Reactivity Profile
ACROLEIN, [INHIBITED] can react violently with oxidizing agents. Polymerizes exothermically on contact with small amounts of acids (including sulfur dioxide), alkalis, volatile amines and pyridines, salts, thiourea, oxidizing agents (air) and on exposure to light and heat. Polymerization initiated by amines and pyridines occurs after a deceptive induction period. Water solutions of mineral acids and metal ions can initiate polymerization. The inhibitor (usually hydroquinone) greatly reduces tendency to polymerize. Undergoes Diels-Alder reaction with itself to give acrolein dimer. This can become a runaway reaction at 90°C [Kirk-Othmer, 4th Ed, Vol. 1]. Mixing in equal molar portions with any of the following substances in a closed container caused the temperature and pressure to increase: 2-aminoethanol, ammonium hydroxide, chlorosulfonic acid, ethylenediamine, ethyleneimine [NFPA 1991].
Air & Water Reactions
Highly flammable. A dangerous fire risk [Hawley]. Water soluble. Reacts slowly and exothermically with water to give 3-hydroxypropionaldehyde. A hazard can develop from this reaction if acrolein is stored over a layer of water.
Health Hazard
Extremely toxic; probable oral human lethal dose is 5-50 mg/kg, between 7 drops and one teaspoon for a 70 kg (150 lb.) person. Inhalation of air containing 10 ppm of acrolein may be fatal in a few minutes. Death from cardiac failure accompanied by hyperemia and hemorrhage of the lungs and degeneration of the bronchial epithelium is possible. Acrolein causes acute respiratory and eye irritation; severe gastrointestinal distress with slowly developing pulmonary edema (lungs fill up with fluid); and skin irritation.
Potential Exposure
Used as pharmaceutical; slimicide; and in production of cosmetics and food supplements; as an intermediate in the production of glycerine and in the production of methionine analogs (poultry feed protein supplements). It is also used in chemical synthesis (1,3,6-hexametriol and glutaraldehyde); as a liquid fuel; antimicrobial agent, in algae and aquatic weed control; and as a slimicide in paper manufacture; making plastics, drugs, and tear gas. Also, most allyl compounds may be metabolized to allyl alcohol which is metabolized to acrolein.
Fire Hazard
Under fire conditions, polymerization may occur. If inside a container, violent rupture of the container may take place. When heated to decomposition, ACROLEIN, INHIBITED emits highly toxic fumes. Alkalis or strong acids act as catalysts, causing a condensation reaction and liberating energy. Reaction may be very rapid and violent. Readily converted by oxygen to hazardous peroxides and acids. Unstable, avoid exposure to alkalis, strong acids, oxygen, elevated temperatures, such as fire conditions. (Polymerization inside container could cause violent rupture of container under fire conditions.)
First aid
If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 minutes, occasionally lifting upper and lower lids. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attentionGive large quantities of water and induce vomiting. Do not make an unconscious person vomit. Medical observation is recommended for 24 to 48 hours after breathing overexposure, as pulmonary edema may be delayed
Shipping
Acrolein, stabilized, Hazard class: 6.1; Labels: 6.1-Poison Inhalation Hazard, 3-Flammable liquids. Inhalation Hazard Zone A.
Incompatibilities
May form explosive mixture with air. Elevated temperatures or sunlight may cause explosive polymerization. A strong reducing agent; reacts violently with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.); contact may cause fires or explosions. Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides. Polymerizes exothermically on contact with small amounts of acids (including sulfur dioxide), alkalis, volatile amines and pyridines, salts, thiourea, oxidizing agents (air) and on exposure to light, and heat. Polymerization initiated by amines and pyridines occurs after a deceptive induction period. Water solutions of mineral acids and metal ions can initiate polymerization. The inhibitor (usually hydroquinone) greatly reduces tendency to polymerize. Reacts with acids, alkalis, ammonia, amines, oxygenperoxides. Shock-sensitive peroxides or acids may be formed over time. Attacks zinc and cadmium
Description
The first time that acrolein was produced as a commercial
product was in the 1930s through the vapor-phase condensation
of acetaldehyde and formaldehyde. Another method was
developed in the 1940s, which involved the vapor-phase
oxidation of propylene. In the 1960s, some advances were
found in propylene oxidation process by the introduction of
bismuth molybdate-based catalysis, and that became the
primary method used for the commercial production of acrolein.
Some bioproducts formed for this reaction are acrylic acid,
carbon oxides, acetaldehyde, acetic acid, formaldehyde, and
polyacrolein. In World War I, it was used as a chemical weapon
(pulmonary irritant and lachrymatory agent). Commercial
acrolein contains 95.5% or more of the compound, the main
impurities being water (<3.0% by weight) and other carbonyl
compounds (<1.5% by weight), mainly propanol and acetone.
Hydroquinone is added as an inhibitor of polymerization
(0.1–0.25% by weight).
Waste Disposal
Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant (≥100 kg/mo) must conform with EPA regulations governing storage, transportation, treatment, and waste disposal. Incineration. Conditions are 816 C, 0.5 second minimum for primary combustion; 1093 C, 1.0 second for secondary combustion.
Physical properties
Colorless to yellow, clear, watery liquid imparting a very sharp, acrid, pungent, or irritating odor.
Odor threshold concentrations reported were 0.11 mg/kg by Guadagni et al. (1963), 0.21 ppmv by
Leonardos et al. (1969), and 36 ppbv by Nagata and Takeuchi (1990). In addition, Katz and Talbert
(1930) reported an experimental detection odor threshold concentration of 4.1 mg/m3 (1.8 ppmv).
Definition
A colorless liquid unsaturated aldehyde with a pungent odor. It can
be polymerized to make acrylate resins.
Flammability and Explosibility
Acrolein is a highly flammable liquid (NFPA rating = 3) and its vapor can travel a
considerable distance and "flash back." Acrolein vapor forms explosive mixtures
with air at concentrations of 2.8 to 31% (by volume). Carbon dioxide or dry
chemical extinguishers should be used for acrolein fires.
Carcinogenicity
Acrolein is a reactive intermediate
of the commonly used chemotherapeutic drugs cyclophosphamide
and ifosphamide. Acrolein-modified
DNA was found in human peripheral blood lymphocytes
from cancer patients previously treated with cyclophosphamide
(a chemotherapeutic), but no association was
found for cyclophosphamine. Acrolein has a classification
of C, possible human carcinogen, based on limited
animal carcinogenicity data and paucity of human evidence
for this effect.
Source
Reported in cigarette smoke (150 ppm) and gasoline exhaust (0.2 to 5.3 ppm) (quoted,
Verschueren, 1983). May be present as an impurity in 2-methoxy-3,4-dihydro-2H-pyran (Ballantyne et al., 1989a).
Acrolein was detected in diesel fuel at a concentration of 3,400 μg/g (Schauer et al., 1999).
Gas-phase tailpipe emission rates from California Phase II reformulated gasoline-powered
automobiles with and without catalytic converters were 0.06 and 3.8 mg/km, respectively (Schauer
et al., 2002).
Schauer et al. (2001) measured organic compound emission rates for volatile organic
compounds, gas-phase semi-volatile organic compounds, and particle phase organic compounds
from the residential (fireplace) combustion of pine, oak, and eucalyptus. The gas-phase emission
rates of acrolein were 63 mg/kg of pine burned, 44 mg/kg of oak burned, and 56 mg/kg of
eucalyptus burned.
Environmental Fate
Biological. Microbes in site water degraded acrolein to β-hydroxypropionaldehyde
(Kobayashi and Rittman, 1982). This product also forms when acrolein is hydrated in
distilled water (Burczyk et al., 1968). When 5 and 10 mg/L of acrolein were statically
incubated in the dark at 25°C with yeast extract and settled domestic wastewater inoculum,
complete degradation was observed after 7 days (Tabak et al., 1981). Activated sludge
was capable of degrading acrolein at concentrations of 2,300 ppm but no other information
was provided (Wierzbicki and Wojcik, 1965)
Photolytic. Photolysis products include carbon monoxide, ethylene, free radicals and
a polymer (Calvert and Pitts, 1966). Anticipated products from the reaction of acrylonitrile
with ozone or hydroxyl radicals in the atmosphere are glyoxal, forma
Groundwater. The half-life for acrolein in groundwater was estimated to range from
14 days to 8 weeks (Howard et al., 1991)
Chemical/Physical. Wet oxidation of acrolein at 320°C yielded formic and acetic acids
(Randall and Knopp, 1980). May polymerize in the presence of light and explosively in
the presence of concentrated acids (Worthing and Hance, 1991) forming disacryl, a white
plastic solid (Windholz et al., 1983; Humburg et al., 1989). In distilled water, acroleinwas hydrolyzed to β-hydroxypropionaldehyde (Burczyk et al., 1968; Reinert and Rodgers,
1987; Kollig, 1993). The reported hydrolysis rate constant at pH 7 is 6.68 × 108/year
(Kollig, 1993). The estimated hydrolysis half-life in water is 22 days (Burczyk et al., 1968)
Metabolic pathway
When fish are exposed to 14C-acrolein, the
metabolites are identified from the edible tissues and
there is very little similarity in the metabolism of
acrolein among the test species. The most notable
observation is that acrolein is never detected in any
tissues sampled, and glycidol, glycerol, 1,3-
propanediol, and glyceric acid are the major
metabolites found in catfish, crayfish, bluegill, and
clams, respectively.
storage
Work with acrolein
should be conducted in a fume hood to prevent exposure by inhalation, and splash
goggles and butyl rubber gloves should be worn at all times to prevent eye and skin
contact. Acrolein should be used only in areas free of ignition sources. Containers of
acrolein should be stored in secondary containers in areas separate from amines,
oxidizers, acids, and bases.
Purification Methods
Purify acrolein by fractional distillation, under nitrogen, drying with anhydrous CaSO4 and then distilling under vacuum. Blacet, Young and Roof [J Am Chem Soc 59 608 1937] distilled it under nitrogen through a 90cm column packed with glass rings. To avoid formation of diacryl, the vapour is passed through an ice-cooled condenser into a receiver cooled in an ice-salt mixture and containing 0.5g catechol. The acrolein is then distilled twice from anhydrous CuSO4 at low pressure, catechol being placed in the distilling flask and the receiver to avoid polymerization. [Alternatively, hydroquinone (1% of the final solution) can be used.] [Beilstein 1 IV 3435.]
Toxicity evaluation
The main acrolein route of exposure is through smoke. Acrolein
is produced as a by-product of combustion of organic
compounds, being present in a large spectrum of different
smoke produced by, for example, cigarettes, petrochemical
fuels (like gasoline or oil), synthetic polymers, paraffin wax,
trees, plants, food, animals, vegetables fats, and building fires.
Additional exposure can be linked to traffic accidents or to
water treated with biocides that contain acrolein. Improperly
handled hazardous waste sites can release acrolein into the
nearby environment (air, water, or soil).
