryloyl) phenyl methacrylate) and 11‐(4‐cyanobiphenyl‐4(‐oxy) undekan‐1‐ol (LC11)) by molecular self‐assembly processes via hydrogen bond formation between nitrogen of the HBCP and hydroxyl group of the LC11. The formation of H bond was confirmed by using Fourier transform infrared (FTIR) spectroscopy. The phase transition temperatures and liquid crystalline phases of the HBCP were examined by DSC and POM measurements. The dielectric properties of HBCP have been determined by impedance analyzer within the frequency interval of 100 Hz–15 MHz. According to Cole–Cole plot, the equivalent circuit of the LC system has been found as a capacitor in parallel with a resistor. The resonance frequency, fr, of the R–C circuit has also been calculated as 1.59 MHz by phase angle versus frequency curve. The dielectric relaxation type of HBCP has been determined as nearly‐Debye type because the absorption coefficient, α, equals to 0.01655. From the conductivity point of view, HBCP displays dc conductivity at the low and high frequency regions that correspond to 100 Hz–12 kHz and 3.3 MHz–15 MHz, respectively. On the other hand, it has been revealed that the ac conductivity of the LC system investigated obeys Super Linear Power Law (SLPL) at the intermediate frequency domain. Copyright © 2015 John Wiley &amp; Sons, Ltd.