4,4'-methylenediphenyldiisocyanate and 2,4'-diisocyanatodiphenylmethane and their oligomerisation reaction products with 2,2'-oxydiethanol, propane-1,2-diol and butane-1,3-diol

Guidance on Safe Use

First-aid measures

Description of first aid measures

Remove contaminated clothing immediately and clean before re-use or dispose it if necessary.

If inhaled: Keep patient calm, remove to fresh air, seek medical attention.

On skin contact: After contact with skin, wash immediately with plenty of water. Consult a doctor if skin irritation persists.

On contact with eyes: Immediately wash affected eyes for at least 15 minutes under running water with eyelids held open, consult an eye specialist.

On ingestion: Immediately rinse mouth and then drink plenty of water, do not induce vomiting, seek medical attention.

Most important symptoms and effects, both acute and delayed

Symptoms: tightness in the chest, coughing, difficulty breathing, Eye irritation, skin irritation, allergic symptoms

Hazards: Symptoms can appear later.

Indication of any immediate medical attention and special treatment needed

Treatment: Treat according to symptoms (decontamination, vital functions), no known specific antidote, administer corticosteroid dose aerosol to prevent pulmonary odema.

Fire-fighting measures

Suitable extinguishing media: Foam, CO2 or dry powder. Water spray may be used if no other available and then in copious quantities. Reaction between water and hot isocyanate may be vigorous. Prevent washings from entering water courses, keep fire exposed containers cool by spraying with water.

Unsuitable extinguishing media: High volume water jet.

Combustion products may include: carbon oxides (CO, CO2) nitrogen oxides (NO, NO2 etc.) hydrocarbons, isocyanate vapors and hydrogen cyanide.

In the event of fire and/or explosion do not breathe fumes.

Fire in vicinity poses risk of pressure build-up and rupture. Containers at risk from fire should be cooled with water and, if possible, removed from the danger area. Due to reaction with water producing CO2-gas, a hazardous build-up of pressure could result if contaminated containers are re-sealed. Containers may burst if overheated.

Fire-fighters should wear appropriate protective equipment and self-contained breathing apparatus (SCBA) with a full face-piece operated in positive pressure mode. PVC boots, gloves, safety helmet and protective clothing should be worn.

Do not allow contaminated extinguishing water to enter the soil, ground-water or surface waters.

Accidental release measures

Personal precautions: Immediately contact emergency personnel. Evacuate the area. Keep upwind to avoid inhalation of vapours. Clean-up should only be performed by trained personnel. People dealing with major spillages should wear full protective clothing including respiratory protection. Use suitable protective equipment (section 8). Keep unauthorized persons away.

Environmental precautions: Avoid dispersal of spilt material and runoff and contact with soil, waterways, drains and sewers. Do not empty into drains. Do not discharge into the subsoil/soil.

Methods for cleaning up: If the product is in its solid form: Spilled MDI flakes should be picked up carefully. The area should be vacuum cleaned to remove remaining dust particles completely.

If the product is in its liquid form: Absorb spillages onto sand, earth or any suitable adsorbent material. Leave to react for at least 30 minutes. Do not absorb onto sawdust or other combustible materials. Shovel into open-top drums for further decontamination. Wash the spillage area with water. Test atmosphere for MDI vapour. Neutralise small spillages with decontaminant. Remove and dispose of residues. The compositions of liquid decontaminants are : (percentages by weight or volume) :

Decontaminant 1 : *- sodium carbonate : 5 - 10 % *- liquid detergent : 0.2 - 2 % *- water : to make up to 100 %

Decontaminant 2 : *- concentrated ammonia solution : 3 - 8 % *- liquid detergent : 0.2 - 2 % *- water : to make up to 100 %

Decontaminant 1 reacts slower with diisocyanates but is more environmentally friendly than decontaminant 2.

Decontaminant 2 contains ammonia. Ammonia presents health hazards. (See supplier safety information.)

Additional advice: -

Handling and storage

Handling: Provide sufficient air exchange and/or exhaust in work rooms. In all workplaces or parts of the plant where high concentrations of isocyanate aerosols and/or vapors may be generated (e.g. during pressure release, mold venting or when cleaning mixing heads with an air blast), appropriately located exhaust ventilation must be provided in order to prevent occupational exposure limits from being exceeded. The air should be drawn away from the personnel handling the product.

The efficiency of the ventilation system must be monitored regularly because of the possibility of blockage. Atmospheric concentrations should be minimised and kept as low as reasonably practicable below the occupational exposure limit.

Products freshly manufactured from isocyanates can contain incompletely reacted isocyanates and other dangerous substances, e.g. primary aromatic amines. Industrial cleaning with aprotic polar solvents (meeting the IUPAC definition) may lead to formation of hazardous primary aromatic amine (>0,1%).

             

Contact with skin and eyes and inhalation of vapors must be avoided under all circumstances. Keep equipment clean.

A basic essential in sampling, handling and storage is the prevention of contact with water. Keep stocks of decontaminant readily available. The compositions of liquid decontaminants are described under "Accidental release measures".

             

Storage :

Keep away from water. Segregate from foods and animal feeds. Segregate from acids and bases.

Suitable materials for containers: Carbon steel (Iron), High density polyethylene (HDPE), Low density polyethylene (LDPE), tinned carbon steel (Tinplate), Stainless steel 1.4301 (V2)

Unsuitable materials for containers: Paper/Fibreboard

Further information on storage conditions: Keep container tightly closed in a cool, well-ventilated place. Protect against moisture.

Transport information

Land transport (UN RTDG/ADR/RID)

UN number:

Not dangerous goods

Shipping

Labels:

Not dangerous goods

SpecialProvisions

Inland waterway transport (UN RTDG/ADN(R))

UN number:

Not dangerous goods

Shipping

Labels:

Not dangerous goods

Remarks

Marine transport (UN RTDG/IMDG)

UN number:

Not dangerous goods

Shipping information

Proper shipping name and description:

Not dangerous goods

Chemical name:

Not dangerous goods

Labels:

Not dangerous goods

Remarks

Air transport (UN RTDG/ICAO/IATA)

UN number:

Not dangerous goods

Shipping information

Proper shipping name and description:

Not dangerous goods

Chemical name:

Not dangerous goods

Labels:

Not dangerous goods

Remarks

SpecialProvisions

Exposure controls / personal protection

Personal protective equipment

Respiratory protection: Respiratory protection in case of vapour/aerosol release. (Combination filter EN 14387 A-P2)

Hand protection: Chemical resistant protective gloves (EN 374). Suitable materials also with prolonged, direct contact (Recommended: Protective index 6, corresponding > 480 minutes of permeation time according to EN 374):

butyl rubber (butyl) - 0.7 mm coating thickness

nitrile rubber (NBR) - 0.4 mm coating thickness

chloroprene rubber (CR) - 0.5 mm coating thickness

Unsuitable materials:

polyvinylchloride (PVC) - 0.7 mm coating thickness

Polyethylene-Laminate (PE laminate) - ca. 0.1 mm coating thickness

Suitable materials that provide sufficient protection for industrial cleaning with aprotic polar solvents (meeting the IUPAC definition):

butyl rubber (butyl) - 0.7 mm coating thickness

nitrile rubber (NBR) - 0.4 mm coating thickness

chloroprene rubber (CR) - 0.5 mm coating thickness

Eye protection: Safety glasses with side-shields (frame goggles) (e.g. EN 166)

Body protection: safety shoes (e.g. according to EN 20346)

General safety and hygiene measures

Do not breathe vapour/spray. With products freshly manufactured from isocyanates body protection and chemical resistant protective gloves is recommended. Wearing of closed work clothing is required additionally to the stated personal protection equipment. No eating, drinking, smoking or tobacco use at the place of work. Take off immediately all contaminated clothing. Hands and/or face should be washed before breaks and at the end of the shift. At the end of the shift the skin should be cleaned and skin-care agents applied.

Stability and reactivity

No hazardous reactions if stored and handled as prescribed/indicated.

Reacts with water, with formation of carbon dioxide. Risk of bursting. Reacts with substances which contain active hydrogen. Avoid moisture.

Disposal considerations

Incinerate in suitable incineration plant, observing local authority regulations. Dispose of isocyanate waste in dry containers and never mix together with other wastes (reaction, dangerous pressure build up).

Waste key: 08 05 01 waste isocyanates

Contaminated packaging: Contaminated packaging should be emptied as far as possible; then it can be passed on for recycling after being thoroughly cleaned. This material and its container must be disposed of in a safe way.