公开(公告)号：US20090048099A1

公开(公告)日：2009-02-19

申请号：US12086319

申请日：2006-12-04

Applicant: Christoph Kiener ,  Ingo Treffkorn ,  Guido Funk

Inventor： Christoph Kiener ,  Ingo Treffkorn ,  Guido Funk

IPC: B01J21/08 ,  B01J21/06

CPC classification number: C08F10/00 ,  B01J21/08 ,  B01J35/08 ,  B01J35/1023 ,  B01J35/1047 ,  B01J37/036 ,  C01B33/16 ,  C01G9/02 ,  C01G23/047 ,  C01G25/02 ,  C01P2004/32 ,  C01P2004/61 ,  C01P2006/12 ,  C01P2006/14 ,  C01P2006/82 ,  C08F4/24 ,  C08F4/025

Abstract: The invention relates to a process for preparing an essentially spherical support for olefin polymerization catalysts, which comprises the steps: preparation of a hydrogel comprising a cogel of silicon oxide and at least one further metal oxide, if appropriate, washing of the hydrogel until the content of alkali metal ions is less than 0.1% by weight, based on the weight of solids, extraction of the water from the hydrogel until the water content is less than 5% by weight, based on the total content of liquid, and drying of the hydrogel to form a xerogel. According to the invention, the extraction step comprises at least one first extraction with a first organic solvent which is at least partially miscible with water down to a water content of 50% by weight, followed by at least one second extraction with a second organic solvent which is at least partially miscible with water.

Abstract translation: 本发明涉及一种制备用于烯烃聚合催化剂的基本上为球形的载体的方法，其包括以下步骤：制备包含氧化硅和至少一种其它金属氧化物的共凝胶的水凝胶（如果合适的话），洗涤水凝胶，直到含量 的碱金属离子的含量小于0.1重量％，基于固体的重量，从水凝胶中提取水直到水含量低于5重量％，基于液体的总含量，并干燥 水凝胶形成干凝胶。 根据本发明，提取步骤包括至少一次首先用第一有机溶剂进行萃取，所述第一有机溶剂至少部分地与水混合至水含量为50重量％，然后用第二有机溶剂至少一次萃取 其至少部分地与水混溶。

公开(公告)号：US20060063666A1

公开(公告)日：2006-03-23

申请号：US10538536

申请日：2003-12-09

Applicant: Wolfgang Rohde ,  Guido Funk ,  Andreas Haufe ,  Anke Bold ,  Neil Nadalin

Inventor： Wolfgang Rohde ,  Guido Funk ,  Andreas Haufe ,  Anke Bold ,  Neil Nadalin

IPC: B01J23/26

CPC classification number: C08F210/16 ,  C08F4/24 ,  C08F210/14 ,  C08F2500/18 ,  C08F2500/12 ,  C08F2500/07 ,  C08F2500/04 ,  C08F2500/13

Abstract: Process for preparing supported, titanized chromium catalysts, which comprises the following steps: A) bringing a support material into contact with a protic medium comprising a titanium compound and a chromium compound, B) optionally removing the solvent, C) optionally calcining the precatalyst obtained after step B) and D) optionally activating the precatalyst obtained after step B) or C) in an oxygen-containing atmosphere at from 400° C. to 1100° C.

Abstract translation: 制备负载的钛化铬催化剂的方法，其包括以下步骤：A）使载体材料与包含钛化合物和铬化合物的质子介质接触，B）任选除去溶剂，C）任选地煅烧所获得的预催化剂 在步骤B）和D）之后，任选地在步骤B）或C）中在400℃至1100℃的含氧气氛中活化预催化剂。

公开(公告)号：US06645900B2

公开(公告)日：2003-11-11

申请号：US10087012

申请日：2002-02-28

Applicant: Paulus de Lange ,  Guido Funk ,  Andreas Deckers ,  Peter Kölle

Inventor： Paulus de Lange ,  Guido Funk ,  Andreas Deckers ,  Peter Kölle

IPC: B01J29035

CPC classification number: C08F10/00 ,  B01J21/08 ,  B01J37/0072 ,  B01J37/036 ,  C08F4/02 ,  C08F4/24

Abstract: The invention relates to a catalyst support and to a method for the production of the catalyst support comprising the following steps: a) production of a silicic acid hydrogel having a solids content of from 10 to 25% by weight (calculated as SiO2) whose particles are substantially spherical, b) extraction of the hydrogel particles with an alcohol until at least 60% of the water present in the hydrogel has been removed, c) drying of the resultant hydrogel until the residual alcohol content is less than 10% by weight (xerogel formation) at temperatures of ≧160° C. at atmospheric pressure using an inert entraining gas, d) setting of the desired particle size of the resultant xerogel, in which the hydrogel particles have a particle size of ≧8 mm before the extraction, and to a catalyst and to a method for the production of the catalyst by loading the catalyst support with a chromium compound. The invention also relates to a method for the production of polyolefins using the catalyst.

Abstract translation: 本发明涉及一种催化剂载体和用于生产催化剂载体的方法，包括以下步骤：a）制备固体含量为10至25重量％（以SiO 2计）的硅酸水凝胶，其颗粒 基本上是球形的，b）用醇萃取水凝胶颗粒，直到水凝胶中存在的至少60％的水已被除去，c）干燥所得的水凝胶，直到残余的醇含量低于10重量％ 干燥剂形成），在大气压下使用惰性夹带气体，在大气压力= 160℃的温度下，d）设定所得干燥剂的所需粒度，其中水凝胶颗粒的颗粒尺寸> 萃取和催化剂的制备方法，以及通过用铬化合物负载催化剂载体来生产催化剂的方法。 本发明还涉及使用该催化剂生产聚烯烃的方法。

公开(公告)号：US06599969B1

公开(公告)日：2003-07-29

申请号：US08804665

申请日：1997-02-25

Applicant: Wolfgang Rohde ,  Guido Funk ,  Hans-Helmut Görtz ,  Rolf Osterloh

Inventor： Wolfgang Rohde ,  Guido Funk ,  Hans-Helmut Görtz ,  Rolf Osterloh

IPC: C08K513

CPC classification number: C08F6/02 ,  C08L23/00

Abstract: A process for preparing stabilized olefin polymers which have a low cold heptane extractables content by polymerization of olefins with Ziegler or Phillips catalysts, wherein the polymer is, immediately after leaving the polymerization reactor, brought into contact with an involatile phenol derivative.

Abstract translation: 一种制备稳定的烯烃聚合物的方法，其通过用齐格勒或菲利普斯催化剂聚合烯烃而具有低的冷庚烷可提取物含量，其中聚合物在离开聚合反应器之后立即与非挥发性苯酚衍生物接触。

公开(公告)号：US5625013A

公开(公告)日：1997-04-29

申请号：US422937

申请日：1995-05-24

Applicant: Hans-Joachim Mueller ,  Godofredo Follmer ,  Rainer Konrad ,  Roland Saive ,  Martin Lux ,  Hans-Helmut Goertz ,  Guido Funk

Inventor： Hans-Joachim Mueller ,  Godofredo Follmer ,  Rainer Konrad ,  Roland Saive ,  Martin Lux ,  Hans-Helmut Goertz ,  Guido Funk

IPC: C08F4/02 ,  C08F4/22 ,  C08F4/24 ,  C08F10/00 ,  B01J35/08

CPC classification number: C08F10/00

Abstract: A process for the preparation of a supported catalyst for the polymerization of .alpha.-olefins, in which(1) a silicon dioxide-containing support gel is prepared by(1.1) introducing a sodium water glass or potassium water glass solution into a swirling stream of an aqueous mineral acid longitudinally and tangentially to the stream, spraying the resultant silica hydrosol in drop form into a gaseous medium and allowing it to solidify to form a hydrogel, and freeing the resultant hydrogel from salts by washing without prior ageing,(1.2) drying the hydrogel resulting from (1.1) to form the support gel,(2) the support gel (1) is charged with chromium trioxide or a chromium compound which can be converted into chromium trioxide under the conditions of process step (3), giving a chromium-containing support gel, and(3) the chromium-containing support gel (2) is heated at from 400.degree. to 1100.degree. C. for from 10 to 1000 minutes in an anhydrous gas stream containing oxygen in a concentration of greater than 10% by volume,comprises drying the hydrogel resulting from step (1.1) in step (1.2) within a time of not more than 60 seconds in a shaping, high-speed dryer at an inlet temperature of from 80.degree. to 400.degree. C.

Abstract translation: 一种制备用于α-烯烃聚合的负载催化剂的方法，其中（1）含二氧化硅的载体凝胶通过（1.1）将钠水玻璃或钾水玻璃溶液引入旋流 将水性无机酸纵向和切向于料流，将所得的二氧化硅水溶胶以液滴形式喷雾到气态介质中并使其固化形成水凝胶，并通过在没有预先熟化的情况下洗涤将所得水凝胶从盐中释放，（1.2）干燥 由（1.1）产生的形成支持凝胶的水凝胶，（2）载体凝胶（1）中加入三氧化铬或铬化合物，其可以在工艺步骤（3）的条件下转化为三氧化铬，得到 含铬载体凝胶，（3）含铬载体凝胶（2）在含有浓度浓度的氧的无水气流中在400〜1100℃下加热10〜1000分钟 大于10体积％包括在入口温度为80°至400°的成形高速干燥器中在不超过60秒的时间内将步骤（1.2）中由步骤（1.1）得到的水凝胶干燥 DEG C.

公开(公告)号：US5414064A

公开(公告)日：1995-05-09

申请号：US274692

申请日：1994-07-14

Applicant: Martin Lux ,  Guido Funk ,  Roland Saive ,  Hans-Helmut Goertz ,  Rainer Konrad

Inventor： Martin Lux ,  Guido Funk ,  Roland Saive ,  Hans-Helmut Goertz ,  Rainer Konrad

IPC: C09K3/16 ,  C08F2/34 ,  C08F2/44 ,  C08F10/00 ,  C08F10/02 ,  C08F110/02 ,  C08K5/17 ,  C08K5/20 ,  C08L23/02

CPC classification number: C08F10/02 ,  C08F110/02 ,  Y10S526/901 ,  Y10S526/904

Abstract: Homopolymers of ethylene or copolymers of ethylene with minor amounts of other C.sub.3 -C.sub.12 -alk-1-enes are prepared by catalytic polymerization in a suspension or in the gas phase in the presence of an antistatic agent at from 50 to 120.degree. C. and from 5 to 50 bar by a process in which the antistatic agent used is a mixture of the following substances:a) a metal salt of medialanic acid of the formula (I) ##STR1## b) a metal salt of an anthranilic acid of the general formula (II) ##STR2## where the organic radical R.sup.1 is either.alpha.)--CO--(CH.sub.2).sub.x --CH.sub.3 (II.alpha.)or.beta.)--CO--(CH.sub.2).sub.y --CH.dbd.CH--(CH.sub.2).sub.z --CH.sub.3(III.beta.)and x, y and z are each an integer and are from 6 to 18 for x, from 1 to 16 for y, from 1 to 16 for z and from 4 to 17 for y+z, andc) a polyamine obtainable by reacting epichlorohydrin and an aliphatic primary monoamine or an N-alkylalkylenediamine of the general formula (IV)R.sup.2 NH--R.sup.3 --NH.sub.2 (IV),whereR.sup.2 is C.sub.8 -C.sub.24 -alkyl andR.sup.3 is C.sub.2 -C.sub.6 -alkylene.

Abstract translation: 乙烯均聚物或乙烯与少量其它C 3 -C 12烷-1-烯的共聚物通过在50至120℃的抗静电剂存在下在悬浮液或气相中催化聚合制备，以及 使用的抗静电剂为以下物质的混合物的方法为5〜50巴：a）式（I）的中间体金属盐（a）b）邻氨基苯甲酸的金属盐 通式（II）的酸其中有机基团R1是α）-CO-（CH2）x-CH3（IIa）或β）-CO-（CH2）y-CH = CH - （CH 2）z -CH 3（IIIβ），x，y和z各自为整数，x为6至18，y为1至16，z为1至16，y为4至17 + z，和c）通过使表氯醇和通式（IV）R 2 NH-R 3 -NH 2（IV）的脂族伯单胺或N-烷基亚烷基二胺反应得到的多胺，其中R 2是C 8 -C 24 - 烷基，R 3是C 2 -C 6-亚烷基。

公开(公告)号：US5310712A

公开(公告)日：1994-05-10

申请号：US953629

申请日：1992-09-30

Applicant: Guido Funk ,  Rainer Hemmerich ,  Hans Gropper ,  Erich Kolk ,  Godofredo Follmer

Inventor： Guido Funk ,  Rainer Hemmerich ,  Hans Gropper ,  Erich Kolk ,  Godofredo Follmer

IPC: C08F4/02 ,  C08F4/06 ,  C08F4/22 ,  C08F4/24 ,  C08F4/69 ,  C08F10/00 ,  B01J35/08 ,  B01J37/08

CPC classification number: C08F10/00

Abstract: In a novel process for the preparation of a supported catalyst for the polymerization of .alpha.-olefins, a carrier gel (1) is first prepared by a method in which a sodium or potassium waterglass solution is introduced into a stream of an aqueous mineral acid which is subjected to angular momentum and may contain aluminum ions, longitudinally and tangentially to the stream, the resulting silica hydrosol sprayed in the form of drops into a gaseous medium and allowed to solidify into a hydrogel, and the resulting hydrogel is freed from salts by washing without prior aging and, if necessary, freed from some of the water by extraction with alcohols and/or ketones and is then dried. This gives the carrier gel (1), which is milled and is fractionated according to particle size. In a second process step, the carrier gel (1) is laden with chromium trioxide or with a chromium compound which can be converted into chromium trioxide, after which the resulting chromium-containing carrier gel (2) is heated at from 400.degree. to 1100.degree. C. for from 10 to 1,000 minutes in an anhydrous gas stream containing oxygen in a concentration of more than 10% by volume. In the novel process, it is essential that the drying of the hydrogel be carried out with formation of the carrier gel (1) in a fast dryer in the course of not more than 300 seconds at an inlet temperature of from 200.degree. to 600.degree. C. The supported catalyst prepared in this manner gives homo- and copolymers of ethylene having excellent low temperature impact strength.

Abstract translation: 在制备用于α-烯烃聚合的负载催化剂的新方法中，首先通过一种方法制备载体凝胶（1），其中将钠或钾水玻璃溶液引入无机酸水溶液的流中， 经受角动量并且可以包含与流纵向和切向的铝离子，所得到的二氧化硅水溶胶以液滴的形式喷入气态介质中并使其固化成水凝胶，并且通过洗涤将所得水凝胶除去盐 没有预先老化，如果需要，通过用醇和/或酮萃取除去一些水，然后干燥。 这得到载体凝胶（1），其被研磨并根据粒度进行分级。 在第二工艺步骤中，载体凝胶（1）装载有三氧化铬或可以转化成三氧化铬的铬化合物，之后将所得含铬载体凝胶（2）在400℃加热至1100℃ 在含有浓度超过10体积％的氧气的无水气流中10分钟至1000分钟。 在新颖的方法中，必须在200〜600℃的入口温度下，在不超过300秒的快速干燥器中形成载体凝胶（1），进行水凝胶的干燥。 C.以这种方式制备的负载催化剂得到具有优异的低温冲击强度的乙烯均聚物和共聚物。

公开(公告)号：US5189123A

公开(公告)日：1993-02-23

申请号：US599873

申请日：1990-10-19

Applicant: Hans Gropper ,  Guido Funk ,  Erich Kolk ,  Dieter Oeder

Inventor： Hans Gropper ,  Guido Funk ,  Erich Kolk ,  Dieter Oeder

IPC: C08F4/02 ,  C08F4/18 ,  C08F4/22 ,  C08F4/24 ,  C08F10/00 ,  C08F110/02

CPC classification number: C08F10/00 ,  C08F110/02

Abstract: The present invention relates to a novel catalyst for the preparation of high molecular weight homopolymers and copolymers of ethene, which catalyst is obtainable by(1) loading a support based on silicon dioxide with(2) either chromium trioxide or a chromium compound capable of being converted to chromium trioxide under the conditions of stage (3) below and then(3) heating the resulting intermediate in a gas stream containing oxygen.the support (1) being a special silica xerogel obtained by extracting not more than 30% of the water from a silica hydrogel by means of an alkanol, an alkanone or a mixture thereof followed by drying, comminution and fractional screening.

Abstract translation: 本发明涉及一种用于制备乙烯的高分子量均聚物和共聚物的新催化剂，该催化剂可通过以下步骤获得：（1）将基于二氧化硅的载体与（2）三氧化铬或能够形成 在下面的阶段（3）的条件下转化成三氧化铬，然后（3）在含氧的气流中加热得到的中间体。 载体（1）是通过链烷醇，烷酮或其混合物从二氧化硅水凝胶中提取不超过30％的水而获得的特殊二氧化硅干凝胶，然后干燥，粉碎和分级筛选。

公开(公告)号：US4814308A

公开(公告)日：1989-03-21

申请号：US110872

申请日：1987-10-21

Applicant: Rainer Konrad ,  Guido Funk ,  Juergen Schmidt-Thuemmes ,  Rudolf Mueller-Mall ,  Guenther Schweier

Inventor： Rainer Konrad ,  Guido Funk ,  Juergen Schmidt-Thuemmes ,  Rudolf Mueller-Mall ,  Guenther Schweier

IPC: C08F4/02 ,  C08F4/24 ,  C08F4/48 ,  C08F4/62 ,  C08F10/02

CPC classification number: C08F10/02

Abstract: Ethene polymerization by Phillips catalysis is carried out using (1) a supported catalyst, which is laden with chromium, phosphorus and aluminum, and (2) a cocatalyst, (1) being obtained by a method in which (1.1) a catalyst intermediate laden with chromium, phosphorus and aluminum is prepared from a silicate carrier, a selected chromium compound, a selected phosphorus compound and a selected aluminum compound, and then (1.2) the catalyst intermediate is heated in an oxygen-containing gas stream. In this process, the component (1) used is one which is obtained by a method in which, in each case in a specific manner, (1.1) in a first stage, (1.1.1) first a suspension is prepared from (1.1.1.1) a finely divided silicate carrier and (1.1.1.2) an inert organic solvent, (1.1.2) then, (1.1.2.1) in an inert organic solvent, (1.1.2.2) an organic chromium compound is combined with (1.1.2.3) an aluminum trialkyl, (1.1.3) then (1.1.3.1) the suspension resulting from (1.1.1) is combined with (1.1.3.2) a phosphoric acid or phosphite and (1.1.3.3) the product obtained from (1.1.2), (1.1.4) finally, the suspension obtained in (1.1.3) is evaporated to dryness, and then (1.2) in a second stage, first (1.2.1) the intermediate obtained from (1.1) is treated with a stream of nitrogen, then (1.2.2) the intermediate obtained from (1.2.1) is heated in an oxygen-containing gas stream, and finally (1.2.3) the intermediate obtained from (1.2.2) is treated with a stream of nitrogen, and both a lithiumalkyl and a boronalkyl are used as (2).

Abstract translation: 通过菲利普斯催化进行的乙烯聚合使用（1）负载催化剂，其载有铬，磷和铝，和（2）助催化剂，（1）通过以下方法获得：（1）将载体催化剂中间体 由硅酸盐载体，选择的铬化合物，选择的磷化合物和选择的铝化合物制备铬，磷和铝，然后（1.2）在含氧气流中加热催化剂中间体。 在该方法中，所使用的组分（1）是通过在每种情况下以具体方式（1.1）在第一阶段（1.1.1）中首先从（1.1）制备悬浮液的方法获得的组分 .1.1）精细分散的硅酸盐载体和（1.1.1.2）惰性有机溶剂（1.1.2）然后，（1.1.2.1）在惰性有机溶剂（1.1.2.2）中将有机铬化合物与（ 1.1.2.3）三烷基铝（1.1.3）然后（1.1.3.1）将由（1.1.1）得到的悬浮液与（1.1.3.2）磷酸或亚磷酸酯和（1.1.3.3）得到的产物 从（1.1.2），（1.1.4）最终得到的（1.1.3）中得到的悬浮液蒸发至干，然后在第二阶段（1.2）中，首先（1.2.1）从（1.1 ）用氮气流处理，然后（1.2.2）从（1.2.1）获得的中间体在含氧气流中加热，最后（1.2.3）从（1.2.2）得到的中间体 用氮气流和二氧化钛处理 和硼烷基用作（2）。

公开(公告)号：US07803736B2

公开(公告)日：2010-09-28

申请号：US10538536

申请日：2003-12-09

Applicant: Wolfgang Rohde ,  Guido Funk ,  Andreas Haufe ,  Anke Bold ,  Neil Nadalin

Inventor： Wolfgang Rohde ,  Guido Funk ,  Andreas Haufe ,  Anke Bold ,  Neil Nadalin

IPC: B01J23/00 ,  B01J21/00 ,  B01J20/00

CPC classification number: C08F210/16 ,  C08F4/24 ,  C08F210/14 ,  C08F2500/18 ,  C08F2500/12 ,  C08F2500/07 ,  C08F2500/04 ,  C08F2500/13

Abstract: A process for preparing supported, titanized chromium catalysts is disclosed. The process comprises A) bringing a support material into contact with a protic medium comprising a titanium compound and a chromium compound; B) optionally removing the solvent; C) optionally calcining the precatalyst obtained after step B); and D) optionally activating the precatalyst obtained after step B) or C) in an oxygen-containing atmosphere at from 400° C. to 1100° C.

Abstract translation: 公开了制备负载的钛化铬催化剂的方法。 该方法包括：A）使载体材料与包含钛化合物和铬化合物的质子介质接触; B）任选地除去溶剂; C）任选地煅烧在步骤B）之后获得的预催化剂; 和D）任选地在步骤B）或C）中在400℃至1100℃的含氧气氛中活化预催化剂。