ArticleInternational journal of molecular sciences2025
Kinetic and Mechanistic Study of Polycarbodiimide Formation from 4,4'-Methylenediphenyl Diisocyanate.
Article in International journal of molecular sciences, 2025. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.
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Abstract
In the polyurethane industry, catalytically generated carbodiimides can modify the properties of isocyanate and, thus, the resulting foams. In this work, a kinetic reaction study was carried out to investigate the formation of a simple, bifunctional carbodiimide from a widely used polyurethane raw material: 4,4'-methylenediphenyl diisocyanate (MDI). The experimental section outlines a catalytic process, using a 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO) catalyst in ortho-dichlorobenzene (ODCB) solvent, to model industrial circumstances. The reaction produces carbon dioxide, which was observed using gas volumetry at between 50 and 80 °C to obtain kinetic data. A detailed regression analysis with linear and novel nonlinear fits showed that the initial stage of the reaction is second-order, and the temperature dependence of the rate constant is k(T)=(3.4±3.8)‧106⋅e-7192±389T. However, the other isocyanate group of MDI reacts with new isocyanate groups and the reaction deviates from the second-order due to oligomer (polycarbodiimide) formation and other side reactions. A linearized Arrhenius equation was used to determine the activation energy of the reaction, which was
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