Phenol-formaldehyde resin adhesives

The synthesis in 1912 of phenol—formaldehyde resins by Baekeland, which forms the basis of many modern day adhesives. 

Amino and Phenolic Resins. The largest use of formaldehyde is in the manufacture of urea—formaldehyde, phenol—formaldehyde, and melamine—formaldehyde resins, accounting for over one-half (51%) of the total demand (115). These resins find use as adhesives for binding wood products that comprise particle board, fiber board, and plywood. Plywood is the largest market for phenol—formaldehyde resins particle board is the largest for urea—formaldehyde resins. Under certain conditions, urea—formaldehyde resins may release formaldehyde that has been alleged to create health or environmental problems (see Amino RESINS AND PLASTICS). 

Woodflour, a fine sawdust preferably obtained from softwoods such as pine, spruce and poplar, is the most commonly used filler. Somewhat fibrous in nature, it is not only an effective diluent for the resin to reduce exotheim and shrinkage, but it is also cheap and improves the impact strength of the mouldings. There is a good adhesion between phenol-formaldehyde resin and the woodflour and it is possible that some chemical bonding may occur. 

Tackifiers. Resins are generally added to adjust the desired tack. In general, resins must be used with plasticizers to obtain a good balance between tack and cohesive strength. Typical tackifiers are polyterpenes, although hydrocarbon resins and modified rosins and rosin esters can also be used. In some cases, terpene-phenolics or phenol-formaldehyde resins are added to increase adhesion. 

Nitrile rubber is compatible with phenol-formaldehyde resins, resorcinol-formaldehyde resins, vinyl chloride resins, alkyd resins, coumarone-indene resins, chlorinated rubber, epoxies and other resins, forming compositions which can be cured providing excellent adhesives of high strength, high oil resistance and high resilience. On the other hand, NBR adhesives are compatible with polar adherends such as fibres, textiles, paper and wood. Specific formulations of NBR adhesives can be found in [12]. 

Phenolics are also used in a variety of other applications such as adhesives, paints, laminates for building, automobile parts, and ion exchange resins. Global production of phenol-formaldehyde resins exceeded 5 billion pounds in 1997. 

The route to crosslinked phenol-formaldehyde resins via resoles corresponds to that used by Baekeland in his original commercial technique. They now tend to be used for adhesives, binders, and laminates. The resole... 

Phenol—formaldehyde resins, 10 408—409 Phenol—formaldehyde reactions, 18 760 Phenolic acetates, 20 45 Phenolic adhesives, 1 543—544 Phenolic antioxidants, 10 806... 

The two major uses of phenol in 1995 were the production of bisphenol-A (35%) and the production of phenolic resins (34%) (CMR 1996). The largest use for bisphenol-A is as an intermediate in the production of epoxy resins (Thurman 1982). Phenol-formaldehyde resins comprise over 95% of this market (Thurman 1982). The plywood adhesive industry required 26% of the total production of phenolic resins in 1977. These low-cost, versatile, thermoset resins have other major uses in the construction, automotive, and appliance industries (Thurman 1982). 

Recent work has concentrated on the use of ALCELL lignin as a substitute for phenol-formaldehyde resins in wood adhesives, particularly wafer-board. Some of the results obtained when a PF resin (Bakelite 9111) was replaced with different levels of hardwood ALCELL lignin in waferboard manufacture will be briefly discussed below. Table III shows the conditions used for waferboard manufacture. 

In the April, 1975, issue of Plywood Panel magazine, we find reported square feet, quarter inch basis, domestic hardwood plywood manufactured in this country was approximately 3.5 billion and softwood plywood was 27.5 billion. This means 89 percent of the total plywood produced was softwood plywood, and 97 percent of this production was glued with phenol-formaldehyde resin adhesives, according to the American Plywood Association. This leaves 11 percent domestic hardwood plywood which was 95 percent glued with urea-formaldehyde resin adhesives,... 

In this solution, the volume of phenol-formaldehyde resin exceeds 1,250 million pounds per year. Most plywood adhesive resins are shipped in bulk quantities of 4,000 to 10,000 gallons via tankwagon or tankcar to the plywood mills and stored in storage tanks. Other ingredients are collected in a glue mix area and combined with adhesive resin. 

Phenol-formaldehyde resins find numerous applications in such areas as wood composites, fiber bonding, laminates, foundry resins, abrasives, friction and molding materials, coatings and adhesives, and flame retardants (JL). From a specialty chemicals standpoint, they are also used as developer resins in carbonless papers (2.). Conventional methods of preparation involve condensation of a phenol with formaldehyde under either acidic (novolak) or basic (resole) conditions (2). Their typical molecular weight range is from 800-4000 daltons (D) and includes a wide variety of alkyl or aryl substituted phenols (A)- The... 

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. 

The phenol-formaldehyde resin used as a control adhesive was a commercial resin (control P) characterized previously (0). A second phenolic resin (control C), used once, is reported to have 40.1% nonvolatiles, a viscosity of 0.42 Pa-s, and a specific gravity of 1.180 at 25 °C. Its measured pH was 11. For use, it was mixed with 15% walnut shell flour. 

Poly(vinyl alcohol) is utilized as a component of starch-based adhesives.11121114 Other patents report the use of partially oxidized starch,1115 dextrins,1116 dextrins and urea,1117 borax,1118 boric acid,1119 and vinyl methyl ether-maleic acid copolymers.1120 Other patents indicate the use of poly (vinyl alcohol) with partially hydrolyzed poly(vinyl acetate),1121 nonhy-drolyzed poly(vinyl acetate),1122 and poly(vinyl chloride).1123 A few patents have reported such poly acrylic additives as poly (acrylic acid)1124 and its salts,1125 poly(acrylamide),1126 1127 A-methylacrylamide or poly(A-acryl-amide),1128 and polyethyleneimine.1129 Polystyrene has also been used,1130 as well as more complex copolymers such as a maleic acid monobutyl ester-methyl vinyl ether copolymer, together with dextrin and polyacrylamide),1131 carboxylated ethyl acrylate-styrene zinc salt copolymer,1132 ethylene-methyl acrylate-vinyl acetate copolymer,1133 vinyl acetate-vinyl pyr-rolidone copolymer,1134 and ethylene-vinyl acetate copolymer.1135 Some adhesives are compounded with SBR latex1136 1138 and phenol-formaldehyde resins.1139... 

Himmelblau D.A. (1996) Phenol-Formaldehyde Resin Substitutes from Biomass Tars. In Wood Adhesives 1995, Forest Products Society, Madison, WI. 

In contrast to the linear thermoplastic polymers, which are soluble and fusible, the cross-linked network polymers are insoluble and infusible. They are formed from polymerizing systems containing monomers or prepolymers with a functionality of three or more. A good example is the phenol-formaldehyde resin systems. The cross-linking reaction takes place in the bond under applied pressure and heat, and the whole adhesive bond might consist of only one super giant molecule. Such resins are, therefore, called thermosetting resins. 

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