新穎含三芽胺基苯並三唑苯酚氧基之鋅錯合物在環酯類開環聚合反應的催化研究

Novel Zinc Complexes Incorporating Tridentate Amino-Benzotriazole Phenoxide Ligands as Efficient Catalysts for Ring-Opening Polymerization of Cyclic Esters

李佳螢(Jia-Ying Li)

指導教授 ： 柯寶燦

中原大學/理學院/化學研究所/碩士(2011年)

https://doi.org/10.6840/cycu201100640

摘要

本論文利用苯並三唑苯酚、及過量的三聚甲醛和二級胺迴流下進行mannich反應，成功合成出一系列具胺基側臂的配位基(alkyl = CH3,C1DEABTP-H (A),C1PIBTP-H (C), C1MOBTP-H (D), alkyl = C8H17, C8DEABTP-H (B))。將配位基(A)、(B)、(C)和(D)與1.2當量的ZnEt2反應皆生成單取代四配位雙體的錯合物[(C1DEABTP)ZnEt]2 (1), [(C8DEABTP)ZnEt]2 (2), [(C1PIBTP)ZnEt]2 (3) and [(C1MOBTP)ZnEt]2 (4)。而(B)與0.5當量ZnEt2反應，其架構為雙取代四配位[(C1PIBTP)2Zn] (5)。錯合物(3)與一當量DMAP則形成四配位單體錯合物[(C1PIBTP)ZnEt(DMAP)] (6)。(3)和(4)與1當量水反應可得以四個氫氧根橋接鋅金屬的四核錯合物[(C1PIBTP)4Zn4(OH)4] (7)和[(C1MOBTP)4Zn4(OH)4] (8)，每個中心金屬皆為四配位構型。藉由單晶X-ray繞射、1H NMR、13CNMR光譜及元素分析鑑定證明已成功合成出四個化合物、八個鋅錯合物。當存在9-蒽甲醇(9-AnOH)時，鋅錯合物(1)、(3)、(4)對環己內酯和環丁內酯開環聚合反應的催化活性及控制性皆佳，並且具有活性聚合的性質，其分子量分佈度可控制在相當窄的範圍內。另外利用錯合物(8)對環己內酯開環聚合反應可得到兩端為氫氧基之聚己內酯，並可由MALDI-TOF質譜光譜證明。最後，探討錯合物(6)對外消旋環丁內酯開環聚合，很驚訝地發現4-二甲基氨基吡啶(DMAP)在反應中作為一Lewis base，可幫助提升高分子的立體規則，並維持原有聚合反應的控制性。

關鍵字

開環聚合 ； 鋅 ； 環己內酯 ； 環丁內酯

並列摘要

A series of amino-benzotriazole phenol ligands, (alkyl = CH3, C1DEABTP-H (A),C1PIBTP-H(C), C1MOBTP-H(D), and alkyl = C8H17, C8DEABTP-H(B)) were prepared through the Mannich condensation of 4-alkyl-2-(2H-benzotriazol-2-yl)phenol with the mixtures of excess paraformaldehyde and secondary amine under reflux conditions. The reaction of ZnEt2 with C1DEABTP-H(A), C8DEABTP-H(B),C1PIBTP-H(C), C1MOBTP-H(D) (1.2 equiv.) produces the tetra-coordinated dimeric zinc complexes [(C1DEABTP)ZnEt]2 (1) , [(C8DEABTP)ZnEt]2 (2), [(C1PIBTP)ZnEt]2 (3) and [(C1MOBTP)ZnEt]2 (4). Bis-adduct complex [(C1PIBTP)2Zn] (5) can be obtained by the treatment of ZnEt2 with 2.0 molar equiv of C1PIBTP-H in toluene. [(C1PIBTP)ZnEt(DMAP)] (6), which was formed quantitatively upon reaction of [(C1PIBTP)ZnEt]2 (3) with 2.0 molar equiv of DMAP. Furthermore, complexes (3)-(4) react with 1.0 molar equiv. of water to yield the zinc hydroxide complexes [(C1PIBTP)4Zn4(OH)4] (7), [(C1MOBTP)4Zn4(OH)4] (8), in which four zinc atoms are bridged by four hydroxy groups. These zinc complexes supported by amino-benzotriazole phenoxide ligands were confirmed by X-ray diffraction, 1H NMR, 13C NMR and EA studies. Experimental results indicate that complex (1), (3) and (4) catalyze the ring-opening polymerization(ROP) of ε-caprolactone(ε-CL) and β-butyrolactone(β-BL) in the presence of 9-anthracenemethanol with good catalytic activities in a controlled character. Moreover, complex (8) catalyzes the ROP of ε-CL, and is vertified by the MALDI-TOF mass spectrum. The application of catalyst (6) for the controlled and stereoselective polymerization of rac-β-BL and effect of Lewis base-DMAP on the stereoselectivity were also discussed.

並列關鍵字

Zinc ； Ring-Opening Polymerization ； ε-caprolactone ； β-butyrolactone

參考文獻

1. Labet, M.; Thielemans, W. Chem. Soc. Rev., 2009, 38, 3484.

4. O’Keefe, B.; Hillmyer, M. A.; Tolman, W. B. J. Chem. Soc., Dalton Trans. 2001, 2215.

12. Dittrich, W.; Schulz, R. C. Angew. Makromol. Chem. 1971, 15, 109.

13. Kricheldorf, H. R.; Berl, M.; Scharnagl, N. Macromolecules 1988, 21, 286.

16. (a) Williams, C.K.; Brooks, N.R.; Hillmyer, M.A.; Tolman, W.B.; Chem. Commun. 2002, 2132; (b) Williams, C.K.; Breyfogle, L.E.; Choi, S.K.; Nam, W.; Young, V.G.Jr.; Hillmyer, M.A.; Tolman,W.B. J. Am. Chem. Soc. 2003, 125, 11350; (c) Alcazar-Roman, L.M.; O’Keefe, B.J.; Hillmyer, M.A.; Tolman, W.B.; Dalton Trans. 2003, 3082; (d) Chen, C.-T.; Huang, C.-A.; Huang,B.-H. Dalton Trans. 2003, 3799; (e) Chen, C.-T.; Huang, C.-A.; Huang, B.-H. Macromolecules 2004, 37, 7968; (f) Breyfogle, L.E.; Williams, C.K.; Young, V.G.Jr.; Hillmyer, M.A.; Tolman, W.B. Dalton Trans. 2006, 928; (g) Amgoune, A.; Thomas, C.M.; Ilinca, S.; Roisnel, T.; Carpentier, J.-F. Angew. Chem. Int. Ed. 2006, 45, 2782; (h) Ajellal, N.; Bouyahyi,M.; Amgoune, A.; Thomas, C.M.; Bondon, A.; Pillin, I.; Grohens, Y.; Carpentier, J.-F. Macromolecules 2009,42, 987.