A new generation of poly(lactide/ε‐caprolactone) polymeric biomaterials for application in the medical field

Abstract Thermoplastic biodegradable polymers displaying an elastomeric behavior are greatly valued for the regeneration of soft tissues and for various medical devices. In this work, terpolymers composed of ε‐caprolactone (CL), d‐lactide (d‐LA), and l‐lactide (l‐LA) were synthesized. These poly(lactide‐ε‐caprolactone) (PLCLs) presented an elevated randomness character (R∼1), glass transition temperatures (T_g) higher than 20°C and adjusted l‐LA content. In this way, the l‐LA average sequence length (l_L‐LA) was reduced to below 3.62 and showed little or no crystallization capability during in vitro degradation. As a result, the obtained materials underwent homogenous degradation exhibiting K_Mw ranging from 0.030 to 0.066 d⁻¹ and without generation of crystalline remnants in advanced stages of degradation. Mechanical performance was maintained over a period of 21 days for a rac‐lactide‐ε‐caprolactone copolymer composed of ∼85% d,l‐LA and ∼15% CL and also for a terpolymer composed of ∼72% l‐LA, ∼12% d‐LA and ∼16% CL. Terpolymers having l‐LA content from ∼60 to 70% and CL content from ∼10 to 27% were also studied. In view of the results, those materials having CL and d‐LA units disrupting the microstructural arrangement of the l‐LA crystallizable chains, an l‐LA content <72% and a random distribution of sequences, may display proper and tunable mechanical behavior and degradation performance for a large number of medical applications. Those with a CL content from 15 to 30% will fulfill the demand of elastomeric materials of T_g higher than 20°C whereas those with a CL content from 5 to 15% might be applied as ductile stiff materials. © 2013 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 102A: 3573–3584, 2014.