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1. 发明授权

US06355747B1 Asymmetric silicon-bridged metallocenes useful as catalysts in the polymerization of &agr;-olefins, process for their preparation and use of said metallocenes for the polymerization of &agr;-olefins 失效
标题翻译：可用作α-烯烃聚合中催化剂的不对称硅桥接金属茂，其制备方法和所述茂金属用于α-烯烃聚合的方法
公开(公告)号：US06355747B1
公开(公告)日：2002-03-12
申请号：US09376179
申请日：1999-08-17
申请人： Marvin D. Rausch , Emma J. Thomas , Serge Bettonville , Fabian Siberdt
发明人： Marvin D. Rausch , Emma J. Thomas , Serge Bettonville , Fabian Siberdt
IPC分类号： C08F442
CPC分类号： C08F10/00 , C07F17/00 , C08F4/65912 , C08F110/02 , C08F110/06 , Y10S526/943 , C08F4/65927 , C08F2500/15 , C08F2500/20
摘要： Asymmetric silicon-bridged metallocenes represented by the general formula: wherein M represents a transition metal selected from Ti, Zr and Hf. X and X′ represent a halogen atom, R1, R2, R3 represent alkyl groups containing 1 or 2 carbon atoms or hydrogen atoms, providing that at least two of R1, R2, R3 are alkyl groups, and R4 and R5 represent alkyl or aryl group containing from 1 to 10 carbon atoms. A process for their preparation and polymerization of olefins in the presence of the asymmetric silicon-bridged metallocenes are disclosed.
摘要翻译：由以下通式表示的不对称硅桥连金属茂：其中M表示选自Ti，Zr和Hf的过渡金属.X和X'表示卤素原子，R1，R2，R3表示含有1或2个碳原子或氢原子的烷基条件是R 1，R 2，R 3中的至少两个是烷基，R 4和R 5表示含有1至10个碳原子的烷基或芳基。公开了在不对称硅桥连金属茂存在下制备和聚合烯烃的方法。

2. 发明授权

US06448424B1 Tetrahydrofluorenyl containing group 4 metallocenes useful as catalysts for the polymerization of olefins, process for their preparation and use of said metallocenes for the polymerization of olefins 失效
标题翻译：可用作烯烃聚合催化剂的第4族金属茂的四氢芴基，其制备方法和所述茂金属用于烯烃聚合的方法
公开(公告)号：US06448424B1
公开(公告)日：2002-09-10
申请号：US09562861
申请日：2000-05-01
申请人： Marvin D. Rausch , Emma J. Thomas , Serge Bettonville
发明人： Marvin D. Rausch , Emma J. Thomas , Serge Bettonville
IPC分类号： C07F708
CPC分类号： C07F17/00 , Y10S526/943
摘要： Novel silylene or ethylene bis(tetrahydrofluorenyl)metallocenes are synthesized and used as olefin polymerization catalysts.
摘要翻译：合成了新的亚甲硅烷基或亚乙基双（四氢芴基）茂金属并用作烯烃聚合催化剂。

3. 发明授权

US6100416A Asymmetric ethylene-bridged metallocenes useful as catalysts in the polymerization of olefins and process for preparing said metallocenes 失效
标题翻译：用作烯烃聚合中的催化剂的不对称乙烯桥连金属茂和制备所述金属茂的方法
公开(公告)号：US6100416A
公开(公告)日：2000-08-08
申请号：US87981
申请日：1998-06-01
申请人： Marvin D. Rausch , Emma J. Thomas , Serge Bettonville , Didier Grandfils
发明人： Marvin D. Rausch , Emma J. Thomas , Serge Bettonville , Didier Grandfils
IPC分类号： C07F7/00 , C07F17/00 , C08F4/64 , C08F4/659 , C08F4/6592 , C08F10/00
CPC分类号： C07F17/00 , C08F10/00 , C08F110/02 , C08F210/16 , C08F4/65912 , Y10S526/943
摘要： Novel asymmetric ethylene-bridged metallocenes useful as catalysts in the polymerization of olefins and process for preparing said metallocenes.The novel metallocenes are represented by the general formula: ##STR1## wherein M represents a transition metal selected from titanium, zirconium and hafnium and X and X' represent a halogen atom. Preferably, the transition metal is Zr and the halogen atoms are both chlorine.Process for producing the novel metallocenes of general formula (I) comprising the steps of:a) reacting fluorenyllithium with 1,2-dibromoethane to produce 1-(9-fluorenyl)-2-bromoethane,b) reacting the said 1-(9-fluorenyl)-2-bromoethane with 2,4,7-trimethylindenyllithium to produce 1-(9-fluorenyl)-2-[1-(2,4,7-trimethyl)indenyl]ethane precursor,c) reacting the said 1-(9-fluorenyl)-2-[1-(2,4,7-trimethyl)indenyl]ethane precursor with butyllithium to produce its dilithium salt andd) reacting the said dilithium salt with a transition metal halide selected from halides of Ti, Zr and Hf to produce the metallocenes.The novel metallocenes are useful as catalysts for the polymerization of olefins such as ethylene and propylene and, in particular, for the production of higly isotactic polypropylene.
摘要翻译：用于烯烃聚合中的催化剂的新型不对称乙烯桥连金属茂和制备所述金属茂的方法。新型茂金属由通式表示：其中M表示选自钛，锆和铪的过渡金属，X和X'表示卤素原子。优选地，过渡金属是Zr，并且卤素原子都是氯。制备通式（I）的新金属茂的方法，包括以下步骤：a）使芴基锂与1,2-二溴乙烷反应，生成1-（9-芴基）-2-溴乙烷，b）使所述1-（9 芴基）-2-溴乙烷与2,4,7-三甲基茚基锂反应，生成1-（9-芴基）-2- [1-（2,4,7-三甲基）茚基]乙烷前体，c）使所述1 - （9-芴基）-2- [1-（2,4,7-三甲基）茚基]乙烷前体与丁基锂反应生成其二锂盐，和d）使所述二锂盐与选自Ti ，Zr和Hf以产生金属茂。新型金属茂可用作烯烃如乙烯和丙烯的聚合催化剂，特别是用于生产高度全同立构聚丙烯的催化剂。

4. 发明授权

US06538082B2 Asymmetric silicon-bridged metallocenes useful as catalysts in the polymerization of &agr;-olefins, process for their preparation and use of said metallocenes for the polymerization of &agr;-olefins 失效
标题翻译：可用作α-烯烃聚合中催化剂的不对称硅桥接金属茂，其制备方法和所述茂金属用于α-烯烃聚合的方法
公开(公告)号：US06538082B2
公开(公告)日：2003-03-25
申请号：US09729099
申请日：2000-12-05
申请人： Marvun D. Rausch , Emma J. Thomas , Serge Bettonville
发明人： Marvun D. Rausch , Emma J. Thomas , Serge Bettonville
IPC分类号： C08F472
CPC分类号： C07F17/00 , Y10S526/943
摘要： Novel asymmetric silicon-bridged metallocenes useful as catalysts in the polymerization of olefins and process for preparing said metallocenes. The novel metallocenes are represented by the general formula (I): (SiR′R″)(Cp)(Cp′)MXX′ (I) wherein Cp is a partially or fully hydrogenated fluorenyl moiety selected from those of formula (II) and (III) Cp′ is an indenyl group selected from those of formula (IV) M represents a transition metal selected from Ti, Zr and Hf, X and X′ represent, same or different from each other, a halogen atom, R1, R2 and R3 are, same or different from each other, an alkyl group containing 1 or 2 carbon atoms, an aryl group containing from 6 to 10 carbon atoms or a hydrogen atom, (SiR′R″) is a divalent group which bridges the two groups Cp and Cp′ repectively on position 9 and 1, R′ and R″ are, same or different from each other, an alkyl or aryl group containing from 1 to 10 carbon atoms. Process for producing said metallocenes and process for the polymerization of &agr;-olefins such as ethylene and propylene by means of said metallocenes.
摘要翻译：新型不对称硅桥接金属茂可用作烯烃聚合中的催化剂和制备所述金属茂的方法。新型金属茂由通式（I）表示：其中Cp是部分或完全氢化的芴基部分，其选自式（II ）和（III）Cp'是选自式（IV）的茚基，M表示选自Ti，Zr和Hf的过渡金属，X和X'表示相同或不同的卤素原子，R1 中，R2和R3彼此相同或不同，含有1或2个碳原子的烷基，含有6至10个碳原子的芳基或氢原子，（SiR'R“）是二价基团，在位置9和1上分别桥接两个基团Cp和Cp，R'和R“彼此相同或不同，含有1至10个碳原子的烷基或芳基。用于制备所述金属茂和方法用于α-烯烃如乙烯的聚合和丙烯通过所述金属茂。

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