公开(公告)号：US06180731B2

公开(公告)日：2001-01-30

申请号：US09000011

申请日：1997-01-22

申请人： Wolfgang Rohde ,  Roland Saive ,  Dieter Lilge ,  Martin Lux ,  Peter Bauer

发明人： Wolfgang Rohde ,  Roland Saive ,  Dieter Lilge ,  Martin Lux ,  Peter Bauer

IPC分类号： C08F442

CPC分类号： C08F10/00 ,  C08F4/61904 ,  C08F4/61912 ,  C08F4/61925 ,  C08F210/16 ,  Y10S526/943 ,  C08F210/14 ,  C08F2500/13 ,  C08F2500/12 ,  C08F2500/07 ,  C08F2500/26 ,  C08F4/63904 ,  C08F4/69

摘要： Polymers of ethylene are obtainable by polymerization of ethylene and, if desired, further comonomers in the presence of a catalyst system comprising as active constituents I) a Phillips catalyst, II) a solid which is different from I) and comprises a component which is derived from the metallocene complexes of the formula (A) in which the substituents and indices have the following meanings:  R1 to R10 are hydrogen, C1-C10-alkyl, 5-to 7-membered cycloalkyl which may in turn bear C1-C6-alkyl groups as substituents, C6-C15-aryl or aryalkyl, where two adjacent radicals may also together form a cyclic group having from 4 to 15 carbon atoms, or Si(R11)3, where R11 is C1-C10-alkyl, C6-C15-aryl or C3-C10-cycloalkyl, or the radicals R4 and R9 together form a group —[Y(R12R13)]m—, where Y is silicon, germanium, tin or carbon, and R12, R13 are hydrogen C1-C10-alky, C3-C10-cycloalyl or C6-C15-aryl, M is a metal of transition groups IV to VIII or a metal of the lanthanide series, Z1, Z2 are fluorine, chlorine, bromine, iodine, hydrogen, C1-C20-alkyl or aryl, —OR14, —OOCR14,  where R14 is hydrogen or C1-C20-alkyl; R15 is C1-C20-alkyl; m is 1,2,3 or 4; n is 0, or 2; r is 0, 1 or 2; the sum n+r is likewise 0, 1 or 2, and, if desired, III) an organometallic component selected from groups IA, IIA, IIB and IIIA of the Periodic Table of the Elements.

摘要翻译： 乙烯的聚合物可以通过在包含作为活性成分的催化剂体系的存在下乙烯和如果需要的情况下进一步的共聚单体获得。I）菲利普斯催化剂，II）与I）不同的固体，并且包含衍生自 式（A）的金属茂络合物，其中取代基和指数具有以下含义：R 1至R 10是氢，C 1 -C 10 - 烷基，5-至7-元环烷基，其也可以含有C 1 -C 6 - 烷基 作为取代基，其中两个相邻基团也可以一起形成具有4至15个碳原子的环状基团的C 6 -C 15 - 芳基或芳烷基，或其中R 11是C 1 -C 10 - 烷基，C 6 -C 15 - 芳基或C 3 -C 10 - 环烷基，或基团R 4和R 9一起形成 - [Y（R 12 R 13）] m - 基团，其中Y是硅，锗，锡或碳，R 12，R 13是氢C1-C10-烷基 C 3 -C 10 - 环烷基或C 6 -C 15 - 芳基，M为Ⅳ〜Ⅷ族金属或镧系金属，Z 1，Z 2为氟， 氯，溴，碘，氢，C 1 -C 20烷基或芳基，-OR 14，-OOCR 14，其中R 14是氢或C 1 -C 20烷基; R 15是C 1 -C 20 - 烷基; m为1,2,3或4; n为0或2; r为0,1或2; 总和n + r同样为0,1或2，如果需要，III）选自元素周期表的IA，IIA，IIB和IIIA族的有机金属组分。

公开(公告)号：US5210160A

公开(公告)日：1993-05-11

申请号：US410047

申请日：1989-09-19

申请人： Roland Saive ,  Guido Funk ,  Rainer Hemmerich

发明人： Roland Saive ,  Guido Funk ,  Rainer Hemmerich

IPC分类号： C08F4/607 ,  C08F4/642 ,  C08F4/647 ,  C08F4/65 ,  C08F4/685 ,  C08F10/02

CPC分类号： C08F10/02

摘要： Homopolymerization and copolymerization of ethene is carried out using a Ziegler catalyst system consisting of (1) a transition metal catalyst component, (2) an organoaluminum catalyst component and (3) an organohalogen catalyst component. The component (1) used is the solid-phase product (VI) which has been obtained by a method in which (1.1) first (1.1.1) an inorganic oxidic substance (I) as a carrier and (1.1.2) a solution (II) of (IIa) a certain oxahydrocarbon and (IIb) a mixture of (IIb1) a vanadium trichloride/alcohol complex and (IIb2) a titanium trihalide or titanium trihalide/alcohol complex and (IIc) a silicon or boron compound are combined with formation of a suspension (III) and the latter is evaporated to form a solid-phase intermediate (IV) and (1.2) then (1.2.1) the intermediate (IV) obtained in (1.1) and (1.2.2) a dissolved organoaluminum compound (V) are combined with formation of a suspension, the solid-phase product (VI) formed as the suspended substance being the transition metal catalyst component (1).

摘要翻译： 使用由（1）过渡金属催化剂组分，（2）有机铝催化剂组分和（3）有机卤化物催化剂组分组成的齐格勒催化剂体系进行乙烯的均聚和共聚。 所使用的组分（1）是通过以下方法获得的固相产物（VI）：（1.1）第一（1.1.1）作为载体的无机氧化物质（I）和（1.1.2）a （IIa）的某些氧杂烃的溶液（II）和（IIb）（IIb1）三氯化钒/醇络合物和（IIb2）三卤化钛或三卤化钛/醇络合物和（IIc）硅或硼化合物的混合物 （IV）和（1.2）然后（1.2.1）（1.1）和（1.2.2）中得到的中间体（Ⅳ），然后蒸发形成悬浮液（III） 将溶解的有机铝化合物（V）与形成悬浮液组合，形成为作为过渡金属催化剂组分（1）的悬浮物质的固相产物（VI）。

公开(公告)号：US5557021A

公开(公告)日：1996-09-17

申请号：US512556

申请日：1995-08-08

申请人： Hans-Joachim Mueller ,  Kaspar Evertz ,  Siegfried Weber ,  Guido Funk ,  Rainer Konrad ,  Roland Saive

发明人： Hans-Joachim Mueller ,  Kaspar Evertz ,  Siegfried Weber ,  Guido Funk ,  Rainer Konrad ,  Roland Saive

IPC分类号： C08F2/42 ,  C08F4/00 ,  C08F4/02 ,  C08F4/06 ,  C08F4/22 ,  C08F4/24 ,  C08F10/00 ,  C08F10/02 ,  C07C2/24

CPC分类号： C08F10/00

摘要： A novel Phillips catalyst for the copolymerization of ethylene with .alpha.-olefins, contains, as a catalytically active component, a finely divided, aluminum silicate-supported, phosphorus-containing chromium catalyst. This can be prepared by applying at least one organic phosphorus(III), (IV) and/or (V) compound and at least one chromium(III) compound which does not react with said phosphorus compounds under the reaction conditions used, in succcession in any order or simultaneously, to a finely divided aluminum silicate hydrogel or xerogel with formation of a catalyst intermediate and activating the catalyst intermediate at elevated temperatures in an oxidizing atmosphere, with the result that the chromium catalyst is formed. The novel Phillips catalyst gives ethylene/.alpha.-olefin copolymers in which the comonomers are more uniformly distributed over the copolymer chains than is the case with ethylene/.alpha.-olefin copolymers which have been prepared with the aid of conventional Phillips catalysts. Moldings which have been produced from the ethylene/.alpha.-olefin copolymers obtained in the novel procedure have a particularly high environmental stress cracking resistance and an excellent creep rupture strength.

摘要翻译： 用于乙烯与α-烯烃共聚的新颖的菲利普斯催化剂包含作为催化活性组分的细碎的含硅酸铝载体的含磷的铬催化剂。 这可以通过在所用的反应条件下施用至少一种不与所述磷化合物反应的有机磷（III），（IV）和/或（V）化合物和至少一种铬（III）化合物来制备， 以任何顺序或同时的方式，在形成催化剂中间体的细分的硅酸铝水凝胶或干凝胶中，并在氧化气氛中在高温下活化催化剂中间体，结果形成铬催化剂。 新型菲利普斯催化剂提供了乙烯/α-烯烃共聚物，其中共聚单体比共聚物链更均匀地分布在使用常规菲利普斯催化剂制备的乙烯/α-烯烃共聚物的情况下。 由新方法得到的乙烯/α-烯烃共聚物制成的成型品具有特别高的耐环境应力开裂性和优异的抗蠕变断裂强度。

公开(公告)号：US5188998A

公开(公告)日：1993-02-23

申请号：US671591

申请日：1991-03-19

申请人： Ulrich Bueschges ,  Roland Saive

发明人： Ulrich Bueschges ,  Roland Saive

IPC分类号： C08F4/616 ,  C08F4/622 ,  C08F4/68 ,  C08F10/00

CPC分类号： C08F10/00

摘要： A transition-metal catalyst component for a Ziegler catalyst system, obtainable by1) mixing an inorganic, oxidic carrier with a transition-metal starting component in an organic solvent,2) removing the solvent by evaporation,3) mixing the solid-phase intermediate from step (2) with3.1) an organoaluminum catalyst component of the formula AlR.sub.m X.sub.3-m, whereR is a C.sub.1 - to C.sub.18 -hydrocarbon radical,m is from 1 to 3, andX is OR, chlorine, bromine or hydrogen, and3.2) an organic carboxylate or an organosilicon compound or a mixture thereof in an organic solvent, and4) if desired, isolating the solid-phase intermediate by filtration, washing and drying,and the use thereof for the homopolymerization or copolymerization of ethene are described.

摘要翻译： 一种齐格勒催化剂体系的过渡金属催化剂组分，其可通过以下步骤获得：1）将无机氧化载体与过渡金属起始组分混合在有机溶剂中，2）通过蒸发除去溶剂; 3）将固相中间体 从步骤（2）与3.1）式AlRmX3-m的有机铝催化剂组分，其中R是C 1 -C 18烃基，m为1至3，X为OR，氯，溴或氢，以及 3.2）在有机溶剂中的有机羧酸盐或有机硅化合物或其混合物，以及4）如果需要，通过过滤，洗涤和干燥分离固相中间体，并描述其用于乙烯均聚或共聚的用途 。

公开(公告)号：US5112928A

公开(公告)日：1992-05-12

申请号：US416410

申请日：1989-10-03

申请人： Roland Saive ,  Guido Funk ,  Robert Bachl

发明人： Roland Saive ,  Guido Funk ,  Robert Bachl

IPC分类号： C08F4/68 ,  C08F10/00

CPC分类号： C08F10/00

摘要： The homopolymerization and copolymerization of ethene are carried out using a Ziegler catalyst system consisting of(1) a transition metal catalyst component,(2) an organoaluminum catalyst component and(3) an organohalogen catalyst component.In the homopolymerization or copolymerization, the solid-phase product (VI) used as (1) is the product which has been obtained by a method in which (1.1) first (1.1.1) an inorganic oxidic substance (I) as the carrier and (1.1.2) a solution (II) of (IIa) a certain oxahydrocarbon and (IIb) a vanadium trichloride/alcohol complex and (IIc) a silicon or boron compound are combined with formation of a suspension (III), the latter is evaporated down to form a solid-phase intermediate (IV), and (1.2) then (1.2.1) the intermediate (IV) obtained in (1.1) and (1.2.2) a dissolved organoaluminum compound (V) are combined with the formation of a suspension, the solid-phase product (VI) obtained as the suspended substance being the transition metal catalyst component (1).

摘要翻译： 使用由（1）过渡金属催化剂组分，（2）有机铝催化剂组分和（3）有机卤化物催化剂组分组成的齐格勒催化剂体系进行乙烯的均聚和共聚。 在均聚或共聚时，用作（1）的固相产物（VI）是通过以下方法获得的产物：其中（1.1）第一（1.1.1）无机氧化物质（I）作为载体 和（1.1.2）（IIa）（IIa）的某种氧杂烃和（IIb）三氯化钒/醇络合物和（IIc）硅或硼化合物的溶液（II）与形成悬浮液（III） 蒸发掉形成固相中间体（Ⅳ），然后（1.2）然后（1.2.1）将（1.1）和（1.2.2）中得到的中间体（Ⅳ）溶解的有机铝化合物（Ⅴ）与 形成悬浮液时，作为悬浮物质得到的固相物（VI）为过渡金属催化剂成分（1）。

公开(公告)号：US4831090A

公开(公告)日：1989-05-16

申请号：US108457

申请日：1987-10-15

申请人： Robert Bachl ,  Guido Funk ,  Konrad Richter ,  Rainer Hemmerich ,  Roland Saive

发明人： Robert Bachl ,  Guido Funk ,  Konrad Richter ,  Rainer Hemmerich ,  Roland Saive

IPC分类号： C08F4/60 ,  C08F4/62 ,  C08F4/639 ,  C08F4/64 ,  C08F4/68 ,  C08F4/685 ,  C08F10/00 ,  C08F10/02

CPC分类号： C08F10/00

摘要： Homopolymerization and copolymerization of ethene are carried out using a Ziegler catalyst system consisting of (1) a transition metal catalyst component prepared by a method in which (1.1) first (1.1.1) an inorganic oxide substance (I) as a carrier and (1.1.2) a solution (II) of (IIa) a certain oxahydrocarbon and (IIb) a mixture of (IIb1) a vanadium trichloride/alcohol complex, (IIb2) a titanium trihalide or titanium trihalide/alcohol complex and, if desired, (IIb3) a zirconium tetrahalide, are combined with formation of a suspension (III), the latter is evaporated down to form a solid-phase intermediate (IV), (1.2) then (1.2.1) the solid-phase intermediate (IV) obtained from (1.1), and (1.2.2) a dissolved organoaluminum compound (V), are combined with formation of a suspension, the resulting suspended substance being a solid-phase product (VI), (2) an organoaluminum catalyst component and (3) an organohalogen catalyst component. In this process, the transition metal catalyst component (1) used is one prepared by a method in which (1.3) in addition (1.3.1) the product (VI) obtained from (1.2) is reacted with (1.3.2) oxygen, the resulting solid-phase end product (VII) being the novel transition metal catalyst component (1).

摘要翻译： 乙烯的均聚和共聚使用齐格勒催化剂体系进行，所述齐格勒催化剂体系由（1）通过以下方法制备的过渡金属催化剂组分：（1.1）第一（1.1.1）作为载体的无机氧化物（I）和（ 1.1.2）（IIa）某种氧杂烃的溶液（II）和（IIb）（IIb1）三氯化钒/醇络合物的混合物，（IIb2）三卤化钛或三卤化钛/醇络合物的混合物，如果需要， （IIb3）四卤化锆与形成悬浮液（III）组合，将其蒸发掉形成固相中间体（IV），（1.2）然后（1.2.1）固相中间体（IV ）和（1.2.2）溶解的有机铝化合物（V）与形成悬浮液结合，得到的悬浮物质为固相产物（VI），（2）有机铝催化剂组分 和（3）有机卤素催化剂组分。 在该方法中，使用的过渡金属催化剂组分（1）是通过（1.3）另外（1.3.1）从（1.2）获得的产物（VI）与（1.3.2）氧气反应的方法制备的 得到的固相终产物（Ⅶ）是新型过渡金属催化剂组分（1）。

公开(公告)号：US06197901B1

公开(公告)日：2001-03-06

申请号：US08935664

申请日：1997-09-23

申请人： Wolfgang Rohde ,  Roland Saive ,  Hans-Helmut Goertz ,  Guenther Schweier

发明人： Wolfgang Rohde ,  Roland Saive ,  Hans-Helmut Goertz ,  Guenther Schweier

IPC分类号： C08F408

CPC分类号： C08F10/00 ,  C08F4/63912 ,  C08F4/63916 ,  Y10S526/943 ,  C08F4/63925

摘要： Polyalk-1-enes are prepared by polymerization of alk-1-enes with the aid of the compound bis(cyclopentadienyl)-chromium(II) in which the cyclopentadienyl rings may carry inert organic radicals, said compound being adsorbed on an inorganic oxide carrier, by a process in which the polymerization is carried out in the presence of an organometallic compound of a metal of main groups I to III or of a metal hydride, in particular of n-butyl-lithium.

摘要翻译： 聚炔-1-烯通过在其中环戊二烯基环可以携带惰性有机基团的化合物双（环戊二烯基） - 铬（II）的聚合反应制备烷-1-烯，所述化合物被吸附在无机氧化物载体上 通过在主要I〜III族金属或金属氢化物，特别是正丁基锂的金属的有机金属化合物的存在下进行聚合的方法。

公开(公告)号：US5480852A

公开(公告)日：1996-01-02

申请号：US247479

申请日：1994-05-23

申请人： Hans-Joachim Mueller ,  Kaspar Evertz ,  Siegfried Weber ,  Guido Funk ,  Rainer Konrad ,  Roland Saive

发明人： Hans-Joachim Mueller ,  Kaspar Evertz ,  Siegfried Weber ,  Guido Funk ,  Rainer Konrad ,  Roland Saive

IPC分类号： C08F2/42 ,  C08F4/00 ,  C08F4/02 ,  C08F4/06 ,  C08F4/22 ,  C08F4/24 ,  C08F10/00 ,  C08F10/02 ,  B01J27/182

CPC分类号： C08F10/00

摘要： A novel Phillips catalyst for the copolymerization of ethylene with .alpha.-olefins, contains, as a catalytically active component, a finely divided, aluminum silicate-supported, phosphorus-containing chromium catalyst. This can be prepared by applying at least one organic phosphorus(III), (IV) and/or (V) compound and at least one chromium(III) compound which does not react with said phosphorus compounds under the reaction conditions used, in succcession in any order or simultaneously, to a finely divided aluminum silicate hydrogel or xerogel with formation of a catalyst intermediate and activating the catalyst intermediate at elevated temperatures in an oxidizing atmosphere, with the result that the chromium catalyst is formed. The novel Phillips catalyst gives ethylene/.alpha.-olefin copolymers in which the comonomers are more uniformly distributed over the copolymer chains than is the case with ethylene/.alpha.-olefin copolymers which have been prepared with the aid of conventional Phillips catalysts. Moldings which have been produced from the ethylene/.alpha.-olefin copolymers obtained in the novel procedure have a particularly high environmental stress cracking resistance and an excellent creep rupture strength.

摘要翻译： 用于乙烯与α-烯烃共聚的新颖的菲利普斯催化剂包含作为催化活性组分的细碎的含硅酸铝载体的含磷的铬催化剂。 这可以通过在所用的反应条件下施用至少一种不与所述磷化合物反应的有机磷（III），（IV）和/或（V）化合物和至少一种铬（III）化合物来制备， 以任何顺序或同时的方式，在形成催化剂中间体的细分的硅酸铝水凝胶或干凝胶中，并在氧化气氛中在高温下活化催化剂中间体，结果形成铬催化剂。 新型菲利普斯催化剂提供了乙烯/α-烯烃共聚物，其中共聚单体比共聚物链更均匀地分布在使用常规菲利普斯催化剂制备的乙烯/α-烯烃共聚物的情况下。 由新方法得到的乙烯/α-烯烃共聚物制成的成型品具有特别高的耐环境应力开裂性和优异的抗蠕变断裂强度。

公开(公告)号：US5039765A

公开(公告)日：1991-08-13

申请号：US429800

申请日：1989-10-31

申请人： Roland Saive ,  Guido Funk ,  Juergen Schmidt-Thuemmes ,  Rainer Konrad ,  Peter Bauer

发明人： Roland Saive ,  Guido Funk ,  Juergen Schmidt-Thuemmes ,  Rainer Konrad ,  Peter Bauer

IPC分类号： C08F6/00 ,  C08F2/00 ,  C08F2/14 ,  C08F2/34 ,  C08F4/68 ,  C08F6/06 ,  C08F8/00 ,  C08F8/14 ,  C08F10/02 ,  C08F210/16

CPC分类号： C08F8/14 ,  C08F10/02 ,  C08F210/16 ,  C08F2810/30

摘要： High density ethylene polymers are prepared by polymerizing the monomers in the presence of a Ziegler catalyst system by a process in which the resulting solid ethylene polymer is reacted in the melt with an additive capable of binding acids by esterification. The ester-forming additives are preferably epoxide compounds.

摘要翻译： 高密度乙烯聚合物是通过在齐格勒催化剂体系存在下使单体聚合而制得的，其中所得固体乙烯聚合物在熔体中与能通过酯化结合酸的添加剂反应。 酯形成添加剂优选为环氧化合物。

公开(公告)号：US5455216A

公开(公告)日：1995-10-03

申请号：US124047

申请日：1993-09-21

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

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

IPC分类号： C08F4/02 ,  C08F4/22 ,  C08F4/24 ,  C08F10/00 ,  B01J35/08 ,  B01J37/08

CPC分类号： C08F10/00

摘要： 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.

摘要翻译： 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.