Chemistry:Hexamethylenediamine

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Hexamethylenediamine[1][2]
Skeletal formula of hexamethylenediamine
Ball and stick model of hexamethylenediamine
Spacefill model of hexamethylenediamine
Names
Preferred IUPAC name
Hexane-1,6-diamine[3]
Other names
  • 1,6-Diaminohexane
  • 1,6-Hexanediamine
Identifiers
3D model (JSmol)
1098307
ChEBI
ChEMBL
ChemSpider
DrugBank
EC Number
  • 204-679-6
2578
MeSH 1,6-diaminohexane
RTECS number
  • MO1180000
UNII
UN number 2280
Properties
C6H16N2
Molar mass 116.208 g·mol−1
Appearance Colourless crystals
Density 0.84 g/mL
Melting point 39 to 42 °C (102 to 108 °F; 312 to 315 K)
Boiling point 204.6 °C; 400.2 °F; 477.7 K
490 g L−1
log P 0.386
Thermochemistry
−205 kJ mol−1
Hazards
GHS pictograms GHS05: Corrosive GHS07: Harmful
GHS Signal word DANGER
H302, H312, H314, H335
P261, P280, P305+351+338, P310
NFPA 704 (fire diamond)
Flammability code 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 fuelHealth code 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasReactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no codeNFPA 704 four-colored diamond
2
3
0
Flash point 80 °C (176 °F; 353 K)
Explosive limits 0.7–6.3%
Lethal dose or concentration (LD, LC):
  • 750 mg kg−1 (oral, rat)
  • 1.11 g kg−1 (dermal, rabbit)
Related compounds
Related alkanamines
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

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.[4]

Synthesis

Hexamethylenediamine was first reported by Theodor Curtius.[5] It is produced by the hydrogenation of adiponitrile:

NC(CH2)4CN + 4 H2 → H2N(CH2)6NH2

The hydrogenation is conducted on molten adiponitrile diluted with ammonia,[6] typical catalysts being based on cobalt and iron. The yield is good, but commercially significant side products are generated by virtue of reactivity of partially hydrogenated intermediates. These other products include 1,2-diaminocyclohexane, hexamethyleneimine, and the triamine bis(hexamethylenetriamine).

An alternative process uses Raney nickel as the catalyst and adiponitrile that is diluted with hexamethylenediamine itself (as the solvent). This process operates without ammonia and at lower pressure and temperature.[4]

Applications

Hexamethylenediamine is used almost exclusively for the production of polymers, an application that takes advantage of its structure.[7][8] It is difunctional in terms of the amine groups and tetra functional with respect to the amine hydrogens. The great majority of the diamine is consumed by the production of nylon 66 via condensation with adipic acid. Otherwise hexamethylene diisocyanate (HDI) is generated from this diamine by phosgenation as a monomer feedstock in the production of polyurethane.[9][10] The diamine also serves as a cross-linking agent in epoxy resins.[11][12][13]

Safety

Hexamethylenediamine is moderately toxic, with -1">50 of 792–1127 mg/kg.[4][14][15] Nonetheless, like other basic amines, it can cause serious burns and severe irritation. Such injuries were observed in the accident at the BASF site in Seal Sands, near Billingham (UK) on 4 January 2007 in which 37 persons were injured, one of them seriously.[16][17]

See also

References

  1. ↑ Merck Index, 11th Edition, 4614.
  2. ↑ MSDS
  3. ↑ "1,6-diaminohexane - Compound Summary". PubChem Compound. USA: National Center for Biotechnology Information. 26 March 2005. Identification and Related Records. https://pubchem.ncbi.nlm.nih.gov/summary/summary.cgi?cid=16402&loc=ec_rcs#x291. Retrieved 29 May 2012. 
  4. ↑ 4.0 4.1 4.2 Robert A. Smiley "Hexamethylenediamine" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005. doi:10.1002/14356007.a12_629
  5. ↑ Curtius, Theodor and Clemm, Hans (1900) "Synthese des 1,3-Diaminopropans und 1,6-Diaminohexans aus Glutarsäure resp. Korksäure" (Synthesis of 1,3-diaminopropane and 1,6-diaminohexane from glutaric acid and suberic acid, respectively), Journal für praktische Chemie, 2nd series, 62 : 189–211.
  6. ↑ "SRIC Report - Report 31C - Advances in Adiponitrile (ADN) and Hexamethylenediamine (HMDA) Processes | IHS Markit". https://ihsmarkit.com/products/SRICReport-Report31C-AdvancesinAdiponitrileADNandHexamethylenediamineHMDAProcesses.html. 
  7. ↑ Longseng, Rutchanon; Khaokong, Chuanpit (2020-12-01). "Hexamethylene diamine-modified epoxidized natural rubber and its effect on cure characteristics and properties of natural rubber blends" (in en). Iranian Polymer Journal 29 (12): 1113–1121. doi:10.1007/s13726-020-00865-x. ISSN 1735-5265. https://doi.org/10.1007/s13726-020-00865-x. 
  8. ↑ Hu, Juncheng; Feng, Xia; Liu, Zhengyi; Zhao, Yiping; Chen, Li (July 2017). "Surface amine-functionalization of UHMWPE fiber by bio-inspired polydopamine and grafted hexamethylene diamine: Surface amine-functionalization of UHMWPE fiber by PDA and HMDA" (in en). Surface and Interface Analysis 49 (7): 640–646. doi:10.1002/sia.6203. https://onlinelibrary.wiley.com/doi/10.1002/sia.6203. 
  9. ↑ Kim, C. K.; Kim, B. K.; Jeong, H. M. (1991-09-01). "Aqueous dispersion of polyurethane ionomers from hexamethylene diisocyanate and trimellitic anhydride" (in en). Colloid and Polymer Science 269 (9): 895–900. doi:10.1007/BF00657306. ISSN 1435-1536. https://doi.org/10.1007/BF00657306. 
  10. ↑ Hu, Jin; Chen, Zhuo; He, Yong; Huang, Hong; Zhang, Xinya (2017-05-01). "Synthesis and structure investigation of hexamethylene diisocyanate (HDI)-based polyisocyanates" (in en). Research on Chemical Intermediates 43 (5): 2799–2816. doi:10.1007/s11164-016-2795-1. ISSN 1568-5675. https://doi.org/10.1007/s11164-016-2795-1. 
  11. ↑ Luňák, S.; Dušek, K. (2007-03-08). "Curing of epoxy resins. II. Curing of bisphenol a diglycidyl ether with diamines" (in en). Journal of Polymer Science: Polymer Symposia 53 (1): 45–55. doi:10.1002/polc.5070530108. https://onlinelibrary.wiley.com/doi/10.1002/polc.5070530108. 
  12. ↑ Dušek, K.; Pleštil, J.; Lednický, F.; Luňák, S. (1978-04-01). "Are cured epoxy resins inhomogeneous?" (in en). Polymer 19 (4): 393–397. doi:10.1016/0032-3861(78)90243-4. ISSN 0032-3861. https://dx.doi.org/10.1016/0032-3861%2878%2990243-4. 
  13. ↑ Lainioti, Georgia Ch.; Savva, Panagiota; Druvari, Denisa; Avramidis, Pavlos; Panagiotaras, Dionisios; Karellou, Eva Iris Eleftheria; Kallitsis, Joannis K. (2021-08-01). "Cross-linking of antimicrobial polymers with hexamethylene diamine to prevent biofouling in marine applications" (in en). Progress in Organic Coatings 157: 106336. doi:10.1016/j.porgcoat.2021.106336. ISSN 0300-9440. https://www.sciencedirect.com/science/article/pii/S0300944021002071. 
  14. ↑ "MSDS - H11696". https://www.sigmaaldrich.com/MSDS/MSDS/DisplayMSDSPage.do?country=US&language=en&productNumber=H11696&brand=ALDRICH&PageToGoToURL=https://www.sigmaaldrich.com/catalog/product/aldrich/h11696?lang=en. 
  15. ↑ Kennedy, Gerald L. (2005). "Toxicity of hexamethylenediamine". Drug and Chemical Toxicology 28 (1): 15–33. doi:10.1081/dct-39681. ISSN 0148-0545. PMID 15720033. https://pubmed.ncbi.nlm.nih.gov/15720033/. 
  16. ↑ BBC News
  17. ↑ BBC News



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