Isocyanates with two or more functional groups are required for the formation of polyurethane polymers. Volume wise, aromatic isocyanates account for the vast majority of global diisocyanate production. Aliphatic and cycloaliphatic isocyanates are also important building blocks for polyurethane materials, but in much smaller volumes. There are a number of reasons for this. First, the aromatically linked isocyanate group is much more reactive than the aliphatic one. Second, aromatic isocyanates are more economical to use. Aliphatic isocyanates are used only if special properties are required for the final product. For example, light stable coatings and elastomers can only be obtained with aliphatic isocyanates. Even within the same class of isocyanates, there is a significant difference in reactivity of the functional groups based on steric hindrance. In the case of 2,4-toluene diisocyanate, the isocyanate group in the para position to the methyl group is much more reactive than the isocyanate group in the ortho position.
Phosgenation of corresponding amines is the main technical process for the manufacture of isocyanates. The amine raw materials are generally manufactured by the hydrogenation of corresponding nitro compounds. For example, toluenediamine (TDA) is manufactured from dinitrotoluene, which then converted to toluene diisocyanate (TDI). Diamino diphenylmethane or methylenedianiline (MDA) is manufactured from nitrobenzene via aniline, which is then converted to diphenylmethane diisocyanate (MDI).
The two most important aromatic isocyanates are toluene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI). TDI consists of a mixture of the 2,4- and 2,6-diisocyanatotoluene isomers. The most important product is TDI-80 (TD-80), consisting of 80% of the 2,4-isomer and 20% of the 2,6-isomer. This blend is used extensively in the manufacture of polyurethane flexible slabstock and molded foam.12 TDI, and especially crude TDI and TDI/MDI blends can be used in rigid foam applications, but have been supplanted by polymeric MDI. TDI-polyether and TDI-polyester prepolymers are used in high performance coating and elastomer applications. Prepolymers are available that have been vacuum stripped of TDI monomer, which greatly reduces their toxicity. Diphenylmethane diisocyanate (MDI) has three isomers, 4,4'-MDI, 2,4'-MDI, and 2,2'-MDI, and is also polymerized to provide oligomers of functionality three and higher.
Only the 4,4'-MDI monomer is sold commercially as a single isomer. It is provided either as a frozen solid or flake, or in molten form, and is used to manufacture high performance prepolymers. Monomer blends, consisting of approximately 50% of the 4,4'-isomer and 50% of the 2,4'-isomer, are liquid at room temperature and are used to manufacture prepolymers for polyurea spray elastomer applications. 4,4'-MDI blends containing MDI uretonimine, carbodiimide, and allophonate moieties are also liquid at room temperature, and are used in the manufacture of integral skin and microcellular foams. 4,4'-MDI-glycol prepolymers offer increased mechanical properties in the same applications, but are prone to freezing at temperatures below 20�C. Polymeric MDI (PMDI) is used in rigid pour-in-place, spray foam, and molded foam applications. Polymeric MDI that contains a very high portion of high-functionality oligomers is used to manufacture polyurethane and polyisocyanurate rigid insulation boardstock. Modified PMDI, which contains high levels of MDI monomer, is used in the production of polyurethane flexible molded and microcellular foam. The relative percentage of the 4,4'- and 2,4'- isomers is adjusted to change the reactivity and storage stability of the isocyanate blend, as well as the firmness and other physical properties of the finished goods. Other aromatic isocyanate include p-phenylene diisocyante (PPDI), naphthalene diisocyanate (NDI), and o-tolidine diisocyanate (TODI).
The most important aliphatic and cycloaliphatic isocyanates are 1,6-hexamethylene diisocyanate (HDI), 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate, IPDI), and 4,4'-diisocyanato dicyclohexylmethane (H12MDI). They are used to produce light stable, non-yellowing polyurethane coatings and elastomers. Because of their toxicity, aliphatic isocyanate monomers are converted into prepolymers, biurets, dimers, and trimers for commercial use. HDI adducts are used extensively for weather and abrasion resistant coatings and lacquers. IPDI is used in the manufacture of coatings, elastomeric adhesives and sealants. H12MDI prepolymers are used to produce high performance coatings and elastomers with optical clarity and hydrolysis resistance. Other aliphatic isocyanates include cyclohexane diisocyanate (CHDI), tetramethylxylene diisocyanate (TMXDI), and 1,3-bis(isocyanatomethyl)cyclohexane (H6XDI).
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