<sup>13</sup>C CP/MAS NMR as a Direct Probe of the Wood-Phenol Formaldehyde Adhesive Bondline

Authors

  • Robert G. Schmidt
  • Charles E. Frazier

Keywords:

Phenol formaldehyde, adhesion, CP/MAS NMR, cure

Abstract

Resole phenol formaldehyde resin was synthesized using 13C labeled paraformaldehyde. Wood flake model composites were prepared with the labeled resin, cured for various times and temperatures, and then characterized by 13C CP/MAS NMR. The relative degrees of adhesive cure were determined from the corrected peak areas of the methylene and hydroxymethyl carbon signals. Similar cure information was provided by measuring rotating frame proton spin-lattice relaxation times. However, cure measurements via relaxation times were less sensitive because of the effects of spin diffusion within the cured resin. Relaxation measurements revealed that wood induces heterogeneity in cured PF, whereas neat-cured PF is normally more homogeneous. This method provides cure and morphological information for intact bondlines. The procedure is readily applicable to pilot or industrial scale manufacturing processes, allowing the direct evaluation of resin cure within a wood-based composite.

References

Fyfe, C. A. 1983. Solid state NMR for chemists. CFC Press., Guelph, Ontario, Canada. 336 pp.nMcBrierty, V. J., and D. C. Douglass. 1981. Recent advances in the NMR of solid polymers. J. Polymer Sci.: Macromolecular Rev. 16:295-366.nMehring, M. 1983. High resolution NMR spectroscopy in solids, 2nd ed. Springer-Verlag, Berlin, Germany. 286 pp.nParmer, J. F., L. C. Dickinson, J. C. W. Chien, and R. S. Porter. 1987. Polymer-polymer miscibility determination via CP/MAS NMR in blends of deuterated and protonated polymers. Macromolecules 20:2308-2310.nRammon, R. M., W. E. Johns., J. Magnuson, and A. K. Dunker. 1986. The chemical structure of UF resins. J. Adhesion 19:115-135.nSchaefer, J., E. O. Stejskal, T. R. Steger, M. D. Sefcik, and R. A. McKay. 1980. Carbon-13 T1p experiments on solid glassy polymers. Macromolecules 13:1121-1126.nSchmidt, R. G., and C. E. Frazier. 1997. Network characterization of phenol formaldehyde thermosetting wood adhesive. Int. J. Adhesion and Adhesives (in press).nSlichter, C. P., and D. Ailion. 1965. Lowfield relaxation and the study of ultraslow atomic motions by magnetic resonance. Phys. Rev. 135A:1099-1110.nTomita, B., and S. Hatono. 1978. Urea-formaldehyde resins. III. Constitutional characterization by 13C Fourier transform NMR spectroscopy. J. Polymer Sci.: Polymer Chem. Ed. 16:2509-2525.nWendler, S. L., and C. E. Frazier. 1996a. The effects of cure temperature and time on the isocyanate-wood adhesive bondline by 15N CP/MAS NMR. Int. J. Adhesion and Adhesives 16:179-186.nWendler, S. L., and C. E. Frazier. 1996b. Effect of moisture content on the isocyanate/wood adhesive bondline by 15N CP/MAS NMR. J. Appl. Polym. Sci. 61:775-782.nWerstler, D. D. 1981. Quantitative 13C NMR characterization of aqueous formaldehyde resins:2. Resorcinol-formaldehyde resins. Polymer 27:757-764.n

Downloads

Published

2007-06-19

Issue

Section

Research Contributions