Modified phenolic adhesives applications

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 most widely used thermoplastic polymer is the ethylene—vinyl acetate copolymer, which is obtainable in a wide range of molecular weights as well as in a variety of compositions. Often flexibilizers or plasticizers are added in order to improve both the mechanical shock resistance and the thermal properties of the adhesive. Polybutenes, phthalates, and tricresyl phosphate have been used as plasticizers. Tackifying agents can also be added. Because hot-melt adhesives are frequendy ethylene-based, they are subject to oxidation if, as in a typical situation, the adhesive sits in an applicator for long periods before use. Thus, antioxidants such as hindered phenols are often used, as are fillers. Fillers are added to opacify or to modify the adhesive s flow characteristics, as well as to reduce cost. Wax is also a very important component. Wax alters surface characteristics by decreasing both the liquid adhesive s surface tension and its viscosity in the melt. Upon solidification, however, the wax acts to increase the strength of the adhesive. Both paraffin and microcrystalline wax are used (see Waxes). 

A variety of two component adhesives and sealants are currently available for applications requiring the ultimate in bonding and sealing efficiency and performance. Included among these conventional systems are epoxies, urethanes, polyesters, silicones, polysulfides and some modified phenolics and acrylics. Although their performance can be and usually is quite satisfactory, most are limited by pot life and fixturing requirements - and the need for thorough substrate treatment and cleanliness. 

A large number of commercially important condensation polymers are employed as homopolymers. These include those polymers that depend on crystallinity for their major applications, such as rylons and fiber-forming polyesters, and the bulk of such important thermosetting materials like phenolics and urea-formaldehyde resins. In many applications, condensation polymers are used as copolymers. For example, fast-setting phenolic adhesives are resorcinol-modified, while melamine has sometimes been incorporated into the urea-formaldehyde resin structure to enhance its stability. Copolyesters find application in a fairly broad spectrum of end uses. 

During World War II, synthetic rubber and resin-modified phenolics were used to bond aluminum sheets (available only in in. thickness at that time) into billets from which airplane propellers were carved, thus replacing laminated wood, which often shattered on impact with a bullet. Similar adhesives were used to bond rubber to metal in a variety of vibration-damping applications. The most successful widely known product of the new technology was the automotive bonded brake lining first introduced in 1947, and now regarded as a symbol of quality and integrity [12, p. 490]. 

The loose term renewable resources adhesives has been used to identify polymerie eom-pounds of natural, vegetable origin that have been modified and/or adapted to the same use as some classes of purely synthetic adhesives [1]. At present two classes of these adhesives exist one already extensively commercialized in the southern hemisphere and the other on the slow way to commercialization. These two types of resins are tannin-based adhesives [2] and lignin adhesives [3 ]. Both types are aimed primarily at substituting synthetic phenolic resins. In some aspects, such as performance, they closely mimic, or are even superior to, synthetic phenolic adhesives, while in others they behave in a vastly different manner from their synthetic counterparts. In this chapter we focus primarily on tannin-based adhesives because they have already been in extensive industrial use in the southern hemisphere, in certain fields of application, for the past 20 years. These adhesives are of some interest not only for their excellent performance in some applications but also for their mostly environmentally friendly composition. Lignin adhesives are treated briefly here and in detail in Chap. 28. 

Aqueous dispersions are used in fiber bonding, paper coating, friction and abrasive applications, and laminates and wood bonding. Phenolic dispersions improve the strength of latex-contact adhesive applications. Epoxy-modified phenolic dispersions are prepared by dispersion of the phenolic epoxy resin. The systems are used for baked primer applications and bonding requirements. Minimum baking conditions are 20 min at 150°C (26). 

CNSL is obtained as a by-product of the cashew nut industry, mainly containing anacardic acid 80.9%, cardol 10-15%, cardanol, and 2-methyl cardol (Fig. 10). CNSL occurs as a brown viscous fluid in the shell of cashewnut, a plantation product obtained from the cashew tree, Anacardium oxidentale (Bhunia, et al., 2000). CNSL is used in the manufacture of industrially important materials such as cement, primers, specialty coatings, p)aints, varnishes, adhesives, foundry core oils, automotive brake lining industry, laminating and rubber compounding resins, epoxy resins, and in the manufacture of anionic and non-ionic surface active agents. CNSL modified phenolic resins are suitable for many applications and perform improved corrosion and insulation resistance. 

Various types of polymeric modifiers have been researched as possible candidates to impart impact resistance of epoxy resins. Sometimes, properties other than impact resistance are to be modified. For example, for adhesive applications, the main focus is usually on improving shear and peel strength. In these cases, epoxies blended with elastomeric nitrile rubbers (Hycar CTBN, B.F. Goodrich), phenolics, nylons (soluble types such as DuPont Zytel-61), and pol5nirethanes are commonly used. For impact modification, there are several approaches, as discussed below. 

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. 

As discussed in the Introduction, in addition to hot-melt adhesives, one of the most important forms of adhesives for the future is the waterborne system. In general, an advantage of the waterborne system is that it is free from the solvent-pollution problem. For this reason, we shall describe several new waterborne systems in detail acrylics, modified ethylene-vinyl acetate, polyurethanes, phenolics, epoxies, isocyanates, and tackifiers. Applications of these systems range from PSA s contact adhesives, and laminating adhesives to wood adhesives. 

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