Ethyl acrylate

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Structural formula
Structural formula of ethyl acrylate
General
Surname Ethyl acrylate
other names
  • Ethyl acrylate
  • Ethyl propenoate
  • Ethyl propenate
Molecular formula C 5 H 8 O 2
Brief description

colorless liquid with a pungent odor

External identifiers / databases
CAS number 140-88-5
EC number 205-438-8
ECHA InfoCard 100.004.945
PubChem 8821
Wikidata Q343014
properties
Molar mass 100.12 g mol −1
Physical state

liquid

density

0.92 g cm −3

Melting point

<-75 ° C

boiling point

100 ° C

Vapor pressure
  • 39.1 h Pa (20 ° C)
  • 65.9 hPa (30 ° C)
  • 107 hPa (40 ° C)
  • 167 hPa (50 ° C)
solubility

poor in water (20 g l −1 at 25 ° C)

Refractive index

1.406 (20 ° C)

safety instructions
GHS hazard labeling from  Regulation (EC) No. 1272/2008 (CLP) , expanded if necessary
02 - Highly / extremely flammable 06 - Toxic or very toxic

danger

H and P phrases H: 225-302-312-331-315-317-319-335-412
P: 210-261-273-302 + 352-312-304 + 340-311-403 + 233
MAK
  • DFG : 2 ml m −3 , 8.3 mg m −3
  • Switzerland: 2.5 ml m −3 or 10 mg m −3
  • Austria: 5 ml m −3 , 20 mg m −3
Toxicological data

400 mg kg −1 ( LD 50 ,  rat ,  oral )

As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions . Refractive index: Na-D line , 20 ° C

Acrylic acid ethyl ester , often also called ethyl acrylate , is an organic chemical compound from the group of carboxylic acid esters (more precisely the acrylic acid esters ). It is in the form of a highly flammable and volatile liquid with an unpleasant, pungent odor.

history

Ethyl acrylate has been produced commercially since the early 1930's. With an annual production volume of approx. 500,000 tons, ethyl acrylate is now the most important acrylic acid ester worldwide after butyl acrylate. In 2006, 262 kt in the USA, 63 kt in Western Europe, 35 kt in South Africa and 50 kt in South Korea, and 94 kt in China in 2009, ethyl acrylate was produced.

Extraction and presentation

Ethyl acrylate can be prepared by several methods. It can be obtained as a catalyst by reacting acrylonitrile with ethanol and sulfuric acid . It can also be obtained from acetylene , carbon monoxide and ethanol. According to a process by Celanese Corp. In the USA, ethyl acrylate was also produced by reacting acrylic acid with ethylene and sulfuric acid via the intermediate sulfuric acid esters ethyl sulfate and diethyl sulfate .

EA from acrylic acid + ethylene

In a pilot plant of ADM Corp. the catalytic conversion of biomass (corn stalks) in the reaction sequence glucose → glycerine → acrolein → acrylic acid + ethanol → acrylic acid ethyl ester is investigated.

Today, ethyl acrylate is produced almost exclusively by direct esterification of acrylic acid with ethanol (yield approx. 93% of theory).

properties

Acrylic acid ethyl ester is chemically unstable and tends to spontaneous (partly explosive) polymerisation under the influence of light, at elevated temperatures and on contact with peroxides, even in a stabilized form . The heat of polymerization is −78 kJ mol −1 or −779 kJ kg −1 . It has a viscosity of 0.55 mPa · s at 25 ° C and a specific heat capacity of 1.98 kJ / (kg · K). Because of the high tendency to polymerize, ethyl acrylate is stabilized with 15 ± 5 ppm MEHQ . However, when stored in the absence of light in the presence of polymerization-inhibiting oxygen and at temperatures below 35 ° C, the storage time is one year.

Safety-related parameters

Acrylic acid ethyl ester forms highly flammable vapor-air mixtures. The compound has a flash point of 9 ° C. The explosion range is between 1.7% by volume (69 g / m 3 ) as the lower explosion limit (LEL) and 13% by volume (540 g / m 3 ) as the upper explosion limit (UEL). This results in an upper one Explosion point of 6 ° C. The maximum explosion pressure is 8.9 bar. The limit gap width was determined to be 0.86 mm. This results in an assignment to explosion group IIB. The ignition temperature is 350 ° C. The substance therefore falls into temperature class T2.

use

Ethyl acrylate reacts under catalysis by Lewis acids in a Michael addition with amines in high yields to form β-alanine derivatives

Michael addition of amine to EA

The nucleophilic addition to ethyl acrylate as an α, β-unsaturated carbonyl compound is the recurring motif in the synthesis of pharmaceutical intermediates that lead to (now obsolete) active ingredients such as the hypnotic glutethimide or the vasodilator vincamine or newer therapeutic agents such as the COPD active ingredient cilomilast or the nootropic Leteprinim lead.

With dienes , ethyl acrylate enters into a dienophile Diels-Alder reactions , which z. B. react with 1,3-butadiene in a [4 + 2] cycloaddition with high yield to form a cyclohexene carboxylic acid ester.

Diels-Alder reaction of butadiene with EA

Acrylic acid ethyl ester is the starting material for homologous acrylic acid esters (alkyl acrylates) through transesterification with higher alcohols by means of acidic or basic catalysis. Special acrylates are accessible, such as B. the 2-ethylhexyl acrylate used for pressure-sensitive adhesives (from 2-ethylhexanol ), the cyclohexyl acrylate used for automotive clear coats (from cyclohexanol ), the z. B. with diisocyanates to form swellable gels crosslinkable 2-hydroxyethyl acrylate (from ethylene glycol ), which as a comonomer for comb polymers that lower the solidification point of paraffin oils, useful long-chain acrylates (from C 18+ alcohols) and for the production of flocculants for wastewater treatment and Papermaking important 2-dimethylaminoethyl acrylate (from dimethylaminoethanol ).

As a reactive monomer, ethyl acrylate is used in homopolymers and copolymers with u. a. Ethylene, acrylic acid and its salts, amides and esters, methacrylates, acrylonitrile, maleic acid esters, vinyl acetate, vinyl chloride, vinylidene chloride, styrene, butadiene, unsaturated polyesters,

Copolymers of ethyl acrylate with ethylene ( English EEA / ethylene-ethyl acrylate copolymer ) are useful as ethylene-vinyl acetate copolymers as adhesives and polymer additives, copolymers increase with acrylic acid the cleaning action of liquid detergents, copolymers with methacrylic acid are used as enteric tablet coatings (Eudragit®) .

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 from paints and adhesives to paper, textile and leather auxiliaries to cosmetic and pharmaceutical products.

Acrylic acid ethyl ester is also used as a flavoring agent. It was found as a volatile component in pineapple and Beaufort cheese and is a secondary component in the vanilla aroma, which is obtained in quantities of over 1ppm during the hot extraction of vanilla and, in such high concentrations, negatively affects the extract aroma. In view of its toxicological data, the targeted use of ethyl acrylate as a flavoring in consumer goods must be viewed critically.

safety instructions

In contact with ethyl acrylate there is a risk of skin sensitization . Indications from animal experiments that ethyl acrylate may be carcinogenic cannot be transferred to humans. The high toxicity of ethyl acrylate (LD 50 1,000 mg / kg rat oral and LD 50 1,800 mg / kg rabbit dermal) makes it necessary to handle the substance in closed compartments. The pungent odor of the ethyl acrylate can, however, be perceived at concentrations of approx. 1 ppb, which are far below the EPA's reference value for acute exposure ( Acute Exposure Guideline Level / AEGL-1 ) of 8.3 ppm.

Individual evidence

  1. ↑ a b c d e f g h i j k l m n o p q r Entry on ethyl acrylate in the GESTIS substance database of the IFA , accessed on June 12, 2017(JavaScript required) .
  2. ↑ Data sheet Ethyl acrylate, ≥99.5%, stabilized, FG from Sigma-Aldrich , accessed on May 4, 2016 ( PDF ).
  3. ↑ Entry on ethyl acrylates in the Classification and Labeling Inventory of the European Chemicals Agency (ECHA), accessed on February 1, 2016. Manufacturers or distributors can expand the harmonized classification and labeling .
  4. ↑ Swiss Accident Insurance Fund (Suva): Limits - Current MAK and BAT values (search for 140-88-5 or ethyl acrylate ), accessed on September 16, 2019.
  5. ↑ Limit values ​​for working materials ( Memento from 23 September 2015 in the Internet Archive ) Ordinance of the Federal Minister for Labor, Social Affairs and Consumer Protection ( Limit Values Ordinance GKV 2011), Austria
  6. ↑ US Department of Labor: Ethyl Acrylate ( Memento from May 28, 2010 in the Internet Archive )
  7. ↑ IARC : Ethyl acrylate, Evaluation 1986
  8. ↑ CEH Marketing Research Report Acrylic Acid and Esters, SRI Consulting, July 2007
  9. ↑ China Chemical Reporter, November 6, 2010, Competition in the acrylic industry is becoming fiercer ( Memento of February 22, 2016 in the Internet Archive ) .
  10. ↑ Patent US4507495 : Process for production of ethyl acrylate. Published March 26, 1985 , Applicant: Celanese Corp., Inventor: Edward F. Dougherty, Mark O. Scates, James L. Paul. ‌
  11. ↑ TP Binder, Conversion of Lignocellulosic Biomass to Ethanol and Ethyl Acrylate , Biomass Program IBR Platform Peer Review, February 3, 2011
  12. ↑ Brandrup, J .; Immergut, EH; Grulke, EA; Abe, A .; Bloch, DR: Polymer Handbook , 4th Edition, Wiley-VCH 2003, ISBN 978-0-471-47936-9 , p. II / 368.
  13. ↑ BASF AG: Technical Data Sheet, Ethyl acrylate, August 2003 , accessed on May 4, 2016
  14. ↑ a b c d e f E. Brandes, W. Möller: Safety-related parameters. Volume 1: Flammable Liquids and Gases. Wirtschaftsverlag NW - Verlag für neue Wissenschaft, Bremerhaven 2003.
  15. ↑ Jose Cabral, Pierre Laszlo, Loïc Mahé, Marie-Thérèse Montaufier, S. Lalatiana Randriamahefa: Catalysis of the specific Michael addition: The example of acrylate acceptors . In: Tetrahedron Letters . tape 30 , no. 30 , 1989, pp. 3969-3972 , doi : 10.1016 / S0040-4039 (00) 99297-9 .
  16. ↑ Active pharmaceutical ingredients: syntheses, patents, applications ; by A. Kleemann u. J. Engel; 2., rework. u. exp. Ed .; Stuttgart, New York; Thieme; 1982, ISBN 3-13-558402-X
  17. ↑ D. Lednicer, The Organic Chemistry of Drug Synthesis , Volume 7, J. Wiley & Sons, 2008, ISBN 978-0-470-10750-8
  18. ↑ KPC Vollhardt, NE Schore, Organische Chemie , 5th ed., Wiley-VCH, 2012, ISBN 978-3-527-33250-2
  19. ↑ Patent WO1999031042 : Method for conditioning long chain alkyl acrylates. Applied on December 10, 1998 , published on June 24, 1995 , applicant: Elf Atochem SA, inventor: J.-M. Paul, J.-P. Gamet. ‌
  20. ↑ Patent EP1284954 : Process for the production of esters of unsaturated carboxylic acids. Published on August 4, 2004 , applicant: BASF Aktiengesellschaft, inventor: Gerhard Nestler, Jürgen Schröder. ‌
  21. ↑ Technical Data Sheet - Ethyl Acrylate (PDF) dow.com. Archived from the original on July 18, 2012. Retrieved February 20, 2013.
  22. ↑ DuPont TM Elvaloy ® AC Products and Properties . dupont.com. Retrieved February 20, 2013.
  23. ↑ Patent US5409629 : Use of acrylic acid / ethyl acrylate copolymers for enhanced clay soil removal in liquid laundry detergents. Published April 25, 1995 , Applicant: Rohm and Haas Company, Inventor: Jan E. Shulman, Charles E. Jones. ‌
  24. ↑ EUDRAGIT® L 100-55 - EUDRAGIT® - Targeted Drug Release and Tailored Service . evonik.com. Retrieved February 20, 2013.
  25. ↑ Ethyl Acrylate (PDF; 43 kB) iarc.fr. Retrieved February 20, 2013.
  26. ^ Sensory-Directed Flavor Analysis , Ray Marsili edit., CRC Press, Taylor & Francis Group, Boca Raton, 2007, ISBN 1-57444-568-5
  27. ↑ IUCLID DATA SET Ethyl acrylate, European Commission - European Chemicals Bureau, creation date: 18-FEB-2000
  28. ↑ http://worldaccount.basf.com/wa/PublicMSDS~en_US/PDF/09007af88008fb84.pdf Genealogie {Dead Link | url = http: //worldaccount.basf.com/wa/PublicMSDS~en_US/PDF/09007af88008fb84.pdf | date = 2018-08 | archivebot = 2018-08-22 01:08:30 InternetArchiveBot}} (link not available)
  29. ↑ a b SCOEL / SUM / 47, October 2004
  30. ↑ Basic Acrylic Monomer Manufacturers, Inc., The European Union Consumer Products Safety & Quality Unit Does Not Recognize ethyl acrylate as a Possible Human Carcinogen , Last Updated: 03/04/12
  31. ↑ ETHYL ACRYLATE ( English ) epa.gov. Retrieved February 20, 2013.
  32. ↑ Ethyl acrylate Results ( English ) epa.gov. Retrieved February 20, 2013.