Online monitoring of synthesis and curing of phenol–formaldehyde resol resins by Raman spectroscopy

Abstract

The synthesis and curing of phenol–formaldehyde resol resins were monitored online by Raman spectroscopy. The synthesis of the resins (F/P 2.0, alkalinity 4.5wt%) was studied at rising temperature (40–90°C) for 90min and at constant temperatures (80°C, 90°C, 100°C, and 110°C) for 120min. The progress of the curing was investigated isothermally (80°C, 90°C, 100°C, and 110°C) for 120min for three resins with different degrees of condensation. The synthesis and curing of the resins were started in the reactor and the advancement of the methylolation and condensation reactions was followed through the window of the reactor in the wave number region of 2000–400cm−1 with use of a fiber optic probe for the data collection. The Raman spectra of six model compounds (formaldehyde, phenol, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2-benzylphenol, and 4-benzylphenol) were analyzed to facilitate the interpretation of the spectra of the resins. The consumptions of free phenol and free formaldehyde, as well as the progress of the methylolation and condensation reactions were easily monitored by following the changes in intensity of the characteristic Raman bands. The results for the cured resins obtained by Raman spectroscopy were in good agreement with the structures and residual reactivities studied by CP/MAS 13C NMR spectroscopy and differential scanning calorimetry (DSC), respectively. The results of the study show Raman spectroscopy to be a promising tool for the online monitoring and control of phenol–formaldehyde resol resin synthesis and curing; in addition, Raman spectroscopy offers an effective and fast method for structural study of the solid state resins.