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研究生： 林濤
Tao Lin
論文名稱： Self assembly of Inorganic/Block Copolymer Hybrid System
指導教授： 何榮銘
Rong Ming Ho
口試委員:
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2005
畢業學年度： 93
語文別： 英文
論文頁數： 92
中文關鍵詞： hybrid system 、block copolymer 、gold 、coordination
外文關鍵詞： hybrid system, block copolymer, gold, coordination
相關次數： 點閱：2  下載：0 
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    • Abstract

    A series of Poly(4-vinyl pyridine)-b-poly(ε-caprolactone) diblock copolymers, P4VP-PCL, has been synthesized through sequential living ring-opening polymerization and atom transfer radical polymerization. A hybridization of inorganic and organic components can be achieved by protonation of P4VP block with gold precursor (HAuCl4). In-situ growth of gold (Au) nanoparticles in the phase-separated P4VP microdomains was formed by reduction of Au metal ions. The reduction as traced by Fourier transform infrared and ultraviolet analyses was carried out in dichloromethane solution by using hydrazine (N2H4) as reduction agent.
    Interesting morphological evolution was observed by introducing various amounts of gold precursors to P4VP-PCL system. For instance, a significant phase transformation from cylindrical to lamellar nanostructure can be identified for diblock copolymer of VP27CL46 (fPVPv=37%) blended with gold precursors (as small particles) at the molar ratio of nitrogen to gold around 7. By contrast, phase-separated nanostructure of P4VP-PCL might be destructed by strong coordination (equimolar addition of gold precursor). The hybrid morphology is strongly dependent upon the added amount of inorganic materials in hybrid system.
    The observed morphological evolution in the hybrid system of P4VP-PCL/Au hybrid system is consistent to that of theoretical prediction on the basis of mean-field calculation. Owing to the interaction of Au precursors and the P4VP block, the introduction of Au precursors (i.e., Au ions), having size much smaller than the radius of gyration of the P4VP chains, in the hybrid system is similar to the mixing of low-molecular-weight P4VP homopolymers with P4VP-PCL. As a result, the effective volume fraction of P4VP-rich phase is constantly increased with the added amounts of gold ions so as to induce phase transformation. Eventually, the ordered self-assembly morphology might be destructed without the appearance of ordered microphase separation. By contrast, we speculate that the reduction of Au precursors may lead to the localization behavior at which the formed Au nanoparticles might be too large to be accommodated by P4VP chains, finally forming the self-assembled ordered arrays of Au nanoparticles. Detailed studies with respect to the size effect of reductive Au nanoparticles on morphological evolution in the hybrid system will be systematically examined.

    Contents Abstract………………………………………………………………………………..I Contents......................................................................................................................III List of Figures……………………………………………………………………….Ⅴ Chapter 1. Introduction……..………………………………….……………….…….1 1.1 Self-assembly Behavior of Block Copolymer……………………………....4 1.2 Homopolymer/BCP blending system……………………………………….6 1.3 Mixing of Inorganic/BCP hybrid System…..………….…………………….9 1.4 Incorporation of Inorganic/ Block Copolymer Hybrid System.....................10 1.4.1 Functional Polymers……………………………….………..……….10 1.4.2 Biodegradable Materials…………………………………….…….....13 1.4.3 Hybrid System with Different Kinds and Ratios of Inorganic Metal..15 1.4.4 Bonding mechanism between metal and pyridine…………...……….16 1.5 The kinds of Reduction…………………….................................................17 1.5.1 Electron Beam Reduction……………………………………...……..18 1.5.2 Ultraviolet Radiation Reduction……………………………………...18 1.5.3 Reduction by Chemical Agents............................................................19 1.6 Mixing Theory of Hybrid System…………………………...……………..20 Chapter 2. Objectives………………………………………………………………..47 Chapter 3. Experimental Details.................................................................................50 3.1 Instruments....................................................................................................50 3.2 Synthesis of P4VP-b-PCL…………………….............................................50 3.3 Sample Preparation and Experimental Methods…………………………...52 Chapter 4. Results and Discussion..............................................................................57 4.1 Thermal Behavior of VP27CL46 (fPVP=0.37)................................................57 4.2 Microphase-Separated Morphology of VP 27CL46………..........................58 4.3 Protonation of VP27CL46 and Gold Precursors...........................................59 4.4 Phase Transformation Behavior in Hybrids...................................................60 4.5 Reduction…………………………………………………………………...65 4.5.1 Reduction rate control (VP27CL46)………….………………..……..66 Chapter 5. Conclusion……………………………………………………………….82 Chapter 6. Future Works..............................................................................................84 Chapter 7. References………………………..............................................................86

    Chapter 7
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