含三芽苯並三唑苯酚氧配位基之鋁、銅與鋅錯合物合成、結構鑑定及其開環聚合反應的催化應用

Synthesis and Structural Characterization of Aluminum，Copper and Zinc Complexes Supported by Benzotriazol Phenoxide Ligand:Efficient Catalysts for Ring-Opening Polymerization of Cyclic Esters

王俊翰(Jun-Han Wang)

指導教授 ： 柯寶燦

中原大學/理學院/化學研究所/碩士(2012年)

https://doi.org/10.6840/cycu201200384

摘要

本論文利用苯並三唑苯酚、及過量的甲醛和二級胺迴流下進行Mannich反應，成功合成出具胺基側臂的大立體配位基(C8DIABTP-H) (A)。利用配位基(A)與1.2當量的二乙基鋅試劑反應可生成單取代四配位雙體的錯合物[(-C8DIABTP)ZnEt]2 (1)。而且將配位基(A)與0.6當量鋅金屬試劑及0.5當量4-二甲基氨基吡啶(DMAP)反應，則形成雙取代五配位單體錯合物[(C8DIABTP)2Zn(DMAP)] (2)，此化合物是以吡啶上的氮原子配位於鋅金屬，鋅原子中心分別為雙C8DIABTP取代五配位的幾何結構。再者，錯合物(1)與1.0當量苯甲醇反應可得以四個烷氧基橋接鋅金屬的四核錯合物 [(-OBn)(C8DIABTP)Zn]4 (3)，每個鋅原子中心金屬皆為四配位構型。另外，將配位基(A)與1.0當量的三甲基鋁反應，可得到單取代四配位單體錯合物[(C8DIABTP)AlMe2] (4)。雙取代五配位單體錯合物[(C8DIABTP)2AlMe] (5)可由配位基(A)與0.5當量鋁試劑反應而獲得，鋁原子中心分別為甲基及雙C8DIABTP取代五配位的幾何結構。而從錯合物(5)再結晶過程又可意外得到錯合物[(-O){(C8DIABTP)2Al}2] (6)。錯合物(6)是以氧原子橋鍵至兩個鋁金屬，鋁原子中心分別為雙C8DIABTP取代五配位的幾何結構。錯合物[(C8DIABTP)Al2Me5] (7)經由配位基(A)與2.0當量的鋁試劑反應而獲得。其一鋁金屬與苯酚氧基及苯並三唑上的氮原子鍵結、另一鋁金屬與側臂胺基配位，形成單體雙核的幾何結構。最後，將配位基(A)與0.5當量的醋酸銅反應，可得到單體四配位之錯合物[(C8DIABTP)2Cu] (8)。上述配位基(A)及錯合物(1)-(7)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。當存在9-蒽甲醇(9-AnOH)時，鋅錯合物(3)對環酯類開環聚合反應具有良好的催化活性及控制性，表現出活性聚合(Living)的性質。此外，利用鋁錯合物(5)在外加9-蒽甲醇(9-AnOH)的反應條件下，對環己內酯的開環聚合反應有非常好的反應性與控制性，表現出活性聚合的性質。另外將銅錯合物(8)與左旋乳酸交酯於外加9-蒽甲醇時進行開環聚合反應，發現具有良好的催化活性。由實驗結果顯示，當增加配位基立體效應，使得催化劑在溶液中可能以單一活性位置(single-site)的形式存在，以便能得到分子量可控制性及狹窄之分子量分佈度。

關鍵字

開環聚合 ； 鋅 ； 銅 ； 鋁 ； 乳酸交酯

並列摘要

A bulky amino-benzotriazole phenol ligand (C8DIABTP-H (A)) were prepared through the Mannich condensation of 2-(2H-benzotriazol-2-yl)-4-alkyl-phenol (alkyl = C8H17) with the mixtures of excess paraformaldehyde and diisopropylamine under reflux conditions. Aluminum，copper and zinc complexes supported by N,O-bidentate C8DIABTP ligand were synthesized and fully characterized. The reaction of diethyl zinc (ZnEt2) with C8DIABTP-H (1.1 equiv.) yields tetra-coordinated dimeric zinc complex [(-C8DIABTP)ZnEt]2 (1). Furthermore, the penta-coordinated monomeric zinc complex [(C8DIABTP)2Zn(DMAP)] (2) results from treatment of ZnEt2 with C8DIABTP (two equiv.) in the presence of 4-dimethylaminopyridine (DMAP, one equiv) in toluene. Complex (1) further reacts with a stoichimetric amount of benzyl alcohol (BnOH) to yield the tetra-coordinated zinc alkoxide complex [(-OBn)(C8DIABTP)Zn]4 (3), in which four zinc atoms are bridged by four oxygen atom of the benzyl alkoxy group. The reaction of C8DIABTP-H with AlMe3 (1.1 equiv.) in hexane producs mono-adduct aluminum complex [(C8DIABTP)AlMe2] (4). The penta-coordinated bis-adduct Al complex [(C8DIABTP)2AlMe] (5) is synthesized through the reaction of AlMe3 with C8DIABTP-H (two equiv.) in hexane. While the complex (4) was extracted with hexane, it was found to produce the dimmeric aluminum complex [(-O){(C8DIABTP)2Al}2] (6), in which the oxo ligand acts as a chelating group linearly bridging two aluminium centers. However, treatment of C8DIABTP-H with two molar equivalents of AlMe3 afford of [(C8DIABTP)Al2Me5] (7). (1)/(9-anthracenemethanol (9-AnOH)), (5)/(9-anthracenemethanol (9-AnOH)) and (3) are efficient catalysts for the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) and -butyrolactone (-BL). Experimental results indicate that complex (3) exhibits the greatest activity with well-controlled character among these complexes. The polymerizations of -CL and -BL catalyzed by (3) are also demonstrated in a ‘‘living’’ character with narrow polydispersity indices (monomer-to-initiator ratio in the range of 25-200, PDI < 1.15).

並列關鍵字

ROP ； cyclic ester ； Aluminum ； Copper ； Zinc

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