Epoxy room temperature amine curing

ROOM TEMPERATURE AMINE CURING OF HYDANTOIN EPOXY RESINS... 

The pot life of polyamide or amidoamine cured epoxy adhesives is generally on the order of hours at room temperature. Full cure is achieved in 5 to 7 days at room temperature, and handling strength is achieved in about 16 to 24 h. A faster cure can be achieved in 20 min to 4 h by heating to 60 to 150°C. When room temperature cures are required, an accelerator such as an amine is often added to the formulation. 

Other latent curing agents that are used in solid adhesives are dihydrazides and BF3-MEA complexes. These compositions are also stable at room temperature but cure when heated. Solid anhydrides can be used in one-component powder blends (e.g., 10 pph of trimellitic anhydride accelerated with 0.5 pph of 2-methylimidazole). Solid systems with aromatic diamines are prepared by comelting the solid epoxy with the amine. Typically 30 pph of curing agent is used.1... 

All of the commercial epoxy adhesives presented in App. B bond well to aluminum and to a wide variety of other materials. Sell22 has ranked a number of aluminum adhesives in order of decreasing durability as follows nitrile-phenolics, high-temperature epoxies, elevated-temperature curing epoxies, elevated-temperature curing rubber-modified epoxies, vinyl epoxies, two-part room temperature curing epoxy paste with amine cure, and two-part urethanes. 

It is possible to make one-package epoxy adhesives that can have very long shelf lives at room temperature but cure rapidly when heated. One amine curative widely used to make single-package heat-cured epoxy adhesives is dicyandiamide (cyanoguanadine), commonly known as dicy. 

Two-part, room-temperature-curing epoxy paste with amine cure... 

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 aUphatic diamines such as diethylenetriamine [111-40-0] ... 

Meta-phenylenediamine, a crystalline solid with a melting point of about 60°C, gives cured resins with a heat distortion temperature of 150°C and very good chemical resistance. It has a pot life of six hours for a 200 g batch at room temperature whilst complete cures require cure times of four to six hours at 150°C. About 14 pts phr are used with the liquid epoxies. The main disadvantages are the need to heat the components in order to mix them, the irritating nature of the amine and persistent yellow staining that can occur on skin and clothing. The hardener finds use in the manufacture of chemical-resistant laminates. 

With the diglycidyl derivative of bisphenol A, aromatic amines such as 4,4 -methylene dianiline or diaminodiphenyl sulfone provide good thermal stability for the final cured resin. Although aliphatic primary amines react more rapidly (triethylenetetramine cures the above epoxy resin based on bisphenol A in 30 min at room temperature and causes it to exotherm up to 200°C), they are more difficult to handle and offer poor thermal stability. 

Preparation of Ozonized Lignin/Epoxy Resins. Each ozonized lignin (1.0 g) was mixed with DGEBA and heated at 120°C with stirring as described in the previous section. After heating for 30 min, the mixture was cooled to room temperature. The solidified reactants were dissolved in acetone (2 ml) and the curing reagents, diethylenetriamine (DETA) or hexamethylenedi-amine (HMDA), were added at 90% of the stoichiometric amount to epoxy equivalent. 

The two most common BF3 amine catalysts used commercially to cure epoxies are boron trifluoride monoethylamine, BF3 NH2C2H5, and boron trifluoride piperidine, BF3 NHCsHi0, complexes. Such complexes are latent catalysts at room temperature but enhance epoxide group reactivity at higher temperatures. 

Another possible preassembly reaction mechanism has been noted with regard to amine cured epoxy resins.10 A variability and reduction in the rate of conversion of epoxy groups in DGEBA epoxy resin cured at room temperature with diethylene triamine (DETA) was noticed. This is due to a side reaction of the amine with air, resulting in bicarbonate formation. As a result, the adhesive strength decreased drastically when the uncured epoxy amine was exposed to ambient air for a significant period of time. 

Other amines, such as aromatic or cycloaliphatic, are less reactive and generally require elevated-temperature cures that result in higher heat distortion temperatures (140 to 150°C). However, aromatic amine adducts of liquid epoxies can be accelerated to cure at room temperature. Aliphatic amines can also be accelerated. 

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. 

The lower reactivity of the aromatic amines in adhesive formulations is an advantage in that epoxy resin mixtures can be B-staged at room temperature (react to a glassy but fusible and thermoplastic intermediate structure) and will not fully cure for months. In this way, dry films and solid powders can be formulated as elevated-temperature curing, one-component adhesives with long shelf life. 

Aromatic Amine Eutectics. There are several curing agents available that consist of eutectics of various aromatic amines. These perform very much as MPDA and MDA do. However, the eutectics are liquids with viscosity of approximately 2000 cP at room temperature. They are readily miscible with liquid epoxy resins at room temperature. 

Solvent Solutions. Certain solvent solutions of aromatic amines have been noticed to polymerize epoxy resins at room temperature.11 The effect of the solvent is probably to allow sufficient mobility of the polymer chains for an adequate degree of crosslinking to occur before the viscosity becomes so high that the molecules are immobilized. The aromatic amine solutions are usually used with a cure accelerator to achieve practical cure rates at room temperature. 

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. 

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. 

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