Maleic anhydride

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 coatings and
polymers.[5]

Maleic anhydride[1]
 Maleic anhydride

Names

Preferred IUPAC name

Furan-2,5-dione[2]

Other names
Maleic anhydride[2]
cis-Butenedioic anhydride
 cis-Butenedioic anhydride
2,5-Furanedione

Maleic acid anhydride

Toxilic anhydride

Identifiers

CAS Number 108-31-6  

3D model (JSmol) Interactive image

ChEBI CHEBI:474859  

ChEMBL ChEMBL374159  

ChemSpider 7635  

ECHA InfoCard 100.003.247

EC Number 203-571-6

PubChem CID 7923

RTECS number UE5950000

UNII V5877ZJZ25  
UNII V5877ZJZ25

InChI
InChI=1S/C4H2O3/c5-3-1-2-4(6)7-3/h1-2H 
Key: FPYJFEHAWHCUMM-UHFFFAOYSA-N 

InChI=1/C4H2O3/c5-3-1-2-4(6)7-3/h1-2H
Key: FPYJFEHAWHCUMM-UHFFFAOYAP

SMILES
C1=CC(=O)OC1=O

Properties

Chemical formula C4H2O3

Molar mass 98.06 g·mol−1

Appearance White crystals or

needles[3]

Odor irritating, choking[3]

Density 1.48 g/cm3

Melting point 52.8 °C (127.0 °F;

325.9 K)

Boiling point 202 °C (396 °F; 475 K)

Solubility in water Reacts

Solubility in water Reacts

Vapor pressure 0.2 mmHg (20°C)[3]

Magnetic -35.8·10−6 cm3/mol

susceptibility (χ)

Hazards

Safety data sheet MSDS at J. T. Baker

EU classification Corrosive (C)

(DSD) (outdated)

R-phrases (outdated) R22, R34, R42/43

S-phrases (outdated) (S2), S22, S26,

S36/37/39, S45

NFPA 704 1
3 1

Flash point 102 °C (216 °F; 375 K)

Explosive limits 1.4%-7.1%[3]

Lethal dose or concentration (LD, LC):

LD50 (median dose) 465 mg/kg (oral,

 LD50 (median dose) 465 mg/kg (oral,
mouse)
850 mg/kg (oral, rat)
875 mg/kg (oral,
rabbit)
390 mg/kg (oral,
guinea pig)
400 mg/kg (oral,
rat)[4]

US health exposure limits (NIOSH):

PEL (Permissible) TWA 1 mg/m3 (0.25

ppm)[3]

REL (Recommended) TWA 1 mg/m3 (0.25

ppm)[3]

IDLH (Immediate 10 mg/m3[3]

danger)

Related compounds

Related acid
Related acid Succinic anhydride
anhydrides
Related compounds Maleic acid

Except where otherwise noted, data are given

for materials in their standard state (at 25 °C
[77 °F], 100 kPa).

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Infobox references

Production
Maleic anhydride is produced by vapor-
phase oxidation of n-butane. The
overall process converts the methyl
groups to carboxylate and
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 oxidation of benzene
or other aromatic compounds. 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:[5]

C4H10 + 3.5 O2 →C H C O
2 2 2 3 + 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 the regulations of benzene
emissions. 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 material efficient.[6]
Parallels exist with the production of
phthalic anhydride: While older
methods use naphthalene, modern
methods use o-xylene as feedstock.

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

Maleic anhydride is a classic substrate

for Diels-Alder reactions.[7] 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 converted to many
pesticides and pharmaceuticals.

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.[8]

Maleic anhydride dimerizes in a

photochemical reaction to form
cyclobutane tetracarboxylic
dianhydride (CBTA). This compound is
used in the production of polyimides
and as an alignment film for liquid
crystal displays.[9]

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

Uses
Maleic anhydride is used in many
applications.[5]

Around 50% of world maleic anhydride

output is used in the manufacture of
unsaturated polyester resins (UPR).
Chopped glass fibers are added to UPR
to produce fibreglass reinforced
plastics that are used in a wide range
of applications such as pleasure boats,
bathroom fixtures, automobiles, tanks
and pipes.

Maleic anhydride is hydrogenated to

1,4-butanediol (BDO), used in the
production of thermoplastic
polyurethanes, elastane/Spandex
fibers, polybutylene terephthalate (PBT)
resins and many other products.

Malathion is a popular herbicide that is derived

from maleic anhydride.
 

Structure of sodium sulfosuccinate esters,

common class of surfactants derived from maleic
anhydride.

Alkenylsuccinic anhydrides, which are derived

from maleic anhydride, are widely used in
papermaking.

Diels-Alder reaction of maleic

anhydride and butadiene and isoprene
gives the respective tetrahydrophthalic
anhydrides which can be hydrogenated
to the corresponding
hexahydrophthalic anhydrides. These
species are used a curing agents in
epoxy resins. Another market for
maleic anhydride is lubricating oil
additives, which are used in gasoline
and diesel engine 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.

A number of smaller applications for

maleic anhydride. The food industry
uses maleic anhydride in artificial
sweeteners and flavour enhancements.
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.
Major producers
Company Location Capacity (KMT/Year)

Bartek Ingredients Inc. Canada 28

Sasol-Huntsman Germany 105

DSM NV The Netherlands 100

Flint Hills Resources LP USA 50

Huntsman Corporation USA 155

Huntsman Performance Products USA 100

Lanxess Corporation USA 75

Lonza Group AG Switzerland 100

Marathon Petroleum Company LLC 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

Suzhou Synthetic Chemical Co, Ltd. China 15

Source: Kirk & Othmer

Solid State Chemicals, Ltd. started

production of solid maleic anhydride
pastilles in the USA in 2014.

World Maleic Anhydride Capacity By

Region
Data in: kilotonnes per annum

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

Source: Kirk & Othmer

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 °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 pastilles are

transported by transport trucks.
Packaging is generally in 25 kg
polyethylene bags.

Storage
Requirements for storage buildings
Local exhaust systems to take
vapours away from the places of
emission, and general ventilation
in rooms.
Protection against static
charges.
Impervious floor which makes it
possible to collect the spilled
material and which prevents its
 entry to the sewage system.
Storage rooms should be cool
and dry.
Storage conditions
Keep ignition sources away - do
not smoke. Product dust may
form explosive air-dust mixtures.
Keep humidity away from
storage rooms.
Keep containers tightly closed.
Store them in cool, dry and well
ventilated places.
Tanks / containers must be
properly marked.
 Hand-operated / portable fire-
fighting equipment should be
available in storage rooms.
Neutral gas blanketing is
required inside storage tanks.

Effects on human health

and the environment
This compound poses relatively low-
risk environmental hazards, an
important feature for some
applications. In humans, 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.[10]

Maleic anhydride is a low hazard profile

chemical. Maleic anhydride rapidly
hydrolyzes to form maleic acid in the
presence of water and hence
environmental exposures to maleic
anhydride itself are unlikely. Maleic
acid is biodegradable under aerobic
conditions in sewage sludge as well as
in 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.[11]

References
1. Merck Index, 11th Edition, 5586.
2. Nomenclature of Organic Chemistry :
IUPAC Recommendations and Preferred
Names 2013 (Blue Book). Cambridge:
The Royal Society of Chemistry. 2014.
p. 835. doi:10.1039/9781849733069-
FP001 . ISBN 978-0-85404-182-4.
FP001 . ISBN 978-0-85404-182-4.
3. "NIOSH Pocket Guide to Chemical
Hazards #0376" . National Institute for
Occupational Safety and Health
(NIOSH).
4. "Maleic anhydride" . Immediately
Dangerous to Life and Health
Concentrations (IDLH). National
Institute for Occupational Safety and
Health (NIOSH).
5. Kurt Lohbeck; Herbert Haferkorn;
Werner Fuhrmann; Norbert Fedtke
(2005), "Maleic and Fumaric Acids",
Ullmann's Encyclopedia of Industrial
Chemistry, Weinheim: Wiley-VCH,
doi:10.1002/14356007.a16_053
doi:10.1002/14356007.a16_053
6. Bertram Philipp, Peter Stevens:
Grundzüge der Industriellen Chemie,
VCH Verlagsgesellschaft mbH, 1987, S.
179, ISBN 3-527-25991-0.
7. Samuel Danishefsky; Takeshi
Kitahara & Paul F. Schuda (1983).
"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". Org. Synth. 61: 147.
8. US 4146543 E.Gutierrez
9. Horie, T.; Sumino, M.; Tanaka, T.;
Matsushita, Y.; Ichimura, T.; Yoshida, J.
I. (2010). "Photodimerization of Maleic
Anhydride in a Microreactor Without
Clogging". Organic Process Research &
Development. 14 (2):
100128104701019.
doi:10.1021/op900306z .
10. "Substance Evaluation Report:
Maleic anhydride" (PDF). Environment
Agency Austria.
11. "Tainted starch found in Tainan yet
again" . Want China Times. 2013-12-19.

External links
 International Chemical Safety Card
0799
"NIOSH Pocket Guide to Chemical
Hazards #0376" . National Institute
for Occupational Safety and Health
(NIOSH).
Chronic toxicity summary
Maleic anhydride at Occupational
Safety & Health Administration

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