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TOLUENE 2,4-DIISOCYANATE

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Classification   |    Detailed evidence-based information

Substances Included Synonyms

Therapeutic Toxic Class

    A) Toluene 2,4-diisocyanate is a component in polyurethane coatings.

Specific Substances

    A) SYNONYMS FOR THE PURE COMPOUND (CAS# 584-84-9):
    1) AI3-15101
    2) BENZENE, 2,4-DIISOCYANATO-1-METHYL-
    3) CRESORCINOL DIISOCYANATE
    4) DESMODUR-T
    5) DESMODUR T80
    6) DI-ISOCYANATE DE TOLUYLENE (FRENCH)
    7) DI-ISO-CYANATOLUENE
    8) n,n-DI-ISO-1-CYANATOLTOLUENE
    9) DIISOCYANATOMETHYLBENZENE
    10) 2,4-DIISOCYANATO-1-METHYLBENZENE
    11) 2,4-DIISOCYANATOTOLUENE
    12) DIISOCYANAT-TOLUOL (GERMAN)
    13) HYLENE T ORGANIC ISOCYANATE
    14) HYLENE TCPA
    15) HYLENE TLC
    16) HYLENE TM
    17) HYLENE TM-65
    18) HYLENE TRF
    19) ISOCYANIC ACID, METHYL PHENYLENE ESTER
    20) ISOCYANIC ACID, 4-METHYL-M-PHENYLENE ESTER
    21) META-TOLUENE DIISOCYANATE
    22) 4-METHYL-META-PHENYLENE DIISOCYANATE
    23) 4-METHYL-M-PHENYLENE ISOCYANATE
    24) 4-METHYL-PHENYLENE DIISOCYANATE
    25) 4-METHYL-PHENYLENE ISOCYANATE
    26) METHYL-META-PHENYLENE ISOCYANATE
    27) 4-METHYL-META-PHENYLENE DIISOCYANATE
    28) MONDUR TDS
    29) NCI-C50533
    30) NIAX TDI
    31) NIAX TDI-P
    32) 2,4-TDI
    33) TOLUEEN-DIISOCYANAAT (DUTCH)
    34) TOLUEN-DISOCIANATO (ITALIAN)
    35) 2,4-TOLUENE DIISOCYANATE
    36) TOLUENE DIISOCYANATE (65:35)
    37) TOLUENE DIISOCYANATE (80:20)
    38) TOLUENE-2,4-DIISOCYANATE
    39) TOLUENE, 2,4-DIISOCYANATO-
    40) TOLUILENODWUIZOCYJANIAN (POLISH)
    41) 2,4-TOLYENE DIISOCYANATE
    42) 2,4-TOLYLENE DIISOCYANATE
    43) TOLUYLENE-2,4-DIISOCYANATE
    44) TOLYENE-2,4-DIISOCYANATE
    45) m-TOLYLENE DIISOCYANATE
    46) TOLYLENE-2,4-DIISOCYANATE
    47) TULUYLENDIISOCYANAT (GERMAN)
    48) Editor's note: Many of the utilized references do not clearly distinguish between the pure chemical and the isomer mixture. This is the case for synonyms and trade names as well as for toxicity listings and physical properties. Throughout this document, an effort was made to indicate whether the information was related to the pure chemical or the isomer mixture.
    SYNONYMS FOR THE ISOMER MIXTURE (CAS# 26471-62-5):
    1) BENZENE-, 1,3-DIISOCYANATOMETHYL-
    2) DESMODUR T100
    3) DIISOCYANATOMETHYLBENZENE
    4) 1,3-DIISOCYANATOMETHYLBENZENE
    5) DIISOCYANATOTOLUENE
    6) HYLENE-T
    7) ISOCYANIC ACID, METHYLPHENYLENE ESTER
    8) METHYL-META-PHENYLENE ISOCYANATE
    9) METHYL-M-PHENYLENE ISOCYANATE
    10) METHYLPHENYLENE ISOCYANATE
    11) MONDUR-TD
    12) MONDUR TD-80
    13) NACCONATE-100
    14) NIAX ISOCYANATE TDI
    15) RUBINATE TDI
    16) RUBINATE TDI 80;20
    17) RUBINATE TDI 80/20
    18) T 100
    19) TDI
    20) TDI 80
    21) TDI 80-20
    22) TOLUENE 2,4- AND 2,6-DIISOCYANATE
    23) TOLUENE 2,4- AND 2,6-DIISOCYANATE, 80/20 MIXTURE
    24) TOLUENE DIISOCYANATES
    25) TOLYLENE DIISOCYANATE
    26) TOLYLENE ISOCYANATE
    27) Editor's note: Many of the utilized references do not clearly distinguish between the pure chemical and the isomer mixture. This is the case for synonyms and trade names as well as for toxicity listings and physical properties. Throughout this document, an effort was made to indicate whether the information was related to the pure chemical or the isomer mixture.
    SYNONYM REFERENCES
    1) (Ashford, 1994; (CHRIS, 2001); Grant, 1993; HSDB, 2001; IARC, 1986; ILO, 1998; Lewis, 2000a; NIOSH , 2001; NFPA, 1997; OHM/TADS, 2000; Pohanish & Greene, 1997; RTECS, 2001; Sittig, 1991)

    1.2.1) MOLECULAR FORMULA
    1) C9-H6-N2-O2 CH3C6H3(NCO)2 1-CH3C6H3(NCO)2-2,4 2,4-CH3C6H3(NCO)2 (OC=N)2(C6H3)CH3

Available Forms Sources

    A) FORMS
    1) 2,4-TDI is a clear to pale yellow liquid. It has a sharp, pungent, unpleasant odor (AAR, 2000; ACGIH, 1991a; Ashford, 1994; IARC, 1986). Its odor has also been described as fruity and sweet (Sittig, 1991).
    2) 2,4-TDI is a water-white liquid that turns straw-yellow upon standing. It exists as clear to light yellow liquid or crystals, depending upon temperature and pressure (ILO, 1998).
    3) It can be colorless to pale yellow, solid or liquid (above 71 degrees F) (ILO, 1998; NIOSH , 2001; Sittig, 1991). The liquid solidifies below about 2 degrees C (Lewis, 1998).
    4) Presence of 2,6-TDI isomer is considered an impurity (HSDB, 2001).
    5) The most common form of the commercially available type of toluene diisocyanate contains a mixture of 80% 2,4-TDI and 20% 2,6-TDI. Also available is a mixture containing 65% 2,4-TDI and 35% 2,6-TDI, as well as 99.5 % pure 2,4-TDI (Ashford, 1994; IARC, 1986; CHRIS, 2000). 2,4-TDI is also available in 100% pure form (ACGIH, 1991a; Ashford, 1994).
    a) All isomer mixtures have similar characteristics (CHRIS, 2000).
    b) In the USA, toluene diisocyanate with the 80:20 isomer ratio is produced in two forms: type I and type II. These types differ slightly with respect to acidity and amount of hydrolysable chloride introduced during the synthesis process (IARC, 1986).
    c) Analysis of the 80:20 isomer mixture produced in the US typically shows the following (IARC, 1986):
    1) 99.5% purity;
    2) 80+/-1% 2,4-TDI;
    3) 20+/-1% 2,6-TDI;
    4) 0.001-0.011% (varies) acidity as hydrochloric acid;
    5) 0.010-0.014% maximum hydrolysable chloride;
    6) 0.01-0.02% maximum total chlorine.
    d) Analysis of the 80:20 isomer mixture produced in Japan typically shows the following (IARC, 1986):
    1) 99.6% minimum purity;
    2) 78.0-81.0% 2,4-TDI;
    3) 19.0-22.0% 2,6-TDI;
    4) 0.004% maximum acidity as hydrochloric acid;
    5) 0.01% maximum hydrolytic hydrochloric acid;
    6) 0.07% maximum total hydrochloric acid.
    e) Analysis of the 65:35 isomer mixture produced in Japan typically shows the following (IARC, 1986):
    1) 99.5% minimum purity;
    2) 63-67% 2,4-TDI;
    3) 33-37.0% 2,6-TDI;
    4) 0.010-0.013% maximum acidity as hydrochloric acid;
    5) 0.01-0.013% maximum hydrolytic hydrochloric acid;
    6) 0.05% maximum total hydrochloric acid.
    f) In Japan, pure 2,4-TDI is also commercially available. Analysis usually shows the following (IARC, 1986):
    1) 99.5% minimum purity;
    2) minimum 97.5% 2,4-TDI;
    3) maximum 2.5% 2,6-TDI;
    4) 0.010-0.013% acidity as hydrochloric acid;
    5) 0.01-0.013% hydrolytic hydrochloric acid;
    6) 0.05% total hydrochloric acid.
    B) SOURCES
    1) It is unknown whether 2,4-TDI occurs naturally (IARC, 1986).
    2) 2,4-TDI is primarily obtained from coal tar and petroleum (Lewis, 1998).
    3) 2,4-TDI is usually manufactured from toluene-2,4-diamine and phosgene (Budavari, 2000).
    4) Toluene diisocyanate was first produced commercially in the late 1930s. It is primarily produced through reaction of phosgene with 2,4/2,6-toluenediamine (Ashford, 1994; IARC, 1986).
    a) During the initial reaction, toluene is nitrated to 2,4-dinitrotoluene and 2,6-dinitrotoluene. Following catalytic reduction of the nitration products to diaminotoluene and dissolution in organic solvents, the diaminotoluene isomers react with phosgene for several hours at gradually increasing temperatures. The final toluene diisocyanate is then recovered via fractional distillation, isolating it from generated hydrogen chloride and unreacted phosgene (IARC, 1986).
    5) In Japan, a process was developed that generates toluene diisocyanate without the use of phosgene (IARC, 1986).
    a) In this process, carbonylation of dinitrotoluene initially produces the diurethane, which is then converted thermally to toluene diisocyanate and alcohol (IARC, 1986; HSDB, 2001).
    6) The free monomer of toluene diisocyanate isomers can be detected in urethane foam fabric coating at concentrations of less than 200 mg/kg (IARC, 1986).
    7) 2,4-TDI is purified through distillation. This process removes contained hydrogen chloride (Lewis, 1997a).
    C) USES
    1) Toluene diisocyanate isomer mixtures are industrial chemicals that are manufactured in large volumes (IARC , 2000).
    2) These isomer mixtures are used as cross-linking agent for Nylon-6 (Lewis, 1997a).
    3) Many Spandex-formulations use 2,4-toluene diisocyanate as a component (HSDB, 2001).
    4) Approximately 90% of the supply of toluene diisocyanate isomer mixtures are used in the production of flexible and rigid polyurethane foams (IARC, 1986).
    a) These foams can be manufactured through two synthetic methods:
    1) In the 'one-shot' technique, toluene diisocyanate reacts with a di- or polyfunctional alcohol, producing the polyurethane backbone of the polymer. Reaction between excess toluene diisocyanate and water results in formation of amines. These amines in turn further react with the toluene diisocyanate, thereby introducing urea groups into the polymer chain. Interaction between these urea groups and toluene diisocyanate results in cross-linkage between chains.
    2) The second method is a prepolymer process that involves the reaction between toluene diisocyanate and a polyl. During this reaction, a prepolymer with isocyanate end groups is formed. This prepolymer is the reacted with glycols or diamines to cross-link the chains (IARC, 1986).
    5) Toluene diisocyanate isomer mixture is also used as a component in polyurethane coatings and elastomer systems (IARC, 1986).
    a) These coatings can be used as floor finishes, wood finishes and paints (alkyds), wood and concrete sealants and floor finishes (moisture-curing coatings) and as aircraft, truck and passenger car coatings (prepolymer systems) (IARC, 1986). They are also used on leather, wire, tank linings, and masonry (ACGIH, 1991a).
    b) Because urethane elastomers are abrasion- and solvent-resistant, they are used in adhesive and sealant compounds, automobile parts, shoe soles, roller skate wheels, pond liners, blood bags, oils fields and mines. Certain elastomers are produced from pure 2,4-TDI rather than the 80:20 isomer mixture (ACGIH, 1991a; IARC, 1986).
    c) Paints used as top coats now rarely contain toluene diisocyanate isomer mixtures. They often were replaced by isocyanates with higher molecular weights (such as 4,4-diphenyl-methane diisocyanate (MDI)) or by prepolymers (ILO, 1998).
    6) Polymeric foams generated from the commercially available 80:20 isomer mixture are biologically inert and are widely used in furniture, packing, insulation, and boat building (ACGIH, 1991a).
    7) In 1984, the US Food and Drug Administration determined that the use of 2,4-TDI and 2,6-TDI as components of adhesives that come in contact with food was acceptable. Also acceptable was the use of these toluene diisocyanates as components of polyurethane resins that form a surface contacting the food (IARC, 1986).

Overview

Life Support

    A) This overview assumes that basic life support measures have been instituted.

Clinical Effects

    0.2.1) SUMMARY OF EXPOSURE
    A) Toluene 2,4-diisocyanate (TDI) is irritating to the eyes, skin, and mucous membranes. Ingestion can result in a sore throat, irritation of the mouth and stomach, abdominal pain, and diarrhea.
    B) Inhalation of the vapors can cause irritation of the nose, throat, and lungs; wheezing; cough; chemical pneumonitis; bronchospasm; bronchitis; insomnia; euphoria; ataxia; loss of consciousness; personality changes; irritability; and depression. Pulmonary edema may occur from severe inhalation poisoning. It is one of the leading causes of occupational asthma.
    C) Dermal exposure can cause redness, pain, swelling, and blistering. Chronic dermal exposure can lead to skin sensitization and allergic eczema.
    D) Splash contact to the eyes may result in redness, pain, blurred vision, severe irritation, lacrimation, conjunctivitis, keratitis, and corneal damage.
    E) Repeated exposure can cause lung disease psychological effects, chest tightness, sneezing, cyanosis and collapse, chronic obstructive bronchitis, emphysema, chemical bronchitis, and asthmatic syndrome. Exposure can result in chemical pneumonitis, bronchospasm, bronchitis, and pulmonary edema; it is one of the leading causes of occupational asthma. Neurologic symptoms may include euphoria, loss of coordination, loss of consciousness, memory loss, and depression.
    0.2.4) HEENT
    A) Severe conjunctival irritation and lacrimation from liquid or high vapor concentrations is likely. Corneal edema may also occur. Lower concentrations may produce a burning or prickling sensation.
    0.2.6) RESPIRATORY
    A) Burning or irritation of the nose and throat, cough, laryngitis, chest pain, and asthmatic syndrome (chemical bronchitis with severe bronchospasm), sensation of oppression or constriction of the chest, bronchitis, pulmonary edema, and cor pulmonale may occur.
    B) Occupational asthma, emphysema, decreased pulmonary function, and hypersensitization may occur from chronic exposure.
    0.2.7) NEUROLOGIC
    A) Acute exposures may produce headache, insomnia, euphoria, ataxia, anxiety neurosis with depression, paranoid tendencies, or impotence.
    0.2.8) GASTROINTESTINAL
    A) Inhalation of vapor or aerosol may produce vomiting and abdominal pain. Epigastric and substernal pain may be secondary to the paroxysmal or persistent cough associated with inhalation.
    0.2.14) DERMATOLOGIC
    A) Irritation and inflammation are common. TDI is corrosive. Skin sensitization and allergic eczema may occur.
    0.2.20) REPRODUCTIVE
    A) At the time of this review, no data were available to assess the teratogenic potential of this agent.
    B) At the time of this review, no data were available to assess the potential effects of exposure to this agent during pregnancy or lactation.
    0.2.21) CARCINOGENICITY
    A) A 47 year old nonsmoking spray painter who had been exposed to toluene diisocyanate and 4,4-methylenediphenyl diisocyanate for 15 years developed an adenocarcinoma of the lung.
    B) A slight, but not significant, increase in rectal cancer and non-Hodgkin's lymphoma was found in workers in a polyurethane foam manufacturing plant.

Laboratory Monitoring

    A) Monitor respiratory function closely. Serum and urine toluenediamine levels should also be monitored.

Treatment Overview

    0.4.2) ORAL/PARENTERAL EXPOSURE
    A) Due to the irritant nature of this substance, emesis is not advised.
    B) 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.
    1) CONTRAINDICATIONS: Loss of airway protective reflexes or decreased level of consciousness in unintubated patients; following ingestion of corrosives; hydrocarbons (high aspiration potential); patients at risk of hemorrhage or gastrointestinal perforation; and trivial or non-toxic ingestion.
    C) 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.
    D) Monitor patient for respiratory distress. If a cough or difficulty in breathing develops, evaluate for respiratory tract irritation, bronchitis and pneumonia.
    E) Allergic reaction - Sensitized individuals should be cautioned to avoid further exposure as serious allergic reactions may result.
    F) NOTE: See treatment of oral exposure in the main body of this document for complete information.
    0.4.3) INHALATION EXPOSURE
    A) 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.
    B) The specific role of bronchodilators for treatment of severe bronchoconstriction has not been evaluated. Asthma from TDI can be induced in the absence of airway hyperresponsiveness; in these cases bronchodilator use may contribute little to modifying severity.
    C) NOTE: See treatment of inhalation exposure in the main body of this document for complete information.
    0.4.4) EYE EXPOSURE
    A) 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.
    B) NOTE: See treatment of eye exposure in the main body of this document for complete information.
    0.4.5) DERMAL EXPOSURE
    A) OVERVIEW
    1) 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).
    2) NOTE: See treatment of dermal exposure in the main body of this document for complete information.

Range Of Toxicity

    A) The minimum lethal human dose to this agent has not been delineated.

Clinical Effects

Summary Of Exposure

    A) Toluene 2,4-diisocyanate (TDI) is irritating to the eyes, skin, and mucous membranes. Ingestion can result in a sore throat, irritation of the mouth and stomach, abdominal pain, and diarrhea.
    B) Inhalation of the vapors can cause irritation of the nose, throat, and lungs; wheezing; cough; chemical pneumonitis; bronchospasm; bronchitis; insomnia; euphoria; ataxia; loss of consciousness; personality changes; irritability; and depression. Pulmonary edema may occur from severe inhalation poisoning. It is one of the leading causes of occupational asthma.
    C) Dermal exposure can cause redness, pain, swelling, and blistering. Chronic dermal exposure can lead to skin sensitization and allergic eczema.
    D) Splash contact to the eyes may result in redness, pain, blurred vision, severe irritation, lacrimation, conjunctivitis, keratitis, and corneal damage.
    E) Repeated exposure can cause lung disease psychological effects, chest tightness, sneezing, cyanosis and collapse, chronic obstructive bronchitis, emphysema, chemical bronchitis, and asthmatic syndrome. Exposure can result in chemical pneumonitis, bronchospasm, bronchitis, and pulmonary edema; it is one of the leading causes of occupational asthma. Neurologic symptoms may include euphoria, loss of coordination, loss of consciousness, memory loss, and depression.

Heent

    3.4.1) SUMMARY
    A) Severe conjunctival irritation and lacrimation from liquid or high vapor concentrations is likely. Corneal edema may also occur. Lower concentrations may produce a burning or prickling sensation.
    3.4.3) EYES
    A) CONJUNCTIVITIS - Severe conjunctival irritation and lacrimation occur from liquid or high vapor concentrations (Axford et al, 1976). Burning or pricking sensations occur with lower concentrations (ACGIH, 1991).
    B) CORNEAL EDEMA - Nine workers in a polyurethane foam production plant who were exposed to high vapor concentrations of TDI developed microcytic corneal epithelial edema with subjective impression of foggy or smoky vision. These findings were attributed to TDI; however, there are reasons to suspect that the amines used in the manufacture of polyurethane foam were more likely responsible (Grant, 1993).

Respiratory

    3.6.1) SUMMARY
    A) Burning or irritation of the nose and throat, cough, laryngitis, chest pain, and asthmatic syndrome (chemical bronchitis with severe bronchospasm), sensation of oppression or constriction of the chest, bronchitis, pulmonary edema, and cor pulmonale may occur.
    B) Occupational asthma, emphysema, decreased pulmonary function, and hypersensitization may occur from chronic exposure.
    3.6.2) CLINICAL EFFECTS
    A) IRRITATION SYMPTOM
    1) Burning or irritation of the nose and throat, choking sensation, cough which may or may not produce sputum, laryngitis, retrosternal soreness, chest pain, asthmatic syndrome (chemical bronchitis with severe bronchospasm), sensation of oppression or constriction of chest, chronic bronchitis, emphysema and cor pulmonale may occur (Axford et al, 1976; (ILO, 1998).
    B) ACUTE CHEMICAL BRONCHITIS
    1) Exposure to high concentrations of TDI may lead to chemical bronchitis with chemical pneumonitis, severe bronchospasm, pulmonary edema, headache, and insomnia (ACGIH, 1991).
    C) ACUTE LUNG INJURY
    1) Severe poisoning from inhalation of vapors causes chest constriction, cough, choking, bronchospasms, bronchitis, and pulmonary edema (Budavari, 1996; Baselt, 1997; Lewis, 1998; ILO, 1998).
    D) CHEST PAIN
    1) Epigastric and substernal pain may be secondary to the paroxysmal or persistent cough associated with inhalation.

Neurologic

    3.7.1) SUMMARY
    A) Acute exposures may produce headache, insomnia, euphoria, ataxia, anxiety neurosis with depression, paranoid tendencies, or impotence.
    3.7.2) CLINICAL EFFECTS
    A) CENTRAL NERVOUS SYSTEM FINDING
    1) Firefighters exposed to TDI and possibly other substances experienced neurologic complaints of euphoria, loss of coordination, and loss of consciousness. Long-lasting symptoms of personality change, irritability, depression, and memory loss were also reported (McKekrrow, 1970; O'Donoghue, 1985).
    2) Inhalation of the vapor may cause temporary headache, irritability, insomnia, paranoid depression, and personality changes (Sittig, 1991; Lewis, 1998).
    B) IMPOTENCE
    1) Firefighters exposed to TDI and possibly other substances suffered from impotence for some time after exposure. This was thought to be due to an indirect neurologic effect rather than to direct toxicity to the male genitalia (Le Quesne et al, 1976).

Gastrointestinal

    3.8.1) SUMMARY
    A) Inhalation of vapor or aerosol may produce vomiting and abdominal pain. Epigastric and substernal pain may be secondary to the paroxysmal or persistent cough associated with inhalation.
    3.8.2) CLINICAL EFFECTS
    A) NAUSEA AND VOMITING
    1) Nausea and vomiting may occur from inhalation of vapor or aerosol (Axford et al, 1976).
    B) ABDOMINAL PAIN
    1) Abdominal pain may be noted from inhalation exposure (Axford et al, 1976; Lewis, 1998).

Dermatologic

    3.14.1) SUMMARY
    A) Irritation and inflammation are common. TDI is corrosive. Skin sensitization and allergic eczema may occur.
    3.14.2) CLINICAL EFFECTS
    A) SKIN IRRITATION
    1) Irritation is common (Lewis, 1998; ILO, 1998).
    B) BURN OF SKIN
    1) TDI is corrosive and skin contact may cause redness, pain, swelling, and blistering. TDI may be absorbed through the skin (Sittig, 1991).
    C) HYPERSENSITIVITY REACTION
    1) Skin sensitization and allergic eczema may occur (Sittig, 1991; Budavari, 1996; ILO, 1998).

Reproductive

    3.20.1) SUMMARY
    A) At the time of this review, no data were available to assess the teratogenic potential of this agent.
    B) At the time of this review, no data were available to assess the potential effects of exposure to this agent during pregnancy or lactation.
    3.20.2) TERATOGENICITY
    A) LACK OF INFORMATION
    1) At the time of this review, no data were available to assess the teratogenic potential of this agent.
    3.20.3) EFFECTS IN PREGNANCY
    A) LACK OF INFORMATION
    1) At the time of this review, no data were available to assess the potential effects of exposure to this agent during pregnancy or lactation in humans.
    B) ANIMAL STUDIES
    1) Mated female CD rats exposed to 0 to 0.5 ppm TDI vapor on gestational days 6 through 15 demonstrated no significant treatment-related changes, including pre- and post-implantation loss, sex ratio/litter or fetal body weights/litter (Tyl et al, 1999b).
    2) A two-generation study on 2,6-TDI inhaled nearly continuously at levels between 0 and 0.3 ppm demonstrated no reproductive toxicity, reproductive organ pathology or effect on lactation/gestation at any exposure level (Tyl et al, 1999a).

Carcinogenicity

    3.21.1) IARC CATEGORY
    A) IARC Carcinogenicity Ratings for CAS584-84-9 (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):
    1) Not Listed
    3.21.2) SUMMARY/HUMAN
    A) A 47 year old nonsmoking spray painter who had been exposed to toluene diisocyanate and 4,4-methylenediphenyl diisocyanate for 15 years developed an adenocarcinoma of the lung.
    B) A slight, but not significant, increase in rectal cancer and non-Hodgkin's lymphoma was found in workers in a polyurethane foam manufacturing plant.
    3.21.3) HUMAN STUDIES
    A) CARCINOMA
    1) A 47 year old nonsmoking spray painter who had been exposed to toluene diisocyanate and 4,4-methylenediphenyl diisocyanate for 15 years developed an adenocarcinoma of the lung (HSDB , 1998).
    2) A slight, but not significant, increase in rectal cancer and non-Hodgkin's lymphoma was found in workers in a polyurethane foam manufacturing plant (Hagmaar et al, 1993).
    3.21.4) ANIMAL STUDIES
    A) CARCINOMA
    1) Rats and mice fed commercial grade toluene diisocyanate developed hemangiosarcomas in the liver, ovaries, and peritoneum; hepatocellular adenomas; pancreatic acinar cell adenomas; pancreatic islet cell adenomas; mammary gland tumors; and subcutaneous fibromas and fibrosarcomas (HSDB , 1998; Dieter et al, 1990).
    2) Chronic exposure studies in experimental animals have shown 2,4-TDI to be carcinogenic in mice and rats by the oral route (NTP, 1981), but this study has been criticized (Clement, 1982). It was not carcinogenic in mice or rats exposed by inhalation (Loeser, 1983; Owen P, 1980).

Genotoxicity

    A) TDI induced mutations in S typhimurium and an increased incidence of sister chromatid exchanges occurred in Chinese hamster ovary cells. TDI did not induce chromosomal aberrations in Chinese hamster ovary cells.

Laboratory Monitoring

Monitoring Parameters Levels

    4.1.1) SUMMARY
    A) Monitor respiratory function closely. Serum and urine toluenediamine levels should also be monitored.
    4.1.2) SERUM/BLOOD
    A) Determination of toluenediamine serum concentrations can be used to monitor worker exposure to TDI. Concentrations in workers chronically exposed at the current TLV of 0.005 ppm should remain below 10 mcg/L. The plasma half-life of toluenediamine averages 21 days; the plasma concentrations will reflect cumulative exposure to TDI over many weeks (Baselt, 1997; Harbison, 1998).
    B) Plasma toluenediamine may be measured as an index of exposure by gas chromatography-mass spectrometry (Baselt, 1997).
    4.1.3) URINE
    A) At the current TLV, urinary excretion rates for the toluenediamine isomers should remain below 0.10 mcg/hr in specimens collected during or at the end of a shift (Baselt, 1997).
    B) A study of 9 workers exposed to TDI-based polyurethane foam, validated the use of urinary toluene diamine in postshift samples as an indicator of preceding 8-hour exposure to toluene diisocyanate (Maitre et al, 1993).
    C) Urine toluenediamine may be measured as an index of exposure by gas chromatography-mass spectrometry (Baselt, 1997). A high performance liquid chromatography method may also be used for accurate determinations of toluenediamines in urine (Carbonnelle et al, 1996).
    4.1.4) OTHER
    A) OTHER
    1) Monitor respiratory function closely. A preplacement medical examination should be performed and should include pulmonary function testing (FEV1, FVC, AND FEV1/FVC), a history of diisocyanate exposure, smoking history, and history of respiratory conditions (Zenz, 1994).

Treatment

Life Support

    A) Support respiratory and cardiovascular function.

Monitoring

    A) Monitor respiratory function closely. Serum and urine toluenediamine levels should also be monitored.

Oral Exposure

    6.5.2) PREVENTION OF ABSORPTION
    A) EMESIS/NOT RECOMMENDED
    1) Due to the irritant nature of this substance, emesis is NOT advised.
    B) GASTRIC LAVAGE
    1) INDICATIONS: Consider gastric lavage with a large-bore orogastric tube (ADULT: 36 to 40 French or 30 English gauge tube {external diameter 12 to 13.3 mm}; CHILD: 24 to 28 French {diameter 7.8 to 9.3 mm}) after a potentially life threatening ingestion if it can be performed soon after ingestion (generally within 60 minutes).
    a) Consider lavage more than 60 minutes after ingestion of sustained-release formulations and substances known to form bezoars or concretions.
    2) PRECAUTIONS:
    a) SEIZURE CONTROL: Is mandatory prior to gastric lavage.
    b) AIRWAY PROTECTION: Place patients in the head down left lateral decubitus position, with suction available. Patients with depressed mental status should be intubated with a cuffed endotracheal tube prior to lavage.
    3) LAVAGE FLUID:
    a) Use small aliquots of liquid. Lavage with 200 to 300 milliliters warm tap water (preferably 38 degrees Celsius) or saline per wash (in older children or adults) and 10 milliliters/kilogram body weight of normal saline in young children(Vale et al, 2004) and repeat until lavage return is clear.
    b) The volume of lavage return should approximate amount of fluid given to avoid fluid-electrolyte imbalance.
    c) CAUTION: Water should be avoided in young children because of the risk of electrolyte imbalance and water intoxication. Warm fluids avoid the risk of hypothermia in very young children and the elderly.
    4) COMPLICATIONS:
    a) Complications of gastric lavage have included: aspiration pneumonia, hypoxia, hypercapnia, mechanical injury to the throat, esophagus, or stomach, fluid and electrolyte imbalance (Vale, 1997). Combative patients may be at greater risk for complications (Caravati et al, 2001).
    b) Gastric lavage can cause significant morbidity; it should NOT be performed routinely in all poisoned patients (Vale, 1997).
    5) CONTRAINDICATIONS:
    a) Loss of airway protective reflexes or decreased level of consciousness if patient is not intubated, following ingestion of corrosive substances, hydrocarbons (high aspiration potential), patients at risk of hemorrhage or gastrointestinal perforation, or trivial or non-toxic ingestion.
    C) ACTIVATED CHARCOAL/CATHARTIC
    1) CHARCOAL ADMINISTRATION
    a) Consider administration of activated charcoal after a potentially toxic ingestion (Chyka et al, 2005). Administer charcoal as an aqueous slurry; most effective when administered within one hour of ingestion.
    2) CHARCOAL DOSE
    a) Use a minimum of 240 milliliters of water per 30 grams charcoal (FDA, 1985). Optimum dose not established; usual dose is 25 to 100 grams in adults and adolescents; 25 to 50 grams in children aged 1 to 12 years (or 0.5 to 1 gram/kilogram body weight) ; and 0.5 to 1 gram/kilogram in infants up to 1 year old (Chyka et al, 2005).
    1) Routine use of a cathartic with activated charcoal is NOT recommended as there is no evidence that cathartics reduce drug absorption and cathartics are known to cause adverse effects such as nausea, vomiting, abdominal cramps, electrolyte imbalances and occasionally hypotension (None Listed, 2004).
    b) ADVERSE EFFECTS/CONTRAINDICATIONS
    1) Complications: emesis, aspiration (Chyka et al, 2005). Aspiration may be complicated by acute respiratory failure, ARDS, bronchiolitis obliterans or chronic lung disease (Golej et al, 2001; Graff et al, 2002; Pollack et al, 1981; Harris & Filandrinos, 1993; Elliot et al, 1989; Rau et al, 1988; Golej et al, 2001; Graff et al, 2002). Refer to the ACTIVATED CHARCOAL/TREATMENT management for further information.
    2) Contraindications: unprotected airway (increases risk/severity of aspiration) , nonfunctioning gastrointestinal tract, uncontrolled vomiting, and ingestion of most hydrocarbons (Chyka et al, 2005).
    6.5.3) TREATMENT
    A) DILUTION
    1) Due to the irritant nature of this substance, emesis is not advised. Immediately dilute the ingested substance with milk or water.
    B) AIRWAY MANAGEMENT
    1) Monitor patient for respiratory distress, if a cough or difficulty in breathing develops, evaluate for respiratory tract irritation, bronchitis, and pneumonia.
    C) ACUTE ALLERGIC REACTION
    1) Sensitized individuals should be cautioned to avoid further exposure as serious allergic reactions may result.

Inhalation Exposure

    6.7.1) DECONTAMINATION
    A) Move patient from the toxic environment to fresh air. Monitor for respiratory distress. If cough or difficulty in breathing develops, evaluate for hypoxia, respiratory tract irritation, bronchitis, or pneumonitis.
    B) OBSERVATION: Carefully observe patients with inhalation exposure for the development of any systemic signs or symptoms and administer symptomatic treatment as necessary.
    C) INITIAL TREATMENT: Administer 100% humidified supplemental oxygen, perform endotracheal intubation and provide assisted ventilation as required. Administer inhaled beta-2 adrenergic agonists, if bronchospasm develops. Consider systemic corticosteroids in patients with significant bronchospasm (National Heart,Lung,and Blood Institute, 2007). Exposed skin and eyes should be flushed with copious amounts of water.
    D) Monitor for allergic reactions.
    6.7.2) TREATMENT
    A) GENERAL TREATMENT
    1) Treatment is SYMPTOMATIC and SUPPORTIVE.
    B) BRONCHOSPASM
    1) The specific role of bronchodilators for treatment of severe bronchoconstriction has not been evaluated. Asthma from TDI can be induced in the absence of airway hyperresponsiveness; in these cases bronchodilator use may contribute little to modifying severity.
    C) Treatment should include recommendations listed in the ORAL EXPOSURE section when appropriate.

Eye Exposure

    6.8.1) DECONTAMINATION
    A) EYE IRRIGATION, ROUTINE: 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, an ophthalmologic examination should be performed (Peate, 2007; Naradzay & Barish, 2006).
    6.8.2) TREATMENT
    A) GENERAL TREATMENT
    1) Treatment is SYMPTOMATIC and SUPPORTIVE.
    B) Treatment should include recommendations listed in the ORAL EXPOSURE section when appropriate.

Dermal Exposure

    6.9.1) DECONTAMINATION
    A) DERMAL DECONTAMINATION
    1) DECONTAMINATION: Remove contaminated clothing and wash exposed area thoroughly with soap and water for 10 to 15 minutes. A physician may need to examine the area if irritation or pain persists (Burgess et al, 1999).
    6.9.2) TREATMENT
    A) GENERAL TREATMENT
    1) Treatment is SYMPTOMATIC and SUPPORTIVE.
    B) Treatment should include recommendations listed in the ORAL EXPOSURE section when appropriate.

Range Of Toxicity

Summary

    A) The minimum lethal human dose to this agent has not been delineated.

Minimum Lethal Exposure

    A) The minimum lethal human dose to this agent has not been delineated.

Maximum Tolerated Exposure

    A) Carcinogenicity Ratings:
    1) According to IARC, there is sufficient evidence that toluene diisocyanates are carcinogens in experimental animals (IARC, 1999).
    2) "NIOSH considers this substance to be a potenital occupational carcinogen" (NIOSH , 2001).
    3) ACGIH classification is as A4 - "Not Classifiable as a Human Carcinogen" (ACGIH, 2000).
    4) IARC ranks toluene diisocyanate isomer mixtures as possibly carcinogenic in humans (Group 2B) (IARC, 1999).
    B) 2,4-TDI is considered hazardous at any concentration (Lewis, 1998).
    C) Most toxicological studies do not specify which toluene diisocyanate isomer was used in their study. In many studies, the commercial 80:20 isomer mixture was used. There is no known important distinction in toxicological effects between the 2,4- and the 2,6-isomer (ACGIH, 1991).
    D) The US EPA established an Inhalation Reference Concentration (RfC) of 7x10(-5) mg/m(3) for the 80:20 isomer mixture. This value was calculated using an Uncertainty Factor of 30, and a Multiplication Factor of 1 ((IRIS, 2001)).
    E) Human studies:
    1) Nine workers of polyurethane foam producing plant were exposed to high concentrations of toluene diisocyanate vapors. All developed microcystic corneal epithelial edema, accompanied with the impression of foggy or smoky vision, but without discomfort. It was found that exposure for one day was sufficient to develop the edema. While visual acuity was only minimally reduced using the Snellen chart, slit-lamp examination showed microcystic changes in the corneal epithelium. This change was spontaneously reversible within 12 to 48 hours after a one day exposure, or within several days after repeated daily exposure. It was later suspected that amines, rather than the diisocyanates, used in the manufacture of polyurethane foams were responsible for the development of the edema and the haziness of vision (Grant, 1993).
    2) Toluene diisocyanates reportedly form antigenic complexed with proteins, thereby transforming lymphocytes in sensitized individuals and inducing the formation of specific antibodies (HSDB, 2001a).
    3) At breathing zone concentrations of 0.5 ppm, respiratory response is imminent. Respiratory symptoms will develop with a latent period of 4 to 8 hours. Onset is dependent upon length of exposure and level of concentrations above 0.5 ppm. Concentrations above 0.5 ppm will produce a sensation of oppression or constriction of the chest (Hathaway et al, 1996).
    4) Respiratory sensitization occurred after repeated exposure to levels of 0.02 ppm and below. Initial symptoms often occur at night. Susceptibility to toluene diisocyanate-induced asthma does not require a prior history of atopy or allergic conditions. Following sufficient exposure to toluene diisocyanates, any individual may become sensitized to this compound. Nightly symptoms may develop even long after the end of a work shift. Individuals with toluene diisocyanate-induced asthma may continue to show dyspnea, wheezing and bronchial hyperreactivity for 2 or more years after cessation of exposure. Due to current work practices, skin sensitization is uncommon. Little relation seems to exist between skin sensitivity and respiratory sensitivity to toluene diisocyanates (Hathaway et al., 1996).
    5) 2.5% of workers exposed to 0.02 ppm (0.14 mg/m(3)) of toluene diisocyanate isomer mixture developed bronchial hypersensitivity. Individuals 'sensitized' to this mixture developed severe respiratory symptoms when exposure continued. In most cases, improvement occurs when exposure ceases (IARC, 1986).
    6) Dose-dependent changes in the rate of loss of pulmonary function were described in a cohort of workers exposed to toluene diisocyanate isomer mixture. An excess rate was observed at a concentration of 0.002 to 0.003 ppm (0.01 to 0.021 mg/m(3)) (IARC, 1986).
    7) No respiratory effects were observed following exposure to approximately 0.001 ppm (0.007 mg/m(3)) for five to ten years (IARC, 1986).
    8) Exposure to toluene diisocyanate isomer mixture may cause chronic restrictive pulmonary disease and hypersensitivity pneumonitis. Exposure to high concentrations or repeatedly low concentrations of toluene diisocyanate isomer mixture has been associated with the development of chronic bronchitis. Sensitized workers may develop persistent respiratory symptoms even after exposure was terminated (IARC, 1986).
    9) Exposure to very high concentrations of toluene diisocyanate isomer mixture can have effects on the nervous system, and can lead to headache, poor memory, difficulty concentrating, confusion, changes in personality, irritability and depression (IARC, 1986).
    10) One report describes the development of an adenocarcinoma in the lung of a 47-year old non-smoking spray painter. The worker had been exposed to toluene diisocyanate isomer mixture and 4,4'-methylenediphenyl diisocyanate for 15 years. It was thought that the lung disease was caused by exposure to isocyanates. IARC states however that this report was inadequate to evaluate the carcinogenicity of toluene diioscyanantes to humans (IARC, 1986) IARC, 1999).
    11) Between 1957 and 1962, 42 cases of occupational TDI intoxication were reported from 14 plants in Massachusetts. For 14 of these cases, average vapor concentration of toluene diisocyanates in the workroom was about 0.03 ppm; in a few samples, the average concentration were greater than 0.05 ppm. In 11 cases, the average concentration was measured at 0.015 ppm, and in 9 cases the average concentration was below 0.01 ppm. In the remaining cases, no measurements were possible. It was found that all plants with average concentrations greater than 0.01 ppm had cases with related respiratory illness. No such illnesses were reported in plants with average concentrations of 0.007 ppm or less (ACGIH, 1991).
    12) Although repeated exposure to lower concentrations of the isomer mixture has been shown to produce chronic-like syndromes in humans, and may be related to hypersensitization, exposure to moderately elevated levels of the mixture (mean 0.07 ppm, peak 0.2 ppm) does not result in interstitial pulmonary fibrosis (ACGIH, 1991).
    13) An investigation of 83 cases of occupational intoxication following exposure to the isomer mixture showed that the maximum incidence occurred at a concentration of approximately 0.1 ppm, whereas very few complaints were noted when the concentration was approximately 0.01 ppm. Another study showed a high incidence of illness at concentrations between 0.03 and 0.07 ppm, but no complaints when the concntration was kept below 0.03 ppm (ACGIH, 1991).
    14) In one study, respiratory sensitization was observed in workers who were only exposed to toluene diisocyanate vapors during trimming and sewing of polyurethane cushions. Air concentration was measured at only 0.003 ppm (Zenz, 1994).
    15) In a plant manufacturing polyurethane foam ice chests and picnic jugs, workers were exposed to 0.005 ppm of the isomer mixture during normal operations but had been exposed to unknown relatively high concentrations of the mixture during spills in the past. Nine of 13 symptomatic workers showed decreased forced vital capacity (FVC) and decreased forced expiratory volume in one second (FEV1) (ACGIH, 1991).
    16) Even in asymptomatic workers, ventilatory capacity can be reduced over a work shift following exposure to toluene diisocyanate vapors at low (below 0.02 ppm and 0.001 ppm) or high (greater than 0.9 ppm) concentrations. In the latter, an acute loss of forced expiratory volume (FEV1) of 0.18L over 8 hours has been reported (Zenz, 1994).
    17) During an 18-month period, respiratory sensitization was observed in 5% of 99 workers, who were exposed to the isomer mixture usually below 0.02 ppm. It was assumed that the sensitization was a result of exposure to higher concentrations in spill situations (ACGIH, 1991).
    18) Four of 47 office workers became sensitized from exposure to exhaust air containing "unknown but probably quite low" concentrations of the isomer mixture. The air inlet of the office was 23 feet from the ventilation outlet of a nearby isomer mixture-manufacturing plant (ACGIH, 1991).
    F) Animal studies:
    1) Mice exposed to 0.4 ppm of 2,4-TDI experienced a 50% decrease in respiratory rate. Exposure at this concentration for 5 days (6 hours per day) resulted in lesions in the nasal cavities of the animals with a distinct anterior-posterior gradient in severity (HSDB, 2001a).
    2) Results from a study performed in guinea pigs suggested that exposure to 29 ppb of toluene diisocyanates (97.8% of 2,4-TDI and 2.2% of 2,6-TDI) had a direct, dose-dependent effect on tracheal smooth muscle activity (HSDB , 2001).
    3) Commercial grade isomer mixture was found to be carcinogenic inF344/N rats. Exposure resulted in increased number of subcutaneous fibromas and fibrosarcomas in male and female animals; pancreatic acinar cell adenomas in male animals; pancreatic islet cell carcinomas, neoplastic nodules of the liver, and mammary gland fibroadenomas in female animals. The same isomer mixture was not considered to be carcinogenic for male B6C3F1 mice but was judged carcinogenic for female B6C3F1 mice. Exposure of female mice resulted in hemangiomas or hemangiosarcomas and hepatocellular adenomas. Concentrations of the isomer mixture (administered via gavage, dissolved in corn oil) used for both rats and mice were as follows: male rats 23 or 49 mg/kg; female rats and female mice 49 or 108 mg/kg; male mice 108 or 202 mg/kg (ACGIH, 1991; NTP , 1986).
    4) In one animal study, where mice and rats of both genders were exposed to the commercial isomer mixture, the pattern of multiple tumor sites was similar to that seen following exposure to 2,4-diamino toluene. Since common metabolites are produced from 2,4-TDI and 2,4-diamino toluene, it was suggested that 2,4-TDI contained in commercial mixture is responsible for the mixture's carcinogenic effect (Hathaway et al., 1996).
    5) Inhalation exposure of rats and mice to production-grade isomer mixture at concentrations of 0.05 ppm and 0.15 ppm did not show evidence for carcinogenicity. Exposure durations were 6 hours/day, 5 days/week, 108 to 110 weeks (rats) or 104 weeks (mice). Exposures in this study were later found to be below the maximum tolerated dose, based on mortality and gross body weight data (ACGIH, 1991).

Workplace Standards

    A) ACGIH TLV Values for CAS584-84-9 (American Conference of Governmental Industrial Hygienists, 2010):
    1) 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.
    a) Adopted Value
    1) Toluene-2,4- or 2,6-diisocyanate (or as a mixture)
    a) TLV:
    1) TLV-TWA: (0.005 ppm)
    2) TLV-STEL: (0.02 ppm)
    3) TLV-Ceiling:
    b) Notations and Endnotes:
    1) Carcinogenicity Category: A4
    2) Codes: SEN
    3) Definitions:
    a) A4: Not Classifiable as a Human Carcinogen: Agents which cause concern that they could be carcinogenic for humans but which cannot be assessed conclusively because of a lack of data. In vitro or animal studies do not provide indications of carcinogenicity which are sufficient to classify the agent into one of the other categories.
    b) SEN: The designation SEN refers to the potential for an agent to produce sensitization, as confirmed by human or animal data. The notation does not imply that this is the critical effect or that this is the sole basis for the TLV. Although, for those TLVs that are based on sensitization, the TLV is meant to protect workers from induction of this effect, but cannot protect workers who have already become sensitized. The notation should be used to assist in identifying sensitization hazards and reducing respiratory, dermal, and conjunctival exposures to sensitizing agents in the workplace. Please see "Definitions and Notations" (in TLV booklet) for full definition.
    c) TLV Basis - Critical Effect(s): (Resp sens)
    d) Molecular Weight: 174.15
    1) For gases and vapors, to convert the TLV from ppm to mg/m(3):
    a) [(TLV in ppm)(gram molecular weight of substance)]/24.45
    2) For gases and vapors, to convert the TLV from mg/m(3) to ppm:
    a) [(TLV in mg/m(3))(24.45)]/gram molecular weight of substance
    e) Additional information:
    1) See Notice of Intended Changes; Adopted values enclosed in parentheses are those for which changes are proposed in the Notice of Intended Changes.
    b) Notice of Intended Changes
    1) Toluene-2,4- or 2,6-diisocyanate (or as a mixture)
    a) TLV:
    1) TLV-TWA: 0.001 ppm
    2) TLV-STEL: 0.003 ppm
    3) TLV-Ceiling:
    b) Notations and Endnotes:
    1) Carcinogenicity Category: A3
    2) Codes: IFV, SEN, Skin
    3) Definitions:
    a) A3: Confirmed Animal Carcinogen with Unknown Relevance to Humans: The agent is carcinogenic in experimental animals at a relatively high dose, by route(s) of administration, at site(s), of histologic type(s), or by mechanism(s) that may not be relevant to worker exposure. Available epidemiologic studies do not confirm an increased risk of cancer in exposed humans. Available evidence does not suggest that the agent is likely to cause cancer in humans except under uncommon or unlikely routes or levels of exposure.
    b) IFV: Inhalable fraction and vapor.
    c) SEN: The designation SEN refers to the potential for an agent to produce sensitization, as confirmed by human or animal data. The notation does not imply that this is the critical effect or that this is the sole basis for the TLV. Although, for those TLVs that are based on sensitization, the TLV is meant to protect workers from induction of this effect, but cannot protect workers who have already become sensitized. The notation should be used to assist in identifying sensitization hazards and reducing respiratory, dermal, and conjunctival exposures to sensitizing agents in the workplace. Please see "Definitions and Notations" (in TLV booklet) for full definition.
    d) Skin: This refers to the potential significant contribution to the overall exposure by the cutaneous route, including mucous membranes and the eyes, either by contact with vapors or, of likely greater significance, by direct skin contact with the substance. It should be noted that although some materials are capable of causing irritation, dermatitis, and sensitization in workers, these properties are not considered relevant when assigning a skin notation. Rather, data from acute dermal studies and repeated dose dermal studies in animals or humans, along with the ability of the chemical to be absorbed, are integrated in the decision-making toward assignment of the skin designation. Use of the skin designation provides an alert that air sampling would not be sufficient by itself in quantifying exposure from the substance and that measures to prevent significant cutaneous absorption may be warranted. Please see "Definitions and Notations" (in TLV booklet) for full definition.
    c) TLV Basis - Critical Effect(s): Asthma
    d) Molecular Weight: 174.15
    1) For gases and vapors, to convert the TLV from ppm to mg/m(3):
    a) [(TLV in ppm)(gram molecular weight of substance)]/24.45
    2) For gases and vapors, to convert the TLV from mg/m(3) to ppm:
    a) [(TLV in mg/m(3))(24.45)]/gram molecular weight of substance
    e) Additional information:

    B) NIOSH REL and IDLH Values for CAS584-84-9 (National Institute for Occupational Safety and Health, 2007):
    1) Listed as: Toluene-2,4-diisocyanate
    2) REL:
    a) TWA:
    b) STEL:
    c) Ceiling:
    d) Carcinogen Listing: (Ca) NIOSH considers this substance to be a potential occupational carcinogen (See Appendix A in the NIOSH Pocket Guide to Chemical Hazards).
    e) Skin Designation: Not Listed
    f) Note(s): See Appendix A
    3) IDLH:
    a) IDLH: 2.5 ppm
    b) Note(s): Ca
    1) Ca: NIOSH considers this substance to be a potential occupational carcinogen (See Appendix A).

    C) Carcinogenicity Ratings for CAS584-84-9 :
    1) ACGIH (American Conference of Governmental Industrial Hygienists, 2010): A4 ; Listed as: Toluene-2,4- or 2,6-diisocyanate (or as a mixture)
    a) A4 :Not Classifiable as a Human Carcinogen: Agents which cause concern that they could be carcinogenic for humans but which cannot be assessed conclusively because of a lack of data. In vitro or animal studies do not provide indications of carcinogenicity which are sufficient to classify the agent into one of the other categories.
    2) ACGIH (American Conference of Governmental Industrial Hygienists, 2010): A3 ; Listed as: Toluene-2,4- or 2,6-diisocyanate (or as a mixture)
    a) A3 :Confirmed Animal Carcinogen with Unknown Relevance to Humans: The agent is carcinogenic in experimental animals at a relatively high dose, by route(s) of administration, at site(s), of histologic type(s), or by mechanism(s) that may not be relevant to worker exposure. Available epidemiologic studies do not confirm an increased risk of cancer in exposed humans. Available evidence does not suggest that the agent is likely to cause cancer in humans except under uncommon or unlikely routes or levels of exposure.
    3) EPA (U.S. Environmental Protection Agency, 2011): Not Listed
    4) 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
    5) NIOSH (National Institute for Occupational Safety and Health, 2007): Ca ; Listed as: Toluene-2,4-diisocyanate
    a) Ca : NIOSH considers this substance to be a potential occupational carcinogen (See Appendix A in the NIOSH Pocket Guide to Chemical Hazards).
    6) MAK (DFG, 2002): Category 3A ; Listed as: Toluene-2,4-diisocyanate
    a) Category 3A : Substances for which the criteria for classification in Category 4 or 5 are fulfilled but for which the database is insufficient for the establishment of a MAK value.
    7) NTP (U.S. Department of Health and Human Services, Public Health Service, National Toxicology Project ): Not Listed

    D) OSHA PEL Values for CAS584-84-9 (U.S. Occupational Safety, and Health Administration (OSHA), 2010):
    1) Listed as: Toluene-2,4-diisocyanate (TDI)
    2) Table Z-1 for Toluene-2,4-diisocyanate (TDI):
    a) 8-hour TWA:
    1) ppm: 0.02
    a) Parts of vapor or gas per million parts of contaminated air by volume at 25 degrees C and 760 torr.
    2) mg/m3: 0.14
    a) Milligrams of substances per cubic meter of air. When entry is in this column only, the value is exact; when listed with a ppm entry, it is approximate.
    3) Ceiling Value: (C) - An employee's exposure to this substance shall at no time exceed the exposure limit given.
    4) Skin Designation: No
    5) Notation(s): Not Listed

Toxicity Information

    7.7.1) TOXICITY VALUES
    A) ACGIH, 1991 RTECS, 2001a)
    1) LD50- (ORAL)RAT:
    a) 5800 mg/kg -- Changes in Gastrointestinal system
    2) TCLo- (INHALATION)HUMAN:
    a) 80 ppb -- Changes in Sense Organs and Special Senses (Nose, Eye, Ear, and Taste); changes in Lung, Thorax, or Respiration
    b) 500 ppb -- Changes in Sense Organs and Special Senses (Nose, Eye, Ear, and Taste); changes in Lung, Thorax, or Respiration
    c) 20 ppb for 2Y -- Cough; Sputum
    d) Female, 300 ppt for 8H/5D -- Respiratory obstruction
    3) TCLo- (INHALATION)MOUSE:
    a) 990 ppb for 6H/14D - intermittent --Changes in Sense Organs and Special Senses (Nose, Eye, Ear, and Taste)
    4) TCLo- (INHALATION)RAT:
    a) 204 mcg/m(3) for 24H/84D - continuous -- Muscle contraction or spasticity; Effect on true cholinesterase; Effect on lipids including transport
    b) 102 ppb for 24H/7D - continuous -- Structural or functional change in trachea or bronchi
    c) 26 ppm for 6H/5W - intermittent -- Structural or functional change in trachea or bronchi; Chronic pulmonary edema; Death
    B) ACGIH, 1991 RTECS, 2001a)
    1) LD50- (ORAL)MOUSE:
    a) 1950 mg/kg (RTECS, 2001b)
    2) LD50- (ORAL)RAT:
    a) 4130 mg/kg (RTECS, 2001b)
    b) 5800 mg/kg (OHM/TADS, 2001)
    3) TCLo- (INHALATION)HUMAN:
    a) 0.5 ppm (OHM/TADS, 2001)
    4) TCLo- (INHALATION)MOUSE:
    a) 1 ppm for 6H/5D intermittent -- Weight loss or decreased weight gain; Death (RTECS, 2001b)
    5) TCLo- (INHALATION)RAT:
    a) 100 ppb for 6H/81D intermittent -- Changes in Lung, Thorax, or Respiration (RTECS, 2001b)
    b) 10 mcg/m(3) for 24H/22W continuous -- Changes in Recordings from specific areas of CNS; Changes in bone marrow; Effects on true cholinesterase (RTECS, 2001b)
    c) 2 ppm for 6H/5D intermittent - Death (RTECS, 2001b)
    d) 2830 ppb for 6H/3W intermittent -- Structural or functional change in trachea or bronchi; Changes in erythrocyte (RBC) count; Weight loss or decreased weight gain (RTECS. 2001b)
    7.7.2) RISK ASSESSMENT VALUES
    A) ACGIH, 1991 RTECS, 2001a)
    1) NOEL- (INHALATION)GUINEA_PIG:
    a) 0.02 ppm for 6H (ACGIH, 1991)
    b) 0.05 ppm for 6H (ACGIH, 1991)
    2) NOEL- (INHALATION)RABBIT:
    a) 0.1 ppm for 6H once a week for 58W (ACGIH, 1991)

Physicochemical

Physical Characteristics

    A) Both 2,4-TDI and the isomer mixture are a clear water-white to pale yellow liquid, depending on pressure, temperature and relative conditions of the isomers (IARC, 1986; ILO, 1998) Lewis, 2000a; ((OHM/TADS, 2001)).
    B) It can be colorless to pale yellow, solid or liquid (above 71 degrees F) (ILO, 1998; NIOSH , 2001; Sittig, 1991).
    C) It is liquid at room temperature (Budavari, 2000; (OHM/TADS, 2001)). At 15 degrees C and 1 atm pressure, it is a solid ((CHRIS, 2001)).
    D) Its odor has been described as sharp and pungent, or as sharp, sweet and fruity (Budavari, 2000; (CHRIS, 2001)) Lewis, 2000a; (NIOSH , 2001; Sittig, 1991).
    E) The isomer mixture is colorless in water ((OHM/TADS, 2001)).
    F) 2,4-TDI and the isomer mixture are heavier than water and will sink to the bottom ((CHRIS, 2001); (OHM/TADS, 2001)).
    G) 2,4-TDI and the isomer mixture darken when exposed to sunlight. Their reaction with water generates carbon dioxide (Budavari, 2000; (OHM/TADS, 2001)).
    H) Editor's note: please be aware that the behavior of 2,4-TDI or the isomer mixture in water is likely to be affected by their reactivity with water.
    I) At normal temperatures, this compound is relatively non-corrosive ((OHM/TADS, 2001)).
    J) When exposed to water, toluene diisocyanate isomers break down into their corresponding diaminotoluenes (2,4 diaminotoluene) (ACGIH, 1991; IARC, 1986).
    1) In man, 2,4-TDI is metabolized into 2,4-diaminotoluene. The plasma half-life of the metabolite averages 21 days (Baselt, 1997).
    K) Due to its high reactivity with the functional groups of tissue proteins, 2,4-TDI is mainly distributed or eliminated as the metabolite rather than the intact compound. Following inhalation, 2,4-TDI is rapidly absorbed and irreversibly bound to plasma proteins. Within 24 hours following exposure, 15-23% of the absorbed dose of 2,4-TDI is excreted in the urine as 2,4-toluenediamine, apparently as the acetyl conjugate of the parent compound. Urinary elimination occurs as a biphasic process, with an early half-life of 2-5 hours and a late half-life of 6-11 days (Baselt, 1997).
    L) Editor's note: ACGIH provides information on the chemical and physical properties of the 80:20 isomer mixture, but also states "the chemical and physical properties of 2,4-TDI are similar" (ACGIH, 1991).

Molecular Weight

    A) 174.16
    B) 80:20 isomer mixture: 174.15 (ACGIH, 1991)

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