Ethoxylated Trimethylolpropane Triacrylate Research Articles

Photoembossing of surface relief structures in polymer films for biomedical applications

Photoembossing is a technique used to create relief structures using a patterned contact photo-mask exposure and a thermal development step. Typically, the photopolymer consists of a polymer binder and a monomer in a 1/1 ratio together with a photo-initiator, which results in a solid and non-tacky material at room temperature. Here, new mixtures for photoembossing are presented which are potentially biocompatible. Poly(methyl methacrylate) is used as a polymer binder and two different acrylate monomers trimethylolpropane ethoxylate triacrylate (TPETA) and dipentaerythritol penta-/hexa-acrylate (DPPHA) are tested. PMMA-TPETA had a higher surface relief features. Biocompatibility is evaluated by culturing human umbilical vein endothelial cells (HUVECs) on films of these photopolymer blends. PMMA with TPETA and PMMA-DPPHA films showed enhanced cell adhesion compared to PMMA. The cells also showed alignment on surface textured films with the highest degree of alignment on films with 20 μm pitch and 2 μm height. This study shows that photoembossing is a feasible method to produce surface textures on films that can be adopted in the field of tissue engineering to promote cell adhesion and alignment.

Thin, Deformable, and Safety‐Reinforced Plastic Crystal Polymer Electrolytes for High‐Performance Flexible Lithium‐Ion Batteries

A new class of highly thin, deformable, and safety‐reinforced plastic crystal polymer electrolytes (N‐PCPEs) is demonstrated as an innovative solid electrolyte for potential use in high‐performance flexible lithium‐ion batteries with aesthetic versatility and robust safety. The unusual N‐PCPEs are fabricated by combining a plastic crystal polymer electrolyte with a porous polyethylene terephthalate (PET) nonwoven. Herein, the three‐dimensional reticulated plastic crystal polymer electrolyte matrix is formed directly inside the PET nonwoven skeleton via in‐situ UV‐crosslinking of ethoxylated trimethylolpropane triacrylate (ETPTA) monomer, under co‐presence of plastic crystal electrolyte. The PET nonwoven is incorporated as a compliant skeleton to enhance mechanical/dimensional strength of N‐PCPE. Owing to this structural uniqueness, the N‐PCPE shows significant improvements in the film thickness and deformability with maintaining advantageous features (such as high ionic conductivity and thermal stability) of the PCE. Based on structural/physicochemical characterization of N‐PCPE, its potential application as a solid electrolyte for flexible lithium‐ion batteries is explored by scrutinizing the electrochemical performance of cells. The high ionic conductance of N‐PCPE, along with its excellent deformability, plays a viable role in improving cell performance (particularly at high current densities and also mechanically deformed states). Notably, the cell assembled with N‐PCPE exhibits stable electrochemical performance even under a severely wrinkled state, without suffering from internal short‐circuit failures between electrodes.

Adhesion improvement of UV-curable ink using silane coupling agent onto glass substrate

In order to enhance the adhesions of the UV-curable inks onto glass substrate, the silane coupling agents were added into the mixture of monomer and oligomer. The monomer, containing high functionality or surface tension could lead to a high cross-link density of the polymeric network and low adhesions of UV-curable inks. With the amount of ethyoxyls of ethoxylated trimethylolpropane triacrylate increasing, adhesions of the oligomers were improved. As the monomer concentration increased, the adhesion ability of UV-curable ink onto glass was decreased. The adhesion ability of UV-curable inks onto glass was increased via adding silane coupling agents. When the concentration of the silane coupling agents was more than 12%, the adhesion ability of UV-curable inks onto glass was decreased. Silane coupling agents (3-methacryloxypropyl) trimethoxy silane (KH570) and (3-aminopropyl) triethoxy silane (KH550) were more effective than (3-glycidoxypropyl) trimethoxy silane (KH560) in the inks under the same concentration. Video microscope and scraper fineness test revealed that the pigment particles declined with the increase of grinding times, whereas the adhesions of UV-curable inks were enhanced.

A study of the effects of thiols on the frontal polymerization and pot life of multifunctional acrylate systems with cumene hydroperoxide

ABSTRACTIn an effort to create frontal polymerization systems with a “fail‐safe” curing mechanism, we studied the effects of thiols on the thermal frontal polymerization velocity and pot life of a mixture of a multifunctional acrylate, kaolin clay (filler), and cumene hydroperoxide with either trimethylolpropane tris(3‐mercaptopropionate) or 1‐dodecanethiol (DDT). The acrylates were trimethylolpropane triacrylate, trimethylolpropane ethoxylate triacrylate, 1,6‐hexanediol diacrylate, and di(ethylene glycol) diacrylate. Without a thiol, frontal polymerization did not occur. The front velocity increased with the concentration of either thiol, which has not been observed with peroxide initiators. The use of DDT yielded longer pot lives than the trithiol. The front velocities were inversely related to the pot lives. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3850–3855

A green protocol to prepare monodisperse poly(TMPTMA–styrene) microspheres by photoinitiated precipitation polymerization in low-toxicity solvent

To prepare monodisperse polymer microspheres under mild conditions, a green protocol is set up by means of photoinitiated precipitation polymerization. The work is carried out with three novel parameters, including: new type crosslinker of trifunctionality, low-toxicity solvent, and ambient temperature. Firstly, trihydroxymethyl propane triacrylate (TMPTMA) is selected as the most suitable crosslinker to prepare microspheres under ambient temperature, after comparing the morphology of its polymerization products with those of other two similar crosslinkers, i.e., trimethylolpropane triacrylate and ethoxylated trimethylolpropane triacrylate. In addition, as high as possible concentrations of TMPTMA and styrene are attempted to harvest the largest amounts of microspheres; however, a threshold of monomer concentration is found at 6 %. One kind of low-toxicity solvent, i.e., ethanol, is used as the reaction media to replace the commonly used toxic organic solvents, and it is proven to be the near Θ solvent for the present polymerization. Observation from scanning electron microscopy indicates that photoinitiation is an effective way to control the growth of microspheres, and highly monodisperse microspheres of 2.67 μm are achieved at polymerization time of 120 h. Finally, the reactive vinyl groups on microsphere surface are confirmed, which indicate that the microspheres from this green protocol is in favor of further functionalization and bio-medical application.

Compliant polymer network-mediated fabrication of a bendable plastic crystal polymer electrolyte for flexible lithium-ion batteries

We demonstrate a bendable plastic crystal polymer electrolyte (referred to as “B-PCPE”) for use in flexible lithium-ion batteries. The B-PCPE proposed herein is composed of a plastic crystal electrolyte (PCE, 1 M lithium bis-trifluoromethanesulphonimide (LiTFSI) in succinonitrile (SN)) and a UV (ultraviolet)-cured polymer network bearing long linear hydrocarbon chains (here, trimethylolpropane propoxylate triacrylate (TPPTA) polymer is exploited). The solid electrolyte characteristics of the B-PCPE are investigated in terms of plastic crystal behavior, mechanical bendability, ionic conductivity, and cell performance. Owing to the presence of long linear hydrocarbon chains attached to crosslinkable acrylate groups, the TPPTA polymer network in the B-PCPE acts as a compliant mechanical framework, thereby exerting a beneficial influence on bendability and also interfacial resistance with lithium metal electrodes. Meanwhile, the B-PCPE exhibits slightly lower ionic conductivity than a control sample (referred to as “R-PCPE”) incorporating a rigid and stiff polymer network of ethoxylated trimethylolpropane triacrylate (ETPTA). This unique behavior of the B-PCPE is discussed with an in-depth consideration of the polymer network structure and its specific interaction with the lattice defect phase of SN in the PCE. Although relatively sluggish ionic transport is observed in the B-PCPE, its intimate interfacial contact with electrodes (possibly due to the mechanically compliant TPPTA polymer network) may beneficially contribute to imparting satisfactory cycling performance.

Mechanically compliant and lithium dendrite growth-suppressing composite polymer electrolytes for flexible lithium-ion batteries

We demonstrate mechanically compliant and lithium dendrite growth-suppressing composite polymer electrolytes for use in flexible lithium-ion batteries. This new composite polymer electrolyte (referred to as “CPE”) is fabricated via an exquisite combination of UV (ultraviolet)-cured ethoxylated trimethylolpropane triacrylate macromer (serving as a mechanical framework) and Al2O3 nanoparticles (as a functional filler) in the presence of a high boiling point liquid electrolyte. A distinctive structural feature of the CPE is the close-packed Al2O3 nanoparticles in the liquid electrolyte-swollen ETPTA macromer matrix. Owing to this unique morphology, the CPE provides significant improvements in the mechanical bendability and suppression of lithium dendrite growth during charge–discharge cycling.

2차 아미노기를 갖는 실리카 나노입자와 (메타)아크릴레이트 단량체와의 마이클 부가반응에 대한 분광학적 분석

In this study, we modified silica nanoparticles with bis[3-(trimethoxysilyl)propyl]amine (BTMA) silane coupling agent to introduce secondary amino groups on the silica surface. After modification of silica, we investigated effects of different types of (meth)acrylate group containing monomers on the Michael addition reaction to introduce reactive (meth)acrylate groups on the BTMA modified silica surface. We used two kinds of (meth)acrylate monomers, trimethylolpropane ethoxylate triacrylate (TMPET) which has three identical acrylate groups, and 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM) which has one acrylate and one methacrylate group. We used fourier transform infrared spectroscopy (FTIR), elemental analysis (EA) and solid state cross-polarization magic angle spinning (CP/MAS) nuclear magnetic resonance spectroscopy (NMR) to understand reactions between NH groups on the silica surface with (meth)acrylate groups of TMPET and AHM monomers. We found almost complete Michael addition reaction between all three acrylate groups of TMPET with NH groups on the BTMA modified silica. But, for the AHM treatment of BTMA modified silica, we found Michael addition reaction occurred only between acrylate groups of AHM and NH groups of silica surface, not between methacrylate groups of AHM and NH groups of BTMA modified silica surface.

UV-curable semi-interpenetrating polymer network-integrated, highly bendable plastic crystal composite electrolytes for shape-conformable all-solid-state lithium ion batteries

Download options Please wait... Article information DOI https://doi.org/10.1039/C2EE03025J Article type Paper Submitted 31 Oct 2011 Accepted 17 Jan 2012 First published 17 Feb 2012 Download Citation Energy Environ. Sci., 2012,5, 6491-6499 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions UV-curable semi-interpenetrating polymer network-integrated, highly bendable plastic crystal composite electrolytes for shape-conformable all-solid-state lithium ion batteries H. Ha, E. Kil, Y. H. Kwon, J. Y. Kim, C. K. Lee and S. Lee, Energy Environ. Sci., 2012, 5, 6491 DOI: 10.1039/C2EE03025J To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Social activity Tweet Share Search articles by author Hyo-Jeong Ha Eun-Hye Kil Yo Han Kwon Je Young Kim Chang Kee Lee Sang-Young Lee

Properties of UV-Curable Hyperbranched Urethane-Acrylate Modified Acrylic Monomer Coatings

In this work it is suggested to modify trimethylolpropane ethoxylate triacrylate (TMPETA) with solvent born difunctional urethane acrylate oligomer (UA) of hyperbranched structure and high molecular weight. In this case the photopolymer composition initial UV-precuring was replaced by thermal action. Under heating at 70 °C temperature solvent (butyl acetate) evaporates and layer with proper deformation properties for microrelief embossing was obtained. After microrelief embossing UV-curing of photopolymer follows and photoinitiator initiated radical photopolymerization of TMPETA monomer and UA oligomer proceeds. The goal of this work - to investigate the influence of the acrylic composition on the UV-cured coating mechanical properties and on the geometrical parameters and optical properties of replicated microrelief. It was defined that coatings with UA oligomer possess higher deformation and mechanical properties due to the increase in layer flexibility. The replicated microrelief of geometrical parameters and diffraction efficiency close to those of master matrix to be used was obtained using compositions containing  30 wt. % - 40 wt. % of  UA.http://dx.doi.org/10.5755/j01.ms.17.4.772

High Throughput Micropatterning of Optical Oxygen Sensor for Single Cell Analysis

In this paper, we present our results from process development and characterization of optical oxygen sensors that are patterned by traditional UV lithography. An oxygen sensitive luminescent probe, platinum octaethylporphyrin (PtOEP), was encapsulated in commercially purchased photoresist (AZ5214) to form uniform thin sensor films on fused silica substrates. Plasticizer ethoxylated trimethylolpropane triacrylate (SR454) was added to the dye-photoresist sensor mixtures to improve the oxygen sensitivity. The optimum sensor mixture composition that can be patterned with maximum sensitivity was identified. The microfabrication process conditions, cell adherence and oxygen sensitivity results from patterned structures were characterized in detail. Down to 3 µm features have been fabricated on fused silica substrates using the developed techniques. The result implies the developed methods can provide a feasible way to miniaturize the optical sensor system for single cell analysis with precise control of sensor volume and response.

Preparation of UV curing crosslinked polyviologen film and its photochromic and electrochromic performances

Polyether urethane diacrylate matrix (PEUDA) and acrylate-functional viologen (ACV2+) were successfully synthesized and characterized in detail by FTIR and 1H NMR spectra, respectively. Subsequently, they were used to prepare UV curing crosslinked polyviologen film in combination with 2-hydroxyethyl methacrylate (HEMA), trimethylolpropane ethoxylate triacrylate (TMPTA) and diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide (TPO). UV curing approach confined the polyviologen film on ITO electrode, which imparted the film excellent adhesion ability to ITO glass, good solvent resistance, excellent chemical stability, excellent optical and electrochemical properties. The crosslinked PACV2+ film exhibited excellent photochromic and electrochromic performances. After UV illumination for 60s, the crosslinked PACV2+ film can swiftly change its color from pale yellow to deep blue, while the optical transmission of crosslinked PACV2+ film at 610nm did not change significantly and still retained about 63.6% after 30 cycles. Simultaneously, the cyclic voltammetry experiment showed the PACV2+ film can undergo repeatable electrochemical redox reactions with good reversibility beyond the 10th scan. Furthermore, the electrochromic device composed of the PACV2+ film and gel electrolyte film can undergo reversible color change in response to the external voltages of −2.0V and 2.0V, respectively, while the contrast of EC device at 610nm did not change significantly and still retained about 39.5% after 10 cycles. This UV curing approach to preparing viologen-functional film offers a method to preparing large-scale photo- and electrochromic device, which is relatively simple, high productivity, energy saving, and environmental protection.

A self-standing, UV-cured polymer networks-reinforced plastic crystal composite electrolyte for a lithium-ion battery

We demonstrate a facile approach to fabrication of a self-standing plastic crystal composite electrolyte for a lithium-ion battery, wherein UV (ultraviolet)-cured ethoxylated trimethylolpropane triacrylate (ETPTA) networks are incorporated into a plastic crystal electrolyte (PCE, 1 M lithium bis-trifluoromethanesulphonimide (LiTFSI) in succinonitrile (SN)). An ETPTA monomer having trifunctional groups is successfully crosslinked within a very short UV-exposure time of 20 s without using any solvent, leading to the formation of a self-standing, transparent, and non-sticky plastic crystal composite electrolyte (X-PCCE). Owing to the introduction of the UV-cured ETPTA networks, the X-PCCE is capable of providing unprecedentedly robust mechanical strength even at a high concentration of PCE (i.e., ETPTA/PCE = 15/85%, w/w), along with affording high ionic conductivity. In contrast, a conventional plastic crystal composite electrolyte (F-PCCE) comprising polyvinylidenefluoride-co-hexafluoropropylene (PVdF-HFP) and PCE is difficult to be fabricated as a self-standing film and easily deformed by weak external stress. Notably, the X-PCCE shows significant improvement in electrochemical stability and interfacial resistance toward lithium metal electrodes. Ionic conductivities of the X-PCCE and the F-PCCE are examined as a function of temperature and discussed under consideration of the interaction between SN, LiTFSI, and polymers in the plastic crystal composite electrolytes.

Magnetochromatic Microcapsule Arrays for Displays

AbstractAn approach to construct displays based on magnetochromatic microcapsules with narrow size distribution has been proposed. These magnetochromatic microcapsules are fabricated by a microfluidic technology. The shell layer of the obtained microcapsule is composed of transparent photocurable ethoxylated trimethylolpropane triacrylate (ETPTA) resin while the core is formed by the aqueous droplet containing monodisperse magnetic nanospheres. The capsule size, shell thickness, and morphology can be easily controlled by the flow rates during the fabrication. In the multipixel array formed by these microcapsules, each microcapsule acts as an individual display unit. The nanospheres in the core droplet can be influenced by an external magnetic field, forming ordered structures which determine light diffraction; therefore, various distinct colors are observed according to the intensity of the external magnetic field. These microcapsules have the advantage of long time stability, viewing angle independence, and dynamic tunable optics.

Flow-through immunosensors using antibody-immobilized polymer monoliths

High-sensitivity and rapid flow-through immunosensors based on photopolymerized surface-reactive polymer monoliths are investigated. The porous monoliths were synthesized within silica capillaries from glycidyl methacrylate and ethoxylated trimethylolpropane triacrylate precursors, providing a tortuous pore structure with high surface area for the immobilization of antibodies or other biosensing ligands. The unique morphology of the monolith ensures efficient mass transport and interactions between solvated analyte molecules and covalently immobilize antibodies anchored to the monolith surface, resulting in rapid immunorecognition. The efficacy of this approach is demonstrated through a direct immunoassay model using anti-IgG as a monolith-bound capture antibody and fluorescein-labeled IgG as an antigen. In situ antigen measurements exhibited a linear response over a concentration range between 0.1 and 50 ng/mL with 5 min assay times, while controllable injection of 1 μL volumes of antigen through the monolith elements yielded a mass detection limit of 100 pg (∼700 amol). These results suggest that porous monolith supports represent a flexible and promising material for the fabrication of rapid and sensitive immunosensors suitable for integration into capillary or microfluidic devices.

Multilayered Magnetic Nanoparticles as a Support in Solid-Phase Peptide Synthesis

The synthesis of multilayered magnetic nanoparticles (MNPs) for use as a support in solid-phase peptide synthesis (SPPS) is described. Silanization of magnetite (Fe3O4) nanoparticles with 3-(trimethoxysilyl)propyl methacrylate introduced polymerizable groups on the surface. Polymerization with allylamine, trimethylolpropane trimethacrylate, and trimethylolpropane ethoxylate (14/3 EO/OH) triacrylate provided a polymeric coating and amino groups to serve as starting points for the synthesis. After coupling of an internal reference amino acid and a cleavable linker, the coated MNPs were applied as the solid phase during synthesis of Leu-enkephalinamide and acyl carrier protein (65-74) by Fmoc chemistry. A “high-load” version of the MNP support (0.32 mmol/g) was prepared by four consecutive cycles of Fmoc-Lys(Fmoc)-OH coupling and Fmoc deprotection. Successful synthesis of Leu-enkephalin was demonstrated on the “high-load” MNPs. Chemical stability studies proved the particles to be stable under SPPS conditions and magnetization measurements showed that the magnetic properties of the particles were maintained throughout derivatizations and SPPS. The MNPs were further characterized by high-resolution transmission electron microscopy, inductively coupled plasma atomic emission spectrometry, elemental analysis, and nitrogen gas adsorption measurements.

Photocurable Pickering Emulsion for Colloidal Particles with Structural Complexity

We prepared polymeric microparticles with coordinated patches using oil-in-water emulsion droplets which were stabilized by adsorbed colloidal polystyrene (PS) latex particles. The oil phase was photocurable ethoxylated trimethylolpropane triacrylate (ETPTA), and the particle-armored oil droplets were solidified by UV irradiation within a few seconds to produce ETPTA-PS composite microparticles without disturbing the structures. Large armored emulsion drops became raspberry-like particles, while small emulsion drops with a few anchored particles were transformed into colloidal clusters with well-coordinated patches. For high-molecular-weight PS particles with low chemical affinity to the ETPTA monomer, the morphology of the patchy particle was determined by the volume of the emulsion drop and the contact angle of the emulsion interface on the PS particle surface. Meanwhile, for low-molecular-weight PS particles with high affinity, the ETPTA monomers were likely to swell the adsorbed PS particles, and distinctive morphologies were induced during the shrinkage of emulsion drops and the phase separation of ETPTA from the swollen PS particles. In addition, colloidal particles with large open windows were produced by dissolving the PS particles from the patchy particles. We observed photoluminescent emission from the patchy particles in which dye molecules were dispersed in the ETPTA phase. Finally, we used Surface Evolver simulation to predict equilibrium structures of patchy particles and estimate surface energies which are essential to understand the underlying physics.

Preparation, characterization, and heat resistance studies of a holographic photopolymer based on SU-8 epoxy resin

A holographic photopolymer based on SU-8 epoxy resin as the binder and trimethylolpropane ethoxylate triacrylate as the monomer with an iodonium salt photoinitiator was studied. A diffraction efficiency of 93% and a refractive index modulation (Delta n) of 1.3 x 10(-2) were obtained from a 16 microm thick sample with write beam intensities of 50 mW/cm(2) at a wavelength of 514.5 nm, an exposure time of 60 s, and a postbaking at 65 degrees C for 1 h. The material exhibits good heat resistance in the range from 40 degrees C to 160 degrees C and long projected life.

Functional polymers by two-photon 3D lithography

In the presented work, two-photon 3D lithography and selective single-photon photopolymerization in a prefabricated polydimethylsiloxane matrix is presented as an approach with potential applicability of waveguide writing in 3D by two-photon polymerization. Photopolymers based on acrylate chemistry were used in order to evaluate the optical capabilities of the available two-photon system. Several photoinitiators, tailored for two-photon absorption, were tested in a mixture of trimethylolpropane triacrylate and ethoxylated trimethylolpropane triacrylate. Best results were obtained with a recently synthesized diynone-based photoinitiator. Feature resolutions in the range of 300 nm were achieved. Due to the cross-conjugated nature of that donor-π-acceptor-π-donor system a high two-photon absorption activity was achieved. Therefore, a resin mixture containing only 0.025 wt% of photoinitiator was practical for structuring by two-photon polymerization. The required initiator content was therefore a factor of 100 lower than in traditional one-photon lithography. The aim of the second part of this work was to fabricate optical waveguides by selectively irradiating a polymer network, which was swollen by a monomer. The monomer was polymerized by conventional single-photon polymerization and the uncured monomer was removed by evaporation at elevated temperatures. This treatment leads to a local change in refractive index. Refractive index changes in the range of Δ n = 0.01 (Δ n/ n = 0.7%) were achieved, which is sufficient for structuring waveguides for optoelectronic applications.

Magnetic CLEAR Supports for Solid-Phase Synthesis of Peptides and Small Organic Molecules

Paramagnetic versions of the CLEAR supports were prepared by entrapment of magnetite particles during suspension polymerization of allylamine, trimethylolpropane ethoxylate (14/3 EO/OH) triacrylate, and trimethylolpropane trimethacrylate. Swelling studies in a broad range of solvents showed comparable swelling of magnetic beads and regular CLEAR beads. The application of the magnetic beads as the support in solid-phase synthesis of peptides (Leu-enkephalinamide, substance P, acyl carrier protein (65–74) amide, and amyloid β-protein (34–42) amide) and small organic affinity ligands based on the s-triazine scaffold was demonstrated. Adequate stability of the beads and retention of their magnetic properties were observed throughout the synthesis steps.