Title

單雙咪唑苯酚基鋁錯合物之合成、鑑定及對環己內酯開環聚合反應之應用

Translated Titles

Aluminium Complexes Containing Imidazolylphenolate or Bis-imidazolylphenolate ligands: Synthesis,Characterization and Application in Ring-Opening Polymerization of ε-Caprolactone

Authors

龍之雋

Key Words

咪唑苯酚 ; 鋁錯合物 ; 開環聚合反應 ; imidazolylphenolate ; aluminium complexes ; polymerization

PublicationName

中興大學化學系所學位論文

Volume or Term/Year and Month of Publication

2016年

Academic Degree Category

碩士

Advisor

陳繼添

Content Language

繁體中文

Chinese Abstract

本論文利用咪唑甲基甲醛苯酚與雙甲醛甲基苯酚,藉由三種不同從醛基合成咪唑的配方,合成出一系列甲基咪唑苯酚R1-R3及2R1-2R3,[R1 = HOPhMeImph;R2 = HOPhMeImH;R3 = HOPhMeImMe與甲基雙咪唑苯酚2R1 = HOPhMebis-Imph ;2R2 = HOPhMebis-ImH;2R3 = HOPhMebis-ImMe]。以1當量的甲基咪唑苯酚配位基前驅物R1-R3與2R2-2R3和1當量的三甲基鋁試劑反應可以成功合成出鋁錯合物14-18。鋁錯合物14及16-18對環己內酯的開環聚合反應在外加9-蒽甲醇的條件下,皆表現出良好的催化活性與狹窄的PDI值分佈,其中鋁錯合物16在100倍與200倍的單體開環聚合反應有良好的控制,但在300倍單體的反應不佳,而鋁錯合物16及17 在不外加醇類的情形下對環己內酯的開環聚合反應有良好的活性,但其做出聚合物呈黏稠狀其分子量與PDI的分佈都偏高。

English Abstract

A series of imidazole-phenolate and bis-imidazole-phenolate ligand precursors R1-R3 and 2R1-2R3,[R1 = HOPhMeImph;R2 = HOPhMeImH;R3 = HOPhMeImMe ;2R1 = HOPhMebis-Imph ;2R2 = HOPhMebis-ImH;2R3 = HOPhMebis-ImMe] have been discovered. These ligand precursors can react with trimethyl aluminum to make complexes 14-18. Complexes 14-18 show good activity and low PDI toward ε-caprolactone ring-opening polymerization with 9-AnOH. The complex 16 shows good activity toward 100 and 200-fold concentrationε-caprolactone,but it shows less control when the concentration of ε-caprolactone reaches 300-fold. The complex 16 and 17 show activity towardε-caprolactone ring-opening polymerization without adding alcohol,while the molecular weight and PDI are much higher than respect.

Topic Category 基礎與應用科學 > 化學
理學院 > 化學系所
Reference
  1. 1.J. A. Ivar do Sul, M.F. Costa, Environ. Pollut., 185, 2014, 352
    連結:
  2. 2.Krow, Grant R(1993). "The Baeyer-Villiger Oxidation of Ketones and Aldehydes". Organic Reactions 43 (3): 251–798.
    連結:
  3. 3.S. Matsumura, K. Mabuchi, K. Toshima, Macromol. Rapid Commun 1997, 18, 477
    連結:
  4. 5.H. R. Kricheldorf, R. Dunsing, Makromol. Chem. ,1986,187,1611
    連結:
  5. 6.V. W. Dittrich, R. Schul, Appl Macromol Chem Phys Angew Makromol Chem, 1971, 15, 109
    連結:
  6. 9.A. Kowalski, A. Duda, and S. Penczek, Macromolecules 1998, 31, 2114
    連結:
  7. 10.B. –T. Ko and C. –C. Lin, Macromolecules 1999, 32, 8296,
    連結:
  8. 12.(a) C. –T. Chen, C. –A. Huang, and B. –H. Huang, Macromolecules 2004, 37, 7968 (b) C. K. Williams, L. E. Breyfogle, S. K. Choi, W. Nam, V. G. Young, Jr.,M. A. Hillmyer, and W. B. Tolman, J. Am. Chem. Soc. 2003, 125, 11350 (c) P. Hormnirun, E. L. Marshall, V. C. Gibson, A. J. P. White, and D. J. Williams, J. Am. Chem. Soc., 2004, 126, 2688 (d) S. K. Roymuhury,D. Chakraborty ,V. Ramkumar, Eur. Polym. J., 2015 ,70,203
    連結:
  9. 19.J. Peng, H. –J. Yang, Z. Weia and C. –Y. Guo, RSC Adv., 2015, 5, 53063
    連結:
  10. 20.S. E. Ghachtouli, B. L. Kaiser, R. Guillot, and A. Aukauloo, Eur. J. Inorg. Chem. 2014, 4750
    連結:
  11. 4.A. P. Dove, H. Li, R. C. Pratt, B. G. G. Lohmeijer, D. A. Culkin, R. M. Waymouth and J. L. Hedrick, Chem. Commun., 2006, 2881
  12. 7.H. R. Kricheldorf, M. Berl, N. Scharnagl, Macromolecules, 1988,21, 286
  13. 8.A. Kowalski, J. Libiszowski, A. Duda, and S. Penczek, Macromolecules, 2000, 33, 1964
  14. 11.R. Olejník, J. Bažantová, Z. Růžičková , J. Merna, Z. Hošťálek, A. Růžička, Inorg. Chem. Commun. 2015,55,161
  15. 13.(a) N. Nomura, T. Aoyama, R. Ishii, and T. Kondo, Macromolecules 2005, 38, 5363 (b) M. Bouyhayia, Y. Sarazina, O. L. Casagrande Jrb and J. F. Carpentiera, Appl. Organometal. Chem., 2012, 26, 681
  16. (c) X. –F. Yu and Z.-X. Wang, Dalton Trans., 2013, 42, 3860
  17. 14.(a) Z. Zhong, P. J. Dijkstra, and J. Feijen, Angew. Chem. Int. Ed., 2002, 41, 4510 (b) N. Nomura, R. Ishii, Y. Yamamoto,and T. Kondo, hem. Eur. J., 2007, 13, 4433 (c) Z. Zhong, P. J. Dijkstra, and J. Feijen, J. Am. Chem. Soc., 2003, 125, 11291
  18. 15.W. Zhang , Y. Wang , Lin Wang a, C. Redshaw ,W. –Hua. Sun, J. Organomet. Chem., 2014, 65
  19. 16.X. Wang, K.-Q. Zhao, M. R. J. Elsegood, T. J. Prior, X. Liu, L. Wu, S. Sanz, E. K. Brechine and C. Redshaw, RSC Adv., 2015, 5, 57414
  20. 17.Q. Chu, D. A. Medvetz, M. J. Panzner and Y. Pang, Dalton Trans., 2010, 39, 5254
  21. 18.J. –J. Wu, M. –L. Cao and B. –Hui. Ye, Chem. Commun., 2010, 46, 3687
  22. 21.A. O. Eseola, O. Adepitan, H. Gorls and W. Plass, New J. Chem., 2012, 36, 891