臺灣博碩士論文加值系統

有機無機複合奈米粒子利用粒子表面有機基團和摻混的小分子或寡聚體，其間氫鍵作用力，提供了更多變更廣範的功能性奈米材料，並且有效提升原始材料的光學性、電性以及機械性質。在合適的狀況下，小分子或寡聚體經由分子設計摻混其它種類的小分子可形成某特殊形態結構，展現類似高分子的流變、機械及熱性質的行為。因此運用分子設計，製備具有自組裝特性的奈米級粒子已受到許多的科學研究學者的矚目與探討。
首先，我們合成具有四&;#21537;啶基星狀化合物(TNMM)和八酚的多面體聚矽氧烷(OP-POSS)材料，文中我們觀察&;#21537;啶與酚基間的氫鍵變化，摻混不同比例得到不同氫鍵比例組成的分子網狀結構，以OP-POSS為計量基準，隨著TNMM的含量增加，酚基與&;#21537;啶基間的氫鍵比例跟著增加，不同比例的摻混，其熱性質呈現熱可逆的特性，相較於室溫為黏稠液體的OP-POSS (具低玻璃轉移溫度，Tg=14.4 °C)，摻混40 wt %的TNMM的氫鍵複合網狀結構呈現透明玻璃狀固體，Tg為37 °C。此外，在碳膜稀薄溶液，溶劑揮發過程即除潤(Dewetting)程序，摻混40 wt %的TNMM的氫鍵複合超分子呈現數微米直徑的圓環微結構。
在第二個部分中，我們摻混聚苯乙烯(PS)、苯乙烯-丁二烯橡膠(SRB)及苯乙烯-丁二烯-苯乙烯三段共聚物(SBS)獲得較佳的機械性質及微結構以利微孔發泡形成具緻密封閉性泡孔的多孔性高分子結構體，混入不同比例的交聯劑(架橋劑)、發泡劑、交聯劑、填充劑及助劑等進行密閉高溫發泡以獲得不同孔洞大小以及分佈的發泡材料，發現增加架橋劑可以補強發泡孔洞結構，提升的機械性質包括硬度、收縮性、抗拉伸強度、撕裂&;#24378;度、斷裂伸長率和壓縮率。

Inorganic nanoparticles (NPs) enclosed within hydrogen bonding between small molecules or oligomers provide new opportunities for the development of functional hybrid materials that exhibit enhanced optical, electrical, and mechanical properties. Under suitable experimental conditions, such assemblies can display polymer-like rheological or mechanical properties, because of their macromolecular architecture. As an alternative to these fabrication pathways, routes that use the self-assembly of nanoparticle are attracting increasing attention.
(1) In part one, a pyridine-functionalized pentaerythritol star polyester compound (TNMM) and an octakis[dimethyl(4-hydroxyphenethyl)siloxy]silsesquioxane (OP-POSS) were synthesized and used as tetrahedral and cubic building blocks, respectively, for three-dimensional, hydrogen bond–mediated, POSS-based supramolecular network structures. With noncovalent chain extension of hydrogen bonds between its pyridine and phenol groups, the POSS-based supramolecular networks exhibited thermally reversible properties. Compared with the glass transition temperature of OP-POSS (ca. 14.4 °C) and the melting temperature of TNMM (ca. 160 °C), the hydrogen bond-mediated miscible blend of 40 wt % TNMM in OP-POSS exhibited a single and higher glass transition temperature (37 °C). Because of its strong intermolecular hydrogen bonding, the dewetting pattern of the blend of 40 wt% TNMM in OP-POSS formed ring-like structures, rather than the droplets formed by pure OP-POSS. A transparent, brittle, and glassy solid at room temperature, the blend of 40 wt% TNMM in OP-POSS is an explicit and successful example of a POSS-based hydrogen-bonded supramolecular network.
(2) This study investigates the effect of peroxide crosslinking on the structure and mechanical properties for PS/PB foams composed of polystyrene (PS), polystyrene-block-polybutadiene (SBR), and polystyrene-block-polybutadiene-block- polystyrene (SBS). The cell size and its distribution of PS/PB foams was investigated by SEM images, showing the smaller and denser of hollow cells for the PS/PB foam containing the more concentration of DCP (dicumyl peroxide). As expected, the density of the PS/PB foams increases with increasing the content of DCP. The high density of polymeric foams exhibit the high mechanical properties such as hardness, shrinkage, tensile strength, tear strength, elongation at break, and compression set.

Chapter 1 Introduction to POSS and Hydrogen-Bonding 1
1-1 A history of Polyhedral Oligomeric Silsesquioxane(POSS) 1
1-2 Silsesquioxanes and Polyhedral Oligomeric Silsesquioxane(POSS) 2
1-3 POSS Polymers and Copolymers 5
1-4 The Definition of Hydrogen-Bonding 6
1-5 Hydrogen bond in polymer blends 8
1-6 Introduction to Painter-Coleman Association Model 9
1-7 Influence factors of hydrogen bonds 12
1-7.1 Acidity of the proton donor and basicity of the proton acceptor 12
1-7.2 Intramolecular screening effect on hydrogen bond 14
1-7.3 Functional group accessibility effect on hydrogen bond 16
1-7.4 Temperature effect on hydrogen bond 19
1-7.5 Solvent effect on hydrogen bond 20
1-8 Experimental Characterization of hydrogen bonds 21
1-9 References 24
Chapter 2 Introduction to Foams and Thermoplastic Elastomers 27
2-1 The concept of a cell 27
2-2 Fundamental Principles of Foam Formation 29
2-3 Foaming of Thermoplastic Elastomers 30
2-4 References 33
Chapter 3 Hydrogen Bond-Mediated Self-Assembly of POSS-Based Supramolecules 34
3-1 Introduction 35
3-2 Experimental Section 39
3-2.1 Materials 39
3-2.2 Octakis[dimethyl(4-acetoxyphenethyl)siloxy]silsesquioxane (OA-POSS) 39
3-2.3 Octakis[dimethyl(4-hydroxyphenethyl)siloxy]silsesquioxane (OP-POSS) 41
3-2.4 Tetrakis(nicotinoxymethyl)methane (TNMM) 42
3-2.5 OP-POSS/TNMM Blends 42
3-2.6 Characterization 43
3-3 Results and Discussion 44
3-3.1 Synthesis and Characterization of OP-POSS and TNMM 44
3-3.2 Intermolecular Interactions of OP-POSS/TNMM Supramolecules 46
3-3.3 Thermal Properties of OP-POSS/TNMM Complexes 57
3-3.4 TEM Microscopy of Aggregate Structures 61
3-4 Conclusions 64
3-6 References 65
Chapter 4 Thermal and Mechanical Properties of Microcellular Thermoplastic PS/PB Copolymer: Effect of Crosslinking 71
4-1 Introduction 72
4-2 Experimental Section 78
4-2.1 Materials 78
4-2.2 Sample Preparation 79
4-2.3 Characterization 79
4-3 Results and Discussion 82
4-3.1 Design of Formula and Process 82
4-3.2 Microstructures 85
4-3.3 Thermal Properties 91
4-4 Conclusions 96
4-5 References 97
Chapter 5 Conclusions 102
List of Publications 104
Introduction to the Author 105

1. Lichtenhan, J. D.; Feher, F. J.; Gilman, J. W. Macromolecules 1993, 26, 2141.
2. Lichtenhan, J. D.; Otonari, Y.; Carr, M. J. Macromolecules 1995, 28, 8435.
3. Laine, R. M.; Sellinger, A. Macromolecules 1996, 29, 2327.
4. Mather, P. T.; Haddad, T. S.; Oviatt, H. W.; Schwab, J. J.; Chaffee, K. P.; Lichtenhan, J. D. Polym Prepr 1998, 39, 611.
5. Baney, R. H.; Itoh, M.; Sakakibara, A.; Suzuki, T. Chem. Rev. 1995, 95, 1409.
6. Zhang, X.; Shi, L. Chin J. Polym. Sci. 1987, 5, 197.
7. Brown, Jr. J. F. J. Polym. Sei. C 1963, 1, 83.
8. Xie, Z.; He, Z.; Dai, D.; Zhang, R. Chin. J. Polym. Sci. 1989, 7, 183
9. Maciel, G. E.; Sullivan, M. J.; Sindorf, D. W. Macromolecules 1981, 14, 1607.
10. Engelhavdt, G.; Jancke, H.; Lippmaa, E.; Samoson, A. J. Organomet. Chem. 1981, 210, 295.
11. Frye, C. L.; Collins, W. T. J. Am. Chem.Soc.1970, 92, 5586.
12. Belot, V.; Corriu, R.; Leclerq, D.; Mutin, P. H.; Vioux, A. Chem. Mater. 1991, 3,127
13. Adachi, H.; Hayashi, O.; Okahashi, K. Japanese Patent Kokoku-H-2-15863.
14. Adachi, H.; Hayashi, O.; Okahashi, K. Japanese Patent Kokai-S-60-108841.
15. Adachi, E.; Aiba, Y. Adachi, H. Japanese Patent Kokai-H-2-277255.
16. Aiba, Y.; Adachi, E.; Adachi, H. Japanese Patent Kokai-H-3-6845.
17. Shoji, F.; Sudo, R.; Watanabe, T. Japanese Patent Kokai-S-56-146120.
18. Imai, E.; Takeno, H. Japanese Patent Kokai-S-59-129939.
19. Mishima, T.; Nishimoto, H. Japanese Patent Kokai-H-4-247406.
20. Saito, Y.; Tsuchiya, M.; Itoh, Y. Japanese Patent Kokai-S-58-14928.
21. Mine, T.; Komasaki, S. Japanese Patent Kokai-S-60-210570.
22. Lichtenhan, J. D.; Schwab, J. J.; Reinerth, Sr. W. A. Chem. Innovat. 2001, 1, 3.
23. Ellsworth, M. W.; Gin, D. L. Polym. News 1999, 24,331.
24. Errera, J.; Mollet, P. Nature 1936, 138, 882.
25. Schwager, F.; Marand, E.; Davis, R. M. J. Phys. Chem. 1996, 100, 19268.
26. Van Ness, H. C.; Winkle, J. V.; Richtol, H. H.; Hollinger, H. B. J. Phys. Chem. 1967, 71, 1483.
27. Johari, G. P.; Dannhauser, W. J. Phys. Chem. 1968, 72, 3273.
28. Johari, G. P.; Dannhauser, W. J. Phys. Chem. 1968, 72, 3273.
29. Dannhauser, W. J. Chem. Phys. 1968, 48, 1991.
30. Musa, R. S.; Eisner, M. J. Chem. Phys. 1959, 30, 227.
31. Pauling, L.; Corey, R. B.; Branson, H. R. Proc. Nat. Acad. Sci. 1951, 37, 205.
32. Pauling, L.; Corey, R. B. Proc. Nat. Acad. Sci. 1951, 37, 729.
33. Watson, J. P.; Crick, F. H. Nature 1953, 171, 737.
34. Pimental, G. C.; McClellan, A. L. “The Hydrogen Bond”, W. H. Freeman and Company, San Francisco, 1960.
35. Lee, J. Y.; Painter, P. C.; Coleman, M. M. Macromolecules 1988, 21, 954.
36. Coleman, M. M.; Painter, P. C. Prog. Polym. Sci. 1995, 20, 1.
37. Kuo, S. W.; Chan, S. C.; Chang, F. C. Macromolecules 2003, 36, 6653.
38. Dai, J.; Goh, S. H.; Lee, S. Y.; Siow, K. S. Polymer 1996, 37, 3259.
39. Coleman, M. M.; Painter, P. C. Macromol. Chem. Phys. 1998, 199, 1307.
40. Painter, P. C.; Veytsman, B.; Kumar, S.; Shenoy, S.; Graf, J. F.; Xu, Y.; Coleman, M. M. Macromolecules 1997, 30, 932.
41. Coleman, M. M.; Pehlert, G. J.; Painter, P. C. Macromolecules 1996, 29, 6820.
42. Pehlert, G. J.; Painter, P. C.; Veytsman, B.; Coleman, M. M. Macromolecules 1997, 30, 3671.
43. Coleman, M. M.; Graf, J. F.; Painter, P. C. Specific Interactions and the Miscibility of Polymer Blends; Technomic Publishing, Inc.; Lancaster, PA, 1991.
44. He, Y.; Asakawa, N.; Inoue, Y. Macromol. Chem. Phys. 2001, 202, 1035.
45. Kamlet, M. J.; Taft, R. W. J. Am. Chem. Soc. 1976, 98, 377.
46. Kamlet, M. J.; Abboud, J. L. M.; Abraham, M. H.; Taft, R. W. J. Org. Chem. 1983, 48, 2877.
47. Jiang, M.; Qiu, X.; Qin, W.; Fei, L. Macromolecules 1995, 28, 730.
48. Jeffery, G. A. “An Introduction to Hydrogen Bonding” Oxford University Press: New York, 1997, Ch.6.