Adhesives thermoplastic types

Polyamide Resins. Another class of polyamide resins, in addition to the Hquid resins used as epoxy hardeners, are the thermoplastic type, prepared generaHy by the condensation reaction of polyamines with polybasic fatty acids. These resins find use in certain hot-melt adhesives, coatings, and inks. Diamines, typicaHy EDA (233), are the principal amine reactant however, tri- and tetramines are sometimes used at low levels to achieve specific performance. 

Figure 6. Adhesion at the rubber-resin interface in the rubber-reinforced thermoplastics, type III (assuming that most of the grafting takes place on the surface of latex particles)...

Nylons are synthetic thermoplastic polyamides of relatively high molecular weight that have been used as the basis for several types of adhesive systems. They are used as solution adhesives, as hot-melt adhesives, and as components of other adhesive-alloy types (nylon-epoxy and phenolic-nylon). The high-molecular-weight products are generally referred to as modified nylons. Low- and intermediate-molecular-weight materials are also available. The latter two are more commonly used in hot-melt formulations and the modified nylons are often blended with small amounts of a phenolic resin to improve surface wetting (hence nylon-phenolic). 

The general formula of an emulsified polyurethane or aqueous dispersion used for adhesive purposes is shown in Fig. 8.11. Aqueous polyurethane dispersions usually have 40% solids of a thermoplastic type (for aqueous inertness), aliphatic diisocyanate polymer (for light stability) and an anionic surfactant is used. However, if a polyurethane ionomer is prepared this does not contain added emulsifier, the polyurethane itself having its own emulsifier function. The incorporation of this function in the polyurethane chains as (a) sodium sulphonate or (b) sodium carboxylate groups is seen in Fig. 8.11. 

The cured polymers are hard, clear, and glassy thermoplastic resins with high tensile strengths. The polymers, because of their highly polar stmcture, exhibit excellent adhesion to a wide variety of substrate combinations. They tend to be somewhat britde and have only low to moderate impact and peel strengths. The addition of fillers such as poly (methyl methacrylate) (PMMA) reduces the brittleness somewhat. Newer formulations are now available that contain dissolved elastomeric materials of various types. These mbber-modifted products have been found to offer adhesive bonds of considerably improved toughness (3,4). 

This type of adhesive is generally useful in the temperature range where the material is either leathery or mbbery, ie, between the glass-transition temperature and the melt temperature. Hot-melt adhesives are based on thermoplastic polymers that may be compounded or uncompounded ethylene—vinyl acetate copolymers, paraffin waxes, polypropylene, phenoxy resins, styrene—butadiene copolymers, ethylene—ethyl acrylate copolymers, and low, and low density polypropylene are used in the compounded state polyesters, polyamides, and polyurethanes are used in the mosdy uncompounded state. 

Early phenoHc resins consisted of self-curing, resole-type products made with excess formaldehyde, and novolaks, which are thermoplastic in nature and require a hardener. The early products produced by General BakeHte were used in molded parts, insulating varnishes, laminated sheets, and industrial coatings. These areas stiH remain important appHcations, but have been joined by numerous others such as wood bonding, fiber bonding, and plywood adhesives. The number of producers in the 1990s is approximately 20 in the United States and over 60 worldwide. 

Type AD-G is used in an entirely different sort of formulation. The polymer is designed for graft polymerisation with methyl methacrylate. Typically, equal amounts of AD-G and methyl methacrylate are dissolved together in toluene, and the reaction driven to completion with a free-radical catalyst, such as bensoyl peroxide. The graft polymer is usually mixed with an isocyanate just prior to use. It is not normally compounded with resin. The resulting adhesive has very good adhesion to plasticised vinyl, EVA sponge, thermoplastic mbber, and other difficult to bond substrates, and is of particular importance to the shoe industry (42,43). 

Global consumption of thermoplastic mbbers of all types is estimated at about 600,000 t/yr (51). Of this, 42% was estimated to be consumed in the United States, 39% in Western Europe, and 19% in Japan. At present, the woddwide market is estimated to be divided as follows styrenic block copolymers, 48% hard polymer/elastomer combinations, 26% thermoplastic polyurethanes, 12% thermoplastic polyesters, 4% and others, 9%. The three largest end uses were transportation, 23% footwear, 18% and adhesives, coatings, etc, 16%. The ranges of the hardness values, prices, and specific gravities of commercially available materials are given in Table 4. 

Whilst approximately twice the raw material cost of TPO- and S-B-S-type polymers, thermoplastic polyurethane elastomers find applications where abrasion resistance and toughness are particular requirements. Uses include gears, timing and drive belts, footwear (including ski boots) and tyre chains. Polyether-based materials have also achieved a number of significant medical applications. There is also some minor use as hot melt adhesives, particularly for the footwear industry. 

PVAc is another important type of adhesive, especially in furniture manufacturing and for carpentry. They form the bond line in a physical process by losing their water content to the two wooden adherends. PVAc adhesives are ready to use, have short setting time and give flexible and invisible joints. They are easy to clean and show long storage life. Limitations are their thermoplasticity and the creep behavior. 

Many engineering thermoplastics (e.g., polysulfone, polycarbonate, etc.) have limited utility in applications that require exposure to chemical environments. Environmental stress cracking [13] occurs when a stressed polymer is exposed to solvents. Poly(aryl ether phenylquin-oxalines) [27] and poly(aryl ether benzoxazoles) [60] show poor resistance to environmental stress cracking in the presence of acetone, chloroform, etc. This is expected because these structures are amorphous, and there is no crystallinity or liquid crystalline type structure to give solvent resistance. Thus, these materials may have limited utility in processes or applications that require multiple solvent coatings or exposures, whereas acetylene terminated polyaryl ethers [13] exhibit excellent processability, high adhesive properties, and good resistance to hydraulic fluid. 

The frictional properties of TPs, specifically the reinforced and filled types, vary in a way that is unique from metals. In contrast to metals, even the highly reinforced plastics have low modulus values and thus do not behave according to the classic laws of friction. Metal-to-thermoplastic friction is characterized by adhesion and deformation resulting in frictional forces that are not proportional to load, because friction decreases as load increases, but are proportional to speed. The wear rate is generally defined as the volumetric loss of material over a given unit of time. Several mechanisms operate simultaneously to remove material from the wear interface. However, the primary mechanism is adhesive wear, which is characterized by having fine particles of plastic removed from the surface. 

Figure 15.4 gives the stress-strain diagrams for a typical fiber, plastic, and elastomer and the average properties for each. The approximate relative area under the curve is fiber, 1 elastomers, 15 thermoplastics, 150. Coatings and adhesives, the two other types of end-uses for polymers, will vary considerably in their tensile properties, but many have moduli generally between elastomers and plastics. They must have some elongation and are usually of low crystallinity. 

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