에틸렌이민

에틸렌이민 속성

에틸렌이민 C화학적 특성, 용도, 생산

개요

Ethyleneimine is a colourless liquid with an ammonia-like smell or pungent odour. It is highly flammable and reacts with a wide variety of materials. Ethyleneimine is used in polymerisation products, as a monomer for polyethyleneimine and as a comonomer for polymers, for example, with ethylenediamine. Polymerised ethyleneimine is used in paper, textile chemicals, adhesive binders, petroleum, refining chemicals, fuels, lubricants, coating resins, varnishes, lacquers, agricultural chemicals, cosmetics, ion-exchange resins, photographic chemicals, colloid flocculants, and surfactants. Ethyleneimine readily polymerises, and it behaves like a secondary amine. Ethyleneimine is highly caustic, attacking materials such as cork, rubber, many plastics, metals, and glass except those without carbonate or borax. It polymerises explosively on contact with silver, aluminium, or acid. The activity of ethyleneimine is similar to that of nitrogen and sulphur mustards. Ethyleneimine is used as an intermediate in the production of triethylenemelamine.

화학적 성질

Ethyleneimine is a colorless liquid with an ammonia-like smell or pungent odor. It is highly flammable and reacts with a wide variety of materials. Ethyleneimine is used in polymerization products, as a monomer for polyethyleneimin, and as a comonomer for polymers, e.g., with ethylenediamine. Polymerized ethylenimine is used in paper, textile chemicals, adhesive binders, petroleum, refi ning chemicals, fuels, lubricants, coating resins, varnishes, lacquers, agricultural chemicals, cosmetics, ion-exchange resins, photographic chemicals, colloid fl occulants, and surfactants. Ethyleneimine readily polymerizes, and it behaves like a secondary amine. Ethyleneimine is highly caustic, attacking materials such as cork, rubber, many plastics, metals, and glas except those without carbonate or borax. It polymerizes explosively on contact with silver, aluminum, or acid. The activity of ethyleneimine is similar to that of nitrogen and sulfur mustards. Ethyleneimine is used as an intermediate in the production of triethylenemelamine. Polymerized ethyleneimine is used in paper, textile chemicals, adhesive binders, petroleum, refi ning chemicals, fuels, lubricants, coating resins, varnishes, lacquers, agricultural chemicals, cosmetics, ion-exchange resins, photographic chemicals, colloid fl occulants, and surfactants

물리적 성질

Clear, colorless, very flammable liquid with a very strong ammonia odor. Odor threshold concentration is 1.5 ppm (quoted, Amoore and Hautala, 1983).

용도

Ethyleneimine is used to manufacture triethylenemelamine and is used in its polymeric form in paper and textile chemicals, adhesive binders, petroleum-refining chemicals, fuels and lubricants, coating resins, varnishes, lacquers, agricultural chemicals, cosmetics, ion-exchange resins, photographic chemicals, colloid flocculants, and surfactants.

생산 방법

Industrial quantities are made with monoethanolamine via a two-step chemical dehydration process using sulphuric acid and sodium hydroxide, or by reacting 1,2-dichloroethane with ammonia. The U.S. production in 1978 was over 1500 metric tons (Ham 1978).

Origin

Ethylenimine was first prepared in 1888 by G_ABRIEL, who mistakenly called it vinylamine. He prepared the ethylenimine by reacting 2-bromoethylamine hydrobromide with silver oxide or potassium hydroxide.

일반 설명

A clear colorless liquid with an ammonia-like odor. Flash point 12°F. Less dense than water. Flammable over a wide range of vapor-air concentrations. Vapors irritate the skin, eyes, nose, and throat. May be toxic by prolonged inhalation, skin absorption, or ingestion. Carcinogenic. Vapors heavier than air. May polymerize exothermically if heated or contaminated. If the polymerization takes place inside a container, the container may rupture violently.

공기와 물의 반응

Highly flammable. Soluble in water.

반응 프로필

ETHYLENEIMINE vapors are not inhibited and may form polymers in vents or flame arresters, resulting in stopping of the vents. Produces toxic oxides of nitrogen during combustion. Reacts with sodium hypochlorite and other chlorinating agents to give the explosive compound 1-chloroazidine. Decomposes if heated under pressure. or else hazardous polymerization may occur. Incompatible with silver or aluminum, which induce polymerization May polymerize explosively upon contact with acids. Polymerization is catalyzed by carbon dioxide [EPA, 1998].

위험도

Corrosive, absorbed by skin, causes tumors; exposure should be minimized; a carcinogen. Dangerous fire and explosion hazard, flammable limits in air 3.6–46%. Toxic by skin absorption; possible carcinogen.

건강위험

Ethyleneimine is classified as extremely toxic with a probable oral lethal dose of 5-50 mg/kg which is approximately 7 drops to 1 teaspoonful for a 70 kg (150 lb.) person. Ethyleneimine gives inadequate warning when over-exposure is by inhalation or skin absorption. It is a severe blistering agent, causing third degree chemical burns of the skin. Also, it has a corrosive effect on mucous membranes and may cause scarring of the esophagus. It is corrosive to eye tissue and may cause permanent corneal opacity and conjunctival scarring. Severe exposure may result in overwhelming pulmonary edema. Renal damage has been described. Hemorrhagic congestion of all internal organs has been observed.

화재위험

Irritating vapors are generated when heated. Vapor is heavier than air and may travel a considerable distance to a source of ignition and flash back. May polymerize in fires with evolution of heat and container rupture. Runoff to sewer may create fire or explosion hazard. Ethyleneimine vapors are not inhibited and may form polymers in vents or flame arresters, resulting in stopping of the vents. Toxic oxides of nitrogen are produced during combustion. Upon treatment with sodium hypochlorite, Ethyleneimine gives off the explosive compound 1-chloroazidine. Avoid acids, sodium hypochlorite. If heated under pressure, instability may result. Hazardous polymerization may occur. Avoid contact with silver or aluminum. Explosive polymerization may occur upon contact with acids. Polymerization is catalyzed by carbon dioxide.

화학 반응

Reactivity with Water: Mild reaction, non-hazardous; Reactivity with Common Materials: Contact with silver or aluminum may cause polymerization; Stability During Transport: Stable unless heated under pressure; Neutralizing Agents for Acids and Caustics: Flush with water; Polymerization: Explosive polymerization can occur when in contact with acids; Inhibitor of Polymerization: None used.

공업 용도

Approximately 50% of ethylenimine produced in the U.S. is polymerized to polyethyleneimine, used as a flocculant in water treatment, and as a wet-strength additive in the textile and paper industries. Polyethylenimine is also used in various adhesives and coatings and to laminate plastic films to paper, other cellulose materials, and metal foils for making cartons in the food industry. The adhesion properties of acrylic latex paints are improved by reaction of acid groups with ethylenimine. Ethylenimines are utilized in the textile industry to improve durability, crease resistance, flame resistance, and dyeing properties. Other uses are found in ion-exchange resin synthesis, in electroplating, as a rocket propellant binder, as a lubricating oil dispersant, and as a hardening agent in the preparation of photographic films. Ethylenimine is used in the manufacture of triethylene melamine, a cancer chemotherapy drug; various ethylenimines are used as insect chemosterilant agents for pest control (Ham 1978).

Safety Profile

Confirmed carcinogen with experimental carcinogenic, neoplastigenic, tumorigenic, and teratogenic data. Other experimental reproductive effects. Poison by ingestion, skin contact, inhalation, and intraperitoneal routes. Human mutation data reported. A skin, mucous membrane, and severe eye irritant. An allergc sensitizer of skin. Causes opaque cornea, keratoconus, and necrosis of cornea (experimentally). Has been known to cause severe human eye injury. Drinking of carbonated beverages is recommended as an antidote to ths material in stomach. A very dangerous fire and explosion hazard when exposed to heat, flame, or oxidzers. Reacts violently with acids, aluminum chloride + substituted anilines, acetic acid, acetic anhydride, acrolein, acrylic acid, allyl chloride, CS2, Cl2, chlorosulfonic acid, epichlorohydrin, glyoxal, HCl, HF, HNO3, oleum, P-propiolactone, Ag, NaOCl, H2SO4, vinyl acetate. Reacts with chlorinating agents (e.g., sodum hypochlorite solution) to form the explosive 1 chloroaziridine. Reacts with silver or its alloys to form explosive silver derivatives. Dangerous; heat and/or the presence of catalytically active metals or chloride ions can cause a violent exothermic reaction. To fight fire, use alcohol foam, CO2, dry chemical. When heated to decomposition it emits acrid smoke and irritating fumes.

잠재적 노출

Ethyleneimine is used in production of binding agents; formation of plastics; and improving paper strength; in many organic syntheses; as an intermediate and monomer for fuel oil and lubricating refining. The polymerization products, polyethyleneimines, are used as auxiliaries in the paper industry and as flocculation aids in the clarification of effluents. It is also used in the textile industry for increasing wet strength, flame-, water-, shrinkproofing, and stiffening

Carcinogenicity

The carcinogenicity of ethyleneimine was evaluated in two strains of mice, and both gave positive results. Groups of 18 male and 18 female mice of B6C3F1 or B6AKR strains were treated orally (initially by gavage, then in the diet) from age 7 days through 77–78 weeks. The time-weighted average (TWA) dose was about 1.8 mg/kg/day. The incidence of hepatomas and lung adenomas was significantly elevated in both strains and sexes. In B6C3F1 mice, the incidence of hepatomas and pulmonary adenomas was 15/17 and 15/17 in males and 11/15 and 15/15 females, respectively. In the B6AKR strain, hepatomas and adenomas occurred in 9/16 and 12/16 males and in 2/11 and 10/11 females, respectively. In the control groups, hepatomas were 8/79 and 0/87 in male and female B6C3F1 mice and 5/90 and 1/82 in male and female B6AKR mice. The respective incidence of pulmonary adenomas was 5/79, 3/87, 10/90, and 3/82. The incidence of hepatomas and pulmonary adenomas (reported as combined tumors) was significantly (p＜0.01) elevated.

환경귀착

Photolytic. The vacuum UV photolysis (λ = 147 nm) and γ radiolysis of ethylenimine resulted in the formation of acetylene, methane, ethane, ethylene, hydrogen cyanide, methyl radicals, and hydrogen (Scala and Salomon, 1976). Photolysis of ethylenimine vapor at krypton and xenon lines yielded ethylene, ethane, methane, acetylene, propane, butane, hydrogen, ammonia, and ethyleneimino radicals (Iwasaki et al., 1973).
Chemical/Physical. Polymerizes easily (Windholz et al., 1983). Hydrolyzes in water forming ethanolamine (HSDB, 1989). The estimated hydrolysis half-life in water at 25 °C and pH 7 is 154 d (Mabey and Mill, 1978).

신진 대사

When male Dow-Wistar rats were injected intraperitoneally with [¹⁴C]-ethylenimine (80mug), approximately half of the dose was excreted in the urine (Wright and Rowe 1967). The major portion of the radioactivity in the urine consisted of unidentified products, although a small amount was excreted unchanged. A small portion, 3-5%, was expired as ¹⁴C02, and 1-3% was expired as a volatile, basic material, probably ethylenimine, during 24 h. Significant amounts of radioactivity were accumulated in liver, intestines, cecum, spleen, and kidneys. After 24 h, tissue radioactivity became constant and essentially unavailable for further metabolism. The aziridine ring of drugs is readily cleaved by microsomal enzymes, possibly with intermediate formation of an N-oxide (Oelschlager and Al Shaik 1985).

운송 방법

UN1185 Ethyleneimine, stabilized, Hazard class: 6.1; Labels: 6.1-Poison Inhalation Hazard, 3-Flammable liquid, Inhalation Hazard Zone A. PGI

Purification Methods

Redistil it in an Ar or N2 atmosphere in a fume hood, and store it over KOH in sealed bottles in a refrigerator. Commercial aziridine has been dried over sodium and distilled from the metal through an efficient column before use [Jackson & Edwards J Am Chem Soc 83 355 1961, Wenker J Am Chem Soc 57 2328 1935]. It is a weaker base than Me2NH (pK2 5 10.87) but is caustic to the skin. It should not be inhaled, causes inflammation of the eyes, nose and throat, and one may become sensitized to it. It is soluble in H2O, has an ammoniacal smell and reacts with CO2. Pure aziridine is comparatively stable but polymerises in the presence of traces of H2O and is occasionally explosive in the presence of acids. CO2 is sufficiently acidic to cause polymerisation (forms linear polymers) which is not free radical promoted. It is stable in the presence of bases. The violet 2:1 Cu complex crystallises from EtOH containing a few drops of aziridine and adding Et2O, and has m 142o(dec). The picrate has m 142o. [O'Rourke et al. J Am Chem Soc 78 2159 1956.] It has also been dried over BaO and has been distilled from sodium under nitrogen. [Allen et al. Org Synth Coll Vol IV 433 1963, Beilstein 20 III/IV 1.] TOXIC.

비 호환성

May form explosive mixture with air. Ethyleneimine is a medium strong base. Contact with acids, aqueous acid conditions, oxidizers, aluminum, or carbon dioxide may cause explosive polymerization. Explosive silver derivatives may be formed with silver alloys e.g., silver solder). Self-reactive with heat or atmospheric carbon dioxide. May accumulate static electrical charges, and may cause ignition of its vapors. Attacks rubber, coatings, plastics, and chemically active metals. Ethyleneimine vapors are not inhibited and may form polymers in vents or flame arresters, resulting in stopping of the vents.

폐기물 처리

Controlled incineration; incinerator equipped with a scrubber or thermal unit to reduce nitrogen oxides emissions

주의 사항

During use of ethyleninime, students and occupational workers should wear protective equipment, such as gloves, safety glasses, and should have good ventilation. Ethyleninime should be handled as a carcinogen. Ethyleninime vapor/air mixtures are explosive and pose a risk of fi re and explosion on contact with acid(s), oxidants.

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