Vinyl acetate

Vinyl acetate
Skeletal formula
Ball-and-stick model
Names
Preferred IUPAC name
Ethenyl acetate
Systematic IUPAC name
Ethenyl ethanoate
Other names
  • Acetic acid vinyl ester
  • Vinyl ethanoate
  • Acetoxyethene
  • VyAc
  • VAM
  • Vinyl acetate monomer
  • Acetic acid ethenyl ester
  • 1-Acetoxyethylene
Identifiers
3D model (JSmol)
1209327
ChEBI
ChemSpider
ECHA InfoCard 100.003.224 Edit this at Wikidata
EC Number
  • 203-545-4
KEGG
MeSH C011566
UNII
UN number 1301
  • InChI=1S/C4H6O2/c1-3-6-4(2)5/h3H,1H2,2H3 ☒N
    Key: XTXRWKRVRITETP-UHFFFAOYSA-N ☒N
  • InChI=1/C4H6O2/c1-3-6-4(2)5/h3H,1H2,2H3
    Key: XTXRWKRVRITETP-UHFFFAOYAB
  • C=COC(C)=O
Properties
C4H6O2
Molar mass 86.090 g·mol−1
Appearance Colorless liquid
Odor Sweet, pleasant, fruity; may be sharp and irritating[1]
Density 0.934 g/cm3
Melting point −93.5 °C (−136.3 °F; 179.7 K)
Boiling point 72.7 °C (162.9 °F; 345.8 K)
−46.4×10−6 cm3/mol
Hazards
GHS labelling:
GHS02: FlammableGHS07: Exclamation markGHS08: Health hazard
Danger
H225, H332, H335, H351
P201, P202, P210, P233, P240, P241, P242, P243, P261, P271, P280, P281, P303+P361+P353, P304+P312, P304+P340, P308+P313, P312, P370+P378, P403+P233, P403+P235, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 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 −8 °C (18 °F; 265 K)
427 °C (801 °F; 700 K)
Explosive limits 2.6–13.40%
NIOSH (US health exposure limits):
PEL (Permissible)
 none[2]
Safety data sheet (SDS) ICSC 0347
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

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.[3]

Production

The worldwide production capacity of vinyl acetate was estimated at 6,969,000 tonnes/year in 2007, with most capacity concentrated in the United States (1,585,000 all in Texas), China (1,261,000), Japan (725,000) and Taiwan (650,000).[4] The average list price for 2008 was US$1600/tonne. Celanese is the largest producer (ca 25% of the worldwide capacity), while other significant producers include China Petrochemical Corporation (7%), Chang Chun Group (6%), and LyondellBasell (5%).[4]

It is a key ingredient in furniture glue.[5]

Preparation

Vinyl acetate is the acetate ester of vinyl alcohol. Since vinyl alcohol is highly unstable (with respect to acetaldehyde), the preparation of vinyl acetate is more complex than the synthesis of other acetate esters.

The major industrial route involves the reaction of ethylene and acetic acid with oxygen in the presence of a palladium catalyst.[6]

This method has replaced the addition of acetic acid to acetylene. The main side reaction is the combustion of organic precursors.

Mechanism

Isotope labeling and kinetics experiments suggest that the mechanism involves PdCH2CH2OAc-containing intermediates. Beta-hydride elimination would generate vinyl acetate and a palladium hydride, which would be oxidized to give hydroxide.[7]

Alternative routes

Vinyl acetate was once mainly prepared by hydroesterification, i.e., the addition of acetic acid to acetylene in the presence of metal catalysts. Using mercury(II) catalysts, vinyl acetate was first prepared by Fritz Klatte in 1912.[3] Presently, zinc acetate is used as the catalyst:

CH3CO2H + C2H2 → CH3CO2CHCH2

Approximately 1/3 of the world's production relies on this route, which, because it is environmentally messy, is mainly practiced in countries with relaxed environmental regulations, such as China.

Another route to vinyl acetate involves thermal decomposition of ethylidene diacetate:

(CH3CO2)2CHCH3 → CH3CO2CHCH2 + CH3CO2H

Polymerization

It can be polymerized to give polyvinyl acetate (PVAc). With other monomers it can be used to prepare various copolymers such as ethylene-vinyl acetate (EVA), vinyl acetate-acrylic acid (VA/AA), polyvinyl chloride acetate (PVCA), and polyvinylpyrrolidone (Vp/Va copolymer, used in hair gels).[8] Due to the instability of the radical, attempts to control the polymerization by most "living/controlled" radical processes have proved problematic. However, RAFT (or more specifically, MADIX) polymerization offers a convenient method of controlling the synthesis of PVA by the addition of a xanthate or a dithiocarbamate chain transfer agent.

Other reactions

Vinyl acetate is useful in organic synthesis.[9] Transacetylation is used to obtain enantioenriched alcohols and esters. Iridium-catalyzed transacetylation have also been demonstrated:[10][11]

ROH + CH2=CHOAc → ROCH=CH2 + HOAc

Transvinylation is also possible using vinyl acetate. It undergoes Diels-Alder reactions with dienes.

Vinyl acetate undergoes many of the reactions anticipated for an alkene and an ester. Bromine adds to give the dibromide. Hydrogen halides add to give 1-haloethyl acetates, which cannot be generated by other methods because of the non-availability of the corresponding halo-alcohols. Acetic acid adds in the presence of palladium catalysts to give ethylidene diacetate, CH3CH(OAc)2. It undergoes transesterification with a variety of carboxylic acids.[12] The alkene also undergoes Diels–Alder and 2+2 cycloadditions.

Toxicity evaluation

Tests suggest that vinyl acetate has low toxicity. Oral LD50 for rats is 2920 mg/kg.[3]

On January 31, 2009, the Government of Canada's final assessment concluded that exposure to vinyl acetate is not harmful to human health.[13] This decision under the Canadian Environmental Protection Act (CEPA) was based on new information received during the public comment period, as well as more recent information from the risk assessment conducted by the European Union.

In the context of large-scale release into the environment, it is classified as an extremely hazardous substance in the United States as defined in Section 302 of the U.S. Emergency Planning and Community Right-to-Know Act (42 U.S.C. 11002), under which it "does not meet toxicity criteria[,] but because of its acute lethality, high production volume [or] known risk is considered a chemical of concern". By this law, it is subject to strict reporting requirements by facilities that produce, store, or use it in quantities greater than 1000 pounds.[14]

See also

References

  1. ^ "Public Health Statement for Vinyl Acetate". Agency for Toxic Substances and Disease Registry, Centers for Disease Control. It has a sweet, pleasant, fruity smell, but the odor may be sharp and irritating to some people.
  2. ^ NIOSH Pocket Guide to Chemical Hazards. "#0656". National Institute for Occupational Safety and Health (NIOSH).
  3. ^ a b c Bienewald, Frank; Leibold, Edgar; Tužina, Pavel; Roscher, Günter (2019). "Vinyl Esters". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. pp. 1–16. doi:10.1002/14356007.a27_419.pub2. ISBN 978-3-527-30385-4.
  4. ^ a b H. Chinn (September 2008). "CEH Marketing Research Report: Vinyl Acetate". Chemical Economics Handbook. SRI consulting. Retrieved 2011-07-01.[dead link‍]
  5. ^ Karl Shmavonian (2012-10-24). "Madhukar Parekh's Pidilite Industries Earns His Family $1.36 Billion". Forbes.com. Retrieved 27 January 2013. though Pidilite has had to contend with the rising price of vinyl acetate monomer, its key raw material
  6. ^ Y.-F. Han; D. Kumar; C. Sivadinarayana & D. W. Goodman (2004). "Kinetics of Ethylene Combustion in the Synthesis of Vinyl Acetate over a Pd/SiO2 Catalyst" (PDF). Journal of Catalysis. 224: 60–68. doi:10.1016/j.jcat.2004.02.028. Archived from the original (PDF) on 2008-03-07. Retrieved 2006-11-05.
  7. ^ Stacchiola, D.; Calaza, F.; Burkholder, L.; Schwabacher Alan, W.; Neurock, M.; Tysoe Wilfred, T. (2005). "Elucidation of the Reaction Mechanism for the Palladium-Catalyzed Synthesis of Vinyl Acetate". Angewandte Chemie International Edition. 44 (29): 4572–4574. doi:10.1002/anie.200500782. PMID 15988776.
  8. ^ "VP/VA Copolymer". Personal Care Products Council. Archived from the original on 16 October 2012. Retrieved 13 December 2012.
  9. ^ Manchand, Percy S. (2001). "Vinyl Acetate". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rv008. ISBN 0-471-93623-5.
  10. ^ Tomotaka Hirabayashi; Satoshi Sakaguchi; Yasutaka Ishii (2005). "Iridium-catalyzed Synthesis of Vinyl Ethers from Alcohols and Vinyl Acetate". Org. Synth. 82: 55. doi:10.15227/orgsyn.082.0055.
  11. ^ Yasushi Obora; Yasutaka Ishii (2012). "Discussion Addendum: Iridium-catalyzed Synthesis of Vinyl Ethers from Alcohols and Vinyl Acetate". Org. Synth. 89: 307. doi:10.15227/orgsyn.089.0307.
  12. ^ D. Swern & E. F. Jordan, Jr. (1963). "Vinyl Laurate and Other Vinyl Esters" (PDF). Organic Syntheses, Collected Volume. 4: 977. Archived from the original (PDF) on 2011-06-05. Retrieved 2007-11-11.
  13. ^ "Summary of Public Comments Received on the Government of Canada's Draft Screening Assessment Report on Vinyl Acetate (CAS No. 108-05-4)" (PDF). Health Canada. 2009.
  14. ^ "40 C.F.R: Appendix A to Part 355—The List of Extremely Hazardous Substances and Their Threshold Planning Quantities" (PDF). Code of Federal Regulations. title 40, vol. 30, part 355, app. A (EPA) (December 2017 ed.). Government Printing Office: 474. December 2017. Retrieved 7 March 2018 – via US GPO.