Methylene diphenyl

diisocyanate

Methylene diphenyl diisocyanate, most

often abbreviated as MDI, is an aromatic
diisocyanate. Three isomers are common,
varying by the positions of the isocyanate
groups around the rings: 2,2'-MDI, 2,4'-MDI,
and 4,4'-MDI. The 4,4' isomer is most
widely used, and is also known as 4,4'-
diphenylmethane diisocyanate.[3] This
isomer is also known as Pure MDI. MDI
reacts with polyols in the manufacture of
polyurethane. It is the most produced
diisocyanate, accounting for 61.3% of the
global market in the year 2000.[4]
 4,4'-Methylene diphenyl diisocyanate

Names

Preferred IUPAC name

1,1'-Methylenebis(4-isocyanatobenzene)

Other names
Bis(4-isocyanatophenyl)methane
1-Isocyanato-4-[(4-
isocyanatophenyl)methyl]benzene
4,4'-Methylene diphenyl diisocyanate
4,4'-Diphenylmethane diisocyanate
Bayer Desmodur 44
Methylene bis(4-phenyl isocyanate)
Pure MDI
 Identifiers
CAS Number 101-68-8  

3D model (JSmol) Interactive image

Interactive image

ChEBI CHEBI:53218  

ChemSpider 7289  

ECHA InfoCard 100.002.697

PubChem CID 7570

RTECS number NQ9350000

UNII B0LO6BBS8C  

CompTox Dashboard DTXSID7025180

(EPA)

InChI
InChI=1S/C15H10N2O2/c18-10-16-14-5-1-12(2-6-14)9-13-3-7-15(8-4-13)17-11-19/h1-8H,9H2 
Key: UPMLOUAZCHDJJD-UHFFFAOYSA-N 

SMILES
O=C=NC(C=C2)=CC=C2CC1=CC=C(N=C=O)C=C1
O=C=N\c1ccc(cc1)Cc2ccc(\N=C=O)cc2
Chemical formula Properties
C15H10N2O2

Molar mass 250.25 g/mol

Appearance White or pale yellow

solid

Density 1.230 g/cm3, solid

Melting point 40 °C (104 °F; 313 K)

Boiling point 314 °C (597 °F; 587 K)

Solubility in water Reacts

Vapor pressure 0.000005 mmHg

(20 °C)[1]

Hazards
EU classification (DSD) Harmful (Xn)
(outdated)

R-phrases (outdated) R20, R36/37/38, R42/43

S-phrases (outdated) (S1/2), S23, S36/37,

S45
Flash point 212–214 °C (Cleveland
open cup)

Lethal dose or concentration (LD, LC):

LD50 (median dose) 2200 mg/kg (mouse,
oral)[2]
LDLo (lowest 31,690 mg/kg (rat,
published)
oral)[2]

LC50 (median 369 mg/m3 (rat, 4 hr)

concentration)
380 mg/m3 (rat, 4 hr)
178 mg/m3 (rat)[2]

US health exposure limits (NIOSH):

PEL (Permissible) C 0.2 mg/m3 (0.02

ppm)[1]
REL (Recommended) TWA 0.05 mg/m3
(0.005 ppm) C
0.2 mg/m3
 (0.020 ppm) [10-
minute][1]3[1]
IDLH (Immediate 75 mg/m
danger)

Related compounds
Related Isocyanates Toluene diisocyanate
Naphthalene
diisocyanate
Hexamethylene
diisocyanate
Isophorone
diisocyanate

Related compounds Polyurethane

Except where otherwise noted, data are given for

materials in their standard state (at 25 °C [77 °F],
100 kPa).

 verify (what is   ?)

Infobox references
Production
Total world production of MDI and
polymeric MDI is over 7.5 million tonnes
per year (in 2017). The largest producer is
Wanhua Group followed closely by
Covestro.[5] Other major producers are
BASF, Dow, Huntsman, Tosoh, Kumho
Mitsui Chemicals. All major producers of
MDI are members of the International
Isocyanate Institute, whose aim is the
promotion of the safe handling of MDI and
TDI in the workplace, community and
environment.
The first step of the production of MDI is
the reaction of aniline and formaldehyde,
using hydrochloric acid as a catalyst to
produce a mixture of diamine precursors,
as well as their corresponding polyamines:

Then, these diamines are treated with

phosgene to form a mixture of
isocyanates, the isomer ratio being
determined by the isomeric composition
of the diamine.
Distillation of the mixture gives a mixture
of oligomeric polyisocyanates, known as
polymeric MDI, and a mixture of MDI
isomers which has a low 2,4' isomer
content. Further purification entails
fractionation of the MDI isomer mixture.[6]

Reactivity of the isocyanate

group
The positions of the isocyanate groups
influences their reactivity. In 4,4'-MDI, the
two isocyanate groups are equivalent but
in 2,4'-MDI the two groups display highly
differing reactivities. The group at the 4-
position is approximately four times more
reactive than the group at the 2-position
due to steric hindrance.[4]

Applications
The major application of 4,4'-MDI is the
production of rigid polyurethane.[7] These
rigid polyurethane foams are good thermal
insulators and used in nearly all freezers
and refrigerators worldwide, as well as
buildings. Typical polyols used are
polyethylene adipate (a polyester) and
poly(tetramethylene ether) glycol (a
polyether).

4,4'-MDI is also used as an industrial

strength adhesive, which is available to
end consumers as various high-strength
bottled glue preparations.[8]

Safety
MDI is the least hazardous of the
commonly available isocyanates but is not
benign.[9] Its very low vapour pressure
reduces its hazards during handling
compared to the other major isocyanates
(TDI, HDI). However, it, like the other
isocyanates, is an allergen and sensitizer.
Persons developing sensitivity to
isocyanates may have dangerous
systemic reactions to extremely small
exposures, including respiratory failure.
Handling MDI requires strict engineering
controls and personal protective
equipment.[10] Compared to other organic
cyanates, MDI has a relatively low human
toxicity. It is a potentially violently reactive
material towards water and other
nucleophiles.

References
1. NIOSH Pocket Guide to Chemical
Hazards. "#0413" . National Institute
 for Occupational Safety and Health
(NIOSH).
2. "Methylene bisphenyl isocyanate" .
Immediately Dangerous to Life and
Health Concentrations (IDLH).
National Institute for Occupational
Safety and Health (NIOSH).
3. Pubchem. "4,4'-Diphenylmethane
diisocyanate | C15H10N2O2 -
PubChem" .
pubchem.ncbi.nlm.nih.gov. Retrieved
2017-06-25.
4. Randall, D.; Lee, S. (2003). The
Polyurethanes Book. New York: Wiley.
ISBN 978-0-470-85041-1.
5. Gal, J. (2012-02-20). "To the Rescue".
ICIS Chemical Business.
6. Six, C.; Richter, F. "Isocyanates,
Organic". Ullmann's Encyclopedia of
Industrial Chemistry. Weinheim: Wiley-
VCH.
doi:10.1002/14356007.a14_611 .
7. Boustead, I. (2005). "Polyurethane
rigid foam" (PDF). Eco-Profiles of the
European Plastics Industry. Brussels:
PlasticsEurope. Archived from the
original (PDF) on 2013-09-25.
8. US patent 6884904 , Smith, A. K.;
Goddard, R. J.; Paulsen, E. J. L., "MDI-
based polyurethane prepolymer with
 low monomeric MDI content", issued
2005-04-26
9. Allport, D. C.; Gilbert, D. S.; Outterside,
S. M., eds. (2003). MDI and TDI: Safety,
Health and the Environment: A Source
Book and Practical Guide. Wiley.
ISBN 978-0-471-95812-3.
10. Almaguer, D.; et al. (September 2006).
"Preventing Asthma and Death from
MDI Exposure During Spray-on Truck
Bed Liner and Related Applications"
(PDF). NIOSH Alert. The National
Institute for Occupational Safety and
Health. DHHS (NIOSH) Publication No.
2006–149. Retrieved 2012-08-14.
External links
International Chemical Safety Card
0298
IARC Monograph: "4,4'-
Methylenediphenyl Diisocyanate"
NIOSH Safety and Health Topic:
Isocyanates , from the website of the
National Institute for Occupational
Safety and Health (NIOSH)
Isofact American Chemistry Council
Diisocyanates Panel
Azom Chemical database on
Polyurethane chemistry
MDI and the Environment - 2005
presentation by Center for the
 Polyurethanes Industry
International Isocyanate Institute
Concise International Chemical
Assessment Document 27

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