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    Process for the preparation of a supported catalyst for the polymerization of .alpha.-olefins
    1.
    发明授权
    Process for the preparation of a supported catalyst for the polymerization of .alpha.-olefins 失效
    制备用于α-烯烃聚合的负载型催化剂的方法

    公开(公告)号：US5310712A

    公开(公告)日：1994-05-10

    申请号：US953629

    申请日：1992-09-30

    申请人： Guido Funk ,  Rainer Hemmerich ,  Hans Gropper ,  Erich Kolk ,  Godofredo Follmer

    发明人： Guido Funk ,  Rainer Hemmerich ,  Hans Gropper ,  Erich Kolk ,  Godofredo Follmer

    IPC分类号： C08F4/02 ,  C08F4/06 ,  C08F4/22 ,  C08F4/24 ,  C08F4/69 ,  C08F10/00 ,  B01J35/08 ,  B01J37/08

    CPC分类号： C08F10/00

    摘要： In a novel process for the preparation of a supported catalyst for the polymerization of .alpha.-olefins, a carrier gel (1) is first prepared by a method in which a sodium or potassium waterglass solution is introduced into a stream of an aqueous mineral acid which is subjected to angular momentum and may contain aluminum ions, longitudinally and tangentially to the stream, the resulting silica hydrosol sprayed in the form of drops into a gaseous medium and allowed to solidify into a hydrogel, and the resulting hydrogel is freed from salts by washing without prior aging and, if necessary, freed from some of the water by extraction with alcohols and/or ketones and is then dried. This gives the carrier gel (1), which is milled and is fractionated according to particle size. In a second process step, the carrier gel (1) is laden with chromium trioxide or with a chromium compound which can be converted into chromium trioxide, after which the resulting chromium-containing carrier gel (2) is heated at from 400.degree. to 1100.degree. C. for from 10 to 1,000 minutes in an anhydrous gas stream containing oxygen in a concentration of more than 10% by volume. In the novel process, it is essential that the drying of the hydrogel be carried out with formation of the carrier gel (1) in a fast dryer in the course of not more than 300 seconds at an inlet temperature of from 200.degree. to 600.degree. C. The supported catalyst prepared in this manner gives homo- and copolymers of ethylene having excellent low temperature impact strength.

    摘要翻译： 在制备用于α-烯烃聚合的负载催化剂的新方法中，首先通过一种方法制备载体凝胶（1），其中将钠或钾水玻璃溶液引入无机酸水溶液的流中， 经受角动量并且可以包含与流纵向和切向的铝离子，所得到的二氧化硅水溶胶以液滴的形式喷入气态介质中并使其固化成水凝胶，并且通过洗涤将所得水凝胶除去盐 没有预先老化，如果需要，通过用醇和/或酮萃取除去一些水，然后干燥。 这得到载体凝胶（1），其被研磨并根据粒度进行分级。 在第二工艺步骤中，载体凝胶（1）装载有三氧化铬或可以转化成三氧化铬的铬化合物，之后将所得含铬载体凝胶（2）在400℃加热至1100℃ 在含有浓度超过10体积％的氧气的无水气流中10分钟至1000分钟。 在新颖的方法中，必须在200〜600℃的入口温度下，在不超过300秒的快速干燥器中形成载体凝胶（1），进行水凝胶的干燥。 C.以这种方式制备的负载催化剂得到具有优异的低温冲击强度的乙烯均聚物和共聚物。

    Preparation of Ziegler-Natta type catalyst systems
    2.
    发明授权
    Preparation of Ziegler-Natta type catalyst systems 失效
    齐格勒 - 纳塔型催化剂体系的制备

    公开(公告)号：US5658840A

    公开(公告)日：1997-08-19

    申请号：US457280

    申请日：1995-06-05

    申请人： Peter Kolle ,  Patrik Muller ,  Rainer Hemmerich ,  Erich Kolk

    发明人： Peter Kolle ,  Patrik Muller ,  Rainer Hemmerich ,  Erich Kolk

    IPC分类号： C08F4/64 ,  C08F4/642 ,  C08F4/646 ,  C08F10/00

    CPC分类号： C08F10/00

    摘要： A process for the preparation of Ziegler-Natta type catalyst systems, containing, as active constituentsa) a titanium-containing solid component, which contains in addition to a compound of titanium at least one electron donor compound, and is present in an inert solvent in the form of a suspension, and, as co-catalyst,b) an aluminum compound andc) optionally further electron donor compoundsin which, following the preparation of the titanium-containing solid component a), the inert solvent present in the suspension is removed by first filtering the suspension in a first step, and then removing further solvent from the filtered material in a second step by applying a pressure difference at temperatures of not more than 100.degree. C.

    摘要翻译： 一种制备齐格勒 - 纳塔型催化剂体系的方法，其含有作为活性组分的a）含钛固体组分，其除了含有至少一种电子给体化合物的钛化合物外，还存在于惰性溶剂中 作为助催化剂，b）铝化合物和c）任选的其它电子给体化合物，其中在制备含钛固体组分a）之后，存在于悬浮液中的惰性溶剂 通过在第一步骤中首先过滤悬浮液，然后在第二步骤中通过在不超过100℃的温度下施加压差而从过滤的材料中除去另外的溶剂来​​除去。

    Preparation of homopolymers of ethene and copolymers of ethene with higher a-monoolefins using a Ziegler catalyst system
    3.
    发明授权
    Preparation of homopolymers of ethene and copolymers of ethene with higher a-monoolefins using a Ziegler catalyst system 失效
    使用齐格勒催化剂体系制备乙烯与乙烯共聚物与高级单环戊二烯的共聚物

    公开(公告)号：US5210160A

    公开(公告)日：1993-05-11

    申请号：US410047

    申请日：1989-09-19

    申请人： Roland Saive ,  Guido Funk ,  Rainer Hemmerich

    发明人： Roland Saive ,  Guido Funk ,  Rainer Hemmerich

    IPC分类号： C08F4/607 ,  C08F4/642 ,  C08F4/647 ,  C08F4/65 ,  C08F4/685 ,  C08F10/02

    CPC分类号： C08F10/02

    摘要： Homopolymerization and copolymerization of ethene is carried out using a Ziegler catalyst system consisting of (1) a transition metal catalyst component, (2) an organoaluminum catalyst component and (3) an organohalogen catalyst component. The component (1) used is the solid-phase product (VI) which has been obtained by a method in which (1.1) first (1.1.1) an inorganic oxidic substance (I) as a carrier and (1.1.2) a solution (II) of (IIa) a certain oxahydrocarbon and (IIb) a mixture of (IIb1) a vanadium trichloride/alcohol complex and (IIb2) a titanium trihalide or titanium trihalide/alcohol complex and (IIc) a silicon or boron compound are combined with formation of a suspension (III) and the latter is evaporated to form a solid-phase intermediate (IV) and (1.2) then (1.2.1) the intermediate (IV) obtained in (1.1) and (1.2.2) a dissolved organoaluminum compound (V) are combined with formation of a suspension, the solid-phase product (VI) formed as the suspended substance being the transition metal catalyst component (1).

    摘要翻译： 使用由（1）过渡金属催化剂组分，（2）有机铝催化剂组分和（3）有机卤化物催化剂组分组成的齐格勒催化剂体系进行乙烯的均聚和共聚。 所使用的组分（1）是通过以下方法获得的固相产物（VI）：（1.1）第一（1.1.1）作为载体的无机氧化物质（I）和（1.1.2）a （IIa）的某些氧杂烃的溶液（II）和（IIb）（IIb1）三氯化钒/醇络合物和（IIb2）三卤化钛或三卤化钛/醇络合物和（IIc）硅或硼化合物的混合物 （IV）和（1.2）然后（1.2.1）（1.1）和（1.2.2）中得到的中间体（Ⅳ），然后蒸发形成悬浮液（III） 将溶解的有机铝化合物（V）与形成悬浮液组合，形成为作为过渡金属催化剂组分（1）的悬浮物质的固相产物（VI）。

    Preparation of homopolymers of ethene and copolymers of ethene with higher .alpha.-monoolefins using a Ziegler catalyst system
    6.
    发明授权
    Preparation of homopolymers of ethene and copolymers of ethene with higher .alpha.-monoolefins using a Ziegler catalyst system 失效
    使用齐格勒催化剂体系制备乙烯均聚物和乙烯与较高级α-单烯烃的共聚物

    公开(公告)号：US4831090A

    公开(公告)日：1989-05-16

    申请号：US108457

    申请日：1987-10-15

    申请人： Robert Bachl ,  Guido Funk ,  Konrad Richter ,  Rainer Hemmerich ,  Roland Saive

    发明人： Robert Bachl ,  Guido Funk ,  Konrad Richter ,  Rainer Hemmerich ,  Roland Saive

    IPC分类号： C08F4/60 ,  C08F4/62 ,  C08F4/639 ,  C08F4/64 ,  C08F4/68 ,  C08F4/685 ,  C08F10/00 ,  C08F10/02

    CPC分类号： C08F10/00

    摘要： Homopolymerization and copolymerization of ethene are carried out using a Ziegler catalyst system consisting of (1) a transition metal catalyst component prepared by a method in which (1.1) first (1.1.1) an inorganic oxide substance (I) as a carrier and (1.1.2) a solution (II) of (IIa) a certain oxahydrocarbon and (IIb) a mixture of (IIb1) a vanadium trichloride/alcohol complex, (IIb2) a titanium trihalide or titanium trihalide/alcohol complex and, if desired, (IIb3) a zirconium tetrahalide, are combined with formation of a suspension (III), the latter is evaporated down to form a solid-phase intermediate (IV), (1.2) then (1.2.1) the solid-phase intermediate (IV) obtained from (1.1), and (1.2.2) a dissolved organoaluminum compound (V), are combined with formation of a suspension, the resulting suspended substance being a solid-phase product (VI), (2) an organoaluminum catalyst component and (3) an organohalogen catalyst component. In this process, the transition metal catalyst component (1) used is one prepared by a method in which (1.3) in addition (1.3.1) the product (VI) obtained from (1.2) is reacted with (1.3.2) oxygen, the resulting solid-phase end product (VII) being the novel transition metal catalyst component (1).

    摘要翻译： 乙烯的均聚和共聚使用齐格勒催化剂体系进行，所述齐格勒催化剂体系由（1）通过以下方法制备的过渡金属催化剂组分：（1.1）第一（1.1.1）作为载体的无机氧化物（I）和（ 1.1.2）（IIa）某种氧杂烃的溶液（II）和（IIb）（IIb1）三氯化钒/醇络合物的混合物，（IIb2）三卤化钛或三卤化钛/醇络合物的混合物，如果需要， （IIb3）四卤化锆与形成悬浮液（III）组合，将其蒸发掉形成固相中间体（IV），（1.2）然后（1.2.1）固相中间体（IV ）和（1.2.2）溶解的有机铝化合物（V）与形成悬浮液结合，得到的悬浮物质为固相产物（VI），（2）有机铝催化剂组分 和（3）有机卤素催化剂组分。 在该方法中，使用的过渡金属催化剂组分（1）是通过（1.3）另外（1.3.1）从（1.2）获得的产物（VI）与（1.3.2）氧气反应的方法制备的 得到的固相终产物（Ⅶ）是新型过渡金属催化剂组分（1）。

    Catalyst systems of the Ziegler-Natta type
    8.
    发明授权
    Catalyst systems of the Ziegler-Natta type 失效
    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。

    Ziegler-Natta catalyst systems modified during their preparation
    10.
    发明授权
    Ziegler-Natta catalyst systems modified during their preparation 失效
    齐格勒 - 纳塔催化剂体系在制备过程中改进

    公开(公告)号：US6156691A

    公开(公告)日：2000-12-05

    申请号：US928394

    申请日：1997-09-12

    申请人： Stephan Huffer ,  Ulrich Moll ,  Ian David McKenzie ,  Franz Langhauser ,  Peter Kolle ,  Roland Hingmann ,  Gunther Schweier ,  Rainer Hemmerich ,  Jurgen Kerth

    发明人： Stephan Huffer ,  Ulrich Moll ,  Ian David McKenzie ,  Franz Langhauser ,  Peter Kolle ,  Roland Hingmann ,  Gunther Schweier ,  Rainer Hemmerich ,  Jurgen Kerth

    IPC分类号： C08F4/02 ,  C08F4/642 ,  C08F4/646 ,  C08F4/654 ,  C08F4/658 ,  C08F10/00 ,  B01J31/00

    CPC分类号： C08F10/00

    摘要： In catalyst systems of the Ziegler-Natta type modified during their preparation and comprising as active constituentsa) a titanium-containing solid component which is obtained by reacting a compound of titanium with a compound of magnesium, a halogen, an inorganic oxide as support, a C.sub.1 -C.sub.8 -alkanol and a carboxylic ester as electron donor compound,and also as cocatalystb) an aluminum compound andc) if desired, a further electron donor compound,the titanium-containing solid component a) is prepared by first, in a first stage, admixing an inorganic oxide as support with a solution of a chlorine-free compound of magnesium in an inert solvent, stirring this mixture for from 0.5 to 5 hours at from 10 to 120.degree. C. and subsequently reacting it while stirring continually in an inert solvent with a C.sub.1 -C.sub.8 -alkanol in an at least 1.3-fold excess, based on the compound of magnesium, to give a chlorine-free intermediate, then, without purification or extraction of the intermediate, adding a compound of trivalent or tetravalent titanium and a carboxylic ester as electron donor compound to this intermediate, stirring the resulting mixture for at least 30 minutes at from 20 to 130.degree. C., subsequently filtering off and washing the solid thus obtained and subsequently, in a second stage, extracting the solid obtained from the first stage in an inert solvent comprising at least 5% by weight of titanium tetrachloride and washing it with a liquid alkane.

    摘要翻译： 在其制备过程中改性的齐格勒 - 纳塔型催化剂体系中，包含作为活性成分的含钛固体成分a）通过使钛化合物与镁，卤素，无机氧化物作为载体反应而得到的含钛固体成分， 作为电子给体化合物的C1-C8-链烷醇和羧酸酯，以及作为助催化剂的b）铝化合物，和c）如果需要，另外的电子给体化合物，含钛固体组分a）首先在 第一阶段，将无机氧化物作为载体与无氯化合物的镁在惰性溶剂中的溶液混合，在10至120℃下搅拌该混合物0.5至5小时，随后在持续搅拌下反应 在基于镁化合物的至少1.3倍过量的C 1 -C 8烷醇的惰性溶剂中，得到无氯中间体，然后不经纯化或萃取中间体，加入一种 磅三价或四价钛和羧酸酯作为电子给体化合物，在20至130℃下搅拌所得混合物至少30分钟，随后过滤并洗涤由此获得的固体，随后在 第二阶段，在包含至少5重量％的四氯化钛的惰性溶剂中萃取从第一阶段获得的固体，并用液体烷烃洗涤。