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公开(公告)号：DE2721058A1
公开(公告)日：1978-11-23
申请号：DE2721058
申请日：1977-05-11
Applicant: BASF AG
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公开(公告)号：DE2604549A1
公开(公告)日：1977-08-11
申请号：DE2604549
申请日：1976-02-06
Applicant: BASF AG
Inventor： GRUBER WOLFGANG DIPL CHEM DR , FRIELINGSDORF HANS DIPL ING DR , MUELLER-TAMM HEINZ DIPL CHEM D
Abstract: A process for the manufacture of olefin polymers by polymerizing alpha -monoolefins of 2 to 8 carbon atoms by means of a catalyst which is obtained from a silicon-containing material (component a), an organo-metallic compound containing alkyl groups (component b) and a chromium compound (component c), wherein the catalyst employed is obtained by (1) first bringing into contact (1.1) an alkogel (component a) of the empirical formula SiO2 x m Al2O3 x n ROH, where m is a number from 0 to 2, n is a number such that the content of ROH in the alkogel is from 1 to 85 per cent by weight and R is alkyl of 3 to 8 carbon atoms, and (1.2) an aluminum compound containing certain alkyl groups (component b), with intimate mixing, to form a solid-phase reaction product, (2) then bringing into contact (2.1) the solid-phase reaction product obtained from stage (1) and (2.2) a solution of a particular chromium compound (component c), with intimate mixing and evaporation of the solvent, and (3) finally heating the product, obtained from stage (2), in an anhydrous stream of gas containing oxygen, with the proviso that the product obtained from stage (1) or from stage (2) is dried and comminuted before it is used further in the next stage. This process makes it possible to influence the essential properties of the polymers in relatively diverse ways, in the desired direction, by relatively slight modifications of the catalyst.
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公开(公告)号：DE2540278A1
公开(公告)日：1977-03-24
申请号：DE2540278
申请日：1975-09-10
Applicant: BASF AG
Inventor： MUELLER-TAMM HEINZ DR , FRIELINGSDORF HANS DIPL ING DR , GONSIOR LEONHARD DR , GRUBER WOLFGANG DR
Abstract: 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, AND 3. 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 by A. 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 and D. freeing the resulting substantially spherical hydrogel from salts by washing, without prior aging. The catalyst gives polymers having good processability.
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14.发明专利
公开(公告)号：DE2455557A1
公开(公告)日：1976-05-26
申请号：DE2455557
申请日：1974-11-23
Applicant: BASF AG
Inventor： BACHL ROBERT DIPL CHEM DR , FRIELINGSDORF HANS DIPL ING DR , GRUBER WOLFGANG DIPL CHEM DR , MUELLER-TAMM HEINZ DIPL CHEM D , GONSIOR LEONHARD DIPL CHEM DR
Abstract: Silicic acid-xerogel/Cr2O3 catalyst for polymsn. of olefins is obtd. by (1) first forming a finely divided (10-200 mu-m. dia.) silicic acid xerogel, (2) charging the xerogel with 0.1-10wt.% (w.r.t. the xerogel and calc. as Cr) of Cr2O3 or a Cr cpd. which forms Cr2O3 in step (3), and (3) holding the resulting prodt. in a water-free gas stream contg. >10vol.% 02, for 10-1000 mins. at 400-1100 degrees C, the silicic acid-xerogel being produced by (1.ue starting from a 0.1-20wt.% solids (calc. as SiO2) contg. aq. soln. of water glass, (1.2) exchanging the Na+ ion in the soln. for H+ with an ion exchanger until the Na content (calc. as Na2O) in the silicic acid xerogel amts. to is not >0.2wt.%, (1.3) adding to the soln. a water-sol Al salt (and opt. water) of such a kind that a wt. ratio water:silicic acid (calc. as SiO2) of 100:0.05-100:24 as well as a wt. ratio SiO2:Al2O3 of 100:100-100: 2 is obtd., (1.4) opt. bringing the resulting soln. to a pH of 0.1-3.5 with an aq.inorganic acid soln. of such a kind that the wt.ratio water:silicic acid and SiO2:Al2O3 remain as in (1.3), (1.5) bring the resulting soln. to a pH of 4-12 with a water-sol. neutralising nitrogen base, (1.6) extracting the resulting solid phase prodt. (silicic acid hydrogel) using a 1-4C alkanol and/or 3-5C alkanone until the organic liq. takes up no more water, and finally (1.7) drying the dehydrated gel, which is satd. with organic liq. until at 120 degrees C no further wt. loss occurs (xerogel-formation). The resulting catalyst can be used for polymsn. of olefins in the absence of M.W- regulators or in presence of a comparatively small amt. of M.W. regulator.
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15.发明专利
公开(公告)号：DE2411734A1
公开(公告)日：1975-09-25
申请号：DE2411734
申请日：1974-03-12
Applicant: BASF AG
Inventor： FRIELINGSDORF HANS DIPL ING DR , GRUBER WOLFGANG DIPL CHEM DR , MUELLER-TAMM HEINZ DIPL CHEM D , GONSIOR LEONHARD DIPL CHEM DR
Abstract: Olefin polymsn. catalysts are made by (1) forming a finely divided silica xerogel with a particle size of 10 to 2000 mu m by (a) making a 10-25 wt. % solids (as SiO2) silicic acid hydrogel, (b) extracting water from the hydrogel with a 1-4 C alkanol and/or a 3-5 C alkanone until the org. liq. takes up no more water and (c) drying the dewatered gel, satd. with the org. liq. until no further wt. loss occurs on heating at 180 degrees C/10 Torr for 30 mins.; (2) mixing the resulting xerogel with solid, finely divided CR2O3 and heating at 100-300 degrees C/0.01-250 Torr until the xerogel has taken up 0.1-10 wt. % Cr2O3 (calculated as Cr), and (3) treating the prod. for 10-1000 min. at 40-1100 degrees C in a moisture-free gas stream contg. >10 vol. % O2. The catalyst give high yields and have high activity, and the resulting polymers have relatively narrow particle size distribution, low fines content and a sufficiently high melt index when made in the absence of mol. wt. regulators.
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Patent Agency Ranking
公开(公告)号：DE2854150A1
公开(公告)日：1980-07-03
申请号：DE2854150
申请日：1978-12-15
Applicant: BASF AG
Inventor： KLAERNER PETER DIPL CHEM DR , SCHWEIER GUENTER DIPL CHEM DR , FRIELINGSDORF HANS DIPL ING DR
Abstract: In the prepn. of a Ziegler catalyst component by (1) dry milling a Ti (III) or (IV) chloride, oxychloride or 1-8C alkoxy chloride, or mixed chloride TiCl3. AlCl3, (in which z is less than 5), with a chlorination prod.z of a cpd. of formula (Mea)6.(Meb)2(OH)16CO3(H2O)4, (in which Mea is Mg, Ca, Zn or Mn; Meb is Al or Cr), in wt. ratio 1:2-200 for 5-100 h. under milling acceleration of 4-6m/s2, (2) 1 part of the prod. is then mixed with 0.01-1 part 1-12C alkanol (V) and 1-1000 parts 5-12C alkene (VI) for 0.5-60 mins. at 0-195 degrees C. This is opt. followed by (3) mixing the suspension with a metal cpd. (VIII) of formula MtGs-tEt, (in which Mt is Al or Si; G is a 1-12C hydrocarbon gp. E is Cl, Br, H or -OD; D is as G; s is the valency of Mt; t is 0-2 when Mt is Al, or 0-4 when Mt is Si) until the atomic ratio Ti: mt is 1 : 0.5-20. Used for homo and co-polymerisation of 2-6C alpha-mono-olefins. Polymer yield per unit wt. of Ti is increased, and amt. of fine-grain polymer below 0.1 mm size is reduced.
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公开(公告)号：DE2852902A1
公开(公告)日：1980-06-26
申请号：DE2852902
申请日：1978-12-07
Applicant: BASF AG
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18.发明专利
公开(公告)号：DE2847758A1
公开(公告)日：1980-05-14
申请号：DE2847758
申请日：1978-11-03
Applicant: BASF AG
Inventor： BACHL ROBERT DIPL CHEM DR , FRIELINGSDORF HANS DIPL ING DR , HOEHR LOTHAR DIPL CHEM DR , SCHWEIER GUENTHER DIPL CHEM DR , STAIGER GERHARD DIPL CHEM DR
Abstract: The Ti component of a Ziegler catalyst is made by a two-stage process in which (1) an oxide (I) of formula SiO2.aAl2O3 (in which a is 0-2), with particle size 1-1000 mu m, pore vol. 0.3-3 cm3/g and surface area 100-1000 m2/g, is dispersed in a mixt. (II) of (a) 100 parts 1-8C satd. alcohol, (b) 0.01-6 parts (as Ti) of TiX3 (in which X is Cl and/or Br) and (c) 0.01-4 parts (as Mg) of a Mg alcoholate, carboxylate or salt of a CH-acid cpd., to give oxide/Ti wt. ratio 1:0.01-0.2 and oxide/Mg ratio 1:0.01-0.2. The dispersion is dried to a solid phase at above the m.pt. of (a) and below 200 degrees C, and (2) mixed with (V) an acyl halide, opt. dissolved in organic solvent, to give a molar ratio of Ti to (V) of 1:0.01-100 in the catalyst component. Used in combination with organic cpds. of Al, Mg, or Zn, as catalysts for homo- or co-polymerisation of 2-6C alpha-olefines, at 30-200 degrees C under 0.1-200 bar. Morphological properties of the (co)polymers, e.g. bulk density and free-flowing properties are improved.
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公开(公告)号：DE2847757A1
公开(公告)日：1980-05-14
申请号：DE2847757
申请日：1978-11-03
Applicant: BASF AG
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公开(公告)号：DE2846185A1
公开(公告)日：1980-05-08
申请号：DE2846185
申请日：1978-10-24
Applicant: BASF AG
Inventor： KLAERNER PETER DIPL CHEM DR , SCHWEIER GUENTHER DIPL CHEM DR , BACHL ROBERT DIPL CHEM DR , FRIELINGSDORF HANS DIPL ING DR
Abstract: Prodn. of a Ti-contg. component for ziegler catalyst comprises first forming a dispersion by contacting (1) a suspension of (a) 100 pts. wt. of an inert liq. hydrocarbon and (b) 0.1-100 pts. wt. of a finely divded porous inorganic oxide material (I) with a particle size of 1-1000 mu, a pore vol. of 0.3-32 cm3/g. and a surface of 100-1000m2/g., with formula SiO2.aAl2O3 in which a =0-2, with (2) a soln. of (a) 100 pts. wt. of a liq. alcohol Z-OH in which Z is 1-8C satd. hydrocarbon gp., the alcohol being 10vol.% soluble in the inert hydrocarbon (1a), (b) 0.01-6 pts. wt. (as Ti) of a Ti trihalide in which the halogen is Cl and/or Br, and (c) 0.01-4 ptS. wt. (as Mg) of a Mg cpd. which is soluble in the alcohol (2a). The wt. ratio (I):T2 = 1:0.01-1:0.2 and the wt. ratio (I):Mg is 1:0.01-1:0.25. The resulting dispersion is then subjected to azeotropic distn. at 10-140 degrees C, opt. with replenishment of the hydrocarbon (1a), until alcohol is no longer present in the distillate, to form a suspension. Catalysts are less hazardous to handle and cause less environmental pollution than prior art carrier catalysts. The catalysts give high polymerisation yields and constant specific yields with time. The polymers produced have good morphological properties, esp. a high apparent density and a low fine grain content.
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