Esterification Of Acrylic Acid Research Articles

Reactive distillation configuration for the production of ethyl acrylate

Esters of acrylic acid have many industrial applications, but existing industrial processes are not economical. Ethyl acrylate, a precursor to polymers and other chemicals is one of them. The existing method of production of ethyl acrylate by esterification of acrylic acid with ethanol using a homogeneous catalyst and reactor-distillation combination has limitation in terms of product purity, corrosion and existence of possible side reactions. The present work proposes a novel reactive distillation (RD) column configuration for ethyl acrylate production, with 99.99 % acrylic acid conversion and 99.99 % ethyl acrylate purity with no effluent stream. The proposed configuration is analyzed using Aspen Plus steady-state simulation software. Sequential iterative sensitivity analysis is performed to obtain all structural and operating parameters leading to a minimum Total Annual Cost (TAC). The result shows that, there is 10.8 % improvement in the purity of aqueous stream using RD configuration compared to existing method and the overall TAC of the process at desired conditions is 87.77 × 103 $/year.

Preparation and characterization of photocurable fluorinated polyether‐based reactive inks

AbstractPhotocurable polymer provides fast curable properties via ultraviolet (UV) light for 3D‐printed propellants. This work outlines the preparation and characterization of photocurable fluorinated polyether‐based reactive inks. Acrylate‐terminated poly‐2‐((2,2,3,3,3‐pentafluoropropoxy)‐methyl) ethylene oxide (P5F‐AA) was synthesized as photocurable binder through the esterification of acrylic acid, and the terminal hydroxyl group of poly‐2‐((2,2,3,3,3‐pentafluoropropoxy)‐methyl) ethylene oxide (P5F), which was synthesized through cationic ring‐opening polymerization of 2‐((2,2,3,3,3‐pentafluoropropoxy)methyl) oxy‐ethane (PFEE) by using butane diol as initiator. In comparison with P5F, P5F‐AA had a lower glass transition temperature (Tg) of −63.3°C. A new type of photocurable resin, which may be used for additive manufacturing of energetic materials, was prepared via UV radiation in an LED UV curing tank by using P5F‐AA as prepolymer, diphenyl (2,4,6‐trimethyl benzoyl) phosphine oxide (TPO) as photo‐initiator, and tri‐fluoroethyl acrylate (3F‐AA) and 1,6‐hexanediol diacrylate (HDDA) as mono‐ and multifunctional diluents, respectively. When the mass ratio of P5F‐AA/3F‐AA/HDDA binder matrix was 1:1:0.5, the sample exhibited maximal mechanical strength of 6.56 MPa with elongation at break of 13.38%, which was due to the introduction of HDDA effectively increasing the “entanglement” between molecular chains. Thermogravimetric analysis (TGA‐DTG) was utilized to evaluate the ability to decompose thermally of the binder matrix, and the results showed the initial degradation temperature started at nearly 181°C and two consecutive stages in thermal decomposition. Overall, the obtained results from the different techniques suggested that P5F‐AA/3F‐AA/HDDA binder matrix may be a photocurable reactive ink for 3D‐printed propellants, which would provide a certain reference value and guiding importance for design of reactive inks.

Outperformance in Acrylation: Supported D-Glucose-Based Ionic Liquid Phase on MWCNTs for Immobilized Lipase B from Candida antarctica as Catalytic System.

This study presents a highly efficient method of a synthesis of n-butyl acrylate via esterification of acrylic acid and n-butanol in the presence of supported ionic liquid phase (SILP) biocatalyst consisting of the lipase B from Candida antarctica (CALB) and multi-walled carbon nanotubes (MWCNTs) modified by D-glucose-based ionic liquids. Favorable reaction conditions (acrylic acid: n-butanol molar ratio 1:2, cyclohexane as a solvent, biocatalyst 0.150 g per 1 mmol of acrylic acid, temperature 25 °C) allowed the achievement of a 99% yield of n-butyl acrylate in 24 h. Screening of various ionic liquids showed that the most promising result was obtained if N-(6-deoxy-1-O-methoxy-α-D-glucopyranosyl)-N,N,N-trimethylammonium bis-(trifluoromethylsulfonyl)imide ([N(CH3)3GlcOCH3][N(Tf)2]) was selected in order to modify the outer surface of MWCNTs. The final SILP biocatalyst–CNTs-[N(CH3)3GlcOCH3][N(Tf)2]-CALB contained 1.8 wt.% of IL and 4.2 wt.% of CALB. Application of the SILP biocatalyst led to the enhanced activity of CALB in comparison with the biocatalyst prepared via physical adsorption of CALB onto MWCNTs (CNTs-CALB), as well as with commercially available Novozyme 435. Thus, the crucial role of IL in the stabilization of biocatalysts was clearly demonstrated. In addition, a significant stability of the developed biocatalytic system was confirmed (three runs with a yield of ester over 90%).

Synthesis of amphiphilic (meth)acrylates with oligo(ethylene glycol) and (or) oligo(propylene glycol) blocks by the esterification of (meth)acrylic acid

AbstractThermoresponsive PEG‐based (PEG stands polyethylene glycol) polymers are unique for use in medicine because of their low toxicity, good biocompatibility and biodegradability, but usually more hydrophobic and more toxic comonomers are used to adjust lower critical solution temperature (LCST). A convenient way to overcome this problem and to finely tune LCST is to use alkoxy oligo(ethylene glycol)‐ or alkoxy oligo(propylene glycol) (meth)acrylates as starting comonomers. Here we report on the conditions for the simple and affordable synthesis of methoxy oligo(propylene glycol) (meth)acrylate‐ and methoxy oligo(propylene glycol)‐block‐oligo(ethylene glycol) (meth)acrylate‐based macromonomers with high yields (80%–98.7%) by the acid‐catalyzed esterification of (meth)acrylic acid with alkoxy oligo(alkylene glycols) containing oligo(ethylene glycol) (OEG) and/or oligo(propylene glycol) (OPG) blocks. p‐Toluene sulphonic acid (pTSA), alkyl(C12–C14)benzene sulfonic acid (ABSA) and H2SO4 were used as catalysts. It has been shown that pTSA and ABSA are practically the same in catalytic activity and are superior to sulfuric acid. The reaction orders with respect to catalyst was found to be close to 1 in all cases. It has been shown that the reaction is actually insensitive to the lengths of OEG and OPG blocks, as well as to the structure of the terminal alkyl group, while the esterification of acrylic acid (AA) proceeds much faster compared to methacrylic acid (MAA) one under the same conditions. The influence of temperature on the equilibrium conversions of alcohols was determined, which were found to be 89%–93% for the esterification of AA and 61%–86% for MAA in the temperature range of 60–120°C. A further increase in conversion was achieved by introducing an azeotropic agent (toluene), its optimal concentration was found to be 10%–15%.

Synthesis of a polyethylene glycolylated polysiloxane system through a two‐step procedure and its compatibility

ABSTRACTAcrylic macromonomer was synthesized by esterification of acrylic acid (AA) and PEGylated siloxane alcohol. And the acrylic macromonomer was employed as unsaturated precursor for the hydrosilylation with polymethylhydrosiloxane (PMHS). FTIR, 1H, 13C, 29Si‐NMR, and TGA proved that PEGylated polysiloxane was successfully synthesized. The morphological studies revealed that the dimples in the cross sections were attributed to polyethylene glycol (PEG) phase domains with diameters of 5–15 μm. The contribution of polar and dispersion factor toward surface energy was studied by contact angle (CA) measurement. The results showed that wetting behavior could transform from hydrophobic to hydrophilic with the CA from 122° to 54°. The final PEGylated polysiloxane provided sufficient compatibility and good wetting behavior, in contrast with silane ethers or alkyl silanes, indicating that it might be utilized as an alternate candidate for personal care. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47889.

Production and Isolation of n‐Butyl Acrylate Using Pervaporation‐Aided Esterification Reaction: Kinetics and Optimization

AbstractSynthesis of n‐butyl acrylate by esterification of acrylic acid with n‐butyl alcohol was carried out in a batch membrane reactor. Optimization and design of the experiment was accomplished by response surface methodology with Box‐Behnken experimental design. The effects of different parameters like reaction temperature, catalyst concentration, molar ratio of alcohol to acid, and ratio of membrane surface to initial volume on water flux and conversion of acrylic acid were evaluated. A kinetic model for the esterification‐coupled pervaporation process was developed. Kinetic parameters were estimated by a nonlinear optimization technique in the MATLAB optimization toolbox. The experimental and simulation results were applied for developing a concept to effectively conduct a pilot‐scale esterification‐pervaporation experiment.

Study on Preparation of Low Hydration Thermal Polycarboxylate Superplasticizer by Low Temperature Esterification

A low hydration thermal polycarboxylate superplasticizer (P-DR) is obtained by unsaturated monomer (P1) with isoprenol polyoxyethylene ether. P1 is obtained by esterification of acrylic acid with (2-Hydroxyphenyl)phosphoric acid at 70°C, having a benzene ring and a phosphate group. The experimental results show that the prepared P-DR has a higher water reduction rate and can significantly reduce the 1d hydration heat of cement.

Esterification of acrylic acid with ethanol using pervaporation membrane reactor

Esterification of acrylic acid with ethanol was carried out using an in-situ reactor with an integrated pervaporation assembly (IPAE) made of polyvinyl alcohol (PVA) membrane and was compared with a non-integrated (NIE) system. Effect of reaction temperature (T r ), catalyst loading (C C ), molar ratios of reactants (MR) and ratio of effective membrane area to unit volume of reaction mixture (S/V o ) on kinetics of esterification reaction were studied. Conversions achieved in IPAE were found to be distinctly higher than the NIE. The highest conversion of acrylic acid was obtained as 83.3% at T r =60 °C, M R =3 : 1, C C =2% and S/V o =14.1 m−1. Equilibrium conversion of acrylic acid in NIE was obtained as 55.1% at 60 °C, 1 : 1 in 7 h, while using IPAE conversion enhances to 67.6%. Esterification of acrylic acid and ethanol with presently studied operating parameters provides a new approach to existing literature reported esterification-pervaporation system.

Synthesis and Surface Active Properties of Sulfonated Acrylate Esters Based on Al‐Cedre Oil

AbstractSulfonated acrylate esters have been synthesized by using renewable raw materials such as fatty alcohols of Al‐Ceder oil. Mixed fatty acids were isolated from Al‐Ceder oil by hydrolysis; both saturated and unsaturated fatty acids were isolated from the mixed fatty acids. The methyl esters of mixed fatty acid, saturated and unsaturated acids of Al‐Cedre oil were subjected to reduction with (LiAlH4) to give the corresponding fatty alcohols. The products of the reduction process were saponified and the hydroxyl values were estimated to further confirm the reduction occurrence. The acrylate esters were synthesized by esterification of acrylic acid with fatty alcohols of C16:0, C18:0, C18:1, and C18:2 mixed saturated, mixed unsaturated and mixed fatty acids of Al‐Cedre oil, respectively. This esterification was followed by addition of NaHSO3 to form bisulfite adducts. The structures of the prepared surfactants were characterized by IR and 1HNMR spectroscopy. A series of useful surface parameters, stability towards acids and base hydrolysis and calcium stability have been determined.

N-Butyl acrylate production by esterification of acrylic acid with n-butanol combined with pervaporation

In this study, the esterification reaction of acrylic acid and n-butanol to produce n-butyl acrylate and water was studied using the pervaporation–esterification hybrid process to perform the separation and reaction simultaneously to increase the conversion of limiting reactant. A Pervap 2201 polymeric membrane was used to separate water and also to shift the equilibrium. The Pervap 2201 membrane showed high selectivity to water in the n-butanol, acrylic acid, n-butyl acrylate, and water reaction system. The effects of temperature, the initial molar ratio of n-butanol to acrylic acid, catalyst loading, and the ratio of membrane area to reaction volume (S/V) were studied. The maximum conversion of acrylic acid was calculated as 96.3% at a temperature of 358K, a molar ratio of 8, with a catalyst loading of 10g/L and an S/V ratio of 70m−1.

Kinetic Study of the Esterification of Acrylic Acid with Methanol Catalyzed by Strong-acid Cation Exchange Resin

Kinetic Study of the Esterification of Acrylic Acid with Methanol Catalyzed by Strong-acid Cation Exchange Resin

Esterification of Acrylic Acid and n-Butanol in a Pilot-Scale Reactive Distillation Column—Experimental Investigation, Model Validation, and Process Analysis

Due to a high risk of polymerization and complex thermodynamic behavior of the chemical system, the current production process for n-butyl acrylate synthesis is cost-intensive and challenging. Reactive distillation integrates chemical reactions and distillation into one unit at the same time and is one of the best-known examples of process intensification. To facilitate industrial application of this concept for the production of n-butyl acrylate, reliable experimental data are required. This article presents an experimental and theoretical investigation of the synthesis of n-butyl acrylate using reactive distillation. Experiments were conducted in a pilot-scale reactive distillation column, and the decisive operational parameters were varied. To predict the experimental results, a nonequilibrium-stage model was applied and the model was validated using the experimental data. The validated model was then used to perform a process analysis, showing trends in the conversion of acrylic acid and n-butanol and the purity of n-butyl acrylate that can be used for prospective optimization studies.

Computer-aided solvent screening for biocatalysis

Abstract A computer-aided solvent screening methodology is described and tested for biocatalytic systems composed of enzyme, essential water and substrates/products dissolved in a solvent medium, without cells. The methodology is computationally simple, using group contribution methods for calculating constrained properties related to chemical reaction equilibrium, substrate and product solubility, water solubility, boiling points, toxicity and others. Two examples are provided, covering the screening of solvents for lipase-catalyzed transesterification of octanol and inulin with vinyl laurate. Esterification of acrylic acid with octanol is also addressed. Solvents are screened and candidates identified, confirming existing experimental results. Although the examples involve lipases, the method is quite general, so there seems to be no preclusion against application to other biocatalysts.

Formation of heavy adducts in esterification of acrylic acid: A DFT study

Esterification of acrylic acid with alcohols and the side reactions were studied at the B3LYP/6-31G ** level. The main model reaction is predicted to be endoergic which is in line with experimental findings. It appeared that the activation barriers for the esterification reactions in vacuum are equal to ca. 68 ± 3 kcal/mol, they decrease in presence of the H + ion to ca. 47.5 ± 3.5 kcal/mol, and are relatively insensitive to change of environment simulated by PCM method (a matter of 0.5 kcal/mol). Out of four side reactions studied, the lowest activation barrier (36.5 ± 1.5 kcal/mol) is for addition of the acrylic acid molecule to double bond in acrylates. Next, relatively easily occurring side reactions are the additions of water and alcohols to acrylates (barriers of ca. 48 ± 1 kcal/mol in presence of the H + ion). Activation barrier for dimerisation of acrylic acid, i.e., addition of one molecule to the double bond of the other, in catalytic reaction is equal to 56.5 kcal/mol. Finally, the addition of alcohol to the acid dimer (leading to the same product as addition of acid to an acrylate) needs to overcome the 61 kcal/mol barrier. Based on the above results we discuss qualitatively our experimental findings of technology using heterogeneous acid catalysts.

Finishing of silk by acrylic acid in the presence of sodium citrate and potassium per sulphate as catalysts under thermal treatment

AbstractSilk fabric was finished using acrylic acid (AA) as the finishing agent in the presence of sodium citrate and potassium per oxodisulphate catalysts separately or in selected combinations employing a pad‐dry‐cure technique. Treatment with 6% AA at 30°C and at pH 7 produced optimum effects; a batching time of 45–60 min at 30°C, followed by drying of the batched fabric at 95°C for 5 min and curing of the dried fabric at 140°C for 5 min produced most balanced improvements in the properties such as wrinkle recovery, extensibility, and moisture regain with retention of more than 80% of original strength. Sodium citrate catalyst allowed esterification of AA with proteineous constituent of silk and potassium per sulfate catalyst allowed radical polymerization of free AA or silk bound AA moieties; the said process ultimately led to some degree of crosslinking of the chain polymers of silk. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Modification of hydroxylated multi-walled carbon nanotubes with a block copolymer

A novel approach was used to improve the dispersibility of multi-walled carbon nanotubes(MWCNTs) in a solvent.Vinyl-functionalized MWCNTs were prepared by the esterification of acrylic acid with hydroxylated MWCNTs.The block copolymer,polystyrene-b-hydroxyethyl methacrylate was synthesized by means of atom transfer radical polymerization.Then the block copolymer was attached to the surface of the MWCNTs through an addition reaction.The products were characterized by FTIR,TGA and TEM.Results indicated that the copolymer was attached to the surface of the MWCNTs by covalent bonds with a content of 42.9%,i.e.every 277 carbon atoms were grafted with a block copolymer chain.The resulting products had a good dispersibility in ethanol.

Theoretical study on the mechanisms of the conversion of methyl lactate over sodium polyphosphate catalyst

The conversion of methyl lactate (ML) over sodium tripolyphosphate, a model catalyst derived from silica supported sodium polyphosphate, was studied systematically by quantum mechanical calculations using MP2 and B3LYP methods. The reaction profiles of ML and its reaction products, acrylic acid (AA), methyl acrylate (MA) and lactic acid (LA) via various reactions such as dehydration, decomposition, decarbonylation, hydrolysis and esterification has been determined with the catalyst. For each reaction, the intermediate and transition state as well as their energetics were calculated. Over the catalyst, the main consumption routes for ML were identified to be the direct decomposition to AA and methanol and decarbonylation to acetaldehyde (AD), methanol and carbon monoxide. Both of the above reactions start from the same reaction intermediate. The main route for the formation of MA was supposed to be via esterification of AA with methanol. The values of activation barriers also indicate that over the sodium polyphosphate catalyst conversion of ML to AA has a higher selectivity than that from LA to AA.

Esterification of Acrylic Acid with 1,4‐Butanediol in a Batch Distillation Column Reactor over Amberlyst 15 Catalyst

AbstractThe esterification reaction of acrylic acid (AA) with 1,4‐butanediol (BD) to produce 4‐hydroxybutyl acrylate (HBA) was carried out in a batch reactive distillation mode over the Amberlyst 15 catalyst. The reactive distillation was highly desirable to increase the reaction rate of BD and eventually to obtain the high purity of HBA because the unreacted BD was not easily separable to the produced HBA after the reaction. The reaction pressure below 760 mm Hg was used to remove the by‐product water from the reaction zone. The air‐bubbling operation was successfully applied to prevent the polymerization of reactants and products under the vacuum condition (400 ∼ 760 mm Hg). The reaction rates were strongly dependent on the reaction pressure, especially, the reaction rate of BD disappearance. The increased reaction rate of BD by the reactive distillation enabled to produce a high purity of HBA.

Preparation and Catalytic Application of Novel Water Tolerant Solid Acid Catalysts of Zirconium Sulfate/HZSM-5

Esterification of acrylic acid(AA) to produce AA esters has widespread application in the chemical industry. A series of water tolerant solid acid catalysts was prepared, and characterized by XRD, nitrogen adsorption, TGA-DTA, XPS, and ammonia adsorption FTIR. The effects of Si/Al ratio, zirconium sulfate(ZS) loading on HZSM-5 and calcination temperature on the esterification were investigated. When 20% (mass fraction) ZS is loaded on HZSM-5, the conversion of AA reaches 100%. XRD analysis indicates that ZS is highly dispersed on HZSM-5 because no crystalline structure assigned to ZS is found. Catalytic activity and hydrophobicity of ZS supported on HZSM-5 are higher compared with those of parent ZS or HZSM-5. Results show that this kind of novel catalysts is an efficient water tolerant solid acid catalyst for esterification reactions.

Esterification of acrylic acid with but-1-ene over sulfated Fe- and Mn-promoted zirconia

Abstract The role of Mn and Fe as promoters of sulfated zirconia (ZS) has been studied in the reaction of acrylic acid (AA) esterification by but-1-ene to sec-butyl acrylate (SBA) at 343 K. The main result is that Mn and Fe did not improve the catalytic properties of sulfated zirconia as far as activity and selectivity to sec-butyl acrylate (90–95%) are concerned but strongly improved its resistance to deactivation, which makes this system attractive for substituting Amberlyst resins or sulfuric acid. The deactivation was shown not to be due to sulfated species and/or promoters leaching or to zirconia tetragonal phase transformation. It is proposed that in all cases acid sites are poisoned by the accumulation of unsaturated species primarily issue from the acrylic acid. Pyridine adsorption and n -butane isomerisation reaction at 473 K showed that the acidity of sulfated promoted zirconia was not increased by the addition of the promoters. Mn was observed by XPS to be slightly reduced during reaction while the oxidation state of the Fe was not changed. But this was shown not to be related to the deactivation process.