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Adiponitrile

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Adiponitrile
Structural formula of adiponitrile
Ball-and-stick model of the adiponitrile molecule
Names
IUPAC name
Hexanedinitrile[1]
Other names
  • Adipic acid dinitrile
  • Adipic acid nitrile
  • Adipyldinitrile
  • 1,4-Dicyanobutane
  • Hexanedioic acid dinitrile
  • Nitrile adipico
  • Tetramethylene cyanide
  • Tetramethylene dicyanide
Identifiers
3D model (JSmol)
1740005
ChemSpider
ECHA InfoCard 100.003.543 Edit this at Wikidata
EC Number
  • 203-896-3
MeSH adiponitrile
RTECS number
  • AV2625000
UNII
UN number 2205
  • InChI=1S/C6H8N2/c7-5-3-1-2-4-6-8/h1-4H2 checkY
    Key: BTGRAWJCKBQKAO-UHFFFAOYSA-N checkY
  • N#CCCCCC#N
Properties
C6H8N2
Molar mass 108.144 g·mol−1
Appearance Colourless liquid
Density 951 mg mL−1
Melting point 1 to 3 °C; 34 to 37 °F; 274 to 276 K
Boiling point 295.1 °C; 563.1 °F; 568.2 K
50 g/L (20 °C)
Vapor pressure 300 mPa (at 20 °C)
1.438
Thermochemistry
84.5–85.3 kJ mol−1
Hazards
GHS labelling:
GHS06: Toxic
Danger
H301, H315, H319, H330, H335
P260, P284, P301+P310, P305+P351+P338, P310
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 4: Very short exposure could cause death or major residual injury. E.g. VX 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 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
4
2
0
Flash point 93 °C; 199 °F; 366 K (open cup)[2]
550 °C (1,022 °F; 823 K)
Explosive limits 1.7–4.99%
Lethal dose or concentration (LD, LC):
155 mg kg−1 (oral, rat)
NIOSH (US health exposure limits):
PEL (Permissible)
 none[2]
REL (Recommended)
 TWA 4 ppm (18 mg/m3)[2]
IDLH (Immediate danger)
 N.D.[2]
Related compounds
Related alkanenitriles
 Glutaronitrile
Related compounds
 hexanedioic acid
hexanedihydrazide
hexanedioyl dichloride
hexanediamide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Adiponitrile is the organic compound with the formula (CH2)4(CN)2. This dinitrile, a viscous, colourless liquid, is an important precursor to the polymer nylon-6,6. In 2005, about one billion kilograms were produced annually.[4]

Production

Early routes

Because of the industrial value of adiponitrile, many methods have been developed for its synthesis. Early industrial routes started from furfural and later by the chlorination of butadiene to give 1,4-dichloro-2-butene, which with sodium cyanide, converts to 3-hexenedinitrile, which in turn can be hydrogenated to adiponitrile:[4]

ClCH2CH=CHCH2Cl + 2 NaCN → NCCH2CH=CHCH2CN + 2 NaCl
NCCH2CH=CHCH2CN + H2 → NC(CH2)4CN

Adiponitrile has also been produced from adipic acid, by dehydration of the diamide, but this route is rarely employed.

Modern routes

The majority of adiponitrile is prepared by the nickel-catalysed hydrocyanation of butadiene, as discovered at DuPont, pioneered by Drinkard. The net reaction is:

CH2=CHCH=CH2 + 2 HCN → NCCH2CH2CH2CH2CN

The process involves several stages, the first of which involves monohydrocyanation (addition of one molecule of HCN), affording isomers of pentenenitriles as well as 2- and 3-methylbutenenitriles. These unsaturated nitriles are subsequently isomerized to the 3-and 4-pentenenitriles. In the final stage, these pentenenitriles are subjected to a second hydrocyanation, in an anti-Markovnikov sense, to produce adiponitrile.[4]

Research has shown that the 3-pentenenitrile, formed in the first hydrocyanation, can undergo alkene metathesis to give dicyanobutenes, which are readily hydrogenated as described above.

The other major industrial route involves electrosynthesis, starting from acrylonitrile, which is dimerized:

2 CH2=CHCN + 2 e− + 2 H+ → NCCH2CH2CH2CH2CN

The electrolytic coupling of acrylonitrile was discovered at Monsanto Company.

Applications

Almost all adiponitrile is hydrogenated to 1,6-diaminohexane for the production of nylon:[5]

NC(CH2)4CN + 4 H2 → H2N(CH2)6NH2

Like other nitriles, adiponitrile is susceptible to hydrolysis. The resulting adipic acid however is more cheaply prepared by other routes.

Safety

The LD50 for adiponitrile is 300 mg/kg for oral ingestion by rats.[4]

In 1990, ACGIH adopted a time weighted average Threshold Limit Value of 2ppm for work related skin exposure. [6]

The NIOSH recommended skin exposure limit for a work related time weighted average concentration is 4ppm (18mg/m3). [7]

References

  1. ^ "adiponitrile - Compound Summary". PubChem Compound. USA: National Center for Biotechnology Information. 26 March 2005. Identification. Retrieved 15 June 2012.
  2. ^ a b c d NIOSH Pocket Guide to Chemical Hazards. "#0015". National Institute for Occupational Safety and Health (NIOSH).
  3. ^ http://www.nmsu.edu/safety/programs/chem_safety/NFPA-ratingA-C.htm
  4. ^ a b c d M. T. Musser, "Adipic Acid" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005. doi:10.1002/14356007.a01 269
  5. ^ Robert A. Smiley "Hexamethylenediamine" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005. doi:10.1002/14356007.a12 629
  6. ^ 2009 TLVs and BEIs, American Conference of Governmental Industrial Hygienists, Signature Publications, page 11 of 254.
  7. ^ NIOSH Pocket Guide NIOSH Publication 2005-149; September 2005
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