【作者】 高爱红；

【导师】 母瀛；

【作者基本信息】 吉林大学 ， 有机化学， 2009， 博士

【摘要】 脂肪族聚酯尤其是聚ε-己内酯（PCL）、聚乙交酯（PGA）、聚丙交酯（PLA）以及它们之间的共聚物,由于具有良好的生物降解性、生物适应性和可渗透性等特点,在药物控释、骨胳内固定材料、外科缝合线等方面得到广泛的应用,是公认的优良的可生物降解高分子材料。本论文首次合成了四个系列十七个未见报道的新型铝、锌、铬金属配合物,并得到七个金属配合物的晶体结构,并通过元素分析、核磁共振和X-射线单晶衍射等测试手段对所合成的配合物进行了结构表征。对其中铝、锌十四个金属配合物进行了催化己内酯、丙交酯开环聚合的性质研究和测定,研究了他们的聚合机理,初步研究了三个铬配合物的催化乙烯聚合条件。利用N, N-二甲基苯胺为原料合成了一系列二齿胺铝配合物ortho-（ArNCH₂） C₆H₄NMe₂AlMe₂（Ar=2,6-iPr2C₆H₃,3a; 2,6-Et2C₆H₃, 3b; 2,6-Me₂C₆H₃, 3c; 4-MeC₆H₄, 3d; Ph, 3e）, ortho-（ArNCH₂） C₆H₄NMe₂Al2Me5 （Ar=4-MeC₆H₄, 4d; Ph, 4e）。并对3c、3e和4e进行了单晶结构分析。利用所合成的单核铝金属配合物作为催化剂在苄醇存在下催化己内酯开环聚合,反应活性很高,且配合物3a-3e具有活性聚合的特点。所有配体和配合物均经元素分析和核磁进行了表征。分离和表征了活性物种5并研究了聚合的机理.利用N, N-二甲基苯胺为原料合成了一系列二齿NO铝、锌金属配合物AlMe₂OCPh2-2-NMe₂C₆H₄ （2a）, AlMe₂OCHPh-2-NMe₂C₆H₄ （2b）, AlMe₂O-CH（2-F- Ph）-2-NMe₂C₆H₄ （2c）, ZnEtOCHPh-2-NMe₂C₆H₄ （3b）, AlMe₂O-CH（2-F-Ph）-2- NMe₂C₆H₄ （3c）以及双核配合物Al2Me5OCHPh-2-NMe₂C₆H₄ （4b）, Al2Me5O- CH（2-F- Ph）-2-NMe₂C₆H₄ （4c）。并对2a、3b, 4b和4c进行了单晶结构分析。利用以上单核铝配合物作为催化剂在苄醇存在下催化己内酯开环聚合,反应活性很高且配合物2a– 2c具有活性聚合的特点。利用以上锌配合物3b-3c作为催化剂在苄醇存在下催化丙交酯开环聚合,反应活性很高,且配合物具有活性聚合的特点。利用二齿NO配体合成了相应的Cr（III）配合物（L¹）₂CrCl, （L²）₂CrCl, （L³）₂CrCl。并对配合物（L¹）₂CrCl进行了单晶结构分析。在三乙基铝作为助催化剂的条件下,用Cr（III）配合物对乙烯聚合做了初步研究。更多还原

【Abstract】 In this work 18 metal complexes such as Al, Zn, Cr were synthesized and characterized by 1H and 13C NMR spectroscopy and elemental analyses, as well as X-ray diffraction analysis. The ring opening polymerization of caprolactone initiated by Al, Zn complexes was investigated. The ethylene polymerization initiated by Cr complexes was studied.N, N ligands [ortho-C₆H₄（NMe₂）CH₂NHAr （Ar = 2,6-iPr2C₆H₃, 2a; Ar = 2,6-Et2C₆H₃, 2b; Ar = 2,6-Me₂C₆H₃, 2c; Ar = 4-MeC₆H₄, 2d; Ar = Ph, 2e）] were synthesized from the starting material N,N-dimethylaniline. Treatment of the ligands 2a–e with 1 equiv. of AlMe3 yields Al complexes ortho-（ArNCH₂） C₆H₄NMe₂AlMe₂ （Ar = 2,6-iPr2C₆H₃, 3a; 2,6-Et2C₆H₃, 3b; 2,6-Me₂C₆H₃, 3c; 4-MeC₆H₄, 3d; Ph, 3e） in toluene by alkane elimination reaction. Reaction of ligands 2d, 2e with two equiv. of AlMe3 gets the binuclear Al complexes （Me3Al）[ortho-C₆H₄（NMe₂）- CH₂ArN-μ2]AlMe₂ （Ar = 4-MeC₆H₄, 4d, Ar = Ph, 4e）. The new complexes were characterized by 1H and 13C NMR spectroscopy and elemental analyses, and the molecular structures of 3c, 3e and 4e were determined by X-ray diffraction analysis. The Al complexes are efficient catalysts for ring-opening polymerization ofε-caprolactone in the presence of benzyl alcohol in a living fashion yielding polymers with narrow polydispersity values. In order to study the mechanism of polymerization, the active site complex 5 was separated and characterized.N, O ligands （2-dimethylaminophenyl）alcohols [1-HOCPh2-2-NMe₂ C₆H₄ （1a）, 1-HOCHPh-2-NMe₂C₆H₄（1b）, 1-HOCH（2-F-Ph）-2-NMe₂C₆H₄ （1c）] were synthesized from the starting material N, N-dimethylaniline. Treatment of the ligands 1a–1c with 1 equiv. of AlMe3 yields Al complexes [AlMe₂OCPh2-2-NMe₂C₆H₄ （2a）, AlMe₂OCHPh-2- NMe₂C₆H₄ （2b）, AlMe₂O-CH（2-F-Ph）-2- NMe₂C₆H₄ （2c）] in toluene by alkane elimination reaction. Reaction of ligands 1b, 1c with two equiv. of AlMe3 gets the binuclear Al complexes （Me₃Al）AlMe₂OCHPh-2-NMe₂C₆H₄ 4b), （Me3Al） AlMe₂OCH-（2-F-Ph）-2- NMe₂C₆H₄ 4c)]. 1b-1c react with ZnEt2 in toluene to get the Zn complexes [ZnEtOCHPh-2-NMe₂C₆H₄ （3b）, ZnEtOCH（2-F-Ph）-2-NMe₂C₆H₄ （3c）]. The new complexes were characterized by 1H and 13C NMR spectroscopy and elemental analyses, and the molecular structures of 2a, 4b, 4c and 3b were determined by X-ray diffraction analysis. The Al complexes are efficient catalysts for ring-opening polymerization ofε-caprolactone in the presence of benzyl alcohol in a living fashion yielding polymers with narrow polydispersity values. The Zn complexes 3b-3c are efficient catalysts for ring-opening polymerization of LA in the presence of benzyl alcohol in a controlled manner.Reaction of the lithium salt of 1a-1c with CrCl3（THF）3 in THF gives the four-coordinated Cr（III） complexes （L1）2CrCl, （L2）2CrCl, （L3）2CrCl. Molecular structure of the （L1）2CrCl complex was determined by X-ray crystallography. Upon activation with AlMe3 as cocatalysts, the ethylene polymerization intiated by the Cr（III） complex was investigated.更多还原