Propylene oxide is an acutely toxic and carcinogenic organic compound with the molecular formula C3H6O. This colourless volatile liquid with an odour similar to ether, is produced on a large scale industrially. Its major application is its use for the production of polyether polyols for use in making polyurethane plastics. It is a chiralepoxide, although it is commonly used as a racemic mixture.
This compound is sometimes called 1,2-propylene oxide to distinguish it from its isomer 1,3-propylene oxide, better known as oxetane.
Production
Industrial production of propylene oxide starts from propylene.[8] Two general approaches are employed, one involving hydrochlorination and the other involving oxidation.[9] In 2005, about half of the world production was through chlorohydrin technology and one half via oxidation routes. The latter approach is growing in importance.[10]
Hydrochlorination route
The traditional route proceeds via the conversion of propene to propylene chlorohydrin according to the following simplified scheme:
The mixture of 1-chloro-2-propanol and 2-chloro-1-propanol is then dehydrochlorinated. For example:
Hydrogen peroxide is the oxidant in the hydrogen peroxide to propylene oxide (HPPO) process, catalyzed by a titanium-doped silicalite:
C3H6 + H2O2 → C3H6O + H2O
In principle, this process produces only water as a side product. In practice, some ring-opened derivatives of PO are generated.[12]
Propylene oxide is chiral building block that is commercially available in either enantiomeric form ((R)-(+) and (S)-(–)). The separated enantiomers can be obtained through a Co(III)-salen-catalyzed hydrolytic kinetic resolution of the racemic material.[13]
Reactions
Like other epoxides, PO undergoes ring-opening reactions. With water, propylene glycol is produced. With alcohols, reactions, called hydroxylpropylation, analogous to ethoxylation occur. Grignard reagents add to propylene oxide to give secondary alcohols.
Some other reactions of propylene oxide include:[14]
The United States Food and Drug Administration has approved the use of propylene oxide to pasteurize raw almonds beginning on September 1, 2007, in response to two incidents of contamination by Salmonella in commercial orchards, one incident occurring in Canada and one in the United States.[17][18]Pistachio nuts can also be subjected to propylene oxide to control Salmonella.
Microscopy
Propylene oxide is commonly used in the preparation of biological samples for electron microscopy, to remove residual ethanol previously used for dehydration. In a typical procedure, the sample is first immersed in a mixture of equal volumes of ethanol and propylene oxide for 5 minutes, and then four times in pure oxide, 10 minutes each.
Munition
Propylene oxide is sometimes used in thermobaricmunitions as the fuel in fuel–air explosives. In addition to the explosive damage from the blast wave, unexploded propylene oxide can cause additional effects from direct toxicity.[19]
Safety
Propylene oxide is both acutely toxic and carcinogenic. Acute exposure causes respiratory tractirritation, eventually leading to death.[20] Signs of toxicity after acute exposure include salivation, lacrimation, nasal discharge, gasping, lethargy and hypoactivity, weakness, and incoordination. Propylene oxide is also neurotoxic in rats, and presumably in humans [21]
^Nijhuis TA, Makkee M, Moulijn JA, Weckhuysen BM (2006). "The Production of Propene Oxide: Catalytic Processes and Recent Developments". Industrial & Engineering Chemistry Research. 45 (10): 3447–3459. doi:10.1021/ie0513090. hdl:1874/20149.
^ abNijhuis TA, Makkee M, Moulijn JA, Weckhuysen BM (2006). "The Production of Propene Oxide: Catalytic Processes and Recent Developments". Industrial & Engineering Chemistry Research. 45 (10): 3447. doi:10.1021/ie0513090. hdl:1874/20149.
^Russo V, Tesser R, Santacesaria E, Di Serio M (2013). "Chemical and Technical Aspects of Propene Oxide Production via Hydrogen Peroxide (HPPO Process)". Industrial & Engineering Chemistry Research. 52 (3): 1168–1178. doi:10.1021/ie3023862.
^Ohnishi A, Murai Y (February 1993). "Polyneuropathy due to ethylene oxide, propylene oxide, and butylene oxide". Environmental Research. 60 (2): 242–247. doi:10.1006/enrs.1993.1032. PMID8472653.
-Propylene_oxide_molecule_ball.png)
