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1. 发明授权

US6156691A Ziegler-Natta catalyst systems modified during their preparation 失效
标题翻译：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。

2. 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。

3. 发明授权

US5658840A Preparation of Ziegler-Natta type catalyst systems 失效
标题翻译：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。

4. 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。

5. 发明授权

US5310712A Process for the preparation of a supported catalyst for the polymerization of .alpha.-olefins 失效
标题翻译：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。

6. 发明授权

US5210160A Preparation of homopolymers of ethene and copolymers of ethene with higher a-monoolefins using a Ziegler catalyst system 失效
标题翻译：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）。

7. 发明授权

US5034481A Avoidance of colored impurities in the preparation of ultrahigh molecular weight ethylene polymers by means of a titanium-containing catalyst system 失效
标题翻译：通过含钛催化剂体系制备超高分子量乙烯聚合物时避免有色杂质
公开(公告)号：US5034481A
公开(公告)日：1991-07-23
申请号：US409343
申请日：1989-09-19
申请人： Guido Funk , Siegfried Weber , Juergen Kerth , Rainer Hemmerich
发明人： Guido Funk , Siegfried Weber , Juergen Kerth , Rainer Hemmerich
IPC分类号： C08F2/00 , C08F2/34 , C08F4/60 , C08F4/64 , C08F10/02 , C08F110/02
CPC分类号： C08F10/02 , Y10S526/901
摘要： Ultrahigh molecular weight ethylene polymers are prepared in the gas phase in a thoroughly mixed bed of finely divided polymer by continuous introduction of the monomer into a polymerization system at 60.degree.-120.degree. C. and 5-60 bar in the presence of a reaction product of a titanium-containing catalyst and an antistat.
摘要翻译：超细分子量乙烯聚合物在气相中通过在60-120℃和5-60巴的反应产物存在下将聚合体系连续引入聚合体系中，在细分聚合物的充分混合床中制备的含钛催化剂和抗静电剂。

8. 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。

9. 发明授权

US5034480A Avoidance of colored impurities in the preparation of ultrahigh molecular weight ethylene polymers by means of titanium-containing catalyst system 失效
标题翻译：通过含钛催化剂体系避免在超高分子量乙烯聚合物的制备中产生有色杂质
公开(公告)号：US5034480A
公开(公告)日：1991-07-23
申请号：US409581
申请日：1989-09-19
申请人： Guido Funk , Siegfried Weber , Rainer Hemmerich
发明人： Guido Funk , Siegfried Weber , Rainer Hemmerich
IPC分类号： C08F4/64 , C08F2/34 , C08F2/44 , C08F4/60 , C08F10/02
CPC分类号： C08F10/02 , C08F110/02 , Y10S526/901
摘要： Ultrahigh molecular weight ethylene polymers are prepared in the gas phase in a thoroughly mixed bed of finely divided polymer by continuous introduction of the monomer into a polymerization system at 60.degree.-120.degree. C. and 5-60 bar in the presence of a reaction product of a titanium-containing catalyst and an antistat and in the presence of a monohydric or polyhydric alcohol.
摘要翻译：超细分子量乙烯聚合物在气相中通过在60-120℃和5-60巴的反应产物存在下将聚合体系连续引入聚合体系中，在细分聚合物的充分混合床中制备的含钛催化剂和抗静电剂，并在一元或多元醇的存在下进行。

10. 发明授权

US4857613A Preparation of homopolymers and copolymers of propene using a Ziegler-Natta catalyst system 失效
标题翻译：使用齐格勒 - 纳塔催化剂体系制备丙烯的均聚物和共聚物
公开(公告)号：US4857613A
公开(公告)日：1989-08-15
申请号：US236213
申请日：1988-08-25
申请人： Ralf Zolk , Juergen Kerth , Rainer Hemmerich
发明人： Ralf Zolk , Juergen Kerth , Rainer Hemmerich
IPC分类号： C08F4/58 , C08F4/60 , C08F4/64 , C08F10/06
CPC分类号： C08F10/06
摘要： Polymers of propene are prepared using a Ziegler-Natta catalyst system consisting of (1) a titanium component which is based on a finely divided, shape-imparting silica gel and contains titanium, magnesium, chlorine and a benzenecarboxylic acid derivative, (2) an aluminum component and (3) a silane component. In the process, a titanium component (1) is employed which is obtained by (1.1) first preparing (I) a carrier from (Ia) a silica gel which has a relatively high moisture content, (Ib) an organomagnesium compound and (Ic) a gaseous chlorinating agent by a method in which (1.1.1) first (Ia) is reacted with (Ib), (1.1.2) then (Ic) is passed into the mixture obtained in (1.1.1), and (I) is isolated, (1.2) thereafter a solid-phase intermediate is prepared from (I), (II) an alkanol, (III) titanium tetrachloride and (IV) a phthalic acid derivative by a procedure in which (1.2.1) first (I) is reacted with (II), (1.2.2) then (III) is introduced into the mixture resulting from (1.2.1), with the proviso that (IV) is also introduced during (1.2.1) and/or (1.2.2), (1.3) then the solid-phase product resulting from (1.2) is extracted with titanium tetrachloride or a titanium tetrachloride/hydrocarbon mixture, and (1.4) finally the solid-phase product resulting from (1.3) is washed with a liquid hydrocarbon.
摘要翻译：丙烯聚合物使用齐格勒 - 纳塔催化剂体系制备，该催化剂体系由（1）基于精细分散的形状赋予硅胶并含有钛，镁，氯和苯甲酸衍生物的钛组分组成，（2）铝成分和（3）硅烷成分。在该方法中，使用钛成分（1），其通过（1.1）首先制备（I）来自（Ia）具有较高水分含量的硅胶的载体（Ib）有机镁化合物和（Ic））气态氯化剂，其中（1.1.1）第一（Ia）与（Ib），（1.1.2）反应，然后将（Ic）转化为（1.1.1）中获得的混合物和（ I）分离，（1.2）之后，通过（I），（II）烷醇，（III）四氯化钛和（Ⅳ）邻苯二甲酸衍生物，通过步骤（1.2.1）制备固相中间体，第一（I）与（II），（1.2.2）反应，然后将（III）引入由（1.2.1）得到的混合物中，条件是在（1.2.1）期间引入（IV）和 /或（1.2.2），（1.3），然后用四氯化钛或四氯化碳/烃混合物萃取由（1.2）得到的固相产物，（1.4）最后由（1.3）得到的固相产物用液体水溶液洗涤碳。

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