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研究生： 郭蔚慈
Kuo, Wei-Tzu
論文名稱： Interplay Between the Phase Transitions at Different Length Scales in the Supramolecular Comb-Coil Block Copolymers Bearing (AB)n Multiblock Architecture
指導教授： 陳信龍
Chen, Hsin-Lung
口試委員: 曹正熙
陳文章
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： 2014
畢業學年度： 102
語文別： 英文
論文頁數： 39
中文關鍵詞： 高分子自組裝 、comb-coil 團聯式共聚物 、小角度X光散射實驗
外文關鍵詞： comb-coil block copolymers, multiblock copolymer, temperature-dependent small angle X-ray scattering, self-assembly behavior
相關次數： 點閱：3  下載：0 
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    • ABSTRACT

    We have introduced the concept of comb-coil supramolecule into linear (AB)n-type multiblock copolymer and investigated the self-assembly behavior of the copolymer as a function of the unit number n. Linear (polystyrene-block-poly(2-vinylpyridine))n (denoted as (PS-b-P2VP)n) (n =1, 2, 3) with symmetric compositors were complexed with dodecylbenzenesulfonic acid (DBSA) to yield the comb-coil multiblock copolymers in which DBSA bound stoichiometrically with P2VP block by ionic bonding. The phase behavior of the copolymers was studied by temperature-dependent small angle X-ray scattering (SAXS). All three comb-coil block copolymers, including diblock (n=1), tetrablock (n=2) and hexablock (n=3), self-organized to form cylinder-within-lamellae morphology at the lower temperature, where the cylindrical microdomains formed by the PS block embedded in the matrix composed of the lamellar mesophase organized by the P2VP(DBSA) comb block. The disordering of the smaller-scale lamellar mesophase formed by the comb block occurred upon heating. At the same time, the larger-scale cylindrical domains transformed to body-centered-cubic (BCC) packed spheres in the diblock complex and to another hexagonally-packed cylinder (HEX) structure with smaller domain spacing in tetrablock and hexablock complexes, indicating that the order-disorder transition (ODT) of the smaller-scale structure drove an order-order transition (OOT) of the larger-scale structure irrespective of n. The transition temperatures were found to increase with increasing n due to the increase of the enthalpy of transition arising from the larger interfacial energy contribution in the multiblock.
    Another aim of this study is to understand the relative orientation between the larger-scale copolymer domain and the smaller-scale lamellae in multiblock comb-coil copolymer. The two-dimensional (2-D) SAXS patterns of the samples treated by large amplitude oscillatory shear revealed that the relative orientation varied with the binding fraction (x) of DBSA to P2VP block, but is independent of n. At the lower binding fraction (x ≤ 0.5), the smaller-scale lamellae showed an edge-on arrangement around the PS cylinders. At the higher binding fraction (x > 0.5), the two type of structures exhibited the orthogonal orientation, where the smaller-scale lamellae stacked along the long axis of the PS cylinders.

    CONTENTS Acknowledgment I ABSTRACT II CONTENTS III List of Figures IV Chapter 1 Introduction 1 1.1 General introduction of block copolymers 1 1.2 Supramolecular comb-coil diblock copolymers 2 1.3 Self-assembly behavior of linear (AB)n-type multiblock copolymer 4 1.4 Motivation and objective of this study 4 Chapter 2 Experimental Section 13 2.1 Materials 13 2.2 Sample preparation 13 2.3 Characterization 14 Chapter 3 Results and discussion 17 3.1 Hierarchical Structures and Phase Transition of the Comb-Coil Diblock Copolymer (n=1) 17 3.2 Hierarchical Structures and Phase Transition of the Multiblock Comb-Coil Copolymer 18 3.2.1 Tetrablock system (n=2) 18 3.2.2 Hexablock system (n=3) 19 3.3 The relative orientation of the hierarchical structures of comb-coil multiblock copolymers 24 Chapter 4 Conclusions 37 References 38

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