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21. 发明授权

US06200923B1 Polymerization catalyst composition containing magnesium, titanium, halogen, and carboxylic acid ester 有权
标题翻译：含有镁，钛，卤素和羧酸酯的聚合催化剂组合物
公开(公告)号：US06200923B1
公开(公告)日：2001-03-13
申请号：US09155446
申请日：1998-11-30
申请人： Thomas Garoff , Timo Leinonen , Sirpa Ala-Huikku
发明人： Thomas Garoff , Timo Leinonen , Sirpa Ala-Huikku
IPC分类号： B01J3100
CPC分类号： C08F10/00 , C07F7/003 , C08F10/06 , C08F110/06 , C08F210/06 , C08F4/651 , C08F4/6543 , C08F2500/18 , C08F2500/12 , C08F210/16
摘要： A novel soluble composition containing magnesium, titanium, a halogen and a carboxylic acid ester has been invented. The composition has mainly the composition according to Formula (I): (MgX32)xTiX44(R(COOR′)n)y (I) wherein X3 is a halogen, X4 is a halogen, R(COOR′)n is a carboxylic acid higher alkyl ester containing at least 8·n carbon atoms, wherein R is an n-valent substituted or unsubstituted C1-C34 hydrocarbon group, R′ is a C1-C20 alkyl group, and n is an integer from 1 to 4, x is between 0.5 and 4.0, and y is between 0.8/n and 2.4/n.
摘要翻译：已经发明了含有镁，钛，卤素和羧酸酯的新型可溶性组合物。该组合物主要具有式（I）的组成：其中X 3为卤素，X 4为卤素，R（COOR'）n为含有至少8.n个碳原子的羧酸高级烷基酯，其中R为 n价取代或未取代的C 1 -C 34烃基，R'为C 1 -C 20烷基，n为1至4的整数，x为0.5至4.0，y为0.8 / n至2.4 / n 。

22. 发明授权

US5767215A Coarse-grained polyolefin, its production method and a catalyst used in the method 失效
标题翻译：粗粒聚烯烃，其制备方法和该方法中使用的催化剂
公开(公告)号：US5767215A
公开(公告)日：1998-06-16
申请号：US468624
申请日：1995-06-06
申请人： Thomas Garoff , Timo Leinonen , Eero Iiskola
发明人： Thomas Garoff , Timo Leinonen , Eero Iiskola
IPC分类号： C08F4/654 , C08F10/00 , C08F110/06
CPC分类号： C08F110/06 , C08F10/00
摘要： The invention relates to a method for preparing polyolefins. In the polymerization, a procatalyst composition is being used, which has been prepared by contacting MgCl.sub.2, a lower alcohol, a titanium compound and a phthalic acid ester. The polyolefin is given the adequate coarseness by using a procatalyst of the said type, which has been prepared by carrying out a transesterification between the lower alcohol and the phthalic acid ester and by selecting dioctyl phthalate (DOP) as phthalic acid ester.
摘要翻译：本发明涉及一种制备聚烯烃的方法。在聚合反应中，使用主催化剂组合物，其通过使MgCl 2，低级醇，钛化合物和邻苯二甲酸酯接触而制备。通过使用所述类型的前催化剂，通过进行低级醇和邻苯二甲酸酯之间的酯交换并通过选择邻苯二甲酸二辛酯（DOP）作为邻苯二甲酸酯制备聚烯烃，得到足够的粗糙度。

23. 发明授权

US5472923A Preparation of a solid Ziegler catalyst by using a multi-functional, pivoting, inclinable reactor 失效
标题翻译：通过使用多功能，可旋转，可倾斜的反应器制备固体齐格勒催化剂
公开(公告)号：US5472923A
公开(公告)日：1995-12-05
申请号：US196225
申请日：1994-03-22
申请人： Jukka Koskinen , Thomas Garoff , Jarmo Louhelainen
发明人： Jukka Koskinen , Thomas Garoff , Jarmo Louhelainen
IPC分类号： B01D21/24 , B01J8/00 , B01J8/10 , B01J19/18 , C08F4/02 , C08F4/60 , C08F4/61 , C08F4/64 , C08F4/65 , C08F10/00 , B01J33/00 , B01J37/00
CPC分类号： B01J19/18 , B01D21/24 , B01J8/006 , B01J8/10 , C08F10/00 , B01J2219/00051 , B01J2219/00173 , B01J2219/00182 , B01J2219/185 , B01J2219/187 , Y10S502/514
摘要： A method for the preparation of a solid procatalyst suitable for the polymerization of olefins wherein the procatalyst comprises a transition metal compound reacted with a carrier by carrying out in the method the following consecutive steps: (a) feeding the transition metal compound and particles of the carrier into a vessel, which in its initial position has an essentially horizontal bottom sieve, (b) mixing and reacting the metal transitional compound and the particles of the carrier to produce raw procatalyst particles and a liquid reaction residue, (c) removing the liquid reaction residue through the bottom sieve of the vessel, (d) washing the raw procatalyst particles with a washing liquid, so that impurities in the raw procatalyst are removed through the bottom sieve, (e) drying the washed raw procatalyst particles by conducting an inert gas therethrough to give the solid procatalyst, and (f) removing the solid procatalyst from the vessel.
摘要翻译： PCT No.PCT / FI92 / 00323 Sec。 371日期：1994年3月22日 102（e）1994年3月22日PCT 1997年11月27日PCT公布。公开号WO93 / 11165 日期：1993年10月6日。一种制备适用于烯烃聚合的固体前催化剂的方法，其中前催化剂包括与载体反应的过渡金属化合物，该方法通过以下连续步骤进行：（a）过渡金属化合物和载体颗粒进入容器，其初始位置具有基本上水平的底部筛子，（b）将金属过渡化合物和载体的颗粒混合并反应以产生原始的原催化剂颗粒和液体反应残余物，（c）通过容器的底部筛子除去液体反应残渣，（d）用洗涤液洗涤原始催化剂颗粒，通过底部筛子除去原料前催化剂中的杂质，（e）干燥洗涤过的通过将惰性气体通过其中以产生固体前催化剂，和（f）从容器中除去固体前催化剂，从而生产原料催化剂颗粒。

24. 发明授权

US5436213A Procatalyst composition containing substituted maleic or fumaric acid esters as an electron donor for olefin polymerization 失效
标题翻译：含有取代的马来酸或富马酸酯作为烯烃聚合的电子给体的主催化剂组合物
公开(公告)号：US5436213A
公开(公告)日：1995-07-25
申请号：US66098
申请日：1993-08-02
申请人： Eero Iiskola , Katriina Mills , Thomas Garoff , Timo Leinonen
发明人： Eero Iiskola , Katriina Mills , Thomas Garoff , Timo Leinonen
IPC分类号： C08F4/654 , C08F4/60 , C08F4/65 , C08F10/00 , B01J31/00
CPC分类号： C08F10/00
摘要： It is known that an electron donor together with a compound of tetravalent titanium on a magnesium halide carrier is usable if it is a mono- or polyester of an unsaturated polycarboxylic acid in which at least two carboxyl groups are joined to contiguous carbon atoms which form double bonds. It has now been observed that activity and stereospecificity increase if at least one of the said carbon atoms, or a carbon atom joined thereto by a double bond, is substituted by a hydrocarbon group having 1-20 carbon atoms. Maleic and fumaric acid esters substituted with the said hydrocarbon group can be mentioned as examples.
摘要翻译： PCT No.PCT / FI92 / 00264 Sec。 371日期：1993年8月2日 102（e）日期1993年8月2日PCT提交1992年10月1日PCT公布。公开号WO93 / 07182 日期是1993年4月15日。已知如果电子供体与卤化镁载体上的四价钛化合物一起使用，如果它是至少两个羧基连接的不饱和多元羧酸的单酯或聚酯到形成双键的连续碳原子。现在已经观察到，如果至少一个所述碳原子或通过双键连接到其上的碳原子被具有1-20个碳原子的烃基取代，则活性和立体定向性增加。作为实例，可以提及被所述烃基取代的马来酸和富马酸酯。

25. 发明授权

US5234879A Method for the modification of catalysts intended for the polymerization of olefins 失效
标题翻译：用于烯烃聚合的催化剂的改性方法
公开(公告)号：US5234879A
公开(公告)日：1993-08-10
申请号：US983285
申请日：1992-11-30
申请人： Thomas Garoff , Timo Leinonen , Eero Iiskola
发明人： Thomas Garoff , Timo Leinonen , Eero Iiskola
IPC分类号： C08F4/649 , C08F10/00
CPC分类号： C08F10/00
摘要： When asymmetric olefins or a monomer mixture containing asymmetric monomers is polymerized by a catalyst composition containing esters of carboxylic acid e.g. as a so-called donor, and alcohol the ester group can be transesterified with the alcohol to an ester containing another alkyl group during the preparation and/or polymerization of the catalyst. This is advantageous particularly when an adduct of a so-called spray-crystallized Mg-halide and alcohol is used as the catalyst carrier, because the alkoxy group of the alcohol of the carrier and the alkoxy group of the ester of the donor can be transesterified and thus obtain the preferable effects of both esters on the run of the polymerization reaction. Hereby, a solvent having a high boiling point should be used as the intermediate agent, so that the transesterification reaction can take place. Most preferable have been found hydrocarbons having high boiling points, especially nonane and decane.
摘要翻译：当不对称烯烃或含有不对称单体的单体混合物通过含羧酸酯的催化剂组合物聚合时，作为所谓的供体，醇可以在催化剂的制备和/或聚合期间与醇酯交换成含有另一个烷基的酯。这是有利的，特别是当使用所谓的喷雾结晶的卤化镁和醇的加合物作为催化剂载体时，因为载体的醇的烷氧基和供体的酯的烷氧基可以被酯交换从而获得两种酯对聚合反应进行的优选效果。因此，应当使用具有高沸点的溶剂作为中间体，从而可以进行酯交换反应。已经发现最优选的是具有高沸点的烃，特别是壬烷和癸烷。

26. 发明申请

US20120095172A1 IMPROVED ETHYLENE POLYMERIZATION CATALYST COMPOSITION 审中-公开
标题翻译：改进的乙烯聚合催化剂组合物
公开(公告)号：US20120095172A1
公开(公告)日：2012-04-19
申请号：US13263173
申请日：2010-04-26
申请人： Thomas Garoff , Paivi Waldvogel , Kalle Kallio , Virginie Eriksson
发明人： Thomas Garoff , Paivi Waldvogel , Kalle Kallio , Virginie Eriksson
IPC分类号： C08F4/646 , C08F4/648 , C08F210/14 , C08F2/00 , C08F210/08
CPC分类号： C08F210/16 , C08F4/6555 , C08F210/08 , C08F2500/12 , C08F2500/18 , C08F2500/08
摘要： Ziegler-Natta catalyst composition capable of producing ethylene/alpha-olefins copolymers, particularly linear low density polyethylene; the composition having an improved stability of its behaviour during polymerization in respect to time. The Ziegler-Natta catalyst composition comprises: 1. Ziegler-Natta catalyst composition for the production of ethylene copolymers comprising A) a procatalyst, which procatalyst comprises a) an Al compound having the formula Al(alkyl)xCl3-x (I), where alkyl is an alkyl group with 1 to 12 and 0≦x≦3, b) a magnesium hydrocarbyloxy compound of formula Mg(OR1)2-n(R2)n (II), wherein each R1 and R2 is independently a C1-20 hydrocarbon residue which may optionally be substituted with halogen and 0≦n
摘要翻译：能够生产乙烯/α-烯烃共聚物，特别是线性低密度聚乙烯的齐格勒 - 纳塔催化剂组合物; 该组合物在聚合过程中相对于时间具有改进的其行为稳定性。齐格勒 - 纳塔催化剂组合物包括：1.用于生产乙烯共聚物的齐格勒 - 纳塔催化剂组合物，其包含A）前催化剂，其前体催化剂包含a）具有式Al（烷基）xCl 3-x（I）的Al化合物，其中烷基是具有1至12和0和nlE; x和nlE; 3，b）式Mg（OR 1）2-n（R 2）n（II）的镁烃氧基化合物的烷基，其中每个R 1和R 2独立地是C 1-20 可以任选被卤素取代的烃残基，n <2和c）式ClyTi（OR 3）4-y（III）的含氯钛化合物，其中R3是C2-20烃基，y是 1,2,3或4，化合物a），b）和c）负载在颗粒状无机载体上，B）式（Ⅳ）卤代烷基铝助催化剂（C 1 -C 4烷基）m-Al- X3-m，其中X是氯，溴，碘或氟，m是1或2。

27. 发明申请

US20110306737A1 MULTI-STAGE PROCESS FOR PRODUCING MULTI-MODAL ETHYLENE POLYMER COMPOSITION 审中-公开
公开(公告)号：US20110306737A1
公开(公告)日：2011-12-15
申请号：US13123106
申请日：2010-02-22
申请人： Thomas Garoff , Päivi Waldvogel , Kalle Kallio , Virginie Eriksson , Aki Aittola , Esa Kokko
发明人： Thomas Garoff , Päivi Waldvogel , Kalle Kallio , Virginie Eriksson , Aki Aittola , Esa Kokko
IPC分类号： C08F10/02 , C08F2/01
CPC分类号： C08F10/00 , C08F110/02 , C08F210/16 , Y02P20/52 , C08F4/6357 , C08F4/685 , C08F2/001 , C08F2500/07 , C08F2500/12 , C08F2500/05 , C08F2500/18 , C08F210/14 , C08F2500/08
摘要： Multi-stage polymerization process for the production of a multi-modal linear low density polyethylene in at least two staged reactors connected in series comprising at least (i) polymerizing in a first slurry phase stage ethylene monomers and optionally one or more alpha-olefin comonomers, in the presence of a Ziegler-Natta polymerization catalyst system to obtain a first polyethylene fraction component (A) (ii) polymerizing in a second gas or slurry phase stage ethylene monomers and one or more alpha-olefin comonomers, in the presence of a Ziegler-Natta polymerization catalyst system to obtain a second polyethylene fraction component (B), whereby the Ziegler-Natta polymerization catalyst system comprises 1) a solid procatalyst formed by contacting at least: a) a Mg-alcoholate complex of the formula (I): Mg(OR1)2-n(R1)n, wherein each R1 independently represents a C1-C20 hydrocarbyl group and 0≦n

28. 发明申请

US20110263801A1 MULTI-STAGE PROCESS FOR PRODUCING MULTI-MODAL LINEAR LOW DENSITY POLYETHYLENE 有权
标题翻译：用于生产多模式线性低密度聚乙烯的多级方法
公开(公告)号：US20110263801A1
公开(公告)日：2011-10-27
申请号：US13126496
申请日：2010-02-22
申请人： Thomas Garoff , Päivi Waldvogel , Kalle Kallio , Virginie Eriksson , Aki Aittola , Esa Kokko
发明人： Thomas Garoff , Päivi Waldvogel , Kalle Kallio , Virginie Eriksson , Aki Aittola , Esa Kokko
IPC分类号： C08F10/02 , C08F4/685 , C08F2/34 , C08F2/12
CPC分类号： C08F10/00 , C08F110/02 , C08F210/16 , C08F2410/03 , Y10T428/139 , C08F4/6357 , C08F4/685 , C08F2/001 , C08F2500/07 , C08F2500/12 , C08F2500/05 , C08F2500/18 , C08F210/14 , C08F2500/08
摘要： Multi-stage polymerization process for the production of a multi-modal linear low density polyethylene in at least two staged reactors connected in series comprising at least (i) polymerizing in a first slurry phase stage ethylene monomers and optionally one or more alpha-olefin comonomers, in the presence of a Ziegler-Natta polymerization catalyst system to obtain a first polyethylene fraction component (A) (ii) polymerizing in a second gas or slurry phase stage ethylene monomers and one or more alpha-olefine comonomers, in the presence of a Ziegler-Natta polymerization catalyst system to obtain a second polyethylene fraction component (B), whereby the Ziegler-Natta polymerization catalyst system comprises: 1) a solid procatalyst formed by contacting at least: a) a Mg-alcoholate complex of the formula (I): Mg(OR1)2-n(R1)n, wherein each R1 independently represents a C1-C20 hydrocarbyl group and 0
摘要翻译：用于在至少两个串联反应器中连续串联生产多模式线性低密度聚乙烯的多级聚合方法，包括至少（i）在第一浆料相阶段聚合乙烯单体和任选的一种或多种α-烯烃共聚单体在齐格勒 - 纳塔聚合催化剂体系存在下，得到第一聚乙烯级分组分（A）（ⅱ）在第二种气相或淤浆相阶段中聚合乙烯单体和一种或多种α-烯烃共聚单体，在齐格勒 - 纳塔聚合催化剂体系，以获得第二聚乙烯部分组分（B），由此齐格勒 - 纳塔聚合催化剂体系包括：1）通过使至少与下式接触形成的固体前催化剂：a）式）：Mg（OR 1）2-n（R 1）n，其中每个R 1独立地表示C 1 -C 20烃基且0

29. 发明授权

US07608555B2 Method for the preparation of olefin polymerization catalysts 失效
标题翻译：烯烃聚合催化剂的制备方法
公开(公告)号：US07608555B2
公开(公告)日：2009-10-27
申请号：US11759086
申请日：2007-06-06
申请人： Thomas Garoff , Kari Pesonen , Päivi Waldvogel , Timo V. Laine , Peter Denifl , Jarmo Lindroos
发明人： Thomas Garoff , Kari Pesonen , Päivi Waldvogel , Timo V. Laine , Peter Denifl , Jarmo Lindroos
IPC分类号： C08F4/02 , C08F4/642
CPC分类号： C08F10/00 , C08F4/651 , C08F4/6546 , C08F4/6555
摘要： The present invention relates to a process for the production of catalysts, particularly of Ziegler-Natta type of catalysts for olefin polymerisation, to the catalysts as such, and to their use in polymerising olefins.
摘要翻译：本发明涉及用于生产催化剂，特别是用于烯烃聚合的齐格勒 - 纳塔型催化剂催化剂的方法，以及它们在烯烃聚合中的用途。

30. 发明申请

US20080275200A1 Production Of Olefin Polymerization Catalysts 有权
标题翻译：烯烃聚合催化剂的生产
公开(公告)号：US20080275200A1
公开(公告)日：2008-11-06
申请号：US12044350
申请日：2008-03-07
申请人： Peter Denifl , Erik Van Praet , Michael Bartke , Marita Oksman , Marja Mustonen , Thomas Garoff , Kari Pesonen
发明人： Peter Denifl , Erik Van Praet , Michael Bartke , Marita Oksman , Marja Mustonen , Thomas Garoff , Kari Pesonen
IPC分类号： C08F4/76 , C07F7/00
CPC分类号： C08F10/00 , C08F4/65925 , C08F4/65927 , C08F10/02 , C08F110/02 , Y10S526/943 , C08F4/65912 , C08F2/22
摘要： The invention provides a process for producing an olefin polymerisation catalyst, comprising an organometallic compound of a transition metal or of an actinide or lanthanide, in the form of solid catalyst particles, comprising forming a liquid/liquid emulsion system which comprises a solution of one or more catalyst components dispersed in a solvent immiscible therewith; and solidifying said dispersed phase to convert said droplets to solid particles comprising the catalyst and optionally recovering said particles.
摘要翻译：本发明提供了一种生产烯烃聚合催化剂的方法，其包括固体催化剂颗粒形式的过渡金属或锕系元素或镧系元素的有机金属化合物，其包括形成液体/液体乳液体系，其包含一种或多种更多的催化剂组分分散在与其不混溶的溶剂中; 并固化所述分散相以将所述液滴转化成包含催化剂的固体颗粒，并任选地回收所述颗粒。

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