Diketene

84.07340

84.07

211-617-1

0DZ97C3Z7D

1280

93783

2521

DTXSID9027289

Colorless liquid; turns brownish-yellow upon standing at room temperature|Colorless liquid when pure|Light colored liquid

26.30000

0.44700

COLOURLESS LIQUID

1.0897 g/cm³

-6.5 °C

127.4 °C

34

1.439

Solubility in water: reaction

2-8ºC

7.9 mm Hg ( 20 °C)

2.9 (vs air)

Explosive limits , vol% in air: 2-11.7

Pungent odor

Henry's Law constant = 6.07X10-4 atm-cu m/mol at 25 °C (est)

BP: 126-127 °C with slight decomposition; 69-71 °C at 100 mm Hg. MP: -7.5 °C|Readily polymerizes on standing|Specific gravity: 1.0939 at 18 °C/4 °C; 1.0905 at 23 °C/4 °C|Specific gravity: 1.09471 at 20 °C/4 °C; 1.088754 at 25 °C/4 °C|Decomposes in water, can react with oxidizing materials|There is no known inhibitor /of polymerization/. Polymerization of uncontaminated diketene is negligible if kept at or near 0 °C.|For more Other Experimental Properties (Complete) data for Acetyl ketene (9 total), please visit the HSDB record page.

Highly flammable. Slightly soluble in water.

Esters, Sulfate Esters, Phosphate Esters, Thiophosphate Esters, and Borate Esters

Highly Flammable

DIKETENE is a very reactive dimer, it may undergo a spontaneous decomposition followed by explosion or ignition [Vervalin, 1973, p.86]. In the presence of bases, amines, mineral acids or Lewis acids a violent polymerization will occur, accompanied by gas evolution [Zdenek, F. et al., Czech Pat. 156 584, 1975].

590 °F (310 °C)|275 °C

42.89 kJ/mol at 25 °C

Critical temperature: 310 °C (583.16 K); critical pressure: 5.47 MPa

I

6.1(a)

UN 2521

2

R10; R20

S3

RQ8225000

Xn

Fireproof. Separated from acids, bases and food and feedstuffs. Cooled. Dry. Store only if stabilized.

READILY POLYMERIZES ON STANDING

P261-P301 + P312 + P330-P304 + P340 + P312-P403 + P233-P403 + P235

H226-H302-H331

SRP: Recycle any unused portion of the material for its approved use or return it to the manufacturer or supplier. Ultimate disposal of the chemical must consider: the material's impact on air quality; potential migration in air, soil or water; effects on animal, aquatic and plant life; and conformance with environmental and public health regulations. If it is possible or reasonable use an alternative chemical product with less inherent propensity for occupational harm/injury/toxicity or environmental contamination.

... Can react vigorously with oxidizing materials. A violent polymerization reaction is catalyzed by acids, bases, or sodium acetate.|Reacts with water to form acetone and carbon dioxide.|Presence of mineral, or Lewis acids, or bases including amines, will catalyze violent polymerization.

Excerpt from ERG Guide 131P [Flammable Liquids - Toxic]: HIGHLY FLAMMABLE: Will be easily ignited by heat, sparks or flames. Vapors may form explosive mixtures with air. Vapors may travel to source of ignition and flash back. Most vapors are heavier than air. They will spread along ground and collect in low or confined areas (sewers, basements, tanks). Vapor explosion and poison hazard indoors, outdoors or in sewers. Those substances designated with a (P) may polymerize explosively when heated or involved in a fire. Runoff to sewer may create fire or explosion hazard. Containers may explode when heated. Many liquids are lighter than water. (ERG, 2016)|Flammable. Above 33 °C explosive vapour/air mixtures may be formed. Risk of fire and explosion on contact with acids, bases or water.|Flammable - 3rd degree, Reactive - 2nd degree

|Warning|H226: Flammable liquid and vapor [Warning Flammable liquids]|P210, P233, P240, P241, P242, P243, P261, P271, P280, P303+P361+P353, P304+P312, P304+P340, P312, P370+P378, P403+P235, and P501|Danger|H226 (100%): Flammable liquid and vapor [Warning Flammable liquids]|P210, P233, P240, P241, P242, P243, P260, P261, P264, P270, P271, P280, P284, P301+P310, P301+P312, P302+P352, P303+P361+P353, P304+P312, P304+P340, P305+P351+P338, P310, P311, P312, P320, P321, P330, P332+P313, P362, P370+P378, P403+P233, P403+P235, P405, and P501|Aggregated GHS information provided by 76 companies from 4 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.|P210, P233, P240, P241, P242, P243, P260, P264, P270, P271, P280, P284, P301+P312, P302+P352, P303+P361+P353, P304+P340, P305+P351+P338, P309+P311, P310, P320, P321, P330, P332+P313, P362, P370+P378, P403+P233, P403+P235, P405, and P501

Excerpt from ERG Guide 131P [Flammable Liquids - Toxic]: As an immediate precautionary measure, isolate spill or leak area for at least 50 meters (150 feet) in all directions. SPILL: See ERG Table 1 - Initial Isolation and Protective Action Distances on the UN/NA 2521 datasheet. FIRE: If tank, rail car or tank truck is involved in a fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consider initial evacuation for 800 meters (1/2 mile) in all directions. (ERG, 2016)

Excerpt from ERG Guide 131P [Flammable Liquids - Toxic]: Fully encapsulating, vapor-protective clothing should be worn for spills and leaks with no fire. ELIMINATE all ignition sources (no smoking, flares, sparks or flames in immediate area). All equipment used when handling the product must be grounded. Do not touch or walk through spilled material. Stop leak if you can do it without risk. Prevent entry into waterways, sewers, basements or confined areas. A vapor-suppressing foam may be used to reduce vapors. SMALL SPILL: Absorb with earth, sand or other non-combustible material and transfer to containers for later disposal. Use clean, non-sparking tools to collect absorbed material. LARGE SPILL: Dike far ahead of liquid spill for later disposal. Water spray may reduce vapor, but may not prevent ignition in closed spaces. (ERG, 2016)

Excerpt from ERG Guide 131P [Flammable Liquids - Toxic]: Wear positive pressure self-contained breathing apparatus (SCBA). Wear chemical protective clothing that is specifically recommended by the manufacturer. It may provide little or no thermal protection. Structural firefighters' protective clothing provides limited protection in fire situations ONLY; it is not effective in spill situations where direct contact with the substance is possible. (ERG, 2016)

Flammable.|... Moderate fire risk.|Flammable when exposed to heat or flame ... .

Explosive limits , vol% in air: 2-11.7

To fight fire, use alcohol foam.|Approach fire from upwind to avoid hazardous vapors and toxic decomposition products. Fight fire from protected location or maximum possible distance. Use water spray to keep fire-exposed containers cool. Use flooding quantities of water as fog or spray. Carbon dioxide may be used. Extinguish fire using agent suitable for surrounding fire.|If material on fire or involved in fire: Do not extinguish fire unless flow can be stopped. Use water in flooding quantities as fog. Solid streams of water may be ineffective. Cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible. Use "alcohol" foam, dry chemical or carbon dioxide. Keep run-off water out of sewers and water sources. /Diketene, stabilized/

Vapors are heavier than air and may travel to a source of ignition and flash back. Closed containers may rupture violently when heated. Thermally unstable.

Environmental considerations - land spill: Dig a pit, pond, lagoon, holding area to contain liquid or solid material. /SRP: If time permits, pits, ponds, lagoons, soak holes, or holding areas should be sealed with an impermeable flexible membrane liner./ Dike surface flow using soil, sand bags, foamed polyurethane, or foamed concrete. Absorb bulk liquid with fly ash, cement powder, or commrcial sorbents. /Diketene, stabilized/|Environmental considerations - water spill: Use natural barriers or oil spill control booms to limit spill travel. Remove trapped material with suction hoses. /Diketene, stabilized/|Environmental considerations - air spill: Apply water spray or mist to knock down vapors. Disperse vapors using fans or blowers. /Diketene, stabilized/|Wear special protective clothing and positive pressure self-contained breathing apparatus. Eliminate all ignition sources. Approach release from upwind. Use water spray to cool and disperse vapors, protect personnel, and dilute spills to form nonflammable mixtures. Stop or control the leak, if this can be done without undue risk. Control runoff and isolate discharged material for proper disposal. Releases may require isolation or evacuation.

SRP: The scientific literature for the use of contact lenses by industrial workers is inconsistent. The benefits or detrimental effects of wearing contact lenses depend not only upon the substance, but also on factors including the form of the substance, characteristics and duration of the exposure, the uses of other eye protection equipment, and the hygiene of the lenses. However, there may be individual substances whose irritating or corrosive properties are such that the wearing of contact lenses would be harmful to the eye. In those specific cases, contact lenses should not be worn. In any event, the usual eye protection equipment should be worn even when contact lenses are in place.|If material not on fire and not involved in fire: Keep sparks, flames, and other sources of ignition away. Keep material out of water sources and sewers. Buils dikes to contain flow as necessary. Attempt to stop peak if without undue personnel hazard. Use water spray to knock-down vapors /Diketene, stabilized/|Personnel protection: Avoid breathing vapors. Keep upwind. ... Avoid bodily contact with the material. ... Do not handle broken packages unless wearing appropriate personal protective equipment. Wash away any material which may have contacted the body with copious amounts of water or soap and water. Wear positive positive pressure self-contained breathing apparatus when fighting fires involving this material. If contact with the material anticipated, wear appropriate chemical protective clothing. /Diketene, stabilized/

If ... THERE IS NO FIRE, go directly to the Table of Initial Isolation and Protective Action Distances /(see table below)/ ... to obtain initial isolation and protective action distances. IF THERE IS A FIRE, or IF A FIRE IS INVOLVED, go directly to the appropriate guide /(see guide(s) below)/ and use the evacuation information shown under PUBLIC SAFETY. /Diketene, stabilized/|/GUIDE 131P FLAMMABLE LIQUIDS - TOXIC/ Fire or Explosion: HIGHLY FLAMMABLE: Will be easily ignited by heat, sparks or flames. Vapors may form explosive mixtures with air. Vapors may travel to source of ignition and flash back. Most vapors are heavier than air. They will spread along ground and collect in low or confined areas (sewers, basements, tanks). Vapor explosion and poison hazard indoors, outdoors or in sewers. Those substances designated with a (P) may polymerize explosively when heated or involved in a fire. Runoff to sewer may create fire or explosion hazard. Containers may explode when heated. Many liquids are lighter than water. /Diketene, stabilized/|/GUIDE 131P FLAMMABLE LIQUIDS - TOXIC/ Health: TOXIC; may be fatal if inhaled, ingested or absorbed through skin. Inhalation or contact with some of these materials will irritate or burn skin and eyes. Fire will produce irritating, corrosive and/or toxic gases. Vapors may cause dizziness or suffocation. Runoff from fire control or dilution water may cause pollution. /Diketene, stabilized/|/GUIDE 131P FLAMMABLE LIQUIDS - TOXIC/ Public Safety: CALL Emergency Response Telephone Number on Shipping Paper first. If Shipping Paper not available or no answer, refer to appropriate telephone number listed on the inside back cover. As an immediate precautionary measure, isolate spill or leak area for at least 50 meters (150 feet) in all directions. Keep unauthorized personnel away. Stay upwind, uphill and/or upstream. Ventilate closed spaces before entering. /Diketene, stabilized/|For more DOT Emergency Guidelines (Complete) data for Acetyl ketene (9 total), please visit the HSDB record page.

No person may /transport,/ offer or accept a hazardous material for transportation in commerce unless that person is registered in conformance ... and the hazardous material is properly classed, described, packaged, marked, labeled, and in condition for shipment as required or authorized by ... /the hazardous materials regulations (49 CFR 171-177)./|The International Air Transport Association (IATA) Dangerous Goods Regulations are published by the IATA Dangerous Goods Board pursuant to IATA Resolutions 618 and 619 and constitute a manual of industry carrier regulations to be followed by all IATA Member airlines when transporting hazardous materials. Diketene, stabilized is included on the dangerous goods list. /Diketene, stabilized/|The International Maritime Dangerous Goods Code lays down basic principles for transporting hazardous chemicals. Detailed recommendations for individual substances and a number of recommendations for good practice are included in the classes dealing with such substances. A general index of technical names has also been compiled. This index should always be consulted when attempting to locate the appropriate procedures to be used when shipping any substance or article. Diketene, stabilized is included on the dangerous goods list. /Diketene, stabilized/

A skin and severe eye irritant.

Remove all ignition sources. Evacuate danger area! Consult an expert! Personal protection: filter respirator for organic gases and vapours adapted to the airborne concentration of the substance. Collect leaking liquid in covered containers. Absorb remaining liquid in sand or inert absorbent. Then store and dispose of according to local regulations. NEVER direct water jet on liquid.

Separated from acids, bases and food and feedstuffs. Well closed. Fireproof. Cool. Dry. Store only if stabilized.

No indication can be given about the rate at which a harmful concentration of this substance in the air is reached on evaporation at 20 °C.

The substance may be irritating to the respiratory tract, eyes and skin.

NO open flames, NO sparks and NO smoking. NO contact with acids, bases or water. Above 33 °C use a closed system, ventilation and explosion-proof electrical equipment.

PREVENT GENERATION OF MISTS!

Use ventilation, local exhaust or breathing protection.

Protective gloves. Protective clothing.

Wear safety goggles or eye protection in combination with breathing protection.

This action promulgates standards of performance for equipment leaks of Volatile Organic Compounds (VOC) in the Synthetic Organic Chemical Manufacturing Industry (SOCMI). The intended effect of these standards is to require all newly constructed, modified, and reconstructed SOCMI process units to use the best demonstrated system of continuous emission reduction for equipment leaks of VOC, considering costs, non air quality health and environmental impact and energy requirements. Diketene is produced, as an intermediate or a final product, by process units covered under this subpart.

| 3 - Materials that, under emergency conditions, can cause serious or permanent injury.| 3 - Liquids and solids that can be ignited under almost all ambient temperature conditions. Materials produce hazardous atmospheres with air under almost all ambient temperatures or, though unaffected by ambient temperatures, are readily ignited under almost all conditions.| 2 - Materials that readily undergo violent chemical changes at elevated temperatures and pressures.|W - No water: Materials that react violently or explosively with water.

IDENTIFICATION AND USE: Acetyl ketene is a colorless liquid, which turns brownish-yellow upon standing at room temperature. It is used in the production of acetoarylamides, pigments and toners, pesticides, food preservatives, pharmaceutical intermediates. It is also used as a reagent in synthetic organic chemistry. HUMAN STUDIES: There are no data available. ANIMAL STUDIES: it was not carcinogenic in mice following dermal application or sc injection, and in rats after sc injection. Extended toxicity testing on mice, rats, guinea pigs and rabbits showed that ten minute exposures to concentrations of freshly generated acetyl ketene as low as 116 ppm was lethal.

LD50 Rat oral 560 mg/kg|LC50 Guinea pig inhalation 3 g/cu m/2 hr|LD50 Rabbit dermal 2830 mg/kg

Acetyl ketene's use as a reagent in synthetic organic chemistry(1) and chemical intermediate for acetoacetic esters and acetoacetanilides, dyes, pharmaceuticals, food preservatives, and insecticides(2) may result in its release to the environment through various waste streams(SRC).

TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 6(SRC), determined from a structure estimation method(2), indicates that acetyl ketene is expected to have very high mobility in soil(SRC). Volatilization of acetyl ketene from moist soil surfaces is expected to be an important fate process(SRC) given an estimated Henry's Law constant of 6.1X10-4 atm-cu m/mole(SRC), developed using a fragment constant estimation method(2). Acetyl ketene is expected to volatilize from dry soil surfaces(SRC) based upon a vapor pressure of 10.7 mm Hg at 25 °C(3). Utilizing the Japanese MITI test, 94% of the Theoretical BOD was reached in 4 weeks(4) indicating that biodegradation is an important environmental fate process in soil(SRC).|AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 6(SRC), determined from a structure estimation method(2), indicates that acetyl ketene is not expected to adsorb to suspended solids and sediment(SRC). Volatilization from water surfaces is expected(3) based upon an estimated Henry's Law constant of 6.1X10-4 atm-cu m/mole(SRC), developed using a fragment constant estimation method(2). Using this Henry's Law constant and an estimation method(3), volatilization half-lives for a model river and model lake are 4 hrs and 4 days, respectively(SRC). According to a classification scheme(4), an estimated BCF of 3(SRC), from an estimated log Kow of -0.39(2) and a regression-derived equation(2), suggests the potential for bioconcentration in aquatic organisms is low(SRC). Utilizing the Japanese MITI test, 94% of the Theoretical BOD was reached in 4 weeks(5) indicating that biodegradation is an important environmental fate process in water(SRC).|ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), acetyl ketene, which has a vapor pressure of 10.7 mm Hg at 25 °C(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase acetyl ketene is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals(SRC); the half-life for this reaction in air is estimated to be 7.5 hrs(SRC), calculated from its rate constant of 5.2X10-11 cu cm/molecule-sec at 25 °C(SRC) that was derived using a structure estimation method(3). Vapor-phase acetyl ketene is degraded in the atmosphere by reaction with ozone(SRC); the half-life for this reaction in air is estimated to be 24 hrs(SRC), calculated from its rate constant of 1.1X10-17 cu cm/molecule-sec at 25 °C(SRC) that was derived using a structure estimation method(3). Acetyl ketene contains chromophores that absorb at wavelengths >290 nm(4) and, therefore, may be susceptible to direct photolysis by sunlight(SRC).

The rate constant for the vapor-phase reaction of acetyl ketene with photochemically-produced hydroxyl radicals has been estimated as 5.2X10-11 cu cm/molecule-sec at 25 °C(SRC) using a structure estimation method(1). This corresponds to an atmospheric half-life of about 7.5 hours at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm(1). The rate constant for the vapor-phase reaction of acetyl ketene with ozone has been estimated as 1.1X10-17 cu cm/molecule-sec at 25 °C(SRC) that was derived using a structure estimation method(1). This corresponds to an atmospheric half-life of about 24 hrs at an atmospheric concentration of 7X10+11 ozone molecules per cu cm(2). Water hydrolyzes acetyl ketene only very slowly, to unstable acetoacetic acid, which further decomposes to acetone and carbon dioxide(3). Acetyl ketene contains chromophores that absorb at wavelengths >290 nm(4) and, therefore, may be susceptible to direct photolysis by sunlight(SRC).

An estimated BCF of 3 was calculated in fish for acetyl ketene(SRC), using an estimated log Kow of -0.39(1) and a regression-derived equation(1). According to a classification scheme(2), this BCF suggests the potential for bioconcentration in aquatic organisms is low(SRC).

Using a structure estimation method based on molecular connectivity indices(1), the Koc of acetyl ketene can be estimated to be 6(SRC). According to a classification scheme(2), this estimated Koc value suggests that acetyl ketene is expected to have very high mobility in soil(SRC).

The Henry's Law constant for acetyl ketene is estimated as 6.1X10-4 atm-cu m/mole(SRC) developed using a fragment constant estimation method(1). This Henry's Law constant indicates that acetyl ketene is expected to volatilize from water surfaces(2). Based on this Henry's Law constant, the volatilization half-life from a model river (1 m deep, flowing 1 m/sec, wind velocity of 3 m/sec)(2) is estimated as 4 hours(SRC). The volatilization half-life from a model lake (1 m deep, flowing 0.05 m/sec, wind velocity of 0.5 m/sec)(2) is estimated as 4 days(SRC). Acetyl ketene's Henry's Law constant indicates that volatilization from moist soil surfaces may occur(SRC). Acetyl ketene is expected to volatilize from dry soil surfaces(SRC) based upon a vapor pressure of 10.7 mm Hg(3).

According to the 2012 TSCA Inventory Update Reporting data, 1 reporting facility estimated the number of persons reasonably likely to be exposed during the manufacturing, processing, or use of acetyl ketene in the United States is not reasonably known; the data may be greatly underestimated(1).|Occupational exposure to acetyl ketene may occur through inhalation and dermal contact with this compound at workplaces where acetyl ketene is produced or used. Use data indicate that the general population is not likely to be exposed to acetyl ketene. (SRC)

Excerpt from ERG Guide 131P [Flammable Liquids - Toxic]: TOXIC; may be fatal if inhaled, ingested or absorbed through skin. Inhalation or contact with some of these materials will irritate or burn skin and eyes. Fire will produce irritating, corrosive and/or toxic gases. Vapors may cause dizziness or suffocation. Runoff from fire control or dilution water may cause pollution. (ERG, 2016)

Excerpt from ERG Guide 131P [Flammable Liquids - Toxic]: Ensure that medical personnel are aware of the material(s) involved and take precautions to protect themselves. Move victim to fresh air. Call 911 or emergency medical service. Give artificial respiration if victim is not breathing. Do not use mouth-to-mouth method if victim ingested or inhaled the substance; give artificial respiration with the aid of a pocket mask equipped with a one-way valve or other proper respiratory medical device. Administer oxygen if breathing is difficult. Remove and isolate contaminated clothing and shoes. In case of contact with substance, immediately flush skin or eyes with running water for at least 20 minutes. Wash skin with soap and water. In case of burns, immediately cool affected skin for as long as possible with cold water. Do not remove clothing if adhering to skin. Keep victim calm and warm. Effects of exposure (inhalation, ingestion or skin contact) to substance may be delayed. (ERG, 2016)

Fresh air, rest. Refer for medical attention.

Remove contaminated clothes. Rinse skin with plenty of water or shower. Refer for medical attention if skin irritation occurs.

First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention.

Immediate first aid: Ensure that adequate decontamination has been carried out. If patient is not breathing, start artificial respiration, preferably with a demand-valve resuscitator, bag-valve-mask device, or pocket mask, as trained. Perform CPR if necessary. Immediately flush contaminated eyes with gently flowing water. Do not induce vomiting. If vomiting occurs, lean patient forward or place on left side (head-down position, if possible) to maintain an open airway and prevent aspiration. Keep patient quiet and maintain normal body temperature. Obtain medical attention. /Ketones and related compounds/|Basic treatment: Establish a patent airway (oropharyngeal or nasopharyngeal airway, if needed). Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if necessary. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if necessary ... . For contamination, flush eyes immediately with water. Irrigate each eye continuously with 0.9% saline (NS) during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 mL/kg up to 200 mL of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool. Administer activated charcoal ... . /Ketones and related compounds/|Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious, has severe pulmonary edema, or is in severe respiratory distress. Positive-pressure ventilation techniques with a bag-valve-mask device may be beneficial. Consider drug therapy for pulmonary edema ... . Consider administering a beta agonist such as albuterol for severe bronchospasm ... . Monitor cardiac rhythm and treat arrhythmias if necessary ... . Start IV administration of D5W /SRP: "To keep open", minimal flow rate/. Use 0.9% saline (NS) or lactated Ringer's (LR) if signs of hypovolemia are present. For hypotension with signs of hypovolemia, administer fluid cautiously. Watch for signs of fluid overload ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Ketones and related compounds/

diketene

The substance can be absorbed into the body by inhalation of its vapour and by ingestion.

Cough. Sore throat.

Redness. Pain.

Redness. Pain.

All other basic organic chemical manufacturing|2-Oxetanone, 4-methylene-: ACTIVE|Diketene is now generally consumed at the site of production, because of its extreme reactivity and hazardous properties.

Diketene can conveniently be analyzed by standard gc methods. ir and nmr have mainly been used for identification purposes. nmr analysis can also be valuable to follow the degree of polymerization of stored diketene.

Fire Hazards -> Flammable - 3rd degree, Reactive - 2nd degree