塩化カルボニル

塩化カルボニル 化学特性,用途語,生産方法

性質

ホスゲンは、融点が-128℃、沸点が8℃、液体時の相対密度が1.4で、ガス時の相対密度が3.4です。、、四塩化炭素に容易に溶けますが、水にはわずかに溶けてとに加水分解します。と反応してを、また第三アミンの存在下アルコールと反応してクロルギ酸エステルを生じます。

反応

ホスゲンは、ジオールと反応して直鎖状または環状の炭酸塩のいずれかを生成します (HOCR₂-X-CR₂OH+COCl₂→1/n[OCR₂-X-CR₂OC(O)-]_n+2HCl)。また、アミンと反応すると、イソシアネートを生成します (RNH₂+COCl₂→RN=C=O+2HCl)。さらに、ホスゲンはカルボン酸から塩化アシルを製造するためにも使われています (RCO₂H+COCl₂→RC(O)Cl+HCl+CO₂)。

解説

ホスゲン(phosgene)ともいう．四塩化炭素と発煙硫酸との反応や，無水塩化アルミニウムの存在下で四塩化炭素とホルムアルデヒドとの反応で得られる．無色，特有臭(濃いと刺激臭，薄めると乾草臭)のある気体．気体分子は平面三角形型構造．密度1.43 g cm－3(－19 ℃，液体)．C-O約1.17 Å，C-Cl約1.74 Å．∠Cl-C-Cl約112°．融点－126 ℃，沸点8.2 ℃．冷水に難溶．水で徐々に，熱水ではより速く加水分解してCOとHClを生じる．ベンゼン，四塩化炭素，酢酸などに易溶．加熱するとCOと Cl2 に分解する．反応性に富む．HFと反応すると塩化フッ化カルボニルCOClFに，NH3と反応するとクロロギ酸アミドH2NCOClを経て尿素(NH2)2COに，第一級アミンRNH2と反応すると塩化カルバモイルRNHCOClになる．

用途

染料及び染料中間体の原料、イソシアネート類の原料として弾性体、接着剤、塗料などのポリウレタン系諸製品及び繊維処理剤、除草剤に利用、医薬品、可塑剤及びポリカーボネート樹脂の原料、その他火薬安定剤、紫外線吸収剤の原料。
ホスゲンの用途はイソシアネート(80%)とポリカーボネート樹脂(10%)がほとんどを占め、残りの約10%には医薬品や農薬の中間体などが含まれます。イソシアネートはMDIとTDIが主で、MDIの場合はてポリメリックジフェニルメタンジアミン(MDA)、TDIの場合はトルエンジアミン(TDA)がホスゲンと反応します。ポリカーボネート(PC)は耐衝撃性・耐熱性に優れるエンジニアリングプラスチックとして使われており、ホスゲンとビスフェノールA(Bis-A)の反応によって合成されます。イソシアネートやPC樹脂の合成にホスゲンを使わない方法が模索されたこともありますが、結局前駆体の合成にホスゲンを使わなければならないなど、ホスゲンの代替技術は確立されていません。

製法

（1）工業的には，一酸化炭素と塩素を活性炭触媒の存在下で加熱して合成する塩化カルボニル．
（2）ホスゲン合成の化学反応式は非常に簡単なもので、一酸化炭素と塩素の反応によって合成されます。ホスゲン専業のメーカーは無く、イソシアネートを生産する大手化学メーカーが中間体としてホスゲンを生産しています。安全に生産する技術が確立されているため、近年では事故は発生していません。なお、ホスゲンは融点8℃・沸点20℃の気体であるため実験室レベルでのイソシアネート合成では液体で扱いやすいトリホスゲンが使われます。

危険性

ホスゲンは過去に毒ガス兵器として使われていたこともあり、確かに危険な物質です。加水分解されて塩酸を発生させるため体内に侵入すると刺激症状が出ます。吸引量が多い場合は呼吸困難や肺炎の原因となり、高濃度の場合は短時間の吸引でも命の危険を及ぼします。1999年には実際に国内工場で事故が発生しました。ホスゲンの配管内で2人の作業員が清掃作業を行っているにも関わらず連絡ミスによってホスゲンが流れ込み、1人が死亡しました。2008年にも別の工場で漏洩事故が発生し、敷地内の12人と近隣住民1人が体調不良を訴えました。もちろん管理の厳格化は進められていますが、製造現場では常に注意しなければならない物質です。

説明

Phosgene is a colourless, reactive, non-flammable gas that is heavier than air with a musty hay odour. Phosgene is commonly stored under high pressure as a liquid. Phosgene reacts with water to form corrosive acids, reacts with most metals in the presence of moisture, liberating hydrogen, an extremely flammable gas, and reacts violently with alkalis. As an industrial and commercially important chemical, phosgene is a precursor material/chemical intermediate, and has extensive application in the manufacture of a wide range of products such as polymers – polyurethanes and polycarbonates – pesticides, medicines, dyestuffs, some insecticides, pharmaceuticals, and in metallurgy.

化学的特性

Phosgene, COCL2, also known as carbonyl chloride and chlorofonnyl chloride, is a colorless,poisonous gas produced by the action of chlorine and carbon monoxide. It condenses at 0 °C (32 OF) to a fuming liquid. Phosgene was used as a war gas, but is now used in the production of metal chlorides, pharmaceuticals, isocyanate resins,and perfumes.

物理的性質

Colorless gas at ambient temperature; strong, pungent odor; density of the gas 4.045 g/L at 25°C; density of the liquid 1.392 g/mL at 4°C; liquefies to a light yellow fluid at 8.2°C; freezes at -128°C; critical temperature 182°C, critical pressure 55.96 atm, critical volume 190 cm³/mol; slightly soluble in water with slow hydrolysis; soluble in benzene, toluene and acetic acid.

使用

PHOSGENE is an intermediate in organic synthesis, especially production of toluene diisocyanate and polymethylene polyphenylisocyanate; in metallurgy to separate ores by chlorination of the oxides and volatilization; occurs as a product of combustion whenever a volatile chlorine compound comes in contact with a flame or very hot metal; originally manufactured as an agent for chemical warfare during World War I.

製造方法

Phosgene is prepared by the reaction of carbon monoxide and chlorine. The mixture of these gases is passed over activated carbon:
CO + Cl2 → COCl2
Alternatively, phosgene can be made by reacting carbon monoxide with nitrosyl chloride, or by treating carbon tetrachloride with oleum.

定義

ChEBI: An acyl chloride obtained by substitution of both hydrogens of formaldehyde by chlorine.

調製方法

Phosgene is manufactured in many facilities in the United States and in many other countries. Typical production processes involve the reaction of carbon monoxide with nitrosyl chloride, or the reaction of carbon tetrachloride with oleum.

空気と水の反応

Decomposes slowly in water or moist air (or when inhaled) to form very corrosive hydrogen chloride gas (hydrochloric acid) and carbon monoxide.

反応プロフィール

PHOSGENE is water reactive. Incompatible with strong oxidizing agents, alcohols, amines, alkali. May react violently with aluminum, alkali metals (lithium, potassium, sodium), alcohols (isopropyl alcohol, 2,4-hexadiyn-1,6-diol), sodium azide [Bretherick, 5th ed., 1995, p. 134]. May react vigorously or explosively if mixed with diisopropyl ether or other ethers in the presence of trace amounts of metal salts [J. Haz. Mat., 1981, 4, 291]. PHOSGENE reacts with phosphate or silicate salts, yielding water-reactive and toxic POCl3 with phosphates (Dunlap, K.L. 2005. PHOSGENE. In Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley & Sons, Inc.).

危険性

Phosgene is a strong irritant to the eyes, is highly toxic by inhalation, and may be fatal if inhaled. The TLV is 0.1 ppm, and the IDLH is 2 ppm in air. The boiling point is 46°F, and it is noncombustible. When carbon tetrachloride comes in contact with a hot surface, phosgene gas is evolved, which is one of the main reasons that carbon tetrachloride fire extinguishers are no longer approved. The four-digit UN identification number is 1076. The NFPA 704 designation is health 4, flammability 0, and reactivity 1. It is shipped in steel cylinders, special tank cars, and tank trucks.

健康ハザード

PHOSGENE is a lung toxicant that causes damage to the capillaries, bronchioles and alveoli of the lungs, by decomposition to hydrochloric acid. There is little immediate irritant effect upon the respiratory tract, and the warning properties of the gas are therefore very slight. Pulmonary edema, bronchopneumonia and occasionally lung abscesses develop. Degenerative changes in the nerves have been reported as later developments. A concentration of 25 ppm is dangerous for exposures lasting 30-60 minutes and 50 ppm is rapidly fatal after even short exposure.

火災危険

When heated to decomposition or on contact with water or steam, PHOSGENE will react to produce toxic and corrosive fumes. Reacts violently with aluminum; tert-butyl azido formate; 2,4-hexadiyn-1,6-diol; isopropyl alcohol; potassium; sodium; hexafluoro isopropylidene; amino lithium; lithium. Stable in steel containers if dry. Avoid moisture.

燃焼性と爆発性

Noncombustible.

使用用途

ホスゲンは、の原料となるイソシアン酸エステルRNCOの合成、染料および中間体の原料、イソシアネートの製造、ポリウレタン製品の処理剤、医薬品の製造、農薬の原料、可塑剤およびの原料化学工業分野で使用されています。

また、代表的な窒息性毒ガスで、吸引により催涙、くしゃみ、呼吸困難などの急性症状が出て、数時間後に肺水腫を起して死に至ります。塩素と共に窒息性の物質として、重いガスであるため、敵の塹壕をすぐに満たしてしまう効果を期待され、第1次世界大戦で毒ガス兵器として使用されました。

法規情報

ホスゲンは、労働基準法で「疾病化学物質」、労働安全衛生法で「名称等を表示・通知すべき危険物・有害物」、「危険性又は有害性等を調査すべき物」「特定化学物質第3類物質」などに該当します。化学物質排出把握管理促進法 (PRTR法) には指定がありませんが、毒物及び劇物取締法では「毒物」、消防法では「貯蔵等の届出を要する物質」に指定されており、使用の際には注意が必要です。

取扱いおよび保管上の注意

取扱い及び保管上の注意は、下記の通りです。

• 保管容器は、換気の良い場所で保管する。
• 屋外や換気の良い区域のみで使用する。
• 使用時は保護手袋、保護眼鏡、保護衣、保護面を着用する。
• 激しく反応するため、エタノール、強酸化剤、アンモニア、アミンおよびアルミニウムとの接触を避ける。
• 水と接触すると腐食性の塩酸を生成するため、接触を避ける。
• 取扱い後はよく手を洗浄する。
• 吸入した場合、空気の新鮮な場所に移し、呼吸しやすい姿勢で休息させ、医師に連絡する。
• 皮膚に付着した場合は、多量の水と石鹸で洗い流す。
• 眼に入った場合は、水で数分間注意深く洗う。

工業用途

The common name for carbonyl chloride, COCl₂, a colorless, poisonous gas made by the action of chlorine on carbon monoxide. It was used as a poison war gas. But it is now used in the manufacture of metal chlorides and anhydrides, pharmaceuticals, perfumes, isocyanate resins, and for blending in synthetic rubbers.
Because of its toxicity, most phosgene is produced and employed immediately in captive applications. The biggest use of the material is for toluene diisocyanate (TDI), which is then reacted into polyurethane resins for foams, elastomers, and coatings. Polycarbonate is used for making breakresistant housings, signs, glazings, and electrical tools. Phosgene also is a reactant for the isocyanates that are used in pesticides, and the di- and polyisocyanates are adhesives, coatings, and elastomers.

安全性プロファイル

A human poison by inhalation, A severe eye, skin, and mucous membrane irritant. In the presence of moisture, phosgene decomposes to form hydrochloric acid and carbon monoxide. This occurs in the bronchioles and alveoli of the lungs, resulting in pulmonary edema followed by bronchopneumonia and occasionally lung abscess. There is little immediate irritating effect upon the respiratory tract, and the warning properties of the gas are therefore very slight. There may be no immedate warning that dangerous concentrations are being inhaled. After a latent period of 2 to 24 hours, the patient complains of burning in the throat and chest, shortness of breath, and increasing dyspnea. Where the exposure has been severe, the development of pulmonary edema may be so rapid that the patient dies within 36 hours after exposure. In cases where the exposure has been less, pneumonia may develop several days after the occurrence of the accident. In patients who recover, no permanent residual disability is thought to occur. A common air contaminant. Under the appropriate conditions it undergoes hazardous reactions with Al, tertbutyl azido formate, 2,4-hexadiyn-l,6-diol, isopropyl alcohol, K, Na, sodium azide, hexafluoroisopropylideneamino lithium, lithium. When heated to decomposition or on contact with water or steam it will react to produce toxic and corrosive fumes of CO and Cl-. Caution: Arrangements should be made for monitoring its use

職業ばく露

Phosgene can be deadly at a concentration as low as 2 ppm. Phosgene is used as an intermediate in the manufacture of many industrial chemicals, including dyes and plastics; in the making of dyestuffs based on triphenylmethane, coal tar, and urea. It is also used in the organic synthesis of isocyanates and their derivatives, carbonic acid esters (polycarbonates); and acid chlorides. Other applications include its utilization in metallurgy; and in the manufacture of some insecticides and pharmaceuticals. Exposure to phosgene may occur during arc welding and in fires involving vinyl chloride; released from household paint removers and degreasers when they are used in the presence of heat. Phosgene (CG) has been used as a military choking, pulmonary agent since WW I, and has become a staple of chemical arsenals in many countries

貯蔵

In particular, work with phosgene 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. Containers of phosgene solutions should be stored in secondary containers, and phosgene cylinders should be stored in a cool, wellventilated area separate from incompatible materials.

輸送方法

UN1076 Phosgene, Hazard Class: 2.3; Labels: 2.3-Poisonous gas, 8-Corrosive material, Inhalation, Hazard Zone A. Cylinders must be transported in a secure upright position, in a well-ventilated truck. Protect cylinder and labels from physical damage. The owner of the compressed gas cylinder is the only entity allowed by federal law (49CFR) to transport and refill them. It is a violation of transportation regulations to refill compressed gas cylinders without the express written permission of the owner. Military driver shall be given full and complete information regarding shipment and conditions in case of emergency.AR 50-6 deals specifically with the shipment of chemical agents. Shipments of agent will be escorted in accordance with AR 740-32

純化方法

Dry the gas with Linde 4A molecular sieves, de-gas it and distil it under vacuum at low temperature. This should be done in a closed system such as a vacuum line. It is hydrolysed by H2O but does not fume in moist air. It is available in cylinders and as a ~20% solution in toluene. It is HIGHLY TOXIC and should not be inhaled. If it is inhaled, the operator should lie still and, be made to breathe in ammonia vapour which reacts with phosgene to give urea. [Pope et al. J Chem Soc 117 1410 1920, Beilstein 3 IV 41.]

不和合性

Moisture, alkalis, ammonia, alcohols, copper. Reacts slowly in water to form corrosive hydrogen chloride and carbon dioxide. Violent reaction with strong oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.); contact may cause fires or explosions. Keep away from alcohols, alkaline materials, strong acids, strong bases, alcohols, ammonia, amines, aluminum, alkali metals. Attacks many metals in presence of water. Phosgene (CG) reacts violently with strong oxidants, amines, alkalis, and many metals. Above 300C, phosgene decomposes in the presence of moisture to form hydrochloric acid and carbon dioxide. In the presence of moisture, phosgene attacks plastic, rubber, coatings and many metals.

塩化カルボニル 上流と下流の製品情報

原材料

準備製品

75-44-5(塩化カルボニル)キーワード:

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• 75-44-5
• Carbon oxychloride
• carbondichlorideoxide
• carbone(oxychlorurede)
• carbone(oxychlorurede)(french)
• Carbonic chloride
• carbonicaciddichloride
• carbonicchloride
• Carbonicdichloride
• carbonio(ossiclorurodi)
• carbonoxychloride
• Carbonylchlorid
• Carbonyldichlorid
• carbonyldichloride
• chlorformylchloride
• Chloro-formyl
• Chloroformyl chloride
• chloroformylchloride
• combatgas
• Dichloroformaldehyde
• Fosgeen
• Fosgen
• fosgen(polish)
• Fosgene
• Hhloroformylchloride
• Koolstofoxychloride
• NCI-C60219
• phosgene1010
• phosgenecyl.with0.40l(net~500g)
• Rcra waste number P095
• rcrawastenumberp095
• 塩化カルボニル
• カルボニルジクロリド
• 炭酸ジクロリド
• カルボニルクロリド
• 二塩化炭酸
• クロロホルミルクロリド
• ホスゲン
• オキシ塩化炭素
• カルボニルクロライド
• ジクロロケトン
• ジクロロメタノン
• 化カルボニル