Epoxy adhesives Esters

Despite all precautions, urethanes can be used most effectively within certain thermal and oxidation limits. Outside these parameters, other adhesives, such as certain epoxies, cyanate esters, and other high-temperature adhesives, should be considered. 

Chelating agents such as triethanolamine borate also behave as latent catalysts at elevated temperatures. Other boron-containing compounds, cadmium or zinc bromide dieth-ylenetriamine, and salts of aluminum acetoacetic ester have also been suggested as curing agents for high-temperature epoxy adhesives. 

It has also been shown in several studies that the combination of stress, temperature, and moisture can accelerate the hydrolytic instability of certain epoxy adhesives. In an FTIR study of the effect of moisture on DGEBA epoxy cured with nadic methyl anhydride, spectra changes were observed in stressed specimens aged for 155 days at 80°C and 100 percent RH.47 This was attributed to the slow, stress-induced hydrolysis of ester groups. In another study,... 

Thermosetting adhesives, on the other hand, soften as the temperature is increased to the glass-transition temperature, but do not melt and resolidify. Instead, because of their highly cross-linked macrostructures, they decompose and char on reaching their decomposition temperatures. Epoxies, cyanate esters, and phenolics are generally thermosetting types. 

Although a major advantage of epoxy adhesives is their ability to be formulated without solvents, under certain circumstances solvents may be included. On porous substrates solvents may be added to reduce viscosity and assist penetration. On certain nonporous substrates, particularly some plastics, addition of a small percentage (1 to 3%) of a suitable solvent will improve adhesion. Common solvents are low-boiling aromatic solvents, ketones, or esters. 

Both paints and adhesives are commonly formulated as polymer blends or grafts. In fact, some compositions resemble semi-IPN s or AB crosslinked copolymers (Section 8.7). For example, epoxy adhesive resins are often cured with polyamides (Bikerman, 1968). The product is tougher than materials cured with low-molecular-weight amines, possibly because of a separate amide phase in this AB crosslinked copolymer. A more complex molecular architecture is exhibited by the alkyd resins common in oil-based paints (Martens, 1968, Chapters 3 and 4). The major component is a polyester, which often forms a network structure on drying. The polyester component is reacted with various drying oils, such as linseed oil or tung oil (Martens, 1968, Chapters 3 and 4). These oils form an ester link to the polyester structures and also polymerize through their multiple double bonds. Latex paints always contain thickeners, such as cellulosics, poly(acrylic acid), casein. 

UV-curing adhesives are available in a number of chemical systems, most of which are polymer based. These systems include acrylics and acrylates, epoxies, polyurethanes, polyesters, silicones, and vinyl and vinyl esters. The most common UV-curable adhesive is the acrylics. Specially modified acrylic and epoxy adhesives can be cured rapidly by UV radiation. In the case of epoxy adhesives, the adhesives can be pre-irradiated after application to the substrate before closing the bond line. These adhesive systems are offered by most major suppliers. ... 

There are many possible rubbery materials which can hypothetically be used as toughening agents for epoxy adhesives, but there are only three main classes used—those based on polybutadiene homo- or copolymers, polyacrylate esters, and, to a lesser extent, poly(alkylene oxides). In the case of the polybutadiene polymers, tougheners with functional groups... 

Elastomer-modified epoxy resins are used in composites and structural adhesives, coatings, and electronic applications. Similar approach to toughen epoxy vinyl esters using other elastomeric materials has been reported (204). Other elastomer-modified epoxies include epoxy-terminated urethane prepolymers, epoxy-terminated polysulfide, epoxy-acrylated urethane, and epoxidized polybutadiene. Preformed dispersions of epoxy-insoluble elastomers have been developed and reported to achieve toughening without Tg reduction (205,206). 

A 121"C cure toughened cyanate ester film adhesive formulated for use in specific applications where low moisture absorption and/or low dielectric constant/low loss are of utmost importance. The system s strength and toughness when bonding solid, honeycomb or foam core structures, is a>mparable and often greater than high performance epoxy adhesives, particularly at elevated temperatures. 

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