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1. 发明授权

US5557021A Phillips catalyst and its use for the preparation of ethylene/.alpha.-olefin copolymers 失效
标题翻译：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。

2. 发明授权

US5480852A Phillips catalyst and its use for the preparation of ethylene/alpha-olefin copolymers 失效
标题翻译：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。

3. 发明授权

US5352658A Phillips catalyst and its use for the preparation of ethylene homopolymers and copolymers 失效
标题翻译：菲利普斯催化剂及其在制备乙烯均聚物和共聚物中的应用
公开(公告)号：US5352658A
公开(公告)日：1994-10-04
申请号：US16277
申请日：1993-02-11
申请人： Kaspar Evertz , Roland Saive , Guido Funk , Peter Koelle , Rainer Konrad , Hans Gropper
发明人： Kaspar Evertz , Roland Saive , Guido Funk , Peter Koelle , Rainer Konrad , Hans Gropper
IPC分类号： C08F2/42 , C08F4/00 , C08F4/02 , C08F4/06 , C08F4/22 , C08F4/24 , C08F4/69 , C08F10/00 , C08F10/02 , B01J31/00
CPC分类号： C08F10/00
摘要： 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.
摘要翻译：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。

4. 发明授权

US5455216A Preparation of a supported catalyst for the polymerization of .alpha.-olefins 失效
标题翻译：制备用于α-烯烃聚合的负载型催化剂
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.

5. 发明授权

US5625013A Preparation of a supported catalyst for the polymerization of .alpha.-olefins 失效
标题翻译：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.

6. 发明授权

US5039765A Preparation of ethylene polymers using a Ziegler catalyst system, and ethylene polymers prepared in this manner and having less odor 失效
标题翻译：使用齐格勒催化剂体系制备乙烯聚合物，以及以这种方式制备并具有较少气味的乙烯聚合物
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。

7. 发明授权

US5414064A Preparation of homopolymers of ethylene or copolymers of ethylene 失效
标题翻译：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。

8. 发明授权

US06699947B1 Method for producing Phillips catalysts for polymerizing olefins with better productivity rates in the particle-form process 失效
标题翻译：用于在颗粒形成方法中以更好的生产率生产用于聚合烯烃的菲利普斯催化剂的方法
公开(公告)号：US06699947B1
公开(公告)日：2004-03-02
申请号：US10070805
申请日：2002-03-11
申请人： Kaspar Evertz , Guido Funk , Paulus de Lange , Peter Kölle , Andreas Deckers
发明人： Kaspar Evertz , Guido Funk , Paulus de Lange , Peter Kölle , Andreas Deckers
IPC分类号： C08F424
CPC分类号： C08F10/02 , B01J23/26 , C08F110/02 , C08F4/24 , C08F2/14 , C08F4/025 , C08F2500/12 , C08F2500/18
摘要： In a process for producing Phillips catalysts in which an oxidic support material is treated in suspension with a chromium salt solution and subsequently, after removing the solvent, calcined in an oxygen-containing atmosphere at above 300° C., the oxidic support material and/or the catalyst after calcination are/is, according to the present invention, comminuted until a mean particle size of
摘要翻译：在制备菲利普斯催化剂的方法中，其中氧化载体材料用铬盐溶液悬浮处理，随后在除去溶剂之后，在含氧气氛中在300℃以上煅烧，氧化载体材料和/ 或根据本发明的煅烧后的催化剂粉碎直至达到<100μm的平均粒度，并且尺寸<50μm的颗粒的比例为至少30％，优选在该范围内从40％到80％。还提供了在通过本发明的方法生产的催化剂存在下，在30至150℃的压力范围内，在环管反应器中制备乙烯的均聚物或共聚物的方法。

9. 发明授权

US5210160A Preparation of homopolymers of ethene and copolymers of ethene with higher a-monoolefins using a Ziegler catalyst system 失效
标题翻译：使用齐格勒催化剂体系制备乙烯与乙烯共聚物与高级单环戊二烯的共聚物
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）。

10. 发明授权

US5112928A Preparation of homopolymers of ethene and copolymers of ethene with high .alpha.-monoolefins using a Ziegler catalyst system 失效
标题翻译：使用齐格勒催化剂体系制备高（ALPHA） - 烯烃的乙烯和乙烯共聚物的共聚物
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）。

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