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Vinyl acetate

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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, zeset T, VAM vinyl acetate monomer, acetic acid ethenyl ester, 1-acetoxyethylene
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.003.224 Edit this at Wikidata
EC Number
  • 203-545-4
KEGG
MeSH C011566
UNII
  • 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 86.09 g/mol
Appearance Colorless liquid
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)
Hazards
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[1]
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 CH3CO2CHCH2. A colorless liquid with a pungent odor, it is the precursor to polyvinyl acetate, an important polymer in industry. Unlike many other acetate esters, the odor of vinyl acetate is thoroughly disagreeable and is not used to any substantial degree as an odorant.

Production

The worldwide production capacity of vinyl acetate monomer (VAM) was estimated at 6,154,000 tonnes/annum 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).[2] The average list price for 2008 was $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%).[2]

It is a key ingredient in furniture glue.[3]

Preparation

The major industrial route involves the reaction of ethylene and acetic acid with oxygen in the presence of a palladium catalyst.[4]

C2H4 + CH3CO2H + 1⁄2 O2 → CH3CO2CHCH2 + H2O

The main side reaction is the combustion of organic precursors. Vinyl acetate was once prepared by hydroesterification. This method involves the gas-phase addition of acetic acid to acetylene in the presence of metal catalysts. By this route, using mercury(II) catalysts, vinyl acetate was first prepared by Klatte in 1912.[5] Another route to vinyl acetate involves thermal decomposition of ethylidene diacetate:

(CH3CO2)2CHCH3 → CH3CO2CHCH2 + CH3CO2H

Polymerization

It can be polymerized to give polyvinyl acetate (PVA). With other monomers can be used to prepare 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).[6] Due to the instability of the radical, attempts to control the polymerization via 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 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.[7] The alkene also undergoes Diels-Alder and 2+2 cycloadditions.

Toxicity evaluation

On January 31, 2009, the Government of Canada's final assessment concluded that exposure to vinyl acetate is not considered to be harmful to human health.[8] 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.

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), and is subject to strict reporting requirements by facilities which produce, store, or use it in significant quantities.[9]

See also

References

  1. ^ NIOSH Pocket Guide to Chemical Hazards. "#0656". National Institute for Occupational Safety and Health (NIOSH).
  2. ^ a b H. Chinn (September 2008). "CEH Marketing Research Report: Vinyl Acetate". Chemical Economics Handbook. SRI consulting. Retrieved July 2011. {{cite web}}: Check date values in: |accessdate= (help)
  3. ^ 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
  4. ^ 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. {{cite journal}}: Unknown parameter |last-author-amp= ignored (|name-list-style= suggested) (help)
  5. ^ G. Roscher "Vinyl Esters" in Ullmann's Encyclopedia of Chemical Technology, 2007 John Wiley & Sons: New York. doi:10.1002/14356007.a27_419
  6. ^ "VP/VA Copolymer". Personal Care Products Council. Retrieved 13 December 2012.
  7. ^ D. Swern; E. F. Jordan, Jr. (1963). "Vinyl Laurate and Other Vinyl Esters" (PDF). Organic Syntheses, Collected Volume 4: 977. {{cite journal}}: Unknown parameter |lastauthoramp= ignored (|name-list-style= suggested) (help)
  8. ^ http://www.ec.gc.ca/ese-ees/59EC93F6-2C5D-42B4-BB09-EB198C44788D/batch2_108-05-4_pc_en.pdf
  9. ^ "40 C.F.R.: Appendix A to Part 355—The List of Extremely Hazardous Substances and Their Threshold Planning Quantities" (PDF) (July 1, 2008 ed.). Government Printing Office. Retrieved October 29, 2011. {{cite journal}}: Cite journal requires |journal= (help)CS1 maint: postscript (link)
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