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Epichlorohydrin

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(±)-Epichlorohydrin[1]
Epichlorohydrin skeletal structure
(R)-Epichlorohydrin
(S)-Epichlorohydrin
Names
Preferred IUPAC name
2-(Chloromethyl)oxirane
Other names
(Chloromethyl)oxirane
Epichlorohydrin
1-Chloro-2,3-epoxypropane
γ-Chloropropylene oxide
Glycidyl chloride
ECH
Identifiers
3D model (JSmol)
79785
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.003.128 Edit this at Wikidata
EC Number
  • 203-439-8
164180
KEGG
RTECS number
  • TX4900000
UNII
UN number 2023
  • InChI=1S/C3H5ClO/c4-1-3-2-5-3/h3H,1-2H2 checkY
    Key: BRLQWZUYTZBJKN-UHFFFAOYSA-N checkY
  • InChI=1/C3H5ClO/c4-1-3-2-5-3/h3H,1-2H2
    Key: BRLQWZUYTZBJKN-UHFFFAOYAY
  • ClCC1CO1
Properties
C3H5ClO
Molar mass 92.52 g/mol
Appearance colorless liquid
Odor garlic or chloroform-like
Density 1.1812 g/cm3
Melting point −25.6 °C (−14.1 °F; 247.6 K)
Boiling point 117.9 °C (244.2 °F; 391.0 K)
7% (20°C)[2]
Vapor pressure 13 mmHg (20°C)[2]
Hazards
GHS labelling:
GHS02: FlammableGHS05: CorrosiveGHS06: ToxicGHS07: Exclamation markGHS08: Health hazard
Danger
H226, H301, H311, H314, H317, H331, H350
P201, P202, P210, P233, P240, P241, P242, P243, P260, P261, P264, P270, P271, P272, P280, P281, P301+P310, P301+P330+P331, P302+P352, P303+P361+P353, P304+P340, P305+P351+P338, P308+P313, P310, P311, P312, P321, P322, P330, P333+P313, P361, P363, P370+P378, P403+P233, P403+P235, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 3: Liquids and solids that can be ignited under almost all ambient temperature conditions. Flash point between 23 and 38 °C (73 and 100 °F). E.g. gasolineInstability 2: Undergoes violent chemical change at elevated temperatures and pressures, reacts violently with water, or may form explosive mixtures with water. E.g. white phosphorusSpecial hazards (white): no code
3
3
2
Flash point 32 °C (90 °F; 305 K)
Explosive limits 3.8–21%[2]
Lethal dose or concentration (LD, LC):
3617 ppm (rat, 1 hr)
2165 ppm (rat, 1 hr)
250 ppm (rat, 8 hr)
244 ppm (rat, 8 hr)
360 ppm (rat, 6 hr)[3]
250 ppm (rat, 4 hr)[3]
NIOSH (US health exposure limits):
PEL (Permissible)
 TWA 5 ppm (19 mg/m3) [skin][2]
REL (Recommended)
 Carcinogen[2]
IDLH (Immediate danger)
 Ca [75 ppm][2]
Safety data sheet (SDS) External MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)

Epichlorohydrin (abbreviated ECH) is an organochlorine compound and an epoxide. Despite its name, it is not a halohydrin. It is a colorless liquid with a pungent, garlic-like odor, moderately soluble in water, but miscible with most polar organic solvents.[4] It is a chiral molecule generally existing as a racemic mixture of right-handed and left-handed enantiomers. Epichlorohydrin is a highly reactive electrophilic compound and is used in the production of glycerol, plastics, epoxy glues and resins, epoxy diluents and elastomers.

Production

[edit]

Epichlorohydrin is traditionally manufactured from allyl chloride in two steps, beginning with the addition of hypochlorous acid, which affords a mixture of two isomeric alcohols:[5][6]

In the second step, this mixture is treated with base to give the epoxide:

In this way, more than 800,000 tons (1997) of epichlorohydrin are produced annually.[7]

Glycerol routes

[edit]

Epichlorohydrin was first described in 1848 by Marcellin Berthelot. The compound was isolated during studies on reactions between glycerol and gaseous hydrogen chloride.[8]

Reminiscent of Berthelot's experiment, glycerol-to-epichlorohydrin (GTE) plants have been commercialized. This technology capitalizes on the availability of cheap glycerol from biofuels processing.[9] In the process developed by Dow Chemical, glycerol undergoes two substitution reactions when treated with hydrogen chloride in the presence of a carboxylic acid catalyst. This is the same intermediate formed in the allyl chloride/hypochlorous acid process, and is likewise then treated with base to form epichlorohydrin.[10]

Other routes

[edit]

Routes that involve fewer chlorinated intermediates have continued to attract interest. One such process entails epoxidation of allyl chloride.[11]

Applications

[edit]

Glycerol and epoxy resins synthesis

[edit]

Epichlorohydrin is mainly converted to bisphenol A diglycidyl ether, a building block in the manufacture of epoxy resins.[12] It is also a precursor to monomers for other resins and polymers. Another usage is the conversion to synthetic glycerol. However, the rapid increase in biodiesel production, where glycerol is a waste product, has led to a glut of glycerol on the market, rendering this process uneconomical. Synthetic glycerol is now used only in sensitive pharmaceutical, and biotech applications where quality standards are very high.[13]

Minor and niche applications

[edit]

Epichlorohydrin is a versatile precursor in the synthesis of many organic compounds. For example, it is converted to glycidyl nitrate, an energetic binder used in explosive and propellant compositions.[14] The epichlorohydrin is reacted with an alkali nitrate, such as sodium nitrate, producing glycidyl nitrate and alkali chloride. It is used as a solvent for cellulose, resins, and paints, and it has found use as an insect fumigant.[15]

Polymers made from epichlorohydrin, e.g., polyamide-epichlorohydrin resins, are used in paper reinforcement and in the food industry to manufacture tea bags, coffee filters, and sausage/salami casings as well as with water purification.[16]

An important biochemical application of epichlorohydrin is its use as crosslinking agent for the production of Sephadex size-exclusion chromatographic resins from dextrans.[17]

Safety

[edit]

Epichlorohydrin is classified by several international health research agencies and groups as a probable or likely carcinogen in humans.[18][19][20] Prolonged oral consumption of high levels of epichlorohydrin could result in stomach problems and an increased risk of cancer.[21] Occupational exposure to epichlorohydrin via inhalation could result in lung irritation and an increased risk of lung cancer.[22]

References

[edit]
  1. ^ Merck Index, 12th Edition, 3648.
  2. ^ a b c d e f NIOSH Pocket Guide to Chemical Hazards. "#0254". National Institute for Occupational Safety and Health (NIOSH).
  3. ^ a b "Epichlorohydrin". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  4. ^ "EPA consumer factsheet". Epa.gov. Retrieved 2011-12-02.
  5. ^ Braun, G. (1936). "Epichlorohydrin and Epybromohydrin". Organic Syntheses. 16: 30. doi:10.15227/orgsyn.016.0030.
  6. ^ Guenter Sienel; Robert Rieth; Kenneth T. Rowbottom. "Epoxides". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a09_531. ISBN 978-3527306732.
  7. ^ Ludger Krähling; Jürgen Krey; Gerald Jakobson; Johann Grolig; Leopold Miksche. "Allyl Compounds". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a01_425. ISBN 978-3527306732.
  8. ^ Berthelot, Marcellin (1854). "Sur les combinaisons de la glycérine avec les acides et sur la synthèse des principes immédiats des graisses animaux". Ann. Chim. Phys. Série 3. 41: 216–319. Archived from the original on 2015-04-02. Retrieved 2015-03-02.
  9. ^ Doris de Guzman (2011-01-20). "Growing glycerine-to-ECH plants". ICIS Green Chemicals. Archived from the original on 2012-04-19. Retrieved 2012-03-05.
  10. ^ Bell, Bruce M.; Briggs, John R.; Campbell, Robert M.; Chambers, Susanne M.; Gaarenstroom, Phil D.; Hippler, Jeffrey G.; Hook, Bruce D.; Kearns, Kenneth; et al. (2008). "Glycerin as a Renewable Feedstock for Epichlorohydrin Production. The GTE Process" (PDF). CLEAN - Soil, Air, Water. 36 (8): 657. Bibcode:2008CSAW...36..657B. doi:10.1002/clen.200800067. Archived from the original (full text reprint) on 2012-07-18. Retrieved 2012-03-05.
  11. ^ Jun Li; Gongda Zhao; Shuang Gao; Ying Lv; Jian Li; Zuwei Xi (2006). "Epoxidation of Allyl Chloride to Epichlorohydrin by a Reversible Supported Catalyst with H2O2 under Solvent-Free Conditions". Org. Process Res. Dev. 10 (5): 876–880. doi:10.1021/op060108k.
  12. ^ Pham, Ha Q.; Marks, Maurice J. (2012). "Epoxy Resins". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a09_547.pub2. ISBN 978-3-527-30673-2.
  13. ^ Taylor, Phil (16 October 2008). "Synthetic glycerine is back (but never really went away)!". In-Pharma Technologist. Retrieved 29 November 2018.[permanent dead link‍]
  14. ^ Gould, R.F. Advanced Propellant Chemistry, ACS Chemistry Series 54, 1966
  15. ^ "Suburban Water Testing Labs:Epichlorohydrin Fact Sheet". H2otest.com. Archived from the original on 2012-04-05. Retrieved 2011-12-02.
  16. ^ "Government of Canada Chemical Substances: Oxirane,(chloromethyl)-(Epichlorohydrin) CAS Registry Number 106-89-8". 13 February 2008. Retrieved 2013-05-07.
  17. ^ "Size Exclusion Chromatography | Cytiva (cytivalifesciences.com)". Size Exclusion Chromatography | Cytiva (cytivalifesciences.com). cytivalifesciences.com. Retrieved 2024-07-01.
  18. ^ "EPA Integrated Risk Information System: Epichlorohydrin (CASRN 106-89-8)". Retrieved 2013-05-07.
  19. ^ "Government of Canada: Screening Assessment for Epichlorohydrin". 27 January 2010. Retrieved 2013-05-07.
  20. ^ "NIOSH Pocket Guide to Chemical Hazards - Epichlorohydrin". Retrieved 2013-09-20.
  21. ^ "Basic Information about Epichlorohydrin in Drinking Water". Retrieved 2013-05-07.
  22. ^ "Government of Canada: Screening Assessment for Epichlorohydrin". 27 January 2010. Retrieved 2013-05-07.
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