handling_guide_tdi

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Toluene

DiisocyanateHandling Guide


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Introduction

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


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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


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4

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 theseisomers are shown below in Figure

1.

Figure 1: Structural Formulasof TDI Isomers

F

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 andT100 grades.

TDI has a sharp, pungent and

sweetish odor. Its vapors are toxic.

Certain precautions are necessary

when handling or using toluenediisocyanate. Before using TDI,

obtain and study Perstorp'sMaterial

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

Chemical: TDI reacts readily with

compounds containing activehydrogens, such as acids and

alcohols. Contact with bases, such

as caustic soda or tertiary amines,

might cause uncontrollable

polymerization and rapid evolution

of heat.

Water: On contact with water,

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 causeformation of dimer and

discoloration of the TDI. This

phenomenon is time temperature-related (see Figure 2).


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5

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).

P

a

g

e

5

Physical Properties & Sales Specifications of TDI-

80 Produced at the Pont de Claix Plant

Typical Properties

Molecular Weight 174.163

Density (g. per cm3)

@15.5C (60F) 1.22

@20C (68F) 1.21

@38C (100

F) 1.20

@60C (140F) 1.18

Viscosity (cs)

@50C (122F) 1.5

@100C (212F) 0.8

@135C (275F) 0.5

Freezing/Melting Point Range

T80 (C) 13.5-14.5

T65 (C) 6.0-8.0

TX (C) 20-21

T100 (C) 21.5-22.0

Freezing Point

2,4-isomer (C) 15.0

2,6-isomer (C) 7.2

Boiling Point

@10mm Hg (C) 121

@760mm Hg (C) 250

Flash Point, COC (C) 132

Fire Point, COC (C) 142

Latent Heat of Evaporation (Kcal/Kg)

@120C 72.8

@180C 67.2

Vapor Air Density, air = 1 6

Vapor Pressure, approx. (mm Hg)@20C (68F) 0.01

@120C (248F) 11

@130C (266F) 16

Sales Specifications T80 T65

Assay, min (%) >99.5 >99.5

Isomer Ration (%) 2,4-isomer 80+1 68+1

2,6-isomer 20+1 32+1

Acidity, as HCI (%)


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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 tankoperators

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 pumpspecifications

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 thisdocument.


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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


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Thawing TDI

Thawing TDI in Tank CarsTDI 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 FrozenDetermine 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 andwill 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 fortechnical 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 causedimerization 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 theTDI. 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 bulkstorage tank and circulate for two to three hours

before use.


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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 possiblehazards and describe what to do in an emergency.

Plant personnel should be thoroughly familiar with

these procedures.

Reactivity HazardsTDI 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 sodaand 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 uncontrollablepolymerization, 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.

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 highone-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 sensitizedpersons, 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 ofTDI 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 ofTDI 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.


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TDI Safety and Handling (continued)

Additional Information The web site www.diisocyanates.orglists studies

sponsored in full or in part by the InternationalIsocyanate 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 coversor drum plugs

Connecting and disconnecting hoses and pipesPlacing and operating pumpsOperating and servicing pumpsBreaking TDI piping, including piping

previously decontaminated

Flushing (cleaning) TDI drumsPouring 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. Acceptableboots, 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 hazardousconcentrations. 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 otheremergency situations when air concentrations are

likely to be high, individuals must make use of a

supplied air respirator with escape capability or a

self-contained breathing apparatus (SCBA). Whenissuing respirators to employees, ensure that national

regulations are followed specifically for selection,

use, maintenance and training.

Hard Hat

Goggles

Full Face CartridgeRespirator or Air-Supplied Respirator

Impermeable ChemicalSuit 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 towww.isofacts.org or ask for assistance from Perstorp

Chemical Company.


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Emergency Actions

The following section contains basic information on

what to do in the event of an accident. Please refer

to theMaterial 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 withwater 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 shouldmonitor exposed personnel.

Handling Spills and LeaksWear 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 thespill by surrounding it with a dry noncombustible

absorbent.

2. Apply additional dry non-combustible absorbentto the spill. Add approximately 10 partsdecontamination solution to every one part

spilled TDI.

Suggested Formulation forDecontamination 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 decontaminationsolution 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 decontaminationsolution (see above) into the container. Insure that

the walls are triple rinsed.

2.Leave container standing unsealed for a minimumof 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 ServiceTechnical 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 anyinformation 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.

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