Synthesis Of Acrylate Research Articles

Heterogeneous h-BN@Cyclodextrin@Pd(II) nanomaterial: Fabrication, characterization and application as a highly efficient and recyclable catalyst for C—C coupling reactions

An efficient and ligand-free method for the Suzuki and Heck cross-coupling reactions has been successfully developed using h-BN-supported palladium as the catalyst. This green methodology represents a cost-effective and operationally convenient process for the synthesis of biaryls, stilbenes and acrylates. Wide scope of substrates, good to excellent yields, low reaction time, water as solvent, ligand-free, non-toxicity and recyclability of the catalyst are the main merits of these protocols. In addition, the h-BN@γ-CD@Pd(II) nanomaterial has been fully characterized by TG, SEM, IR, XRD, XPS and ICP-AES analysis. And it could be easily recovered and reused for at least nine times without any considerable loss of catalytic activity. Above all, this work demonstrates the possibility of using cyclodextrin-modified h-BN as an efficient support for the hydrophilic heterogeneous catalysts.

One-Step Synthesis of Methyl Acrylate Using Methyl Acetate with Formaldehyde in a Fluidized Bed Reactor

A fluidized bed process for the one-step synthesis of methyl acrylate (MA) using methyl acetate (Ma) and formaldehyde (FA) was developed for the first time. New spherical antiwear acid–base catalysts Cs–P/γ-Al2O3 were prepared using ultrasonic impregnation method and characterized with XRD, BET, SEM, PSD, ICP, TG/DTA, NH3-TPD, and CO2-TPD methods. Catalytic performance was evaluated, and 10.0 wt % Cs–5.0 wt % P/γ-Al2O3 with weak acid–base sites was determined to be the best catalyst for MA production. Response surface methodology (RSM) was employed to optimize aldol condensation of Ma with FA over 10.0 wt % Cs–5.0 wt % P/γ-Al2O3. The effects of various process parameters such as reaction temperature, molar ratio of Ma and FA, and liquid hourly space velocity (LHSV) on MA yield were addressed by Box–Behnken experimental design (BBD). The coefficient of determination (R2) of this model was 0.997, and 39.5 mol % yield of MA was obtained after optimization. The developed catalyst exhibited high stability, with no significant decrease in catalytic activity after 1000 h of lifetime evaluation.

Synthesis and characterization of UV-curable polyurethane acrylates with PLA and PEG

ABSTRACTTo reduce carbon dioxide emission of materials, two eco-friendly diols, poly(lactide) (PLA) diol and poly(ethylene glycol) (PEG) were applied for the synthesis of polyurethane acrylates (PUAs). PUAs with acrylate-ended groups were synthesized and then their mixtures were copolymerized by UV. The cured PUAs were characterized by fourier transform infrared spectroscopy, differential scanning calorimetry, drop shape analysis, universal testing machine, and dynamic mechanical analyzer. The cured PUAs showed single Tg due to well distribution of diols. Tensile strength and Tg of the cured PUAs increased with the content of PLA diol. As the content of PEG in the PUAs increases, thermal stability and hydrophilicity were improved. The results showed that the mechanical and thermal properties of synthesized PUAs could be controlled by diol ratio.

The effect of tunable morphology on the potential application of p(acrylic acid-co-2-ethylhexyl acrylate)/silica nanohybrids

AbstractThe present study deals with the one-pot synthesis of acrylate copolymers/silica latexes through the use of simultaneous radical polymerization of acrylic monomers and a silica sol-gel precursor. In presence of 3-methacryloxypropyltrimethoxysilane (γ-MPS) and 3-aminopropyltriethoxysilane (APTS), compatibility of acrylate chains to the silica species was improved by the chemical bonds as revealed by Fourier transform infrared spectroscopy (FTIR) analysis. Transmission electron microscopy (TEM) demonstrated the successful formation of p(acrylic acid-co-2-ethylhexyl acrylate)/silica nanohybrids with core-shell morphology. The nanohybrids have been used to modify a glassy carbon electrode (GCE). Cyclic voltammetry and electrochemical impedance spectra were utilized to investigate the properties of the modified electrode in a 1.0mKCl solution that contained 1.0 mmK4[Fe(CN)6]/K3[Fe(CN)6], and the interface properties of electrode surfaces. The result showed a dramatic decrease in redox activity as compared to the bare GCE electrode. This revealed a slight increase in electron transfer resistance and the conductivity of the copolymer oligomers and silica species in the hybrid nanostructure. All the electrochemical results illustrated that the p(acrylic acid-co- 2-ethylhexyl acrylate)/silica nanohybrids could immobilize the selective analytes on the electrodes, which had electrochemical catalytic activity. The barrier properties of the hybrid films were also examined via ultraviolet (UV) absorption capacity of the films. It could be concluded that the adsorption capacity was a function of the silica content and uniform dispersion of the nanoparticles in the resultant films.

Performance Evaluation of Pervaporation Technology for Process Intensification of Butyl Acrylate Synthesis

Pervaporation-based hybrid processes have been investigated to overcome the drawbacks of equilibrium-limited reactions. Pervaporation processes are strongly recommended for heat-sensitive products and azeotropic mixtures as in the butyl acrylate system case, since pervaporation can operate at lower temperatures than distillation. In this work, experimental pervaporation data for multicomponent mixtures in the absence of reaction were measured for the compounds involved in the esterification reaction of acrylic acid with n-butanol at different temperatures: 323, 353, and 363 K. A commercial tubular microporous silica membrane from Pervatech was used which is highly selective to water, and its performance was evaluated by studying several parameters, like the selectivity, permeate fluxes, driving force of species, and separation factor. The effects of temperature and feed composition were assessed for binary, ternary, and quaternary mixtures. Increasing the temperature increases significantly the total perm...

One-step and in-situ catalytic synthesis of acrylates from acetates (or propionates) and trioxane at room temperature

Abstract One-step synthesis of acrylates from acetates and trioxane via aldol reaction at 623 K–653 K was reported. But proceeding this process at room temperature is still a challenge due to ester activation and trioxane decomposition. Herein, series of acrylates were firstly achieved, with the one-step and in-situ catalytic strategy, from acetates (or propionates) and trioxane at 293 K. Selectivity of product reaches up to 94.4% with a 80.8% yield. 1 H NMR confirmed the soft enolization of ester, the decomposition of trioxane was catalyzed by TMSOTf, and the generated ionic liquid has catalytic performance on aldol condensation step.

Synthesis of Methyl Acrylate by Aldol Condensation of Methyl Acetate with Formaldehyde Over Al2O3-Supported Barium Catalyst

Vapor phase aldol condensation of methyl acetate with formaldehyde was first studied over Al2O3 with different calcination temperatures and Al2O3-supported barium with different amounts of barium catalysts. The catalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, N2 adsorption–desorption, the pyridine absorption performed via Fourier transform infrared spectroscope, NH3 and CO2 temperature-programmed desorption. The results indicated that the calcination temperature affected the strength and the number of surface acid and base sites over the alumina catalysts. In addition, the moderate Lewis acid and weak base sites were critical to promote this aldol condensation reaction. Adding barium species, which could effectively modified the acid–base properties of Al2O3, clearly improved the catalytic activity and selectivity. The stability and regeneration of the optimum catalyst were also investigated and did not exhibit an obvious decrease in efficiency. Al2O3-supported barium catalyst was found to be an effective catalyst for vapor phase aldol condensation of methyl acetate with formaldehyde as a result of the appropriate intensity of acid and base.

Kinetic and thermodynamic studies on one-step synthesis of methyl acrylate promoted by generated ionic liquid at mild temperature

One-step aldol condensation of methyl acetate with formaldehyde (or trioxane) for preparing methyl acrylate at 623K–653K has stimulated researchers’ attention in recent years. Herein, a new methodology for one-step synthesis of methyl acrylate from methyl acetate and trioxane promoted by generated trifluoromethanesulfonate ionic liquid, via aldol condensation, at mild temperature was developed. The kinetic and thermodynamic studies on this new process were also firstly investigated systematically. Experiments were conducted in a batch reactor under the temperatures of 283K–298K and reaction times of 10min–100min, wherein the side reactions could be ignored. The proposed mechanism-based kinetic model was established and simulated with experimental data. The model showed good agreement with experimental results within the range of acceptable deviation, thereby the pre-exponential factor and activation energy of each reaction step were obtained. Moreover, the equilibrium constant and enthalpy change of each reversible reaction were also calculated through Van’t Hoff formula.

Synthesis of β-Dihydropyrrolyl and β-Pyrrolyl Acrylates and Their Antiproliferative Activity against HCT-116 and HL-60 Cells

Synthesis of β-Dihydropyrrolyl and β-Pyrrolyl Acrylates and Their Antiproliferative Activity against HCT-116 and HL-60 Cells

Enhanced Activity and Recyclability of Palladium Complexes in the Catalytic Synthesis of Sodium Acrylate from Carbon Dioxide and Ethylene

AbstractThe Pd‐catalysed synthesis of sodium acrylate from ethylene and CO2 in the presence of alcoholate bases has been improved significantly. We used amide solvents such as N‐cyclohexylpyrrolidone or N,N‐dibutylformamide to achieve turnover numbers greater than 500 in one run, which is significantly higher than that of systems for this reaction reported previously. For the first time, we were able to recycle the catalyst without any additional regeneration step. With this system, it is possible to use the simple and easily recycled alcoholate base sodium isopropoxide to achieve good turnover numbers up to 200.

Synthesis of acrylates from methyl propionate, propionic acid and formaldehyde in the gas phase on solid catalysts

Development of active and selective catalysts for the process of obtaining methacrylic acid and methyl methacrylate from methyl propionate, propionic acid and formaldehyde is one of important stages to industrial implementation of this process. In order to solve this problem, we designed catalysts based on oxides of boron and phosphorus that were promoted by oxides of zirconium, tungsten and bismuth with varied content of oxides. The effect of temperature was examined on the conversion of reagents, the selectivity of formation and the yield of methyl methacrylate and methacrylic acid on the created catalysts. With increasing temperature, the conversion increases, the selectivity of formation of acrylates decreases and the total yield of acrylates has the maximum. It was found that without adding methanol, the optimal catalyst by acrylates yield is the one, in which the molar ratio of the ZrO 2 :WO 3 promoters is 0.15:0.15. The total yield of the target products at optimum temperature of 593 K is 52.3 % with the total selectivity of their formation at 96.4 % and the conversion of reagents of 54.2 %. We determined the effect of adding methanol to the reagent mixture. Adding methanol increases the ratio of products MMA/MAA, and the optimal catalyst by the total selectivity of formation of the target products is the one promoted by bismuth oxide with the molar ratio of Bi 2 O 3 /Р 2 О 5 – 0.3, which at a temperature of 593 K provides for the selectivity of formation of acrylates of 100 % with the yield of 33 %. The maximum total single­pass yield of MMA and MAA on this catalyst at a temperature of 623 K is 51.5 %, at the total selectivity of their formation of 91.6 %. However, the share of MMA in products is lower in comparison to the catalyst, promoted by the mixture of tungsten and zirconium oxides.

Enhanced Simulated Moving Bed Reactor Process for Butyl Acrylate Synthesis: Process Analysis and Optimization

A novel process design based on the simulated moving bed technology for the synthesis of butyl acrylate (BAc) was investigated in order to get a more competitive industrial process. For that, a fixed-bed reactor was coupled with a simulated moving bed reactor. Reactive separation regions were determined for different conditions of process configurations and feed compositions allowing the optimal operating parameters to be found. Furthermore, the process integration was accomplished and the desorbent (n-butanol) recovery was also investigated ensuring the minimal BAc purity required (99.5% w/w). The viability and competitiveness of this process were evaluated after an economic analysis which showed that it required similar production costs and energy consumption as well for the highest production capacity when compared with other state-of-the-art processes for the BAc synthesis, presented so far.

Study on the Synthesis of Waterborne UV Curable Polyurethane Acrylate

Water-brone UV-curable polyurethane acrylate was synthesized based on the toluene diisocynate, polypropylene glycol, dihydroxy methyl acrylic acid and hydroxyethyl acrylate. The structure and the influencing factors on the water solubility and photosensitivity of the waterbrone UV-curable polyurethane acrylate were analyzed. Results show that the water solubility of the resin is enhanced with the increasing of the content of hydrophilic group in the resin. The UV-curing rate of the waterborne coating is good by adding the 819-DW photoinitiator. Triethylamine is a good neutralizer in the waterbrone UV-curable system for having 90% neutralization degree.

ChemInform Abstract: One‐Pot Synthesis of Ethyl‐3‐aryl‐2‐(1H‐tetrazol‐5‐yl)acrylates and 3‐(1H‐Tetrazol‐5‐yl)coumarins via Tandem [2 + 3] Dipolar Cycloaddition Reaction‐Knoevenagel Condensation.

AbstractA one‐pot, three‐component, two‐step, and tandem method is described for the synthesis of tetrazolyl acrylates from aromatic aldehydes.

Synthesis of Sodium Acrylate and Acrylamide Copolymer/GO Hydrogels and Their Effective Adsorption for Pb2+ and Cd2+

A serial of cross-linked sodium acrylate and acrylamide copolymer/graphene oxide (P(AANa-co-AM)/GO) hydrogels with different mass ratios of acrylic acid (AA) to acrylamide (AM) and different contents of N,N-methylenebis(acrylamide) (MBA) were prepared via dispersive polymerization. The prepared hydrogels were characterized by XRD, FT-IR, TGA, SEM, and BET in detail. The removal efficiency of Pb2+ and Cd2+ on the P(AANa-co-AM)/GO hydrogel have been improved significantly due to the addition of 1.0 wt % of GO. The P(AANa-co-AM)/GO hydrogel with AA/AM = 1 and 0.8 wt % of MBA has the highest removal efficiency for Pb2+ and Cd2+ and a suitable swelling ratio, which was selected as the adsorbent for systematic adsorption of Pb2+ and Cd2+ from aqueous solutions. The adsorption capacity and removal efficiency of Pb2+ and Cd2+ on the P(AANa-co-AM)/GO hydrogel were dependent on pH, initial heavy metal ion concentration, and adsorbent dosage. The presence of 0.01–0.05 M Mg2+ or Ca2+ has an obvious effect on the adso...

Synthesis of acrylates from olefins and CO2 using sodium alkoxides as bases

We have discovered a simple procedure for an industrially applicable alternative synthesis of sodium acrylate via the catalytic carboxylation of ethylene with CO2. We identified tert-butoxide as suitable base in this catalytic transformation, which was excluded in previous reports, based on investigations on the stability of the corresponding carbonates. In addition, we were able to access a completely zinc-free procedure for the sodium acrylate formation by introducing a regeneration step during the catalyst recycle. Due to the basicity of the sodium tert-butoxide, it was also possible to carboxylate different terminal and internal olefins, which could not be achieved using the previously reported nickel system using phenolate bases.

Synthesis and Characterization of 1-octyl 2-cyano Acrylate for Wound Healing Applications

Cyanoacrylate glues are quick setting materials which rapidly cure to hard, clear glassy resins. Its synthesis too has not been reported in the open literature so far. Synthetic methods, which engage esterification of cyanoacetic acid with a preferred alcohol, polymerization by knoevenagel condensation and successive depolymerization, are applied to the synthesis of lower membered alkyl cyanoacryaltes in which the alkyl groups carry less than 8 carbons. We have synthesized 1-octyl cyanoacetate by a traditional method involving p-toluene sulphonic acid as the catalyst. In the second step, we have attempted the preparation of poly (n-octyl cyanoacrylate) by the reaction of formaldehyde with n-octyl-2-cyanoacetate in the presence of both piperidine and potassium carbonate in the absence of any solvents. Its FTIR spectrum confirmed its functional groups: Its –OH stretching yielded a broad band around 3400 cm-1. The polymer was depolymerized using poly phosphoric acid catalyst under vacuum to obtain the monomer. A simple method of obtaining monomer was also attempted by the reaction of 1-octyl- 2-cyano acetate and diiodomethane in the presence of potassium carbonate. This process directly yields the monomer. The second method looks better than the others, and it can be applied to any type of alcohols.

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.

Catalysts, kinetics and process optimization for the synthesis of methyl acrylate over Cs–P/γ-Al2O3

Bifunctional catalysts Cs–P/γ-Al2O3 were developed and firstly applied in a one-step synthesis of methyl acrylate using methyl acetate (Ma) and formaldehyde (FA).

Palladium‐ and Nickel‐Catalyzed Synthesis of Sodium Acrylate from Ethylene, CO2, and Phenolate Bases: Optimization of the Catalytic System for a Potential Process

AbstractThe synthesis of sodium acrylate through catalytic carboxylation of ethylene with CO2 in the presence of a base is a reaction of high interest. To develop a more efficient and sustainable method to access this valuable acrylate monomer, we optimized the system in a one‐step homogeneous nickel‐ or palladium‐catalyzed reaction, without the need for stoichiometric amounts of an additional reducing agent. Suitable nontoxic solvents such as anisole instead of the previously reported tetrahydrofuran or chlorobenzene were found to lead to acrylate formation. In combination with appropriate phenolate bases, this could allow a rational process concept for a simple catalyst recycling, product separation, and base regeneration.