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1. 发明申请

US20050202959A1 Solid catalytic component and catalytic system of the ziegler-natta type, process for their preparation and their use in the polymerisation of alk-1-enes 失效
标题翻译：齐格勒 - 纳塔型固体催化组分和催化体系，其制备方法及其在烷-1-烯的聚合中的应用
公开(公告)号：US20050202959A1
公开(公告)日：2005-09-15
申请号：US10504702
申请日：2003-01-28
申请人： Wolf Spaether , John Lynch , Joachim Rosch , Rainer Hemmerich
发明人： Wolf Spaether , John Lynch , Joachim Rosch , Rainer Hemmerich
IPC分类号： C08F10/00 , C08F4/64 , C08F4/658 , C08F10/06 , C08F110/06 , B01J31/00 , C08F4/44
CPC分类号： C08F110/06 , C08F4/651 , C08F4/025 , C08F4/6546 , C08F2500/12 , C08F2500/15 , C08F2500/24
摘要： The present invention relates to a new solid catalytic component, which can be used in combination with an aluminum compound as co-catalyst and optionally an external electron donor as additional co-catalyst to form a catalytic system of the Ziegler-Natta-catalyst-type. The solid catalytic system comprises titanium or vanadium compound, a compound of magnesium containing at least one halogen, a particulate porous support, and optionally an internal electron donor.
摘要翻译：本发明涉及一种新的固体催化组分，其可以与作为助催化剂的铝化合物和任选的外部电子给体一起用作另外的助催化剂以形成齐格勒 - 纳塔催化剂型催化体系。固体催化体系包括钛或钒化合物，含有至少一个卤素的镁的化合物，颗粒状多孔载体和任选的内部电子给体。

2. 发明授权

US06864208B2 Method for production of a solid catalyst for olefin polymerization 失效
标题翻译：烯烃聚合用固体催化剂的制备方法
公开(公告)号：US06864208B2
公开(公告)日：2005-03-08
申请号：US10168268
申请日：2000-12-11
申请人： Carsten Süling , Wolf Spaether , Nicola Paczkowski , Joachim Rösch , Joachim Wulff-Döring , Wolfgang Bidell
发明人： Carsten Süling , Wolf Spaether , Nicola Paczkowski , Joachim Rösch , Joachim Wulff-Döring , Wolfgang Bidell
IPC分类号： C08F4/614 , C08F4/02 , C08F4/04 , C08F4/6192 , C08F4/64 , C08F4/658 , C08F4/659 , C08F4/6592 , C08F10/00 , C08F10/06 , C08F110/06 , B01J31/00 , B01J37/00 , C08F4/60
CPC分类号： C08F10/06 , C08F4/65912 , C08F4/65927 , C08F110/06 , C08F4/022 , C08F4/65916 , C08F2500/03
摘要： A catalyst solid for olefin polymerization comprising A) at least one magnesium halide, B) at least one metallocene complex and C) at least one compound capable of forming metallocenium ions, is prepared by i) firstly preparing finely divided support particles consisting of the magnesium halide A) and an C1-C8-alcohol having a mean particle diameter of from 1 to 200 μm from an adduct of the magnesium halide A) and a C1-C8-alcohol, where the adduct contains from 1.5 to 5 mol of the C1-C8-alcohol per mole of magnesium halide, ii) then depositing the compound C) capable of forming metallocenium ions on the finely divided support particles and iii) subsequently bringing the reaction product hereby obtained into contact with the metallocene complex B). This catalyst solid can be used for the polymerization or copolymerization of olefins.
摘要翻译：一种用于烯烃聚合的催化剂固体，其包括：A）至少一种卤化镁，B）至少一种茂金属络合物和C）至少一种能够形成金属茂离子的化合物，其通过以下步骤制备：首先制备由卤化镁A）组成的细分散的载体颗粒，和来自卤化镁A）和C1-C8-醇的加合物的平均粒径为1至200μm的C1-C8-醇，其中加合物含有1.5至5mol的C1-C8- 醇，然后将能够在细分散的载体颗粒上形成金属茂离子的化合物C）沉积，并且ii）随后使由此得到的反应产物与茂金属络合物B）接触。该催化剂固体可用于烯烃的聚合或共聚。

3. 发明授权

US07071137B2 Method of making a ziegler-natta catalyst 有权
标题翻译：制备齐格勒 - 纳塔催化剂的方法
公开(公告)号：US07071137B2
公开(公告)日：2006-07-04
申请号：US10925596
申请日：2004-08-25
申请人： Douglas D. Klendworth , Frank Wolf Spaether
发明人： Douglas D. Klendworth , Frank Wolf Spaether
IPC分类号： B01J37/00
CPC分类号： C08F10/00 , C08F110/06 , C08F4/6543 , C08F4/022 , C08F4/025 , C08F4/6494
摘要： A method for making a Ziegler-Natta catalyst support includes the steps of contacting a fumed silica with a surface modifying agent such as a compound having the formula RMgX MgR′R″ wherein R, R′ and R″ are each individually a moiety selected from an alkyl group, cycloalkyl, aryl or alkaryl group, and X is a halogen selected from the group consisting of chlorine, bromine and iodine, to provide a pretreated silica seeding agent. The pretreated silica seeding agent is then dispersed in a non-aqueous liquid magnesium halide/alkanol complex, and the magnesium halide is crystallized onto the silica particles to form catalyst support particles especially suitable for Ziegler-Natta catalysts.
摘要翻译：制备齐格勒 - 纳塔催化剂载体的方法包括使热解二氧化硅与表面改性剂如具有式RMgX MgR'R“的化合物接触的步骤，其中R，R'和R”各自为一部分选自烷基，环烷基，芳基或烷芳基，X是选自氯，溴和碘的卤素，以提供预处理的二氧化硅接种剂。然后将预处理的二氧化硅接种剂分散在非水性液体卤化镁/烷醇络合物中，并将卤化镁结晶到二氧化硅颗粒上以形成特别适合齐格勒 - 纳塔催化剂的催化剂载体颗粒。

4. 发明授权

US06524995B2 Catalyst systems of the Ziegler-Natta type 失效
标题翻译：齐格勒 - 纳塔型催化剂系统
公开(公告)号：US06524995B2
公开(公告)日：2003-02-25
申请号：US09750715
申请日：2001-01-02
申请人： Wolf Spaether , Stephan Hüffer , John Lynch , Wolfgang Bidell , Joachim Rösch , Günther Schweier , Roland Hingmann , Alexandre Segul , Rainer Hemmerich , Ingo Treffkorn
发明人： Wolf Spaether , Stephan Hüffer , John Lynch , Wolfgang Bidell , Joachim Rösch , Günther Schweier , Roland Hingmann , Alexandre Segul , Rainer Hemmerich , Ingo Treffkorn
IPC分类号： B01J2302
CPC分类号： C08F10/00 , C08F110/06 , C08F4/025 , C08F4/6546 , C08F2500/12 , C08F2500/24
摘要： Catalyst systems of the Ziegler-Natta type comprise as active constituents a) a solid component comprising a compound of titanium or vanadium, a compound of magnesium, a particulate inorganic oxide as support and an internal electron donor compound, and as cocatalyst b) an aluminum compound and c) if desired, a further, external electron donor compound, wherein the particulate, inorganic oxide used has a specific surface area of from 350 to 1000 m2/g and a mean particle diameter {overscore (D)} in the range from 5 to 60 &mgr;m and comprises particles which are composed of primary particles having a mean particle diameter {overscore (d)} in the range from 1 to 10 &mgr;m and contain voids or channels between the primary particles, where the macroscopic proportion of voids or channels having a diameter of greater than 1 &mgr;m in the particles of the inorganic oxides is in the range from 5 to 30% by volume and the molar ratio of the compound of magnesium to the particulate, inorganic oxide is from 0.5:1 to 2.0:1.
摘要翻译：齐格勒 - 纳塔型的催化剂体系包括作为活性成分的a）包含钛或钒的化合物的固体组分，镁的化合物，作为载体的颗粒状无机氧化物和内部电子给体化合物，以及作为助催化剂）铝化合物和），其中所用的颗粒状无机氧化物的比表面积为350〜1000m2 / g，平均粒径（超芯（D在5〜60μm的范围内）和包含由平均粒径（超芯（d在1-10μm范围内）并且在初级颗粒之间含有空隙或通道的初级颗粒组成的颗粒，其中空隙或通道的宏观比例具有大于1的直径无机氧化物颗粒中的母体在5至30体积％的范围内，镁与颗粒的无机氧化物的摩尔比为0.5:1至 2.0：1。

5. 发明授权

US07893175B2 Ziegler-natta catalyst, preparation, and use for the polymerization of alkenes 有权
标题翻译：齐格勒 - 纳塔催化剂，制备和用于烯烃聚合的用途
公开(公告)号：US07893175B2
公开(公告)日：2011-02-22
申请号：US12001729
申请日：2007-12-12
申请人： Frank Wolf Spaether , David Andrew Presken
发明人： Frank Wolf Spaether , David Andrew Presken
IPC分类号： C08F4/42
CPC分类号： C08F10/00 , C08F110/06 , C08F4/025 , C08F4/6546 , C08F4/651 , C08F2500/12
摘要： A method for making a solid catalytic component for a Ziegler-Natta catalyst includes contacting a particulate porous support with a solution of a hydrocarbon soluble organomagnesium precursor compound in a hydrocarbon solvent; and reacting said hydrocarbon soluble organo-magnesium precursor compound with an amount of aliphatic or aromatic alcohol, said amount being within an acceptable range of a molar equivalent of aliphatic or aromatic alcohol calculated according to formula (I): Equ Alkanol = 2 · [ ( mmole ⁢ ⁢ MgR / g ⁢ ⁢ support ) - 2.1 - 0.55 · wt ⁢ ⁢ % ⁢ ⁢ ( H 2 ⁢ O ) / support ] [ mmole ⁢ ⁢ MgR / g ⁢ ⁢ support ] ( I ) wherein EquAlkanol=molar equivalents of aliphatic or aromatic alkanol relative to the molar amount of magnesium-organic precursor, (mmole MgR/g support)=mmoles of magnesium-organic precursor per gram of particulate solid support, wt % (H2O)/support=weight percent of physically adsorbed water on the solid support, and said magnesium organic precursor compound being converted to a magnesium-oxygen compound.
摘要翻译：用于制备齐格勒 - 纳塔催化剂的固体催化组分的方法包括使颗粒状多孔载体与烃溶性有机镁前体化合物在烃溶剂中的溶液接触; 并使所述烃溶性有机镁前体化合物与一定量的脂族或芳族醇反应，所述量在根据式（I）计算的摩尔当量的脂族或芳族醇的可接受范围内：AlKanol = 2·[（（H 2 O）/支撑体] [mmole·gel MgR / g·支撑体]（I）其中Equ Alkanol =摩尔当量脂族或芳族链烷醇相对于镁 - 有机前体的摩尔量（毫摩尔MgR / g载体）=每克微粒固体载体的镁 - 有机前体的毫摩尔％wt％（H 2 O）/载体=物理吸附水的重量百分数在固体载体上，并且所述镁有机前体化合物转化为镁 - 氧化合物。

6. 发明授权

US07232785B2 Solid catalytic component and catalytic system of the ziegler-natta type, process for their preparation and their use in the polymerization of alk-1-enes 失效
标题翻译：齐格勒 - 纳塔型固体催化组分和催化体系，其制备方法及其在烷-1-烯的聚合中的应用
公开(公告)号：US07232785B2
公开(公告)日：2007-06-19
申请号：US10504702
申请日：2003-01-28
申请人： Wolf Spaether , John Lynch , Joachim Rösch , Rainer Hemmerich
发明人： Wolf Spaether , John Lynch , Joachim Rösch , Rainer Hemmerich
IPC分类号： B01J37/00 , B01J31/12
CPC分类号： C08F110/06 , C08F4/651 , C08F4/025 , C08F4/6546 , C08F2500/12 , C08F2500/15 , C08F2500/24
摘要： The present invention relates to a new solid catalytic component, which can be used in combination with an aluminum compound as co-catalyst and optionally an external electron donor as additional co-catalyst to form a catalytic system of the Ziegler-Natta-catalyst-type. The solid catalytic system comprises titanium or vanadium compound, a compound of magnesium containing at least one halogen, a particulate porous support, and optionally an internal electron donor.
摘要翻译：本发明涉及一种新的固体催化组分，其可以与作为助催化剂的铝化合物和任选的外部电子给体一起用作另外的助催化剂以形成齐格勒 - 纳塔催化剂型催化体系。固体催化体系包括钛或钒化合物，含有至少一个卤素的镁的化合物，颗粒状多孔载体和任选的内部电子给体。

7. 发明授权

US07329626B2 Ziegler-Natta catalyst, preparation, and use for the polymerization of alkenes 有权
公开(公告)号：US07329626B2
公开(公告)日：2008-02-12
申请号：US10935211
申请日：2004-09-07
申请人： Frank Wolf Spaether , David Andrew Presken
发明人： Frank Wolf Spaether , David Andrew Presken
IPC分类号： B01J37/00 , C08F4/02
CPC分类号： C08F10/00 , C08F110/06 , C08F4/025 , C08F4/6546 , C08F4/651 , C08F2500/12
摘要： A method for making a solid catalytic component for a Ziegler-Natta catalyst includes contacting a particulate porous support with a solution of a hydrocarbon soluble organomagnesium precursor compound in a hydrocarbon solvent; and reacting said hydrocarbon soluble organo-magnesium precursor compound with an amount of aliphatic or aromatic alcohol, said amount being within an acceptable range of a molar equivalent of aliphatic or aromatic alcohol calculated according to formula (I): Equ Alkanol = 2 ⁢ · [ ( mmole ⁢ ⁢ MgR ⁢ / ⁢ g ⁢ ⁢ support ) - 2.1 - 0.55 ⁢ · ⁢ wt ⁢ ⁢ % ⁢ ⁢ ( H 2 ⁢ O ) ⁢ / ⁢ support ] [ mmole ⁢ ⁢ MgR ⁢ / ⁢ g ⁢ ⁢ support ] ( I ) wherein EquAlkanol=molar equivalents of aliphatic or aromatic alkanol relative to the molar amount of magnesium-organic precursor, (mmole MgR/g support)=mmoles of magnesium-organic precursor per gram of particulate solid support, wt % (H2O)/support=weight percent of physically adsorbed water on the solid support, and said magnesium organic precursor compound being converted to a magnesium-oxygen compound.

8. 发明授权

US06831032B2 Ziegler-Natta catalyst and methods of making and using same 失效
标题翻译：齐格勒 - 纳塔催化剂及其制备和使用方法
公开(公告)号：US06831032B2
公开(公告)日：2004-12-14
申请号：US10223561
申请日：2002-08-19
申请人： Wolf Spaether
发明人： Wolf Spaether
IPC分类号： B01J3100
CPC分类号： C08F10/00 , C08F110/06 , C08F4/651 , C08F4/6546 , C08F2500/15 , C08F2500/12 , C08F2500/24
摘要： A method for making a solid catalyst component for use in a Ziegler-Natta catalyst includes combining a porous particulate support with a magnesium source in a hydrocarbon solvent to form a mixture, the magnesium source including a hydrocarbon soluble organomagnesium compound and a hydrocarbon insoluble anhydrous inorganic magnesium-halogen compound. The organomagnesium compound is halogenated and the mixture is reacted with a titanium compound or vanadium compound to form the solid catalyst component. The solid catalyst component is then recovered and combined with an organoaluminum cocatalyst to form a Ziegler-Natta catalyst which is advantageously used for the polymerization of olefins, particularly alk-1-enes such as ethylene, propylene, 1-butene, and the like. The catalyst can optionally include internal and external electron donors.
摘要翻译：制备用于齐格勒 - 纳塔催化剂的固体催化剂组分的方法包括在烃溶剂中将多孔颗粒载体与镁源组合以形成混合物，所述镁源包括可溶于烃的有机镁化合物和不溶于烃的无水无机无机物镁 - 卤素化合物。将有机镁化合物卤化，并将混合物与钛化合物或钒化合物反应形成固体催化剂组分。然后回收固体催化剂组分并与有机铝助催化剂组合以形成齐格勒 - 纳塔催化剂，该催化剂有利地用于烯烃聚合，特别是烯-1-烯如乙烯，丙烯，1-丁烯等。催化剂可以任选地包括内部和外部电子给体。

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