| Revision as of 08:25, 18 February 2012 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Saving copy of the {{chembox}} taken from revid 472646940 of page Methyl_acrylate for the Chem/Drugbox validation project (updated: 'ChEMBL', 'KEGG'). |
Latest revision as of 21:49, 27 September 2024 edit Smokefoot (talk | contribs)Autopatrolled, Extended confirmed users, Pending changes reviewers, Rollbackers74,617 edits →Production: specify substrate |
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{{distinguish|methyl methacrylate}} |
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{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}} |
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{{chembox |
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{{chembox |
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| Verifiedfields = changed |
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| verifiedrevid = 472645251 |
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| Watchedfields = changed |
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| Name = Methyl acrylate |
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| verifiedrevid = 477501764 |
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| ImageFileL1 = Methyl acrylate.png |
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| Name = Methyl acrylate |
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| ImageSizeL1 = 100px |
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| ImageFileL1 = Methylacrylat.svg |
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| ImageNameL1 = Skeletal formula of methyl Acrylate |
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| ImageSizeL1 = 110px |
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| ImageFileR1 = Methyl-acrylate-3D-balls.png |
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| ImageAltL1 = Skeletal formula of methyl Acrylate |
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| ImageSizeR1 = 125px |
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| ImageFileR1 = Methyl acrylate molecule ball.png |
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| ImageNameR1 = Ball-and-stick model of methyl acrylate |
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| ImageSizeR1 = 135px |
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| IUPACName = Methyl propenoate |
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| ImageAltR1 = Ball-and-stick model of the methyl acrylate molecule |
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| OtherNames = |
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| PIN = Methyl prop-2-enoate<ref name="pubchem">{{cite web | url=https://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=7294 | title=methyl acrylate - Compound Summary | work=PubChem | access-date=June 30, 2012}}</ref> |
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| Section1 = {{Chembox Identifiers |
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| OtherNames = Methyl acrylate<br/>Methyl propenoate<br/>Methoxycarbonylethylene<br/>Curithane 103<ref name="pubchem" /> |
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| SMILES = C=CC(OC)=O |
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|Section1={{Chembox Identifiers |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| SMILES = C=CC(OC)=O |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo = 96-33-3 |
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| CASNo = 96-33-3 |
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| KEGG_Ref = {{keggcite|correct|kegg}} |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = WC487PR91H |
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| KEGG = <!-- blanked - oldvalue: C19443 --> |
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| KEGG_Ref = {{keggcite|changed|kegg}} |
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| ChEMBL = 9019 |
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| KEGG = C19443 |
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| ChEMBL_Ref = {{ebicite|correct|EBI}} |
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| ChEMBL = 9019 |
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| PubChem = 7294 |
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| PubChem = 7294 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 7022 |
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| ChemSpiderID = 7022 |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| InChI = 1/C4H6O2/c1-3-4(5)6-2/h3H,1H2,2H3 |
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| InChIKey = BAPJBEWLBFYGME-UHFFFAOYAO |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI = 1S/C4H6O2/c1-3-4(5)6-2/h3H,1H2,2H3 |
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| StdInChI = 1S/C4H6O2/c1-3-4(5)6-2/h3H,1H2,2H3 |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = BAPJBEWLBFYGME-UHFFFAOYSA-N |
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| StdInChIKey = BAPJBEWLBFYGME-UHFFFAOYSA-N |
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}} |
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}} |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| C=4|H=6|O=2 |
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| C=4 | H=6 | O=2 |
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| Appearance = Colorless liquid |
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| Appearance = Colorless liquid |
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| Density = 0.95 g/cm³<ref name=GESTIS>{{GESTIS|ZVG=13020}}</ref> |
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| Odor = Acrid<ref name=PGCH>{{PGCH|0394}}</ref> |
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| Density = 0.95 g/cm<sup>3</sup><ref name=GESTIS>{{GESTIS|ZVG=13020}}</ref> |
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| Solubility = |
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| Solubility = 5 g/100 mL |
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| MeltingPtC = -74 |
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| MeltingPtC = -74 |
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| Melting_note = <ref name=GESTIS/> |
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| MeltingPt_ref = <ref name=GESTIS/> |
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| BoilingPtC = 80 |
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| BoilingPtC = 80 |
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| Boiling_note = <ref name=GESTIS/> |
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| BoilingPt_ref = <ref name=GESTIS/> |
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| VaporPressure = 65 mmHg (20°C)<ref name=PGCH/> |
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| Viscosity = {{plainlist| |
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* 0.391 mPa·s at 35 °C<ref name="George2002">{{cite journal | last=George | first=John | last2=Sastry | first2=Nandhibatla V. | last3=Patel | first3=Sunil R. | last4=Valand | first4=Mahendra K. | title=Densities, Viscosities, Speeds of Sound, and Relative Permittivities for Methyl Acrylate + 1-Alcohols (C1−C6) atT= (308.15 and 318.15) K | journal=Journal of Chemical & Engineering Data | publisher=American Chemical Society (ACS) | volume=47 | issue=2 | year=2002 | issn=0021-9568 | doi=10.1021/je010268l | pages=262–269}}</ref> |
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* 0.333 mPa·s at 45 °C<ref name="George2002"/>}} |
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}} |
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}} |
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| Section7 = {{Chembox Hazards |
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|Section7={{Chembox Hazards |
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| MainHazards = Harmful (Xn); Highly flammable (F+) |
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| MainHazards = Harmful (Xn); Highly flammable (F+) |
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| ExternalMSDS = |
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| ExternalSDS = |
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| FlashPtC = -3 |
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| FlashPt = {{convert|-3|C|F}}<ref name=GESTIS/> |
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| FlashPt_ref = <ref name=GESTIS/> |
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| IDLH = 250 ppm<ref name=PGCH/> |
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| LC50 = 3575 ppm (mouse)<br/>1350 ppm (rat, 4 hr)<br/>1000 ppm (rat, 4 hr)<br/>2522 ppm (rabbit, 1 hr)<ref name=IDLH>{{IDLH|96333|Methyl acrylate}}</ref> |
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| PEL = TWA 10 ppm (35 mg/m<sup>3</sup>) <ref name=PGCH/> |
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| REL = TWA 10 ppm (35 mg/m<sup>3</sup>) <ref name=PGCH/> |
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| ExploLimits = 2.8–25%<ref name=PGCH/> |
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}} |
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}} |
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'''Methyl acrylate''' is an ], more accurately the ] of ]. It is a colourless liquid with a characteristic acrid odor. It is mainly produced to make ] fiber, which is used to weave synthetic carpets.<ref name=Ullmann>{{cite encyclopedia|author=Takashi Ohara |author2=Takahisa Sato |author3=Noboru Shimizu |author4=Günter Prescher Helmut Schwind |author5=Otto Weiberg |author6=Klaus Marten |author7=Helmut Greim |title=Acrylic Acid and Derivatives|encyclopedia=Ullmann's Encyclopedia of Industrial Chemistry|year=2003|publisher=Wiley-VCH|location=Weinheim| doi=10.1002/14356007.a01_161.pub2|isbn=3-527-30673-0}}</ref> It is also a ] in the synthesis of various pharmaceutical intermediates. Owing to the tendency of methyl acrylate to polymerize, samples typically contain an inhibitor such as ]. |
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==Production== |
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The standard industrial reaction for producing methyl acrylate is ] of acrylic acid with ] under acid catalysis (], ] or acidic ion exchangers.<ref>{{Cite web | title = Esterification: Acrylate esters (MA, EA, BA, MMA, 2-EHA) | url = http://www.amberlyst.com/acrylate.htm | publisher = amberlyst.com | access-date = 2013-02-21}}</ref>). The transesterification is facilitated because methanol and methyl acrylate form a low boiling ] (] 62–63 °C).<ref>{{OrgSynth|author= Chessie E. Rehberg |year=1955|title=n-Butyl acrylate|volume=26|pages=18|collvol=3|collvolpages=146|prep=CV3P0146}}</ref> |
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The patent literature<ref>{{cite patent |
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| country = US |
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| number = 3925463 |
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| title = Process for the production of methyl acrylate |
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| pubdate = 1975-12-09 |
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| inventor1-last = Ferlazzo |
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| inventor1-first = Natale |
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| inventor2-last = Buzzi |
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| inventor2-first = Gian Fausto |
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| inventor3-last = Ghirga |
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| inventor3-first = Marcello |
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| assign1 = Societa' Italiana Resine S.I.R., S.p.A. |
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}}</ref> describes a one-pot route involving vapor-phase oxidation of propene or 2-propenal with oxygen in the presence of methanol. |
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===Other methods=== |
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Methyl acrylate can be prepared by ] of methyl 2,3-dibromopropanoate with ].<ref name="Beilstein">F. Beilstein: ''Handbuch der organischen Chemie'', 3. Auflage, 1. Band. Verlag Leopold Voss, 1893, S. 501. .</ref> Methyl acrylate is formed in good ] on ] of ] in the presence of ] (ketene).<ref>{{cite patent |
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| country = US| number = 2417748| title = Preparation of methyl acrylate| pubdate = 1947-03-18 |
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| inventor1-first = Hugh J.| inventor1-last = Hagemeyer| assign1 = ]}}</ref> Methyl lactate is a renewable "]". Another patent<ref>{{cite patent| country = US| number = 5250729| title = Process for preparing unsaturated carboxylic acid or ester thereof| inventor1-last=Abe | inventor1-first=Takafumi | inventor2-last=Hieda | inventor2-first=Shinichi | assign1 = ]|pubdate=1993-10-05}}</ref> describes the dehydration of methyl lactate over ]s. |
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The nickel tetracarbonyl-catalyzed ] of acetylene with carbon monoxide in the presence of methanol also yields methyl acrylate.<ref>W. Reppe, J. Liebigs Ann. Chem., 582 (1), 116-132 (1953)</ref> The reaction of methyl formate with acetylene in the presence of transition metal catalysts also leads to methyl acrylate.<ref>{{cite patent | number= 6022990 | inventor1-last=Liu| inventor1-first=Zhao-Tie | inventor2-last=Zhang| inventor2-first=Jia-Qi | inventor3-last= Yang| inventor3-first=Xian-Gui| title = Method for synthesizing methyl acrylate | pubdate = 2000-02-08 | country = US | assign1 = ]|assign2=National Research and Engineering Centre for Coal Slurry Gasification and Coal Chemical Industry}}</ref> Both, the alcoholysis of propiolactone with methanol as well as the methanolysis of acrylonitrile via intermediately formed acrylamide sulfate<ref>H.-J. Arpe, ''Industrielle Organische Chemie'', 6. Aufl., Wiley-VCH Verlag, Weinheim, 2007, {{ISBN|978-3-527-31540-6}}.</ref> are also proven but obsolete processes. |
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==Use== |
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Methyl acrylate is after ] and ] the third most important acrylic ester with a worldwide annual production of about 200,000 tons in 2007.<ref>''CEH Marketing Research Report Acrylic Acid and Esters,'' SRI Consulting, July 2007.</ref> Poly(methyl acrylate) is a tacky material near room temperature, and as such it is not particularly useful as a structural material. Commonly, methyl acrylate (and other acrylate esters) are ]ized with other alkenes to give useful engineering plastics.<ref>{{cite book |doi=10.1002/14356007.a21_157.pub2|chapter=Polyacrylates |title=Ullmann's Encyclopedia of Industrial Chemistry |year=2018 |last1=Penzel |first1=Erich |last2=Ballard |first2=Nicholas |last3=Asua |first3=José M. |pages=1–20 |isbn=978-3-527-30673-2 }}</ref> A variety of ]s are used, including ] and other acrylates.<ref>DOW Methyl acrylate, Product Safety Assessment</ref> The resulting copolymers give acrylic paints that are harder and more ] than those with the homologous acrylates. Copolymerizing methyl acrylate with acrylonitrile improves their melt processability to fibers, which could be used as precursors for carbon fibers.<ref>{{citation|author=V. A. Bhanu |display-authors=et al|periodical=]|title=Synthesis and characterization of acrylonitrile methyl acrylate statistical copolymers as melt processable carbon fiber precursors|year=2002|volume=43|issue=18|pages=4841–4850|language=German|doi=10.1016/S0032-3861(02)00330-0|url=https://www.researchgate.net/publication/229126444 |format=PDF}}</ref> Methyl acrylate is the precursor to fibers that are woven to make carpets. |
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===Amino derivatives=== |
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Methyl acrylate reacts catalysed by ]s in a ] with ]s in high yields to β-alanine derivatives which provide amphoteric surfactants when long-chain amines are used and the ester function is hydrolysed subsequently. |
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Acrylates are also used in the preparation of ] (PAMAM) ]s typically by Michael addition with a primary ]. |
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] |
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Methyl acrylate is used for the preparation of ] by transesterification with ] in significant quantities of over 50,000 tons / year.<ref>{{cite patent|country=WO| number = 2010136696| title = Composition including dialkyl tin oxide and use thereof as a transesterification catalyst for the synthesis of (meth)acrylic esters| pubdate = 2010-12-02| |
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| inventor1-last=Paul| inventor1-first=Jean-Michel | inventor2-last=Tonnelier| inventor2-first=Boris | inventor3-last= Augustin| inventor3-first=Francis |
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| assign1 = ]}}</ref> |
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== Reactions == |
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Methyl acrylate is a classic Michael acceptor, which means that it adds nucleophiles at its terminus. For example, in the presence of a base catalyst, it adds hydrogen sulfide to give the thioether:<ref>{{OrgSynth|author= Edward A. Fehnel and Marvin Carmack |year=1950|title=Methyl-β-dipropionate|volume=30|pages=65|collvol=4|collvolpages=669|prep=CV4P0669}}</ref> |
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:2 CH<sub>2</sub>CHCO<sub>2</sub>CH<sub>3</sub> + H<sub>2</sub>S → S(CH<sub>2</sub>CH<sub>2</sub>CO<sub>2</sub>CH<sub>3</sub>)<sub>2</sub> |
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It is also a good ]. |
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==Safety== |
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It is an acute toxin with an {{LD50}} (rats, oral) of 300 mg/kg and a ] of 10 ppm. |
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==References== |
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{{reflist}} |
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{{Authority control}} |
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] |
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] |
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] |