Aminic epoxy resin hardeners as reactive solvents for conjugated polymers: polyaniline base/epoxy composites for anticorrosion coatings

Polyaniline (PANI) has much been studied in the context of corrosion prevention, particularly on steel and aluminium. To prepare epoxy coatings consisting of PANI has turned to be nontrivial, due to its relatively rigid conformation and poor solubility. Therefore, as the aim has typically been to dissolve PANI in the epoxy component before curing, auxiliary solvents have been required, and less attractive Lewis-type hardeners have been required if the conducting salt form has been used. In this work, we describe a particularly simple concept where emeraldine base (EB) form of PANI is first dissolved in specific aminic hardeners which are observed to be solvents for EB at low concentrations, and the mixtures are unconventionally cross-linked upon adding epoxy resin, diglycidyl ether of bisphenol-A (DGEBA). Suitable hardeners are N,N,N0,N0-tetrakis(3-aminopropyl)-1,4-butanediamine (DAB-AM-4) and trimethylhexanediamine (TMDA). Even if the subsequent cross-linking promotes phase separation, the forming cross-link sites may also control the phase separation. As a result, sufficiently homogeneous coatings are identified which contain only 1 wt% EB in the cured EB/DGEBA/TMDA composites where in aqueous 3.5% NaCl solution the corrosion front propagation is suppressed, and electrochemical impedance studies indicate the formation of a charged interface or reaction product layer between EB and steel. For reference, similar net EB/DGEBA/TMDA-compositions were prepared, where EB was first mixed in DGEBA without any solubility and which were cured by added TMDA, and they gave essentially no anticorrosion effect. We expect that the present concept opens new ways to prepare cured epoxy composites also with other conjugated or nonconjugated polymers for anticorrosion and other functional purposes.