Properties and degradation of castor oil-based fluoridated biopolyurethanes with different lengths of fluorinated segments

Abstract

To develop a durable, biodegradable polymer, this study successfully synthesized a castor-oil-based prepolymer by using methylene diphenyl diisocyanate as a hard segment, polycaprolactone as a soft segment, and castor oil as a functional monomer. We added perfluorinated alkyl segments with varying chain lengths into the castor-oil-based polymer to synthesize castor-oil-based fluoridated biopolyurethanes (FCOPUs) with different fluorinated segment lengths. The castor-oil-based polyurethanes with different fluorinated segment lengths had similar molecular weights, which enabled accurate analysis of the effect of the lengths of fluorinated segments on FCOPUs. Nuclear magnetic resonance (NMR) was used to perform ¹H NMR, ¹⁹F NMR, ¹⁹F–¹⁹F COSY, ¹H–¹⁹F COSY, and HMBC analyses on the FCOPU structures. The results of Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy curve fitting verified the interaction between C–F⋯H–N and C–F⋯CO. This interaction increased as the fluorinated segments became longer. Regarding the thermal properties of the FCOPUs, the thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis results revealed that long fluorinated segments were associated with increased thermal stability in the FCOPUs. The atomic force microscopy and tensile strength test suggested that long fluorinated segments contained in the FCOPUs increased the degree of phase separation and tensile strength in FCOPUs. Finally, we dipped the FCOPUs in a 3 wt% NaOH solution, calculated the weight loss of the FCOPUs, and observed their surface structure by using scanning electron microscopy.