Epoxy resins tertiary amines

Amines. Tertiary amines R3N are catalysts that open the epoxy ring and thus catalyze the polymerization reaction. They may be used with hydroxyl-containing molecules to catalyze homopolymeiization (Fig. 3.26), but more often they are used to catalyze copolymerization of epoxy resins with amine or acid curing agents. Several more specialized amines are also mentioned as catalysts (Fig. 3.27). 

As indicated in the preceding section, amine hardeners will cross-link epoxide resins either by a catalytic mechanism or by bridging across epoxy molecules. In general the primary and secondary amines act as reactive hardeners whilst the tertiary amines are catalytic. 

The intrinsic moisture sensitivity of the epoxy resins is traceable directly to the molecular structure. The presence of polar and hydrogen bonding groups, such as hydroxyls, amines, sulfones and tertiary nitrogen provides the chemical basis for moisture sensitivity, while the available free volume and nodular network structure represent its physical aspect. 

Phenol-epoxy reaction. See also Epoxy-phenolic reaction entries tertiary amine-catalyzed, 412 triphenylphosphine-catalyzed, 412 Phenol-formaldehyde novolac resin, preparation of, 429... 

By contrast with tertiary amines used in catalytic quantities, primary and secondary amines or acid anhydrides may be used to bring about the cure of epoxy resins by reaction in stoichiometric proportions. A typical amine curing agent used at this level is diaminodiphenylmethane (DDM), which reacts with an individual epoxy-group in the way shown in Reaction 4.17. 

Epoxy (Anhydride-Cured) Epoxy resins may be crosslinked with various anhydrides by using a tertiary amine accelerator and heat. These cured polymers generally have good chemical resistance especially to acids. 

Epoxides can react with alcohols via acidic or basic catalysed reaction mechanisms. However, since both strong acids and bases will degrade the cell wall polymers of wood, the reaction is usually catalysed via the use of amines, which are more strongly nucleophilic than the OH group. For example, whereas the production of epoxy-phenolic resins requires temperatures in the region of 180-205 °C, reaction between epoxides and primary or secondary amines takes place at 15 °C (Turner, 1967). Reaction of epoxides with wood often involves the use of tertiary amines as catalysts (Sherman etal., 1980). The sapwood is more reactive towards epoxides than heartwood (Ahmad and Harun, 1992). 

Crosslinking of epoxy resins with carboxylic acid anhydrides is catalyzed by tertiary amines thus,if 50 mg /V,/V-dimethyl aniline are added to the initial mixture in the above example, the curing process is already complete after 1 h at 120 °C. 

Tertiary amines (TA) may be utilized both as independent curing agents for epoxy resins and as catalysts in the reaction of epoxy compounds with alcohols, phenols, carboxylic adds and their anhydrides i - 5. Besides, the three-... 

Tertiary amines catalyze the homopolymerization of epoxy resins in the presence of hydroxyl groups, a condition which generally exists since most commercial resins contain varying amounts of hydroxyl functionality (B-68MI11501). The efficiency of the catalyst depends on its basicity and steric requirements (B-67MI11501) in the way already discussed for amine-catalyzed isocyanate reactions. A number of heterocyclic amines have been used as catalytic curatives pyridine, pyrazine, iV,A-dimethylpiperazine, (V-methylmorpholine and DABCO. Mild heat is usually required to achieve optimum performance which, however, is limited due to the low molecular weight polymers obtained by this type of cure. 

Tertiary amines are used to accelerate both amine and anhydride cures of epoxy resins (B-67MI11501). Certain heterocyclic amines have been used for this purpose, including pyridine and piperidine. In the case of anhydride cures, the use of an amine catalyst not only accelerates the cure, but also improves the thermal stability of the cured resin. 

For the copolymerization of epoxides with cyclic anhydrides and curing of epoxy resins, Lewis bases such as tertiary amines are most frequently used as initiators. In this case, terminal epoxides react with cyclic anhydrides at equimolar ratios. The time dependence of the consumption of epoxide and anhydride is almost the same for curing 35-36> and for model copolymerizations 39,40,45). The reaction is specific 39,40) to at least 99 %. In contrast, the copolymerization with non-terminal epoxides does not exhibit this high specificity, probably because of steric hindrances. The copolymerization of vinylcyclohexene oxide or cyclohexene oxide is specific only to 75-80 % and internal epoxides such as alkylepoxy stearates react with anhydrides only to 60-65 %. On the other hand, in the reaction of epoxy resins with maleic anhydride the consumption of anhydride is faster 65the products are discoloured and the gel is formed at a low anhydride conversion 39). Fischer 39) assumes that the other resonance form of maleic anhydride is involved in the reaction according to Eq. (33). 

Tanaka and Kakiuchi35 361 found a proportionality between the rate of curing of epoxy resins with hexahydrophthalic anhydride and the concentrations of epoxide, anhydride and tertiary amine (Eq. (82)), and also first-order kinetics with respect to the proton donors if present (Eq. (83)). 

Massing described a synthesis of systematically modified cationic lipids by solid-phase chemistry starting with the immobihsation of (/f)-2,3-epoxy-1 -propanol on 4-methoxytrityl chloride resin [157], Reaction of the epoxide with distinct long-chained amines was followed by reductive animation and tertiary amine quatemisation (see Fig. lib). This interesting method allowed the solid-phase coupling of three different lipophUic moieties on an amino group and the synthesis... 

The primary and secondary amines are discussed in this section. The secondary amines are derived from the reaction product of primary amines and epoxies. They have rates of reactivity and crosslinking characteristics that are different from those of primary amines. The secondary amines are generally more reactive toward the epoxy group than are the primary amines, because they are stronger bases. They do not always react first, however, due to steric hindrance. If they do react, they form tertiary amines. Tertiary amines are primarily used as catalysts for homopolymerization of epoxy resins and as accelerators with other curing agents. 

The stoichiometry for DEAPA cured systems is less critical than with DETA or TETA since DEAPA acts as both a crosslinking agent and a catalyst. Due to the reactivity of the tertiary amine group, the concentration required is also less (4 to 8 pph in DGEBA epoxy resins with an EEW of 190). 

These compounds do not readily react with epoxy resins except in the presence of water, alcohol, or some other base, called an accelerator. Tertiary amines, metallic salts, and imidazoles often act as accelerators for anhydride cured epoxy systems. The reaction between acid anhydride and epoxy resins is illustrated in Fig. 5.7. 

The reactivity of the epoxy-anhydride reaction is slow therefore, an accelerator is often used at 0.5 to 3 percent to speed the gel time and cure. Most often the accelerator is a tertiary amine, and the optimum concentration is dependent on the anhydride, the resin used, and the cure conditions. The accelerator concentration, like the anhydride concentration, is usually determined experimentally based on a specific set of end properties. 

The most popular catalysts for epoxy resins are tertiary amines, tertiary amine salts, boron trifluoride complexes, imidazoles, and dicyandiamide. Many of these catalysts provide very long pot lives (months) at room temperatures and require elevated temperatures for reaction with the epoxy groups. These catalysts are often referred to as latent hardeners. 

Generally, when used as a sole catalyst, tertiary amines are used only in specialty applications where short pot life can be tolerated and where maximum physical or chemical properties are not required. DMP-10 and DMP-30 are used at concentrations of 4 to lOpph with liquid DGEBA epoxy resins. They achieve fairly fast cures overnight, even at room temperatures since the hydroxyl groups present in the epoxy molecule enhance the catalytic activity of the tertiary amine groups. 

Tertiary amine salts of DMP-30 provide extended room temperature pot life (6 to 10 h at 20°C) when used at concentrations of 10 to 14 pph in liquid DGEBA epoxy resins. They cure at moderately elevated temperatures (4 to 8 h at 60°C), or even at room temperature with a heat bump. The acid moiety blocks the tertiary amine centers and deactivates them. The salt then dissociates on heating, freeing the amine groups, which are then able to react with the epoxy group. 

The tertiary amine salts are claimed to provide epoxy formulations with very good adhesion to metal. The cured resins also show a hydrophobic effect when in contact with water or at high humidities. The strength, toughness, and elongation (4.7 percent) of the cured epoxy resin are very good. However, heat distortion temperature is only in the range of 70 to 80°C, and chemical resistance is relatively poor for an epoxy. The physical properties fall off rapidly with any rise in temperature. 

Benzyldimethylamine (BDMA) is another tertiary amine that can be used as either a sole catalyst or an accelerator with other curing agents. It is used with DGEBA epoxy resins at 6 to 10 pph. The pot life is generally 1 to 4 h, and the cure will be complete in about 6 days at room temperature. When used by itself, BDMA can provide epoxy adhesive formulations with high-temperature resistance (Chap. 15). However, BDMA is mostly used as an accelerator for anhydride and dicyandiamide cured epoxy resins. 

The early reaction mechanism of DICY with epoxy resin consists of the epoxy reaction with all four hydrogen atoms on DICY and the epoxy-to-epoxy reaction that is catalyzed by the tertiary amines. The final curing mechanism is between hydroxyl groups in the partly cured resins and DICY cyano groups. This results in the disappearance of the cyano groups to form amino groups. This step is also catalyzed by tertiary amines. 

Suitable curatives for the polysulfide-epoxy reaction include liquid aliphatic amines, liquid aliphatic amine adducts, solid amine adducts, liquid cycloaliphatic amines, liquid amide-amines, liquid aromatic amines, polyamides, and tertiary amines. Primary and secondary amines are preferred for thermal stability and low-temperature performance. Not all amines are completely compatible with polysulfide resins. The incompatible amines may require a three-part adhesive system. The liquid polysulfides are generally added to the liquid epoxy resin component because of possible compatibility problems. Optimum elevated-temperature performance is obtained with either an elevated-temperature cure or a postcure. 

As with amidoamine and polyamide cured adhesives, epoxy resins cured with aliphatic amines exhibit tensile shear strength that is dependent on the type of filler and concentration. Table 11.10 shows the effect of filler loading on strength of a simple general-purpose, room temperature curing epoxy adhesive composed of liquid DGEBA epoxy mixed with 10 pph of a tertiary amine. 

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