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

Abstract

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.

Hybrid Porous Polymers Combination of Octavinylsilsesquioxane/Pyrene with Benzothiadiazole Units for Robust Energy Storage and Efficient Photocatalytic Hydrogen Production from Water

“…A developed porous material, based on polyhedral oligomeric silsesquioxanes (POSS), demonstrates variable properties and a highly symmetrical three-dimensional structure with specified nanometer-sized dimensions. − Its potential lies in the combination of versatile and flexible organic shells surrounding a rigid silica core. It is a promising candidate for synthesizing hybrid nanocomposites that exhibit properties midway between organics and ceramics, − The increasing demand for POSS in scientific research and industry is attributed to their customizable physical and chemical properties. − Another crucial aspect of functionalized silsesquioxanes is their physicochemical properties arising from their hybrid (organic–inorganic) nature. − The Si–O–Si framework, corresponding to silica with a well-defined structure, could serve as an intriguing material for modifying polymers and acting as fillers (nanofillers). − The precise control of molecule sizes and the variation in functional groups within the POSS core allow for their accurate deposition and embedding in a polymer matrix. − This, in turn, results in the creation of composite materials with unique characteristics. These organic–inorganic hybrid materials showcase a diverse range of fascinating physicochemical properties, including alterations in solubility, enhanced dielectric characteristics, improved resistance to oxidation and fire, elevated decomposition and glass transition temperatures, reduced heat transfer rates, and an impact on the hardness of the resulting materials. − …”

“…Additionally, the incorporation of OVS brings the added advantage of modifying the energy gap of the resulting materials. Additionally, the cost-effectiveness of OVS makes it a highly favorable choice for large-scale production. − Porous organic polymers (POPs) derived from OVS, showcase noteworthy attributes, including impressive surface area, well-defined pore size, heat stability, and excellent electrochemical performance. − …”

Construction of micelles and hollow spheres via the self-assembly behavior of poly(styrene-alt-pHPMI) copolymers with poly(4-vinylpyridine) derivatives mediated by hydrogen bonding interactions

“…For example, a PS- b -P4VP self-assembly forms lamellae, double gyroids, and cylinders in bulk-state or spherical micelles in DMF with a PS core and a P4VP corona. 7–11 However, this strategy to form desirable micelle structures is restricted by the molecular weight of block copolymers, leading to a complicated synthesis process. 12–14 Furthermore, the covalent bond interaction at the core and shell interface made the core structure hard to remove to obtain further hollow spheres, for instance, via chemical degradation or calcination.…”

Enhancing Char Formation and Flame Retardancy of Ethylene-Vinyl Acetate Copolymer (EVA)/Aluminum Hydroxide (ATH) Composites by Grafting Ladder Phenyl/Vinyl Polysilsesquioxane (PhVPOSS)

“…Polyhedral oligomeric silsesquioxanes (POSSs) are organic and inorganic hybrid materials with both organic functional groups and inorganic Si-O-Si structures, which usually have good compatibility with polymers and excellent thermal stability [ 17 , 18 , 19 ]. As efficient synergist agents, POSSs can significantly improve flame retardant efficiency without producing harmful gases during processing and reducing the insulation properties of the polymer composites [ 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 ].…”