从“镍效应”到低压聚乙烯：纪念低压聚乙烯问世40周年

一在众星闪烁的诺贝尔奖获得者之中,德国化学家齐格勒(Karl Ziegler)是一颗光彩照人、耀眼夺目的巨星。     

Syntheses of Some New Group 4 non-Cp Complexes Bearing Schiff-base, Thiophene Diamide Ligands Respectively and Their Catalytic Activities for α-Olefin Polymerization

Introduction Tremendous advances have been witnessed during the last decade in the syntheses and application of Group 4 metal complexes because of the motivity which comes from both academic and industrial field. Among them, studies have been dominated by the complexes supported by bis or mono cyclopentadienyl ligands, such as Cp2MX2 or half sandwich amide (CGC) com-plexes.1-6 At that time chemists paid a little attention to the non-cyclopentadienyl complexes, but in recent years, many chem…     

Synthesis and Catalytic Application of Homo-bimetallic Metallocene Complexes as Ethylene Polymerization Catalysts

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镍配合物催化的亚磷酸烯丙酯重排反应

烯丙基化合物在钯配合物催化下和亲核试剂的反应,已发展成为有机合成中的有用方法,我们曾在烯丙基化合物经钯催化的反应活性研究中,发现亚磷酸酯也是一个中等活性的离去基团;并发现在四(三苯膦)钯的催化下,亚磺酸烯丙酯能顺利地重排成相应的砜。但用四(三苯膦)钯为催化剂和亚磷酸烯丙酯反应时,不能分离得重排产物;进一步研究发现:在双(环辛二烯)镍的催化下,亚磷酸烯丙酯能够重排成相应的膦酸酯,反应温度要比相应的热重排低得多,而且时间短,产率高。     

亚乙基桥联-(4-取代茚)(芴)锆金属络合物的合成及其催化α-烯烃聚合反应

首次合成了3个C1-对称亚乙基桥联型-(4-取代茚)(芴)锆络合物2a～2c.并以甲基铝氧烷(MAO)为助催化剂用于催化丙烯聚合反应,所得聚丙烯具有较高的等规立构规整度,且随聚合温度的降低而升高.0℃时茚环2-位有甲基取代的络合物2a表现出最高的等规选择性,为93.6%;而60℃时络合物2a～2c都表现出最高的催化活性...     

四氯化钛配合物/甲基锂体系催化降冰片烯开环移位聚合的研究

The ring opening metathesis polymerization of cyclic monomers is relatively a newcomer to the field of polymer chemistry. Depending on the monomer and the catalyst used, this type of reaction yields a wide range of products that have found important industrial applications.     

Syntheses of Some New Group 4 non-Cp Complexes Bearing Schiff-base, Thiophene Diamide Ligands Respectively and Their Catalytic Activities for a-Olefin Polymerization

Totally sixteen new titanium and zirconium non-Cp complexes supported by Schiff-base, or thiophene diamide ligands have been synthesized. The complexes are obtained by the reaction of M(OPr-i)4(M=Ti,Zr) with the corresponding Schiff-base ligand in 1:1 molar ratio in good yield. The thiophene diamide titanium complex has been prepared from trimethylsilyl amine [N,S,N] ligand and TiCl4 in toluene at 120℃. All complexes are well charac-terized by ^1H NMR, IR, MS and elemental analysis. When activated by excess methylaluminoxane (MAO), complexes show moderate catalytic activity for ethylene polymerization, and complex If (R^1=CH3,R^2=Br) exhibits the highest activity for ethylene and styrene polymerization. When the complexes were preactivated by triethylaluminum (TEA), both polymerization activities and syndiotacticity of the polymers were greatly improved.     

含氟苯基水杨醛亚胺配体的中性镍络合物的合成、表征及对乙烯齐聚的催化活性

合成了一系列含N-氟苯基-水杨醛亚胺配体的中性镍络合物，并对代表性的络合物4进行了X-ray晶体结构分析以进一步确证其结构。这种中性镍络合物在助催化剂烷基铝氧烷(MAO)的作用下，具有较高的催化乙烯齐聚的活性和对C₆烯烃的选择性，催化活性高达4.22×l05 g o1igomers/(mol Ni•h)，对C6烯烃的选择性达到94％。     

含茂、非茂混合配体钛族络合物的合成与催化烯烃聚合的研究进展

目前金属有机钛族络合物的发展呈现出多元化的趋势:茂络合物、非茂络合物以及茂非茂混合配体络合物,而其中茂、非茂混合配体络合物是近年来发展的一个新亮点.关于茂钛族络合物、非茂钛族络合物近年已经有过许多的综述,而关于茂、非茂混合配体钛族络合物的综述却很少.综述了近年来茂、非茂混合配体钛族络合物合成与催化烯烃聚合的研究进展.