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Self-supporting Polymer from a POSS Derivative
(2011-06-16)
Cheng, Chih-Chia
;
Yen, Ying-Chieh
;
Chang, Feng-Chih
;
應用化學系
;
Department of Applied Chemistry
A new polyhedral oligomeric silsesquioxane macromer, octakis[N-(6-aminopyridin-2-yl)-undecanamide-10-dimethyl-siloxy]silsesquioxane (POSS-C11-Py), containing eight diaminopyridine arms, is able to self-assemble to form a physically crosslinked polymer-like structure with good mechanical properties (tensile strength = 46.1 MPa, tensile modulus = 0.58 GPa, elongation = 49.3%) through quadruple hydrogen bonding interactions between these arms. POSS-C11-Py is the first organic/inorganic supermolecule possessing polymer-like mechanical properties as a result of self-complementary interactions, providing a potential route toward the design and fabrication of polymer-like supramolecular materials.
Micellar morphologies of self-associated diblock copolymers in acetone solution
(2007-05-21)
Tung, Pao-Hsiang
;
Kuo, Shiao-Wei
;
Chen, Shih-Chien
;
Lin, Chen-Lung
;
Chang, Feng-Chih
We describe the synthesis and solution morphologies of poly(vinyl phenol-b-styrene) (PVPh-b-PS) micelles and the effects that changing the copolymer composition and concentration have on self-assembly structures of PVPh-b-PS in acetone (a good solvent for PVPh). These PVPh-b-PS copolymers aggregated into spherical, rod-like, and vesicular morphologies. The transformations of the PVPh-b-PS block copolymer micelles in acetone depended on a number of parameters, including the relative block lengths, their concentrations, and the degree of self-association through hydrogen bonding of the coronal PVPh chains. We also investigated the morphologies of the micelles formed from acetone solutions of poly (4-tert-butoxystyrene-b-styrene) (PtBOS-b-PS) copolymers having the same degree of polymerization as the precursor of PVPh-b-PS copolymer before hydrolysis reaction. Our results indicate that the micelles formed from PVPh-b-PS copolymers in acetone were more complicated than those prepared from PtBOS-b-PS copolymers in acetone because hydrogen bonding occurs in the micelle corona of the PVPh block. Finally, we also discussed the morphology transition when the self-association hydrogen bonding of PVPh block was destroyed by adding proton acceptor poly(4-vinylpyridine) (P4vp). (c) 2007 Elsevier Ltd. All rights reserved.
Syntheses and characterizations of the multiple morphologies formed by the self-assembly of the sernicrystalline P4VP-b-PCL diblock copolymers
(2007-08-10)
Chan, Shih-Chi
;
Kuo, Shiao-Wei
;
Lu, Chu-Hua
;
Lee, Hsin-Fang
;
Chang, Feng-Chih
A series of semicrystalline diblock copolymers of poly(4-vinylpyridine-b-epsilon-caprolactone) (P4VP-b-PCL) have been synthesized by the living ROP of CL followed by the TEMPO polymerization of 4-VP. Depending on the relative block length and different solvent compositions, these copolymers self-assemble into different supramolecular structures in toluene/dichloromethane (DCM) solution, including spherical micelles, bowl-shaped vesicles, multilayer vesicles, porous spheres, and large compound micelles. In methanol/DCM solution system, the crystalline PCL core disturbs the balance of free energy, thus results in a series of morphological changes including spherical micelles, worm-like rods, vesicles, coexisted vesicles and lamella, and finally platelet lamella. (c) 2007 Elsevier Ltd. All rights reserved.
Supramolecular micellization of diblock copolymer mixtures mediated by hydrogen bonding for the observation of separated coil and chain aggregation in common solvents
(2008-02-01)
Kuo, Shiao-Wei
;
Tung, Pao-Hsaing
;
Lai, Chih-Ling
;
Jeong, Kwang-Un
;
Chang, Feng-Chih
This paper describes a new approach towards preparing self-assembled hydrogen-bonded complexes that have vesicle and patched spherical structures from two species of block copolymer in non-selective solvents. The assembly of vesicles from the intermolecular complex formed after mixing polystyrene-block-poly(4-vinyl phenol) (PS-b-PVPh) with poly(methyl methacrylate)-block-poly(4-vinylpyridine) (PMMA-b-P4VP) in tetrahydrofuran (THF) is driven by strong hydrogen bonding between the complementary binding sites on the PVPh and P4VP blocks. In contrast, well-defined patched spherical micelles form after blending PS-b-PVPh with weaker hydrogen bonds form between the PVPh and P4VP blocks in DMF, relative to those in THF, which results in the formation of spherical micelles that have compartmentalized coronas that consist of PS and PMMA blocks.
Synthesis and self-assembly of helical polypeptide-random coil amphiphilic diblock copolymer
(2008-05-01)
Kuo, Shiao-Wei
;
Lee, Hsin-Fang
;
Huang, Chih-Feng
;
Huang, Cheng-Jynn
;
Chang, Feng-Chih
Three amphiphilic rod-coil diblock copolymers, poly(2-ethyl-2-oxazoline-b-/-benzyl-L-glutamate) (PEOz-b-PBLG),G), incorporating the same-length PEOz block length and various lengths of their PBLG blocks, were synthesized through a combining of living cationic and N-carboxyanhydride (NCA) ring-opening polymerizations. In the bulk, these block copolymers display thermotropic liquid crystalline behavior. The self-assembled aggregates that formed from these diblock copolymers in aqueous solution exhibited morphologies that differed from those obtained in alpha-helicogenic solvents, that is, solvents in which the PBLG blocks adopt rigid alpha-helix conformations. In aqueous solution, the block copolymers self-assembled into spherical micelles and vesicular aggregates because of their amphiphilic structures. In helicogenic solvents (in this case, toluene and benzyl alcohol), the PEOz-b-PBLG copolymers exhibited rod-coil chain properties, which result in a diverse array of aggregate morphologies (spheres, vesicles, ribbons, and tube nanostructures) and thermoreversible gelation behavior. (C) 2008 Wiley Periodicals, Inc.
Surface Modification of Gold Nanoparticles with Polyhedral Oligomeric Silsesquioxane and Incorporation within Polymer Matrices
(2009-04-15)
Kuo, Shiao-Wei
;
Wu, Yung-Chien
;
Lu, Chu-Hua
;
Chang, Feng-Chih
;
應用化學系
A new approach to achieve polymer-mediated gold ferromagnetic nanocomposites in a polyhedral oligomeric silsesquioxane (POSS)-containing random copolymer matrix has been developed. Stable and narrow distributed gold nanoparticles modified by 3-mercaptopropylisobutyl POSS to form Au-POSS nanoparticles are prepared by two-phase liquid-liquid method. These Au-POSS nanoparticles form partial particle aggregation by blending with poly(n-butyl methacrylate) (PnBMA) homopolymer because of poor miscibility between Au-POSS and PnBMA polymer matrix. The incorporation the POSS moiety into the PnBMA main chain as a random copolymer matrix displays well-dispersed gold nanoparticles because the POSS-POSS interaction enhances miscibility between gold nanoparticles and the PnBMA-POSS copolymer matrix. This gold-containing nanocomposite exhibits ferromagnetic phenomenon at room temperature. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 811-819, 2009
Star Block Copolymers Through Nitroxide-Mediated Radical Polymerization From Polyhedral Oligomeric Silsesquioxane (POSS) Core
(2010-06-15)
Lu, Chu-Hua
;
Wang, Jui-Hsu
;
Chang, Feng-Chih
;
Kuo, Shiao-Wei
;
應用化學系
A series of star block copolymers were prepared through nitroxide-mediated radical polymerization (NMRP) from polyhedral oligomeric silsesquioxanes (POSS) nanoparticle by core-first polymerization. Eight N-alkoxyamine groups were incorporated onto the eight corners of a POSS cube through quantitative hydrosilylation through addition of octakis(dimethylsiloxy)silsesquioxane (O(8)M(8)(H) POSS) with 1-(2-(allyloxy)-1-phenylethoxy)-2,2,6,6-tetramethyl-piperidine (allyl-TEMPO) and Karstedt's agent (a platinum divinylsiloxane complex) was used as a catalyst. Octa-N-alkoxyamines POSS (OT-POSS) were used as platform to synthesize star polystyrene-POSS ((PS)(8)-POSS) homopolymer and diblock copolymers of poly(styrene-block-4-vinyl-pyridine)-POSS ((PS-b-P4VP)(8)-POSS) and poly(styrene-block-acetoxystyrene) ((PS-b-PAS)(8)-POSS) through NMRP. In addition, subsequent selective hydrolysis of the acetyl protective group of (PS-b-PAS)(8)-POSS, the poly(styrene-block-vinyl phenol) ((PS-b-PVPh)(8)-POSS) with strong hydrogen bonding group was obtained. The detailed chemical structure and self-assembled structures of these star block copolymers based on POSS were characterized by (1)H NMR, FTIR, SEC, TEM, and SAXS analyses.

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