To provide high-temperature polyimide matrix resins, novel carborane-containing thermosetting polyimides are presented. First, the low-viscosity carborane-containing imide oligomers are synthesized using newly designed 1-(3-amino-4-tolyl)-2-(4-aminophenyl)-o-carborane and aromatic dianhydride as monomers, 4-phenylethynyl phthalic anhydride as the end-capping reagent. Followed by thermal curing, the resulting polyimides show high T (≥500 °C) and above 92.1% char yield at 800 °C both in nitrogen and air atmosphere due to the incorporation of the bulky carborane cages. Aging studies, performed at 400 and 500 °C for 5 h in air on a carborane-containing polyimide and a carborane-free polyimide, show that the polyimide with carborane groups possesses excellent thermo-oxidative stability. Moreover, the novel polyimides exhibit constant and relatively low coefficient of thermal expansion values over a wide range of temperature, indicative of a remarkable dimensional stability. Thus, this study clearly demonstrates the viability of the incorporation of carborane cages to access polyimide thermosets with ultrahigh T and thermo-oxidative stability.

No abstract

In this study, we report the preparation of thermosetting polyimides (PIs) based on carborane-containing tetramine and their characterizations. The novel tetramine 1,2-bis(4-(3,5-diaminobenzoic acid phenyl ester))carborane (CBNH) was synthesized and characterized firstly. Then, it was used in the preparation of two kinds of branched imide oligomers via the method of thermal imidization. The cure behavior of the obtained phenylethynyl-terminated oligomers was investigated by differential scanning calorimetry. The effect of carborane substituent on the thermal properties of PIs was studied by comparing with a similar structure without the carborane group. The thermal properties of PIs and carbon fiber/PI composites were investigated by thermal gravimetric analysis and dynamic mechanical analysis, respectively. Because of the introduction of high steric hindrance of carborane structure, the resulting thermosets and carbon fiber/PI composites had excellent thermal property with a high char yield at 800°C (>66.5%) and a high glass transition temperature (up to 500°C), respectively.

Novel carborane-containing bismaleimides with excellent heat resistance and dimensional stability for advanced composites are presented. First, a new kind of carborane-containing mono-maleimido-terminated monomer 1-(4-tolyl)-2-(4-maleimido phenyl)- o-carborane (CB-MI) was synthesized and characterized by FT-IR and 1H-NMR. Then, it was used as a modifier for bismaleimide resin 4,4’-bismaleimidodiphenylmethane (BDM) with different weight fraction of CB-MI. The curing behavior and thermal property of the CB-MI/BDM resin systems were studied and presented here. Results displayed that a wide processing window and low curing temperature provided a good processability for the CB-MI/BDM resin system. Due to the effect of carborane groups, the char yield at 600°C of the cured resin systems tended to be increased with the addition of CB-MI. Moreover, the coefficient of thermal expansion of the resin was found to be reduced with the increase of CB-MI, indicative of a remarkable dimensional stability. This study might open up great opportunities for the preparation and design of various novel bismaleimides in a simple and feasible way and the resins with good thermal property and processability at the same time.

A novel carborane-containing imide monomer (CB-PEPA) was synthesized and used as a modifier for phenylethynyl-terminated imide oligomer (PI-mPDA) to study the effect on the performance of the oligomers and thermosetting polyimide materials. The curing behavior of the blends of CB-PEPA and PI-mPDA was investigated by differential scanning calorimetry (DSC). It showed that CB-PEPA had a melting point at 183°C. Nonisothermal DSC showed that imide monomer had higher activation energy than that of bifunctional imide oligomer. Rheometer study showed that the monomer CB-PEPA could be used as a reactive diluent for PI-mPDA to reduce the minimum melt viscosity and broaden the process window of imide system. Thermogravimetric analysis showed that the char yield of resin increased with the addition of CB-PEPA. The resin derived from a 25 wt% CB-PEPA loading in PI-mPDA exhibited a high char yield of 81.0% at 800°C in nitrogen. Due to the steric hindrance and rigid group of carborane, the Tg of composites also increased with the addition of CB-PEPA. Composites derived from a 10 wt% CB-PEPA loading in PI-mPDA exhibited the relatively higher flexural strength and interlaminar shear strength.