含四芽胺基苯並三唑苯酚氧基之鋅與鎂錯合物之合成、結構鑑定及環酯類聚合反應的催化應用

Synthesis and Structural Characterization of Zn and Mg Complexes Supported by Tetradentate Amino-Benzotriazole Phenoxide Ligands : Efficient Catalysts for Ring-Opening Polymerization of Cyclic Esters

宋昌豫(Chang-Yu Sung)

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/CYCU.2011.00210

摘要

本論文利用Mannich condensation將苯並三唑苯酚(benzotriazole phenol，BTP-H)與N,N,N-Trimethylethylenediamine和 N-(2-Methoxy- ethyl)methylamine兩種二級胺成功在酚氧基的鄰位形成具有四芽的配位基(C8NNBTP-H)(L1)、(C8NOBTP-H)(L2)。然後將上述配位基與二乙基鋅或二正丁基鎂在不同比例條件下可得到單取代及雙取代的錯合物(1)-(6)。並經由1H NMR光譜、13C NMR光譜、元素分析以及單晶X-ray繞射儀鑑定證明其結構。其中以(L1)為配位基之鋅、鎂錯化合物皆以單核形式存在，而以(L2)為配位基之鋅、鎂錯合物是以雙核形式存在。其中以單取代[(C8NNBTP)ZnEt](1)與[(C8NOBTP)ZnEt]2¬(4)兩種具備單一活化中心的錯化合物對於環酯類的開環聚合具有較佳的催化活性。
將錯合物(1)與(4)兩種催化劑分別對環己內酯和乳酸交酯進行開環聚合反應，由實驗結果顯示除了錯合物(1)對環己內酯效果不佳外其餘結果皆具有”活性聚合”的性質。而錯合物(4)不論是在活性、控制性都明顯優於錯化合物(1)，於是將錯合物(4)對環丁內酯進行開環聚合反應，其結果也具有”活性聚合”的性質。另外在立體選擇性方面，選用外消旋乳酸交酯來進行比較，可以發現以錯合物(1)為催化劑，其排列方式是趨向stereoblock isotactic PLA，以錯合物(4)為催化劑，其排列方式是趨向heterotactic PLA。將雙取代的錯合物(2)(3)(5)和(6)進行UV-Vis、PL的測試，可以發現在吸收波長的位置都比原來的配位基(L1)和(L2)有些許紅位移的現象，推測可能為配位基接上金屬後，微結構的形態有所改變而造成的現象。

關鍵字

酯類聚合反應 ； 四芽胺基苯並三唑苯酚氧基

並列摘要

Two novel amino-benzotriazole phenol ligands, 2-(2H-benzotriazol-2-yl) -6-((N,N,N-trimethylethylenediamine)methyl)-4-tert-octylphenyl-phenol and 2- (2H-benzotriazol-2-yl)-6-((N-(2-methoxyethyl)methylamine)methyl)-4-tert-octylphenyl-phenol (C8NNBTP-H,C8NOBTP-H) were prepared though the Mannich condensation of 4-tert-octylphenyl-2-(2H-benzotriazol-2-yl)phenol with the mixtures of excess paraformaldehyde and N,N,N-trimethylethylenediamine) methylamine or N-(2-methoxyethyl)methyl amine under reflux condition. Zinc and magnesium complexes (1-6) supported by amino-benzotriazole phenoxide ligands were synthesized and fully characterized. Among them, complex 1 and 4 are demonstrated to catalyze ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) and L-lactide in the presence of 9-anthracenemethanol. However, the catalytic activity and “controlled” character of complex 4 are higher than those of complex 1. Additionally, complex 4 is also a good catalyst for “controlled” ROP of β-butyrolactone (β-BL).
To examine stereoselectivity of PLAs, complex 1 and 4 were employed as catalysts towards ROP of rac-lactide. Expermental results exhibit that complex 1 catalyzes LA to produce stereoblock isotactic-enrich PLA (Pm=0.59), and complex 4 favors to yield heterotactic-enrich PLA (Pr=0.65).
According to spectroscopic studies of UV-Vis and PL in bis-adduct complexes 2, 3, 5 and 6. We found that absorption and emission wavelengths of complexes are red-shifted in comparison with those of ligands (L1 and L2). It’s believed that the little red-shift (＜20nm) results from the change of ligand structure after coordinating to the metal center.

並列關鍵字

Tetradentate Amino-Benzotriazole Phenoxide ； Ring-Opening Polymerization of Cyclic Esters

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