Hydrogen Bond Interactions Mediate Hierarchical Self-Assembly of POSS-Containing Block Copolymers Blended with Phenolic Resin

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• 作者：Chin-Wei Chiou ; Yung-Chih Lin ; Lei Wang ; Rina Maeda ; Teruaki Hayakawa ; Shiao-Wei Kuo
• 刊名：Macromolecules
• 出版年：2014
• 出版时间：December 23, 2014
• 年：2014
• 卷：47
• 期：24
• 页码：8709-8721
• 全文大小：958K
• ISSN：1520-5835

文摘

Poly(methyl methacrylate)-b-poly(methacryloyl polyhedral oligomeric silsesquioxane) (PMMA-b-PMAPOSS) block copolymers of various compositions were prepared through anionic living polymerization. We employed differential scanning calorimetry, Fourier transform infrared spectroscopy, small-angle X-ray scattering, transmission electron microscopy, and wide-angle X-ray diffraction to investigate the miscibility, specific interactions, and hierarchical self-assembly of PMMA-b-PMAPOSS block copolymers blended with a phenolic resin. We found that the added phenolic resin interacted preferentially with the PMMA blocks through hydrogen bonding between the OH groups of the former and the C鈺怬 groups of the PMAPOSS. In other words, the OH groups of the phenolic resin did not interact with the C鈺怬 groups of the PMAPOSS blocks, resulting in their immiscibility. Accordingly, this phenolic/PMMA-b-PMAPOSS blend behaved as a blend of homopolymer C and immiscible A-b-B diblock copolymer, where C is immiscible with B but interacts favorably with A; therefore, it displayed an order鈥搊rder phase transition with increased phenolic resin content. Hierarchical self-assembly led to the formation of hexagonally packed cylindrical or lamellar nanostructures through microphase separation of the diblock copolymer segment, with POSS aggregates packing into a hexagonal lattice oriented perpendicular to the direction of the nanostructures.