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
Perstorp’s 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
(MSDS).
Reactivity
Perstorp TDI is a clear liquid, water-
white to light yellow in color. It
yellows on exposure to light.
Figure 2: TDI Dimer Formulation Over time
at Various Temperatures
4
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.
aromatic poly-substituted ureas are
formed, and carbon dioxide and heat
will develop. In time, white
aromatic polyurea crystals will
precipitate.
Heat: High temperatures can cause
formation of dimer and
discoloration of the TDI. This
phenomenon is time temperature-
related (see Figure 2).
Physical Properties & Sales Specifications of TDI-
80 Produced at the Pont de Claix Plant
Typical Properties
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.

Molecular Weight 174.163 Temperatures below 15°C (59°F) cause TDI to freeze.
Density (g. per cm3) Frozen TDI is also white and crystalline. If frozen, TDI
@15.5°C (60°F) 1.22 may be thawed by heating (see Thawing TDI, page 8,
@20°C (68°F) 1.21 for methods and proper precautions).
@38°C (100°F) 1.20
@60°C (140°F) 1.18
Viscosity (cs) Sales Specifications T80 T65
@50°C (122°F) 1.5
Assay, min (%) >99.5 >99.5
@100°C (212°F) 0.8 Isomer Ration (%) 2,4-isomer 80+1 68+1
@135°C (275°F) 0.5 2,6-isomer 20+1 32+1
Freezing/Melting Point Range Acidity, as HCI (%) <0.004 0.005
T80 (°C) 13.5-14.5 Hydrolyzable Chlorides (%) 0.007 0.010
T65 (°C) 6.0-8.0 Chlorine, max (%) <0.07 <0.1
TX (°C) 20-21 Color (APHA) <40 <40
T100 (°C) 21.5-22.0
Sales Specifications TX T100
Freezing Point
2,4-isomer (°C) 15.0 Assay, min (%) >99.5 >99.5
2,6-isomer (°C) 7.2 Isomer Ration (%) 2,4-isomer >95 <99.0
Boiling Point 2,6-isomer <5 <1.0
@10mm Hg (°C) 121 Acidity, as HCI (%) <0.0015 <0.0130
@760mm Hg (°C) 250 Hydrolyzable Chlorides (%) <0.01 <0.0150
Chlorine, max (%) <0.10 <0.07
Flash Point, COC (°C) 132
Color (APHA) <40 <30
Fire Point, COC (°C) 142
Latent Heat of Evaporation (Kcal/Kg)
@120°C 72.8
@180°C 67.2
Vapor Air Density, air = 1 6
Vapor Pressure, approx. (mm Hg)
@20°C (68°F) 0.01
@120°C (248°F) 11 P
@130°C (266°F) 16 a
g
e

5
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
• ISOPA’s Mutual Aid Scheme for providing
assistance at transport/unloading
emergencies
6
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

7
Thawing TDI
Thawing TDI in Tank Cars
TDI is shipped in insulated tank cars. During the
winter, it is loaded at temperatures between 30°C
and 35°C. 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 15°C
(59°F); the 2,6-isomer at 7.2°C (45°F). 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 18°C, 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.
8
How to Heat a TDI Tank Car
The TDI should be heated to 35°C - 40°C until all
the frozen TDI has thawed. Never allow the TDI
temperature to exceed 40°C. 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 40°C. 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 35°C - 40°C, 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-to-
date 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.
9
Fire Hazards
TDI has a flash point of 132°C* 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 likely to be high, individuals must make use of a

The web site www.diisocyanates.org lists studies supplied air respirator with escape capability or a
sponsored in full or in part by the International self-contained breathing apparatus (SCBA). When
Isocyanate Institute. This may be useful for more issuing respirators to employees, ensure that national
technical information. regulations are followed specifically for selection,
use, maintenance and training.
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 Hard Hat
to:

• Opening tank car hatches, truck manway covers

or drum plugs
Goggles
• Connecting and disconnecting hoses and pipes
• Placing and operating pumps
• Operating and servicing pumps Impermeable Chemical
• Breaking TDI piping, including piping Full Face Cartridge Suit or Apron
Respirator or Air-
previously decontaminated Supplied Respirator
• Flushing (cleaning) TDI drums
• Pouring foams, in operations where ventilation
may not be adequate

Where liquid TDI spills can occur, protective

Gloves
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 Figure 3. Protective Clothing and Equipment
the ISOPA web site at www.isopa.org for additional
information.
The equipment necessary to properly protect any
individual who may come into contact with liquid
The odor warning of TDI is insufficient to be used as
TDI is shown in Figure 3.
a method for detecting the presence of hazardous
concentrations. Whenever there is a chance that
For more detailed information on PPE and links to
airborne levels of TDI vapors could exceed the
the regulations associated with their usage, go to
recommended Threshold Limit Value (0.005 ppm as
www.isofacts.org or ask for assistance from Perstorp
an 8-hour time-weighted average or a 0.02 ppm as a
Chemical Company.
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
10
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.
11
Suggested Formulation for
Decontamination Solution:
% by Weight
Water 75%
Liquid soap solution 20%
n-propanol 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.
 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.