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 di- or polyfunctional alcohols or amines (a copolymer). Figure 1b shows the structure of a TDI-based polyisocyanate. Prepolymers: Species possessing free isocyanate groups, prepared from the reaction of a polyol with an excess of di- or polyisocyanate (Figure 1c).5 Commercially available isocyanate products frequently contain prepolymers in lieu of more volatile isocyanate monomers.

CH3 N

C

O

N C O

Oligomeric Isocyanates (Oligomers): Relatively low molecular weight polyisocyanates. Intermediates: Species possessing free isocyanate groups, formed during use of an isocyanate product by partial reaction of the isocyanate species with a polyol. This discussion covers isocyanate-containing compounds, except monofunctional isocyanates, because monofunctional isocyanates have different industrial applications, such as the manufacture of pesticides, and have very different toxicities. 2. BACKGROUND The feature common to all diisocyanates (monomers) is the presence of two -N=C=O (isocyanate) functional groups attached to an aromatic or aliphatic parent compound. These compounds are widely used in surface coatings, polyurethane foams, adhesives, resins, elastomers, binders, and sealants. In general, the types of exposures encountered during the use of isocyanates (i.e., monomers, prepolymers, polyisocyanates, and oligomers) in the workplace are related to the vapor pressures of the individual compounds. The lower molecular weight isocyanates tend to volatilize at room temperature, creating a vapor inhalation hazard. Conversely, the higher molecular weight isocyanates do not readily volatilize at ambient temperatures, but are still an inhalation hazard if aerosolized or heated in the work environment. The latter is important since many reactions involving isocyanates are exothermic in nature, thus providing the heat for volatilization. As exposure limits decrease, the volatility of solid materials becomes an issue. To reduce the vapor hazards associated with the lower molecular weight diisocyanates, prepolymer and polyisocyanate forms of these diisocyanates were developed and have replaced the monomers in many product formulations. An example is the biuret of HDI, which consists of three molecules of HDI monomer joined together to form a higher molecular weight oligomer having similar characteristics to those found in the monomer. Also, many MDI product formulations consist of a combination of MDI monomer and a MDI-based polyisocyanate (such as polymethylene polyphenyl isocyanate). Many prepolymer and polyisocyanate formulations contain a small fraction (usually less than 1%) of unreacted monomer. Isocyanates exist in many different physical forms in the workplace. Not only are workers potentially exposed to the unreacted monomer, prepolymer, polyisocyanate, and/or oligomer species found in a given product formulation, they can also be exposed to partially reacted

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NIOSH Manual of Analytical Methods