ISOPA PRODUCT STEWARDSHIP PROGRAMMES
“One Step Ahead – 2nd Generation”
TDI Users
1
Version 01/2014
2
One Step Ahead - TDI Users
Content
 Essential data
 Good practice
 When things go wrong . . .
 Informing session
3
Appearance of TDI
Liquid
TDI
Clear to pale yellow
Sharp, pungent
Reacted
White
Foamy
4
TDI Label Information
 Very toxic by inhalation
 Irritating to eyes, respiratory system and skin
 May cause sensitisation by inhalation and
skin contact
 Limited evidence of a carcinogenic effect
 Harmful to aquatic organisms , may cause
long-term adverse effects in the aquatic
environment
5
TDI Physical Properties

TDI has a significant vapour pressure giving a high concentration in air
above the liquid
Temp.
in °C
TDI
in mg/m3
20
98
40
548
60
2390
80
8509
100
25597
J. Chem. Eng. Data, 1975, 20, 1, 13-15.
(Data for 2,4-TDI isomer)

The exposure limit of 0.035 mg/m3 is below the odor limit
WHEN YOU SMELL TDI YOU ARE ABOVE THE EXPOSURE LIMIT
6
TDI Physical Properties

TDI has a significant vapour pressure giving a high concentration in air
above the liquid
Always
protect yourself
from breathing
TDI!

Temp.
in °C
TDI
in mg/m3
20
98
40
548
60
2390
80
8509
100
25597
J. Chem. Eng. Data, 1975, 20, 1, 13-15.
(Data for 2,4-TDI isomer)
The exposure limit of 0.035 mg/m3 is below the odor limit
WHEN YOU SMELL TDI YOU ARE ABOVE THE EXPOSURE LIMIT
7
TDI Chemical Properties
TDI will react with many compounds – especially
water, polyol, amines, ammonium hydroxide, alkalines
Higher temperatures mean faster reactions
(beware temperatures > 40 °C)
In your region these temperatures and higher are normal present on
a day to day basis!
During reaction heat & gases (CO2) will be formed
 Risk of burns/dangerous pressures
Where do you find these conditions ?
8
Where do you find these conditions?
 Drums proper cleaning with decontaminant
 Polyol / diisocyanate stored together
 Spillage into a drain
 Opening drums
 Off-loading of wrong chemical into a bulk storage tank
 TDI in face /eyes or mouth (soft tissue )
 TDI in wet disposal (waste) drums
 In the foam curing, crushing and
storage unit
9
Effect of TDI on your health
Short term / one-off exposure above safe level
-
Irritates mouth, throat, lungs
Tight chest, coughing
Difficulty in breathing
Eyes watering
Itching, red skin (immediately or delayed)
May be hot or burn
Symptoms can occur up to 24hrs
after exposure
Seek medical assistance
Immediately with MSDS !
10
Effect of TDI on your health
Long term/repeated over-exposure from breathing or skin
contact leads to risk of sensitisation
Symptoms such as occasional breathing difficulties similar
to asthma, hay fever, sneezing
When sensitised, potentially severe asthma in the case of
even low TDI exposure
Sensitisation will prevent working with diisocyanates for life
Sensitisation is non-reversible and is a reaction of the
immune system. Not to be confused with irritation
11
Typical examples of unsafe behaviour
12
Typical examples of safe behaviour
Emptying a
pump using
a pump
Getting qualified
medical
attention
Cleaning up
a spill
Don’t forget to wear PPE each and every time !
13
Safe handling of TDI
 Is the workplace clean and do you have good personal
hygiene?
 Does anyone eat, drink or smoke in the workplace?
 Is there good workplace ventilation?
 Is there continuous use of the correct PPE –
including during plant maintenance?
 Do you have emergency equipment?
Do you know where to find emergency equipment?
 Are TDI levels measured in the workplace?
 Do you have and practice emergency procedures?
 Are regular medical health checks performed?
14
Good personal hygiene
 Wash with soap & water after finishing
work and before eating,
drinking or smoking
 Do not use solvents for washing
 Use disposable or clean towels
 Do not re-use contaminated
clothing or gloves
15
Clean and safe workplace
 Keep work area clean and tidy
 Respiratory equipment should be readily available
(and well maintained)
 Know the locations of safety showers
and eyebaths / eye wash bottles
They should easily be accessible
 Do not eat, drink or smoke in the workplace
 Segregate your personal protective equipment (PPE)
and work clothes
Do not take the PPE or work clothes home or in areas
where food is consumed.
16
Good workplace ventilation
• A good ventilation is key for a safe
work environment
• For sufficient ventilation an extraction
system is needed
• Further openings (doors, windows) in
the building can support an efficient
ventilation of the workplace
Analysis of the ventilation flow-direction
Bad
Best
17
Good workplace* ventilation

Check that extraction system is switched on

Place hood as near as possible above
the source

Repeatedly check flow-direction

A fume hood is most appropriate for
laboratory areas

Foam production on a conveyor requires very
good extraction in the tunnel and at the cut off
area.

Air curtains improve the extraction efficiency
* includes warehouse
18
Continuous use of the correct PPE
Wear eye protection
• Butyl rubber
Wear protective
liquid- tight
gloves
Wear overall
& boots
In emergencies
wear overall
and/or heavy
duty apron
• Neoprene
• Nitrile
19
Respiratory Equipment
If in doubt, always wear respiratory protection equipment
20
Common Types of respiratory protection
Lung Powered Air Purifying Equipment
• Full face mask
• Half face mask
Self Contained Breathing Apparatus
• Positive pressure equipment
• Pressure demand equipment
21
Best Practice Masks
• For hygiene reasons only use your personal
equipment
• Conduct fit and leakage testing
• Consideration of gasmask availability and accessibility
for emergency procedures
• Masks should be replace based on usage frequency
• Inspection of physical condition must be done before
each use.
If respirator is damaged, it must be replaced
22
Best Practice (Filters)
• Replace filters frequently
• Use only filters that are recommended by the producer
for chemicals in use
• Write date of seal breaking and personal initials onto
the filter
• Close filters again after usage and store
in a dry place in a suited gasmask cupboard in a
dedicated bag or bo
• Track and document the change frequency
23
Best Practice (Cleaning)
• After use remove the filter and rinse your mask in
warm water.
• Use suited disinfection spray
• Leave the disinfection product on the mask for a few
minutes.
• Rinse the mask again in warm water and let it dry.
• Do NOT use any organic solvents.
24
Use of respiratory Protection
 Use an appropriate cartridge / canister (min. AP2) for
maximum 8 hours and throw it out 24 hours after the seal
has been broken
25
Dealing with a spillage of TDI
VIDEO CLIP
26
Dealing with a spillage of TDI

Evacuate area

Inform neighbours and authorities according to the emergency plan

Put on PPE including self-contained breathing apparatus

Prevent TDI entering drains

Cover with fire extinguishing foam to prevent escape of TDI vapours

Control spill with wet sand absorbent

Use decontamination solution

Put contaminated sand in steel drums (max 2/3 full),
leave open to prevent pressure build up and monitor emissions

Drum can only be closed when temperature is low and falling

Treat as TDI waste

Measure TDI levels in the atmosphere
27
Loading / Unloading of drums
28
Handling of drums
29
Drum decontamination
For the decontamination of one drum, the following products are
required :
– Liquid / yellow soap:
0,2 – 2%
– Sodium carbonate:
5 – 10%
– Water:
to make up to 100%
30
Drum decontamination - Procedure
31
Disposal of decontaminated drums

The drum content
The different diisocyanate residues are converted by the corresponding
decontaminant solution into harmless polyurea / polyurethane compounds
and carbon dioxide gas. These may remain in the drum together with the
residual decontaminant solution and will be collect by the drum recondition /
recycler. The decontaminant solution consists of PEG 400, liquid/yellow
soap and inert polyurea/polyurethane compounds.

Identification of the decontaminated drums
After decontamination, it is strongly recommended to identify the drums in
order to enable the forwarder, the reconditioner or recycler to recognize them
as decontaminated.
32
Do you have and do you know where to find the
emergency equipment?
 Decontaminant solution
 Shovels
 Brushes and waste container
 Absorbent material such as sand
33
First Aid equipment
Know where your first aid equipment is
Know what to do
Know who to tell
Shower
Soap
Clean running water is best
Eyebath or eye wash bottle
And don’t panic !
Telephone number of medical doctor - Refer to MSDS emergency
telephone numbers / procedures
34
Emergency procedures
VIDEO CLIP:
Know First Aid for TDI
35
Emergency procedures
Know First Aid for TDI

Force open the eyelids

Flush with lots of water for at least 15 minutes

If in doubt, keep flushing

See eye specialist as soon as possible

Immediately remove contaminated clothing

Immediately wash, wash,
wash with soap & water

Go outside into fresh air

Doctor has to be consulted and a Material Safety
Data Sheet has to be handed out to him for more
product and emergency information
36
Examples of First Aid Equipment
Emergency
shower
Emergency
Eye wash
shower
37
Emergency procedures - Exposure to TDI

A single high exposure to TDI is one possible cause of sensitisation

Early treatment is important

Remember that symptoms may occur later

Help is available for the doctor from ISOPA
member companies
38
Emergency procedures - Exposure to TDI

A single high exposure to TDI is one possible cause of sensitisation

Early treatment is important

Remember that symptoms may occur later

Help is available for the doctor from ISOPA
•Speed is essential
• Practice how to carry
member companies
out First Aid Procedures
• Seek medical advice
39
Emergency procedures
Fire involving TDI
Follow your normal factory emergency procedure

Sound Alarm

EVACUATE immediately

Use trained specialists to fight fire

Ensure protection from TDI emissions

Remember TDI fires are not self extinguishing
Follow your factory emergency procedure
40
Handling of fresh TDI-based foam
Hazards:

TDI, additives and release agent

Heat generated during reaction

Dust from sawing
 Wear PPE (see previous slides)
 Good ventilation is important
41
Foam Exotherm

Foam fire is the most important risk
associated to foam production.

The heat generated by the chemical
reactions during foaming can induce fire
if exotherm is too high.

Foam Fire can also occur for external
reason (sparks, flame, cigarettes, etc.)
42
Foam Exotherm & Fire Risk
Monitoring reaction temperature in foam
Temperature
FIRE
>175 °C
High Fire Risk
Between 165 - 175 °C
< 165 °C
Critical area
OK
Normal Foam
Time
About 4-6 hours after
foam formation
43
Foam Exotherm & Fire Risk
Warnings:

Warm raw materials lead to higher exotherms

The maximum quantity of TDI in a foam
formulation without Methylene chloride
should NOT exceed 55 php in order to
get a safe exotherm.

This type of formula gives only a theoretical
estimation of a foam exotherm, assuming
that the meetering of every chemical is
correct during production.
Estimating the Foam
Exotherm
＋ 69
＋ Raw Material Temperature (ºC)
＋ 1.394 × php TDI
– 1.17 × php Methylene Chloride
= Exotherm in ºC
Note: php = per hundred polyol: The quantities
of TDI and Methylene Chloride in the formula are
according to 100 parts of polyol.

Theoretical exotherm should always be <165ºC

Always keep on the safe side and contact your suppliers in case of doubt.

The bigger the block size the longer it takes to cool down
44
Foam Exotherm & Fire Risk
It is crucial to measure foam temperature after production and to check
that it remains within reasonable limits and habitual value for a given
foam grade.
Segregate the start blocks, grade change, end blocks and measure their
temperatures: these are unstable areas with high fire risk.
In case the foam temperature is rising too high
 move the foam out of the factory and any flammable material
 cut the foam in small pieces
 finally apply water on or into
the foam to cool it down
45
Setting up an Emergency Plan for Spillages,
Accidents and fires
 Set up scenarios of possible emergency cases including fires,
accidents and spillages
 Define procedures for different scenarios
 Implement periodic employee trainings
 Implement periodic audit of PPE, safety and emergency
equipment
46
Some questions...
What would you do if?
An isocyanate pump which is being
serviced is still mistakenly under
pressure. A technician is sprayed in
the face with TDI
Burst drum of hot TDI in factory
47
Answers
An isocyanate pump which is being serviced is still mistakenly under pressure.
A technician is sprayed in the face with TDI
Most important Actions, see also slide 32
• Activate alarm to warn others and seal off contaminated area
• Take victim to emergency shower and eye washer and use large
amounts of water and soap
• Take patient into fresh air
• Remove contaminated clothing
• Seek medical attention
• Avoid spill entering into drainage
• Cleaning of spill
 Use proper PPE to enter area (including mask)
 Use absorbent material and decontaminant solution
 Check quality of atmosphere before declaring the area safe
48
Answers
Burst drum of hot TDI in factory
Actions
•
•
•
•
Activate alarm to warn others and seal off contaminated area
Use proper PPE (including mask)
Put the drum in an oversize (salvaged) drum, leave drum open
Leave the drum to cool down and handle as waste TDI
49
Disclaimer
These product stewardship initiatives of ISOPA and its members
do not exempt customers, producers and others in the supply
chain of their occupational health, safety and environmental duties
and regulatory obligations. With respect to this, ISOPA and its
associated members disclaim any liability in connection with the
use of services rendered and of the related information provided. It
is the responsibility of the user to verify the accuracy of the
services and the related information which can be used by the user
at his own risk.
50