Biomedical segmented polyurethanes based on polyethylene glycol, poly(ε-caprolactone-co-D,L-lactide), and diurethane diisocyanates with uniform hard segment: Synthesis and properties

Abstract

ABSTRACTIn the study, a new approach for synthesizing biomedical segmented polyurethanes (SPUs) based on polyethylene glycol (PEG, Mn = 800), poly(ε-caprolactone-co-D,L-lactide) (PCLA) and aliphatic diurethane diisocyanates with a long uniform hard segment was developed. By the chain extension of a mixture of PEG diol and PCLA diol with diurethane diisocyanates based on inexpensive 1,6-hexanediisocyanate, three SPUs (SPU-I, SPU-II, and SPU-III) with different contents of hydrophilic segments (PEG) and hard segments were obtained. The chemical structures of diurethane diisocyanates, PCLA and SPUs were confirmed by 1H NMR, 13C NMR, FT-IR, HR-TOF-MS, and GPC. The SPU films exhibited similar thermostability, indicating that the hard segment content marginally affects on the thermostability. From the results of differential scanning calorimetry, two glass transition temperatures were observed, suggesting the microphase separation of soft and hard segments. The SPU films exhibited satisfactory mechanical properties with ultimate stress of 17.4–22.3 MPa and strain at break of 890–1060%, and the initial modulus increased with the increasing content of hard segments. In vitro degradation studies indicated that the time of SPU films to become fragments was 22–33 days, and the degradation rate increased with the increasing content of hydrophilic segments in SPU. Hence, the degradation time of SPU films could be controlled by adjusting the PEG content in SPU, which made them good candidates for further biomedical applications. Studies of in vitro drug release were conducted using vitamin B1 as model drugs. Drug-loaded films exhibited a high initial release rate and matrix-controlled release for more than two weeks, thereby demonstrating a promising material for a long-acting controlled release system. Cytotoxicity test of film extracts and cell attachment on the film surface were conducted using L929 mouse fibroblasts, and the results indicated that the SPU films possess excellent cytocompatibility and cell adhesive ability.