Quantitative IR characterization of urea groups in waterborne polyurethanes

The purpose of this study is to propose a correlation between IR spectra and the urea fraction of waterborne polyurethanes (PUs) to investigate the side reaction, that is, isocyanate–water reaction, during polymerization. This method is based on the decomposition of the spectrum in amide I range, that is, 1600–1800 cm−1, where the bands of interest overlap. Several individual bands present in this region were resolved by employing Fourier self-deconvolution (FSD) and Gaussian curve-fitting techniques, and the intensity ratio of urethane's CO to urea's CO was determined. To realize some quantitative measurements, a calibration curve was established with some polyurethane-urea samples, characterized by 1H NMR, which were used as standards. The concentration ratios of urethane groups to urea groups were determined from 1H NMR. A good correlation was evidenced between IR and 1H NMR measurements. Moreover, waterborne PUs were prepared by miniemulsion polymerization of IPDI with diols. From quantitative IR analysis, it was shown that a vinylic monomer, as a solvent of polyaddition, restrained the isocyanate–water reaction, and this side reaction was influenced by the hydrophilicity of the vinylic monomers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2433–2444, 2008