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Poly(ε-caprolactone) has become an important biocompatible and biodegradable polymer. Indeed, due to its multiple biomedical applications, the synthesis of polycaprolactone has received increased attention in the past few decades. Moreover, microwave irradiation is a very clean modern technique widely used for green chemistry. Here, several polymers were synthesized by microwave irradiation, without any solvent, using nontoxic, biologically acceptable lanthanide halides as initiators. Reaction times varied between 2 and 90 min. The molecular weights of the obtained polymer products were between 3,000 and 16,000 g/mol. After polymerization, the polycaprolactone polymers were functionalized by reaction with 2-hydroxyethyl methacrylate. Hydrolytic and enzymatic degradation of the synthesized polymers were compared and discussed. [ABSTRACT FROM AUTHOR]