臺灣博碩士論文加值系統

Part A:
本研究選擇了多種配位基: ( DMF-DMA，MBAA，DPM，benzanilide，8-quinolinamine，BAP，BHT，和 dipyridine )，分別將這些配位基外加到 Sn(Oct)2 對 CL 進行開環聚合反應，也選擇了配位基：( DMF-DMA, 8-quinolinamine 和 p-thiocresol )，分別將這些配位基外加到 Sn(Oct)2 對 L-LA 進行開環聚合反應。
當配位基配位到錫上時，會改變錫錯合物的特性，可提升錫錯合物的反應活性，並且減少生產成本。而且多了配位基的保護，聚合物的分子量控制以及分子量分佈度也都比較好。此外，本研究也經由動力學的探討去研究外加配位基改善反應活性的原因。
Part B:
本研究探討 Mg(BHT)2(THF)2對環己內酯 (??-CL) 進行開環聚合反應的催化特性，Mg(BHT)2(THF)2 分別搭配多種起始劑，包括 :苯甲醇 BnOH，甲氧基聚乙二醇 (mPEG)，N, N-二甲基乙醇胺 (DMAE)，2-羟乙基二硫化物 (BHEDS)，在對 CL 進行開環聚合反應皆表現良好的反應活性。此外 Mg(BHT)2(THF)2 在常溫空氣下也可對 CL 進行開環聚合反應。

　Part A:　The research of the promotion about caprolactone and lactide polymerization by tin octate was studied with added ligands: (N,N-dimethylformamide diethyl acetal(DMF-DEA), methyl-2- (dibenzylamino) acetate(MBAA), di(1H-pyrazol-1-yl)methane(DPM), benzanilide, 8-quinolinamine, 2-bromoacetophenone(BAP), 2,6-di-tert-butyl-4-methylphenol(BHT), and dipyridine), were active for caprolactone(CL) polymerization respectively. Beside DMF-DMA, 8-quinolinamine and p-thiocresol were useful for L-lactide(L-LA) polymerization.The chemical property of tin is affect by ligand bonding and its promotive reactivity decreases the production costs. The molecular weight controlling and molecular weight distribution of polymers are improved by ligands protection. Besides, the reasons of the activity improvement by adding these ligands are investigated by kinetic study.
Part B:
　A magnesium complex Mg(BHT)2(THF)2 was synthesized and its catalytic activities toward ring-opening polymerization (ROP) of caprolactone (CL) was investigated. Experimental results indicate that Mg(BHT)2(THF)2 is an efficient catalyst for the ring-opening polymerization of ??-caprolactone in the presence of benzyl alcohol (BnOH), methoxypoly (ethylene glycol) (mPEG),
2-dimethylaminoethanol (DMAE), and bis(2-hydroxyethyl) disulfide (BHEDS) respectively. Besides, the polymerization also can be proceeded in the atmospheric condition at room temperature.

目錄
目錄......................................III
圖目錄....................................V
表目錄.................................... X
Part A
第一章 緒論 ..............................1
1-1 文獻回顧 ............................. 4
1-2 研究目的 ............................. 13
第二章 實驗部份...........................14
2-1 儀器部份 ............................14
2-2 試藥、溶劑來源及前處理 .............. 14
2-3 實驗操作技巧 ........................21
2-4 試藥的配製 .......................... 21
2-5 配位基的合成 .........................23
2-6 錯合物的合成 .........................24
2-7 聚合物的合成 .........................25
第三章 結果與討論........................ 29
3-1 動力學探討 .......................... 32
3-2 大分子量PCL 和PLA 的合成 ........... 54
3-3 多種錫的錯合物應用在開環聚合反應的探討 ...... 61
第四章 結論...................................... 64
IV
Part B
第一章 緒論...................................... 1
1-1 文獻回顧 ................................. 1
1-2 研究目的 ................................. 24
第二章 實驗步驟.............................. 26
2-1 催化劑的合成 ............................. 26
2-2 聚合物的合成 .......................... 26
第三章 結果與討論........................... 30
第四章 結論................................... 39
參考文獻...................................... Ref-1
附錄........................................... S-1

1. (a) Nijenhuis A. J., G. D. W., Pennings A. J. ,
Macromolecules 1992, 25 6414-6424; (b) Doi, Y. J. L.,
P. J.; Nijenhuis, A. J.; van Aert, H. A.; M.;
Bastiaansen, C., Macromolecules 1995, 28, 2124; (c)
Degée, P. D., P. ; Jacobsen, S. ; Fritz, R. Jéróme,
H.-G. , J. Polym. Sci., Part A: Polym. Chem. 1999,
37, 2413; (d) Schwach, G. C., J.; Engel, R.; Vert, M.
J. , Polym. Chem., Part A: Polym. Chem. 1997, 35,
3431; (e) Kricheldorf, H. R. K.-S., I.; Stricker, A.
J. Nijenhuis, D. W. Grijpma, and A. J.Pennings,
Macromolecules 2000, 33, 702; (f) Ryner, M. S., K.;
Albertsson, A.-C., Macromolecules 2001, 34, 3877; (g)
Storey, R. F. S., J. W., Macromolecules 2002, 35,
1504.
2. Dechy-Cabaret, O.; Martin-Vaca, B.; Bourissou, D., Chem.
Rev. 2004,104, 6147-6176.
3. Kalmi, M.; Lahcini, M.; Castro, P.; Lehtonen, O.;
Belfkira, A.; Leskelä, M.; Repo, T., J. Polym. Sci.,
Part A: Polym. Chem. 2004, 42,1901–1911.
4. Aubrecht, K. B.; Hillmyer, M. A.; Tolman, W. B.,
Macromolecules 2002, 35, 644-650.
5. Nimitsiriwat, N.; Gibson, V. C.; Marshall, E. L.; White,
A. J. P.; Daleb, S. H.; Elsegoodb, M. R. J., Dalton
Trans. 2007, 4464-4471.
6. Dove, A. P.; Gibson, V. C.; Marshall, E. L.; Rzepa, H.
S.; White, A. J. P.; Williams, D. J., J. Am. Chem. Soc.
2006, 128, 9834-9843.
7. Phomphrai, K.; Pongchan-o, C.; Thumrongpatanaraks, W.;
Sangtrirutnugul, P.; Kongsaeree, P.; Pohmakotr, M.,
Dalton Trans. 2011, 40 (2157-2159).
8. Kamber, N. E.; Jeong, W.; Waymouth, R. M., Chem. Rev.
2007, 107, 5813–5840.
9. Chun-Yan Qi, Z.-X. W., J. Polym. Sci., Part A: Polym.
Chem. 2006, 44, 4621–4631.
10. Nimitsiriwat, N.; Gibson, V. C.; Marshall, E. L.;
Elsegood, M. R. J.,Inorg. Chem. 2008, 47, 5417-5424.
11. Vitanova, D. V.; Hampel, F.; Hultzsch, K. C., J.
Organomet. Chem. 2005 690, 5182–5197.
12. Wyk, J. L. v.; Mapolie, S. F.; Lennartson, A.;
Håkansson, M.; Jagner, S., Inorg. Chim. Acta 2008,
361 2094–2100.
13. Kidwai, M.; Bhardwaj, S.; Mishra, N. K.; Bansal, V.;
Kumar, A.; Mozumdar, S., Catal. Commun. 2009, 10,
1514–1517.
14. Andrade, C. K. Z.; Barreto, A. d. F. S.; Silva,W. A., ARKIVOC 2008, 226-232.
15. Cui, X.; Shi, F.; Tse, M. K.; Gördes, D.; Thurow, K.;
Beller, M.; Deng, Y., Advanced Synthesis & Catalysis
351 (17), 2949–2958.
16. Trofimenlo, S.; Calabrease, J. C.; Thompson, J. S.,
Inorg. Chem.1987, 26, 1507-1514.
17. Babudri, F.; Ciminale, F.; Nunno, L. D.; Florio, S.,
Tetrahedron 1982,38, 557-561.
18. Lee, D. H.; Park, S.-E.; Cho, K.; Kim, Y.; Athar, T.;
Lee, I.-M., Tetrahedron Lett. 2007, 48, 8281–8284.
19. Kosmalski, T.; Wojtczak, A.; Zaidlewicz, M.,
Tetrahedron: Asymmetry 2009, 20 (10), 1138-1143.
20. Chang, Y.-H.; Fu, C.-F.; Liu, Y.-H.; Peng, S.-M.; Chen,
J.-T.; Liu,S.-T., Dalton Trans. 2009, 861–867.
21. Klappa, J. J.; Rich, A. E.; McNeill, K., Org. Lett.
2002, 4, 435-437.
22. Shirase, H.; Saito, M.; Arakawa-Itoh, M.; Fukuda, Y.,
Bull. Chem. Soc. Jpn. 2009, 82, 230-235.
23. Menuela, S.; Jolyb, J.-P.; Courcotc, B.; Elyséec, J.;
Ghermanid, N.-E.; Marsura, A., Tetrahedron 2007, 63,
1706-1714.
24. Chisholm, M. H.; Huffman, J. C.; Phomphrai, K., Dalton
Trans. 2001, 222–224.
25. Chisholm, M. H.; Gallucci, J.; Phomphrai, K., Inorg.
Chem.2002, 41, 2785-2794.
26. Chamberlain, B. M.; Cheng, M.; Moore, D. R.; Ovitt, T.
M.; Lobkovsky, E. B.; Coates, G. W., J. Am. Chem. Soc.
2001, 123,3229-3238.
27. Dove, A. P.; Gibson, V. C.; Marshall, E. L.; White, A.
J. P.; Williams, D. J., Dalton Trans . 2004, 570 – 578.
28. Drouin, F.; Whitehorne, T. J. J.; Schaper, F., Dalton
Trans.2011, 40, 1396–1400.
29. Shueh, M.-L.; Wang, Y.-S.; Huang, B.-H.; Kuo, C.-Y.;
Lin, C.-C., Macromolecules 2004, 37, 5155-5162.
30. Yu, T.-L.; Wu, C.-C.; Chen, C.-C.; Huang, B.-H.; Wu,
J.; Lin, C.-C.,Polymer 2005, 46, 5909–5917.
31. Wu, J.; Chen, Y.-Z.; Hung, W.-C.; Lin, C.-C.,
Organometallics 2008, 27, 4970–4978.
32. Chen, P.-S.; Liu, Y.C.; Lin, C.-H.; Ko, B.-T., J.
Polym. Sci., Part A:Polym. Chem. 2010, 48, 3564–3572.
33. Shen, M.-Y.; Peng, Y.-L.; Hung, W.-C.; Lin, C.-C.,
Dalton Trans. 2009, 9906–9913.
34. Ejfler, J.; Kobyłka, M.; Jerzykiewicz, L. B.; Sobota,
P., Dalton Trans . 2005, 2 0 4 7 – 2 0 5 0.
35. Poirier, V.; Roisnel, T.; Carpentier, J.-F.; Sarazin,
Y., Dalton Trans. 2009, 9820–9827.
36. Wang, Z.-X.; Qi, C.-Y., Organometallics 2007, 26,
2243-2251.
37. Ireland, B. J.; Wheaton, C. A.; Hayes, P. G.,
Organometallics 2010, 29, 1079–1084.
38. Lee, W.-Y.; Hsieh, H.-H.; Hsieh, C.-C.; Lee, H. M.;
Lee, G.-H.; Huang, J.-H.; Wu, T.-C.; Chuang, S.-H., J.
Org. Chem. 2007, 692, 1131–1137.
39. Tang, H.-Y.; Chen, H.-Y.; Huang, J.-H.; Lin, C.-C.,
Macromolecules 2007, 40, 8855-8860.
40. Hung, W.-C.; Lin, C.-C., Inorg. Chem. 2009, 48, 728-734.
41. Tsai, Y.-H.; Lin, C.-H.; Lin, C.-C.; Ko, B.-T., J.
Polym. Sci., Part A: Polym. Chem. 2009, 47, 4927–4936.
42. Chisholm, M. H.; Eilerts, N. W., Chem. Commun. 1996,
853-854.
43. Chisholm, M. H.; Eilerts, N. W.; Huffman, J. C.; Iyer,
S. S.; Pacold, M.; Phomphrai, K., J. Am. Chem. Soc.
2000, 122, 11845-11854.
44. Sánchez-Barba, L. F.; Garcés, A.; Fajardo, M.; Alonso-
Moreno, C.; Fernández-Baeza, J.; Otero, A.; Antiñolo,
A.; Tejeda, J.; Lara-Sánchez, A.; López-Solera, M. I.,
Organometallics 2007, 26, 6403-6411.
45. Lian, B.; Thomas, C. M.; Jr., O. L. C.; Roisnel, T.;
Carpentier, J.-F., Polyhedron 2007, 26, 3817–3824.
46. Duff, A. W.; Hitchcock, P. B.; Lappert, M. F.; Taylor,
R. G.; Segal, J. A., J. Org. Chem. 1985, 293, 271-283.
47. Calabrese, J.; Jr., M. A. C.; Ittel, S. D., Inorg.
Chem. 1988, 27,867-870.