Organic‐Inorganic Phenolic/POSS Hybrids Provide Highly Ordered Mesoporous Structures Templated by High Thermal Stability of PS‐b‐P4VP Diblock Copolymer

• Published in: Chemistry : a European journal 2023-05, Vol.29 (30), p.e202300538-n/a
• Main Authors: Chou, Ting‐Chih, Chen, Wei‐Cheng, Mohamed, Mohamed Gamal, Huang, Yen‐Chi, Kuo, Shiao‐Wei
• Format: Article
• Language: English
• Subjects: Block copolymers; Bonding strength; Chemistry; Fourier transforms; Hybrids; Hydrogen bonding; Infrared analysis; Infrared spectroscopy; mesoporous materials supercapacitors; Mixtures; Phenolic compounds; Phenolic resins; Phenols; Polyhedral oligomeric silsesquioxane; Polymerization; Polystyrene resins; Pyridines; self-assembled structures; Self-assembly; Styrene; supramolecular interaction; Thermal stability; Transmission electron microscopy
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202300538

Anionic living polymerization was used to prepare a diblock copolymer of poly(styrene‐b‐4‐vinyl pyridine) (PS‐b‐P4VP), and a phenolic resin with a double‐decker silsesquioxane (DDSQ) cage structure was used to form a phenolic/DDSQ hybrid (PDDSQ‐30 with 30 wt.% DDSQ). Strong intermolecular hydrogen bonding could be confirmed through the hydroxyl (OH) groups of PDDSQ hybrid with the pyridine group of the P4VP block in PDDSQ‐30/PS‐b‐P4VP blends based on Fourier transform infrared spectroscopy analyses, where increasing PDDSQ concentrations resulted in a higher proportion of hydrogen‐bonded pyridine groups. After thermal polymerization at 180 °C, the self‐assembled structures of these PDDSQ/PS‐b‐P4VP blends were revealed by data from small‐angle X‐ray scattering (SAXS) and transmission electron microscopy (TEM), where the d‐spacing increased with raising PDDSQ concentration. Because relatively higher thermal stability of the PDDSQ hybrid than pure phenolic resin and PS‐b‐P4VP template, we can obtain the long ranger order of mesoporous PDDSQ hybrids after removing the PS‐b‐P4VP template, which reveals the high surface area and high pore volume with cylindrical and spherical structures corresponding to the PDDSQ compositions that are rarely observed by using pure phenolic resin as the matrix and could be used in supercapacitor application. Mesoporous PDDSQ hybrids were prepared by using PS‐b‐P4VP as a template by mediated the hydrogen bonding interaction through the hydroxyl (OH) groups of PDDSQ hybrid with the pyridine group of the P4VP block. The highly ordered structures reveal the high surface area and high pore volume that could be used in supercapacitor application.