Adiponitrile

Last updated
Adiponitrile
Adiponitrile Structural formula V.3.svg
Adiponitrile 3D ball.png
Names
Preferred 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 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 203-896-3
MeSH adiponitrile
PubChem CID
RTECS number
  • AV2625000
UNII
UN number 2205
  • InChI=1S/C6H8N2/c7-5-3-1-2-4-6-8/h1-4H2 Yes check.svgY
    Key: BTGRAWJCKBQKAO-UHFFFAOYSA-N Yes check.svgY
  • N#CCCCCC#N
Properties
C6H8N2
Molar mass 108.144 g·mol−1
AppearanceColourless 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:
GHS-pictogram-skull.svg
Danger
H301, H315, H319, H330, H335
P260, P284, P301+P310, P305+P351+P338, P310
NFPA 704 (fire diamond)
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
1,4-diisocyanobutane
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 ?)

Adiponitrile is an organic compound with the chemical formula (CH2)4(CN)2. This viscous, colourless dinitrile is an important precursor to the polymer nylon 66. In 2005, about one million tonnes of adiponitrile were produced. [4]

Contents

Production

Early methods

Because of the industrial value of adiponitrile, many methods have been developed for its synthesis. Early industrial methods 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 is rarely employed.

Modern methods

After patent application in 2004, the majority of adiponitrile is prepared by the nickel-catalysed hydrocyanation of butadiene, as discovered at DuPont, pioneered by William C. Drinkard. The net reaction is:

CH2=CHCH=CH2 + 2 HCN → NC(CH2)4CN

ButadieneHydrocyanation.svg

The process involves several stages, the first of which involves monohydrocyanation (the addition of one molecule of HCN), affording isomers of pentenenitriles as well as 2- and 3-methylbutanenitriles. 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]

3-pentenenitrile, formed in the first hydrocyanation, can undergo alkene metathesis to give dicyanobutenes, which are readily hydrogenated as described above. A useful byproduct of the production of adiponitrile is 2-methylglutaronitrile.

The other major industrial method involves hydrodimerization, starting from acrylonitrile: [5] [6]

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

AdiponitrileSynthesis.png

The electrolytic coupling of acrylonitrile was discovered at Monsanto Company.

Applications

Almost all adiponitrile is hydrogenated to hexane-1,6-diamine for the production of nylon: [7]

NC(CH2)4CN + 4 H2 → H2N(CH2)6NH2

Like other nitriles, adiponitrile is susceptible to hydrolysis; however, the resulting adipic acid is less expensively prepared via other routes.

Production

In 2018, there existed approximately 1.5 million metric tons of capacity.[ citation needed ] The main producers of adiponitrile were: [8] [9]

BASF closed the 128 kt/y ADN plant at Seal Sands in 2009. [10]

In 2015, the Shandong Runxing New Material 100 kt/y plant suffered an explosion and was not reopened. [8] In 2022, Invista plans to open a 300–400 kt/y plant in Shanghai. [11]

Safety

The LD50 (median lethal dose) of 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. [12]

The NIOSH recommended skin exposure limit for a work-related time weighted average concentration is 4ppm (18 mg/m3). [13]

Adiponitrile is classified as an extremely hazardous substance in the United States as defined in Section 302 of the U.S. Emergency Planning and Community Right-to-Know Act (42 U.S.C. 11002), and is subject to strict reporting requirements by facilities which produce, store, or use it in significant quantities. [14]

Related Research Articles

Hydrogen cyanide, sometimes called prussic acid, is a chemical compound with the formula HCN and structure H−C≡N. It is a colorless, extremely poisonous, and flammable liquid that boils slightly above room temperature, at 25.6 °C (78.1 °F). HCN is produced on an industrial scale and is a highly valued precursor to many chemical compounds ranging from polymers to pharmaceuticals. Large-scale applications are for the production of potassium cyanide and adiponitrile, used in mining and plastics, respectively. It is more toxic than solid cyanide compounds due to its volatile nature.

<span class="mw-page-title-main">Sodium cyanide</span> Chemical compound

Sodium cyanide is a poisonous compound with the formula NaCN. It is a white, water-soluble solid. Cyanide has a high affinity for metals, which leads to the high toxicity of this salt. Its main application, in gold mining, also exploits its high reactivity toward metals. It is a moderately strong base.

Acetonitrile, often abbreviated MeCN, is the chemical compound with the formula CH3CN and structure H3C−C≡N. This colourless liquid is the simplest organic nitrile. It is produced mainly as a byproduct of acrylonitrile manufacture. It is used as a polar aprotic solvent in organic synthesis and in the purification of butadiene. The N≡C−C skeleton is linear with a short C≡N distance of 1.16 Å.

Acrylonitrile is an organic compound with the formula CH2CHCN and the structure H2C=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. In terms of its molecular structure, it consists of a vinyl group linked to a nitrile. It is an important monomer for the manufacture of useful plastics such as polyacrylonitrile. It is reactive and toxic at low doses. Acrylonitrile was first synthesized by the French chemist Charles Moureu (1863–1929) in 1893.

In organic chemistry, a nitrile is any organic compound that has a −C≡N functional group. The prefix cyano- is used interchangeably with the term nitrile in industrial literature. Nitriles are found in many useful compounds, including methyl cyanoacrylate, used in super glue, and nitrile rubber, a nitrile-containing polymer used in latex-free laboratory and medical gloves. Nitrile rubber is also widely used as automotive and other seals since it is resistant to fuels and oils. Organic compounds containing multiple nitrile groups are known as cyanocarbons.

In organic chemistry, hydrocyanation is a process for conversion of alkenes to nitriles. The reaction involves the addition of hydrogen cyanide and requires a catalyst. This conversion is conducted on an industrial scale for the production of precursors to nylon.

<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).

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

Butyronitrile or butanenitrile or propyl cyanide, is a nitrile with the formula C3H7CN. This colorless liquid is miscible with most polar organic solvents.

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

Isobutanol (IUPAC nomenclature: 2-methylpropan-1-ol) is an organic compound with the formula (CH3)2CHCH2OH (sometimes represented as i-BuOH). This colorless, flammable liquid with a characteristic smell is mainly used as a solvent either directly or as its esters. Its isomers are 1-butanol, 2-butanol, and tert-butanol, all of which are important industrially.

Nitrile rubber, also known as nitrile butadiene rubber, NBR, Buna-N, and acrylonitrile butadiene rubber, is a synthetic rubber derived from acrylonitrile (ACN) and butadiene. Trade names include Perbunan, Nipol, Krynac and Europrene. This rubber is unusual in being resistant to oil, fuel, and other chemicals.

<span class="mw-page-title-main">Malononitrile</span> Organic compound with formula CH2(CN)2

Malononitrile is an organic compound nitrile with the formula CH2(CN)2. It is a colorless or white solid, although aged samples appear yellow or even brown. It is a widely used building block in organic synthesis.

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

Succinonitrile, also butanedinitrile, is a nitrile, with the formula of C2H4(CN)2. It is a colorless waxy solid which melts at 58 °C.

1,1-Dichloroethene, commonly called 1,1-dichloroethylene or vinylidene chloride or 1,1-DCE, is an organochloride with the molecular formula C2H2Cl2. It is a colorless liquid with a sharp odor. Like most chlorocarbons, it is poorly soluble in water, but soluble in organic solvents. 1,1-DCE was the precursor to the original clingwrap, Saran, for food, but this application has been phased out.

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

Hexamethylenediamine is the organic compound with the formula H2N(CH2)6NH2. The molecule is a diamine, consisting of a hexamethylene hydrocarbon chain terminated with amine functional groups. The colorless solid (yellowish for some commercial samples) has a strong amine odor. About 1 billion kilograms are produced annually.

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">Ammoxidation</span> Chemical process for producing nitriles from ammonia and oxygen

In organic chemistry, ammoxidation is a process for the production of nitriles using ammonia and oxygen. It is sometimes called the SOHIO process, acknowledging that ammoxidation was developed at Standard Oil of Ohio. The usual substrates are alkenes. Several million tons of acrylonitrile are produced in this way annually:

<span class="mw-page-title-main">Allyl acetate</span> Chemical compound

Allyl acetate is an organic compound with formula C3H5OC(O)CH3. This colourless liquid is a precursor to especially allyl alcohol, which is a useful industrial intermediate. It is the acetate ester of allyl alcohol.

Propionitrile, also known as ethyl cyanide and propanenitrile, is an organic compound with the formula CH3CH2CN. It is a simple aliphatic nitrile. The compound is a colourless, water-soluble liquid. It is used as a solvent and a precursor to other organic compounds.

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

2-Methylglutaronitrile is the organic compound with the formula NCCH2CH2CH(CH3)CN. This dinitrile is obtained in the large-scale synthesis of adiponitrile. It is a colorless liquid with an unpleasant odor. It is the starting compound for the vitamin nicotinamide and for the diester dimethyl-2-methylglutarate and the ester amide methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate, which are promoted as green solvents. 2-Methylglutaronitrile is chiral but is mainly encountered as the racemate.

Nylon 1,6 is a type of polyamide or nylon. Unlike most other nylons, nylon 1,6 is not a condensation polymer, but instead is formed by an acid-catalyzed synthesis from adiponitrile, formaldehyde, and water. The material was produced and studied by researchers at DuPont in the 1950s. Synthesis can be performed at room temperature in open beakers.

References

  1. ↑ "adiponitrile - Compound Summary". PubChem Compound. USA: National Center for Biotechnology Information. 26 March 2005. Identification. Retrieved 15 June 2012.
  2. 1 2 3 4 NIOSH Pocket Guide to Chemical Hazards. "#0015". National Institute for Occupational Safety and Health (NIOSH).
  3. "Archived copy". Archived from the original on 2015-04-02. Retrieved 2015-03-26.{{cite web}}: CS1 maint: archived copy as title (link)
  4. 1 2 3 4 M. T. Musser, "Adipic Acid" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005. doi : 10.1002/14356007.a01_269
  5. ↑ Cardoso, D. S.; Šljukić, B.; Santos, D. M.; Sequeira, C. A. (2017). "Organic Electrosynthesis: From Laboratorial Practice to Industrial Applications". Organic Process Research & Development (published July 17, 2017). 21 (9): 1213–1226. doi:10.1021/acs.oprd.7b00004.
  6. ↑ Baizer, Manuel M. (1964). "Electrolytic Reductive Coupling". Journal of the Electrochemical Society. 111 (2): 215. doi:10.1149/1.2426086.
  7. ↑ Robert A. Smiley "Hexamethylenediamine" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005. doi : 10.1002/14356007.a12_629
  8. 1 2 Alexander, Tullo (7 Oct 2018). "The chemical industry is bracing for a nylon 6,6 shortage". cen.acs.org. 96 (40). Retrieved 2 March 2021.
  9. ↑ "Ascend Finalizes $175 Million ADN Project in Alabama | CHEManager". www.chemanager-online.com. Retrieved 2 March 2021.
  10. ↑ Gale, Lindsay (1 April 2009). "End of the line for Seal Sands". KHL Group. Retrieved 2 March 2021.
  11. ↑ "INVISTA China ADN project receives final construction permit". invista.com. Retrieved 2 March 2021.
  12. ↑ 2009 TLVs and BEIs, American Conference of Governmental Industrial Hygienists, Signature Publications, page 11 of 254.
  13. ↑ NIOSH Pocket Guide NIOSH Publication 2005-149; September 2005
  14. ↑ "40 C.F.R.: Appendix A to Part 355—The List of Extremely Hazardous Substances and Their Threshold Planning Quantities" (PDF) (July 1, 2008 ed.). Government Printing Office. Archived from the original (PDF) on February 25, 2012. Retrieved October 29, 2011.{{cite journal}}: Cite journal requires |journal= (help)
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