2-hydroxypropyl Methacrylate Research Articles

Influence of Acrylic Emulsion on Polymer-Cement Waterproof Coating

In this study, effects of polymer-cement (P/C) ratio, glass transition temperature (Tg); amounts of functional monomers (acrylic acid, hydroxypropyl methacrylate, ammonium polyacrylate, diacetone acrylamide) on properties of polymer cement mortar were investigated. According of the tensile test, breaking elongation (ε) and the tensile strength (δ) of polymer latex-cement composites with low P/C ratio were mainly depended on Tg, differential Tg value between layer and shell in acrylic latex (ΔTg) and the amounts of functional monomer. Additionally, at a low P/C ratio, it was found that the cross-linking rate had small effect of tensile property. It was determined that the waterproofing coatings III with a low P/C (0.12) showed the excellent tensile property when the Tg and the ΔTg of the acrylic latex were controlled at -24°Cand -20°C, respectively.

Micropatterned Surfaces for Atmospheric Water Condensation via Controlled Radical Polymerization and Thin Film Dewetting.

Inspired by an example found in nature, the design of patterned surfaces with chemical and topographical contrast for the collection of water from the atmosphere has been of intense interest in recent years. Herein we report the synthesis of such materials via a combination of macromolecular design and polymer thin film dewetting to yield surfaces consisting of raised hydrophilic bumps on a hydrophobic background. RAFT polymerization was used to synthesize poly(2-hydroxypropyl methacrylate) (PHPMA) of targeted molecular weight and low dispersity; spin-coating of PHPMA onto polystyrene films produced stable polymer bilayers under appropriate conditions. Thermal annealing of these bilayers above the glass transition temperature of the PHPMA layer led to complete dewetting of the top layer and the formation of isolated PHPMA domains atop the PS film. Due to the vastly different rates of water nucleation on the two phases, preferential dropwise nucleation of water occurred on the PHPMA domains, as demonstrated by optical microscopy. The simplicity of the preparation method and ability to target polymers of specific molecular weight demonstrate the value of these materials with respect to large-scale water collection devices or other materials science applications where patterning is required.

Disulfide-Functionalized Diblock Copolymer Worm Gels.

Two strategies for introducing disulfide groups at the outer surface of RAFT-synthesized poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate) (PGMA-PHPMA, or Gx-Hy for brevity) diblock copolymer worms are investigated. The first approach involved statistical copolymerization of GMA with a small amount of disulfide dimethacrylate (DSDMA, or D) comonomer to afford a G54-D0.50 macromolecular chain transfer agent (macro-CTA); this synthesis was conducted in relatively dilute solution in order to ensure mainly intramolecular cyclization and hence the formation of linear chains. Alternatively, a new disulfide-based bifunctional RAFT agent (DSDB) was used to prepare a G45-S-S-G45 (or (G45-S)2) macro-CTA. A binary mixture of a non-functionalized G55 macro-CTA was utilized with each of these two disulfide-based macro-CTAs in turn for the RAFT aqueous dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA). By targeting a PHPMA DP of 130 and systematically varying the molar ratio of the two macro-CTAs, a series of disulfide-functionalized diblock copolymer worm gels were obtained. For both formulations, oscillatory rheology studies confirmed that higher disulfide contents led to stronger gels, presumably as a result of inter-worm covalent bond formation via disulfide/thiol exchange. Using the DSDB-based macro-CTA led to the strongest worm gels, and this formulation also proved to be more effective in suppressing the thermosensitive behavior that is observed for the nondisulfide-functionalized control worm gel. However, macroscopic precipitation occurred when the proportion of DSDB-based macro-CTA was increased to 50 mol %, whereas the DSDMA-based macro-CTA could be utilized at up to 80 mol %. Finally, the worm gel modulus could be reduced to that of a nondisulfide-containing worm gel by reductive cleavage of the inter-worm disulfide bonds using excess tris(2-carboxyethyl)phosphine (TCEP) to yield thiol groups. These new biomimetic worm gels are expected to exhibit enhanced muco-adhesion.

Characterization of Diblock Copolymer Order-Order Transitions in Semidilute Aqueous Solution Using Fluorescence Correlation Spectroscopy

The temperature and pH-dependent diffusion of poly(glycerol monomethacrylate)-block-poly(2-hydroxypropyl methacrylate) nanoparticles prepared via polymerization-induced self-assembly in water is characterized using fluorescence correlation spectroscopy (FCS). Lowering the solution temperature or raising the solution pH induces a worm-to-sphere transition and hence an increase in diffusion coefficient by a factor of between four and eight. FCS enables morphological transitions to be monitored at relatively high copolymer concentrations (10% w/w) compared to those required for dynamic light scattering (0.1% w/w). This is important because such transitions are reversible at the former concentration, whereas they are irreversible at the latter. Furthermore, the FCS data suggest that the thermal transition takes place over a very narrow temperature range (less than 2 °C). These results demonstrate the application of FCS to characterize order-order transitions, as opposed to order-disorder transitions.

Preparation of Pickering double emulsions using block copolymer worms.

The rational formulation of Pickering double emulsions is described using a judicious combination of hydrophilic and hydrophobic block copolymer worms as highly anisotropic emulsifiers. More specifically, RAFT dispersion polymerization was utilized to prepare poly(lauryl methacrylate)–poly(benzyl methacrylate) worms at 20% w/w solids in n-dodecane and poly(glycerol monomethacrylate)–poly(2-hydroxypropyl methacrylate)–poly(benzyl methacrylate) worms at 13% w/w solids in water by polymerization-induced self-assembly (PISA). Water-in-oil-in-water (w/o/w) double emulsions can be readily prepared with mean droplet diameters ranging from 30 to 80 μm using a two-stage approach. First, a w/o precursor emulsion comprising 25 μm aqueous droplets is prepared using the hydrophobic worms, followed by encapsulation within oil droplets stabilized by the hydrophilic worms. The double emulsion droplet diameter and number of encapsulated water droplets can be readily varied by adjusting the stirring rate employed during the second stage. For each stage, the droplet volume fraction is relatively high at 0.50. The double emulsion nature of the final formulation was confirmed by optical and fluorescence microscopy studies. Such double emulsions are highly stable to coalescence, with little or no change in droplet diameter being detected over storage at 20 °C for 10 weeks as judged by laser diffraction. Preliminary experiments indicate that the complementary o/w/o emulsions can also be prepared using the same pair of worms by changing the order of homogenization, although somewhat lower droplet volume fractions were required in this case. Finally, we demonstrate that triple and even quadruple emulsions can be formulated using these new highly anisotropic Pickering emulsifiers.

Graft and block copolymers of chitosan with vinyl monomers: Synthesis, structure, and properties

Block and graft copolymers of chitosan with methyl acrylate, 2-ethylhexyl acrylate, 2-hydroxy- ethyl methacrylate, 2-hydroxypropyl methacrylate, and styrene with different spatial orientations of natural and synthetic chains and molecular masses are synthesized. The effects of the structures of the copolymers on the physicomechanical properties of their films and their biodegradability by micromycetes are revealed.

Testing the vesicular morphology to destruction: birth and death of diblock copolymer vesicles prepared via polymerization-induced self-assembly.

Small angle X-ray scattering (SAXS), electrospray ionization charge detection mass spectrometry (CD-MS), dynamic light scattering (DLS), and transmission electron microscopy (TEM) are used to characterize poly(glycerol monomethacrylate)55-poly(2-hydroxypropyl methacrylate)x (G55-Hx) vesicles prepared by polymerization-induced self-assembly (PISA) using a reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization formulation. A G55 chain transfer agent is utilized to prepare a series of G55-Hx diblock copolymers, where the mean degree of polymerization (DP) of the membrane-forming block (x) is varied from 200 to 2000. TEM confirms that vesicles with progressively thicker membranes are produced for x = 200–1000, while SAXS indicates a gradual reduction in mean aggregation number for higher x values, which is consistent with CD-MS studies. Both DLS and SAXS studies indicate minimal change in the overall vesicle diameter between x = 400 and 800. Fitting SAXS patterns to a vesicle model enables calculation of the membrane thickness, degree of hydration of the membrane, and the mean vesicle aggregation number. The membrane thickness increases at higher x values, hence the vesicle lumen must become smaller if the external vesicle dimensions remain constant. Geometric considerations indicate that this growth mechanism lowers the total vesicle interfacial area and hence reduces the free energy of the system. However, it also inevitably leads to gradual ingress of the encapsulated water molecules into the vesicle membrane, as confirmed by SAXS analysis. Ultimately, the highly plasticized membranes become insufficiently hydrophobic to stabilize the vesicle morphology when x exceeds 1000, thus this PISA growth mechanism ultimately leads to vesicle “death”.

The role of acrylic acid impurity as a sensitizing component in electrocardiogram electrodes

Allergic contact dermatitis caused by (meth)acrylates is well known, both in occupational and in non-occupational settings. Contact hypersensitivity to electrocardiogram (ECG) electrodes containing (meth)acrylates is rarely reported. To report the first case of contact dermatitis caused by acrylic acid impurity in ECG electrodes. Patch tests were performed with separate components of electrodes and some (meth)acrylates. This was followed by high-performance liquid chromatography of electrode hydrogel. The patient was contact-allergic to electrode hydrogel but not to its separate constituents. Positive reactions were observed to 2-hydroxyethyl methacrylate (2-HEMA), 2-hydroxypropyl methacrylate (2-HPMA) and ethyleneglycol dimethacrylate (EGDMA). Subsequent analysis showed that the electrode hydrogel contained acrylic acid as an impurity. The latter was subsequently patch tested, with a positive result. The sensitization resulting from direct contact with ECG electrodes was caused by acrylic acid, present as an impurity in ECG electrodes. Positive reactions to 2-HEMA, 2-HPMA and EGDMA are considered to be cross-reactions.

Contact allergy to acrylates and methacrylates in consumers and nail artists - data of the Information Network of Departments of Dermatology, 2004-2013.

Allergic contact dermatitis caused by (meth)acrylates used in artificial nails is a relevant problem in both nail artists and consumers. To analyse the frequency of this problem in the contact allergy surveillance network Information Network of Departments of Dermatology in 2004-2013, and address possible time trends and patterns of co-sensitization. A retrospective analysis of patch test results with (meth)acrylates, along with clinical and demographic data, was performed. These were used to subdivide patients according to (i) a potentially exposed occupation and (ii) nail cosmetics as the suspected cause of contact dermatitis. Among the 114 440 patients patch tested, 72 244 were female and were considered further. Eighty-seven patients both worked as nail artists/cosmetologists and suspected nail cosmetics as the cause of dermatitis. Among these, 47.1% reacted to at least one (meth)acrylate, most often to 2-hydroxyethyl methacrylate (n = 27), 2-hydroxypropyl methacrylate, and hydroxyethyl acrylate (n = 26 each), with marked coupled reactivity. In other subgroups of interest, frequencies of sensitization to (meth)acrylates were less elevated but higher than in all remaining female patients (n = 69 419). The results indicate a not entirely common, but potentially serious, problem, especially concerning occupationally exposed, and sensitized, nail artists. Adequate protective measures should be taught as part of the vocational training.

Hydroxypropyl Methacrylate Interaction and Chitosan Coating for Enhanced UV Detection Sensitivity of Colloidal Nanoparticles in Capillary Electrophoresis Analysis

The binding interactions between silica (SiO2), titania (TiO2) or polymeric nanoparticles with hydroxypropyl methacrylate (HPMA) were investigated for enhancing the ultraviolet (UV) detection sensitivity of these nanoparticles in capillary electrophoresis (CE) analysis. HPMA interacted with colloidal SiO2 nanoparticles, producing a larger CE-UV peak at a slightly shorter migration time. An increase in particle size with HPMA binding was validated using dynamic light scattering. The interaction was selective as HPMA did not interact with TiO2 nanoparticles in aqueous suspension. Chitosan coating of SiO2 or TiO2 nanoparticles produced significantly larger hydrodynamic diameters to further enhance the sensitivity of their UV detection. The analytical technique, which involves coating SiO2 nanoparticles with chitosan first and binding with HPMA next, is novel. It has allowed us to achieve a significant enhancement of 50 folds in detection sensitivity.

Polysulfobetaine-based diblock copolymer nano-objects via polymerization-induced self-assembly

A zwitterionic polysulfobetaine-based macro-CTA is used for the synthesis of spheres, worms or vesiclesviaaqueous RAFT dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA). These new diblock copolymer nano-objects exhibit high tolerance of added salt.

PH-responsive non-ionic diblock copolymers: ionization of carboxylic acid end-groups induces an order-order morphological transition.

A carboxylic acid based reversible additionfragmentation transfer (RAFT) agent is used to prepare gels composed of worm-like diblock copolymers using two non-ionic monomers, glycerol monomethacrylate (GMA) and 2-hydroxypropyl methacrylate (HPMA). Ionization of the carboxylic acid end-group on the PGMA stabilizer block induces a worm-to-sphere transition, which in turn causes immediate degelation. This morphological transition is fully reversible as determined by TEM and rheology studies and occurs because of a subtle change in the packing parameter for the copolymer chains. A control experiment where the methyl ester derivative of the RAFT agent is used to prepare the same diblock copolymer confirms that no pH-responsive behavior occurs in this case. This end-group ionization approach is important for the design of new pH-responsive copolymer nano-objects as, unlike polyacids or polybases, only a minimal amount of added base (or acid) is required to drive the morphological transition.

Oil resistance and mechanical properties of polysiloxane nanocomposites prepared by in situ reaction of reactive polar monomers

ABSTRACTA series of poly(methylvinylsiloxane) elastomer (VMQ) composites with improved oil resistance were prepared by introducing uniform polar polymer phases into VMQ matrix through the in situ reaction of reactive polar monomers—hydroxyethyl methacrylate (HEMA) and hydroxypropyl methacrylate (HPMA)—during peroxide curing. Differential scanning calorimetry and Fourier transform infrared measurements demonstrated that HEMA and HPMA had high reactivity and most of the monomers participated in the in situ reaction during peroxide curing. Transmission electron microscopic images showed that the uniform nanophases with the diameters in the range of 20–50 nm formed in the VMQ vulcanizates. The generated nanophases could interact with silica to form a strong filler network in the VMQ matrix, resulting in a significant increase of the modulus at low elongation of the VMQ vulcanizates. With increasing the content of polar monomers, the tensile strength decreased slightly, the elongation at break, the hardness and the 100% modulus increased, but the 300% modulus decreased significantly due to the decrease of the crosslink density. The incorporation of HEMA or HPMA into VMQ matrix could significantly improve the oil resistance of polysiloxane elastomer, and the oil resistance of the composites containing HEMA was a little better than that of the composites containing HPMA. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40983.

Polymer coatings for sensitive analysis of colloidal silica nanoparticles in water

A new analytical approach has been developed for the sensitive detection of trace nanomaterials in water using silica as model inorganic nanoparticles. Our novel approach is based on coating of the nanoparticles with a polymer to make them larger in size for better ultraviolet (UV) light absorption. These polymer-coated nanoparticles can be separated from the monomer and polymer by capillary electrophoresis (CE) due to differences in their ionic charge, size, and surface functionality. Controlled polymerization of 2-hydroxypropyl methacrylate (HPMA) on silica nanoparticles increased their UV detection sensitivity by 5–7-fold. A second coating with polydopamine produced an extra 2-fold increase of the UV detection sensitivity. With both polyhydroxypropyl methacrylate and polydopamine coatings, a significant total enhancement of 10–14-fold in detection sensitivity was attained. Alternatively, addition of bisphenol A or polyvinyl alcohol to the HPMA polymerization mixture resulted in 9–10-fold increase of SiO2 detection sensitivity due to additional absorption of the UV detector light.

RAFT Aqueous Dispersion Polymerization Yields Poly(ethylene glycol)-Based Diblock Copolymer Nano-Objects with Predictable Single Phase Morphologies

A poly(ethylene glycol) (PEG) macromolecular chain transfer agent (macro-CTA) is prepared in high yield (>95%) with 97% dithiobenzoate chain-end functionality in a three-step synthesis starting from a monohydroxy PEG113 precursor. This PEG113-dithiobenzoate is then used for the reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA). Polymerizations conducted under optimized conditions at 50 °C led to high conversions as judged by 1H NMR spectroscopy and relatively low diblock copolymer polydispersities (Mw/Mn < 1.25) as judged by GPC. The latter technique also indicated good blocking efficiencies, since there was minimal PEG113 macro-CTA contamination. Systematic variation of the mean degree of polymerization of the core-forming PHPMA block allowed PEG113-PHPMAx diblock copolymer spheres, worms, or vesicles to be prepared at up to 17.5% w/w solids, as judged by dynamic light scattering and transmission electron microscopy studies. Small-angle X-ray scattering (SAXS) analysis revealed that more exotic oligolamellar vesicles were observed at 20% w/w solids when targeting highly asymmetric diblock compositions. Detailed analysis of SAXS curves indicated that the mean number of membranes per oligolamellar vesicle is approximately three. A PEG113-PHPMAx phase diagram was constructed to enable the reproducible targeting of pure phases, as opposed to mixed morphologies (e.g., spheres plus worms or worms plus vesicles). This new RAFT PISA formulation is expected to be important for the rational and efficient synthesis of a wide range of biocompatible, thermo-responsive PEGylated diblock copolymer nano-objects for various biomedical applications.

Aqueous worm gels can be reconstituted from freeze-dried diblock copolymer powder.

Worm-like diblock copolymer nanoparticles comprising poly(glycerol monomethacrylate) (PGMA) as a stabilizer block and poly(2-hydroxypropyl methacrylate) (PHPMA) as a core-forming block were readily synthesized at 10% w/w solids via aqueous dispersion polymerization at 70 °C using Reversible Addition-Fragmentation chain Transfer (RAFT) chemistry. On cooling to 20 °C, soft transparent free-standing gels are formed due to multiple inter-worm interactions. These aqueous PGMA-PHPMA diblock copolymer worms were freeze-dried, then redispersed in water with cooling to 3-5 °C before warming up to 20 °C; this protocol ensures molecular dissolution of the copolymer chains, which aids formation of a transparent aqueous gel. Rheology, SAXS and TEM studies confirm that such reconstituted gels comprise formed PGMA-PHPMA copolymer worms and they possess essentially the same physical properties determined for the original worm gels prior to freeze-drying. Such worm gel reconstitution is expected to be highly beneficial in the context of various biomedical applications, since it enables worm gels to be readily prepared using a wide range of cell growth media as the continuous aqueous phase.

The effect of the cross-linker content on the swelling properties of intelligent gels

This paper presents the procedure for the synthesis of hydrogels based on N-isopropylacrylamide (NIPAM) and 2-hydroxypropyl methacrylate (HPMet) using dioxan as a solvent. Hydrogels were obtained by radical polymerization using different contents of ethylene glycol dimethacrylate as a cross-linker and benzoyl peroxide as the initiator. In the FTIR spectra of poly(N-isopropylacrylamide-co- 2-hydroxypropylmethacrylate) (p(NIPAM-HPMet)) xerogel, new absorption bands are present and there are no specific bands characteristic of a monomer NIPAM, which indicates that copolymerization was performed. SEM micrographs show porous surfaces of xerogels. The aim of this work was the investigation of the swelling behavior for all synthesized hydrogels with different cross-linker content at the temperature from 20 to 40°C. The sample of p(NIPAM-HPMet) with the lowest cross-linker content reached the highest swelling degree at 20°C (α=20.23). The degree of swelling decreased with increa-sing the cross-linker content and temperature, so the samples with highest cross-linker content at 40°C reached the swelling degree of 2.05.

Partitioning of Functional Monomers in Emulsion Polymerization: Distribution of Hydroxy (Meth)acrylate Monomers between Water and Single and Multimonomer Systems

We have studied the partitioning behavior of a series of hydroxy acrylate monomers (2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate) between water and a variety of styrene, acrylate, and methacrylate homo-, co-, and termonomer phases. The distribution coefficients for both single and multicomponent systems strongly depend upon the hydrogen bond acceptor characteristics of the organic phase, but not on the pH of the aqueous phase. These measured distribution coefficients for multicomponent monomer systems can be adequately predicted by applying an appropriate “mixing rule” to the distribution and dimerization coefficients obtained from single monomer systems. The logarithms of these binary coefficients correlate linearly with the molar volume of the (meth)acrylate monomer phase. Hydroxy acrylate monomers are subject to dimerization and multimer formation in organic phases and those equilibrium coefficients are roughly equal for the three monomers studied here, despite their wide difference in polarities. When vinyl acid and hydroxy acrylate monomers are used simultaneously, the distribution coefficients for both monomers increase. These effects depend upon the polarity of the organic phase, the polarities of both functional monomers, and the amount of the functional monomers used in the system. We found minor effects of temperature and negligible effects of ionic strength for the usual emulsion polymerization conditions.

Swelling–shrinking behavior of hydrated noncross‐linked copolymer films in response to photoreversible isomerizaton and metal complexation of spiropyran units of the copolymers

The copolymer of hydroxypropyl methacrylate (HPMA) and photochromic spiropyran methacrylate (SPMA) has been synthesized. The films of the copolymer (P(HPMA‐SPMA)) in a hydrated state showed reversible swelling–shrinking behavior in response to photoreversible isomerization and metal complexation of SPMA units in spite of covalently noncross‐linked copolymers. In addition, the protonated open form of the SPMA units of the copolymer was possibly stabilized thermodynamically by the HPMA units from ultraviolet–visible absorption measurement of the hydrated P(HPMA‐SPMA) film. On the other hand, the difference in color of the hydrated films between P(HPMA‐AABMA) and P(NIPMA‐AABMA), which was a copolymer of N‐isopropyl methacryl amide (NIPMA) and azobenzene methacrylate (AABMA) as a pH indicator, was suggestive of the interference of the proximal hydroxyl groups of the immobilized HPMA units with protonation of the AABMA units. The HPMA units of the copolymers also contributed to improvement of thermodynamic stability of the metal complexes with the SPMA units. Copyright © 2013 John Wiley &amp; Sons, Ltd.

Silane-Treated E-Glass Fiber-Reinforced Telechelic Macromer-Based Polymer-Matrix Composites

The aim of this in vitro study was to investigate the water sorption and flexural properties of fiber reinforced composites (FRC) prepared from telechelic macromer extended urethane dimethacrylate (PEG-400-E-UEDMA)(PEG), hydroxypropyl methacrylate (HPMA) and E-glass fibers. Three experimental groups of test specimens based on poly(PEG-400-E-UEDMA-HPMA) polymer matrices and continuous unidirectional E-glass fibers were light polymerized and stored in deionized water for 0, 4, 12 or 24 weeks. The weight ratios (%) of PEG-HPMA were 27.5–70.5, 49.0–49.0 and 70.5–27.5 with an initiator-activator percentage of 1.0–1.0. After each time period of storage the water absorption and flexural properties were measured. There were six test specimens in each of the test groups (N = 6) and the specimen’s fracture surfaces were analyzed using scanning electron microscopy (SEM). All the PEG-HPMA groups exhibited the highest water absorption at the time point of two days (5.5 to 6.4 %), which thereafter decreased to the level of 3.8–4.7 % at the time point of 30 days. The flexural strength varied from dry specimens’ 128 to 283 MPa to the 30 days water-stored specimens’ of 30 to 49 MPa. The flexural modulus exhibited values from 7.9 to 14.8 GPa (dry specimens) and ca. 0.5 to 1.8 GPa after 30 days of water-storage. Both the flexural strength and modulus decrease dramatically with a longer water storage time. The SEM images showed good adhesion between the fibers and the resin matrix. In the wet conditions, the telechelic macromer based hydrophilic PEG polymer-matrix FRCs formed a plasticized composite that decreased the flexural properties.