含亞胺基苯並三唑苯酚氧基之鋅錯合物合成、結構鑑定及應用於環酯類開環聚合反應的催化研究

本論文利用Duff reaction將苯並三唑苯酚(benzotriazole phenol，BTP-H)，形成有醛官能基的配位基C1AldBTP-H，分別與2,6-dimethylaniline、2,6-diisopropylaniline、benzylamine和aniline經亞胺基化(imination)反應，形成含亞胺的配位基C1DMeIBTP-H (A)、C1DIPIBTP-H (B)、C1PhIBTP-H (C)、C1BnIBTP-H (D)。將配位基(A)、(B)分別與二乙基鋅在1：1的條件下反應生成[(-C1DMeIBTP)ZnEt]2 (1)和(-C1DIPIBTP)ZnEt]2 (2)。而四配位雙取代鋅錯合物[(C1PhIBTP)2Zn] (3)和[(C1BnIBTP)2Zn] (4)可藉由配位基(C)、(D)分別與二乙基鋅在2：1的條件下反應得到。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。將錯合物(1)、(2)在外加9-蒽甲醇(9-AnOH)的條件下分別對環己內酯、環丁內酯以及左旋乳酸交酯進行開環聚合反應，皆有良好的催化活性，並具有活性聚合(Living)的性質。另外，更進一步地利用錯合物(1)對環己內酯、環丁內酯以及左旋乳酸交酯進行開環聚合反應的實驗結果，做反應速率差異的探討。另一方面，將錯合物(1)和(2)對環丁內酯進行立體選擇性的探討，發現錯合物(1)和(2)其聚合狀態皆為atactic (Pr = 0.48)；錯合物(1)對外消旋乳酸交酯進行立體選擇性的探討，聚合狀態傾向heterotactic，最佳的Pr值為0.66。最後，錯合物(3)和(4)在外加9-蒽甲醇的條件下分別對左旋乳酸交酯進行開環聚合反應，其實驗結果顯示，錯合物(3)在催化活性與反應時間皆明顯優於錯合物(4)。

關鍵字

鋅；乳酸交酯；開環聚合

並列摘要

Four imino-benzotriazole phenoxide ligands, C1DMeIBTP-H (A), C1DIPIBTP-H (B), C1PhIBTP-H (C) and C1BnIBTP-H (D) were prepared in good yield(≧70%) from the condensation of 3-(2H-benzotriazol-2-yl)-2-hydroxy- 5-methyl benzaldehyde (C1AldBTP-H) with benzylamine or arylamine (aniline, 2,6-dimethylaniline and 2,6-diisopropylaniline (1.1 equiv.)) in solvent (toluene or ether). Zinc catalysts supported by imino-benzotriazole phenoxide ligands were characterized by microanalyses as well as single-crystal X-ray structural determinations. Treatment of the ligand (C1DMeIBTP-H or C1DIPIBTP-H) with 1.0 mol equiv. of ZnEt2 in toluene under the same stoichiometric proportion afforded the dimeric zinc complexes ([(-C1DMeIBTP)ZnEt]2 (1); [(-C1DIPIBTP)ZnEt]2 (2)) in 50% and 53% yields, respectively. The reaction of diethyl zinc (ZnEt2) with C1PhIBTP-H or C1BnIBTP-H (2.0 equiv.) yields tetra-coordinated monomeric zinc complex [(C1PhIBTP)2Zn] (3) or [(C1BnIBTP)2Zn] (4). Catalysis for ring-opening polymerization (ROP) of -caprolactone (-CL), -butyrolactone (-BL), and L-lactide (L-LA) of complexes 1-2 are investigated. Zinc complexes 1 and 2 catalyze the ring-opening polymerization of -caprolactone (-CL) in the presence of 9-anthracenemethanol (9-AnOH) with efficient catalytic activities in a controlled fashion. Additionally, polymerizations of -butyrolactone (-BL) catalyzed by complex 1 and 2 are demonstrated in a “living” character with the expected molecular weights and narrow molecular weight distributions. To examine stereoselectivity of PHB, complex 1 and 2 were employed as catalysts toward ROP of -BL. Experimental results exhibit that complex 1 or complex 2 catalyzes -BL to produce atactic PHB (Pr = 0.48). Furthermore, complex 1 catalyzes rac-LA to yield heterotactic PLA (Pr = 0.66). We also investigate the reaction rate of ring-opening polymerization by complex 1 in the presence of 9-AnOH catalyzes -CL, -BL, and L-LA. In addition, complex 3 and complex 4 are demonstrated to catalyze the ROP of L-LA in the presence of 9-AnOH. However, the catalytic activity and reaction time of complex 3 are much better than complex 4.

並列關鍵字

Zinc ； ROP ； lactide

參考文獻

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含亞胺基苯並三唑苯酚氧基之鋅錯合物合成、結構鑑定及應用於環酯類開環聚合反應的催化研究

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