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1. 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。

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

WO1992011296A1 A METHOD FOR THE PREPARATION OF A POLYMERIZING CATALYST COMPONENT, A POLYMERIZING CATALYST COMPONENT PREPARED BY THE METHOD AND ITS USE 审中-公开
标题翻译：一种聚合催化剂组分的制备方法，该方法制备的聚合催化剂组分及其用途
公开(公告)号：WO1992011296A1
公开(公告)日：1992-07-09
申请号：PCT/FI1991000391
申请日：1991-12-17
申请人： NESTE OY , GUSTAFSSON, Bill , KOSTIAINEN, Arja , SORMUNEN, Pekka
发明人： NESTE OY
IPC分类号： C08F04/02
CPC分类号： C08F10/00 , C08F4/6565 , C08F4/6555
摘要： The invention relates to a process for the preparation of a solid procatalyst composition of catalyst system for the polymerization of olefins wherein a magnesium halide such as magnesium chloride is dissolved and/or suspended into an alkyl ester of a monocarboxylic acid such as ethyl acetate, impregnated to a carrier, treated with an organometallic compound or a silicon compound and thereafter with a transition metal compound. The invention also relates to a procatalyst composition and its use together with a cocatalyst for the polymerization of olefins. The activity has been enhanced according to the invention by the use of a carrier containing hydroxyl groups, which carrier is kept at a temperature of at most about 200 DEG C prior to the impregnation so that the hydroxyl groups are retained in the carrier to an essential extent until the impregnation step. The carrier is preferably silica which is treated thermally at 100-200 DEG C so that the water present is removed but the hydroxyl groups are retained to a considerable extent. The organometal compound is preferably an aluminumalkyl compound such as triethylaluminum, and the transition metal compound is preferably titanium tetrachloride.
摘要翻译：本发明涉及一种制备用于烯烃聚合的催化剂体系的固体前催化剂组合物的方法，其中将卤化镁如氯化镁溶解和/或悬浮于单羧酸如乙酸乙酯的烷基酯中，浸渍与载体接触，用有机金属化合物或硅化合物处理，然后用过渡金属化合物处理。本发明还涉及前催化剂组合物及其与烯烃聚合用助催化剂的使用。通过使用含有羟基的载体，根据本发明已经增强了活性，该载体在浸渍之前保持在至多约200℃的温度，使得羟基保留在载体中成为必需的直到浸渍步骤。载体优选二氧化硅，其在100-200℃下热处理，以便除去存在的水，但羟基保留在相当大的程度上。有机金属化合物优选为三乙基铝等铝烷基化合物，过渡金属化合物优选为四氯化钛。

4. 发明申请

WO1991009881A1 PROCESS FOR PREPARATION OF A PROCATALYST COMPOSITION FOR POLYMERIZATION OF OLEFINS AND USE OF THE COMPOSITION 审中-公开
标题翻译：用于制备烯烃聚合的方法组合物的方法和组合物的使用
公开(公告)号：WO1991009881A1
公开(公告)日：1991-07-11
申请号：PCT/FI1990000314
申请日：1990-12-27
申请人： NESTE OY , ANDELL, Ove
发明人： NESTE OY
IPC分类号： C08F04/02
CPC分类号： C08F10/00 , C08F4/6567 , C08F4/6555
摘要： The invention relates to a process for preparation of a procatalyst for polymerization of olefins wherein a metal-containing complex compound or mixture of compounds is applicated into a porous, particulate carrier and is chlorinated with a suitable chlorinating agent. The invention also relates to the use of the prepared procatalyst composition together with a co-catalyst for polymerization or copolymerization of olefins. The invention is characterized in that magnesium or its compound, a titanium compound, aluminum or its compound and, optionally, a compound comprising a hydroxyl group are reacted with each other so that an alkoxide or alkylalkoxide solution containing said metals in an inert solvent is obtained, which solution is impregnated into the carrier at a single step, whereafter the extra solvent is removed. The carrier can be an inorganic oxide such as silica, from which the free hydroxyl groups have been removed, magnesium, titanium and aluminum compounds can be organic, the compound comprising a hydroxyl group can be an alcohol and the chlorination agent can be e.g. a suitable organic aluminum-chloride. The impregnated solution according to the invention can be provided by a simple mixing and the morphology and polymerization activity of the obtained procatalyst composition have proved to be good.
摘要翻译：本发明涉及一种制备用于烯烃聚合的前催化剂的方法，其中将含金属络合物或化合物的混合物应用于多孔的颗粒载体中，并用合适的氯化剂进行氯化。本发明还涉及制备的前催化剂组合物与助催化剂在烯烃聚合或共聚中的用途。本发明的特征在于，镁或其化合物，钛化合物，铝或其化合物以及任选的包含羟基的化合物彼此反应，从而获得在惰性溶剂中含有所述金属的醇盐或烷基醇盐溶液，将该溶液在一个步骤中浸渍到载体中，然后除去额外的溶剂。载体可以是诸如二氧化硅的无机氧化物，其中游离羟基已经被除去，镁，钛和铝化合物可以是有机的，包含羟基的化合物可以是醇，氯化剂可以是例如乙酸。合适的有机氯化铝。根据本发明的浸渍溶液可以通过简单的混合来提供，并且所得前催化剂组合物的形态和聚合活性证明是良好的。

5. 发明申请

WO1997045459A1 MODIFIED POLYSILOXANE CATALYSTS AND A METHOD OF USING THE SAME 审中-公开
标题翻译：改性聚硅氧烷催化剂及其使用方法
公开(公告)号：WO1997045459A1
公开(公告)日：1997-12-04
申请号：PCT/US1997008982
申请日：1997-05-28
申请人： LYONDELL PETROCHEMICAL COMPANY
发明人： LYONDELL PETROCHEMICAL COMPANY , NAGY, Sandor , TYRELL, John, A. , CRIBBS, Leonard, V.
IPC分类号： C08F04/02
CPC分类号： C08F10/00 , C08F4/61912 , C08F4/61916 , C08F4/6192 , C08F110/02 , C08F210/16 , Y10S526/943 , C08F2500/12 , C08F210/08
摘要： Catalysts for the polymerization of olefins contain units of formula (I) wherein: each R is independently selected from a C1 to C10 aliphatic or cycloaliphatic group or a C6 to C18 aryl, aralkyl, or alkaryl; each R is independently selected from hydride, R, and Q radicals wherein at least one R is Q; Q has the general formula: LM L'rXp-r-1, wherein L is a monoanionic aromatic ancillary ligand pi-bonded to M and covalently bonded to Si; L' is a monoanionic aromatic ancillary ligand pi-bondned to M and optionally bonded to L through a covalent bridging group; M is a metal selected from Groups 3-10 of the Periodic Table or lanthanides; X is independently selected from a hydride radical, halide radical, hydrocarbyl radical, halocarbyl radical, silahydrocarbyl, alkoxy radical, aryloxy radical, alkylsulfonate radical, arylesulfonate radical or (R)2N- radical; or two X groups are joined with M to form a metallacycle, silametallacycle or pi-diene metallacycle moiety; p is the valence of M; r is 0 or 1; and n is an integer between about 10 and about 500.
摘要翻译：用于烯烃聚合的催化剂包含式（I）的单元，其中：每个R独立地选自C 1至C 10脂族或脂环族基团或C 6至C 18芳基，芳烷基或烷芳基; 每个R 2独立地选自氢化物，R和Q基团，其中至少一个R 2是Q; Q具有以下通式：其中L是与M键合并与Si共价结合的单阴离子芳族辅助配体; L'是单键阴离子芳族辅助配体，其键合到M并且任选地通过共价桥连基团与L键合; M是选自元素周期表第3-10族或镧系元素的金属; X独立地选自氢化物基团，卤化物基，烃基，卤代烃基，硅烷烃基，烷氧基，芳氧基，烷基磺酸根，芳基磺酸根或（R）或两个X基团与M连接以形成金属环，硅烷环或者偕二烯金属环部分; p是M的化合价; r为0或1; n为约10至约500的整数。

6. 发明申请

WO1996040796A1 HALOGENATED SUPPORTS AND SUPPORTED ACTIVATORS 审中-公开
标题翻译：支持支持和支持的激活器
公开(公告)号：WO1996040796A1
公开(公告)日：1996-12-19
申请号：PCT/US1996006471
申请日：1996-05-07
申请人： W.R. GRACE & CO.-CONN.
发明人： W.R. GRACE & CO.-CONN. , WARD, David, George
IPC分类号： C08F04/02
CPC分类号： C08F10/00 , C08F4/02 , C08F4/619 , C08F4/61904 , C08F4/61908 , C08F4/61916
摘要： The present invention is a halogenated support, supported activator and supported transition metal catalyst system involving reacting a carrier containing reactive functionalities with a halogenated organic in the presence of base and contacting a catalytic activator of the formula [C+] [M (Q1 - Qn+1)] and/or M Qn a transition metal catalytic precursor with the halogenated support.
摘要翻译：本发明是一种卤化载体，负载型活化剂和负载型过渡金属催化剂体系，其包括在碱存在下使含有反应性官能团的载体与卤代有机反应并使式[C +] - [M n >（Q1-Qn + 1）]和/或Mnn是具有卤化载体的过渡金属催化前体。

7. 发明申请

WO1995007939A1 POLYMERIZATION CATALYST SYSTEMS, THEIR PRODUCTION AND USE 审中-公开
标题翻译：聚合催化剂体系，其生产和使用
公开(公告)号：WO1995007939A1
公开(公告)日：1995-03-23
申请号：PCT/US1994009629
申请日：1994-08-29
申请人： EXXON CHEMICAL PATENTS INC.
发明人： EXXON CHEMICAL PATENTS INC. , JEJELOWO, Moses, Olukayode , BAMBERGER, Robert, Lee , SAGAR, Vispi, Ruston
IPC分类号： C08F04/02
CPC分类号： C08F10/00 , C08F4/63904 , C08F4/63908 , C08F4/63912 , C08F4/63916 , C08F4/6392 , C08F210/16 , C08F210/08 , C08F2500/12
摘要： This invention is generally directed toward a supported catalyst system useful for polymerizing olefins. The method for supporting the catalyst of the invention provides for a supported bulky ligand transition metal metallocene catalyst having improved activity which when utilized in a polymerization process substantially reduces the reactor fouling and sheeting particularly in a gas phase polymerization process. In one embodiment a method is provided to produce a supported bulky ligand transition metal catalyst system by contacting a porous carrier with at least one bulky ligand transition metal compound, such as a metallocene compound, followed by the addition of a cocatalyst or activator. In another embodiment a method is provided to produce a supported catalyst system by contacting a porous carrier with an organometallic compound then adding at least one metallocene component followed by an activator. In another embodiment the activator of the invention is hydrolyzed at least once after its initial formation. In another embodiment of the invention, there is provided a process for producing polyolefins by contacting olefin monomer, optionally with comonomer in the presence of the catalyst system described above.
摘要翻译：本发明通常涉及用于聚合烯烃的负载型催化剂体系。用于支撑本发明的催化剂的方法提供了具有改善的活性的支撑的大体积配体过渡金属茂金属催化剂，其在聚合过程中使用时，特别是在气相聚合方法中基本上减少反应器结垢和压片。在一个实施方案中，提供了通过使多孔载体与至少一种大体积配体过渡金属化合物如茂金属化合物接触，然后加入助催化剂或活化剂来制备支撑的大体积配体过渡金属催化剂体系的方法。在另一个实施方案中，提供了通过使多孔载体与有机金属化合物接触然后加入至少一种茂金属组分，然后加入活化剂来制备负载型催化剂体系的方法。在另一个实施方案中，本发明的活化剂在其初始形成后至少水解一次。在本发明的另一个实施方案中，提供了一种通过在上述催化剂体系存在下任选与共聚单体接触的烯烃单体来生产聚烯烃的方法。

8. 发明申请

WO1993023439A2 METHOD FOR MAKING AND USING A SUPPORTED METALLOCENE CATALYST SYSTEM 审中-公开
标题翻译：制备和使用支持的金属催化剂体系的方法
公开(公告)号：WO1993023439A2
公开(公告)日：1993-11-25
申请号：PCT/US1993004628
申请日：1993-05-17
申请人： EXXON CHEMICAL PATENTS INC.
发明人： EXXON CHEMICAL PATENTS INC. , BURKHARDT, Terry, John , MURATA, Masahide , BRANDLEY, William, Barry
IPC分类号： C08F04/02
CPC分类号： C08F10/00 , C08F4/61912 , C08F4/61916 , C08F4/6192 , C08F4/65912 , C08F4/65922 , C08F110/02 , C08F110/06 , C08F210/16 , Y10S526/943 , C08F2500/18 , C08F2500/12 , C08F2500/03 , C08F2500/16 , C08F2500/15 , C08F210/06 , C08F2500/17 , C08F4/65916
摘要： The invention relates to a novel process for producing a supported metallocene catalyst system useful for the polymerization and/or copolymerization of olefins, alpha-olefins, and/or diolefins which results in a catalyst product which during polymerization, produces minimal to no reactor fouling and polymer of controlled morphology. The invention is particularly useful for but not limited to polymerizing propylene or copolymerizing propylene with olefins having two or more carbon atoms. The novel support technique described herein results in a catalyst which will obtain polymer product having controlled, uniform particle size, narrow molecular weight distribution, high bulk density and depending upon the metallocene employed and monomers polymerized, stereoregularity.

9. 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。

10. 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。

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