Ethyl acrylate

Last updated
Ethyl acrylate [1] [2]
Ethyl acrylate.png
Ethyl acrylate molecule ball.png
Names
Preferred IUPAC name
Ethyl prop-2-enoate
Other names
Ethyl propenoate
Ethyl acrylate
Acrylic acid ethyl ester
Ethyl ester of acrylic acid
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.004.945 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 205-438-8
KEGG
PubChem CID
RTECS number
  • AT0700000
UNII
UN number 1917
  • InChI=1S/C5H8O2/c1-3-5(6)7-4-2/h3H,1,4H2,2H3 Yes check.svgY
    Key: JIGUQPWFLRLWPJ-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C5H8O2/c1-3-5(6)7-4-2/h3H,1,4H2,2H3
    Key: JIGUQPWFLRLWPJ-UHFFFAOYAN
  • CCOC(=O)C=C
Properties
C5H8O2
Molar mass 100.117 g·mol−1
AppearanceClear liquid
Odor Acrid [3]
Density 0.9405 g/mL
Melting point −71 °C (−96 °F; 202 K)
Boiling point 99.4 °C (210.9 °F; 372.5 K)
1.5 g/100 mL
Vapor pressure 29 mmHg (20°C) [3]
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Carcinogenic
GHS labelling:
GHS-pictogram-flamme.svg GHS-pictogram-exclam.svg
Danger
H225, H302, H312, H315, H317, H319, H332, H335
P210, P233, P240, P241, P242, P243, P261, P264, P270, P271, P272, P280, P301+P312, P302+P352, P303+P361+P353, P304+P312, P304+P340, P305+P351+P338, P312, P321, P322, P330, P332+P313, P333+P313, P337+P313, P362, P363, P370+P378, P403+P233, P403+P235, P405, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 3: Liquids and solids that can be ignited under almost all ambient temperature conditions. Flash point between 23 and 38 °C (73 and 100 °F). E.g. gasolineInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazards (white): no code
2
3
2
Flash point 15 °C (59 °F; 288 K)
Explosive limits 1.4%-14% [3]
Lethal dose or concentration (LD, LC):
2180 ppm (rat, 4 hr)
3894 ppm (mouse) [4]
1204 ppm (rabbit, 7 hr)
1204 ppm (guinea pig, 7 hr) [4]
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 25 ppm (100 mg/m3) [skin] [3]
REL (Recommended)
Carcinogen [3]
IDLH (Immediate danger)
Ca [300 ppm] [3]
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 ?)

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. [5] It is also a reagent in the synthesis of various pharmaceutical intermediates.

Contents

Production

Ethyl acrylate is produced by acid-catalysed esterification of acrylic acid, which in turn is produced by oxidation of propylene. It may also be prepared from acetylene, carbon monoxide and ethanol by a Reppe reaction. Commercial preparations contain a polymerization inhibitor such as hydroquinone, phenothiazine, or hydroquinone ethyl ether. [5]

Reactions and uses

Precursor to polymers and other monomers

Ethyl acrylate is used in the production of polymers including resins, plastics, rubber, and denture material. [6]

Ethyl acrylate is a reactant for homologous alkyl acrylates (acrylic esters) by transesterification with higher alcohols through acidic or basic catalysis. In that way speciality acrylates are made accessible, e.g. 2-ethylhexyl acrylate (from 2-ethylhexanol) used for pressure-sensitive adhesives, cyclohexyl acrylate (from cyclohexanol) used for automotive clear lacquers, 2-hydroxyethyl acrylate (from ethylene glycol) which is crosslinkable with diisocyanates to form gels used with long-chain acrylates (from C18+ alcohols) [7] as comonomer for comb polymers for reduction of the solidification point of paraffin oils and 2-dimethylaminoethyl acrylate (from dimethylaminoethanol [8] ) for the preparation of flocculants for sewage clarification and paper production.

As a reactive monomer, ethyl acrylate is used in homopolymers and copolymers with e.g. ethene, acrylic acid and its salts, amides and esters, methacrylates, acrylonitrile, maleic esters, vinyl acetate, vinyl chloride, vinylidene chloride, styrene, butadiene and unsaturated polyesters. [9] Copolymers of acrylic acid ethyl ester with ethene (EPA/ethylene-ethyl acrylate copolymers) are suitable as adhesives and polymer additives, just like ethene vinyl acetate copolymers. [10] Copolymers with acrylic acid increase the cleaning effect of liquid detergents, [11] copolymers with methacrylic acid are used as gastric juices tablet covers (Eudragit). [12]

The large number of possible comonomer units and their combination in copolymers and terpolymers with ethyl acrylate allows the realization of different properties of the acrylate copolymers in a variety of applications in paints and adhesives, paper, textile and leather auxiliaries together with cosmetic and pharmaceutical products.

As Michael acceptor and HX acceptor

Ethyl acrylate reacts with amines catalyzed by Lewis acids in a Michael addition to β-alanine derivatives in high yields: [13]

Michael-Addition von Amin an EA.svg

The nucleophilic addition at ethyl acrylate as an α,β-unsaturated carbonyl compound is a frequent strategy in the synthesis of pharmaceutical intermediates. Examples are the hypnotic glutethimide or the vasodilator vincamin (obsolete by now) [14] or more recent therapeutics such as the COPD agent cilomilast or the nootropic leteprinim. [15]

Ethyl 3-bromopropionate is prepared by hydrobromination of ethyl acrylate. [16]

Dienophile

With dienes, ethyl acrylate reacts as a good dienophile in Diels–Alder reactions e.g. with buta-1,3-diene in a [4+2] cycloaddition reaction to give a cyclohexene carboxylic acid ester in a high yield. [17]

Natural occurrence

Ethyl acrylate is also used as a flavoring agent. It has been found as a volatile component in pineapples and Beaufort cheese [18] and is a secondary component in vanilla flavor obtained from heat extraction of vanilla in amounts of up to 1 ppm. In such high concentrations it negatively affects the extracted aroma. [19]

Safety

The International Agency for Research on Cancer stated, "Overall evaluation, ethyl acrylate is possibly carcinogenic to humans (Group 2B)." [20] The United States Environmental Protection Agency (EPA) states, "Human studies on occupational exposure to ethyl acrylate... have suggested a relationship between exposure to the chemical(s) and colorectal cancer, but the evidence is conflicting and inconclusive. In a study by the National Toxicology Program (NTP), increased incidence of squamous cell papillomas and carcinomas of the forestomach were observed in rats and mice exposed via gavage (experimentally placing the chemical in the stomach). However, the NTP recently determined that these data were not relevant to human carcinogenicity since humans do not have a forestomach, and removed ethyl acrylate from its list of carcinogens." [21] However, ethyl acrylate also increased the incidence of thyroid follicular cell adenoma in male mice, and thyroid follicular cell adenoma or carcinoma (combined) in male rats exposed through inhalation. [22]

It is possibly carcinogenic and it is toxic in large doses, with an LD50 (rats, oral) of 1020 mg/kg. As of October 2018, the FDA withdrew authorization for its use as a synthetic flavoring substance in food. [23]

One favorable safety aspect is that ethyl acrylate has good warning properties; the odor threshold is much lower than the concentration required to create an atmosphere immediately dangerous to life and health. Reports of the exact levels vary somewhat, but, for example, the U.S. E.P.A. reports an odor threshold of 0.0012 parts per million (ppm), [21] but the E.P.A.'s lowest level of health concern, the Acute Exposure Guideline Level-1 (AEGL-1) is 8.3 ppm, [24] which is almost 7000 times the odor threshold.

However, as a possible carconigen, NIOSH maintains "that there is no safe level of exposure to a carcinogen. Reduction of worker exposure to chemical carcinogens as much as possible through elimination or substitution and engineering controls is the primary way to prevent occupational cancer." [25]

Related Research Articles

Acrylonitrile is an organic compound with the formula CH2CHCN and the structure H2C=CH−C≡N. It is a colorless, volatile liquid although commercial samples can be yellow due to impurities. 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. Acrylonitrile was first synthesized by the French chemist Charles Moureu (1863–1929) in 1893.

<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">Ethyl acetate</span> Organic compound (CH₃CO₂CH₂CH₃)

Ethyl acetate is the organic compound with the formula CH3CO2CH2CH3, simplified to C4H8O2. This colorless liquid has a characteristic sweet smell and is used in glues, nail polish removers, and in the decaffeination process of tea and coffee. Ethyl acetate is the ester of ethanol and acetic acid; it is manufactured on a large scale for use as a solvent.

<span class="mw-page-title-main">Ethylbenzene</span> Hydrocarbon compound; precursor to styrene and polystyrene

Ethylbenzene is an organic compound with the formula C6H5CH2CH3. It is a highly flammable, colorless liquid with an odor similar to that of gasoline. This monocyclic aromatic hydrocarbon is important in the petrochemical industry as a reaction intermediate in the production of styrene, the precursor to polystyrene, a common plastic material. In 2012, more than 99% of ethylbenzene produced was consumed in the production of styrene.

<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">Ethyl formate</span> Chemical compound

Ethyl formate is an ester formed when ethanol reacts with formic acid. Ethyl formate has the characteristic smell of rum and is also partially responsible for the flavor of raspberries. It occurs naturally in the body of ants and in the stingers of bees.

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

2-Butoxyethanol is an organic compound with the chemical formula BuOC2H4OH (Bu = CH3CH2CH2CH2). This colorless liquid has a sweet, ether-like odor, as it derives from the family of glycol ethers, and is a butyl ether of ethylene glycol. As a relatively nonvolatile, inexpensive solvent, it is used in many domestic and industrial products because of its properties as a surfactant. It is a known respiratory irritant and can be acutely toxic, but animal studies did not find it to be mutagenic, and no studies suggest it is a human carcinogen. A study of 13 classroom air contaminants conducted in Portugal reported a statistically significant association with increased rates of nasal obstruction and a positive association below the level of statistical significance with a higher risk of obese asthma and increased child BMI.

Bromoethane, also known as ethyl bromide, is a chemical compound of the haloalkanes group. It is abbreviated by chemists as EtBr. This volatile compound has an ether-like odor.

<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.

1,1-Dichloroethene, commonly called 1,1-dichloroethylene or vinylidene chloride or 1,1-DCE, is an organochloride with the molecular formula C2H2Cl2. It is a colorless liquid with a sharp odor. Like most chlorocarbons, it is poorly soluble in water, but soluble in organic solvents. 1,1-DCE was the precursor to the original clingwrap, Saran, for food, but this application has been phased out.

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

Glycidol is an organic compound that contains both epoxide and alcohol functional groups. Being bifunctional, it has a variety of industrial uses. The compound is a slightly viscous liquid that is slightly unstable and is not often encountered in pure form.

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

Hexachloroethane (perchloroethane) is an organochlorine compound with the chemical formula (CCl3)2. It is a white or colorless solid at room temperature with a camphor-like odor. It has been used by the military in smoke compositions, such as base-eject smoke munitions.

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

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. 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.

<span class="mw-page-title-main">1-Bromopropane</span> Chemical compound

1-Bromopropane (n-propylbromide or nPB) is an organobromine compound with the chemical formula CH3CH2CH2Br. It is a colorless liquid that is used as a solvent. It has a characteristic hydrocarbon odor. Its industrial applications increased dramatically in the 21st century due to the phasing out of chloro­fluoro­carbons and chloro­alkanes such as 1,1,1-Trichloro­ethane under the Montreal Protocol.

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

Methyl cyanoacrylate (MCA) is an organic compound that contains several functional groups: a methyl ester, a nitrile, and an alkene. It is a colorless liquid with low viscosity. Its chief use is as the main component of cyanoacrylate glues. It can be encountered under many trade names. Methyl cyanoacrylate is less commonly encountered than ethyl cyanoacrylate.

Methacrylonitrile, MeAN in short, is a chemical compound that is an unsaturated aliphatic nitrile, widely used in the preparation of homopolymers, copolymers, elastomers, and plastics and as a chemical intermediate in the preparation of acids, amides, amines, esters, and other nitriles. MeAN is also used as a replacement for acrylonitrile in the manufacture of an acrylonitrile/butadiene/styrene-like polymer. It is a clear and colorless liquid, that has a bitter almond smell.

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.

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.

<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. ↑ Merck Index, 11th Edition, 3715.
  2. ↑ Ethyl acrylate Datasheet at Inchem.org
  3. 1 2 3 4 5 6 NIOSH Pocket Guide to Chemical Hazards. "#0261". National Institute for Occupational Safety and Health (NIOSH).
  4. 1 2 "Ethyl acrylate". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  5. 1 2 Ohara, Takashi; Sato, Takahisa; Shimizu, Noboru; Prescher, Günter; Schwind, Helmut; Weiberg, Otto; Marten, Klaus; Greim, Helmut; Shaffer (2020). "Acrylic Acid and Derivatives". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. pp. 1–21. doi:10.1002/14356007.a01_161.pub4.
  6. ↑ Ethyl acrylate Archived 2006-10-12 at the Wayback Machine Hazardous Substance Fact Sheet, New Jersey Department of Health and Senior Services
  7. ↑ WO 1999031042,J.-M. Paul, J.-P. Gamet,"Method for conditioning long chain alkyl acrylates",published 1995-06-24, assigned to Elf Atochem S.A.
  8. ↑ EP 1284954,Gerhard Nestler, Jürgen Schröder,"Verfahren zur herstellung von estern ungesättigter carbonsäuren",published 2003-02-26, assigned to BASF Aktiengesellschaft
  9. ↑ "Technical Data Sheet – Ethyl Acrylate" (PDF). dow.com. Archived from the original (PDF) on 2012-07-18. Retrieved 2013-02-20.
  10. ↑ "DuPont Elvaloy AC Products and Properties". dupont.com. Archived from the original on 2013-03-13. Retrieved 2013-02-20.
  11. ↑ US 5409629,Jan E. Shulman, Charles E. Jones,"Use of acrylic acid/ethyl acrylate copolymers for enhanced clay soil removal in liquid laundry detergents",published 1995-04-25, assigned to Rohm and Haas Company
  12. ↑ "EUDRAGIT L 100-55 - EUDRAGIT - Targeted Drug Release and Tailored Service". evonik.com. Archived from the original on 2013-08-12. Retrieved 2013-02-20.
  13. ↑ Jose Cabral, Pierre Laszlo, Loïc Mahé, Marie-Thérèse Montaufier, S. Lalatiana Randriamahefa (1989), "Catalysis of the specific Michael addition: The example of acrylate acceptors", Tetrahedron Letters (in German), vol. 30, no. 30, pp. 3969–3972, doi:10.1016/S0040-4039(00)99297-9 {{citation}}: CS1 maint: multiple names: authors list (link)
  14. ↑ Pharmazeutische Wirkstoffe: Synthesen, Patente, Anwendungen; von A. Kleemann u. J. Engel; 2., neubearb. u. erw. Aufl.; Stuttgart, New York; Thieme; 1982, ISBN   3-13-558402-X
  15. ↑ D. Lednicer, The Organic Chemistry of Drug Synthesis, Volume 7, J. Wiley & Sons, 2008, ISBN   978-0-470-10750-8
  16. ↑ Mozingo, Ralph; Patterson, L. A. (1940). "Methyl β-Bromopropionate". Organic Syntheses. 20: 64. doi:10.15227/orgsyn.020.0064.
  17. ↑ K.P.C. Vollhardt, N.E. Schore, Organische Chemie, 5. Aufl., Wiley-VCH, 2012, ISBN   978-3-527-33250-2
  18. ↑ "Ethyl Acrylate" (PDF; 43 kB). iarc.fr. Retrieved 2013-02-20.
  19. ↑ Sensory-Directed Flavor Analysis, Ray Marsili edit., CRC Press, Taylor & Francis Group, Boca Raton, 2007, ISBN   1-57444-568-5
  20. ↑ IARC Monographs on the Evaluation of Carcinogenic Risks to Humans, Volume 71, International Agency for Research on Cancer (1999)
  21. 1 2 EPA Technology Transfer Network, Air Toxics Web Site Archived 2012-05-11 at the Wayback Machine , United States Environmental Protection Agency (accessed 2008)
  22. ↑ Kromhout, Hans; Friesen, Melissa; Marques, M Mathilde; Sergi, Consolato Maria; Abdallah, Mohamed; Benke, Geza; Cesta, Mark; Germolec, Dori; Houck, Keith; Ichihara, Gaku; Jameson, Charles William; Kanno, Jun; Pogribny, Igor; Svendsen, Camilla; Benbrahim-Tallaa, Lamia (2018-08-01). "Carcinogenicity of isobutyl nitrite, β-picoline, and some acrylates". The Lancet Oncology. 19 (8): 1020–1022. doi:10.1016/S1470-2045(18)30491-1. ISSN   1470-2045.
  23. ↑ 83 FR 50490
  24. ↑ "Ethyl acrylate". Acute Exposure Guideline Levels. United States Environmental Protection Agency. Retrieved 2019-04-28.
  25. ↑ "Occupational Cancer - NIOSH Chemical Carcinogen Policy | NIOSH | CDC". www.cdc.gov. 2023-05-08. Retrieved 2023-06-27.
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