Factors Affecting the Coordination Mode of Aluminum Amidates and the Synthesis, Characterization and Application of Metal Alkoxides

本論文中說明了四個乙醯胺鋁錯化物的合成,並對影響其配位模式的因素加以討論;此外也合成了七個金屬烷氧錯化物,利用這些錯化物催化己內酯與交酯的開環聚合反應,同時也利用理論計算對反應機構加以推論．Several metal complexes, {Me2Al[N(tBu)C(CF3)O]}2 (1), {Me2Al[N(Ph)C(CF3)O]}2 (2), {Me2Al[N(Bn)C(CF3)O]}2 (3), {Et2Al[N(Bn)C(Ph)O]}2 (4), [(-2,4-tBu2-C6H3O)Al(iBu)2]2 (5), [(MMPEP)Al(-OCH2C6H4CH2Cl)]2 (6), [(MMPEP)Mg(THF)]2 (7), [(MMPEP)Zn(THF)]2 (8), [(MMPEP)(ZnEt)2]2 (9), [(MMPEP-H)Li(HOBn)]2 (10) and [(MMPEP-H)Li(p-CH2Cl(C6H4)OH)]2 (11) have been synthesized and their structures have been determined by X-ray single crystal diffraction. Aluminum amidates 1-4 are obtained by the reactions of amides with trialkylaluminum in which compound 1 is a penta-coordinated dimeric complex while compounds 2-4 are tetra-coordinated dimeric complexes. By comparison the structural data of these four complexes and other aluminum amidates prepared in our laboratory, factors affecting the coordination mode of aluminum amidates will be discussed. Ring-opening polymerization of -caprolactone initiated by 5 and 6 has been investigated. Poly(-caprolactone) (PCL) obtained by the initiation of 6 can be used as a macroinitiator to the preparation of poly(-caprolactone)-b-polyacrylonitrile (PCL-b-PAN) diblock copolymer, a potential precursor to nanomaterials. Complex 7 has shown great catalytic activity toward ROP of -caprolactone in the presence of BnOH. Theoretical study of ROP mechanism of -caprolactone catalyzed by 7 demonstrates that the initiator, benzyl alcohol, is activated by the formation of a hydrogen bond with the phenoxy oxygen of MMPEP2- ligand.Abstract I Chapter 1 Introduction 1-1 Part A. Reactions of Amides with Trialkylaluminum 1-1 Part B. Biodegradable Polymers 1-4 Part C. Block-Copolymers of Polyacrylonitrile and the Morphology 1-7 Chapter 2 Reaction of Amides with Organoaluminum Complexes: Factors Affecting the Coordination Mode of Aluminum Amidates 2-1 Introduction 2-1 Results and Discussion 2-4 Synthesis 2-4 Molecular Structure Studies 2-5 Compared with Other Complexes 2-10 Summary 2-14 Experimental Section 2-14 Chapter 3 Preparation, Characterization and Catalytic Reactions of Metal Phenoxides, Efficient Initiators/Catalysts for Ring- Opening Polymerization of -Caprolactone and L-Lactide. 3-1 Introduction 3-1 Results and Discussion 3-2 Synthesis and Crystallographic Studies 3-2 ROP of -Caprolactone Initiated by Complex 5 3-11 ROP of p-(Methylchloride)benzyl Ester End-functionalized -Caprolactone Initiated by Complex 6 3-12 ROP of -Caprolactone Catalyzed by Complex 7 in the Presence of BnOH 3-15 ROP of Benzyl and p-(Methylchloride)benzyl Ester End -functionalized L-Lactide Initiated by 10 and 11. 3-18 The Theoretical Mechanistic Study for ROP of -Caprolactone by 7 in the Presence of BnOH 3-22 Summary 3-27 Experimental Section 3-28 Chapter 5 Conclusions 5-1 Reference

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一种绝缘体上硅的波导光栅耦合器，所述耦合器采用绝缘体上硅材料，包括：一衬底；一限制层，该限制层制作在衬底上；一波导层，该波导层制作在限制层上，该波导层上面的一端横向制作有衍射光栅；一光子器件，该光子器件的光发射端或接收端置于波导层上的衍射光栅的上方

绝缘体上硅的波导光栅耦合器及其制作方法

一种绝缘体上硅的波导光栅耦合器，所述耦合器采用绝缘体上硅材料，包括：一衬底；一限制层，该限制层制作在衬底上；一波导层，该波导层制作在限制层上，该波导层上面的一端横向制作有衍射光栅；一光子器件，该光子器件的光发射端或接收端置于波导层上的衍射光栅的上方

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以脱钠赤泥、粉状褐煤为原料,羧甲基纤维素钠为黏结剂,采用碳热还原法制备了可替代商业铁炭微电解填料的廉价铁炭材料,用于去除废水中的Cr(Ⅵ)。考察了不同的制备参数(炭化温度、炭化时间、赤泥/煤质量比)和吸附条件(溶液pH、浓度),以提升Cr(Ⅵ)去除效果。结果表明质量比(赤泥/煤)为1/3、800℃炭化1h的赤泥/煤基铁炭材料,可达到最大Cr(Ⅵ)吸附量(4.03 mg&middot;g~(-1))、最低铁溶出量(</p

赤泥煤基铁炭材料的制备及其脱除废水cr的性能

以脱钠赤泥、粉状褐煤为原料,羧甲基纤维素钠为黏结剂,采用碳热还原法制备了可替代商业铁炭微电解填料的廉价铁炭材料,用于去除废水中的Cr(Ⅵ)。考察了不同的制备参数(炭化温度、炭化时间、赤泥/煤质量比)和吸附条件(溶液pH、浓度),以提升Cr(Ⅵ)去除效果。结果表明质量比(赤泥/煤)为1/3、800℃炭化1h的赤泥/煤基铁炭材料,可达到最大Cr(Ⅵ)吸附量(4.03 mg·g~(-1))、最低铁溶出量