High-performance thermal insulating materials are highly desirable in several fields, especially for thermal insulation of buildings to reduce energy consumption. Owing to the remarkable thermal stability, high porosity, low density, and outstanding mechanical features, polyimide (PI) aerogels have attracted great attention. In this work, chemical cross-linked PI (CCPI) aerogels were fabricated via freeze-drying and thermal imidization, which possess outstanding mechanical properties, good thermal stability, and excellent thermal insulation characteristics. The chemically cross-linked structure can effectively inhibit shrinkage, while retaining the structural integrity, resulting in the lower density and lower shrinkage of the materials. In this paper, completely imidized and highly cross-linked polyimide aerogels were synthesized by using p-phenylenediamine (PDA), 3,3′,4,4′biphenyltetracarboxylic dianhydride (BPDA), and the cross-linker 2,3,6,7,14,15-hexaaminotriptycene (HMT). The CCPI aerogels with excellent properties, such as covalently cross-linked chemical structure, low density (0.069 g/cm 3 ), low volume shrinkage (10%), high decomposition temperature (T d5% = 587 °C), and low thermal conductivity (25 mW m −1 K −1 ) are in high demand in the field of thermal insulation. This work furnishes a new method for the development of polymer-based thermal insulation materials for various prospective applications.
