我們利用小角度X光散射實驗解析各種分子量與組成的嵌段共聚物poly(ethylene oxide)-block-poly (4-vinylpyridine) (PEO-b-P4VP)以及參混界面活性劑dodecylbenzene sulfonic acid(DBSA)的相轉換行為。結果發現，PEO-b-P4VP共聚物可以呈現一種極不尋常的「低臨界有序化」(lower critical orderingtransition，LCOT)行為，即在低溫時PEO與P4VP鏈段互容，但當加熱至一臨界溫度時，兩鏈段發生微相分離，呈現一種「無序到有序態的轉化」(disorder-to-order transition，DOT)。奈米結構的形態乃是受控於兩鏈段的分離強度(χN)和體積分率，在多組不同分子量的PEO-b-P4VP中，我們發現兩相中較不對稱比例和較小的分子量，會導致無序到有序態之轉化溫度的上升。除了以實驗建構相圖之外，我們亦將運用文獻上的理論模型定量計算PEO-b-PVP系統的相圖，藉由與實驗相圖的擬和，揭露共聚物呈現LCOT相行為的機制與驅動力。根據P4VP以及其異構物P2VP，一個給定的組成和分子量，PEO-b-P4VP共聚物的無序到有序態之轉化溫度低於PEO-b-P2VP，這是由於P4VP和P2VP的溶解度參數之間的差距。另外，當PEO-b-P4VP(DBSA)中的DBSA增量時，會導致無序到有序態之轉化溫度上升，由於產生不對稱的組成和兩相之間的χ參數的改變。

We have investigated the phase transition behavior of poly(ethylene oxide)-block-poly(4-vinyl pyridine) (PEO-b-P4VP) and its complexes with dodecylbenzenesulfonic acid (DBSA). PEO-b-P4VP was found to exhibite an unusual lower critical ordering transition (LCOT), where the diblock, which was in the disordered state at lower temperature, underwent microphase separation upon heating. The disorder-order transition temperature (TDOT) of PEO-b-P4VP was in general significantly lower than that of PEO-b-P2VP under a given composition and molecular weight. This was attributed to the larger solubility parameter of P4VP than that of P2VP. The complexation of P4VP block with DBSA drastically increased the TDOT due to the shift of the copolymer composition to more asymmetric value and the modification of the χ parameter between the two blocks. The supramolecular comb-coil diblock copolymers thus formed exhibited the structure-within-structure morphology above TDOT.

Abstract I
Index II
Figure Index III
Table Index VII
Chapter 1 Introduction 1
1.1 Phase Behavior of Block Copolymers 1
1.2 Lower Critical Ordering Transition of Block Copolymer 5
1.3 Supramolecular Comb-Coil Block Copolymer 7
1.4 Motivation and Objectives of the Study 19
Chapter 2 Experimental Section 20
2.1 Materials 20
2.2 Complex Preparation 21
2.3 Characterization 23
2.3-1 Small Angle X-ray Scattering (SAXS) Measurements 23
2.3-2 Transmission Electron Microscopy (TEM) Measurements 24
Chapter 3 Results and Discussion 25
3.1 Thermally-induced phase transitions of PEO-b-P4VP 25
3.2 Analysis of the LCOT phase behavior based on phase diagram calculation of PEO/P4VP and PEO/P2VP homopolymer blends 27
3.3 Thermally-induced phase transitions of the PEO-b-P4VP (DBSA)x comb-coil diblock copolymer 31
Chapter 4 Conclusion 45
Chapter 5 References 46

(1) Hamley, I. W. The Physics of Block Copolymers, Oxford, New York, 1998.
(2) Bates, F. S.; Schulz, M. F.; Khaidpur, A. K.; Forster, S.; Rosedale, J. H.; Almdal, K.; Mortensen, K. Faraday Discuss. 1994, 98, 7.
(3) Bates, F. S.; Fredrickson, G. H.Aitnu. Rev. Chent. 1990,41, 525.
(4) Meier, D. J. Journal of Polymer Science, part C.1969, 26, 81.
(5) Leary, D.; Williams, M. Journal of Polymer Science B 1970, 8, 335.
(6) Leary, D.; Williams, M. Journal of Polymer Science: Polymer Physics 1973, 11, 345.
(7) Leary, D.; Williams, M. Journal of Polymer Science: Polymer Physics 1974, 12, 265.
(8) Helfand, E. Macromolecules 1975, 8, 552.
(9) Helfand, E.; Wasserman, Z. R. Macromolecules 1976, 9, 879.
(10) Helfand, E.; Wasserman, Z. R. Macromolecules 1980, 13, 994.
(11) Helfand, E.; Wasserman, Z. R. Macromolecules 1978, 11, 960.
(12) Matsen, M. W.; Bates, F. S. Journal of Polymer Science B: Polymer Physics 1997, 35, 945.
(13) Leibler, L. Macromolecules 1980, 13, 1602.
(14) Matsen, M. W.; Schick, M. Physical Review Letters 1994, 72, 2660.
(15) Matsen, M. W.; Bates, F. S. Macromolecules 1996, 29, 1091.
(16) Matsen, M. W.; Bates, F. S. Macromolecules 1996, 29, 7641.
(17) Hashimoto, T.; Koizumi, S.; Hasegawa, H.; Izumitani, T.; Hyde, S. T. Macromolecules 1992, 25, 1433.
(18) Hamley, I. W. The Physics of Block Copolymers; Oxford University Press: New York, 1998.
(19) Ruzzete, A. V.; Leibler, L. Nature Mater. 2005, 4, 19.
(20) Matsen, M. W.; Bates, F. S. Macromolecules 1996, 29, 1091.
(21) Ruzette, A.-V. G.; Mayes, A. M. Macromolecules 2001, 34, 1894.
(22) Ruzette, A.-V. G.; Mayes, A. M.; Russell, T. P. J. Chem. Phys. 2001, 114, 8205.
(23) Cowie, J. M. G.; Arrighi, V. Polymers: Chemistry and Physics of Modern Materials, 3rd ed.; CRC Press: New York, 2008.
(24) Pollard, M.; Russell, T. P.; Ruzette, A.-V. G.; Mayes, A. M.; Gallot, Y. Macromolecules 1998, 31, 6493.
(25) Yeung, C.; Desai, R. C.; Shi, A.-C.; Noolandi, J. Phys. Rev. Lett. 1994, 72, 1834.
(26) Russell, T. P.; Karis, T. E.; Gallot, Y.; Mayes, A. M. Nature 1994, 368, 729.
(27) Toshiahi, H.; Prausnitz, J. M. Macromolecules 1998, 31, 2636.
(28) Du, Y. R.; Unyong, J.; Jin, K. K.; Russell. T. P. Nature Materials 2002, 1, 114.
(29) Valkama, S. Functional Materials Based on Self-Assembled Comb-Shaped Supramolecules; Doctoral Dissertation, 2006; Section 1-1
(30) Ikkala, O.; ten Brinke, G. Science 2002, 295, 2407
(31) Ruokolainen, J.; Mäkinen, R.; Torkkeli, M.; Mäkelä, T.; Serimaa, R.; ten Brinke, G.; Ikkala, O. Science 1998, 280, 557.
(32) Ruokolainen, J.; Saariaho, M.; Ikkala, O.; ten Brinke, G.; Thomas, E. L.; Torkkeli, M.; Serimaa, R. Macromolecules 1999, 32, 1152.
(33) Osuji, C.; Chao, C.-Y.; Bita, I.; Ober, C. K.; Thomas, E. L., Adv. Funct. Mater. 2002, 12, 753.
(34) Osuji, C.; Ferreira, B. J.; Mao, G.; Ober, C. K.; Vander Sande, J. B.; Thomas, E.L. Macromolecules 2004, 37, 9903.
(35) Ruokolainen, J.; ten Brinke, G.; Ikkala, O. Adv. Mater. 1999, 11, 777.
(36) Valkama, S.; Ruokolainen, T.; Nyka1nen, A.; Laiho, A.; Kosonen, H.; ten Brinke, G.; Ikkala, O.; Ruokolainen, J. Macromolecules 2006, 39, 9327.
(37) Kosonen, H.; Valkama, S.; Ruokolainen, J.; Torkkeli, M.; Serimaa, R.; ten Brinke, G; Ikkala, O. The European Physical Journal E 2003, 10, 69.
(38) Ruokolainen, J.; Mäkinen, R.; Torkkeli, M.; Mäkelä, T.; Serimaa, R.; ten Brinke, G.; Ikkala, O. Science, 1998, 280, 557.
(39) Valkama, S.; Kosonen, H.; Ruokolainen, J.; Torkkeli, M.; Serimaa, R.; ten Brinke, G.; Ikkala, O. Nat. Mater., 2004, 3, 872.
(40) Valkama, S.; Ruokolainen, T.; Nyka1nen, A.; Laiho, A.; Kosonen, H.; ten Brinke, G.; Ikkala, O.; Ruokolainen, J. Macromolecules 2006, 39, 9327.
(41) Chen, H. L.; Lu, J. S.; Yu, C. H.; Yeh, C. L.; Jeng, U. S.; Chen, W. C. Macromolecules 2007, 40, 3271.
(42) Chian, W. S.; Lin, C. H.; Yeh, C. L.; Nandan, B.; Hsu, P. N.; Lin, C. W.; Chen, H. L.; Chen, W. C. Macromolecules 2009, 42, 2304
(43) Valkama, S.; Lehtonen, O.; Lappalainen, K.; Kosonen, H.; Castro, P.; Repo, T.; Torkkeli, M.; Serimaa, R.; ten Brinke, G.; Leskelä, M.; Ikkala, O. Macromol. Rapid Communications.2003, 24, 556.
(44) Sidorenko, A.; Tokarev, I.; Minko, S.; Stamm, M. Journal of the American Chemical Society. 2003, 125, 12211.
(45) Yeh, C. L.; Hou, T.; Chen, H. L.; Yeh, L. Y.; Chiu, F. C.; Muller, A. J.; Hadjichristidis, N. Macromolecules 2011, 44, 440.
(46) van Krevelen, D. W.; Hoftyzer, P. J. Properties of Polymers. Correlation with Chemical Structure; Elsevier: New York, 1972.
(47) Weibin, Z; Han, C. D.; Lee, D. H.; Han, S. H.; Kim, J. K.; Kang, J. H.; Park, C. Macromolecules 2007, 40, 2109.