ABSTRACT
A comprehensive picture on the mechanism of the epoxy-carboxylic acid curing reactions is presented using the density functional theory B3LYP/6-31G(d,p) and simplified physical molecular models to examine all possible reaction pathways. Carboxylic acid can act as its own promoter by using the OH group of an additional acid molecule to stabilize the transition states, and thus lower the rate-limiting barriers by 45 kJ/mol. For comparison, in the uncatalyzed reaction, an epoxy ring is opened by a phenol with an apparent barrier of about 107 kJ/mol. In catalyzed reaction, catalysts facilitate the epoxy ring opening prior to curing that lowers the apparent barriers by 35 kJ/mol. However, this can be competed in highly basic catalysts such as amine-based catalysts, where catalysts can enhance the nucleophilicity of the acid by forming hydrogen-bonded complex with it. Our theoretical results predict the activation energy in the range of 71 to 94 kJ/mol, which agrees well with the reported experimental range for catalyzed reactions. © 2017 Wiley Periodicals, Inc.
ABSTRACT
A comprehensive picture on the mechanism of the epoxy-phenol curing reactions is presented using the density functional theory B3LYP/ 6-31G(d,p) and simplified physical molecular models to examine all possible reaction pathways. Phenol can act as its own promoter by using an addition phenol molecule to stabilize the transition states, and thus lower the rate-limiting barriers by 27.0-48.9 kJ/mol. In the uncatalyzed reaction, an epoxy ring is opened by a phenol with an apparent barrier of about 129.6 kJ/mol. In catalyzed reaction, catalysts facilitate the epoxy ring opening prior to curing that lowers the apparent barriers by 48.9-50.6 kJ/mol. However, this can be competed in highly basic catalysts such as amine-based catalysts, where catalysts are trapped in forms of hydrogen-bonded complex with phenol. Our theoretical results predict the activation energy in the range of 79.0-80.7 kJ/mol in phosphine-based catalyzed reactions, which agrees well with the reported experimental range of 54-86 kJ/mol.
ABSTRACT
The effects of conversion beyond the gel point on the structure-property relationships of epoxy thermosets using formulations representative of the most commonly used epoxy resin and amine curing agents at balanced stoichiometry with an emphasis on the thermal, tensile, and fracture properties were studied. The range of T(g) from just beyond the gel point to full conversion typically is >100 degrees C. Fracture toughness (as K(1c)) of the epoxy thermosets cured with relatively flexible amines such as ethylenediamine (EDA), diethylenetriamine (DETA), and m-xylylenediamine (MXDA) reaches near its full cure value at only approximately 65-70% conversion. The maximum in K(1c) for these types of epoxy thermosets is at approximately 90% conversion for EDA and DETA but just below its full cure for MXDA. Isophoronediamine represents a special case for fracture behavior because of its apparent substantial cyclization during cure. In the 4,4'-diaminodiphenylsulfone series, K(1c) generally increases with conversion as the concentrations of their strongly antiplasticizing soluble and pendant fractions decrease. A uniform trend of decreasing tensile modulus with increasing conversion was observed in each formulation and is consistent with the expected decrease in the cohesive energy density as monomer glass is transformed into polymer glass.
