Acrylate Mixture Research Articles

Monodispersed polymer encapsulated superparamagnetic iron oxide nanoparticles for cell labeling

Polymer encapsulation of raw ferrofluids was carried out by free radical emulsion polymerization using macro-RAFT copolymers as stabilizers. The iron oxide cores with positively charged surface at the pH of encapsulation were dispersed in a solution of negatively charged random macro-RAFT copolymer by ultrasonication. Uniform polymer encapsulated super paramagnetic iron oxide nanoparticles (SPIONs) were produced by feeding the mixture of methyl methacrylate (MMA) and n-butyl acrylate (BA) monomers into the dispersion containing water soluble initiator 4,4’-azobis (4-cyanopentanoic acid) (V501). Shell thickness could be controlled by adjusting the amount of coating monomer added. Polymer encapsulation of SPIONs aligned in a magnetic field produced polymer encapsulated SPION rods. Monodispersed sterically stabilized crosslinked polymer encapsulated SPIONs were synthesized using diblock and random macro-RAFT copolymers as stabilizers. Rhodamine labeled SPIONs were found to be non-cytotoxic and suitable for cell labeling.

Reactive compatibilization of poly(styrene‐ran‐acrylonitrile)/poly(ethylene) blends through the acid–epoxy reaction

ABSTRACTTwo families of acid functional styrene/acrylonitrile copolymers (SAN) for application as dispersed phase barrier materials in poly(ethylene) (PE) were studied. One type is SAN made by nitroxide mediated polymerization (NMP), which was subsequently chain extended with a styrene/tert‐butyl acrylate (S/tBA) mixture to provide a block copolymer (number average molecular weight Mn = 36.6 kg mol−1 and dispersity Đ = 1.34, after which the tert‐butyl protecting groups were converted to acid groups (SAN‐b‐S/AA). The other acid functional SAN is made by conventional radical terpolymerization (SAN‐AA). SAN‐AA and SAN‐b‐S/AA were each melt blended with PE grafted with epoxy functional glycidyl methacrylate (PE‐GMA) at 160 °C in a twin screw extruder (70:30 wt % PE‐GMA:SAN co/terpolymer). The non‐reactive PE‐g‐GMA/SAN blend had a volume to surface area diameter = 3.0 μm while the reactive blends (via epoxy/acid coupling) (PE‐GMA/SAN‐b‐SAA and PE‐GMA/SAN‐AA) had = 1.7 μm and 1.1 μm, respectively. After thermal annealing, the non‐reactive blend coarsened dramatically while the reactive blends showed little signs of coarsening, suggesting that the acid/epoxy coupling was effective for morphological stability. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44178.

Flexible Nonstick Replica Mold for Transfer Printing of Ag Ink.

We report the fabrication of flexible replica molds for transfer printing of Ag ink on a rigid glass substrate. As mold precursors, acrylic mixtures were prepared from silsesquioxane-based materials, silicone acrylate, poly(propylene glycol) diacrylate, 3,3,4,4,5,5,6,6,7,7,8,8, 9,9,10,10,10-heptadecafluorodecyl methacrylate, and photoinitiator. By using these materials, the replica molds were fabricated from a silicon master onto a flexible substrate by means of UV-assisted molding process at room temperature. The wettability of Ag ink decreased with increase in the water contact angle of replica molds. On the other hand, the transfer rate of Ag ink onto adhesive-modified substrates increased with increase in the water contact angle of replica molds. Transferred patterns were found to be thermally stable on the photocurable adhesive layer, whereas Ag-ink patterns transferred on non-photocurable adhesives were distorted by thermal treatment. We believe that these characteristics of replica molds and adhesives offer a new strategy for the development of the transfer printing of solution-based ink materials.

Building Energy Storage Panel Based on Paraffin/Expanded Perlite: Preparation and Thermal Performance Study.

This study is focused on the preparation and performance of a building energy storage panel (BESP). The BESP was fabricated through a mold pressing method based on phase change material particle (PCMP), which was prepared in two steps: vacuum absorption and surface film coating. Firstly, phase change material (PCM) was incorporated into expanded perlite (EP) through a vacuum absorption method to obtain composite PCM; secondly, the composite PCM was immersed into the mixture of colloidal silica and organic acrylate, and then it was taken out and dried naturally. A series of experiments, including differential scanning calorimeter (DSC), scanning electron microscope (SEM), best matching test, and durability test, have been conducted to characterize and analyze the thermophysical property and reliability of PCMP. Additionally, the thermal performance of BESP was studied through a dynamic thermal property test. The results have showed that: (1) the surface film coating procedure can effectively solve the leakage problem of composite phase change material prepared by vacuum impregnation; (2) the optimum adsorption ratio for paraffin and EP was 52.5:47.5 in mass fraction, and the PCMP has good thermal properties, stability, and durability; and (3) in the process of dynamic thermal performance test, BESP have low temperature variation, significant temperature lagging, and large heat storage ability, which indicated the potential of BESP in the application of building energy efficiency.

Synthesis and characterization of comb-like acrylic-based polymer latexes containing nano-sized crystallizable domains

The synthesis in a two step miniemulsion polymerization of (meth)acrylic dispersions containing crystalline domains was investigated. The first step consisted of the homopolymerization of stearyl acrylate (SA), which led to formation of crystalline domains. The degree of crystallinity was controlled by the conversion of SA achieved in the first step and by the way in which the short side chain (meth)acrylates (a mixture of methyl methacrylate, n-butyl acrylate and acrylic acid) were fed in the second step. The effect of the polymerization strategy and comonomer composition on crystallinity, polymer architecture, and particle and film morphology was investigated.

Hydrophobic/hydrophilic P(VDF‐TrFE)/PHEA polymer blend membranes

ABSTRACTPolymer blend membranes have been obtained consisting of a hydrophilic and a hydrophobic polymers distributed in co‐continuous phases. In order to obtain stable membranes in aqueous environments, the hydrophilic phase is formed by a poly(hydrohyethyl acrylate), PHEA, network while the hydrophobic phase is formed by poly(vinylidene fluoride‐co‐trifluoroethylene) P(VDF‐TrFE). To obtain the composites, in a first stage, P(VDF‐TrFE) is blended with poly(ethylene oxyde) (PEO), the latter used as sacrificial porogen. P(VDF‐TrFE)/PEO blend membranes were prepared by solvent casting at 70°C followed by cooling to room temperature. Then PEO is removed from the membrane by immersion in water obtaining a P(VDF‐TrFE) porous membrane. After removing of the PEO polymer, a P(VDF‐TrFE) membrane results in which pores are collapsed. Nevertheless the pores reopen when a mixture of hydroxethyl acrylate (HEA) monomer, ethyleneglycol dimethacrylate (as crosslinker) and ethanol (as diluent) is absorbed in the membrane and subsequent polymerization yields hybrid hydrophilic/hydrophobic membranes with controlled porosity. The membranes are thus suitable for lithium‐ion battery separator membranes and/or biostable supports for cell culture in biomedical applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 672–679

Bubble-point measurement for the binary mixture of propargyl acrylate and propargyl methacrylate in supercritical carbon dioxide

Acrylate and methacrylate (acrylic acid type) are compounds with weak polarity which show a non-ideal behaviour. Phase behaviour of these systems play a significant role as organic solvents in industrial processes. High pressure phase behaviour data were reported for binary mixture of propargyl acrylate and propargyl methacrylate in supercritical carbon dioxide. The bubble-point curves for the (carbon dioxide+propargyl acrylate) and (carbon dioxide+propargyl methacrylate) mixtures were measured by static view cell apparatus at temperature range from 313.2K to 393.2K and at pressures below 19.14MPa. The (carbon dioxide+propargyl acrylate) and (carbon dioxide+propargyl methacrylate) systems exhibit type-I phase behaviour. The (carbon dioxide+(meth)acrylate) systems had continuous critical mixture curves with maximums in pressure located between the critical temperatures of carbon dioxide and propargyl acrylate or carbon dioxide and propargyl methacrylate. The solubility behaviour of propargyl (meth)acrylate in the (carbon dioxide+propargyl acrylate) and (carbon dioxide+propargyl acrylate) systems increases as the temperature increases at a fixed pressure. The experimental results for the (carbon dioxide+propargyl acrylate) and (carbon dioxide+propargyl methacrylate) systems correlate with the Peng–Robinson equation of state using a van der Waals one-fluid mixing rule. The critical properties of propargyl acrylate and propargyl methacrylate were predicted with the Joback–Lyderson group contribution and Lee–Kesler method.

Environmentally-friendly processing of thermosets by two-stage sequential aza-Michael addition and free-radical polymerization of amine–acrylate mixtures

A new dual-curing, solvent-free process is described for the preparation of tailor-made materials from offstoichiometric amine–acrylate formulations.

Thermal and mechanical properties of poly(lactic acid) modified by poly(ethylene glycol) acrylate through reactive blending

Poly(lactic acid) (PLA) was modified using a simple reactive blending method, where a low molecular weight poly(ethylene glycol) acrylate (PEGA) was blended with PLA in the presence of a radical initiator. To examine the initiation effect on the modification of PLA, various amounts of radical initiator (between 0 and 1.5 %) were added to the PLA/PEG acrylate mixture. The modified PLAs (PLMs) were characterized by gel permeation chromatography, Fourier transform infrared spectroscopy, wide-angle X-ray diffraction, and solvent extraction. The properties of the PLMs were investigated using tensile testing, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy, and hydrolytic degradable analysis. The PEGA significantly influenced the molecular structure and properties of the modified PLA. The glass transition temperature of the PLMs was decreased by approximately 15 °C (for PLM15) from 59.3 °C of PLA, whereas their toughness increased considerably compared to PLA. In addition, PEG acrylate facilitates hydrolytic degradation, even after radical polymerization by reactive blending.

Raman spectroscopy and chemometrics for quantitative analysis of complex flows in an industrial transesterification process

A method based on Raman spectroscopy has been used for determination of ester acrylate mixture composition from an industrial production of acrylic monomers. Five molecules of the industrial mixture have been studied: main components and an impurity. Experiments were carried out with an immersion probe on the spectral range of 100–3425 cm−1. Usually, monitoring a complex industrial flow by spectroscopic analysis requires a lot of samples in order to have a representative prediction model. Here only 60 samples from the process were necessary to build the model. The statistics was then artificially increased by synthetically increasing the number of samples. A qualitative study by principal component analysis was at first done, and then a partial least squares method was performed to assess the feasibility of quantitative measurements in such transesterification process. Internal and external validations methods have been used and their results show a RMSEP below 1% of samples predicted concentration ranges. The repeatability and reproducibility of Raman measurements are also discussed. Copyright © 2014 John Wiley & Sons, Ltd.

Synthesis of Poly(methylene oxy-alt PPO)glycols and Its Effect on the Properties of Polyurethane UV-Cured Film

In this study, we synthesized MPPG including the methylene-oxy group from polypropylene glycol (PPG) with the molecular weight (g/mol) of 200. Also UV curable resins were prepared from the mixture of polyurethane acrylate (PUA) oligomer which was synthesized with synthesized MPPG, TMPTA, HDDA, and HP-8 to investigate the possibility of its application for optical film materials. The Tg was higher for UAMP oligomer with MPPG as well as MPPG than that of PPG and UAP oligomer. The refractive index and the pencil hardness of UCM were higher than those of UC while the optical transmittances of UCM and UC were much the same.

Microwave induced synthesis of graft copolymer of binary vinyl monomer mixtures onto delignified Grewia optiva fiber: application in dye removal.

Grafting method, through microwave radiation technique is very effective in terms of time consumption, cost effectiveness and environmental friendliness. Via this method, delignified Grewia optiva identified as a waste biomass, was graft copolymerized with methylmethacrylate (MMA) as an principal monomer in a binary mixture of ethyl methacrylate (EMA) and ethyl acrylate (EA) under microwave irradiation (MWR) using ascorbic acid/H2O2 as an initiator system. The concentration of the comonomer was optimized to maximize the graft yield with respect to the primary monomer. Maximum graft yield (86.32%) was found for dGo-poly(MMA-co-EA) binary mixture as compared to other synthesized copolymer. The experimental results inferred that the optimal concentrations for the comonomers to the optimized primary monomer was observed to be 3.19 mol/L × 10−1 for EMA and 2.76 mol/L × 10−1 for EA. Delignified and graft copolymerized fiber were subjected to evaluation of physicochemical properties such as swelling behavior and chemical resistance. The synthesized graft copolymers were characterized with Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and X-ray diffraction techniques. Thermal stability of dGo-poly(MMA-co-EA) was found to be more as compared to the delignified Grewia optiva fiber and other graft copolymers. Although the grafting technique was found to decrease percentage crystallinity and crystallinity index among the graft copolymers but there was significant increase in their acid/base and thermal resistance properties. The grafted samples have been explored for the adsorption of hazardous methylene dye from aqueous system.

Ionic Liquids as Catalysts for the Radical Acrylate Polymerization Co-initiated by Imine Bases

The catalysis of the imine base acrylate (IBA) polymerization by Ionic Liquids (ILs) is reported. Addition of IL traces (~10-50 mM) to an imine base / acrylate mixture leads to both a significant decrease of the activation temperature (40 °C) required for the IBA polymerization process and an increase in the polymerization rate by a factor of 5-40 depending on the IL species. The radical character of the polymerization is proved by copolymerization experiments using methyl methacrylate (MMA) and methacrylonitrile (MAN) and comparison with literature known values of copolymerization parameters rMMA and rMAN of these co-monomers. The influence of the IL on the polymerization kinetics is quantified by the polymerization rate law; the order referring to the IL is 1 indicating its crucial impact on the monomer activation. The IBA activation properties are strongly dependent on the IL interaction strengths with the IBA components verified by the KAMELT-TAFT hydrogen bond donating ability α. The stronger the interaction (higher α) is, the less the IBA polymerization activation. The temperature dependence of four different IL catalysed IBA polymerization is investigated, allows a classification and anomalous non-ARRHENIUS regimes are discussed. Activation energies EA,P span over 20 and 50 kJ·mol−1, which is between the values of thermal- (~80 kJ·mol−1) and photo-initiation (~20 kJ·mol−1).

The effect of modifying agent on mechanical and thermal properties of titanium dioxide-filled poly(methyl methacrylate) film

Poly(methyl)methacrylate (PMMA) composites with various contents of titanium dioxide (TiO2) were prepared. The effects of fiber content and modification on the mechanical properties and thermal behavior of PMMA composite film were studied. The use of organosolv lignin and acrylic acid together as a binary modifying agent for TiO2 filler increased both the strength and the ultimate strain of treated PMMA composites as compared to the untreated ones. The higher temperature dramatically increased the weight loss of all three sample categories. The organosolv lignin and acrylic acid mixture was more effective than a single modifying agent in reducing the thermal decomposition of PMMA/TiO2 composites.

Synthesis, morphology, and properties of waterborne m-TMXDI-based anionic polyurethane and hybrids

In this study, waterborne polyurethane (WPU) hybrid emulsions with a weight ratio of 2/1 were prepared by emulsion polymerization using a mixture of styrene (St) and/or butyl acrylate (BA) monomers with WPU dispersion. WPU dispersion was synthesized with isocyanic acid and m-tetramethylxylene diisocyanate (m-TMXDI)-based anionic poly(urethane-urea) dispersions using the prepolymer mixing process. The structures of WPU and hybrids were characterized by FTIR spectroscopy. The size and morphology of the latex particles were investigated using dynamic light scattering and transmission electron microscopy, respectively. The stability of the emulsions was determined according to their shelf life and particle size using the dispersion analyser LUMiSizer® with STEP™-Technology. The thermal and mechanical properties of these films were examined by thermogravimetric analysis and strain-stress curves.

Modification of copolymers using nucleophilic reactions between glycidyl methacrylate and 9-anthracene carboxylic acid

Epoxide ring opening reaction is a route that explains the chemical modification of glycidyl methacrylate (GMA) polymers with nucleophilic reagent containing hydroxyl, carboxyl or amine groups. In this work copolymers of GMA have been modified by incorporation of bulky 9-anthracene carboxylic acid groups. The glycidyl methacrylate polymers were prepared by radical copolymerization of GMA methyl, methacrylate, ethyl methacrylate, methyl acrylate and butyl acrylate mixtures. The polymers were modified through epoxy functional groups in two steps: (i) the glycidyl methacrylate copolymers were dissolved in N,N-di-methyl formamide; (ii) 9-anthracene carboxylate salt was added to the copolymers solutions prepared in step (i). The structure of all the resulting polymers was characterized and confirmed by FT-IR and 1H-NMR spectroscopic techniques. The presence of bulky 9-anthracene carboxylate groups in polymer side chain leads to different applications in the polymer industry and also a series of novel modified polymers are obtained.

Straightforward Synthesis of Symmetrical Multiblock Copolymers by Simultaneous Block Extension and Radical Coupling Reactions

In situ combination of a polymerization step with a coupling reaction is demonstrated to accelerate the synthesis protocols for symmetrical multiblock copolymers. Predici simulations and experiments prove on the example of cobalt-mediated radical polymerization and coupling (CMRP/C) reactions that such synthesis strategy can be very effective and easy to conduct. Treatment of a cobalt-terminated poly(acrylonitrile) precursor with a mixture of acrylate and isoprene led to the rapid polymerization of the acrylate before isoprene-assisted radical coupling of the macroradical chains forming a well-defined poly(acrylonitrile)-b-poly(acrylate)-b-poly(acrylonitrile) triblock. The degree of polymerization of the central block, resulting from the balance between propagation and coupling, could be tuned by adjusting the relative concentration and varying the structure of the acrylate and diene. The same convergent strategy also permits the synthesis of ABCBA-type pentablock copolymer starting from a cobalt-functional diblock. Simultaneous radical polymerization and coupling is thus a powerful macromolecular engineering approach for the straightforward design of symmetrical multiblock copolymers.

Photoswitchable Hydrogel Surface Topographies by Polymerisation‐Induced Diffusion

Herein, we describe the preparation of patterned photoresponsive hydrogels by using a facile method. This polymer-network hydrogel coating consists of N-isopropylacrylamide (NIPAAM), cross-linking agent tripropylene glycol diacrylate (TPGDA), and a new photochromic spiropyran monoacrylate. In a pre-study, a linear NIPAAM copolymer (without TPGDA) that contained the spiropyran dye was synthesised, which showed relatively fast photoswitching behaviour. Subsequently, the photopolymerisation of a similar monomer mixture that included TPGDA afforded freestanding hydrogel polymer networks. The light-induced isomerisation of protonated merocyanine into neutral spiropyran under slightly acidic conditions resulted in macroscopic changes in the hydrophilicity of the entire polymer film, that is, shrinkage of the hydrogel. The degree of shrinkage could be controlled by changing the chemical composition of the acrylate mixture. After these pre-studies, a hydrogel film with spatially modulated cross-link density was fabricated through polymerisation-induced diffusion, by using a patterned photomask. The resulting smooth patterned hydrogel coating swelled in slightly acidic media and the swelling was higher in the regions with lower cross-linking densities, thus yielding a corrugated surface. Upon exposure to visible light, the surface topography flattened again, thus showing that a hydrogel coating could be created, the topography of which could be controlled by light irradiation.

Synthesis of new nanocopolymer containing β-lactams

Several new monocyclic β-lactam monomers bearing the NO2 group 2a–g were synthesized via a [2 + 2] ketene–imine cycloaddition reaction (Staudinger reaction). Calculation of coupling constant of H-3 and H-4, and the X-ray crystallography of β-lactam 2e confirmed the cis stereochemistry of these β-lactams. Then aminophenyl β-lactams were synthesized by the reduction of NO2 to NH2 group in the presence of Raney Ni and hydrazine hydrate. Treatment of these aminophenyl β-lactams with acryloyl chloride and sodium bicarbonate (NaHCO3), afforded the monomers bearing the NHCOCH=CH2 group. These acrylated β-lactam monomers were dissolved in a warm mixture of butyl acrylate and styrene and then were converted to the corresponding polyacrylate nano β-lactams by emulsion polymerization in water. A unique feature of this methodology is the ability to incorporate water-insoluble compounds directly into the nanoparticle framework. Structures of the synthesized compounds were confirmed by physical and spectral analyses. Dynamic light scattering analysis and transmission electron microscopy of the final emulsions show that the nanoparticles were about 50–70 nm in diameter.

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