硬質鏈段不規則性對PU奈米形態之影響

以作者查詢圖書館館藏

、以作者查詢臺灣博碩士

、以作者查詢全國書目

、勘誤回報

、線上人數：16

、訪客IP：18.222.69.248

姓名

葉智哲(Chih-Che Yeh) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

硬質鏈段不規則性對PU奈米形態之影響
(The effect of chemical structure irregularity in hard segment on PU nano-scale morphology)

相關論文

★ PU橡膠血液相容性之探討	★ PU發泡體的結構與性質
★ POLY IP發泡體結構與性質之探討	★ 非極性式poly-ip based PU軟質段末端改質的影響
★ 高韌性環氧樹脂底膠之開發	★ 水性PU之流變性質研究
★ 完全相分離PU之完整形態研究	★ 含矽膠PU之合成與血液相容性研究
★ 奈米級嵌段式PU之動態機械性質與微結構型態研究	★ Hydroxyl Terminated Polyisoprene(HTIP)陰離子型水性PU合成與性質研究
★ 陰離子型水性PU/有機蒙特納土奈米複合材料之製備與分析	★ 非極性式poly-ip based PU 之軟質段末端改質對形態的影響
★ 硬質鏈段不規則性對PU奈米形態之影響(II)	★ 苦楝油對於水性PU膨潤效應的性質研究
★ 尼龍表面親疏水性之研究	★ 吸附性高自由體積粉粒之製備與應用

檔案

[Endnote RIS 格式]

[Bibtex 格式]

[相關文章]

[文章引用]

[完整記錄]

[館藏目錄]

[檢視]

[下載]

本電子論文使用權限為同意立即開放。
已達開放權限電子全文僅授權使用者為學術研究之目的，進行個人非營利性質之檢索、閱讀、列印。
請遵守中華民國著作權法之相關規定，切勿任意重製、散佈、改作、轉貼、播送，以免觸法。

摘要(中)

本研究以Polyisoprene(polyIP)為非極性軟質段，4,4-diphenylmethane diisocyanate(MDI)為主要硬質段異氰酸鹽、1,4-Butanediol(BD)為鏈延劑，分別以不同比例(0、10、20、30 mole %)Toluene diisocyante (TDI，2,4含80%，2,6含20%)來取代硬質段主鏈上的MDI，合成一系列非極性式PU彈性體。以低溫超薄切片機製備超薄試片進行Transmission Electron Microscopy(TEM)測試，觀察其奈米級相微域結構變化，並同時採用Differential Scanning calorimetry(DSC)、Dynamic Mechanical Analysis(DMA)、Tensile Strength的測試，深入探討此微域形態與其形態變化的交互關係與機械性質。
經由TEM測試結果可發現，在硬質段含量HC=30%的條件下，硬相以短圓柱狀排列，其domain大小約為4~5nm，且隨TDI取代量的增加而略為上升。在HC=45%條件下，硬相圓柱長寬則略大於HC=30%者。當硬質段含量增加到55%以上時，domain size寬度約為5~6nm，且形態隨著TDI加入量起了極大的變化，從原來純MDI-BD的硬相圓柱形態逐漸轉變成薄板lamellar形態。
經DSC熱分析結果顯示，軟質段玻璃轉移溫度與玻璃轉移寬度不隨硬質段含量改變而有很大的變化，証再次映証文獻中所提及的結果，軟段分子鏈不含醚、酯類官能基的非極性式寡聚物二元醇，因其與硬質段的極性差異大，產生互不相溶的現象。在高硬質段含量下，純MDI-BD的T2 long range order吸熱峰隨著TDI量增多變得較不明顯，這應該是由於TDI的化學結構不對稱性破壞了MDI-BD所形成之long range order所造成。另一方面，從DMA測試亦與DSC相互呼映的結果，系列PU高溫區鬆弛行為隨TDI用量愈多，鬆弛溫度愈往低溫偏移。經拉伸測試之後發現，在TDI含量30%(mole%)、硬質段HC=65%的情況下，可獲得降伏強度達28.9MPa、斷裂強度25.2MPa、斷裂延伸率47.7%的優良機械性質，這是非極性式PU系統中難得一見的。

關鍵字(中)

★ 拉伸
★ 微分熱分析
★ 聚胺基甲酸酯
★ 動態機械分析
★ 穿透式電子顯微鏡
★ 非極性

關鍵字(英)

★ TENSILE
★ DMA
★ DSC
★ TEM
★ nonpolar
★ PU
★ polyurethane
★ TDI
★ isoprene
★ MDI
★ BDI

論文目次

目錄
摘要---------------------------------------------------------------------------------Ⅰ
目錄---------------------------------------------------------------------------------Ⅲ
圖目錄-------------------------------------------------------------------------------Ⅴ
表目錄-------------------------------------------------------------------------------Ⅷ
第一章緒論-------------------------------------------------------------------------1
第二章文獻回顧-------------------------------------------------------------------3
2-1 PU的熱性質--------------------------------------------------------------------4
2-2 硬質相的規則度------------------------------------------------------------7
2-3 物理老化焓鬆弛(Physical aging)-----------------------------------------8
2-4 相分離程度或兩相組成比例計算-------------------------------------------------9
2-5 相分離動力學----------------------------------------------------------------14
2-6 PU的形態與結構--------------------------------------------------------------15
2-7 PU的機械性質----------------------------------------------------------------17
2-8 PU硬質段的結構組成----------------------------------------------------------22
第三章實驗
3-1 化學藥品--------------------------------------------------------------------25
3-2 儀器設備--------------------------------------------------------------------26
3-3 實驗流程--------------------------------------------------------------------26
第四章結果與討論
4-1 相分離之評鑑----------------------------------------------------------------30
4-2 穿透式電子顯微鏡(TEM)對PU形態分析-------------------------------------------30
4-3 DSC熱分析-------------------------------------------------------------------38
4-4 動態機械性質測試------------------------------------------------------------41
4-5 FTIR分析--------------------------------------------------------------------44
4-6 拉伸性質測試----------------------------------------------------------------45
第五章結論-----------------------------------------------------------------------48
參考文獻---------------------------------------------------------------------------51

參考文獻

參考文獻
1.K. Ono, H. Shimada, , T. Nishimura, S. Yamashita, H. Okamoto, and Y. Minoura, Appl. Polym. Sci., 1971, 21, 3323.
2.N. S. Schneider and R. W. Matton, Polym. Eng. Sci., 1979, 19 1122.
3.C. M. Brunette, S. L. Hsu, W. J. Macknight, N. S. Schneider, Polym. Eng. Sci., 1981, 21, 163.
4.B. Bengtson, C. Feger, W. J. Macknight and N. S. Schneider. Polymer, 1985, 26, 895.
5.C. Li, S. L. Goodman, R. M. Albercht and S. L. Cooper, Macromolecules, 1988, 21, 2367.
6.T. K. Chen, C. J. Hwung, C. C. Hou, Polym. Eng. Sci., 1992, 32, 115.
7.國立中央大學化學工程與材料工程系邱家永博士論文。
8.國立中央大學化學工程與材料工程系謝天壽博士論文。
9.T. K. Chen, Jia yeong Chui, and Tien Shou Shieh, Macromolecules, 1997, 30, 5068.
10.T. A. Speckhard, G. V. Strate, P. E. Gibson, S. L. Cooper, Polym. Eng. Sci., 1983, 23, 337.
11.T. A. Speckhard, P. E. Gibson, S. L. Cooper, V. S. C. and J. P. Kennedny, Polymer, 1985, 26, 55.
12.T. A. Speckhard, K. K. S. Hwang, S. L. Cooper, V. S. C. Chang and J. P. Kennedny, Polymer, 1985, 26, 70.
13.Y. Xu, M. R. Nagarajan, T. G. Grasel, P. E. Gibson and S. L. Cooper, J. Polym. Sci, Polym. Phys. Edn., 1985, 26, 70.
14.R. A. Philips, J. C. Stevenson, M. R. Nagarajan and S. L. Cooper, J. Macromol. Sci. Phys., 1988, B27, 245.
15.G. M. Ester, S. L. Cooper and A. V. Tohosky, J. Macromol. Sci- Rev. Macromol. Chem., 1970, 4, 313.
16.J. A. Toutsky, N. V. Hein and S. L. Cooper, J. Polym. Sci., 1970, 8, 23.
17.N. S. Schneider, C. R. Desper, J. L. illinger and A. O. King, J. Macromol. Sci-Phys., 1975, B11, 527
18.X. Xu, W. J. Macknight, C. H. Chen and E. L. Thomas, Polymer, 1983, 24, 1327.
19.C Li, X. Yu, T. A. Speckhard and S. L. Cooper, J. Polymer. Sci., Polym. Phys. Ed., 1988, 26, 315.
20.J. W. Van Bogart, P. E. Gibson and S. L. Cooper, J. Polym. Sci. Phys. Ed., 1988, 26, 315.
21.N. S. Schneider and R. W. Matton, Polym. Eng. Sci., 1979, 19, 1122.
22.C. H. Y. Chen, R. M. Briber, E. L. Thomas, M. Xu and W. J. Macknight, Polymer, 1983, 24, 133.
23.C. Li., S. L. Goodman. R. M. Albercht and S. L. Cooper, Macromolecules, 1988, 21, 2367.
24.C. M. Brunette, S. L. Hsu, M. Rossman, W. J. Macknight and N. S. Schneider, Polymer. Eng. Sci., 1981, 21, 668.
25.Y. Xu, M. R. Nagarajan, T. G. Grasel, P. E. Gibson and S. L. Cooper, J. Polym. Sci., Polym. Phys. Ed., 1985, 23, 2319.
26.S. Dong, Huh and S. L. Cooper, Polym. Eng. Sci., 1971,11, 369.
27.C. Z. Yang, K. K. S. and S. L. Cooper, Macromol. Chem., 1983, 184, 651
28.T. A. Speckhard, K. K. S. Hwang, C. Z. Yang, W. R. Laupan and S. L. Cooper, J Macromol. Sci-Phys., 1984, B23, 175.
29.J. T. Koberstein, A. F. Galambos, L. M. Leung, Macromolecules, 1992, 25, 6195.
30.J. T. Koberstein, L. M. Leung, Macromolecules, 1992, 25, 6205.
31.Y. Camberlin, J. P. Pascault, M. Letoffe and P. Claudy, J. Polym. Sci. Polym. Phys. Ed. 1982, 20, 1445.
32.I. Yilgor, J. S. Rifle, G. L. Wilkes, J. E. McGrath, Polym. Bull., 1982, 8, 535.
33.Y. Gamberlin, J. P. Pascault, J. M. Ltoffe’, P. Glaudy, J. Polym. Sci. Polym. Chem. Ed., 1982, 20, 383.
34.Y. Li, T. Gao, J. Liu, K. Linliu, C. R. Desper and B. Chu, Macromolecules, 1992, 25, 7365.
35.J. T. Koberstein, A. F. Galambos, Macromolecules, 1992, 25, 5618.
36.J. W. C. Van Bogart, P. A.Bluemke and S. L. Cooper, Polymer, 1981, 22, 1428.
37.L. Cuve’, J. P. Pascualt and G. Boiteux, Polymer, 1992, 33, 3957.
38.L. M. Leung, J. T. Koberstein, Macromolecules, 1973, 6, 48.
39.J. T. Koberstein, T. P. Russell, Macromolecules, 1986, 19. 714.
40.T. R. Hesketh, J. W. C. Van Bogart and S. L. Cooper, Polym .Eng. Sci., 1980, 20, 853.
41.W. Hu and J. T. Koberstein, Polym. Sci., Polym Phys. Ed., 1994, 32. 437.
42.T. K. Chen, T. S. Shieh, J. Y. Chui., Macromolecules, 1998, 31, 1312.
43.Z. S. Petrovic’, and I. J. Soda-So, J. Polym. Sci., polym. Phys. Ed., 1989, 27, 545.
44.Y. Camberlin and J. P. Pascault, J. Polym. Sci., Polym. Phys. Ed. 1994, 32, 437.
45.C. H. Y. Chen-Tsai, E. L. Thomas, W. J. Macknight and N. S. Scneider, Polymer, 1986, 27, 659.
46.D. Tyagi, J. E. McGrath, G. L. Wilkes, Polym. Edg. Sci., 1986, 26, 1371.
47.T. K. Kwei, J Appl. Polym. Sci., 1982, 27, 2891.
48.Y. Camberlin and J. P. Pascault, J. Polym. Sci., Polym. Phys. Ed., 1984, 22 1835.
49.H. S. Lee, S. L. Hus, Macromolecules, 1989, 22, 1100.
50.H. S. Lee, Y. K. Wang, W.J . Macknight and S. L. Hus, Macromolecules, 1988, 21, 270.
51.K. K. Che and R. J. Farris, J Appl. Polym. Sci. 1984, 29, 2529.
52.A. F. Calambos, T. P. Russel and J. T. Koberstein, Polym. Mater. Sci. Eng., 1989, 61, 359.
53.C. Li, S. L. Goodman., R. M Albrecht and S. L. Cooper, Macromolecules, 1988, 21, 2367.
54.M. Serrano, W. J. Macknight, E. L. Thomas, J. M. Ottno, Polymer, 1987, 28, 1667.
55.M. Serrano, W. J. Macknight, E. L. Thomas, J. M. Ottno, Polymer, 1987, 28, 1674
56.D. J. Kinning, E. L. Thomas and J. M. Ottno, Macromolecules, 1987, 20,1129.
57.K. J. Meier, Polym. Prepr. Am. Chem. Soc. Div. Polym. Chem. 1970, 11, 400.
58.L. M. Leung and J. T. Koberstein, J. polym. Sci., polym. Phys. Ed., 1985, 23 1883.
59.J. W. C. Van Bogart, P. E. Gibson and S. L. Cooper, J. Polym. Sci. Polym. Phys. Ed., 1983, 21, 65.
60.S. Mitsuhiro, S Masakaus, S. Shinichi, Y. Tomoyuki and N. Shunji, Macromolecules, 1974, 7, 355.
61.I. Kimura, H. Ishihara, H. Ono, N. Yoshihara, S. Nomura and H. Kawai, Macromolecules, 1974, 7 ,355.
62.J. A. Mller, S. L. Cooper, C. C. Han and G. Pruckmeyer, Macromolecules, 1984, 17, 63.
63.T. A. Speckhard and S. L. Cooper, Rubber Chemistry and Elastomers, Vol.59, 405.
64.D. J. Martin, G. F. Meijs, G. M. Renwick, S. J. Maccarthy and P. A. Gunatillake, J. Appl. Polym. Sci, 1996, 62, 1377.
65.S. L. Cooper, G. M. Estes, “Multiphase Polymer”, Adv. Chem. Ser.176, American Chemical Society, Washington D. C., 1979.
66.J. Blackwell and K. H. Gardner, Polymer, 1979, 20, 13.
67.J. Blackwell and M. R. Nagarajan, Polymer, 1981, 22, 202.
68.J. Blackwell, M. R. Nagarajan and T. B. Hoitink, Polymer, 1982, 23, 950.
69.J. Blackwell, M. R. Nagarajan and T. B. Hoitink, Polymer, 1981, 22, 1534.
70.A. Saiani, C. Rochas, G. Eeckhaut, W. A. Daunch, J. W. Leenslag and J. S. Hingins, Macromolecules, 2004, 37, 1411.
71.E. Amitay-Sadovsky, K. Komvopoulos, R. Ward, and G. A. Somorjai, J. Phys. Chem. B, 2003, 107, 6377.
72.Da-Kong Lee, Hong-Bing Tsai, J. Appl. Polym. Sci., 2000, 75, 167.
73.Polyurethane Elastomers, C. Hepburn, Institude of Polymer Technology, Loughborough University of Technology, Loughborough, Leicestershire, UK
74.G. Tenbrinke, R. Grooten, Colloid Polym. Sci., 1989, 267, 992.
75.Israel D. Fridman and Edwin L. Thomas, Polymer, 1980, 21, 388.
76.Darren J. Martin, Gordon F. Meijs, Gordon M. Renwick, Simon J. Mccarthy, and Pathiraja A. Gnatillake, J. Appl. Polym. Sci., 1996, 62, 1377.
77.Darren J. Martin, Gordon F. Meijs, Pathiraja A. Gunatillake, Simon J. Mccarthy, Gordon M. Renwick. J. Appl. Poly. Sci., 1997, 64, 803.

指導教授

陳登科(Teng-Ko Chen)

審核日期

2005-7-19

推文