Epoxy resin curing agents Aliphatic amines

Curing agents account for much of the potential hazard associated with use of epoxy resins. There are several major types of curing agents aliphatic amines, aromatic amines, cycloaliphatic amines, acid anhydrides, polyamides, and catalytic curing agents. The latter two types are true catalysts, in that they do not participate in the curing process. 

A great variety of aromatic diamines and aliphatic di- and poly-amines are used as epoxy resin curing agents, and tert-amines can act as catalysts for anionic epoxide homopolymerisation. 

Typically, a low molecular weight solid epoxy resin and latent curing agent, such as dicyandiamide dissolved in an appropriate solvent, are widely used in dry lay-up formulations for electrical laminates for computers, aerospace applications, and communications equipment. Wet lay-up systems are almost exclusively based on low-viscosity resins cured with aliphatic amines. These ambient cure resin systems are used primarily for manufacture of large chemical-resistant tanks, ducting, and scrubbers. Filament winding is used... 

Asthma due to exposure to ethylene amines in manufacture has been reported by Dernehl (1951), and after exposure to aliphatic polyamine or epoxy resin curing agents (Dernehl 1963). Phthalic anhydride, often used in hot curing systems, is a recognised irritant of the respiratory tract and asthma has been reported (American Industrial Hygiene Association Journal 1967 Malten and Zielhuis 1964 Petit et al. 1961). 

Amines are used commonly as curing agents for epoxy resins and adhesives. Aliphatic primary amines provide a fast room-temperature cure but provide poor elevated-temperature resistance. They also produce resin systems with a very high exotherm. Common primary amines used in these formulations include diethyltri-amine BETA) and triethylenetetramine (TETA). 

The liquid polymer is converted to the rubbery state by reagents that react with mercaptan (-SH) and side groups of the polymer segments by oxidation, addition or condensation to effect sulfide (-S-S-) bond formation. The oxidation reactions are exothermic and accelerated by an alkaline environment. The most commonly employed oxidizing agents which are suitable for curing liquid polymers are cobalt or manganese or lead octoate, p-quinonedioxime and di- or tri-nitrobenzene. Epoxy resin also reacts with liquid polysulfide polymers by addition in the presence of an aliphatic or aromatic amine and polyamide activator as shown in Equation 5.8 ... 

The mechanisms of radiation damage and effects of hardeners were studied recently by pulse radiolysis [89], The epoxy resins require a relatively large amount of curing agents (hardeners), most of them are aromatic and aliphatic amines such as diamino diphenyl methane or triethylene tetramine. On the basis of the emission spectra and kinetic behavior of excited states observed, the radiation resistance of aromatic and aliphatic amine curing epoxy resin was explained by internal radiation protection effects due to energy transfer. 

In adhesive formulations, aliphatic amines are most commonly used to cure the DGEBA type of epoxy resin. Aliphatic amines are not widely used with the non-glycidyl ether resins, since the amine-epoxy reaction is slow at low temperatures. The reaction usually requires heat and accelerators for an acceptable rate of cure. Aliphatic amines are primarily used with lower-viscosity DGEBA resins because of the difficulty in mixing such low-viscosity curing agents with the more viscous epoxy resins. 

Two curing agents that have found their way into many epoxy adhesive formulations are the polyamides and amidoamines. These are commonly used in the hardware store variety two-part epoxy resins that cure at room temperature. Both are reaction products of aliphatic amines, such as diethylenetriamine, and should be included under the subclassification of modified amines. However, these products have such widespread and popular use, they are addressed here as a separate classification. 

Amidoamine or polyamidoamine curing agents have reactivity with DGEBA epoxy resins that is similar to the polyamides. However, they are lower-viscosity products and are also lower in color. Amidoamines are derivatives of monobasic fatty carboxylic acids and aliphatic polyamines. Since the amidoamines have only one amide group per molecule, they are lower in molecular weight, viscosity, and amine functionality than the polyamides. 

Table 11.12 shows two rapid-setting, room temperature cure epoxy adhesives based on epoxy acrylate resins with aliphatic amine curing agents. These adhesives have gel times of less than 5 min for a 100-g mass. The bond strength development is rapid with handling strength occurring in about 1 h at room temperature. 

Table 14.4 presents formulation information for bisphenol A and polyfunctional epoxy resin emulsions that are cured with an aliphatic amidoamine curing agent. Adhesive performance data are also provided for substrates common to the automotive industry. Both formulas are based on a 1 1 epoxy-amine stoichiometry and they are reduced to 45 percent nonvolatiles with water. The working life of each system is several hours at room temperature. 

Multifunctional POSS, containing four epoxide groups on the periphery, copolymerized with aliphatic diepoxides and an amine-curing agent increased and broadened the Tg, increased the tensile modulus, but lowered the flexural modulus over that of the neat epoxy resin [2] (Fig. 3). 

The two-part epoxy adhesive, readily available in hardware stores or other consumer outlets, comes in two tubes. One tube contains the epoxy resin, the other contains an amine hardener. Common diamine room temperature epoxy curing agents are materials such as the polyamides, available under the trade name Versamid. These polyamides are the reaction products of dimer acids and aliphatic diamines such as diethylenetriamine [111 -40-0], C4H13N3. Other room temperature curing agents are triethylenetetraamine [112-24-3], and the polypropylene glycol diamines, known as the Jeffamines. The... 

Carboxylic acid and anhydride curing agents are used to a lesser extent in aerospace applications as compared to the amines which have mechanical properties and cure conditions that can be tailored to a wider variety of specific applications. Anhydrides tend to be somewhat brittle but offer useful service as high as 250 °C with novolac-type epoxy resins. In addition, the aliphatic dicarboxylic acid anhydrides give tough and sometimes flexible properties which are useful in encapsulation applications. 

---