Methacrylic acid

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Methacrylic acid
Methacrylic acid.svg
Methacrylic acid molecule ball.png
Names
IUPAC name
Methacrylic acid [1]
Preferred IUPAC name
2-Methylprop-2-enoic acid
Other names
Methacrylic acid
2-Methyl-2-propenoic acid
α-Methacrylic acid
2-Methylacrylic acid
2-Methylpropenoic acid
Identifiers
3D model (JSmol)
AbbreviationsMAA
ChEBI
ChemSpider
ECHA InfoCard 100.001.096 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 201-204-4
MeSH C008384
PubChem CID
UNII
  • InChI=1S/C4H6O2/c1-3(2)4(5)6/h1H2,2H3,(H,5,6)
    Key: CERQOIWHTDAKMF-UHFFFAOYSA-N
  • CC(C(O)=O)=C
Properties
C4H6O2
Molar mass 86.09 g/mol
AppearanceColorless liquid
Odor Acrid, repulsive [2]
Density 1.015 g/cm3
Melting point 14 to 15 °C (57 to 59 °F; 287 to 288 K)
Boiling point 161 °C (322 °F; 434 K)
9% (25 °C) [2]
Vapor pressure 0.7 mmHg (20 °C) [2]
Hazards
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 2: Must be moderately heated or exposed to relatively high ambient temperature before ignition can occur. Flash point between 38 and 93 °C (100 and 200 °F). E.g. diesel fuelInstability 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
3
2
2
Flash point 77.2 °C (171.0 °F; 350.3 K)
NIOSH (US health exposure limits):
PEL (Permissible)
none [2]
REL (Recommended)
TWA 20 ppm (70 mg/m3) [skin] [2]
IDLH (Immediate danger)
N.D. [2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Methacrylic acid, abbreviated MAA, is an organic compound with the formula CH2=C(CH3)CO2H. This colorless, viscous liquid is a carboxylic acid with an acrid unpleasant odor. It is soluble in warm water and miscible with most organic solvents. Methacrylic acid is produced industrially on a large scale as a precursor to its esters, especially methyl methacrylate (MMA), and to poly(methyl methacrylate) (PMMA).

Contents

Production

In the most common route, methacrylic acid is prepared from acetone cyanohydrin, which is converted to methacrylamide sulfate using sulfuric acid. This derivative in turn is hydrolyzed to methacrylic acid, or esterified to methyl methacrylate in one step. Another route to methacrylic acid starts with isobutylene, which obtainable by dehydration of tert-butanol. Isobutylene is oxidized sequentially to methacrolein and then methacrylic acid. Methacrolein for this purpose can also be obtained from formaldehyde and ethylene. Yet a third route involves the dehydrogenation of Isobutyric acid. [3]

Various green routes have been explored but they have not been commercialized. Specifically, the decarboxylation of itaconic acid, citraconic acid, and mesaconic acids affords methacrylic acid. [4] Salts of methacrylic acid have been obtained by boiling citra- or meso-brompyrotartaric acids with alkalis.[ citation needed ]

Pyrolysis of ethyl methacrylate efficiently gives methacrylic acid. [5]

Uses and occurrence

The main use of methacrylic acid is its polymerization to poly(methyl methacrylate). [6]

It is used in some nail primers to help acrylic nails adhere to the nail plate. [7]

Copolymers consisting partially of methacrylic acid are used in certain types of tablet coatings in order to slow the tablet's dissolution in the digestive tract, and thus extend or delay the release of the active ingredient. [8]

MAA occurs naturally in small amounts in the oil of Roman chamomile.[ citation needed ]

MMA is used in the synthesis of some vinyl ester resins.

Typical vinyl ester resin derived from bisphenol A diglycidyl ether and methacrylic acid. MethmethacrylateBPA-glyc.png
Typical vinyl ester resin derived from bisphenol A diglycidyl ether and methacrylic acid.

Reactions

For commercial applications, MAA is polymerized using azobisisobutyronitrile as a thermally activated free-radical catalyst. Otherwise, MAA is relatively slow to polymerize thermally or photochemically. [6]

Methacrylic acid undergoes several reactions characteristic of α,β-unsaturated acids (see acrylic acid). These reactions include the Diels–Alder reaction and Michael additions. Esterifications are brought about by acid-catalyzed condensations with alcohols, alkylations with certain alkenes, and transesterifications. Epoxide ring-opening gives hydroxyalkyl esters. [3] Sodium amalgam reduces it to isobutyric acid. A polymeric form of methacrylic acid was described in 1880. [10]

See also

Related Research Articles

Acrylates are the salts, esters, and conjugate bases of acrylic acid. The acrylate ion is the anion CH2=CHCO−2. Often, acrylate refers to esters of acrylic acid, the most common member being methyl acrylate. These acrylates contain vinyl groups. These compounds are of interest because they are bifunctional: the vinyl group is susceptible to polymerization and the carboxylate group carries myriad functionalities.

<span class="mw-page-title-main">Acrylic acid</span> Chemical compound

Acrylic acid (IUPAC: propenoic acid) is an organic compound with the formula CH2=CHCOOH. It is the simplest unsaturated carboxylic acid, consisting of a vinyl group connected directly to a carboxylic acid terminus. This colorless liquid has a characteristic acrid or tart smell. It is miscible with water, alcohols, ethers, and chloroform. More than a million tons are produced annually.

<span class="mw-page-title-main">Isobutylene</span> Unsaturated hydrocarbon compound (H2C=C(CH3)2)

Isobutylene is a hydrocarbon with the chemical formula (CH3)2C=CH2. It is a four-carbon branched alkene (olefin), one of the four isomers of butylene. It is a colorless flammable gas, and is of considerable industrial value.

<span class="mw-page-title-main">Methyl methacrylate</span> Chemical compound

Methyl methacrylate (MMA) is an organic compound with the formula CH2=C(CH3)COOCH3. This colorless liquid, the methyl ester of methacrylic acid (MAA), is a monomer produced on a large scale for the production of poly(methyl methacrylate) (PMMA).

Vinyl ester resin, or often just vinyl ester, is a resin produced by the esterification of an epoxy resin with acrylic or methacrylic acids. The "vinyl" groups refer to these ester substituents, which are prone to polymerize and thus an inhibitor is usually added. The diester product is then dissolved in a reactive solvent, such as styrene, to approximately 35–45 percent content by weight. Polymerization is initiated by free radicals, which are generated by UV-irradiation or peroxides.

<span class="mw-page-title-main">Acrylate polymer</span> Group of polymers prepared from acrylate monomers

An acrylate polymer is any of a group of polymers prepared from acrylate monomers. These plastics are noted for their transparency, resistance to breakage, and elasticity.

Synthetic resins are industrially produced resins, typically viscous substances that convert into rigid polymers by the process of curing. In order to undergo curing, resins typically contain reactive end groups, such as acrylates or epoxides. Some synthetic resins have properties similar to natural plant resins, but many do not.

<span class="mw-page-title-main">Ethyl acrylate</span> Chemical compound

Ethyl acrylate is an organic compound with the formula CH2CHCO2CH2CH3. It is the ethyl ester of acrylic acid. It is a colourless liquid with a characteristic acrid odor. It is mainly produced for paints, textiles, and non-woven fibers. It is also a reagent in the synthesis of various pharmaceutical intermediates.

<span class="mw-page-title-main">(Hydroxyethyl)methacrylate</span> Chemical compound

Hydroxyethylmethacrylate is the organic compound with the chemical formula H2C\dC(CH3)CO2CH2CH2OH. It is a colorless viscous liquid that readily polymerizes. Hydroxyethylmethacrylate is a monomer that is used to make various polymers.

Acetone cyanohydrin (ACH) is an organic compound used in the production of methyl methacrylate, the monomer of the transparent plastic polymethyl methacrylate (PMMA), also known as acrylic. It liberates hydrogen cyanide easily, so it is used as a source of such. For this reason, this cyanohydrin is also highly toxic.

<span class="mw-page-title-main">Methyl acrylate</span> Chemical compound

Methyl acrylate is an organic compound, more accurately the methyl ester of acrylic acid. It is a colourless liquid with a characteristic acrid odor. It is mainly produced to make acrylate fiber, which is used to weave synthetic carpets. It is also a reagent in the synthesis of various pharmaceutical intermediates. Owing to the tendency of methyl acrylate to polymerize, samples typically contain an inhibitor such as hydroquinone.

In polymer chemistry, a comonomer refers to a polymerizable precursor to a copolymer aside from the principal monomer. In some cases, only small amounts of a comonomer are employed, in other cases substantial amounts of comonomers are used. Furthermore, in some cases, the comonomers are statistically incorporated within the polymer chain, whereas in other cases, they aggregate. The distribution of comonomers is referred to as the "blockiness" of a copolymer.

<span class="mw-page-title-main">Methyl cyanoacrylate</span> Chemical compound

Methyl cyanoacrylate is an organic compound that contains several functional groups: a methyl ester, a nitrile, and an alkene. It is a colorless liquid with low viscosity. Its chief use is as the main component of cyanoacrylate glues. It can be encountered under many trade names. Methyl cyanoacrylate is less commonly encountered than ethyl cyanoacrylate.

<span class="mw-page-title-main">Poly(methacrylic acid)</span> Chemical compound

Poly(methacrylic acid) (PMAA) is a polymer made from methacrylic acid (preferred IUPAC name, 2-methylprop-2-enoic acid), which is a carboxylic acid. It is often available as its sodium salt, poly(methacrylic acid) sodium salt. The monomer is a viscous liquid with a pungent odour. The first polymeric form of methacrylic acid was described in 1880 by Engelhorn and Fittig. The use of high purity monomers is required for proper polymerization conditions and therefore it is necessary to remove any inhibitors by extraction (phenolic inhibitors) or via distillation. To prevent inhibition by dissolved oxygen, monomers should be carefully degassed prior to the start of the polymerization.

<span class="mw-page-title-main">2-Vinylpyridine</span> Chemical compound

2-Vinylpyridine is an organic compound with the formula CH2CHC5H4N. It is a derivative of pyridine with a vinyl group in the 2-position, next to the nitrogen. It is a colorless liquid, although samples are often brown. It is used industrially as a precursor to specialty polymers and as an intermediate in the chemical, pharmaceutical, dye, and photo industries. Vinylpyridine is sensitive to polymerization. It may be stabilized with a polymerisation inhibitor such as tert-butylcatechol. Owing to its tendency to polymerize, samples are typically refrigerated.

Butyl acrylate is an organic compound with the formula C4H9O2CCH=CH2. A colorless liquid, it is the butyl ester of acrylic acid. It is used commercially on a large scale as a precursor to poly(butyl acrylate). Especially as copolymers, such materials are used in paints, sealants, coatings, adhesives, fuel, textiles, plastics, and caulk.

In industrial chemistry, carboalkoxylation is a process for converting alkenes to esters. This reaction is a form of carbonylation. A closely related reaction is hydrocarboxylation, which employs water in place of alcohols

<span class="mw-page-title-main">Butyl methacrylate</span> Chemical compound

Butyl methacrylate is the organic compound with the formula C4H9O2CC(CH3)=CH2. A colorless liquid, it is a common monomer for the preparation of methacrylate polymers. It is typically polymerized under free-radical conditions.

<span class="mw-page-title-main">Ethyl methacrylate</span> Organic compound

Ethyl methacrylate is the organic compound with the formula C2H5O2CC(CH3)=CH2. A colorless liquid, it is a common monomer for the preparation of acrylate polymers. It is typically polymerized under free-radical conditions.

α,β-Unsaturated carbonyl compound Functional group of organic compounds

α,β-Unsaturated carbonyl compounds are organic compounds with the general structure (O=CR)−Cα=Cβ-R. Such compounds include enones and enals, but also carboxylic acids and the corresponding esters and amides. In these compounds, the carbonyl group is conjugated with an alkene. Unlike the case for carbonyls without a flanking alkene group, α,β-unsaturated carbonyl compounds are susceptible to attack by nucleophiles at the β-carbon. This pattern of reactivity is called vinylogous. Examples of unsaturated carbonyls are acrolein (propenal), mesityl oxide, acrylic acid, and maleic acid. Unsaturated carbonyls can be prepared in the laboratory in an aldol reaction and in the Perkin reaction.

References

  1. International Union of Pure and Applied Chemistry (2014). Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. The Royal Society of Chemistry. p. 746. doi:10.1039/9781849733069. ISBN   978-0-85404-182-4.
  2. 1 2 3 4 5 6 NIOSH Pocket Guide to Chemical Hazards. "#0386". National Institute for Occupational Safety and Health (NIOSH).
  3. 1 2 William Bauer Jr. (2002). "Methacrylic Acid and Derivatives". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a16_441. ISBN   978-3527306732.
  4. Le Nôtre, Jérôme; Witte-van Dijk, Susan C. M.; van Haveren, Jacco; Scott, Elinor L.; Sanders, Johan P. M. (September 2014). "Synthesis of Bio-Based Methacrylic Acid by Decarboxylation of Itaconic Acid and Citric Acid Catalyzed by Solid Transition-Metal Catalysts". ChemSusChem. 7 (9): 2712–2720. Bibcode:2014ChSCh...7.2712L. doi:10.1002/cssc.201402117. PMID   25045161.
  5. W. P. Ratchford (1949). "Acrylic Acid I. Pyrolysis Method". Organic Syntheses. 29: 2. doi:10.15227/orgsyn.029.0002. This article also describes pyrolysis of ethyl methacrylate.
  6. 1 2 Stickler, Manfred; Rhein, Thoma (2000). "Polymethacrylates". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a21_473. ISBN   3-527-30673-0.
  7. "Products - Nail Care Products". www.fda.gov. U.S. Food and Drug Administration. 2018-03-06. Retrieved 2019-04-03.
  8. "Aqueous enteric coatings with methacrylic acid copolymer type C on acidic and basic drugs in tablets and pellets, part I: Acetylsalicylic acid tablets and crystals".
  9. Pham, Ha Q.; Marks, Maurice J. (2012). "Epoxy Resins". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a09_547.pub2. ISBN   978-3-527-30673-2.
  10. F. Engelhorn (1880). Rudolph Fittig (ed.). "II. Untersuchungen über die ungesättigten Säuren. Zur Kenntnis der Methacrylsäure" [II. Investigations on the unsaturated acids. On the characterisation of methacrylic acid.]. Justus Liebigs Annalen der Chemie. 200: 70. doi:10.1002/jlac.18802000103..