公开(公告)号：US5756627A

公开(公告)日：1998-05-26

申请号：US954429

申请日：1992-09-30

申请人： Hans Gropper ,  Guido Funk ,  Erich Kolk ,  Dieter Oeder

发明人： Hans Gropper ,  Guido Funk ,  Erich Kolk ,  Dieter Oeder

IPC分类号： C08F4/02 ,  C08F4/18 ,  C08F4/22 ,  C08F4/24 ,  C08F10/00 ,  C08F110/02 ,  C08F10/02

CPC分类号： C08F10/00 ,  C08F110/02

摘要： The present invention relates to high molecular weight homopolymers and copolymers of ethene, which homopolymer or copolymer is obtained by polymerizing the monomer(s) at a temperature of from 70.degree. to 150.degree. C. and under a pressure of from 2 to 150 bar in contact witha chromium trioxide catalyst, (1) loading a support based on silicon dioxide with (2) either chromium trioxide or a chromium compound capable of being converted to chromium trioxide under the conditions of stage (3) below and then (3) heating the resulting intermediate in a gas stream containing oxygen, the support (1) being a special silica xerogel obtained by extracting not more than 30% of the water from a silica hydrogel by means of an alkanol, an alkanone or a mixture thereof followed by drying, comminution and fractional screening.

摘要翻译： 本发明涉及乙烯的高分子量均聚物和共聚物，其均聚物或共聚物是通过在70℃至150℃的温度和2至150巴的压力下将单体聚合而获得的 与三氧化铬催化剂接触，（1）在下述阶段（3）的条件下，将（2）三氧化铬或能够转化成三氧化铬的铬化合物（2）加载基于二氧化硅的载体，然后（3）加热 在含有氧的气流中产生中间体，所述载体（1）是通过使用烷醇，烷酮或其混合物从二氧化硅水凝胶中提取不超过30％的水而获得的特殊二氧化硅干凝胶，然后干燥， 粉碎和分数筛选。

公开(公告)号：US5189123A

公开(公告)日：1993-02-23

申请号：US599873

申请日：1990-10-19

申请人： Hans Gropper ,  Guido Funk ,  Erich Kolk ,  Dieter Oeder

发明人： Hans Gropper ,  Guido Funk ,  Erich Kolk ,  Dieter Oeder

IPC分类号： C08F4/02 ,  C08F4/18 ,  C08F4/22 ,  C08F4/24 ,  C08F10/00 ,  C08F110/02

CPC分类号： C08F10/00 ,  C08F110/02

摘要： The present invention relates to a novel catalyst for the preparation of high molecular weight homopolymers and copolymers of ethene, which catalyst is obtainable by(1) loading a support based on silicon dioxide with(2) either chromium trioxide or a chromium compound capable of being converted to chromium trioxide under the conditions of stage (3) below and then(3) heating the resulting intermediate in a gas stream containing oxygen.the support (1) being a special silica xerogel obtained by extracting not more than 30% of the water from a silica hydrogel by means of an alkanol, an alkanone or a mixture thereof followed by drying, comminution and fractional screening.

摘要翻译： 本发明涉及一种用于制备乙烯的高分子量均聚物和共聚物的新催化剂，该催化剂可通过以下步骤获得：（1）将基于二氧化硅的载体与（2）三氧化铬或能够形成 在下面的阶段（3）的条件下转化成三氧化铬，然后（3）在含氧的气流中加热得到的中间体。 载体（1）是通过链烷醇，烷酮或其混合物从二氧化硅水凝胶中提取不超过30％的水而获得的特殊二氧化硅干凝胶，然后干燥，粉碎和分级筛选。

公开(公告)号：US5310712A

公开(公告)日：1994-05-10

申请号：US953629

申请日：1992-09-30

申请人： Guido Funk ,  Rainer Hemmerich ,  Hans Gropper ,  Erich Kolk ,  Godofredo Follmer

发明人： Guido Funk ,  Rainer Hemmerich ,  Hans Gropper ,  Erich Kolk ,  Godofredo Follmer

IPC分类号： C08F4/02 ,  C08F4/06 ,  C08F4/22 ,  C08F4/24 ,  C08F4/69 ,  C08F10/00 ,  B01J35/08 ,  B01J37/08

CPC分类号： C08F10/00

摘要： In a novel process for the preparation of a supported catalyst for the polymerization of .alpha.-olefins, a carrier gel (1) is first prepared by a method in which a sodium or potassium waterglass solution is introduced into a stream of an aqueous mineral acid which is subjected to angular momentum and may contain aluminum ions, longitudinally and tangentially to the stream, the resulting silica hydrosol sprayed in the form of drops into a gaseous medium and allowed to solidify into a hydrogel, and the resulting hydrogel is freed from salts by washing without prior aging and, if necessary, freed from some of the water by extraction with alcohols and/or ketones and is then dried. This gives the carrier gel (1), which is milled and is fractionated according to particle size. In a second process step, the carrier gel (1) is laden with chromium trioxide or with a chromium compound which can be converted into chromium trioxide, after which the resulting chromium-containing carrier gel (2) is heated at from 400.degree. to 1100.degree. C. for from 10 to 1,000 minutes in an anhydrous gas stream containing oxygen in a concentration of more than 10% by volume. In the novel process, it is essential that the drying of the hydrogel be carried out with formation of the carrier gel (1) in a fast dryer in the course of not more than 300 seconds at an inlet temperature of from 200.degree. to 600.degree. C. The supported catalyst prepared in this manner gives homo- and copolymers of ethylene having excellent low temperature impact strength.

摘要翻译： 在制备用于α-烯烃聚合的负载催化剂的新方法中，首先通过一种方法制备载体凝胶（1），其中将钠或钾水玻璃溶液引入无机酸水溶液的流中， 经受角动量并且可以包含与流纵向和切向的铝离子，所得到的二氧化硅水溶胶以液滴的形式喷入气态介质中并使其固化成水凝胶，并且通过洗涤将所得水凝胶除去盐 没有预先老化，如果需要，通过用醇和/或酮萃取除去一些水，然后干燥。 这得到载体凝胶（1），其被研磨并根据粒度进行分级。 在第二工艺步骤中，载体凝胶（1）装载有三氧化铬或可以转化成三氧化铬的铬化合物，之后将所得含铬载体凝胶（2）在400℃加热至1100℃ 在含有浓度超过10体积％的氧气的无水气流中10分钟至1000分钟。 在新颖的方法中，必须在200〜600℃的入口温度下，在不超过300秒的快速干燥器中形成载体凝胶（1），进行水凝胶的干燥。 C.以这种方式制备的负载催化剂得到具有优异的低温冲击强度的乙烯均聚物和共聚物。

公开(公告)号：US4074040A

公开(公告)日：1978-02-14

申请号：US758208

申请日：1977-01-10

申请人： Dieter Oeder ,  Hans Gropper ,  Friedrich Urban

发明人： Dieter Oeder ,  Hans Gropper ,  Friedrich Urban

IPC分类号： C08F10/00 ,  C08F2/02 ,  C08F2/34 ,  C08F10/02

CPC分类号： C08F10/02

摘要： Ethylene polymers are manufactured by polymerizing ethylene under high pressure at high temperatures in an autoclave reactor. The heat of reaction generated by the polymerization is removed, within the reactor, by a cooling system in which the cooling medium is ethylene; the pressure of the monomer in the cooling system should differ by from 0 to 200 bars from the pressure prevailing in the polymerization system, and the temperature of the monomer on entering the cooling system is at least 40.degree. C. lower than the temperature prevailing in the autoclave. The process permits an increase in the conversion achieved in the polymerization reaction.

摘要翻译： 乙烯聚合物通过在高压釜反应器中在高压下高压聚乙烯来制造。 在反应器内通过冷却介质为乙烯的冷却系统除去聚合产生的反应热; 冷却系统中单体的压力应与聚合体系中的压力相差0至200巴，进入冷却系统的单体温度低于低于常温下的温度至少40℃ 高压灭菌器 该方法允许在聚合反应中实现的转化率增加。

公开(公告)号：US3987020A

公开(公告)日：1976-10-19

申请号：US569271

申请日：1975-04-18

申请人： Hans Gropper ,  Dieter Oeder ,  Friedrich Urban

发明人： Hans Gropper ,  Dieter Oeder ,  Friedrich Urban

IPC分类号： C08F10/00 ,  C08F2/34 ,  C08F10/02 ,  C08F110/02 ,  C08F210/16 ,  C08F2/02 ,  C08F2/38

CPC分类号： C08F10/02 ,  C08F110/02 ,  C08F210/16

摘要： Ethylene polymers are produced at pressures between 1000 and 4000 atmospheres and temperatures of from 120.degree. to 300.degree. C in a reaction zone having an 1/d ratio of from 10:1 to 20:1 while shear forces act on the reaction mixture. The ethylene is fed continuously and radially to the reaction zone at a velocity of from 2 to 20 m/sec. The average residence time of the reaction mixture in the reaction zone is from 20 to 90 seconds. The products show a broad molecular weight distribution and are particularly advantageous for use as extruded coatings.

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。

公开(公告)号：US5189120A

公开(公告)日：1993-02-23

申请号：US605002

申请日：1990-10-30

申请人： Norbert Hasenbein ,  Peter Bauer ,  Lothar Schlemmer ,  Alfred F. Hauss ,  Hans Gropper ,  Rainer Ohlinger

发明人： Norbert Hasenbein ,  Peter Bauer ,  Lothar Schlemmer ,  Alfred F. Hauss ,  Hans Gropper ,  Rainer Ohlinger

IPC分类号： C08F255/02 ,  C09J151/06

CPC分类号： C09J151/06 ,  C08F255/02

摘要： In a process for the peroxide-free grafting of ethylenically unsaturated carboxylic acids, carboxylic anhydrides and/or their derivatives to a homopolymer or copolymer of ethylene having a density less than 0.930 g/cm.sup.3, the monomers to be grafted are used in a concentration of from 0.01 to 0.5% by weight and the grafting reaction is carried out at from 210.degree. to 300.degree. C. in a conventional extruder or mixer in the absence of a free radical initiator. The graft copolymers are used for the preparation of ionomers and adhesion promoters.

摘要翻译： 在将烯键式不饱和羧酸，羧酸酐和/或其衍生物过氧化物接枝到密度小于0.930g / cm 3的乙烯的均聚物或共聚物的方法中，待接枝的单体的浓度为 在常规挤出机或混合器中，在不存在自由基引发剂的情况下，接枝反应在210-300℃下进行。 接枝共聚物用于制备离聚物和粘合促进剂。

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。

公开(公告)号：US4076919A

公开(公告)日：1978-02-28

申请号：US741939

申请日：1976-11-15

申请人： Friedrich Urban ,  Oskar Buechner ,  Ulrich Hartig ,  Hans Gropper

发明人： Friedrich Urban ,  Oskar Buechner ,  Ulrich Hartig ,  Hans Gropper

IPC分类号： C08F2/00 ,  C08F4/28 ,  C08F10/00 ,  C08F10/02

CPC分类号： C08F10/02

摘要： Ethylene polymers are manufactured in a tubular reactor under high pressure and at high temperatures in the presence of polymerization initiators. The polymerization is carried out in two different zones of the reactor, a mixture of ethylene, oxygen and regulator being fed into the first zone and a co-initiator having a half-life temperature, measured in benzene, of above 140.degree. C being additionally fed into the second zone. The co-initiator may be a peroxide or a hydroperoxide. The melt index, or the haze and gloss of a film produced from the resulting ethylene polymer, can be varied advantageously through the choice of the co-initiator.

摘要翻译： 乙烯聚合物在管式反应器中在高压和高温下在聚合引发剂存在下制备。 在反应器的两个不同区域进行聚合，将乙烯，氧气和调节剂的混合物进料到第一区域中，另外在苯中测定的具有半衰期温度的共引发剂在140℃以上 进入第二区。 共引发剂可以是过氧化物或氢过氧化物。 可以通过选择共引发剂来有利地改变由所得乙烯聚合物制备的膜的熔体指数或雾度和光泽度。

公开(公告)号：US4710552A

公开(公告)日：1987-12-01

申请号：US876299

申请日：1986-06-18

申请人： Robert Bachl ,  Volker Warzelhan ,  Guenther Schweier ,  Hans Gropper ,  Wolfgang Ball

发明人： Robert Bachl ,  Volker Warzelhan ,  Guenther Schweier ,  Hans Gropper ,  Wolfgang Ball

IPC分类号： C08F4/00 ,  C08F4/60 ,  C08F4/64 ,  C08F4/642 ,  C08F4/658 ,  C08F4/68 ,  C08F10/00 ,  C08F10/02 ,  C08F210/02

CPC分类号： C08F10/00 ,  C08F10/02 ,  Y10S526/901

摘要： Homopolymers and copolymers of ethene are prepared using a Ziegler catalyst system comprising (1) a transition metal catalyst component, (2) an organoaluminum catalyst component and (3) an organohalogen catalyst component, by a method in which the transition metal catalyst component (1) employed is a solid-phase product (VI) obtained by (1.1) first combining (1.1.1) an inorganic oxidic substrate (I), as the carrier, with (1.1.2) a solution (II) consisting 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 required, (IIb3) a zirconium tetrahalide to form a suspension (III), evaporating down this suspension to form a solid-phase intermediate (IV), and (1.2) then (1.2.1) combining the solid-phase intermediate (IV) obtained from (1.1) with (1.2.2) a solution of an organoaluminum compound (V) to form a suspension, the resulting suspended solid-phase product (VI) being the transition metal catalyst component (1).

摘要翻译： 使用齐格勒催化剂体系制备乙烯的均聚物和共聚物，所述齐格勒催化剂体系包括（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，通过其中过渡金属催化剂组分 ）是通过（1.1）首先将作为载体的无机氧化物基质（I）与（1.1.2）由（IIa）组成的溶液（II）首先组合（1.1.1）获得的固相产物（VI） ）（IIb）（IIb1）三氯化钒/醇络合物，（IIb2）三卤化钛或三卤化钛/醇络合物的混合物（IIb），如果需要，（IIb3）四卤化锆以形成悬浮液（III ），将该悬浮液蒸发以形成固相中间体（IV），和（1.2）然后（1.2.1）将由（1.1）获得的固相中间体（IV）与（1.2.2）得到的固相中间体 有机铝化合物（V）以形成悬浮液，得到的悬浮固相产物（VI） 过渡金属催化剂组分（1）。