Safety data sheet reference · CAS 101-68-8
Methylene diphenyl diisocyanate SDS
also: methylene diphenyl diisocyanate MSDS · safety data sheet · CH2(C6H4NCO)2 · CAS 101-68-8 · EC 202-966-0 · MDI · 4,4'-MDI · diisocyanate
Official PDF from supplier
This page is a reference, not the legal document.
CAS number
101-68-8
EC number
202-966-0
CLP Annex VI index
615-005-00-9
Molecular formula
CH2(C6H4NCO)2
§ 02 · Hazards identification
Methylene diphenyl diisocyanate harmonised EU classification
CLP Annex VI · Index 615-005-00-9. A supplier SDS may add self-classified hazards — this is the legal minimum.
Precautionary statements
Codes ending in a colon introduce the action that follows — on a label they are printed as combined statements, such as P305+P351+P338.
§ 03 · Composition and identifiers
Methylene diphenyl diisocyanate molecular structure
Methylene diphenyl diisocyanate is a molecular compound. The skeletal formula below is drawn from its PubChem SMILES string, and every value in this section is computed from that structure.
2D skeletal formula · CH2(C6H4NCO)2
Functional groups
aromatic ring, isocyanate
Electron count
92 valence e⁻ · 6 lone pairs
Identifiers from PubChem (NIH, public domain). Structure diagram drawn with RDKit from the SMILES string. Geometry and hybridisation are computed from the connection table, not measured.
§ 04 · First-aid measures
Methylene diphenyl diisocyanate first aid measures
Call your national emergency number first. These are published first-aid measures, not medical advice, and they do not replace emergency services, a poison control centre or the supplier's safety data sheet.
§4–§6 below reproduce the CAMEO Chemicals entry DIPHENYLMETHANE-4,4'-DIISOCYANATE. CAMEO publishes response data per product entry, so the entry can describe a solution, a refrigerated liquid or a molten form rather than the pure substance in §9 — check it matches what you are handling.
EYES
First check the victim for contact lenses and remove if present. Flush victim's eyes with water or normal saline solution for 20 to 30 minutes while simultaneously calling a hospital or poison control center. Do not put any ointments, oils, or medication in the victim's eyes without specific instructions from a physician. IMMEDIATELY transport the victim after flushing eyes to a hospital even if no symptoms (such as redness or irritation) develop.
SKIN
IMMEDIATELY flood affected skin with water while removing and isolating all contaminated clothing. Gently wash all affected skin areas thoroughly with soap and water. IMMEDIATELY call a hospital or poison control center even if no symptoms (such as redness or irritation) develop. IMMEDIATELY transport the victim to a hospital for treatment after washing the affected areas.
INHALATION
IMMEDIATELY leave the contaminated area; take deep breaths of fresh air. IMMEDIATELY call a physician and be prepared to transport the victim to a hospital even if no symptoms (such as wheezing, coughing, shortness of breath, or burning in the mouth, throat, or chest) develop. Provide proper respiratory protection to rescuers entering an unknown atmosphere. Whenever possible, Self-Contained Breathing Apparatus (SCBA) should be used; if not available, use a level of protection greater than or equal to that advised under Protective Clothing.
INGESTION
If the victim is conscious and not convulsing, give 1 or 2 glasses of water to dilute the chemical and IMMEDIATELY call a hospital or poison control center. Generally, the induction of vomiting is NOT recommended outside of a physician's care due to the risk of aspirating the chemical into the victim's lungs. However, if the victim is conscious and not convulsing and if medical help is not readily available, consider the risk of inducing vomiting because of the high toxicity of the chemical ingested. Ipecac syrup or salt water may be used in such an emergency. IMMEDIATELY transport the victim to a hospital. If the victim is convulsing or unconscious, do not give anything by mouth, ensure that the victim's airway is open and lay the victim on his/her side with the head lower than the body. DO NOT INDUCE VOMITING. IMMEDIATELY transport the victim to a hospital.
Source: NTP, 1992 — via CAMEO Chemicals (NOAA), public domain.
§ 05 · Fire-fighting measures
Methylene diphenyl diisocyanate fire fighting measures
ERG 2024 · GUIDE 156 Substances - Toxic and/or Corrosive (Combustible / Water-Sensitive)ERG guidance is written per response guide, not per substance — Guide 156 covers every material assigned to it, so a few sentences reference other UN numbers in the same group.
Fire and explosion hazard
Special Hazards of Combustion Products: Toxic vapors are generated when heated.
Behavior in Fire: Solid melts and burns
Extinguishing media and tactics
Note: Most foams will react with the material and release corrosive/toxic gases. CAUTION: For Acetyl bromide (UN1716), use CO2 or dry chemical only.
SMALL FIRECO2, dry chemical, dry sand, alcohol-resistant foam.
LARGE FIREWater spray, fog or alcohol-resistant foam. FOR CHLOROSILANES, DO NOT USE WATER; use alcohol-resistant foam. If it can be done safely, move undamaged containers away from the area around the fire. Avoid aiming straight or solid streams directly onto the product.
FIRE INVOLVING TANKS, RAIL TANK CARS OR HIGHWAY TANKSFight fire from maximum distance or use unmanned master stream devices or monitor nozzles. Do not get water inside containers. Cool containers with flooding quantities of water until well after fire is out. Withdraw immediately in case of rising sound from venting safety devices or discoloration of tank. ALWAYS stay away from tanks in direct contact with flames.
Source: ERG, 2024 — via CAMEO Chemicals (NOAA), public domain. Entry: DIPHENYLMETHANE-4,4'-DIISOCYANATE.
§ 06 · Accidental release measures
Methylene diphenyl diisocyanate spill and leak response
Containment and clean-up
ELIMINATE all ignition sources (no smoking, flares, sparks or flames) from immediate area. All equipment used when handling the product must be grounded. Do not touch damaged containers or spilled material unless wearing appropriate protective clothing. Stop leak if you can do it without risk. A vapor-suppressing foam may be used to reduce vapors. FOR CHLOROSILANES, use alcohol-resistant foam to reduce vapors. DO NOT GET WATER on spilled substance or inside containers. Use water spray to reduce vapors or divert vapor cloud drift. Avoid allowing water runoff to contact spilled material. Prevent entry into waterways, sewers, basements or confined areas.
SMALL SPILLCover with DRY earth, DRY sand or other non-combustible material followed with plastic sheet to minimize spreading or contact with rain. Use clean, non-sparking tools to collect material and place it into loosely covered plastic containers for later disposal.
Initial isolation and evacuation
IMMEDIATE PRECAUTIONARY MEASUREIsolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids.
SPILLIncrease the immediate precautionary measure distance, in the downwind direction, as necessary.
FIREIf tank, rail tank car or highway tank is involved in a fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consider initial evacuation for 800 meters (1/2 mile) in all directions.
Source: ERG, 2024 — via CAMEO Chemicals (NOAA), public domain. Entry: DIPHENYLMETHANE-4,4'-DIISOCYANATE.
§ 07 · Handling and storage
Methylene diphenyl diisocyanate computed storage compatibility
Derived from CLP Annex VI classification and CAMEO reactive-group data — not copied from a PDF.
Full interactive verdict — reactions, gas release on contact, ADR forms →
§ 08 · Exposure controls
Methylene diphenyl diisocyanate exposure limits (IDLH)
IDLH
Immediately Dangerous to Life or Health
75 mg/m3
NIOSH Pocket Guide — Methylene diphenyl diisocyanate →
IDLH from the NIOSH Pocket Guide to Chemical Hazards (CDC, U.S. public domain), via CAMEO Chemicals. Occupational exposure limits — OSHA PEL, NIOSH REL and EU IOELV — are not published on this page yet.
§ 09 · Physical and chemical properties
Methylene diphenyl diisocyanate physical properties
Fire-relevant values first — flash point and explosion limits decide the storage and ventilation regime.
Flash point
218.3 °C
Source: CAMEO Chemicals (NOAA, public domain); per-value source references stored in the database.
§ 10 · Stability and reactivity
Reactive group (CAMEO/NOAA): Isocyanates and Isothiocyanates. Our database documents 32 incompatible and 17 caution reaction-partner groups for methylene diphenyl diisocyanate — including which combinations release gas on contact. See the per-partner breakdown with gas release →
32
Incompatible
17
Caution
§ 13 · Disposal considerations
Dispose of waste and residues in accordance with local and national regulations — in the EU under the Waste Framework Directive 2008/98/EC. Never discharge to drains or municipal waste; hand contaminated packaging and unused product to an authorised waste-disposal company. The supplier's SDS section 13 lists the applicable waste codes for the specific product.
§ 14 · Transport information
Methylene diphenyl diisocyanate road transport — ADR 2025
UN number
Class · PG
6.1 · II / III
Classification code
T1
Transport category
2
ADR labels
6.1
2 ADR entries under UN 2206
PG II ISOCYANATES, TOXIC, N.O.S. or ISOCYANATE SOLUTION, TOXIC, N.O.S.
PG III ISOCYANATES, TOXIC, N.O.S. or ISOCYANATE SOLUTION, TOXIC, N.O.S.
Hazard ID (Kemler) / UN plate
Top: hazard identification number (Kemler). Bottom: UN number — as carried on the orange plate of the transport unit.
Source: UN ADR 2025 (ECE/TRANS/352), Table A. Road (ADR) only — for sea (IMDG) and air (IATA), consult the supplier's SDS §14.
MSDS vs SDS
Methylene diphenyl diisocyanate MSDS vs SDS: is there a difference?
MSDS (Material Safety Data Sheet) is the older name for the same document. In the US, OSHA's Hazard Communication Standard (2012) adopted the GHS-standardised 16-section Safety Data Sheet; in the EU the format is set by REACH Annex II. So a "methylene diphenyl diisocyanate MSDS" and a "methylene diphenyl diisocyanate SDS" refer to the same document — today it is issued as an SDS. Full breakdown of the differences →
Compliance hub
From classification to SDS
The classification above corresponds to Section 2 of a Safety Data Sheet. Learn how a compliant 16-section SDS is structured and authored →
GHS label maker
Build the label for methylene diphenyl diisocyanate
Pictograms, signal word and H-statements combined into a compliant label layout →
§ 16 · Sources
- Classification: Regulation (EC) No 1272/2008 (CLP), Annex VI
- Transport: UN ADR 2025 (UNECE), Table A
- Reactivity: NOAA CAMEO Chemicals reactive-group matrix (public domain)
- Physical properties: CAMEO Chemicals (NOAA, public domain) — per-value source references stored in the database
- Emergency response (§4–§6): ERG 2024 (PHMSA) · NIOSH Pocket Guide (CDC) · CHRIS (USCG) · NTP · EPA — via CAMEO Chemicals (NOAA), all US federal public domain, reproduced verbatim
- Substance data: PubChem · ECHA
Reference aid only. This page summarises the harmonised EU classification and computed storage guidance — it is not a Safety Data Sheet and does not replace one. Always verify hazards, handling and storage against the supplier's SDS (sections 7 and 10) and local regulations before use. Page updated 2026-08-11.
Frequently asked questions about methylene diphenyl diisocyanate
Is an MSDS the same as an SDS?
In practice, yes. MSDS (Material Safety Data Sheet) is the older name for the same document. In the US, OSHA's Hazard Communication Standard (2012) adopted the GHS-standardised 16-section Safety Data Sheet; in the EU the SDS format is set by REACH Annex II. A document you find labelled "methylene diphenyl diisocyanate MSDS" is today issued as an SDS.
What GHS pictograms does methylene diphenyl diisocyanate require?
Under the harmonised EU classification (CLP Annex VI), methylene diphenyl diisocyanate carries GHS07 and GHS08 with the signal word "Danger". Hazard statements: H351, H332, H335, H373, H315, H319, H334, H317. A supplier's SDS may add self-classified hazards on top of this harmonised minimum.
Where can I download an official methylene diphenyl diisocyanate SDS PDF?
From your own supplier — an SDS is issued per product and supplier, so the correct PDF for an inspection is the one matching the product you actually purchased. The supplier links on this page lead to the official SDS libraries of major distributors.
Call emergency services first
112 in the EU · 911 in the US. This screen is published response information, not medical advice, and it does not replace emergency services, a poison centre or the supplier's safety data sheet.
Text below is the CAMEO Chemicals entry DIPHENYLMETHANE-4,4'-DIISOCYANATE — confirm it matches the form in front of you.
01 · First aid
What to do for the person
EYES
First check the victim for contact lenses and remove if present. Flush victim's eyes with water or normal saline solution for 20 to 30 minutes while simultaneously calling a hospital or poison control center. Do not put any ointments, oils, or medication in the victim's eyes without specific instructions from a physician. IMMEDIATELY transport the victim after flushing eyes to a hospital even if no symptoms (such as redness or irritation) develop.
SKIN
IMMEDIATELY flood affected skin with water while removing and isolating all contaminated clothing. Gently wash all affected skin areas thoroughly with soap and water. IMMEDIATELY call a hospital or poison control center even if no symptoms (such as redness or irritation) develop. IMMEDIATELY transport the victim to a hospital for treatment after washing the affected areas.
INHALATION
IMMEDIATELY leave the contaminated area; take deep breaths of fresh air. IMMEDIATELY call a physician and be prepared to transport the victim to a hospital even if no symptoms (such as wheezing, coughing, shortness of breath, or burning in the mouth, throat, or chest) develop. Provide proper respiratory protection to rescuers entering an unknown atmosphere. Whenever possible, Self-Contained Breathing Apparatus (SCBA) should be used; if not available, use a level of protection greater than or equal to that advised under Protective Clothing.
INGESTION
If the victim is conscious and not convulsing, give 1 or 2 glasses of water to dilute the chemical and IMMEDIATELY call a hospital or poison control center. Generally, the induction of vomiting is NOT recommended outside of a physician's care due to the risk of aspirating the chemical into the victim's lungs. However, if the victim is conscious and not convulsing and if medical help is not readily available, consider the risk of inducing vomiting because of the high toxicity of the chemical ingested. Ipecac syrup or salt water may be used in such an emergency. IMMEDIATELY transport the victim to a hospital. If the victim is convulsing or unconscious, do not give anything by mouth, ensure that the victim's airway is open and lay the victim on his/her side with the head lower than the body. DO NOT INDUCE VOMITING. IMMEDIATELY transport the victim to a hospital.
02 · Fire
Extinguishing and tactics
Fire and explosion hazard
Special Hazards of Combustion Products: Toxic vapors are generated when heated.
Behavior in Fire: Solid melts and burns
Extinguishing media and tactics
Note: Most foams will react with the material and release corrosive/toxic gases. CAUTION: For Acetyl bromide (UN1716), use CO2 or dry chemical only.
SMALL FIRECO2, dry chemical, dry sand, alcohol-resistant foam.
LARGE FIREWater spray, fog or alcohol-resistant foam. FOR CHLOROSILANES, DO NOT USE WATER; use alcohol-resistant foam. If it can be done safely, move undamaged containers away from the area around the fire. Avoid aiming straight or solid streams directly onto the product.
FIRE INVOLVING TANKS, RAIL TANK CARS OR HIGHWAY TANKSFight fire from maximum distance or use unmanned master stream devices or monitor nozzles. Do not get water inside containers. Cool containers with flooding quantities of water until well after fire is out. Withdraw immediately in case of rising sound from venting safety devices or discoloration of tank. ALWAYS stay away from tanks in direct contact with flames.
03 · Spill
Containment, isolation, evacuation
Containment and clean-up
ELIMINATE all ignition sources (no smoking, flares, sparks or flames) from immediate area. All equipment used when handling the product must be grounded. Do not touch damaged containers or spilled material unless wearing appropriate protective clothing. Stop leak if you can do it without risk. A vapor-suppressing foam may be used to reduce vapors. FOR CHLOROSILANES, use alcohol-resistant foam to reduce vapors. DO NOT GET WATER on spilled substance or inside containers. Use water spray to reduce vapors or divert vapor cloud drift. Avoid allowing water runoff to contact spilled material. Prevent entry into waterways, sewers, basements or confined areas.
SMALL SPILLCover with DRY earth, DRY sand or other non-combustible material followed with plastic sheet to minimize spreading or contact with rain. Use clean, non-sparking tools to collect material and place it into loosely covered plastic containers for later disposal.
Initial isolation and evacuation
IMMEDIATE PRECAUTIONARY MEASUREIsolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids.
SPILLIncrease the immediate precautionary measure distance, in the downwind direction, as necessary.
FIREIf tank, rail tank car or highway tank is involved in a fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consider initial evacuation for 800 meters (1/2 mile) in all directions.
Sources: ERG 2024 (PHMSA) · NIOSH Pocket Guide (CDC) · CHRIS (USCG) · NTP · EPA — via CAMEO Chemicals (NOAA), public domain. Text reproduced verbatim.