本研究係以不同分子量的poly(styrene-block-2-vinyl pyridine) (PS-b-P2VP)與不同結構的聚合物進行混摻，以小角度X光散射及穿透式電子顯微鏡觀察其結構及相行為的變化，並透過傅立葉紅外線光譜儀探討不同比例的摻合體所形成的氫鍵強度。對稱型的PS-b-P2VP與poly(styrene-block-acrylic acid) (PS-b-PAA)及poly(styrene-graft-acrylic acid) (PS-g-PAA)混摻時，當PS-b-PAA及PS-g-PAA的分子量大於PS-b-P2VP時，會使添加物無法進入PS-b-P2VP的有序結構中，而形成巨觀相分離。若添加物的分子量小於PS-b-P2VP時，在PS-b-P2VP/PS-g-PAA的系統中，PS-g-PAA可進入PS-b-P2VP的PS domain中，使得整體尺寸變大；在PS-b-P2VP/PS-b-PAA的系統中，PS-b-PAA則落於PS-b-P2VP的界面，以氫鍵作用力降低PAA與P2VP鏈段間的不相容性，並拉近兩鏈段的距離，造成整體domain尺寸變小。若為PS-b-P2VP與均聚物h-PAA的系統中，由於h-PAA可直接進入PS-b-P2VP的P2VP domain中形成氫鍵以降低不相容性，因此會造成整體的domain尺寸變大。
在非對稱型的PS-b-P2VP的混摻系統中，若P2VP的鏈段大於PS的鏈段，不論添加較高分子量的PS-g-PAA(H)或較低分子量的PS-g-PAA(L)，均會使添加物進入PS-b-P2VP的PS domain，造成domain尺寸變大；若PS的鏈段大於P2VP的鏈段，添加兩種分子量的PS-g-PAA均會進入PS-b-P2VP(HL)的界面處。而添加PS-g-PAA(H)會因為對界面曲率的影響較小，使得PS-b-P2VP(HL)維持原有結構；另一方面，添加PS-g-PAA(L)則對界面曲率影響較大，進而造成結構上出現有序－有序的相轉變。

This research focuses on the effect of hydrogen bonding on the phase behavior of polymer mixtures comprising polystyrene-block-poly(2 vinylpyridine) (PS-b-P2VP) and polyacrylic acid (PAA) based polymer, including poly(styrene-graft-acrylic acid) (PS-g-PAA), poly(styrene-block-acrylic acid) (PS-b-PAA), and PAA homopolymer. The phase behavior of each system was investigated using small angle X-ray scattering and transmission eletron microscopy, and the hydrogen bonding strengh in each blend was characterized using Fourier transform infrared spectroscopy. In these self-assembled blends, PAA and P2VP chains interacted due to hydrogen bonding. In PS-b-P2VP/PS-g-PAA blends, PS-g-PAA was segregated into the PS phase and the domain size increased with an increase in the content of PS-g-PAA. In PS-b-P2VP/PS-b-PAA blends, PS-b-PAA was located at the interface between PS and P2VP microdomains in PS-b-P2VP, which resulted in the reduction of domain size.
In the blends composed of asymmetric PS-b-P2VP and PS-g-PAA copolymers, when the P2VP segment was larger than PS segment, the added PS-g-PAA copolymers segregated into the PS domain regardless of the molecular weight of PS-g-PAA. By contrast, when the PS segment was larger than the P2VP segment, PS-g-PAA preferred to locate at the interface between the PS and P2VP microdomains. However, the addition of the higher molecular-weight PS-g-PAA did not alter the cylindrical structure because of the less influence on the interfacial curvature. On the other hand, the addition of the lower molecular-weight PS-g-PAA induced an order-order transition showing the greater change on the interfacial curvature.

[1] K. Ariga, J. P. Hill, M. V. Lee, A. Vinu, R. Charvet, and S. Acharya, Science and Technology of Advanced Materials, 2008, 9, 1
[2] S. Forster, and T. Plantenberg, Angewandte Chemie International Edition, 2002, 41, 689
[3] G. M. Whitesides, and B. Grzybowski, Science, 2002, 295, 2418
[4] J. Kim, I. A. Levitsky, D. T. McQuade, and T. M. Swager, Journal of the American Chemical Society, 2002, 124, 7710
[5] V. Percec, M. Glodde, M. Peterca, A. Rapp, I. Schnell, H. W. Spiess, T. K. Bera, Y. Miura, V. S. K. Balagurusamy, E. Aqad, and P. A. Heiney, Journal of the American Chemical Society, 2006, 12, 6298
[6] L. Shi, and C. Berkland, Macromolecules, 2007, 40, 4635
[7] M. W. Matsen and F. S. Bates, Macromolecules, 1996, 29, 1091
[8] F. S. Bates and G. H. Fredrickson, Physical Today, 1999, 52, 32
[9] F. S. Bates, Science, 1991, 254, 898
[10] F. S. Bates and G. H. Fredrickson, Annual Review of Physical Chemistry, 1990, 41, 525
[11] K. W. Guarini, C. T. Black, and S. H. I. Yeung, Advanced Materials, 2002, 14, 1290
[12] S. Krause, Pure and Applied Chemistry, 1986, 58, 1553
[13] R. A. Segalman, Materials Science and Engineering, 2005, 48, 191
[14] A. A. Gavrilov, Y. V. Kudryavtsev and A. V. Chertovich, The Journal of Chemical Physics, 2013, 139, 224901
[15] M. F. Schulz, A. K. Khandpur, and F. S. Bates, Macromolecules, 1996, 29, 2857
[16] T. Hashimoto, M. Shibayama, and H. Kawai, Macromolecules, 1980, 13, 1237
[17] L. Leibler, Macromolecules, 1980, 13, 1602
[18] A. Rebei, and D. Pablo, The Journal of Physical Review E, 2001, 63
[19] J. Melenkeviz, and M. Muthukumar, Macromolecules, 1991, 24, 4199
[20] M. D. Whitemore, and J. J. Noolandi, The Journal of Chemical Physics, 1990, 93, 2946
[21] E. Sivaniah, S. Matsubara, Y. Zhao;T. Hashimoto, K. Fukunaga, E. J. Kramer, and T. E. Mates, Macromolecules, 2008, 41, 2584
[22] W. Zheng, and Z. G. Wang, Macromolecules, 1995, 28, 7215
[23] C. Auschra, and R. Stadler, Macromolecules, 1993, 26, 2171.
[24] R. Stadler, C. Auschra, J. Beckmann, U. Krappe, I. V. Martin, and L. Leibler, Macromolecules, 1995, 28, 3080
[25] S. W. Kuo, C. L. Lin, and F. C. Chang, Polymer, 2002, 43, 3943
[26] S. W. Kuo, I. H. Lin, and F. C. Chang, Polymer, 2009, 50, 5276
[27] M. M. Coleman, G. J. Pehlert, and P. C. Painter, Macromolecules, 1996, 29, 6820
[28] H. Tanaka, H. Hasegawa, and T. Hashimoto, Macromolecules, 1991, 24, 240
[29] C. Luo, X. Han, Y. Gao, H. Liu, and Y. Hu, Journal of Applied PolymerScience, 2009, 113, 907
[30] X. Quan, I. Gangarz, and J. T. Koberstein, Journal of Polymer Science Part B: Polymer Physics, 1987, 25, 641
[31] T. Hashimoto, H. Tanaka, and H. Hasegawa, Macromolecules, 1990, 23, 4378
[32] S. H. Han, V. Pryamitsyn, D. Bae, J. Kwak, V. Ganesan, and J. K. Kim, ACS NANO, 2012, 6, 7966
[33] D. C. Kim, S. I. Yoo, S. W. Moon, and W. C. Zin, Polymer, 2005, 46, 6595
[34] Y. Matsushita, N. Torikai, Y. Mogi, and I. Noda, Macromolecules, 1993, 26, 6346
[35] K. K. Tenneti, X. Chen, C. Y. Li, Y. Tu, X. Wan, Q. F. Zhou, I. Sics, and B. S. Hsiao, Journal of the American Chemical Society, 2005, 127, 15481
[36] H. J. Chiu, H. L. Chen, and J. S Lin, Polymer, 2001, 42, 5749
[37] G. R. Strobl, and M. Schneider, Journal of Polymer Science: Polymer Physics Edition, 1980, 18, 1343
[38] F. Court, and T. Hashimoto, Macromolecules, 2001, 34, 2536
[39] F. Court, D. Yamaguchi, and T. Hashimoto, Macromolecules, 2008, 41, 4828
[40] B. D. Olsen, and R. A. Segalman, Macromolecules, 2007, 40, 6922