Epoxy dicyandiamide

TABLE 14.5 Waterborne Epoxy-Dicyandiamide Adhesive Tensile Shear Data16... 

Overheating of the adhesive is always a critical concern with induction curing. This is especially true when the adhesive cures with a high exotherm, such as epoxy-dicyandiamide systems. Several proprietary epoxy curing agents have been developed that provide lower exotherm yet faster cure rate than typical dicyandiamide reactions.27,28 Tertiary amines and modified polyamines29 are often used to accelerate the cure of dicyandiamide-epoxy... 

Waterborne epoxy-dicyandiamide adhesive tensile shear data... 

Propylimidazle, 2-methylimidazole 2-Ehtyl-4-methyl imidazole and derivatives Epoxy/epoxy, epoxy/dicyandiamide, epoxy/anhydride... 

Quaternary bases (benzyltrimethylammonium chloride) Epoxy/dicyandiamide, epoxy/anhydride, epoxy/phenol... 

Cyanamide and its aromatic derivative, such as 4,4 -methylene bis(phenyl cyanamide), were reported to cure an epoxy resin at elevated temperatures.(4) It is also well known that the dimer of cyanamide (dicyandiamide) is the most important epoxy curing agent in one-package epoxy compounding.(5) Unfortunately, this dimer precipitates from the dispersion causing uneven mixing upon standing. 

This may not be the case if during the network formation there are two (or more) possible reaction paths in competition e.g., epoxy networks obtained using dicyandiamide as hardener (Amdouni et al., 1990). 

Two-layered GRPs for copper clad laminates are obtained with one layer consisting of the three-component system (e.g. BPA/DC, BMI, brominated epoxide resin, Zn octoate and triethylenediamine in methylethylketone). The other layer has the usual epoxy matrix (brominated epoxide resin, dicyandiamide as a hardener and 2-ethyl-4-methylimidazole as curing accelerator) [119]. As similar two-layered laminate contains BPA/DC, BMI, epoxynovolak resin, Zn acetate and triethylenediamine in the first layer and BPA/DC only with the same catalysts in the second layer [120]. 

The catalytic curing agents commonly used include tertiary amines, Lewis acids and bases, and dicyandiamide. Since their function is truly catalytic, the catalyst is added at relatively low concentrations (0 to 5% by weight) to the epoxy formulation. Homopolymerization generally requires both the presence of catalysts and elevated temperatures for the reaction to proceed. Like the polyaddition reaction, the homopolymerization reaction is accelerated by hydroxyl groups or tertiary amines. 

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. 

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. 

Latent imidazole catalysts have also been developed to provide cure rates considerably faster than those of dicyandiamide cured epoxy resins.18 They also exhibit excellent adhesive characteristics and heat and chemical resistance. 

A unique feature of these imidazole catalysts is that they do not have the high exotherm that dicyandiamide produces when cured in epoxy resins. Thus, they do not char or burn when exposed to high cure temperatures for fast cure. This is an important factor for adhesives that are cured via induction or dielectric heating. These adhesive systems are also much safer to ship via ah freight than conventional dicyandiamide catalyzed epoxy formulations due to their low exotherm. 

Dicyandiamide (DICY) is a solid latent catalyst that reacts with both the epoxy terminal groups and the secondary hydroxyl groups. DICY has the advantage that it only reacts with the epoxy resins on heating beyond an activation temperature, and once the heat is removed, the reaction stops. It is widely used with epoxy resins where long shelf life (up to... 

Dicyandiamide (sometimes referred to as dicy ) or its derivatives are used in most commercial one-component epoxy adhesives. This curative is a white crystalline solid and is easy to incorporate into an epoxy formulation as a finely ground powder. When cured with epoxy resin, dicyandiamide provides an excellent set of performance properties. 

A typical dicyandiamide cured epoxy adhesive formulation is described in Table 12.7. These formulations are unaccelerated so that they have a shelf life of greater than 6 months at room temperatures. The adhesives will cure in 30 to 90 min at 149 to 177°C. Tensile shear strength on aluminum is in the range of 2500 to 3000 psi. 

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. 

Probably the most effective accelerator for dicyandiamide systems is the substituted ureas because of their synergistic contribution to the performance properties of the adhesive and their exceptionally good latency. It has been shown that adding 10 pph of a substituted urea to 10 pph of dicyandiamide will produce an adhesive system for liquid DGEBA epoxy resins that can cure in only 90 min at 110°C. Yet this adhesive will exhibit a shelf life of 3 to 6 weeks at room temperature. Cures can be achieved at temperature even down to 85°C if longer cure times are acceptable.10... 

Table 12.8 shows the effect of three commercially available substituted ureas on shelf life, cure rate, exotherm, and glass transition temperature of a dicyandiamide cured epoxy adhesive. The accelerators are compared at use levels of 1, 3, and 5 pph in a one-component adhesive consisting of 100 pph of DGEBA epoxy, 8 pph of dicyandiamide, and 3 pph of... 

Table 12.9 shows a formulation for an accelerated general-purpose one-component, dicyandiamide cured epoxy adhesive compared to one with a modified aliphatic amine curing agent. Notice that the dicyandiamide cured system provides a higher glass transition tem-... 

The BF3-MEA complex offers a slightly faster rate of cure and a reduced shelf live in liquid epoxy systems when compared to unaccelerated dicyandiamide cured epoxy formulations. However, when used as a sole curing agent, BF3-MEA has not had the commercial success of dicyandiamide because of their lower bond strength and brittleness. The BF3-MEA complex compounds also hydrolyze in the presence of moisture, so that mixtures with epoxy resins must be stored in tightly closed containers to maintain shelf life. 

Table 12.14 shows a comparison of dicyandiamide cured epoxy adhesives formulated with and without a CTBN adduct. When compared to the control epoxy, the toughened formulation exhibits significantly higher peel strength and moderately higher tensile shear strength. CTBN modified epoxy adhesives are generally one-part systems, cured with dicyandiamide at elevated temperature. 

Latent curing agents such as dicyandiamide are dissolved into solvent solutions of solid epoxy resins. This is then followed by evaporation of the solvent. 

Dicyandiamide is a true latent catalyst for epoxy resin curing. It is also considered to be the workhorse of one-component adhesives due to its ease of use, excellent performance properties, long shelf stability, and low toxicity. In certain admixtures with DGEBA, it has demonstrated a room temperature storage life in excess of 4 years. Dicyandiamide is usually added to the solid epoxy resin in concentrations of about 3 to 6 pph. It melts at about 150°C. Cures can be conducted in the range of 120 to 175°C but are very slow at the lower temperatures. As a result, it is common practice to add accelerators such as benzyl-dimethylamine (BDMA) and mono- or dichlorophenyl substituted ureas to these systems. 

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