本論文利用微分掃瞄卡計(DSC)、13C固態核磁共振光譜(SSNMR)、一維和二維傅利葉轉換紅外線光譜(FT-IR)、凝膠滲透層析儀(GPC)、等，來研究高分子聚摻行為特殊作用力。並且探討聚羥基丁酯(Poly(3-hydroxybutyrate), PHB)與聚苯乙烯-聚酚乙烯 (poly(styrene-co-vinyl phenol), PS-co-PVPh)共聚物混摻後，藉由改變氫氧基團(酚乙烯)在共聚物中的含量後，探討氫鍵作用力對高分子相溶性所造成的影響。
我們將利用FT-IR光譜來觀察羰基和酚基之間的氫鍵作用力。並且當PHB/PS-co-PVPh混摻系統裡，共聚物中的酚乙烯含量超過20 mol %時，將使得混摻系統轉變為單一相溶相態，並且實驗數據符合Painter–Coleman association model(PCAM)的理論預測。
The vinyl-terminated benzoxazine (VB-a)是可以藉由開環聚合的方式交聯，是用bisphenol A, formaldehyde, and allylamine反應而成。VB-a單體與環氧樹脂混摻後加熱交聯可得到epoxy/VB-a之網狀共聚物。為了了解epoxy/VB-a的硬化動力，以熱微分掃描卡計 (DSC) 做量測，再用Kissinger 和 Flynn-Wall-Osawa methods分析。紅外光光譜可觀察出硬化過程中"交聯情形"和epoxy/VB-a中氫鍵作用力的相互影響。同時，可觀察樹脂中烯丙基與開環交聯有明顯的增加。這些互穿聚合物經由動態黏彈機械分析儀(DMA) 和熱重分析儀 (TGA)量測可得知，當增加epoxy/VB-a中VB-a的含量其熱性質也會提升。

Differential scanning calorimetry (DSC), 13C solid state nuclear magnetic resonance (SSNMR), one- and two-dimensional fourier transform infrared spectroscopes (FT-IR), Gel Permeation Chromatography (GPC) have been used to investigate the miscibility behavior and specific interactions of Poly(3-hydroxybutyrate), (PHB) blending with poly(styrene-co-vinyl phenol), (PS-co-PVPh) through hydrogen bonding complex upon varying the vinyl phenol contents in copolymer.
We describe FT-IR spectra reveal that hydrogen bonding between carbonyl and phenol. A miscibility window exists when the vinyl phenol fraction in the copolymer is greater than 20 mol% in the PHB/PS-co-PVPh blend system, as predicted using the Painter–Coleman association model.
The vinyl-terminated benzoxazine (VB-a), which can be polymerized through ring opening polymerization, was synthesized through the Mannich condensation of bisphenol A, formaldehyde, and allylamine. This VB-a monomer was then blending with epoxy resin, followed by thermal curing concurrently, to form epoxy/VB-a copolymers network. To understand the curing kinetics of this epoxy/VB-a copolymer, dynamic differential scanning calorimetry measurements were performed by Kissinger and Flynn-Wall-Osawa methods. The FTIR analyses revealed the presence of thermal curing reactions and hydrogen bonding interaction of epoxy/VB-a copolymers. Meanwhile, the significant enhancement of the ring opening and allyl polymerizations of the epoxy was observed. For these IPNs, DMA and TGA results indicate that the thermal properties increase with the increase of VB-a contents in epoxy/VB-a copolymers.

中文摘要 I
英文摘要 III
目錄 V
表目錄 IX
圖目錄 X
第一章 緒論 1
1-1前言 1
1-2文獻回顧 2
1-2-1 氫鍵作用力概說 2
1-2-2 摻合原理 4
1-2-3 氫鍵摻合系統原理 5
1-2-4 Painter-Coleman Association Model應用於二相摻合系統 8
1-3 研究動機 10
第二章 利用氫鍵作用力提升聚羥基丁酯與聚苯乙烯之相溶性 11
2-1引言 11
2-2簡介 11
2-3實驗 13
2-3-1使用藥品 13
2-3-2樣品製備 14
2-4 實驗方法與儀器使用 15
2-4-1 氫核磁共振光譜儀(Proton Nuclear Resonance Spectrometer 1H-NMR) 型號: Varian® Unity Inova-500。 15
2-4-2 傅利葉轉換紅外線光譜儀(Fourier Transform Infrared Spectrometer, FT-IR) 型號﹕Bruker Tensor-27 16
2-4-3 微差掃瞄卡計(Differential Scanning Calorimeter, DSC) 型號：TA Q-20 17
2-4-4 凝膠滲透層析儀(Gel Permeation Chromatography, GPC) 型號：恆溫槽SUPER CO-150，泵浦:PU-2080，偵測器:UV-2070 & RI-2031 18
2-4-5 固態核磁共振儀(Solid State Nuclear Magnetic Resonance Spectrometer) 型號：Varian UNITY INOVA-500 19
2-5結果與討論 20
2-5-1 DSC, FTIR分析 20
2-5-2 PVPh/PHB混摻時之平衡常數 22
2-5-3二維紅外線光譜分析 23
2-5-4 固態核磁共振分析 26
2-5-5 PS-co-PVPh/PHB混摻分析 27
2-5-6 互溶圖視窗的預測 28
2-6結論 29
第三章 環氧樹脂/Benzoxazine複合材料的探討 44
3-1引言 44
3-2簡介 44
3-2-1 何謂環氧樹脂 44
3-2-2 環氧樹脂簡介 45
3-2-3 環氧樹脂的硬化 45
3-2-4 Bz簡介 50
3-2-5 Bz的合成 52
3-2-6 Bz的聚合 54
3-3實驗 56
3-3-1使用藥品 56
3-3-2 Bz合成 56
3-3-3 樣品製備 57
3-4 實驗方法與儀器使用 58
3-4-1 氫核磁共振光譜儀(Proton Nuclear Resonance Spectrometer 1H-NMR) 型號: Varian® Unity Inova-500。 58
3-4-2 傅利葉轉換紅外線光譜儀(Fourier Transform Infrared Spectrometer, FT-IR) 型號﹕Bruker Tensor-27 58
3-4-3 微差掃瞄卡計(Differential Scanning Calorimeter, DSC) 型號：TA Q-20 58
3-4-4 動態黏彈機械分析儀(Dynamic Mechanical Analyzer, DMA) 型號：PerkinElmer DMA 8000 59
3-4-5 熱重量分析儀(Thermogravimetric Analysis, TGA) 型號：TA Q-50 60
3-5結果與討論 61
3-5-1 VB-a的特性 61
3-5-2 Epoxy/ VB-a Copolymer硬化動力 61
3-5-3硬化過程 63
3-5-4 機械動力學分析Dynamic Mechanic Analyses (DMA) 64
3-6 結論 65
第四章 總結 79
參考文獻 80
作者簡介 87

1. Park, P.; Zimmerman, S. C. J. Am. Chem. Soc. 2006, 128, 11582.
2. Kim, J. K.; Jang, J.; Lee, D. H.; Ryu, D. Y. Macromolecules 2004, 37, 8599.
3. Jeon, H. K.; Kim, J. K. Macromolecules 2000, 30, 8200.
4. Kuo, S. W.; Chang, F. C. Macromolecules 2001, 34, 5224.
5. Kuo, S. W.; Chang, F. C. Macromolecules 2001, 34, 4089.
6. Kuo, S. W.; Huang, W. J.; Huang, C. F.; Chan, S. C.; Chang, F. C. Macromolecules 2004, 37, 4164.
7. Huang, H.; Hu, Y.; Zhang, J.; Sato, H.; Zhang, H.; Noda, I.; Ozaki, Y. J. Phys. Chem. B. 2005, 109, 19175.
8. He, Y.; Zhu, B.; Inoue Y. Prog. Polym. Sci. 2004, 29, 1021.
9. Jiang, M.; Mei, L.; Xiang, M.; Zhou, H. Adv. Polym. Sci. 1999, 146, 121.
10. Chen, D.; Jiang, M. Acc. Chem. Res. 2005, 38, 494.
11. Yi, J. Z.; Goh, S. H.; Wee, A. T. S. Macromolecules 2001, 34, 4662.
12. Chien, Y. Y.; Perace, E. M.; Kwei, T. K. Macromolecules 1988, 21, 1616.
13. Kuo, S. W.; Chang, F. C. Polymer 2001, 42, 9843.
14. Kuo, S. W.; Chang, F. C. Macromolecules 2001, 34, 7737.
15. Kuo, S. W. J. Polym. Res. 2008, in press.
16. de Mefathi, M. V.; Frechet, J. M. J. Polymer 1988, 29, 477.
17. Prinos, A.; Dompros, A.; Panayiotou, C. Polymer 1998, 39, 3011 .
18. Zhu, K. J.; Wang, L. Q.; Yang, S. L. Macromol. Chem. Phys. 1994, 195, 1965.
19. Zhuang, H. F.; Pearce, E. M.; Kwei, T. K. Macromolecules 1994, 27, 6398.
20. Smith J. R. Prog. Polym. Sci. 1996, 21, 209.
21. Watson, J. D.; Berry, A. DNA: The Secret of Life; Knopf: New York, 2003.
22. Kyogoku, Y.; Lord, R. C.; Rich, A. J. Am. Chem. Soc. 1967, 89, 496.
23. Coleman, M. M.; Graf, J. F.; Painter, P. C. “Specific Interactions and the Miscibility of Polymer Blends” Technomic Publishing, Lancaster, PA, 1991.
24. Coleman, M. M. ; Painter, P. C. “Miscible Polymer Blend-Background and Guide for Calculations and Design” DEStech Publications, Inc., 2006.
25. Watson, J. P.; Crick, F. H. Nature 1953, 171, 964.
26. Beatty, A. M. Cryst. Eng. Comm. 2001, 51, 1.
27. Barlow, J.W.; Paul, D. R. Polym. Eng. Sci. 1984, 24, 525.
28. Paul, D. R.; Newman, S. Eds.“Polymer Blends”, Vol. I and II , Academic, New York, 1987.
29. Gaylord, N. G. J. Macromol. 1989, 28, 1211.
30. Pauling, L.; Corey, R. B.; Branson, H. R. Proc. Nat. Acad. Sci. 1951, 37, 205.
31. Pauling, L.; Corey, R. B. Proc. Nat. Acad. Sci. 1951, 37, 729.
32. Pimemtel, G. C.; McClellan, A. L. The Hydrogen Bond W. H. Freeman and Co., San Francisco and London, 1960.
33. Yang, X.; Painter, P. C.; Coleman, M. M.; Pearce, E. M.; Kwei, T. K. Macromolecules 1992, 25, 2156.
34. Coleman, M. M.; Yang, X.; Painter, P. C.; Graf, J. F. Macromolecules 1992, 25, 4414.
35. Coleman, M. M.; Yang, X.; Zhang, H.; Painter, P. C.; Scherer Jr, K. V. J. Polym. Sci., Polym. Chem. Edn 1993, 31, 2039.
36. Coleman, M. M.; Yang, X.; Zhang, H.; Painter, P. C. J. Macromol. Sci. Phys. 1993, B32, 295.
37. Coleman, M. M.; Yang, X.; Painter, P. C.; Kim, Y. H. J. Polym. Sci., Polym. Chem. Edn 1994, 32, 1817.
38. Painter, P. C.; Veytsman, B.; Coleman, M. M. J. Polym. Sci., Polym. Chem. Edn 1994, 32, 1189.
39. Coleman, M. M.; Xu, Y.; Painter, P. C. Macromolecules 1994, 27, 127.
40. Sudesh, K.; Abe, H.; Doi, Y. Prog. Polym. Sci. 2000, 25, 1503.
41. Ha, C.; Cho, W. Prog. Polym. Sci. 2002, 27, 759.
42. Abe, H,; Doi, Y.; Aoki, H.; Akehata, T. Macromolecules 1998, 31, 1791.
43. Sato, H.; Nakamura, M.; Pademshoke, A.; Yamaguchi, H.; Terauchi, H.; Ekgasit, S.; Noda, I.; Ozaki, Y. Macromolecules 2004, 37, 3763.
44. King, P. P.; J. Chem. Tech. Biotechnol. 1982, 32, 2.
45. Huang, H.; Hu, Y.; Zhang, J.; Sat, H.; Zhang, H.; Noda, I.; Ozaki, Y. J. Phys. Chem. B 2005, 109, 19175.
46. Iriondo, P.; Iruin, J. J.; Fernadez-Berrdi, M. J. Macromolecules 1996, 29, 5605.
47. Xing, P.; Dong, L.; An, Y.; Feng, Z.; Avella, M.; Martuscelli, E. Macromolecules 1997, 30, 2726.
48. Iriondo, P.; Iruin, J. J.; Fernandez-Berrdi, M. J. Macromolecules 1995, 36, 3235.
49. Chee, M. J. K.; Ismail, J,; Kummerlowe, C.; Kammer, H. W. Polymer 2002, 43, 1235.
50. Yang, H.; Li, Z. S.; Shin, T. K.; Choi, H. J.; Jhon, M. S. Polymer 2001, 42, 5737.
51. Zhang, L. L.; Deng, X. M.; Zhao, S. J.; Huang, Z. T. Polymer 1997, 38, 6001.
52. Scandola, M.; Ceccorulli, G.; Pizzoli, M. Macromolecules 1992, 25, 6441.
53. Ceccorulli, G.; Pizzoli, M.; Scanodola, M. Macromolecules 1993, 26, 6722.
54. Huang, H.; Hu, Y.; Zhang, J.; Sato, H.; Zhang, H.; Noda, I.; Ozaki, Y. J. Phys. Chem. B 2005, 109, 19175.
55. Zhang, J.; Sato, H.; Furukawa, T.; Tsuji, H.; Noda, I.; Ozaki, Y. J. Phys. Chem. B 2006, 110, 24463.
56. Kuo, S. W.; Chang, F. C. Macromolecules 2001, 34, 5224.
57. Kuo, S. W.; Chang, F. C. J. Phys. Sci. : Polym. Phys. Ed. 2002, 40, 1661.
58. Lin, C. L.; Chen, W. C.; Liao, C. S.; Su, Y. C.; Huang, C. F.; Kuo, S. W.; Chang, F. C. Macromolecules 2005, 38, 6435.
59. Kuo, S. W.; Liu, W. P.; Chang, F. C. Macromol. Chem. Phys. 2005, 206, 2307.
60. Lee, H. F.; Kuo, S. W.; Huang, C. F.; Lu, J. S.; Chan, S. C.; Chang, F. C. Macromolecules 2006, 39, 5458.
61. Chen, W. C.; Kuo, S. W.; Jeng, U. S.; Chang, F. C. Macromolecules 2008, 41, 1401.
62. Huang, M. W.; Kuo, S. W.; Wu, H. D.; Chang, F. C.; Fang, S. Y. Polymer 2002, 43, 2479.
63. Kuo, S. W.; Chang, F.C. Macromol. Chem. Phys. 2001, 202, 3112.
64. Kuo, S. W.; Lin, C. L.; Chang, F. C. Polymer 2002, 43, 3943.
65. Kuo, S. W.; Chang, F. C. Polymer 2001, 42, 9843.
66. Kuo, S. W.; Chang, F. C. Macromol. Chem. Phys. 2002, 203, 868.
67. Kuo, S. W.; Chan, S. C.; Chang, F. C. J. Polym. Sci.: Polym. Phys. Ed. 2004, 42, 117.
68. Huang, C. F.; Kuo, S. W.; Lin, H. C.; Chen, J. K.; Chen, Y. K.; Xu, H.; Chang, F. C. Polymer 2004, 45, 5913.
69. Huang, C. F,; Kuo, S. W.; Lin, F.J.; Huang, W. J.; Wang, C. F.; Chang, F.C. Macromolecules 2006, 39, 300.
70. Kuo, S. W.; Chan, S. C.; Chang, F. C. Macromolecules 2003, 36, 6653.
71. Kuo, S. W.; Lin, C. L.; Wu, H. D.; Chang, F, C. J. Polym. Res. 2003, 10, 87.
72. Kuo, S. W.; Chan, S. C.; Wu, H. D.; Chang, F. C. Macromolecules 2005, 38, 4729.
73. Kuo, S. W.; Chang, F. C. Macromolecules 2001, 34, 7737.
74. Kuo, S. W. Polymer 2008, 49, 4420.
75. Coleman, M. M.; Graf, J. F.; Painter, P. C. “Specific Interactions and the Miscibility of Polymer Blends,” Technomic Publishing, Lancaster, PA, 1991.
76. Coleman, M. M.; Painter, P. C. “Miscible Polymer Blend-Background and Guide for Calculations and Design,” DEStech Publications, Inc., 2006.
77. Kennedy, J. P.; Kelen, T.; Tudos, F. J. Polym. Sci. : Polym. Chem. Ed. 1975, 13, 2277.
78. Kelen, T.; Tudos, F. F. Macromol Sci Chem (A) 1975, 9, 1.
79. Lin, H. C.; Wang, C. F.; Kuo, S. W.; Tung, P. H.; Lin, C. H.; Chang, F. C. J Phys Chem B 2007, 111, 3404.
80. Kwei, T. K. J. Polym. Sci. Polym. Lett. Ed. 1984, 22, 307.
81. Sato, H.; Murakami, R.; Padermshoke, A.; Hirose, F.; Senda, K.; Noda, I.; Ozaki, Y. Macromolecules 2004, 37, 7203.
82. Zhang, J.; Sato, H.; Noda, I.; Ozaki, Y. Macromolecules 2005, 38, 4274.
83. Furukawa, T.; Sato, H.; Murakami, R.; Zhang, J.; Duan, Y.; Noda, I.; Ochiai, S.; Ozaki, Y. Macromolecules 2005, 38, 6445.
84. Noda I, Ozaki Y. “Two-Dimensional Correlation Spectroscopy,” John Wiley & Sons, 2004.
85. Riccardi, C. C.; Williams, R. J. J. J. Appl. Polm. Sci. 1986, 32, 3445
86. 傅雅卿，高折射率環氧樹脂之合成及其研究，台灣大學材料科學與工程學研究所碩士論文 , 2001
87. Lee, S. S.; Kim, S. C. Journal of Applied Polymer Science 1988, 69, 1291
88. Rao, B. S.; Reddy, K. R.; Pathak S. K.; Pasala A. R. Polym. Int. 2005, 54, 1371
89. Holly, F. W.; Cope, A. C. J. Am. Chem. Soc. 1944, 66, 1875
90. Burke, W. J. J. Am. Chem. Soc. 1949, 71, 609
91. Ning, X.; Ishida, H. J. Polym. Sci. Pant A: Polym Chem 1994, 32, 1121
92. Agag, T.; Takeichi, T. J. Polym. Sci. Pant A: Polym Chem 2007, 45, 1878
93. Riess, G.; Schwob, J.M.; Guth, G.; Roche, M.; Lange, B. in Advance in polymer synthesis, B. M. Culbertson and J. E. McGrth, Eds., New York, 1985
94. Huang, J. M.; Kuo, S. W.; Lee, Y. J. Chang, F. C. J Polym Sci, Polym Phys 2007, 45, 644
95. Agag, T.; Takeichi, T. Macromolecules 2003, 36, 6010.
96. Kissinger, H. E. Anal Chem 1957, 29, 1702.
97. Ozawa, T.J Therm Anal 1970, 2, 301.
98. Kimura, H.; Matsumoto, A.; Ohtsuka, K. J. Appl. Polym. Sci. 2008, 109, 124