公开(公告)号：US4037042A

公开(公告)日：1977-07-19

申请号：US720249

申请日：1976-09-02

申请人： Heinz Mueller-Tamm ,  Hans Frielingsdorf ,  Leonhard Gonsior ,  Wolfgang Gruber

发明人： Heinz Mueller-Tamm ,  Hans Frielingsdorf ,  Leonhard Gonsior ,  Wolfgang Gruber

IPC分类号： C08F4/00 ,  C08F4/06 ,  C08F4/24 ,  C08F10/00 ,  C08F4/02 ,  C08F10/02

CPC分类号： C08F10/00

摘要： A process for the manufacture of olefin polymers by polymerization of .alpha.-monoolefins by means of a silicic acid xerogel/chromium trioxide catalyst, which is obtained by a method wherein (1) a finely divided silicic acid xerogel is first manufactured by (1.1) employing a silicic acid hydrogel of relatively high solids content, (1.2) extracting at least 60% of the water contained in the hydrogel from the latter by means of a particular organic liquid, (1.3) drying the gel thus obtained until there is no further loss in weight (xerogel formation) and (1.4) reducing the xerogel thus obtained to particles of diameter from 20 to 2,000 .mu.m,2. this xerogel is then charged with the desired amount of chromium from a solution of chromium trioxide or a solution of a chromium compound which under the conditions of stage (3) is converted to chromium trioxide, with evaporation of the solvent, and3. finally the product thus obtained is heated in an anhydrous stream of gas containing oxygen. The process according to the invention is charaterized in that a catalyst is employed which is manufactured under such conditions that in stage (1) the starting material is a silicic acid hydrogel (1.1) which is substantially spherical, has a particle diameter of from 1 to 8 mm and is obtained byA. introducing a solution of sodium waterglass or potassium waterglass both longitudinally and tangentially into a vortical stream of an aqueous inorganic acid,B. spraying droplets of the resulting silicic acid hydrosol into a gaseous medium,C. allowing the sprayed hydrosol to solidify to a hydrogel in the gaseous medium andD. freeing the resulting substantially spherical hydrogel from salts by washing, without prior aging. The catalyst gives polymers having good processability.

摘要翻译： 一种通过使用硅酸干凝胶/三氧化铬催化剂聚合α-单烯烃制备烯烃聚合物的方法，其通过以下方法获得：其中（1）细分硅酸干凝胶首先由（1.1）采用 具有相对较高固体含量的硅酸水凝胶，（1.2）借助于特定的有机液体从后者中提取水凝胶中至少60％的水，（1.3）干燥所获得的凝胶，直至不再有损失 重量（干凝胶形成）和（1.4）将由此获得的干凝胶还原至直径为20至2,000μm的颗粒。2.该XEROGEL随着三氯化铬溶液或A溶液中所需的铬量而充满 在三级条件下（3）的铬化合物转化为三氧化二铬，溶剂的蒸发，以及3.最终获得的产物在含有氧气的气体的不稳定流中被加热。 根据本发明的方法的特征在于，使用在这样的条件下制造的催化剂：在步骤（1）中，起始材料是基本上为球形的硅酸水凝胶（1.1），其粒径为1至 8毫米，通过A.将钠水玻璃或钾水玻璃的溶液纵向和切向地引入无机酸水溶液的涡旋流中，将所得硅酸水溶胶的液滴喷射到气体介质中，C.允许 喷雾的水溶胶固化成气态介质中的水凝胶，并且通过洗涤将所得到的基本上球形的水凝胶从盐中释放，而无需预先熟化。 该催化剂产生具有良好加工性能的聚合物。

公开(公告)号：US4042770A

公开(公告)日：1977-08-16

申请号：US631642

申请日：1975-11-13

申请人： Robert Bachl ,  Hans Frielingsdorf ,  Wolfgang Gruber ,  Heinz Mueller-Tamm ,  Leonhard Gonsior

发明人： Robert Bachl ,  Hans Frielingsdorf ,  Wolfgang Gruber ,  Heinz Mueller-Tamm ,  Leonhard Gonsior

IPC分类号： C08F4/00 ,  C08F4/06 ,  C08F10/00 ,  C08F4/02 ,  C08F4/24

CPC分类号： C08F10/00 ,  Y02P20/52

摘要： This invention relates to a process for the manufacture of olefin polymers by polymerization of monoolefins with the aid of a silicic xerogel/chromium trioxide catalyst obtained by (1) synthesizing a particulate silicic xerogel, (2) doping this xerogel with chromium trioxide or a chromium compound which converts to chromium trioxide under conditions of stage (3) and (3) maintaining the resulting product at an elevated temperature in a water-free oxygen-containing stream of gas. The characteristic feature of the process of the invention is that the silicic xerogel/chromium trioxide catalyst used is one obtained by (1) synthesizing the silicic xerogel in the first stage as follows: (1.1) taking an aqueous solution of a sodium silicate, (1.2) substituting substantially all of the sodium ions contained in said solution by hydrogen ions by means of an ion exchanger, (1.3) introducing a water-soluble aluminum salt into the resulting aqueous silicic acid solution, (1.4) adjusting the pH of the solution obtained in stage (1.3) to from 0.1 to 3.5, if necessary, (1.5) adjusting the solution obtained in (1.3) or (1.4) to a pH of from 4 to 12 by means of a nitrogen-base compound, (1.6) extracting the product forming the solid phase in stage (1.5) (silicic hydrogel) by means of an alkanol and/or alkanone until the organic liquid absorbs no more water and, finally, (1.7) drying the dehydrated gel saturated with organic liquid resulting from stage (1.6) (xerogel formation). This process makes it possible to obtain polymers having a satisfactory particle size distribution and a favorable melt index.

摘要翻译： 本发明涉及一种通过使用（1）合成硅氧烷干凝胶得到的硅胶干凝胶/三氧化铬催化剂，通过单烯烃的聚合制备烯烃聚合物的方法，（2）将这种干凝胶与三氧化铬或铬 在阶段（3）和（3）的条件下转化成三氧化铬的化合物在无水的含氧气流中保持所得产物在升高的温度。 本发明方法的特征在于，使用的硅干燥剂/三氧化铬催化剂是通过（1）在第一阶段合成硅干凝胶得到的催化剂如下：（1.1）取硅酸钠水溶液（ 1.2）通过离子交换器用氢离子基本上全部取代所述溶液中所含的所有钠离子，（1.3）将水溶性铝盐引入所得水性硅酸溶液中，（1.4）调节溶液的pH （1.3）中得到的化合物为0.1至3.5，如果需要，（1.5）通过氮碱化合物将（1.3）或（1.4）中获得的溶液调节至4至12的pH，（1.6） 通过链烷醇和/或烷酮萃取在阶段（1.5）（硅水凝胶）中形成固相的产物，直到有机液体吸收不再多的水，最后（1.7）干燥由有机液体饱和的脱水凝胶 阶段（1.6）（干凝胶形成）。 该方法可以获得具有令人满意的粒度分布和良好熔融指数的聚合物。