HEXAMETHYLENE DIISOCYANATE
HAZARDTEXT ®
Information to help in the initial response for evaluating chemical incidents
-IDENTIFICATION
SYNONYMS
DESMODUR H DESMODUR N 1,6-DIISOCYANATOHEXANE DIISOCYANATE D'HEXAMETHYLENE DIISOCYANATOHEXANE HDI HDI-BT HEXAMETHYLENEDIISOCYANAT HEXAMETHYLENE DIISOCYANATE HEXAMETHYLENDIISOKYANAT (Czech) HEXAMETHYLENE-1,6-DIISOCYANATE 1,6-HEXAMETHYLENE DIISOCYANATE HEXANE 1,6-DIISOCYANATE HEXANE, 1,6-DIISOCYANATO- 1,6-HEXANEDIOL DIISOCYANATE 1,6-HEXYLENE DIISOCYANATE HMDI ISOCYANIC ACID, DIESTER WITH 1,6-HEXANEDIOL ISOCYANIC ACID, HEXAMETHYLENE ESTER METYLENO-BIS-FENYLOIZOCYJANIAN (Polish) SZESCIOMETYLENODWUIZOCYJANIAN (Polish) TL 78
IDENTIFIERS
USES/FORMS/SOURCES
Hexamethylene diisocyanate is mainly used as a cross-linking agent (hardener) in the manufacturing of dental materials, contact lenses, medical adsorbents, nylon, and higher molecular weight biuret polyisocyanate products (which are subsequently used as curing agents in the formulation of polyurethane paint systems for automobile refinishing, marine coatings, industrial maintenance, and other high performance coating systems) (ACGIH, 1991; Clayton & Clayton, 1994) Hathaway, 1996; (HSDB , 1999; ILO, 1998). Diisocyantes are used in the productions of flexible polyurethane foam (where the reaction involves water) and rigid polyurethane foam (Raffle et al, 1994; (Sittig, 1991). Diisocyanates are used are used in inks and as laminating adhesives (during the production of flexible packaging) (Raffle et al., 1994).
-CLINICAL EFFECTS
GENERAL CLINICAL EFFECTS
- Hexamethylene diisocyanate may be irritating to the eyes, skin, and mucous membranes. Symptoms of exposure may include cough, dyspnea, wheezing, asthma, chest tightness, and pulmonary edema. Blisters and burns may occur following skin contact; conjunctivitis, keratitis, glaucoma, and corneal damage may also occur.
- POTENTIAL HEALTH HAZARDS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004)
TOXIC; inhalation, ingestion or contact (skin, eyes) with vapors, dusts or substance may cause severe injury, burns or death. Contact with molten substance may cause severe burns to skin and eyes. Reaction with water or moist air will release toxic, corrosive or flammable gases. Reaction with water may generate much heat that will increase the concentration of fumes in the air. Fire will produce irritating, corrosive and/or toxic gases. Runoff from fire control or dilution water may be corrosive and/or toxic and cause pollution.
ACUTE CLINICAL EFFECTS
- HDI is a skin, eye, and mucous membrane irritant and a respiratory and dermal sensitizer (Hathaway et al, 1991; Schmidt & Bomhard, 1983).
- Acute respiratory symptoms can develop after exposure to concentrations of 0.5 ppm or higher, and may be delayed in onset by 4 to 8 hours (Hathaway et al, 1991). Increased secretions, cough, dyspnea, and pulmonary edema can develop (Hathaway et al, 1991).
- One case of acute hemorrhagic pneumonitis has been seen in a spray painter with high levels of IgG and IgE antibodies specific for HDI and toluene diisocyanate. This reaction was thought to be similar to the hemorrhagic pneumonitis induced by trimellitic anhydride, and developed after the painter sprayed paint onto a warm surface (Patterson et al, 1990). Because of the mixed exposure, however, the effects could not be attributed specifically to HDI.
- The action of HDI appears to be similar to that of TOLUENE 2,4-DIISOCYANATE (TDI) (ACGIH, 1991). TDI is a model diisocyanate often used in toxicologic studies. As with other isocyanates, the mechanism of respiratory toxicity of HDI may be complex, and may involve acute irritant, pharmacologic, inflammatory and/or immunologic components (Hathaway et al, 1991). It is possible that different mechanisms may predominate in the same individual at different times.
- HDI is a sensory irritant in mice, with a 3-hour RD50 (concentration reducing respiratory rate by 50 percent) of 1.17 mg/m(3) (Sangha et al, 1981).
- The average half-life for urinary elimination of 1,6-hexamethylene diamine, a major metabolite of HDI, was 2.5 hours in human volunteers exposed to HDI airborne concentrations of 11.9 to 22.1 mcg/m(3) (Tinnerberg et al, 1995).
CHRONIC CLINICAL EFFECTS
- Workers who had been exposed to HDI at concentrations of 0.04 ppm or less reported eye, nose, and throat irritation, and coughing and chest discomfort in the absence of abnormal pulmonary function measurements. Because other chemicals were also present, it is not clear if similar effects would occur from exposure to such low levels of HDI alone (Hervin & Thoburn, 1975).
- HDI is a potent respiratory sensitizer and can induce occupational asthma, with effects usually appearing after several months of exposure (Belin & Wass, 1982; Hathaway et al, 1991; Cockcroft, 1982; Malo et al, 1983; Vandenplas et al, 1993). Spray painters with occupational asthma linked to HDI have also reacted to the nonvolatile prepolymer component of the paint (Vandenplas et al, 1993).
- Onset of symptoms may be insidious and may become progressively more severe with continued exposure (Hathaway et al, 1991). Symptoms often appear at night, with dyspnea and/or cough progressing to bronchospasm (Hathaway et al, 1991). The delay between exposure and onset of symptoms often makes it difficult to associate the effects with earlier exposure.
- Significant decline in respiratory function can accompany development of isocyanate asthma, and may persist for many months after termination of exposure. In one case, a spray painter experienced a 41 percent reduction in respiratory function within 3 hours after an HDI challenge, and enhanced nonspecific reactivity to histamine persisted for 18 months (Cockcroft & Mink, 1979). Another spray painter developed wheezing, dyspnea and sweating hours after using a polyurethane paint containing HDI; airway obstruction and exertional dyspnea were still evident one year later (Charles et al, 1976).
- Respiratory sensitivity to HDI may be either of the immediate or delayed type. In one study, one painter experienced an early asthmatic reaction, and two developed late responses, after an HDI challenge. Nonspecific bronchial reactivity was also increased 3- to 8-fold (Cockcroft et al, 1979).
- Generally 5 percent to 10 percent of workers exposed to isocyanates develop asthma, but the proportion may be as high as 20 percent when exposure levels are high (Baur, 1996).
- Hypersensitivity pneumonitis (extrinsic allergic alveolitis) has also been linked with exposure to HDI and its oligomers or prepolymers in isolated cases (Selden et al, 1989; Usui et al, 1992; Baur, 1995; Baur, 1996).
- There is some indication from controlled exposures that respiratory sensitization to HDI does not develop at exposure levels less than 0.005 ppm (34 mcg/m(3)). In one study, 5 healthy male subjects did not develop HDI-specific IgG or IgE antibodies or changes in spirometry or bronchial reactivity after exposure to approximately 25 mcg/m(3) HDI for 7.5 hours (Brorson et al, 1990).
- It should be noted, however, that controlled exposures with human volunteers are for a much shorter period of time than is required for the asthmatic response to develop under conditions of occupational exposure. If development of HDI-induced asthma follows a linear time-dose function, then lower concentrations may be able to induce an allergic reaction if exposure occurs over a long period of time.
- Dermal sensitization can also occur with HDI (Schmidt & Bomhard, 1983). Allergic dermatitis has been reported from occupational exposures to HDI as an ingredient of a fabric finish in approximately 10 percent of exposed workers (Wilkinson et al, 1991).
- Certain immunologic signs have accompanied respiratory responses to HDI. As many as 10 percent of 455 asymptomatic workers had elevated titers of HDI-specific IgG in the serum, and IgE is also present in some, but not all, persons with HDI-induced asthma (Selden et al, 1989). An individual with hypersensitivity pneumonitis suspected to be caused by HDI had increased levels of cytotoxic T lymphocytes in bronchoalveolar lavage fluid and increased natural killer (NK) cells in peripheral blood (Usui et al, 1992). Anti-double-stranded DNA autoantibodies were found in persons occupationally exposed to HDI and other isocyanates (Czuppon et al, 1993).
- Once sensitized to HDI, individuals may cross-react with other diisocyanates, such as TOLUENE DIISOCYANATE or DIPHENYLMETHANE DIISOCYANATE (O'Brien et al, 1979).
- Headache, sweating, weakness, disturbed dreams, breathing difficulty and enlarged liver were reported in workers exposed to HDI and also to phosgene and chlorobenzene (Filatova, 1968). Because of the mixed exposures, these effects could not be attributed specifically to HDI. Hepatotoxicity has not been a consistent finding in other studies of HDI.
- In rats chronically exposed to various concentrations of HDI, the critical determinant for establishment of the inhalation reference concentration (RfC) was degeneration of the olfactory epithelium; based on this effect, the RfC is 0.01 mcg/m(3) (Foureman et al, 1994).
- Mice and rats exposed to HDI by inhalation developed upper respiratory damage and hematologic disorders (Lomonova & Frolova, 1968). The hematologic effects have not been repeated in other studies.
-MEDICAL TREATMENT
LIFE SUPPORT
- Support respiratory and cardiovascular function.
SUMMARY
- FIRST AID - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004)
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. For minor skin contact, avoid spreading material on unaffected skin. Keep victim warm and quiet. Effects of exposure (inhalation, ingestion or skin contact) to substance may be delayed. Ensure that medical personnel are aware of the material(s) involved and take precautions to protect themselves.
FIRST AID EYE EXPOSURE - Immediately wash the eyes with large amounts of water, occasionally lifting the lower and upper lids. Get medical attention immediately. Contact lenses should not be worn when working with this chemical. DERMAL EXPOSURE - Immediately flush the contaminated skin with soap and water. If this chemical penetrates the clothing, immediately remove the clothing and flush the skin with water. If irritation persists after washing, get medical attention. INHALATION EXPOSURE - Move the exposed person to fresh air at once. If breathing has stopped, perform artificial respiration. Keep the affected person warm and at rest. Get medical attention as soon as possible. ORAL EXPOSURE - If this chemical has been swallowed, get medical attention immediately. TARGET ORGANS - Eyes, skin, and respiratory system (National Institute for Occupational Safety and Health, 2007).
GENERAL Move victims of inhalation exposure from the toxic environment and administer 100% humidified supplemental oxygen with assisted ventilation as required. Exposed skin and eyes should be copiously flushed with water. Ingestion may result in significant esophageal or gastrointestinal tract irritation or burns, and EMESIS SHOULD NOT BE INDUCED. Cautious gastric lavage followed by administration of activated charcoal may be of benefit if the patient is seen soon after the exposure.
INHALATION EXPOSURE INHALATION: Move patient to fresh air. Monitor for respiratory distress. If cough or difficulty breathing develops, evaluate for respiratory tract irritation, bronchitis, or pneumonitis. Administer oxygen and assist ventilation as required. Treat bronchospasm with an inhaled beta2-adrenergic agonist. Consider systemic corticosteroids in patients with significant bronchospasm. If bronchospasm and wheezing occur, consider treatment with inhaled sympathomimetic agents. ACUTE LUNG INJURY: Maintain ventilation and oxygenation and evaluate with frequent arterial blood gases and/or pulse oximetry monitoring. Early use of PEEP and mechanical ventilation may be needed.
DERMAL EXPOSURE DECONTAMINATION: Remove contaminated clothing and jewelry and place them in plastic bags. Wash exposed areas with soap and water for 10 to 15 minutes with gentle sponging to avoid skin breakdown. A physician may need to examine the area if irritation or pain persists (Burgess et al, 1999). Treat dermal irritation or burns with standard topical therapy. Patients developing dermal hypersensitivity reactions may require treatment with systemic or topical corticosteroids or antihistamines.
EYE EXPOSURE DECONTAMINATION: Remove contact lenses and irrigate exposed eyes with copious amounts of room temperature 0.9% saline or water for at least 15 minutes. If irritation, pain, swelling, lacrimation, or photophobia persist after 15 minutes of irrigation, the patient should be seen in a healthcare facility.
ORAL EXPOSURE Because of the potential for gastrointestinal tract irritation, DO NOT induce emesis. Significant esophageal or gastrointestinal tract irritation or burns may occur following ingestion. The possible benefit of early removal of some ingested material by cautious gastric lavage must be weighed against potential complications of bleeding or perforation. GASTRIC LAVAGE: Consider after ingestion of a potentially life-threatening amount of poison if it can be performed soon after ingestion (generally within 1 hour). Protect airway by placement in the head down left lateral decubitus position or by endotracheal intubation. Control any seizures first. ACTIVATED CHARCOAL: Administer charcoal as a slurry (240 mL water/30 g charcoal). Usual dose: 25 to 100 g in adults/adolescents, 25 to 50 g in children (1 to 12 years), and 1 g/kg in infants less than 1 year old. Observe patients with ingestion carefully for the possible development of esophageal or gastrointestinal tract irritation or burns. If signs or symptoms of esophageal irritation or burns are present, consider endoscopy to determine the extent of injury.
-RANGE OF TOXICITY
MINIMUM LETHAL EXPOSURE
MAXIMUM TOLERATED EXPOSURE
- Carcinogenicity Ratings for CAS822-06-0 :
ACGIH (American Conference of Governmental Industrial Hygienists, 2010): Not Listed ; Listed as: Hexamethylene diisocyanate ACGIH (American Conference of Governmental Industrial Hygienists, 2010): Not Listed ; Listed as: Hexamethylene diisocyanate EPA (U.S. Environmental Protection Agency, 2011): Not Assessed under the IRIS program. ; Listed as: 1,6-Hexamethylene diisocyanate IARC (International Agency for Research on Cancer (IARC), 2016; International Agency for Research on Cancer, 2015; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2010; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2010a; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2008; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2007; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2006; IARC, 2004): Not Listed NIOSH (National Institute for Occupational Safety and Health, 2007): Not Listed ; Listed as: Hexamethylene diisocyanate MAK (DFG, 2002): Not Listed NTP (U.S. Department of Health and Human Services, Public Health Service, National Toxicology Project ): Not Listed
TOXICITY AND RISK ASSESSMENT VALUES
- EPA Risk Assessment Values for CAS822-06-0 (U.S. Environmental Protection Agency, 2011):
Oral: Inhalation: Unit Risk: RfC: 1x10(-5) mg/m3
Drinking Water:
-STANDARDS AND LABELS
WORKPLACE STANDARDS
- ACGIH TLV Values for CAS822-06-0 (American Conference of Governmental Industrial Hygienists, 2010):
Editor's Note: The listed values are recommendations or guidelines developed by ACGIH(R) to assist in the control of health hazards. They should only be used, interpreted and applied by individuals trained in industrial hygiene. Before applying these values, it is imperative to read the introduction to each section in the current TLVs(R) and BEI(R) Book and become familiar with the constraints and limitations to their use. Always consult the Documentation of the TLVs(R) and BEIs(R) before applying these recommendations and guidelines.
- AIHA WEEL Values for CAS822-06-0 (AIHA, 2006):
- NIOSH REL and IDLH Values for CAS822-06-0 (National Institute for Occupational Safety and Health, 2007):
- OSHA PEL Values for CAS822-06-0 (U.S. Occupational Safety, and Health Administration (OSHA), 2010):
- OSHA List of Highly Hazardous Chemicals, Toxics, and Reactives for CAS822-06-0 (U.S. Occupational Safety and Health Administration, 2010):
ENVIRONMENTAL STANDARDS
- EPA CERCLA, Hazardous Substances and Reportable Quantities for CAS822-06-0 (U.S. Environmental Protection Agency, 2010):
Listed as: Hexamethylene-1,6-diisocyanate Final Reportable Quantity, in pounds (kilograms): Additional Information:
- EPA CERCLA, Hazardous Substances and Reportable Quantities, Radionuclides for CAS822-06-0 (U.S. Environmental Protection Agency, 2010):
- EPA RCRA Hazardous Waste Number for CAS822-06-0 (U.S. Environmental Protection Agency, 2010b):
- EPA SARA Title III, Extremely Hazardous Substance List for CAS822-06-0 (U.S. Environmental Protection Agency, 2010):
- EPA SARA Title III, Community Right-to-Know for CAS822-06-0 (40 CFR 372.65, 2006; 40 CFR 372.28, 2006):
Listed as: Hexamethylene-1,6-diisocyanate Effective Date for Reporting Under 40 CFR 372.30: 1/1/95 Lower Thresholds for Chemicals of Special Concern under 40 CFR 372.28:
- DOT List of Marine Pollutants for CAS822-06-0 (49 CFR 172.101 - App. B, 2005):
- EPA TSCA Inventory for CAS822-06-0 (EPA, 2005):
SHIPPING REGULATIONS
- DOT -- Table of Hazardous Materials and Special Provisions for UN/NA Number 2281 (49 CFR 172.101, 2005):
- ICAO International Shipping Name for UN2281 (ICAO, 2002):
LABELS
- NFPA Hazard Ratings for CAS822-06-0 (NFPA, 2002):
-HANDLING AND STORAGE
SUMMARY
Hexamethylene diisocyanate should be kept away from water, amines, carboxylic acids, strong bases, and alcohols. It should be stored in a tightly closed container and kept in a cool, well-ventilated area (Sittig, 1991).
HANDLING
- Wear appropriate personal protective clothing when handling to prevent skin contact (HSDB , 1999). Do not handle broken packages without proper personal protective equipment (AAR, 1998).
STORAGE
- ROOM/CABINET RECOMMENDATIONS
Hexamethylene diisocyanate should be kept away form acids, alcohols, amines, bases, and oxidants (ILO, 1998). Hexamethylene diisocyanate should be stored away from moisture or water (Sittig, 1991). Hexamethylene diisocyanate should be kept away from heat (HSDB , 1999; Urben, 1996). Contact with metals should be avoided (HSDB , 1999). Organic isocyanates are extremely reactive high-energy species; they can react with themselves and with nucleophiles, and can generate runaway exotherms. Hexamethylene diisocyanate can be readily oxidized with the covalent cyano group as endothermic and reactive (Urben, 1996).
-PERSONAL PROTECTION
SUMMARY
- RECOMMENDED PROTECTIVE CLOTHING - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004)
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.
- For the estimated 50,000-100,000 workers exposed to isocyanate in various occupations (Raffle et al, 1994), appropriate personal protective gear should be made available. Protective clothing and equipment should worn while working with the substance. Skin contact should be avoided, and skin area should be washed immediately when it becomes contaminated. Work clothing that is wet or significantly contaminated should be removed or replaced. Facilities for quickly drenching the body need to be provided within the immediate work area for emergency use where there is a possibility of exposure. These facilities should provide a sufficient quantity or flow of water to quickly remove the substance from body areas likely to be exposed (AAR, 1998; (HSDB , 1999). All protective clothing (suits, gloves, footwear, and headgear) should be clean and available each day to be put on before work (Sittig, 1991). Positive pressure self-contained breathing apparatus should be worn; dusts and fumes from burning materials should not be inhaled (AAR, 1998).
EYE/FACE PROTECTION
- Wear splash-proof chemical goggles, face shield, or full face-piece respiratory protection equipment (Sittig, 1991). Eyewash fountains should be provided within the immediate work area (HSDB , 1999).
RESPIRATORY PROTECTION
- Refer to "Recommendations for respirator selection" in the NIOSH Pocket Guide to Chemical Hazards on TOMES Plus(R) for respirator information.
PROTECTIVE CLOTHING
- CHEMICAL PROTECTIVE CLOTHING. Search results for CAS 822-06-0.
-PHYSICAL HAZARDS
FIRE HAZARD
- FLAMMABILITY CLASSIFICATION
- NFPA Flammability Rating for CAS822-06-0 (NFPA, 2002):
- FIRE CONTROL/EXTINGUISHING AGENTS
- FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004)
- SMALL FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004)
- LARGE FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004)
Water spray, fog or alcohol-resistant foam. FOR CHLOROSILANES, DO NOT USE WATER; use AFFF alcohol-resistant medium expansion foam. Move containers from fire area if you can do it without risk. Use water spray or for; do not use straight streams.
- TANK OR CAR/TRAILER LOAD FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004)
Fight fire from maximum distance or use unmanned hose holders or monitor nozzles. Do not get water inside containers. Cool containers with flooding quantities of water until well after fire is out. Withdraw immediately in case of rising sound from venting safety devices or discoloration of tank. ALWAYS stay away from tanks engulfed in fire.
- NFPA Extinguishing Methods for CAS822-06-0 (NFPA, 2002):
- It is important to keep fire-exposed containers cool (Sittig, 1991). Most foams will react with the material and release corrosive/toxic gases. Dry chemical, dry sand, carbon dioxide, or alcohol-resistant foam can be used in small fires. Spray, fog, or alcohol-resistant foam can be used in large fires. The use of straight streams should be avoided (HSDB , 1999).
- Fight fire from maximum distance or use unmanned hose holders (or monitor nozzles) in fire involving tanks or car/trailer loads. Withdraw immediately in case of rising sound from venting safety devices or discoloration of tank. Stay away from the ends of tanks (HSDB , 1999).
EXPLOSION HAZARD
- Hexamethylene diisocyanate reacts violently with acids, alcohols, amines, bases, and oxidants causing fire and explosion hazard (ILO, 1998).
- Explosion may occur upon reaction with water (HSDB , 1999; Sittig, 1991).
- When heated, vapors may form explosive mixtures with air: indoors, outdoors, and in sewers. Vapors may travel to source of ignition and flash back (HSDB , 1999).
- Containers may explode when heated in fire (HSDB , 1999; Sittig, 1991).
DUST/VAPOR HAZARD
- Avoid breathing dusts and fumes from burning material. Keep upwind. Wear positive pressure self-contained breathing apparatus (AAR, 1998).
- When hexamethylene diisocyanate reacts with water, flammable, toxic, or corrosive gases and runoff are released. When hexamethylene diisocyanate contacts with metal, flammable hydrogen gas may evolve (HSDB , 1999).
- When heated, vapors may form explosive mixtures with air: indoors, outdoors, and in sewers. Most vapors are heavier than air, and they will spread along ground and collect in low or confined areas (sewers, basements, and tanks). Vapors may travel to source of ignition and flash back (HSDB , 1999).
REACTIVITY HAZARD
- Organic isocyanates are responsible for the worst chemical industry accident to date (Urben, 1996). Hexamethylene diisocyanate reacts violently with acids, alcohols, amines, bases, and oxidants causing fire and explosion hazard (ILO, 1998). Base-catalyzed reactions of isocyanates with alcohols may be explosively violent in absence of diluting( chemically inert) solvents (HSDB , 1999; Urben, 1996)
- Hexamethylene diisocyanate should be stored away from moisture or water (Sittig, 1991). The rate of reaction with water ranges from readily to slow (<1% in 10 minutes at 30 degrees C) (HSDB , 1999). It is a complex decomposition reaction and usually involves several mechanisms: an initial unstable intermediate (acid) is formed that decomposes to the amine with liberation of carbon dioxide, and the amine can react with more isocyanate to form a polyurea. Explosion may occur upon reaction with water (HSDB , 1999) Raffle et al, 1994; (Sittig, 1991). Flammable, toxic, or corrosive gases and runoff can be released when hexamethylene diisocyanate reacts with water (HSDB , 1999).
- When heated, vapors may form explosive mixtures with air: indoors, outdoors, and in sewers. Most vapors are heavier than air, and they will spread along ground and collect in low or confined areas (sewers, basements, and tanks). Vapors may travel to source of ignition and flash back. Containers may explode if heated (HSDB , 1999). When heated, decomposition may occur. It is important to keep polymerization temperature below 180 degrees C during generation of polyurethane polymers with polyols (Urben, 1996). The urethane reaction is exothermic, and the heat generated is sufficient to evaporate hexamethylene diisocyanate due to its high vapor pressure (Raffle et al, 1994).
- Contact with metals may evolve flammable hydrogen gas (HSDB , 1999).
- Organic isocyanates are extremely reactive high-energy species; they can react with themselves and with nucleophiles generating runaway exotherms. Hexamethylene diisocyanate can be readily oxidized with the covalent cyano-group as endothermic and reactive (Urben, 1996).
EVACUATION PROCEDURES
- Editor's Note: This material is not listed in the Table of Initial Isolation and Protective Action Distances.
- SPILL - PUBLIC SAFETY EVACUATION DISTANCES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004)
Increase, in the downwind direction, as necessary, the isolation distance of at least 50 meters (150 feet) for liquids and 25 meters (75 feet) for solids in all directions.
- FIRE - PUBLIC SAFETY EVACUATION DISTANCES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004)
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.
- PUBLIC SAFETY MEASURES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004)
CALL Emergency Response Telephone Number on Shipping Paper first. If Shipping Paper not available or no answer, refer to appropriate telephone number: MEXICO: SETIQ: 01-800-00-214-00 in the Mexican Republic; For calls originating in Mexico City and the Metropolitan Area: 5559-1588; For calls originating elsewhere, call: 011-52-555-559-1588.
CENACOM: 01-800-00-413-00 in the Mexican Republic; For calls originating in Mexico City and the Metropolitan Area: 5550-1496, 5550-1552, 5550-1485, or 5550-4885; For calls originating elsewhere, call: 011-52-555-550-1496, or 011-52-555-550-1552; 011-52-555-550-1485, or 011-52-555-550-4885.
ARGENTINA: CIQUIME: 0-800-222-2933 in the Republic of Argentina; For calls originating elsewhere, call: +54-11-4613-1100.
BRAZIL: PRÓ-QUÍMICA: 0-800-118270 (Toll-free in Brazil); For calls originating elsewhere, call: +55-11-232-1144 (Collect calls are accepted).
COLUMBIA: CISPROQUIM: 01-800-091-6012 in Colombia; For calls originating in Bogotá, Colombia, call: 288-6012; For calls originating elsewhere, call: 011-57-1-288-6012.
CANADA: UNITED STATES:
For additional details see the section entitled "WHO TO CALL FOR ASSISTANCE" under the ERG Instructions. As an immediate precautionary measure, isolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids. Keep unauthorized personnel away. Stay upwind. Keep out of low areas. Ventilate enclosed areas.
- Avoid breathing dusts and fumes from burning materials. Keep upwind. Avoid bodily contact with the material (AAR, 1998). Use a air-purifying, full-facepiece respirator (gas mask) with a chin-style, front- or back-mounted organic vapor canister, or any escape-type self-contained breathing apparatus when escape from suddenly occurring respiratory hazards (HSDB , 1999; NIOSH , 1999).
- AIHA ERPG Values for CAS822-06-0 (AIHA, 2006):
- DOE TEEL Values for CAS822-06-0 (U.S. Department of Energy, Office of Emergency Management, 2010):
Listed as Hexamethylene diisocyanate (1,6-Diisocyanatohexane) TEEL-0 (units = ppm): 0.005 TEEL-1 (units = ppm): 0.3 TEEL-2 (units = ppm): 2 TEEL-3 (units = ppm): 2 Definitions: TEEL-0: The threshold concentration below which most people will experience no adverse health effects. TEEL-1: The airborne concentration (expressed as ppm [parts per million] or mg/m(3) [milligrams per cubic meter]) of a substance above which it is predicted that the general population, including susceptible individuals, could experience notable discomfort, irritation, or certain asymptomatic, nonsensory effects. However, these effects are not disabling and are transient and reversible upon cessation of exposure. TEEL-2: The airborne concentration (expressed as ppm or mg/m(3)) of a substance above which it is predicted that the general population, including susceptible individuals, could experience irreversible or other serious, long-lasting, adverse health effects or an impaired ability to escape. TEEL-3: The airborne concentration (expressed as ppm or mg/m(3)) of a substance above which it is predicted that the general population, including susceptible individuals, could experience life-threatening adverse health effects or death.
- AEGL Values for CAS822-06-0 (National Research Council, 2010; National Research Council, 2009; National Research Council, 2008; National Research Council, 2007; NRC, 2001; NRC, 2002; NRC, 2003; NRC, 2004; NRC, 2004; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; United States Environmental Protection Agency Office of Pollution Prevention and Toxics, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; 62 FR 58840, 1997; 65 FR 14186, 2000; 65 FR 39264, 2000; 65 FR 77866, 2000; 66 FR 21940, 2001; 67 FR 7164, 2002; 68 FR 42710, 2003; 69 FR 54144, 2004):
- NIOSH IDLH Values for CAS822-06-0 (National Institute for Occupational Safety and Health, 2007):
CONTAINMENT/WASTE TREATMENT OPTIONS
SPILL OR LEAK PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004) 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 damaged containers or spilled material unless wearing appropriate protective clothing. Stop leak if you can do it without risk. A vapor suppressing foam may be used to reduce vapors. FOR CHLOROSILANES, use AFFF alcohol-resistant medium expansion foam to reduce vapors. DO NOT GET WATER on spilled substance or inside containers. Use water spray to reduce vapors or divert vapor cloud drift. Avoid allowing water runoff to contact spilled material. Prevent entry into waterways, sewers, basements or confined areas.
RECOMMENDED PROTECTIVE CLOTHING - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004) 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.
Use a vapor-suppressing foam to reduce vapor. Minimize spreading (HSDB , 1999). Use equipment that is grounded to handle the product. Do not touch damaged containers or spilled material unless wearing appropriate protective clothing (HSDB , 1999). Restrict persons not wearing protective equipment from area of spill or leak until clean up is complete (AAR, 1998; (Sittig, 1991).
SMALL SPILL PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 156 (ERG, 2004) Cover with DRY earth, DRY sand or other non-combustible material followed with plastic sheet to minimize spreading or contact with rain. Use clean non-sparking tools to collect material and place it into loosely covered plastic containers for later disposal.
Eliminate all ignition sources (no smoking, flares sparks, or flames in immediate area). Prevent entry into waterways, sewers, basements or confined areas. Absorb liquids in fly ash, cement powder, vermiculite, dry sand, dirt, or similar substances before deposit in sealed containers (AAR, 1998; (Sittig, 1991). Cover small spills with plastic sheet to minimize spreading or contact with rain following absorption by non-combustible substance. Use clean non-sparking tools to collect material, and deposit in sealed containers (HSDB , 1999; Sittig, 1991). Ventilate area of spill or leak (Sittig, 1991). Use natural barriers or oil spill control booms to limit spill travel if spilled in water (AAR, 1998).
Eliminate all ignition sources (no smoking, flares sparks, or flames in immediate area). Prevent entry into waterways, sewers, basements, or confined areas (HSDB , 1999). Dig a pit, pond, lagoon, or holding area to contain material. Dike surface flow using soil, sandbags, foamed polyurethane, or foamed concrete (AAR, 1999). Absorb liquids in fly ash, cement powder, vermiculite, dry sand, dirt, or similar materials before deposit in sealed containers if feasible (AAR, 1998; (Sittig, 1991). Use natural barriers or oil spill control booms to limit spill travel if spilled in water (AAR, 1998).
Although without catalysts reaction with water is slow (<1% in 10 minutes at 30 degrees C), hexamethylene diisocyanate will be degraded by reaction with water (ACGIH, 1991; HSDB , 1999). It is a complex reaction and usually involves several mechanisms: an initial unstable intermediate (acid) is formed that decomposes to the amine with liberation of carbon dioxide, and the amine can react with more isocyanate to form a polyurea (HSDB , 1999; Sittig, 1991). Waste management activities associated with material disposition are unique to individual situations. Proper waste characterization and decisions regarding waste management should be coordinated with the appropriate local, state, or federal authorities to ensure compliance with all applicable rules and regulations.
-ENVIRONMENTAL HAZARD MANAGEMENT
POLLUTION HAZARD
- From 0.5-1.6% (ACGIH, 1991) or from 0.5-1.0% (HSDB , 1999) of free hexamethylene diisocyanate monomer can be released to the environment during spray application of polymer paints and coating systems. Waste streams generated at sites of industrial manufacture and polymer production could also release hexamethylene diisocyanate to the environment (HSDB , 1999).
ENVIRONMENTAL FATE AND KINETICS
If released into the atmosphere, hexamethylene diisocyanate will exist in the vapor-phase in the ambient atmosphere. It will be degraded in the atmosphere by the vapor-phase reaction with photochemically produced hydroxyl radicals. An estimated half-life of approximately 2 days has been reported when released in air. Atmospheric degradation may also occur through contact with water vapor, clouds, fog, or rain (HSDB , 1999).
SURFACE WATER Since hexamethylene diisocyanate readily reacts with water and degrades (forming amines and polyureas), only low concentrations of monomeric hexamethylene diisocyanate are expected to be found in waste water streams (HSDB , 1999).
ABIOTIC DEGRADATION
- Isocyanates typically have aqueous hydrolysis half-lives of <10 minutes. Hexamethylene diisocyanate is expected to be hydrolyzed more rapidly (to form amines and polyureas) than degradation by microorganisms. Hexamethylene diisocyanate can undergo photolysis, hydroxyl radical oxidations, and other reactions in atmosphere (HSDB , 1999).
BIOACCUMULATION
Hexamethylene diisocyanate reacts with water to form amines and polyureas; therefore, bioaccumulation of monomeric hexamethylene diisocyanate in aquatic organisms or along the food chain is unlikely to occur (HSDB , 1999).
ENVIRONMENTAL TOXICITY
- Since hexamethylene diisocyanate reacts with water and degrades, environmental toxicity of monomeric hexamethylene diisocyanate is low. There is very little chance that it will accumulate in the food chain. Leaching should not be important. Volatilization of monomeric hexamethylene diisocyanate from water should not be significant (HSDB , 1999).
-PHYSICAL/CHEMICAL PROPERTIES
MOLECULAR WEIGHT
DESCRIPTION/PHYSICAL STATE
- Hexamethylene diisocyanate is a clear, colorless to pale yellow liquid with a sharp pungent odor (ACGIH, 1991) Hathaway, 1996; (ILO, 1998; Lewis, 1997; NIOSH , 1999; Sittig, 1991).
VAPOR PRESSURE
- 0.05 mmHg (at 25 degrees C) (HSDB , 1999)
- 0.05 mmHg (at 24 degrees C) (ACGIH, 1991)
- 0.5 mmHg (at 77 degrees F) (NIOSH , 1999)
SPECIFIC GRAVITY
- OTHER TEMPERATURE AND/OR PRESSURE
DENSITY
- NORMAL TEMPERATURE AND PRESSURE
(25 degrees C; 77 degrees F and 760 mmHg) 1.04 g/cm(3) (NIOSH , 1999; Lewis, 1997)
- OTHER TEMPERATURE AND/OR PRESSURE
FREEZING/MELTING POINT
BOILING POINT
- 212.8 degrees C (ACGIH, 1991)
- 213 degrees C (Sittig, 1991)
- 225 degrees C (ILO, 1998)
- 124 degrees C; 255 degrees F (at 0.013 bar) (Kohler & Meyer, 1993)
- 127 degrees C (at 1.3 kPa) (Ashford, 1994)
- 415 degrees F (NIOSH , 1999)
FLASH POINT
- 140 degrees C (open cup) (Ashford, 1994; ILO, 1998; Lewis, 1997; Sittig, 1991)
- 284 degrees F (closed cup) (NIOSH , 1999)
AUTOIGNITION TEMPERATURE
- 454 degrees C (ILO, 1998)
EXPLOSIVE LIMITS
SOLUBILITY
OTHER/PHYSICAL
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