Phenol‐urea‐formaldehyde cocondensed resol resins: Their synthesis,curing kinetics,and network properties

Several phenol‐urea‐formaldehyde (PUF) cocondensed resol resins were synthesized by different procedures. The curing kinetics and network properties of these PUF resins were examined by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). A kinetic study indicated that the activation energy values of PUF resins are generally higher than those of phenol‐formaldehyde (PF) resins during curing processes, but the curing rates of PUF resins are faster than those of PF resins. The pH values of PUF systems have a significant influence on the rate constants, although they affect the activation energy very slightly. Moreover, the dependence of activation energy on the conversion showed that there are more individual reactions with different activation energies occurring during the curing processes in PUF resins than in PF resins. The decomposition of methylene ether bridges to form methylene bridges probably occurs at high temperature in PUF resins. DMTA data indicated that the network rigidity of PUF resins is slightly lower than that of PF resin. The gel point and T_{tan δ2} transition measured by DMTA were consistent with the kinetic results obtained from the DSC data, but they were also related to the physical and mechanical properties of the network, especially with regard to the T_{tan δ2} transition. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1929–1938, 2003