1. Diisocyanate Monomers (HDI, IPDI, H12MDI)
Safe Handling of
Diisocyanate Monomers (HDI, IPDI, H12MDI)
June 2011 version

2. We Take Responsibility for Health, Safety and the Environment
ALIPA = The European ALiphatic Isocyanates Producers Association
Comprises leading European manufacturers of aliphatic isocyanates and polyisocyanates

3. Diisocyanate Monomers Users
Content
Essential data
Best practice
When things go wrong …

4. Diisocyanate Monomers
Diisocyanates are industrial intermediates for the manufacture of:
Polyisocyanate resins (NCO-terminated, hardeners)
Prepolymers
Adducts
Oligomers (e.g.biuret, isocyanurate, uretdione)
Urethane resins (blocked or reacted isocyanate groups)
Blocked polyisocyanates
Polyurethanes
Polyurethane dispersions
Urethane acrylates
Such products are basic components for formulating
Paints and lacquers  Adhesives
Sealants  Elastomers

5. Most Important Aliphatic Diisocyanates
1,6-Hexamethylene diisocyanate (HDI)
CAS-No
Isophorone diisocyanate (IPDI)
(3-Isocyanatomethyl-3,5,5-trimethyl-cyclohexylisocyanate),
mixture of cis- and trans- isomers,
CAS-No
4,4‘-Dicyclohexylmethane diisocyanate (H12MDI),
main component, mixture of isomers
CAS-No

6. Diisocyanate Classification & Labelling*
GHS Classification of HDI
Acute toxicity, Oral, Category 4 (H302)
Acute toxicity, Inhalative, Category 1 (H330)
Skin irritation, Category 2 (H315)
Eye irritation, Category 2 (H319)
Sensitization of the respiratory airways, Category 1 (H334)
Sensitization of the skin, Category 1 (H317)
Specific target organ toxicity (single exposure), Category 3 (H335)
Labelling of HDI (on the package)
Signal word : Danger
Hazard statements
H302 Harmful if swallowed.
H315 Causes skin irritation.
H317 May cause an allergic skin reaction.
H319 Causes serious eye irritation.
H330 Fatal if inhaled.
H334 May cause allergy or asthma symptoms or breathing difficulties if inhaled.
H335 May cause respiratory irritation.
* European Legislation according to Regulation (EC) No. 1272/2008 (CLP) , Annex VI, Part 3, Table 3.1, modified by self classification, if needed 6 6

7. Diisocyanate Classification & Labelling*
GHS Classification of H12MDI
Acute toxicity, Inhalative, Category 1 (H330)
Skin irritation, Category 2 (H315)
Eye irritation, Category 2 (H319)
Sensitization of the respiratory airways, Category 1 (H334)
Sensitization of the skin, Category 1 (H317)
Specific target organ toxicity (single exposure), Category 3 (H335)
Labelling of H12MDI (on the package)
Signal word : Danger
Hazard statements
H315 Causes skin irritation.
H317 May cause an allergic skin reaction.
H319 Causes serious eye irritation.
H330 Fatal if inhaled.
H334 May cause allergy or asthma symptoms or breathing difficulties if inhaled.
H335 May cause respiratory irritation.
* European Legislation according to Regulation (EC) No. 1272/2008 (CLP), Annex VI, Part 3, Table 3.1, modified by self classification, if needed 7 7

8. Diisocyanate Classification & Labelling*
GHS Classification of IPDI
Acute toxicity, Inhalative, Category 1 (H330)
Skin irritation, Category 2 (H315)
Eye irritation, Category 2 (H319)
Sensitization of the respiratory airways, Category 1 (H334)
Sensitization of the skin, Category 1 (H317)
Specific target organ toxicity (single exposure), Category 3 (H335)
Hazardous to the aquatic environment, Category 2 (H411)
Labelling of IPDI (on the package)
Signal word : Danger
Hazard statements
H315 Causes skin irritation.
H317 May cause an allergic skin reaction.
H319 Causes serious eye irritation.
H330 Fatal if inhaled.
H334 May cause allergy or asthma symptoms or breathing difficulties if inhaled.
H335 May cause respiratory irritation.
H411Toxic to aquatic life with long lasting effects.
* European Legislation according to Regulation (EC) No. 1272/2008 (CLP) , Annex VI, Part 3, Table 3.1, modified by self classification, if needed 8 8

9. Diisocyanate Classification & Labelling*
DSD Classification of HDI and H12MDI
Toxic by inhalation
Irritating to eyes, respiratory system and skin
May cause sensitisation by inhalation and skin contact
Labelling of HDI and H12MDI (on the package)
Symbol : T
Risk phrases: R 23-36/37/38-42/43
* European Legislation according to Regulation (EC) No. 1272/2008 (CLP), Annex VI, Part 3, Table 3.2 (67/548/EEC)

10. Diisocyanate Classification & Labelling*
DSD Classification of IPDI
Toxic by inhalation
Irritating to eyes, respiratory system and skin
May cause sensitisation by inhalation and skin contact
Toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment
Labelling of IPDI (on the package)
Symbol : T, N
Risk phrases: R 23-36/37/38-42/43-51/53
* European Legislation according to Regulation (EC) No. 1272/2008 (CLP), Annex VI, Part 3, Table 3.2 (67/548/EEC)

11. Are you Aware of the Physical Behaviour of Diisocyanates?
HDI and IPDI have a significant vapour pressure
H12MDI has a low vapour pressure but may exceed the OEL (Occupational Exposure Limit) already at low temperatures
Evaporation can lead to high concentration in air if uncontrolled
Volatility and concentration in air increase rapidly with rising temperature
You must always
protect yourself
against breathing
in diisocyanates
Saturated vapour concentration of diisocyanates in air
(indicative values –
not true to scale)

12. Do You Know About the Chemical Behaviour of Aliphatic Diisocyanates?
Will react with many compounds – especially water, alcohols incl. polyols, amines, ammonia solutions, alkaline compounds
Specific metal and amine compounds may speed up reaction (catalysis)
During reaction heat will be formed
Higher temperatures mean faster reactions
(beware of temperatures > 40°C)
Reaction with water will lead to formation of gases (CO2)
 Risk of dangerous pressures

13. Where Can Such Chemical Reactions Happen?
Decontamination of drums
Storage of polyol/diisocyanate together
Spillage into a drain
Bulk off-loading of wrong chemical into a bulk tank
Diisocyanate in wet disposal drums
High temperature operations

14. Safety .....Take Care That You Care!
What percentage of all industrial accidents
is attributable to careless handling?
20, 40, 60 or 80 percent?
80%

15. Typical Examples of Unsafe Behaviour

16. Effects of Aliphatic Diisocyanates 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 burn
Symptoms can occur up to 24 hrs
after exposure

17. Effects of Aliphatic Diisocyanates on Your Health
Long term / repeated over-exposure from breathing or skin contact leads to risk of sensitisation
Skin symptoms of contact dermatitis like eczema
Respiratory symptoms such as occasional breathing difficulties similar to asthma, hay fever, sneezing
When sensitised, potentially severe asthma in the case of even low diisocyanate 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!

18. A Few Questions on Safe Handling of Diisocyanate Monomers
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 Personal Protective Equipment (PPE) – including during plant maintenance?
Do you know where to find emergency equipment?
Are monomer levels measured in the workplace?
Do you know and practice emergency procedures?
Are regular health checks performed?

19. Take Care of Yourself Avoid inhaling diisocyanates
Avoid skin contact with diisocyanates
Avoid eye contact with diisocyanates
Pre-placement medical evaluation or medical surveillance recommended or required by authorities
Take care of small spillages
Continous use of PPE
Medical surveillance

20. Best Practice: Ventilation
Use closed systems as far as possible (closed reactors, pipes, ….)
Use and place local extraction as near as possible above the source
Use hoods for laboratory works
Check that the extraction systems / hoods are well maintained and are working properly

21. Best Practice: Continuous Use of the Correct PPE*
Wear eye protection
Wear protective gloves, clothing and boots
In emergencies wear disposable overall and/or heavy duty apron
* Personal Protective Equipment

22. Best Practice: Respiratory Equipment
In the event of insufficient ventilation or if in doubt, always wear respiratory protection equipment
Check that your respiratory equipment is properly used and well maintained

23. Best Practice: Clean and Safe Workplace
Keep work area clean and tidy
Do not contaminate the area by the use of contaminated gloves
Know the locations of safety showers, respiratory equipment and eyebaths
Do not eat, drink or smoke in the workplace

24. Best Practice: Good Personal Hygiene
Prevent skin dryness: use barrier and moisturizing creams before starting work
Wash with soap & water after finishing work and before eating, drinking or smoking
Do not use solvents for washing
Use disposable towels
Do not re-use contaminated clothing or gloves

25. Best Practice
Even when working with closed systems certain operations need PPE and local extractions:
Sampling
Feeding
Maintenance work
Emptying /decontamining drums
Handling waste

26. When Things Go Wrong … You are trained in handling diisocyanates
You know all the safety precautions to protect yourself and the environment
But let's be honest… an accident can happen!
What then?

27. Spillage! How to Deal with It?
Evacuate area
Put on PPE including self-contained breathing apparatus
Prevent the diisocyanate entering drains
Cover spillage with fire extinguishing foam to prevent escape of the diisocyanate 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 (CO2 gas) and monitor emissions
Close drum only when temperature is low enough
Treat as a diisocyanate waste
Measure the diisocyanate levels in the atmosphere
Not all of these measures may be necessary for small spillages 27

28. Spillage! Be sure to Know Where to find Emergency Equipment
Decontamination solution
Shovels
Brushes and waste container
Absorbent material such as sand
PPE (Personal Protective Equipment)
Respiratory protection
Overalls/coveralls
Impermeable boots
Gloves
Face and eye protection 28

29. Emergency Procedures Speed is essential
Practice how to carry out first aid procedure
Seek medical advice
Remember:
Prepared in and used to best practice,
you will not panic.

30. Emergency! How about 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
Telephone number of doctor 30

31. Emergency Procedures: First Aid
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 skin Wash, wash, wash – with soap and water
Go outside into fresh air
Doctor must be called or patient taken to medical facility
If more information is needed contact your supplier 31

32. Emergency Procedures: Fire!
Follow your normal factory emergency procedure.
It may include:
Sound alarm
Evacuate, according to Seveso Directive
Use trained specialists to fight fire
Ensure protection from emissions
Remember diisocyanate fires are not self-extinguishing
Danger Boiling Liquid Expanding Vapour Explosion (BLEVE)
Do not use water as extinguishing media 32

33. Now Give your Knowledge a Test
What would you do if:
A diisocyanate pump which is being serviced is still
mistakenly under pressure. A technician is sprayed in
the face with the diisocyanate?
A maintenance worker is replacing a pump.
Why should he need skin and respiratory protection?

34. Disclaimer
These product stewardship initiatives of ALIPA and its members do not exempt customers, producers and others in the supply chain from their occupational health, safety and environment duties and regulatory obligations. With respect to this, ALIPA 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.