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SECTION 1. CHEMICAL IDENTIFICATION

CHEMINFO Record Number: 83
CCOHS Chemical Name: Toluene-2,4-diisocyanate

Synonyms:
Di-isocyanate de toluylène
2,4-Diisocyanate-1-methylbenzene
2,4-Diisocyanatotoluene
Isocyanic acid, 4-methyl-m-phenylene ester
2,4-TDI
2,4-Toluenediisocyanate
Toluene diisocyanate
Toluylene-2,4-diisocyanate
Tolylene-2,4-diisocyanate

Chemical Name French: 2,4-Diisocyanate de toluène
Chemical Name Spanish: Diisocianato de 2,4-tolueno

Trade Name(s):
Hylene T
Mondur TDS

CAS Registry Number: 584-84-9
UN/NA Number(s): 2078
RTECS Number(s): CZ6300000
EU EINECS/ELINCS Number: 209-544-5
Chemical Family: Isocyanic acid ester / isocyanate / diisocyanate / aromatic diisocyanate
Molecular Formula: C9-H6-N2-O2
Structural Formula: CH3-C6H3-(NCO)2

SECTION 2. DESCRIPTION

Appearance and Odour:
Water white to pale yellow liquid or crystals with a sweet, fruity, pungent odour. Darkens on exposure to sunlight.(11)

Odour Threshold:
0.05 ppm (detection) (3); 0.1-1.0 ppm (detection) (1,20); 0.45 ppm (low); 2.4 ppm (high) (21). Irritating concentration: 0.56 ppm (4 mg/m3).(21);

Warning Properties:
NOT RELIABLE - Odour threshold is above the TLV. Irritation of the eyes and nose at concentrations above the TLV.

Composition/Purity:
Commercially available as pure toluene-2,4-diisocyanate (2,4-TDI) or as mixtures of 80% 2,4-TDI : 20% 2,6-TDI, and 65% 2,4-TDI : 35% 2,6-TDI. This record presents information for pure 2,4-TDI where possible. CHEMINFO records are available for the mixtures of 80% 2,4-TDI : 20% 2,6-TDI (134) and 65% 2,4- TDI : 35% 2,6-TDI (135).

Uses and Occurrences:
Manufacture of flexible and rigid polyurethane foams, elastomers and coatings such as polyurethane paints, varnishes and wire enamels.


SECTION 3. HAZARDS IDENTIFICATION

EMERGENCY OVERVIEW:
Colourless to pale yellow liquid or crystals, with a sharp, fruity, pungent odour. Can probably burn if strongly heated. Can decompose at high temperatures forming toxic gases, such as nitrogen oxides and hydrogen cyanide. May polymerize if heated. Reacts vigorously with water above 50 deg C. Closed containers may develop pressure and rupture on prolonged exposure to heat or if contaminated with water. VERY TOXIC. May be fatal if inhaled. Irritating to respiratory tract. May cause lung injury--effects may be delayed. RESPIRATORY SENSITIZER. May cause severe allergic respiratory reaction. Causes skin and eye irritation. SKIN SENSITIZER. May cause allergic skin reaction. SUSPECT CANCER HAZARD - may cause cancer.



POTENTIAL HEALTH EFFECTS

Effects of Short-Term (Acute) Exposure

Inhalation:
Short-term exposure to isocyanates, such as toluene-2,4-diisocyanate (TDI), can cause respiratory and mucous membrane irritation at vapour levels of 0.05 ppm and above.(22) Symptoms include eye and nose irritation, dry or sore throat, runny nose, shortness of breath, wheezing and laryngitis. Coughing with chest pain or tightness may also occur, frequently at night. These symptoms may occur during exposure or may be delayed for several hours.
Higher exposures could cause inflammation of the lung tissue (chemical pneumonitis), chemical bronchitis with severe asthma-like wheezing, severe coughing spasms and accumulation of fluid in the lungs (pulmonary edema), which could prove fatal.(2,5) Symptoms of pulmonary edema may not appear until several hours after exposure and are aggravated by physical exertion.
Some people may become sensitized to TDI--see Effects of Long-term (Chronic) Exposure for information.
Effects such as euphoria, muscle incoordination and loss of consciousness have been reported after a single severe exposure to TDI. Headache, difficulty in concentration, poor memory and confusion may persist for up to 4 years.(13)

Skin Contact:
Liquid TDI produces a marked inflammatory reaction.(2) Prolonged or further contact can cause severe inflammation, redness, rash, swelling, blistering and burns.(1) Isocyanates, in general, can cause skin discolouration (staining) and hardening of the skin after repeated exposures. Skin contact is not expected to result in the absorption of harmful amounts.(22) Skin sensitization may occur in some individuals, but it is not common.(2)

Eye Contact:
Liquid 2,4-TDI can cause watering of the eyes, severe irritation and possible clouding of the cornea. Human volunteers exposed to concentrations greater than 0.08 ppm developed mild eye irritation which was more severe at 0.1 ppm. At 0.5 ppm, the volunteers described the eye irritation as "stabbing and annoying" and tearing occurred.(3) Exposure to high TDI vapour concentrations can lead to formation of solid particles in the eye fluid which can cause mechanical irritation hours after exposure.(23)

Ingestion:
Swallowing TDI could cause irritation and corrosion of the tissues lining the mouth, throat and stomach.

Effects of Long-Term (Chronic) Exposure

Respiratory Sensitization:
Respiratory sensitization has developed in people working with TDI.(4,5) Sensitization is usually caused by a very large exposure, or by multiple exposures.(5) Symptoms of sensitization have occurred in some workers exposed frequently to low levels of TDI (0.0003 to 0.03 ppm).(13) Although varying periods of exposure (1 day to years) may elapse before sensitization occurs, it develops more often during the first few months of exposure.
Sensitized individuals react to very low levels of TDI (below 0.001 ppm) that have no effect on unsensitized people.(4) At first, the symptoms may appear to be a cold or mild hay fever. However, severe asthmatic symptoms can develop and include wheezing, chest tightness, shortness of breath, difficulty breathing and/or coughing. Fever, chills, general feelings of discomfort, headache, and fatigue can also occur. Symptoms may occur immediately upon exposure (within an hour), several hours after exposure or both, and/or at night.(4,5,13,15) Typically, the asthma improves with removal from exposure (e.g. weekends or vacations) and returns, in some cases, in the form of an "acute attack", on renewed exposure.(13) Sensitized people who continue to work with 2,4-TDI may develop symptoms sooner after each exposure. The number and severity of symptoms may increase. Death has occurred in sensitized individuals accidently exposed to relatively low concentrations of TDI.(13)
Animal studies indicate that respiratory sensitivity to TDI may result from dermal as well as inhalation exposures.(5)
Following removal from exposure, some sensitized workers may continue to show a slow decline in lung function and have persistent respiratory problems such as asthmatic symptoms, chronic bronchitis and hypersensitivity to TDI for months or years.(4,5,16) Others recover complete lung function within months if they have no further isocyanate exposure.(5,16)
TDI may also cause hypersensitivity pneumonitis, another allergic lung disease, which is characterized by symptoms such as shortness of breath, fever, malaise, non-productive cough, and chills.(5,13) Several studies have shown that long-term exposure to 2,4-TDI at levels as low as 0.002-0.003 ppm may cause impaired lung function such as diminished respiratory capacity.(5,13) Exposure to isocyanates is likely to cause aggravation to individuals with existing respiratory disease, such as chronic bronchitis, and emphysema.(8)
Cross-sensitization between different isocyanates may occur. People sensitized to TDI have shown sensitization to methylene bisphenyl isocyanate (MDI) and hexamethylene-1,6- diisocyanate (HDI), where no previous exposure to MDI or HDI was known.(8,13)

Skin Sensitization:
Repeated skin contact with TDI has caused skin sensitization in humans, although the condition is not common.(2,8) Once a person is sensitized, contact with even a small amount of TDI can cause outbreaks of dermatitis with symptoms such as redness, rash, itching and swelling. This can spread from the hands or arms to the face and body. Some people who inhaled TDI developed extensive skin rashes that lasted 1 to 1.5 weeks. There was no direct skin contact with the liquid.(15)

Carcinogenicity:

The risk of cancer associated with exposure to isocyanates has been examined in 4 human population studies. No strong association or consistent pattern has been observed. The International Agency for Research on Cancer (IARC) has determined there is inadequate evidence for the carcinogenicity of toluene diisocyanates in humans. There is sufficient evidence for the carcinogenicity of toluene diisocyanates in experimental animals.(31)

The International Agency for Research on Cancer (IARC) has concluded that this chemical is possibly carcinogenic to humans (Group 2B).

The American Conference of Governmental Industrial Hygienists (ACGIH) has designated this chemical as not classifiable as a human carcinogen (A4).

NOTE: ACGIH has published a Notice of Intended Change proposing that the carcinogenicity designation be changed to A3 (animal carcinogen).

The US National Toxicology Program (NTP) has listed this chemical as reasonably anticipated to be a human carcinogen.

Teratogenicity and Embryotoxicity:
No human or animal information is available.

Reproductive Toxicity:
No human or animal information is available.

Mutagenicity:
It is not possible to conclude that 2,4-TDI is mutagenic. There is no human information available. Technical grade TDI (80% 2,4-TDI and 20% 2,6-TDI) induced chromosome aberrations in cultured human lymphocytes, with and without metabolic activation. It did not significantly affect the number of sister chromatid exchanges, with and without metabolic activation.(18,19) Negative results have been obtained in rats and mice exposed to toluene diisocyanate (80%) 2,4-TDI:20% 2,6-TDI mixture).

Toxicologically Synergistic Materials:
No information is available.

Potential for Accumulation:
2,4-TDI probably does not accumulate in the body. It can enter the body by inhalation or by ingestion. It is probably metabolized to 2,4-toluenediamine (11), which is metabolized further and excreted.

Health Comments:
Many reports have not adequately identified the TDI forms (2,4- and 2,6-TDI) involved. Also, certain sampling/analysis methods may be inaccurate for 2,6-TDI and may underestimate exposure to total TDI.


SECTION 4. FIRST AID MEASURES

Inhalation:
Take proper precautions to ensure your own safety before attempting rescue, e.g. wear appropropriate protective equipment, use the "buddy" system. Remove source of contamination or move victim to fresh air. If breathing is difficult, oxygen may be beneficial if administered by trained personnel, preferably on a doctor's advice. DO NOT allow victim to move about unnecessarily. Symptoms of pulmonary edema can be delayed up to 48 hours after exposure. Immediately transport victim to an emergency care facility.

Skin Contact:
Avoid direct contact with this chemical. Wear chemical protective gloves and respiratory protection if necessary. Remove contaminated clothing, shoes and leather goods (e.g. watchbands, belts) and place in covered container. As quickly as possible, flush contaminated area with lukewarm, gently running water for at least 20 minutes or until the chemical is removed. Obtain medical attention immediately. Discard contaminated clothing, shoes and leather goods.

Eye Contact:
Avoid direct contact with this chemical. Wear chemical protective gloves and respiratory protection, if necessary. Gently blot or brush away excess chemical quickly. SOLID: Do not allow victim to rub eye(s). Let the eye(s) water naturally for a few minutes. Have victim look right and left, and then up and down. If particle/dust does not dislodge, flush with lukewarm, gently flowing water for 5 minutes or until particle/dust is removed, while holding the eyelid(s) open. If irritation persits, obtain medical attention. DO NOT attempt to manually remove anything stuck to eye(s). LIQUID: Immediately flush the contaminated eye(s) with lukewarm, gently flowing water for 20 minutes or until the chemical is removed, while holding the eyelid(s) open. Take care not to rinse contaminated water into the unaffected eye or onto the face. Obtain medical attention immediately.

Ingestion:
Never give anything by mouth if victim is rapidly losing consciousness or is unconscious or convulsing. Rinse mouth thoroughly with water. DO NOT INDUCE VOMITING. Have victim drink about 250 mL (8 oz.) of water to dilute material in stomach. If vomiting occurs naturally, repeat administration of water. Obtain medical attention immediately.

First Aid Comments:
Provide general supportive measures (comfort, warmth, rest). Consult a doctor and/or the nearest Poison Control Centre for all exposures except minor instances of inhalation or skin contact. Some recommendations in the above sections may be considered medical acts in some jurisdictions. These recommendations should be reviewed with a doctor and appropriate delegation of authority obtained, as required. All first aid procedures should be periodically reviewed by a doctor familiar with the material and its condition of use in the workplace.



SECTION 5. FIRE FIGHTING MEASURES

Flash Point:
127 deg C (260 deg F) (closed cup) (26); 132 deg C (270 deg F) (open cup) (1)

Lower Flammable (Explosive) Limit (LFL/LEL):
0.9% by volume (26)

Upper Flammable (Explosive) Limit (UFL/UEL):
9.5% by volume (26)

Autoignition (Ignition) Temperature:
620 deg C (1148 deg F) (26)

Sensitivity to Mechanical Impact:
Information not available

Sensitivity to Static Charge:
Information not available. Probably not sensitive, since 2,4-TDI has a high flash point.

Combustion and Thermal Decomposition Products:
Hydrogen cyanide, nitrogen oxides

Fire Hazard Summary:
This material can burn if strongly heated. During a fire, irritating/toxic nitrogen oxides and hydrogen cyanide may be generated. May react violently with water at temperatures above 50 deg C. Closed containers may rupture violently when heated.

Extinguishing Media:
Water spray, carbon dioxide, foam, dry chemical powder.(22) Water or foam may cause frothing.(26)

Fire Fighting Instructions:
Evacuate area and fight fire from a safe distance or a protected location. Approach fire from upwind to avoid hazardous vapours and toxic decomposition products.

Water or water-based foam, if used in very large quantities, may be effective for fighting fires involving toluene-2,4-diisocyanate (2,4-TDI). However, care must be taken since the reaction between water or water-based foam and hot 2,4- TDI can be vigorous.(22)

Isolate materials not yet involved in the fire and protect personnel. Move containers from fire area if this can be done without risk. Otherwise, keep fire-exposed tanks or containers cool by spraying with water to minimize the risk of rupture, but avoid direct contact of 2,4-TDI with water. Water spray or fog can be used to absorb heat and protect exposed material of structures. If a leak or spill has not ignited, use water spray to disperse the vapours and to protect personnel attempting to stop a leak. After the fire has been extinguished, the area should not be considered safe until air monitoring for residual isocyanate has been carried out by properly protected personnel.

2,4-TDI and its decomposition products, such as hydrogen cyanide and nitrogen oxides, are extremely hazardous to health. Do not enter any fire area without wearing specialized protective equipment suitable for the situation. Firefighter's normal protective clothing (Bunker Gear) will not provide adequate protection. Chemical resistant clothing (e.g. chemical splash suit) and positive pressure self-contained breathing apparatus (MSHA/NIOSH approved or equivalent) may be necessary.



NATIONAL FIRE PROTECTION ASSOCIATION (NFPA) HAZARD IDENTIFICATION

NFPA - Health: 3 - Short exposure could cause serious temporary or residual injury.
NFPA - Flammability: 1 - Must be preheated before ignition can occur.
NFPA - Instability: 2 - Undergoes violent chemical change at elevated temperatures and pressures, or reacts violently with water, or may form explosive mixtures with water.

SECTION 9. PHYSICAL AND CHEMICAL PROPERTIES

Molecular Weight: 174.16

Conversion Factor:
1 ppm = 7.11 mg/m3; 1 mg/m3 = 0.14 ppm at 25 deg C (calculated)

Physical State: Solid
Melting Point: 22 deg C (72 deg F) (1,20,22)
Boiling Point: 251 deg C (484 deg F) (1,21); 120 deg C (248 deg F) at 1.3 kPa (10 mm Hg) (1,20)
Relative Density (Specific Gravity): 1.22 at 25 deg C (water = 1) (1,20)
Solubility in Water: Insoluble (reacts with water) (1)
Solubility in Other Liquids: Soluble in all proportions in benzene, diethyl ether, carbon tetrachloride, chlorobenzene; soluble in acetone, ethyl acetate, kerosene, toluene, olive oil (1,11)
Coefficient of Oil/Water Distribution (Partition Coefficient): Not applicable (reacts with water)
pH Value: Not applicable (reacts with water)
Viscosity-Dynamic: 3-6 centipoises (3-6 mPa.s) at 25 deg C (estimated) (22)
Surface Tension: 25 dynes/cm at 25 deg C (estimated)
Vapour Density: 6.0 (air = 1)
Vapour Pressure: 0.0033 kPa (0.025 mm Hg) at 25 deg C (22)
Saturation Vapour Concentration: Approx. 33 ppm at 25 deg C (calculated)
Evaporation Rate: Not available

Physical Properties Comments:
The physical state of toluene-2,4-diisocyanate varies from solid to liquid depending on the environmental temperature, the purity of the material and the presence of moisture.


SECTION 10. STABILITY AND REACTIVITY

Stability:
Normally stable. 2,4-TDI self-reacts at elevated temperatures to form dimers, trimers and polymers giving off carbon dioxide and heat.(20,26)

Hazardous Polymerization:
TDI may undergo uncontrollable exothermic polymerization upon contact with water at elevated temperatures or other materials which react with TDI. It may also polymerize if heated above 177 deg C or above 45 deg C for prolonged periods. Carbon dioxide and heat are generated during the polymerization process.(11,20,26) The resulting heat and pressure build-up could rupture closed containers.

Incompatibility - Materials to Avoid:

NOTE: Chemical reactions that could result in a hazardous situation (e.g. generation of flammable or toxic chemicals, fire or detonation) are listed here. Many of these reactions can be done safely if specific control measures (e.g. cooling of the reaction) are in place. Although not intended to be complete, an overview of important reactions involving common chemicals is provided to assist in the development of safe work practices.


WATER - Reacts non-violently at normal room temperature with release of heat to form carbon dioxide and inert material made up of polyureas which could rupture closed containers.(22) 2,4- Toluene-diamine is formed as an intermediate product in the reaction.(2) Above 50 deg C, the reaction becomes progressively more vigorous which could rupture closed containers.(22)
AMINES, ALCOHOLS, ACIDS, OR BASES - May react violently with generation of heat.(22,26)
METAL COMPOUNDS (e.g. organometallic catalysts, such as organotin compounds) - May polymerize with the generation of heat and pressure.(20,26)
AMIDES, PHENOLS, MERCAPTANS, URETHANES, UREAS AND SURFACE ACTIVE AGENTS (surfactants, e.g. non-ionic detergents) - May react vigorously or violently with the generation of heat.(20,22)

Hazardous Decomposition Products:
2,4-Toluenediamine (formed by reaction of 2,4-TDI with water).(11)

Conditions to Avoid:
Moisture, heat, direct sunlight

Corrosivity to Metals:
May cause some corrosion to copper, zinc and their alloys, and aluminum.(22)

Stability and Reactivity Comments:
Isocyanates are very reactive compounds and are highly reactive toward a large number of compounds with active hydrogens, particularly at high temperatures and in the presence of catalysts. See reference 20 for some of the reactions of isocyanates. May attack and embrittle plastic (e.g. polyethylene, polypropylene and polyurethane) and rubber materials in a short time.(22)


SECTION 11. TOXICOLOGICAL INFORMATION

LC50 (guinea pig): 13 ppm (3-hour exposure) (11.3 ppm - equivalent 4-hour exposure) (2,4-TDI) (1)
LC50 (rabbit): 1.5 ppm (3-hour exposure) (1.3 ppm - equivalent 4-hour exposure) (2,4-TDI) (1)

LD50 (oral, rat): 5,800 mg/kg (2,4-TDI) (1)

LD50 (dermal, rabbit): 10,000 mg/kg (TDI, unspecified composition) (1)

Eye Irritation:

Application of 100 mg in a Standard Draize test caused severe irritation in rabbits.(1,6) Application of a drop of toluene-2,4- diisocyanate (2,4-TDI) caused immediate pain, tearing and swelling of the lids in rabbits. There was only mild corneal damage.(7) In another study, application of TDI (unspecified composition and concentration) produced clouding of the cornea and irritation which persisted in some rabbits for 18-30 days.(8)

Skin Irritation:

Application of 500 mg in an Open Draize test caused severe irritation in rabbits. Application of 500 mg for 24 hours in a Standard Draize test produced moderate irritation in rabbits.(1,6) In another study, application of TDI (unspecified composition) ranging from 2.5 to 9.4 mg/kg resulted in delayed skin irritation in rabbits, including moderate to severe redness, swelling, and leathery skin. All skin lesions healed by the 14th day.(8)

Effects of Short-Term (Acute) Exposure:

Inhalation:
Inhalation of sublethal concentrations by mice, rats, rabbits and guinea pigs has caused severe respiratory effects such as bronchitis, bronchopneumonia, emphysema and bleeding of the lungs (pulmonary hemorrhage).(2) All rats died following two, three or five 6-hour exposures to 10 ppm of 2,4-TDI. Death resulted from severe peribronchitis and bronchial pneumonia.(3) 2,4-TDI is a sensory irritant. Sensory irritants inhibit respiration. A single 6-hour exposure to 0.18 ppm TDI (unspecified composition) reduced the respiratory rate of guinea pigs by 50% (RD50). Lower concentrations of 0.02 to 0.05 ppm had no effect on the breathing rate. Significant reductions in breathing rate were noted in animals who had been exposed to high levels (2 to 5 ppm) when they were subsequently exposed to levels as low as 0.02 ppm.(4) In a study with mice, the RD50 was found to be 0.39 ppm.(11) Studies with mice using 2,4-TDI have shown that the decrease in respiratory rate is both concentration and time dependent. The RD50 value at 30 minutes was found to be approximately 0.5 ppm, while that at 3 and 4 hours was 0.2 ppm.(14) A cumulative effect was observed when the 2,4-TDI concentration was greater than 23 ppb. With repeated daily exposures to the same concentration, irritation became more severe and overnight recovery was not complete. However, after several days without exposure, responses to renewed exposure were the same as those seen in animals that had not previously been exposed.(14)

Ingestion:
TDI has been reported to have gastrointestinal effects and effects on the liver and kidneys when given to animals orally.(1,8)

Effects of Long-Term (Chronic) Exposure:

Inhalation:
Rats, guinea pigs and rabbits exposed to 0.1 ppm, 6 hours/day, 5 days/week for up to 58 exposures or 6 hours/day for 38 consecutive days, developed lung inflammation. Lung damage generally increased in severity for several days after exposure ended.(2,4) No effects on other organs were observed. No lung changes were seen in rats and rabbits exposed to 0.01 ppm once a week for 38 weeks.(4)

Skin Sensitization:
Skin sensitization was produced in animals by direct application of 2,4-TDI to the skin. One drop (50 uL) TDI (in concentrations of 1-100%) was applied to the skin of guinea pigs. A 10% solution of TDI caused skin sensitization.(9)

Respiratory Sensitization:
Concentration dependent respiratory sensitization has been produced in guinea pigs. Threshold levels of 0.25 to 0.36 ppm have been observed. No sensitization was observed below these concentrations.(5,12) Respiratory sensitization was produced in animals by direct application of 2,4-TDI to the skin. One drop (50 uL) TDI (in concentrations of 1-100%) was applied to the skin of guinea pigs. 100% TDI produced respiratory sensitivity in 30 to 40% of the animals.(9)

Carcinogenicity:
No animal information is available on the carcinogenicity of pure 2,4-TDI. No tumours were observed in male and female rats and mice that inhaled 0.05 and 0.15 ppm of production grade TDI (80% 2,4-TDI:20% 2,6-TDI) for 6 hours/day, 5 days/week for approximately 2 years.(10) However, tumours did develop at a number of sites after male and female rats were given large daily oral doses of commercial grade TDI (80:20 mixture) (30 mg/kg to 240 mg/kg), 5 days/week for 105 or 106 weeks. No tumours were observed in male mice.(10,11) There was reduced survival in all groups of dosed rats and high dose male mice. In spite of the reduced survival, there was unequivocal evidence of dose- related increases in tumours in rats and mice.(10) The International Agency for Research on Cancer (IARC) has determined there is sufficient evidence for the carcinogenicity of toluene diisocyanate to experimental animals.(11,17,31)

Mutagenicity:
A commercial mixture (80% 2,4-TDI:2,6-TDI) gave negative results in live animals.(10,31)
2,4-TDI has produced positive and negative results in cultured mammalian cells.(31) 2,4-TDI gave positive results in 2 strains of Salmonella typhimurium with metabolic activation and negative results in 2 other strains, both with and without activation.(1)


SECTION 16. OTHER INFORMATION

Selected Bibliography:
(1) Daugherty, M.L. Toluene diisocyanate (TDI). Chemical hazard information profile: draft report. United States Environmental Protection Agency, July 1984
(2) Criteria for a recommended standard: occupational exposure to toluene diisocyanate. NIOSH, 1973
(3) Henschler, D., et al. The toxicology of toluene diisocyanates. Archiv fur Toxikologie. Vol. 19 (1962). p. 364-387 (English translation: NIOSHTIC Control No. 00102123)
(4) Documentation of the threshold limit values and biological exposure indices. 5th ed. ACGIH, 1986. p. 580-585
(5) Karol, M.H. Respiratory effects of inhaled isocyanates. Critical Reviews in Toxicology. Vol. 16, no. 4 (1986). p. 349-379
(6) RTECS record for benzene, 2,4-diisocyanato-1-methyl-. Date of last update: 9307
(7) Duprat, P., et al. Irritant and allergic action of two isocyanates: toluene diisocyanate (TDI) and diphenyl methane diisocyanate (MDI). European Journal of Toxicology. Vol. 9, no. 1 (1956). p. 41-53 (English translation: NIOSHTIC No. 0010587)
(8) Woolrich, P.F. Toxicology, industrial hygiene and medical control of TDI, MDI and PMPPI. American Industrial Hygiene Association Journal. Vol. 43, no. 2 (February 1982). p. 89-97
(9) Karol, M.H., et al. Dermal contact with toluene diisocyanate (TDI) produces respiratory tract hypersensitivity in guinea pigs. Toxicology and Applied Pharmacology. Vol. 58 (1981). p. 221-230
(10) NTP technical report on the toxicology and carcinogenesis studies of commercial grade 2,4 (80%)- and 2,6 (20%)- toluene diisocyanate (CAS no. 26471- 62-5) in F344/N rats and B6C3F1 mice (gavage studies). (NTP TR 251). US Department of Health and Human Services, 1986
(11) IARC Monographs on the evaluation of the carcinogenic risk of chemicals to humans. Vol. 39. IARC, 1985. p. 287-323
(12) Karol, M.H. Concentration-dependent immunologic response to toluene diisocyanate (TDI) following inhalation exposure. Toxicology and Applied Pharmacology. Vol. 68 (1983). p. 229-241
(13) Musk, A.W., et al. Isocyanates and respiratory disease: current status. American Journal of Industrial Medicine. Vol. 13 (1988). p. 331-349
(14) Sangha, G.K., et al. Sensory irritation by toluene diisocyanate in single and repeated exposures. Toxicology and Applied Pharmacology. Vol. 50 (1979). p. 533-547
(15) Karol, M.H., et al. Longitudinal study of tolyl-reactive IgE antibodies in workers hypersensitive to TDI. Journal of Occupational Medicine. Vol. 21, no. 5 (May 1979). p. 354-358
(16) Mapp, C.E., et al. Persistent asthma due to isocyanates: a follow-up study of subjects with occupational asthma due to toluene diisocyanate (TDI). American Review of Respiratory Diseases. Vol. 137 (1988). p. 1326-1329
(17) IARC Monographs on the evaluation of carcinogenic risks to humans. Suppl. 7. IARC, 1987. p. 61, 72
(18) Maki-Paakkanen, J., et al. Chromosome aberrations and sister-chromatid exchanges induced by technical grade toluene diisocyanate and methylenediphenyl diisocyanate in cultured human lymphocytes. Toxicology Letters. Vol. 36 (Mar. 1987). p. 37-43
(19) Marczynski, B., et al. Indication of DNA strand breaks in human white blood cells after in vitro exposure to toluene diisocyanate (TDI). Toxicology and Industrial Health. Vol. 8, no. 3 (1992). p. 157-169
(20) Kirk-Othmer encyclopedia of chemical technology. Vol. 13, 3rd ed. John Wiley & Sons, 1981. 789-818
(21) Ruth, J.H. Odor thresholds and irritation levels of several chemical substances: a review. American Industrial Hygiene Association Journal. Vol. 47 (Mar. 1986). p. A-142 to A-151
(22) Recommendations for the handling of toluene diisocyanate (TDI). International Isocyanate Institute, Inc. Ed.: Jan. 1976. Revised Nov. 1980.
(23) Precautions for the proper usage of polyurethanes, polyisocyanurates, and related materials (technical bulletin 107). 2nd edition. Kalamazoo, MI : The Upjohn Company, 1980
(24) NIOSH pocket guide to chemical hazards. NIOSH, June 1994. p. 312-313
(25) Forsberg, K., et al. Quick selection guide to chemical protective clothing. 4th ed. Van Nostrand Reinhold, 2002
(26) Fire protection guide to hazardous materials. 13th ed. Edited by A.B. Spencer, et al. National Fire Protection Association, 2002. NFPA 325; NFPA 49; NFPA 491 (toluene diisocyanate; isocyanates)
(27) Key-Schwartz, R.J. Analytical problems encountered with NIOSH method for total isocyanates. AIHA Journal. Vol. 56 (1995). p. 474-479
(28) Streicher, R.P., et al. Investigation of the ability of MDHS method 25 to determine urethane-bound isocyanate groups. AIHA Journal. Vol. 56 (1995). p. 437-442
(29) Report on Carcinogens. 11th ed. US Department of Health and Human Services, Public Health Service, National Toxicology Program
(30) European Communities (EC). Commission Directive 2004/73/EC. Apr. 29, 2004
(31) International Agency for Research on Cancer (IARC). IARC monographs on the evaluation of carcinogenic risks to humans. Vol. 71, parts 1, 2 and 3. Re-evaluation of some organic chemicals, hydrazine and hydrogen peroxide. IARC, 1999

Information on chemicals reviewed in the CHEMINFO database is drawn from a number of publicly available sources. A list of general references used to compile CHEMINFO records is available in the database Help.


Review/Preparation Date: 1994-06-28

Revision Indicators:
WHMIS (effects) 1994-11-01
Acute exposure (inhalation) 1994-11-01
Chronic effects 1994-11-01
First aid (eyes) 1994-11-01
First aid (skin) 1994-11-01
Handling 1994-11-01
Sampling 1995-09-01
Respiratory guidelines 1995-09-01
NFPA (reactivity) 1995-09-01
WHMIS (proposed class) 1997-07-01
US Transport 1998-03-01
Mutagenicity 1999-12-01
Toxicological info 1999-12-01
EU Class 2000-05-01
EU Risk 2000-05-01
EU Safety 2000-05-01
EU Comments 2000-05-01
ERPG-1 2002-05-23
ERPG-2 2002-05-23
ERPG-3 2002-05-23
TDG 2002-05-27
NFPA (reactivity) 2003-04-14
Extinguishing media 2003-04-14
NFPA (specific hazards) 2003-04-19
PEL-TWA final 2003-11-06
PEL-STEL final 2003-11-06
PEL transitional comments 2003-11-06
PEL-C transitional 2003-11-06
TLV basis 2004-01-01
TLV definitions 2004-01-01
Resistance of materials for PPE 2004-03-28
EU comments 2005-01-26
EU classification 2005-01-26
Bibliography 2005-02-02
Physical Properties Comments 2005-10-14
TLV-TWA 2006-03-15
TLV-STEL 2006-03-15
TLV definitions 2006-03-15
TLV proposed changes 2006-03-15
Carcinogenicity 2006-03-16
WHMIS detailed classification 2006-03-16



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