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    Phillips catalyst and its use for the preparation of ethylene/alpha-olefin copolymers
    1.
    发明授权
    Phillips catalyst and its use for the preparation of ethylene/alpha-olefin copolymers 失效
    菲利普斯催化剂及其用于制备乙烯/α-烯烃共聚物的用途

    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。

    Phillips catalyst and its use for the preparation of ethylene/.alpha.-olefin copolymers
    4.
    发明授权
    Phillips catalyst and its use for the preparation of ethylene/.alpha.-olefin copolymers 失效
    菲利普斯催化剂及其在制备乙烯/α-烯烃共聚物中的应用

    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。

    Preparation of homopolymers and copolymers of ethene by Phillips catalysis
    6.
    发明授权
    Preparation of homopolymers and copolymers of ethene by Phillips catalysis 失效
    通过菲利普斯催化制备乙烯的均聚物和共聚物

    公开(公告)号：US4728703A

    公开(公告)日：1988-03-01

    申请号：US28651

    申请日：1987-03-20

    申请人： Rainer Konrad ,  Volker Warzelhan ,  Hans Gropper ,  Guenther Schweier

    发明人： Rainer Konrad ,  Volker Warzelhan ,  Hans Gropper ,  Guenther Schweier

    IPC分类号： C08F2/24 ,  C08F4/22 ,  C08F10/02

    CPC分类号： C08F10/02 ,  C08F2410/01

    摘要： Ethene polymers are prepared by Phillips catalysis using (1) a supported catalyst which is loaded with chromium and titanium and (2) a co-catalyst, (1) having been obtained by preparing (1.1) a chromium- and titanium-loaded catalyst intermediate from (1.1.a) a silicate carrier material, (1.1.b) a selected chromium compound and (1.1.c) a selected titanium compound and then (1.2) heating said catalyst intermediate in an oxygen-containing gas stream, the (1) used having been obtained by, in general terms, (1.1) preparing in the first stage (1.1.1) a suspension from (1.1.1.1) a finely divided silicate carrier material and (1.1.1.2) a liquid alkane, (1.1.2) then (1.1.2.1) combining the suspension resulting from (1.1.1.) with (1.1.2.2.) a finely divided chromium trioxide, (1.1.3) thereupon (1.1.3.1) combining the suspension obtained from (1.1.2) with (1.1.3.2) an alkanol, (1.1.4) thereafter (1.1.4.1) combining the suspension formed in (1.1.3) with (1.1.4.2) a titanium compound of the formula Ti(OR).sub.4, where R is alkyl, aryl or cycloalkyl, and (1.1.5) finally evaporating the suspension obtained in (1.1.4) to dryness, and then (1.2) in the second stage first (1.2.1) treating the catalyst intermediate obtained in the first state (1.1) with a nitrogen stream, thereupon (1.2.2) heating the intermediate obtained in (1.2.1) in an oxygen-containing gas stream, and finally (1.2.3) treating the intermediate obtained in (1.2.2) with a nitrogen stream; and as (2) with an alkyllithium.

    摘要翻译： 通过菲利普斯催化法，使用（1）载有铬和钛的载体催化剂和（2）助催化剂制备乙烯聚合物，（1）通过制备（1.1）载有铬和钛的催化剂中间体 从（1.1.a）硅酸盐载体材料，（1.1b）选择的铬化合物和（1.1.c）所选择的钛化合物，然后（1.2）在含氧气流中加热所述催化剂中间体，（1 ）（1.1）在第一阶段（1.1.1）中制备了（1.1.1.1）细分硅酸盐载体材料和（1.1.1.2）液体烷烃（1.1 （1.1.2.1）将由（1.1.1。）得到的悬浮液与（1.1.2.2。）细碎的三氧化铬（1.1.3）（1.1.3.1）组合，得到的悬浮液 1.1.2）与（1.1.3.2）链烷醇（1.1.4）（1.1.4.1）将（1.1.3）中形成的悬浮液与（1.1.4.2）结合形成式 Ti（OR）4，其中R是烷基，芳基或环烷基，和（1.1.5）最终将（1.1.4）中得到的悬浮液蒸发至干，然后在第二阶段（1.2.1）中蒸发（1.2） 用氮气流处理在第一状态（1.1）中获得的催化剂中间体，随后（1.2.2）在含氧气流中加热（1.2.1）中获得的中间体，最后（1.2.3）处理 （1.2.2）中获得的中间体与氮气流; 和（2）与烷基锂反应。

    Preparation of a supported catalyst for the polymerization of .alpha.-olefins
    7.
    发明授权
    Preparation of a supported catalyst for the polymerization of .alpha.-olefins 失效
    制备用于α-烯烃聚合的负载型催化剂

    公开(公告)号：US5625013A

    公开(公告)日：1997-04-29

    申请号：US422937

    申请日：1995-05-24

    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

    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.

    Preparation of homopolymers of ethylene or copolymers of ethylene
    8.
    发明授权
    Preparation of homopolymers of ethylene or copolymers of ethylene 失效
    制备乙烯均聚物或乙烯共聚物

    公开(公告)号：US5414064A

    公开(公告)日：1995-05-09

    申请号：US274692

    申请日：1994-07-14

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

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

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

    CPC分类号： C08F10/02 ,  C08F110/02 ,  Y10S526/901 ,  Y10S526/904

    摘要： 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.

    摘要翻译： 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。

    Preparation of homopolymers and copolymers of ethene by Phillips catalysis
    10.
    发明授权
    Preparation of homopolymers and copolymers of ethene by Phillips catalysis 失效
    通过菲利普斯催化制备乙烯的均聚物和共聚物

    公开(公告)号：US4814308A

    公开(公告)日：1989-03-21

    申请号：US110872

    申请日：1987-10-21

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

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

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

    CPC分类号： C08F10/02

    摘要： 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).

    摘要翻译： 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）。