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The production of toluene diisocyanate (TDI) starts from toluene, which is converted in a continuous
process to a mixture of 2,4and 2,6-dinitrotoluene. This mixture is hydrogenated with hydrogen to
give 2,4- and 2,6toluenediamine(TDA).Thereactionwithphosgene is usually carried out in a
continuous process, using e.g., toluene, chlorobenzene, or 1,2dichlorobenzene as solvents, at 65–
180◦C and at excess pressure. In the course of this process hydrogen chloride (reaction product),
phosgene (excessreactant),andfinallythesolventaresuccessively separated. The end product TDI is
purified by distillation.
For the production of methylenediphenyl diisocyanate (MDI), aniline is used as the starting material.
It is condensed with formaldehyde to form a mixture of isomeric methylenediphenyldiamines
(MDA). The subsequent reaction of this amine mixture with phosgene is
similartothatdescribedaboveforTDI.Theend product is a mixture of isomeric MDI and various PMDI
types. Distillative purification is not carried out.
Aliphatic diisocyanates are important starting materials for polyurethanes used in coatings.
Monoisocyanates, such as isopropyl isocyanate, phenyl isocyanate, and chlorophenyl isocyanates,
are important intermediates in the manufacture of herbicides and insecticides.
Urea Azo Dyes. The treatment of aminoazo dyes with phosgene in aqueous solution to produce
symmetrical urea azo dyes, has been practiced since the end of the 19th century (→Azo Dyes, Chap.
4.1.6.).
Other Uses. Phosgene undergoes commercially important cyclization reactions with aminocarboxylic
acids, aminophenols, and diamines. Acid chlorides are often prepared by reaction of carboxylic acids
with phosgene (for suitable catalysts see [68]). Examples are the production of isophthaloyl
dichloride and terephthaloyl dichloride on the large industrial scale.
Phosgene disproportionates to form carbon tetrachloride and carbon dioxide at high temperatures
(→Chlorinated Hydrocarbons).