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11.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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公开(公告)号：DE3136254A1
公开(公告)日：1983-03-31
申请号：DE3136254
申请日：1981-09-12
Applicant: BASF AG
Abstract: The invention relates to a process for the preparation of finely divided polymers of alpha -monoolefins by polymerisation in liquid i-butane - in which the monomer to be polymerised is in dissolved form and the finely divided polymer formed is in suspended form - by means of a Ziegler catalyst system comprising 1) a vanadium-containing catalyst component and 2) a metal compound carrying hydrocarbon groups, characterised in that the vanadium-containing catalyst component 1) is the solid-phase product (VII) obtained by 1.1) first bringing 1.1.1) a finely divided, porous, inorganic oxide (I) having a certain specification and 1.1.2) a solution (II) as obtained on combining (IIa) a lower alcohol and (IIb) a vanadium trihalide, into contact with one another to form a dispersion (III), and evaporating this dispersion to a dry consistency - formation of a solid-phase intermediate (IV) - and 1.2) then 1.2.1) bringing the solid-phase intermediate (IV) obtained from step 1.1) and 1.1.2) an aluminium compound (V) having hydrocarbon groups dissolved in an organic solvent into contact with one another to form a dispersion (VI), and in this way isolating, with the solid-phase product (VII) resulting as the dispersed components, the novel vanadium-containing catalyst component 1). This is distinguished, inter alia, by the fact that it is capable of giving polymers having particularly good morphological properties.
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13.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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Patent Agency Ranking
公开(公告)号：DE2843825A1
公开(公告)日：1980-04-24
申请号：DE2843825
申请日：1978-10-07
Applicant: BASF AG
Inventor： BACHL ROBERT DIPL CHEM DR , HOEHR LOTHAR DIPL CHEM DR , KLAERNER PETER DIPL CHEM DR , SCHWEIER GUENTER DIPL CHEM DR
Abstract: A Ti contg. Ziegler catalyst is prepd. by (1) contacting a finely divided support (I) with a soln. comprising 100 pts. wt. alcohol (II) Z-OH (where Z is satd. 1-8C hydrocarbon), 0.01-6 pts. wt. (calculated as Ti) titanium trihalide where the halogen is Cl and/or Br and 0.01-4 pts. wt. (calculated as Mg) (II) soluble Mg cpd. of formula Mg6Alw(OH)xYy(B-OH)z (where Y is Cl or Br, B is 1-8C satd. hydrocarbon, w is 0-3, x is 0-8, y is 12+3w-z and z is 0-36) to form a dispersion, the wt. ratio of (I) to Ti being 1:0.01-1:0.02 and the wt. ratio of (I) to Mg being 1:0.01-1:0.25; and stripping the dispersion at 200 degrees C but above the m.pt. of (II) to form a solid intermediate prod. This is followed by (2) contacting the intermediate with an acyl halide (III) RCOX (where R is 1-18C satd. hydrocarbon opt. substd. by up to 3 Cl or Br atoms and X is F, Cl, Br or I) opt. dissolved in an organic solvent to form a suspension. The mol. ratio of Ti in the intermediate to (III) is 1:0.01-1:100. Mol. wt. of the polymers can be regulated with lower amts. of mol. wt. regulators esp. H2 and the polymers have improved morphological properties e.g. bulk density and flowability.
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公开(公告)号：DE2543235A1
公开(公告)日：1977-04-14
申请号：DE2543235
申请日：1975-09-27
Applicant: BASF AG
Inventor： SCHWEIER GUENTHER DIPL CHEM DR , BACHL ROBERT DIPL CHEM DR , MUELLER-TAMM HEINZ DIPL CHEM D , FRIELINGSDORF HANS DIPL ING DR , GRUBER WOLFGANG DIPL CHEM DR , KOLK ERICH DIPL CHEM DR
Abstract: Prepn. of Ti and/or vanadium catalyst components for Ziegler catalyst systems comprises (a) mixing (1) a porous mineral oxide of formula Al2O3 or SiO2.a Al2O3 (where a is 0-2) with (2) an aluminium deriv. of formula AlB3-p Yp (where B is 1-12C hydrocarbyl; X is Cl, Br, I, H or OR; R is 1-12C hdyrocarbyl; p is 0-3) dissolved in an organic solvent, the wt. ratio (1)/(2) being 1/0.05-1; (b) mixing (3) the solid prod. from stage (a) with (4) a magnesium cpd. dissolved in an organic solvent, the wt. ratio (3)/(4) being 1/0.01-0.25; and (c) mixing (5) the solid prod from stage (c) with (b) a titanium or vanadium deriv., the wt. ratio (5)/(6) being 1/0.01-20. Cpd. (1) consists of fine particles having a size range of 1-1000 mu, a pore volume of 0.3-3 cm3/g. and an active surface of 100-1000 m2/g. Initiation of polymn. is relatively slow, the max. activity being attained very progressively. This considerably facilitates control of polymerisation, and gives polymers having good morphological properties, esp. a uniform particle size and high apparent density. Can be used in liquid suspension or the dry phase. Gives high yields of polyms with a low halogen content.
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公开(公告)号：DE2543272A1
公开(公告)日：1977-04-07
申请号：DE2543272
申请日：1975-09-27
Applicant: BASF AG
Inventor： SCHWEIER GUENTHER DIPL CHEM DR , BACHL ROBERT DIPL CHEM DR , MUELLER-TAMM HEINZ DIPL CHEM D , FRIELINGSDORF HANS DIPL ING DR , GRUBER WOLFGANG DIPL CHEM DR , KOLK ERICH DIPL CHEM DR
Abstract: (Co)polymerisation of 2-10C alpha-mono-olefins at 30-200 degrees C/0.1-200 bars press., is effected in the presence of a Ziegler type catalyst system composed of (1) a fraction contg. Ti and/or V (component A) and (2) a metallic cpd. (component B) of formula (I): (Me-Am-nXn (I) (where Me is Al, Mg or Zn or their mixt.; A is 1-12, pref. 2-8C hydrocarbon radical; X is Cl, Br, I or H; m = valency of Me; n is a value between 0 and m-1, pref. 0 or 1). The respective proportions of A and B are such that the atomic ratio between the transition metal of A and the metal Me of B is 1:0.1-1:500, pref. 1:0.2-1:200. The novel component A is a solid prod. prepd. by (a) mixing finely particulate porous SiO2 (prod. I) of particle size 1-1000 u, pref. 1-400 u, a pre vol. of 0.3-3, pref. 1-2.5 cm3/g and an active surface area of 100-1000 pref. 200-400 m2/g with a Mg cpd. (prod. II) dissolved in an organic solvent, in such proportions that the wt. ratio between SiO2 and the Mg cpd. is 1:0.01-1:0.25, pref. 1:0.05-1:0.2, (b) mixing the solid prod. from (a) prod. (III) with a deriv. of Ti and/or V (prod. Iv), in the solid or liq. state or dissolved in an organic solvent, in such proportions that the wt. ratio between prod. III and the transition metal of prod. IV is 1:0.01-1:20, the resulting solid prod. V comprising A. Used for e.g. propene, butene, hexene-1, etc. with component (A), the initiation of the polymerisation is relatively slow and its max. activity is reached progressively, thus allowing control of the polymerisation reaction. The polymers obtd. e.g. polyethylene, have morphologically properties.
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