Material Safety Data Sheet #4979 EMERGENCY CONTACTS:    •     Spills, Leaks, Fire or Exposure Call Chemtrec: (800) 424-9300    •     Medical Emergency Information: (800) 228-5635 Ext. 181 SECTION 1: CHEMICAL PRODUCT AND COMPANY IDENTIFICATION Product Name: PERMAX® 700-A Product Use: Component of a polyurethane RESIN TECHNOLOGY COMPANY    •     2270 Castle Harbor Place, Ontario, CA 91761    •     Phone: (800) 729-0795    •     Fax: (909) 923-9617    •     Date prepared or revised: 11/10/00 SECTION 2: COMPOSITION/INFORMATION ON INGREDIENTS HAZARDOUS INGREDIENT(S) %(w/w) ACGIH TLV CAS NO. 4,4'-Diphenylmethane Diisocyanate      •    (4,4' MDI) 30-60 0.005 ppm 101-68-8      •    Modified 4,4'-MDI 30-60 Not Listed Not Disclosed This material is classified as hazardous under OSHA Hazard Communication Standard (29 CFR 1910.1200) SECTION 3: HAZARDS IDENTIFICATION EMERGENCY OVERVIEW Health Hazards: Irritating to eyes, respiratory system and skin. Inhalation at levels above the occupational exposure limit could cause respiratory sensitization and risk of serious damage to respiratory system. The onset of the respiratory symptoms may be delayed for several hours after exposure. A hyper-reactive response to even minimal concentrations of MDI may develop in sensitized persons. Sensitized persons should not be exposed to any mixture containing unreacted MDI. HMIS: Health: 2, Flammability: 1, Reactivity: 1 Physical Hazards: Reacts slowly with water to produce carbon dioxide which may rupture closed containers. This reaction accelerates at higher temperatures. Appearance: Liquid. Odor: Slightly musty. Read the entire MSDS for a more thorough assessment of the hazard information on this product. SECTION 4 : FIRST AID MEASURES General: In case of accident or if you feel unwell, seek medical advice IMMEDIATELY (show the label where possible). Inhalation: Remove patient from exposure, keep warm and at rest. Obtain medical attention. Treatment is symptomatic for primary irritation or difficulty in breathing. If breathing is labored, oxygen should be administered by qualified personnel. Apply artificial respiration if breathing has ceased or shows signs of failing. Skin Contact: Remove contaminated clothing. Immediately wash affected areas thoroughly with soap and water. Some organic materials such as corn oil or propylene glycol are effective in decontaminating MDI from the skin when applied immediately. If irritation, redness, or a burning sensation develops and persists, obtain medical advice. Contaminated clothing should be thoroughly cleaned before reuse. Eye Contact: Immediately flush eyes with running water for a minimum of 15 minutes. Hold eyelids open during flushing. If irritation persists, repeat flushing. Obtain medical attention IMMEDIATELY. Ingestion: Do NOT induce vomiting. Provided that the patient is conscious, wash out mouth with water then give 1 or 2 glasses of water to drink. Refer person to medical personnel for immediate attention. Note to Physicians: Symptomatic and supportive therapy as needed. Following severe exposure medical follow-up should be monitored for at least 48 hours. SECTION 5: FIRE-FIGHTING MEASURES Fire and Explosion Hazards: Containers may burst under intense heat. Due to reaction with water, a hazardous build-up of pressure could result if contaminated containers are re-sealed. Extinguishing media: Water, carbon dioxide, dry chemical, or appropriate foam. If water is used, very large quantities are required. Reaction between water and hot isocyanate may be vigorous. Contain run-off water with temporary barriers. Fire Fighting Procedures: As appropriate for surrounding materials/equipment. Fire Fighting Protective Equipment: Use self-contained breathing apparatus and full protective clothing (Bunker gear). Flash point: >230 °F (110°C) Flammable Limits (Lower): Not available Flammable Limits (Upper): Not available Auto Ignition Temperature: 240 °C(464 °F) (4,4'-Diphenylmethane Diisocyanate) Decomposition Temperature: Not available. Rate of Burning: Not available. Explosive Power: None. Sensitivity to Mechanical Impact: None. Sensitivity to Static Discharge: None Combustion Products: Carbon monoxide, carbon dioxide, nitrogen oxides and some HCN. SECTION 6: ACCIDENTAL RELEASE MEASURES      •    For major spills call Chemtrec (800-424-9300) Spills, Leaks, or Releases: Clean-up should only be performed by trained personnel. People dealing with major spillages should wear full protective clothing including appropriate respiratory protection. Evacuate the area. Prevent further leakage, spillage or entry into drains. Contain and absorb large spillages onto an inert, non-flammable absorbent carrier (such as earth or sand). Shovel into open-top drums or plastic bags for further decontamination, if necessary. Wash the spillage area clean with liquid decontaminant. Test atmosphere for MDI. Neutralize small spillages with decontaminant. Remove and properly dispose of residues. (See Section 13) for disposal considerations). Notify applicable government authorities if release is reportable. The CERCLA RQ for MDI is 5,000 lbs (see CERCLA in Section 15). Preparation of Decontamination Solution: Prepare a decontamination solution of 0.2-0.5% liquid detergent and 3-8% concentrated ammonium hydroxide in water (5-10% sodium carbonate may be substituted for the ammonium hydroxide). Follow the precautions on the supplier's material safety data sheets when preparing and using solution. Use of Decontamination Solution: Allow deactivated material to stand for at least 30 minutes before shoveling into drums. Do not tighten the bungs. Mixing with wet earth is also effective, but slower. SECTION 7: HANDLING AND STORAGE Handling: Avoid personal contact with the product or reaction mixture. Use only with adequate ventilation to ensure that the occupational exposure limit is not exceeded. The efficiency of the ventilation system must be monitored regularly because of the possibility of blockage. Avoid breathing aerosols, mists and vapors. (See Section 8-Exposure Control for details). Storage Requirements: Keep containers properly sealed and when stored indoors, in a well ventilated area. Keep contents away from moisture. Due to reaction with water, producing CO2-gas, a hazardous build-up of pressure could result if contaminated containers are re-sealed. Do not reseal contaminated containers. Uncontaminated containers, free of moisture, may be resealed only after placing under a nitrogen blanket. Do not store in containers made of copper, copper alloys or galvanized surfaces. Storage Temperature: Ideal storage temperature is 16-38 °C (60-100 °F). Keep stocks of decontaminant (See Section 6) readily available. SECTION 8: EXPOSURE CONTROLS/PERSONAL PROTECTION PREVENTIVE MEASURES: Conditions of use, adequacy of engineering or other control measures, and actual exposures will dictate the need for specific protective devices at your workplace. Engineering Controls: Use local exhaust ventilation to maintain airborne concentrations below the TLV. Suitable respiratory equipment should be used in cases of insufficient ventilation or where operational procedures demand it. For guidance on engineering control measures refer to publications such as the ACGIH current edition of "Industrial Ventilation, a Manual of Recommended Practice." Personal Protective Equipment: Eye Protection: Chemical safety goggles. If there is a potential for splashing, use a full face shield. Skin Protection: The following protective materials are recommended: Gloves-neoprene, nitrile rubber, butyl rubber. Thin latex disposable gloves should be avoided for repeated or long term use. Protective clothing should be selected and used in accordance with "Guidelines for the Selection of Chemical Protective Clothing" published by ACGIH. Respiratory Protection: When the product is sprayed or heated without adequate ventilation, an approved NIOSH/MSHA positive pressure, supplied-air respirator may be required. Air purifying respirators equipped with organic vapor cartridges and a HEPA (P100) particulate filter may be used under certain conditions when a cartridge change-out schedule has been developed in accordance with the OSHA respiratory protection standard (29 C.F.R. 1910.134). EXPOSURE GUIDELINES: Medical supervision of all employees who handle or come in contact with respiratory sensitizers is recommended. Persons with respiratory problems including asthmatic-type conditions, chronic bronchitis, other chronic respiratory diseases or recurrent skin eczema or skin allergies should be evaluated for their suitability of working with this product. Once a person is diagnosed as sensitized, no further exposure to the material that caused the sensitization should be permitted. HAZARDOUS INGREDIENT(S): 4,4'-Diphenylmethane Diisocyanate:      •    ACGIH TLV 0.05 mg/M3 (8-hour, 40 hours/week)      •    OSHA PEL CEILING 0.20 mg/M3      •    NIOSH REL/TWA 0.05 mg/M3 (10-hour, 40 hours/week)      •    NIOSH REL/CEILING 0.20 mg/M3 (10-minute) NOTE: The Occupational Exposure Limits listed for isocyanates do not apply to previously sensitized individuals. SECTION 9: PHYSICAL AND CHEMICAL PROPERTIES Chemical Name: Not applicable (mixture). Chemical Family: Diisocyanate Molecular Formula: Not applicable (mixture). Appearance: Liquid. Odor: Slightly musty. Odor Threshold: 4.0 mg/M3 (4,4'-Diphenylmethane Diisocyanate)~400 ppb pH: Not applicable. Flash Point: >230°F(110°C) Vapor Pressure (mm Hg at 20°C): Approx. 4 x 10-6 Vapor Density (Air=1): 8.5 approx. Boiling Point: Not applicable Melting Point: Not available Solubility (Water): (Reacts with water) Solubility (Other): Soluble in most organic solvents. Specific Gravity: 1.12 approx. (at 25°C) Evaporation Rate: Not available. SECTION 10: STABILITY AND REACTIVITY Hazardous Decomposition Products: Highly unlikely under normal industrial use. See Section 5. Chemical Stability: Stable at room temperature. Conditions to Avoid: Avoid high temperatures. Avoid freezing. Incompatibility with other Substances: This product will react with any materials containing active hydrogens such as water, alcohol, amines, bases and acids. The reaction with water is very slow under 50°C (122°F) but is accelerated at higher temperatures. Hazardous Polymerization: Polymerization may occur at elevated temperatures in the presence of alkalies, tertiary amines and metal compounds. SECTION 11: TOXICOLOGICAL INFORMATION Polymeric MDI:    •     Oral LD50 (rat) > 5,000 mg/kg    •     Dermal LD50 (rabbit) >5,000 mg/kg MUTAGENICITY (EFFECTS ON GENETIC MATERIAL): Mutagenicity data on MDI are inconclusive. MDI was weakly positive in some in-vitro (test tube) studies; other in-vitro studies were negative. A mutagenicity study in animals was negative. POTENTIAL HEALTH EFFECTS: Inhalation: This product is a respiratory irritant and potential respiratory sensitizer. Inhalation of vapor or aerosol at levels above the occupational exposure limit could cause respiratory sensitization and lung injury. Symptoms may include irritation to the eyes, nose, throat and lungs, possibly combined with dryness of the throat, tightness of chest and difficulty in breathing and/or flu-like symptoms. The onset of the respiratory symptoms may be delayed for several hours after exposure. A hyper-reactive response to even minimal concentrations of MDI may develop in sensitized persons. In a single evaluation of 5 men occupationally exposed to MDI and hydrocarbon solvent vapors under conditions where adequate ventilation or other safety precautions were not used, neuropsychologic findings were attributed to MDI. Skin Contact: Moderate irritant. Repeated and/or prolonged contact may cause skin sensitization. There is limited evidence from animal studies that skin contact may play a role in respiratory sensitization. These results emphasize the need for protective clothing including gloves to be worn at all times when handling these chemicals or in maintenance work. Eye Contact: The aerosol, vapor or liquid will irritate human eyes following contact. Ingestion: Ingestion may cause irritation of the gastrointestinal tract. Based on the acute oral LD50, this product is considered practically non-toxic by ingestion. Chronic Effects: A study was conducted where groups of rats were exposed for 6 hours/day, 5 days/week for a lifetime to atmospheres of respirable polymeric MDI aerosol either at concentrations of 0, 0.2, 1 or 6 mg/M3. No adverse effects were observed at 0.2, mg/M3. At the 1 mg/M3 concentration, minimal nasal and lung irritant effects were seen. Only at the top concentration (6.0 mg/M3) was there an increased incidence of a benign tumor of the lung (adenoma). One malignant pulmonary tumor (adenocarcinoma) was seen in the 6.0 mg/M3 group. MDI administration to rats in this study did not change the distribution and incidence of tumors from those seen in control animals. The increased incidence of lung tumors is associated with prolonged respiratory irritation and the concurrent accumulation of yellow material in the lung. In the absence of prolonged exposure to high concentrations leading to chronic irritation and lung damage, it is highly unlikely that tumor formation will occur. There are reports that excessive chronic exposure to diisocyanates may result in permanent decrease in lung function. Carcinogenicity: The ingredients of this product are not classified as carcinogenic by ACGIH or IARC, not regulated as carcinogens by OSHA, and not listed as carcinogens by NTP. Multigenicity: There is no substantial evidence of mutagenic potential. Reproductive Effects: No adverse reproductive effects are anticipated. Teratogenicity and Fetoxicity: No birth defects were seen in two independent animal (rat) studies. Fetoxicity was observed at doses that were extremely toxic (including lethal) to the mother. Fetoxicity was not observed at doses that were not maternally toxic. The doses used in these studies were maximal, respirable concentrations well in excess of the defined occupational limits. SECTION 12: ECOLOGICAL INFORMATION Environmental Fate and Distribution: It is unlikely that significant environmental exposure in the air or water will arise, based on consideration of the production and use of the substance. Persistence and Degradation: Immiscible with water, but will react with water to produce inert and non-biodegradable solids. Toxicity: Polymeric MDI.    •     LC50 (Zebra Fish) >1000 mg/l(At the highest level tested of 1000 mg/l there were no deaths).    •     EC50 (Daphnia magna)(24 hour) >1000 mg/l    •     EC50 (E.Coli) >100 mg/l SECTION 13: DISPOSAL CONSIDERATIONS The generation of waste should be avoided or minimized wherever possible. Disposal should be in accordance with local, state, provincial or national regulations. This material is not a hazardous waste under RCRA 40 CFR 261. Small quantities should be treated with a decontaminant solution (See Section 6). The treated waste is not a hazardous material under RCRA 40 CFR 261. Chemical waste, even small quantities, should never be poured down drains, sewers or waterways. Empty containers should be decontaminated and either passed to an approved drum recycler or destroyed. SECTION 14: TRANSPORTATION INFORMATION DOT: Single containers less that 5,000 lbs. are not regulated. Single containers with 5,000 lbs. or more of 4,4'-MDI are regulated as: Other Regulated Substances, Liquid, N.O.S. (Methylene Diphenyl Diisocyanate), 9, NA3082, PGIII, RQ. Transportation Emergency Telephone Number: 1-800-424-9300 (Chemtrec) TDG: Not Regulated. IMO: Not Regulated. IATA/ICAO Class: Not regulated. SECTION 15: REGULATORY INFORMATION USA CLASSIFICATION: OSHA Classification: This product is classified as a hazardous material under the criteria outlined in the OSHA Hazard Communication Standard (HCS)(29 CFR 1910.1200). TSCA (Toxic Substances Control Act) Regulations: All ingredients are on the TSCA Chemical Substance Inventory. EPCRA Section 313 (40 CFR 372): This product contains the following chemical(s) subject to reporting requirements: ~36% 4,4-MDI. CERCLA (Comprehensive Environmental Response, Compensation and Liability Act): 4,4-Methylene diphenyl diisocyanate (CAS 101-68-8) has a 5,000 lb. RQ (reportable quantity). Any spill or release above the RQ must be reported to the National Response Center (800-424-8802). The % of 4,4-MDI in this product is listed in Section 2 of this MSDS. This product does not contain nor is it manufactured with ozone depleting substances. Other Regulations/Legislation which apply to this product: Massachusetts Right-to-Know, Pennsylvania Right-to-Know, New Jersey Right-to-Know, CERCLA. California Prop 65: This product does not contain any substance(s) which are defined by the State of California to cause cancer, birth defects, or other reproductive effects. CANADIAN CLASSIFICATION: This product has been classified in accordance with the hazard criteria of the CPR (Controlled Products Regulations) and this MSDS (Material Safety Data Sheet) contains all the information required by the CPR. Controlled Products Regulations (WHMIS) Classification: D-1A; D-2A and D-2B. CEPA/Canadian Domestic Substances List (DSL): The substance(s) in this product is/are on the Canadian Domestic Substances List (CEPA DSL). SECTION 16: OTHER INFORMATION Glossary:    •     ACGIH - American Conference of Governmental Industrial Hygienists    •     IARC - International Agency for Research on Cancer    •     NTP - National Toxicology Program    •     OSHA - Occupational Safety and Health Administration For Your Protection: The information and recommendations in this publication are, to the best of our knowledge, reliable. The toxicity and risk characteristics of products made by Resin Technology Company will necessarily differ from the toxicity and risk characteristics that occur when such products are used with other materials during a manufacturing process. The resulting risk characteristics should be determined and made known to ultimate end-users and processors. Resin Technology Company MAKES NOW WARRANTIES OF ANY KIND, EXPRESS OR IMPLIED, INCLUDING THOSE OF MERCHANTABILITY AND FITNESS FOR A PARTICULAR PURPOSE. Prepared By: Polyurethanes Applied Toxicology/Regulatory Services (856) 423-8484


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