Wattle tannin-based adhesives

Problems and facts that in the author s personal experience arise in the industrial application of tannin-based adhesives for timber sometimes indicate lack of correspondence with laboratory practice and results. These are often problems related to unusual characteristics of the adhesive itself, or of its application technique, which could not be noticed during research under laboratory conditions, but the existence of which could easily jeopardize successful implementation of laboratory technology into industrial practice. Correcting the credibility gap between research focus and industrial usage is seen as a critical step toward market expansion for these new products. Important considerations are consistency of tannins, extracts and adhesives properties due to the natural raw material variability formulation in cold-setting adhesives and application conditions (such as wood moisture and adhesive-content or pressing time) in particleboard adhesives. These problems have been overcome in use of wattle tannin-based adhesives as shown by a visual comparison of tannin-, phenolic-, and melamine-bonded particleboards exposed to the weather for 15 years and the growing use of tannin-based adhesives in other countries. 

Figure 5. World production and use of wattle tannin-based adhesives.

Progress in the use of condensed tannins in adhesive formulations might be expected to be more rapid than is the case for lignins because of the impetus provided by the commercialization of wattle tannin-based adhesives and because of the extraordinarily high reactivity of tannins in reactions with formaldehyde. This reactivity offers an opportunity to substitute tannin for resorcinol (currently priced at about 1.80/lb) instead of phenol (about 0.40/lb). Now that wattle tannins have been successfully introduced, their application can be expected to continue to expand. The situation remains difficult, on the other hand, for use of conifer bark tannins in adhesives. Herb Hergert is certainly... 

Most of the recent efforts to develop uses for the condensed tannins have centered on their application in wood adhesives. Reviews by Pizzi (182, 186) and others (15, 78, 87, 93, 208) provide references to several hundred papers and patents on this subject. Despite world-wide research efforts on other sources of tannins, particularly since the 1972-1973 petroleum shortage, the mimosa or wattle tannins extracted from the bark of black wattle Acacia mearnsii) remain the major source of condensed tannins exploited commercially for adhesive manufacture. Of the approximately 100000 tons of wattle tannin produced annually, only about 10000 tons are used in wood adhesives, predominantly in South Africa but also in Australia and New Zealand (186). The extensive use of wattle tannins by the wood products industry of South Africa is impressive indeed, as these tannins have partly replaced phenol and resorcinol usage in adhesives for bonding of particleboard, plywood, and laminated timbers (182, 186, 213). Three factors have contributed to the success in use of wattle tannin-based adhesives, namely the comparatively high costs of phenol and resorcinol in the Southern Hemisphere, their resorcinolic functionality and low molecular weight and, perhaps most importantly, the commitment by the research and industrial communities of these countries to reduce the reliance of the forest products industry on petroleum-based adhesives. 

Table 10.3.1 Properties of exterior particleboards bonded with wattle tannin-based adhesives (136)...

Interest in use of condensed tannins as components of adhesive formulations began about three decades ago. While research studies have been carried out in widely scattered laboratories around the world, three major areas of activity can be distinguished. These are 1) development of bark extracts and commercial production facilities on the west coast of North America, 1953 to 1975 2) application of tannins in adhesive formulations in South Africa based on indigenously produced mimosa (wattle) tannin, early 1970 s to the present and 3) a resurgence of interest in pine bark as raw material for tannin-based adhesives, beginning in the middle 1970 s. Each of these activities has been characterized by parallel efforts on structural identification of the tannins and development of unique methods for incorporating the isolated tannins into adhesives. 

The development of wattle tannin-based plywood adhesives occurred concurrently with the particleboard adhesives and, although quite different adhesive properties are required to bond these two types of furnish, many of the basic premises on which their development were based are the same. A series of wattle tannin-based plywood adhesives that provide exterior bond qualities have been described in detail by Pizzi (182, 186). All recent formulations use low-molecular-weight polymers, as first suggested by MacLean and Gardner (131), rather than formaldehyde for crosslinking agents. 

Wattle tannin-based plywood adhesives were also crosslinked with 10% to 20% (by weight of solids) of either a phenol-formaldehyde resol or a phenol-resorcinol-formaldehyde polymer with approximately 20% resorcinol, to which paraformaldehyde was added to provide crosslinking between the resorcinol and... 

Wattle tannins have been used as fortifiers in starch-based adhesives for corrugated carton manufacture in order to improve the moisture resistance of boxes used in shipment of fruit, for example (144, 217). Addition of 4% wattle tannin based on resin solids substantially improved the durability of these cartons. Wattle tannin urethane-based varnishes with excellent durability have been developed by Saayman (214). Other adhesive applications based on reactions of wattle tannins with isocyanates have been developed for specialty applications such as the bonding of aluminum (181). 

Natural phenolic compounds are used as both replacements for substantial portions of synthetic phenol in plywood adhesive resins and as glue mix additives to improve performance 4 to 6% is added, based on phenolic resin solids. They bring about improvements in assembly time tolerance and flow with no significant change in adhesion. Glue mix additions of wattle tannin or other condensed flavonoid tannin extracts with or... 

The adhesive developed for the manufacture of damp-ply-resistant corrugated cardboard are based on the addition of spray-dried wattle extract, urea-formaldehyde resin, and formaldehyde to a typical Stein-Hall starch formula of 18 to 22% starch content [60,61]. The wattle tannin-urea-formaldehyde copolymer formed in situ, and any free... 

The best adhesive formulation for phloroglucinolic tannins, such as pine tannin extracts is, instead, a comparatively new and is also capable of giving excellent results when using resorcinol tannins such as a wattle tannin extract [68-71]. The adhesive gluemix consists only of a mix of an unmodified tannin extract 50 per cent solution to which paraformaldehyde and polymeric nonemulsifiable 4,4 -diphenylmethane diisocyanate (commercial pMDI) are added [68-71]. The proportion of tannin extract solids to pMDI can be as high as 70/30 w/w, but can be much lower in pMDI content. This adhesive is based on the peculiar mechanism by which the pMDI in water, is hardly deactivated to polyureas because it reacts faster with the hydroxymethyl groups of a formaldehyde-based resin, be it a tannin or another resin [69,71]. 

The adhesives developed for the manufacture of damp-ply-resistant corrugated cardboard are based on the addition of spray-dried wattle extract, urea-formaldehyde resin, and formaldehyde to a typical Stein-Hall starch formula with 18-22 per cent starch content [75, 76]. The wattle tannin-urea-formaldehyde copolymer formed in situ and any free formaldehyde left in the glue line are absorbed by the wattle tannin extract. The wattle extract powder should be added at level of 4—5 per cent of the total starch content of the mix (i.e. carrier plus slurry). Successful results can be achieved in the range of 2-12 per cent of the total starch content, but 4 per cent is the recommended starting level. The final level is determined by the degree of water hardness and desired bond quality. This wattle extract UF-fortifier system is highly flexible and can be adapted to damp-proof a multitude of basic starch formulations. 

A similar climate exists for development of adhesives from Pinus radiata bark in Australia and New Zealand. A 22 ton/day bark extraction plant was built by New Zealand Forest Products Ltd. at Kinleith, New Zealand. These extracts have proved to be more difficult to use than wattle tannin due to their comparatively high molecular weight, the high viscosity of most extract preparations, their rapid rate of reaction with formaldehyde, and the often higher proportion of carbohydrate impurities. Current information (L. J. Porter, 1987) is that production of tannin by New Zealand Forest Products Ltd. has now ceased. In an attempt to make more uniform extracts with lower proportions of carbohydrates, ultrafiltration (257, 258) fractionation on Amberlite XAD-B gel (239), and fermentation (220) purifications have been investigated. Various reactions such as sulfonation and either acid- or base-catalyzed cleavage have been employed to reduce the viscosity of these extracts. A number of adhesive formulations based on P radiata bark extracts have been developed. However, technical difficulties continue to inhibit the commercial use of Pinus radiata bark extracts in wood adhesives. 

In the use of spraying blenders, the following technique can be successfully applied. All the paraformaldehyde powder hardener and 30% of the tannin adhesive spray-dried powder is removed from the liquid glue mix. The paraformaldehyde and wattle adhesive powder are then added to the wood chips just before the adhesive blender where the liquid glue mix is sprayed onto the wood particles. Core material MCs of 10 to 12% and face material MCs of 20 to 22% can then easily be achieved in spite of the high viscosity of tannin solutions. The percentage of paraformaldehyde used should be 14% based on wattle extract solids. The adhesive pH should be, in optimal cases, 6.5 to 6.7 for face material and 6.9 to 7.3 for core material. The percentage of resin solids on dry wood should be 11% for core material and 14 to 18% for face material. 

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