Maleic anhydride: Difference between revisions

| Verifiedfields = changed

| Watchedfields = changed

| verifiedrevid = 409750643

| Reference=<ref>''[[Merck Index]]'', 11th Edition, '''5586'''.</ref>

| Name = Maleic anhydride

| ImageFileL1_Ref = {{chemboximage|correct|??}}

| ImageFileL1 = Maleic anhydride (vertical).svg

| ImageSizeL1 = 80px

| ImageNameL1 = Maleic anhydride

| ImageFileR1 = Maleic anhydride-3d.png

| ImageSizeR1 = 150px

| ImageFile2 = Sample of Maleic anhydride.jpg

| PIN = Furan-2,5-dione<ref name=iupac2013>{{cite book | title = Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book) | publisher = [[Royal Society of Chemistry|The Royal Society of Chemistry]] | date = 2014 | location = Cambridge | page = 835 | doi = 10.1039/9781849733069-FP001 | isbn = 978-0-85404-182-4| chapter = Front Matter }}</ref>

| OtherNames = Maleic anhydride<ref name=iupac2013 /><br />''cis''-Butenedioic anhydride<br />2,5-Furanedione<br />Maleic acid anhydride<br />Toxilic anhydride

|Section1={{Chembox Identifiers

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

| Beilstein = 106909

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

| ChEBI = 474859

| ChEMBL_Ref = {{ebicite|correct|EBI}}

| ChEMBL = 374159

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

| ChemSpiderID = 7635

| EC_number = 203-571-6

| Gmelin = 2728

| PubChem = 7923

| RTECS = ON3675000

| UNNumber = 2215

| UNII_Ref = {{fdacite|correct|FDA}}

| InChIKey = FPYJFEHAWHCUMM-UHFFFAOYAP

| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}

| SMILES = C1=CC(=O)OC1=O

|Section2={{Chembox Properties

| C=4 | H=2 | O=3

| Appearance = White crystals or needles<ref name=PGCH/>

| Odor = irritating, choking<ref name=PGCH/>

| Solubility = Reacts

| MeltingPtC = 52.8

| BoilingPtC = 202

| Density = 1.48 g/cm³

| VaporPressure = 0.2 mmHg (20°C)<ref name=PGCH/>

| MagSus = -35.8·10⁻⁶ cm³/mol

|Section3={{Chembox Structure

| Dipole =

|Section7={{Chembox Hazards

| ExternalSDS =[http://hazard.com/msds/mf/baker/baker/files/m0364.htm MSDS at J. T. Baker]

| NFPA-H = 3

| NFPA-R = 1

| NFPA-F = 1

| GHSPictograms = {{GHS05}}{{GHS07}}{{GHS08}}

| GHSSignalWord = Danger

| HPhrases = {{H-phrases|302|314|317|334|372}}

| PPhrases = {{P-phrases|260|261|264|270|272|280|285|301+312|301+330+331|302+352|303+361+353|304+340|304+341|305+351+338|310|314|321|330|333+313|342+311|363|405|501}}

| FlashPtC = 102

| PEL = TWA 1 mg/m³ (0.25 ppm)<ref name=PGCH>{{PGCH|0376}}</ref>

| ExploLimits = 1.4%-7.1%<ref name=PGCH/>

| IDLH = 10 mg/m³<ref name=PGCH/>

| LD50 = 465 mg/kg (oral, mouse)<br/>850 mg/kg (oral, rat)<br/>875 mg/kg (oral, rabbit)<br/>390 mg/kg (oral, guinea pig)<br/>400 mg/kg (oral, rat)<ref>{{IDLH|108316|Maleic anhydride}}</ref>

| REL = TWA 1 mg/m³ (0.25 ppm)<ref name=PGCH/>

|Section8={{Chembox Related

| OtherFunction_label = [[acid anhydride]]s

| OtherFunction = [[Succinic anhydride]]

| OtherCompounds = [[Maleic acid]]

'''Maleic anhydride''' is an [[organic compound]] with the formula C₂H₂(CO)₂O. It is the [[acid anhydride]] of [[maleic acid]]. It is a colorless or white solid with an acrid odor. It is produced industrially on a large scale for applications in [[coating]]s and [[polymer]]s.<ref name = ullmann>{{Ullmann | title = Maleic and Fumaric Acids | author1 = Kurt Lohbeck | author2 = Herbert Haferkorn | author3 = Werner Fuhrmann | author4 = Norbert Fedtke | doi = 10.1002/14356007.a16_053 }}</ref>

==Production==

Maleic anhydride is produced by vapor-phase oxidation of [[butane|''n''-butane]]. The overall process converts the methyl groups to carboxylate and [[dehydrogenation|dehydrogenates]] the backbone. The selectivity of the process reflects the robustness of maleic anhydride, with its conjugated double-bond system. Traditionally maleic anhydride was produced by the [[organic oxidation|oxidation]] of [[benzene]] or other [[aromatic compound]]s. As of 2006, only a few smaller plants continue to use benzene.

In both cases, benzene and butane are fed into a stream of hot air, and the mixture is passed through a catalyst bed at high temperature. The ratio of air to hydrocarbon is controlled to prevent the mixture from igniting. [[Vanadium pentoxide]] and [[molybdenum trioxide]] are the catalysts used for the benzene route, whereas [[vanadium phosphate]] is used for the butane route:<ref name = ullmann/>

:C₄H₁₀ + 3.5 O₂ → C₄H₂O₃ + 4 H₂O ∆H = −1236 kJ/mol

The main competing process entails full combustion of the butane, a conversion that is twice as exothermic as the partial oxidation.

The traditional method using benzene became uneconomical due to the high and still rising benzene prices and by complying with the [[regulation]]s of benzene [[Emission standard|emission]]s. In addition, in the production of maleic anhydride (4 C-atoms) a third of the original carbon atoms is lost as carbon dioxide when using benzene (6 carbon atoms). The modern catalytic processes start from a 4-carbon molecule and only attaches [[oxygen]] and removes water; the 4-C-base body of the molecule remains intact. Overall, the newer method is therefore more [[Atom economy|material efficient]].<ref name=Philipp>Bertram Philipp, Peter Stevens: ''Grundzüge der Industriellen Chemie'', VCH Verlagsgesellschaft mbH, 1987, S. 179, {{ISBN|3-527-25991-0}}.</ref>

Parallels exist with the production of [[phthalic anhydride]]: While older methods use [[naphthalene]], modern methods use [[o-xylene|''o''-xylene]] as feedstock.

The chemistry of maleic anhydride is very rich, reflecting its ready availability and bifunctional reactivity. It hydrolyzes, producing [[maleic acid]], ''cis''-HOOC&ndash;CH=CH&ndash;COOH. With alcohols, the half-ester is generated, e.g., ''cis''-HOOC&ndash;CH=CH&ndash;COOCH₃.

Maleic anhydride is a classic substrate for [[Diels-Alder reaction]]s.<ref>{{cite journal |author1=Samuel Danishefsky |author2=Takeshi Kitahara |author3=Paul F. Schuda |name-list-style=amp | title = Preparation and Diels-Alder Reaction of a Highly Nucleophilic Diene: trans-1-Methoxyl-3-Trimethylsiloxy-1,3-Butadiene and 5β-Methoxycyclohexan-1-one-3β,4β-Dicarboxylic acid Andhydride | journal = Org. Synth. | year = 1983 | volume = 61 | pages = 147 | doi=10.1002/0471264180.os061.30}}</ref> It was used for work in 1928, on the reaction between maleic anhydride and 1,3-butadiene, for which [[Otto Paul Hermann Diels]] and [[Kurt Alder]] were awarded the [[Nobel Prize]] in 1950. It is through this reaction that maleic anhydride is converted to many pesticides and pharmaceuticals. Their 1928 patent also provided many other examples of reactions involving maleic anhydride, such as the reaction with [[cyclopentadiene]] to form [[nadic anhydride]].<ref name="dielsalder">{{cite patent |country=United States |number=US1944731A |title=Organic compound having hydrogenated ring systems and process of preparing it |pubdate=January 23, 1934 |gdate= |fdate= |pridate= |invent1=[[Otto Diels]] |invent2=[[Kurt Alder]] |url=https://worldwide.espacenet.com/patent/search/family/007750680/publication/US1944731A?q=US1944731}}</ref>

:[[File:Maleic anhydride Diel.Alder reaction with butadiene.svg|450px]]

[[Michael reaction]] of maleic anhydride with active methylene or methine compounds such as malonate or acetoacetate esters in the presence of sodium acetate catalyst. These intermediates were subsequently used for the generation of the Krebs cycle intermediates aconitic and isocitric acids.<ref>US 4146543 E.Gutierrez</ref>

Likewise at higher temperatures, the half salts, half esters of maleic acid undergo the [[Michael reaction]] with active methylene or methine compounds. These intermediates were used for the same Krebs cycle intermediates aconitic and isocitric acids.<ref>US 4123458 E.Gutierrez, V.Lamberti</ref>

Maleic anhydride [[dimerization (chemistry)|dimerizes]] in a [[photochemical reaction]] to form [[cyclobutane tetracarboxylic dianhydride]] (CBTA). This compound is used in the production of [[polyimide]]s and as an alignment film for [[liquid crystal display]]s.<ref>{{Cite journal| doi = 10.1021/op900306z| title = Photodimerization of Maleic Anhydride in a Microreactor Without Clogging| year = 2010| last1 = Horie | first1 = T.| last2 = Sumino | first2 = M.| last3 = Tanaka | first3 = T.| last4 = Matsushita | first4 = Y.| last5 = Ichimura | first5 = T.| last6 = Yoshida | first6 = J. I.| journal = Organic Process Research & Development| pages = 100128104701019| issue = 2| volume = 14 }}</ref>

:[[File:MaleicAnhydrideDimerization.svg|Maleic anhydride dimerization]]

It is also a ligand for low-valent metal complexes, examples being Pt(PPh₃)₂(MA) and Fe(CO)₄(MA).

On account of its cycle of 4 π electrons in an array of 5 atoms with p orbitals, maleic anhydride was long thought to exhibit [[antiaromaticity]]. However, a thermochemical study concluded that only 8 kJ/mol of destabilization energy can be ascribed to this effect, making it weakly antiaromatic at best.<ref>{{Cite journal|last1=Roux|first1=María Victoria|last2=Jiménez|first2=Pilar|last3=Martín-Luengo|first3=Maria Ángeles|last4=Dávalos|first4=Juan Z.|last5=Sun|first5=Zhiyuan|last6=Hosmane|first6=Ramachandra S.|last7=Liebman|first7=Joel F.|date=May 1997|title=The Elusive Antiaromaticity of Maleimides and Maleic Anhydride: Enthalpies of Formation ofN-Methylmaleimide,N-Methylsuccinimide,N-Methylphthalimide, andN-Benzoyl-N-methylbenzamide|journal=The Journal of Organic Chemistry|language=en|volume=62|issue=9|pages=2732–2737|doi=10.1021/jo9621985|pmid=11671632|issn=0022-3263}}</ref>

==Uses==

<gallery>

Malathion.png|[[Malathion]] is a popular insecticide derived from maleic anhydride

SulfosuccinateRR'.png|[[Sodium sulfosuccinate esters]], common class of surfactants derived from maleic anhydride

AlkylsuccinicAnhydrideC18again.png|[[Alkenylsuccinic anhydrides]], which are derived from maleic anhydride, are widely used in papermaking

Rubratoxin A.png|Rubratoxin A is one of many natural products containing a maleic anhydride-like subunit.

</gallery>

Maleic anhydride has many applications.<ref name = ullmann/>

=== Plastics & resins ===

Around 50% of world maleic anhydride output is used in the manufacture of [[unsaturated polyester resin]]s (UPR). [[Chopped glass fiber]]s are added to UPR to produce fiberglass reinforced plastics that are used in a wide range of applications such as [[Boating|pleasure boats]], bathroom fixtures, automobiles, tanks and pipes.

Maleic anhydride is hydrogenated to [[1,4-butanediol]] (BDO), used in the production of [[Thermoplastic polyurethane|thermoplastic polyurethanes]], elastane/Spandex fibers, [[polybutylene terephthalate]] (PBT) resins and many other products.

=== Curing agents ===

[[Diels-Alder reaction]] of maleic anhydride and [[butadiene]] and [[isoprene]] gives the respective [[tetrahydrophthalic anhydride]]s which can be hydrogenated to the corresponding hexahydrophthalic anhydrides. These species are used as curing agents in [[epoxy resin]]s. Another market for maleic anhydride is lubricating oil additives, which are used in gasoline and diesel engine [[Crankcase dilution|crankcase oils]] as dispersants and corrosion inhibitors. Changes in lubricant specifications and more efficient engines have had a negative effect on the demand for lubricating oil additives, giving flat growth prospects for maleic anhydride in this application.

=== Others ===

A number of smaller applications exist for maleic anhydride. Personal care products consuming maleic anhydride include hair sprays, adhesives and floor polishes. Maleic anhydride is also a precursor to compounds used for water treatment detergents, insecticides and fungicides, pharmaceuticals, and other copolymers.

The maleic anhydride group occurs in several natural products, some of which show promising therapeutic or pesticidal activity.<ref>{{cite journal |doi=10.1021/cr050029r |title=Natural Products with Maleic Anhydride Structure: Nonadrides, Tautomycin, Chaetomellic Anhydride, and Other Compounds |date=2007 |last1=Chen |first1=Xiaolong |last2=Zheng |first2=Yuguo |last3=Shen |first3=Yinchu |journal=Chemical Reviews |volume=107 |issue=5 |pages=1777–1830 |pmid=17439289 }}</ref>

==Major producers==

{| class="wikitable"

|-

!Company !! Location !! Capacity (KMT/Year)

|-

| Yongsan Chemicals, Inc. || South Korea || 38

|-

| Bartek Ingredients Inc. || Canada || 28

|-

| Sasol-Huntsman || Germany || 105

|-

| DSM NV || The Netherlands || 100

|-

| INEOS || USA || 50

|-

| Huntsman Corporation|| USA || 155

|-

| Huntsman Performance Products || USA || 100

|-

| Lanxess Corporation || USA || 75

|-

| Lonza Group AG || Switzerland || 100

|-

| AOC Materials || USA || 55

|-

| Mitsubishi Chemical Corporation || Japan || 32

|-

| Mitsui Chemicals, Inc || Japan || 33

|-

| Mitsui Chemicals Polyurethanes, Inc. || Japan || 100

|-

| Nippon Shokubai Co., Ltd || Japan || 35

|-

| NOF Corporation || Japan || 12

|-

| Polynt SpA || Italy || 96

|-

| Mysore Petro Chemicals Ltd. || India || 15

|}

<small>'''''Source''': Kirk & Othmer''</small>

Solid State Chemicals, Ltd. started production of solid maleic anhydride pastilles in the USA in 2014.

'''World Maleic Anhydride Capacity By Region'''

<br>Data in: ''kilotonnes per annum''

{| class="wikitable"

|-

! Region !! 2002 !! 2012 !! 2015 (KMT/Year)

|-

| North America || 235 || 311 || 370

|-

| South & Central America || 44 || 41 || 46

|-

| Western Europe || 168 || 456 || 307

|-

| Central & Eastern Europe || 64 || 58 || 60

|-

| Asia || 315 || 483 || 1864

|-

| Africa || 10 || 10 || 14

|-

| Total || 836 || 1359 || 2771

|}

<small>'''''Source''': Kirk & Othmer ''</small>{{full citation needed|date=September 2014}}

==Packing and transport==

Liquid maleic anhydride is available in road tankers and/or tank-containers which are made of stainless steel, which are insulated and provided with heating systems to maintain the temperature of 65-75&nbsp;°C. Tank cars must be approved for the transport of molten maleic anhydride.

Liquid/molten maleic anhydride is a dangerous material in accordance with RID/ADR.

Solid maleic anhydride pellets are transported by trucks. Packaging is generally in 25&nbsp;kg polyethylene bags.

==Effects on human health and the environment==

This compound poses relatively low-risk environmental hazards, an important feature for some applications. In [[human]]s, exposure to maleic anhydride may cause irritation to the [[respiratory tract]], [[eyes]], exposed [[mucosa]], and [[skin]]. Maleic anhydride is also a skin and respiratory sensitizer.<ref>{{cite web | url = http://echa.europa.eu/documents/10162/9801478/sev1_203_571_6_report_en.pdf | title = Substance Evaluation Report: Maleic anhydride | publisher = Environment Agency Austria | access-date = 2014-10-13 | archive-url = https://web.archive.org/web/20141018174452/http://echa.europa.eu/documents/10162/9801478/sev1_203_571_6_report_en.pdf | archive-date = 2014-10-18 | url-status = dead }}</ref>

Maleic anhydride is a low hazard profile chemical. Maleic anhydride rapidly [[hydrolysis|hydrolyzes]] to form maleic acid in the presence of water and hence environmental exposures to maleic anhydride itself are unlikely. Maleic acid is [[biodegradation|biodegradable]] under aerobic conditions in [[sewage sludge]] as well as in [[compost|soil]] and [[water]].

Food starch for use in night markets sold from a supplier in [[Tainan]] city, [[Taiwan]], were found to contain maleic anhydride in December 2013. The supplier was investigated regarding the 300 tons of tainted starch; an earlier inspection in November had found 32 tons.<ref>{{cite news | url = http://www.wantchinatimes.com/news-subclass-cnt.aspx?id=20131219000005&cid=1103 | title = Tainted starch found in Tainan yet again | publisher = Want China Times | date = 2013-12-19 | access-date = 2013-12-19 | archive-url = https://web.archive.org/web/20131219152045/http://www.wantchinatimes.com/news-subclass-cnt.aspx?id=20131219000005&cid=1103 | archive-date = 2013-12-19 | url-status = dead }}</ref>

*[https://web.archive.org/web/20070611162734/http://www.oehha.ca.gov/air/chronic_rels/pdf/maleic.pdf Chronic toxicity summary]

{{Authority control}}

[[Category:Carboxylic anhydrides]]