Epoxy resins amine accelerators

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. 

Mixing of propylene oxide and epoxy resin in a waste bottle led to an explosion, probably owing to the polymerisation of the oxide catalysed by the amine accelerator in the resin. 

Reactivity of Amine Accelerators with Anhydride-Epoxy Resin Systems ... 

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 ... 

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. 

The catalytic effect has been explained in terms of the activation of the anhydride by interaction with the amine to give a zwitterionic intermediate (47 Scheme 10) (B-68MI11501). Imidazoles have also been suggested as accelerators for anhydride cures (68USP3394105). A review of the patent literature (B-77MI11502) shows that several heterocyclic compounds are of interest as curatives for epoxy resins. 

In general the amine-epoxy resin curing reactions show complex kinetics typified by an initial acceleration due to autocatalysis, while the later post-gelation stages may exhibit retardation as the mechanism becomes diffusion-controlled. However some workers 72 80) have found that over a limited range of conversion the kinetic data may be described by the simple models of Eq. (2-6) or (2-9). 

The cure kinetics of some epoxy resin powder coating composition were reported by Olcese et al.108). These were mixtures of BADGE resins with DICY and an epoxide-amine adduct or an imidazole as accelerator, together with TiOz and plasticisers. Data from DSC scans were analysed using Eq. (2-12) to obtain the apparent activation energy, E. Also Eq. (2-13) and (2-13 a) were used to obtain estimates of E and order... 

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. 

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. 

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. 

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. 

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 polymercaptans can also be used to accelerate the curing of epoxy resins systems blended with polyamines, amidoamines, or amines. The other curatives serve as the base to accelerate mercaptans, and the mercaptans react rapidly, generating the heat to accelerate the cure with the other hardener. 

The effect of solvent type on the curing rate of epoxy reactions has been well defined. Hydroxyl compounds, such as alcohols, act as catalysts and accelerate curing. However, these solvents are not serious competitors with amines for reacting with the epoxy ring. Water, functioning as a hydroxyl compound, also accelerates the reaction, even more than alcohols. Aprotic solvents, such as aromatic hydrocarbons or mineral spirits, have no effect on the amine-epoxy resin and behave as inert diluents. Carbonyl solvents, such as acetone and methyl ethyl ketone, retard the reaction. 

Accelerators for dicyandiamide cured epoxy adhesive formulations include tertiary amines, modified aliphatic amines, imidiazoles, and substituted ureas. All except the substituted ureas can cure epoxy resins by themselves. All these materials provide good latency and excellent adhesive applications. 

DADPS also provides excellent high-temperature properties and chemical resistance. Of the amine curing agents, DADPS provides the best retention of strength after prolonged exposure to elevated temperatures. It melts at 135°C and can be cured with epoxy resins at 20 to 30 pph with cure temperatures ranging from 115 to 150°C. Because of the low reactivity of this system, an accelerator, such as BF3-MEA, is usually employed at about 1 pph. 

It is made by dimerizing cyanamide in basic aqueous solution, and is a colorless solid melting at 208°C. Dicyandiamide is soluble in polar solvents, but at room temperature is insoluble in bisphenol A epoxy resins. It can be made into a very fine powder and milled into epoxy resins to form stable dispersions. Because the dicy is insoluble in the epoxy, the only possible reaction sites are at the particle surfaces. Although some reaction certainly occurs over a short time, the adhesives easily can have a useful shelf life of six months. On heating to about 150°C, the dicyandiamide becomes soluble in the epoxy resin, and the adhesive polymerizes rapidly. Cure can be accelerated by incorporation of tertiary aromatic amines or substituted ureas. 

The accelerated decomposition of brominated epoxy resin by other materials contained in the encapsulant resin was studied by GC-MS from the amount of methylbromide that was emitted from the resin. The Teflon vessel used in the previous experiment was again used to study the corrosion of the device. The results are shown in Table II. The results show that the decomposition of brominated epoxy resin is significantly accelerated by amine and silicone. 

Amine and silicone contained in the encapsulant resin accelerated the degradation of brominated epoxy resin. 

Adhesives which are meant to cure at temperatures of 120 or 171°C require curatives which are latent at room temperature, but react quickly at the cure temperatures. Dicyanodiamide [461-58-5], (TH INI is one such latent curative for epoxy resins. It is insoluble in the epoxy at room temperature but rapidly solubilizes at elevated temperatures. Other latent curatives for 171°C are complexes of imidazoles with transition metals, complexes of Lewis acids (eg, boron trifluoride and amines), and diaminodiphenylsulfone, which is also used as a curing agent in high performance composites. For materials which cure at lower temperatures (120°C), these curing agents can be made more soluble by alkylation of dicyanodiamide. Other materials providing latency at room temperature but rapid cure at 120°C are the blocked isocyanates, such as the reaction products of toluene diisocyanate and amines. At 120°C the blocked isocyanate decomposes to regenerate the isocyanate and liberate an amine which can initiate polymerization of the epoxy resin. Materials such as Monuron can also be used to accelerate the cure of dicyanodiamide so that it takes place at 120°C. 

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