Degradation and controlled release behavior of epsilon-caprolactone copolymers in biodegradable antifouling coatings

Copolymers of caprolactone with delta-valerolactone and L-lactide were synthesized by ring-opening polymerization in the presence of tetrabutoxytitane in order to decrease the crystallinity of polycaprolactone (PCL) and to enlarge its potential applications. The kinetics of degradation and controlled release of bioactive molecules were investigated in aqueous medium at room temperature for 9 months. The influence of the comonomer structures, their molar ratio, and the presence of fillers on these kinetics were examined. Complementary analytical methods were used (i) to quantify the degradation of the copolymers by titration of products of degradation (lactic acid, hydroxycaproic acid, and hydroxypentanoic acid) and (ii) to reveal the degradation processes by determination of molecular weights and thermal characteristics. After aging, films were observed by scanning electronic microscopy and EDX microanalysis to check their capabilities for the release of bioactive agent. The results showed that the incorporation of a comonomer such as L-lactide or delta-valerolactone led to a faster degradation than that of PCL homopolymer. The release of biocides could be correlated with the degradation of copolymer but depended on the structure of the leached molecule.