臺灣博碩士論文加值系統

本研究利用微分熱掃描卡計 (DSC)、 偏光顯微鏡 (POM) 、掃描式電子顯微鏡 (SEM) 、傅立業紅外線光譜儀 (FT-IR)，探討poly(butylene adipate-co-butylene terephthalate )/poly(bisphenol-A carbonate) ((P(BA-co-BT) /PC)兩成分摻合系統之相容性與交酯化反應。DSC分析(P(BA-co-BT) /PC摻合物之全部組成雖皆單一Tg；但摻合物系統中只有PC含量較多的組成之Tg值，才會隨著組成變化位移。POM與SEM觀察相型態，證實此兩成分系統為部分相容，但是經高溫熱處理後，DSC分析Tg的變化，並輔以POM與SEM觀察相型態發現，系統經過高溫熱處理會由部分相容變為相容的系統，利用Gordon-Taylor equation分析得到的k值由0.2變為0.4，顯示經過高溫熱處理摻合物間的作用力有增加。進一步觀察隨著熱處理的時間增加對Tg的影響，發現Tg值會隨著反應時間增加改變。研究中FT-IR光譜的官能基吸收峰進行分析，發現隨著熱處理的時間增加，系統之間確實有交酯化反應發生，本研究中並提出(P(BA-co-BT)共聚酯與PC之交酯化反應機制。

Miscibility and transesterification of the poly(butylene adipate-co-butylene terephthalate )/poly(bisphenol-A carbonate) ((P(BA-co-BT) /PC) blends were investigated by using differential scanning calorimeter (DSC), polarizing optical microscope (POM), scanning electron microscopy (SEM) and fourier-transform infrared spectroscopy (FT-IR). In the study, the homogeneous phase of the copolyester/PC blends was shown by POM and SEM, but the glass transition temperature (Tg) of the blends varied with the compositions of the blends with the rich PC composition. These results demonstrated partial miscibility of the copolyester/PC blends. Furthermore, the homogeneous phase and only one Tg of the P(BA-co-BT)/PC blends were found after the blends were heated above 260oC. The influence of heat treatment on the Tg and morphology was discussed by DSC, POM, SEM and FTIR. The k constant of Gordon-Taylor equation was changed from 0.2 to 0.4; this result indicated that the interaction between P(BA-co-BT) copolyester and PC was different after heat treatment at 260oC. Additionally, the Tg of the P(BA-co-BT)/PC blends which varied with the heat treatment time was observed. Spectrogram of FT-IR showed the interchange reaction in P(BA-co-BT) copolyester and PC blends after heat treatment at 260oC. Finally, the reaction mechanisms of transesterification in the P(BA-co-BT)/PC blend were suggested in the work.

中文摘要 Ⅰ
英文摘要 Ⅱ
致謝 Ⅲ
總目錄 Ⅳ
表目錄 Ⅵ
圖目錄 Ⅶ

第一章 簡介 1
第二章 原理 12
§2-1 高分子摻合系統混合熱力學 13
§2-2玻璃相轉移行為 15
§2-3 交酯化反應機制 17
第三章 實驗 22
§3-1 實驗所用的高分子與試藥 22
§3-2 實驗試樣之製備 23
§3-3 實驗所用儀器 24
第四章 結果與討論 27
§4-1 P(BA-co-BT)/PC 相容性之探討 27
§4-2 P(BA-co-BT)/PC交酯化之探討 61
第五章 結論 87
參考文獻 88
自述 93

1.楊惠娣，降解塑料通訊，2，38-48 (1996).
2.蘇家齊，化工科技動態，2，4-7 (1995).
3.戈進杰，生物降解高分子材料，5-7, 218-256 (2002).
4.W. Amass, A. Amass, B. Tighe, Polym. Int., 47, 89 (1998).
5.Y. Zheng, E. K. Yanful, A. S. Bassi, Critical Review in Biotechnology, 25, 243 (2005)
6.Z. Qiu, S. Fujinami, M. Komura, K. Nakajima, T. Ikehara, T. Nishi, Macromol. Symp., 216, 255 (2004).
7.P. Zhang, F. Huang, B. Wang, Polym.-Plast. Technol. Eng., 41(2), 273 (2002).
8.Y. Hori, M. Suzuki, A. Yamaguchi, T. Nishishita, Macromolecules, 26, 5533 (1993).
9.Y. Hori, Y. Takahashi, A. Yamaguchi, T. Nishishita, Macromolecules, 26, 4388 (1993).
10.B Evans, Plastics Technology, 36(5), 41 (1990).
11.Y. Tokiwa, T. Suzuki, J. Appl. Polym. Sci., 26, 441 (1981).
12.Y. Tokiwa et al., Polym. Mater. Sci. Eng., 63, 742 (1990).
13.A. Iwamoto, Y. Tokiwa, Polym. Degrad. Stab., 45, 205 (1994)
14.A. Iwamoto, Y. Tokiwa, J. Appl. Polym. Sci., 52, 1357 (1994).
15.U. Witt, R.-J. Müller, W.-D. Deckwer, J. Environ. Polym. Degrad., 3(4), 215 (1995).
16.U. Witt, R.-J. Müller, W.-D. Deckwer, Macromol. Chem. Phys., 197, 1525 (1996).
17.U. Witt, R.-J. Müller, W.-D. Deckwer, J. Environ. Polym. Degrad., 5(2), 81 (1997).
18.U. Witt, M. Yamamoto, U. Seeliger, R.-J. Müller, V. Warzelhan, Angew. Chem. Int. Edn., 38, 10 (1999).
19.U. Witt, T. Einig, M. Yamamoto, I. Kleeberg, W.-D. Deckwer, R.-J. Müller, Chemosphere, 44, 289 (2001).
20.X.-G. Li, M.-R. Huang, Polym. Int., 48, 387 (1999).
21.S.-J. Chiu, T.-H. Liou, C.-T. Tsai, X.-H. Jian, Int. J. Polym. Materials, 55, 909 (2006).
22.L. A. Utracki, Polymer Alloys and Blends: Thermodynamics and Rheology, Oxford Univ. Press, New York(1990).
23.M. J. Folkes and P. S. Hope, Polymer Blends and Alloys, Blackie Academic and Professional, London(1993).
24.J. M. Adduci, Polymudes, vol. 2, K. L. Mittal, ed., Plenum press, New York(1984).
25.S. Choe, W. J. Mackinght, and F. E. Karasz, Polyimides: Material, Chemistry and Characterization, C. Feger, ed., Elsevier Sci. Pub., Amsterdam(1989).
26.J. J. Ziska, J. W. Barlow, D. R. Paul, Polymer, 22, 918(1981).
27.J. E. Harris, S. H. Goh, D. R. Paul, J. W. Barlow, J. Appl. Polym. Sci., 27, 839(1982).
28.C. A. Cruz, D. R. Paul, J.W. Barlow, J. Appl. Polym. Sci., 24, 2101(1979).
29.A. C. Fernandes, J. W. Barlow, D. R. Paul, J. Adv. Polym. Sci., 29, 1971(1984).
30.T. S. Ellis, Polymer, 39(20), 4741 (1998).
31.D. G. Hamilton, R. R. Gallucci, J. Appl. Polym. Sci., 48, 2249 (1993).
32.D. Delimoy, C. Bailly, J. Devaux, R. Legras, Polym. Eng. Sci., 28(2), 104 (1988).
33.J. Devaux, P. Godard, J. P. Mercier, J. Polym. Sci., Polym. Phys. Edn., 20, 1875 (1982).
34.J. Devaux, P. Godard, J. P. Mercier, J. Polym. Sci., Polym. Phys. Edn., 20, 1881 (1982).
35.J. Devaux, P. Godard, J. P. Mercier, J. Polym. Sci., Polym. Phys. Edn., 20, 1895 (1982).
36.J. Devaux, P. Godard, J. P. Mercier, J. Polym. Sci., Polym. Phys. Edn., 20, 1901 (1982).
37.R. S. Halder, M. Joshi, A. Misra, J. Appl. Polym. Sci., 39, 1251 (1990).
38.G. v.d. Velden, G. Kolfschoten-Smitsmans, A. Veermans, Polym. Commun., 28, 169 (1987).
39.A. W. Birley, X. Y. Chen, Br. Polym. J., 16, 77 (1984).
40.D. C. Wahrmund, D. R. Paul, J. W. Barlow, J. Appl. Polym. Sci., 22, 2155 (1978).
41.J. Devaux, P. Godard, J. P. Mercier, Polym. Eng. and Sci., 22, 229 (1982).
42.M. Okamoto, T. Inoue, Polymer, 35(2), 257 (1994).
43.B. D. Hanrahan, S. R. Angeli, J. Runt, Polym. Bull., 14, 399 (1985).
44.I. Hopfe, G. Pompe, K.-J. Eichhorn, L. Hauβler, J. Molecl. Structure, 349, 443(1995).
45.G. Pompe, L. Hauβler, Polymer , 35, 2161(1997).
46.A. Yavari, A. Asadinezhad, S. H. Jafari, H. A. Khonakdar, F. Bhme, R. Hassler, Eur. Polym. J., 41, 2880 (2005).
47.S. R. Murff, J. W. Barlow, D. R. Paul, J. Appl. Polym. Sci., 29, 3231 (1984).
48.P. Godard, J. M. Dekoninck, V. Devlesaver, J. Devaux, J. Polym. Sci., Polym. Chem. Edn., 24, 3301 (1986).
49.A. M. Kenwright, S. K. Peace, Polymer, 40, 5851 (1999).
50.S. Collins, A. M. Kenwright, R. W. Richards, Macromolecules, 33, 2974 (2000).
51.A. M. Kenwright, S. K. Peace, R. W. Richards, Polymer, 40, 2053 (1999).
52.G. Montaudo, C. Puglisi, Macromolecules, 31, 650 (1998).
53.P. Godard, J. M. Dekoninck, V. Pevlesaver, J. Devaux, J. Polym. Sci., Polym. Chem. Edn., 24, 3315 (1986).
54.J. M. Jonza, R. S. Porter, Macromolecules, 1946, 650 (1986).
55.C. A. Cruz, D. R. Paul, J. N. Barlow, J. Appl. Polym. Sci., 23, 589 (1979).
56.B. K. Kim, H. M. Jeong, Y. H. Lee, J. Appl. Polym. Sci., 40, 1805 (1990).
57.J. I. Equiázaval, M. Coratazar, J. J. Iruin, J. Appl. Polym. Sci., 42, 489 (1991).
58.R. J. Young, P. A. Lovell, “Introduction to polymer”, Chapman & Hall (1991).
59.D. R. Paul, S. Newman, “Polymer Blend”, Academic Press Inc.(1987).
60.L. H. Sperling, “Introduction to physical polymer science”, John Wiley & Sons (1992).
61.D. J. Walsh, J. S. Higgins, A. Maconndchie, “Polymer Blends and Mixtures”, Mijhoff Publishers (1985).
62.T. G. Fox, S. Loshaek, J. Polym. Sci., 15, 371 (1955).
63.T. G. Fox, Bull. Am. Phys. Soc., 1, 23 (1956).
64.M. Gordon, S. J. Taylor, J. Appl. Chem, 2, 493 (1952).
65.K.-F. Cheung, K. R. Carduner, A. Golovoy, H. Van Oene , J. Appl. Polym. Sci., 171, B29 (1990).
66.J. I. Equiázaval, M. Coratazar, J. J. Iruin, J. Appl. Polym. Sci., 42, 489 (1991).
67.R. S. Porter, L.-H. Wang, Polymer, 33, 2019 (1992).
68.R. Yamadera, M. Murano, J. Polym. Sci., A-1, 5, 2259 (1967).
69.K. Kuwabara, Z. Gan, T. Nakamura, H. Abe, Y. Doi, Biomacromolecules, 3, 390 (2002).
70.E. Cranston, J. Kawada, S. Raymond, F. G.. Morin, R. H. Marchessault, Biomacromolecules, 4, 995 (2003).
71.T. Suzuki, H. Tanaka, T. Nishi, Polymer, 30, July, 1287 (1989).
72.A. M. Kotliar, J. Polym. Sci., Macromol. Rev., 16, 367 (1981).
73.D. L. Pavia, G. M. Lampman, G. S. Kriz,” Introduction to spectroscopy： A Guide for students of organic chemistry”, Saunders College (1979).
74.D. H. Huang, Department of Chemical Engineering, National Cheng Kung University, Tainan, Taiwan (2003).
75.S. C. Kuan, Department of Chemical Engineering, National Cheng Kung University, Tainan, Taiwan (2003).
76.C. P. Chiang, Department of Chemical Engineering, National Cheng Kung University, Tainan, Taiwan (2004).