Phenyl isocyanate

Excerpt from ERG Guide 155 [Substances - Toxic and/or Corrosive (Flammable / Water-Sensitive)]:；Note: Most foams will react with the material and release corrosive/toxic gases. CAUTION: For Acetyl chloride (UN1717), use CO2 or dry chemical only.；SMALL FIRE: CO2, dry chemical, dry sand, alcohol-resistant foam.；LARGE FIRE: Water spray, fog or alcohol-resistant foam. FOR CHLOROSILANES, DO NOT USE WATER; use alcohol-resistant foam. If it can be done safely, move undamaged containers away from the area around the fire. Avoid aiming straight or solid streams directly onto the product.；FIRE INVOLVING TANKS, RAIL TANK CARS OR HIGHWAY TANKS: Fight fire from maximum distance or use unmanned master stream devices 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 in direct contact with flames. (ERG, 2024)

Use dry powder, carbon dioxide, alcohol-resistant foam. NO water. In case of fire: keep drums, etc., cool by spraying with water. NO direct contact with water.

Fresh air, rest. Half-upright position. Artificial respiration may be needed. Refer for medical attention.

Remove contaminated clothes. Rinse and then wash skin with water and soap. Refer for medical attention .

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

Rinse mouth. Give one or two glasses of water to drink. Do NOT induce vomiting. Refer for medical attention .

· CALL 911. Then call emergency response telephone number on shipping paper. If shipping paper not available or no answer, refer to appropriate telephone number listed on the inside back cover.；· Keep unauthorized personnel away.；· Stay upwind, uphill and/or upstream.；· Ventilate closed spaces before entering, but only if properly trained and equipped.

· ELIMINATE all ignition sources (no smoking, flares, sparks or flames) from 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 alcohol-resistant 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.；Small Spill；· 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.

Excerpt from ERG Guide 155 [Substances - Toxic and/or Corrosive (Flammable / Water-Sensitive)]:；Refer to the "General First Aid" section. Specific First Aid: For corrosives, in case of contact, immediately flush skin or eyes with running water for at least 30 minutes. Additional flushing may be required. (ERG, 2024)

General First Aid:；· Call 911 or emergency medical service.；· Ensure that medical personnel are aware of the material(s) involved, take precautions to protect themselves and avoid contamination.；· Move victim to fresh air if it can be done safely.；· Administer oxygen if breathing is difficult.；· If victim is not breathing:；-- DO NOT perform mouth-to-mouth resuscitation; the victim may have ingested or inhaled the substance.；-- If equipped and pulse detected, wash face and mouth, then give artificial respiration using a proper respiratory medical device (bag-valve mask, pocket mask equipped with a one-way valve or other device).；-- If no pulse detected or no respiratory medical device available, provide continuous compressions. Conduct a pulse check every two minutes or monitor for any signs of spontaneous respirations.；· Remove and isolate contaminated clothing and shoes.；· For minor skin contact, avoid spreading material on unaffected skin.；· In case of contact with substance, remove immediately by flushing skin or eyes with running water for at least 20 minutes.；· For severe burns, immediate medical attention is required.；· Effects of exposure (inhalation, ingestion, or skin contact) to substance may be delayed.；· Keep victim calm and warm.；· Keep victim under observation.；· For further assistance, contact your local Poison Control Center.；· Note: Basic Life Support (BLS) and Advanced Life Support (ALS) should be done by trained professionals.；Specific First Aid:；· For corrosives, in case of contact, immediately flush skin or eyes with running water for at least 30 minutes. Additional flushing may be required.

· Wear positive pressure self-contained breathing apparatus (SCBA).；· Wear chemical protective clothing that is specifically recommended by the manufacturer when there is NO RISK OF FIRE.；· Structural firefighters' protective clothing provides thermal protection but only limited chemical protection.

TIH (Toxic Inhalation Hazard) - Term used to describe gases and volatile liquids that are toxic when inhaled. Some are TIH materials themselves, e.g., chlorine, and some release TIH gases when spilled in water, e.g., chlorosilanes. [ERG 2016].

If material on fire or involved in fire: Use water in flooding quantities as fog. Use foam, dry chemical, or carbon dioxide. Keep run-off water out of sewers and water sources. Cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible.

Evacuation: If fire becomes uncontrollable or container is exposed to direct flame - consider evacuation of one-third (1/3) mile radius.

Where there is a fire involving isocyanates, carbon dioxide or powder extinguishers must be employed. Firemen must be equipped with self-contained breathing apparatus. /Isocyanates/

Isocyanates are transported in railroad tank cars, tank trucks, tanks in ships, containers, and drums. They are stored in steel tanks and processed in steel equipment. For long-term storage stainless steel is recommended. To avoid contamination by atmospheric moisture, a dry air or inert gas blanket is essential. /Isocyanates/

Decontamination of spilled isocyanates and disposal of isocyanate waste are best conducted by using aqueous ammonia (3-8% concentrated ammonia solution in 90-95% water with 0.2-5% liquid detergent) or aqueous sodium carbonate (5-10% sodium carbonate in 90-95% water and 0.2-5% liquid detergent). An alcoholic solution (50% ethanol, isopropyl alcohol, or butanol; 45% water; and 5% concentrated ammonia) may be preferred because of the low miscibility of isocyanates with water. /Isocyanates/

Excerpt from ERG Guide 155 [Substances - Toxic and/or Corrosive (Flammable / Water-Sensitive)]:；ELIMINATE all ignition sources (no smoking, flares, sparks or flames) from 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 alcohol-resistant 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.；SMALL SPILL: 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. (ERG, 2024)

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

SRP: Wastewater from contaminant suppression, cleaning of protective clothing/equipment, or contaminated sites should be contained and evaluated for subject chemical or decomposition product concentrations. Concentrations shall be lower than applicable environmental discharge or disposal criteria. Alternatively, pretreatment and/or discharge to a permitted wastewater treatment facility is acceptable only after review by the governing authority and assurance that "pass through" violations will not occur. Due consideration shall be given to remediation worker exposure (inhalation, dermal and ingestion) as well as fate during treatment, transfer and disposal. If it is not practicable to manage the chemical in this fashion, it must be evaluated in accordance with EPA 40 CFR Part 261, specifically Subpart B, in order to determine the appropriate local, state and federal requirements for disposal.

Personal protection: chemical protection suit including self-contained breathing apparatus. Ventilation. Remove all ignition sources. Collect leaking and spilled liquid in sealable containers as far as possible. Absorb remaining liquid in sand or inert absorbent. Then store and dispose of according to local regulations.

Antidotes to cyanide poisoning include hydroxocobalamin and sodium nitrite, which release the cyanide from the cytochrome system, and rhodanase, which is an enzyme occurring naturally in mammals that combines serum cyanide with thiosulfate, producing comparatively harmless thiocyanate. Oxygen therapy can also be administered. (L97)

Exposure to high levels of cyanide for a short time harms the brain and heart and can even cause coma, seizures, apnea, cardiac arrest and death. Chronic inhalation of cyanide causes breathing difficulties, chest pain, vomiting, blood changes, headaches, and enlargement of the thyroid gland. Skin contact with cyanide salts can irritate and produce sores. (L96, L97)

TERRESTRIAL FATE: Isocyanates hydrolyze rapidly in water(1); therefore, soil mobility, biodegradation, and volatilization of phenyl isocyanate in moist soil are not expected to be important environmental fate processes(SRC). Volatilization of phenyl isocyanate from dry soils is expected based on an extrapolated vapor pressure of 2.6 mm Hg at 25 °C(2).

AQUATIC FATE: Since isocyanates hydrolyze rapidly in water(1) (hydrolysis half-lives of phenyl isocyanate range from 20 seconds(2) to 75.5 minutes)(3), biodegradation, aquatic bioconcentration, volatilization, and adsorption to sediment of phenyl isocyanate are not expected to be important fate processes(SRC).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), phenyl isocyanate, which has an extrapolated vapor pressure of 2.6 mm Hg at 25 °C(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase phenyl isocyante is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals(SRC); the half-life for this reaction in air is estimated to be 5 days(SRC), calculated from its rate constant of 2.1X10-12 cu cm/molecule-sec at 25 °C(SRC) that was derived using a structure estimation method(3).

Lacrimator (Lachrymator) - A substance that irritates the eyes and induces the flow of tears.；Skin Sensitizer - An agent that can induce an allergic reaction in the skin.；Asthma - Reversible bronchoconstriction (narrowing of bronchioles) initiated by the inhalation of irritating or allergenic agents.；Toxic Pneumonitis - Inflammation of the lungs induced by inhalation of metal fumes or toxic gases and vapors.

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

Oral (L96) ; inhalation (L96) ; dermal (L96)

IDENTIFICATION AND USE: Phenyl isocyanate is a liquid with an acrid odor. It decomposes in water, alcohol; very soluble in ether. It is used as a chemical intermediate and as a reagent. HUMAN EXPOSURE AND TOXICITY: Workers exposed to phenyl isocyanate showed increases in asthmatic symptoms. Exposure to isocyanates is irritating to the skin, mucous membranes, eyes and respiratory tract. Contact dermatitis can result in symptoms such as rash, itching, hives and swelling of the extremities. Phenyl isocyanate is a potent chemical sensitizer. A worker suspected of having isocyanate induced asthma/sensitization will exhibit traditional symptoms of acute airway obstruction coughing, wheezing, shortness of breath, tightness of chest and nocturnal awakening. Isocyanate induced hypersensitivity pneumonitis symptoms are flu like which includes shortness of breath, nonproductive cough, fever, chills sweats and malaise and nausea. An irreversible decline in pulmonary function and interstitial fibrosis have also been observed. At high doses isocyanates affect the mucous membranes of the respiratory tract and may lead to fatal pulmonary edema or chromic catarrh. ANIMAL STUDIES: The toxic effects of repeated inhalation exposures to phenyl isocyanate vapors in male rats was conducted. Animals experienced decreased weight gain, hypoactivity, hypothermia, and signs of respiratory tract irritation. There was delayed onset of mortality, and changes in organ weights. Pulmonary function tests demonstrated decreased forced expiratory flow volume. Arterial hypoxia was also observed. Pregnant mice were given phenyl isocyanate on select days of gestation. Phenyl isocyanate did demonstrate embryotoxicity. In a micronucleus assay, male and female mice received a single administration of phenyl isocyanate ip; there was an altered ratio between polychromatic and normochromatic erythrocytes in the bone marrow, and no clastogenic effect was observed. Phenyl isocyanate did not cause significant indu

Cyanide is an inhibitor of cytochrome c oxidase in the fourth complex of the electron transport chain (found in the membrane of the mitochondria of eukaryotic cells). It complexes with the ferric iron atom in this enzyme. The binding of cyanide to this cytochrome prevents transport of electrons from cytochrome c oxidase to oxygen. As a result, the electron transport chain is disrupted and the cell can no longer aerobically produce ATP for energy. Tissues that mainly depend on aerobic respiration, such as the central nervous system and the heart, are particularly affected. Cyanide is also known produce some of its toxic effects by binding to catalase, glutathione peroxidase, methemoglobin, hydroxocobalamin, phosphatase, tyrosinase, ascorbic acid oxidase, xanthine oxidase, succinic dehydrogenase, and Cu/Zn superoxide dismutase. Cyanide binds to the ferric ion of methemoglobin to form inactive cyanmethemoglobin. (L97)

Cough. Sore throat. Burning sensation. Laboured breathing. Shortness of breath. Symptoms may be delayed.

Redness. Blisters. Pain. Skin burns.

Watering of the eyes. Redness. Pain. Severe deep burns.

Burning sensation. Abdominal pain. Shock or collapse.

Cyanide poisoning is identified by rapid, deep breathing and shortness of breath, general weakness, giddiness, headaches, vertigo, confusion, convulsions/seizures and eventually loss of consciousness. (L96, L97)

Phenyl Isocyanate (CAS# 103-71-9) was evaluated for acute inhalation toxicity in groups of 4 male and 4 female albino rats (strain not specified) exposed to unspecified concentrations of test material for one-hour. The use of controls was not specified. Animals were observed for 14-days post-exposure. Clinical obervations include piloerection, weight loss, and respiratory distress. Mortality and necropsy data were not specified. Histopathological data were not specified. The LC50 for male and female albino rats was 12.6 (8.4-19.0) ppm.

/HUMAN EXPOSURE STUDIES/ Sera of six workers with conclusive evidence for IgE-mediated sensitization to isocyanates were used for evaluation of immunologic cross-reactivities among eight different isocyanate-protein conjugates. In all cases RAST and/or skin-test investigations revealed the presence of IgE antibodies reacting specifically with HSA conjugated with those isocyanates to which workers were exposed as well as with other isocyanates with which they had not been in contact. By the RAST inhibition technique, moderate to strong mutual cross-reactivities between all tested isocyanate-HSA conjugates--even between aromatic and aliphatic ones--could be demonstrated in tests with five sera. The magnitudes of cross-reactivities differed, however, from one patient to another. One serum contained IgE antibodies that were almost completely specific to TDI-HSA; with this serum only weak cross-reactivities with other isocyanate conjugates could be demonstrated. These results indicate the predominance of closely related antigenic determinants in HSA conjugated with different isocyanates. The common antibody-binding regions are obviously recognized to different extents by antibodies of clinically sensitized workers, indicating individual differences in specificities and avidities of antibody populations. Nearly complete lack of IgE binding of ovalbumin-bound TDI in RAST and RAST inhibition indicates carrier-specific antigenicity of isocyanate-protein conjugates. In addition, since unmodified HSA did not bind IgE, antigenic determinants of the conjugates studied should be predominantly formed by the isocyanate-protein bond regions and concurrently by neighboring amino acid residues of the HSA molecule. /Isocyanates/

/SIGNS AND SYMPTOMS/ Workers exposed to isocyanates including phenyl isocyanate showed specific IgE for isocyanate-albumin conjugates. These workers also showed asthmatic symptoms...A comparison of the toxic effects of 4-chlorophenyl isocyanate, phenyl isocyanate and 4-isopropylphenyl isocyanate in humans ...is also presented. In humans, the only toxic effect described is an itchy erythema after repeated contact with chlorophenyl isocyanate.

/SIGNS AND SYMPTOMS/ Strong mucous membrane irritation causes eye, pulmonary, and gastrointestinal tract symptoms. These compounds are potent pulmonary sensitizers which cause bronchospasm, even in patients without prior airway hyperreactivity. Diisocyanate compounds act either as inducers of nonspecific bronchial hyperreactivity or as direct pharmacologic agonists. Isocyanates apparently have the potential to sensitize certain segments of the population. Elevated humoral antibodies (ie, specific IgE antibodies to the p-tolyl determinant but not the diisocyanate conjugate) were detected in sensitized workers, but cell-mediated immunity also may produce hypersensitivity reactions. In the absence of renewed exposure, radioallergosorbent titers may not distinguish sensitive from nonsensitized workers. At high doses, toluene diisocyanate may act directly on bronchial mucosa by interfering with cholinergic and adrenergic mechanisms. /Isocyanates/

Chemical: Benzene, isocyanato-

Benzene, isocyanato- is listed on the EPA's Chemical Data Reporting (CDR) system. Manufacturers and importers of Benzene, isocyanato- are required to report information about their production and use of this chemical to the EPA under the Toxic Substances Control Act (TSCA). (40 eCFR Part 711)

Status: Active Update: 14-08-2022 https://echa.europa.eu/registration-dossier/-/registered-dossier/33957；Status: Active Update: 03-05-2023 https://echa.europa.eu/registration-dossier/-/registered-dossier/12563；Status: Active Update: 01-03-2013 https://echa.europa.eu/registration-dossier/-/registered-dossier/8140

Phenyl isocyanate: HSNO Approval: HSR004628 Approved with controls

The New Jersey Worker and Community Right to Know Act requires public and private employers to provide information about hazardous substances at their workplaces. (N.J.S.A. 34:5A-1 et. seq.)

Section 8(a) of TSCA requires manufacturers of this chemical substance to report preliminary assessment information concerned with production, exposure, and use to EPA as cited in the preamble in 51 FR 41329. Effective date: 10/29/90; Reporting date: 12/27/90.

Pursuant to section 8(d) of TSCA, EPA promulgated a model Health and Safety Data Reporting Rule. The section 8(d) model rule requires manufacturers, importers, and processors of listed chemical substances and mixtures to submit to EPA copies and lists of unpublished health and safety studies. Benzene, isocyanato- is included on this list. Effective date: 10/29/90; Sunset date: 6/30/98.