Polyurethane-urea substitution reactions

Industrially, polyurethane flexible foam manufacturers combine a version of the carbamate-forming reaction and the amine—isocyanate reaction to provide both density reduction and elastic modulus increases. The overall scheme involves the reaction of one mole of water with one mole of isocyanate to produce a carbamic acid intermediate. The carbamic acid intermediate spontaneously loses carbon dioxide to yield a primary amine which reacts with a second mole of isocyanate to yield a substituted urea. 

Step-growth polymerization is a very important method for the preparation of some of the most important engineering and specialty polymers. Polymers such as polyamides [7], poly(ethylene terephthalate) [8], polycarbonates [9], polyurethanes [10], polysiloxanes [11], polyimides [12], phenol polymers and resins, urea, and melamine-formaldehyde polymers can be obtained by step-growth polymerization through different types of reactions such as esterification, polyamidation, formylation, substitution, and hydrolysis. A detailed list of reaction types is shown in Table 3.2. 

The contribution which the different types of polar groups make to the properties of polyurethane elastomers depends in part upon their ability to enter into strong hydrogen-bonded associations. The substituted urea linkage, formed by the reaction of an isocyanate with an amine, is regarded as exceptional in its contribution to the physical properties, and it is therefore a preferred component in many bulk elastomers where the structural irregularity introduced by the use of a non-symmetrical diisocyanate or polyol is compensated by the strong urea interactions. 

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