Synthesis and Properties of Thermally Self-Healing PET Based Linear Polyurethane Containing Diels–Alder Bonds

Abstract

A Diels–Alder (DA) bond containing poly(tetrahydrofuran)-co-(ethyleneoxide) (PET) based linear polyurethane (PET-DA-PU) was synthesized via a prepolymer process using PET as raw material, DA diol as chain extender agent, and toluene-2,4-diisocyanate (TDI) as coupling agent. The structure of PET-DA-PU was characterized by attenuated total reflectance-Fourier transform-infrared spectroscopy (ATR-FTIR), proton nuclear magnetic resonance spectrometry (1H NMR) and carbon nuclear magnetic resonance spectrometry (13C NMR). The thermal performance and self-healing behavior of PET-DA-PU were investigated by differential scanning calorimetry (DSC), polarized optical microscope, universal testing machine, scanning electron microscopy (SEM) and NMR, respectively. The glass transition temperature of PET-DA-PU was found to be −59 °C. Under the heat treatment at 100 °C, the crack on PET-DA-PU film completely disappeared in 9 min, and the self-healing efficiency that was determined by the recovery of the largest tensile strength after being damaged and healed at 100 °C for 20 min can reach 89.1%. SEM images revealed the micro-cracks along with the blocky aggregated hard segments which were the important reasons for fracture. NMR spectroscopy indicated that the efficiency of retro DA reaction of PET-DA-PU was 70% after 20 min heating treatment at 100 °C. Moreover, the PET-DA-PU/Al/Na2SO4 composite was also prepared to simulate propellant formulation and investigated by universal testing machine and SEM; its healing efficiency was up to 87.8% under the same heat treatment process and exhibits good self-healing ability. Therefore, PET-DA-PU may serve as a promising thermally self-healing polymeric binder for future propellant formulations.