Organic compound (CH2=CH?C≡N)
Acrylonitrile
|
|
Names
|
Preferred IUPAC name
|
Other names
Acrylonitrile
2-Propenenitrile
Cyanoethene
Vinyl
cyanide
(VCN)
Cyanoethylene
[1]
Propenenitrile
[1]
Vinyl nitrile
|
Identifiers
|
|
|
|
|
ChEBI
|
|
ChEMBL
|
|
ChemSpider
|
|
ECHA InfoCard
|
100.003.152
|
EC Number
|
|
KEGG
|
|
|
|
RTECS number
|
|
UNII
|
|
UN number
|
1093
|
|
|
InChI=1S/C3H3N/c1-2-3-4/h2H,1H2
Y
Key: NLHHRLWOUZZQLW-UHFFFAOYSA-N
Y
InChI=1/C3H3N/c1-2-3-4/h2H,1H2
Key: NLHHRLWOUZZQLW-UHFFFAOYAG
|
|
Properties
|
|
C
3
H
3
N
|
Molar mass
|
53.064
g·mol
?1
|
Appearance
|
Colourless liquid
|
Density
|
0.81 g/cm
3
|
Melting point
|
?84 °C (?119 °F; 189 K)
|
Boiling point
|
77 °C (171 °F; 350 K)
|
|
70 g/L
|
log
P
|
0.19
[2]
|
Vapor pressure
|
83 mmHg
[1]
|
Hazards
|
Occupational safety and health
(OHS/OSH):
|
Main hazards
|
flammable
reactive
toxic
potential occupational carcinogen
[1]
|
NFPA 704
(fire diamond)
|
|
Flash point
|
?1 °C; 30 °F; 272 K
|
|
471 °C (880 °F; 744 K)
|
Explosive limits
|
3?17%
|
Lethal dose
or concentration (LD, LC):
|
|
500 ppm (rat, 4 h)
313 ppm (mouse, 4 h)
425 ppm (rat, 4 h)
[3]
|
|
260 ppm (rabbit, 4 h)
575 ppm (guinea pig, 4 h)
636 ppm (rat, 4 h)
452 ppm (human, 1 h)
[3]
|
NIOSH
(US health exposure limits):
|
|
TWA 2 ppm C 10 ppm [15-minute] [skin]
[1]
|
|
Ca TWA 1 ppm C 10 ppm [15-minute] [skin]
[1]
|
|
85 ppm
[1]
|
Safety data sheet
(SDS)
|
ICSC 0092
|
Related compounds
|
|
acetonitrile
propionitrile
|
Related compounds
|
acrylic acid
acrolein
|
Except where otherwise noted, data are given for materials in their
standard state
(at 25 °C [77 °F], 100 kPa).
|
Chemical compound
Acrylonitrile
is an
organic compound
with the
formula
CH
2
CHCN
and the
structure
H
2
C=CH?C≡N
. It is a colorless,
volatile
liquid. It has a pungent odor of garlic or onions.
[4]
Its
molecular structure
consists of a
vinyl group
(
?CH=CH
2
) linked to a
nitrile
(
?C≡N
). It is an important
monomer
for the manufacture of useful
plastics
such as
polyacrylonitrile
. It is
reactive
and
toxic
at low doses.
[5]
Acrylonitrile is one of the components of
ABS plastic (Acrylonitrile butadiene styrene)
.
[6]
Structure and basic properties
[
edit
]
Acrylonitrile is an
organic compound
with the
formula
CH
2
CHCN
and the
structure
H
2
C=CH?C≡N
. It is a colorless,
volatile
liquid although commercial samples can be yellow due to
impurities
. It has a pungent odor of garlic or onions.
[4]
Its
molecular structure
consists of a
vinyl group
(
?CH=CH
2
) linked to a
nitrile
(
?C≡N
). It is an important
monomer
for the manufacture of useful
plastics
such as
polyacrylonitrile
. It is
reactive
and
toxic
at low doses.
[5]
Production
[
edit
]
Acrylonitrile was first synthesized by the French chemist
Charles Moureu
in 1893.
[7]
Acrylonitrile is produced by
catalytic
ammoxidation
of
propylene
, also known as the
SOHIO
process. In 2002, world production capacity was estimated at 5 million tonnes per year,
[5]
[8]
rising to about 6 million tonnes by 2017.
[9]
Acetonitrile
and
hydrogen cyanide
are significant byproducts that are recovered for sale.
[5]
In fact, the
2008?2009 acetonitrile shortage
was caused by a decrease in demand for acrylonitrile.
[10]
- 2 CH
3
?CH=CH
2
+ 2 NH
3
+ 3 O
2
→ 2 CH
2
=CH?C≡N + 6 H
2
O
In the SOHIO process,
propylene
,
ammonia
, and air (oxidizer) are passed through a
fluidized bed reactor
containing the catalyst at 400?510 °C and 50?200 kPa
g
. The reactants pass through the reactor only once, before being quenched in aqueous sulfuric acid. Excess propylene, carbon monoxide, carbon dioxide, and dinitrogen that do not dissolve are vented directly to the atmosphere, or are incinerated. The aqueous solution consists of acrylonitrile, acetonitrile,
hydrocyanic acid
, and
ammonium sulfate
(from excess ammonia). A recovery column removes bulk water, and acrylonitrile and acetonitrile are separated by distillation. One of the first useful catalysts was
bismuth
phosphomolybdate
(
Bi
9
PMo
12
O
52
)
supported
on silica.
[11]
Further improvements have since been made.
[5]
Alternative routes
[
edit
]
Various
green chemistry
routes to acrylonitrile are being explored from renewable feedstocks, such as
lignocellulosic biomass
,
glycerol
(from
biodiesel
production), or
glutamic acid
(which can itself be produced from renewable feedstocks). The lignocellulosic route involves fermentation of the biomass to
propionic acid
and
3-hydroxypropionic acid
, which are then converted to acrylonitrile by dehydration and
ammoxidation
.
[12]
[9]
The glycerol route begins with its
dehydration
to
acrolein
, which undergoes ammoxidation to give acrylonitrile.
[13]
The glutamic acid route employs
oxidative decarboxylation
to 3-cyanopropanoic acid, followed by a decarbonylation-elimination to acrylonitrile.
[14]
Of these, the glycerol route is broadly considered to be the most viable, although none of these green methods are commercially competitive.
[12]
[13]
Uses
[
edit
]
Acrylonitrile is used principally as a
monomer
to prepare
polyacrylonitrile
, a
homopolymer
, or several important
copolymers
, such as
styrene-acrylonitrile
(SAN),
acrylonitrile butadiene styrene
(ABS),
acrylonitrile styrene acrylate
(ASA), and other
synthetic rubbers
such as
acrylonitrile butadiene
(NBR).
Hydrodimerization
of acrylonitrile
[15]
[16]
affords
adiponitrile
, used in the synthesis of certain
nylons
:
- 2 CH
2
=CHCN + 2 e
?
+ 2 H
+
→ NCCH
2
?CH
2
?CH
2
?CH
2
CN
Acrylonitrile is also a precursor in the manufacture of
acrylamide
and
acrylic acid
.
[5]
Synthesis of chemicals
[
edit
]
Hydrogenation of acrylonitrile is one route to propionitrile. Hydrolysis with sulfuric acid gives acrylamide sulfate,
CH=CHC(O)NH
2
·H
2
SO
4
. This salt can be converted to
acrylamide
with treatment with base or to
methyl acrylate
by treatment with
methanol
.
[5]
The reaction of acrylonitrile with protic nucleophiles is a common route to a variety of specialty chemicals. The process is called
cyanoethylation
:
- YH + H
2
C=CHCN → Y?CH
2
?CH
2
CN
Typical protic nucleophiles are
alcohols
,
thiols
, and especially
amines
.
[17]
Acrylonitrile and derivatives, such as 2-chloroacrylonitrile, are
dienophiles
in
Diels?Alder reactions
.
Health effects
[
edit
]
Acrylonitrile is moderately
toxic
with
LD50
= 81 mg/kg (rats). It undergoes
explosive
polymerization
. The burning material releases fumes of
hydrogen cyanide
and
oxides of nitrogen
. It is classified as a
Class 2B carcinogen
(possibly carcinogenic) by the
International Agency for Research on Cancer
(IARC),
[18]
and workers exposed to high levels of airborne acrylonitrile are diagnosed more frequently with
lung cancer
than the rest of the population.
[19]
Acrylonitrile is one of seven
toxicants
in
cigarette
smoke that are most associated with
respiratory tract
carcinogenesis
.
[20]
The mechanism of action of acrylonitrile appears to involve oxidative stress and oxidative DNA damage.
[21]
Acrylonitrile increases cancer in high dose tests in male and female rats and mice
[22]
and induces
apoptosis
in human umbilical cord
mesenchymal stem cells
.
[23]
It evaporates quickly at room temperature (20 °C) to reach dangerous concentrations;
skin irritation
, respiratory irritation, and eye irritation are the immediate effects of this exposure.
[24]
Pathways of exposure for humans include
emissions
,
auto exhaust
, and
cigarette smoke
that can expose the human subject directly if they inhale or smoke. Routes of exposure include inhalation, oral, and to a certain extent dermal uptake (tested with volunteer humans and in rat studies).
[25]
Repeated exposure causes skin sensitization and may cause central nervous system and
liver damage
.
[24]
There are two main excretion processes of acrylonitrile. The primary method is excretion in urine when acrylonitrile is metabolized by being directly conjugated to
glutathione
. The other method is when acrylonitrile is enzymatically converted into 2-cyanoethylene oxide which will produce
cyanide
end products that ultimately form
thiocyanate
, which is excreted via urine.
[25]
Exposure can thus be detected via blood draws and urine sampling.
[18]
Incidents
[
edit
]
A large amount of acrylonitrile (approximately 6500 tons) leaked from an industrial polymer plant owned by
Aksa Akrilik
after the violent
17 August earthquake
in Turkey. Over 5000 people were affected and the exposed animals had died.
[26]
The leak was only noticed by the company 8 hours after the incident. Healthcare workers did not know about the health effects of acrylonitrile and tried to treat the victims with painkillers and IV fluids.
[27]
One lawyer, Ay?e Akdemir, sued the company with 44 families as the plaintiffs.
[27]
Aksa Akrilik was sued by 200 residents who were affected by acrylonitrile.
[28]
An increase in cancer cases in the area was confirmed by the
Turkish Medical Association
,
[28]
as the cancer rate in the affected area has increased by 80%, from 1999 to April 2002.
[27]
In 2003, the owner of Aksa Akrilik has died from lung cancer related to acrylonitrile exposure.
[27]
As of 2001, this is the largest acrylonitrile leak known.
[26]
Occurrence
[
edit
]
Acrylonitrile is not naturally formed on Earth. It has been detected at the sub-ppm level at industrial sites. It persists in the air for up to a week. It decomposes by reacting with oxygen and hydroxyl radical to form
formyl cyanide
and
formaldehyde
.
[29]
Acrylonitrile is
harmful to aquatic life
.
[24]
Acrylonitrile has been detected in the atmosphere of
Titan
, a moon of
Saturn
.
[30]
[31]
[32]
Computer simulations suggest that on Titan conditions exist such that the compound could form structures similar to
cell membranes
and
vesicles
on Earth, called
azotosomes.
[30]
[31]
References
[
edit
]
- ^
a
b
c
d
e
f
g
h
NIOSH Pocket Guide to Chemical Hazards.
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- ^
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.
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.
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.
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.
External links
[
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]