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
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