CS213373B2 - Method of catalytic production of the ethylene copolymere - Google Patents

Description

TESKOLLOVENSKA

SOCIALISTIC PUBLIC (19)

DESCRIPTION OUT

THE PATENT

(51) Int. Cl.3C 08 F 210 / 02C 08 F 4 50 C 08 F 4/76

Registered 22 03 79 (21) (PV 2147-79) (32) (31) (33) Priority from 27 02 79 (014414) United States (40) Published 31 08 81

OftAD SO ZY

AND DISCOVERIES (45) Published 15 08 84 (72)

Author of the Invention (73)

Patent owner

KAROL FREDERICK JOHN, GOEKE GEORGE LEONARD, WAGNERBURKHARD ERIC, BELLE MEAD, NEW JERSEY, FRASER WILLIAM ALLEN, PRINCETON, NEW JERSEY, JORGENSEN ROBERT JAMES, DUNBAR, WEST VIRGINIA, FRIIS NILS, MACUNGIE, PENNSYLVANIA

UNION CARBIDE CORPORATION, NEW YORK, NEW YORK (54) Method of catalytic production of ethylene copolymer 1

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to catalytic copolymerization of ethylene using high activity complex catalysts containing magnesium with titanium at low pressure gas phase formation of co-polymers of ethylene with a density of 910 kg / ml3 including up to 960 kg / mi3 and melt flow rate (defined below). ranging from 22 inclusive to 32 inclusive. Until recently, low density polyethylene (i.e., with a density of 940 kg / m 5 or less) was industrially produced mostly by high pressure homo polymerization of ethylene (ie, at a pressure of 103 MPa and above) in the gaseous phase of the mixed and long tubular reactors. in the absence of solvents and with the use of free radical initiators. At the world scale, the annual amount of polyethylene at a low density produced in this way is more than 450,000 tons.

As recently disclosed in US Patent No. 4,011,382 and in Belgian Patent No. 839,380, it has been found that. low-pressure polyethylene can be industrially produced at pressures below 6.87 MPa by gas-phase reaction in the absence of solvents using certain chromium- and titanium-containing catalysts (and fluorine, respectively) and specific fluid bed process conditions.

However, the products produced by the methods described in the 2 methods of U.S. Pat. No. 4,011,382 and Belgian Patent No. 839,380 have a relatively wide molecular weight distribution Mw / Mn of from 6 to 20 (including cutoffs). As such, they are useful in many applications for wire and cable insulation and hose manufacturing, but are not well suited for injection molding. They are also not widely used for the production of films, since films made from these resins have poor optical and mechanical properties.

In order to be useful in the gas-phase industrial process, the catalysts are used in the fluidized bed according to U.S. Pat. Nos. 3,709,853, 4,003,712 and 4,011,382, Canadian Patent 991798 and Belgian Patent 839,380, must have high activity, i.e., have a productivity of at least 50,000 and preferably at least 100,000 kg of polymer per kg of main metal, which forms a catalyst or higher. This is because no procedures for removing catalyst residues are conventionally used in the gas phase.

The catalyst residues in the polymer must therefore be so small that they can be left in the polymer without the need for difficulties in the processing of the resin or in the application thereof at the end of the process. where high active catalysts are used successfully in such fluidized bed processes, the heavy resin content of the resin is of the order of 20 ppm of the master or lower with a productivity of at least 50,000 or. higher and 10 ppm or less of the productivity of at least 100,000 or. higher and 3ppm 'or lower at 300,000 or higher. The low catalyst residue content is also important when the catalyst contains chlorine-containing substances such as titanium, magnesium and / or aluminum chlorides used in so-called Ziegler or Ziegler-Natta catalysts. The high content of chlorine-forming resin can cause pitting and; other corrosion of the metal surfaces of the forming devices. A chlorine content of 200 ppm or more is unacceptable for industrial production. U.S. Pat. No. 3,989,881 discloses the use of a highly active catalyst for a pro-suspension process for the production of ethylene polymers having a relatively low molecular weight Mw / Mn distribution in the range of 2.7 to 3.1. Attempts have been made to use catalysts similar to those described in USA Patent No. 3,989,881 to produce polyethylene having a narrow molecular weight distribution by ethylene polymerization alone or in conjunction with propylene gas phase fluidized bed conditions using equipment and conditions similar to equipment and conditions described in U.S. Pat. However, these attempts have been unsuccessful. Abybylo. the use of the solvents used in the catalytic systems of the type described in U.S. Pat. No. 3,989,881 can be avoided, the titanium-containing components and the magnesium component being dried. However, the dried substance had a viscous, resinous, pyrophoric composition which was not well dosed because it was not free to move. However, when this fluid was mixed with silicon dioxide and dosed with a reactors, this was not achieved. industrially acceptable. results. . Catalyst productivity was low, or the catalyst was pyrophoric and difficult to handle, or had a low bulk density, i.e., less than or equal to 97.3 kg / m @ 3, at a density of 940 kg / m @ 3 or less. Substances with such a low bulk density cannot be readily accepted by the fluidized bed process under acceptable operating conditions.

Polymers of such bulk density are desirable from an industrial point of view because they are dusty in nature. If the polymer is to be stored or sold in granular form, considerably more space is required for the storage and transport of such products. Although the granular polymer is processed into pellets prior to shipment, the processing of a large amount of low bulk density in a pelletizing apparatus requires significantly longer processing times compared to the time for processing the same amount of high bulk bulk material on the same extruder. U.S. Pat. No. 4,124,532 discloses the polymerization of ethylene and propylene using highly active catalysts. These catalysts include complexes which may include halo-magnesium and titanium. Said complexes are prepared by reacting a general halide MXz (where M can be magnesium) with a compound of the general formula kde (wherein M’ can be titanium and Y halogen or an organic residue) in the electron donor compound. These complexes are then isolated by either crystallization, solvent evaporation, or precipitation.

The polymerization is carried out using those catalytic complexes and an alkyl carbonate compound.

However, U.S. Pat. No. 4,124,532 does not disclose any particular technique or methods of preparing a catalyst to achieve the desired results in the method of the invention described in these references. The use of the catalysts described in U.S. Pat. special methods would not result in an industrial fluidized bed process suitable for the production of polyethylene on an industrial scale. In addition, the vapor phase examples do not describe co-polymerization that is produced by high density polyethylene copolymers, but a practical method of producing low density specialty copolymers described herein.

U.S. Pat. Nos. 3,922,322 and 4,035,560 disclose the use of several titanium and magnesium-containing catalysts for the production of granular ethylene polymers by fluidized bed gas phase pressure below 6.87 MPa. However, it has considerable disadvantages. Using the catalyst of U.S. Pat. No. 3,922,322, as is exemplified in this patent, polymers having a very high catalyst residue, i.e. a residue of about 100 ppm Ti and greater than about 300 ppm Cl, are obtained.

In addition, as disclosed in U.S. Pat. No. 3,922,322, the catalyst is used in the form of a prepolymer and very high volumes of catalyst composition must be metered into the reactor. The use of this catalyst therefore requires the use of a relatively large-scale device for the production, storage and delivery of the catalyst.

Also, using the catalysts of U.S. Pat. No. 4,035,560, polymers containing a high amount of catalyst residues are obtained, and the catalyst compositions used are obviously used, as is apparent from the types and amounts of the reagents used in these catalysts, pyropharic.

It has now surprisingly been found that copolymers of ethylene with a wide range of densities from 910 to 960 kg / m 3 and with a melt flow ratio of 22 to 32, including limit values, which are relatively low in catalyst residue can be produced by copolymerization at relatively high productivity. ethylene with one or more C 3 -C 8 α-clephins in the gas phase in the presence of a highly active catalyst comprising a magnesium-titanium complex described below, prepared under specific activation conditions by an organoaluminum compound and an inert carrier. SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a process for the preparation of ethylene copolymers having a density of from about 910 to about 960 kg / m 3, a melt flow rate ratio of about 22 to 32 with a relatively low low-pressure cathode catalyst residue. It is another object of the present invention to provide ethylene copolymers suitable for numerous applications. The accompanying drawing shows a fluidized bed reaction system for the gas phase process in which a catalytic system according to the invention can be used.

According to the process of the invention, co-polymers containing, as the main molar fraction of ethylene (90%) and as minor molar proportion (w 10%) one or more C 5 to C 6 α-olefins can be produced, which should not contain any branching h and none of their If a C 3 -C 8 α-olefin is used, copolymers are obtained, in the case of using C α to C 5 O 5 olefins, ter- or tetra-polymers and the like are obtained. These α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, and 1-octene. butene, 1-hexene, 4-methyl-1-pentene and 1-octene • Copolymers have a liquid velocity ratio of from 22 to 32, preferably from 25 to 30, including limit values. the mass ratio of the polymer (MFR) 22 to 32 (including cut-off values) corresponds to an Mw / Mn in the range of about 2.7 to 4.1 and an MFR of 25 to 30 including limit values corresponds to a ratio Mw / Mn of about 2.8 to 3.6 .

The copolymers have a density of about 910 to 960, including limit values. The density of the copolymer can be controlled at a given melt index, in particular by the amount of Cs to Conomer to be copolymerized with ethylene. In the absence of comonomer, ethylene homopolymerized with the catalyst of the present invention to form homopolymers having a density of about 0.96.

The introduction of increasing amounts of comonomers into polymers results in a gradual process

B reducing the density of copolymers. Under the same reaction conditions, the amount of each of the different C 3 to C 5 comonomers needed to achieve the same result changes the monomer to the monomer.

In order to achieve the same results, i.e. the same densities at a certain melt index, increasing molar amounts of comonomers in the Cs series> C4> C5> C6 >> C7> Cs are required.

The melt index of the polymers is an image of its molecular weight. Relatively high molecular weight polymers have a relatively low melt index. The ultra high molecular weight ethylene polymers have a melt flow index at a higher load (HLMI) of about 0.0 and a high molecular weight polymers have a melt index at a higher load of about 0.0 to about 1.0 g / 10 min.

Such high molecular weight polymers are difficult to mold in conventional injection molding machines and sometimes impossible at all. By contrast, the polymers produced by the process of the present invention are easily formed in such a device. They have a normal flow (MI) flow index of from 0.0 to about 100, preferably from about 0.5 to 80, and a higher load index (HLMI) of about 1.1. do asi2000. The melt flow index of the polymers produced by the process of the invention is dependent on the combination of the reaction temperature during the polymerization, the density of the copolymers and the hydrogen / methane ratio in the reaction system.

The melt index increases with increasing. and / or decreasing the polymer density and / or increasing the hydrogen / moindmer ratio. In addition to hydrogen, other chain transfer agents such as dialkyl zinc compounds can be used to further increase the flow of melt copolymers.

The copolymers of the invention contain. with 1a, typically> 0.1 to 0,3 0.3 double bonds C - C per 1000 carbon atoms.

The copolymers produced by the process of the present invention have a n-hexane extractable component content (at less than about 3% and preferably less than about 2% by weight at 50 ° C).

The copolymers of the present invention contain as catalysts in the order of from 0 to 20 ppm Ti inclusive with a productivity of 50,000 or more from 0 to 10 ppm Ti, including a productivity of 100,000 or higher and 0 to 3 ppm including a productivity of 300,000 or more. If the Cl, Br, or I residue residues depend on the content of these elements in the copolymers on their contents in the precursor. From the value of the titanium to chlorine, bromine or iodine ratio in the original precursor, calculate the content of chlorine, bromine or iodine residues based on the known value of productivity relative to the titanium residue alone. chlorine-containing catalytic system (Cl / 213373 7 8 / Ti == 7) can be calculated from 0 to 140 ppm inclusive, with a productivity of 60,000 or more from 0 to 70 ppm, with a productivity of 100,000 or more from 0 to 20 ppm at a productivity of 300,000 or higher In the process of the invention, the sequopolymers readily produce about 1,000,000 at a productivity of up to 10 µl.

The copolymers of the invention are granular materials having an average particle size of the order of about 0.127 to about 1.78 mm and preferably about 0.5 to about 1 mm. The particle size is important for the easy fluidization of the polymer particles in the fluidized bed reactor as described below. The copolymers of the invention have a bulk density of from about 243 to about 503 kg / m 3.

The production of films preferably uses copolymers according to the invention having a density of about 912 to 940, preferably 916 to 928 kg / m3, including limit values, of a molecular weight distribution of 2.7 g Mw / Mu g 3.6, preferably 2.8 g Mw / Mn g 3.1 and a melt flow standard index (MFI) of 0.5 µg g 5.0, preferably about 0.7 g MFI ně4.0.

The copolymers of the present invention suitable for injection molding into flexible articles, such as articles used in households, preferably have a density of 920 to 940, preferably 925 to 930 kg / m3, including limit values, a molecular weight distribution range of 2.7 g. Mw / Mn g 3.6, preferably 2.8 g Mw / Mn 3, 6, preferably about 8 gMFI g 80.

For the manufacture of solid injection molded articles, for example buckets, preferably a polymer according to the invention is used with a density of 950 to 958, preferably 953 to 955 kg / m3, including limit values, molecular weight distribution of 2/7 g_Mw / Mn w of 3.6, preferably 2.8 g. Mw / Mn g3, Ia standard melt flow index 1 g MFI g 40, preferably 5 g MFI g 20.

The compounds used in the preparation of the high-activity catalyst include at least one titanium compound, at least one magnesium compound, at least one electron donor compound, at least one activating compound, and at least one inert carrier as defined below.

The titanium compound has the structure represented by the general formula

Ti (OR) and Xb wherein R represents a C 1 to C 14 aliphatic or an aromatic hydrocarbon radical or. the remainder of formula COR ', where R' is a C 1 to C 14 aliphatic or aromatic hydrocarbon radical, X is chloro, bromo, iodo or a mixture thereof. a represents the number 0 or 1, b represents the number · 2 to 4 inclusive, the sum of a -j- b being 3 or · 4,

The titanium compound may be used singly or in mixtures and include compounds of formula

TiCl 3, TiCl 4, Ti (OCH 3) Cl 3, T 1 (OC 6 H 5) Cl 3, Ti (OCOCH 3) Cl 3 and Ti (OCOC 5 H 5) Cl 3.

The magnesium compound has a structure corresponding to the general formula

MgXz wherein X is chloro, bromo, iodo, or a mixture thereof. These magnesium compounds can be used singly or in combinations and include the compounds of the formulas MgCl 2, MgBr 3 and Mgh. Anhydrous magnesium chloride is particularly preferred for magnesium compounds. About 0.5 to 56, preferably 1 to 10, moles of the magnesium compound are used per mole of titanium compound to prepare the catalysts used in the present invention.

The titanium compound and the magnesium compound are expediently used in a form that facilitates their dissolution in the electron donor compound as described below.

The electron donor compound is an organic compound which is liquid at 25 ° C and which is partially or completely soluble in the titanium compound and the magnesium compound. Electron donor compounds are known either by this name or under the name Lewis base.

The term electron donor compounds refers to such compounds as aliphatic and aromatic carboxylic acid alkyl esters, aliphatic ethers, cyclic ethers and aliphatic ketones. Of these electron donor compounds, C 1 to C 4 saturated aliphatic carboxylic acid esters, C 7 -C 6 aromatic carboxylic acid alkyl esters, C 2 to C 6 and preferably C 3 to C 10 aliphatic ethers are preferred, C 1 to C 4 cyclic ethers and preferably C 4 cyclic mono esters. or di-ethers, C 5 to C 6 and preferably C 8 to C 4 aliphatic ketones. Most preferred of these electron donor compounds are methyl formate, ethyl acetate, butyl acetate, ethyl ether, hexyl ether, tetrahydrofuran, dioxane, acetone methyl isobutyl ketone.

The electron donor compound is organic or in mixtures. About 2 to 85 and preferably about 3 to 10 moles of the electron donor compound are used per mole of titanium. 9 10 213 3 7 3

The activating compound has a structure corresponding to the general formula

Al (R 'jcX'dHe where X' is chloro or a group of the general formula OR '' or any of R 'and R' ', which are the same or different, represents a C 1 to C 14 saturated hydrocarbon residue, d is 0 to 1.5, e represents the number 1 or 0, paying that the sum of ο-ιψ d -f- e is 3.

Activating compounds may be used singly or in combinations, and examples of such compounds are the compounds of the formula

Al (C 2 H 5) a, C 1 -C 5 H 5 Cl 2 Cl, Al (1 C 4 H 9) 3, Al 2 (C 6 H 13) 3 Cl, Al (1-C 4 H 9) 2 H, Al (C 6 H 13) 3, Al (C 8 H 17) 13, AlCaH 5, 3 H and

Al (C 2 H 5) 3 (OO and H 5). When activating the catalysts used according to the invention, about 10 to 400 and preferably about 10 to 100 moles of the activating compound are used. 1 mol of titanium compound. The carriers used are particulate solids which are inert to the other components of the catalytic composition and to the other active ingredients of the reaction system. These carriers include inorganic agents such as silica and aluminum, molecular sieves and organic substances such as olefin polymers such as polyethylene. The carriers are used in the form of dry powders having a mean particle size of about 10 to 250, preferably about 50. up to 150 μπι. They are also preferably porous and have a specific surface area of at least 3 and preferably at least 50 m 2 / g.

The carrier should be dry, ie, not containing absorbed water. Drying of the carrier is carried out by heating to a temperature of at least 600 ° C. Alternatively, the carrier can be dried at a temperature of at least 200 ° C and then treated with 1 to 8% by weight of one or more alkyl compounds described above. This modification of the carrier with aluminum-aluminum compounds provides the catalyst system with enhanced activity and use of Also, such a catalytic system has better morphology in the resulting ethylene polymer.

The catalyst of the present invention is prepared by not producing titanium compounds first, the precursor compound of the magnesium compound and the compound of the compound of formula (I) below, and then applying the carrier to the activator compound in one or more stages as described below.

The precursor is prepared by dissolving the titanium compound and the magnesium compound in the electron donor compound at a temperature of about 20 ° C to about the boiling point of the electron donor compound. The titanium compound can be added to the electron donor compound before or at the same time as adding the magnesium compound.

The dissolution of the titanium compound and the magnesium compound can be assisted by stirring and, in some cases, by heating the two compounds, in the electron donor compound, to reflux. Upon dissolution of the titanium compound and the magnesium compound, the precursor can be isolated by crystallization or precipitation, with a C 5 -C 8 aliphatic or aromatic hydrocarbon such as hexane, isopropanol or benzene.

The crystallized or precipitated precursor can be isolated in the form of fine, free-flowing particles of medium size, about 10 to 100 μΐη and a bulk density of about -292 to about 535 kg / m3.

The precursor thus prepared has a composition corresponding to the general formula

MgmTiii (OR) nXp [ED] q where. ED is an electron donor compound, m is from 0.5 to 56, preferably from 1.5 to 5 including limit values, μ is · from Q 1 to 1, p is from 6 to 116, preferably from 6 to 14, including limit values, q is from 2 to 85, preferably from 4 to 11, including limits, R is a C0 to C14 aliphatic or aromatic hydrocarbon radical or a radical of the general formula COR 'where R' is Ci to Cit an aliphatic or aromatic hydrocarbon radical and X represents chlorine, bromine or iodine or a mixture thereof.

Index for elemental titanium (Ti) denotes Arabic number one.

The polymerization activity of the fully activated catalyst is high in the process according to the invention that it is necessary to dilute the precursor with a carrier for effective control of the action rate. The precursor dilution can be carried out before the precursor is partially or completely inactivated, as described below, or simultaneously with this activation. The precursor dilution is carried out by mechanical agitation or mixing with a mass of 0.033 to 1, and preferably about 0.1 to 0.3, 3 parts precursor with 1 part by weight of carrier.

In order to be able to use it in the process of the invention, the precursor must be completely or partially activated, i.e. it must be treated with a sufficient amount of the activating compound to convert the titanium atoms present in the precursor into active host. However, it has been found that the process of activating the catalyst is very important for obtaining the active ingredient in the presence of an inert carrier. When, for example, attempts have been made to activate the catalyst in a manner similar to that described in U.S. Patent No. 3,989,881, that the total amount of reducing agent needed for the complete catalyst is added to the precursor in the hydrocarbon slurry and then the suspension is dried at 20 to 80 ° C (including limit values) to remove the solvent and allow the catalyst to be used in In the gas phase, a product was obtained which was not sufficiently active in the industrial-scale flushed bed gas phase described below. In the preparation of a useful catalyst, activation is required such that at least the last stage of activation takes place in the absence of a solvent, so that the active catalyst is not necessarily dried to remove the solvent. Two approaches have been developed to achieve this. According to the first method, the precursor is completely inactivated outside the reactor in the absence of solvent by mixing the precursor with dry activating compound. In this dry mixing, the activating compound is preferably used in the impregnated state in the carrier. However, this process has the disadvantage that the resulting fully activated catalyst is pyrophoric when it contains above 10% by weight of the activating compound.

In a second preferred process, the precursor is partially activated by the polymerization reactor. This partial inactivation is carried out in a hydrocarbon solvent suspension. The resulting product is then dried to remove the solvent. The partially activated impregnated precursor is introduced into a polymerization reactor in which activation with an additional activator, which may be the same or another compound, is completed. In the preparation of the catalyst by mixing in the dry state, the solid precursor in the particulate form is uniformly mixed with the solid particles of the porous support in which the activating compound is absorbed. The activating compound is absorbed into the carrier from its solution in a hydrocarbon solvent such that 10 to 50% by weight of activator is deposited in 90 to 50% by weight of carrier. The amount of precursor, activator and carrier is selected to: achieve the desired molecular ratio And / or to obtain a resulting catalyst with a weight ratio of the transducer to the carrier of less than about 0.50, preferably less than about 0.33.

This amount of carrier provides the necessary dilution of the activated catalyst to permit the desired regulation of the catalyst polymerization activity in the reactor. When the final catalyst contains more than 10% by weight activator, it is pyrophoric. During dry mixing, which can be carried out at ambient temperature (25 ° C) or lower, the dry blend is well mixed to prevent heat build-up on subsequent activation, which is initially exothermic. Thus, a catalyst is obtained which is fully activated and can be used in a polymerization reactor. Free-flowing (loose) substance.

According to a second preferred process, the catalyst is activated at least in stages. In the first step, the particulate solid sprayer is partially reacted and partially reduced with an amount of activating compound to provide a partially reduced precursor in which the activator to titanate molar ratio is 1 to 10: 1 and preferably about 4 to about 8. 1. This partial activation is carried out in a hydrocarbon solvent suspension. The resulting product is then dried to remove the solvent at a temperature of 20 to 80 ° C, preferably 50 to 70 ° C. The resulting product has the character of a free-flowing particulate material and can be readily introduced into the polymerization reactor. In addition, the activator may be used in part in the absorbed form of the carrier used to dilute the activator. The partially activated precursor is preferably weakly effective as the polymerization catalyst according to the invention. In order to activate the partially activated precursor for the polymerization of ethylene, an additional activator must be introduced into the polymerization reactor. This completes the activation of the precursor in the reactor. The additional activating compound and the partially inactivated precursor are preferably introduced into the reactor by separate conduits; The additional activating compound can be injected into the reactor as a solution in a hydrocarbon solvent such as isopentane, hexane, or mineral oil. This solution usually contains about 2 to 30% by weight of the activating compound. The activator can also be added to the reactor in solid form, absorbed in the carrier. The carrier usually contains 10 to 50% by weight of activator. The additional activating compound is added to the reactor in such an amount that, in addition to the amount of the activating compound, the titanium compound is present in the form of a partially activated pro-cursor of an Al / TIAI molar ratio of 10 to 400 *, and preferably about 15 to 60. The additional amount of activator compound introduced into the reactor is reacted with the partially activated β-recursor and complete the titanium compound activation in the reactor. In a continuous gas phase process, such as the flushed bed process described below, discrete batches of partially or completely activated precursor are continuously fed to the reactor over the course of the polymerization, with the concomitant release of the additional activating compound required to complete activation. the partially activated precursor thus replacing the active sites of the catalyst which has been consumed during the reaction.

Polymeiration is carried out by introducing the stream of ethylene in the gas phase, for example by the fluidized bed process described below, essentially in the absence of catalytic poisons such as moisture, oxygen, carbon monoxide, carbon dioxide and acetylera, with a catalytically effective amount of activated precursor (catalyst) under pressure and temperature sufficient to initiate polymerization.

In order to obtain the desired copolymer density, a sufficient amount of carbon-carbon mono-carbon copolymers of 3 or 4 carbon atoms must be copolymerized with the ethylene to provide up to 10 mole percent of the C3 to Cs comonomers in the copolymers. The amount of comonomer required to achieve the desired result depends on the particular comonomer or comonomer used. The following table lists a number of different monomers that can be used to co-polymerize ethylene to produce polymers having a density within the desired range at any given melt induction. The table shows the amount of comonomers needed in the copolymer to achieve these properties and the required comonomer concentration in mmo. % in the gaseous stream of monomers being fed to the reactor.

Co-monomer for opylene lrbutene 1-peintene 1-hexene 1-octene

Comonomer content needed in copolymers [mol%]> 0 to 10> 0 to 7.0> 0 to 6.0> 0 to 5.0> 0 to 4.5

Molar ratio of monomers to ethylene in the gas stream> 0 to 0.9> 0 to 0.7> 0 to 0.45> 0 to 0.4> 0 to 0.35

The fluidized bed reaction system used in the process of the present invention is illustrated in FIG. 1. The reactor 10 consists of a reaction zone 12 and a speed reduction zone 14.

The reaction zone 12 comprises a bed of growing polymer particles, the polymer particles formed, and a smaller amount of catalyst fluidized by a continuous flow of polymerizable and moietifiable gaseous constituents formed by the filler; gas and gas recycled to the reaction zone. In order to keep the fluidized bed fluidized, the mass flow rate of the bed must have a value greater than the minimum flow rate required for fluidization. Preferably, a suitable mass flow rate of the bed is about 1.5 to about 10X higher, preferably about 3 to 6X higher than the minimum gas flow rate required for fluidization (Gmf). The Gmf designation for the minimum gas flow rate required to achieve fluidization was suggested by C. Y. Wen and Y. H. Yu, "Mecbanische of Fluidization", ChemicalEngineering Progress Symposium Series, Vol. 62, pp. 100-111 (1966). it is important that the beds always contain particles that would prevent the formation of "hot spots" and trap and distribute the powdery catalyst in the reaction zone. Typically, at the start of operation, a polymeric particle is introduced into the reaction zone as the basis of the polymer particle before the gas stream is started. The TiO 2 particles may be identical to the disintegrating polymer or may be different. When different, they are drawn off with the resulting polymer particles as a forward product. Finally, the fluidized bed of particles required! of the polymer displaces the starter bed. The partially or completely activated precursor (catalyst) used in the fluidized bed is preferably stored in an emergency reservoir 32 under an inert gas atmosphere such as nitrogen or argon.

Fluidization is achieved by a high velocity of the recycle gas introduced into the bed and the bed, which is typically of the order of about 50 X higher the rate of refueling. The fluidized bed usually looks like a dense mass of moving particles flowing in a free vortex resulting from the passage of gas through the bed. The bed pressure is equal to or somewhat higher than the bed weight divided by the bed cross section, depending on the reactor geometry.

The refueling gas is introduced into the bed at the same rate as the particulate polymer product is drawn off: The refill gas composition is determined by means of an analyzer 18 located above the bed. The analyzer determines the loss of components in the gas to be recycled, and accordingly the composition of the make-up gas is adjusted accordingly; maintaining the composition of the gaseous mixture in the reaction zone substantially at steady state.

In order to ensure complete fluidization, the reactor sediment introduces the recycle gas and optionally a refill portion via the inlet 18b. Above the inlet 18 there is a gas separating pad 28 which facilitates the fluidization of the bed. A portion of the gaseous stream which does not react with the bed is a recycled gas which is preferably discharged from the polymerization zone by passing it over zone 14 located above the bed at 213373 15 which reduces the speed and entrains the entrained particles back into the bed . Particle separation may be aided by the inclusion of a cyclone 22, which may either be part of a rate-reducing zone 14, which may be in the zone. If necessary, the recycled gas can be passed through a filter 24 which is arranged to separate the small particles at high flux rates so as to prevent dust depositing on the heat transfer surface and the compressor presses.

The recycle gas is then compressed in a 2S compressor and passed through a heat exchanger 26 where it is deprived of heat of reaction before being returned to the bed. By constantly evacuating the heat of reaction, there is no apparent temperature gradient at the top of the beds. The temperature gradient exists in the lower 152 to 304 mm bed, between the inlet gas temperature and the bed temperature. It was noted that the bed almost instantly adjusts the recycle gas temperature above (this 152 to 304 forces the bed zone to bed temperature so that the bed temperature is substantially constant under steady-state conditions. The manifold 25 may also be disposed in a fluidized bed by a distributor plate 20. The compressor 25 may also be disposed by a heat exchanger 26 in the direction of flow.

The partitioning plate 20 plays an important role in the operation reactor. The flush bed contains both growing and formed polymer particles and catalyst particles. Since the polymer particles are hot and possibly active, they must be prevented from settling, since if any calm mass is formed, the active catalyst contained in these particles could cause the reaction to continue and the heat generated to dissolve. it is therefore important that the recycle gas is allowed to pass through the bed at a rate sufficient to flush the particles at the bottom of the bed.

The bottom of the bed is formed by a distributor plate 20, and the plate can be a screen, a plate with slits, a perforated plate, a plate of a cap (analogous to the plates of a desilatory column), etc. All parts of the plate may be stationary, or the plate may be a movable ityp, As already described in U.S. Pat. No. 3,228,792, the design of the plate is any such that it must desiccate the recycle gas between the bed bottom and keep it fluidized. The moving parts of the plate may be used to displace polymer particles retained on or in the plate.

As the chain transfer agent, hydrogen may be used in the polymerization of the invention. The hydrogen / ethylene molar ratio which can be used is in the range of from about 0 to about 2.0 mole percent on the md1 monomer in the gaseous stream. Any gas which is inert to the catalyst and reactants may also be present in the gas stream. Preferably, the activating compound is added to the gas recycle system at its hottest portion. Preferably, the activator is therefore introduced into the downstream tubes by a heat sink, such as from reservoir 27 through conduit 27A.

Compounds of the general formula can also be used together with the catalysts according to the invention as catalysts for the molecular weight control, i.e. as chain transfer agents.

Zn (Ra) (Rb) where

R a and R b are the same or different C 1 to C 8 aliphatic or aromatic hydrocarbon radicals. This results in a further increase in the melt index value of the produced copolymers. About Ό to 50 and preferably about 20 to 30 moles of zinc compound (calculated as 2n) per mole of titanium compound can be added to the gaseous stream introduced into the reactor (calculated as Ti). The zinc compound may preferably be introduced into the reactor in the form of a dilute solution (2 to 30% by weight) in a hydrocarbon solvent or in absorbed form in a solid diluent, such as silica, of the type described above, in an amount of from about 10 to 50% by weight. These substances are pyrogenic.

The zinc compounds can be added alone or optionally together with the addition of an activator to be introduced into the reactor. These compounds are introduced into the hottest part of the recycle gas system from a dispenser that is not contiguous and which is adjacent to the dispensing device 27.

The fluidized bed reactor must operate at a temperature below the sintering temperature of the polymer particles. In order to avoid caking it is necessary to keep the working temperature below the sintering temperature. In the production of the copolymers according to the invention, the ethylene process is preferably carried out at a temperature of about 30 ° C to 115 ° C, most preferably 75 ° C to 95 ° C. Temperatures of about 75 to 90 ° C are used to produce products with a density of about 910 to 920 kg / mi 3 and temperatures of about 80 to 100 ° C are used to produce products at a density of about 920 to 940 kg / m 3 and temperatures of about 90 to 115 ° C are it uses a density of about 940 to 960 kg / m 3 for producing products.

The fluidized bed reactor operates at a pressure of up to about 6.87 MPa, preferably at a pressure of about 1.03 to about 2.40 MPa, and when working at higher pressures within this range, heat transfer is facilitated because consequence of increasing the unit volume of gas heat capacity. The partially or fully activated precursor is injected into the bed at a rate that is the same as the rate at which it is consumed by the inlet 30 'located above the manifold 213373 18 17 20. An important feature of the invention is that the catalyzer is injected at a location above the manifold . Since the catalysts used according to the invention are highly active, injection into the space under the manifold could result in the initiation of polymerization at this point, which could eventually lead to blockage of the manifold plate. Conversely, injecting the catalyst into the fluidized bed helps to divide the catalyst in the bed and prevent the formation of sites with a high catalyst concentration that could lead to hot spots.

A catalyst which is inert to the catalyst, such as nitrogen or argon, is used to introduce the partially or completely reduced precursor and any activating compound or transfer agent which is gaseous in the bed.

The bed productivity is regulated by the catalyst injection rate. Bed productivity can easily be increased by increasing the catalyst injection rate and reducing the catalyst injection rate.

Since any change in the rate of catalyst introduction results in a change in the rate of evolution of the reaction heat, the temperature of the recycle gas is adjusted up or down to adjust the rate of heat output. This ensures a substantially constant bed temperature. Of course, both the fluidized bed and the recycle gas cooling system must, of course, be equipped with appropriate apparatus, to detect temperature changes in the insert and the cooling system, so as to allow the operator to adjust the recycle gas temperature appropriately. Under some combination of operating conditions, the fluidized bed is maintained at substantially the same height by withdrawing a portion of the bed as a product at the same rate as the rate of particle formation of the polymer product. for the rate of polymer particle formation at a constant gas velocity determining the increase in gas gas along the reactor (i.e., the temperature difference between the inlet gas temperature and the exhaust gas temperature). The polymeric product particles are preferably withdrawn continuously through the conduit 34 or adjacent to the manifold plate 20. The particles are removed as a slurry with a portion of the gaseous stream that is vented before the particles settle to prevent further polymerization of sintering before the particles reach the zone where gather. The suspension gas can also be used, as already mentioned, to convert the product from one reactor to another. Suitably, the polymer product particles are withdrawn by means of two successive time-adjusted valves 36a, 33, between which a garment zone 40 is provided. When the valve 38 is closed, the valve 36 is opened so that the gas / product mixture passes into zone 40. Then the valve 38 is opened to the product was transferred to the external isolation zone. The valve 38 is then closed and closed until the next product is taken off.

Finally, the fluidized bed reactor is equipped with a suitable venting system which allows the bed to be vented during start-up and end of operation. The reactor does not require the use of any mixing devices and / or wall scraping devices.

The carrier catalyst system of the invention provides a fluidized bed product with an average particle size of about 0.13 to 1.78 mm, preferably about 0.51 to 1.0 m 2.

The feed stream of gaseous monomer, optionally with inert gaseous diluents, is introduced to the reactors at a rate such as to yield a space-based yield and a portion of 32.4 to about 162.2 kg / hr / m 3 bed volume.

As used herein, the term "crude resin or polymer" refers to a polymer in a granular form as obtained from a polymerization reactor. The following examples serve to illustrate the invention in more detail, but do not limit the scope of the invention in any way.

The properties of the polymers produced in the examples are determined by the following test methods:

Density U of polymers with a density below 940 kg / m < 3 > is used according to ASTM-1505 and the plate is tempered for 1 hour at 100 [deg.] C. to bring the equilibrium crystallinity to a modified process using a modified 940 kg / m < 3 > the test plate is tempered for 1 hour at 120 ° C to bring it to a level of equilibrium crystallinity and then rapidly cool to room temperature. All values are given in kg / m?. Density measurements are performed in a gradient density column in all cases.

Melt Index (MI) ASTM D-1238-Condiition EMC is performed at 190 ° C, data in g per 10 minutes.

Flow rate (melt flow index at higher load) (HLMI) ASTM D-1238-Condition FM is performed using a 10-fold load than at the liquid index. 213373 19

Flow rate ratio Flow rate _ Melt index

Productivity

The resin product sample was spun down and the% by weight ash was determined, since the ash was essentially a catalyst. Thus, productivity is given in kg of catalyst consumed. The amount of titanium, magnesium and chlorine in the ash is determined by elemental analysis.

Movie rating

The film sample is monitored with the naked eye to determine the size and distribution of the ghetto particles or other foreign particles compared to the standard film sample. The film is then compared to a standard sample and rated by an appropriate degree of descent from —100 (very poor film) Ido — j — 100 (excellent film). N-hexane extractable substances (FDA-test used for polyethylene films to come into contact with groceries ].

A sample of 0.038 mm thick film and 1290 cm 2 area was cut into strips of 2.54 X 15.24 cm and weighed to an accuracy of 0.1 mg. The strips are placed in a container and extracted with 300 ml of n-hexane at 50 + 1 ° C for 2 hours. The extract is then decanted into a balanced culture dish. Drying the extract was weighed to 0.1 mg with the culture dish. The amount of extract calculated on the original weight of the sample is then reported as the mass fraction of the n-hexane extractable substances.

Density

Pour the resin through a funnel with a diameter of 9.5 mm into a 100 ml graduated cylinder up to the 100 ml mark. Do not shake the cylinder during filling. The weight difference is determined by weighing.

Molecular Weight Distribution (Mw / Mn)

It is determined by gel chromatography, in the case of resins with a density below 940 kg / m 3, the Styrogeluse stationary phase is used with pore sizes of 6, 104, 10 3, 10 2 and 6 nm and as perchlorethylene solvent, operating at 117 ° C. In the case of resins having a density of 940 kg / m 3 or higher, Styrogel uses a sequence of the pore sizes ΙΟ6, ΙΟ3, 10 4 43.3, 6 nm. O-dichlorobenzene at 135 ° C is used as solvent. The detection is carried out in all cases by infrared radiation at 3.45 µm. 20

EXAMPLE I Preparation of Precursor 16.0 g (0.168 mol) of anhydrous magnesium chloride are mixed with 850 ml of pure tetrahydrofuran in a 5 L flask equipped with a mechanical stirrer. The mixture is stirred at room temperature (about 25 ° C) and 13.0 µg (0.069 mol) of titanium tetrachloride is added dropwise. After the addition was complete, the flask was refluxed for 1-2 hours to dissolve the solids. The system was cooled to room temperature and 3 liters of n-hexane was added slowly over a period of time. A yellow solid precipitated. The supernatant is decanted and the solid is washed three times with one liter of n-hexane. The solids were then filtered off and dried by rotary evaporation at 40-6 ° C. 55 g of a solid precursor are obtained.

The precursor may at this time be analyzed for its magnesium and titanium content, since some of the magnesium and / or non-titanium compounds may be lost in the recovery of the precursor. The empirical formulas used herein to characterize the precursor composition are derived assuming that the magnesium and titanium still exist in the form of compounds that were originally added to the electron donor compound and that the remaining weight of the precursor is an electron donor compound.

Analysis of the solid showed the composition of Mg: 6.1%, Ti: 4.9%, corresponding to the formula

TiMg2J45'Cl89 (THF) 7, O 'where THF represents tetrahydrofuran.

Example II

Activation procedures

Procedure A

This activation procedure involves the activation of the precursor in several stages. Activation of this process is accomplished by reducing the precursor only partially to the polymerization reactor and completing the reduction in the reactor.

The required weighing of the dry inert carrier is placed in the mixing vessel or drum. In the examples described herein as carrier, about 500 g of silicon dioxide and about 1000 g of polyethylene carrier are used. The inert carrier is then mixed with a sufficient amount of the anhydrous aliphatic hydrocarbon diluent, such as isopentane, to form a slurry. Usually, 4 to 7 ml of diluent per 1 g of inert carrier should be used. The desired weight of the precursor is then placed downstream of the mixing vessel and mixed thoroughly with the suspension. In the examples herein, 213373 2122 of about 80-135 g of a precursor containing 1 + 0.1 mmol of titanium per gram of precursor are used for the production of catalysts. The desired amount of activator required for partial activation of the precursor is added to the blend contents. An amount of activator is used to make the Al / Ti ratio in the partially reduced precursor 10: 1 and preferably 4: 8: 1. The activator is added to the mixing drum in the form of a solution containing about 20% by weight of activator (in these examples triethylinium) in an inert aliphatic hydrocarbon solvent (in these hexane examples). All operations described above are carried out at room temperature and atmospheric pressure under an inert atmosphere. The resulting slurry is dried with a dry inert gas stream such as nitrogen or aargon at atmospheric pressure and up to 60 ° C to remove the hydrocarbon diluent. This usually requires about 3 to 5 hours. The substance is in the form of a free-flowing, dusty material formed by a uniform mixture of an activated precursor with an inert carrier. The dried product is stored under inert gas.

When an additional activator according to Process A is introduced into the polymerization reactor to complete the activation of the precursor, the activator can first be absorbed in an inert carrier such as silica gel or polyethylene, most preferably the reactor is introduced into the reactor in the form of a dilute hydrocarbon solution. solvent such as isopenicane.

When the activator is to be absorbed in a silica gel carrier, the two substances are mixed together in an oven containing about 4 ml of isopentane per gram of carrier. The resulting suspension is then dried for 3 to 5 hours with a stream of nitrogen at atmospheric pressure at 65 ± 1 ° to remove the hydrocarbon diluent.

When the activator is injected into the polymeric system in the form of a dilute solution, a concentration of about 5 to 10% by weight is preferably used.

Regardless of the method of introducing the activator in the polymerization reactor to complete the activation of the precursor, the activator is used in an amount such that the Al / Ti ratio in the polymerization reactor is maintained at from 10 to 400: 1, and preferably from 10 to 100: 1, including limit values. Before use, the silica was dried for at least 4 hours at at least 200 ° C.

Process B In this process, the complete activation of the precursor is carried out by contacting the precursor with an activator absorbed in an inert carrier during mixing.

The activator is absorbed in an inert carrier by suspending it together with the carrier in a hydrocarbon solvent and then drying the suspension to remove the solvent. The resulting mixture contains about 10 to 50% by weight of the fastener. Thus, 500 g of silicon dioxide (previously dried at 800 ° C for 4 hours) are introduced into a mixing vessel. The desired amount of activator in the form of a 20% (w / w) solution in a hydrocarbon solvent such as hexane is then added to the mixing vessel and mixed, suspended with an inert carrier at room temperature and atmospheric pressure. The solvent is then evaporated by drying the resulting suspension at 65 ± 10 ° C for 3 to 5 hours under atmospheric pressure with a dry inert gas stream. The dried mixture is in the form of particulate particles having the same size as the carrier used.

About 500 g of dried silica on which an activator is applied (50/50 by weight) is added to the mixing vessel and the desired weight of the precursor (80-100 g) is added. The substances are thoroughly mixed for 1-3 hours at room temperature and atmospheric pressure under a dry inert gas such as nitrogen or argon. The resulting mixture is in the form of a physical mixture of particulate matter having a size of the order of 10 to 150 microns. During mixing, the activator comes into contact with the precursor on the carrier and activates it completely. During the exothermic reaction that occurs, the catalyst temperature would exceed 50 ° C to avoid any deactivation of the catalyst. The resulting activated catalyst has an Al / Ti ratio of about 10 to 50 and, if it contains more than 10% by weight of activator, may be pyrophoric. It is stored under a dry inert gas such as nitrogen or argon before being introduced into the reactor. Examples 1 to 15

Ethylene is copolymerized with propylene or 1-butadiene (in Examples 1-7 with propylene and in Examples 8-15 with 1-butyl). In all examples, a catalyst prepared as described above and activated by activating procedure A was used.

They are made with polymers having a density of 940 kg / m 3. In all cases, the precisely activated precursor has a molar Al / Ti of 2.4 to 5.0. The activation of the precursor activation in the polymerization reactor is carried out with triethyl aluminum, which is used in the form of an iso-pentane solution either at a concentration of 2.6 or 5% by weight in such a way as to obtain a fully activated catalyst with a molar Al / Tiasi ratio 12 to 17.

Each reaction is carried out in a fluidized bed reaction system for 1 hour from equilibrium at 85 bC and at a pressure of 2.06 MPa at a gas velocity corresponding to five to six times Gmf and 213373 23 24 heavily based on space and time 48.7. up to 97.3 kg / mP / h. The reaction system described above is used as described above. Its lower part is 3.05 m and its inner diameter is 0.343 m. The upper part is 4.88 m high and its inner diameter is 0.597 m. In several examples, diethylzinc is added during the reaction (as a solution in isopentane at a concentration of 2; 6% by weight to maintain a constant molar ratio of Zn / Ti. When diethyl zinc is used, triethylaluminum is also added in the form of an iso-pennan solution of 2.6% by weight. The following Table I lists the various working conditions used in Examples 1 to 15, i.e. the content of the precursor in the mixture of precursor and silica (% by weight); Al / Ti ratio in partially activated precursor, Al / Ti ratio maintained in reactor; polymerization temperature; ethylene content in the reactor (° C / vol); the hydrogen / ethylene molar ratio; the comonomer molar ratio (Cx) to ethylene (Cz) in the reactor; catalyst productivity and Zn / Ti molar ratio. Table II lists the properties of the granular raw resins produced in Examples 1 to 15, ie density, melt index (M1), melt flow rate (MFR), ash content (% by weight), titanium content (ppm), bulk density and medium size. particles. 213373 ta £ 5'Λ cd .3 &amp; > t- <a> o. η 'and T3

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In all 14 examples, ethylene with propylene or 1-butene (in Examples 16-17 with propylene and in Examples 18-28 with 1-butene) was copolymerized using a catalyst prepared as described above and activated by activating procedure A. polymers with a density of 940kg / mi3 or less. The completion of the activation of the precursor in the polymerization reactor is carried out using triethylaluminum. Examples 16 to 18 and 21 to 28 use a 5% w / w solution of tri-aluminum carbonate in isopentane, and in Examples 19 and 20, triethyl aluminum adsorbed on silica is used at 50:50 triethylaluminum. in all cases, a fully activated catalyst having a molar ratio of Al / Ti of about 29! to 140.

The polymerizations were carried out in the same manner as in Examples 1-15. Table III lists the reaction conditions used in Examples 16 to 28 and Table IV shows the properties of the granular crude resins produced in these Examples. 213373

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Claims (3)

Table 21Features of the polymers produced in Examples 16 to 28 Density (kg / m3) Flow Index (Melts (g / 10 min) 16,927 22.0 17,929 24.0 18,925 0 61 19,931 12.0 20,923 1.47 21,919 3.41 22,925 2.90 23,919 3.10 24,929 16/5 25,929 15.3 26,928 11.5 27,929 20.7 28,929 29, 2 Volumetric Medium Volume Flow Rate Mass Particle Melt (kg / m3) 24.4 272.5 0.584 23.4 283.8 0.584 27.1 272.5 0.762 26.7 272.5 0.698 28.2 253 , 0 1.026 25.9 272J5 1.397 24.5 283.8 1.499 24.6 262.8 1.447 24.1 280.6 0.592 24.0 269.2 0.594 24.1 271.0 0.630 24.3 280.6 0.655 26.1 272.5 0.523 The unsaturation measurement is carried out using an infrared spectrophotometer (Perkin Elmer Model 2.1). 0.635 mm thick moldings are produced from the resin to serve as test specimens. transvinylldene non-sycenoids, at 11.0 μια in the case of terminal vinyl unsaturation and at 11.25 μτη in The absorbance at 1 mm of the thickness of the blank is the mass proportional to the multiple of the concentration and the absorbency. The absorbance values are taken from the literature of R. J. deKock, et al., J. Polymer Science, Part B, 2,339 (1964). A process for the catalytic production of ethylene copolymer using a titanium-containing catalyst at a productivity of at least 50,000 kg of polymer per kg of titanium in a pressurized reactor below 6.87 MPa in the gas phase, wherein the polymer is in granular form and has a density of 910 to 960 kg / m3, including limit values and melt flow rate ratio 22 to 312 including limit values, characterized in that ε-ethylene is copolymerized with at least one C 3 -C 8 α-olefin at (temperature 30 ° to 115 ° C such that the monomer feed indicates the in the presence of 0 to 2.0 moles of hydrogen, ethylene is molten in the reaction zone for the reaction phase of the reaction with particles of the catalytic system consisting of an activated precursor, the precursor having the formula of the general formula MgmTii (OR) nXp [ED] q where ED represents a liquid organic electron-trondonorm compound in which the precursor and its titanium-containing constituent and the magnesium-containing constituent are is soluble, selected from the group consisting of alkyl esters of aliphatic and aromatic carboxylic acids, aliphatic ethers, cyclic ethers, and aliphatic ketones, m is from 0.5 to 56, including the limit values, n is 0 or 1, p is the number from 6 to 116, including the limit values, q is from 2 to 85, including the limit values, R is a C 1 to C 14 aliphatic or aromatic hydrocarbon radical or the radical of the general formula COR 'wherein R 1 is C 1 to C 14 aliphatic or aromatic hydrocarbon the residue and X are chlorine, bromine or iodine, or a mixture thereof, and diluted with at least one solid inert carrier, the precursor is further fully activated before dosing the activated precursor into the reaction zone of 10-400 moles, including the activator adsorbed in the carrier, based on the titanium compound in the precursor so that a solid dry ka is prepared the safety analyzer of its heating above 50 ° C, or less than 10 mole of activator, per mole of the titanium compound in the precursor, is activated before the activated precursor is fed into the reaction zone and is fully activated in the reaction zone 10 to 400 moles of activator per mole of the titanium compound in the precursor, wherein the activator is a compound of the formula 30 213373 23 Al (R ") c X d 'H, wherein X' is a chloro or a group of the general formula OR" 'and R 'and R' ', which are the same or different, represent a C 1 to C 14 saturated hydrocarbon residue, d represents a number 0 to 1.5, e represents a number 1 or 0, with the sum of c + d -j-e being 3. 2. A process as claimed in claim 1, wherein the precursor is a reaction product which can be prepared by dissolving at least one magnesium compound and at least one titanium compound in the electrophoresis compound and then isolating the precursor from the solution by precipitation or crystallization. the magnesium compound used is a compound of the general formula MgXz wherein X is as defined above, as the titanium compound is a compound of the general formula Ti (OR) and Xb where a is the number 0 'or 1 and b is the number 2 to 4 including wherein the sum of a + b is 3 or 4, and R and X are as defined above, wherein the magnesium compound, the titanium compound, and the electron donor compound are used in such amounts to satisfy the significance of the symbols m, n, p ta · q. 3. A process as claimed in claim 1, wherein the process is carried out in a flushed bed process. 1 sheet of drawings xerography, n., Itvod 1, Uoet