Toluene Diisocyanate

Handling Guide

Introduction
Toluene diisocyanate (TDI) is produced at the Perstorp TDI SCA ISO 9002-certified plant in Pont de Claix, France. This plant is operated by Perstorp.

Table of Contents

Properties........................................................................ 4-5 Guidelines for Loading/Unloading Transportation/Storage of TDI (Bulk).............................6 Management of Empty TDI Drums .................................7 Thawing TDI ......................................................................8 TDI Safety and Handling ............................................ 9-10 Emergency Actions ..........................................................11 First Aid ..........................................................................11 Handling Spills and Leaks ..............................................11 Technical Service............................................................11 Emergency number .........................................................12

Properties

Perstorps toluene diisocyanate is referred to as TDI-80; it is an 80:20 mixture of the 2,4- and 2,6-isomers of TDI. Structural formulas of these isomers are shown below in Figure 1.
Figure 1: Structural Formulas of TDI Isomers

T80 is mainly used in the foam industry. The Pont de Claix plant produces TDI with different 2.4/2.6 isomers ratio, such as T65, TX and T100 grades.

TDI has a sharp, pungent and sweetish odor. Its vapors are toxic. Certain precautions are necessary when handling or using toluene diisocyanate. Before using TDI, obtain and study Perstorp's Material Water: On contact with water, Safety Data Sheet aromatic poly-substituted ureas are (MSDS). formed, and carbon dioxide and heat will develop. In time, white Reactivity aromatic polyurea crystals will precipitate. Perstorp TDI is a clear liquid, waterwhite to light yellow in color. It Heat: High temperatures can cause yellows on exposure to light. formation of dimer and discoloration of the TDI. This phenomenon is time temperaturerelated (see Figure 2).

Chemical: TDI reacts readily with compounds containing active hydrogens, such as acids and alcohols. Contact with bases, such as caustic soda or tertiary amines, might cause uncontrollable polymerization and rapid evolution of heat.

Figure 2: TDI Dimer Formulation Over time

at Various Temperatures

Physical Properties & Sales Specifications of TDI80 Produced at the Pont de Claix Plant

Typical Properties Molecular Weight Density (g. per cm3) @15.5C (60F) @20C (68F) @38C (100F) @60C (140F) Viscosity (cs) @50C (122F) @100C (212F) @135C (275F) Freezing/Melting Point Range T80 (C) T65 (C) TX (C) T100 (C) Freezing Point 2,4-isomer (C) 2,6-isomer (C) Boiling Point @10mm Hg (C) @760mm Hg (C) Flash Point, COC (C) Fire Point, COC (C) Latent Heat of Evaporation (Kcal/Kg) @120C @180C Vapor Air Density, air = 1 Vapor Pressure, approx. (mm Hg) @20C (68F) @120C (248F) @130C (266F) 174.163 1.22 1.21 1.20 1.18 1.5 0.8 0.5 13.5-14.5 6.0-8.0 20-21 21.5-22.0 15.0 7.2 121 250 132 142 72.8 67.2 6 0.01 11 16

When the level of dimer approaches 1% by weight, solid dimer forms as needle-like crystals. These crystals cannot be completely filtered out because the solution is supersaturated, and new crystals are formed to replace those that are removed. Temperatures below 15C (59F) cause TDI to freeze. Frozen TDI is also white and crystalline. If frozen, TDI may be thawed by heating (see Thawing TDI, page 8, for methods and proper precautions).
Sales Specifications Assay, min (%) Isomer Ration (%) 2,4-isomer 2,6-isomer Acidity, as HCI (%) Hydrolyzable Chlorides (%) Chlorine, max (%) Color (APHA) Sales Specifications Assay, min (%) Isomer Ration (%) 2,4-isomer 2,6-isomer Acidity, as HCI (%) Hydrolyzable Chlorides (%) Chlorine, max (%) Color (APHA) T80 >99.5 80+1 20+1 <0.004 0.007 <0.07 <40 TX >99.5 >95 <5 <0.0015 <0.01 <0.10 <40 T65 >99.5 68+1 32+1 0.005 0.010 <0.1 <40 T100 >99.5 <99.0 <1.0 <0.0130 <0.0150 <0.07 <30

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Guidelines for Safe Loading/Unloading Transportation /Storage of TDI (Bulk)

All following information related to loading/ unloading and transportation/storage of bulk TDI can be found on the ISOPA web site: www.isopa.org/htdocs/isopa_site/documents_ns/gui delines-English.pdf This information includes: Personal safety equipment Design and construction of bulk transport units Safety auditing of road haulers and tank operators Product training for drivers Loading operations Transport by road Transport by rail Transport by sea or inland water ISOPAs Mutual Aid Scheme for providing assistance at transport/unloading emergencies

Additional TDI technical information is available upon request from Perstorp: Bulk loading facilities specifications Bulk storage specifications Bulk unloading facilities with dry air specifications Bulk unloading facilities with pump specifications Hose specifications Isotank specification Loading arm specifications Piping specifications Pump specifications RTC specifications Sample bottle specifications Sampling facilities specifications Vessel specifications.

Please see contact information at the end of this document.

Guidelines for the Responsible Management of empty TDI Drums

The following information related to TDI drum activity can be found on the ISOPA web site: www.isopa.org/htdocs/isopa_site/documents_ns/em pty_drums.pdf This information includes the following: Regulations Emptying of drums Decontamination Preparation of shipment Selection of qualified reconditioners and recyclers Additional TDI technical information is available upon request from Perstorp: Drum storage facility specifications Drum facility specifications

Thawing TDI
Thawing TDI in Tank Cars TDI is shipped in insulated tank cars. During the winter, it is loaded at temperatures between 30C and 35C. Despite these precautions, there may be substantial heat loss before the car reaches its final destination. Therefore, during the winter, all incoming tank cars of TDI should be checked for freezing. The 2,4-isomer of TDI-80 freezes at 15C (59F); the 2,6-isomer at 7.2C (45F). Between these two temperatures, only the 2,4-isomer freezes. If this happens, isomer stratification takes place. N0TE: After thawing TDI, the layers remain separated. If they are not mixed, processing problems can be expected. However, if proper care is taken in thawing and remixing TDI, the quality can be maintained and no processing problems should occur. How to Determine Whether TDI Is Frozen Determine whether TDI is frozen is done by taking its temperature while wearing proper protective equipment. Do not open the manway to inspect it visually. Temperature measurement is accurate and will detect frozen TDI, even when it is not visible. When to Heat a TDI Tank Car If the TDI temperature is less than 18C, the car should be heated before it is unloaded. N0TE: If the car is not to be heated immediately, it should be re-pressurized to 35 to 70 Kpa with nitrogen to prevent crystals from forming as the result of contamination of the TDI with water. It should be depressurized before heating and unloading.

How to Heat a TDI Tank Car The TDI should be heated to 35C - 40C until all the frozen TDI has thawed. Never allow the TDI temperature to exceed 40C. If TDI is overheated, dimerization may take place. (See discussion under Heat on page 4 and graph showing conditions for dimer formation, Figure 3, page 4.) If dimer forms, the TDI should not be used. Call Perstorp for technical assistance. Heat Sources: The best way to thaw frozen TDI is with tempered hot water, thermostatically controlled to 40C. Hot water is less likely to cause dimerization than steam. If tempered hot water is not available, an alternate source of heat is 1.5 bar steam, mixed with cold water. A steam/water mixing system can be used to obtain the desired temperature. Plants that have only steam available should avoid pressures above 1.5 bar. High-pressure steam, if not watched very carefully, will rapidly overheat the TDI. Even at lower temperatures, careful monitoring must take place. After TDI Is Thawed After the TDI has been heated to 35C - 40C, it must be completely mixed to eliminate isomer separation. Unload the entire contents into a bulk storage tank and circulate for two to three hours before use.

TDI Safety and Handling

The following contains selected health and safety information as of April, 2006. For complete, up-todate information, obtain and read the current Material Safety Data Sheet (MSDS) available on www.perstorp.com. Toluene diisocyanate is a toxic and highly reactive compound. It should be kept in closed, isolated systems and transferred with care. The sections below briefly discuss some possible hazards and describe what to do in an emergency. Plant personnel should be thoroughly familiar with these procedures. Reactivity Hazards TDI is a stable compound with a relatively high flash point. However, it will react with water, acids, bases and other organic and inorganic compounds. TDI is also affected by heat and, like any organic compound, will burn. Water: When TDI comes in contact with water, aromatic polyurea is formed; heat is generated, and carbon dioxide is evolved. Pressure build-up from the carbon dioxide will occur. This pressure could rupture a storage vessel. To help prevent reactions with water, TDI should be kept under a nitrogen pad. Closed containers with unreacted TDI and water should never be sealed. Leaving the bung open or drum lid slightly ajar will prevent over pressurization. Chemical: Contact between TDI and acids should be avoided. Contact with bases, such as caustic soda and primary and secondary amines, might produce a violent reaction. The heat given off causes pressure build-up, and the storage vessel may rupture. Contact with tertiary amines commonly used as urethane catalysts may cause uncontrollable polymerization, with a similar result. High temperatures may also cause dimerization. TDI should be kept away from certain rubber and plastics. These materials will rapidly become embrittled; cracks may develop and their strength may be weakened.
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Fire Hazards TDI has a flash point of 132C* and therefore does not constitute a severe fire hazard as a combustible, not flammable material. However, it should be remembered that TDI is an organic material and will burn when exposed to fire. In a fire situation, TDI may decompose to release toxic gases. TDI is highly toxic through inhalation and, if inhaled in significant quantities, can produce serious respiratory health effects, including asthma. Although technically listed as a low-ranking carcinogen, inhalation studies (most appropriate for assessing risk) have shown no increased incidence of tumors. TDI has a characteristically pungent odor; however, it is considered to have poor warning properties. If you can smell it, the concentration of TDI would be in excess of the occupational exposure limit of 0.005 ppm (0.035 mg/m3) as an eight-hour time-weighted average. Inhalation: Repeated overexposure and/or a high one-time accidental exposure to TDI may cause allergic lung sensitization or asthma. Symptoms may include wheezing, choking, tightness in the chest and shortness of breath. Any individual exposed to TDI above the occupational exposure limit may develop these symptoms; however, for sensitized persons, these symptoms may occur at or below the occupational exposure limit. Repeated overexposure to TDI may also produce a cumulative decrease in lung function, or the onset of asthma. Dermal and Oral Exposure: The liquid and vapor of TDI can cause moderate to severe irritation to the eyes, skin and mucous membranes. If not rinsed off immediately, burns to the eyes and skin may occur with the possibility of producing visual impairment. While the oral toxicity of TDI is low, ingestion of TDI can result in severe irritation to the gastrointestinal tract and produce nausea and vomiting.
*the value of 132.4 degrees C was determined using the Pensky-Martens closed cup method.

TDI Safety and Handling (continued)

Additional Information The web site www.diisocyanates.org lists studies sponsored in full or in part by the International Isocyanate Institute. This may be useful for more technical information. Personal Protective Equipment (PPE) Because of the health hazards associated with TDI, protective clothing and equipment (see Figure 3) must be worn whenever there is a possibility of contact. Such occasions include, but are not limited to: Opening tank car hatches, truck manway covers or drum plugs Connecting and disconnecting hoses and pipes Placing and operating pumps Operating and servicing pumps Breaking TDI piping, including piping previously decontaminated Flushing (cleaning) TDI drums Pouring foams, in operations where ventilation may not be adequate Where liquid TDI spills can occur, protective clothing should be worn. If any article of clothing becomes contaminated, it should be removed immediately and discarded promptly. Acceptable boots, gloves and chemical suits vary by material of construction, thickness and manufacturer. Consult the ISOPA web site at www.isopa.org for additional information. The odor warning of TDI is insufficient to be used as a method for detecting the presence of hazardous concentrations. Whenever there is a chance that airborne levels of TDI vapors could exceed the recommended Threshold Limit Value (0.005 ppm as an 8-hour time-weighted average or a 0.02 ppm as a ceiling value), an EN Standard approved respirator with a CE mark should be worn. The type of respiratory protection worn may depend upon the situation. Jobs that are routine and have been characterized by air monitoring to be of relatively low exposure potential may be accomplished using an air-purifying respirator. During a line pluggage, a potentially pressurized line break, spills, or other emergency situations when air concentrations are
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likely to be high, individuals must make use of a supplied air respirator with escape capability or a self-contained breathing apparatus (SCBA). When issuing respirators to employees, ensure that national regulations are followed specifically for selection, use, maintenance and training.

Hard Hat

Goggles

Full Face Cartridge Respirator or AirSupplied Respirator

Impermeable Chemical Suit or Apron

Gloves

Figure 3. Protective Clothing and Equipment

The equipment necessary to properly protect any individual who may come into contact with liquid TDI is shown in Figure 3. For more detailed information on PPE and links to the regulations associated with their usage, go to www.isofacts.org or ask for assistance from Perstorp Chemical Company.

Emergency Actions
The following section contains basic information on what to do in the event of an accident. Please refer to the Material Safety Data Sheet (MSDS) for more specific information. For more information related to emergency management system in Europe, please go to the ISOPA web site: www.isopa.org/htdocs/isopa_site/emergency.htm First Aid If there is known contact with toluene diisocyanate, take the following steps: Eye Contact: Flush the eyes with clean, lukewarm water, then periodically flush for 20 to 30 minutes. Seek prompt medical attention. Skin Contact: Immediately flush thoroughly with water for 15 minutes. Seek medical attention if ill effect or irritation develops. Inhalation: Immediately move victim to fresh air. Symptoms of exposure to TDI vapors include: tightness in the chest, watering eyes, dry throat, nausea, dizziness and headaches. The onset of symptoms may be delayed, so a doctor should monitor exposed personnel. Handling Spills and Leaks Wear a positive-pressure, supplied-air respirator. Recommended personal protective equipment includes: clothing, gloves and boots made of butyl rubber. Spill and Leak Clean-Up: 1. Stop the source of the spill. Stop the spread of the spill by surrounding it with a dry noncombustible absorbent. 2. Apply additional dry non-combustible absorbent to the spill. Add approximately 10 parts decontamination solution to every one part spilled TDI.
Suggested Formulation for Decontamination Solution:

% by Weight

Water Liquid soap solution n-propanol

75% 20% 5%

3. Sweep up material and place in proper DOT-

approved container. Use more decontamination solution to clean remaining surfaces and also place this residue in a container. 4. Loosely apply lid. Do not seal for 48 hours, since gas generation may occur during neutralization. Isolate the container in a well-ventilated place. 5. Discard all contaminated clothing. Decontaminate personnel and equipment using approved procedures. Decontamination of Empty Containers: 1. Spray or pour 5 to 20 L of decontamination solution (see above) into the container. Insure that the walls are triple rinsed. 2. Leave container standing unsealed for a minimum of 48 hours to allow for a complete neutralization of TDI. Disposal: 1 Care should be taken to prevent environmental contamination from the use of this material. 2. Dispose of the contaminated product, empty containers and materials used in cleaning up leaks, spills or containers in a manner approved for this material. 3. The user of this material is responsible for disposing of unused materials, residues and containers in compliance with all relevant federal, state and local laws and regulations regarding treatment, storage and disposal of hazardous and non-hazardous wastes. 4. Insure that drums are labeled with correct hazardous waste code. Technical Service Technical service is available to facilitate use of TDI. If you have questions, please contact Perstorp TDI France.

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Emergency Telephone Number

Perstorp TDI France SAS: + 33 4 76 69 56 56

Visit us at our Web site: www.perstorp.com

Perstorp TDI France SAS Rue Lavoisier, 38800 Le-Pont-de-Claix France

Telephone: +33-4-76 69 50 00 Fax; +33-4-76 98 73 09

__________________________________________________________________________________________________________________________ The information in this brochure is believed to be accurate as of the date of publication. It is the sole responsibility of the customer to determine whether the product is appropriate and suitable for the customer's specific use. Perstorp makes no warranties, express or implied regarding the product or any information contained herein. The applicable Material Safety Data Sheet (MSDS) should be reviewed by customer before handling the Perstorp product. Perstorp disclaims any liability for infringement of any patent by reason of customer's use of any Perstorp products in combination with other materials or in any process. The product that would result from use of these formulas has not been tested or otherwise substantiated for safety by Perstorp. The safety of any formulation incorporating a Perstorp product is the sole responsibility of the customer.