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Small amounts of fluorinated polyethers, and in particular a nonionic fluorinated polyether, can upgrade considerably the cold-water swelling and internal bond strength of wood particleboard bonded with urea–formaldehyde (UF) resins. The effect is maximized at an additive concentration of about 0.1 wt % with respect to the adhesive resin solid content. The effect of the fluorinated polyether appears to be greater with older UF resins, which have a more pronounced colloidal state. The mechanism appears to be somewhat related to the reduction of the interfacial tension of the resins, with improved substrate wetting leading to better adhesion. The addition of a fluorinated polyether well in advance of resin use further enhances the improvement. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007

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 ∞ of the zero-frequency viscosity, and by determining the point at which the value of tan δ 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 diffusion-controlled 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.

Good correspondence of the gel-time values obtained by two different methods, G′ = G″ and 1/η00, was observed for different types of natural and modified tannin extracts. The pH presents the predominant effect on both the activation energies and the gel times observed, while the proportion of a paraformaldehyde hardener has a much lesser effect on these parameters. The rate constants of the different phases of the reaction of polycondensation with formaldehyde, both before and after the gel point, were obtained for the six commercial tannin extracts tested. The viscoelastic properties of the different tannins/formaldehyde gels were measured. The gel stiffness S, relaxation coefficient n, and relaxation time λ were determined and their dependence on the proportion of the formaldehyde hardener, on the temperature, and on the type of tannin was determined. The gel stiffness S appears to be influenced considerably by the proportion of the formaldehyde hardener. Its value decreased as the percentage of the hardener increased: This was due to early network immobilization and the resulting lower level of crosslinking resulting from it. The influence on S of the temperature is not very pronounced. The relaxation coefficient n appears to depend mainly on the reactivity of the tannin used: The faster the reactivity, the higher was the value of n. This appears to be valid exclusively in tannin extracts where the colloidal state is still present, while it is not valid in extracts where the colloidal state was eliminated by, for example, solvent extraction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 864–871, 2002

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

TTT and CHT curing diagrams for tannin-based adhesives were built by thermomechanical analysis (TMA) by following the in situ hardening directly in a wood joint, and the curve trends observed were similar to those previously observed for synthetic polycondensation resins on lignocellulosic substrates. Of the parameters that most influence the relative position of vitrification and gel curves on the diagrams (i.e., where the influence has been quantified), chief among them is the reactivity of the tannin with formaldehyde and any factor influencing it: thus, the inherent higher reactivity of the A-ring of the tannin (such as in procyanidins versus prorobinetinidins) and the pH of the tannin solution. The percentage formaldehyde hardener has some influence in CHT diagrams, especially for the slower-reacting tannins, but practically no influence in TTT diagrams within the 4–10% formaldehyde range used. As in the case of synthetic polycondensation adhesive resins, regression equations relating the internal bond strength of a wood particleboard, prepared under controlled conditions, with the inverse of the minimum deflection, obtained by constant heating rate TMA of a wood joint during resin cure, have been obtained for the two types of tannins of lower reactivity (profisetinidins/prorobinetinidins) but not for the faster-reacting procyanidin and prodelphinidin tannins. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3220–3230, 2001

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. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 249–259, 2000