接枝效應對超分子共聚物薄膜微相分離形態之影響

李治宏

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接枝效應對超分子共聚物薄膜微相分離形態之影響

Grafting effects on the morphology of block copolymer–based supramolecular thin films

李治宏 , Masters　　Advisor：童世煌　　

繁體中文

超分子；共聚物薄膜；自組裝；溶劑退火；接枝度； Supramolecular ； copolymer thin film ； self-assembly ； solvent annealing ； bonding fraction

Abstract │ Reference (73) │ Altmetrics

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Our research is based on comb-coil supramolecular microphase separation. Well-ordered nanostructured polymer thin films have been fabricated from the supramolecular assembly of poly(styrene-block-4-vinylpyridine) (PS-P4VP) and 3-n-Pentadecylphenol (PDP) by solvent annealing. In this system, the microphase separation occurs not only between PS and P4VP but also P4VP and PDP hydrophobic tails. Therefore, these thin films form both large-scaled microdomains (~40nm) and small-scaled (~4nm) lamellae, i.e. hierarchical structures. Interestingly, the orientation can be tailored by PDPs: after thin films are solvent annealed, the microdomains formed by block copolymers, including cylinders and lamellae, can be oriented perpendicular to the surface, while the small-scaled lamellae formed by PDP are parallel to the surface. We found that the amount of incorporated PDP is the key for such transformation and thus we conclude that the orientation is controlled by small-scaled lamellae. The mechanism will be discussed in the thesis.
  In this research we also found that the use of high polar solvents, such as THF and 1,4-dioxane, to anneal thin films will reduce the strength of hydrogen bonds between PDP and 4VP, which would hinder the formation of perpendicular block copolymer microdomains. In the final part of the thesis, we will discuss how solvent vapor pressure and different casting solvents affect the final morphology of thin films.

Reference ( 73 ) 〈TOP〉

1. Tung, S.H., et al., Hierarchical assemblies of block-copolymer-based supramolecules in thin films. Macromolecules, 2008. 41(17): p. 6453-6462.
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2. van Zoelen, W., E. Polushkin, and G. ten Brinke, Hierarchical Terrace Formation in PS-b-P4VP(PDP) Supramolecular Thin Films. Macromolecules, 2008. 41(22): p. 8807-8814.
連結：
3. Lehn, J.M., SUPRAMOLECULAR CHEMISTRY - SCOPE AND PERSPECTIVES MOLECULES, SUPERMOLECULES, AND MOLECULAR DEVICES. Angewandte Chemie-International Edition in English, 1988. 27(1): p. 89-112.
連結：
4. Ciferri, A., Supramolecular liquid crystallinity as a mechanism of supramolecular polymerization. Liquid Crystals, 1999. 26(4): p. 489-494.
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5. Meier, D.J., THEORY OF BLOCK COPOLYMERS .I. DOMAIN FORMATION IN A-B BLOCK COPOLYMERS. Journal of Polymer Science Part C-Polymer Symposium, 1969(26PC): p. 81-&.
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