Low‐condensation phenol‐formaldehyde (PF) resins coreacted under alkaline conditions with up to 42% molar urea on phenol during resin preparation yielded PUF resins capable of faster hardening times than equivalent pure PF resins prepared under identical conditions and presented better performance than the latter. The water resistance of the PUF resins prepared seemed comparable to pure PF resins when used as adhesives for wood particleboard. Part of the urea was found by 13C‐NMR to be copolymerized to yield the alkaline PUF resin; whereas, especially at the higher levels of urea addition, unreacted urea was still present in the resin. Increase of the initial formaldehyde to phenol molar ratio decreased considerably the proportion of unreacted urea and increased the proportion of PUF resin. A coreaction scheme of phenolic and aminoplastic methylol groups with reactive phenol and urea sites based on previous model compounds work has been proposed, copolymerized urea functioning as a prebranching molecule in the forming, hardened resin network. The PUF resins prepared were capable of further noticeable curing acceleration by addition of ester accelerators; namely, glycerol triacetate (triacetin), to reach gel times as fast as those characteristic of catalyzed aminoplastic resins, but at wet strength values characteristic of exterior PF resins. Synergy between the relative amounts of copolymerized urea and ester accelerator was very noticeable at the lower levels of the two parameters, but this effect decreased in intensity toward the higher percentages of urea and triacetin. 13C‐NMR assignements of the relevant peaks of the PUF resins are reported and compared with what has been reported in the literature for mixed, coreacted model compounds and pure PF and urea‐formaldehyde (UF) resins. The relative performance of the different PUF resins prepared was checked under different conditions by thermomechanical analysis (TMA) and by preparation of wood particleboard, and the capability of the accelerated PUF resins to achieve press times as fast as those of aminoplastic (UF and others) resins was confirmed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 359–378, 1999

ABSTRACT:Guanidine carbonate is shown to be an accelerator of phenol-formaldehyde (PF) resins that while yielding slightly slower gel times than triacetin when added to a PF resin glue mix, is also capable of giving glue-mix pot lives on the order of several days. Hence, this is long enough to be premixed with the resin long before use. Both triacetin and guanidine carbonate used as simple glue-mix additives are shown to increase the ultimate strength of the resin bond, whatever the length of the curing time used for the purpose. This is shown by thermomechanical analysis and the application to wood particleboard. Triacetin is shown to be usable during PF resin preparation rather than just being added to the glue mix, yielding better resins capable of giving higher bond values without a great acceleration of the geling of the resin itself. The mechanisms involved in the acceleration of PF resins introduced by both compounds appears to be based on facilitating reactions of crosslinking involving carbonic acid ions present in the resin solution.

Commercial, industrially produced mimosa, quebracho, pine, and pecan polyflavonoid tannin extracts water solutions of different concentrations were examined by rheometry by measuring dynamic moduli both as a function of strain amplitude and at varying frequency. The water solutions of these materials have been found to behave in general mainly as viscous liquids at the concentrations that are generally used for their main industrial applications. Clear indications of viscoelastic response are also noticeable, among these the crossover of the elastic and viscous moduli curves at the lower concentrations of the range investigated, with some differences being noticeable between each tannin and the others—pine and quebracho tannin extracts showing the more marked viscoelastic behavior. Other than pH dependence (and related structural considerations), the parameters found to be of interest as regards the noticeable viscoelastic behavior of the tannin extracts were the existence in the solutions of labile microstructures that can be broken by applied shear. This is supported by the well‐known thixotropic behavior of concentrated, commercial polyflavonoid tannin extracts water solutions. Such microstructures appear to be due (1) to the known colloidal interactions of these materials already reported, or (b) to other types of secondary interactions between tannin oligomers and particularly between tannin and carbohydrate oligomers. The latter is supported by the dependence of this effect from both the average molecular masses of the tannin and of the carbohydrate oligomers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1634–1642, 2001

ABSTRACT:The gelling and hardening reactions of different, commercial polyflavonoid tannin extracts of the prorobitenedin/profisetinidin, procyanidin, and prodelphinidin types with formaldehyde were studied by parallel-plate rheometry. To do this, methods to determine the rheological characteristics of tannin-formaldehyde polycondensation reactions both before and after the gel point were developed. The validity of some modifications of known methods was checked on the best-known commercial tannin extract, namely, the reaction of the mimosa tannin extract with 5% paraformaldehyde, over a range of different temperatures. The gel point was determined by three different methods, namely, by the crossover point of viscous and elastic moduli, by the extrapolation to ϱ of the zero-frequency viscosity, and by determining the point at which the value of tan ␦ is constant whatever frequency is used in the measurement. The results obtained were critically compared. The comparisons obtained were good and were reproducible when the first two methods were used, but not when the third one was used. This allowed the determination of the energy of activation at different stages in the tannin-aldehyde polycondensation reaction and the calculation of the degree of conversion of the tannin-aldehyde polycondensation before, at, and after the gel point. Mathematical expressions defining the degree of conversion for tannin-aldehyde reactions before, at, and after the gel point as a function of different moduli were developed and checked with the experimental data obtained. Methods and mathematical expressions for the determination of the rate constants of the different stages of the reaction were also developed and checked. After the gel point, the system was modeled using both a diffusioncontrolled model and a second-order kinetic law. The applied results obtained indicated that, although a certain element of diffusion control is present, a second order, diffusion-independent kinetic is more valid under the experimental conditions used. This indicates that the rheometry approach to a polycondensation network is limited mostly by the capability of the equipment to the region after the gel point, where diffusion control does not as yet play a predominant role.

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