In this study, we prepared ordered mesoporous phenolic resins templated by poly(ethylene oxide)-b-(ε-caprolactone) (PEO-b-PCL) diblock copolymers blended with a star PEO octa-functionalized polyhedral oligomeric silsesquioxane (PEO-POSS) homopolymer. Increasing the PEO-POSS content, and thereby increasing the PEO-to-PCL ratio in the template film, allowed us to tune and enhance the long-range order of the mesoporous phenolic resin. The increased pore size and the more ordered structure were accompanied by a narrower pore size distribution. In addition, we observed an ordered-to-ordered mesophase transition, from a bicontinuous gyroid to a hexagonally packed cylinder structure, upon blending with the star PEO-POSS homopolymer. We anticipate that this approach could be extended to the preparation of other large-pore, long-range-ordered mesoporous materials, such as silica and other metal oxides.
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