4,4'-methylenediphenyldiisocyanate and 2,4'-diisocyanatodiphenylmethane and their oligomerisation reaction products with 2,2'-oxydiethanol, propane-1,2-diol and butane-1,3-diol

Hydrolysis

Description of key information

The test substance reacts with water to form predominantly solid, inert polyurea. Yakabe et al (1994) found that for loadings of 400 - 10,000 mg/L, and under heterogeneous conditions, a structural analogue had a half-life of ca. 20h at 25°C.

Key value for chemical safety assessment

Half-life for hydrolysis:

20 h

at the temperature of:

25 °C

Additional information

The test substance is covered by the category approach of methylenediphenyl diisocyanates (MDI). Hence, data of the category substances can be used to cover this endpoint. Yakabe et al (1994) found that for loadings of 400 - 10,000 mg/L, and under heterogeneous conditions, oligomeric MDI had a half-life of ca. 20h at 25°C when the disappearance rate was fitted to a zero-order kinetic model. However the rate constant increased approximately linearly with the nominal concentration of oligomeric MDI for all constituents. For the two-ring constituents the rate constant was found to be 0.5h^-1 for a loading of 1000 mg/L oligomeric MDI.

The findings in the Yakabe et al (1994) study concur with the generally accepted chemistry of hydrolysis of an isocyanate whereby the initially produced carbamate decarboxylates to amine which then reacts very readily with more isocyanate to produce a urea. For a diisocyanate of low solubility such as MDI, the reaction system is usually heterogenous and these reactions, leading to insoluble polyureas, occur in both organic and aqueous phases and at the interface, where in each case differing concentrations of reagents and intermediates lead to different product distributions. Under conditions typical of many types of environmental contact, i.e. with relatively poor dispersion of the denser isocyanate, the interfacial reaction leads to the formation of a solid crust encasing partially or unreacted material. This crust restricts ingress of water and egress of amine, and hence slows and modifies hydrolysis. An important consequence of general significance to all aquatic tests of MDI, is that, in reality, it is the breakdown products that are being studied and the technique used for introduction or dispersal of the substance can affect the physical form and composition of the product (although under all tested conditions the predominant products are solid, insoluble polyureas).