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Usage

Uses

Used in Nail Lacquers:
Methyl acrylate is used in some nail lacquers for its ability to form a hard, durable film that provides a glossy finish and long-lasting wear.
Used in Fiber Production:
Methyl acrylate is used as a comonomer with acrylonitrile in the production of acrylic and modacrylic fibers. These fibers, which usually contain about 85% acrylonitrile, are used to fabricate clothing, blankets, carpets, and curtains.
Used in Coatings:
Methyl acrylate is used in the preparation of thermoplastic coatings, providing properties such as adhesion, flexibility, and resistance to chemicals and weathering.
Used in Chemical Synthesis:
Methyl acrylate serves as a chemical intermediate in the synthesis of various compounds, including acrylic polymers, amphoteric surfactants, and vitamin B1.
Used in Plastic Films and Textiles:
Methyl acrylate is a monomer used in the manufacture of plastic films, textiles, and paper coatings, contributing to their strength, durability, and versatility.
Used in Amphoteric Surfactants:
Methyl acrylate is also used in the production of amphoteric surfactants, which are important in the formulation of personal care and cleaning products due to their mildness and foaming properties.
Used in Elastomers and Plastics:
Methyl acrylate is utilized in the production of elastomers and plastics, enhancing their elasticity, toughness, and resistance to deformation.
Used in Ionic Exchange Resins:
Methyl acrylate is found in ionic exchange resins, which are used in water treatment, food processing, and various industrial applications to remove ions from solutions.
Used in Barrier Film Resins:
Methyl acrylate is used in the production of barrier film resins, which are employed in the creation of films with improved barrier properties for packaging and other applications.
Used in Antioxidant Intermediates:
Methyl acrylate is also used as an intermediate in the synthesis of antioxidants, which are important additives in various industries to prevent oxidation and degradation of materials.

Preparation

Acrylate esters can be produced in a number of ways. The most commonly used method, developed in 1970, involves a propylene oxidation process. The reaction occurs initially with the oxidation of propylene to acrolein, which in turn is oxidized to acrylic acid. Once the acrylic acid is formed, it is reacted with methanol which causes the formation of the methyl acrylate. This reaction is shown as follows: An older method, the Reppe process, involves reacting acetylene with nickel carbonyl and methyl alcohol in the presence of an acid to produce methyl acrylate. More recent methods for producing acrylate esters involve the use of organic carbonates as esterifying agents or isolating 2-halo- 1-alkenes from hydrocarbon feedstocks to produce the acrylate esters (Haggin, 1985).

Production Methods

Methyl acrylate is manufactured via a reaction of nickel carbonyl and acetylene with methanol in the presence of an acid; more commonly, however, it is manufactured via oxidation of propylene to acrolein and then to acrylic acid. The acid is reacted with methanol to yield the ester.

Air & Water Reactions

Highly flammable. Forms peroxides when exposed to air that may initiate spontaneous, exothermic polymerization. Peroxide formation usually proceeds slowly. Slightly soluble in water.

Reactivity Profile

METHYL ACRYLATE ignites readily when exposed to heat, flame or sparks. Offers a dangerous fire and explosion hazard. Reacts vigorously with strong oxidizing materials. Forms peroxides when exposed to air that may initiate spontaneous exothermic polymerization. Peroxide formation usually proceeds slowly. Added inhibitor retards polymerization. If the inhibitor is consumed during long storage, explosive polymerization may occur [MCA Case History No. 2033]. Also subject to strongly exothermic polymerization if heated for prolonged periods or contaminated.

Hazard

Flammable, dangerous fire and explosion risk. Toxic by inhalation, ingestion, and skin absorption; irritant to skin, eyes and upper respiratory tract irritant; eye damage. Questionable carcinogen.

Health Hazard

The liquid is a strong irritant, and prolongedcontact with the eyes or skin may causesevere damage. Inhalation of its vapors cancause lacrimation, irritation of respiratorytract, lethargy, and at high concentrations,convulsions. One-hour exposure to a concen tration of 700–750 ppm in air caused deathto rabbits. The oral toxicity of methyl acry late in animals varied from low to moderate,depending on species, the LD50 values ranging between 250 and 850 mg/kg. The liquidmay be absorbed through the skin, producingmild toxic effects.

Fire Hazard

Flammable liquid; flash point (closed cup) -4°C (25°F), (open cup) -3°C (27°F); vapor pressure 68 torr at 20°C (68°F); vapor density 3.0 (air = 1); the vapor is heavier than air and can travel a considerable distance to a source of ignition and flashback; autoignition tem perature not established; fire-extinguishing agent: dry chemical, CO2, or “alcohol” foam; use water to keep the fire-exposed containers cool and to flush or dilute any spill; the vapors may polymerize and block the vents.The vapors of methyl acrylate form explo sive mixtures with air, over a relatively wide range; the LEL and UEL values are 2.8 and 25.0% by volume in air, respectively. Methyl acrylate undergoes self-polymerization at 25°C (77°F). The polymerization reaction proceeds with evolution of heat and the increased pressure can cause rupture of closed containers. The reaction rate is accelerated by heat, light, or peroxides. Vigorous to violent reaction may occur when mixed with strong oxidizers (especially nitrates and peroxides) and strong alkalie.

Flammability and Explosibility

Flammable

Safety Profile

Poison by ingestion and intraperitoneal routes. Moderately toxic by skin contact. Mddly toxic by inhalation. Human systemic effects by inhalation: olfaction effects, eye effects, and respiratory effects. A skin and eye irritant. Mutation data reported. Chronic exposure has produced injury to lungs, liver, and kidneys in experimental animals. Questionable carcinogen. Dangerously flammable when exposed to heat, flame, or oxidzers. Dangerous explosion hazard in the form of vapor when exposed to heat, sparks, or flame. Can react vigorously with oxidzing materials. A storage hazard; it forms peroxides, which may initiate exothermic polymerization. To fight fire, use foam, COa, dry chemical. When heated to decomposition it emits acrid smoke and irritating fumes. See also ESTERS.

Safety

It is an acute toxin with an LD50 (rats, oral) of 300 mg/kg and a TLV of 10 ppm.

Potential Exposure

Methyl acrylate is used in production of acrylates, copolymers, barrier resins; and surfactants for shampoos; as a monomer in the manufacture of polymers for plastic films, textiles, paper, and leather coating resins. It is also used as a pesticide intermediate and in pharmaceutical manufacture.

Carcinogenicity

Methyl acrylate was not shown to be carcinogenic in male and female rats in a lifetime inhalation study .

Environmental fate

Photolytic. Polymerizes on standing and is accelerated by heat, light, and peroxides (Windholz et al., 1983). Methyl acrylate reacts with OH radicals in the atmosphere (296 K) and aqueous solution at rates of 3.04 x 10-12 and 2.80 x 10-12 cm3/molecule?sec, respectively (Wallington et al., 1988b). Chemical/Physical. Begins to polymerize at 80.2 °C (Weast, 1986). Slowly hydrolyzes in water forming methyl alcohol and acrylic acid (Morrison and Boyd, 1971). Based on a hydrolysis rate constant of 0.0779/M?h at pH 9 at 25 °C, an estimated half-life of 2.8 yr at pH 7 was reported (Roy, 1972). The reported rate constant for the reaction of methacrylonitrile with ozone in the gas phase is 2.91 x 10-18 cm3 mol/sec (Munshi et al., 1989a).

storage

Methyl acrylate is stored in a flammable materials storage room or cabinet below 20°C (68°F), separated from oxidizing substances. It is inhibited with 200 ppm ofhydroquinone monomethyl ether to preventself-polymerization. It is shipped in bottles,cans, drums, or tank cars.

Shipping

UN1919 Methyl acrylate, stabilized, Hazard Class: 3; Labels: 3-Flammable liquid.

Purification Methods

Wash the ester repeatedly with aqueous NaOH until free from inhibitors (such as hydroquinone), then wash it with distilled water, dry (CaCl2) and fractionally distil it under reduced pressure in an all-glass apparatus. Seal it under nitrogen and store it at 0o in the dark. [Bamford & Han J Chem Soc, Faraday Trans 1 78 855 1982, Beilstein 2 IV 1457.]

Toxicity evaluation

Methyl acrylate (MA) is moderately toxic to fish (LC50 1.1 - 7.5 mg/l), crustaceans (LC50/EC50 0.31 - 2.6 mg/l) and algae(EC50 6.9 - 15.0 mg/l). In Selenastrum capricornutum, MA is algistatic at a concentration of 19 mg/l.It is of low acute toxicity to bacteria and protozoa.

Incompatibilities

Forms explosive mixture in air. Incompatible with nitrates, oxidizers, such as peroxides, strong alkalis. Polymerizes easily from heat, light, peroxides; usually contains an inhibitor, such as hydroquinone.

Waste Disposal

Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber. All federal, state, and local environmental regulations must be observed. Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant (≥100 kg/mo) must conform to EPA regulations governing storage, transportation, treatment, and waste disposal

InChI:InChI=1/C4H6O2/c1-3-4(5)6-2/h3H,1H2,2H3

Upstream product

• 463-51-4 Ketene 
• 547-64-8 methyl lactate 
• 50-00-0 formaldehyd 
• 79-20-9 acetic acid methyl ester 
• 67-56-1 methanol 
• 57-57-8 β-Propiolactone 
• 75-93-4 methyl bisulfate 
• 77-78-1 dimethyl sulfate 
• 6288-11-5 2-methoxycarbonyloxy-propionic acid methyl ester 
• 6284-75-9 methyl 2-acetoxypropionate 
• 110-67-8 3-Methoxypropionitrile 
• 2544-06-1 3-Methoxypropionic acid 
• 3852-09-3 methyl 3-methoxypropionate 
• 13515-97-4 methyl 2-aminopropanoate monohydrochloride 

Downstream Products

• 113091-10-4 1-benzyl-3-methoxycarbonyl-3-(2-methoxycarbonyl-ethyl)-1-methyl-4-oxo-piperidinium; chloride 
• 102025-71-8 4-cyano-4-phenyl-4-[2]pyridyl-butyric acid methyl ester 
• 66839-22-3 4-((3-methoxy-3-oxopropyl)amino)benzoic acid 
• 111241-00-0 4-[bis-(2-methoxycarbonyl-ethyl)-amino]-benzoic acid 
• 66839-23-4 4-(2-methoxycarbonyl-ethylamino)-benzoic acid ethyl ester 
• 102310-16-7 bis-[2-(2-methoxycarbonyl-ethyl)-cyclohexylidene]-hydrazine 
• 99421-05-3 2-chloro-3-(4-nitro-phenyl)-propionic acid methyl ester 
• 19766-10-0 methyl 2,2,4-trimethylcyclohex-3-enecarboxylate 
• 16778-09-9 4,4,4-triphenylbutanoic acid 
• 859306-63-1 2-isobutyl-glutaric acid dimethyl ester 
• 456-08-6 4-fluoro-cyclohex-3-enecarboxylic acid methyl ester 
• 108170-04-3 4,5-dimethyl-2-(2-methyl-propenyl)-cyclohex-3-enecarboxylic acid methyl ester 
• 105540-13-4 2-isopropyl-4-methyl-cyclohex-3-enecarboxylic acid methyl ester 
• 76441-19-5 3-Amino-thiocarbonylmercapto-propionsaeuremethylester 

Relevant academic research and scientific papers

Scalable Total Synthesis of (-)-Triptonide: Serendipitous Discovery of a Visible-Light-Promoted Olefin Coupling Initiated by Metal-Catalyzed Hydrogen Atom Transfer (MHAT)

An efficient and scalable total synthesis of (-)-triptonide is accomplished based on a metal-catalyzed hydrogen atom transfer (MHAT)-initiated radical cyclization. During the optimization of the key step, we discovered that blue LEDs significantly promoted the efficiency of reaction initiated by Co(TPP)-catalyzed MHAT. Further exploration and optimization of this catalytic system led to development of a dehydrogenative MHAT-initiated Giese reaction.

METHOD FOR MAKING BIO-BASED ACRYLIC ACID

Described herein are methods for the preparation of bio-based acrylic acid from bio-based methyl lactate. Some methods involve the use of an azeotropic distillate of methyl acrylate and methanol. The methods enhance bio-based acrylic acid production yield.

Method for preparing methyl acrylate from methyl acetate

The invention provides a method for preparing methyl acrylate from methyl acetate, which comprises the following steps: in the presence of a solid base catalyst, methyl acetate reacts with an aldehyde source to obtain methyl acrylate, and the solid base catalyst comprises the following components in parts by mass: a) a catalytic amount of alkali metal oxide; and b) 50 to 80 parts of a carrier; wherein the carrier is silicon dioxide of which the silicon hydroxyl density is 0.6-1.5 Si-OH/nm. The invention also provides a solid base catalyst, and an application and a preparation method thereof. The methyl acrylate synthesis route and the corresponding solid base catalyst have the advantages that the yield and selectivity are improved, and the catalytic activity can be maintained for a long time, so that the industrialization can be realized, and the problem that the production capacity of methyl acetate is greatly excessive is solved.

Acid- And base-switched palladium-catalyzed γ-C(sp3)-H alkylation and alkenylation of neopentylamine

The functionalization of remote unactivated C(sp3)-H and the reaction selectivity are among the core pursuits for transition-metal catalytic system development. Herein, we report Pd-catalyzed γ-C(sp3)-H-selective alkylation and alkenylation with removable 7-azaindole as a directing group. Acid and base were found to be the decisive regulators for the selective alkylation and alkenylation, respectively, on the same single substrate under otherwise the same reaction conditions. Various acrylates were compatible for the formation of C(sp3)-C(sp3) and C(sp3)-C(sp2) bonds. The alkenylation protocol could be further extended to acrylates with natural product units and α,β-unsaturated ketones. The preliminary synthetic manipulation of the alkylation and alkenylation products demonstrates the potential of this strategy for structurally diverse aliphatic chain extension and functionalization. Mechanistic experimental studies showed that the acidic and basic catalytic transformations shared the same six-membered dimer palladacycle.

Pd-Catalyzed Intermolecular Transthiolation of Ar-OTf Using Methyl 3-(Methylthio) Propanoate as a Thiol Surrogate

A method for the odorless synthesis of unsymmetrical sulfides via Csp2?O and Csp3?S bond activation is presented. Using methyl 3-(methylthio) propanoate as a MeSH surrogate, a series of substituted aryl methyl sulfides have been obtained in moderate to good yields. This catalytic protocol can also tolerate methyl 3-(methylthio)propionate derivatives to afford the corresponding aryl sulfides.

Phosphine-Catalyzed Cascade Annulation of MBH Carbonates and Diazenes: Synthesis of Hexahydrocyclopenta[c]pyrazole Derivatives

A phosphine-catalyzed cascade annulation of Morita-Baylis-Hillman (MBH) carbonates and diazenes was achieved, giving tetrahydropyrazole-fused heterocycles bearing two five-membered rings in moderate to excellent yields. The reaction underwent an unprecedented reaction mode of MBH carbonates, in which two molecules of MBH carbonates were fully merged into the ring system.

METHOD FOR PREPARING ACRYLIC ACID AND METHYL ACRYLATE

The present invention provides a method for preparing acrylic acid and methyl acrylate. The method comprises passing the feed gas containing dimethoxymethane and carbon monoxide through a solid acid catalyst to generate acrylic acid and methyl acrylate with a high conversion rate and selectivity at a reaction temperature in a range from 180 to 400 and a reaction pressure in a range from 0.1 MPa to 15.0 MPa, the mass space velocity of dimethoxymethane in the feed gas is in a range from 0.05 h?1 to 10.0 h?1, and the volume percentage of dimethoxymethane in the feed gas is in a range from 0.1% to 95%.

The effect of viscosity on the coupling and hydrogen-abstraction reaction between transient and persistent radicals

The effect of viscosity on the radical termination reaction between a transient radical and a persistent radical undergoing a coupling reaction (Coup) or hydrogen abstraction (Abst) was examined. In a non-viscous solvent, such as benzene (bulk viscosity bulk 99% Coup/Abst selectivity, but Coup/Abst decreased as the viscosity increased (89/11 in PEG400 at 25 °C [bulk = 84 mPa s]). While bulk viscosity is a good parameter to predict the Coup/Abst selectivity in each solvent, microviscosity is the more general parameter. Poly(methyl methacrylate) (PMMA)-end radicals had a more significant viscosity effect than polystyrene (PSt)-end radicals, and the Coup/Abst ratio of the former dropped to 50/50 in highly viscous media (bulk = 3980 mPa s), while the latter maintained high Coup/ Abst selectivity (84/16). These results, together with the low thermal stability of dormant PMMA-TEMPO species compared with that of PSt-TEMPO species, are attributed to the limitation of the nitroxide-mediated radical polymerization of MMA. While both organotellurium and bromine compounds were used as precursors of radicals, the former was superior to the latter for the clean generation of radical species.

METHOD FOR PREPARING LOW-GRADE UNSATURATED FATTY ACID ESTER

Provided is a method for preparing a lower unsaturated fatty acid ester, which comprises carrying out an aldol condensation reaction between dimethoxymethane (DMM) and a lower acid or ester with a molecular formula of R1—CH2—COO—R2 on an acidic molecular sieve catalyst in an inert atmosphere to obtain a lower unsaturated fatty acid or ester(CH2═C(R1)—COO—R2), wherein R1 and R2 are groups each independently selected from the group consisting of H- and C1-C4 saturated alkyl group.

Continuous Radio Amplification by Stimulated Emission of Radiation using Parahydrogen Induced Polarization (PHIP-RASER) at 14 Tesla

Nuclear Magnetic Resonance (NMR) is an intriguing quantum-mechanical effect that is used for routine medical diagnostics and chemical analysis alike. Numerous advancements have contributed to the success of the technique, including hyperpolarized contrast agents that enable real-time imaging of metabolism in vivo. Herein, we report the finding of an NMR radio amplification by stimulated emission of radiation (RASER), which continuously emits 1H NMR signal for more than 10 min. Using parahydrogen induced hyperpolarization (PHIP) with 50 % para-hydrogen, we demonstrated the effect at 600 MHz but expect that it is functional across a wide range of frequencies, e.g. 101–103 MHz. PHIP-RASER occurs spontaneously or can be triggered with a standard NMR excitation. Full chemical shift resolution was maintained, and a linewidth of 0.6 ppb was achieved. The effect was reproduced by simulations using a weakly coupled, two spin-1/2 system. All devices used were standard issue, such that the effect can be reproduced by any NMR lab worldwide with access to liquid nitrogen for producing parahydrogen.