Abstract Photocurable polymer provides fast curable properties via ultraviolet (UV) light for 3D‐printed propellants. This work outlines the preparation and characterization of photocurable fluorinated polyether‐based reactive inks. Acrylate‐terminated poly‐2‐((2,2,3,3,3‐pentafluoropropoxy)‐methyl) ethylene oxide (P5F‐AA) was synthesized as photocurable binder through the esterification of acrylic acid, and the terminal hydroxyl group of poly‐2‐((2,2,3,3,3‐pentafluoropropoxy)‐methyl) ethylene oxide (P5F), which was synthesized through cationic ring‐opening polymerization of 2‐((2,2,3,3,3‐pentafluoropropoxy)methyl) oxy‐ethane (PFEE) by using butane diol as initiator. In comparison with P5F, P5F‐AA had a lower glass transition temperature (Tg) of −63.3°C. A new type of photocurable resin, which may be used for additive manufacturing of energetic materials, was prepared via UV radiation in an LED UV curing tank by using P5F‐AA as prepolymer, diphenyl (2,4,6‐trimethyl benzoyl) phosphine oxide (TPO) as photo‐initiator, and tri‐fluoroethyl acrylate (3F‐AA) and 1,6‐hexanediol diacrylate (HDDA) as mono‐ and multifunctional diluents, respectively. When the mass ratio of P5F‐AA/3F‐AA/HDDA binder matrix was 1:1:0.5, the sample exhibited maximal mechanical strength of 6.56 MPa with elongation at break of 13.38, which was due to the introduction of HDDA effectively increasing the “entanglement” between molecular chains. Thermogravimetric analysis (TGA‐DTG) was utilized to evaluate the ability to decompose thermally of the binder matrix, and the results showed the initial degradation temperature started at nearly 181°C and two consecutive stages in thermal decomposition. Overall, the obtained results from the different techniques suggested that P5F‐AA/3F‐AA/HDDA binder matrix may be a photocurable reactive ink for 3D‐printed propellants, which would provide a certain reference value and guiding importance for design of reactive inks.
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