Some effects of structure, composition and cure on the water absorption and glass transition temperature of amine-cured epoxies

The effect of structure, composition, and cure on the water absorption and Tg of amine-cured epoxies was investigated. Water absorption is considered to depend on the polar group concentration and type, and on the amount of free volume in the polymer network. The contribution of polar groups in terms of their hydrogen bonding capabilities is reflected by the effect of meta (with respect to the diglycidylamino group) chloro, bromo, and methyl substituents on the water absorption of bis[N,N-bis(2,3-epoxypropyl)-4-aminophenyl]methane cured with 4,4′-diaminodiphenylsulphone. The observed water absorptions are in line with the expected electronic effects of the substituents on the basicity of the amine group. Substituents in the ortho position adversely affect the hydrogen bonding capability of the amine group and limit the extent of reaction by steric interference. Examination of four O-glycidyl systems (Epon 825, Epon 1153/114, Epon 1031, and Dow XD-7342) cured with 4,4′-diaminodiphenylsulphone has revealed quite a good linear relationship between the equilibrium water absorption and Tg for a particular hardener concentration irrespective of the epoxy compound employed. Networks ranged from those of low Tg (110°C) and water absorption (1.3%) to those of high values (300°C and 6.1%) for these parameters. Differences in slope for low (50-65%) and high (100%) stoichiometric amounts of hardener are attributed to differences in the relative importance of OH/epoxy and NH2 or NH/epoxy reactions. The theoretical polar group concentrations and polar group type are much the same for these different systems and thus, free volume is considered to be a function of Tg and to play an important part in determining the level of water absorption.