臺灣博碩士論文加值系統

對位性聚苯乙烯具有許多極佳的物理性質，但因其特殊之結晶型態及不具備極性官能基之種種特性，造成物性上(如低耐衝擊強度與脆性)的不足，這些物性上面的問題，限制了對位聚苯乙烯聚合物材料之應用空間。本論文針對現今工業應用與學術研究領域都相當熱門的發光高分子材料進行相關之合成研究，使對位性聚苯乙烯不但保有部分原有特性，更進一步改質為具有發光等特殊性質的材料。這些高分子其結構都具有芳香性( aromaticity )與高度共軛(conjugated)之特徵，而研究的內容則包含下列三個方向：
(Ⅰ) 使用Cp*Ti(OMe)3/MAO觸媒系統聚合4-氯苯乙烯單體，以合成具有對位性立體規則之對位聚4-氯苯乙烯(sP4CS)。在此系統中加入二甲基苯基乙烯基矽烷(dimethylphenylvinylsilane)作為鏈轉移劑，以合成分子量可控制之聚合物 (sP4CS)。再使用鈀金屬觸媒系統，誘導聚合物進行Suzuki 耦合反應，改質苯對位位置之化學結構，以合成對位乙烯基芳香環聚合物。
(Ⅱ) 將苯對位位置帶有halides 側鏈基的單體(4-溴苯乙烯)，使用鈀金屬觸媒系統進行Buchwald-Hartwig 耦合反應，誘導4-溴苯乙烯單體與立體障礙較大的胺類化合物進行胺化銜接反應，合成出苯對位位置帶有胺類取代基之乙烯基芳香族單體。此一結構經實驗證實具備photoluminescence效應，再使用Cp*Ti(OMe)3/MAO觸媒系統進行聚合反應，合成苯對位位置具有胺類取代基之發光對位乙烯芳香環聚合物(Light emitting syndiotactic polyvinyl arenes)。
(Ⅲ) 將上述合成出的高分子材料進行調幅式微差掃描熱卡計(MDSC)實驗檢測或激發螢光光譜實驗(photoluminescence)檢測其發光性質。

Syndiotactic polystyrene (sPS) possesses many good properties, (e.g, high melting temperature, high glass transition temperature, high crystallinity, good hardness and a fast crystallization rate,) to be used as a high performance engineering plastic. However, the high crystallinity of sPS also results in brittleness and low impact strength which substantially limits applications of sPS material. In this study, we focus on the syntheses of syndiotactic polystyrene derivatives based light-emitting polymer, which may offer important industrial applications and attract tremendous interests. These light emitting syndiotactic polyvinylarene based polymers are structurally modified from the syndiotactic polystyrene by adding additional aromatic ring to enhance the
π-conjugation system of sPS ; thus, offer the motified syndiotactic vinylarene polymers with light emitting characteristics.
　　Our syntheses of these unique vinylarene -based polymers are based on the following methods:
　　In the presence of dimethylphenylvinylsilane (DMPhVS) as the chain transfer agent, syndiotactic poly-4-chlorostyrene (sP4CS) can be selectively produced using Cp*Ti(OMe)3/MAO as the catalyst . Subsequently, syndiotactic poly-4-chlorostyrene (sP4CS) can be used to undergo the Suzuki coupling reaction for the generation of syndiotactic vinlyarene which prossess additional aromatic substituents at the para-position.
　　On the other hand, the original styrene structure can also be field into the 4-amino-styrene compounds, by coupling 4-bromostyrene with aromatic amine in via the palladium-catalyst-mediated Buchwald-Hartwig reaction. The resulting 4-phenylaminostyrene can be used as the monomers to undergo the syndiospectific polymerization reaction for providing syndiotactic polymers by using the Cp*Ti(OMe)3/MAO as the catalyst.
　　The resulting syndiotactic polymers were found not only to have the well-defined chemical structures but also to exhibit light-emitting properties as demonstrated by PL analyses.

中文摘要 I
目錄 V
圖目錄 VIII
表目錄 XI
第一章　緒論 1
1-1　前言 1
1-2　材料介紹 4
1-2-1　聚苯乙烯簡介 4
1-2-2　共軛高分子簡介 (conjugated polymer) 7
1-2-2-1　共軛高分子的結構 8
1-3　原理介紹及文獻回顧 9
1-3-1　Suzuki耦合反應簡介 9
1-3-1-1　Suzuki耦合反應─觸媒與配位基 13
1-3-1-2　胺化反應簡介 14
1-3-2　有機金屬茂 (metallocene)觸媒系統簡介─緣起與發展 17
1-3-3　助觸媒（MAO）簡介 19
1-3-3-1　助觸媒MAO在metallocene觸媒中提升活性的機制 20
1-3-3-2　metallocene觸媒的聚合反應機制 21
1-3-4　發光機制 26
1-3-5　影響光致發光的因素 28
1-3-5-1　AIE和ACQ效應 30
1-4　研究大綱 34
第二章 實驗部份 36
2-1　實驗藥品 36
2-2　單體與溶劑之純化 40
2-3　實驗設備與分析儀器 42
2-4　分析儀器原理 44
2-4-1　調幅式微差掃描熱分析儀 44
2-4-2　凝膠滲透層析儀( Gel Permeation Chromatography ) 45
2-4-3　核磁共振分析儀( Nuclear Magnetic Resonance ) 48
2-5　藥品配製方法與實驗步驟 52
2-5-1　藥品配製 52
2-5-2　合成對位性乙烯基芳香環聚合物 54
2-5-3　合成對位性胺類取代基之乙烯基芳香族單體 56
2-5-4　合成對位性乙烯芳香環聚合物 59
第三章、結果與討論 62
3-1 CP*TI(OME)3/MAO反應機制之探討 64
3-2　影響DMPVS-capped SP4CS 分子量分佈探討 66
3-2-1 鏈轉移劑(DMPVS)與單體4-氯苯乙烯的比例對於sP4CS分子 量的影響 66
3-2-2 溫度對於聚合sP4CS分子量的影響 68
3-3 SP4CS　末端官能化反應之研究 69
3-3-1　DMPVS-t-sP4CS 之微結構探討及圖譜分析 72
3-3-2　Vinyl-t-sP4CS 之微結構探討及圖譜分析 81
3-3-3　OH-t-sP4CS之微結構探討及圖譜分析 84
3-4　鈀金屬觸媒反應機制之探討 86
3-4-1　合成 sP4FPS轉化率的影響因素 92
3-4-2　sP4FPS 微結構探討及圖譜分析 93
3-4-3　sP4FPS 13C對1H HMQC以及 HMBC二維NMR圖譜分析 96
3-4-4　sP4FPS之DSC圖譜 99
3-5　4-N,N(R1R2)styrene 微結構探討及圖譜分析 100
3-5-1　4-N,N-ethylphenylstyrene (4N,NEPS)微結構探討 100
3-5-2　4-N,N-diphenylstyrene (4N,NPh2S)微結構探討 103
3-5-3　4-N,N-bis(trimethylsilyl)amino-styrene (4-N,ND(TMS)S)微結 構探討 105
3-5-4　利用Cp*Ti(OMe)3/MAO觸媒系統進行聚合反應 107
3-5-3　sP4N,NEPS微結構探討及1H NMR圖譜分析 109
3-5-4　sP4N,NEPS 13C-DEPT135 NMR圖譜分析 111
3-5-5　sP4N,NEPS 13C對1H HMQC以及 HMBC二維NMR圖譜 分析 113
3-5-6　sP4N,NDPS微結構探討及1H NMR圖譜分析 118
3-5-7　sP4N,NDPS 13C-DEPT135 NMR圖譜分析 120
3-5-8　sP4N,NDPS HMQC二維NMR圖譜分析 123
3-5-9　sP4-N,N-bis(trimethylsilyl)amino-styrene (sP4N,ND(TMS)S)微結構探討 125
3-5-10 sP4N,ND(TMS)S 13C-DEPT135 NMR圖譜分析 127
3-6　 激發螢光光譜實驗(Photoluminescence) 129
3-6-1　poly 4N,NEPS發光現象探討 132
3-6-2　poly 4-N,N-diphenylstyrene發光現象探討 137
第四章　結論 142
參考文獻 144

1.紀慕雅. 新型對位聚苯乙烯接枝含極性枝鏈共聚物之合成與應用. 國立中正大學2002.
2.江昆諒. 以同一反應器直接合成乙烯苯乙烯共聚橡膠接枝對位性聚苯乙烯之合成方法及其材料應用研究.
國立中正大學2002.
3.施人誠. 對位性聚苯乙烯接枝雜排聚苯乙烯共聚物之合成及其合膠應用之探討. 國立中正大學2002.
4.陳智榮. 鏈移轉反應研究及其應用於合成雙嵌段式對位性聚苯乙烯共聚合物. 國立中正大學2003.
5.蕭浩然.乙烯基矽烷化合物誘導之選擇性鏈轉移劑轉移反應：合成含對位聚苯乙烯之雙嵌段共聚物之新合成方
法. 國立中正大學2009
6.蕭丁瑞.製備具自我組裝奈米結構之含對位性立體規則性聚苯乙烯雙團聯共聚物. 國立中正大學2010
7.Pellecchia, C.; Longo, P.; Proto, A.; Zambelli, A. Die Makromolekulare Chemie Rapid
Communications 1992, 13, (5), 265-268.
8.Dias, M. L.; Giarrusso, A.; Porri, L. Macromolecules 1993, 26, (24), 6664-6666.
9.Grassi, A.; Longo, P.; Proto, A.; Zambelli, A. Macromolecules 1989, 22, (1), 104-108.
10.Zambelli, A.; Oliva, L.; Pellecchia, C. Macromolecules 1989, 22, (5), 2129-2130.
11.Soga, K.; Nakatani, H.; Monoi, T. Macromolecules 1990, 23, (4), 953-957.
12.Chien, J. C. W.; Salajka, Z.; Dong, S. Macromolecules 1992, 25, (12), 3199-3203.
13.Ishihara, N.; Kuramoto, M.; Uoi, M. Macromolecules 1986,19, (10), 2464-2465.
14.Ishihara, N.; Kuramoto, M.; Uoi, M. Macromolecules 1988, 21, (12), 3356-3360.
15.(a)Suzuki, A. In Metal-Catalyzed Cross-Coupling Reactions, Diederich, F., and Stang,
P. J., Eds.;Wiley-VCH: New York, 1998, 49-97
(b) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457–2483
16.G. C. Fu and A. F. Littke Angew.Chem.Int.Ed. 2002,41,4176-4211
17.P. Fitton, E. A. Rick, J. Organomet. Chem. 1971, 28,287
18.(a)Suzuki, A. J. Organometallic Chem. 1999, 576, 147–168.
(b)Adam F. Littke, Chaoyang Dai, and Gregory C. Fu* J. Am. Chem. Soc. 2000, 122,
4020-4028
19.John P. Wolfe,† Hiroshi Tomori, Joseph P. Sadighi,‡Jingjun Yin, and Stephen L.
Buchwald* J. Org.Chem. 2000, 65, 1158-1174
20.John P. Wolfe, Seble Wagaw, and Stephen L.Buchwald* J. Am. Chem. Soc. 1996, 118,7215-
7216
21.Wolfe, J. P.; Singer, R. A.; Yang, B. H.; Buchwald, S. L. J. Am. Chem. Soc. 1999,
121, 9550–9561.
22.Breslow, D. S.; Newburg, N. R. Journal of the American Chemical Society 1957, 79,
(18), 5072-5073.
23.Sinn, H.; Kaminsky, W.; Stone, F. G. A.; Robert, W. Advances in Organometallic
Chemistry 1980, 18, 99-149.
24.Breslow, D. S.; Newburg, N. R. Journal of the American Chemical Society 1959, 81,
(1), 81-86.
25.Phillips, G. W.; Carrick, W. L. Journal of the American Chemical Society 1962, 84,
(6), 920-925.
26.(a)Guangxue Xu and T. C.Chung* Macromolecules2000, 33, 5803-5809
(b) Ting-jui Hsiao, Jing-cherng Tsai* Journal of Polymer Science: Part A: Polymer
Chemistry, 2010 ,Vol. 48, 1690–1698
27.M. Gratzel, J. K. Thomas, in: Modern Fluorescence Spectroscopy, Vol.2, E.L.Wehry,
Ed, Plenum Press, New York, N.Y., 1976, 169.
28.T. Förster, K. Kasper, Z. Phys. Chem. (Munich) 1954, 1, 275.
29.B. Z. Tang, Chem. Commun., 2009, 4332.
30.S. Holdcroft, Macromolecules, 2002, 35 (18), 6900
31.B.Z. Tang, J. Phys. Chem. B, 2008, 112 (31), 9281.
32.B. Z. Tang, Macromolecules, 2006, 39, 6997.
33.B. Z. Tang, Macromolecules, 2003, 36, 1108.
34.Sun, R. G.; Masuda, T.; Kobayashi, T Jpn. J. Appl. Phys. 1996,
35, L1434
35.Xi, Z.; Song, Z.; Liu, G.; Liu, X.; Takahashi, T. The Journal of Organic Chemistry
2006, 71, (8), 3154-3158.
36.Brown, H. C.; Zweifel, G. Journal of the American Chemical Society 1961, 83, (11),
2544-2551.
37.Brown, H. C.; Gupta, S. K. Journal of the American Chemical Society 1972, 94, (12),
4370-4371.
38.Sabatini, A.; Sacconi, L. Journal of the American Chemical Society 1964, 86, (1), 17-
20.
39.Feil, F.; Harder, S. Macromolecules 2003, 36, (9), 3446-3448.