Resin Transfer Moldable Fluorinated Phenylethynyl-Terminated Imide Oligomers with High T_g: Structure-Melt Stability...

Phenylethynyl-terminated aromatic polyimides meet requirements of resin transfer molding (RTM) and exhibits high glass transition temperature (T_g) were prepared. Moreover, the relationship between the polyimide backbones structure and their melting stability was investigated. The phenylethynyl-terminated polyimides were based on 4,4'-(hexafluorosiopropylidene)-diphthalic anhydride (6FDA) and different diamines of 3,4'-oxydianiline (3,4'-ODA), m-phenylenediamine (m-PDA) and 2,2'-bis(trifluoromethyl)benzidine (TFDB) were prepared. These oligoimides exhibit excellent melting flowability with wide processing temperature window and low minimum melt viscosities (<1 Pa·s). Two of the oligoimides display good melting stability at 280-290 °C, which meet the requirements of resin transfer molding (RTM) process. After thermally cured, all resins show high glass transition temperatures (T_gs, 363-391 °C) and good tensile strength (51-66 MPa). The cure kinetics studied by the differential scanning calorimetry (DSC), ¹³C nuclear magnetic resonance (¹³C NMR) characterization and density functional theory (DFT) definitely confirmed that the electron-withdrawing ability of oligoimide backbone can tremendously affect the curing reactivity of terminated phenylethynyl groups. The replacement of 3,4'-ODA units by m-PDA or TFDB units increase the electron-withdrawing ability of the backbone, which increase the curing rate of terminated phenylethynyl groups at processing temperatures, hence results in the worse melting stability.