Prevention of polyurethane oxidative degradation with phenolic antioxidants covalently attached to the hard segments: Structure–function relationships

Abstract

Oxidative degradation of the polyurethane elastomeric (PU) components greatly reduces the efficacy of PU-containing cardiovascular devices. Covalently appending the phenol-based antioxidant, 4-substituted 2,6-di-tert-butylphenol (DBP), to PU hard segments effectively reduced oxidative degradation of the PU in vivo and in vitro in prior studies by our group. In these experiments, we analyze the contribution of the tethering molecule to the antioxidant capabilities of the DBP-modified PU. Bromoalkylation chemistry was used to link DBP to the hard segment of the polyether PU, Tecothane, via our original linker (PU-DBP) or variants containing side chains with one (PU-C-DBP) or three (PU-3C-DBP) carbons. Two additional DBP variants were fabricated in which the DBP group was appended to the alkyl chain via an oxygen atom (PU-O-DBP) or an amide linkage in the middle of the tether (PU-NHCO-DBP). All DBP variant films and unmodified control films were subject to oxidative degradation via 15-day immersion in a solution of 20% H₂O₂ + 0.1M CoCl₂. At the end of the oxidation protocol, films were analyzed for the presence of oxidation-related endpoints via scanning electron microscopy, contact angle measurements, and Fourier transformation infrared spectroscopy (FTIR). All DBP-containing variants resisted oxidation damage significantly better than the unmodified control PU. SEM analysis of oxidized PU-C-DBP and PU-O-DBP showed evidence of surface cracking, consistent with oxidative degradation of the PU surfaces. Similarly, there was a trend in increased ether crosslinking, a marker for oxidative degradation, in PU-C-DBP and PU-NHCO-DBP films. Consistent with these FTIR results, both PU-C-DBP and PU-NHCO-DBP had significant reductions in measured surface hydrophobicity as a result of oxidation. These data show for the first time that the choice of linker molecule significantly affects the efficiency of the linked phenolic antioxidant. © 2010 Wiley Periodicals, Inc. J Biomed Mater Res Part A, 2010