Biuret links

Calculated assuming all amine groups form urea links and all excess isocyanate reacts with urea links to form biuret links. 

The chemical reactions which occur during the formation of rigid foams correspond to those described for flexible foams. However, since water is generally absent (although a small amount may be added to the formulation in order to boost the volatilization of the halocarbon with the isocyanate-water exotherm), biuret links are not produced. 

HjN—amine—NH—CO—NH—prepolymer—NH—CO—NH—amine—N—CO—NH—etc. Portion of cured elastomer with biuret link... 

The water reaction evolves carbon dioxide and is to be avoided with solid elastomers but is important in the manufacture of foams. These reactions cause chain extension and by the formation of urea and urethane linkages they provide sites for cross-linking, since these groups can react with free isocyanate or terminal isocyanate groups to form biuret or allophanate linkages respectively (Figure 27.5). 

From these, prepolymers are prepared where the diisocyanates may be completely reacted as in the case of the urethane oils which resemble the oil-modified alkyds but have urethane (—NHCOO—) links in place of the ester (—COO—) links of the alkyds, or where one only of the isocyanate groups is combined, leaving the other to participate in crosslinking reactions. Such a reactive prepolymer is the biuret that may be prepared from hexamethylene diisocyanate, has the following structure ... 

With an excess isocyanate in the above systems, allophanate and biuret reactions take place (Eqs (2.25) and (2.26)), resulting in further cross-linking. When increased rigidity and high-temperature performance are desired, further crosslinking may be accomplished via isocyanurate formation (Eq. (2.29)). Base catalysts such as alkoxides, quaternary ammonium or phosphonium, etc., promote this reaction. Aromatic isocyanates give iso-cyanurates far more easily than aliphatic ones. 

Amines produce polyurethanes with better mechanical properties than when diols are used for curing. Amines produce polyurethanes with a lower temperature resistance than when diols are used. The use of catalysts has been found to direct the cross-linking reactions away from the biuret to the allophanate reactions. 

In the preparation of a prepolymer, every effort is made to prevent the formation of any unplanned branching such as biuret groups. The prepolymer is essentially linear except when some cross-link sites have been introduced by using a multifunctional isocyanate or triol. 

Some cross-linking takes place in the form of side reactions such as biuret and allophanate bonds. Deliberate introduction of covalent cross-linking can be carried out by the introduction of multifunctional agents (mainly triols) into either the prepolymer or chain extension system. 

A variety of polymeric subunits is used to make polyurethanes. These include polyesters and polyethers. The major interchain linkages are molecular forces such as hydrogen bonding and the London force. Depending on the type of chain extender and processing temperature, there also may be biuret or allophanate cross-links. 

Subsidiary chemical reactions can take place. The major of these is the formation of an allophanate cross-link, as illustrated in Figure 2.6. This reaction normally needs a temperature of between 120 and 140°C to take place. The presence of a urea group at 100°C can react with the isocyanate group to form a biuret linkage. This is shown in Figure 2.7. 

Other reactions which lead to branching and cross-linking are the formation of allophanate and biuret linkages. The allophanate linkages occurs when the hydrogen on the nitrogen atom of the urethane group reacts with an isocyanate ... 

Isocyanates also can react with each other to produce carbodiimides with the loss of carbon dioxide. This reaction requires high temperatures unless catalyzed by specific phosphorus compounds. Formation of carbodiimides normally is not an important cross-linking mechanism in polyurethane adhesives. However, carbodiimides are sold by Dow Chemicals (Ucarlnk ), Nisshinbo Industries (Carbodilite ), and Stahl USA (XR-2569). They have been recommended as water scavengers, crosslinkers, and stabilizers for carboxyl functional polyurethanes. The carbodiimide can react with water to give a urea, which still can react with additional isocyanate to produce a biuret. 

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