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1. 发明授权

US06291611B1 Supported olefin polymerization catalyst, its preparation and use 失效
标题翻译：负载型烯烃聚合催化剂，其制备与应用
公开(公告)号：US06291611B1
公开(公告)日：2001-09-18
申请号：US08481336
申请日：1995-08-02
申请人： Kalle Kallio , Ove Andell , Hilkka Knuuttila , Ulf Palmqvist
发明人： Kalle Kallio , Ove Andell , Hilkka Knuuttila , Ulf Palmqvist
IPC分类号： C08F4642
CPC分类号： C08F10/00 , C08F4/63912 , C08F4/63916 , C08F4/6392 , C08F110/02 , Y10S526/943 , C08F2500/12 , C08F2500/18 , C08F2500/24
摘要： Olefin polymerization comprising catalysts based on a metallocene, an alumoxane and a support are disclosed. The process for the preparation of a supported olefin ploymerization catalyst comprises: a) a metallocene/activator reaction product, a solvent capable of dissolving it, and a porous support are brought into mutual contact, and b) the solvent is removed, and wherein step a) is carried out so that the porous support is impregnated with a volume of the metallocene/activator reaction product and solvent, which does not exceed the total pore volume of the support.
摘要翻译：公开了包含基于茂金属，铝氧烷和载体的催化剂的烯烃聚合。负载型烯烃聚合催化剂的制备方法包括：a）茂金属/活化剂反应产物，能够溶解的溶剂和多孔载体相互接触，b）除去溶剂，其中步骤a ），使得多孔载体用一定体积的金属茂/活化剂反应产物和溶剂浸渍，其不超过载体的总孔体积。

2. 发明授权

US06780809B1 Catalyst for the (co)polymerization of ethylene and a method for the preparation thereof 失效
标题翻译：乙烯（共）聚合的催化剂及其制备方法
公开(公告)号：US06780809B1
公开(公告)日：2004-08-24
申请号：US09601652
申请日：2003-05-21
申请人： Arild Follestad , Vidar Almquist , Ulf Palmqvist , Harri Hokkanen
发明人： Arild Follestad , Vidar Almquist , Ulf Palmqvist , Harri Hokkanen
IPC分类号： B01J3100
CPC分类号： C08F10/00 , C08F4/63912 , C08F4/63916 , C08F4/63925 , C08F4/65912 , C08F4/65925 , C08F10/02 , C08F110/02 , C08F210/16 , C08F4/63904 , C08F4/24 , C08F2500/12 , C08F2500/17 , C08F2500/07 , C08F210/14 , C08F2500/02
摘要： A particulate, modified chromium oxide catalyst for the polymerisation of ethylene or ethylene with &agr;-olefins, comprising: a) a chromium-oxide catalyst, b) a transition metal compound, and c) a catalyst activator. A method for the preparation of the catalyst comprises the steps of: a) subjecting a chromium oxide catalyst precursor, which comprises a chromium oxide compound combined with an inorganic support, to a temperature in the range of from 400 to 950° C. under oxidising conditions, and b) impregnating the obtained chromium catalyst with a catalyst activator and with a transition metal compound which comprises at least one cyclopentadienylic ring bonded to said transition metal and at least ligand selected from the group comprising alkoxy, amido and hydrocarbyl radicals, halogen and hybride bonded to said transition metal, which cyclopentadienylic ring may contain hetero atoms, be unsubstituted or substituted, be bonded to said transition metal through a bridge, and optionally annealed to other substituted or unsubstituted ring structures, and if two cyclopentadienyl rings are present they may be bonded to each other through a bridge, and c) subjecting the thus obtained particulate catalyst to drying conditions. This catalyst is suitable for producing polyethylenes under conditions of continuous feeding of all reactants.
摘要翻译：一种用于乙烯或乙烯与α-烯烃聚合的颗粒状改性氧化铬催化剂，包括：a）氧化铬催化剂，b）过渡金属化合物，和c）催化剂活化剂。制备催化剂的方法包括以下步骤：a）将氧化铬催化剂前体（其包含与无机载体结合的氧化铬化合物）在400-950℃的温度下氧化条件，以及b）用催化剂活化剂和过渡金属化合物浸渍所获得的铬催化剂，所述过渡金属化合物包含至少一个与所述过渡金属键合的环戊二烯基环和至少选自烷氧基，酰胺基和烃基的配体的卤素和杂环结合到所述过渡金属上，该环戊二烯基环可以含有杂原子，是未取代的或被取代的，通过桥键合到所述过渡金属上，并任选地退火至其它取代或未取代的环结构，如果存在两个环戊二烯基环，则它们可以通过桥接物彼此结合，并且c）对由此获得的颗粒催化剂进行处理干燥条件。该催化剂适用于在连续供给所有反应物的条件下生产聚乙烯。

3. 发明授权

US5324698A New carrier catalyst for the polymerization of ethylene 失效
标题翻译：用于乙烯聚合的新载体催化剂
公开(公告)号：US5324698A
公开(公告)日：1994-06-28
申请号：US947967
申请日：1992-09-21
申请人： Sirpa Ala-Huikku , Ulf Palmqvist , Marjaana Lommi , Eero Iiskola
发明人： Sirpa Ala-Huikku , Ulf Palmqvist , Marjaana Lommi , Eero Iiskola
IPC分类号： C08F4/654 , C08F4/659 , C08F4/6592 , C08F10/00 , C08F110/02 , C08F4/636
CPC分类号： C08F10/00 , C08F110/02 , C08F4/65912 , C08F4/65916 , C08F4/6592 , Y10S526/941
摘要： A problem in the conventional olefin polymerization catalyst systems, the procatalysts of which are based on a solid carrier and a titanium compound and an electron donor on its surface, is that unsufficiently high activities are achieved by the morphology of the carrier. Moreover, the active age of such a catalyst in the polymerization is too short. These problems have now been solved by the olefin polymerization catalyst system according to the invention, the procatalyst of which comprises a solid carrier and a layer on its surface consisting of a titanium compound, a magnesium compound and an electron donor. The advantages of the invention become more emphasized when using monocyclopentadienyl titaniumtrichloride as the titanium compound.
摘要翻译：传统的烯烃聚合催化剂体系中，其原催化剂基于固体载体和钛化合物及其表面上的电子给体的问题是通过载体的形态实现了不足够的高活性。此外，聚合中这种催化剂的活性时间太短。这些问题现在已经通过本发明的烯烃聚合催化剂体系解决了，其主催化剂包含固体载体和在其表面上由钛化合物，镁化合物和电子给体组成的层。当使用单环戊二烯基二氯化钛作为钛化合物时，本发明的优点变得更加突出。

4. 发明授权

US06225420B1 Procatalyst and process for the preparation of a multimodal ethylene polymer 失效
标题翻译：用于制备多峰乙烯聚合物的主催化剂和方法
公开(公告)号：US06225420B1
公开(公告)日：2001-05-01
申请号：US09093765
申请日：1998-06-09
申请人： Ulf Palmqvist , Solveig Johansson , Lars Thorn , Peter Idelmann , Anders Wahlström , Daniel Lindgren
发明人： Ulf Palmqvist , Solveig Johansson , Lars Thorn , Peter Idelmann , Anders Wahlström , Daniel Lindgren
IPC分类号： C08F234
CPC分类号： C08F297/08 , C08F10/00 , C08F210/16 , Y10S526/901 , C08F4/6555 , C08F2/001 , C08F210/08 , C08F2500/12 , C08F2500/07 , C08F2500/18 , C08F2500/24
摘要： A procatalyst and a process for the preparation of a multimodal ethylene homopolymer or copolymer by gas-phase polymerisation is described. The procatalyst used in the process is prepared by: a) contacting the support, preferably silica with a halogenating agent, preferably ethyl aluminium dichloride to obtain a first reaction product, b) contacting the first reaction product with a compound or mixture containing hydrocarbyl and one or more of hydrocarbyloxy, monoalkylamido, dialkylamido, carboxylato and alkoxymethoxy groups linked to magnesium, thereby to obtain a second reaction product (the procatalyst precursor), and c) contacting the second reaction product with a titanium compound, preferably TiCl4. In step a) the molar ratio of the alkyl metal chloride to the surface hydroxyls of the inorganic oxide is preferably between 1:1 and 10:1. In step b) the atomic ratio of the magnesium to the chlorine of the alkyl metal chloride of step a) preferably is between 1:1.5 to 1:2.5. In step c) the atomic ratio of magnesium of step b) to titanium preferably is between 1.4 and 5.
摘要翻译：描述了主催化剂和通过气相聚合制备多峰乙烯均聚物或共聚物的方法。该方法中使用的主催化剂是通过以下步骤制备的：a）将载体，优选二氧化硅与卤化剂，优选二氯化乙基铝接触，得到第一反应产物，b）使第一反应产物与含有烃基和一个或多个与镁连接的烃氧基，单烷基酰氨基，二烷基酰氨基，羧基和烷氧基甲氧基，从而得到第二反应产物（前催化剂前体），和c）使第二反应产物与钛化合物，优选TiCl 4接触。在步骤a）中，烷基金属氯化物与无机氧化物的表面羟基的摩尔比优选在1:1至10:1之间。在步骤b）中，步骤a）的烷基金属氯化物的镁与氯的原子比优选在1:1.5至1:2.5之间。在步骤c）中，步骤b）的镁与钛的原子比优选为1.4〜5。

5. 发明授权

US6034026A Procatalyst for ethylene polymer production, method for its preparation and use 失效
标题翻译：用于乙烯聚合物生产的主催化剂，其制备和使用方法
公开(公告)号：US6034026A
公开(公告)日：2000-03-07
申请号：US14674
申请日：1998-01-28
申请人： Thomas Garoff , Solveig Johansson , Ulf Palmqvist , Daniel Lindgren , Marita Sutela , Paivi Waldvogel , Arja Kostiainen
发明人： Thomas Garoff , Solveig Johansson , Ulf Palmqvist , Daniel Lindgren , Marita Sutela , Paivi Waldvogel , Arja Kostiainen
IPC分类号： C08F4/654 , B01J37/00 , C08F4/02 , C08F4/64 , C08F4/646 , C08F4/651 , C08F4/655 , C08F4/658 , C08F10/00 , C08F10/02 , C08F110/02 , C08F110/06 , B01J31/00
CPC分类号： C08F110/02 , C08F110/06
摘要： The invention relates to a process for the preparation of a high activity procatalyst for the production of ethylene polymers. The process according to the present invention comprises the following steps:(a) contacting the inorganic support with an alkyl metal chloride which is soluble in non-polar hydrocarbon solvents, and has the formula(R.sub.n MeCl.sub.3-n).sub.m (1)wherein R is a C.sub.1 -C.sub.20 aklyl group, Me is a metal of group III(13) of the periodic table, n=1 or 2 and m=1 or 2, to give a first reaction product,(b) contacting said first reaction product with a compound or mixture containing hydrocarbyl and hydrocarbyl oxide linked to magnesium which is soluble in non-polar hydrocarbon solvents, to give a second reaction product, and(c) contacting said second reaction product with a titanium compound which contains chlorine, having the formulaCl.sub.x Ti(OR.sup.IV).sub.4-x (2)wherein R.sup.IV is a C.sub.2 -C.sub.20 hydrocarbyl group and x is 3 or 4, to give said procatalyst.
摘要翻译：本发明涉及制备用于生产乙烯聚合物的高活性前催化剂的方法。根据本发明的方法包括以下步骤：（a）使无机载体与可溶于非极性烃溶剂的烷基金属氯化物接触，并具有式（RnMeCl 3-n）m（1）其中R为 C 1 -C 20亚烷基，Me是周期表III（13）的金属，n = 1或2，m = 1或2，得到第一反应产物，（b）使所述第一反应产物与与可溶于非极性烃溶剂的镁连接的烃基和烃基氧化物的化合物或混合物，得到第二反应产物，和（c）使所述第二反应产物与含有氯的钛化合物接触，所述钛化合物具有式Cl x Ti（ ORIV）4-x（2）其中RIV为C 2 -C 20烃基，x为3或4，得到所述前催化剂。

6. 发明授权

US6043326A Process for copolymerizing ethene and alpha-olefins 失效
标题翻译：乙烯和α-烯烃共聚方法
公开(公告)号：US6043326A
公开(公告)日：2000-03-28
申请号：US716298
申请日：1996-11-26
申请人： Leona Sillantaka , Ulf Palmqvist , Eero Iiskola , Susanna Koivujarvi
发明人： Leona Sillantaka , Ulf Palmqvist , Eero Iiskola , Susanna Koivujarvi
IPC分类号： C08F4/658 , C08F4/44 , C08F4/655 , C08F210/00 , C08F210/02 , C08F210/16
CPC分类号： C08F210/16
摘要： Ethene having a profitable .alpha.-olefin distribution and an .alpha.-olefin copolymer have been prepared with a process comprising reacting of at least the following components with each other:a) a procatalyst comprising a halogen compound of a transition metal in any of groups 4 to 8 of the periodic table of elements,b) a cocatalyst comprising an organohalogenous compound of a metal in group 2 or 3 of the periodic table of elements,c) ethene andd) one or more .alpha.-olefins copolymerizing with ethene, being characterised in that the organohalogenous compound of the metal in group 2 or 3 is prepared by reacting the organic compound of the metal in group 2 or 3 and a catalytically non-toxic halogen compound during copolymerization, or not earlier than 3 hours before copolymerization.
摘要翻译： PCT No.PCT / FI95 / 00152 Sec。 371日期1996年11月26日 102（e）日期1996年11月26日PCT 1995年3月23日PCT公布。出版物WO95 / 25758 日期1995年9月28日已经制备了具有有利的α-烯烃分布和α-烯烃共聚物的方法，该方法包括使至少以下组分彼此反应：a）包含过渡金属的卤素化合物的前催化剂元素周期表第4至8族中的任一个，b）包含元素周期表第2或3族中的金属的有机光致化合物的助催化剂，c）乙烯和d）一种或多种α-烯烃与乙烯，其特征在于组2或3中的金属的有机光致化合物通过在共聚合期间或不早于3小时内使第2或3族中的金属的有机化合物与催化无毒卤素化合物反应来制备共聚。

7. 发明授权

US5770540A Procatalyst for ethylene polymer production, method for its preparation and use 失效
标题翻译：用于乙烯聚合物生产的主催化剂，其制备和使用方法
公开(公告)号：US5770540A
公开(公告)日：1998-06-23
申请号：US492799
申请日：1995-06-20
申请人： Thomas Garoff , Solveig Johansson , Ulf Palmqvist , Daniel Lindgren , Marita Sutela , Paivi Waldvogel , Arja Kostiainen
发明人： Thomas Garoff , Solveig Johansson , Ulf Palmqvist , Daniel Lindgren , Marita Sutela , Paivi Waldvogel , Arja Kostiainen
IPC分类号： C08F4/06 , C08F4/655 , C08F110/02 , C08F110/06 , B01J31/00
CPC分类号： C08F4/6555 , C08F110/02 , C08F110/06
摘要： The invention relates to a procatalyst for the production of ethylene polymers, which procatalyst comprises an inorganic support, a chlorine compound carried on said support, a magnesium compound carried on said support, a titanium compound carried on said support, whereby the chlorine compound can be different from or the same as the magnesium compound and/or the titanium compound. The activity balance AB of the procatalyst in specified polymerization conditions, is AB>3.2 wherein AB=�(A+A'):2!.multidot.�log (MFR.sub.2 ':MFR.sub.2):(A-A')!, A means polymerization activity expressed an kg PE/g cat .multidot.h, MFR.sub.2 means the melt flow rate in g/min units at a load of 2,16 kg, according to the standard ISO 1133, the absence of the upper index ' means low melt flow rate polymerization and the presence of the upper index ' means high melt flow polymerization. This means that the catalyst activity is relatively independent of the presence of chain transfer agents.
摘要翻译：本发明涉及一种用于生产乙烯聚合物的前催化剂，其主催化剂包括无机载体，载体上携带的氯化合物，载体上的镁化合物，载于所述载体上的钛化合物，其中氯化合物可以是与镁化合物和/或钛化合物不同或相同。在规定的聚合条件下，前催化剂的活性平衡AB为AB> 3.2其中AB = [（A + A'）：2] x [log（MFR 2'：MFR 2）:( A-A'）]]，A表示聚合活性表示kg PE / g cat xh，MFR2是指根据ISO 1133标准，在2,16kg载荷下的熔体流动速率，单位为g / min，上限指数为“低熔体流动速率聚合”，上指数的存在意味着高熔体流动聚合。这意味着催化剂活性相对独立于链转移剂的存在。

8. 发明授权

US5494965A Process for manufacturing olefin polymers and products prepared by the process 失效
标题翻译：通过该方法制备烯烃聚合物和产品的方法
公开(公告)号：US5494965A
公开(公告)日：1996-02-27
申请号：US217510
申请日：1994-03-24
申请人： Ali Harlin , Ulf Palmqvist
发明人： Ali Harlin , Ulf Palmqvist
IPC分类号： C08F10/00 , C08L23/02 , C08L23/04 , C08L23/10 , C08L23/18
CPC分类号： C08F10/00 , C08L23/02 , C08L23/04 , C08L23/06
摘要： A process for manufacturing bimodal olefin polymers and copolymers having a ratio between low molecular weight fractions within the range of 40:60-70:30, by mixing under shear conditions 5-50 percent by weight of a low molecular weight unimodal polyolefin having a molecular weight (Mw) between 15,000-30,000, and 95-50 percent by weight of a bimodal polyolefin having a ratio between low molecular weight fractions and high molecular weight fractions within the range of 30:70-55:45. According to a preferred embodiment, there is used a multi-phase process including a loop reactor followed by a gas-phase reactor, wherein a part of the product coming out from the loop reactor is separated and combined with the bimodal product coming out from the gas-phase reactor.
摘要翻译：通过在剪切条件下混合5-50重量％的具有分子量的低分子量单峰聚烯烃的制备双峰烯烃聚合物和共聚物的方法，其具有在40:60-70:30的范围内的低分子量分数之间的比例重量（Mw）为15,000-30,000和95-50重量％的在30:70-55:45范围内的低分子量级分与高分子量级分之间的比例的双峰聚烯烃。根据优选实施方案，使用多相方法，其包括循环反应器，随后是气相反应器，其中从环管反应器出来的一部分产物被分离并与从该反应器出来的双峰产物组合气相反应器。

9. 发明授权

US5204303A Preparation and use of a new ziegler-natta catayst component 失效
标题翻译：制备和使用新的齐格勒 - 纳塔催化剂组分
公开(公告)号：US5204303A
公开(公告)日：1993-04-20
申请号：US759809
申请日：1991-09-16
申请人： Inkeri T. Korvenoja , Arja-Liisa Kostiainen , Fero I. Iiskola , Pekka J. E. Sormunen , Bill B. B. Gustatsson , Hilkka R. Knuuttila , Ulf Palmqvist
发明人： Inkeri T. Korvenoja , Arja-Liisa Kostiainen , Fero I. Iiskola , Pekka J. E. Sormunen , Bill B. B. Gustatsson , Hilkka R. Knuuttila , Ulf Palmqvist
IPC分类号： C08F10/00
CPC分类号： C08F10/00 , Y10S526/904
摘要： The invention relates to a method for the preparation of a supported procatalyst intended for the polymerization of olefines, in which particles are formed of magnesium dihalide and alcohol, the particles are reacted with an organic compound of a metal from the groups I-III, the thus obtained particulate product is activated by means of a titanium and/or vanadium compound and optionally a donor, and optionally a prepolymerization is carried out for the activated particles. A problem of such a method is how to form particles of magnesium dihalogenide and alcohol having a structure advantageous for the polymerization of olefins. The problem has in the present invention been solved so that the particles are formed by spray crystallizing (spray freezing) a mixture of magnesium dihalide and alcohol to complex particles of magnesium dihalide and alcohol. The hydroxyl content of the particles so obtained is much greater than earlier, which results in a much more active procatalyst than the preceding ones.
摘要翻译：本发明涉及一种用于制备用于聚合烯烃的负载型前催化剂的方法，其中颗粒由二卤化镁和醇形成，颗粒与来自I-III族的金属有机化合物反应，由此获得的颗粒产物通过钛和/或钒化合物和任选的供体活化，并且任选地对活化的颗粒进行预聚合。这种方法的问题是如何形成具有有利于烯烃聚合的结构的二卤化镁和醇的颗粒。解决了本发明中的问题，使得通过将二卤化镁和醇的混合物喷雾结晶（喷雾冷冻）到二卤化镁和醇的复合颗粒来形成颗粒。如此获得的颗粒的羟基含量远大于较早，这导致比前述催化剂更加活泼的前催化剂。

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