アジリジン 化学特性,用途語,生産方法
性質
アジリジンの融点は-77.9°C、沸点は55〜56°Cであり、無色で透明の液体です。アジリジンは、のような特有の匂いを有します。
アジリジンの酸解離定数は7.9であり、直鎖状脂肪族アミンと比較すると塩基性は弱いです。
解説
ethyleneimine．C2H5N(43.07)．エチレンイミンともいう．硫酸水素2-アミノエチルをアルカリと加熱するか，2-ハロエチルアミンにアルカリを作用させてつくる．工業的には，1,2-ジクロロエタンとアンモニアからもつくられる．アジリジン，アンモニア臭をもつ可燃性の液体．沸点56 ℃．d25250.833．n25D1.4123．水溶液にすると加水分解されやすい．第二級アミンとしての性質のほかに，不安定な三員環構造のために開環しやすく，チオール，フェノール，アミンなどと反応して2-アミノエチル誘導体を生じる．酸触媒で重合してポリアミンを生成する．繊維処理剤，接着剤，イオン交換樹脂の製造，エポキシ樹脂の硬化剤のほか，重合体は紙の湿潤強度を高めるのに用いられる．発がん性がある．LD50 15 mg/kg(ネズミ，経口)．森北出版「化学辞典（第2版）
用途
農薬?染料?繊維改質剤原料、有機合成原料
構造
アジリジンは三員環の構造を有します。1個の窒素原子と2個の炭素原子から構成される、ヘテロ三員環化合物です。分子量は43.07で、20°Cでの密度は0.8321g/mlです。
シクロプロパンやエチレンオキシドなどと同じく、角ひずみが生じています。アジリジンの持つ原子の結合角はおよそ60°であり、通常の炭化水素のような109.5°よりも非常に小さいためです。
これらの化合物の結合は、バナナ型結合モデル (英: bent bond) を用いて説明できます。すなわち、バナナのような形をした共有結合のことです。
アジリジンの結合角によって、窒素原子が反転する障壁は十分高いため、N-クロロ-2-メチルアジリジンのトランス体とシス体は分離できます。
毒性
アジリジン，非常に強い毒性をもち，皮膚や粘膜との接触，吸入，経口接触のいずれの場合にも，人体に対して激しい障害を起こす。また引火性，爆発性もある。β‐アミノエチル硫酸に水酸化ナトリウムを作用させて合成する。
合成
アミノ基が隣接したハロゲンの分子間求核置換反応によって、アジリジンをハロアミンから合成可能です。ヒドロキシ基を優れた脱離基に変換すれば、同様の反応はアミノアルコールでも進行します。ハロアミンの環化反応はガブリエルエチレンイミン法 (英: Gabriel Ethylenimine Method) と、アミノアルコールの環化反応はウェンケル合成 (英: Wenker synthesis) と呼ばれています。
アジ化合物の光分解や熱分解によって生じるニトレンが、アルケンに付加すると、アジリジンを合成可能です。また、アジ化合物とアルケンの付加環化反応で得られるトリアゾリンが、熱分解や光分解により窒素原子が脱離すると、アジリジンが生成します。
さらに、エポキシドをアジ化ナトリウムの存在下で開環し、トリフェニルホスフィンを用いた還元によって窒素原子を除去しても、アジリジンが得られます。
説明
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.
化学的特性
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
物理的性質
Clear, colorless, very flammable liquid with a very strong ammonia odor. Odor threshold
concentration is 1.5 ppm (quoted, Amoore and Hautala, 1983).
使用
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.
調製方法
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.
一般的な説明
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.
空気と水の反応
Highly flammable. Soluble in water.
反応プロフィール
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].
危険性
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.
健康ハザード
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.
火災危険
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.
使用用途
アジリジンは、、繊維処理剤、の原料、農薬の原料、の製造などに用いられています。しかし、皮膚や粘膜へのアジリジンの暴露は、人体に非常に強い毒性を示します。有毒であるため、取り扱いには注意が必要です。
アジリジン基を持つアジリジン化合物は、ケミタイトとして販売されています。このケミタイトは、塗料、粘接着剤、コーティング剤の架橋剤に使用されています。
化学反応性
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.
工業用途
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).
安全性プロファイル
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.
職業ばく露
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
発がん性
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.
環境運命予測
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).
代謝
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).
輸送方法
UN1185 Ethyleneimine, stabilized, Hazard class:
6.1; Labels: 6.1-Poison Inhalation Hazard, 3-Flammable
liquid, Inhalation Hazard Zone A. PGI
純化方法
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.
不和合性
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.
廃棄物の処理
Controlled incineration; incinerator equipped with a scrubber or thermal unit to reduce
nitrogen oxides emissions
予防処置
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.
アジリジン 上流と下流の製品情報
原材料
準備製品