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    • 22. 发明授权
    • Preparation of homopolymers and copolymers of .alpha.-monoolefins using
a Ziegler-Natta catalyst system
    • 使用齐格勒 - 纳塔催化剂体系制备α-单烯烃的均聚物和共聚物
    • US4579919A
    • 1986-04-01
    • US673337
    • 1984-11-20
    • Gerhard StaigerWolfgang Gruber
    • Gerhard StaigerWolfgang Gruber
    • C08F4/10C08F4/16C08F10/00C08F4/02
    • C08F10/00
    • .alpha.-Monoolefins are polymerized using a catalyst system which comprises (1) a titanium component obtained by first (1.a) preparing an intermediate from (1.a.1) titanium tetrachloride, (1.a.2) a modifier and (1.a.3) a magnesium alcoholate, and the (1.b) preparing the titanium component from (1.b.1) titanium tetrachloride, (1.b.2) the intermediate from (1.a) and, if required, (1.b.3) a further modifier, (2) an alkylaluminum and (3) a cocatalyst. In this process, (i) the titanium component (1) used is obtained by first (1.1) preparing a first intermediate from (1.1.1) titanium tetrachloride, (1.1.2) a modifier obtained from (1.1.2.1) a titanate and (1.1.2.2) a phthaloyl dichloride, and (1.1.3) a magnesium alcoholate, then (1.2) preparing a second intermediate from (1.2.1) titanium tetrachloride, (1.2.2) the intermediate from (1.1) and, if required, (1.2.3) a phthaloyl dichloride as a further modifier, and finally (1.3) preparing the titanium component from (1.3.1) titanium tetrachloride and (1.3.2) the intermediate from (1.2), and (ii) the cocatalyst (3) used is a trialkoxysilane.
    • α-烯烃使用催化剂体系进行聚合,所述催化剂体系包括(1)通过首先(1.a)从(1.a)四氯化钛制备中间体,(1.a.2)改性剂和( 1.a.3)一种醇镁,和(1.b)从(1.b.1)四氯化钛制备钛组分,(1.b.2)中间体为(1.a),如果 (1.b.3)另一种改性剂,(2)烷基铝和(3)助催化剂。 在该方法中,(i)使用的钛组分(1)首先(1.1)由(1.1.1)四氯化钛制备第一中间体,(1.1.2)由(1.1.2.1)得到的改性剂钛酸酯 和(1.1.2.2)邻苯二甲酰二氯化物,和(1.1.3)醇镁酸盐,然后(1.2)从(1.1.1)四氯化钛(1.2.1)制备第二中间体,(1.2.2)(1.1)中间体, (1.2.3)邻苯二甲酰二氯作为其他改性剂,最后(1.3)从(1.3.1)四氯化钛制备钛组分和(1.3.2)中间体(1.2)和(ii) 所用的助催化剂(3)是三烷氧基硅烷。
    • 26. 发明授权
    • Manufacture of olefin polymers
    • 烯烃聚合物的制造
    • US4037042A
    • 1977-07-19
    • US720249
    • 1976-09-02
    • Heinz Mueller-TammHans FrielingsdorfLeonhard GonsiorWolfgang Gruber
    • Heinz Mueller-TammHans FrielingsdorfLeonhard GonsiorWolfgang Gruber
    • C08F4/00C08F4/06C08F4/24C08F10/00C08F4/02C08F10/02
    • C08F10/00
    • 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.
    • 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。