臺灣博碩士論文加值系統

本論文探討酚醛樹脂（Phenolic）與聚乙酸乙烯酯（PVAc（poly vinyl acetate））混摻後的氫鍵作用力及相容性。在酚醛樹脂/聚乙酸乙烯酯摻合系統中，酚醛樹脂上的羥基與聚乙酸乙酯上的羰基會產生氫鍵而利於相容。微分掃描熱卡計（DSC）的結果顯示，酚醛樹脂/聚乙酸乙烯酯摻合的所有組成均只有一個玻璃轉移溫度（Tg），顯示此摻合系統為相容。此外，分別以紅外線光譜儀（FT-IR）及固態核磁共振儀（NMR）定量及定性的探討羥基與羰基之間的氫鍵作用力，結果為一致，均顯示隨著酚醛樹脂的加入，羥基與羰基之間產生的氫鍵明顯增加，表示酚醛樹脂上的羥基與聚乙酸乙酯上的羰基可產生強的分子間氫鍵作用力（inter-association）。此外，由質子自旋晶格遲緩時間（T1ρH）的實驗結果中，顯示Phenolic/PVAc摻合系統在2-3nm 以下為相容。更進一步藉由Painter-Coleman association model，可計算出分子間結合作用力平衡常數（inter-association equilibrium constant）及相對焓。

The miscibility and hydrogen bonding of phenolic resin/poly(vinyl acetate) (PVAc) blends were studied. The miscibility of phenolic resin and poly(vinyl acetate) (PVAc) blends was investigated by differential scanning calorimeter (DSC), Fourier transform infrared spectroscopy (FT-IR) and solid state 13C nuclear magnetic resonance (NMR). This blend displays single glass transition temperature (Tg) over entire compositions indicating that this blend system is miscible in the amorphous phase due to the formation of hydrogen bonding between hydroxyl groups of phenolic resin and carbonyl groups of PVAc. Quantitative measurements on fraction of hydrogen-bonded carbonyl group using both 13C solid-state NMR and FT-IR analyses result in good agreement between these two spectroscopic techniques. According to the proton spin-lattice relaxation time in the rotating frame (T1ρH), the phenolic/PVAc blend is intimately mixed on a scale less than 2-3 nm. Furthermore, the inter-association equilibrium constant and its related enthalpy of phenolic/PVAc blends were determined as a function of temperatures by infrared spectra based on the Painter-Coleman association model.

中文摘要……………………………………………………………..…Ⅰ
英文摘要………………………………………………………..……....Ⅱ
誌謝…………………………………………………………………..…Ⅲ
目錄……………………………………………………………………..Ⅴ
圖目錄…………………………………………………………….….…Ⅷ
表目錄…………………………………………………………….…….Ⅹ
研究目的……………………………………………………………….Ⅸ
第一章 緒論
1-1 前言………………………………………………………....…..1
1-2 文獻回顧……………………………………………….….……4
1-3 理論部份─高分子聚摻合物的熱力學性質……………….…12
1-3-1 Huggins-Flory Theory…………………………………….…..12
1-3-2 分子間的交互作用力…………………………………….….14
1-3-3 高分子中的氫鍵………………………………………….….15
1-4 固態核磁共振應用在高分子聚摻合物相容性的原理….……18
1-4-1 交錯極化………………………………………………….….19
1-4-2 魔角旋轉………………………………………………….….22
1-4-3 核磁共振遲緩行為……………………………………….….24
1-4-3-1 Rotation frame中自旋鎖定遲緩時間………………….…..25
1-5酚醛樹脂的自身結合氫鍵參數…………………………….…..26
第二章 實驗
2-1 藥品………………………………………………………….….29
2-2 高分子混摻……………………………………………….…….30
2-3 儀器………………………………………………………….….30
2-4 熱力學性質的運算………………………………………….….32
第三章 結果與討論
3-1 熱分析--微分掃描熱卡計
（Differential scanning Calorimetry, DSC）……………….…...34
3-2 紅外光光譜儀分析
（Fourier Transform Infrared Spectroscopy Analyses）…….….36
3-2-1酚醛樹脂/聚乙酸乙烯酯聚摻合物的紅外線光譜
（hydroxyl region）……………………………………………..36
3-2-2酚醛樹脂/聚乙酸乙烯酯聚摻合物的紅外線光譜
（carbonyl region）及聚摻合物的分子間氫鍵含量…………....37
3-2-3變溫紅外線光譜分析氫鍵含量………………………...…....38
3-3 固態核磁共振光譜儀分析（Solid-State NMR）……………...40
3-3-1 酚醛樹脂/聚乙酸乙烯酯聚摻合物13CCP/MAS核磁共振光譜
…………………………………………………………………40
3-3-2 固態NMR模擬聚摻合物的分子間氫鍵含量………………41
3-3-3 酚醛樹脂/聚乙酸乙烯酯聚摻合物的T1*弛緩時間………...42
3-4 Painter-Coleman Association Model 分析結果………………..44
3-5 模型化合物模擬分子間氫鍵結合平衡常數－KA之測定
（Estimation of the Inter-association Hydrogen Bonding Parameters, KA ）…………… ……………………………………………….47
第四章 結論……………………………………………………………50
參考文獻…………………………………………………………………52
作者簡歷…………………………………………………………………79

1. Martinez de Ilarduya A, Iruin JJ, Fernandez-Berridi MJ. Macromolecules 1995; 28:3707.
2. Wang J, Cheung MK, Mi Y. Polymer 2001; 42:2077.
3. He Y, Asakawa N, Inoue Y. Macromol Chem Phys 2001; 202:1035.
4. Brus J, Dybal J, Schmidt P, Kratochvil J, Baldrain J. Macromolecules 2000; 33:6448.
5. Mekhilef N, Hadjiandreou P. Polymer 1995; 36:2165.
6. Ma CCM, Wu HD, Chu PP, Tseng HT. Macromolecules 1997; 30:5443.
7. Wang FY, Ma CCM, Wu HD. J Appl Polym Sci 1999; 74:2283.
8. Wu HD, Ma CCM, Chang FC. Macromol Chem Phys 2000; 201:1121.
9. Kuo SW, Chang FC. Macromol Chem Phys 2001; in press.
10. Zhang X, Solomon DH. Macromolecules 1994; 27:4919.
11. Wu HD, Ma CCM, Lee MS, Wu YD. Die Angew Makromol Chemie 1996; 235:35.
12. Qin C, Pires ATN, Belfiore LA. Marcromolecules 1991; 24:666.
13. Coleman MM, Yang X, Painter PC, Graf JF. Macromolecules 1992; 25:4414.
14. Hill DJT, Whittaker AK, Wong KW. Macromolecules 1999; 32:5285.
15. Zhong Z, Guo Q, Mi Y. Polymer 1998; 40:27.
16. Zhang X, Takegoshi K, Hikichi K. Macromolecules 1991; 24:5756.
17. Coleman MM, Graf JF, Painter PC. ‘Specific Interaction and the Miscibility of Polymer Blends’, Technomic Publishing: Lancaster, PA, 1991.
18. Whetsel KB, Lady JH. ‘Spectrometry of Fuels’, H Friedel, Ed, Plenum, London, 1979.
19. Paul DR, Bucknall CB. ‘Polymer Blends’, Wiley Publication, New York, 2000.
20. Kuo SW, Chang FC. Macromolecules 2001; 34:5224.
21. Hu Y, Motzer HR, Etxeberria MA, Fernandes-Berridi MJ, Iruin JJ, Painter PC, Coleman MM. Macromol Chem Phys 2000; 201:705.
22. Fahrenholtz SR, Kwei TK. Macromolecules 1981; 14: 4.
23. Moskala EJ, Coleman MM. Polymer Communications 1983; 24:206.
24. Moskala E J, Howe SE, Painter PC, Coleman MM. Macromolecules 1984; 17:1671.
25. Hedrick JL, Yilgor I, Wilkes GL, McGrath JE. Polymer Bulletin, 1985;13:201.
26. Pennacchia JR, Pearce EM, Kwei TK, Bulkin BJ, Chen JP. Macromolecules 1986; 19: 973.
27. Coleman MM, Serman CJ, Painter PC. Macromolecules 1987; 20: 266.
28. Lichkus AM, Painter PC, Coleman MM. Macromolecules 1988; 21: 2636.
29. Kim HI, Pearce EM, Kewi TK. Macromolecules 1989; 22:3374.
30. Zhang X, Takegoshi K, Hikichi K. Macromolecules 1991; 24:5756.
31. Zhang X, Solomon DH. Macromolecules 1994; 27: 4919.
32. Coleman MM, Xu Y, Painter PC. Macromolecules 1994; 27:127.
33. Goh SH, Lee SY, Low SM. Macromolecules 1994; 27:6736.
34. Aggarwal LK, Asthana KK, Lakhani Rajni. Indian Concrete Journal 1995; 69: 269~273.
35. Mekhilef, Nafaa, Hadjiandreou Pavlos. Polymer 1995; 36: 2165.
36. Hatsuo Ishida, Douglous Allen. I. Journal of Polymer Science, Part B:Polymer Physics, 1996; 34:1019.
37. Coleman MM, Pehlert GJ, Yang X, Stallman JB, Painter PC. Polymer 1996; 37:4753.
38. Pehlert GJ, Yang X, Painter PC, Coleman MM. Polymer 1996; 37:4763.
39. Zhong, Zhikai, Guo, Qipeng, Polymer 1997; 38:729.
40. Wu HD, Chu PP, Ma CCM. Polymer 1998; 39:703.
41. Wu HD, Ma CCM, Chu PP, Tseng HT, Lee CT. Polymer 1998; 39:2859.
42. Hill DJT, Whittaker AK, Wong KW. Macromolecules 1999; 32：5285.
43. Hu Y, Motzer HR, Etxeberria AM, Fernandez-Berridi MJ, Iruin JJ, Painter PC, Coleman MM. Macromol Chem Phys 2000; 201:705.
44. Kuo SW, Chang FC. Macromolecules 2001; 34:5224.
45. Chen W, David DJ, MacKnight WJ, Karasz FE. Macromolecules 2001; 34:4277.
46. Leszek A. Utracki, “ Polymer Alloys and Blends - thermodynamics and rheology” Hanser Publishers, 1989, Munich, Vienna, New York.
47. Flory PJ. Chem. Phys. 1942, 10, 51
48. Flory PJ., Principles of Polymer Chemistry, Cornell Univ. Press. Ithaca, N.Y. 1953.
49. Maron SH. J. Polym. Sci. 1959; 38: 329.
50. Purcell EM, Torey HC, Pound ME. Phys. Rev. 1946; 69: 37
51. Pake GE. J. Chem. Phys. 1948, 16, 327.
52. Waugh JS, Huber LM, Haeberlen U. Phys. Rev. Lett. 1986; 20:180.
53. Pines A, Gibby MG, Waugh JS. J. Chem. Phys. 1972; 56:1776.
54. Lauterbur P. C. Nature 1973; 242: 190.
55. Hartmann, S. R.; Hahn. E. L. Phys. Rev, 1962; 128: 2042.
56. Pines A, Gibby MG, Waugh JS. J. Chem. Phys. 1973; 59: 569.
57. Fukushima E, Roeder SBW. Experimental Pulse NMR- A Nuts and Bolts Approach, Addison-Wesley: Reading, 1981.
58. Murphy PD, Taki T, Gerstein BC, Henrichs PM, Massa DJ. J.Magn. Reson. 1982; 49: 99.
59. Rogen N. Ibbett, NMR Spectroscopy of Polymers Blackie Academic & Professional, New York, 1993
60. Clauss J, Schmidt-Rohr K, Spiess HW. Acta Polymer. 1993; 44: 1.
61. Goldman, M. and Shen, L. Phys. Rev. 1966; 144: 321.
62. Hew-Der Wu, Chen-Chi M. Ma, Yi-Feng Su, Ming-Shiu Lee, and Yiu-Don Wu. Journal of Composites, Part A－Applied Science and Manufacturing, 1997; 28A: 895.
63. Kwei T. J Polym Sci, Polym Lett Ed 1984; 22:307.
64. Lee JY, Painter PC, Coleman MM. Macromolecule 1988; 21: 954.
65. Zhang X, Solomon DH. Macromolecules 1994; 27: 4919.
66. Schantz S. Macromolecules 1997; 30:1419.
67. Zhang X, Takegoshi K, Hikichi K. Macromolecules 1991; 24:5756.
68. Coggesthall ND, Saier EL0. J. Am. Chem. Soc. 1951; 71: 5414.
69. Paul DR, Bucknall CB. ‘Polymer Blends’, Wiley Publication, New York, 2000.
70. Fahrenholts SR, Kwei TK. Marcromolecules 1981; 14:1076.