臺灣博碩士論文加值系統

本研究係利用二苯甲酮四羧酸二酐(3,3’, 4,4’benzophenone tetracarboxylic dianhydride, BTDA)與己二胺（1，6 Diaminohexane,HDA）以及不同分子量的丙胺基聚二甲基矽氧烷(α，ωdiaminopyopol polydimethyl Siloxane,APPS)共同進行聚合、環化反應以得到聚亞醯胺與矽氧之多團聯共聚物。
首先以FT-IR、1H-NMR來分析產物的分子結構與組成； TGA及DSC來測試其熱性質Tg、Tm與熱裂解溫度；並以SEM來觀察淬斷面型態。實驗結果顯示所合成的多團聯共物具有三個Tg點分別為-120、22與125℃並在250℃處具有一Tm點，SEM觀察淬斷面，聚矽氧軟鏈段含量85 wt%時聚亞醯胺形成球狀相分離結構。此一微觀相分離性質為日後開發熱塑性彈性體之重要特性。

In this study , we use 3,3’, 4,4’benzophenone tetracarboxylic dianhydride (BTDA) , 1，6 Diaminohexane (HDA) ,α，ωdiaminopyopol polydimethyl siloxane(APPS) of different molecular weigts to undergo polycondensation and imidezation to synthesize the Polyimide and Polydimethylsiloxane multiblock copolymer.
The samples are measured by FT-IR and 1H-NMR to analyze the molecular structure and composition of the polymer. The thermal properties such as Tg、Tm and Td are analyzed with TGA and DSC. The morphology and microseparation are observed by SEM.
The analysis results of products indicate that, copolymer have three Tg each are -120、22 and 125℃, and the Tm of these copolymer are 250℃.
When these multi block copolymer contains on 85 weight percent of soft segment then it will become a ball like microseparation.
The technology of Polyimide and Polydimethylsiloxane multiblock Copolymer synthesis in this research offer reference to develop high additional value thermoplastic rubber products

中文摘要 ---------------------------------------------------------------------- i
英文摘要 ---------------------------------------------------------------------- ii
致謝 ---------------------------------------------------------------------- iii
目錄 ---------------------------------------------------------------------- iv
表目錄 ---------------------------------------------------------------------- v
圖目錄 ---------------------------------------------------------------------- vi
第一章 緒論 ---------------------------------------------------------------------- 1
一、前言 ---------------------------------------------------------------------- 1
二、熱塑性彈性體的優點 ---------------------------------------------------- 3
三、熱塑性彈性體之結構 ---------------------------------------------------- 4
四、塑塑性彈性體所使用的軟鏈段 ---------------------------------------- 8
五、熱塑性彈性體所使用的硬鏈段 ---------------------------------------- 20
六、相關研發現況回顧 ---------------------------------------------------- 26
第二章 實驗材料、設備、流程與方法 ---------------------------------------- 28
一、藥品與材料 ---------------------------------------------------------------- 28
二、藥品及溶劑處理 ---------------------------------------------------------- 30
三、儀器設備 ---------------------------------------------------------------- 31
四、合成實驗 ---------------------------------------------------------------- 33
第三章 結果討論 ---------------------------------------------------------------------- 39
一、合成產物光譜鑑定 ---------------------------------------------------- 39
二、合成產物之熱性質分析 ---------------------------------------------- 59
三、合產成物微結構分析 ---------------------------------------------------- 67
第四章 結論 ---------------------------------------------------------------------------- 71
第五章 參考文獻 ---------------------------------------------------------------------- 72

1.李欣怡，”聚酯彈性體之合成及其性質研究”，(1990)
2.C. S. Schllenberger. H. Scott and G. R. Moor, Rubber world, 137, 549(1958).
3.C. S. Schllenberger, (to Goodrich), U.S. Pat. 2,871,219 (1959).
4.L. M. Porter (to Shell), U.S. Pat. 3,149,812 (1964).
5.R. F. Zelinski (to Shell), U.S. Pat. 3,281,383 (1966)
6.M. M. Wald and M. G. Quamm (to Shell), U.S. Pat. 3,595,492 (1971)
7.W. K. Fisher (to Uniroyal), U.S. Pat. 3,806,558 (1974)
8.J. C, Shivers and W. Chester (to Du Pont), U.S. Pat. 3,023,192 (1962).
9.G. L. Zaister, Past. Eng., 34 (5), 61 (1973).
10.陳誌堅,”熱塑性聚胺基甲酸酯彈性纖維之抽絲、物性及光變色功能之研究”,(1995)
11.P. Dreyfuss, L. J. Fetters, and D. R. Hansen, Rubber. Chem. Tech., 52,728(1980)
12.M. M. Morton, Rubber Techology, Van Norstrand Reinhold Co., New York, (1975)
13.M. M. Morton, J. Poly. Sci. Polym. Symp., 60, 1 (1977)
14.R. K. Admas, G. K. Hoeschele, thermoplastic Elastomer: A Comprehensive Review (Eds. N. R. Legge, G. Holden, H. E. Schroeder) Hanser Publishers, p.163~196, N.Y. (1987).
15.H. Schroeder and R. J. Colla, Encyclopedia of Polymer Science and Engineering, (C. H. Mark, Bikles, C. G. Overberger, G. Menges and J. I. Krochwits Eds.)2nd　Ed., 12,.85~117(1998).
16.R. W. van Berkel, S. A. G. de Graf, F. J. Huntjens and C. M. F. Vrouenraets in Developments in Block Copolymers-1 (Ed. I. Goodman) Applied Science publishers, N.Y. p.261~360(1982).
17.J. R. Wolfe, in Multiphase Polymer, ACS Advances in Chemistry Series 176, (S. C. Cooper and G. M. Estes, Eds.),p129~151, ACS Washington, D. C.(1979)
18.G. Wenger, T, Fujii, W. Meyer and G. Lieser, Angew. Makromol. Chem., 74, 295 (1978).
19.M. G. Voronkov, V. P. Mileshkevich, and Yu. A. Yuzhev-skil, “The Siloxane Bond”, Consultants Burwau New York and London, P. 159, 1978.
20.伊藤邦雄， “シリコーン　その基礎応用”，アイシーエス株式会社，第一章，1991.
21.小野義昭，”シリコーン　広がる用分野と技術動向”，化学工業日報社，第一章，2003.
22.C. Eaborn, “Organosilicone Compound”, Butter Worths Scientific Publication. London, P.100, 1962.
23.鹿目彰， “シリコーン　と その応用”，東芝株式会社，P.21，1982.
24.熊田誠和田正，”シリコーン　最新応用技術”，信越化学工業株式会社，P.53， 1982.
25.W. Noll, “Chemistry and Technology of Siloxane”, Acedemic Press, New York, P.17, 1968.
26.P. V. Wright, “Ring Opening Polymerization”, Elsevier Applied Science Publishes, Chapter 14, 1985.
27.J. Burkhardt, “Silicone Chemistry and Technology”, Vulkan-Verlag Essen, Germany, P.31, 1991.
28. M. G. Voronkov, V. P. Mileshkevich, and Yu. A. Yuzhev-skil, “The Siloxane Bond”, Consultants Bureau, New York P.159
29. W. M. Edwards, I. M. Robinson, U. S. Pat., 2 710 853 a Pat., 2712543 (1955)
30. 林金雀，聚亞醯胺薄膜全球市場及應用現況，化工資刊，13,7,58~62 (1999)
31. N. A. Adrova, M. I. Bessonov, L. A. Laius, A. P. Rudakov, “polyimide: A new class of thermally stable polymers(in Russian)”, Nauka, Leningrad(1968)
32. Shy-Liang Jwo, Wha-Tzong Whang, Journal of Applied Polym. Sci. , 1999 ,p.2832 Vol. 74
33. S. Andre, F. Guida-Pietrasanta Journal of Applied Polym. Sci., 2001, p.2414 Vol. 39
34. W. David Polk “Polydimethylsiloxane containing block copolymer synthesis and characterization of alternating poly(arylene ether phosphine oxide)-b-siloxane and segmented nylon 6,6 –b- siloxane copolymer
35. Jeffrey Mecham, “Synthesis and Characterization of Cycloaliphatic and Aromatic Polyester/Poly(Dimethylsiloxane) Segmented Copolymer” 1997
36. TSUTOMU TAKEICHI, J. Polym. Sci. A: Polym. Chem. 2001, 39, 2633
37. Chenghong Li, “Preparation of Nitrile Containing Siloxane Triblock Copolymers and their Application as Stabilizers for Siloxane magnetic fluids” 1996
38. C. A. Pryde, J.polymer Science, Part A, Polymer Chemistry, 27, 711(1989)
39. R. A. Dine-Hart and W. W. Wright, Die Makromolekulare Chemie, 143, 189(1971)
40. P. D. Frayer, in：Polyimides：Synthesis, Characterization, and Application, Val. 1, K. L. Mittal, ed., Plenum, New York, 1984, P.273
41. H. Ishida, S. T. Wellinghoff, E. Bear, and J. L. Koening, Macromolecules 13, 826(1980)