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    Manufacture of particulate homopolymers or copolymers of ethylene
    1.
    发明授权
    Manufacture of particulate homopolymers or copolymers of ethylene 失效
    颗粒均聚物或乙烯共聚物的制造

    公开(公告)号：US3941760A

    公开(公告)日：1976-03-02

    申请号：US478864

    申请日：1974-06-13

    申请人： Rudolf Herbeck ,  Erich Kolk ,  Guenther Schweier ,  Hans Schick ,  Friedrich Urban

    发明人： Rudolf Herbeck ,  Erich Kolk ,  Guenther Schweier ,  Hans Schick ,  Friedrich Urban

    IPC分类号： C08F4/00 ,  C08F4/60 ,  C08F10/00 ,  C08F4/02 ,  C08F10/02

    CPC分类号： C08F10/00 ,  Y10S526/908 ,  Y10S526/909

    摘要： Particulate polymers of ethylene are prepared by polymerization of ethylene or ethylene/.alpha. -monoalkene mixtures in a dry agitated bed (B) of the particulate polymer by means of a Ziegler/Natta catalyst system consisting of (1) a titanium-containing component and (2) an aluminum-containing component, the said components (1) and (2) being separately fed to the bed (B). Component (1) is a particulate reaction product (U) (of) (1.1) a substance of the formula TiCl.sub.3 . (AlCl.sub.3).sub.n where n is a number equal to from 0 to 0.34, and (1.2) a reaction product (R) of phosgene and a substnace (S) obtained from a substance of the formula Mg.sub.6 . Al.sub.2 . (OH).sub.16 . CO.sub.3 . (H.sub.2 O).sub.4 by calcination (heating), provided that (R) has a chlorine content of from 10 to 76% by weight and (U) has been obtained by milling (1.1) and (1.2) together.

    摘要翻译： 通过由（1）含钛组分和（1）的齐格勒/纳塔催化剂体系在颗粒聚合物的干燥搅拌床（B）中聚合乙烯或乙烯/α-单烯烃混合物来制备乙烯的颗粒聚合物， 2）含铝组分，所述组分（1）和（2）分别进料到床（B）。 组分（1）是式TiCl 3的物质的颗粒反应产物（U）（的）（1.1）。 （AlCl 3）n，其中n是等于0至0.34的数，和（1.2）光气的反应产物（R）和由式Mg 6的物质获得的基团（S）。 Al2。 （OH）16。 CO3。 （H），通过煅烧（加热），（R）的氯含量为10〜76重量％，（U）通过研磨（1.1）和（1.2）得到。

    Manufacture of olefin polymers
    2.
    发明授权
    Manufacture of olefin polymers 失效
    烯烃聚合物的制造

    公开(公告)号：US4175170A

    公开(公告)日：1979-11-20

    申请号：US720777

    申请日：1976-09-07

    申请人： Guenther Schweier ,  Robert Bachl ,  Heinz Mueller-Tamm ,  Hans Frielingsdorf ,  Wolfgang Gruber ,  Erich Kolk

    发明人： Guenther Schweier ,  Robert Bachl ,  Heinz Mueller-Tamm ,  Hans Frielingsdorf ,  Wolfgang Gruber ,  Erich Kolk

    IPC分类号： C08F4/00 ,  B01J35/10 ,  C08F4/60 ,  C08F4/62 ,  C08F10/00 ,  C08F4/02 ,  C08F10/02

    CPC分类号： C08F10/00

    摘要： Manufacture of polymers of .alpha.-monoolefins by polymerization with a Ziegler catalyst system comprising (1) a catalyst component containing titanium and/or vanadium and (2) a particular compound of the metals aluminum, magnesium or zinc. The characteristic feature of the process according to the invention is that the catalyst component (1) containing titanium and/or vanadium is the solid-phase product (VII) contained by first (1.1) bringing a finely divided porous inorganic oxidic material (I), which has the formula Al.sub.2 O.sub.3 or SiO.sub.2.aAl.sub.2 O.sub.3, where a is a number from 0 to 2, into contact with an aluminum compound (II) dissolved in an organic solvent, to form a solid-phase product (III), then (1.2) bringing the solid-phase product (III) obtained in stage (1.1) into contact with a magnesium compound (IV), dissolved in an organic solvent, to form a solid-phase product (V), and finally (1.3) bringing the solid-phase product (V) obtained in stage (1.2) into contact with a compound (VI) of the transition metals titanium and/or vanadium to form a solid-phase product (VII). This process functions better than comparable conventional processes.

    摘要翻译： 通过用齐格勒催化剂体系聚合制备α-单烯烃的聚合物，其包含（1）含有钛和/或钒的催化剂组分和（2）金属铝，镁或锌的特定化合物。 根据本发明的方法的特征在于，含有钛和/或钒的催化剂组分（1）是首先（1.1）所含的固体相产物（VII），使细碎的多孔无机氧化物质（I） ，其中a为0至2的数为Al 2 O 3或SiO 2·aAl 2 O 3，与溶于有机溶剂的铝化合物（II）接触，形成固相产物（III），然后（1.2 ）使得在阶段（1.1）中获得的固相产物（III）与溶解在有机溶剂中的镁化合物（IV）接触形成固相产物（V），最后（1.3） 在阶段（1.2）中获得的固相产物（V）与过渡金属钛和/或钒的化合物（VI）接触以形成固相产物（VII）。 该过程比可比较的常规方法更好。

    Manufacture of homopolymers and copolymers of .alpha.-monoolefins
    3.
    发明授权
    Manufacture of homopolymers and copolymers of .alpha.-monoolefins 失效

    公开(公告)号：US4110523A

    公开(公告)日：1978-08-29

    申请号：US762856

    申请日：1977-01-27

    申请人： Guenther Schweier ,  Erich Kolk ,  Heinz Mueller-Tamm ,  Hans Frielingsdorf ,  Robert Bachl ,  Wolfgang Gruber

    发明人： Guenther Schweier ,  Erich Kolk ,  Heinz Mueller-Tamm ,  Hans Frielingsdorf ,  Robert Bachl ,  Wolfgang Gruber

    IPC分类号： C08F4/00 ,  C08F4/16 ,  C08F4/60 ,  C08F10/00 ,  C08F4/02 ,  C08F10/02

    CPC分类号： C08F10/00

    摘要： A process for the manufacture of homopolymers and copolymers of .alpha.-monoolefins of 2 to 6 carbon atoms by polymerizing the monomer or monomers by means of a Ziegler catalyst system comprising (1) a catalyst component containing titanium and (2) a particular compound of the metals aluminum, magnesium or zinc, the atomic ratio of titanium from catalyst component (1) to metal from catalyst component (2) being from 1:0.1 to 1:500, wherein the titanium-containing catalyst component (1) employed is the solid-phase product (IV) obtained by bringing into contact (1.1) a finely divided, porous, inorganic oxidic material (I) which has the formula SiO.sub.2 . aAl.sub.2 O.sub.3 --, where a is a number from 0 to 2, and (1.2) a solution (II) formed on bringing together (IIa) 100 parts by weight of an alcohol of the general formula Z--OH, where Z is a saturated hydrocarbon radical of 1 to 8 carbon atoms, (IIb) from 0.01 to 6 parts by weight (calculated as titanium) of a titanium trihalide and (IIc) from 0.01 to 4 parts by weight (calculated as magnesium) of a magnesium compound which is soluble in the alcohol (IIa), so as to form a dispersion (III), with the proviso that the weight ratio of inorganic oxidic material (I) to titanium in the titanium trihalide (IIb) is from 1:0.01 to 1:0.2 and the weight ratio of inorganic oxidic material (I) to magnesium in the magnesium compound (IIc) is from 1:0.01 to 1:0.25, and evaporating the dispersion (III) until it has a dry consistency, thus forming the solid-phase product (IV). The new process is particularly advantageous for the manufacture of homopolymers and copolymers having, for example, particularly advantageous morphological properties.

    Preparation of homopolymers and copolymers of ethene by Phillips catalysis
    4.
    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：US4727124A

    公开(公告)日：1988-02-23

    申请号：US047116

    申请日：1987-05-08

    申请人： Rainer Konrad ,  Rudolf Mueller-Mall ,  Guenther Schweier

    发明人： Rainer Konrad ,  Rudolf Mueller-Mall ,  Guenther Schweier

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

    CPC分类号： C08F10/00 ,  C08F2410/01

    摘要： 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).

    摘要翻译： 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）。

    Preparation of homopolymers and copolymers of .alpha.-mono-olefins by means of a Ziegler-Natta catalyst system
    5.
    发明授权
    Preparation of homopolymers and copolymers of .alpha.-mono-olefins by means of a Ziegler-Natta catalyst system 失效

    公开(公告)号：US4385162A

    公开(公告)日：1983-05-24

    申请号：US256129

    申请日：1981-04-21

    申请人： James F. R. Jaggard ,  Peter Klaerner ,  Guenther Schweier

    发明人： James F. R. Jaggard ,  Peter Klaerner ,  Guenther Schweier

    IPC分类号： C08F4/64 ,  C08F10/00

    CPC分类号： C08F10/00 ,  Y10S526/906

    摘要： A process for the preparation of homopolymers and copolymers of .alpha.-monoolefins by means of a Ziegler-Natta catalyst system comprising (1) a titanium-III component, which is prepared by subjecting (1.1) a titanium trichloride/aluminum trichloride compound (a) and (1.2) an ester (b) to a certain type of milling treatment in which (A) a vibratory ball mill providing a relatively high milling acceleration is used, (B) the mill is first charged with the titanium-containing compound (a) and, if appropriate, is run for a certain period, thereafter (C) the ester (b) is added at a certain rate while milling the charge, thereupon (D) the charge is kept at +15.degree. C. or above for a certain period, while continuing the milling, hereupon (E), if appropriate, the product obtained from (D) is milled further for a certain period at +5.degree. C. or below, then (F), if appropriate, but advantageously so, the product obtained from (D) or (E) is kept at +20.degree. C. or above for a certain period, without milling, and thereafter (G), if appropriate, the product obtained from (F) is milled further for a certain period at +5.degree. C. or below, (2) an aluminum-alkyl component containing a chlorine bonded to the aluminum, and (3), if appropriate, a phenolic compound of a certain category, in which process a titanium-III component (1) is employed, in the preparation of which additionally .sup.- (H) a suspension is prepared from (H.sub.1) the product obtained according to (D), (E), (F) or (G), (H.sub.2) a liquid hydrocarbon (c) and (H.sub.3) an oxygen-containing compound (d), consisting of (d.sub.1) an ether of a certain category and/or (d.sub.2) an ester of a certain category, thereafter (I) the suspension obtained according to (H) is kept at an elevated temperature for a certain period, with vigorous agitation, and is then cooled, hereupon (J), if appropriate, the solid is isolated from the suspension obtained according to (I), and, if desired, is washed with a liquid hydrocarbon and dried, the novel titanium-III component (1) being the solid, in suspended form, obtained according to (I) or the solid, in isolated form, obtained according to (J). Using this Ziegler-Natta catalyst system, polymers with relatively high stereo-regularity and advantageous morphological properties can be obtained in relatively high yield.

    Preparation of homopolymers and copolymers of ethylene by means of a Ziegler catalyst system
    8.
    发明授权
    Preparation of homopolymers and copolymers of ethylene by means of a Ziegler catalyst system 失效
    通过齐格勒催化剂体系制备乙烯的均聚物和共聚物

    公开(公告)号：US4845177A

    公开(公告)日：1989-07-04

    申请号：US107996

    申请日：1987-10-14

    申请人： Heinz Vogt ,  Eckard Schauss ,  Guenther Schweier

    发明人： Heinz Vogt ,  Eckard Schauss ,  Guenther Schweier

    IPC分类号： C08F4/50 ,  C08F4/64 ,  C08F10/00

    CPC分类号： C08F10/00 ,  Y10S526/901 ,  Y10S526/904

    摘要： Ethylene is polymerized using a Ziegler catalyst system consisting of (1) a titanium catalyst component and (2) an aluminum catalyst component, the component (1) used being the product (VI) which is obtained by a method in which (1.1) first (1.1.1) a carrier (I) and (1.1.2) a solution (II) of (IIa) a solvent, (IIb) a titanium trichloride and (IIc) magnesium chloride are combined with formation of a dispersion (III) and the latter is evaporated down with formation of an intermediate (IV), and (1.2) then (1.2.2) the intermediate (IV) obtained from (1.1), and (1.2.2) an aluminum component (V) consisting of (1.2.2.1) a complex of a certain oxacycloalkane and a certain aluminum compound and (1.2.2.2) if necessary, a certain free aluminum compound are combined, the resulting product (VI) being the catalyst component (1). In this process, a component (1) is employed which has been prepared using, in (1.1) under (1.1.2), a solution (II) which (i) contains a ketone as (IIa) and (ii) additionally contains (IId) a certain low molecular weight polymeric compound.

    摘要翻译： 使用由（1）钛催化剂组分和（2）铝催化剂组分组成的齐格勒催化剂体系聚合乙烯，所述组分（1）是通过以下方法获得的产物（VI）：其中（1.1）第一 （1.1.1）将（IIa）溶剂（IIb），三氯化钛和（IIc）氯化镁的（IIa）溶液（II）和（1.1.2）与形成分散体（III） （1.2）然后（1.2.2）由（1.1）得到的中间体（Ⅳ）和（1.2.2）由（Ⅳ）组成的铝组分（Ⅴ）组成的铝组分（Ⅴ） （1.2.2.1）某种氧杂环烷烃和某种铝化合物的络合物和（1.2.2.2）（如果需要）合并一定的游离铝化合物，所得产物（VI）是催化剂组分（1）。 在该方法中，使用在（1.1）（1.1.2）中使用（1.1）中的（1.1）制备的组分（1），其中（i）包含酮作为（IIa）和（ii）另外含有 （IId）某种低分子量聚合物。

    Preparation of homopolymers and copolymers of ethene by Phillips catalysis
    9.
    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）。