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    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：US06855783B2

    公开(公告)日：2005-02-15

    申请号：US10412372

    申请日：2003-04-11

    申请人： William J. Gauthier ,  Margaret Kerr ,  Jun Tian ,  David J. Rauscher ,  Constance Hayworth Patrick ,  Shady Henry

    发明人： William J. Gauthier ,  Margaret Kerr ,  Jun Tian ,  David J. Rauscher ,  Constance Hayworth Patrick ,  Shady Henry

    IPC分类号： B01J31/00 ,  B01J37/00 ,  C07F9/00 ,  C07F11/00 ,  C07F17/00 ,  C08F4/02 ,  C08F4/42 ,  C08F4/44 ,  C08F4/60 ,  C08F4/659 ,  C08F4/6592 ,  C08F10/00 ,  C08F110/02 ,  C08F110/06

    CPC分类号： C08F10/00 ,  C08F4/65912 ,  C08F4/65927 ,  C08F110/06 ,  Y10S526/943 ,  C08F4/65916 ,  C08F2500/18 ,  C08F2500/03 ,  C08F2500/12 ,  C08F2500/17 ,  C08F2500/15

    摘要： Supported metallocene catalysts and processes for the use of such catalysts in isotactic polymerization of a C3+ ethylenically unsaturated monomer. The supported catalysts comprise a particulate silica support, an alkyl alumoxane component, and a metallocene catalyst component. The support has an average particle size of 10-50 microns, a surface area of 200-800 m2/g and a pore volume of 0.9-2.1 milliliters per gram (ml/g). Alumoxane is incorporated onto the support to provide a weight ratio of alumoxane to silica of at least 0.8:1. The metallocene is present in an amount of at least 1 weight percent of the silica and the alumoxane and is of the formula B(CpRaRb)(Fl′)MQ2 in which Fl′ is an unsubstituted fluorenyl group or a fluorenyl group symmetrically substituted at the 3 and 6 positions, B is a structural bridge between Cp and Fl′, Ra is a bulky substituent in a distal position, Rb is a less bulky substituent proximal to the bridge and non-vicinal to the distal substituent, M is a Group IVB transition metal or vanadium, and Q is a halogen or a Cl-C4 alkyl group.

    摘要翻译： 负载型金属茂催化剂和在C3 +烯属不饱和单体的全同立构聚合中使用这种催化剂的方法。 载体催化剂包括颗粒二氧化硅载体，烷基铝氧烷组分和茂金属催化剂组分。 载体的平均粒度为10-50微米，表面积为200-800平方米/克，孔体积为0.9-2.1毫升/克（毫升/克）。 将Alumoxane加入到载体上以提供至少0.8:1的铝氧烷与二氧化硅的重量比。 金属茂的存在量为二氧化硅和铝氧烷的至少1重量％，并且具有式B（CpRaRb）（F1'）MQ2，其中F1'是未取代的芴基或在该位置上对称取代的芴基 3和6位，B是Cp和Fl'之间的结构桥，Ra是远端位置的大体积取代基，Rb是靠近桥的较不庞大的取代基，而与远端取代基不相邻，M是IVB族 过渡金属或钒，Q是卤素或C 1 -C 4烷基。

    Catalyst formulation and polymerization processes
    5.
    发明授权
    Catalyst formulation and polymerization processes 失效
    催化剂配方和聚合方法

    公开(公告)号：US06489411B1

    公开(公告)日：2002-12-03

    申请号：US09653607

    申请日：2000-08-30

    申请人： Edwar S. Shamshoum ,  David J. Rauscher ,  Shabbir A. Malbari

    发明人： Edwar S. Shamshoum ,  David J. Rauscher ,  Shabbir A. Malbari

    IPC分类号： C08F4609

    CPC分类号： C08F10/00 ,  C08F110/06 ,  C08F4/651 ,  C08F4/6465 ,  C08F2500/15 ,  C08F2500/18 ,  C08F2500/12

    摘要： Processes for the polymerization of olefins with Zeigler-type catalyst systems which involve transition metal catalyst components comprising 4, 5 or 6 transition metals incorporating internal electron donors to provide desired polymerization characteristics, including yield and polymer characteristics. Specific olefins used in the polymerization process are C2-C4 alpha olefins such as propylene in the production of stereoregular polypropylene. The catalyst system comprised a transition metal component having an internal electron donor in an amount providing an internal donor/transition metal mole ratio of no more than 2/3. This is combined with an organoaluminum co-catalyst component to provide a precusor mixture having an aluminum/transition metal mole ration of at least 100. The precusor mixture is combined with an organosilicon external electron donor component in an amount to provide an aluminum/silicon mole ration of no more than 200. The catalyst system is introduced to a polymerization reactor to effect polymerization of the olefin with the catalyst system.

    摘要翻译： 使用Zeigler型催化剂体系聚合烯烃的方法，其涉及包含4,5或6个过渡金属的过渡金属催化剂组分，该过渡金属包含内部电子给体以提供所需的聚合特性，包括产率和聚合物特性。 在聚合过程中使用的特定烯烃是C2-C4α烯烃，如丙烯在立体规则聚丙烯的生产中。 催化剂体系包含具有内部电子给体的过渡金属组分，其量提供内部供体/过渡金属摩尔比不超过2/3。 这与有机铝助催化剂组分组合以提供具有至少100的铝/过渡金属摩尔比的预混合物。前体混合物与有机硅外电子给体组分结合，其量提供铝/硅摩尔 不超过200的比例。将催化剂体系引入聚合反应器以实现烯烃与催化剂体系的聚合。

    Process for treating silica with alumoxane
    6.
    发明授权
    Process for treating silica with alumoxane 失效
    用铝氧烷处理二氧化硅的方法

    公开(公告)号：US06211109B1

    公开(公告)日：2001-04-03

    申请号：US09085922

    申请日：1998-05-28

    申请人： Edwar S. Shamshoum ,  Christopher G. Bauch ,  B. R. Reddy ,  David J. Rauscher ,  Kevin P. McGovern

    发明人： Edwar S. Shamshoum ,  Christopher G. Bauch ,  B. R. Reddy ,  David J. Rauscher ,  Kevin P. McGovern

    IPC分类号： B01J3112

    CPC分类号： C08F4/025 ,  B01J31/143 ,  B01J31/1616 ,  B01J31/2295 ,  B01J2531/48 ,  Y10S526/904 ,  Y10S526/907 ,  Y10S526/943

    摘要： The invention provides a process for commercial production of syndiotactic polyolefins using a metallocene catalyst supported on silica treated with MAO. The invention includes contacting the supported metallocene catalyst with an aluminum alkyl and aging the catalyst prior to polymerization. In addition, the catalyst is prepolymerized in a tubular reactor prior to being introduced into the polymerization reaction zone. The treated silica is produced by removing water to a level of 0.5-1.08%, slurrying in a nonpolar solvent, adding an alumoxane, heating to reflux, cooling the slurry, and separating the solid product.

    摘要翻译： 本发明提供了使用负载在用MAO处理的二氧化硅上的茂金属催化剂来商业生产间同立构聚烯烃的方法。 本发明包括使负载的茂金属催化剂与烷基铝接触并在聚合之前使催化剂老化。 此外，催化剂在引入聚合反应区之前在管式反应器中预聚合。 处理的二氧化硅通过将水除去至0.5-1.08％的水平，在非极性溶剂中成浆，加入铝氧烷，加热回流，冷却浆料，分离固体产物。

    Catalyst formulation and polymerization processes
    7.
    发明授权
    Catalyst formulation and polymerization processes 失效
    催化剂配方和聚合方法

    公开(公告)号：US06667380B1

    公开(公告)日：2003-12-23

    申请号：US09643540

    申请日：2000-08-22

    申请人： Edwar S. Shamshoum ,  David J. Rauscher ,  Shabbir A. Malbari

    发明人： Edwar S. Shamshoum ,  David J. Rauscher ,  Shabbir A. Malbari

    IPC分类号： C08F11006

    CPC分类号： C08F10/00 ,  C08F4/60 ,  C08F2/00 ,  C08F4/6465 ,  C08F4/655

    摘要： Processes for the formulation of Ziegler-type catalysts from a plurality of catalyst components including transition metal, organosilicon electron donor, and organoaluminum co-catalyst components. The components are mixed together in the course of formulating the Ziegler-type catalyst to be charged to an olefin polymerization reactor. Several orders of addition of the catalyst components can be used in formulating the Ziegler catalyst. One involves mixing of the transition metal component with the organoaluminum co-catalyst to formulate a mixture having an aluminum/transition metal mole ratio of at least 200. This mixture is combined with the organosilicon electron donor component to produce a Ziegler-type catalyst formulation having an aluminum/silicon mole ratio of no more than 50. There may be an initial pre-polymerization of the catalyst prior to introducing the catalyst into an olefin polymerization reactor. The mole ratio of aluminum to silicon in the catalyst formulation within the range of 20 to 50 and the mole ratio of silicon to transition metal within the range of 10-20. Relatively short time sequences can be used in formulating the Ziegler-type catalyst. Another order of addition involves initial contact of the organoaluminum co-catalyst and the organosilicon electron donor to provide a mixture having an aluminum to silicon mole ratio of at least 10. This mixture is then combined with the transition metal component having an aluminum/transition metal mole ratio of at least 200.

    摘要翻译： 用于由多种催化剂组分（包括过渡金属，有机硅电子给体和有机铝助催化剂组分）制备齐格勒型催化剂的方法。 在配制要加入到烯烃聚合反应器中的齐格勒型催化剂的过程中将组分混合在一起。 在配制齐格勒催化剂时可以使用几个加入催化剂组分的顺序。 一个涉及将过渡金属组分与有机铝助催化剂混合以配制铝/过渡金属摩尔比至少为200的混合物。该混合物与有机硅电子给体组分结合以产生齐格勒型催化剂制剂，其具有 铝/硅摩尔比不大于50.在将催化剂引入烯烃聚合反应器之前，可以进行催化剂的初始预聚合。 催化剂配方中铝与硅的摩尔比在20至50范围内，硅与过渡金属的摩尔比在10-20范围内。 相对较短的时间序列可用于配制齐格勒型催化剂。 另外的添加顺序包括有机铝助催化剂和有机硅电子给体的初始接触，以提供铝与硅摩尔比至少为10的混合物。然后将该混合物与具有铝/过渡金属的过渡金属组分 摩尔比至少为200。

    Catalyst formulation and polymerization process
    8.
    发明授权
    Catalyst formulation and polymerization process 失效
    催化剂配方和聚合过程

    公开(公告)号：US5432139A

    公开(公告)日：1995-07-11

    申请号：US846540

    申请日：1992-03-04

    申请人： Edwar S. Shamshoum ,  David J. Rauscher ,  Shabbir A. Malbari

    发明人： Edwar S. Shamshoum ,  David J. Rauscher ,  Shabbir A. Malbari

    IPC分类号： C08F4/60 ,  C08F10/00 ,  B01J31/00

    CPC分类号： C08F10/00 ,  C08F4/60

    摘要： Processes for the formulation of Ziegler-type catalysts from a transition metal component, an electron donor and a co-catalyst which are sequentially mixed together. The co-catalyst is initially contacted with either of the transition metal catalyst or the electron donor for a first contact time of 5-120 seconds. This mixture is then contacted with the remainder of the electron donor or transition metal component for a second contact time of less and 110 seconds. The three component system is then used in olefin polymerization. The olefin contacting step can involve an initial pre-polymerization reaction. A specific order of addition involves mixture of the transition metal component and the co-catalyst component for a contact time of 5-120 seconds followed by contact with an electron donor component for no more than 30 seconds. Another order of addition involves initially contacting the electron donor with the co-catalyst. A further order of addition is such that the electron donor is initially contacted with the transition metal component for up to 40 seconds. The resulting mixture is then contacted with the co-catalyst component for a shorter second contact time up to 20 seconds.

    摘要翻译： 由过渡金属组分，电子给体和助催化剂制备齐格勒型催化剂的顺序混合在一起的方法。 首先将助催化剂与过渡金属催化剂或电子给体中的任一种接触，第一次接触时间为5-120秒。 然后将该混合物与电子给体或过渡金属组分的其余部分接触少于110秒的第二接触时间。 然后将三组分体系用于烯烃聚合。 烯烃接触步骤可以包括初始预聚合反应。 特定的加成顺序包括过渡金属组分和助催化剂组分的混合物，接触时间为5-120秒，随后与电子给体组分接触不超过30秒。 另外的加入顺序包括首先使电子给体与助催化剂接触。 进一步的添加顺序是使电子给体最初与过渡金属组分接触长达40秒。 然后将所得混合物与助催化剂组分接触较短的第二接触时间，最多20秒。

    Polymerization catalyst system using n-butylmethyldimethoxysilane for preparation of polypropylene film grade resins
    9.
    发明授权
    Polymerization catalyst system using n-butylmethyldimethoxysilane for preparation of polypropylene film grade resins 失效
    使用正丁基甲基二甲氧基硅烷制备聚丙烯薄膜级树脂的聚合催化剂体系

    公开(公告)号：US07470764B2

    公开(公告)日：2008-12-30

    申请号：US11700273

    申请日：2007-01-31

    申请人： Kenneth Paul Blackmon ,  David J. Rauscher ,  Michael Ray Wallace

    发明人： Kenneth Paul Blackmon ,  David J. Rauscher ,  Michael Ray Wallace

    IPC分类号： C08F110/06

    CPC分类号： C08F4/6465 ,  B01J31/0212 ,  B01J2231/12 ,  C08F110/06 ,  Y02P20/52 ,  C08F2500/15 ,  C08F2500/26

    摘要： It has been discovered that using n-butylmethyldimethoxysilane (BMDS) as an external electron donor for Ziegler-Natta catalysts can provide a catalyst system that may prepare polypropylene films with improved properties. The catalyst systems of the invention provide for controlled chain defects/defect distribution and thus a regulated microtacticity. Consequently, the curve of storage modulus (G′) v. temperature is shifted such that the film achieves the same storage modulus at a lower temperature enabling faster throughput of polypropylene film through a high-speed tenter.

    摘要翻译： 已经发现，使用正丁基甲基二甲氧基硅烷（BMDS）作为齐格勒 - 纳塔催化剂的外部电子给体可提供可制备具有改进性能的聚丙烯膜的催化剂体系。 本发明的催化剂体系提供受控的链缺陷/缺陷分布，从而提供调节的微量活性。 因此，储能模量（G'）v温度的曲线偏移，使得薄膜在较低温度下实现相同的储能模量，从而能够通过高速拉幅机获得更高的聚丙烯薄膜的生产量。