Thermoplastics adhesive performance

Yoon TH, McGrath JE (1992) Enhanced adhesive performance of thermoplastic po-ly(imide siloxane) segmented copolymer with peek-graphite composites by gas plasma treatment. High Perform Polym 4(4) 203... 

Some of the more interesting and innovative work has occurred in areas combining aspects of more than one chemistry type. For instance, moisture-curable thermoplastic adhesives have received much attention. Hot melt adhesives have been developed that contain active, moisture-curable isocyanate groups. The compositions provide rapid processing on assembly lines because a reasonable bond is formed as soon as the thermoplastic adhesive cools from the melt. However, bond strength and performance improve with time as the composition is slowly crosslinked to a thermoset by reaction of the isocyanates with atmospheric moisture.96,97... 

Thermoplastic rubber block copolymers, with completely new adhesive performance, were developed in 1965 [21]. The first commercial product was Shell Chemical s Kraton 101, of styrene polybutadiene-styrene composition. This development led to the carboxy-terminated nitrile (CTBN) rubber modifiers used to flexibilize epoxy and other brittle resin adhesives in the late 1960s. Today, the thermoplastic rubber block copolymer adhesives are used in hot melt-, solvent- and water-based adhesives, and as hot melt- and solvent-based sealants. Major applications are as pressure-sensitive adhesives, construction adhesives and sealants, and general assembly adhesives. 

Polyester polyols are used widely in urethane adhesives because of their excellent adhesive and cohesive properties. Compared to polyether-based polyols, polyester-based polyol adhesives have higher tensile strengths and improved heat resistance. These benefits come at the sacrifice of hydrolytic resistance, low-temperature performance, and chemical resistance. One of the more important application areas for these products is in the solvent-borne thermoplastic adhesives used in shoe sole binding. These products are typically made from adipic acid and various glycols (see Fig. 15). 

Most of the glued components produced in Europe for non-structural purposes such as joinery use urea-formaldehyde (UF), poly (vinyl acetate) (PVAc) or polyurethane (PUR) adhesives. These adhesives must meet the performance requirements specified in EN 204 (2002) [15] for thermoplastic adhesives or EN 12765 (2002) [16] for thermosetting adhesives when tested in accordance with the following test methods ... 

Elastic Attachment Adhesives. These thermoplastic rubber-based adhesives are usually applied by spraying at 140-165 °C. As difierent elastic materials are used, different adhesives need to be formulated to ve the right adhesion performance for each substrate. 

Surface finish and surface preparation are both key factors in the success of an adhesively bonded joint and, in many applications, roughening the plastic surface can be beneficial to the overall bond strength and the durability. If the adhesive is injection moulded, it is often possible to spark erode the mould tool to give a slightly rougher surface finish at the bond line thus improving the mechanical keying of the adhesive to the surface. A surface finish of between 1 and 2 Ra will invariably improve the adhesion performance of cyanoacrylates to thermoplastics. 

Vinyls. Vinyl resins are thermoplastic polymers made principally from vinyl chloride other monomers such as vinyl acetate or maleic anhydride are copolymerized to add solubUity, adhesion, or other desirable properties (see Maleic anhydride, maleic acid, and fumaric acid). Because of the high, from 4,000 to 35,000, molecular weights large proportions of strong solvents are needed to achieve appHcation viscosities. Whereas vinyls are one of the finest high performance systems for steel, many vinyl coatings do not conform to VOC requirements (see Vinyl polymers). 

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. 

Poly(tetramethylene oxide) polyols (PTMEG) are high performance polyethers that are crystalline waxes at molecular weights above 650 and liquids at lower molecular weights. They are only available as diols, but they produce adhesives with good hydrolysis resistance and moisture resistance, which is why these adhesives are even used in medical devices, blood bags, catheters, and heart-assist devices [25]. Certain thermoplastic polyurethane adhesives and solvent-borne adhesives are also based on PTMEG s. 

Benzylation has been performed on wood in order to impart thermoplastic properties to the substrate (Hon and Ou, 1989). Wood is pre-treated with aqueous NaOH solution, then with benzyl chloride. Benzylation of the surfaces of wood blocks and chips for selfbonding of wood surfaces has also been reported (Kiguchi, 1990a,b Kiguchi and Yamamoto, 1992). A vapour-phase benzylation method has also been developed (Kiguchi, 1993). Carboxymethylation of NaOH-treated wood using various solvent systems has been studied (Shiraishi and Kishi, 1986 Honma and Nakano, 1991). Wood modified in this way has been used to make wood-phenolic adhesives (Kishi and Shiraishi, 1986). 

Addition poly(imide) oligomers are used as matrix resins for high performance composites based on glass-, carbon- and aramide fibers. The world wide market for advanced composites and adhesives was about 70 million in 1990. This amounted to approximately 30-40 million in resin sales. Currently, epoxy resins constitute over 90% of the matrix resin materials in advanced composites. The remaining 10% are unsaturated polyester and vinylester for the low temperature applications and cyanate esters and addition poly(imides) for high temperatures. More recently thermoplastics have become important and materials such as polyimides and poly(arylene ether) are becoming more competitive with addition polyimides. 

STYRENE-MALEIC ANHYDRIDE. A thermoplastic copolymer made by the copolymerization of styrene and maleic anhydride. Two types of polymers are available—impact-modified SMA terpolymer alloys (Cadon ) and SMA copolymers, with and without rubber impact modifiers (Dylark ). These products are distinguished by higher heat resistance than the parent styrenic and ABS families. The MA functionality also provides improved adhesion to glass fiber reinforcement systems. Recent developments include lerpolymer alloy systems with high-speed impact performance and low-temperature ductile fail characteristics required by automotive instrument panel usage. 

Blends of 10% aminosilane F and 90% hydrophobic silanes, i.e. vinylsilane A, chloropropylsilane B, methylsilane G, and phenylsilane I, gave superior adhesion of three types of polyurethane (RIM, thermoplastic, and one-component rigid) to glass compared with aminosilane F alone. Table 3 shows that the blend with phenylsilane I gave the best adhesion overall to all three polyurethanes after 5 h in boiling water. This improved performance is attributed to the enhanced hydrophobicity of the interphase region which is conferred by the replacement of most of the hydrophilic aminosilane with hydrophobic silane. 

Compared to the carboxylated nitrile elastomer additives, the use of thermoplastics has primarily been focused on the aerospace industry. On a cost per pound basis, the two-phase nitrile additives offer the best combination of property improvement without negative impact. The thermoplastic additives, however, may offer better high-temperature performance, but they are more difficult to formulate and to process as adhesives. As a result, the cost of these adhesives is generally much higher than that of other toughened epoxy mechanisms. 

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