METHYLENE DIPHENYL DIISOCYANATE

4,4'-methylene diphenyl diisocyanate
4,4'-methylene diphenyl diisocyanate 4,4'-methylene diphenyl diisocyanate
General
Systematic name	1-isocyanato-4- [(4-isocyanatophenyl)methyl] benzene
Other names	Pure MDI 4,4'-methylene diphenyl diisocyanate 4,4'-diphenylmethane diisocyanate
Molecular formula	C15H10N2O2
SMILES	O=C=NC(C=C2)=CC=C2C C1=CC=C(N=C=O)C=C1
Molar mass	250.25 g/mol
Appearance	white or pale yellow solid
CAS number	[101-68-8]
Properties
Density and phase	1.230 g/cm3, solid
Solubility in water	Reacts
in octane, benzene kerosene	soluble
Melting point	40 °C (313 K)
Boiling point	314 °C (587 K)
Hazards
MSDS	External MSDS
EU classification	Harmful ('Xn')
NFPA 704
R-phrases	, ,
S-phrases	, , ,
Flash point	212–214 °C (Cleveland open cup)
RTECS number	NQ9350000
Supplementary data page
Structure & properties	''n'', ''εr'', etc.
Thermodynamic data	Phase behaviour Solid, liquid, gas
Spectral data	UV, IR, NMR, MS
Related compounds
Related Isocyanates	Toluene diisocyanate Naphthalene diisocyanate
Related compounds	Polyurethane
Except where noted otherwise, data are given for materials in their standard state (at 25°C, 100 kPa)

'Methylene diphenyl diisocyanate', most often abbreviated as 'MDI', is an aromatic diisocyanate. It exists in three isomers, '2,2'-MDI', '2,4'-MDI', and '4,4'-MDI'. The 4,4' isomer is most practically useful, and is also known as 'Pure MDI'. MDI is reacted with a polyol in the manufacture of polyurethane. It is the most produced diisocyanate, accounting for 61.3 % of the global market in the year 2000.^[1]

Contents

Synthesis

Chemistry

Production

Uses

Safety

See also

References

External links

Synthesis

There are six steps to the manufacture of pure 4,4'-MDI:¹

★ ''Nitration:'' Reaction of benzene with nitric acid and a catalyst, to form nitrobenzene

★ ''Hydrogenation:'' Reaction of the nitrobenzene with hydrogen and a catalyst, to form aniline

★ ''Aniline/Formaldehyde condensation:'' Reaction of the aniline with formaldehyde and a catalyst, to form methylene dianiline (MDA), also known as diaminodiphenylmethane (DADPM)

★ ''Phosgenation:'' Reaction of the MDA/DADPM with phosgene, to form an MDI mixture

★ ''Separation:'' Distillation of the MDI mixture to form 'Polymeric MDI' (a mixture of oligomeric polyisocyanates) and a MDI isomer mixture which has a low 2,4' isomer content

★ ''Purification:'' Fractionation of the MDI isomer mixture to form pure 4,4'-MDI and an MDI isomer mixture which has a high 2,4' isomer content

Chemistry

The positions of the isocyanate groups influences their reactivities. 4,4'-MDI is a symmetrical molecule and thus has two groups of equal reactivity. 2,4'-MDI is an asymmetrical molecule and thus has two groups of different reactivities. The group at the 4-position is approximately four times more reactive than the group at the 2-position.¹

Production

Major producers include Bayer, Dow, Huntsman, Elastogran, Repsol, Shell Chemicals, and Tosoh. Total world production of MDI and polymeric MDI is over 2 million tonnes per year (Mt/a).

Uses

4,4'-MDI has one major application, that is the production of rigid polyurethane. Typically, one tonne of polyurethane foam needs 0.616 tonne of MDI and 0.386 tonne of polyol, with 0.054 tonne pentane as a blowing agent. 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.

Safety

MDI is the least hazardous of the commonly available isocyanates, as it has a very low vapour pressure. This 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. MDI should be not be heated or sprayed except with strict engineering controls and personal protective equipment. It has low human toxicity. It is a reactive material and reacts with hydrogen donors, in some cases violently. Its reaction with water produces carbon dioxide which can burst containers and produce aerosols. Since it polymerizes in the presence of water, its ecological risks are low.

See also

★ Toluene diisocyanate

★ Hexamethylene diisocyanate

★ Isophorone diisocyanate

References

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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)

★ Hazards of TDI, MDI, and HDI

★ Isofact American Chemistry Council Diisocyanates Panel

★ Azom Chemical database on Polyurethane chemistry