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    Process and catalyst for producing polyolefins having low molecular weight
    2.
    发明授权
    Process and catalyst for producing polyolefins having low molecular weight 失效
    用于生产低分子量聚烯烃的方法和催化剂

    公开(公告)号：US6114480A

    公开(公告)日：2000-09-05

    申请号：US635274

    申请日：1996-04-19

    申请人： Edwar S. Shamshoum ,  B. Raghava Reddy ,  Margarito Lopez

    发明人： Edwar S. Shamshoum ,  B. Raghava Reddy ,  Margarito Lopez

    IPC分类号： C08F4/64 ,  C08F4/619 ,  C08F4/6192 ,  C08F4/642 ,  C08F4/6592 ,  C08F10/00 ,  C08F110/02 ,  C08F110/06

    CPC分类号： C08F10/00 ,  C08F110/02 ,  C08F110/06 ,  C08F4/61912 ,  C08F4/61927 ,  Y10S526/943

    摘要： The invention provides a metallocene catalyst for use in preparing polyolefins having low molecular weight. The catalyst comprises a metallocene compound generally described by the formula R"(C.sub.5 R.sub.4) (H.sub.2 C.sub.5 C.sub.4 H.sub.4)MeQ.sub.p wherein (C.sub.5 R.sub.4) is a substituted cyclopentadienyl ring; (H.sub.2 C.sub.5 C.sub.4 H.sub.4) is an indenyl ring; (C.sub.5 R.sub.4) has one R substituent in a distal position which is at least as bulky as a t-butyl radical; R" is a structural bridge between the (C.sub.5 R.sub.4) and (H.sub.2 C.sub.5 C.sub.4 H.sub.4) rings to impart stereorigidity; Q is a hydrocarbyl radical, such as an alkyl, aryl, alkenyl, alkylaryl or arylalkyl radical having 1-20 carbon atoms or is a halogen; Me is a Group IIIB, IVB, VB, or VIB metal as positioned in the Periodic Table of Elements; and p is the valence of Me minus 2. This catalyst produces a crystalline or atactic polymer with a low molecular weight and narrow or broad molecular weight distribution depending upon the isomer(s) used in polymerization. A single threo-isomer produces isotactic polypropylene and a single erythro-isomer produces atactic polypropylene, both polymers having narrow molecular weight distribution. When the bridge between the substituted cyclopentadienyl and the indenyl rings is substituted such that four diastereomers are possible, the threo-isomers produce isotactic polypropylene with broad molecular weight distribution.

    摘要翻译： 本发明提供用于制备低分子量聚烯烃的茂金属催化剂。 该催化剂包含一般由式R“（C5R4）（H2C5C4H4）MeQp描述的茂金属化合物，其中（C5R4）是取代的环戊二烯基环; （H2C5C4H4）是茚基环; （C5R4）在远端位置具有至少与叔丁基一样庞大的一个R取代基; R“是（C5R4）和（H2C5C4H4）环之间的结构桥，以赋予立体刚度; Q是烃基，例如具有1-20个碳原子的烷基，芳基，烯基，烷基芳基或芳基烷基，或者是卤素; Me是位于元素周期表中的IIIB，IVB，VB或VIB族金属; 并且p是Me的化合价减去2.该催化剂产生具有低分子量和窄或宽分子量分布的结晶或无规立构聚合物，这取决于聚合中使用的异构体。 单一苏式异构体产生全同立构聚丙烯，单一的异构异构体产生无规聚丙烯，两种聚合物具有窄的分子量分布。 当取代的环戊二烯基和茚基环之间的桥被取代使得四个非对映异构体是可能的时，苏式异构体产生具有宽分子量分布的全同立构聚丙烯。

    Process for producing stereospecific polymers
    3.
    发明授权
    Process for producing stereospecific polymers 失效
    制备立体有择聚合物的方法

    公开(公告)号：US5807800A

    公开(公告)日：1998-09-15

    申请号：US798245

    申请日：1997-02-11

    申请人： Edwar S. Shamshoum ,  Margarito Lopez

    发明人： Edwar S. Shamshoum ,  Margarito Lopez

    IPC分类号： C08F4/02 ,  C08F4/602 ,  C08F4/639 ,  C08F4/6392 ,  C08F4/64 ,  C08F4/642 ,  C08F4/659 ,  C08F4/6592 ,  C08F10/06 ,  C08F12/04 ,  C08F12/08 ,  C08F14/06

    CPC分类号： C08F10/06 ,  C08F10/00 ,  C08F110/06 ,  C08F12/04 ,  C08F4/63927 ,  Y10S526/943

    摘要： Stereospecific catalysts and processes for the stereotactic polymerization of ethylenically unsaturated monomers, specifically C.sub.3 -C.sub.4 alpha olefins involving a molecular sieve supported metallocene catalyst comprising a stereospecific metallocene catalyst component and a co-catalyst component. The metallocene catalyst component incorporates a metallocene ligand structure having two sterically dissimilar cyclopentadienyl ring structures coordinated with the central transition metal atom. Both the metallocene catalyst component and the co-catalyst component are supported on a molecular sieve having an average effective pore size which is less than the kinetic diameter of at least one of said ring structures. This supported catalyst is contacted in a polymerization reaction zone with an ethylenically unsaturated monomer which contains 3 or more carbon atoms or which is a substituted vinyl compound under polymerization conditions to produce stereospecific polymerization of the monomer. The supported catalyst incorporates a molecular sieve support having an average effective pore size within the range of 5-10 angstroms. The metallocene component can be an unbalanced metallocene having a ligand structure in which stereorigidity is imparted by means of a structural bridge extending between dissimilar cyclopentadienyl groups, for example, a fluorenyl group, a cyclopentadienyl group, of a ligand which exhibits bilateral symmetry. The specific zeolite supports are zeolite Y, zeolite X, mordenite, and zeolite .beta.. Others include various zeolites of the ZSM substitutional series, including ZSM-5, ZSM-11, and ZSM-12.

    摘要翻译： 烯属不饱和单体的立体定向聚合的立体定向催化剂和方法，特别是涉及包含立体特异性金属茂催化剂组分和助催化剂组分的分子筛负载金属茂催化剂的C3-C4α烯烃。 茂金属催化剂组分包含具有两个与中心过渡金属原子配位的空间不同的环戊二烯基环结构的茂金属配体结构。 金属茂催化剂组分和助催化剂组分都被负载在平均有效孔径小于所述环结构中的至少一个的动力学直径的分子筛上。 该聚合反应区中的负载型催化剂与含有3个以上碳原子的烯键式不饱和单体接触，或者在聚合条件下与取代的乙烯基化合物接触，生成单体的立体有择聚合。 载体催化剂含有平均有效孔径在5-10埃范围内的分子筛载体。 茂金属组分可以是具有配体结构的不平衡茂金属，其中立体刚性通过在不同的环戊二烯基之间延伸的结构桥，例如具有双侧对称性的配体的芴基，环戊二烯基。 特定的沸石载体是沸石Y，沸石X，丝光沸石和β沸石。 其他还包括ZSM替代系列的各种沸石，包括ZSM-5，ZSM-11和ZSM-12。

    Supported metallocene catalysts
    4.
    发明授权
    Supported metallocene catalysts 有权
    负载金属茂催化剂

    公开(公告)号：US06432860B1

    公开(公告)日：2002-08-13

    申请号：US09273819

    申请日：1999-03-22

    申请人： Edwar S. Shamshoum ,  Margarito Lopez

    发明人： Edwar S. Shamshoum ,  Margarito Lopez

    IPC分类号： B01J3100

    CPC分类号： C08F10/06 ,  C08F4/025 ,  C08F4/65912 ,  C08F4/65927 ,  C08F12/04 ,  C08F110/06 ,  Y02P20/52 ,  Y10S526/943 ,  C08F4/65916 ,  C08F2500/16

    摘要： Supported stereospecific catalysts and processes for the stereotactic propagation of a polymer chain derived from ethylenically unsaturated monomers which contain three or more carbon atoms or which are substituted vinyl compounds, such as styrene and vinyl chloride. One application is the stereospecific propagation of C3-C4 alpha olefins, particularly the polymerization of propylene to produce syndiotactic polypropylene over a supported metallocene catalyst comprising a stereospecific metallocene catalyst component incorporating a metallocene ligand structure having two sterically dissimilar cyclopentadienyl ring structures coordinated to the central transition metal atom. Both of the cyclopentadienyl groups are in a relationship with one another by virtue of bridge or substituent groups, which provide a stereorigid relationship relative to the coordinating transition metal atom to prevent rotation of said ring structures. The metallocene catalyst component and a co-catalyst component, an alumoxane or an alkyl aluminum, are supported on a particulate silica support comprising spheroidal silica particles having an average diameter within the range of 5-40 microns and an average effective pore size within the range of 50-350 angstroms. The particulate silica support contains at least 50 wt. % of the supported catalyst component within the pore volume of the silica support. The particles are preferably toroidal shaped, i.e. donut shaped.

    摘要翻译： 支持的立体定向催化剂和衍生自含有三个或更多个碳原子的乙烯基不饱和单体的聚合物链的立体定向增长的方法，或者是取代的乙烯基化合物如苯乙烯和氯乙烯。 一种应用是C3-C4α烯烃的立体有择性扩增，特别是丙烯在负载金属茂催化剂下产生间同立构聚丙烯的聚合反应，该载体包含立体特异性金属茂催化剂组分，该催化剂组分含有具有两个与中心转移配位的空间不同的环戊二烯基环结构的茂金属配体结构 金属原子。 两个环戊二烯基通过桥或取代基相互关系，其提供相对于配位过渡金属原子的立体刚性关系以防止所述环结构的旋转。 金属茂催化剂组分和助催化剂组分，铝氧烷或烷基铝负载在颗粒状二氧化硅载体上，所述颗粒二氧化硅载体包含平均直径在5-40微米范围内的平均直径范围的球形二氧化硅颗粒，并且平均有效孔径在该范围内 50-350埃。 颗粒状二氧化硅载体含有至少50wt。 负载的催化剂组分的百分比在二氧化硅载体的孔体积内。 颗粒优选为环形，即环形。

    Catalyst efficiency for supported metallocene catalyst
    6.
    发明授权
    Catalyst efficiency for supported metallocene catalyst 有权
    负载金属茂催化剂的催化剂效率

    公开(公告)号：US06225251B1

    公开(公告)日：2001-05-01

    申请号：US09304974

    申请日：1999-05-04

    申请人： Edwar S. Shamshoum ,  Margarito Lopez ,  B. Raghava Reddy ,  Theodore G. Harris

    发明人： Edwar S. Shamshoum ,  Margarito Lopez ,  B. Raghava Reddy ,  Theodore G. Harris

    IPC分类号： B01J3100

    CPC分类号： C08F10/00 ,  C08F4/61912 ,  C08F4/61927 ,  Y10S526/943 ,  C08F4/61916

    摘要： The invention provides a polymerization process with improved catalyst activity of a metallocene catalyst supported on silica treated with MAO, a process for supporting a metallocene compound on silica treated with MAO, a metallocene catalyst supported on silica treated with MAO within a certain temperature range and a process for making a metallocene catalyst supported on silica treated with MAO. The invention includes supporting the metallocene compound on a MAO-treated silica at a temperature of below 0° C. The supported catalyst is activated with an aluminum alkyl. The catalyst may be prepolymerized in a tubular reactor prior to being introduced into the polymerization reaction zone.

    摘要翻译： 本发明提供了一种聚合方法，其具有改进的催化剂活性，其负载在用MAO处理的二氧化硅上的茂金属催化剂，用MAO处理的二氧化硅上负载茂金属化合物的方法，负载在一定温度范围内用MAO处理的二氧化硅上的茂金属催化剂和 制备用MAO处理的二氧化硅上负载的茂金属催化剂的方法。 本发明包括在低于0℃的温度下在MAO处理的二氧化硅上负载茂金属化合物。负载的催化剂用烷基铝活化。 催化剂可以在引入聚合反应区之前在管式反应器中预聚合。

    Process for producing stereospecific polymers
    8.
    发明授权
    Process for producing stereospecific polymers 有权
    制备立体有择聚合物的方法

    公开(公告)号：US06855782B2

    公开(公告)日：2005-02-15

    申请号：US10114185

    申请日：2002-04-02

    申请人： Edwar S. Shamshoum ,  Margarito Lopez

    发明人： Edwar S. Shamshoum ,  Margarito Lopez

    IPC分类号： C08F4/02 ,  C08F4/60 ,  C08F4/6392 ,  C08F4/642 ,  C08F4/659 ,  C08F4/6592 ,  C08F10/06 ,  C08F12/04 ,  C08F110/06

    CPC分类号： C08F10/06 ,  C08F4/025 ,  C08F4/65912 ,  C08F4/65927 ,  C08F12/04 ,  C08F110/06 ,  Y02P20/52 ,  Y10S526/943 ,  C08F4/65916 ,  C08F2500/16

    摘要： Supported stereospecific catalysts and processes for the stereotactic propagation of a polymer chain derived from ethylenically unsaturated monomers which contain three or more carbon atoms or which are substituted vinyl compounds, such as styrene and vinyl chloride. One application is the stereospecific propagation of C3-C4 alpha olefins, particularly the polymerization of propylene to produce syndiotactic polypropylene over a supported metallocene catalyst comprising a stereospecific metallocene catalyst component incorporating a metallocene ligand structure having two sterically dissimilar cyclopentadienyl ring structures coordinated with the central transition metal atom. Both of the cyclopentadienyl groups are in a relationship with one another by virtue of bridge or substituent groups, which provide a stereorigid relationship relative to the coordinating transition metal atom to prevent rotation of said ring structures. The metallocene catalyst component and a co-catalyst component, an alumoxane or an alkyl aluminum, are supported on a particulate silica support comprising spheroidal silica particles having an average diameter within the range of 5-40 microns and an average effective pore size within the range of 50-350 angstroms. The particulate silica support contains at least 50 wt. % of the supported catalyst component within the pore volume of the silica support.

    摘要翻译： 支持的立体定向催化剂和衍生自含有三个或更多个碳原子的乙烯基不饱和单体的聚合物链的立体定向增长的方法，或者是取代的乙烯基化合物如苯乙烯和氯乙烯。 一个应用是C3-C4α烯烃的立体特异性扩增，特别是丙烯在负载金属茂催化剂下聚合制备间同立构聚丙烯的方法，该催化剂包含立体特异性茂金属催化剂组分，该组分含有具有两个与中心转移配位的空间不同的环戊二烯基环结构的茂金属配体结构 金属原子。 两个环戊二烯基通过桥或取代基相互关系，其提供相对于配位过渡金属原子的立体刚性关系以防止所述环结构的旋转。 金属茂催化剂组分和助催化剂组分，铝氧烷或烷基铝负载在颗粒状二氧化硅载体上，所述颗粒二氧化硅载体包含平均直径在5-40微米范围内的平均直径范围的球形二氧化硅颗粒，并且平均有效孔径在该范围内 50-350埃。 颗粒状二氧化硅载体含有至少50wt。 负载的催化剂组分的百分比在二氧化硅载体的孔体积内。