Modified phenol-formaldehyde resins, wood

Xylose Modified Phenol-Formaldehyde Resins. Xylose (I) and byproducts streams containing xylose (e.g., wood prehydrolysates from the production of chemical pulps and waste liquors from the wet process for hardboard production) are readily available. Our previous experiments (2) showed that free reducing sugars are not acceptable modifiers for phenol-formaldehyde resins cured under basic conditions. 

Figure 4. Variation of the dry- and wet- (hatched) wood failures of modified phenol-formaldehyde resins. The moles of modifier were varied as indicated. The mole ratio of phenol to formaldehyde was 1 2.3. The wood failures of xylose- and prehydrolysate-modified resins were similar and were averaged.

In this study, up to about 50% of the phenol-formaldehyde was replaced with carbohydrates and the modified resins used to bond wood veneer panels. The carbohydrate modified resins were formulated and cured under neutral conditions. The resins bond wood with acceptable dry- and wet-shear strengths, and wood failures. Reducing as well as nonreducing carbohydrates can be used as modifiers. The carbohydrate modifiers are being incorporated into the resin via ether linkages between the hydroxyls of the carbohydrate and methylol groups in the phenol-formaldehyde resin. The resins formulated under neutral conditions are very light in color. 

In an earlier paper (2), we determined that carbohydrates could replace a significant portion of the phenol-formaldehyde resin used for bonding plywood veneer. Carbohydrates from renewable resources such as wood can replace up to 50% of the phenol and formaldehyde in resins formulated under basic conditions without significant loss of bond quality. Two-ply, Douglas-fir-veneer panels bonded with these carbohydrate-modified resins have shear strengths approximately equivalent to those for panels bonded with unmodified phenol-formaldehyde resin. 

Phenol-formaldehyde resins modified directly with reducing sugars successfully bond wood veneers at neutral conditions. The dry- and wet-shear strengths of two-ply panels bonded with xylose-modified resins are not adversely affected until the amount of xylose is increased to between 0.6 and 1.0 moles xylose per mole of phenol (Figure 2). However, even resin with 2 moles xylose per mole of... 

Particleboards Wood particles, shives of flax flakes, saw dust, bagasse, hemp, kenaf, jute, cereal straw, coconut coir, corn and cotton stalks, rice husks, vetiver roots, and other fiber sources Urea, melamine, phenol formaldehyde resin, isocyanate, resorcinol, vinyl polyacetate resins and natural polymers, tannins, protein, casein, soybeans, modified starch, lignin activated by enzymatic system polylactic and polyhydroxyhutyric acid... 

At one time urea-formaldehyde was used extensively in the manufacture of plywood but the product is today less important than heretofore. For this purpose a resin (typically U-F molar ratio 1 1.8)-hardener mixture is coated on to wood veneers which are plied together and pressed at 95-110°C under pressure at 200-800 Ibf/in (1.38-5.52 MPa). U-F resin-bonded plywood is suitable for indoor application but is generally unsuitable for outdoor work where phenol-formaldehyde, resorcinol-fonnaldehyde or melamine modified resins are more suitable. 

Modified Synthetic Adhesives. Phenol-formaldehyde (68) and urea-formaldehyde (69) are important synthetic adhesives. Phenol-formaldehyde adhesives (PF) find a variety of applications including bonded abrasives, foundry applications, fiber bonding, and wood bonding. Urea-formaldehyde adhesive resins (UF) are used generally to bond wood products. I will illustrate the modification of synthetic adhesives with carbohydrates using both these general types of adhesives. 

Fig. 2.22 Temperature dependence of oxygen index for various plastics 1 rigid PVC, can not be measured above 105 due to softening 2 asbestos-filled phenol/form-aldehyde moulding compound 3 epoxy-modified melamine moulding compound 4 phenol/ formaldehyde moulding compound filled with wood flour 5 glass fibre-filled epoxy resin moulding...

Phenolics Phenol and resorcinol formaldehyde adhesives cure by condensation polymerisation with the elimination of water, and therefore require high curing pressures. They are normally available as two-component systems consisting of a paste resin and a liquid hardener. Traditional uses include wood bonding and plywood fabrication, but nowadays phenolics, especially modified phenolics, are also used in structural bonding of metals and plastics. 

A wide range of adhesive types and chemistries are used to bond wood elements to one another (Table 2), but relatively few adhesive types are utilized to form the composites themselves. The vast majority of pressed-wood products use synthetic thermosetting adhesives. In North America the most important wood adhesives are the amino resins (qv), eg, urea-formaldehyde (UF) and melamine-formaldehyde (MF), which account for 60% by volume of adhesives used in wood composite products, followed by the phenolic resins (qv) eg, phenol-formaldehyde (PF) and resorcinol-formaldehyde (RF), which account for 32% of wood composite adhesives (12,13). The remaining 9% consists of cross-linked vinyl (X-PVAc) compounds, thermoplastic poly(vinyl acetates) (PVA), soy-modified casein, and polymeric diphenylmethylene diisocyanate (pMDI). Some products may use various combinations of these adhesives to balance cost with performance. 

S Modified phenoiics. Phenolic or phenol formaldehyde is also used as an adhesive for bonding wood. However, because of its brittle nature, this resin is unsuitable alone for more extensive adhesive applications. By modifying phenolic resin with various synthetic rubbers and thermoplastic materials, flexibility is greatly improved. The modified adhesive is well suited for structural bonding of many materials. 

Resorcinol-formaldehyde resins are cold-setting adhesives for wood structures. Urea-formaldehyde adhesives, commonly modified with melamine formaldehyde, are used in the production of plywood and in wood veneering for interior applications. Phenol-form-aldehyde and resorcinol-formaldehyde adhesive systems have the best heat and weather resistance. 

In order to establish control values for the adhesives formulated using tannins, the initial work was done with phenol-resorcinol-formaldehyde (PRF) or resorcinol-formaldehyde (RF) resins on both surfaces, but modified for the honeymoon principle. The PRF resin chosen for this work was Borden s resin LT-75 with Borden s hardener FM-260. The RF resin used for a comparison was Chembond s RF-900. These resins have been used for wood gluing in the United States for more than two decades, especially for the manufacture of structural laminated timbers. 

Natural options exist that might someday replace or supplement the synthetic resins listed previously. Tannins, which are natural phenols, can be modified and reacted with formaldehyde to produce a satisfactory resin. Resins have also been developed by acidifying spent sulfite liquor, generated when wood is pulped for paper. Wet process fibreboards frequently use the lignin inherent in the lignocellulosic as the resin [13]. 

Phenolic materials go back to the patents of Baekeland and are based upon the reaction of phenol and formaldehyde to yield a lower molecular weight resinous material that can be formulated with other resins and sometimes other curatives to yield a paste adhesive or a film adhesive. When phenol and formaldehyde are reacted in the presence of an acidic catalyst with an excess of phenol versus formaldehyde, they yield what are known as novolac resins. These materials are soluble in organic solvents and do not react further with themselves thus, they need to have a curative added. That curative is most often hexamethylene tetraamine. Another type of phenolic resin can be generated with an excess of formaldehyde and under basic conditions. These materials, known as resole phenolics, will react with themselves to yield a ftilly cured phenolic and thus must be stored frozen in order to limit this reaction. Thus, resole phenolics do not need an external CTOsslinker. Resole phenolics are widely used in the binding of paper products and the bonding of wood. Adhesives based upon these materials were brittle and could only be used to bond wood, where it is still widely used. A more widely usable adhesive was developed during World War II which modified the very brittle phenolic adhesive with poly(vinyl formal) resins. These materials were... 

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