SYNOPSISBioabsorbable poly (ester-urethane) networks were synthesized from ethyl 2,6-diisocyanatohexanoate (L-lysine diisocyanate) (LDI) and a series of polyester triols. LDI was synthesized by refluxing L-lysine monohydrochloride with ethanol to form the ester, which was subsequently refluxed with 1,1,1,3,3,3-hexamethyldisilazane to yield a silazane-protected intermediate. This product was then phosgenated using triphosgene. Polyester triols were synthesized from D,L-lactide, c-caprolactone, or comonomer mixtures thereof, using glycerol as initiator and stannous octoate as catalyst. Polyurethane networks were cured using[ NCO] / [ OH] = 1.05 and stannous octoate (0.05 wt % ) for 24 h at room temperature and pressure and 24 h at 5OoC and 0.1 mm Hg. LDI-based polyurethane networks were totally amorphous and possessed very low sol contents. Networks based on poly (D,L-lactide) triols were rigid ( Tg E 60°C) with ultimate tensile strengths of -40-70 MPa, tensile moduli of -1.2-2.0 GPa, and ultimate elongations of -4-10%. Networks based on c-caprolactone triols were low-modulus elastomers with tensile strengths and moduli of -1-4 MPa and -3-6 GPa, respectively, and ultimate elongations of -50-300%. Networks based on copolymers displayed physical properties consistent with monomer composition and were tougher than the networks based on the homopolymers. Tensile strengths for the copolymers were -3-25 MPa with ultimate elongations up to 600%. Hydrolytic degradation under simulated physiological conditions showed that D,L-lactide homopolymer networks were the most resistant to degradation, undergoing virtually no change in mass or physical properties for 60 days. e-Caprolactone-based networks were resistant to degradation for 40 days, and high-lactide copolymer-based networks suffered substantial losses in physical properties after only 3 days.
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