Advanced aromatic polymers with excellent antiatomic oxygen performance derived from molecular precursor strategy and copolymerization of polyhedral oligomeric silsesquioxane

In this contribution, the advanced aromatic polymers with excellent antiatomic oxygen (AO) performance were designed and synthesized using molecular precursor strategy and copolymerization of polyhedral oligomeric silsesquioxane (POSS). A soluble poly(p-phenylene benzobisoxazole) (PBO) precursor, that is, TBS-PBO (tert-butyldimethylsilyl was denoted as TBS), was designed to overcome the poor solubility of PBO in organic solvents. Then the new copolymer of TBS-PBO-POSS was synthesized by the copolymerization of TBS-PBO and POSS, which possessed good solubility and film-forming ability in common organic solvents, such as N-methylpyrrolidone, N,N-dimethylacetamide, and dimethyl sulfoxide. More importantly, the TBS-PBO-POSS films exhibited outstanding antiatomic oxygen properties because of the incorporation of POSS monomers with cagelike structure into the main chain of copolymer, which drastically reduced the AO-induced erosion owing to the formation of the passivating silica layer on the surface of polymers. When the TBS-PBO-POSS films were exposed to AO effective fluences of 1.5495 × 10²⁰ atom cm^-2 (5 h) and 4.6486 × 10²⁰ atom cm^-2 (15 h), the relative mass loss was merely 0.19% and 0.41%, respectively. This work provides a new perspective and efficient strategy for the molecular design of aromatic heterocyclic polymers possessing excellent combination properties including processing convenience and antioxidative and mechanical properties, which can be employed as potential candidates to endure the aggressive environment encountered in low earth orbits.