Epichlorohydrin

Last updated
(±)-Epichlorohydrin [1]
Epichlorohydryna.svg
R-Epichlorohydrin-calculated-MP2-3D-balls.png
(R)-Epichlorohydrin
S-Epichlorohydrin-calculated-MP2-3D-balls.png
(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 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 203-439-8
164180
KEGG
PubChem CID
RTECS number
  • TX4900000
UNII
UN number 2023
  • InChI=1S/C3H5ClO/c4-1-3-2-5-3/h3H,1-2H2 Yes check.svgY
    Key: BRLQWZUYTZBJKN-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C3H5ClO/c4-1-3-2-5-3/h3H,1-2H2
    Key: BRLQWZUYTZBJKN-UHFFFAOYAY
  • ClCC1CO1
Properties
C3H5ClO
Molar mass 92.52 g/mol
Appearancecolorless 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:
GHS-pictogram-flamme.svg GHS-pictogram-acid.svg GHS-pictogram-skull.svg GHS-pictogram-exclam.svg GHS-pictogram-silhouette.svg
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.svgHealth 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).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

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.

Contents

Production

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]

Epichlorohydrin-manufacture-step1-2D-skeletal.png

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

Epichlorohydrin-manufacture-step2-2D-skeletal.png

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

Glycerol routes

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]

GTE-Prozess.svg

Other routes

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

Applications

Glycerol and epoxy resins synthesis

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

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

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]

Related Research Articles

<span class="mw-page-title-main">Epoxide</span> Organic compounds with a carbon-carbon-oxygen ring

In organic chemistry, an epoxide is a cyclic ether, where the ether forms a three-atom ring: two atoms of carbon and one atom of oxygen. This triangular structure has substantial ring strain, making epoxides highly reactive, more so than other ethers. They are produced on a large scale for many applications. In general, low molecular weight epoxides are colourless and nonpolar, and often volatile.

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

Allyl chloride is the organic compound with the formula CH2=CHCH2Cl. This colorless liquid is insoluble in water but soluble in common organic solvents. It is mainly converted to epichlorohydrin, used in the production of plastics. It is a chlorinated derivative of propylene. It is an alkylating agent, which makes it both useful and hazardous to handle.

In organic chemistry a halohydrin is a functional group in which a halogen and a hydroxyl are bonded to adjacent carbon atoms, which otherwise bear only hydrogen or hydrocarbyl groups. The term only applies to saturated motifs, as such compounds like 2-chlorophenol would not normally be considered halohydrins. Megatons of some chlorohydrins, e.g. propylene chlorohydrin, are produced annually as precursors to polymers.

<span class="mw-page-title-main">Chlorobenzene</span> Aromatic organochlorine compound

Chlorobenzene is an aromatic organic compound with the chemical formula C6H5Cl. This colorless, flammable liquid is a common solvent and a widely used intermediate in the manufacture of other chemicals.

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

Diethylenetriamine (abbreviated Dien or DETA) and also known as 2,2’-Iminodi(ethylamine)) is an organic compound with the formula HN(CH2CH2NH2)2. This colourless hygroscopic liquid is soluble in water and polar organic solvents, but not simple hydrocarbons. Diethylenetriamine is structural analogue of diethylene glycol. Its chemical properties resemble those for ethylene diamine, and it has similar uses. It is a weak base and its aqueous solution is alkaline. DETA is a byproduct of the production of ethylenediamine from ethylene dichloride.

<span class="mw-page-title-main">Allyl alcohol</span> Organic compound (CH2=CHCH2OH)

Allyl alcohol is an organic compound with the structural formula CH2=CHCH2OH. Like many alcohols, it is a water-soluble, colourless liquid. It is more toxic than typical small alcohols. Allyl alcohol is used as a raw material for the production of glycerol, but is also used as a precursor to many specialized compounds such as flame-resistant materials, drying oils, and plasticizers. Allyl alcohol is the smallest representative of the allylic alcohols.

Vinyl ester resin, or often just vinyl ester, is a resin produced by the esterification of an epoxy resin with acrylic or methacrylic acids. The "vinyl" groups refer to these ester substituents, which are prone to polymerize and thus an inhibitor is usually added. The diester product is then dissolved in a reactive solvent, such as styrene, to approximately 35–45 percent content by weight. Polymerization is initiated by free radicals, which are generated by UV-irradiation or peroxides.

2-Chloroethanol (also called ethylene chlorohydrin or glycol chlorohydrin) is an organic chemical compound with the chemical formula HOCH2CH2Cl and the simplest beta-halohydrin (chlorohydrin). This colorless liquid has a pleasant ether-like odor. It is miscible with water. The molecule is bifunctional, consisting of both an alkyl chloride and an alcohol functional group.

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

Methacrylic acid, abbreviated MAA, is an organic compound with the formula CH2=C(CH3)COOH. This colorless, viscous liquid is a carboxylic acid with an acrid unpleasant odor. It is soluble in warm water and miscible with most organic solvents. Methacrylic acid is produced industrially on a large scale as a precursor to its esters, especially methyl methacrylate (MMA), and to poly(methyl methacrylate) (PMMA).

Synthetic resins are industrially produced resins, typically viscous substances that convert into rigid polymers by the process of curing. In order to undergo curing, resins typically contain reactive end groups, such as acrylates or epoxides. Some synthetic resins have properties similar to natural plant resins, but many do not.

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

Crotonaldehyde is a chemical compound with the formula CH3CH=CHCHO. The compound is usually sold as a mixture of the E- and Z-isomers, which differ with respect to the relative position of the methyl and formyl groups. The E-isomer is more common (data given in Table is for the E-isomer). This lachrymatory liquid is moderately soluble in water and miscible in organic solvents. As an unsaturated aldehyde, crotonaldehyde is a versatile intermediate in organic synthesis. It occurs in a variety of foodstuffs, e.g. soybean oils.

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

Propargyl alcohol, or 2-propyn-1-ol, is an organic compound with the formula C3H4O. It is the simplest stable alcohol containing an alkyne functional group. Propargyl alcohol is a colorless viscous liquid that is miscible with water and most polar organic solvents.

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

Glycidol is an organic compound that contains both epoxide and alcohol functional groups. Being bifunctional, it has a variety of industrial uses. The compound is a slightly viscous liquid that is slightly unstable and is not often encountered in pure form.

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

Trimethylolpropane (TMP) is the organic compound with the formula CH3CH2C(CH2OH)3. This colourless to white solid with a faint odor is a triol. Containing three hydroxy functional groups, TMP is a widely used building block in the polymer industry.

<span class="mw-page-title-main">Bisphenol A diglycidyl ether</span> Chemical compound

Bisphenol A diglycidyl ether is an organic compound and is a liquid epoxy resin. The compound is a colorless viscous liquid. It is a key component of many epoxy resin formulations. Addition of further Bisphenol A and a catalyst and heat can produce Bisphenol A glycidyl ether epoxy resins of higher molecular weight that are solid.

<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.

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

Cyclohexanedimethanol (CHDM) is a mixture of isomeric organic compounds with formula C6H10(CH2OH)2. It is a colorless low-melting solid used in the production of polyester resins. Commercial samples consist of a mixture of cis and trans isomers. It is a di-substituted derivative of cyclohexane and is classified as a diol, meaning that it has two OH functional groups. Commercial CHDM typically has a cis/trans ratio of 30:70.

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

Allyl glycidyl ether is an organic compound used in adhesives and sealants and as a monomer for polymerization reactions. It is formally the condensation product of allyl alcohol and glycidol via an ether linkage. Because it contains both an alkene and an epoxide group, either group can be reacted selectively to yield a product where the other functional group remains intact for future reactions.

<i>m</i>-Xylylenediamine Chemical compound

m-Xylylenediamine is an organic compound with the formula C6H4(CH2NH2)2. A colorless oily liquid, it is produced by hydrogenation of isophthalonitrile.

4,4'-Diaminodicyclohexylmethane is the name for organic compounds with the formula CH2(C6H10NH2)2. It is classified as a diamine. In the epoxy industry it is often referred to as PACM, short for para-diamino­dicyclohexyl­methane. It is used as a curing agent for epoxy resins It finds particular use in epoxy flooring. Another use is to produce diisocyanates, which are precursors to polyurethanes. The mixture is a colorless solid, but typical samples are yellowish and oily. The compound is produced as a mixture of three isomers by the hydrogenation of methylenedianiline. These isomers are, in decreasing order of their yield from the hydrogenation, trans-trans, cis-trans, and a small amount of cis-cis.

References

  1. ↑ Merck Index, 12th Edition, 3648.
  2. 1 2 3 4 5 6 NIOSH Pocket Guide to Chemical Hazards. "#0254". National Institute for Occupational Safety and Health (NIOSH).
  3. 1 2 "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.
  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.
  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. 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. ↑ "GE Healthcare Life Sciences - Instructions for Sephadex Media". .gelifesciences.com. Archived from the original on 2012-02-18. Retrieved 2011-12-02.
  18. ↑ "EPA Integrated Risk Information System: Epichlorohydrin (CASRN 106-89-8)" . Retrieved 2013-05-07.
  19. ↑ "Government of Canada: Screening Assessment for Epichlorohydrin" . 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" . Retrieved 2013-05-07.
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