1,1'-Methylenebis(4-isocyanatobenzene) and its oligomeric reaction products with [(methylethylene)bis(oxy)]dipropanol

Guidance on Safe Use

First-aid measures

General advice: Soiled, soaked clothing and shoes must be immediately removed, decontaminated and disposed of.

If inhaled: If inhaled, remove to fresh air. If not breathing, give artificial respiration. Get medical attention immediately.

In case of skin contact: In the event of contact with the skin, preferably wash with a cleanser based on polyethylene glycol or with plenty of warm water and soap. Consult a doctor in the event of a skin reaction. Wash clothing before reuse. Clean shoes
thoroughly before reuse.

In case of eye contact: Hold the eyes open and rinse with preferably lukewarm water for a sufficiently long period of time (at least 10 minutes). Get medical attention immediately.

If swallowed: DO NOT induce the patient to vomit, medical advice is required. Never give anything by mouth to an unconscious person. Provided the patient is conscious,
wash out mouth with water.

Notes to physician: The product irritates the respiratory tract and may trigger sensitisation of the skin and respiratory tract. Treatment of acute irritation or bronchial constriction is primarily symptomatic. Following severe exposure the patient should be kept under medical review for at least 48 hours.

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.

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.

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 : Store in accordance with local regulations. Store in original container protected from direct sunlight in a dry, cool and well-ventilated area, away from incompatible materials and food and drink. Keep container tightly closed and sealed until ready for use. Containers that have been opened must be carefully resealed and kept upright to prevent leakage. Do not store in unlabelled containers.
Use appropriate containment to avoid environmental contamination.
Suitable containers: Steel. Stainless steel.
Unsuitable containers: Copper., copper alloy and galvanised surfaces

Transport information

Land transport (ADR/RID)

UN number:

Not dangerous goods

Shipping

Class:

Not dangerous goods

Classification code:

Not dangerous goods

Packaging group:

Not dangerous goods

Labels:

Not dangerous goods

SpecialProvisions

Inland waterway transport (ADN(R))

UN number:

Not dangerous goods

Shipping

Class:

Not dangerous goods

Classification code:

Not dangerous goods

Packaging group:

Not dangerous goods

Labels:

Not dangerous goods

Remarks

Marine transport (IMDG)

UN number:

Not dangerous goods

Proper shipping name and description:

Not dangerous goods

Chemical name:

Not dangerous goods

Class:

Not dangerous goods

Packaging group:

Not dangerous goods

EmS code:

Not dangerous goods

Labels:

Not dangerous goods

Remarks

Air transport ICAO/IATA

UN number:

Not dangerous goods

Proper shipping name and description:

Not dangerous goods

Chemical name:

Not dangerous goods

Class:

Not dangerous goods

Packaging group:

Not dangerous goods

Labels:

Not dangerous goods

Remarks

SpecialProvisions

Exposure controls / personal protection

The use of PPE in the working environment should be seen as last resort when deciding on control measures and should only be used when all other options have been exhausted;
Worker Respiratory Protection Value
Respiratory Protective Equipment with an efficiency of 90 % can be used temporarily for those activities where technical measures such as ventilation are found not to be practical or efficient
1. EN 140 Half face mask equipped with a disposable respirator or
2. EN14387/EN 136 Full face mask equipped with a disposable respirator, providing the same level of protection but offering improved skin protection or
3. EN138 Fresh air hose with half face mask.
For short term activities a fresh air hose with combined filter A2-P2 is recommended.

Disposal of filtering devices: this depends on many factors and it is recommended to replace the filters as instructed by the manufacturer or, following guidance of UK Health and Safety Executive, replace A1 type filters at least every 2 days or for an A2 type filter, change at least once a week. The UK HSE recommends to replace filters more rapidly for sensitising substances, but based on specific testing of the trapping efficiency of these filters for MDI, we regard that for MDI the general guidance is deemed to be applicable.
97.5% efficiency is needed for those activities where aerosols are generated such as spraying [PROC7 or 11], when technical measures such as ventilation are found not to be practical or efficient:
1. EN12942 TM3 powered filtering device with full face mask equipped with AP2 filters as minimum or
2. EN12941 TH3 powered filtering device with hood equipped with AP2 filters as minimum or
3. EN138 a fan assisted fresh air hose with full face mask providing fresh air well away from the work area or
4. EN269 powered fresh air hose providing fresh air well away from the work area or
5. EN14593-1 compressed air line with demand valve breathing apparatus with full face mask or
6. EN14593-2 demand breathing apparatus with full face mask or
7. EN14594 LDH3 constant flow airline breathing apparatus with a hood or full face mask.
Worker body Protective Equipment
For body protection we can state that is at industrial and professional level cotton overalls or disposable coveralls or appropiate worker protection clothes are recommended.
Worker Hand Protection
Use chemical resistant gloves classified under Standard EN374: Protective glove against chemicals and micro-organisms.
The use chemical resistant gloves classified under Standard EN374: Protective glove against chemicals and micro-organisms is prescribed for all products/articles with a residual concentration > 0.1% MDI.
For frequently repeated contact gloves with protection class 5 or higher is recommended, while for brief contact, gloves with a class 3 protection or higher are suitable.

Protective gloves against chemicals and micro-organisms. Examples of preferred glove barrier materials include: Butyl rubber, Polyethylene, Chlorinated polyethylene, Ethyl vinyl alcohol laminate ("EVAL"). Examples of acceptable glove barrier materials include: Viton, Neoprene, Polyvinyl chloride ("PVC" or "vinyl"), Nitrile/butadiene rubber ("nitrile" or "NBR"). When prolonged or frequently repeated contact may occur, a glove with a protection class of 5 or higher (breakthrough time greater than 240 minutes according to EN 374) is recommended. When only brief contact is expected, a glove with a protection class of 3 or higher (breakthrough time greater than 60 minutes according to EN 374) is recommended. Glove thickness alone is not a good indicator of the level of protection a glove provides against a chemical substance as this level of protection is also highly dependent on the specific composition of the
material that the glove is fabricated from. The thickness of the glove must, depending on model and type of material, generally be more than 0.35 mm to offer sufficient protection for prolonged and frequent contact with the substance. As an exception to this general rule it is known that multilayer laminate gloves may offer prolonged protection at thicknesses less than 0.35 mm. Other glove materials with a thickness of less than 0.35 mm may offer sufficient protection when only brief contact is expected. Other types of gloves with available permeation data offering good protection is assumed to have an efficiency of 80%, they could be used e.g. for PROC21, as only < 1% of MDI is expected, providing an assessment has been made that good protection is provided.
Especially in those cases where workers are handling continuously fresh PU articles and the wearing of chemical protective gloves will cause skin problems due to sweating, leading to skin damage, leading to increased risk of absorption through the skin.

NOTICE: The selection of a specific glove for a particular application and duration of use in a workplace should also take into account all relevant workplace factors such as, but not limited to: Other chemicals which may be handled, physical requirements (cut/puncture protection, dexterity, thermal protection), potential body reactions to glove materials, as well as the instructions/specifications provided by the glove supplier.

Based on the above, for cleaning with aprotic polar solvents users of these solvents are recommended to consult their glove manufacturers/suppliers to assess permeation and breakthrough time in order to perform their own assessment about the appropriate skin protection relevant to the solvent and operational conditions being used to protect against potential presence of MDA traces possible formed through hydrolysis due to the water present in these solvents.

We advise against the use of latex gloves.

For PROC7/10 & 11 the use of suitable eye protection is in all cases prescribed and for other PROCs the use of goggles is prescribed when and where there is a likelihood of splashes or when activities are done overhead or when workers need to be close to the source, e.g. for visual inspections.
In general it can be stated that dermal protective equipment is expected to be used for all chemical handling at industrial and professional level [SU3/SU8/SU9/SU10/SU22] and although it might not always be required based on exposure assessment results, industry does not want to lower existing safety standards which are already applicable in chemical industry within the framework of adhering to the ALARP principle [keeping exposure As Low As Reasonably Practical].
Consumer Dermal & Ocular Exposure – Qualitative Risk Assessment
For all consumer products containing > 0.1% by weight of MDI that are being put on the consumer market, gloves that have passed EN 374 tests (http://www.feica.com/library/position-papers/use-of-gloves) are provide together with the product (Commission Regulation EC No 552/2009; REACH Annex XVII OJ L 164/7, 26.6.2009., p.27). During normal use, no product comes in contact with gloves. Besides proper labeling according to Commission Regulation EC No 552/2009; REACH Annex XVII, as an element of good practice and personal hygiene, advice on proper use of the gloves will be part of consumer instructions (DECISION No 1348/2008/EC). Part of the advice will be replacement of the gloves after 5 minutes in case of product spillage onto the gloves.
By way of derogation to this legislation, this does not apply to hot melt adhesives (Commission Regulation EC No 552/2009; REACH Annex XVII).
see as well Appendix 0 in chapter 13

Stability and reactivity

10.1 Reaktivität
Keine Informationen verfügbar.
10.2 Chemische Stabilität
Keine Informationen verfügbar.
10.3 Möglichkeit gefährlicher Reaktionen
Exotherme Reaktion mit Aminen und Alkoholen; mit Wasser CO2 - Entwicklung, in geschlossenen Behältern Druckaufbau; Berstgefahr.
10.4 Zu vermeidende Bedingungen
Keine Informationen verfügbar.
10.5 Unverträgliche Materialien
Keine Informationen verfügbar.
10.6 Gefährliche Zersetzungsprodukte
Keine gefährlichen Zersetzungsprodukte bei sachgemäßer Lagerung und Handhabung.

Disposal considerations

Entsorgung unter Berücksichtigung aller anzuwendenden internationalen, nationalen und lokalen Gesetze, Verordnungen und Satzungen.
Bei der Entsorgung innerhalb der EU ist der jeweils gültige Abfallschlüssel nach dem europäischen Abfallkatalog (EAK) zu verwenden.
13.1 Verfahren zur Abfallbehandlung
Verpackungen müssen direkt nach der letzten Produktentnahme nachentleert werden (tropffrei, rieselfrei, spachtelrein). Nach Unschädlichmachen der an den Wänden haftenden Produktreste sind Produkt- und Gefahrstoffkennzeichnung zu entwerten. Diese Verpackungen können packmittelspezifisch an den Annahmestellen der bestehenden Rücknahmesysteme der chemischen Industrie zur Verwertung abgegeben werden. Die Verwertung muss gemäß nationaler Gesetzgebung und Umweltschutzbestimmungen erfolgen.
Keine Entsorgung über das Abwasser.