Methylene diphenyl diisocyanate

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4,4'-methylene diphenyl diisocyanate
4,4'-methylene diphenyl diisocyanate
IUPAC name 1-isocyanato-4-
[(4-isocyanatophenyl)methyl]
benzene
Other names Pure MDI
4,4'-methylene diphenyl
diisocyanate
4,4'-diphenylmethane
diisocyanate
Identifiers
CAS number [101-68-8]
RTECS number NQ9350000
SMILES O=C=NC(C=C2)=CC=C2C
C1=CC=C(N=C=O)C=C1
Properties
Molecular formula C15H10N2O2
Molar mass 250.25 g/mol
Appearance white or pale yellow solid
Density 1.230 g/cm3, solid
Melting point

40 °C (313 K)
Boiling point

314 °C (587 K)
Solubility in water Reacts
Hazards
EU classification Harmful (Xn)
R-phrases R20, R36/37/38, R42/43
S-phrases (S1/2), S23, S36/37, S45
Flash point 212–214 °C (Cleveland open cup)
Related compounds
Related Isocyanates Toluene diisocyanate
Naphthalene diisocyanate
Hexamethylene diisocyanate
Isophorone diisocyanate
Related compounds Polyurethane
Except where noted otherwise, data are given for
materials in their standard state
(at 25 °C, 100 kPa)
Infobox disclaimer and references

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

[edit] Production

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

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 an 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

[edit] 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]

MDI isomers and polymer


[edit] Applications

The major application of 4,4'-MDI 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.[citation needed] 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.[2]

[edit] 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.

[edit] References

  1. ^ a b c Randall, David; Lee, Steve (2002). The Polyurethanes Book. New York: Wiley. ISBN 0-470-85041-8. 
  2. ^ US6,884,904 (PDF version) (2005-04-26) Smith, Andrea Karen; Goddard, Richard Joseph; Paulsen, Evelyn Jennifer Lin MDI-based polyurethane prepolymer with low monomeric MDI content 

[edit] External links