Safe Handling of Diisocyanate Monomers (HDI, IPDI, H 12 MDI)

1. 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. 822-06-0 Isophorone diisocyanate (IPDI) (3-Isocyanatomethyl-3,5,5-trimethyl-cyclohexylisocyanate), mixture of cis- and trans- isomers, CAS-No. 4098-71-9 4,4‘-Dicyclohexylmethane diisocyanate (H12MDI), main component, mixture of isomers CAS-No. 5124-30-1

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

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

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

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 Medical surveillance Continous use of PPE

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 diisocyanatevapours • 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.