臺灣博碩士論文加值系統

本研究於二甲基甲醯胺（DMF）/四氫呋喃（THF）混合溶劑中用一步法合成出聚矽氧烷/聚醚-氨基甲酸酯（PDMS/PTMG-PUBD）與聚矽氧烷/聚醚-醯亞氨氨基甲酸酯（PDMS/PTMG-PUIM）共聚合體，PDMS/PTMG-PUBD共聚合體的軟鏈結由聚丁醚二醇（PTMG）與聚二甲基矽氧烷二醇（PDMS）所組成、硬鏈結是1,4-丁二醇（1,4-BD）與4,4’-二苯甲基二異氰酸鹽（MDI）所組成的氨基甲酸酯基團，PDMS/PTMG-PUIM共聚合體的軟鏈結與PDMS/PTMG-PUBD共聚合體的相同，而其硬鏈結是3’,3’,4,4’-二苯基四羧酸二酸酐（DSDA）與MDI所回應形成的醯亞氨基團。共聚合體的相分離程度比以非極性PDMS為軟鏈結所得的氨基甲酸酯共聚合體低，這是因為於共聚合體軟鏈結中導入PTMG會增加軟硬鏈結的相容性。DSC測驗結果顯示PDMS/PTMG-PUBD與PDMS/PTMG-PUIM共聚合體軟硬鏈結的相轉移行為，共聚合體軟鏈結相轉移是指PTMG與PDMS的相行為，而只有PDMS/PTMG-PUIM共聚合體有出現結晶相行為。共聚合體出現兩個吸熱區域，其分別與短有序硬鏈結區與長有序硬鏈結區（Region I與Region II）有關，出現下100℃與160℃附近，由老化測試（annealing measurement）說明此吸熱行為與物理老化的焓鬆弛有關。而高硬鏈結含量的PDMS/PTMG-PUBD共聚合體樣品經高溫熱處理一段時間後出現硬鏈結結晶（Region III）。

Siloxane-ether urethane (PDMS/PTMG-PUBD) and siloxane-ether-imide urethane (PDMS/PTMG-PUIM) copolymers prepared from a one step method in the N,N-Dimethyformamide(DMF)/tetrahydrofuran(THF) mixed solvent. The soft-segment of PDMS/PTMG-PU copolymers consist of polydimethylsiloxane (PDMS) and polytetramethylene glycol (PTMG) and hard-segment is urethane segment reacting from 1,4-butane diol(1,4-BD) and 4,4-diphenylmethane diisocyanate(MDI). The soft segment of PDMS/PTMG-PUIM was similar to PDMS/PTMG-PUBD but hard-segment is a imide segment consisting of 3,3', 4,4'-Diphenylsulfone-tetracarboxylic Dianhydride(DSDA) and MDI. The phase-separation degree of copolymers was lower than that the non-polar PDMS polyurethane because the copolymers incorporated PTMG in the soft-segment to increased the miscibility between soft segment and hard segment. The PDMS/PTMG-PUBD and PDMS/PTMG-PUIM in the differential scanning calorimeter (DSC) exhibited soft- and hard-segmented phase-transition. The soft-segmented phase-transition PDMS/PTMG-PUBD and PDMS/PTMG-PUIM including the PDMS and PTMG amorphous phase-transition but the crystal phase-transition only presented on the melting-quenched PDMS/PTMG-PUIM copolymers. There were two endothermal regions, which were respectively the short-range ordering and the long-range ordering of hard segment domains(Region I and II), displaying at around 100℃ and 160℃. The endothermic behavior was demonstrated by annealing measurement displaying was a enthalpy relaxation resulting from prolonged physical aging. Furthermore, the hard-segmented crystal (Region III) appeared on the high hard-segment content of PDMS/PTMG-PUBD sample annealing for a period.

中文摘要.........................................Ⅰ
英文摘要.........................................Ⅱ
誌謝.............................................Ⅲ
目錄.............................................Ⅳ
表目錄...........................................Ⅵ
圖目錄...........................................Ⅶ
第一章 前言.......................................1
1.1聚氨基甲酸酯發展與用途.........................1
1.2聚矽氧烷特性與用途......................1
1.3文獻回顧................................2
1.3.1聚氨基甲酸酯結構...................2
1.3.2聚氨基甲酸酯熱行為與型態...........3
1.3.3聚氨基甲酸酯機械性質...............6
1.4研究目的................................8
第二章 實驗.......................................9
2.1實驗流程.................................9
2.2實驗材料................................10
2.2.1硬鏈節部份........................10
2.2.2軟鏈節部分........................11
2.2.3溶劑..............................11
2.2.4催化劑............................11
2.3聚矽氧烷/聚醚-氨基甲酸共聚合體合成.....12
2.3.1以1,4-丁二醇為鏈延長劑之聚矽氧烷/
聚醚-氨基甲酸酯共聚體（PDMS/PTMG-
PUBD) 製備.......................12
2.3.2以二酸酐為鏈延長劑之聚矽氧烷/聚醚-
氨基甲酸酯共聚合體（PDMS/PTMG-PUIM）
製備.............................15
2.4實驗測試...............................18
2.4.1傅式紅外線光譜分析（FTIR）.......18
2.4.2掃描式熱差分析儀（DSC）..........18
2.4.2.1相轉移區測試...............18
2.4.2.2 緩冷效應測試..............18
第三章 結果與討論................................19
3.1霍氏紅外線光譜..........................19
3.2軟鏈段與硬鏈段之相轉移區................23
3.2.1軟鏈節相轉移區....................24
3.2.1.1聚矽氧烷/聚醚-氨基甲酸酯
（PDMS/PTMG-PUBD）軟鏈節相轉移
區..........................24
3.2.1.2聚矽氧烷/聚醚-氨基甲酸酯-醯亞
胺（PDMS/PTMG-PUIM）共聚合體
軟鏈節相轉移區..............30
3.2.2不同硬鏈節含量在軟鏈節相的影響....35
3.2.2.1硬鏈節含量在PDMS/PTMG-PUBD
軟鏈節相轉移區影響..........35
3.2.2.2硬鏈節含量在PDMS/PTMG-PUIM
軟鏈節相轉移區影響..........39
3.2.3硬鏈節相轉移區....................43
3.2.3.1 PDMS/PTMG-PUBD共聚合體硬鏈
節相轉移區................43
3.2.3.2 PDMS/PTMG-PUIM共聚合體硬鏈
節相轉移區................47
3.3緩冷在PDMS/PTMG-PUBD共聚合體之硬鏈節型
態的效應...............................50
3.3.1溫度效應..........................51
3.3.2時間效應..........................53
第四章 結論......................................56
第五章 參考文獻..................................57

表 目 錄
表2.1 PDMS/PTMG-PUBD共聚合體合成比例與成份........14
表2.2 PDMS/PTMG-PUIM共聚合體合成比例與成份........17
表3.2.1聚矽氧烷/聚醚-氨基甲酸酯樣品初始掃瞄之軟鏈
段玻璃轉移區溫度............................27
表3.2.2聚矽氧烷/聚醚-氨基甲酸酯樣品熔融-急冷掃瞄之
軟鏈段玻璃轉移區
溫度........................................28
表3.2.3聚矽氧烷/聚醚-氨基甲酸酯-醯亞胺初始掃瞄軟鏈
節相轉移區溫度..............................32
表3.2.4聚矽氧烷/聚醚-氨基甲酸酯-醯亞胺初熔融-急冷
掃瞄軟鏈節相轉移區溫度.....................33
表3.2.5 PDMS/PTMG-PUBD共聚合體高硬鏈節含量樣品初
始掃瞄之軟鏈段玻璃轉移區溫度................36
表3.2.6 PDMS/PTMG-PUBD共聚合體高硬鏈節含量樣品熔融
-掃瞄掃瞄之軟鏈段玻璃轉移區溫度............37
表3.2.7 PDMS/PTMG-PUIM共聚合體高醯亞胺含樣品量初始
掃瞄軟鏈段玻璃轉移溫度.....................40
表3.2.8 PDMS/PTMG-PUIM共聚合體高醯亞胺含樣品熔融-急
冷掃瞄之軟鏈段玻璃轉移區溫度...............41

圖 目 錄
圖1.1 硬鏈節區域(Region I~III)的型態模型..........5
圖2.1 實驗流程圖..................................9
圖2.2 PDMS/PTMG-PUBD共聚合體反應式...............13
圖2.3 PDMS/PTMG-PUIM共聚合體反應式...............16
國3.1.1 BD-20樣品FTIR光譜圖......................20
國3.1.2 PD-20樣品FTIR光譜圖......................20
圖3.1.3 (a)(b)PDMS/PTMG-PUBD系列光譜圖...........21
圖3.1.4 (a)(b)PDMS/PTMG-PUIM 系列光譜圖..........22
圖3.2.1聚矽氧烷/聚醚-氨基甲酸酯樣品軟鏈段初始掃瞄
DSC圖......................................29
圖3.2.2聚矽氧烷/聚醚-氨基甲酸酯樣品軟鏈段熔融-急冷
掃瞄DSC圖..................................29
圖3.2.3聚矽氧烷/聚醚-氨基甲酸酯-醯亞胺樣品軟鏈段初
始掃瞄DSC圖................................34
圖3.2.4聚矽氧烷/聚醚-氨基甲酸酯-醯亞胺樣品軟鏈段熔
融-急冷掃瞄DSC圖..........................34
圖3.2.5 PDMS/PTMG-PUBD共聚合體高硬鏈節含量樣品初始
掃瞄DSC圖.................................38
圖3.2.6 PDMS/PTMG-PUBD共聚合體高硬鏈節含量樣品熔融
-急冷掃瞄DSC圖.............................38
圖3.2.7 PDMS/PTMG-PUIM共聚合體高醯亞胺含樣品初始掃
瞄DSC圖...................................42
圖3.2.8 PDMS/PTMG-PUIM共聚合體高醯亞胺含樣品熔融-
掃瞄掃瞄DSC圖.............................42
圖3.2.9 PDMS/PTMG-PUBD樣品初始掃瞄DSC圖..........45
圖3.2.10 PDMS/PTMG-PUBD樣品熔融-急冷掃瞄 DSC圖...45
圖3.2.11高硬鏈節含量PDMS/PTMG-PUBD樣品初始掃瞄DSC
圖.......................................46
圖3.2.12高硬鏈節含量PDMS/PTMG-PUBD樣品熔融-急冷掃
瞄DSC圖..................................46
圖3.2.13 PDMS/PTMG-PUIM樣品初始掃瞄DSC圖.........48
圖3.2.14 PDMS/PTMG-PUIM樣品熔融-急冷掃瞄 DSC圖...48
圖3.2.15高醯亞胺含量PDMS/PTMG-PUIM樣品初始掃瞄DSC
圖.......................................49
圖3.2.16高醯亞胺含量PDMS/PTMG-PUIM樣品熔融-急冷掃
瞄DSC圖..................................49
圖 3.3.1 樣品BD40分別在不同溫度下持溫三小時所的
DSC圖....................................52
圖 3.3.2樣品BD40在80℃下進行不同緩冷時間之DSC圖形54
圖 3.3.3樣品BD40在120℃下進行不同緩冷時間之DSC圖
形........................................54
圖 3.3.4樣品BD40在160℃下進行不同緩冷時間之DSC圖
形........................................55

1. Hepburn, C., ”Polyurethane Elastomers”, Applied Science Publishers, London and New York, 1982,pp.1~2.
2. Woods, G, ”The ICI Polyurethanes Book”, Published jointly by I.C.I and John Wiley & Sons, 1987, pp.1~6.
3. Oertel, G., “Polyurethane Handbook”, Hanser Publisher, Munich Vienna New York, 1985, pp.1~6
4. Grasel, T. G.; Cooper, S. L., Biomaterials, 1986, 7, 315.
5. Lelah, M. D.; Grasel, T. G.; Cooper, S. L. J. Biomed. Mater. Res.,1986, 20, 433.
6. Estes, G. M.; Cooper, S. L.; Tobolsky, A. V. J. Macromol. Sci. Rev. Macromol. Chem. 1970, 4, 313.
7. Schneider, N. S.; Desper, C. R.; Illinger, J. L.; King, A. O. J. Macromol. Sci. Phys. 1975, B11, 527.
8. Van Bogart, J. W. C.; Lilaonitkul, A.; Lerner, L.; Cooper, S. L. J. Macromol. Sci, Phys. 1983, B17, 267
9. Van Bogart, J. W. C.; Gibson, P. E.; Cooper, S. L. Polym. Sci. Polym. Phys. 1983, 21, 65.
10. Speckhard, T. A.; Ver Strate, G.; Gibson, P. E.; Cooper, S. L. Polym. Eng. Sci. 1983, 23, 337.
11. Xu, M.; Macknight, W. J.; Chen, C. H. Y.; Thomas, E. L. Polymer 1983, 24, 1327.
12. Arnold, Jr. C. J. Elast. Plast. 1974, 6, 238.
13. Petroviĉ, Z. S.; Budinski-Simedic, J. Rubber Chem. Technol. 1985, 58, 685.
14. Hesketh, T. R.; Van Bogart, J, W, C.; Cooper, S. L. Polym. Eng. Sci. 1980, 20, 190
15. Lin, M. F.; Shu, Y. C.; Tsen, W. C.; Chuang, F. S. Polym. Int. 1999, 48, 433.
16. Clough, S. B.; Schneider, N. S. J. Macromol. Sci., Phys. 1968, 2, 553.
17. Miller, G. W.; Saunders, J. H. J. Polym. Sci. Part A-1, 1968, 1923.
18. Seymour, R.W.; Cooper, S. L. Macromolecules 1973, 6, 48.
19. Seymour, R.W.; Cooper, S. L. J. Polym. Sci. PartB, 1971, 9, 689.
20. Van Bogart, J. W.; Bluemke, D. A.; Cooper, S. L. Polymer 1981, 22, 1428.
21. Leung, L. M.; Koberstein, J. T. Macromolecules 1986, 19, 706.
22. Koberstein, J. T.; Russell, T. P. Macromolecules 1986, 19, 714.
23. Seymour, R. W.; Estes, G. M.; Cooper, S. L. Macromolecules, 1970, 3, 579.
24. Ng, H. N.; Allegrezza, A. E.; Seymour, R.W.; Cooper, S. L. Polymer, 1973, 14, 255.
25. Kberstein, J. T.; Stein, S. R. J. Polym. Sci., Polym. Phys., 1983,21 1439.
26. Hu, W.; Koberstein, J. T. J. Polym. Sci., Polym. Phys, Ed. 1994, 32, 437.
27. Chen, T. C.; Shieh, T. S.; Chi, J. Y. Macromolecules 1998, 31, 1312.
28. Cooper, S. L.; Tobolsky, A. V. J. Appl. Polym. Sci. 1966, 10, 1837.
29. Camargo, R. E.; Macosko, C. W.;. Tiirrell, M. V.; Wellinghof, S. T. Polym. Eng. Sci. 1982, 22, 719.
30. Fridman, I.; Thomas, E. L.; Lee, L. J.; Macosko, C. W. Polymer 1980, 21, 393
31. Chang, A. L.; Briber, R. M.; Thomas, E. L.; Zdrahala, R. J. Critchfield, F. E. Polymer 1982, 23, 1060.
32. Abouzahr, S.;. Wilkes, G. L. J. Appl. Polym. Sci. 1984, 29, 2695.
33. Miller, J. A.; Lin. S. B.; Hwang, S. K. K.; Wu, K. S.; Gibson, P. E.; Cooper, S. L. Macromolecules 1985, 18, 32.
34. Vallance, M. A.; Castles, J. L.; Cooper, S. L. Polymer 1984, 25, 1734.
35. Speckhand, T. A.; Hwang, K. K. S.; Lin, S. B.; Tsay, S. Y. Koshiba, M.; Ding, Y. S.; Cooper, S. L. J. Appl. Polym. Sci. 1985, 30, 647.
36. Hepburn, C., ”Polyurethane Elastomers”, Applied Science Publishers, London and New York, 1982, Ch.3.
37. Saunder, J. H. Rubber Chem. Technol. 1960, 33, 1259.
38. Smith, T. L. J. Polym. Phys. Ed. 1974, 12, 1825.
39. Smith, T. L. Polym. Eng. Sci. 1977, 17, 129.
40. Shibatanti, K.; Lyman, D. J.; Shieh, D. R.; Knutson, K. J. Polym. Sci., Polym. Chem. Ed. 1977, 15, 1665.
41. Rayn. P. W. Polym. J. 1971, 3, 145.
42. Brunette, C. M.; Hsu, S. L.; Macknight, W. J.; Schneider, N. S. Polym. Eng. Sci. 1981, 21, 163.
43. Brunette, C. M.; Hsu, S. L.; Rossman, M.; Macknight, W. J.; Schneider, N. S. Polym. Eng. Sci. 1981, 21, 663.
44. Ono, K.; Shimada, H.; Nishimura, T.; Yamashita, S.; Okamoto, H.; Minoura, Y. J. Appl. Polym. Sci. 1977, 21, 3323.
45. Speckhard T. A.; Cooper, S. L. Rubber Chem. Technol. 1986, 59, 405.
46. Chen, T. C.; Shieh, T. S.; Chi, J. Y. Macromolecules 1998, 31, 1312.
47. Shu, Y. C.; Lin, M. F.; Tsen, W. C.; Chuang, F. S. J. Appl. Polym Sci. 2001,81,3489.
48. Lin, M. F.; Shu, Y. C.; Tsen, W. C.; Chuang, J. Appl. Polym Sci. 2001,81,3502.
49. Yang, H. H., “Aromatic High-Strength Fiber”, JOHN WILEY & SONS, New York, 1989, pp.702~722.
50. Tenbrinke, G.; Grooten, R. Colloid Polym. Sci. 1989, 267, 992.
51. Hergenrother RW, Yu XH, Cooper SL. Biomaterials, 1994,15, 635.