臺灣博碩士論文加值系統

本論文描述一系列具有含氮側鏈之N,N,O-三牙希夫鹼配位基前驅物，進一步合成出乙基鋅金屬錯合物 [LZnEt] (1) - (9)，做為左旋乳酸交酯開環聚合反應、環氧化物和二氧化碳之反應催化劑。本系列催化劑被鑑定為單核結構，並帶有具推、拉電子和立體障礙效應之取代基，同時探討以本系列錯合物在苯甲醇做為起始劑時對左旋乳酸交酯進行開環聚合反應，以及對環氧化物和二氧化碳之反應實驗。實驗結果顯示，開環聚合反應具有良好的催化活性，且具有狹窄的分子量分佈度；而在n-Bu4NCl做為助催化劑，以本系列錯合物對環氧環己烷和二氧化碳進行反應，除了有良好的轉換效率與催化效果外，更具有優異的選擇性，可得到環狀碳酸酯Cis構型之單一產物。

A series of novel zinc ethyl complexes [LZnEt] (1) - (9) bearing NNO-tridentate Schiff-base ligands with an N-pendant arm have been synthesized and used as catalysts for ring-opening polymerization of L-lactide and the reaction of cyclohexene oxide with carbon dioxide. These complexes were characterized as mono-nuclear species with respect to various electronic and steric effect. Ring-opening polymerization of L-lactide by [LZnEt] in the presence of BnOH and copolymerization of epoxides/CO2 were investigated. Experimental results reveal that the activity of these zinc complexes are dramatically influenced by the electronic and steric effects of ancillary ligands coordinated in ring-opening polymerization. Meanwhile, these zinc complexes also show great activity in the reaction of cyclohexene oxide with CO2 in the presence of co-catalyst n-Bu4NCl and obtained cyclic carbonate in single cis-form.

目錄
第一章 緒論 1
一、 前言 1
二、 生物可分解塑膠 2
三、 開環聚合反應 (Ring-Opening Polymerization) 5
四、 環氧化物與二氧化碳之共聚合反應 10
五、 有機金屬催化劑設計 12
第二章 實驗部份 25
一、 儀器鑑定 25
二、 藥品與溶劑之處理 27
三、 操作技巧 31
四、 配位基前驅物合成 33
五、 錯合物合成 39
六、 聚合物合成 49
第三章 結果與討論 52
一、 配位基前驅物與錯合物1 ~ 9之合成方法與光譜研究 52
二、 錯合物之晶體結構解析 54
三、 開環聚合反應 (Ring-Opening Polymerization) 56
四、 環氧化物/二氧化碳之開環催化反應 (Reaction of Cyclohexene Oxide with Carbon Dioxde) 70
第四章 結論 75
第五章 參考文獻 77
第六章 附錄 81

1.https://www.lifechem.tw/blog/150104
2.Yao, K.; Tang, C. Macromolecules, 2013, 46, 1689.
3.https://www.ebpa.org.tw/know_Polymer.html
4.https://www.researchgate.net/figure/The-cycle-of-PLA-in-nature-While-PLA-can-be-considered-an-eco-friendly-biomaterial-with_fig1_221922647
5.(a) Dorgan, J. R.; Lehermeier, H.; Mang, M. J. Polym. Environ. 2000, 8, 1. (b) Gupta, A. P.; Kumar, V. Eur. Polym. J. 2007, 43, 4053.
6.(a) http://www.kmu.edu.tw/~kmcj/data/9606/7.htm
(b) http://www.zggkhc.com/pro_show.aspx?ID=325
7.Kim, J.; Lee, J.-E.; Lee, S.-H.; Yu, J.-H.; Lee, J.-H.; Park, T.-G.; Hyeon, T. Adv. Mater. 2008, 20, 478.
8.Chisholm, M. H.; Gallucci, J. C.; Quisenberry, K. T.; Zhou, Z. Inorg. Chem., 2008, 47, 2613.
9.Odile, D. C.; Blanca, M. V.; Didier, B. Chem. Rev. 2004, 104, 6147.
10.(a) Kowalski, A.; Penczek, S. Macromolecules 1998, 2114. (b) Ouhadi, T.; Stevens, C.; Teyssie, P. Makromol. Chem. Suppl. 1975, 191.
11.(a) Fischer, R. F. J. Polym. Sci. 1960, 44, 155-172. (b) Inoue, S.; Kitamura K.; Tsuruta, T. Macromol. Chem. Phys. 1969, 126, 250-265
12.Darensbourg, D. J.; Andrew, D. Y. Macromolecules 2013, 46, 83-95
13.Castro-Osma, J. A.; Lamb, K. J.; North, M. ACS Catal. 2016, 6, 5012-5025
14.(a) http://en.wikipedia.org/wiki/Organotin_chemistry (b) http://en.wikipedia.org/wiki/Alzheimer%27s_disease (c) Rondeau V.; Commenges D.; Jacqmin-Gadda H.; Dartigues J. F. Am J Epidemiol 2000, 152 (1), 59.
15.(a) Ko, B.-T.; Lin C.-C. J. Am. Chem. Soc. 2001, 123, 7973. (b) Chisholm, M.-H.; Lin, C.-C.; Gallucci, J.-C.; Ko, B.-T. Dalton Trans. 2003, 406. (c) Hsueh, M.-L.; Huang, B.-H.; Wu, J.; Lin, C.-C. Macromolecules 2005, 38, 9482. (d) Huang, C.-A.; Chen, C.-T. Dalton Trans. 2007, 5561. (e) Chen, H.-Y.; Zhang, J.; Lin, C.-C.; Reibenspiesa, J. H.; Miller S. A. Green Chem. 2007, 1038. (f) Huang, C.-A.; Ho, C.-L.; Chen, C.-T. Dalton Trans. 2008, 3502. (g) Huang, Y.; Tsai, Y.-H.; Hung, W.-C.; Lin, C.-S.; Wang, W.; Huang, J.-H.; Dutta S.; and Lin, C.-C. Inorg. Chem. 2010, 9416. (h) Beatriz C.; Davidson, M. G.; Daniel G.-V. Inorg. Chem. 2011, 3589. (i) Chen, L.-H.; Jia, L.; Cheng, F.-X.; Wang, L.; Lin, C.-C.,Wu, J.-C.; Tang, N. Inorg. Chem. Commu. 2011, 26. (j) Lu, W.-Y.; Hsiao, M.-W.; Hsu, S. C. N.; Peng, W.-T.; Chang, Y.-J.; Tsou, Y.-C.; Wu, T.-Y.; Lai, Y.-C.; Chen Y.; Chen, H.-Y. Dalton Trans. 2012, 3659.
16.(a) Zhang, J.-J.; Jian, C.-L.; Gao, Y.; Wang, L.; Tang, N.; Wu, J.-C. Inorg. Chem. 2012, 13380. (b) Chen, H.-Y.; Mialon, L.; Abboud, K. A.; Miller, S. A. Organometallics 2012, 31, 5252. (c) Roşca, S.-C.; Roşca, D.-A.; Dorcet, V.; Kozak, C. M.; Kerton, F. M.; Carpentier, J.-F.; Sarazin, Y. Dalton Trans. 2013, 9361 (d) Huang, Y.; Wang, W.; Lin, C.-C.; Blake, M. P.; Clark, L.; Schwarzb, A. D.; Mountford. P. Dalton Trans. 2013, 9313 (e) Gallegos, C.; Tabernero, V.; Francisco M. G.-V., Mosquera, M. E. G.; Cuenca, T.; Cano, J. Organometallics 2013, 32, 6624. (f) Ghosh, S.; Chakraborty, D.; Varghese, B. European Polymer Journal 2015, 62, 51. (g) Xiong, J.; Zhang, J.-J.; Sun, Y.-Y; Dai, Z.-R.; Pan, X.-B.; Wu, J.-C. Inorg. Chem. 2015, 1737. (h) Francisco M. G.-V.; Estivill, R.; Gallegos, C.; Cuenca, T.; Mosquera, M. E. G.; Tabernero, V.; Cano, J. Organometallics 2015, 34, 477.
17.(a) O’Keefe, B. J.; Hillmyer, M. A.; Tolman, W. B. Dalton Trans. 2001, 2215. (b) Cabaret, O. D.; Vaca, B. M.; Bourissou, D. Chem. Rev. 2004, 104, 6147. (c) Shueh, M. -L.; Wang,Y. -S.; Huang, B. -H.; Kuo, C. -Y. ; Lin,C.-C. Macromolecules 2004, 37, 5155. (d) Yu, T.-L.; Wu, C. -C.; Chen, C. -C.; Huang, B.-H. ; Wu, J.; Lin, C.-C. Polymer 2005, 46, 5909. (e) Wu, J.-C.; Yu, T.- L.; Chen, C.- T.; Lin, C.-C. Coord. Chem. Rev. 2006, 250, 602. (f) Tang, H.-Y.; Chen, H.-Y.; Huang, J.-H.; Lin, C.-C. Macromolecules 2007, 40, 8855. (g) Wu, J.; Chen, Y.-Z.; Hung, W.-C.; Lin, C.-C. Organometallics 2008, 27, 4970. (h) Huang, Y.; Hung, W.-C.; Liao, M.-Y.; Tsai, T.-E.; Peng, Y.-L.; Lin,C.-C. J. Polym. Sci., Part A: Polym. Chem. 2009, 47, 2318.
18.(a) Chisholm, M. H.; Gallucci, J. C.; Zhen, H.-S. Inorg. Chem. 2001, 40, 5051. (b) Aubrecht, K. B.; Hillmyer, M. A.; Tolman, W. B. Macromolecules 2002, 35, 644. (c) Nimitsiriwat, N.; Marshall, E. L.; Gibson, V. C.; Elsegood, M. R. J.; Dale, S. H. J. Am. Chem. Soc. 2004, 126, 13598. (d) Wu, J.; Huang, B. -H.; Hsueh, M. -L.; Lai, S. -L.; Lin, C. -C. Polymer 2005, 46, 9784. (e) Chen, H.-Y.; Tang, H.-Y.; Lin, C.-C. Macromolecules 2006, 39, 3745-3752. (f) Ejfler, J.; Szafert, S.; Mierzwicki, K.; Jerzykiewicz L. B.; Sobota P.; Dalton Trans. 2008, 6556. (g) Wheaton, C. A.; Ireland, B. J.; Hayes, P. G. Dalton Trans. 2009, 4832. (h) Hung, W.-C.; Huang, Y.; Lin, C.-C. Inorg. Chem. 2009, 48, 728-734. (i) Darensbourg, D. J.; Karroonnirun, O. Inorg. Chem. 2010, 49, 2360.
19.Chamberlain, B. M.; Cheng, M.; Moore, D. R.; Ovitt, T. M.; Lobkovsky, E. B.; Coates, G. W. J. Am. Chem. Soc. 2001, 123, 3229.
20.Liu, Y.-C.; Ko, B.-T.; Lin, C.-C. Macromolecules 2001, 34, 6196.
21.Williams, C. K.; Breyfogle, L. E.; Choi, S. K.; Nam, W.; Young, V. G.; Hillmyer, M. A.; Tolman, W. B. J. Am. Chem. Soc. 2003, 125, 11350
22.Ou, H.-W.; Lo, K.-H.; Du, W.-T.; Lu, W.-Y.; Chung, W.-J.; Huang, B.-H.; Chen, H.-Y.; Lin, C.-C. Inorg. Chem. 2016, 55, 1423-1432.
23.Lu, W.-Y.; Ou, H.-W.; Lee, C.-N.; Vandavasi, J. K.; Chen, H.-Y.; Lin, C.-C. Polymer 2018, 139, 1-10
24.(a) http://en.wikipedia.org/wiki/Hammett_equation (b) Hammett, L. P. J. Am. Chem. Soc. 1937, 59(1), 96-103.
25.徐世賢博士班研究論文(未發表)