DE3202961A1 - Process for the preparation of a solid catalyst, and the use of the catalyst in a process for the preparation of polyolefins - Google Patents

Abstract

alpha -Polyolefins having a narrow particle size distribution and good processing properties can be prepared in the gas phase or in dispersion in the presence of a solid catalyst which has been prepared in a plurality of separate steps. In the first step, magnesium halide is dissolved in hydrocarbons with long-chain alcohols, subsequently reacted with a solvolysable halogen compound of different elements of groups 3, 4 or 5 of the periodic table and finally brought into contact with an insoluble compound of a sub-group element from sub-group 4 or 5. It is crucial that, inter alia, the soluble constituents are always separated from insoluble constituents.

Description

Process for the production of a high solids catalyst

and its use in a process for the manufacture of polyolefins.

The present invention relates to an improved method for Polymerization of aL-olefins in the gas phase or in hydrocarbons as dispersants at pressures from 3 to 40 bar and temperatures from 60 to 100 ° C, if necessary using of hydrogen as a molecular weight regulator with one through organyl compounds of metals of the 2nd or 3rd main group of the periodic table (according to Mendeleev, cf.

also Handbook of Chemistry and Physics, 55th Ed., CRC Press, Cleveland OH, USA 1974; Inside cover) solid catalyst activated as a cocatalyst of magnesium halide treated with an electron donating compound and compounds of elements of the 4th and / or 5th subgroups of the periodic table.

There is already a wide variety of processes for olefin polymerization by means of such catalyst systems, consisting of catalyst and cocatalyst, has been proposed. The properties of the polymer are not only the qualitative and quantitative composition of the so-called UZiegler catalyst, but also determined to a strong, unpredictable degree by the manner in which the Catalyst has been produced. So call seemingly incidental and minimal Changes in the composition of the catalyst or - even if they are identical Composition - the procedure used in the manufacture of the catalyst many times over large and unpredictable changes in the activities of the catalyst and the Properties of the polymer produced with it.

For example, polyolefins are produced using homogeneous catalysis not comparable to those produced under heterogeneous catalysis.

Also heterogeneous catalysts, made for example from titanium trichloride and magnesium halide and with aluminum alkyl compounds as cocatalyst activated can lead to completely different results; for example the activity can still be completely unsatisfactory or the polymer shows unsatisfactory Properties.

The way in which the magnesium halide carrier is manufactured is already decisive Influence on the properties of the catalyst and the polyolefin produced with it, likewise the type and the time of the addition of the transition metal compound and the organyl compound used as cocatalyst.

In DE-OS 21 59 910 (& GB 13 58 437 & = for the same patent family belonging) it is proposed, for example, to polymerize alkylenes so that the polymerization at above 110 ° C with the aid of an organic dispersing agent dissolved catalyst makes, by mixing a titanium compound, z. B. TiCl4, with a magnesium compound, in particular a magnesium dialkoxylate, possibly in the presence of alcohol, esters, acids, aldehydes or ketones for example 14000 is formed. It is essential for this process that aluminum alkyl compounds be added before the above compounds to a greater extent could react with each other. S is expressly recommended to use the individual components preferably fed separately directly into the polymerization zone. The catalyst activity However, it is too low, so that laborious cleaning of the polyolefin for Purpose of the decomposition of the catalyst at the end of the polymerization not waived can be.

In DE-AS 19 39 074 (& US 36 42 746) is therefore a new way trodden to produce a suitable carrier. It is suggested there to be anhydrous Bring magnesium halide into solution with alcohol, or.

to suspend with an organic precipitant, e.g. B. hydrocarbons, again while distilling off the alcohol not bound to the magnesium halide precipitate, filter off the solid and remove it in the absence of hydrocarbon with transition metal halogen compound to implement. In the presence of According to this publication, no effective catalyst can be produced from hydrocarbons will. Furthermore, this catalyst delivers products with a dust content of up to 40% by weight with very low bulk densities.

Also DE-OS 23 46 471 (& US 40 71 674) and DE-OS 23 55 886 (& US 40 71 672) start from a solid of magnesium halide and alcohol or another donor compound that is in suspension with transition metal compound and optionally reacted with silicon or tin halide. Both methods deliver again polyolefin with a high dust content.

In DE-OS 24 61 677 (& GB 14 85 520) a catalyst is produced from a solid magnesium dihalide / electron donor adduct, initially with an organoaluminum compound and then without intermediate treatment with a Titanium compound and further organoaluminum compound is implemented.

A magnesium chloride is used in the production of the catalyst, which has a particle diameter of essentially 1 to 5 e. This will at temperatures up to 40 ° C. in an inert suspending agent with, for example, alcohol added and thereupon without separation of any constituents with an organoaluminum compound implemented. However, the polymers produced with this catalyst have no satisfactory properties, especially e.g. B. in terms of processability.

The same also applies to the polymer which, according to DE-OS 24 40 593 (& GB 14 56 464). The production of catalysts makes a difference of the type described immediately above only in that they are organoaluminum Compound and alcohol at the latest at the same time as the magnesium halide is added can be implemented together.

In SP-A-12 591 a method is described in which similar the aforementioned DE-OS 24 61 677 a magnesium halide / electron donor adduct initially with an organometallic compound of the elements, aluminum, lithium, Sodium, potassium, magnesium, zinc or cadmium, in particular aluminum, to form a solid suspension is converted, this is then subsequently: together with the cocatalyst but separately of a liquid transition metal compound at the same time in the polymerization zone introduced and thus a solution polymerization is carried out.

Finally, there is another from DE-OS 29 49 735 (& GB 20 39 501) Process for the solution polymerization of polyolefins is known. Such polymers differ significantly in their properties from those in dispersion or in the gas phase produced polymers and are unsuitable for many applications. modification the polymerization step of both processes such that Dispersion product results in polymers with unsatisfactory properties.

The invention is therefore an improved method for Production of polyolefins with better properties. The inventive method is characterized by its implementation using a solid catalyst, which does not contain any components soluble in hydrocarbons and in such a way is produced that anhydrous magnesium halide with the addition of straight-chain and / or branched primary, secondary and / or tertiary alcohols with 8 to 20 carbon atoms dissolved in hydrocarbons and from insoluble constituents is released. The resulting solution, which may also be used after cooling at 200C must remain homogeneous and stable, is then with at least one connection implemented by boron, silicon, germanium, tin, phosphorus, titanium and vanadium, respectively contain at least one halogen atom covalently bonded directly to the metal (oid) atom and are solvolyzable. A solid forms here, which is initially removed from in the hydrocarbon-soluble components (impurities) of the reaction mixture is freed and then with at least one insoluble in the hydrocarbons Contacted connection of the elements of the 4th and / or 5th subgroups of the periodic table where these elements are not at least 50 mol% in their compounds are in their highest valence level.

This solid catalyst is used in the polymerization with a conventional cocatalyst used.

Polyolefins that are produced according to the process described here can be derived from a -olefins, which were previously available at pressures of about 2 to 4Q bar in the presence of solid catalysts of the so-called "Ziegler type" could be polymerized. Preference is given to ethylene, which is optionally mixed with up to 10 mol% of ot olefins with 3 - 8 carbon atoms and copolymerized can be. Thus, the term "polymerization" is always intended to include such a copolymerization be understood and involved.

In the preparation of the catalyst used according to the invention goes man.von magnesium halides, preferably magnesium dihalides. you will be used in their so-called anhydrous form. This is generally understood to mean ' that the halides, e.g. B.

the chlorides, bromides and iodides or their mixtures, in particular the chloride, not as hydrates in the sense of Holleman-Wiberg "textbook of inorganic Chemie ", 81st-90th edition, 1976 (ISBN 3-11-005962-2) page 151. It is but not excluded that the halides contain traces of moisture or water may contain. Of course, a hydrate can also be used in a preliminary stage in a hydrogen halide atmosphere in a known manner (cf.e.g. Hollmann-Wiberg, ibid., P. 687) are drained.

Apart from the preferred magnesium dihalides, however, possibly in a mixture with it individually or as mixtures of other magnesium halide compounds a 'are set which, in addition to the halogen atom, also contains an alkoxy, aryloxy, acyloxy, Contain alkyl or aryl group.

The anhydrous magnesium halides are commercially available or can in a known manner äus alkoxy, aryloxy, acyloxy, alkyl or aryl magnesium compounds or of metallic magnesium with halogenating agents e.g. B S-silicon chlorides, Hydrogen chloride, chlorine or halogenated carbon (hydrogen) compounds are produced will. These starting compounds and these ralogenation reactions are known and therefore do not need to be described in more detail here.

Since the magnesium chlorad, among which preferably the magnesium dichloride is understood, is particularly preferred, the further procedure is for the sake of simplicity only further explained using his example. But it applies analogously to them as well other magnesium halide compounds.

Magnesium chloride, the particle size of which has no special requirements are placed, is in the first reaction stage with primary, secondary or tertiary alcohols or mixtures of such alcohols implemented. These alcohols possess 8 to 20 carbon atoms, contain one or more, preferably one hydroxyl group and preferably no heteroatoms in the hydrocarbon residue and are preferred Alkanols or alkenols. However, alcohols can also be used, the aryl, in particular contain phenyl groups.

Preferred examples of the alkanols and alkenols, among which again In particular, the saturated and branched alcohols are preferred are: 2-ethylhexanol, Isononanol, isodecanol, isoundecanol, isodedecanol, tetradecyl alcohol, oleyl alcohol, Stearyl alcohol, tetrahydrolinalool, tetrahydrolinanol.

The reaction between the magnesium chloride and the alcohols will preferably in the presence of a liquid hydrocarbon, preferably at elevated levels Temperature carried out. The optimal reaction conditions depend of course on the type of alcohol, the magnesium halide compound and possibly the hydrocarbon away. The alcohol is preferably in excess over the magnesium halide used. Amounts from 2.5 to 6, preferably from 2.8 to 4, in particular 2.8 to 3.2 moles of alcohol per mole of magnesium halide.

It is important for the correct choice of the reaction conditions that the magnesium chloride largely dissolves when it reacts with the alcohol. this happens advantageously at elevated temperature, d. H. at over 2000, preferably above 50.degree. C., more preferably at least 600.degree. C., in particular at least 7500. Heating above 30,000 is usually superfluous; temperatures are usually sufficient to preferably 14500. Optionally, especially if the boiling points are the liquid reaction components lower than the desired Reaction temperature are, can also be carried out at elevated pressure, so that the reaction is preferred takes place in the liquid phase.

The alcohol adduct of the magnesium chloride is provided the reaction between alcohol and magnesium chloride - as is preferred - not in anyway Was carried out in the presence of hydrocarbon (s), then with hydrocarbon (s) mixed so that a largely homogeneous solution is formed. If solid components or there are turbidities in the solution, the solution thereof is e.g. B. by filtering or centrifugation or. other suitable, commonly known measures thereof freed. It has been shown that this impurities and, for example Moisture contained in the magnesium chloride removed in an advantageous manner will.

The amount of hydrocarbon used is not critical. It has proven to be advantageous if the resulting solution, which is also used in z. B. 200C remains homogeneous, about up to 1, in particular 0.2 to 0.8 mol of magnesium chloride / alcohol adduct contains per liter of hydrocarbon.

The reaction time is not critical and can, for example, from 1 seconds to about 5 hours can be selected, 1 minute to 4 hours being preferred. The optimal reaction time becomes like the other reaction conditions depending on the composition of the reaction mixture selected. Longer response times than to education of the adduct are necessary, have no adverse consequences.

Which, if necessary, freed from constituents and cloudiness that were insoluble at 200.degree Solution of the magnesium chloride adduct is now in the second stage with at least one Compound of silicon, germanium, tin, boron, phosphorus; Titans or Vanadins or mixtures of such compounds. In this implementation a finely divided precipitate which becomes soluble after the reaction is complete Components of the reaction mixture is freed.

The compounds of the elements mentioned used in this course contain at least one halogen atom that is directly covalent to the metal (oid) atom is bound, and are solvolyzable. To simplify matters, these connections are made hereinafter referred to as "halogen compounds".

Some preferred halogen compounds are listed below. For example, silicon, germanium and tin compounds can have the empirical formula Ra¹MX4-a boron compounds of the empirical formula R1bBX3 b, -phosphorus compounds of the empirical formulas R1 cPX3-c X3-dRd¹PO R1ePX5 e Titanium compounds of the molecular formula Rf²TiX4-f and vanadium compounds of the sum formulas X3-gRg²VO VS4 and VX3 are used will. In these formulas, R1 = identical or different radicals from the group the hydrogen atoms, the alkyl, aryl, alkaryl, aralkyl, alkoxy, aralkoxy Aryloxy and alkaryloxy radicals, R² = identical or different alkoxy, aralkoxy, Aryloxy or alkaryloxy radicals, M = Si, Ge, Sn, X = identical or different halogen atoms, in particular chlorine or bromine, particularly preferably chlorine, a = 0 to 3, b = O to 2, c = 0 to 2, d = O to 2, e = 0 to 4, f 5 0 to 3, g = O to 2, Preferred are the Si, the P, the B and the Ti compounds, of which in turn the Si and the Ti compounds.

Preferably in R1 and R2 denote alkyl radicals or the alkyl groups in Alkoxy radicals those with 1 to 12 carbon atoms, aryl radicals or the aryl groups in aryloxy radicals Phenyl. or naphthyl, aralkyl radicals, alkaryl radicals or the aralkyl groups and alkaryl groups in the aralkoxy and alkaryloxy radicals those with 7 to 12 carbon atoms.

In general, it is also particularly preferred to use such compounds to be used in which the indices a to g do not reach the maximum value. So for example e = 3, a and f = 2, b, c, d ,. and g = 1. More preferred are those Compounds in which e = 1 or 2, a, b, c, d, f and g = 1. Ad most however, those compounds are preferred which contain no radicals R1 or R2 and their mixtures. Examples include: MX4, BX3, PX3, OPX3, PX5, OVX3, VX4, VX3 and TiX4, in which M and X have the meanings already mentioned. From these compounds mentioned, the Si, B, P and Ti compounds are preferred. In particular but SiX4 and TiX4 are preferred.

The implementation of the magnesium chloride / alcohol adduct with the halogen compounds can be in several ways take place. For example, the Ealogenverbindungen dissolved in hydrocarbons or, especially if the halogen compounds themselves are liquid, can be used without solvents. Usually the The reaction is advantageously carried out with stirring, since this reduces the reaction times can be shortened.

Reaction times of about 5 minutes to 5 hours are usually sufficient.

A possible variant of the reaction is carried out in the way that the solution of the Magnesiuschloridadduktes submitted and the halogen compound is added dropwise. Preferably, however, the halogen compound (or mixtures such compounds) presented and added dropwise the magnesium halide adduct. the however, both reactants can also be added dropwise to the reaction vessel at the same time are, but preferably the halogen compound is always in such amounts Reaction vessel provides that the molar amount of solvolysable halogen and the molar amount of alcohol contained in the reaction mixture (at least partially in the magnesium chloride adduct bound) are present in stoichiometric amounts or the halogen compound is in excess.

Such an excess, which can also be larger, has no disadvantageous Follow. In most cases, however, it is sufficient if up to per mole of magnesium chloride / alcohol adduct to 10 mol, preferably 5 mol of halogen compound are used. Advantageously 0.2 mol, in particular 0.5 mol of halogen compound per mole of magnesium chloride / Alcohol adduct not fallen below, otherwise the the activity of the catalyst wears off and the advantageous product properties of the product produced with it Polyolefins are no longer achieved, in particular with regard to the particle size distribution will.

As advantageous for the reaction between the magnesium chloride / alcohol adduct and the halogen compound, temperatures between -400C and + 1500C have been found, especially from 2000 to - + 1200C. To achieve special effects, in particular with regard to the powder properties of the catalyst, the various Of course, the temperatures mentioned in the reaction stages of the catalyst preparation are also used can be varied within the stated ranges during the respective implementation. These areas also apply mutatis mutandis to the implementation of the procedure with the other Mg compounds.

As already stated, in this implementation between the adduct and the halogen compound are insoluble in the hydrocarbons Solid, which is freed from soluble components after the reaction. It is often sufficient to decant the supernatant liquid, if necessary after centrifugation, or filtration or other suitable methods for separation known to those skilled in the art of solids and liquids, provided that the dissolved or soluble reaction components be separated from the solid.

Preferably, the solid, which is simplified in the following as a carrier is designated without thereby prejudicing its real function or -should be restricted, but by repeated washing, especially at temperatures from 400C to + 1000C with an inert organic solvent, z. B.

with hydrocarbons, of which alkanes and kerosene are preferred, and separating the washing liquid by one of the aforementioned separating operations cleaned until there are no soluble reaction components in the washing liquid have more to prove.

In the third stage, the thus obtained is preferably purified Carrier that works surprisingly well as a component of a catalyst for polymerization of ot -olefins suitable, so further treated that the finished catalyst solid thereafter at least one solid compound of the metals which is insoluble in hydrocarbons contains the 4th and / or 5th subgroups of the periodic table. In these in the following simply referred to as a solid subgroup compound with the solid in solid compounds in contact the metal atoms of the 4th and / or 5th subgroups are at least 50 mol% in one lower than their highest valence level (valence or formal oxidation level) before.

For example, the titanium compounds are at least 50 mol% the titanium atom is not in its highest oxidation state + 4, but as Ti3 + or Ti2 + before. The same applies to the compounds of Zr, Hf, V, Nb and Ta. In monomers solid subgroup compounds, i.e. those which each have only one subgroup metal atom of the groups mentioned, the only metal atom is of course always in a lower valence level compared to the maximum oxidation level. In oligomeric fixed subgroup connections, the multiple atoms of one or more of the above metals, these metal atoms can be in various Oxidation states exist as long as the majority of these atoms are in a lower one than the maximum oxidation level. All metal atoms are preferably always located in such a lower valence level, z.

B. as Ti3 + and / or Ti2 +, as Zr3 + and / or Zr2 + or as V2 +, V3 + and / or V4 + Essential for the success of the polymerization process according to the invention is that these solid subgroup compounds are used individually or as mixtures can be, at least at the temperature at which by means of the invention Btalysators the inventive polymerization of the sC -olefins is carried out, solid and not in any dispersant used, e.g. B. hydrocarbons, are soluble.

The carrier produced in the first two reaction stages, via its actual function in the catalyst solid, as already indicated (by the chosen term) no statement should and can be made in different Way to be converted to the finished catalyst.

On the one hand, the carrier can with the solid subgroup compounds by grinding or mixing the two components with one another, optionally in the presence of Hydrocarbons as suspending agents for the catalyst solid implemented will.

In a preferred embodiment, the solid subgroup compound, in which the subgroup metal of the 4th and / or 5th subgroups of the periodic table at least 50% in a lower than the maximum formal oxidation level is present, in the presence of the carrier (as defined above).

This advantageously eliminates the need to grind.

In this preferred embodiment, the carrier is preferred in suspension in an inert suspending agent, especially in hydrocarbons, preferably in concentrations of 0.1-1, esp. 0.2-0.8 Nol / l, with at least one subgroup compound soluble in hydrocarbons and possibly liquid and with at least one organometallic compound of main group 2 and / or 3 of the periodic table implemented.

In those mentioned that are soluble in hydrocarbons and possibly liquid Sub-group compounds, which are usually formed by reducing the sub-group metal into the according to the invention can be converted into the catalyst built-in form the metal atoms of the elements of the 4th and / or 5th subgroup of the periodic table mostly in their highest oxidation state.

Are preferred as solid and in hydrocarbons under the polymerization conditions insoluble subgroup compounds those of titanium, zirconium and Vanadium. However, compounds of the general formula YhTi (OR3) 3-h 'are particularly preferred wherein Y is identical or different halogen atoms, preferably chlorine and bromine, in particular Chlorine, R3 identical or different, straight-chain or branched alkyl radicals with 1 to 8 carbon atoms or aryl radicals with 6 to 10 carbon atoms and h 2 or 3, in particular 3, mean. The compounds can be used individually or as mixtures.

In the preparation of these preferably used titanium compounds is preferably of compounds of the general formula YiTi (oR3) 4 ~ i or of Mixtures of such compounds started, in which Y and R3 are those given above Have meanings and i is 2, 3 or 4. I = 4 is particularly preferred; in particular titanium tetrachloride is preferred.

Vanadium compounds suitable as subgroup compounds are already described above for the halogen compounds. Suitable zirconium compounds are those that correspond to the titanium verb described above by the two formulas indung s correspond.

If the solid subgroup compounds are in situ, d. H. according to the preferred embodiment are prepared in the presence of the carrier, they will, provided they are not themselves liquid, preferably in hydrocarbons solved reacted with the carrier and the organometallic compounds. Also the liquid subgroup compounds can be used as such solutions.

The in situ preparation is preferably carried out so that the soluble Subgroup compound is added to the carrier suspension and then said Netallorganyle preferably with stirring in a few minutes (e.g. 15 min) up to several hours (e.g. 2 h) preferably at temperatures from -40 ° C to + 1000C, especially -50C to + 700C.

However, it is also possible that the organometallic compound and then to add the soluble subgroup compound or to dose both at the same time.

The soluble transition metal compound is preferably used in such Amounts used that the catalyst solids per mole of magnesium bound in the solid 0.01 to 5, more preferably 0.05 to 2 mol, especially 0; up to 1 mole bound Contains subgroup metal.

Per mole of soluble subgroup compound are preferably 0.3 to 5, in particular 0.5 to 2.5 mol of organometallic compound of the elements of the 2nd and / or 3. Main groups of the periodic table used.

Among the elements of the 2nd and 3rd main groups of the periodic table are understood here in particular beryllium, magnesium, boron and aluminum, preferably the magnesium and particularly preferably the aluminum.

Among the metal organyl compounds of these elements are such understood that the metal atoms on alkyl and / or aryl radicals with 1 to 20 Contains bonded carbon atoms. Valences not bound by these mentioned residues of the metals can furthermore with hydrogen and / or halogen, preferably chlorine, also with alkoxy, aryloxy and / or siloxy radicals each having 1 to 20 carbon atoms Furthermore, oligomeric alkyl aluminum compounds can be used be, d. H. those compounds in addition to the above. mentioned substituents also contain aluminum-acid-aluminum bonds. Compounds are preferred here the formula AlR4zY3z described in more detail later as examples of preferred compounds of this type are: aluminum triethyl, aluminum tri-n-b.utyl, aluminum triisobutyl, Aluminum tri-n-octyl, aluminum isoprenyl, diethyl aluminum hydride, diisobutyl aluminum hydride, Ethyl aluminum dichloride, diethyl aluminum chloride, ethyl aluminum sesquichloride, diethyl ethoxy aluminum, Ethyldimethylsiloxyaluminum diethyl, bis (di-isopropylaluminum) oxide and mixtures thereof.

Diethylaluminum chloride, ethylaluminum sesquichloride, Aluminum isoprenyl, aluminum tri-n-octyl or mixtures of these compounds.

One mole of a substance mixture is that amount of substance understood the theoretically (conversion = 100% of theory) with the same amount of a reactant reacts like a mole of a pure substance contained in this Substance mixture is included.

It is also possible to react the catalyst according to the invention of the carrier described here in the 3rd and 4th stage according to reaction stages A and B of the European patent applications SP-A-22 250, EP-A 36 211 or DE patent application P 30 25 760.4 to which reference is expressly made here. Only the details disclosed therein are used to streamline the present description not repeated here.

It is also possible to use the catalyst according to the disclosure there to negotiate.

Surprisingly, yields that produced and used according to the invention Catalyst in the polymerization of -olefins with significantly improved polyolefins Properties, e.g. B. in terms of powder rheology, processability and Particle size distribution, and shows good activity, indicating a catalyst decomposition can be dispensed with at the end of the polymerization.

However, these advantages are only achieved by the combination according to the invention the measures disclosed here are achieved. Particularly good polymerisation results can be achieved when the solid (referred to above as carrier) after at every stage of the reaction the catalyst preparation of soluble Components is cleaned by washing several times (as described above).

The preparation of the catalyst solid and the inventive The polymerization must also be carried out with the exclusion of small amounts of Oxygen and. be carried out by water or steam, unless specifically targeted Peroxides are used (cf. DE note P 30 25 760.4).

The catalyst solid prepared in the above manner, which is preferably before it is used in the polymerization again by washing at preferably 0 to 1000C with hydrocarbons, sedimentation and decanting in particular has been freed of soluble metal compounds, is suitable for use in the Polymerization according to the invention of those CL olefins which have hitherto already been used in Presence of catalysts of the "Ziegler type" at pressures from 2 to 40 bar in could be polymerized in the gas phase or in dispersion. In addition to ethylene, you can so z. B.

the olefins mentioned below are also polymerized. In a A preferred embodiment of the process according to the invention is ethylene in a mixture with 0 to 10 mol% olefins with 3 to 8 carbon atoms, e.g. B.

Propene, butene-1, isobutene, pentene-1, hexene-1, ethylenebutyl-1, octene-1, used and (co) polymerized.

Particularly good results are obtained when ethylene is homopolymerized.

The inventive, with described above Catalyst system initiated polymerization can be carried out in the gas phase or in suspension, In the preferred polymerization in suspension, the reactants, preferably dispersed in a hydrocarbon or a hydrocarbon mixture and at pressures of 2 to 40 bar (absolute), preferably 2 to 11 bar and temperatures polymerized from 60 to 1000C. This can optionally be done by adding hydrogen the chain length of the resulting polymers, or, in other words, the degree of polymerization of the products are regulated.

In the context of this application, hydrocarbons are compounds understood, which are composed of the elements carbon and hydrogen, Saturated compounds such as straight-chain, branched and cyclic compounds are preferred Alkanes or paraffinic hydrocarbons, which at the specified temperatures and Pressures are predominantly liquid, e.g. 3. Alkanes with 3 to 20 carbon atoms. Examples are propane, butanes, pentanes, hexanes, heptanes, octanes, the nonanes, the decanes, cyclohexane, kerosene and their mixtures. Here are a matter of course all hydrocarbons included, so in addition to the linear ones also the cyclic ones and branched isomers, e.g. B. n-keptane, isoheptane, n-octane, isooctane, n-decane and isodecane, n-dodecane and isododecane.

To initiate the polymerization, the catalyst solid is through Addition of organometallic compound (s) the II .: and / or III. Main group (s) of the periodic table activated to the polymerization mixture (cocatalyst).

Of the compounds of this type already defined above organoaluminum compounds of the general formula AlR4 z 3-z or mixtures Of these, preference is given to in which R4 are identical or different straight-chain or branched ones Alkyl and / or aryl radicals with 1 to 20 carbon atoms, Y 'hydrogen and / or identical or different halogen atoms, alkoxy, aryloxy and / or siloxy radicals with each 1 to 20 carbon atoms and z is 2 or 3. Particularly preferred s-ind aluminum triisobutyl, aluminum tri-n-octyl and aluminum isoprenyl and their Mixtures.

Also the oligomeric organoaluminum compounds already described can be used here advantageously, where preferably in the above formula Y ' has the meaning AlR4z and z = 2.

The organometallic compounds of II. And III. Main groups of the periodic table are preferred over the subgroup elements bound in the catalyst solid the IV. and V main groups used in excess. It is of course also possible to use a deficit or stoichiometric amounts. In a preferred Embodiment are z. B. 2 to 200, in particular 5 to 150 mol of aluminum compound (s) per mole contained in the catalyst solid and chemically bound subgroup element there used.

The polymerization process of the present invention can be continuous or carried out batchwise. With the discontinuous procedure are catalyst solid prepared in the manner described above, Activator, CC olefin, optionally hydrocarbon and optionally hydrogen placed in the reactor, preferably an autoclave, and then the polymerization carried out. Of course, all or individual components can be wholly or partially can be added subsequently.

In the continuous procedure, the reaction components mentioned are separately or as a mixture in the desired composition in the reactor continuously fed in. Here, too, there is a subsequent dosing of individual partial quantities or all components possible, when using z. B. of tubular reactors also at different Place the reactor.

The process according to the invention can produce polymers that do not need to be subjected to any further post-treatment. This is achieved due to the small amount of des required because of its surprisingly high activity Catalyst system that do not noticeably adversely affect the product can.

Aside from that. The polymers prepared in accordance with the invention are well behaved due to a narrow particle size distribution, in particular with no or only a few Dust and coarse fractions, mainly between 0.1 and 0.3 mm the end.

The invention is illustrated in the following by examples and comparative examples further explained.

The melt index i5 mentioned in the examples is according to DIN (German Industry standard) 53 735 at 190 C and 49.03 N (5 kp) load determines the bulk density SD according to DIN 53 468.

Examples 1-7 4.8 g (50.4 mmol) of commercially available anhydrous magnesium dichloride (This magnesium dichloride was used in all examples and comparative experiments used) in 100 ml of isooctane and 23.5 ml (150.3 mmol) of 2-ethylhexanol were 2 kept at the boil under reflux for h.

After the impurities had been separated off, one also obtained at room temperature clear solution. This solution was at 50 ° C. in the course of 30 min Halogen compound (as defined above) given in 100 ml of isooctane. To Heating at 90 ° C for two hours, a white solid was isolated and repeated several times washed with isooctane until no more soluble metal-containing constituents are detected could become.

The solid thus purified was then suspended in isooctane, with 1.1 ml (10 mmol) of titanium tetrachloride and then with 5 ml (14.5 mmol) of ethylaluminum sesqui chloride * added. After a reaction time of 1 h at 50.degree. the red-brown Dye from soluble components by washing several times with isooctane * solution in hydrocarbons freed and suspended in 300 ml of isooctane. Details are listed in Table 1.

Example 8 4.8 g (50.4 mmol) of MgCl2 were in 100 ml of isooctane with 25.5 mml (145.1 mmol) of isononanol reacted under reflux in 2 h. After separation of The clear solution became contaminated in 30 minutes at 0 ° C. in a solution of 16.5 ml (148.3 mmol) of TiCl4 in 100 ml of isooctane are added dropwise and the mixture is heated to 90 ° C. for 2 h. To repeated washing out of the colorless solid thus obtained with isooctane suspended again in isooctane, with 1.65 ml (155 mmol) of TiCl4 and then with 8 ml (29 mmol) of ethyl aluminum sesquichloride * are added.

After one hour at 50 ° C., the rust-red solid was replaced several times Washing with isooctane freed of soluble components and in 300 ml isooctane suspended (details of the catalyst see Table 1).

* solution in hydrocarbons Table 1 solids analyzes of the catalyst Example Halogen- (ml) Mg (wt.%) Ti (wt.%) Molecular compound ratio Mg: Ti 1 SiCl4 11.5 19.8 6.7 5.82.2 CHfSiCl3 17.65 19.6 6.8 5.68 3 (CH3) 2SiCl2 14G6 18.3 8.7 4.14 4 CH3 SiHCl2 15.5 19.0 7.75 4.83 5 PCl5 31.2 g 19.1 7.8 4.80 6 OPCl3 14 19.0 7.7 4.84 7 BCl3 15 19.1 7.8 4, .82 8 TiCl4 16.5 12.2 14.9 1.61 Examples 9 - 16 The following were placed in a 3 l autoclave: 2 l of isooctane, aluminum alkyl compound. And Catalyst.

The mixture was then heated to the polymerization temperature of 80.degree. C. and Injected hydrogen up to the specified pressure. Eventually it became under continuous Polymerized ethylene supply at a total pressure of 10 bar for two hours.

The obtained polymer was separated by filtration and without purification operations dried. The polymerization results are shown in Table 2.

Table 2: Example catalyst catalyst cocatalyst H2 activity PE i5 the end (mmolTi) (ml) (bar) gPE / gTi (g) example 9 1 0.094 IPRA 2 4 134 000 602 13.1 10 2 0.15 IPRA 2 4 133 000 736 18.1 11 3 0.101 IPRA 2 3 147 000 715 0.55 12 4 0.07 IPRA 2 4 190 000 614 43.0 13 5 0.091 IPRA 2 4 143 000 613 19.4 14 6 0.088 IPRA 2 4 152 000 642 21.7 15 7 0.11 IPRA 2 4 140 000 735 25.6 16 8 0.13 TNOA 2 2.8 144 000 906 4.1 Table 2 (continued): Example particle size distribution by weight (%) SD <0.1 0.1-0.15 0.15-03 0.3 <(mm) (g / l) 9 0.4 40 59 0.6 300 10 0.14 4.2 95.4 0.26 267 11 0.07 3.8 90 6.1 291 12 0.3 0.6 99 0.1 276 13 0.12 2.4 96.8 0.68 281 14 0.2 3.1 95.1 1.6 311 15 0.2 1.6 96.3 1.9 269 16 1.4 24.3 73.1 1.2 332 For abbreviations see Table 3 Comparative Experiments AO Comparative experiments were carried out analogously to Examples 9-16. Some modifications were made to the relevant test descriptions and in Table 3.

Since all comparative tests showed unacceptably high levels of dust, the further differentiation of the particle size was dispensed with.

A 10.39 g of MgCl2 and 100 ml of isooctane were submitted, then were 17.1 ml of 2-ethylhexanol were added dropwise with stirring at 50 ° C. in 30 minutes. After washing out of the colorless suspension with isooctane and taking up in a further 100 ml of isooctane 50 ml of GiCl4 were added and the mixture was heated to 95 ° C. for 2 h. The white solid became washed thoroughly and suspended in 300 ml of isooctane.

The polymerization was carried out at 900.

3 To an initial charge of 9.34 g of MgCl2 and 30 ml of isooctane were added to 95 ° C. in 20 min. 61.5 ml of 2-ethylhexanol were added dropwise with stirring. After another 30 Min. 60 ml of TiCl4 were added within 30 min. At 950C. After further The green-yellow solid formed was washed out thoroughly for 2 h at 95 ° C. and suspended in 700 ml of isooctane.

Polymerization temperature 90 ° C.

C To an initial charge of 9.61 g MgCl2 in 100 ml isooctane were added in 30 At 22 ° C., 15.8 ml of 2-ethylhexanol were added under tubes. After another 30 min. At 30 ° C., 6.6 ml of diethylaluminum chloride were added in 30 minutes at the same temperature added. After a reaction time of 30 minutes at 30 ° C., 5.5 ml TiCl4 added. The mixture was finally after 6 h at 30 ° C with isooctane made up to 300 ml.

45 mmol of titanium were detected in the supernatant solution.

D Comparative experiment C was repeated with 12.52 g of MgCl2, 67.6 ml Isononanol, 25.8 ml diethylaluminum chloride and 7.2 ml TiCl4.

58.7 mmol of titanium were found in the supernatant solution.

E 7.2 g of MgCl2 in 25 ml of isooctane and 47.3 ml of 2-ethylhexanol were Heated to 950C for 2 h and then added 86.8 SiCl4 at 500C in 40 minutes. After adding 20% by volume of the SiCl4, the mixture was diluted with 100 ml of isooctane.

The milky suspension was within 25 min.

50 ml of TiCl4 were added and the mixture was then allowed to stand for 1 h on 80 0C heated. The beige precipitate formed was thoroughly washed off and suspended in 700 ml of isooctane.

Polymerization temperature 90 ° C.

F A mixture of 7.34 g of MgCl2 in 50 ml of isooctane and 52.8 ml of isononanol were kept at 98 ° C. for 90 minutes. It was then cooled to 22 ° C. and with 2.38 g of TiCl3 are added.

A green-blue solution formed which was made up to 300 ml with isooctane has been replenished.

G a) 5.38 g of GiCl3 were placed in 100 ml of isooctane and kept at 950C added 9.5 ml of isononanol in 100 min.

After adding 6 ml of the alcohol, 150 ml of isooctane had to be added be diluted as the reaction mixture became too viscous. After adding the whole With alcohol, the solution was kept at 950 ° C. for a further 2 h and then to 300 ml with isooctane filled up.

b) 6.39 g of MgCl2 and 34.5 ml of isononanol in 100 ml of isooctane were 30 Heated to 98 ° C. for a minute. The solution was then cooled and at room temperature in 30 min.

mixed with 25.5 ml of diethylaluminum chloride. After another 30 min. was made up to 300 ml with isooctane.

The polymerization, the solution a and the suspension b were separated fed to the reactor so that the reaction medium 7.2 mg of magnesium and contained 2.9 mg of titanium.

Polymerization temperature 90 ° C.

H Comparative experiment G was repeated, but with 14.6 mg of magnesium and 5.8 mg of titanium were fed to the reactor.

To an initial charge of 9.31 mg MgCl2 and 100 ml isooctane were added to 400C 50.3 ml of isononanol were added dropwise and the mixture was stirred for one hour. Then were inside 30 min. 17.3 ml of diethylaluminum chloride were added dropwise and a further hour at 40.degree implemented with stirring. Then 6.45 ml of GiC14 and then 8.2 ml of triethylaluminum were added, immediately forming a brown-red suspension, which was made up to 300 ml with isooctane.

Polymerization temperature 85 ° C.

J Comparative experiment I was repeated at one polymerization temperature of 90 ° C.

K To an initial charge of 3.36 g of MgCl2, 35 ml of isooctane and 6.3 ml of diethylaluminum chloride 16.6 ml of 2-ethylhexanol were added dropwise at 80 ° C. within 45 minutes. After an hour stir 7.8 ml of TiCl4 were added at 80 ° C. and reacted at 950 ° C. for 30 minutes. The educated Solid was then washed thoroughly at room temperature and finally in 300 ml of isooctane suspended.

Polymerization temperature 90 ° C.

L Comparative experiment K was repeated with 4.04 g of MgCl2, 40 ml of isooctane, 13.4 ml diethylaluminum chloride, 35.8 ml 2-ethylhexanol and 3.3 ml TiCl4.

M 4.8 g magnesium chloride, 25 ml isooctane and 23.5 ml 2-ethylhexanol were refluxed for 2 h. After the impurities had been separated off, one was obtained clear solution even at room temperature. This solution was at OOC within 1 h in 150 ml SiCl4 containing 2.3 ml ethyl benzoate. After the addition was complete, the mixture became Maintained at 60 ° C. for 12 h. A suspension formed.

After washing out the white solid with isooctane, it was 100 ml of TiCl4 suspended and the mixture stirred at 80 ° C. for 2 h. The yellow solid was finally thoroughly washed with isooctane to remove any solubles freed.

N comparative experiment M is repeated with the modification that the ethyl benzoate is not dissolved in SiCl4 but in TiCl4. It'll be practical in the process the same results as for M are obtained.

Carrying out comparative experiment M without ethyl benzoate shows a higher activity of the catalyst but also a significant increase in the fines content below 0.1 mm, Table 3 Comparative catalyst solid used cocatalyst H2 attempt (mmol Ti) (ml) (bar) Wt% Mg wt% Ti A 24.9 0.1 0.06 IPRA 1.1 5 B 18.1 4.3 0.17 IPRA 3 5 C 15.2 3.3 0.13 IPRA 6 4 D ----------- 0.13 IPRA 6 4 E 20.8 1.4 0.02 IPRA 0.8 5 F ----------- 0.12 IPRA 2.8 4 G ----------- 0.06 IPRA 1.4 7 H ----------- 0.12 TIBA 2.3 5 I 5.0 6.7 0.015 IPRA 0.9 5 J 5.0 6.7 0.055 TEA 1.5 5 K 13.1 0.2 0.018 IPRA 1.8 5 L 20.7 0.4 0.015 TIBA 1.4 5 M 15.2 2.7 0.047 IPRA 2 3 Table 3 (continued) Comparative experiment activity polyethylene dust content SD i5 g / PE / gTi (g) <0.1 mm (g / l) (% by weight) A 88 000 147 11.8 132 10.3 B 38 000 327 49.8 138 23.2 C 48,000 300 77.1 272 1.4 D 68 000 414 75.3 214 1.4 E 500 000 498 92.6 <150 15.3 F 40 600 234 100 160 73.5 G 36 000 108 100 <150 29.6 H 37,000 223 76.2 176 11.4 I 262 000 189 100 <150 3.1 J 135 000 354 77 248 21.2 K 415 000 318 39.8 209 16.9 L 450 000 324 74.7 203 20.8 M 52 700 118 14.3 218 2.5 Abbreviations in Tables 2 and 3: IPRA = isoprenyl aluminum TNOA = trioctyl aluminum TIBA = triisobutyl aluminum TEA = triethyl aluminum PE = polyethylene SD = bulk density

Claims (5)

Claims 1. Process for the production of polyolefins with narrow mesh distribution essentially in the range from 0.1 to 0.3 mm by polymerization of OL-olefins in the gas phase or in hydrocarbons as dispersants at pressures of 2 to 40 bar and temperatures of 60 to 100 ° C, optionally below Use of hydrogen as a molecular weight regulator with an organyl compound activated by metals of the 2nd or 3rd main group of the periodic table as a cocatalyst Solid catalyst made from magnesium halide treated with an electron donor compound and compounds of elements of the 4th and / or 5th subgroup of the periodic table, d a 9 u r c h g e k e n n n -. z e i n e t that none are soluble in hydrocarbons Solid catalyst containing constituents has been produced in such a way that that anhydrous magnesium halide with the addition of primary, secondary and / or tertiary alcohols with 8 to 20 carbon atoms dissolved in hydrocarbons and freed from insoluble constituents amide that the at 200C homogeneous and stable solution then with solvolysable, at least one directly to the metal (oid) atom Compound containing covalently bonded halogen atoms of one of the elements boron, Silicon, germanium, tin, phosphorus, titanium and vanadium was converted into that thereby forming solid with at least one insoluble in the hydrocarbons Connection of the elements of the 4th and / or 5th subgroups was contacted, with these Elements of at least 50 mol% are not in their highest valence state. 2. Use of a solid catalyst prepared in this way has been that anhydrous magnesium halide with the addition of primary, secondary and / or tertiary alcohols having 8 to 20 carbon atoms in hydrocarbons was dissolved and freed from insoluble components that the homogeneous at 20 ° C and stable solution then with solvolysable, at least one directly to the metal (oid) atom Compound containing covalently bonded halogen atoms of one of the elements boron, Silicon, germanium, tin, phosphorus, titanium and vanadium was converted into that thereby forming solid with at least one insoluble in the hydrocarbons Connection of the elements of the 4th and / or 5th subgroups was contacted, with at least 50 mol% of these elements are not in their highest valence state, for the polymerization of α-olefins according to claim 1. 3. Process for the preparation of the catalyst used according to claim 2, it is noted that anhydrous magnesium halide with the addition of primary, secondary and / or tertiary alcohols with 8 to 20 Carbon atoms dissolved in hydrocarbons and from insoluble constituents is freed that the homogeneous and stable solution at 20 ° C then with solvolyzable, at least a covalently bonded directly to the metal (oid) atom Compound containing halogen atom of one of the elements boron, silicon, germanium, Tin,. Phosphorus, titanium and vanadium is converted, the solid that forms in the process with at least one compound of the elements which is insoluble in the hydrocarbons the 4th and / or 5. Subgroups will be contacted, with these elements at least 50 IIol -% - are not in their highest valence level.