公开(公告)号：US06533988B2

公开(公告)日：2003-03-18

申请号：US09728789

申请日：2000-12-05

Applicant: Kalle Kallio ,  Ulf Palmovist ,  Hilkka Knuuttila ,  Anne Marie Fatnes

Inventor： Kalle Kallio ,  Ulf Palmovist ,  Hilkka Knuuttila ,  Anne Marie Fatnes

IPC: C08F402

CPC classification number: C08F210/16 ,  B29C41/003 ,  B29C41/04 ,  C08F4/61912 ,  C08F4/61922 ,  C08F4/61916 ,  C08F210/14 ,  C08F2500/12 ,  C08F2500/18

Abstract: Rotational moulding process for polymerizing or copolmerizing ethylene for manufacturing ethylene polymers or copolymers having a controlled particle size and morphology. Ethylene is polymerized or copolymerized under ethylene polymerizing conditions in the presence of a supported metallocene catalyst, where the average particle size of the catalyst particles is selected within the range of 14-40 &mgr;m and the residence time at the polymerization is selected so as to achieve a polymer where average particle size is between 0.2-0.5 mm and the proportion of fractions between 0.1-0.6 is at least 80%.

Abstract translation: 用于聚合或共聚乙烯以制造具有受控粒度和形态的乙烯聚合物或共聚物的旋转模制方法。 乙烯在乙烯聚合条件下在负载金属茂催化剂存在下聚合或共聚，其中催化剂颗粒的平均粒径选择在14-40μm的范围内，并且选择聚合时的停留时间以达到 平均粒径在0.2-0.5mm之间的聚合物和0.1-0.6之间的分数比例至少为80％。

公开(公告)号：US6143844A

公开(公告)日：2000-11-07

申请号：US58806

申请日：1998-04-13

Applicant: Harri Hokkanen ,  Hilkka Knuuttila ,  Eeva-Liisa Lakomaa ,  Pekka Sormunen

Inventor： Harri Hokkanen ,  Hilkka Knuuttila ,  Eeva-Liisa Lakomaa ,  Pekka Sormunen

IPC: C08F4/02 ,  B01J31/22 ,  B01J37/02 ,  C08F4/619 ,  C08F4/6192 ,  C08F4/639 ,  C08F4/6392 ,  C08F4/64 ,  C08F4/642 ,  C08F4/659 ,  C08F4/6592 ,  C08F4/76 ,  C08F10/00 ,  C08F10/02 ,  C08F110/02 ,  C08F4/44

CPC classification number: B01J31/143 ,  B01J31/1616 ,  B01J31/2295 ,  B01J31/38 ,  B01J37/0238 ,  C08F10/00 ,  C08F10/02 ,  C08F4/65912 ,  B01J21/08 ,  B01J2531/40 ,  B01J2531/46 ,  B01J2531/48 ,  B01J2531/49 ,  B01J2531/50 ,  B01J2531/60 ,  C08F110/02 ,  C08F2410/03 ,  C08F4/6192 ,  C08F4/65908 ,  C08F4/6592 ,  C08F4/65925 ,  Y10S526/901 ,  Y10S526/907 ,  Y10S526/943

Abstract: Provided are heterogeneous catalysts for homo- and copolymerization of olefins as well as a method for preparing these catalysts, which comprise at least one metallocene compound of a Group 4A, 5A or 6A (Hubbard) transition metal on a solid inorganic support. The method comprises the steps of vaporizing the metallocene compound, treating the support material with the vaporized metallocene compound at a temperature which is sufficiently high to keep the metallocene compound in the vaporous state, contacting the support material with an amount of the vaporized metallocene compound which is sufficient to allow for a reaction between the metallocene compound and at least a substantial part of the available surface sites capable of reacting therewith, removing the rest of the metallocene compound not bound to the support, and optionally treating the product thus obtained with an activating agent. The catalysts are active even if very low amounts of activator agents, such as alumoxane, are used. Furthermore, the polymerization performance of the catalysts can be regulated during the preparation of the catalysts. Thus, by using different support pretreatment temperatures, or by using two or more different metallocenes, and by altering the order in which they are added on the support, it is possible to control and regulate the activity of the catalysts and the polymer properties, such as molecular weight and molecular weight distribution.

Abstract translation: 提供了用于烯烃均聚和共聚的非均相催化剂以及制备这些催化剂的方法，其包含至少一种在固体无机载体上的4A，5A或6A族（Hubbard）过渡金属茂金属化合物。 该方法包括以下步骤：气化金属茂化合物，在足够高的温度下用汽化金属茂化合物处理载体材料以保持茂金属化合物处于气态，使载体材料与一定量的气化茂金属化合物接触， 足以允许茂金属化合物与能够反应的至少大部分可用表面位点之间的反应，除去未结合到载体上的其余的金属茂化合物，以及任选地用活化的方法处理由此获得的产物 代理商 即使使用非常少量的活化剂如铝氧烷，催化剂也是有活性的。 此外，可以在制备催化剂期间调节催化剂的聚合性能。 因此，通过使用不同的载体预处理温度，或通过使用两种或更多种不同的金属茂，并通过改变它们在载体上的添加顺序，可以控制和调节催化剂的活性和聚合物性质，例如 作为分子量和分子量分布。

公开(公告)号：US06380332B1

公开(公告)日：2002-04-30

申请号：US09355309

申请日：1999-09-23

Applicant: Kalle Kallio ,  Hilkka Knuuttila ,  Kaisa Suominen

Inventor： Kalle Kallio ,  Hilkka Knuuttila ,  Kaisa Suominen

IPC: C08F416

CPC classification number: C08F10/00 ,  C08F4/65912 ,  C08F4/65927 ,  C08F110/02 ,  C08F210/16 ,  Y10S526/943 ,  C08F4/65916 ,  C08F210/08

Abstract: Aluminoxanes having C2-C10 alkyl groups can conveniently be used in supported olefin polymerization catalyst compositions prepared by contacting a support comprising a solid compound which is one of pure aluminium oxide, a mixed aluminium oxide, an aluminium salt, a magnesium halide, or a C1-C8 alkoxy magnesium halide, in any order with at least a) an organometallic compound, b) a metallocene, and c) an aluminoxane, and recovering said supported olefin polymerization catalyst composition.

Abstract translation: 具有C2-C10烷基的氧化铝可以方便地用于通过使包含纯氧化铝，混合氧化铝，铝盐，卤化镁或C1的固体化合物的载体接触而制备的负载型烯烃聚合催化剂组合物 -C8烷氧基卤化镁，以至少为a的任何顺序）有机金属化合物，b）茂金属和c）铝氧烷，并回收所述负载型烯烃聚合催化剂组合物。

公开(公告)号：US06291611B1

公开(公告)日：2001-09-18

申请号：US08481336

申请日：1995-08-02

Applicant: Kalle Kallio ,  Ove Andell ,  Hilkka Knuuttila ,  Ulf Palmqvist

Inventor： Kalle Kallio ,  Ove Andell ,  Hilkka Knuuttila ,  Ulf Palmqvist

IPC: C08F4642

CPC classification number: C08F10/00 ,  C08F4/63912 ,  C08F4/63916 ,  C08F4/6392 ,  C08F110/02 ,  Y10S526/943 ,  C08F2500/12 ,  C08F2500/18 ,  C08F2500/24

Abstract: 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.

Abstract translation: 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。

公开(公告)号：US06632884B1

公开(公告)日：2003-10-14

申请号：US09857901

申请日：2001-10-01

Applicant: Merete Skar ,  Ole Jan Myhre ,  Arja Lehtinen ,  Harri Hokkanen ,  Hilkka Knuuttila ,  Kalle Kallio ,  Esa Kinnunen ,  Eija Lappi

Inventor： Merete Skar ,  Ole Jan Myhre ,  Arja Lehtinen ,  Harri Hokkanen ,  Hilkka Knuuttila ,  Kalle Kallio ,  Esa Kinnunen ,  Eija Lappi

IPC: C08F2002

CPC classification number: C08F10/02 ,  C08F4/65912 ,  C08F4/65916 ,  C08F110/02 ,  C08F210/16 ,  C08F4/65925 ,  C08F2/001 ,  C08F4/65927 ,  C08F2500/12 ,  C08F2500/07 ,  C08F2500/26 ,  C08F210/08

Abstract: This invention concerns process for producing polyethylene compositions, films prepared thereof and process for the preparation of the films. The process comprises subjecting ethylene, optionally hydrogen and comonomers to polymerization or copolymerization reactions in a multistage polymerization. At least one polymerization stage is conducted essentially in the absence of hydrogen. The polymerization reactions are carried out in the presence of a single-site catalyst capable of forming a composition comprising a low molecular weight component with MFR2 of at least 10 g/10 min and a density higher than the density of the composition and a high molecular weight component. The melt flow rate of the composition is in the range MFR2=0.1-5.0 g/10 min and the density of the composition is 915-960 kg/m3. The invention makes it possible to produce polyethylene compositions for manufacturing films with a good balance between optical and mechanical properties.

Abstract translation: 本发明涉及生产聚乙烯组合物的方法，其制备的薄膜及其制备方法。 该方法包括使乙烯，任选的氢和共聚单体在多级聚合中进行聚合或共聚反应。 基本上在不存在氢的情况下进行至少一个聚合阶段。 聚合反应在能够形成包含至少10g / 10分钟的MFR低于2分子量组分的组合物的单中心催化剂的存在下进行 并且密度高于组合物的密度和高分子量组分。 组合物的熔体流动速率在MFR 2 = 0.1-5.0g / 10min的范围内，组合物的密度为915-960kg / m 2 <3 。 本发明使得可以生产用于制造具有光学和机械性能之间良好平衡的膜的聚乙烯组合物

公开(公告)号：US06316556B1

公开(公告)日：2001-11-13

申请号：US09355308

申请日：1999-07-28

Applicant: Kalle Kallio ,  Hilkka Knuuttila ,  Jyrki Kauhanen

Inventor： Kalle Kallio ,  Hilkka Knuuttila ,  Jyrki Kauhanen

IPC: C08F458

CPC classification number: C08F10/00 ,  C08F4/65912 ,  C08F4/65927 ,  C08F110/02 ,  Y10S526/943 ,  C08F4/65916

Abstract: The present invention relates to an olefin polymerization catalyst composition comprising a metallocene and an aluminoxane containing alkyl groups with at least two (2) carbon atoms which provides more uniformity than methylaluminoxane, offers greater control and reproducibility of olefin polymerization and greater storage stability. The present invention also provides a method for the preparation of the olefin polymerization catalyst composition.

Abstract translation: 本发明涉及包含茂金属和含有至少两个（2）碳原子的烷基的铝氧烷的烯烃聚合催化剂组合物，其提供比甲基铝氧烷更均匀的烯烃聚合催化剂组合物，提供了更好的烯烃聚合的控制和再现性以及更高的储存稳定性。 本发明还提供了制备烯烃聚合催化剂组合物的方法。

公开(公告)号：US5986021A

公开(公告)日：1999-11-16

申请号：US930696

申请日：1998-02-10

Applicant: Harri Hokkanen ,  Hannu Salminen ,  Kalle Kallio ,  Hilkka Knuuttila ,  Ari Palmroos

Inventor： Harri Hokkanen ,  Hannu Salminen ,  Kalle Kallio ,  Hilkka Knuuttila ,  Ari Palmroos

IPC: C08F2/00 ,  C08F2/06 ,  C08F2/34 ,  C08F4/642 ,  C08F210/00 ,  C08F210/02 ,  C08F210/16 ,  C08G85/00

CPC classification number: C08F210/16 ,  Y10S526/904 ,  Y10S526/943

Abstract: Process for manufacturing ethylene copolymers by polymerizing ethylene and a minor amount of C.sub.3 -C.sub.6 alphaolefins in particle form in slurry reactor in the presence of an ethylene polymerizing catalyst. According to the invention the polymerization is carried out in propane diluent by using a metallocene catalyst activated with an alumoxane compound.

Abstract translation: PCT No.PCT / FI96 / 00240 Sec。 371日期1998年2月10日 102（e）1998年2月10日PCT 1996年4月30日PCT PCT。 第WO96 / 34895号公报 日期1996年11月7日在乙烯聚合催化剂存在下，通过在淤浆反应器中聚合乙烯和少量C3-C6α-烯烃制备乙烯共聚物的方法。 根据本发明，通过使用由铝氧烷化合物活化的茂金属催化剂在丙烷稀释剂中进行聚合。

公开(公告)号：US5880055A

公开(公告)日：1999-03-09

申请号：US843610

申请日：1997-04-10

Applicant: Hilkka Knuuttila ,  Pekka Sormunen ,  Eero Iiskola ,  Eeva-Liisa Lakomaa ,  Harri Hokkanen

Inventor： Hilkka Knuuttila ,  Pekka Sormunen ,  Eero Iiskola ,  Eeva-Liisa Lakomaa ,  Harri Hokkanen

IPC: B01J37/02 ,  C08F4/16 ,  C08F10/00 ,  B01J37/00

CPC classification number: C08F10/00 ,  B01J37/0238

Abstract: The present invention concerns heterogeneous catalysts for polymerization of olefins. The catalysts include at least one Group IVa metal compound on a solid inorganic oxidic support. According to the invention the catalysts are prepared by vapourizing at least one solid Group IVa metal halide compound and routing the vapour of the metal halide compound into a reaction chamber, wherein the vapour is reacted with the support at a temperature of about 250.degree. to about 450.degree. C. in order to bind said metal halide compound to said support. Any metal compound not bound to said support as well as any volatile reaction products emanating from the reaction between said metal halide compound and said support are then removed from the reaction chamber in the vapour phase. Optionally, the product obtained is treated with an organic aluminum compound to increase the catalytic activity of said catalyst. The catalysts thus prepared are very well suited for polymerization of ethylene or copolymerization of ethylene with other alpha-olefins, such as propylene, butylene, 4-methyl-1-pentene and hexene. A polymerization process employing the novel catalyst will provide products of the Ultra High Molecular Weight-type (UHMWPE) having very broad MWD.

Abstract translation: 本发明涉及用于烯烃聚合的多相催化剂。 催化剂包括在固体无机氧化物载体上的至少一种IVa族金属化合物。 根据本发明，催化剂是通过将至少一种固体IVa族金属卤化物化合物挥发并将金属卤化物化合物的蒸气引导到反应室中制备的，其中蒸气在约250°至约 450℃，以便将所述金属卤化物化合物结合到所述载体上。 然后在气相中从反应室中除去未结合到所述载体上的任何金属化合物以及从所述金属卤化物和所述载体之间的反应产生的任何挥发性反应产物。 任选地，将获得的产物用有机铝化合物处理以增加所述催化剂的催化活性。 如此制备的催化剂非常适合于乙烯的聚合或乙烯与其它α-烯烃如丙烯，丁烯，4-甲基-1-戊烯和己烯的共聚合。 采用新型催化剂的聚合方法将提供具有非常宽MWD的超高分子量型（UHMWPE）产品。

公开(公告)号：US06720394B1

公开(公告)日：2004-04-13

申请号：US09700996

申请日：2001-01-22

Applicant: Kalle Kallio ,  Marja Mustonen ,  Hilkka Knuuttila

Inventor： Kalle Kallio ,  Marja Mustonen ,  Hilkka Knuuttila

IPC: C08F4642

CPC classification number: C08F10/00 ,  C08F4/65912 ,  C08F4/65927 ,  C08F110/02 ,  Y10S526/943 ,  C08F4/65916

Abstract: Alumoxanes having C2-C12 alkyl groups can conveniently be used in supported olefin polymerization catalyst compositions prepared by contacting, either previous to or immediately before the beginning of the olefin polymerization, a support comprising a porous carrier with (a) an organometallic compound of the general formula R1MXv−1, (b) a metallocene of the general formula (CpY)mM′X′nZo and an alumoxane of the following general formula in any order.

Abstract translation: 具有C 2 -C 12烷基的异氰酸酯可以方便地用于通过在烯烃聚合之前或之前或之前使包含多孔载体的载体与（a）一般的有机金属化合物接触而制备的负载型烯烃聚合催化剂组合物 式（R 1 MXv-1），（b）通式（CpY）mM'X'nZo的茂金属和下列通式的铝氧烷任意有序。

公开(公告)号：US06534431B1

公开(公告)日：2003-03-18

申请号：US08881254

申请日：1997-06-24

Applicant: Tuomo Suntola ,  Eeva-Liisa Lakomaa ,  Hilkka Knuuttila ,  Pekka Knuuttila ,  Outi Krause ,  Sven Lindfors

Inventor： Tuomo Suntola ,  Eeva-Liisa Lakomaa ,  Hilkka Knuuttila ,  Pekka Knuuttila ,  Outi Krause ,  Sven Lindfors

IPC: C23L1608

CPC classification number: B01J37/0238 ,  B01J23/26 ,  B01J23/36 ,  B01J29/061

Abstract: The invention relates to a process and to an apparatus for preparing a heterogeneous catalyst having at least one catalytically active species bound to the surface of a support material. According to the process, the surface of the support is first pretreated. A catalyst reagent containing the catalytically active species or its precursor is vaporized and the vapor is routed into a reaction chamber where it is brought to interact with the support material. The catalyst reagent not bound to the support is withdrawn from the reaction chamber in gaseous form. If necessary, the species bound to the support is posttreated in order to convert it into a catalytically active form. According to the invention, the amount of catalyst reagent brought into the reaction chamber is at least equal to, preferably in excess of the number of available binding sites on the surface. The temperature of the support of kept higher than the condensation temperature of the vapor and at the same time at a sufficiently high level to attain the thermal activation energy needed for forming bonds between the active species and the support. By binding the catalytically active species in this way to the support it is possible to provide a heterogeneous catalyst having a high activity even at small amounts of the active species.

Abstract translation: 本发明涉及一种制备具有结合到载体材料表面的至少一种催化活性物质的多相催化剂的方法和装置。 根据该方法，首先预处理载体的表面。 含有催化活性物质或其前体的催化剂试剂被蒸发，并且蒸气被引导到反应室中，在该反应室中使其与载体材料相互作用。 未与载体结合的催化剂试剂以气态形式从反应室中排出。 如果需要，结合到载体上的物质进行后处理，以将其转化为催化活性形式。 根据本发明，进入反应室的催化剂试剂的量至少等于，优选地超过表面上可用结合位点的数量。 载体的温度保持高于蒸气的冷凝温度，并且同时具有足够高的水平以获得在活性物质和载体之间形成键所需的热活化能。 通过将催化活性物质以这种方式结合到载体上，即使在少量的活性物质中也可以提供具有高活性的多相催化剂。