C-13-NMR STUDY OF ANOMALOUS LINKAGES IN POLYURETHANE

Several kinds of model compounds for anomalous linkages in polyurethanes (branching or crosslinking; allophanate and biuret) were prepared. The phenylisocyanate (PHI) based models were identified by IR and NMR. The C-13-NMR chemical shifts effects due to the anomalous linkages were determined. The 4,4'-diphenylmethane diisocyanate (MDI) based models were purified incompletely but the characteristic signals of the aromatic carbons were nevertheless found in their spectra. Two types of segmented polyurethane (SPU) were prepared and the anomalous linkages were investigated by C-13-NMR. The signals due to the allophanate (Al) and the triphenylbiuret (TB) linkages were observed in the spectra of the SPU prepared at high temperature (> 80-degrees-C) or prepolymer gels yielded by abnormal reaction. A small signal due to a phenyl carbon of biuret (Bi) linkage was observed even in a normally prepared SPU (polyetherurethane-urea). Employing the phenyl carbon signals was advantageous for the determination of anomalous linkages because of their larger intensities.