Hydroxypropyl Acrylate Research Articles

Synthesis and characterization of UV-curable castor oil-based polyfunctional polyurethane acrylate via photo-click chemistry and isocyanate polyurethane reaction

Abstract In this paper, UV-curable castor oil-based polyfunctional polyurethane acrylate (COME-PUA) was synthesized via photo-click chemistry and isocyanate polyurethane reaction. Facile and highly efficient side-chain functionalization of castor oil (CO) was first achieved via thiol-ene photo-click chemistry with β-mercaptoethanol (ME). 1 H NMR result indicated that almost 100% conversion of double-bond in CO was observed within 10 min, and the average hydroxyl functionality of the obtained polyol COME was about 6. Next, COME was modified by isocyanate polyurethane reaction with hydroxypropyl acrylate (HPA), isophorone diisocyanate (IPDI) and PEG-200 as the chain extender in order to prepare the resin COME-PUA. Results of both 1 H NMR and FTIR revealed that the targeted COME and COME-PUA were successfully synthesized. Furthermore, UV-curing kinetic of COME-PUA was revealed by real-time FTIR, showing a higher UV-curing rate than the common CO-PUA. Finally, some physical properties of curing films were studied.

Complexation of thermoresponsive dialkoxynaphthalene end-functionalized poly(oligoethylene glycol acrylate)s with CBPQT4+in water

Four different oligoethylene glycol acrylates (OEGA), namely hydroxypropylacrylate (HPA), methoxy diethylene glycol acrylate (mDEGA), methoxy triethylene glycol acrylate (mTEGA) and 2-hydroxyethylacrylate (HEA) were homopolymerized via RAFT polymerization employing a naphthalene functionalized chain transfer agent resulting in thermoresponsive naphthalene-functionalized POEGAs with different hydrophilicities. Supramolecular inclusion complexes of these POEGAs with electron-deficient cyclophane cyclobis(paraquat-p-phenylene) tetrachloride (CBPQT4+) in water were studied. The association constants (Ka) were determined to study the effect that polymer hydrophilicity has on the Ka and results indicated that the nature of the polymer did not significantly influence the complexation strength and the association is mostly enthalpy driven. The impact of temperature on the host–guest complexes was also investigated. A continuous partial thermally induced dissociation of complexes was observed upon raising the temperature with a more distinct decrease in complexation around the cloud point temperature (TCP) of the POEGA employed, indicating the importance of the polymer phase transition for tuning the recognition properties of dialkoxynaphthalene end-decorated poly(oligoethylene glycol acrylate)s in water.

The shape of protein–polymer conjugates in dilute solution

ABSTRACTProtein–polymer conjugation can significantly affect many different aspects of protein behavior, ranging from their solution properties to their ability to form solution and bulk nanostructured materials. An underlying fundamental question is how the molecular design affects the shape of the conjugate and, consequently, its properties. This work measures the molecular configuration of model protein–polymer conjugates in dilute solution using small‐angle neutron scattering (SANS) and uses quantitative model fitting to understand the shape of the molecules. Form factor measurements of four model bioconjugates of the red fluorescent protein mCherry and the polymers poly(N‐isopropylacrylamide), poly(hydroxypropyl acrylate), poly(oligoethylene glycol acrylate), and poly(ethylene glycol) show that these protein–polymer conjugates are well described by a recently developed scattering function for colloid–polymer conjugates that explicitly incorporates excluded volume interactions in the polymer configuration. In the regime where the protein does not exhibit strong interactions with the polymer, modeling the protein–polymer interactions using a purely repulsive Weeks–Chandler–Andersen potential also leads to a coarse‐grained depiction of the conjugate that agrees well with its scattering behavior. The coarse‐grained model can additionally be used for systems with varying protein–polymer interactions, ranging from purely repulsive to strongly attractive, which may be useful for conjugates with strong electrostatic or hydrophobic attractive interactions. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 292–302

Preparation and characterization of ambient-temperature self-crosslinkable water-soluble acrylic resin for PE film ink

An ambient-temperature self-crosslinkable acrylic resin was synthesized by solution polymerization, with ethanol as solvent; butyl acrylate (BA), methyl methacrylate (MMA), acrylic acid (AA), hydroxypropyl acrylate (HPA), and diacetone acrylamide (DAAM) as monomers; and adipic acid dihydrazide (ADH) as crosslinker. The resin could be diluted by water. The resin was used for PE film ink, and its curing behavior and film properties were studied. FTIR and DSC results indicated that the reaction between ketone carbonyl and hydrazine groups could occur during film curing at ambient temperature and improved glass transition temperature (T g) of the film by 12.67°C. Crosslinking density of film increased with DAAM content and m(ADH)/m(DAAM) ratio. Adhesion on PE film increased with DAAM content, while it first increased then decreased with m(ADH)/m(DAAM) ratio. Water absorption of film decreased with DAAM content, while it first decreased then increased with m(ADH)/m(DAAM) ratio. The optimal m(ADH)/m(DAAM) ratio and DAAM content in this experiment are 0.8:1 and 2%, respectively. Compared with ambient-temperature self-crosslinkable emulsion, this water-soluble resin shows film not only with the same adhesion, but also without any shrinkage void, indicating better film-forming ability on PE film. The ambient-temperature self-crosslinkable water-soluble acrylic resin shows excellent potential application in water-based ink for PE film because of good film-forming ability and adhesion and low water absorption.

Facile synthesis of poly(DMC‐co‐HPA) hydrogels via infrared laser ignited frontal polymerization and their adsorption–desorption switching performance

ABSTRACTIn this work, we report a versatile infrared laser ignited frontal polymerization technique for the fabrication of a series of poly(DMC‐co‐HPA) hydrogels (DMC = methacryloxyethyltrimethyl ammonium chloride, HPA = hydroxypropyl acrylate). Because the method is based on the exothermic reaction, no further energy is required in the reaction once it is initiated. Moreover, we have found the polymerization process is a pure frontal polymerization model without involving any other reaction process. The dependence of frontal velocity and temperature on the reaction time is thoroughly discussed. The as‐prepared hydrogels are pH‐responsive and their maximum equilibrium swelling ratio could reach ∼3,890%. Also, the as‐prepared poly(DMC‐co‐HPA) hydrogels capable of adsorption/desorption switching performance can be utilized for heavy metal ion removal in wastewater treatments. Interestingly, the hydrogels can float on the water surface after intaking heavy metal ions by the combination of kerosene and polyoxyethylene sorbitan monolaurate (Tween 20) in hydrogel components, greatly enhancing treatment efficiency. We believe the method described herein to rapidly construct functional hydrogels with the ability to remove heavy metal ions may find unique applications in emergency processing of water pollution. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2085–2093

Synthesis of Polyfunctional Castor Oil-Based Polyurethane Acrylate by the Auxiliary of Thiol-Ene Click Reaction

In this paper, we report a synthetic method to prepare vegetable oil-based polyurethane acrylate (PUA) resin, which can be used in photo polymerization coating, ink and other fields. First, the mercaptoethanol was introduced into castor oil via thiol-ene photo-click reaction with UV irradiation, forming polyhydroxy compounds, then we added the isocyanate acrylate, which was obtained by the reaction between hydroxypropyl acrylate (HPA) and isophorone diisocyanate (IPDI), into polyhydroxy compounds, the molar ratio of HPA and IPDI is 1:1. Finally, we get the castor oil-based polyurethane acrylate. Different functional acrylate can be obtained by adjusting the hydroxyl content. Furthermore, the structure and performance of Polyurethane acrylate was confirmed by FT-IR and TG. The water absorption and adhesion of synthetic polyurethane acrylate were tested. Meanwhile, the thermal stability was studied. The results indicated that the thiol-ene addition reaction was proceeded and compared to our previous studies, the properties of cured film are greatly improved, especially the hardness and thermal stability.

Estimating Monomer Sequence Distributions in Tetrapolyacrylates

Recently Ting et al. [ACS Macro Lett. 2013, 2, 770−774] described the syntheses of acrylic tetrapolymers with controlled molecular weights and tetramonomer compositions. Relative reactivity ratios of all monomer pairs were determined and used in the Walling–Briggs terminal copolymerization model along with Skeist’s equations to address the expected compositional drift in the monomer feed ratios. The anticipated control of monomer incorporation based on this approach was verified experimentally on several tetrapolyacrylates synthesized by RAFT polymerization, which additionally controlled their molecular weights. Their “new and simple paradigm combining both predictive models provides complementary synthetic and predictive tools for designing macromolecular chemical architectures with hierarchical control over spatially dependent structure–property relationships for complex applications” is extended here to the derivation of expected monad compositions, and diad, triad, and tetrad monomer sequence distributions. These were obtained directly from the comonomer reactivity ratios determined experimentally by Ting et al. Our motivation was twofold: (i) The similar chemical structures of the four acrylate monomers they selected (methyl, 2-carboxyethyl, 2-hydroxypropyl, and 2-propylacetyl acrylate) render the experimental determination of sequence distributions in the resulting tetrapolyacrylates problematic. (ii) Because they are spatially dependent structural parameters, the sequence distributions of monomer diads, triads, tetrads, etc., in co-, tri-, tetrapolymers, etc., are generally expected to correlate more closely with their properties than their overall compositions.

Evaluation of poly(2-ethyl-2-oxazoline) containing copolymer networks of varied composition as sustained metoprolol tartrate delivery systems.

Segmented copolymer networks (SCN) based on poly(2-ethyl-2-oxazoline) and containing 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and/or methyl methacrylate segments have been evaluated as potential sustained release systems of the water soluble cardioselective β-blocker metoprolol tartrate. The structure and properties of the drug carriers were investigated by differential scanning calorimetry, attenuated total reflectance Fourier transform infrared spectroscopy, scanning electron microscopy, and atomic force microscopy. Swelling kinetics of SCNs in various media was followed, and the conditions for effective MT loading were specified. MT-loaded SCNs with drug content up to 80wt.% were produced. The release kinetics of metoprolol tartrate from the systems was studied and it was shown that the conetworks of different structure and composition are able to sustain the metoprolol tartrate release without additional excipients.

Facile functionalization of soybean oil by thiol-ene photo-click reaction for the synthesis of polyfunctional acrylate

Nowadays biosource-based materials have received revitalized interest for their ability to substitute for petrochemical-based materials. In this paper, we report a facile synthetic method of soybean oil-based polyfunctional acrylate (PFA) for UV-curable materials. Specifically, rapid and highly efficient side-chain functionalization of soybean oil was achieved via photoclick thiol-ene reaction, soybean oil-based polycarboxylic acid (PCA) was thus obtained. Next, by DCC (N,N′-dicyclohexylcarbodiimide) catalyzed esterification reaction with hydroxypropyl acrylate, polyfunctional acrylate (PFA) was synthesized at room temperature. Real-FTIR result indicated that almost 100% conversion of double-bond within vegetable oil was observed within 16.7 min, yielding the soybean oil-based polycarboxylic acid quantitatively. Furthermore, the structure of PFA was confirmed by 1H NMR and FTIR. Finally, the excellent UV-curing rate of PFA was revealed by real-FTIR.

Dermal permeation of 2-hydroxypropyl acrylate, a model water-miscible compound: Effects of concentration, thermodynamic activity and skin hydration

The goal of these studies was to measure and interpret the skin permeability characteristics of 2-hydroxypropyl acrylate (HPA) as a model compound that is completely miscible with water. In vitro permeation from HPA-H2O binary mixtures through human epidermis and silicone membranes was measured. Thermodynamic activities of HPA and H2O in these mixtures were determined. Permeation was also measured through epidermis and silicone from donor solutions with constant HPA activity but different H2O activities. Water uptake into desiccated human stratum corneum (SC) equilibrated with HPA-H2O mixtures was determined. Steady-state flux of HPA through silicone was a linear function of HPA activity but not HPA concentration. For epidermis on the other hand, flux increased with HPA activity only for HPA activities ≤ 0.35. At constant HPA activity, flux decreased 4.5-fold as water activity decreased from 1 to 0.8. Incubation of SC with HPA-H2O mixtures resulted in substantial changes in SC water content, dependent on the water activity of the mixture and consistent with measured SC water sorption data. These experiments provide unequivocal evidence of a substantial increase in epidermal barrier function resulting from SC dehydration. Dehydration-related alterations in the SC appear responsible for the observed flux characteristics.

Synthesis and Characterization of PBA-P(MMA-HPMA) Core-Shell Latex Particles

In this paper, Taken the methyl hydroxypropyl acrylate (HPMA) as functional monomer, a novel poly (butyl acrylate)-poly (methyl methacrylate-methyl hydroxypropyl acrylate) (PBA-P(MMA-HPMA)) core-shell latex particles were synthesized by the method of pre-emulsion semi-continuous seeded emulsion polymerization. The structure and morphology of core-shell latex particles were characterized by the way of laser particle size analyzer, transmission electron microscope (TEM), fourier transform infrared spectrometer (FTIR), nonaqueous acid-base titration, differential scanning calorimetry (DSC). Experimental results showed that the average size of PBA-P(MMA-HPMA) core-shell latex particles was 340nm and the average size of PBA core latex particles was 270nm. The functional monomer HPMA really participated in shell layer copolymerization, when the dosage of HPMA was 8% of shell monomer, HPMA content in the shell was the largest and reached 2.16%. Tg value of the copolymer P(MMA-HPMA) was firstly increased and then reduced with the increasing of HPMA content in shell.

Precise Compositional Control and Systematic Preparation of Multimonomeric Statistical Copolymers.

A comprehensive approach to target exact molecular weights and chemical compositions for multimonomeric statistical copolymers using a new controlled statistics method with reversible addition-fragmentation chain transfer free-radical (RAFT) polymerization is presented. The system chosen to illustrate this procedure is an acrylic quarterpolymer consisting of methyl acrylate, 2-carboxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-propylacetyl acrylate, modeling a well-known macromolecule utilized to deliver poorly water-soluble drugs (hydroxypropyl methylcellulose acetate succinate, HPMCAS). The relative reactivities at 70 °C between monomer pairs were measured and employed to predict the feed ratio necessary for synthesizing well-defined compositions based on the Walling-Briggs model. Application of Skeist's equations addressed compositional drift and anticipated the general monomer incorporation distribution as a function of conversion, which was verified experimentally. This new and simple paradigm combining both predictive models provides complementary synthetic and predictive tools for designing macromolecular chemical architectures with hierarchical control over spatially dependent structure-property relationships for complex applications such as oral drug delivery.

Synthesis and properties of a novel UV-curable waterborne hyperbranched polyurethane

A series of ultraviolet (UV)-curable waterborne hyperbranched polyurethane dispersions (WHPUDs) have been successfully synthesized by modifying the hyperbranched polyester H10, which was prepared using pentaerythritol as a core molecule and dimethylolpropionic acid as monomers, with succinic anhydride, toluene diisocyanate (TDI), and hydroxypropyl acrylate (HPA). The H10 was characterized by 1H nuclear magnetic resonance spectroscopy and matrix-assisted laser desorption/ionization time of flight mass spectrometry. The properties of the WHPUDs with different content of succinic anhydride and TDI–HPA have been investigated by measuring the stability, the particle size, and the rheological behavior. The effects of the content of succinic anhydride and TDI–HPA were studied in terms of UV-curing rate, water resistance, and thermogravimetric behaviors of WHPUD coatings. The WHPUDs showed good appearance, particle size, viscosity, and storage stability. The WHPUD films showed superior photosensitivity and the percent conversion of C=C bonds reached about 80% when the radiation time was 50 s. Moreover, the UV-cured films had good water resistance and thermostability, which can benefit a waterborne polyurethane resin for waterborne coatings.

Synthesis of amphiphilic PVC-b-poly(hydroxypropyl acrylate) (PHPA)-b-PVC block copolymers with low PHPA contents and different molecular weights by (Single Electron Transfer)-(Degenerative Chain Transfer) living radical polymerization

The aim of this work was to synthesize new amphiphilic block copolymers, based on poly(vinyl chloride) (PVC) and containing poly(hydroxypropyl acrylate) (PHPA), by using the controlled/“living” radical polymerization (CLRP) method. Various block copolymers containing a small proportion of PHPA were prepared, each having a different molecular weight. The technique used was the same as that employed in the production of commercial PVC made by free-radical polymerization. The materials were characterized in terms of their molecular structure, morphology, particle size, and surface and thermal properties. The CLRP preparation of block copolymers that are based on PVC and have low contents of other monomer units opens the possibility of synthesizing new materials whose properties are close to those of PVC but have new properties that may considerably enhance their performance. The incorporation of small amounts of PHPA into PVC block copolymers provided greater surface hydrophilicity and improved thermal stability while maintaining relevant processing properties, such as particle size and average molecular weight, so that they close to those of conventional PVC homopolymers. J. VINYL ADDIT. TECHNOL., 19:157-167, 2013. © 2013 Society of Plastics Engineers

Poly(vinyl chloride)‐b‐poly(hydroxypropyl acrylate)‐b‐Poly(vinyl chloride): Understanding the synthesis of an amphiphilic PVC block copolymer on a pilot scale

The aim of this work was to develop an understanding of the major difficulties associated with the scale‐up of the technology for the synthesis of poly(vinyl chloride) (PVC) block copolymers that contain hydrophilic segments, thus providing important directions to be followed in order to produce such new materials on the industrial scale. The synthesis was carried out in a two‐step process. First, the macroinitiator α,ω‐di(iodo)poly(hydroxypropyl acrylate) was synthesized in an aqueous medium by (single electron transfer)/(degenerative chain transfer) living radical polymerization (SET‐DTRP) catalyzed by Na2S2O4. The block copolymer was then prepared by SET‐DTRP of vinyl chloride (VC) from the iodine‐terminal active chain ends of the macroinitiator, thereby leading to the formation of the block copolymer poly(vinyl chloride)‐b‐poly(hydroxypropyl acrylate)‐b‐poly(vinyl chloride). This report covers important aspects related to the characterization of the block copolymer produced and to the identification of the major limitations that must be overcome in order to produce this new material on the industrial scale. The results clearly show the differences between the theoretical predictions and the block copolymer compositions obtained by using a suspension polymerization method, which is the most‐used polymerization process in the PVC industry. J. VINYL ADDIT. TECHNOL., 19:94–104, 2013. © 2013 Society of Plastics Engineers

Study of the styrene–acrylic emulsion modified by hydroxyl-phosphate ester and its stoving varnish

A styrene–acrylic copolymer emulsion containing hydroxyl-phosphate as flash-rust functional monomer and hydroxypropyl acrylate as cross-linking monomer was synthesized. The effects of the hydroxyl phosphate dosage, the hydroxypropyl acrylate dosage as well as the ratio of soft to hard monomer on the emulsion and coating film were investigated. The results showed that the emulsion of 4% hydroxyl phosphate function monomer and 3% hydroxypropyl acrylate with soft and hard monomer ratio of 1:1.6 and modified emulsion and amino resin ratio of 6:1 resulted in a coating film with the best performance.

Two decades of occupational (meth)acrylate patch test results and focus on isobornyl acrylate

Acrylates constitute an important cause of occupational contact dermatitis. Isobornyl acrylate sensitization has been reported in only 2 cases. We encountered an industrial process operator with occupational contact dermatitis caused by isobornyl acrylate. (i) To investigate whether it is relevant to add isobornyl acrylate to the (meth)acrylate test series. (ii) To report patients with (meth)acrylate contact allergy at an occupational dermatology clinic. Our patch test database was screened for positive reactions to (meth)acrylates between 1993 and 2012. A selected group of 14 patients was tested with an isobornyl acrylate dilution series: 0.3%, 0.1%, 0.033%, and 0.01%. Readings were performed on D2, D3, and D7. One hundred and fifty-one patients were tested with our (meth)acrylate series; 24 had positive reactions. Most positive reactions were to 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, and diethyleneglycol diacrylate. Hypothetical screening with 2-hydroxypropyl acrylate, ethyleneglycol dimethacrylate, ethoxylated bisphenol A glycol dimethacrylate and trimethylolpropane triacrylate identified 91.7% of the 24 patients. No positive reactions were observed in 14 acrylate-positive patients tested with the isobornyl acrylate dilution series. The 0.3% isobornyl acrylate concentration induced irritant reactions in 3 patients. We report a rare case of allergic contact dermatitis caused by isobornyl acrylate. However, this study provides insufficient support for isobornyl acrylate to be added to a (meth)acrylate series.

Study of the Potential of Amphiphilic Conetworks Based on Poly(2-ethyl-2-oxazoline) as New Platforms for Delivery of Drugs with Limited Solubility

Thermoresponsive amphiphilic conetworks comprising poly(2-ethyl-2-oxazoline) (PEtOx), 2-hydroxyethyl methacrylate, and 2-hydroxypropyl acrylate segments have been studied as new platforms for delivery of drug with limited solubility. Series of conetworks of varied composition were synthesized and swelling kinetics in aqueous media and ethanol were followed. The platforms were loaded with the hydrophobic drug ibuprofen by swelling in its ethanol solution. The structure and properties of the drug carriers were investigated by scanning electron microscopy and differential scanning calorimetry. The release kinetics profiles of ibuprofen from the studied platform were established. The investigation proved the feasibility of the PEtOx-based amphiphilic conetworks as highly effective platforms for sustained ibuprofen delivery.

Preparation and electro‐optical properties of polymer dispersed liquid crystal films with relatively low liquid crystal content

In this paper, polymer dispersed liquid crystals (PDLC) films with LC content as low as 40 wt% were prepared, and the electro‐optical properties were carefully investigated. To accomplish this, different (meth)acrylate copolymerizaiton monomers have been used. The electro‐optical properties and morphologies of the PDLC films were strongly influenced by the chemical structure of copolymerization monomers (hydroxypropyl methacrylate (HPMA), glycidyl methacrylate, hydroxypropyl acrylate) and their feed ratio. Lower driven voltage and higher contrast ratio were achieved when the PDLC films showed a morphology with suitably LC domain size. At high HPMA content, a thin polymer film was formed on the surface of PDLC samples, which is beneficial to decrease the total LC content in PDLC devices. Copyright © 2013 John Wiley & Sons, Ltd.

Biomimetic synthesis of calcium carbonate bilayers interfaced by a diblock copolymer template

Abstract The synthesis of a new class of hybrid materials with two differently oriented layers of calcite at adjacent sides of an organic template is demonstrated. A Langmuir monolayer of the amphiphilic block copolymer poly(butyl acrylate)-b-poly(hydroxypropyl acrylate) directs the formation of a first CaCO3 phase through interaction with the hydrophilic poly(hydroxypropyl acrylate) blocks. After partial hydrolysis of the hydrophobic poly(butyl acrylate) segments a second CaCO3 phase is formed on the monolayer associated to the first mineral phase. Thus, bilayered CaCO3-based hybrid materials are obtained with two differently oriented calcite phases at opposite sides of the polymer film. By using DNA as an additive the crystal orientation in the second layer can be modified.