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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. [ABSTRACT FROM AUTHOR]

In order to enhance the application performance of glycidyl azide polymer (GAP) in solid propellant, an energetic copolyurethane binder, (poly[3,3-bis(2,2,2-trifluoro-ethoxymethyl)oxetane] glycol-block-glycidylazide polymer (PBFMO-b-GAP) was synthesized using poly[3,3-bis(2,2,2-trifluoro-ethoxymethyl)oxetane] glycol (PBFMO), which was prepared from cationic polymerization with GAP as the raw material and toluene diisocyanate (TDI) as the coupling agent via a prepolymer process. The molecular structure of copolyurethanes was confirmed by attenuated total reflectance-Fourier transform-infrared spectroscopy (ATR–FTIR), nuclear magnetic resonance spectrometry (NMR), and gel permeation chromatography (GPC). The impact sensitivity, mechanical performance, and thermal behavior of PBFMO-b-GAP were studied by drop weight test, X-ray photoelectron spectroscopic (XPS), tensile test, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA), respectively. The results demonstrated that the introduction of fluoropolymers could evidently reduce the sensitivity of GAP-based polyurethane and enhance its mechanical behavior (the tensile strength up to 5.75 MPa with a breaking elongation of 1660%). Besides, PBFMO-b-GAP exhibited excellent resistance to thermal decomposition up to 200 °C and good compatibility with Al and cyclotetramethylene tetranitramine (HMX). The thermal performance of the PBFMO-b-GAP/Al complex was investigated by a cook-off test, and the results indicated that the complex has specific reaction energy. Therefore, PBFMO-b-GAP may serve as a promising energetic binder for future propellant formulations. [ABSTRACT FROM AUTHOR]

An azide terminated ethylene oxide‐tetrahydrofuran copolymer with urethane segments (ATUPET) as a novel binder pre‐polymer, has been prepared through ethylene oxide‐tetrahydrofuran random copolymer (PET) end‐capping modification via one‐pot method. The structure characterization of the modifier has been analyzed by FTIR, 1H NMR, 13C NMR and GPC. In comparison with PET, ATUPET has a slightly higher viscosity because it has additional hydrogen bonding interaction generated by the urethane in ATUPET. Triazole cross‐linked elastomers based on ATUPET with various functional molar ratios were prepared using tripropargylamine as a curing agent and cross‐linker. Mechanical properties indicate that the modulus E and tensile strength σb exhibit a parabolic dependence with the increase in R. At around the stoichiometric ratio, the modulus E and tensile strength σb reach a maximum and the elongation at break exhibit an acceptable value at the same time. Swelling tests demonstrate that the apparent cross‐linking densities (N0) have a maximum value at the stoichiometric ratio. Thermal analysis shows that the ATUPET prepolymer and its polytriazoles elastomers exhibit a satisfactory stability. The results demonstrated that ATUPET might be a promising polymeric binder for future propellant formulations especially in the field of isocyanate‐free curing technology. [ABSTRACT FROM AUTHOR]