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1. 发明申请

WO1993011165A1 PREPARATION OF A SOLID ZIEGLER CATALYST BY USING A MULTIFUNCTIONAL, PIVOTING, INCLINABLE REACTOR AND THE EQUIPMENT FOR THIS 审中-公开
标题翻译：通过使用多功能，投放式，不可逆的反应器及其设备来制备固体齐纳尔催化剂
公开(公告)号：WO1993011165A1
公开(公告)日：1993-06-10
申请号：PCT/FI1992000323
申请日：1992-11-27
申请人： NESTE OY , KOSKINEN, Jukka , GAROFF, Thomas , LOUHELAINEN, Jarmo
发明人： NESTE OY
IPC分类号： C08F04/02
CPC分类号： B01J19/18 , B01D21/24 , B01J8/006 , B01J8/10 , B01J2219/00051 , B01J2219/00173 , B01J2219/00182 , B01J2219/185 , B01J2219/187 , C08F10/00 , Y10S502/514 , C08F4/60 , C08F4/651 , C08F4/6545 , C08F110/06 , C08F2500/12
摘要： The invention relates to a method and equipment for the preparation of such a solid catalyst suitable for olefin polymerization that comprises a transition metal compound reacted for a carrier. In the method the reagents mentioned are fed into a reaction vessel (1), reacted to raw procatalyst, after which the liquid reaction residue is removed through a bottom sieve (3) in the vessel (1), the raw procatalyst obtained is washed with a washing liquid, which is also removed through the bottom sieve (3), after which the raw procatalyst is dried and removed from the vessel (1). The problem has previously been that the procatalyst product contains too much harmful, finely-divided material. Now, this disadvantage has been removed by furnishing the vessel (1) with a tilting means (4), whereby the reaction residue liquid and/or the washing liquid along with its impurities can be removed by keeping the vessel (1) tilted to an acute angle with respect to its vertical axis, allowing the raw procatalyst settle to cover the tilted side part of the bottom sieve (3), and by filtering decanting the liquid away from the vessel (1) through the part of the bottom sieve (3) that is not covered by raw procatalyst.
摘要翻译：本发明涉及一种制备适用于烯烃聚合的固体催化剂的方法和设备，其包括对载体反应的过渡金属化合物。在所述方法中，将所述试剂加入到反应容器（1）中，与原始催化剂反应，然后通过容器（1）中的底部筛（3）除去液体反应残余物，将得到的原料前催化剂用洗涤液，也通过底部筛子（3）除去，然后干燥原料主催化剂并从容器（1）中取出。以前的问题是，前催化剂产品含有太多有害的细碎材料。现在，通过用容器（1）提供倾斜装置（4）已经消除了这个缺点，由此可以通过将容器（1）倾斜到相对于其垂直轴线具有锐角，允许原始催化剂沉降以覆盖底部筛（3）的倾斜侧部分，并且通过过滤将液体从容器（1）倾倒通过底部筛（3）的一部分），不包括原始催化剂。

2. 发明申请

WO1992021705A1 METHOD FOR PREPARING SOLID CARRIER PARTICLES OF EQUAL SIZE FOR POLYMERIZATION CATALYST USING ROTATING ATOMIZING MEANS 审中-公开
标题翻译：使用旋转原子化方法制备聚合催化剂的等尺寸固体载体颗粒的方法
公开(公告)号：WO1992021705A1
公开(公告)日：1992-12-10
申请号：PCT/FI1992000170
申请日：1992-05-29
申请人： NESTE OY , KOSKINEN, Jukka , LOUHELAINEN, Jarmo
发明人： NESTE OY
IPC分类号： C08F04/02
CPC分类号： C08F10/00 , C08F4/022
摘要： The active carrier particles of even size of the polymerization catalyst are prepared so that a melt of a complex composition is provided having the formula (I): MgCl2 nROH mED, in which ROH depicts an aliphatic alcohol, R is a C1-C6 alkyl, ED depicts an electron donor, n is 1 to 6 and m is 0 to 1; the melt provided is fed to a nozzle (4); the melt is sprayed from the nozzle (4) to the spraying area (5), in which it is divided into fine melt droplets and possibly partly solidifies; the possibly partly solidified melt particles are transferred to a cooled crystallization area (6), where they crystallize to solid carrier particles; and the solid carrier particles are recovered. The melt mentioned is sprayed through a nozzle (4), which is rotated or which has attached to it a member that rotates and throws melt outwards from the rotating center to the spraying area (5).
摘要翻译：制备具有均匀尺寸的聚合催化剂的活性载体颗粒，使得提供具有式（I）的配合物组合物的熔体：MgCl 2 nROH mED，其中ROH表示脂族醇，R是C1-C6烷基， ED描绘电子给体，n为1至6，m为0至1; 所提供的熔体被供给到喷嘴（4）; 熔体从喷嘴（4）喷射到喷涂区域（5），其中它被分成细熔液滴并且可能部分地固化; 可能部分固化的熔体颗粒被转移到冷却的结晶区域（6），在那里它们结晶成固体载体颗粒; 并回收固体载体颗粒。所提到的熔体通过喷嘴（4）喷射，喷嘴（4）旋转或附接到其上旋转并从旋转中心向喷出的喷射区域（5）向外熔化的部件。

3. 发明申请

WO1993011166A1 METHOD FOR THE PREPARATION OF A PARTICULATE CARRIER FOR A POLYMERIZATION CATALYST 审中-公开
标题翻译：用于制备聚合催化剂的颗粒载体的方法
公开(公告)号：WO1993011166A1
公开(公告)日：1993-06-10
申请号：PCT/FI1992000324
申请日：1992-11-27
申请人： NESTE OY , KOSKINEN, Jukka , GAROFF, Thomas
发明人： NESTE OY
IPC分类号： C08F04/02
CPC分类号： C08F10/00 , C08F4/6543 , C08F4/022
摘要： The invention relates to a method for preparing a particulate carrier for an olefin polymerization procatalyst comprising a transition metal compound reacted for a carrier. In the method a melt Mg Cl2-CH5OH-complex is provided containing in the average 3.3 to 5.5 C2H5OH-molecules as per each MgCl2-molecule, the melt MgCl2-complex is sprayed through a nozzle dispersing it into a chamber, wherein a particulate carrier is formed of it and the ready particulate carrier is removed from the chamber. In the methods known so far difficulties have been encountered in endeavours to produce a carrier having an optimal C2H5OH content. In this invention the problems have been solved by removing by the aid of heat so much C2H5OH from the MgCl2-CH5OH-complex in connection with the spraying that the particulate carrier obtained will continue at the average 2.0 to 3.2 C2H5OH molecules as per each MgCl2 molecule. Such a carrier has a suitable C2H5OH content and a good morphology and spraying it does not raise any difficulties.
摘要翻译：本发明涉及一种制备用于烯烃聚合主催化剂的颗粒载体的方法，其包括与载体反应的过渡金属化合物。在该方法中，根据每个MgCl 2分子，提供含有平均3.3至5.5个C 2 H 5 OH分子的熔融MgCl 2 -CH 5 OH络合物，熔融MgCl 2 - 络合物通过将其分散到室中的喷嘴喷雾，其中颗粒载体由其形成，并且将容器颗粒载体从室中移出。迄今为止已知的方法已经遇到难以产生具有最佳C2H5OH含量的载体的方法。在本发明中，通过加热除去MgCl 2 -CH 5 OH络合物中的多少C 2 H 5 OH与喷雾相结合，已经解决了这些问题，所得到的颗粒载体将按每个MgCl 2分子在平均2.0-3.2的C2H5OH分子上继续。这种载体具有合适的C2H5OH含量和良好的形态和喷雾性，不会造成任何困难。

4. 发明申请

WO1993011164A1 METHOD FOR THE PREPARATION OF AN OLEFIN POLYMERIZATION CATALYST CONSISTING OF PARTICLES OF EQUAL SIZE 审中-公开
标题翻译：制备均匀颗粒颗粒的烯烃聚合催化剂的方法
公开(公告)号：WO1993011164A1
公开(公告)日：1993-06-10
申请号：PCT/FI1992000322
申请日：1992-11-27
申请人： NESTE OY , GAROFF, Thomas , KOSKINEN, Jukka
发明人： NESTE OY
IPC分类号： C08F04/02
CPC分类号： C08F10/00 , C08F4/6543
摘要： In the invention a particular procatalyst composition intended for the polymerization of olefins is prepared by reacting the carrier particles consisting of a MgCl2-C2H5OH-complex with TiCl4. When the method is applied into pilot-scale it was noticed that the procatalyst composition obtained produced olefin polymer, the finely-divided material portion of which was deterioratingly high. This was caused by the fact that the procatalyst composition particles had decomposed to finely-divided material during the synthesis, which was then in the polymerization repeated in the polymer structure due to the so-called replica phenomenon. In the invention it has unexpectedly been noticed that the breaking of the carrier particles is not a result of e.g. mechanical strain but of the fact that when the carrier particles react with the TiCl4 a heavy discharge of hydrogen chloride is first occurring as a result of the reaction which breaks the carrier particles. The carrier particles can, according to the invention, be maintained undamaged during the reaction by distributing the release in the reaction or from the reaction of the hydrogen chloride created in the reaction to a molar velocity not exceeding the fivefold value of the molar mean velocity of the release. This is achieved among other things by adding reagents unusually slowly, by using lower temperatures and heating velocities, by intensifying the agitation, by using an overpressure and/or by conducting diluting inert gas into the reaction mixture.
摘要翻译：在本发明中，用于烯烃聚合的特定主催化剂组合物是通过使由MgCl 2 -C 2 H 5 O-络合物组成的载体颗粒与TiCl 4反应来制备的。当该方法应用于中试规模时，注意到获得的主催化剂组合物产生的烯烃聚合物，其细碎材料部分劣化。这是由于前催化剂组合物颗粒在合成过程中分解成细碎的材料，然后由于所谓的复制现象而在聚合物结构中重复聚合。在本发明中，已经意外地注意到，载体颗粒的破坏不是例如，机械应变，但是当载体颗粒与TiCl 4反应时，由于引起载体颗粒的反应的结果，首先发生重的氯化氢排放。根据本发明，载体颗粒可以在反应期间通过在反应中分配释放或从反应中产生的氯化氢的反应分散到不超过摩尔平均速度的五倍值的摩尔速度发布。通过使用较低的温度和加热速度，通过使用过压和/或通过将惰性气体稀释到反应混合物中来强化搅拌，实现了异常缓慢的添加试剂。

5. 发明申请

WO1993019100A1 A POLYMERIZATION CATALYST CARRIER PREPARED BY SPRAY CRYSTALLIZATION 审中-公开
标题翻译：通过喷雾结晶制备的聚合催化剂载体
公开(公告)号：WO1993019100A1
公开(公告)日：1993-09-30
申请号：PCT/FI1993000116
申请日：1993-03-23
申请人： NESTE OY , KOSKINEN, Jukka , JOKINEN, Petri
发明人： NESTE OY
IPC分类号： C08F04/02
CPC分类号： B01J37/32 , B01J19/088 , B01J19/26 , B01J37/0045 , B01J2219/00119 , B01J2219/00121 , B01J2219/00123 , B01J2219/00159 , C08F10/00 , C08F4/022
摘要： When particulate carriers are prepared for olefin polymerization procatalysts that comprise a transition metal compound reacted upon the carrier, the problem is to achieve particles, the particle size, particle size distribution and particle form, i.e. the morphology, of which is suitable. These problems have been solved in the present invention by a method in which: (a) a heated melt of a complex compound is provided having the formula (I): MgC12.nROH.mED in which ROH depicts a lower (C1-6) aliphatic alcohol, ED depicts an electron donor, n is 1 to 6 and m is 0 to 1, (b) the provided heated melt is fed to a nozzle atomizing it, (c) the melt to be atomized is spayed from said nozzle into a chamber, where it is distributed in the form of atomized melt and then solidified to fine carrier particles and (d) the fine carrier particles are recovered. During this process an electric charge is fed into the melt to be atomized or has been atomized, which decreases the surface tension of the solidified melt and prevents the agglomeration of the formed droplets. The charge can be achieved by arranging in connection with the nozzle an electrode, which together with, for example, the grounded melt forms a static electric couple.
摘要翻译：当为包含过渡金属化合物在载体上反应的烯烃聚合原催化剂制备颗粒载体时，问题是实现颗粒，颗粒尺寸，粒度分布和颗粒形式，即其形态是合适的。这些问题已经通过以下方法解决了：（a）提供了具有式（I）的配位化合物的加热熔体：其中ROH表示低级（C1-6）脂族醇，ED表示电子给体，n为1至6，m为0至1，（b）将所提供的加热熔体进料到雾化雾化器的喷嘴中，（c）待雾化的熔体从所述喷嘴喷射到一个室，其中以雾化的熔体的形式分布，然后固化成细小的载体颗粒，（d）回收细的载体颗粒。在该过程中，将电荷送入熔体中以雾化或已被雾化，这降低了凝固熔体的表面张力并防止形成的液滴的聚集。可以通过与喷嘴结合设置电极来实现电荷，电极与例如接地熔体一起形成静电耦合。

6. 发明申请

WO1992016747A1 METHOD FOR THE DOSAGE OF A FLUIDIZED POLYMERIZATION CATALYST INTO A POLYMERIZATION REACTOR 审中-公开
标题翻译：将聚合催化剂流化成聚合反应器的方法
公开(公告)号：WO1992016747A1
公开(公告)日：1992-10-01
申请号：PCT/FI1992000080
申请日：1992-03-20
申请人： NESTE OY , KOSKINEN, Jukka , NYFORS, Klaus , LESKINEN, Pauli
发明人： NESTE OY
IPC分类号： F04B07/06
CPC分类号： B01J8/003 , B01J8/002 , B01J8/0035 , F04B7/06
摘要： The dosage pump according to the invention comprises a cylinder (2), a piston (4) moving back and forth in it and openable and closable inlet (5) and outlet (6) opening in the piston-swept space (3). The opening and closing of the openings mentioned are carried out by an intermediate pipe (7) arranged movably, and with respect thereto tightly, between the cylinder (2) and the mantles of the piston (4). The transmission opening (8) of the intermediate pipe (7) is transferred by moving the intermediate pipe (7) upon the inlet (5) and the outlet (6) opening, the whole surface of the intermediate pipe always covering one of the inlet (5) and outlet (6) openings mentioned. The dosage pump mentioned can preferably be applied for the dosage of hard-flowing substances, e.g. for feeding solid catalyst or wax into olefin polymerization reactor.
摘要翻译：根据本发明的剂量泵包括气缸（2），在其中前后移动的活塞（4）和在活塞扫掠空间（3）中开口的可开启和关闭的入口（5）和出口（6）。所述开口的打开和关闭由中间管道（7）进行，所述中间管道（7）在所述气缸（2）和所述活塞（4）的外壳之间可移动地并相对于其紧密配置。通过在入口（5）和出口（6）开口处移动中间管（7）来转移中间管（7）的传动开口（8），中间管的整个表面总是覆盖入口（5）和出口（6）开口。所提及的剂量泵可以优选用于硬流动物质的剂量，例如用于将固体催化剂或蜡进料到烯烃聚合反应器中。

7. 发明申请

WO1993007182A1 A PROCATALYST COMPOSITION CONTAINING SUBSTITUTED MALEIC OF FUMARIC ACID ESTERS AS ELECTRON DONOR FOR OLEFIN POLYMERIZATION 审中-公开
标题翻译：含有作为烯烃聚合的电子助剂的取代的马来酸酐的方法组合物
公开(公告)号：WO1993007182A1
公开(公告)日：1993-04-15
申请号：PCT/FI1992000264
申请日：1992-10-01
申请人： NESTE OY , IISKOLA, Eero , MILLS, Katriina , GAROFF, Thomas , LEINONEN, Timo
发明人： NESTE OY
IPC分类号： C08F04/65
CPC分类号： C08F10/00 , C08F4/651
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：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，如果它是不饱和多元羧酸的单酯或聚酯，其中至少两个羧基连接成形成双重的连续碳原子债券。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。

8. 发明申请

WO1993007181A1 A PROCATALYST COMPONENT BASED ON A TRANSITION METAL COMPOUND ON A CARRIER OF MAGNESIUM CHLORIDE AND MANGANESE HALIDE 审中-公开
标题翻译：基于过渡金属化合物的氯化镁和锰黑的载体的处理组分
公开(公告)号：WO1993007181A1
公开(公告)日：1993-04-15
申请号：PCT/FI1992000265
申请日：1992-10-01
申请人： NESTE OY , GAROFF, Thomas , LEINONEN, Timo , IISKOLA, Eero
发明人： NESTE OY
IPC分类号： C08F04/60
CPC分类号： C08F10/00 , C08F110/06 , C08F4/6574 , C08F4/02 , C08F4/695 , C08F2500/15 , C08F2500/12 , C08F2500/24
摘要： Olefin polymerization catalysts the procatalyst component of which comprises a transition-metal compound on a magnesium chloride support material are known to all. Now the procatalyst component has been improved by incorporating a manganese (II) halide into it at a rate of at minimum approx. 0.1 % and at maximum approx. 50 % of the total molar amount of magnesium chloride and manganese (II) halide. The new polymerization catalyst has, among other things, the excellent special property that it yields a polyolefin with a broad molecular weight distribution.
摘要翻译：烯丙基聚合催化剂，其催化剂组分包含在氯化镁载体材料上的过渡金属化合物是已知的。现在通过在其中以最低约5％的速率掺入卤化锰（II）来改进前催化剂组分。 0.1％，最大约氯化镁和卤化锰（II）的总摩尔量的50％。新的聚合催化剂尤其具有优异的特性，即其产生具有宽分子量分布的聚烯烃。

9. 发明申请

WO1993005078A1 A GRANULAR CATALYST COMPONENT FOR POLYMERIZING OLEFINS, ITS USAGE IN THE POLYMERIZATION OF OLEFINS AND A METHOD FOR ITS PREPARATION 审中-公开
标题翻译：用于聚合烯烃的颗粒催化剂组分及其在烯烃聚合中的应用及其制备方法
公开(公告)号：WO1993005078A1
公开(公告)日：1993-03-18
申请号：PCT/FI1992000237
申请日：1992-09-07
申请人： NESTE OY , GAROFF, Thomas , LEINONEN, Timo , METSÄLÄ, Olli
发明人： NESTE OY
IPC分类号： C08F04/02
CPC分类号： C08F10/00 , C08F4/6143
摘要： The invention relates to a granular catalyst component for polymerizing olefins, its usage in the polymerization of olefins and a method for its preparation. A granular catalyst component for polymerization catalysts of olefins, which contain one or more catalytically active transition metal compounds belonging to the groups IV-VIII of the periodic system and combined with a carrier as well as optionally one or more compounds acting as a medium or an electron donor. The catalyst component is formed by layers of particles containing the constituents of the catalyst component essentially smaller than the desired granular size by repeatedly layering on top of the particles a solution or a suspension containing the constituents of said catalyst component, until the desired granular size is obtained.
摘要翻译：本发明涉及用于聚合烯烃的粒状催化剂组分，其在烯烃聚合中的用途及其制备方法。一种用于烯烃聚合催化剂的颗粒状催化剂组分，其含有一种或多种属于周期系统的基团IV-VIII的催化活性过渡金属化合物，并与载体组合，以及任选的一种或多种作为介质的化合物或电子给体。催化剂组分由含有催化剂组分成分基本上小于所需颗粒尺寸的颗粒层形成，通过在颗粒的顶部上重复层叠含有所述催化剂组分的组分的溶液或悬浮液，直到所需的颗粒尺寸为获得。

10. 发明申请

WO1992019658A1 COARSE GRAINED POLYOLEFIN, PRODUCTION THEREOF AND A PROCATALYST CONTAINING A TRANSESTERIFICATION PRODUCT BETWEEN A LOWER ALCOHOL AND DIOCTYLPHTHALATE USED THEREFORE 审中-公开
标题翻译：粗粒状聚烯烃，其生产方法和含有下列醇类和二烃基酯之间的过渡产物的方法
公开(公告)号：WO1992019658A1
公开(公告)日：1992-11-12
申请号：PCT/FI1992000082
申请日：1992-03-23
申请人： NESTE OY , GAROFF, Thomas , LEINONEN, Timo , IISKOLA, Eero
发明人： NESTE OY
IPC分类号： C08F10/00
CPC分类号： C08F110/06 , C08F10/00 , C08F4/651 , C08F4/6543 , C08F2500/18 , C08F2500/24
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 MgCl2, 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。

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