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    Self-assembly of an A-B diblock copolymer blended with a C homopolymer and a C-D diblock copolymer through hydrogen bonding interaction
    (2010-08-19)
    Chen, Wan-Chun
    ;
    Kuo, Shiao-Wei
    ;
    Chang, Feng-Chih
    ;
    應用化學系
    ;
    Department of Applied Chemistry
    In this study, we investigated the miscibility, phase behavior, and self-assembled nanostructures formed from the immiscible crystalline-amorphous diblock copolymer poly(epsilon-caprolactone-b-4-vinyl pyridine) (PCL-b-P4VP, A-B) when blended with the homopolymer poly(vinyl phenol) (PVPh, C) and the diblock copolymer poly(vinyl phenol-b-styrene) (PVPh-b-PS, C-D). Long-range-ordered microphase separation was difficult to achieve in the PCL-b-P4VP/PVPh (A-B/C) blend system because PVPh interacted with both the P4VP and PCL blocks simultaneously through hydrogen bonding interactions. In contrast, we observed sharp, multiple orders of diffraction in the SAXS profiles of the PCL-b-P4VP/PVPh-b-PS (A-B/C D) blend system, indicating that perfect microphase separation occurred because the incorporation of the PS block induced the PVPh block to hydrogen bond preferentially with the P4VP block. This simple A-B/C-D (PCL-b-P4VP/PVPh-b-PS) diblock copolymer mixture exhibited self-assembly behavior (a three-lamella phase) similar to that of a corresponding ABC triblock copolymer. (C) 2010 Elsevier Ltd. All rights reserved.
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    Supramolecular self-assembly through inclusion complex formation between poly(ethylene oxide-b-N-isopropylacrylamide) block copolymer and alpha-cyclodextrin
    (2009-06-19)
    Tu, Cheng-Wei
    ;
    Kuo, Shiao-Wei
    ;
    Chang, Feng-Chih
    ;
    應用化學系
    ;
    Department of Applied Chemistry
    A well-defined poly(ethylene oxide-block-N-isopropylacrylamide) (PEO-b-PNIPAM) diblock copolymer was synthesized by atom transfer radical polymerization and formed the inclusion complexes (ICs) after selective threading of the PEO segment of the block copolymer through the cavities of alpha-cyclodextrin (alpha-CD) units. The formation of the alpha-CD/PEO ICs between alpha-CD and PEO segment of the PEO-b-PNIPAM transformed the system from its original random coil conformation into a rod/coil-like structure. The stacking of the alpha-CD/PEO ICs and phase separation within the alpha-CD/PEO-b-PNIPAM IC resulted in the self-assembly of long-range-ordered lamellar structure exhibiting alternating layers of (i) alpha-CD/PEO ICs with hexagonally packed plates and (ii) amorphous phase of unincluded PEO/PNIPAM with brush conformation. (C) 2009 Elsevier Ltd. All rights reserved.
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    Self-Assembly structures through competitive interactions of miscible crystalline-amorphous diblock copolymer/homopolymer blends
    (2009-10-20)
    Lin, I-Hong
    ;
    Kuo, Shiao-Wei
    ;
    Chang, Feng-Chih
    ;
    應用化學系
    ;
    Department of Applied Chemistry
    A series of miscible crystalline-amorphous diblock copolymers, (poly(epsilon-caprolactone)-b-(vinyl phenol), PCL-b-PVPh) were prepared through sequential ring-opening and controlled living free radical (nitroxide-mediated) polymerizations and then blended with poly(vinyl pyrrolidone) (PVP) homopolymer. Specific interactions, miscibility, and self-assembly morphologies mediated by hydrogen bonding interactions of this new A-B/C type blend, were investigated in detail. Micro-phase separation of these miscible PCL-b-PVPh diblock copolymers occurs by blending with PVP through competitive hydrogen bonding interaction in this A-B/C blend. FTIR, XRD, and DSC analyses provide positive evidences that the carbonyl group of PVP is a significantly stronger hydrogen bond acceptor than PCL, thus the PCL block is excluded from the PVPh/PVP miscible phase to form self-assembly structure. (13)C CP/MAS solid-state NMR spectra provide additional evidence confirming that micro-phase separation occurs in the blend system because of the presence of more than two T(1p)(H) values for this A-B/C blend system. According to the result of the FTIR and SAXS results, the smaller molecular weight system contains a greater fraction of the hydrogen-bonded carbonyl group, cause indirectly the high degree of phase separation among these blends. In addition, the SAXS profiles possess a sharp primary peak and highly long range ordered reflections q/q* ratios of 1:2:3 at lower PVP content, an indication of the lamellar structure in the blend which is consistent with TEM image. The phase behavior and morphology shifts from lamellar to cylinder structure with further increase in the PVP content. (C) 2009 Elsevier Ltd. All rights reserved.