Synthesis Of Acrylate Research Articles

Ultrasound-assisted synthesis of methyl acrylate using Amberlyst-15 catalyst: optimization using response surface method

Ultrasound-assisted synthesis of methyl acrylate was performed in a solvent-free ultrasound batch reactor using acid ion exchange resin (amberlyst-15) as a heterogeneous catalyst. Influence of different reaction parameters such as temperature (40-70°C), alcohol to acid mole ratio (2-8), catalyst loading (0-10 % w/w), and addition of molecular sieves (0-8%), ultrasound power (0-120W), and duty cycle (20-80%) on the activity of reaction were investigated through one parameter at a time. Further, four significant parameters were optimized using response surface methodology using a central composite design. The maximum conversion of acrylic acid 61.02 %, was obtained at optimum reaction conditions at 61°C reaction temperature, 6.5 alcohol to acid mole ratio, 7.85% catalyst loading, and 60% ultrasound duty cycle. The equilibrium conversion improved from 29.2% to 61.02%, with a significant decrease in reaction time as compared to the conventional approach.

Innovative synthesis of multicomponent acrylate based redispersible powder and approaches for application in interior paints

The present work discloses the synthesis of multicomponent acrylate based waterborne latex for especially interior coatings. Redispersible powder (RDP) can be utilized in the paint and coatings industry due to its simplicity of use in variety of applications. In this paper, acrylate based latex was prepared by emulsion polymerization method. Three components were mixed for the preparation of the emulsion of RDP. The prepared acrylic latex was later spray dried and converted into RDP. The obtained dried RDP has very good redispersibility. The characterization of RDP was carried out using a Fourier transform infrared spectrometer (FTIR), Particle size analyzer, Differential scanning calorimeter (DSC), and Field emission scanning electron microscope (FE-SEM). The viscosity, freeze thaw stability, redispersibility and storage stability were also studied for RDP. Results show that the Total solid content (TSC) of synthesized RDP is 89%. Freeze thawing stability shows good quality with a milky white appearance of latex. There is no gelation, setting and coagulation of emulsion. The prepared RDP shows good storage stability with no aggregation of particles after 48 to 96 h of storage. In this study, it is seen that as the inlet temperature of the dryer increases, the percentage of moisture in the final product decreases which leads to a free – flowing powder. It can be seen that RDP was free-flowing in nature having angle of response≈ 38.7° with a bulk density of 270 to 350 kg/m3. In the context of acrylate, FTIR peaks indicate the presence of carbonyl group, which is characteristic of the acrylate functional group. The Particle size of RDP is 133.6 μm. The optimum temperature to melt the powder was found to be 200 °C. SEM micrograph of RDP is recorded at magnification 1.00, 5.00, 5.00, 10.00 KX, and applied voltage 20 kV and scale range of images are 20 μm, 2 μm, 2 μm and 1 μm, respectively. Results showed a dented surface with a shrunken spherical form. In this paper, RDP based paint formulations were synthesized by mixing RDP with water, calcium carbonate, and titanium dioxide. Here, RDP acts as a binder. Paint formulations were applied to the specimen and dried. The resultant paints were characterized by pendulum hardness, cross cut, pencil hardness, methyl ethyl ketone (MEK) rubbing test and gloss test to understand the physical properties of the paint coating.Graphical

PEG-assisted synthesis of highly dispersed Cs/Zr-SiO2 catalyst for aldol condensation of methyl acetate with formaldehyde

The dispersion of active sites plays an imperative role in the promotion of catalytic performance on methyl acrylate synthesis via direct vaporous aldol condensation. Herein, a novel PEG-assisted impregnation method was proposed to synthesize Cs/Zr-SiO2 catalyst with high dispersion of acid and base sites. A series of characterization techniques including NMR, TEM, physical N2 adsorption isotherms, XRD, XPS, NH3-/CO2-TPD, and Py-IR were used to investigate the physico-chemical properties of these prepared catalyst series. The introduction of PEG improved the specific surface area, dispersion of active sites, and density of acid and base sites, resulting in superior catalytic performance of Cs/PEG@Zr-SiO2 by comparison with that of Cs/SiO2 and Cs/Zr-SiO2. The kinetic experiments revealed that the activation energy of aldol condensation was 80.8 kJ/mol over the Cs/PEG@Zr-SiO2 catalyst. The deactivation behavior derived from carbon deposition was discovered, and the spent catalyst could be regenerated by simple thermal treatment.

Sodium Acrylate Synthesis Through CO2 and Ethylene Coupling Catalyzed by Pd: Solvent Effects and PdBr2 as a Surprisingly Suitable Precursor

AbstractPd‐catalyzed carboxylation of ethylene into sodium acrylate is an industrially relevant reaction that has gained increasing attention in the last years. By this process, CO2 can be transformed into a value‐added molecule in a single, high atom economy step. However, there is still some room for improvement since the productivity of the reference catalyst is rather low. A key aspect to achieve this goal concerns the good understanding of reaction mechanism. Herein, we combine experimental and DFT studies to gain some knowledge on the reactivity and catalytic performance of the Pd/dicyclohexylphosphinoethane (dcpe) system. First, we were able to understand the influence of the solvent on the reaction, and we demonstrated that DMF was the best candidate due to the more efficient formation of the Pd‐metallalactone. Moreover, we have demonstrated that highly available and less costly PdBr2 can be a suitable precursor, as PdII is reduced in situ in DMF in the presence of an excess of NaOtBu. Finally, the role of different monophosphine additives has been elucidated, which permitted us to rationally improve the catalytic performance.

Zirconium-Modified Cs/SiO2 Catalyst for Synthesis of Methyl Acrylate via Aldol Condensation of Methyl Acetate with Formaldehyde

Zirconium-Modified Cs/SiO₂ Catalyst for Synthesis of Methyl Acrylate via Aldol Condensation of Methyl Acetate with Formaldehyde

Synthesis of acrylate copolymer‐based super oil adsorption resins and their performances

AbstractIn this paper, an acrylate copolymer‐based oil adsorption resin was designed and synthesized by a suspension polymerization with octadecyl acrylate (SA) and butyl acrylate (BA) as monomers, divinylbenzene (DVB) as a cross‐linking agent, and toluene as a pore‐forming agent. By studying the synthesis conditions, the copolymer “SA‐BA‐DVB” (PSBA) with the best adsorption capacity was obtained, when the molar ratio between SA and BA was about 0.9, the content of the DVB and PVA 1788 was about 0.107 wt% and 1.0 wt%, respectively, accounting for the total mass amount of the monomers. Furthermore, by introducing 2% reactive silica nanoparticles (R‐SiO2), the performances of the PSBA were improved due to its increased hydrophobicity and activity space. The equilibrium adsorption capacity of the resulted R‐SiO2/PSBA to kerosene, diesel oil, benzene, and p‐xylene was 31.90, 34.13, 39.44, and 41.81 mL/g, respectively, which is about 1.12 to 1.21 times higher than that of the PSBA. Also, the R‐SiO2/PSBA show brilliant oil retention rate of about 99% after centrifugation at 3000 rpm for 5 min and recycling ability which can be reusable for at least 10 absorption‐desorption cycles without capacity change, demonstrating that the obtained R‐SiO2/PSBA resin can be used as oil removing agents in the field of oil spill applications.Highlights R‐SiO2 modified acrylate copolymer as an oil adsorption resin was designed and synthesized. The influence of the monomers, cross‐linking agent, and others on the adsorption resin was systematically studied. The adsorption kinetics and performances of the adsorption resin were studied.

Synthesis and characterization of polyurethane acrylate with bio-oil modification for photo-curing 3D printed flexible structures

The use of renewable resources for additive manufacturing has grown significantly as a means of advancing the ongoing shift to a green economy. This study uses bio-oil generated from the rapid pyrolysis of forest waste as a bio-based chemical to partially replace polyethylene glycol to synthesize a new type of bio-oil modified polyurethane acrylate, used in photo-curing 3D printing technology. The study explores the impact of the ratio of bio-oil to polyethylene glycol on the properties of polyurethane resin. As the amount of bio-oil added increases, the molecular weight of polyurethane acrylate decreases. Modified photosensitive resin showcases better suitability for photo-curing 3D printing, with lower viscosity and volume shrinkage, and its printed samples exhibit enhanced mechanical strength and improved thermal stability. In particular, when the bio-oil substitution rate is 20 wt%, the tensile strength of the 3D printed sample increases by 70 %, and the double bond conversion rate reaches 58.07 %. Meanwhile, the hollow and branching structures of 3D printing have the characteristics of high precision and flexibility. Introducing bio-oil into 3D printing technology not only expands the application fields of bio-oil but also provides new considerations for the transition of photosensitive resins from petroleum-based to renewable fields.

Performance analysis of reactive-extractive distillation for multi-azeotropic mixture based on the relationship between economy and conversion rate

The synthesis and purification of ethyl acrylate are of great importance in studying the coupling performance of reaction and separation. In this manuscript, reactive extractive distillation (RED), immiscible-assisted reactive extractive distillation (IRED), and high conversion rate process (HCP) were comprehensively studied. The conceptual design by quaternary phase diagram was demonstrated. The optimal extractant was selected based on relative volatility and quantum chemistry. Multi-objective algorithm was used to minimize gas emissions and total annual cost (TAC). Based on economic, environmental and profit etc., the RED, IRED, and HCP were evaluated. The results show that the TAC, gas emissions, exergy loss, energy consumption, and profit of IRED were decreased by more than 25 %, 21 %, 12 %, 14 %, and 26 % compared to RED. Besides, the profit of the IRED is better than that of the HCP, which indicates that higher conversion rate of the reaction cannot represent better economy of the reactive distillation process.

Heterogeneous Brønsted Catalysis in the Solvent-Free and Multigram-Scale Synthesis of Polyalcohol Acrylates: The Case Study of Trimethylolpropane Triacrylate.

This article presents a thorough investigation into the synthesis of trimethylolpropane triacrylate (TMPTA) via the esterification reaction of trimethylolpropane (TMP) with acrylic acid using Amberlite™ 120 IR (H+), Amberlyst® 15, and Dowex™ 50WX8 resins as heterogeneous catalysts. Preliminary comparative tests explored the impact of air flow on water removal during the reaction and different acid-to-alcohol molar ratios (3:1, 6:1, or 9:1 mol:mol). The findings revealed that introducing air significantly enhances TMPTA yield and -OH group conversion, particularly at a 6:1 acid-to-alcohol molar ratio. Based on cost considerations, Amberlite™ 120 IR (H+) was selected as the preferred catalyst for further optimization. This included evaluating the effect of catalyst loading (10%, 5.0%, and 2.5% w/wtot) and assessing the impact of a pre-drying process on resin efficiency. The study concluded that optimal conditions did not necessitate drying, requiring 120 °C, a catalyst loading of 10% w/wtot, a 4 h reaction time, an acid:alcohol ratio of 6:1 mol:mol, the presence of MEHQ (0.1% mol/molAA), and air bubbling at 6 ± 1 Nl/h. Catalyst recycling was effectively implemented with a slight reduction in catalytic activity over consecutive runs. Furthermore, the study explored a scaled-up system with a mechanical stirrer, demonstrating the potential for multi-hundred grams scale-up. Considerations for optimizing the air flow stripping system are also highlighted. In summary, this study provides valuable insights into designing and optimizing the esterification process for TMPTA synthesis, laying the foundation for potential industrial applications.

Excellence in Acrylation - Scope and Limitation of Glucosyl Imidazolium-coated Novozym 435 Catalyzed (Meth)acryl Ester Synthesis.

The incorporation of carbohydrate based ionic liquids as a support for Novozym 435 was previously studied by the authors for the acrylation of n-butanol as the target substrate, which was used as the foundation for the design of experiments. The combination of carbohydrate based ionic liquids and Novozym 435 remains a key aspect of this work. Building upon this, the reaction parameters were optimized for the Novozym catalyst. Substrate screening was performed to explore the scope and limitations of room temperature acrylation reactions. Herein, different alcohols and reaction conditions were screened extensively for the different acrylate products with yields of up to 99.9 % determined via gas chromatography (GC). Standard straight chain alcohols, 2-functionalized ethanol derivatives with electron donating and withdrawing groups, and more sterically challenging substrates were investigated over a broad concentration region. To further underline the applicability of the modified biocatalyst, two alcohols were converted with methacrylic acid. The presented method offers a greener pathway for acrylate synthesis, which eliminates the need for high reaction temperatures, strongly acidic catalysts and/or polymerization inhibitors as used in non-biocatalytic acrylate synthesis.

Synthesis of water-soluble tetrafunctional urethane acrylate bearing a pentaerythritol core and its radical polymerization behaviors in an aqueous solution

A novel water-soluble tetrafunctional urethane acrylate (TUA) was successfully synthesized by addition reaction of pentaerythritol to 2-isocyanatoethyl acrylate. TUA efficiently underwent radical polymerization and its copolymerization with monofunctional acrylate monomers exhibiting hydrophilicity in an ethanol aqueous solution, affording corresponding networked polymers in high yields. Notably, TUA exhibited much lower volume shrinkage during the radical polymerization compared to a comparative pentaerythritol core based tetrafunctional acrylate containing no urethane bonds. The thermal decomposition temperature of the networked homopolymer, synthesized from TUA, was much higher than those of the linear polymers, synthesized from monofunctional urethane acrylate monomers. TUA is expected to be applied to the development of environmentally sustainable polymer materials.

Revisiting the Synthesis of Cellulose Acrylate and Its Modification via Michael Addition Reactions.

The synthesis of cellulose acrylate from cellulose with acryloyl chloride has been problematic due to unexpected gelation of the reaction mixture, but we discovered that the use of bulky amines was crucial for the reproducibility of the synthesis of cellulose acrylate. The solubility of the obtained cellulose acrylate depended on the reaction conditions due to the possible cross-linking oxa-Michael reaction between a remaining hydroxy group and the introduced acrylate group. The synthesized cellulose acrylate worked as a useful precursor of chemically modified cellulose materials because it reacted with various functionalized nucleophiles such as secondary amines and thiols as a Michael donor. This method was applied to the synthesis of N-methyl-d-glucamine-modified cellulose that works as an adsorbent for the removal of B(OH)3 in water.

Synthesis of styrene, phenyl acrylate and allyloxyphenyl-functionalized porphyrins, and preliminary exploration of their utility for assembling multiple porphyrin units

Three free-base and two Zn(II) porphyrins carrying one alkene-substituted meso-aryl group and three solubilizing pentyl groups were prepared via mixed aldehyde-type syntheses. A meso [Formula: see text]-allyloxyphenyl porphyrin was obtained via the corresponding 5-([Formula: see text]-allyloxyphenyl) dipyrromethane. The porphyrins were fully characterized using a combination of NMR spectroscopy, high-resolution mass spectrometry, and UV-Vis absorption and emission spectroscopies. Two of the free-base porphyrins were heated in the presence of AIBN or benzoyl peroxide as the initiator. The major isolated products of these reactions contained two porphyrin units based on the results of MALDI-MS and 1H NMR analysis data, which was supported by the results of FTIR, UV-Vis absorption and emission spectroscopies, and gel permeation and liquid chromatographies. Additionally, the acrylamide-functionalized porphyrin could be attached to a polylysine scaffold under basic conditions. These results suggest that the olefinic handle can be used to assemble structures containing multiple porphyrinic macrocycles.

Iridium-Catalyzed Enantioselective Formal α-Allylic Alkylation of Acrylonitrile.

A highly enantioselective formal α-allylic alkylation of acrylonitrile is developed using 4-cyano-3-oxotetrahydrothiophene (c-THT) as a safe and easy-to-handle surrogate of acrylonitrile. This two-step process consists of an Ir(I)/(P,olefin)-catalyzed branched-selective allylic alkylation using easily accessible branched rac-allylic alcohols as the allylic electrophile followed by retro-Dieckmann/retro-Michael fragmentation and is shown to be applicable for the enantioselective synthesis of α-allylic acrylates as well as α-allylic acrolein.

Wood pulp industry by-product valorization for acrylate synthesis and bio-based polymer development via Michael addition reaction

It is crucial to adapt the processing of forest bio-resources into biochemicals and bio-based advanced materials in order to transform the current economic climate into a greener economy. Tall oil, as a by-product of the Kraft process of wood pulp manufacture, is a promising resource for the extraction of various value-added products. Tall oil fatty acids-based multifunctional Michael acceptor acrylates were developed. The suitability of developed acrylates for polymerization with tall oil fatty acids-based Michael donor acetoacetates to form a highly cross-linked polymer material via the Michael addition was investigated. With this novel strategy, valuable chemicals and innovative polymer materials can be produced from tall oil in an entirely new way, making a significant contribution to the development of a forest-based bioeconomy. Two different tall oil-based acrylates were successfully synthesized and characterized. Synthesized acrylates were successfully used in the synthesis of bio-based thermoset polymers. Obtained polymers had a wide variety of mechanical and thermal properties (glass transition temperature from –12.1 to 29.6 °C by dynamic mechanical analysis, Young's modulus from 15 to 1 760 MPa, and stress at break from 0.9 to 16.1 MPa). Gel permeation chromatography, Fourier-transform infrared (FT-IR) spectroscopy, matrix-assisted laser desorption/ionization-time of flight mass spectrometry, and nuclear magnetic resonance were used to analyse the chemical structure of synthesized acrylates. In addition, various titration methods and rheology tests were applied to characterize acrylates. The chemical composition and thermal and mechanical properties of the developed polymers were studied by using FT-IR, solid-state nuclear magnetic resonance, thermal gravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, and universal strength testing apparatus.

Light-Dependent RAFT Polymerization of Spiropyran Acrylates.

A light-assisted RAFT copolymerization protocol is established and investigated for the synthesis of 2-hydroxyethyl acrylate (HEA) / spiropyran acrylate (SPA) copolymers with enhanced SPA-contents. Radiation with visible light prevents the spiropyran (SP) motif from isomerizing into the open merocyanine (MC) form which can interfere with the polymerization process by abstracting a hydrogen atom from an active radical via its phenolic oxygen. This article is protected by copyright. All rights reserved.

Synthesis of xylitol-based hyperbranched polyurethane acrylate and its application in self-matting acrylate coatings

Synthesis of xylitol-based hyperbranched polyurethane acrylate and its application in self-matting acrylate coatings

Renewable synthesis of novel acrylates from biomass‐derived 5‐substituted‐2‐furaldehydes by Morita‐Baylis‐Hillman reaction

AbstractBiomass‐derived furfurals are becoming increasingly popular as renewable chemical building blocks for synthesizing specialty chemicals. Morita‐Baylis‐Hillman (MBH) reaction is a classic carbon‐carbon bond‐forming transformation between the α‐position of an activated alkene and a carbon electrophile (e. g., aldehyde) using a nucleophilic catalyst, such as a tertiary amine or phosphine. The MBH reaction is highly atom economical, affords excellent yields of adducts under mild reaction conditions, introduces substantial molecular complexity, and enjoys broad substrate scope. In this work, several novel MBH adducts have been synthesized starting from biomass‐derived 5‐substituted‐2‐furaldehydes and acrylates using 1,4‐diazabicyclo[2.2.2]octane (DABCO) as the organocatalyst. This work reports the first systematic study of the MBH reaction of 5‐substituted‐2‐furaldehydes and acrylates. A general synthetic protocol for the high‐yielding synthesis of MBH adducts has been developed. The reactions were performed at room temperature under solvent‐free conditions, and the spectroscopically pure products were produced in good to excellent isolated yields. Moreover, DABCO was recovered from the reaction mixture and successfully recycled.

Synthesis and characteristics of cardanol-based acrylates as reactive diluents in UV-curing coatings

Two types of cardanol epoxy acrylates (CAR1 and CAR2) were synthesized from bio-based cardanol and used as a reactive diluent. Their dilution effect, curing properties, and thermal and physical properties of UV-cured films as a reactive diluent were compared to those of commercial reactive diluent, 2-phenoxyethyl acrylate (PHEA). CAR series showed a lower dilution effect due to their relatively high viscosity compared to PHEA. However, 10 wt% CAR-diluted films showed similar reactivity and high thermal stability compared to 10 wt% PHEA diluted film, indicating CAR series can be used as partial alternatives to PHEA.

α-Arylsulfonyloxyacrylates: attractive O-centered electrophiles for synthesis of α-substituted acrylates via Pd-catalysed Suzuki reactions.

We herein report α-arylsulfonyloxyacrylates as a kind of useful and attractive O-centered electrophiles for Suzuki cross-coupling reactions. A range of α-(hetero)aryl substituted acrylates has been prepared via the palladium-catalysed C-C cross-coupling reactions between potassium (hetero)aryltrifluoroborates and α-arylsulfonyloxyacrylates. Moreover, α-arylsulfonyloxyacrylate could also react with B-alkyl-9-BBN to produce α-alkyl substituted acrylates. The synthetic application of this new method was demonstrated by the preparation of the intermediate for synthesis of retinoid X receptors-selective retinoids. These Suzuki reaction-based protocols feature broad substrate scope, generality, and mild reaction conditions.