Methyl acrylate

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Methyl acrylate
Methylacrylat.svg
Methyl acrylate molecule ball.png
Names
Preferred IUPAC name
Methyl prop-2-enoate [1]
Other names
Methyl acrylate
Methyl propenoate
Methoxycarbonylethylene
Curithane 103 [1]
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.002.274 OOjs UI icon edit-ltr-progressive.svg
KEGG
PubChem CID
UNII
  • InChI=1S/C4H6O2/c1-3-4(5)6-2/h3H,1H2,2H3 Yes check.svgY
    Key: BAPJBEWLBFYGME-UHFFFAOYSA-N Yes check.svgY
  • C=CC(OC)=O
Properties
C4H6O2
Molar mass 86.090 g·mol−1
AppearanceColorless liquid
Odor Acrid [2]
Density 0.95 g/cm3 [3]
Melting point −74 °C (−101 °F; 199 K) [3]
Boiling point 80 °C (176 °F; 353 K) [3]
5 g/100 mL
Vapor pressure 65 mmHg (20°C) [2]
Viscosity
  • 0.391 mPa·s at 35 °C [4]
  • 0.333 mPa·s at 45 °C [4]
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Harmful (Xn); Highly flammable (F+)
Flash point −3 °C (27 °F; 270 K) [3]
Explosive limits 2.8–25% [2]
Lethal dose or concentration (LD, LC):
3575 ppm (mouse)
1350 ppm (rat, 4 hr)
1000 ppm (rat, 4 hr)
2522 ppm (rabbit, 1 hr) [5]
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 10 ppm (35 mg/m3) [skin] [2]
REL (Recommended)
TWA 10 ppm (35 mg/m3) [skin] [2]
IDLH (Immediate danger)
250 ppm [2]
Safety data sheet (SDS) Oxford MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Methyl acrylate is an organic compound, more accurately the methyl ester of acrylic acid. It is a colourless liquid with a characteristic acrid odor. It is mainly produced to make acrylate fiber, which is used to weave synthetic carpets. [6] It is also a reagent in the synthesis of various pharmaceutical intermediates. Owing to the tendency of methyl acrylate to polymerize, samples typically contain an inhibitor such as hydroquinone.

Contents

Production

The standard industrial reaction for producing methyl acrylate is esterification with methanol under acid catalysis (sulfuric acid, p-toluenesulfonic acid or acidic ion exchangers. [7] ). The transesterification is facilitated because methanol and methyl acrylate form a low boiling azeotrope (boiling point 62–63 °C). [8]

The patent literature [9] describes a one-pot route involving vapor-phase oxidation of propene or 2-propenal with oxygen in the presence of methanol.

Other methods

Methyl acrylate can be prepared by debromination of methyl 2,3-dibromopropanoate with zinc. [10] Methyl acrylate is formed in good yield on pyrolysis of methyl lactate in the presence of ethenone (ketene). [11] Methyl lactate is a renewable "green chemical". Another patent [12] describes the dehydration of methyl lactate over zeolites.

The nickel tetracarbonyl-catalyzed hydrocarboxylation of acetylene with carbon monoxide in the presence of methanol also yields methyl acrylate. [13] The reaction of methyl formate with acetylene in the presence of transition metal catalysts also leads to methyl acrylate. [14] Both, the alcoholysis of propiolactone with methanol as well as the methanolysis of acrylonitrile via intermediately formed acrylamide sulfate [15] are also proven but obsolete processes.

Use

Methyl acrylate is after butyl acrylate and ethyl acrylate the third most important acrylic ester with a worldwide annual production of about 200,000 tons in 2007. [16] Poly(methyl acrylate) is a tacky material near room temperature, and as such it is not particularly useful as a structural material. Commonly, methyl acrylate (and other acrylate esters) are copolymerized with other alkenes to give useful engineering plastics. [17] A variety of vinyl monomers are used, including styrene and other acrylates. [18] The resulting copolymers give acrylic paints that are harder and more brittle than those with the homologous acrylates. Copolymerizing methyl acrylate with acrylonitrile improves their melt processability to fibers, which could be used as precursors for carbon fibers. [19] Methyl acrylate is the precursor to fibers that are woven to make carpets.

Amino derivatives

Methyl acrylate reacts catalysed by Lewis bases in a Michael addition with amines in high yields to β-alanine derivatives which provide amphoteric surfactants when long-chain amines are used and the ester function is hydrolysed subsequently.

Acrylates are also used in the preparation of poly(amidoamine) (PAMAM) dendrimers typically by Michael addition with a primary amine.

Amphotere beta-Alanine.svg

Methyl acrylate is used for the preparation of 2-dimethylaminoethyl acrylate by transesterification with dimethylaminoethanol in significant quantities of over 50,000 tons / year. [20]

Reactions

Methyl acrylate is a classic Michael acceptor, which means that it adds nucleophiles at its terminus. For example, in the presence of a base catalyst, it adds hydrogen sulfide to give the thioether: [21]

2 CH2CHCO2CH3 + H2S → S(CH2CH2CO2CH3)2

It is also a good dienophile.

Safety

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

Related Research Articles

<span class="mw-page-title-main">Ester</span> Compound derived from an acid

In chemistry, an ester is a compound derived from an acid in which the hydrogen atom (H) of at least one acidic hydroxyl group of that acid is replaced by an organyl group. Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well, but not according to the IUPAC.

<span class="mw-page-title-main">Petrochemical</span> Chemical product derived from petroleum

Petrochemicals are the chemical products obtained from petroleum by refining. Some chemical compounds made from petroleum are also obtained from other fossil fuels, such as coal or natural gas, or renewable sources such as maize, palm fruit or sugar cane.

Acrylonitrile is an organic compound with the formula CH2CHCN and the structure H2C=CH−C≡N. It is a colorless, volatile liquid. It has a pungent odor of garlic or onions. Its molecular structure consists of a vinyl group linked to a nitrile. It is an important monomer for the manufacture of useful plastics such as polyacrylonitrile. It is reactive and toxic at low doses.

Acrylates are the salts, esters, and conjugate bases of acrylic acid. The acrylate ion is the anion CH2=CHCO−2. Often, acrylate refers to esters of acrylic acid, the most common member being methyl acrylate. These acrylates contain vinyl groups. These compounds are of interest because they are bifunctional: the vinyl group is susceptible to polymerization and the carboxylate group carries myriad functionalities.

Biodiesel production is the process of producing the biofuel, biodiesel, through the chemical reactions of transesterification and esterification. This involves vegetable or animal fats and oils being reacted with short-chain alcohols. The alcohols used should be of low molecular weight. Ethanol is the most used because of its low cost, however, greater conversions into biodiesel can be reached using methanol. Although the transesterification reaction can be catalyzed by either acids or bases, the base-catalyzed reaction is more common. This path has lower reaction times and catalyst cost than those acid catalysis. However, alkaline catalysis has the disadvantage of high sensitivity to both water and free fatty acids present in the oils. August 10 is international biodiesel day

<span class="mw-page-title-main">Acrylic acid</span> Chemical compound

Acrylic acid (IUPAC: propenoic acid) is an organic compound with the formula CH2=CHCOOH. It is the simplest unsaturated carboxylic acid, consisting of a vinyl group connected directly to a carboxylic acid terminus. This colorless liquid has a characteristic acrid or tart smell. It is miscible with water, alcohols, ethers, and chloroform. More than a million tons are produced annually.

<span class="mw-page-title-main">Methyl formate</span> Chemical compound

Methyl formate, also called methyl methanoate, is the methyl ester of formic acid. The simplest example of a carboxylate ester, it is a colorless liquid with an ethereal odour, high vapor pressure, and low surface tension. It is a precursor to many other compounds of commercial interest.

<span class="mw-page-title-main">Methyl acetate</span> Chemical compound

Methyl acetate, also known as MeOAc, acetic acid methyl ester or methyl ethanoate, is a carboxylate ester with the formula CH3COOCH3. It is a flammable liquid with a characteristically pleasant smell reminiscent of some glues and nail polish removers. Methyl acetate is occasionally used as a solvent, being weakly polar and lipophilic, but its close relative ethyl acetate is a more common solvent being less toxic and less soluble in water. Methyl acetate has a solubility of 25% in water at room temperature. At elevated temperature its solubility in water is much higher. Methyl acetate is not stable in the presence of strong aqueous bases or aqueous acids. Methyl acetate is not considered a VOC in the USA.

<span class="mw-page-title-main">Methyl methacrylate</span> Chemical compound

Methyl methacrylate (MMA) is an organic compound with the formula CH2=C(CH3)COOCH3. This colorless liquid, the methyl ester of methacrylic acid (MAA), is a monomer produced on a large scale for the production of poly(methyl methacrylate) (PMMA).

<span class="mw-page-title-main">Vinyl acetate</span> Chemical compound

Vinyl acetate is an organic compound with the formula CH3CO2CH=CH2. This colorless liquid is the precursor to polyvinyl acetate, ethene-vinyl acetate copolymers, polyvinyl alcohol, and other important industrial polymers.

<span class="mw-page-title-main">Acrylate polymer</span> Group of polymers prepared from acrylate monomers

An acrylate polymer is any of a group of polymers prepared from acrylate monomers. These plastics are noted for their transparency, resistance to breakage, and elasticity.

<span class="mw-page-title-main">Methacrylic acid</span> Chemical compound

Methacrylic acid, abbreviated MAA, is an organic compound with the formula CH2=C(CH3)COOH. This colorless, viscous liquid is a carboxylic acid with an acrid unpleasant odor. It is soluble in warm water and miscible with most organic solvents. Methacrylic acid is produced industrially on a large scale as a precursor to its esters, especially methyl methacrylate (MMA), and to poly(methyl methacrylate) (PMMA).

<span class="mw-page-title-main">Ethyl acrylate</span> Chemical compound

Ethyl acrylate is an organic compound with the formula CH2CHCO2CH2CH3. It is the ethyl ester of acrylic acid. It is a colourless liquid with a characteristic acrid odor. It is mainly produced for paints, textiles, and non-woven fibers. It is also a reagent in the synthesis of various pharmaceutical intermediates.

<span class="mw-page-title-main">2-Vinylpyridine</span> Chemical compound

2-Vinylpyridine is an organic compound with the formula CH2CHC5H4N. It is a derivative of pyridine with a vinyl group in the 2-position, next to the nitrogen. It is a colorless liquid, although samples are often brown. It is used industrially as a precursor to specialty polymers and as an intermediate in the chemical, pharmaceutical, dye, and photo industries. Vinylpyridine is sensitive to polymerization. It may be stabilized with a polymerisation inhibitor such as tert-butylcatechol. Owing to its tendency to polymerize, samples are typically refrigerated.

Butyl acrylate is an organic compound with the formula C4H9O2CCH=CH2. A colorless liquid, it is the butyl ester of acrylic acid. It is used commercially on a large scale as a precursor to poly(butyl acrylate). Especially as copolymers, such materials are used in paints, sealants, coatings, adhesives, fuel, textiles, plastics, and caulk.

<span class="mw-page-title-main">2-Ethylhexyl acrylate</span> Chemical compound

2-Ethylhexyl acrylate is a colorless liquid acrylate with a pleasant odor, used in the making of paints, plastics and adhesives.

1-Vinylimidazole is a water-soluble basic monomer that forms quaternizable homopolymers by free-radical polymerization with a variety of vinyl and acrylic monomers. The products are functional copolymers, which are used as oil field chemicals and as cosmetic auxiliaries. 1-Vinylimidazole acts as a reactive diluent in UV lacquers, inks, and adhesives.

Dimethylaminoethyl acrylate or DMAEA is an unsaturated carboxylic acid ester having a tertiary amino group. It is a colorless to yellowish, water-miscible liquid with a pungent, amine-like odor. DMAEA is an important acrylic monomer that gives basic properties to copolymers.

In organic chemistry, vinylation is the process of attaching a vinyl group to a substrate. Many organic compounds contain vinyl groups, so the process has attracted significant interest, especially since the reaction scope includes substituted vinyl groups. The reactions can be classified according to the source of the vinyl group.

<span class="mw-page-title-main">Hydroxyethyl acrylate</span> Organic chemical-monomer

Hydroxyethyl acrylate is an organic chemical and a aliphatic compound. It has the formula C5H8O3 and the CAS Registry Number 818–61–1. It is REACH registered with an EU number of 212–454–9. It has dual functionality containing a polymerizable acrylic group and a terminal hydroxy group. It is used to make emulsion polymers along with other monomers and the resultant resins are used in coatings, sealants, adhesives and elastomers and other applications.

References

  1. 1 2 "methyl acrylate - Compound Summary". PubChem. Retrieved June 30, 2012.
  2. 1 2 3 4 5 6 NIOSH Pocket Guide to Chemical Hazards. "#0394". National Institute for Occupational Safety and Health (NIOSH).
  3. 1 2 3 4 Record in the GESTIS Substance Database of the Institute for Occupational Safety and Health
  4. 1 2 George, John; Sastry, Nandhibatla V.; Patel, Sunil R.; Valand, Mahendra K. (2002). "Densities, Viscosities, Speeds of Sound, and Relative Permittivities for Methyl Acrylate + 1-Alcohols (C1−C6) atT= (308.15 and 318.15) K". Journal of Chemical & Engineering Data. American Chemical Society (ACS). 47 (2): 262–269. doi:10.1021/je010268l. ISSN   0021-9568.
  5. ↑ "Methyl acrylate". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  6. ↑ Takashi Ohara; Takahisa Sato; Noboru Shimizu; Günter Prescher Helmut Schwind; Otto Weiberg; Klaus Marten; Helmut Greim (2003). "Acrylic Acid and Derivatives". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a01_161.pub2. ISBN   3-527-30673-0.
  7. ↑ "Esterification: Acrylate esters (MA, EA, BA, MMA, 2-EHA)". amberlyst.com. Retrieved 2013-02-21.
  8. ↑ Chessie E. Rehberg (1955). "n-Butyl acrylate". Organic Syntheses . 26: 18.; Collective Volume, vol. 3, p. 146
  9. ↑ US 3925463,Ferlazzo, Natale; Buzzi, Gian Fausto& Ghirga, Marcello,"Process for the production of methyl acrylate",published 1975-12-09, assigned to Societa' Italiana Resine S.I.R., S.p.A.
  10. ↑ F. Beilstein: Handbuch der organischen Chemie, 3. Auflage, 1. Band. Verlag Leopold Voss, 1893, S. 501. Volltext.
  11. ↑ US 2417748,Hagemeyer, Hugh J.,"Preparation of methyl acrylate",published 1947-03-18, assigned to Eastman Kodak Company
  12. ↑ US 5250729,Abe, Takafumi&Hieda, Shinichi,"Process for preparing unsaturated carboxylic acid or ester thereof",published 1993-10-05, assigned to Mitsubishi Gas Chemical Company
  13. ↑ W. Reppe, J. Liebigs Ann. Chem., 582 (1), 116-132 (1953)
  14. ↑ US 6022990,Liu, Zhao-Tie; Zhang, Jia-Qi& Yang, Xian-Gui,"Method for synthesizing methyl acrylate",published 2000-02-08, assigned to Chengdu Institute of Organic Chemistry and National Research and Engineering Centre for Coal Slurry Gasification and Coal Chemical Industry
  15. ↑ H.-J. Arpe, Industrielle Organische Chemie, 6. Aufl., Wiley-VCH Verlag, Weinheim, 2007, ISBN   978-3-527-31540-6.
  16. ↑ CEH Marketing Research Report Acrylic Acid and Esters, SRI Consulting, July 2007.
  17. ↑ Penzel, Erich; Ballard, Nicholas; Asua, José M. (2018). "Polyacrylates". Ullmann's Encyclopedia of Industrial Chemistry. pp. 1–20. doi:10.1002/14356007.a21_157.pub2. ISBN   978-3-527-30673-2.
  18. ↑ DOW Methyl acrylate, Product Safety Assessment
  19. ↑ V. A. Bhanu; et al. (2002), "Synthesis and characterization of acrylonitrile methyl acrylate statistical copolymers as melt processable carbon fiber precursors" (PDF), Polymer (in German), vol. 43, no. 18, pp. 4841–4850, doi:10.1016/S0032-3861(02)00330-0
  20. ↑ WO 2010136696,Paul, Jean-Michel; Tonnelier, Boris& Augustin, Francis,"Composition including dialkyl tin oxide and use thereof as a transesterification catalyst for the synthesis of (meth)acrylic esters",published 2010-12-02, assigned to Arkema
  21. ↑ Edward A. Fehnel and Marvin Carmack (1950). "Methyl-β-dipropionate". Organic Syntheses . 30: 65.; Collective Volume, vol. 4, p. 669
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