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Di-nuclear zinc complexes containing tridentate imino-benzotriazole phenolate derivatives as efficient catalysts for ring-opening polymerization of cyclic esters and copolymerization of phthalic anhydride with cyclohexene oxide
期刊文章

Di-nuclear zinc complexes containing tridentate imino-benzotriazole phenolate derivatives as efficient catalysts for ring-opening polymerization of cyclic esters and copolymerization of phthalic anhydride with cyclohexene oxide

Chin-Hsiang Chang, Hui-Ju Chuang, Ting-Yi Chen, Chen-Yu Li, Chia-Her Lin, Ting-Yu Lee, Bao-Tsan KoHsi-Ya Huang
Journal of Polymer Science, Part A: Polymer Chemistry, 卷.54(5), 頁碼.714-725
03/2016

摘要

catalysis cyclic esters imino-benzotriazole phenolate ligands ring-opening polymerization (ROP) zinc Polymers and Plastics Organic Chemistry Materials Chemistry
Zinc catalysts incorporated by imino-benzotriazole phenolate (IBTP) ligands were synthesized and characterized by single-crystal X-ray structure determinations. The reaction of the ligand precursor ( C1DMe IBTP-H or C1DIP IBTP-H) with diethyl zinc (ZnEt 2 ) in a stoichiometric proportion in toluene furnished the di-nuclear ethyl zinc complexes [(μ- C1DMe IBTP)ZnEt] 2 (1) and [(μ- C1DIP IBTP)ZnEt] 2 (2). The tetra-coordinated monomeric zinc complex [( C1Ph IBTP) 2 Zn] (3) or [( C1Bn IBTP) 2 Zn] (4) resulted from treatment of C1Ph IBTP-H or C1Bn IBTP-H as the pro-ligand under the similar synthetic method with ligand to metal precursor ratio of 2:1. Single-crystal X-ray diffraction of bimetallic complexes 1 and 2 indicates that the C1DMe IBTP or C1DIP IBTP fragment behaves a NON-tridentate ligand to coordinate two metal atoms. Catalysis for ring-opening polymerization (ROP) of ε-caprolactone (ε-CL), β-butyrolactone (β-BL), and lactide (LA) of complexes 1 and 2 was systematic studied. In combination with 9-anthracenemethanol (9-AnOH), Zn complex 1 was found to polymerize ε-CL, β-BL, and L-LA with efficient catalytic activities in a controlled character. This study also compared the reactivity of these ROP monomers with different ring strains by Zn catalyst 1 in the presence of 9-AnOH. Additionally, Zn complex 1 combining with benzoic acid was demonstrated to be an active catalytic system to copolymerize phthalic anhydride and cyclohexene oxide.

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