新穎含胺基雙苯並三唑苯酚氧基之鋁、鋅與鈦錯合物合成、結構鑑定及開環聚合研究

Novel aluminum, zinc and titanium complexes supported by diamino-bis(benzotriazole phenoxide) ligands for ring-opening polymerization of e-caprolactone

劉正堂(Zheng-Tang Liu)

指導教授 ： 陳志德 ； 柯寶燦

中原大學/理學院/化學研究所/碩士(2013年)

https://doi.org/10.6840/cycu201300358

摘要

本論文利用苯並三唑苯酚、及過量的甲醛與二級的二胺類迴流下進行Mannich反應，成功合成出具N,O,N,N,O,N-六芽配位基(C8MEABTP-H2) (A)與(C8BEABTP-H2) (B)。利用配位基(A)及(B)與1當量的四異丙氧基鈦試劑反應可生成單核六配位的錯合物[(C8MEADiBTP)Ti(OiPr)2] (1)和[(C8BEADiBTP)Ti(OiPr)2] (2)。此外，將配位基(A)與2當量三甲基鋁試劑反應，則形成雙金屬四配位錯合物[(C8BEADiBTP)Al2Me4] (3)，此化合物有別於一般類型之salan type的錯合物，錯合物(3)是以苯並三唑苯酚上的氮配位上鋁金屬，而非由Mannich反應的氮進行配位。另外，將配位基(A)與2當量二乙基鋅試劑反應而得到單體雙核錯合物[(C8BEADiBTP)Zn2Et2] (4)，此錯合物(4)以鋅金屬為中心，具有四配位及五配位兩種配位構型。上述配位基(A)及(B)錯合物(1)-(4)經由1H NMR、13C NMR光譜、元素分析及單晶X-ray繞射儀鑑定證明其結構。當外加9-蒽甲醇(9-AnOH)時，錯合物(3)及錯合物(4)對環己內酯的開環聚合反應具有良好的催化活性及較窄的分子量分佈度，並且隨著單體倍率的增加，分子量亦呈線性的成長，充分的表現出其活性聚合(Living)的性質。

關鍵字

含胺基雙苯並三唑苯酚氧基

並列摘要

Two novel diamino-bis(benzotriazole phenoxide) ligands(amineDiBTP-H2), C8MEADiBTP-H2 (A) and C8BEADiBTP-H2 (B) have been prepared by the Mannich condensation of 2-(2H-benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol with the mixtures of excess paraformaldehyde and primary diamine in ethanol under reflux conditions. Catalysts bearing the C8MEADiBTP and C8BEADiBTP ligands have been synthesized and structurally characterized. The reaction of amineDiBTP-H2 with Ti(OiPr)4 (1.0 mol equiv.) produced the mono-adduct complexes [(C8MEADiBTP)Ti(OiPr)2] (1) and [(C8BEADiBTP)Ti(OiPr)2] (2),. Further reaction of C8BEADiBTP-H2 with AlMe3 produced the tetra-coordinated dinuclear aluminum complex [(C8BEADiBTP)Al2Me4] (3).And [(C8BEADiBTP)Zn2Et2] (4) can be obtained by the treatment of ZnEt2 with 2.0 molar equiv of C8BEADiBTP-H2 in CH2Cl2, respectively. Experimental results indicate that complex 4 is efficient catalyst for polymerization of -caprolactone in a controlled manner, yielding polymers with the expected molecular weights and narrow polydispersity indices (PDIs) values (Mw/Mn < 1.14).

並列關鍵字

salan ； diamino-bis(benzotriazole phenoxide)

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