AcrylonitrileDescription Usage History Chemical properties Food fumigants The main purpose and role of acrylonitrile Uses Production method
- Product Name
- CAS No.
- Chemical Name
- VCN;ent54;tl314;ENT 54;TL 314;Ventox;Acritet;Acrylon;CH2CHCN;NSC 6362
- Molecular Formula
- Formula Weight
- MOL File
- Melting point:
- -83 °C (lit.)
- Boiling point:
- 77 °C (lit.)
- 0.806 g/mL at 20 °C
- vapor density
- 1.83 (vs air)
- vapor pressure
- 86 mm Hg ( 20 °C)
- refractive index
- n20/D 1.391(lit.)
- Flash point:
- 32 °F
- storage temp.
- Mild pyridine-like odor at 2 to 22 ppm
- 6.0-7.5 (50g/l, H2O, 20℃)
- Odor Threshold
- explosive limit
- Water Solubility
- Soluble. 7.45 g/100 mL
- Light Sensitive
- Henry's Law Constant
- 1.30 at 30.00 °C (headspace-GC, Hovorka et al., 2002)
- Exposure limits
- NIOSH REL: TWA 1 ppm, 15-min C 1 ppm, IDLH 85 ppm; OSHA PEL: TWA 2 ppm, 15-min C 10 ppm; ACGIH TLV: TWA 2 ppm.
- CAS DataBase Reference
- 107-13-1(CAS DataBase Reference)
- 2B (Vol. 71) 1999
- NIST Chemistry Reference
- EPA Substance Registry System
- Acrylonitrile (107-13-1)
- Hazard Codes
- Risk Statements
- Safety Statements
- UN 1093 3/PG 1
- WGK Germany
- Autoignition Temperature
- 481 °C
- HS Code
- Hazardous Substances Data
- 107-13-1(Hazardous Substances Data)
- LD50 orally in rats: 0.093 g/kg (Smyth, Carpenter)
- Signal word
- Hazard statements
H225Highly Flammable liquid and vapour
H301Toxic if swalloed
H311Toxic in contact with skin
H315Causes skin irritation
H317May cause an allergic skin reaction
H318Causes serious eye damage
H331Toxic if inhaled
H335May cause respiratory irritation
H350May cause cancer
H361Suspected of damaging fertility or the unborn child
H370Causes damage to organs
H411Toxic to aquatic life with long lasting effects
- Precautionary statements
P201Obtain special instructions before use.
P210Keep away from heat/sparks/open flames/hot surfaces. — No smoking.
P260Do not breathe dust/fume/gas/mist/vapours/spray.
P261Avoid breathing dust/fume/gas/mist/vapours/spray.
P273Avoid release to the environment.
P280Wear protective gloves/protective clothing/eye protection/face protection.
P311Call a POISON CENTER or doctor/physician.
P301+P310IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P303+P361+P353IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P305+P351+P338IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continuerinsing.
P308+P313IF exposed or concerned: Get medical advice/attention.
P405Store locked up.
P403+P233Store in a well-ventilated place. Keep container tightly closed.
- Product number
- Product name
- (stabilised with hydroquinone monomethyl ether) for synthesis
- 100 mL
- Product number
- Product name
- ≥99%, contains 35-45 ppm monomethyl ether hydroquinone as inhibitor
- Product number
- Product name
- Acrylonitrile solution
- certified reference material, 5000?μg/mL in methanol
- 1 mL
- Product number
- Product name
- ≥99%, contains 35-45 ppm monomethyl ether hydroquinone as inhibitor
- Product number
- Product name
- (stabilised with hydroquinone monomethyl ether) for synthesis
- 1 L
Acrylonitrile Chemical Properties,Usage,Production
Acrylonitrile is a colourless, flammable liquid. Its vapours may explode when exposed to an open flame. Acrylonitrile does not occur naturally. It is produced in very large amounts by several chemical industries in the United States, and its requirement and demand are increasing in recent years. Acrylonitrile is a heavily produced, unsaturated nitrile. It is used to make other chemicals such as plastics, synthetic rubber, and acrylic fibres. It has been used as a pesticide fumigant in the past; however, all pesticide uses have been discontinued. This compound is a major chemical intermediate used in creating products such as pharmaceuticals, antioxidants, and dyes, as well as in organic synthesis. The largest users of acrylonitrile are chemical industries that make acrylic and modacrylic fibres and high-impact ABS plastics. Acrylonitrile is also used in business machines, luggage, construction material, and manufacturing of styrene-acrylonitrile (SAN) plastics for automotive, household goods, and packaging material. Adiponitrile is used to make nylon, dyes, drugs, and pesticides.
On the eve of World War II, it was discovered that acrylonitrile copolymer can improve the oil resistance and solvent resistance of synthetic rubber and people began to be taken it seriously. During the war, it was developed in Germany of the manufacturing process through epoxidation of ethylene, followed by addition with hydrogen cyanide to produce cyanide ethanol, and finally dehydration. It was later developed of addition of hydrogen cyanide to acetylene under the catalysis of cuprous chloride. After 1960, it had been developed of new production process in the Ohio standard oil company, using propylene as raw material for ammoxidation reaction to obtain it. This process has led to great changes in industrial production. Owing to the availability of raw materials and the reduction in the cost, there is a sudden surge in production of acrylonitrile. In 1983, the world's annual output reached 3 million tons, of which the production amount of Ohio standard oil can account for 90%.
Acrylonitrile is easy to undergo polymerization, being able to produce polyacrylonitrile fiber (under the trade name of acrylic or bulk). Its short fiber is similar to wool, also known as artificial wool. It feels soft by hand with excellent elasticity. It can co-polymerize with vinyl acetate to generate synthetic fibers (under the commercial name of Austrian Lun). In 1950, it was first put into industrial production by the United States DuPont. The majority of acrylonitrile is used for synthetic fiber with the amount accounting for about 40~60% of the total. With copolymerization with butadiene copolymerization, it can generate oil-resistant nitrile rubber. Acrylonitrile dimerization and hydrogenation can be lead to adiponitrile, with then hydrogenation being able to obtain hexamethylene diamine, which is one of the raw materials of polyamide (nylon 66). The co-polymer of acrylonitrile and butadiene, styrene terpolymer is a high-quality engineering plastics, referred to as ABS resin.
Acrylonitrile has very active chemical nature with its molecule containing cyano, carbon-carbon double bond, being able to participate in a variety of reactions:
(1) Figure 1 shows the reaction of acrylonitrile.
(2) Figure 2 shows the reaction of acrylonitrile double bond.
(3) Cyanoethylation reaction: it can have reaction with alcohols, phenols, amines, ketones, aldehydes, nitromethane, diethyl malonate, introducing cyanoethyl group into the molecule. The general formula is as follows: R-H + CH2 = CHCN → R-CH2CH2CN.
(4) Polymerization: acrylonitrile is prone to have polymerization, being a monomer of polyacrylonitrile. It can copolymerize with vinyl chloride to generate dinell fiber, and copolymerize with butadiene to produce butadiene-acrylonitrile rubber. Acrylonitrile is the raw materials of polyacrylamide and polypropylene.
In 1941~1942, the German Degesch Gesellsch company recommended to use acrylonitrile as a food fumigant.
Toxicity: acrylonitrile is of great toxicity to human with comparable toxicity as hydrocyanic acid. Acrylonitrile is highly toxic to insects, and is the most toxic in the main fumigant for controlling various stored grain pests.
Acrylonitrile is used alone or in combination with carbon tetrachloride and has no effect on the germination of many vegetables, grains and flower seeds, but has some damage to maize seeds. The mixture of acrylonitrile and carbon tetrachloride can be used to control the vast majority of stored cereals pests. The results showed that acrylonitrile and carbon tetrachloride, when formulated into mixture in a ratio of 1:1, can be used to control the Phthorimaea operculella Zell occurring in potato under storage without damaging the tubers.
Usage method: Because acrylonitrile and carbon tetrachloride are of high boiling point, upon atmospheric fumigation, in order to be quickly evaporated, it was developed of a simple method which uses cotton cord core to pass through the shallow iron disk bottom. During the beginning of the fumigation, inject a liquid fumigant into the dish and then blow the air through the fan to the cotton core until the evaporation is complete.
Polyacrylonitrile is also known as "acrylic." being a copolymer originated from the copolymerization of acrylonitrile, methyl acrylate and itaconic acid. Its chemical formula is (CH2 = CH-CN) n, being a white powder with the proportion of 1.14 to 1.16. It is almost insoluble in water, fat, weak acid, weak base as well as saliva, gastric liquid. It is soluble in the aqueous solution of dimethyl formamide, dimethyl sulfoxide and inorganic salts (ZnCl2, NaSCN, etc.) and nitric acid. Polyacrylonitrile suitable for making fiber has a molecular weight between 2.05 million and 2.08 million and can be softened and decomposed at 230 °C.
Features: excellent performance, soft, light, warm, and wool close to the "synthetic wool," said. It has high elastic modulus, excellent shape retention, excellent light fastness and radiation resistance, being able to be used in a short time at 180~200 ℃. It has high acid and solvent stability but has poor abrasion resistance and fatigue resistance. It is widely used to replace wool and can be blended with wool, cotton and viscose fiber, making wool fabric, cotton fabric, knitted fabrics, carpets, etc., being especially suitable for outdoor fabric system, and taking advantage of its thermal flexibility to make soft thermal bulk yarn. After the polyacrylonitrile is subject to heat treatment to produce semiconductor fiber, followed by further undergoing high-temperature treatment at 1,000-1,500 °C can lead to high-modulus carbon fiber for producing ablative composite material for artificial satellite or missile shell.
Polyacrylonitrile belongs to low toxicity class. For rats, neither a single oral dose of 2,000~3,000mg/kg nor the inhalation of a concentration of 2,500~3,000 mg /m3 can cause poisoning. It has accumulation property. Polyacrylonitrile fiber is relatively coarse, hard and brittle easy to be broken, similar to glass fiber, being able to produce mechanical stimulation to the skin and mucous membranes, so the spinning worker in contact with polyacrylonitrile fiber can get skin itching and rash. Skin patch test has found no chemical stimulation and sensitization. PRECAUTIONS: Reduce the oligomeric dust through revolutionize the technology; sealing; apply extraction ventilation, and enhance personal protection. Supply iodine and vitamin C-rich foods.
The main purpose and role of acrylonitrile
(1) acrylonitrile can be used for the manufacture of acrylonitrile fiber and carbon fiber; used in the production of sodium L-glutamate (i.e. MSG), acrylate (raw materials of organic synthesis and paint), methine glutaronitrile (ABS modifier, the raw material of 2-methyl-1,5-diamine), α, α-dichloropropionic acid and α, α, β-trichloropropionic acid (used as the raw materials of herbicide), succinonitrile (the raw materials of succinate and 1,2-Butanediol), pimelic acid (for the production of plasticizers, plant growth regulators and pharmaceutical raw materials) and other derivatives.
(2) Important raw materials of organic synthesis for the production of dyes, antioxidants, surfactants and so on.
(3) monomers for synthesis, mainly used in the manufacture of synthetic fibers (acrylic); copolymerization with butadiene can produce oil, cold-resistant nitrile rubber; copolymerization with butadiene and styrene can produce three-way engineering plastics (ABS resin); control of acrylonitrile hydrolysis conditions, under the action of copper as the catalyst, we can obtain acrylamide; after polymerization of acrylamide, we can obtain polyacrylamide, which is an important industrial raw materials.
(4) Acrylonitrile can undergo full hydrolysis under the action sulfuric acid, being able to lead to acrylic acid; electrolytic hydrogenation can obtain adiponitrile, and used for further preparation of hexamethylene diamine (nylon 66 raw materials); for pesticides (livestock anthelmintic) Pharmaceutical raw materials; for grain fumigants.
(5) Acrylonitrile is an excellent aprotic polar solvent.
Since the 1960s, acrylic fibres have remained the major outlet for acrylonitrile production in the United States and especially in Japan and the Far East. Acrylic fibres always contain a comonomer. Fibres containing 85 wt% or more acrylonitrile are usually referred to as 'acrylics' and fibres containing 35–85 wt% acrylonitrile are called 'modacrylics'. Acrylic fibres are used primarily for the manufacture of apparel, including sweaters, fleece wear and sportswear, and home furnishings, including carpets, upholstery and draperies (Langvardt, 1985; Brazdil, 1991).
The production of ABS and SAN resins consumes the second largest quantity of acrylonitrile. The ABS resins are produced by grafting acrylonitrile and styrene onto polybutadiene or a styrene–butadiene copolymer and contain about 25 wt% acrylonitrile. These products are used to make components for automotive and recreational vehicles, pipe fittings, and appliances. The SAN resins are styrene–acrylonitrile copolymers containing 25–30 wt% of acrylonitrile. The superior clarity of SAN resin allows it to be used in automobile instrument panels, for instrument lenses and for houseware items (Langvardt, 1985; Brazdil, 1991).
The chemical intermediates adiponitrile and acrylamide have surpassed nitrile rubbers as end-use products of acrylonitrile in the United States and Japan. Adiponitrile is further converted to hexamethylenediamine (HMDA), which is used to manufacture nylon 6/6. Acrylamide is used to produce water-soluble polymers or copolymers used for paper manufacturing, waste treatment, mining applications and enhanced oil recovery (Langvardt, 1985; Brazdil, 1991).
Nitrile rubbers, the original driving force behind acrylonitrile production, have taken a less significant place as end-use products. They are butadiene–acrylonitrile copolymers with an acrylonitrile content ranging from 15 to 45%, and find industrial applications in areas where their oil resistance and low-temperature flexibility are important, such as in the fabrication of seals (O-rings), fuel hoses and oil-well equipment. New applications have emerged with the development of nitrile rubber blends with poly(vinyl chloride) (PVC). These blends combine the chemical resistance and low-temperature flexibility characteristics of nitrile rubber with the stability and ozone resistance of PVC. This has greatly expanded the use of nitrile rubber in outdoor applications for hoses, belts and cable jackets (Langvardt, 1985; Brazdil, 1991).
Other acrylonitrile copolymers have found specialty applications where good gasbarrier properties are required along with strength and high impact resistance. These barrier resins compete directly with traditional glass and metal containers as well as with poly(ethylene terephthalate) (PET) and PVC in the beverage bottle market. Other applications include packaging for food, agricultural chemicals and medicines (Brazdil, 1991).
A growing specialty application for acrylonitrile is in the manufacture of carbon fibres. These are produced by pyrolysis of oriented polyacrylonitrile fibres and are used to reinforce composites for high-performance applications in the aircraft, defence and aerospace industries. Other minor specialty applications of acrylonitrile are in the production of fatty amines, ion exchange resins and fatty amine amides used in cosmetics, adhesives, corrosion inhibitors and water-treatment resins (Brazdil, 1991). In the past, acrylonitrile was used with carbon tetrachloride as a fumigant for tobacco and in flour milling and bakery food processing (Suta, 1979). Most pesticides containing acrylonitrile have now been withdrawn (Worthing & Hance, 1991).
Acrylonitrile was first prepared in 1893 by dehydration of either acrylamide or ethylene cyanohydrin with phosphorus pentoxide (Fugate, 1963).
Until 1960, acrylonitrile was produced commercially by processes based on hydrogen cyanide and ethylene oxide or acetylene. The growth in demand for acrylic fibres, starting with the introduction of Orlon by DuPont around 1950, spurred efforts to develop improved process technology for acrylonitrile manufacture. This resulted in the discovery in the late 1950s of a heterogeneous vapour-phase catalytic process for acrylonitrile by selective oxidation of propylene and ammonia, commonly referred to as the propylene ammoxidation process. Commercial introduction of this lower-cost process by Sohio in 1960 resulted in the eventual displacement of all other acrylonitrile manufacturing processes. Today, the ammoxidation process accounts for over 90% of the approximately 4000 thousand tonnes produced worldwide each year. In this process, propylene, ammonia and air react in the vapour phase in the presence of a catalyst (bismuth–iron; bismuth–phosphomolybdate; antimony–uranium; ferrobismuth–phosphomolybdate). Hydrogen cyanide and acetonitrile are the chief by-products formed. Sulfuric acid is used to remove excess ammonia from the reaction mixture, and the nitrile compounds are removed by absorption in water. High-purity acrylonitrile is obtained by a series of distillations (Langvardt, 1985; Brazdil, 1991).
Acrylonitrile was first produced in Germany and the United States on an industrial scale in the early 1940s. These processes were based on the catalytic dehydration of ethylene cyanohydrin. Ethylene cyanohydrin was produced from ethylene oxide and aqueous hydrocyanic acid at 60°C in the presence of a basic catalyst. The intermediate was then dehydrated in the liquid phase at 200°C in the presence of magnesium carbonate and alkaline or alkaline earth salts of formic acid. A second commercial route to acrylonitrile was the catalytic addition of hydrogen cyanide to acetylene. The last commercial plants using these process technologies were shut down in 1970 (Langvardt, 1985; Brazdil, 1991).
Acrylonitrile is very toxic and irritant but is also a sensitizer. It caused both irritant and allergic contact dermatitis in a production manufacture.
Acrylonitrile is a colorless, flammable liquid. Its vapors may explode when exposed to an open flame. Acrylonitrile does not occur naturally. It is produced in very large amounts by several chemical industries in the United States and its requirement and demand has increased in recent years. The largest users of acrylonitrile are chemical industries that make acrylic and modacrylic fi bers, high impact acrylonitrile-butadiene-styrene (ABS) plastics. Acrylonitrile is also used in business machines, luggage, and construction material, in the manufacturing of styrene-acrylonitrile (SAN) plastics for automotive and household goods, and in packaging material. Adiponitrile is used to make nylon, dyes, drugs, and pesticides.
The electronegativity of the cyanide group of acrylonitrile produces charge
polarization and electron delocalization of the conjugated double bond.
Because of the electron deficiency of the ?-carbon, acrylonitrile readily adds to nucleophiles (RXH) by cyanoethylation.
This Michael addition reaction occurs almost quantitatively with alcohols, phenols, sulfhydryls, and amines with or without a catalyst (Rails 1959). The double bond with the partial positive charge on the ?-carbon is susceptible to oxidation reactions. The triple nitrile bond is susceptible to acid- or base-catalyzed hydrolysis to yield carboxylic acids.
Clear, colorless to pale yellow-brown, watery, volatile liquid with a sweet, irritating or pungent odor resembling peach pits, onions, or garlic. Evaporates quickly when spilled. Turns dark on exposure to air. Odor threshold concentrations of 1.6 and 8.8 ppmv were reported by Stalker (1973) and Nagata and Takeuchi (1990), respectively.
Acrylonitrile is used in the production of acrylic fibers, resins, and surface coating; as an intermediate in the production of pharmaceuticals and dyes; as a polymer modifier; and as a fumigant. It may occur in fire-effluent gases because of pyrolyses of polyacrylonitrile materials. Acrylonitrile was found to be released from the acrylonitrile–styrene copolymer and acrylonitrile–styrene–butadiene copolymer bottles when these bottles were filled with food-simulating solvents such as water, 4% acetic acid, 20% ethanol, and heptane and stored for 10 days to 5 months (Nakazawa et al. 1984). The release was greater with increasing temperature and was attributable to the residual acrylonitrile monomer in the polymeric materials.
Acrylonitrile is a raw material used for synthesis of many synthetic fibers such as Dralon and acrylic fibers. It is also used as an insecticide.
Manufacture of acrylic fibers. In the plastics, surface coatings, and adhesives industries. As a chemical intermediate in the synthesis of antioxidants, pharmaceuticals, dyes, surface-active agents, etc. In organic synthesis to introduce a cyanoethyl group. As a modifier for natural polymers. As a pesticide fumigant for stored grain. Experimentally to induce adrenal hemorrhagic necrosis in rats.
ChEBI: A nitrile that is hydrogen cyanide in which the hydrogen has been replaced by an ethenyl group.
Acrylonitrile can be prepared by several methods (HSDB 1988). Ethylene oxide is
reacted with hydrogen cyanide to form ethylene cyanohydrin (?-hydroxypropionitrile),
which is then dehydrated in the presence of a catalyst to form acrylonitrile.
A somewhat similar synthesis involves the treatment of ethylene chlorohydrin
with sodium cyanide to form ethylene cyanohydrin. Another method involves the
partial oxidation of natural gas to acetylene which is then reacted with hydrogen
cyanide to form acrylonitrile. Acrylonitrile also can be synthesized from propylene,
oxygen and ammonia with either bismuth phosphomolybdate or a uranium-
based compound as a catalyst (Hawley 1987).
Acrylonitrile is the most extensively produced aliphatic nitrile, ranking 39th on the list of high-volume chemicals produced in the USA in 1987. In 1985, U.S. production of acrylonitrile was 1.17 million tons (HSDB 1989).
Technical grade acrylonitrile is greater than 99% pure with the major impurities being water (present to a maximum of 0.5%), acetone, acetonitrile, acetaldehyde, iron, peroxides, and hydrogen cyanide (USEPA 1983). Polymerization grade acrylonitrile can contain the following impurities or additives: dimethylformamide, hydrogen peroxide, hydroxyanisole, methyl aery late, phenyl ether-biphenyl mixture, sodium metabisulfite, sulfur dioxide, sulfuric acid and titanium dioxide (USEPA 1980).
Acrylonitrile is produced in commercial quantities almost exclusively by the vapor-phase catalytic propylene ammoxidation process developed by Sohio.
C3H6 + NH3 + 2/3O2???→ C3H3N +3 H2O
Acrylonitrile must be stored in tightly closed containers in cool, dry, well-ventilated areas away from heat, sources of ignition, and incompatible chemicals. Storage vessels, such as steel drums, must be protected against physical damage, with outside detached storage preferred. Storage tanks and equipment used for transferring acrylonitrile should be electrically grounded to reduce the possibility of static spark-initiated fire or explosion. Acrylonitrile is regulated in the workplace by OSHA (29 CFR 1910).
A synthetic fiber that consists of a copolymer of 1-cyanoethene (acrylonitrile, vinyl cyanide) and ethenyl ethanoate (vinyl acetate).
Air & Water Reactions
Highly flammable. Soluble in water.
ACRYLONITRILE produces poisonous hydrogen cyanide gas on contact with strong acids or when heated to decomposition. Reacts violently with strong oxidizing agents (dibenzoyl peroxide, di-tert-butylperoxide, bromine) [Sax, 9th ed., p. 61]. Rapidly ignites in air and forms explosive mixtures with air. Polymerizes violently in the presence of strong bases or acids. Underwent a runaway reaction culminating in an explosion on contact with a small amount of bromine or solid silver nitrate [Bretherick, 5th ed., 1995, p. 404].
Acrylonitrile is a highly toxic compound, an irritant to the eyes and skin, mutagenic, teratogenic, and causes cancer in test animals.
Acrylonitrile is a moderate to severe acute toxicant via inhalation, oral intake, dermal absorption, and skin contact. Inhalation of this compound can cause asphyxia and headache. Firefighters exposed to acrylonitrile have reported chest pains, headache, shortness of breath, lightheadedness, coughing, and peeling of skin from their lips and hands (Donohue 1983). These symptoms were manifested a few hours after exposure and persisted for a few days. Inhalation of 110 ppm for 4 hours was lethal to dogs. In humans, inhalation of about 500 ppm for an hour could be dangerous. The toxicity symptoms in humans from inhaling high concentrations of acrylonitrile were somnolence, diarrhea, nausea, and vomiting (ACGIH 1986).
Ingestion and absorption of acrylonitrile through the skin exhibited similar toxic symptoms: headache, lightheadedness, sneezing, weakness, nausea, and vomiting. In humans, the symptoms were nonspecific but related to the central nervous system, respiratory tract, gastrointestinal tract, and skin. Severe intoxication can cause loss of consciousness, convulsions, respiratory arrest, and death (Buchter and Peter 1984).
Investigating the acute and subacute toxicity of acrylonitrile, Knobloch et al. (1971) reported that the compound caused congestion in all types of organs and damage to the central nervous system, lungs, liver, and kidneys. A dose of 50 mg/kg/day given intraperitoneally to adult rats for 3 weeks resulted in body weight loss, leukocytosis, and functional disturbances and degeneration of the liver and kidneys. There was also light damage to the neuronal cells of the brain stem and cortex.
LD50 value, oral (mice): 27 mg/kg
LD50 value, subcutaneous (mice): 34 mg/kg
The lethal effect of acrylonitrile increased in rats when coadministered with organic solvents (Gut et al. 1981), although the latter decreased the formation of cyanide. Metabolic cyanide formation was found to play only a minor role in the inhalation toxicity of acrylonitrile (Peter and Bolt 1985). This was in contrast to the toxicity of methylacrylonitrile, where the observed clinical symptoms suggest a metabolically formed cyanide.
Combination of styrene and acrylonitrile enhanced the renal toxicity of the former in male rats (Normandeau et al. 1984). The lethal effect of acrylonitrile increased with hypoxia or the condition of inadequate supply of oxygen to the tissues (Jaeger and Cote 1982).
Acrylonitrile is a mild skin irritant. It caused severe irritation in rabbits’ eyes. Inhalation and oral and intraperitoneal dosages exhibited birth defects in rats and hamsters. Abnormalities in the central nervous system, as well as cytological changes and postimplantation mortality were the symptoms observed. Acrylonitrile is a mutagen. It tested positive in TRP reversion and histidine reversion–Ames tests. This compound caused cancer in test species. Inhalation and ingestion of this compound produced cancers in the brain, gastrointestinal tract, and skin in rats. An oral dose that was carcinogenic to rats was determined to be 18,000 mg/kg given over 52 weeks (NIOSH 1986).
Acrylonitrile is metabolized via two competing pathways: (1) glutathione conjugation leading to its detoxication and (2) oxidative pathways forming cyanoethylene oxide, a genotoxic epoxide. Thier et al. (2000) have postulated that there was much higher impact of the oxidative metabolism of acrylonitrile in humans than in the rodents. The authors recommend a combination of Nacetylcysteine with sodium thiosulfate for antidote therapy against acute intoxications.
Two independent studies on the oncogenicity of acrylonitrile in rats from oral dosing through drinking water were carried out recently (Quast 2002; Johannsen and Levinska 2002). Quast (2002) reported nontumorous and tumorous lesions in a number of tissues in rats from 2-year exposure. He observed a statistically significant increased incidence of tumors in the central nervous system, forestomach, tongue, small intestine and mammary gland at dose levels ranging between 3 to 25 mg/kg. A no-observed adverse-effect level (NOAEL) could not be determined in this study for toxicity or oncogenicity of acrylonitrile in either sex. Johannsen and Levinska (2002) also observed treatment-related tumors of the central nervous system (brain, spinal cord), ear canal and the gastrointestinal tract, and in females only, the mammary gland (intubation only). The degree of severity of forestomach hyperplasia increased in all high dose groups of animals.
Leonard et al. (1999) investigated mutagenicity, carcinogenicity and teratogenicity of acrylonitrile. Tests for mutagenicity in bacteria have been positive, however, those on chromosome aberrations in vivo were negative. Their studies indicated that the mutagenic effects on man depended on the conditions of exposure. While carcinogenicity of acrylonitrile in human could not be confirmed, the animal data established its carcinogenic potential, however, with certain limitations with respect to the species and the type of tumor. Acrylonitrile was found to be teratogenic in rats and hamsters, manifesting foetal/embryonic toxicity at high doses.
A review of epidemiological studies do not support any adequate evidence of lung cancer from inhalation of acrylonitrile in humans (Sakurai 2000) and therefore, the current occupational exposure limits of 2 ppm reported in such epidemiological studies seemed to be appropriate.
Materials are too dangerous to health to expose fire fighters. A few whiffs of vapor could cause death or vapor or liquid could be fatal on penetrating the fire fighter's normal full protective clothing. The normal full protective clothing and breathing apparatus available to the average fire department will not provide adequate protection against inhalation or skin contact with these materials. Explosion hazard is moderate. Acrylonitrile is flammable and explosive at normal room temperatures. Can react violently with strong acids, amines, strong alkalis. Vapors may travel considerable distance to source of ignition and flash back. Dilute solutions are also hazardous (flash point of a solution of 2 percent in water is 70F). When heated or burned, toxic hydrogen cyanide gas and oxides of nitrogen are formed. Avoid strong acids, amines, alkalis. Incompatible with strong oxidizers (especially bromine) copper and copper alloys. Unstable, moderate hazard is possible when Acrylonitrile is exposed to flames, strong acids, amines and alkalis. May polymerize spontaneously in the container, particularly in absence of oxygen or on exposure to visible light. If polymerization occurs in containers, there is a possibility of violent rupture.
Flammability and Explosibility
Highly flammable liquid (NFPA rating = 3). Vapor forms explosive mixtures with air at concentrations of 3 to 17% (by volume). Hazardous gases produced in fire include hydrogen cyanide, carbon monoxide, and oxides of nitrogen. Carbon dioxide or dry chemical extinguishers should be used to fight acrylonitrile fires.
Reactivity with Water No reaction; Reactivity with Common Materials: Attacks copper and copper alloys; these metals should not be used. Penetrates leather, so contaminated leather shoes and gloves should be destroyed. Attacks aluminum in high concentrations; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: May occur spontaneously in absence of oxygen or on exposure to visible light or excessive heat, violently in the presence of alkali. Pure ACN is subject to polymerization with rapid pressure development. The commercial product is inhibited and not subject to this reaction; Inhibitor of Polymerization: Methylhydroquinone (35-45 ppm).
Acrylonitrile is used in the manufacture of acrylic fibers; in plastics, surface
coatings, and adhesives industries; as a chemical intermediate in the synthesis of
anti-oxidants, pharmaceuticals, dyes, surface-active agents, etc.; and in organic
synthesis to introduce a cyanoethyl group. It is used as a modifier for natural
polymers, and as a pesticide fumigant for stored grain (Hawley 1987; Windholz et
al 1983; HSDB 1989).
Other uses for acrylonitrile includes the cyanoethylation of natural fibers such as cotton, cellulose, and polysaccharides and the production of acrylonitrilecontaining plastics, particularly styrene-acrylonitrile (SAN) and acrylonitrilebutadiene styrene (ABS) co-polymers. Acrylonitrile is also used in the manufacture of various resins, elastomers, and latexes and has a limited use as a fumigant.
The major source of human exposure to acrylonitrile monomer and its release into the environment is during its manufacture, polymerization, or molding to acrylonitrile-based polymers. Disposal of acrylonitrile polymers by burning results in release of additional acrylonitrile monomer. Residual amounts of acrylonitrile monomer also are released from fabrics, such as underwear made of polyacrylonitrile fibers, and acrylonitrile polymer plastics in furniture. The public may also be exposed to acrylonitrile by ingestion of food products containing leached residual acrylonitrile monomer from packaging materials, such as 'Saran Wrap' (Anon. 1977a,b). Cigarette smoke has been shown by gas Chromatographie analysis to contain aliphatic nitriles including acrylonitrile, propionitrile, and methacrylonitrile (Izard and Testa 1968).
Acrylonitrile is a raw material used extensively in industry, mainly for acrylic and modacrylic fibers, acrylonitrile-butadiene-styrene and styrene-acrylonitrile resins, adiponitrile used in nylon’s synthesis, for nitrile rubber, and plastics. It is also used as an insecticide. This very toxic and irritant substance is also a sensitizer and caused both irritant and allergic contact dermatitis in a production manufacturer.
Acrylonitrile is used in the manufacture of synthetic fibers, polymers, acrylostyrene plastics, acrylonitrile butadiene styrene plastics, nitrile rubbers, chemicals, and adhesives. It is also used as a pesticide. In the past, this chemical was used as a room fumigant and pediculicide (an agent used to destroy lice).
Acrylonitrile is reasonably anticipated to be a human carcinogenbased on sufficient evidence of carcinogenicity from studies in experimental animals.
Biological. Degradation by the microorganism Nocardia rhodochrous yielded ammonium ion and propionic acid, the latter being oxidized to carbon dioxide and water
(DiGeronimo and Antoine, 1976). When 5 and 10 mg/L of acrylonitrile 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)
Photolytic. In an aqueous solution at 50°C, UV light photooxidized acrylonitrile to carbon dioxide. After 24 hours, the concentration of acrylonitrile was reduced 24.2% (Knoevenagel and Himmelreich, 1976)
Chemical/Physical. Ozonolysis of acrylonitrile in the liquid phase yielded formaldehyde and the tentatively identified compounds glyoxal, an epoxide of acrylonitrile and acetamide (Munshi et al., 1989). In the gas phase, cyanoethylene oxide was
The hydrolysis rate constant for acrylonitrile at pH 2.87 and 68°C was determined to be 6.4 × 10–3/hour, resulting in a half-life of 4.5 days. At 68.0°C and pH 7.19, no hydrolysis/disappearance was observed after 2 days. However, when the pH was raised to 10.76, the hydrolysis half-life was calculated to be 1.7 hours (Ellington et al., 1986)Acrylonitrile hydrolyzes to acrylamide which undergoes further hydrolysis forming acrylic acid and ammonia (Kollig, 1993)
Extensive metabolic studies have been reported which explain in part, the bioactivation
and degradation of acrylonitrile. Increased blood and urine concentrations
of thiocyanate in animals were reported after acrylonitrile administration (Giacosa
1883). Brieger et al (1952), found that acute acrylonitrile exposure also produced
increased blood concentrations of cyanomethemoglobin. In dogs (which are
particularly susceptible to acrylonitrile toxicity), the concentration of cyanomethemoglobin
increased with length of exposure, so that by the end of the lethal
exposure period most of the methemoglobin present was converted to cyanomethemoglobin.
Acrylonitrile, clearly, is capable of liberating cyanide under biological conditions. However, the percentage of the total urinary excretion of thiocyanate after acrylonitrile administration ranges from 4 to 25% of the administrated dose (Ahmed and Patel 1981; Brieger et al 1952; Benes and Cerna 1959; Farooqui and Ahmed 1981; Paulet et al 1966).
Gut et al (1975) found that the conversion of acrylonitrile to cyanide was dependent on the route of administration and decreased in the following order: oral > intraperitoneal > subcutaneous > intravenous. Thus, the more slowly acrylonitrile enters the system (oral administration), the more extensively it is converted to cyanide. This suggests that conversion of acrylonitrile to cyanide involves saturable metabolic processes.
Ahmed and Patel (1981) studied the metabolism of acrylonitrile to cyanide in both rats and mice. In rats, early signs of acrylonitrile toxicity were cholinomimetic, which were different from the central nervous system disturbances observed after giving potassium cyanide. However, in mice, the only signs of acrylonitrile toxicity were central nervous system effects; these were identical to those seen after giving potassium cyanide. Treatment of rats and mice with phenobarbital, Aroclor 1254, or fasting increased blood cyanide concentrations, whereas treatment with cobaltous chloride or SKF 525A resulted in decreased blood cyanide concentrations. The data previously cited indicates species differences in acrylonitrile toxicity and metabolism which suggest that acrylonitrile is metabolized to cyanide by a mixed-function oxidase (mfo) enzyme system.
In vitro, the metabolism of acrylonitrile to cyanide was localized in the microsomal fraction of rat liver and required NADPH and O2 (Abreu and Ahmed 1979, 1980; Ahmed and Abreu 1982). Metabolism of acrylonitrile was increased in microsomes obtained from phenobarbital, Aroclor 1254, and 3-methylcholanthrene treated rats and decreased after cobaltous chloride treatment. Addition of SKF 525A or carbon monoxide to the incubation mixture inhibited acrylonitrile metabolism. Addition of the epoxide hydrolase inhibitor, 1,1,1-trichloropropane 2,3-oxide, decreased the formation of cyanide from acrylonitrile. The addition of glutathione (GSH), cysteine, D-penicillamine, or 2-mercaptoethanol enhanced the release of cyanide by a cytochrome P-450-dependent mfo system.
Earlier investigators believed that the aliphatic nitriles, including acrylonitrile, might be direct inhibitors of cytochrome c oxidase. The in vitro studies in our laboratory (Ahmed et al 1980; Ahmed and Farooqui 1982), and studies by Willhite and Smith (1981), and Nerudova et al (1981) showed no inhibition of cytochrome c oxidase by nitriles. Nerudova et al (1981) reported that the administration of lethal (100 mg/kg) or sublethal doses (40 mg/kg =LD50) of acrylonitrile to mice inhibited cytochrome c oxidase in liver and brain. In rats, after giving LD50 doses of acrylonitrile, a 50% inhibition of cytochrome c oxidase in liver, kidney and brain was observed by Ahmed and Farooqui (1982). Nerudova et al (1981) suggested that after the administration of a lethal, as well as LD50, dose of acrylonitrile, cyanide is present in the organism in a concentration that produces a 50% inhibition of cytochrome c oxidase.
Work with acrylonitrile should be conducted in a fume hood to prevent exposure by inhalation, and splash goggles and impermeable gloves should be worn at all times to prevent eye and skin contact. Acrylonitrile should be used only in areas free of ignition sources. Containers of acrylonitrile should be stored in secondary containers in the dark in areas separate from oxidizers and bases.
UN1093 Acrylonitrile, stabilized, Hazard Class 3; Labels: 3 Flammable liquids, 6.1-Poisonous materials
Wash acrylonitrile with dilute H2SO4 or dilute H3PO4, then with dilute Na2CO3 and water. Dry it with Na2SO4, CaCl2 or (better) by shaking with molecular sieves. Fractionally distil it under N2. It can be stabilised by adding 10ppm tert-butyl catechol. Immediately before use, the stabilizer can be removed by passage through a column of activated alumina (or by washing with 1% NaOH solution if traces of water are permissible in the final material), followed by distillation. Alternatively, shake it with 10% (w/v) NaOH to extract inhibitor, and then wash it in turn with 10% H2SO4, 20% Na2CO3 and distilled water. Dry for 24hours over CaCl2 and fractionally distil under N2 taking fraction boiling at 75.0-75.5oC (at 734mm). Store it with 10ppm tert-butyl catechol. Acrylonitrile is distilled off when required. [Burton et al. J Chem Soc, Faraday Trans 1 75 1050 1979, Beilstein 2 IV 1473.]
Acrylonitrile is both readily volatile in air and highly soluble in water. These characteristics determine the behavior of acrylonitrile in the environment. The principal pathway leading to the degradation of acrylonitrile in air is photooxidation, mainly by reaction with hydroxyl radicals (OH). Acrylonitrile may also be oxidized by other atmospheric components such as ozone and oxygen. Very little is known about the nonbiologically mediated transformation of acrylonitrile in water. It is oxidized by strong oxidants such as chlorine used to disinfect water. Acrylonitrile is readily degraded by aerobic microorganisms in water.
May form explosive mixture with air. Reacts violently with strong acids; strong alkalis; bromine, and tetrahydrocarbazole. Copper, copper alloys, ammonia, and amines may cause breakdown to poisonous products. Unless inhibited (usually with methylhydroquinone), acrylonitrile may polymerize spontaneously. It may also polymerize on contact with oxygen, heat, strong light, peroxides, and concentrated or heated alkalis. Reacts with oxidizers, acids, bromine, amines. Attacks copper and copper alloys. Attacks aluminum in high concentrations. Heat and flame may cause release of poisonous cyanide gas and nitrogen oxides
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 with provision for nitrogen oxides removal from effluent gases by scrubbers or afterburners. A chemical disposal method has also been suggested involving treatment with alcoholic NaOH; the alcohol is evaporatedand calcium hypochlorite added; after 24 hours the product is flushed to the sewer with large volumes of water. Recovery of acrylonitrile from acrylonitrile process effluents is an alternative to disposal.
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