臺灣博碩士論文加值系統

具有立體規則性的高分子在物理性質上有許多特別之處，相同的高分子在不同立體規則性之下所表現出來的物理及化學性質皆有所差異。本研究針對同位性聚2-乙烯基吡啶(isotactic poly-2-vinylpyridine，iP2VP)作探討，因先前的研究中發現同位性聚2-乙烯基吡啶(iP2VP)在參雜酸性掌性誘導混摻物(chiral dopant) 使其自組裝形成類似生物體的螺旋性結構後進行圓極化雙色光譜儀(CD)之測定效果最佳。因此特別針對iP2VP以不同之格林納試劑反應，進而選擇較佳之觸媒進行合成，並將iP2VP高分子進行一系列末端官能化反應，合成雙嵌段共聚物(block-copolymer)已達研究目的，希望可以進一步達到開發具備新穎特殊物性材料之目的。
為達到合成雙嵌段共聚物之目的，希望合成末端帶有特殊官能基之iP2VP高分子，所以首先使用4-溴苯甲基溴與鎂粉合成出末端帶有雙鍵之格林納試劑，並與2VP單體合成帶有雙鍵之同位聚2-乙烯基吡啶(iP2VP- t-allyl)。
但由於新型格林那觸媒合成出之2VP高分子帶有部分對後續嵌段共聚物的不利因素，因此改由t-BuPhMgBr取代之，並利用末端活性點living的特性行一系列有機化學反應使iP2VP進行末端官能化，依序合成出末端帶有雙鍵(iP2VP-t-allyl)、氫氧基(iP2VP-t-hydroxyl)、溴酯基 (iP2VP-t-bromoester)等特殊官能基高分子起始劑(Macro-initiator)。
最後使用上述之Macro-initiator 與單體caprolactone行開環聚合(Ring Opening polymerization)與Styrene行ATRP聚合反應可分別成功的合成出iP2VP-b-PCL與iP2VP-b-aPS雙嵌段共聚高分子，另外再藉以GPC、NMR、SAX、TEM之儀器驗證結果確認此雙嵌段共聚高分子之成功合成。

Stereoegular tactic Polymers have many unique physical and chemical properties and applications, and hence have drawn tremendous research attentions. In this report, stereoregualr isotactic poly-2-vinylpyridine (iP2VP) was synthesized and used to combine with various chiral dopants to examine if the combination of stereoregualr (tactic) polyolefins and chiral dopants can induced circular dichroism (ICD) driven by the formation of helical conformation along the iP2VP main chain.
In the syntheses of iP2VP, two kinds of Grignard reagents, including para-3-butenylphenylmagnesium bromide and 4-tertbutylphenylmagnesium bromide, were synthesized and used as initiators. Our results indicates that the polymerization of 2-vinylpyridine by using the 2-vinylpyridine as the initiator offers the production of iP2VP with exceptional high isotacticity control (mmmm > 90 %). We also demonstrated that the isospecific polymerization of 2-vinylpyridine initiated by 4-tertbutylphenylmagnesium bromide showed a living polymerization pathway. Accordingly, iP2VP-based block copolymers can be prepared through the living polymeriaztion,funtionalization,and then block copolymerization pathways.
The research focuses on two parts, first, syntheses and structural characterization of new Grignard reagent and second, preparations of iP2VP-based stereoregular diblock copolymers. The resulting iP2VP-based diblock copolymers can be used to combine with chiral dopant to examine the possibility of forming helical assembly via the molecular recognition processes。

摘要 I
ABSTRACT I
目錄 III
圖目錄 VI
表目錄 I
前言 II
第一章 緒論 - 1 -
1-1基本原理簡介 - 1 -
1-1-1 陰離子聚合(Anionic Polymerization) - 1 -
1-1-2 活性聚合(Living Polymerization) - 7 -
1-1-3 立體規則性(Tacticity) - 8 -
1-1-4聚乙烯基吡啶高分子材料 - 11 -
1-1-5 嵌段共聚高分子(Block co-polymers) - 14 -
1-2反應系統介紹及文獻回顧 - 22 -
1-2-1 格林納試劑(Grignard reagent)介紹與應用 - 22 -
1-2-2 格林納試劑聚合同位性聚2-乙烯基吡啶 - 25 -
1-2-3開環聚合(Ring opening metathesis polymerization，ROMP) - 27 -
1-2-4 原子轉移自由基聚合(Atom transfer radical polymerization，ATRP) - 33 -
1-3 研究動機與實驗目的 - 41 -
第二章 實驗部分 - 42 -
2-1 實驗藥品 - 42 -
2-2 實驗設備與分析儀器 - 48 -
2-3 分析儀器原理 - 52 -
2-3-1 凝膠滲透層析儀(Gel Permeation Chromatography，GPC) - 52 -
2-3-2 核磁共振分析儀(Nuclear Magnetic Resonance，NMR) - 56 -
2-3-3圓極化雙色光譜儀(Circular dichroism，CD) - 60 -
2-3-4 調幅式微差掃描熱分析儀(Modulated Differential Scanning Calormetry，MDSC) - 64 -
2-4 溶劑、單體及起始劑純化手續與裝置 - 66 -
2-5實驗步驟及方法 - 67 -
2-5-1　格林納試劑之合成 - 67 -
2-5-2　iP2VP末端官能化部分 - 70 -
2-5-3 以開還聚合方式聚合iP2VP-b-PCL - 75 -
2-5-4 以ATRP方式聚合iP2VP-b-aPS - 76 -
第三章 結果與討論 - 78 -
3-1合成具有雙鍵芳香族之格林納試劑其目的及探討[48] - 79 -
3-1-1具有雙鍵芳香族之格林納試劑1H-NMR圖譜分析 - 80 -
3-1-2利用合成之新型格林納試劑合成同位性isotatic Poly(2-vinylpyridine) (iP2VP)之反應機制探討 - 81 -
3-1-3具備末端雙鍵之iP2VP 1H-NMR圖譜分析 - 82 -
3-1-4具備末端雙鍵之iP2VP氫硼化反應之反應機制探討 - 83 -
3-1-5具備末端氫氧基之iP2VP 1H NMR圖譜及其分析 - 84 -
3-1-6 新型格林納試劑與t-BuPhMgBr合成之高分子之比較 - 85 -
3-2　IP2VP末端官能化反應之研究 - 86 -
3-2-1 iP2VP末端雙鍵之結構證明與圖譜分析 - 88 -
3-2-2　iP2VP末端氫氧基之結構證明與圖譜分析 - 89 -
3-2-3　iP2VP末端溴酯基之結構證明與圖譜分析 - 91 -
3-3經由ROMP合成出IP2VP-B-PCL雙嵌段共聚物 93
3-3-1 iP2VP-b-PCL雙嵌段共聚物之結構證明與圖譜分析 93
3-3-2 iP2VP-b-PCL雙嵌段共聚物型態學(morphology)之分析 94
3-4經由ATRP合成出IP2VP-B-APS雙嵌段共聚物 100
3-4-1 iP2VP-b-aPS雙嵌段共聚物之結構證明與圖譜分析 101
3-4-2以不同ligand改善iP2VP-b-aPS雙嵌段共聚物之分子量分佈 102
3-4-3 iP2VP-b-aPS雙嵌段共聚物之結構證明與圖譜分析(ligand:PMDETA) 103
第四章 結論 105
第五章 參考文獻 106

[1] 鶴田禎二，川上雄資，薛敬和，『高分子設計』，亨信印刷商行2003
[2] R. M. Ho, Y. W. Chiang, C. C. Tsai, C. C. Lin, B. T. Ko and B. H. Huang, J. Am. Chem. Soc., 126, 2704 2004
[3] R. M. Ho, C. K. Chen, Y. W. Chiang, B. T. Ko and C. C. Lin, Adv. Mater., 18, 2355 2006
[4] M. N. Rosenbluth and A. W. Rosenbluth, J. Chen. Phys., 23, 356 1955
[5] N. Hadjichristidis and L. J. Fetters, Macromolecules, 13, 191 1980
[6] M. Morton, "Anionic polymerization: Principles and practice", Academic press, New York 1983
[7] F. S. Bates, G. H. Fredrickson, Annual Review of Physical Chemistry 1990, 41, 525-557.
[8] D. J. Pochan, S. P. Gido, S. Pispas, J. W. Mays, Macromolecules 1996, 29, 5099-5105.
[9] R. N. Young, R. P. Quirk, L. J. Fetters, Advances in Polymer Science 1984, 56, 1-90.
[10] M. Miyamoto, M. Sawamoto, T. Higashimura, Macromolecules 1984, 17, 265-268.
[11] M. Miyamoto, M. Sawamoto, T. Higashimura, Macromolecules 1984, 17, 2228-2230.
[12] K. Matyjaszewski, S. Gaynor, J. S. Wang, Macromolecules 1995, 28, 2093-2095.
[13] J. S. Wang, K. Matyjaszewski, Journal of the American Chemical Society 1995, 117, 5614-5615.
[14] C. H. Ahn, S. Y. Chae, Y. H. Bae, S. W. Kim, Journal of Controlled Release 2004, 97, 567-574.
[15] A. M. de Oliveira, P. C. de Oliveira, A. M. dos Santos, M. H. A. Zanin, M. Ines R Brazilian Journal of Physics, vol. 39, no. 1A, April, 2009
[16] O. Jeon, S. H. Lee, S. H. Kim, Y. M. Lee, Y. H. Kim, Macromolecules 2003, 36, 5585-5592.
[17] J. C. Kuo, W. F. Lin, C. H. Yu, J. C. Tsai, Macromolecules 2008, 41, 7967–7977.
[18] J. C. Tsai, J. C. Kuo, R. M. Ho, T. M. Chung, Macromolecules 2006, 39, 7520-7526.
[19] F. Y. Tzeng, M. C. Lin, J. Y. Wu, J. C. Kuo, J. C. Tsai. M. S. Hsiao, H. L. Chen, and S. Z. D. Cheng , Macromolecules 2009, 42, 3073-3085
[20] J. Y. Lee, M. C. Shiao, F. Y. Tzeng, C. H. Chang, C. K. Tsai, J. C. Tsai, Macromolecules 2012, 45, 2720-2730
[21] Bates, F. S.; Fredrickson, G. H. Annual Review of Physical Chemistry 1990, 41, 525-557.
[22] Pochan, D. J.; Gido, S. P.; Pispas, S.; Mays, J. W. Macromolecules 1996, 29, 5099-5105.
[23] G. Natta, G. Mazzanti, P. Longi, G. Dall’asta and F.Bernardini, J. Polym. Sci., 51, 487 1961
[24] G. O. R. Alberda van Ekenstein, Y. Y. Tan and G. Challa, Polymer, 26, 283 1985
[25] A. Soum and M. Fontanille, Makromol. Chem., 181, 799 1980
[26] A. Soum, and M. Fontanille, Makromol. Chem.,182, 1743 1981
[27] A. Soum, and M. Fontanille, Makromol. Chem.,183, 1145 1982
[28] D. K. Dimov, T. E. Hogen-Esch, Macromolecules, 28, 7394 1995
[29] A. Dworak, W. J. Freeman and H. J. Harwood, Polymer J., 17, 351 1985
[30] P. Dubois, C. Jacobs, R. Jerome, P. Teyssie, Macromolecules
1991, 24, 2266-2270
[31] N. Ropson, P. Dubois, R. Jerome, P. Teyssie, Macromolecules 1994, 27, 5950-5956
[32] O. Coulembier, P. Degee, J. L. Hedrick, P. Dubois, Prog. Polym. Sci. 2006, 31, 723-747
[33] O. D. Cabaret, B. M. Vaca, D. Bourissou, Chem. Rev. 2004, 104, 6147-6176
[34] S. C. Schmidt, M. A. Hillmyer, Macromolecules 1999, 32,4794-4801
[35] A. S. Zalusky, R. O. Valles, J. H. Wolf, M. A. Hillmyer, J. Am. Chem. Soc. 2002, 124, 12761-12773
[36] G. L. Cheng, C. P. Hu and S. K. Ying, Macromol. Rapid Commun., 20, 303 1999
[37] G. L. Cheng, C. P. Hu and S. K. Ying, Journal of Molecular Catalysis A: Chemical, 144, 357 1999
[38] K. Matyjaszewski, Macromolecules, 32, 9051 1999
[39] K. Matyjaszewski and J. Xia, Chem. Rev., 101, 292 2001
[40] W. Tang, Y. Kwak, W. Braunecker, N. V. Tsarevsky, M. L. Coote and K.Matyjaszewski, J. Am. Chem. Soc., 130, 10702 2008
[41] G. G. D. Sart, R. Rachmawati, V. Voet, G. A. V. Ekenstein, E. Polushkin, G. T. Brinke and K. Loos, Macromolecules, 41, 6393 2008
[42] J. Y. Lee, M. C. Shiao, F. Y. Tzeng, C. H. Chang, C. K. Tsai, J. C. Tsai, K. H. Lo, S. C. Lin and R. M. Ho, Macromolecules, 45, 2720 2012
[43] E. Yashima, K. Maeda, H. Lida, Y. Furusho and K. Nagai, Chem. Rev., 109, 6102 2009
[44] E. Yashima, K. Meada and Y. Okamoto, Nature, 399, 449 1999
[45] T. Kawauchi, A. Kitaura, J. Kumaki, H. Kusanagi and E. Yashima, J. Am. Chem. Soc., 130, 11889 2008
[46] T. Kawauchi, J. Kumaki, A. Kitaura, K. Okoshi, H. Kusanagi, K. Kobayashi, T. Sugai, H. Shinohara and E. Yashima, Angew. Chem. Int. Ed., 47, 515 2008
[47] B. Sannigrahi, P. McGeady and I. M. Khan, Maromol. Biosci., 4, 999 2004
[48] Rajiv R. Srivastava, Robert R. Singhaus, and George W. Kabalka J. Org. Chem. 1999, 64, 8495-8500
[49] L. C. Chen, Y. C. Mao, S. C. Lin, M. C. Li, R. M. Ho and J. C. Tsai, Chem. Comm., 48, 3668 2012
[50] 黃明富 國立中正大學 化學工程研究所碩士論文PI-PS-PLLA可分解型三嵌段共聚物之合成與自我組裝研究Degradable Polyisoprene-b-Polystyrene-b-Poly(L-lactide) Triblcok Terpolymers Syntheses and Self-Assembly Studie
[51] 陳志華 國立中正大學 化學工程研究所碩士論文同位性聚2-乙烯基吡啶之合成及其掌性誘導行為研究Structurally well-define isotactic Poly(2-vinylpyridine)：Syntheses and used in the Chiral dopant Induced Circular Dichrorism