公开(公告)号：US5455216A

公开(公告)日：1995-10-03

申请号：US124047

申请日：1993-09-21

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 ,  B01J37/08

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：US5352658A

公开(公告)日：1994-10-04

申请号：US16277

申请日：1993-02-11

Applicant: Kaspar Evertz ,  Roland Saive ,  Guido Funk ,  Peter Koelle ,  Rainer Konrad ,  Hans Gropper

Inventor： Kaspar Evertz ,  Roland Saive ,  Guido Funk ,  Peter Koelle ,  Rainer Konrad ,  Hans Gropper

IPC: C08F2/42 ,  C08F4/00 ,  C08F4/02 ,  C08F4/06 ,  C08F4/22 ,  C08F4/24 ,  C08F4/69 ,  C08F10/00 ,  C08F10/02 ,  B01J31/00

CPC classification number: C08F10/00

Abstract: A novel Phillips catalyst for the homopolymerization of ethylene and the copolymerization of ethylene with .alpha.-olefins contains, as a catalytically active component, a chromium catalyst supported on a finely divided aluminum silicate gel, modified with a fluoride and activated in an oxidizing atmosphere at elevated temperatures. The finely divided aluminum silicate gel (carrier gel) used here has an alumina content of from 0.5 to 6% by weight, the alumina being concentrated in the surface region of the carrier gel particles. The novel Phillips catalyst has high productivity and gives high molecular weight ethylene homopolymers and copolymers which have excellent low temperature impact strength and do not tend to swell in the blow molding process on emergence from the extruder die.

Abstract translation: 用于乙烯均聚和乙烯与α-烯烃共聚的新型菲利普斯催化剂含有负载在细分硅酸铝凝胶上的铬催化剂作为催化活性组分，用氟化物改性并在升高的氧化气氛中活化 温度。 这里使用的细分的硅酸铝凝胶（载体凝胶）的氧化铝含量为0.5〜6重量％，氧化铝浓缩在载体凝胶粒子的表面区域。 该新型菲利普斯催化剂具有高生产率，并得到具有优异的低温冲击强度的高分子量乙烯均聚物和共聚物，并且在吹塑模制过程中不会从挤出机模头出现而膨胀。

公开(公告)号：US5324697A

公开(公告)日：1994-06-28

申请号：US904924

申请日：1992-06-26

Applicant: Hans-Joachim Mueller ,  Rainer Konrad ,  Guenther Schweier ,  Siegfried Weber ,  Roland Saive ,  Peter Koelle

Inventor： Hans-Joachim Mueller ,  Rainer Konrad ,  Guenther Schweier ,  Siegfried Weber ,  Roland Saive ,  Peter Koelle

IPC: C08F4/02 ,  C08F4/24 ,  C08F4/60 ,  C08F4/69 ,  C08F10/00 ,  C08F10/02

CPC classification number: C08F10/02

Abstract: A novel Phillips catalyst for the homopolymerization of ethylene and the copolymerization of ethylene with .alpha.-olefins contains as catalytically active components a specific chromium catalyst on an aluminum phosphate support and cocatalysts of the formula I to IV, ##STR1## where M is lithium, sodium and potassium,M.sup.1 is magnesium and zinc,M.sup.2 is boron and aluminum,R is C.sub.1 -C.sub.10 -alkyl and C.sub.6 -C.sub.20 -aryl,R.sup.1 is R and C.sub.1 -C.sub.10 -alkoxy and C.sub.6 -C.sub.20 -aryloxy,X is chlorine, bromine and iodine,n is 0, 1 and 2The chromium catalyst on an aluminum phosphate support can be obtained by applying chromium compounds to a finely divided aluminum phosphate with a P:A1 molar ratio near to or equal to 1 and a pore volume of >1 cm.sup.3 /g and activating the resulting intermediate at elevated temperatures in an oxidizing atmosphere. The novel Phillips catalyst has an exceptionally long duration of activity and its productivity can be increased further by adding hydrogen.

Abstract translation: 用于乙烯均聚和乙烯与α-烯烃共聚的新型菲利普斯催化剂在磷酸铝载体上含有特定的铬催化剂和式I至IV的助催化剂，MR（I）M1R2（II）M2R3的催化活性组分 -n1Xn（III）MM2RR31（IV）其中M是锂，钠和钾，M1是镁和锌，M2是硼和铝，R是C1-C10-烷基和C6-C20-芳基，R1是R和C1- C10烷氧基和C6-C20芳氧基，X是氯，溴和碘，n是0,1和2。磷酸铝载体上的铬催化剂可以通过将铬化合物施加到具有P： A1摩尔比接近或等于1，孔体积> 1cm 3 / g，并在氧化气氛中在高温下活化所得中间体。 新型菲利普斯催化剂具有非常长的活性持续时间，并且通过加入氢可以进一步提高其生产率。

公开(公告)号：US4845176A

公开(公告)日：1989-07-04

申请号：US105542

申请日：1987-10-08

Applicant: Rainer Konrad ,  Rainer Hemmerich ,  Rudolf Mueller-Mall ,  Guenther Schweier

Inventor： Rainer Konrad ,  Rainer Hemmerich ,  Rudolf Mueller-Mall ,  Guenther Schweier

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

CPC classification number: C08F10/02 ,  Y10S526/908 ,  Y10S526/909

Abstract: Ethene homopolymers and ethene copolymers with minor amounts of higher .alpha.-monoolefins are prepared by polymerization of the monomer or monomers using a chromium trioxide catalyst which is obtained by a method in which (1) a finely divided, porous, silicate carrier is laden with (2) chromium trioxide or a chromium compound which is converted to chromium trioxide under the conditions of stage (3), and then (3) the intermediate resulting from stage (2) is heated in an oxygen-containing gas stream. In this process, a cocatalyst which consists of a lithiumalkyl used in addition to the chromium trioxide catalyst.

Abstract translation: 通过使用三氧化铬催化剂聚合单体或单体来制备具有少量较高级α-单烯烃的乙烯均聚物和乙烯共聚物，该三氧化铬催化剂通过以下方法获得，其中（1）细分多孔硅酸盐载体载有（ 2）三氧化铬或在阶段（3）的条件下转化为三氧化铬的铬化合物，然后（3）将由步骤（2）得到的中间体在含氧气体流中加热。 在该方法中，除了三氧化铬催化剂之外，还使用由使用的烷基锂组成的助催化剂。

公开(公告)号：US4727124A

公开(公告)日：1988-02-23

申请号：US047116

申请日：1987-05-08

Applicant: Rainer Konrad ,  Rudolf Mueller-Mall ,  Guenther Schweier

Inventor： Rainer Konrad ,  Rudolf Mueller-Mall ,  Guenther Schweier

IPC: C08F2/06 ,  C08F4/02 ,  C08F4/22 ,  C08F4/24 ,  C08F4/62 ,  C08F4/64 ,  C08F10/00 ,  C08F10/02 ,  C08F2/24

CPC classification number: C08F10/00 ,  C08F2410/01

Abstract: Ethane polymers are prepared by Phillips catalysis using (1) a supported catalyst which is laden with chromium, phosphorus and titanium and (2) a cocatalyst, (1) being obtained by a procedure in which (1.1) a catalyst intermediate laden with chromium, phosphorus and titanium is prepared from a silicate carrier, a selected chromium compound, a selected phosphorus compound and a selected titanium compound, and (1.2) the catalyst intermediate is then heated in an oxygen-containing gas stream. In the process, the supported catalyst (1) used is one which is obtained (using specific methods and substances in each case) by a procedure in which (1.1) in a first stage (1.1.1), a suspension is first prepared from (1.1.1.1) a finely divided silicate carrier and (1.1.1.2) an inert organic solvent, (1.1.2) a suspension is then prepared from (1.1.2.1) a finely divided chromium trioxide and (1.1.2.2) an inert organic solvent, (1.1.3) thereafter (1.1.3.1) the suspension resulting from (1.1.2) is combined with (1.1.3.2) a phosphate or phosphite, (1.1.4) then (1.1.4.1) the suspension obtained from (1.1.1) is combined with (1.1.4.2) the reaction product obtained in (1.1.3), (1.1.5) thereafter (1.1.5.1) the suspension formed in (1.1.4) is combined with (1.1.5.2) a titanate, (1.1.6) finally the suspension obtained in (1.1.5) is evaporated to dryness and then (1.2) in a second stage, (1.2.1) the intermediate obtained in (1.1) is first treated with a nitrogen stream, (1.2.2) an intermediate obtained in (1.2.1) is then heated in an oxygen-containing gas stream and finally (1.2.3) the intermediate obtained in (1.2.2) is treated with a nitrogen stream, and a lithiumalkyl is used as (2).

Abstract translation: 通过使用（1）载有铬，磷和钛的载体催化剂和（2）助催化剂的菲尼普斯催化剂制备乙烷聚合物，（1）通过以下程序获得，其中（1.1）载有铬的催化剂中间体， 磷和钛由硅酸盐载体，选择的铬化合物，选择的磷化合物和选择的钛化合物制备，然后在含氧气流中加热催化剂中间体。 在该方法中，使用的负载催化剂（1）是通过第一阶段（1.1.1）中的（1.1）的步骤获得的（使用具体方法和每种情况下的物质），悬浮液首先由 （1.1.1.1）细碎的硅酸盐载体和（1.1.1.2）惰性有机溶剂，（1.1.2）悬浮液然后由（1.1.2.1）细碎的三氧化铬和（1.1.2.2）惰性的 有机溶剂（1.1.3）（1.1.3.1）将得自（1.1.2）的悬浮液与（1.1.3.2）磷酸酯或亚磷酸酯（1.1.4）然后（1.1.4.1）合并得到的悬浮液 （1.1.1）与（1.1.4）中得到的反应产物（1.1.3），（1.1.5）（1.1.5.1）中合并（1.1.4），将（1.1.4）中形成的悬浮液与（1.1 0.5.2）钛酸盐（1.1.6）最后，将（1.1.5）中得到的悬浮液在第二阶段蒸发至干，然后（1.2）（1.2.1），首先处理（1.1）中获得的中间体 用氮气流（1.2.2）中间体 然后在含氧气流中加热（1.2.1），最后（1.2.3）用氮气流处理（1.2.2）中得到的中间体，使用烷基锂作为（2）。