Vinyl acetate: Difference between revisions

|Verifiedfields = changed

|Watchedfields = changed

|verifiedrevid = 439823992

|Name = Vinyl acetate

|ImageFile = Vinylacetaat.svg

|ImageSize = 150px

|ImageName = Skeletal formula

|ImageFile1 = Vinyl-acetate-3D-balls.png

|ImageSize1 = 170px

|ImageName1 = Ball-and-stick model

|PIN = Ethenyl acetate

|SystematicName = Ethenyl ethanoate

|OtherNames = {{bulletedlist|Acetic acid vinyl ester|Vinyl ethanoate|Acetoxyethene|VyAc|VAM|Vinyl acetate monomer|Acetic acid ethenyl ester|1-Acetoxyethylene}}

|Section1={{Chembox Identifiers

|CASNo_Ref = {{cascite|correct|CAS}}

|CASNo = 108-05-4

|Beilstein = 1209327

|ChEBI_Ref = {{ebicite|correct|EBI}}

|ChEBI = 46916

|KEGG_Ref = {{keggcite|correct|kegg}}

|KEGG = C19309

|EINECS = 203-545-4

|PubChem = 7904

|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}

|ChemSpiderID = 7616

|MeSHName = C011566

|UNII_Ref = {{fdacite|changed|FDA}}

|UNII = L9MK238N77

|SMILES = C=COC(C)=O

|InChI = 1/C4H6O2/c1-3-6-4(2)5/h3H,1H2,2H3

|InChIKey = XTXRWKRVRITETP-UHFFFAOYAB

|StdInChI_Ref = {{stdinchicite|changed|chemspider}}

|StdInChI = 1S/C4H6O2/c1-3-6-4(2)5/h3H,1H2,2H3

|StdInChIKey_Ref = {{stdinchicite|changed|chemspider}}

|StdInChIKey = XTXRWKRVRITETP-UHFFFAOYSA-N

|UNNumber = 1301

|Section2={{Chembox Properties

|C=4|H=6|O=2

|Appearance = Colorless liquid

|Odor = Sweet, pleasant, fruity; may be sharp and irritating<ref>{{cite web| publisher = Agency for Toxic Substances and Disease Registry, Centers for Disease Control | title = Public Health Statement for Vinyl Acetate | url = https://www.atsdr.cdc.gov/phs/phs.asp?id=669&tid=124 | quote = It has a sweet, pleasant, fruity smell, but the odor may be sharp and irritating to some people.}}</ref>

|Density = 0.934 g/cm³

|MeltingPtC = −93.5

|BoilingPtC = 72.7

|MagSus = −46.4{{e|−6}} cm³/mol

}}

|Section7={{Chembox Hazards

|ExternalSDS = [http://www.inchem.org/documents/icsc/icsc/eics0347.htm ICSC 0347]

|NFPA-H = 2

|NFPA-R = 2

|NFPA-F = 3

|GHSPictograms = {{GHS02}}{{GHS07}}{{GHS08}}

|GHSSignalWord = Danger

|HPhrases = {{H-phrases|225|332|335|351}}

|PPhrases = {{P-phrases|201|202|210|233|240|241|242|243|261|271|280|281|303+361+353|304+312|304+340|308+313|312|370+378|403+233|403+235|405|501}}

|FlashPtC = −8

|AutoignitionPtC = 427

|ExploLimits = 2.6–13.40%

|PEL = none<ref name=NIOSH>{{PGCH|0656}}</ref>

}}

}}

'''Vinyl acetate''' is an [[organic compound]] with the [[Chemical formula|formula]] CH₃CO₂CH=CH₂. This colorless liquid is the precursor to [[polyvinyl acetate]], [[ethylene-vinyl acetate|ethene-vinyl acetate copolymers]], [[polyvinyl alcohol]], and other important industrial polymers.<ref name=Ullmann/>

==Production==

The worldwide production capacity of vinyl acetate was estimated at 6,969,000 [[tonne]]s/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).<ref name=CEH>{{cite web |url=http://www.sriconsulting.com/CEH/Private/Reports/696.5000/ |title=CEH Marketing Research Report: Vinyl Acetate |author=H. Chinn |date=September 2008 |work=Chemical Economics Handbook |publisher=SRI consulting |access-date=2011-07-01}}{{dead-link|date=June 2021}}</ref> 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%).<ref name=CEH/>

It is a key ingredient in furniture glue.<ref>{{cite web |title=Madhukar Parekh's Pidilite Industries Earns His Family $1.36 Billion |url=https://www.forbes.com/sites/forbesasia/2012/10/24/madhukar-parekhs-pidilite-industries-earns-his-family-1-36-billion/print/ |work=Forbes.com |access-date=27 January 2013 |author=Karl Shmavonian |date=2012-10-24 |quote=though Pidilite has had to contend with the rising price of vinyl acetate monomer, its key raw material}}</ref>

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.<ref>{{cite journal |author1=Y.-F. Han |author2=D. Kumar |author3=C. Sivadinarayana |author4=D. W. Goodman |name-list-style=amp |title=Kinetics of Ethylene Combustion in the Synthesis of Vinyl Acetate over a Pd/SiO₂ Catalyst |journal=Journal of Catalysis |volume=224 |year=2004 |pages=60–68 |url=http://www.chem.tamu.edu/rgroup/goodman/pdf%20files/442_joc-224-04-60.pdf |doi=10.1016/j.jcat.2004.02.028 |access-date=2006-11-05 |archive-date=2008-03-07 |archive-url=https://web.archive.org/web/20080307232720/http://www.chem.tamu.edu/rgroup/goodman/pdf%20files/442_joc-224-04-60.pdf |url-status=dead }}</ref>

: <chem>2 C2H4 + 2 CH3CO2H + O2 -> 2 CH3CO2CHCH2 + 2 H2O</chem>

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.<ref>{{cite journal |author1=Stacchiola, D. |author2=Calaza, F. |author3=Burkholder, L. |author4=Schwabacher Alan, W. |author5=Neurock, M. |author6=Tysoe Wilfred, T. |title=Elucidation of the Reaction Mechanism for the Palladium-Catalyzed Synthesis of Vinyl Acetate |journal=Angewandte Chemie International Edition |year=2005 |volume=44 |issue=29 |pages=4572–4574 |doi=10.1002/anie.200500782 |pmid=15988776}}</ref>

===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.<ref name=Ullmann>{{Ullmann|doi=10.1002/14356007.a27_419.pub2|title=Vinyl Esters |year=2019 |last1=Bienewald |first1=Frank |last2=Leibold |first2=Edgar |last3=Tužina |first3=Pavel |last4=Roscher |first4=Günter |pages=1–16 |isbn=978-3-527-30385-4 }}</ref> Presently, [[zinc acetate]] is used as the catalyst:

:{{chem2|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]]:

: {{chem2|(CH3CO2)2CHCH3 -> CH3CO2CHCH2 + CH3CO2H}}

It can be polymerized to give [[polyvinyl acetate]] (PVAc). With other [[monomer]]s it can be used to prepare various [[copolymer]]s such as [[ethylene-vinyl acetate]] (EVA), vinyl acetate-[[acrylic acid]] (VA/AA), [[polyvinyl chloride acetate]] (PVCA), and [[polyvinylpyrrolidone]] (Vp/Va copolymer, used in [[hair gel]]s).<ref>{{cite web |title=VP/VA Copolymer |url=http://www.cosmeticsinfo.org/ingredient_details.php?ingredient_id=1064 |publisher=Personal Care Products Council |access-date=13 December 2012 |archive-date=16 October 2012 |archive-url=https://web.archive.org/web/20121016002040/http://www.cosmeticsinfo.org/ingredient_details.php?ingredient_id=1064 }}</ref> Due to the instability of the radical, attempts to control the polymerization by most "living/controlled" radical processes have proved problematic. However, [[RAFT (chemistry)|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.

Vinyl acetate is useful in [[organic synthesis]].<ref>{{cite book |doi=10.1002/047084289X.rv008|chapter=Vinyl Acetate |title=Encyclopedia of Reagents for Organic Synthesis |year=2001 |last1=Manchand |first1=Percy S. |isbn=0-471-93623-5 }}</ref> [[Transacetylation]] is used to obtain enantioenriched alcohols and esters. Iridium-catalyzed transacetylation have also been demonstrated:<ref>{{cite journal |title=Iridium-catalyzed Synthesis of Vinyl Ethers from Alcohols and Vinyl Acetate |author=Tomotaka Hirabayashi |author2=Satoshi Sakaguchi |author3=Yasutaka Ishii |journal=Org. Synth. |year=2005 |volume=82 |page=55 |doi=10.15227/orgsyn.082.0055 |doi-access=free}}</ref><ref name=Ishii>{{cite journal |title=Discussion Addendum: Iridium-catalyzed Synthesis of Vinyl Ethers from Alcohols and Vinyl Acetate |author=Yasushi Obora |author2=Yasutaka Ishii |journal=Org. Synth. |year=2012 |volume=89 |page=307 |doi=10.15227/orgsyn.089.0307}}</ref>

: ROH + CH₂=CHOAc → ROCH=CH₂ + HOAc

Transvinylation is also possible using vinyl acetate. It undergoes [[Diels-Alder reaction]]s with [[diene]]s.

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 acid]]s.<ref>{{cite journal |author1=D. Swern |author2=E. F. Jordan, Jr. |name-list-style=amp |title=Vinyl Laurate and Other Vinyl Esters |journal=Organic Syntheses, Collected Volume |volume=4 |page=977 |year=1963 |url=http://www.orgsyn.org/orgsyn/pdfs/CV4P0977.pdf |access-date=2007-11-11 |archive-url=https://web.archive.org/web/20110605225303/http://www.orgsyn.org/orgsyn/pdfs/CV4P0977.pdf |archive-date=2011-06-05 }}</ref> 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&nbsp;mg/kg.<ref name=Ullmann/>

On January 31, 2009, the Government of Canada's final assessment concluded that exposure to vinyl acetate is not harmful to human health.<ref>{{cite web |url=http://www.ec.gc.ca/ese-ees/59EC93F6-2C5D-42B4-BB09-EB198C44788D/batch2_108-05-4_pc_en.pdf |title=Summary of Public Comments Received on the Government of Canada's Draft Screening Assessment Report on Vinyl Acetate (CAS&nbsp;No.&nbsp;108-05-4) |publisher=Health Canada |date=2009}}</ref> 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 [[List of extremely hazardous substances|extremely hazardous substance]] in the United States as defined in Section&nbsp;302 of the U.S. [[Emergency Planning and Community Right-to-Know Act]] ({{nobr|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&nbsp;pounds.<ref name="gov-right-know">{{Cite journal |date=December 2017 |title=40 C.F.R: Appendix A to Part 355—The List of Extremely Hazardous Substances and Their Threshold Planning Quantities |url=https://www.gpo.gov/fdsys/pkg/CFR-2017-title40-vol30/pdf/CFR-2017-title40-vol30-part355-appA.pdf |journal=Code of Federal Regulations |edition=December 2017 |publisher=[[United States Government Publishing Office|Government Printing Office]] |volume=title 40, vol. 30, part 355, app. A (EPA) |page=474 |access-date=7 March 2018 |via=US GPO}}</ref>

*[[Vinyl propionate]]

==References==

<references/>

* [http://www.epa.gov/iris/subst/0512.htm EPA health assessment information on vinyl acetate]

* [http://www.chemicalsubstanceschimiques.gc.ca/challenge-defi/summary-sommaire/batch-lot-2/108-05-4-eng.php Summary of risk assessment by the Government of Canada]

{{Authority control}}

[[Category:Commodity chemicals]]

[[Category:Vinyl esters]]