RU2104088C1 - Method of preparing catalytic system for trimerization, oligomerization, and polymerization of olefins (versions) and method for conducting these processes in presence of claimed catalytic system - Google Patents

Abstract

FIELD: polymerization catalysts. SUBSTANCE: known method of preparing chromium-containing compounds, such as chromium pyrrolides, by way of preparing a mixture of chromium salt, metal amide, especially metal pyrrolide, and electronodonor solvent, such as ether, followed by interaction with saturated compound is improved by using pyrrole or its derivatives as pyrrolide and alifatic compounds as unsaturated hydrocarbons. New method of preparing catalytic system includes mixing metal source, pyrrole-containing compound, and metal alkyl omitting stage of preliminary interaction of metal source and pyrrole-containing compound in presence of electronodonor solvent. These catalytic systems and chromium-containing compounds, by themselves or applied on inorganic oxide-based carriers, may, if necessary, be used as co-catalysts jointly with polymerization catalyst, such as chromium- and titanium-containing catalysts, for trimerization, oligomerization, and polymerization of olefins. EFFECT: simplified catalyst preparation procedure. 32 cl, 9 tbl

Description

 This invention relates to the preparation of a catalyst or cocatalyst for the trimerization, oligomerization and / or polymerization of olefins. Catalysts are used in the processes of trimerization, oligomerization and / or polymerization of olefins.

 The supported chromoxide catalysts were a determining factor for the production of olefin polymers, for example, such as polyethylene or a copolymer of ethylene and hexane. These catalysts can be used in various polymerization processes. However, most of the known chromium compounds must be supported on a carrier so that they exhibit catalytic activity. Moreover, most supported chromium compounds can only be used to polymerize olefins. If olefin copolymers are needed, the polymerization process becomes more complex since two different monomers must be fed into the polymerization reactor.

 Catalysts for the trimerization and oligomerization of olefins are also well known in the art. But usually they have insufficient selectivity for the target product and, in addition, provide a product with a low yield. However, the trimerization and / or oligomerization of olefins, if it proceeds efficiently, is a process by which the necessary olefins are obtained. Such olefin products may be further trimerized, oligomerized and / or optionally incorporated into the polymerization process.

EP-A-41-6304 discloses chromium compounds of the formula:
Cr ₅ (C ₄ H ₄ N) ₁₀ (C ₄ H ₃ O) ₄ ;
[Cr (C ₄ H ₄ N) ₄ ] [NaI ₂ ] • 2 (OC ₄ H ₃ );
[Cr (C ₄ H ₄ N) ₅ (OC ₄ H ₃ )] [NaI ₂ ] • 4 (OC ₄ H ₃ );
or
Cr (NC ₄ H ₄ ) ₃ Cl (O ₂ C ₂ H ₄ (CH ₃ ) ₂ ) ₃ Na.

 In accordance with the subject of the above application, such new chromium-containing compounds are prepared from a reaction mixture containing a chromium salt, a metal amide and any electron-donating solvent, such as, for example, ether. Catalytic systems can be used either supported or without a support for the trimerization and / or polymerization of olefins.

 The chromium salt can be one or more organic or inorganic chromium salts, in which the degree of oxidation of chromium varies from 0 to 6. The definition of “chromium salt” used in this invention also includes metal chromium. In general, the chromium salt will have the formula CrXn, where X may be the same or different and may be any organic or inorganic residues, and n is an integer from 1 to 6. Organic residues may contain from about 1 to about 20 carbon atoms in one residue and are selected from the group consisting of alkyl or alkoxy groups, ether, ketone residues and / or amide moiety. Organic residues may be linear or branched, cyclic or acyclic, aromatic and / or aliphatic groups and may consist of mixed aliphatic, aromatic and / or cycloaliphatic groups. Examples of inorganic residues are, but are not limited to, halides, sulfates and / or oxides.

 Preferably, the chromium salt is a halide, for example, chromium (II) fluoride, chromium (III) fluoride, chromium (II) chloride, chromium (III) chloride, chromium (II) bromide, chromium (III) bromide, chromium (II) iodide , chromium (III) iodide and mixtures thereof. Due to the ease of separation of reaction by-products such as sodium chloride, as well as their relatively low cost, the most preferred chromium salt is chloride, for example, chromium (II) chloride and / or chromium (III) chloride.

 The metal amide can be any amide that interacts with a chromium salt to form a chromamide complex. In a broader sense, the metal amide may be any heteroleptic or homoleptic metal complex or salt, in which the amide substituent is any nitrogen-containing organically residue. The metal amide can be added either directly to the reaction mixture or generated in situ. In general, a metal amide will contain from about 1 to about 20 carbon atoms.

 Preferred metal amides include, but are not limited to, lithium dimethylamide, lithium diethylamide, lithium diisopropylamide, lithium dicyclohexylamide, sodium bis (trimethylsilyl) amide, sodium indolide, alkali or alkaline earth metal pyrrolides, or mixtures of two or more of these compounds. Due to the high reactivity and activity with other reagents, the above metal pyrrolides, for example, lithium pyrrolide, sodium pyrrolide, potassium pyrrolide and cesium pyrrolide, are most preferred. Examples of substituted pyrrolides include, but are not limited to, 2,5-dimethylpyrrolide and / or 3,4-dimethyl pyrrolide sodium. When the metal amide is a pyrrolidine ligand, the final chromium compound is chromium pyrrolide.

 According to a first embodiment of the claimed invention, pyrrole itself (hydrogen pyrrolide) or substituted pyrrole are considered acceptable pyrrolides. Pyrrole is the preferred hydrogen pyrrolide. Substituted pyrroles are illustrated below.

 The ether in the reaction mixture may be one or more ether compounds that affect the interaction of a chromium salt with a metal amide. Although in theory the ether should not form a chemical bond, it is believed that it can be a solvent, as well as a possible reagent. As the ester, any aliphatic and / or aromatic compound containing an ROR fragment may be used, where R substituents may be the same or different, but preferably should not be hydrogen atoms. Preferred esters are aliphatic esters, since aromatic esters are toxic to humans. Moreover, preferred esters are those that accelerate the reaction between chromium halide and Group IA or IIA metal pyrrolides, and which can also be easily removed from the reaction mixture. Examples of such compounds are, but are not limited to, compounds of tetrahydrofuran, dioxane, diethyl ether, dimethoxyethane (glyme), diglyme, triglyme, and a mixture of one or more of these compounds. Most preferably, the esters are selected from the group consisting of tetrahydrofuran, tetrahydrofuran derivatives, dimethoxyethane, dimethoxyethane derivatives and mixtures thereof, for the reasons mentioned above, and also because the preferred amine salts are soluble in these esters.

 The three reagents can be mixed in any way under conditions suitable for the formation of a solution containing one or more of the claimed chromium compounds. The reaction preferably proceeds in the absence of oxygen and moisture, therefore, in an inert atmosphere, for example, in an atmosphere of nitrogen and / or argon. The reaction pressure should be sufficient so that the reagents are in a liquid state. In general, a pressure in the range of about atmospheric to about 3 atmospheres is acceptable. To simplify the work, atmospheric pressure is usually used.

 The inventive chromium compounds precipitated can be isolated by any method known in the art. The simplest technique for precipitating a precipitate of chromium-containing compounds is filtration.

 According to a second embodiment of the invention, the metal pyrrolides used in the composition of the catalysts and / or cocatalysts can also be prepared from metal salts other than chromium. Examples of such metals are nickel, cobalt, iron, molybdenum and copper. As in the case of chromium salts, the degree of oxidation of the metal can be any, including zero. The pyrrolides of these metals can be obtained by a method similar to that previously described for chromium pyrrolides.

 Compounds of chromium or other metals prepared by the above method can be used as a catalytic system either supported on a carrier and / or without application for trimerization, oligomerization and / or polymerization of olefins. The supported catalyst system can be prepared with any support suitable for applying a chromium-containing catalyst. Examples of such catalyst supports are, but are not limited to, zeolites, inorganic oxides, either alone or in the form of mixed oxides, phosphated inorganic oxides and mixtures thereof. Particularly preferred are carriers selected from the group consisting of silica, aluminosilicate, alumina, fluorinated alumina, silylated alumina, thorium oxide, aluminophosphate, alumina phosphate, phosphated silica, phosphated alumina, titanosilicate, precipitated silica / dioxide titanium, phosphated / silylated alumina and mixtures thereof, as well as any one or more of those supports which may contain chromium. Currently, the most preferred support for the catalyst, due to the highest activity during trimerization, is the aluminophosphate described in US Pat. U.S. 4,364,855 (1982).

The amount of chromium pyrrolide per gram of carrier can be expressed in different, however, equivalent terms, for example, in moles of chromium per 1 g of carrier. For the reasons stated above, usually less than about 8.6 x 10 ^-3 moles of chromium per gram of carrier is sufficient. Preferably, about 1.7 • 10 ^-6 - 1.7 • 10 ^-5 to 8.6 • 10 ^-4 moles of chromium are used per gram of carrier.

 After the support is added and mixed thoroughly with chromium pyrrolide, the support can be filtered, dried in vacuo, and then an activating compound is added to the support / pyrrolide mixture, usually in the form of a solution of one or more Lewis acids and / or metal alkyls, preferably using as a solvent hydrocarbon. Then, a supported supported catalyst system can be obtained by filtration. In accordance with this description, a Lewis acid is defined as any compound that is an electron acceptor. Preferably, the activating compound is a compound that can be regarded as both a Lewis acid and a metal alkyl. In accordance with a broader definition in this application, the activating compound may contain any number of carbon atoms. However, due to commercial availability and ease of use, activating compounds will typically contain less than about 70 carbon atoms in the metal-alkyl molecule, and preferably less than about 20 carbon atoms.

 Preferred activating compounds, which are both metal alkyls and Lewis acids, are, but are not limited to, aluminum alkyls, boron alkyls, magnesium alkyls, zinc alkyls and / or lithium alkyls. Examples of such metal alkyls include, but are not limited to, metal alkyls from butyl lithium, sec-butyl lithium, t-butyl lithium, diethyl magnesium, dibutyl magnesium, diethyl zinc, triethyl aluminum, trimethyl aluminum, triisobutyl aluminum and mixtures thereof. Most preferably, the activating compounds are selected from the group consisting of non-hydrolyzed, i.e. non-water-contacted, alkyl aluminum compounds, derivatives of alkyl aluminum compounds, halogenated alkyl aluminum compounds and mixtures thereof to improve product selectivity, as well as to increase reactivity, activity and / or catalytic system performance. Examples of such compounds include, but are not limited to, triethylaluminum, tripropylaluminum, tributylaluminum, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum ethoxide, ethylaluminum sesquioxide, or mixtures thereof to obtain a catalyst system with the highest activity and product selectivity. The most preferred compound is triethylaluminium, since when it is used, the best results are achieved in terms of activity of the catalytic system and selectivity for the product.

 Any amount of an activating compound, such as metal alkyl and / or Lewis acid, is sufficient to activate and / or react with a pyrrolidochlorine catalyst. Typically, about 200 g of an activating compound, i.e. metal alkyl and / or Lewis acid, per gram of chromium can be used. Preferably, from about one to about 100 g of an activating compound, such as metal alkyl and / or Lewis acid, per gram of chromium pyrrolide is used, most preferably from about 5 to 30 g of an activating compound, such as metal, to obtain the highest catalytic activity -alkyl and / or Lewis acid per 1 g of chromium pyrrolide. However, the amount of activating compound used, such as metal alkyl and / or Lewis acid, may vary depending on the carrier used. For example, if the support is silica and / or alumina, too much of an activating compound such as metal alkyl or Lewis acid can reduce catalytic activity. However, the same amount of activating compound, such as metal-alkyl and / or Lewis acid, when used with an aluminophosphate support does not significantly reduce catalytic activity.

 The hydrocarbon used as a solvent may be any combination of one or more aromatic or aliphatic unsaturated hydrocarbons. Although theoretically a hydrocarbon should not enter into chemical interaction, it is believed that it can act as a reagent and / or stabilizing component during and / or after the formation of the inventive catalyst system. Examples of unsaturated hydrocarbons, such as, for example, a solvent, can be any unsaturated hydrocarbons that are capable of dissolving an activating compound when the activating compound is a Lewis acid and / or metal-alkyl. Accordingly, in a third embodiment of the invention, in addition to aromatic compounds containing from 6 to 50 carbon atoms in one molecule, used as a solvent, unsaturated aliphatic hydrocarbons containing less than about 20 carbon atoms in a molecule can be used.

 Specific examples of unsaturated aliphatic compounds include, but are not limited to, ethylene, 1-hexane, 1,3-butadiene, and mixtures thereof. The most preferred aliphatic hydrocarbon is ethylene, since its use eliminates the stage of preparation of the catalytic system, and due to the fact that ethylene can be a reagent for trimerization and / or oligomerization. Specific examples of unsaturated aromatic hydrocarbons include, but are not limited to, toluene, benzene, xylene, mesitylene, hexamethylbenzene, and mixtures thereof. The most preferred unsaturated aromatic hydrocarbon solvent is toluene, which can be easily removed and has minimal effect on the resulting catalyst system.

 An unsaturated hydrocarbon may be present either during the initial contact of the chromium pyrrolide and the activating compound, that is, prior to the introduction of trimerization, oligomerization and / or polymerization into the reactor, or the unsaturated hydrocarbon may be introduced directly into the reactor. As indicated above, one or more olefin reactants can be considered as unsaturated hydrocarbons. Preferably, an unsaturated hydrocarbon is present upon initial contacting of the chromium pyrrolide and the activating compound in order to stabilize the resulting catalyst system. In the absence of an unsaturated hydrocarbon, the resulting catalytic system may, after some time, deactivate and lose activity.

 Although any amount of unsaturated hydrocarbon may be used, too much or too little may adversely affect the activity of the catalyst system. Therefore, it is preferred that some excess of unsaturated aromatic hydrocarbon is desorbed from the resulting catalyst system. The desorption of excess unsaturated aromatic hydrocarbon can be carried out by any method known in the art, for example, such as solvent removal methods. Examples of solvent removal methods include, but are not limited to, methods such as filtration, vacuum drying, drying in an inert atmosphere, and a combination of these methods. Although a theoretically unsaturated hydrocarbon does not enter into chemical interaction, it is believed that the remaining unsaturated hydrocarbon can stabilize the resulting catalyst system. If an unsaturated hydrocarbon is absent, then it is believed that the catalyst system will lose activity.

 An alternative and therefore preferred method, in accordance with the invention, of preparing a supported catalyst system is to combine one or more of the inventive solid chromium pyrrolides with an unsaturated hydrocarbon solvent, more generally described herein, in order to include, for example, toluene and / or ethylene, and an activating compound described previously, such as metal alkyl and / or Lewis acid, for example triethylaluminum.

 According to a fourth embodiment of the present invention, a catalyst system can be prepared by combining a metal source, a pyrrole-containing compound and a metal alkyl and preferably an unsaturated hydrocarbon in a common solvent without a preliminary reaction step using an electron-donating solvent (for the interaction between the metal source and the pyrrole-containing compound, like this described above). A likely (optional) unsaturated hydrocarbon, such as toluene, can be used as a common solvent. In the absence of such an unsaturated solvent acting as a common solvent, cyclohexane can be used. These catalyst systems may further comprise a catalyst support. Preferably, the metal source is a chromium source, but may be a source of any other metal described above.

 A chromium source, similarly to the previously described chromium salt, can be one or more organic or inorganic compounds in which chromium has an oxidation state of 0 to 6. In this description, metallic chromium is included in this definition of chromium salts. In general, the chromium source will be of the formula CrXn, where X substituents can be the same or different and can be any organic or inorganic residue, and n takes integer values from 1 to 6. Organic residues can contain from about 1 to about 20 carbon atoms in one residue and are selected from the group consisting of an alkyl group, an alkoxy group, an ester, a ketone residue and / or an amide fragment.

 Organic substituents may be linear or branched, cyclic or acyclic, aromatic or aliphatic, may consist of mixed aliphatic, aromatic and / or cycloaliphatic groups. Inorganic residues include, but are not limited to, halides, sulfates, and / or oxides.

Preferably, the chromium source is chromium (II) - and / or chromium (III) -containing compounds that can form a catalyst system with improved activity in trimerization reactions. The most preferred source of chromium is a chromium (III) compound, since they are convenient to use, accessible and form a catalytic system with increased catalytic activity. Examples of chromium (III) compounds include, but are not limited to, chromium carboxylates, chromium naphthenates, chromium halides, chromium pyrrolides and / or diketone-based chelated chromium compounds (dionates). Specific examples of chromium (III) compounds include chromium (III) 2,2,6,6-tetramethylheptadionate, [Cr (TM DG) ₃ ], chromium (III) 2-ethylhexanoate [Cr (DG) ₃ ], chromium naphthenate [Cr (NF) ₃ ], chromium (III) chloride, tris (2-ethylhexanoate) chromium (III), chromium (III) bromide, chromium (III) chloride, chromium (III) fluoride, chromium (III) oxy-2-ethylhexanoate , chromium (III) acetylacetonate, chromium (III) dichloroethyl hexanoate, chromium (III) acetate, chromium (III) butyrate, chromium (III) neopentanoate, chromium (III) laurate, chromium (III) stearate, chromium (III) pyrrolide (s) ) and / or chromium (III) oxalate, but are not limited to them.

 Specific examples of chromium (II) compounds include, but are not limited to, chromium (II) fluoride, chromium (II) bromide, chromium (II) chloride, chromium (II) iodide, chromium (II) bis (2-ethylhexanoate), chromium (II) acetate, chromium (II) butyrate, chromium (II) neopentanoate, chromium (II) laurate, chromium (II) stearate, chromium (II) pyrrolides and / or chromium oxalate.

The pyrrole-containing compound can be any pyrrole-containing compound that will react with the chromium salt to form a chrompyrrolide complex. As used herein, the term “pyrrole-containing compound” refers to hydrogen pyrrolide, that is, pyrrole (C ₄ H ₅ N), derivatives of hydrogen pyrrolide, as well as metal pyrrolide complexes. A “pyrrolide” (or “pyrrole”, as indicated for the first embodiment of the invention) can be any compound containing a 5 membered nitrogen-containing heterocycle, for example, such as pyrrole, pyrrole derivatives and mixtures thereof. In a broader sense, the pyrrole-containing compound may be pyrrole and / or any heteroleptic or homoleptic metal complex or salt containing a pyrrolide residue or ligand. The pyrrolide-containing compound can either be directly added to the reaction mixture or generated in situ. In general, a pyrrole-containing compound will contain from about 1 to about 20 carbon atoms in one molecule.

 Examples of pyrrolides (or pyrroles) are hydrogen pyrrolide (pyrrole), pyrrole derivatives, substituted pyrrolides (or pyrroles), lithium pyrrolide, sodium pyrrolide, potassium pyrrolide, cesium pyrrolide and / or substituted pyrrolide salts due to their high reactivity and relation to other reagents. Examples of substituted pyrrolides (or pyrroles) include, but are not limited to, pyrrole-2-carboxylic acid, 2-acetylpyrrole, pyrrole-2-carbaldehyde, tetrahydroindole, 2,5-dimethylpyrrole, 2,4-dimethyl-3-ethylpyrrole, 3-acetyl-2,4-dimethylpyrrole, ethyl 2,4-dimethyl-5-ethoxycarbonyl-3-pyrrolpropionate, ethyl 3,5-dimethyl-2-pyrrolecarboxylate. When the pyrrole-containing compound contains chromium, the resulting compound may be called chromium pyrrolide.

The most preferred pyrrole-containing compounds for use in trimerization catalyst systems are selected from the group consisting of hydrogen pyrrolide, i.e. pyrrole (C ₄ H ₅ N) and / or 2,5-dimethylpyrrole. Although all pyrrole-containing compounds can produce catalytic systems with high activity and productivity, the use of pyrrole and / or 2,5-dimethylpyrrole can lead to the formation of catalytic systems with increased activity and selectivity for the target product of trimerization, for example, for the product of the trimerization of ethylene 1-hexene, and can also reduce the yield of polymers.

 Metal acryl, also previously mentioned as an activating compound, can be any heteroleptic or homoleptic metal alkyl. One or more metal alkyls may be used. The metal ligand (s) may (may) be aromatic and / or aliphatic. Preferably, the ligand (s) are an unsaturated aliphatic residue. Metal alkyl can contain any number of carbon atoms. However, due to their commercial availability and ease of use, metal alkyls containing less than about 790 carbon atoms in one molecule, more preferably less than about 20 carbon atoms, are usually used. Preferred metal alkyls are, but are not limited to, alkyl aluminum compounds, alkyl boron compounds, alkyl magnesium compounds, alkyl zinc compounds and / or alkyl lithium compounds. Examples of metal alkyls include, but are not limited to, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, diethyl magnesium, diethyl zinc, triethyl aluminum, trimethyl aluminum, triisobutyl aluminum and mixtures thereof.

 Most preferably, to improve the selectivity for the product, as well as the reactivity, activity and / or productivity of the catalytic system, the activating compound is selected from the group consisting of non-hydrolyzed, i.e. non-water-contacted, alkylaluminum compounds, derivatives of alkylaluminum compounds, halogenated alkylaluminum compounds and mixtures thereof. Examples of these compounds include, but are not limited to, triethylaluminum, tripropylaluminum, tributylaluminum, diethylaluminum chloride, diethylaluminium bromide, diethylaluminum ethoxide, ethylaluminum sesquioxide and mixtures thereof, because they form the best catalyst systems in terms of activity and selectivity. Most preferably, the alkylaluminum compound is triethylaluminum, which forms the best catalyst systems in terms of activity and selectivity, as well as due to commercial availability.

If the desired product is a catalytic system for trimerization, the activating compound should be at least one non-hydrolyzed alkylaluminum compound represented by the general formulas AlR ₃ , AlR ₂ X, AlRX ₂ , AlR ₂ OR, AlRXOR and / or Al ₂ R ₃ X ₃ , where R represents an alkyl group, and X represents a halogen atom. Examples of such compounds include, but are not limited to, triethyl aluminum, tripropyl aluminum, tributyl aluminum, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, triethyl aluminum methoxy chloride and / or one and a half ethyl aluminum. Preferably, the activating compound for the trimerization catalyst system is an aluminum trialkyl compound of the formula AlR ₃ for the reasons stated above. For the same reasons, the most preferred trialkylaluminum compound is triethylaluminum.

 The formation of stable and active catalyst systems can be carried out in the presence of an unsaturated hydrocarbon. As discussed above, an unsaturated hydrocarbon may be present either during the initial contact of the chromium source, pyrrole-containing compound and metal alkyl, or may be introduced directly into the trimerization, oligomerization and / or polymerization reactor. In addition, one or more olefin reactants may be considered as an unsaturated hydrocarbon.

 Any unsaturated aromatic or aliphatic hydrocarbon may be used. Preferably, the unsaturated hydrocarbon is initially present in the reaction mixture, and most preferably the aromatic hydrocarbon and / or ethylene are present at the initial stage in order to obtain a highly active catalyst in terms of activity and selectivity, as well as a stable catalyst system. An unsaturated hydrocarbon can have any number of carbon atoms in a molecule. Unsaturated hydrocarbons that contain less than about 70 carbon atoms, preferably less than 20 carbon atoms, are usually commercially available and easy to handle.

 The unsubstituted hydrocarbon may be gaseous, liquid or solid. Preferably, in order to achieve complete contacting and mixing of the chromium salt, pyrrole-containing compound, metal-alkyl, the unsaturated hydrocarbon should be liquid and / or should be in a dissolved state. Examples of unsaturated aliphatic hydrocarbons include, but are not limited to, ethylene, 1-hexane, 1,3-butadiene, and mixtures thereof. The most preferred unsaturated aliphatic hydrocarbon is ethylene, as it can also be a reagent in the process of trimerization, oligomerization and / or polymerization. Examples of unsaturated aromatic hydrocarbons include, but are not limited to, toluene, benzene, xylene, mesitylene, hexamethylbenzene, and mixtures thereof. Unsaturated hydrocarbons are preferred to improve the stability of the catalyst system, as well as to improve the activity of the catalyst system. To obtain the highest stability and activity of the catalyst system, toluene is the most preferred unsaturated aromatic hydrocarbon.

 If an unsaturated aromatic hydrocarbon is added prior to introducing the chromium compound (s) into the trimerization, oligomerization and / or polymerization reactor, removing or desorbing the unsaturated aromatic hydrocarbon before introducing the chromium compound (s) into the reactor can improve the activity and / or selectivity of the catalyst system for the product. The removal of unsaturated aromatic hydrocarbon can be carried out by any method known in the art, for example by evaporation or evaporation. The resulting product is a concentrated or unsaturated solution of the inventive catalyst system.

 If the unsaturated aromatic hydrocarbon is removed prior to introduction into the reactor, the concentrated or saturated solution of the proposed catalyst system can be dissolved in a solvent compatible with the process of trimerization, oligomerization and / or polymerization, in order to facilitate operation with the proposed catalyst system. In general, the same solvent is used as the diluent in the reactor. Preferred solvents include, but are not limited to, cyclohexane, isobutane, hexane, pentane, or mixtures thereof.

 The reaction, if necessary, can also proceed in the presence of a halide source. The presence of a halide source in the reaction mixture can increase the activity of the catalyst system and its productivity, as well as product selectivity. Examples of halides include, but are not limited to, fluoride, chloride, bromide and / or iodide. Because of their ease of use and availability, chlorides are preferred. From the point of view of improving activity, productivity and / or selectivity, bromides are more preferred halides.

The halide source may be any compound containing a halogen atom. Examples of such compounds include, but are not limited to, compounds of the general formula R _m X _n , where R may be any organic and / or inorganic residue, and X may be a halide selected from the group consisting of fluoride, chloride, bromide and / or iodide, and m + n takes any value greater than 0. If R is an organic residue, then it preferably contains from about 1 to about 70 carbon atoms, most preferably from 1 to 20 carbon atoms to provide better compatibility and catalytic activity system. If R is an inorganic residue, then it is preferably selected from the group consisting of aluminum, silicon, germanium, boron, lithium, tin, gallium, indium, lead, and mixtures thereof. Specific examples of such compounds include, but are not limited to, methylene chloride, chloroform, benzyl chloride, silicon tetrachloride, tin (II) chloride, tin (IV) chloride, germanium tetrachloride, boron trichloride, aluminum trichromide, aluminum trichloride, 1,4-dibromobutane and / or 1-bromobutane.

 In addition, the chromium source, metal-alkyl and / or unsaturated hydrocarbon may contain and provide a halide for the reaction mixture. Preferably, the source of the halide is an aluminum alkyl halide and is used together with aluminum alkyl compounds due to their ease of use and compatibility, and also due to the improved activity and selectivity of the resulting catalyst system. Examples of alkylaluminium halides include, but are not limited to, diisobutylaluminium chloride, diethylaluminium chloride, ethyl sesquioxide, ethylaluminium dichloride, diethylaluminium bromide, diethylaluminium iodide and mixtures thereof.

 When the target product is a trimerization catalyst system, the reaction mixture preferably contains a halide source. Moreover, most preferably, the halide source is selected from the group consisting of tin (IV) halides, germanium halides and mixtures thereof. The halide source is most preferably mixed in the chromium source and the pyrrole-containing compound before metal alkyl is added, that is, the chromium source and the pyrrole-containing compound are pre-treated with the halide source in order to increase the productivity of the catalyst system.

 The amount of each reagent used to prepare the catalytic system for trimerization may be any amount sufficient so that trimerization reactions proceed when mixed with one or more olefins. Typically, in order to obtain a catalytic system for trimerization, approximately one mole of chromium based on elemental chromium (Cr) can be mixed with approximately 1 to 50 moles of pyrrole-containing compound and approximately 1 to 75 moles of aluminum based on elemental aluminum in excess of unsaturated hydrocarbon. If an optional source of halide is present, then its amount is usually 1 to 75 moles of halide based on the element. Preferably, about 1 mole of chromium based on elemental chromium (Cr) can be mixed with about 1-15 moles of pyrrole-containing compound and with about 5 to 40 moles of aluminum based on elemental aluminum (Al) in excess of unsaturated hydrocarbon. If an optional source of halide is present, then preferably its amount is about 1 to 30 moles of halide based on elemental halogen (X). Most preferably, about 1 mole of chromium based on elemental (C) is mixed with 2 to 4 moles of pyrrole-containing compound and with 10 to 20 moles of aluminum based on elemental (Al) in excess of unsaturated hydrocarbon. If an optional source of halide is present, then most preferably the amount is 2 to 15 moles of halide based on element X.

 Excess pyrrole-containing compounds, as it turned out, does not improve the activity, performance and / or selectivity of the catalyst system. An unsaturated hydrocarbon can improve the stability, activity and / or selectivity of the catalyst system. Excess unsaturated hydrocarbon can lead to poor selectivity and / or activity of the catalyst system. Too much alkyl aluminum can lead to a decrease in the activity of the catalytic system and its selectivity for the product. Too small an amount of alkylaluminum can lead to incomplete formation of a catalytic system, which, in turn, leads to low activity of the catalytic system and an increase in the formation of undesirable polymer by-products. An excess of the added optional source of halide can deactivate the catalytic system, and therefore can lead to a decrease in its activity. As indicated previously, the presence of a halide source increases the activity of the catalyst system and its product selectivity.

 According to a fourth embodiment of the invention, preferably the pyrrole-containing compound is in the reaction mixture together with the metal source prior to the introduction of the metal alkyl. If you follow this order of addition, you can get a better catalytic system in terms of activity and productivity.

 The reaction preferably proceeds in the absence of oxygen, which can deactivate the catalyst, under anhydrous conditions, that is, under conditions of an initial absence of water. Therefore, the most preferred dry, inert atmosphere, for example, an atmosphere of nitrogen and / or argon. In addition, metallkyl is a non-hydrolyzed metalalkyl.

 The reaction pressure may be any pressure that does not adversely affect the reaction. In general, a pressure in the range of about atmospheric to about three atmospheres is acceptable. In order to simplify the work, the reaction is usually carried out at atmospheric pressure.

 The reaction temperature may be any. To ensure a more efficient reaction, temperatures are preferred at which the reaction mixture is in a liquid state.

 The reaction time may be any period of time necessary to carry out the reaction. The reaction can be regarded as a dissolution process; any time is sufficient during which almost all reagents can dissolve. Depending on the reagents, as well as on the temperature and pressure of the reaction, the reaction time may vary. Usually less than about one day is enough. Typically, the reaction time is less than 60 minutes. Under optimal conditions, the reaction time varies from about 1 second to about 15 minutes. A longer reaction time does not lead to additional advantages, and a shorter reaction time may not be sufficient to complete it.

 Heterogeneous system i.e. A supported catalyst system can be prepared in accordance with a fourth embodiment of the invention in situ in a reactor by adding a solid support directly to the reactor. As indicated previously, examples of catalytic supports include, but are not limited to, zeolites, inorganic oxides individually or in a mixture, phosphated inorganic oxides, and mixtures thereof. Particularly preferred are carriers selected from the group consisting of silica, aluminosilicate, alumina, fluorinated alumina, silylated alumina, thorium dioxide, aluminophosphate, aluminum phosphate, phosphated silica, phosphated alumina, silica-titanium dioxide, precipitated titanium dioxide / silica, phosphated / silylated alumina and mixtures thereof, as well as one or more of those supports which may contain chromium. Currently, the most preferred support for the catalyst, due to the highest activity in the trimerization reaction, is the aluminophosphate described in US Pat. US 4364855. Obtaining a heterogeneous in situ catalyst system used in trimerization or oligomerization reactions can lead to a reduction in undesired polymer formation.

 Heterogeneous catalyst systems for trimerization, oligomerization and / or polymerization can also be prepared in accordance with this embodiment of the invention by forming a reaction mixture containing a chromium source, pyrrole-containing compounds, metallkyl, unsaturated hydrocarbon and inorganic oxide described above. If necessary, as previously described, a halogen source may be added. The stoichiometry and reaction conditions are similar to the stoichiometry and conditions of the second embodiment of the invention.

Any excess of the chromium source with respect to the inorganic oxide catalyst carrier is sufficient. However, usually less than 5 g of the chrompyrrolide compound per 1 g of carrier is sufficient. Preferably, for the best filling of the carrier and more efficient use of the reagents, approximately 0.001 - 0.01 to 0.5 g of the chrompyrrolide compound or chromium source per 1 g of carrier is recommended. The amount of chrompyrrolide compound or chromium source per 1 g of carrier can be represented by other, but equivalent, concepts, such as, for example, the number of moles of chromium per 1 g of carrier. Usually less than about 8.6 x 10 ^-3 moles of chromium per gram of carrier is sufficient. Preferably, for the reasons stated above, approximately 1.7 • 10 ^-6 - 1.7 • 10 ^-5 to 8.6 • 10 ^-4 moles of chromium are used per gram of carrier.

 The resulting heterogeneous catalyst system can be isolated by filtration to separate the solid catalyst system. To maintain chemical stability and reactivity, the solid catalyst system is preferably stored in a dry inert atmosphere.

 In Heb. EP-A-417477 describes a polymerization catalyst and a cocatalyst system, the cocatalyst comprising chromium compounds Heb. EP-A-416304. In the general case, a catalytic polymerisation system is either a chromium-containing catalyst (also known as a Phillips catalyst) or titanium, zirconium and / or vanadium-containing catalysts.

 Any chromium-containing catalyst system known in the art can be used. Commercially available chromium-containing catalyst systems typically contain chromium, at least a portion of which is in the hexavalent state, supported on an inorganic oxide; if necessary, the polymerization catalyst system may further comprise metal alkyl as a cocatalyst. Examples of chromium-containing catalyst systems are, but are not limited to, the systems disclosed in US Pat. U.S. N 3887494, 3900457, 4053436, 4151122, 4294724, 4392990 and 4405501.

 Any titanium, zirconium and / or vanadium-containing catalyst systems known in the art may also be used. Commercially available titanium, zirconium, and / or vanadium-containing catalyst systems typically contain transition metal halide complexes with organometallic compounds. Examples of magnesium / titanium-containing catalysts include, but are not limited to, the catalysts described in US Pat. U.S. 4394291, 4326988 and 4347158.

 The number of new cocatalyst systems for trimerization and / or oligomerization, including the inventive chromium compounds used as cocatalyst, may be any amount sufficient to generate a comonomer that can be incorporated into the polymer product. Chromium-containing catalyst systems obtained in accordance with various embodiments of the present invention can serve as cocatalysts in combination with titanium, zirconium and / or vanadium-containing catalysts described above.

 According to the method according to the above fourth embodiment of the invention, when mixed with a metal source, a pyrrole-containing compound and a metal alkyl and preferably an unsaturated hydrocarbon, it is not necessary to isolate the first reaction product, as in the methods described in our aforementioned applications. Moreover, the catalyst systems obtained by the method in accordance with the fourth embodiment of the invention have improved performance and selectivity for the desired trimerization product, for example, when producing 1-hexane from ethylene.

 Polymerization reagents.

 The reagents that are used in the polymerization of the catalytic systems and cocatalytic systems in accordance with the present invention are olefinic compounds that can polymerize, that is, interact with the same or with other olefinic compounds. The catalyst systems of this invention can be used to polymerize at least one linear or branched mono-1-olefin containing about 2 to 8 carbon atoms. Examples of such compounds include, but are not limited to, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and mixtures thereof.

 The catalyst systems of the present invention are also useful in oligomerization processes using olefin compounds containing from about 2 to about 30 carbon atoms and having at least one double bond. Examples of such monoolefin compounds are, but are not limited to, acyclic and cyclic olefins, such as, for example, ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 1-hexene, 2- hexene, 3-hexene, 1-heptene, 2-heptene, 3-heptene, four normal octenes, four normal nonenes, and mixtures of any two or more of these compounds. Examples of diolefin compounds include, but are not limited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene. If linear and / or cyclic olefins are used as reagents, although they theoretically do not enter into a chemical reaction, it is believed that steric hindrance may impede the trimerization process. Therefore, the branched and / or cyclic olefin fragment (s) must be removed from the carbon-carbon double bond.

 The trimerization process used in the present invention is defined as the compound of any two, three or more olefins in which the number of double bonds is limited to two. The reagents that can be used in the trimerization process in accordance with the present invention are olefinic compounds that can a) react with themselves, that is, trimerized to form the necessary products, for example, the interaction of ethylene with ethylene can lead to 1-hexene, and the interaction of 1,3-butadiene with itself to 1,5-cyclooctadiene; and / or c) olefinic compounds that can react with other olefinic compounds, i.e., to be trimerized, to give the necessary products, such as, for example, co-equilibration of ethylene and hexene, can lead to 1-decene and / or 1-tetradecene, co-equilibration of ethylene and 1- butadiene gives 1-octene, co-measurement of 1-decene and ethylene can lead to 1-tetradecene and / or 1-docosen, or co-measurement, 1-8-butadiene and 1,5-hexadiene can lead to 1,5-cyclooctadecadiene. For example, the number of olefin bonds in the combination of three ethylene moieties is halved to one olefin bond in 1-hexene. In another example, the number of olefinic bonds when connecting two 1,3-butadiene moieties is halved to two olefinic bonds. Used in the description, the term "trimerization" implies the inclusion in this concept of dimerization of olefins as well as the term "sotrimerization".

 Olefin compounds that can be trimerized contain from about 2 to about 30 carbon atoms and at least one olefinic double bond. Examples of such monoolefin compounds are, but are not limited to, acyclic and cyclic olefins, such as, for example, ethylene, propylene, 1-butene, 2-butene, isobutylene, 1-pentane, 2-pentene, 1-hexene, 2- hexene, 3-hexene, 1-heptene, four normal octenes, four normal nonenes, and mixtures of any two or more of these compounds. Examples of diolefin compounds include, but are not limited to, 1,3-butadiene, 1,4-pentadiene, and 1,5-hexadiene. If branched and / or cyclic olefins are used as reagents, then, although theoretically they do not enter into a chemical reaction, it is believed that steric hindrances could interfere with the trimerization process. Therefore, the branched and / or cyclic olefin fragment (s) should preferably be at a distance from the carbon-carbon double bond.

 The catalyst systems obtained in accordance with the present invention are preferably used as catalyst systems for trimerization.

 Reaction conditions

 The reaction products, that is, trimers and / or polymers, can be obtained on the catalytic systems of the present invention by reactions in solution, reactions in suspension and / or by gas phase reaction methods using conventional equipment and conventional contacting processes. The contacting of the monomers with the catalyst system or with the catalyst system for polymerization and the cocatalyst system of trimerization / oligomerization can be influenced by any method known in the field of homogeneous (liquid) or heterogeneous (solid) catalyst systems. One convenient method is to suspend the catalyst system in an organic medium and mix the mixture in order to keep the catalyst system in suspension throughout the entire process of trimerization, oligomerization and / or polymerization. Other contacting methods may also be used, for example, a fluidized bed, a gravitational layer or a fixed layer. One suitable method for catalyst / cocatalyst systems is to suspend the catalyst system for polymerization in an organic medium and mix the mixture to keep the catalyst system in suspension throughout the entire trimerization and / or polymerization process. Then, the claimed cocatalyst system can be added. The polymerization catalyst system and the inventive co-catalyst system can preferably be simultaneously fed to the polymerization reactor as one or more feed streams of the catalyst and / or cocatalyst system. Other contacting methods, such as a fluidized bed, a gravity bed or a fixed bed, can also be used for all of these catalytic systems.

The reaction temperature and pressure may have any value at which trimerization, oligomerization and / or polymerization of olefin components occurs. Typically, the reaction temperature ranges from about 0 ^° C. to about 250 ^° C. Preferably, the reaction temperature is from about 60 ^° C. to about 200 ^° C., and most preferably from 80 ^° C. to 150 ^° C. The reaction pressure usually lies in the range from atmospheric to approximately 175 atm (2500 psi). Preferably, the pressure is from about atmospheric to about 70 atmospheres (1000 psi) and most preferably from 21 to 49 atmospheres (300 to 700 psi).

 Too low a reaction temperature can lead to the formation of too many unwanted insoluble products, and too high a temperature can cause decomposition of the catalyst system and reaction products. If the reaction pressure is too low, the activity of the catalyst system may decrease. Too high a pressure can result in too many unwanted insoluble products.

 If necessary, hydrogen may be added to the reactor to accelerate the reaction and / or increase the catalytic activity of the system.

The catalyst systems of the present invention are particularly suitable for use in trimerization and / or oligomerization processes. The suspension process is usually carried out in an inert diluent (medium), such as paraffin, cycloparaffins or an aromatic hydrocarbon. Examples of diluents for the reactor include, but are not limited to, isobutane and cyclohexane. Isobutane can reduce the swelling of the polymer product. However, a homogeneous cocatalyst system for trimerization / oligomerization is more soluble in cyclohexane. Therefore, cyclohexane is the preferred diluent for the homogeneous trimerization and oligomerization process, and isobutane is the preferred diluent for the heterogeneous trimerization or oligomerization process. If the reactant is predominantly ethylene, then the reaction temperature is used in the range of from about 0 ^° C. to about 300 ^° C. Preferably, if the preferred reactant is ethylene, the reaction temperature is about 60-150 ^° C.

 In order to obtain a polymer with the desired set of optimal properties, such as, for example, density, melt index, melt index at elevated shear stress and molecular weight, any amount of catalyst system may be present in the polymerization reactor. Typically, up to about 40 wt. hours applied, that is, a heterogeneous cocatalyst system based on each weight part of the catalytic system. To obtain a polymer with the necessary physical and performance characteristics, preferably from about 1 to about 25 parts by weight are present. social system based on 1 wt.h. a catalyst system for polymerization, and most preferably 3 to 15 parts by weight social system for 1 wt.h. catalytic system for polymerization.

 Products The olefin and / or polymer products of this invention are widely used, for example, as monomers in the preparation of homopolymers, copolymers and / or three-link polymers (terpolymers). The polymer products of this invention also find wide application, for example, polyethylene.

 A further understanding of the present invention and its advantages can be obtained from the following examples.

 Examples.

Various abbreviations are used in the description and examples. Below is a list of them:
Triethylaluminium - TEA, Al (C ₂ H ₅ ) ₃
Diethylaluminium chloride - DEAC, Al (C ₂ H ₅ ) ₂ Cl;
Chromium (III) 2-ethylhexanoate - Cr (EG) ₃ , CrEG, CrEG ₃
Hydrogen pyrrolide - pyrrole, Py, PyH, C ₄ H ₅ N
Chromium (III) Acetylacetonate - Cracac, Cracac ₃ , Cr (acac) ₃ , Cr (C ₅ H ₇ O ₂ ) ₃
Chromium (III) pyrrolide - CrPy ₂ , [Na (C ₄ H ₁₀ O ₂ ) ₂ ] [Cr (C ₄ H ₄ N) ₃ Cl (C ₄ H ₁₀ O ₂ )] [Na (DME) ₂ ], [ Cr (C ₄ H ₄ N) ₃ Cl (DME)], [Na (DME) ₂ ] [Cr (Py) ₃ Cl (DME)], product V, compound V.

Tris-tetrahydrofuran-chromium (III) chloride - CrCl ₃ THF ₃ , CrCl ₃ (THF) ₃ .

2,5-Dimethylpyrrole - 2,5-dimethylpyrrolide of hydrogen, C ₆ H ₉ N, 2,5-DMP.

Butene C ₄ =
1-Hexene - 1-C ₆ =
Hexene - C ₆ =
Octen - C ₈ =
Decen - C ₁₀ =
Dodecene - C ₁₂ =
Tetradecene -C ₁₄ =
Example 1

Cycle 1001. In a 25 ml thick-walled tube, 0.14 g (0.29 mmol) of chromium (III) 2-ethylhexanoate (CrEG ₃ ), [Cr (C ₈ H ₁₅ O ₂ ) ₃ ] was weighed. The tube was closed with a self-locking round lid. Using a syringe, 0.062 ml (0.89 mmol) of pyrrole (PyH), [C ₄ H ₅ N] and cyclohexane, which is used as a diluent, were added, and a solution with a total volume of approximately 8 ml was obtained.

Then, to form a catalytic system, in a 1 L autoclave containing 300 ml of cyclohexane, 0.9 ml of a 1.1 M solution (0.99 mmol) of triethylaluminum (TEA) in heptane and an aliquot of 0.9 ml of a CrEG ₃ / Py solution were added to a countercurrent of ethylene (chemically pure). The reactor was closed and ethylene flow was stopped until the temperature in the reactor rose to 80 ^° C. The ethylene pressure was raised to a total reaction pressure of 38.5 atm (550 psi). Then, ethylene was supplied as needed for 30 minutes, which amounted to the cycle time. At the end of the cycle, a sample of the resulting liquid reaction mixture was analyzed using capillary gas chromatography. The remaining liquid reaction mixture was evaporated and the amount of solid product was determined.

 The results are presented below in table 1.

Cycle 1002. The procedure of cycle 1001 was followed, except that for the formation of a solution with a total volume of 10 ml, 8 ml of a 1.1 M solution (8.8 mmol) of TEE in neptane was added directly to the CrEG ₃ / PyH solution, and not to the reactor. An aliquot of a 0.7 ml CrEG ₃ / PyH / TEA solution was added to the autoclave. Additionally, TEA was not introduced into the reactor.

 The results are presented below in table 1.

Cycle 1003. The procedure of cycle 1002 was followed except that instead of CrEG ₃ , 0.10 g (0.29 mmol) of chromium (III) acetylacetonan (Cracac ₃ ), [Cr (C ₅ H ₇ O ₂ ) ₃ ] and 6 ml of 1.1 M solution were used (6.6 mmol) TEA in heptane to prepare a solution of Crocac ₃ / PyH / TEA (total volume 8 ml). 1.4 ml of Cracac ₃ / PyH / TEA solution was added to the autoclave.

 The results are presented below in table 1.

Cycle 1004. The procedure described in cycle 1001 was followed except that 0.9 ml of a 1 M solution (0.9 mmol) of diethylaluminium chloride (DEAC), [AlCl (C ₂ H ₅ ) ₂ ] in hexane was added to a solution of CrEG ₃ / PyH and obtained CrEG ₃ / PyH / DEAC solution. 0.65 ml of a solution of CrEG ₃ / PyH / DEAC and 0.9 ml of a 1.1 M solution (0.99 mmol) of TEA in heptane were added to the autoclave.

 The results are presented below in table 1.

Cycle 1005. The procedure of cycle 1001 was followed except that 0.9 ml of a 1 M solution (0.9 mmol) of DEAC in hexane was added to a solution of CrEG ₃ / PyH and the resulting solution of CrEG ₃ / PyH / DEAC was kept for 1 day in a dry nitrogen atmosphere at room temperature and atmospheric pressure. Then 0.65 ml of an aged CrEG ₃ / PyH / DEAC solution and 0.9 ml of a 1.1 M solution (0.99 mmol) of TEA in heptane were added to an autoclave.

 The results are presented below in table 1.

Cycle 1006. The procedure for Cycle 1001 was followed except that the solution was prepared using 0.13 ml of pyrrole. Additionally, along with TEA, 1.0 ml of a 0.1 M solution (0.1 mmol) of DEAC in hexane was added to the reactor. Used 0.9 ml of a solution of CrEG ₃ / PyH.

 The results are presented below in table 1.

Cycle 1007. The procedure of cycle 1003 was followed except that 3 ml of a 0.9 M solution (5.7 mmol) of TEA in toluene was used and toluene was also used instead of hexane as a diluent in the preparation of CrEG ₃ / PyH / TEA solution. In the reactor, therefore, there was an excess of toluene. Used 0.9 ml of a solution of CrEG ₃ / PyH / TEA.

 The results are presented below in table 1.

Cycle 1008. The procedure of cycle 1002 was followed except that instead of CrEG ₃ , 0.10 g of chromium (III) pyrrolide, (CrPy ₃ ), [Cr (C ₄ H ₄ N) ₃ ClNa (C ₄ H ₁₀ O ₂ ) ₃ ] were used (0.17 mmol) and the solution was prepared using 0.04 μl (0.52 mmol) PyH and 3.5 ml of a 1.1 M solution (3.85 mmol) of TEA in heptane. The final solution volume was approximately 5 ml. Used 1.0 ml of a solution of CrPy ₃ / PyH / TEA.

 The results are presented below in table 1.

Cycle 1009. The procedure of cycle 1008 was followed except that 1.8 ml of a 1.9 M solution (3.42 mmol) of TEA in toluene was used and toluene was used instead of cyclohexane to prepare a CrPy ₃ / PyH / TEA solution. Therefore, there was an excess of toluene in the reactor. Used 1.4 ml of a solution of CrPy ₃ / PyH / TEA.

 The results are presented below in table 1.

Cycle 1010. The procedure of Cycle 1008 was followed except that pure PyH was not added in the preparation of the CrPy ₃ / TEA solution. A 1.4 ml solution of CrPy ₃ / TEA in cyclohexane was used.

 The results are presented below in table 1.

Cycle 1011. The procedure of cycle 1009 was followed except that pure PyH was not added in the preparation of the CrPy ₃ / TEA solution. Used 1.4 ml of a solution of CrPy ₃ / TEA in toluene. Therefore, an excess of toluene was present in the reactor.

 The results are presented below in table 1.

 Example II

 It should be noted that the results presented in table XXIII from example X and the results in table XXIV from example XI cannot be compared directly, since the reactions were carried out in different reactors under different conditions, using different ethylene and cyclohexane as well as various diluents as raw materials . However, direct comparisons within each example can be made.

Cycle 2001. 0.30 g (0.62 mmol) of chromium (III) 2-ethylhexanoate (CrEG ₃ ) (10.15 wt% Cr) was mixed with 0.12 ml (1.73 mmol) of pure pyrrole (PyH) in 10 ml of toluene. 2.8 ml of a 1.9 M solution (5.32 mmol) of triethylaluminum (TEA) in toluene was added and the CrEG ₃ / PyH / TEA solution was stirred for 30 min in a dry nitrogen atmosphere at room temperature and atmospheric pressure. A dark brown CrEG ₃ / PyH / TEA solution was filtered and excess toluene was removed by vacuum stripping. Received 1.0 ml of dark brown oil, which was used as a catalytic system. At a temperature of 80 ^° C, 0.5 ml (0.15 g CrEG ₃ ; 15.2 mg Cr) of the catalytic system and 4.0 ml of nonane (internal reactor standard) were added to a 2 L autoclave containing 1.2 L of cyclohexane at 80 ^° C. The pressure in the reactor was raised to 38.5 atm (550 psi) using ethylene. A cycle time of 30 minutes, with ethylene being supplied as needed.

 The results are presented in table.2.

Cycle 2002. The procedure of Cycle 2001 was followed except that diethylaluminium chloride was added in addition to the CrEG ₃ / PyH / TEA solution.

0.53 g (1.10 mmol) of CrEG ₃ (10.15 wt% Cr) was mixed with 0.52 ml (7.5 mmol) of pure PyH in 15 ml of toluene and stirred for 5 min. 9.0 ml of a 1.9 M solution (17.1 mmol) of TEA in toluene was added, and a CrEg ₃ / PyH / TEA solution was stirred overnight in a dry nitrogen atmosphere at room temperature and atmospheric pressure. From the resulting dark brown solution, excess toluene was removed by vacuum desorption to give 2.5 ml of dark brown oil. 0.5 ml (10.8 mg, 0.2 mmol Cr) of dark brown oil was mixed with 1.0 ml of a 0.87 M solution (0.87 mmol) of diethylaluminium chloride (DEAC) in nonane and the solution of CrEG / PyH / TEA / DEAC was stirred overnight in a dry nitrogen atmosphere at room temperature. temperature and atmospheric pressure. The resulting product was used as a catalytic system.

Directly into a 2 L reactor containing 1.2 L of cyclohexane, at 80 ^° C, 1.3 ml (9.4 mg, 0.18 mmol of Cr) of the catalyst system and 4.0 ml of nonane (internal standard of the reactor) were loaded with ethylene countercurrent. The pressure in the reactor with ethylene was raised to 38.5 atm (550 psi), the reaction cycle time was 30 minutes, and ethylene was supplied as needed.

 The results are presented below in table.2.

Cycle 2003. 0.33 g (0.68 mmol) of CrEG ₃ (10.15 wt% Cr) were mixed with 13 ml (1.87 mmol) of pure PyH in 10 ml of toluene and stirred for 5 min. 1.9 ml of a 1 M solution (1.9 mmol) of DEAH in hexane and a solution of CrEG ₃ / PyH / DEHA were added, stirred for 30 min in a dry nitrogen atmosphere at room temperature and atmospheric pressure. A light yellow-green solution was obtained. 5.1 ml of a 1.9 M solution (9.7 mmol) of diethylaluminium chloride (DEAC) in toluene was added and the CrEG ₃ / PyH / DEAC / TEA solution was stirred for 0.5 h, and a dark tan solution was obtained. Excess toluene and hexane was removed from the dark tan CrEG ₃ / PyH / DEAC / TEA solution by vacuum desorption to obtain a dark tan oil. A dark tan oil was dissolved in cyclohexane and the total volume was adjusted to 25 ml, used as a catalytic system (1.32 mg Cr / ml). 7.0 ml (9.2 mg Cr, 0.178 mmol Cr) of the catalytic system and 4.0 ml of nonane (internal standard of the reactor) were loaded into a 2 L reactor containing 1.2 L of cyclohexane at 80 ^° C under a counterflow of ethylene. Then the pressure in the reactor was raised to 38.5 atm (550 psi) using ethylene. The reaction time is 30 minutes, with ethylene being fed during this period if necessary.

 The results are shown below in table 2.

Cycle 2004. The procedure described in Cycle 2002 was followed, except that the CrEG ₃ / PyH / TEA / DEAC solution was diluted with cyclohexane prior to loading into the reactor, and hydrogen (H ₂ ) (0.35 atm = 50 lb) was added to the reactor. square inch / before the pressure in the reactor was raised to the required using ethylene.

0.30 g (0.62 mmol) of CrEG ₃ (10.15% C) was mixed with 0.12 ml (1.73 mmol) of pure PyH in 10 ml of toluene. 1.7 ml of a 1 M solution of DEAC (1.7 mmol) in hexane was added, and a solution of CrEG ₃ / PyH / DEAC was stirred for 5 min in an atmosphere of dry nitrogen and at room temperature and atmospheric pressure. 1.8 ml of a 1.9 M solution (3.42 mmol) of TEA in toluene was added, and a solution of CrEG ₃ / PyH / DEAC / TEA was stirred for 30 min in a dry nitrogen atmosphere at room temperature and atmospheric pressure. The resulting dark brown solution was filtered and the excess of toluene and hexane was removed by vacuum stripping to obtain 0.8 ml of a dark yellow-brown oil, which was used as a catalytic mixture. 0.4 ml (15.2 mg Cr, 0.29 mmol Cr) of the catalytic system and 4.0 ml of nonane (internal standard of the reactor) were loaded into a 2 L reactor containing 1.2 L of cyclohexane at 80 ^° C under a counterflow of ethylene. Hydrogen (H ₂ ) was supplied to the reactor at a pressure of 3.5 atm (50 psi), and then, using ethylene, the pressure was raised to 38.5 atm (550 psi). The reaction time is 30 minutes, during which ethylene was supplied, if necessary.

 The results are shown below in table 2.

Cycle 2005. In a 500 ml Schlenk flask, 1.98 g (3.4 mmol) of CrPy ₃ (11.1 wt% Cr) was mixed with 40 ml of toluene and 54 ml of a 1.9 M solution (102.6 mmol) of TEA in toluene. The resulting dark brown reaction mixture was stirred for 1 h in an atmosphere of dry nitrogen at room temperature and atmospheric pressure. Excess toluene was removed by vacuum stripping to obtain 13 ml of a dark tan oil and a small amount of precipitate. Dark yellow-brown oil was separated, collecting from the sediment using a syringe, and used as a catalytic system. 2.0 ml of the catalytic system was diluted with 27 ml of cyclohexane and kept for 3 days in dry nitrogen atmosphere at room temperature and atmospheric pressure before use.

3.0 ml (9.3 mg, 0.18 mmol Cr) of the catalytic system in the form of a solution in cyclohexane and 4.0 ml of nonane (internal reactor standard) were loaded directly into a 2 L autoclave containing 1.2 L of cyclohexane at 80 ^° C with ethylene countercurrent. The pressure in the reactor was then raised with ethylene to 38.5 atm (550 psi). The reaction time was 30 minutes, and ethylene was supplied as needed.

The results are shown below in table 2
Cycle 2006. The 2005 Cycle was followed except that less reagents and shorter aging times were used.

0.25 g (0.432 mmol) CrPy ₃ (11.1 wt% Cr) with 10 ml of toluene and 3.4 ml of a 1.9 M solution (6.46 mmol) of TEA in toluene were mixed in a 500 ml Schlenk flask. The resulting dark brown reaction mixture was stirred for 30 minutes in an atmosphere of dry nitrogen at room temperature and atmospheric pressure. Excess toluene was removed by vacuum stripping to give a dark brown oil. All dark brown oil was diluted with cyclohexane to a total volume of 25 ml to obtain a solution containing 1.11 mg Cr / ml, which was used as a catalytic system.

8.0 ml (8.88 mg, 0.171 mmol of Cr) of the catalytic system in the form of a solution in cyclohexane and 4.0 ml of nonane (internal reactor standard) were charged directly into a 2 L autoclave containing 1.2 L of cyclohexane at 80 ^° C with ethylene countercurrent. Then, the pressure in the reactor was raised with ethylene to 38.5 atm (550 psi), the reaction time was 30 minutes, and if necessary, ethylene was supplied.

 The results are shown below in table 2.

 Cycle 2007. The procedure for the 2005 cycle was followed except that there was an excess of toluene in the trimerization reactor.

In a 500 ml Schlenk flask, 1.98 g (3.4 mmol) of CrPy ₃ (11.1 wt% Cr) was mixed with 40 ml of toluene and 54 ml of a 1.9 M solution (102 mmol) of TEA in toluene. The resulting dark brown reaction mixture was stirred for 1 h in an atmosphere of dry nitrogen at room temperature and atmospheric pressure. Excess toluene was removed by vacuum stripping to obtain 13 ml of a dark tan oil and a small amount of a slightly colored precipitate. Dark tan oil was isolated by collecting it from the precipitate using a syringe and used as a catalytic system. 2.0 ml of the catalytic system was diluted with 27 ml of cyclohexane and kept for 3 days in dry nitrogen atmosphere at room temperature and atmospheric pressure before use.

Directly into a 2 L autoclave containing 1.2 L of cyclohexane, at a temperature of 80 ^° C, countercurrent ethylene was charged with 0.5 ml (8.5 mg, 0.163 mmol Cr) of the catalytic system as a solution in cyclohexane, 4.5 ml of toluene and 4.0 ml of nonane (internal reactor standard) . The pressure in the reactor was raised to 38.5 atm (550 psi) using ethylene, the reaction time was 30 minutes, and if necessary, ethylene was supplied.

 The results are shown below in table 2.

 2008 cycle.

0.28 g (0.802 mmol) of Cracac _{3 was} mixed with 0.17 ml (2.45 mmol) of pure pyrrole in 10 ml of toluene and stirred in a dry nitrogen atmosphere at room temperature and atmospheric pressure for 5 min. Then, 6.3 ml of a 1.9 M solution (12.0 mmol) of TEA in toluene was added. The resulting dark brown reaction mixture was stirred for 30 min in an atmosphere of dry nitrogen at room temperature and atmospheric pressure. Excess toluene was removed by vacuum stripping to give a dark tan oil. All the dark tan oil was diluted with cyclohexane to a volume of 25 ml, and a solution containing 0.0112 g of Cracac ₃ / ml was obtained, which was used as a catalytic system.

In a 2 L autoclave containing 1.2 L of cyclohexane, at 80 ^° C, countercurrent ethylene was charged with 7.0 ml (15.2 mg, 0.293 mmol of Cr) of the catalytic system as a solution in cyclohexane and 4.0 ml of nonane (internal reactor standard). The pressure in the reactor was raised to 38.5 atm (550 psi), the reaction time was 30 minutes, and if necessary, ethylene was supplied.

 The results are shown below in table 2.

 Cycle 2009. The methodology of the 2008 cycle was followed, except that chromium (III) naphthenate was used as a chromium source.

0.33 g (0.508 mmol) of CrNf ₃ (8.0 wt% Cr) were mixed with 0.12 ml (1.73 mmol) of pure pyrrole in 10 ml of toluene and stirred in a dry nitrogen atmosphere at room temperature and atmospheric pressure for 5 min. Then, 4.6 ml of a 1.9 M solution (8.74 mmol) of TEA in toluene was added. The resulting dark brown reaction mixture was stirred for 30 min in an atmosphere of dry nitrogen at room temperature and atmospheric pressure. Excess toluene was removed by vacuum stripping to obtain a dark tan oil. All the dark tan oil was diluted with cyclohexane to a volume of 25 ml, and a solution containing 1.056 mg Cr / ml was obtained, which was used as a catalytic system.

In a 2 L autoclave containing 1.2 L of cyclohexane, at 80 ^° C, countercurrent ethylene was charged with 7.0 ml of 7.39 ml, 0.142 mmol of Cr) catalyst system in the form of a solution in cyclohexane and 4.0 ml of nonane (internal standard of the reactor). the pressure in the reactor with ethylene was raised to 38.5 atm (550 psi), the reaction time was 30 minutes, and if necessary, ethylene was supplied.

 The results are shown below in table 2.

 Cycle 2010. The procedure for the 2008 cycle was followed, except that chromium (III) chloride was used as the source of chromium.

0.41 g (1.09 mmol) of CrCl ₃ THF _{3 was} mixed with 0.23 ml (3.32 mmol) of pure pyrrole in 10 ml of toluene and stirred in a nitrogen atmosphere at room temperature and atmospheric pressure for 5 min. Then, 8.8 ml of a 1.9 M solution (16.3 mmol) of TEA in toluene was added. The resulting dark brown reaction mixture was stirred under dry nitrogen at room temperature and atmospheric pressure for 30 minutes. Excess toluene was removed by vacuum stripping to obtain a dark tan oil. 7.5 ml of nonane was added to the dark tan oil and the resulting solution was diluted with cyclohexane to a total volume of 25 ml, a solution was obtained containing 0.0164 g of CrCl ₃ THF ₃ / ml. The solution was filtered and the filtrate was used as a catalytic system.

5.0 ml (11.38 mg, 0.219 mmol of Cr) of the catalytic system in the form of a solution in cyclohexane and nonane and 2.5 ml of nonane (internal standard of the reactor) were charged directly into a 2 L autoclave containing 1.2 L of cyclohexane at 80 ^° C with ethylene countercurrent. The pressure in the reactor was increased to 38.5 atm (550 psi), the reaction time was 30 minutes, and ethylene was supplied as needed.

 The results are shown below in table 2.

 Cycle 2011. The procedure of the 2005 cycle was followed except that excess hexane was charged to the trimerization reactor.

In a 500 ml Schlenk flask, 1.98 g (3.4 mmol) of CrPy ₃ (11.1 wt% Cr) was mixed with 40 ml of toluene and 54 ml of a 1.9 M solution (102.6 mmol) of TEA in toluene. The resulting dark brown reaction mixture was stirred for 1 h in an atmosphere of dry nitrogen at room temperature and atmospheric pressure. Excess toluene was removed by vacuum stripping to obtain 13 ml of a dark tan oil and a small amount of a slightly colored precipitate. Dark yellow-brown oil was separated, collecting it from the precipitate using a syringe, and used as a catalytic system. 2 ml of the catalytic system was diluted with 27 ml of cyclohexane and kept for 3 days in dry nitrogen atmosphere at room temperature and atmospheric pressure before use.

In autoclave 2 liters, containing 1.2 liters of cyclohexane at 80 ^o C at an ethylene countercurrent charged with 1.0 mL (16.9 mg, 0.325 mmole Cr) of the catalyst system as a solution in cyclohexane, 55 ml of 1-hexene and 4.0 ml of nonane (internal reactor standard ) The pressure in the reactor was raised to 38.5 atm (550 psi) using ethylene, the reaction time was 30 minutes, and if necessary, ethylene was supplied.

 The results are shown below in table 2.

 Cycle 2012. The procedure of the 2005 cycle was followed except that chromium (II) pyrrolide (compound I) was used as a chromium source.

0.30 g (approximately 0.85 mmol) of compound I (CrPy ₁₀ THF ₄ ) were mixed with 10 ml of toluene and 6.7 ml of a 1.9 M solution (12.7 mmol) of TEA in toluene. The resulting dark brown reaction mixture was stirred for 30 min in an atmosphere of dry nitrogen at room temperature and atmospheric pressure. Excess toluene was removed by vacuum desorption to obtain a dark tan oil and a small amount of a slightly colored precipitate. The dark tan oil was filtered and the filtrate was diluted to a total volume of 25 ml with cyclohexane to give a solution containing 0.012 g of compound I (CrPy ₁₀ THF ₄ ), which was used as a catalytic system.

In a 2 L autoclave containing 1.2 L of cyclohexane, at 80 ^° C. under countercurrent flow of ethylene, 7.0 ml of the catalytic system was loaded as a solution in cyclohexane and 4.0 ml of nonane (internal standard of the reactor). The pressure in the reactor was raised to 38.5 atm (550 psi) using ethylene, the reaction time was 30 minutes, and if necessary, ethylene was supplied.

 The results are presented below in table.2.

 Example III

Cycle 3001. 0.21 g (0.601 mmol) of Cracac _{3 were} mixed with 0.12 ml (1.73 mmol) of pure pyrrole and 15 ml of toluene. The resulting solution was stirred in an atmosphere of dry nitrogen at room temperature and atmospheric pressure for 5 minutes. Then 6 ml of a 1.9 M solution (11.4 mmol) of TEA in toluene was added. The resulting dark brown reaction mixture was stirred for 5 min in an atmosphere of dry nitrogen at room temperature and atmospheric pressure. Then added 2 g of aluminophosphate carrier (molar ratio P / Al 0.4, activated at 700 ^o C), prepared in accordance with US Pat. USA 4364855 (1982), which was already mentioned, and the resulting suspension was stirred for 12 hours. The product was filtered off, washed at least twice with 10 ml aliquots of toluene and pentane until the filtrate ceased to stain, and the precipitate was dried in vacuum. The dried product was used as a solid supported catalyst system.

In a 2 liter autoclave containing 1 liter of isobutane, 2.1022 g of a solid catalyst system was added in a countercurrent flow of ethylene. Before loading the catalyst, 0.25 ml (16.5 wt%) of a TEA in nonane solution was added to the reactor in order to neutralize any poisons in the ethylene feed. The reactor was closed and ethylene supply was stopped until the reactor temperature reached the required value, for example, 90 ^° C. The ethylene pressure was then increased to 38.5 atm (550 psi) and ethylene was supplied over 30 minutes . At the end of the reaction, a sample of the liquid reaction mixture was taken and analyzed by gas chromatography. The remaining reaction mixture was evaporated and the amount of solid product was determined.

 The results are presented below in table.3.

Cycle 3002. The procedure for Cycle 3001 was followed except that diethylaluminium chloride was added to the Cracac ₃ / PyH solution along with TEA before the aluminophosphate inorganic oxide was added.

In a 30 ml tube with screw cap, 0.21 g of Cracac ₃ (0.6 mmol) was weighed. 0.12 ml of PyH (1.73 mmol) and 15 ml of toluene were added, the resulting solution was closed and stirred for 5 min. Then stirring was continued, 6 ml of a 1.9 M solution (11.4 mmol) of TEA in toluene was added. Then, the Cracac ₃ / PyH / TEA solution was stirred for 5 min, 2.4 ml of a 1M solution (2.4 mmol) of DEAC in hexane was added, and the Cracac ₃ / PyH / TEA / DEAC solution was mixed for 5 min. Added 2 g of aluminophosphate media (molar ratio P / Al 0.4, activated at 700 ^o C), prepared according to the method of Pat. USA 4364855 (1982), and the resulting suspension was stirred for approximately 12 hours. The product was filtered and washed at least twice with 10 ml aliquots of toluene and pentane until the resulting filtrate ceased to stain. The precipitate was dried in vacuo. The dried product was used as a solid supported catalyst system.

0.5048 g of a solid catalyst system was added to a 2 L autoclave containing 1 L of isobutane, with countercurrent ethylene. Before loading the catalyst, 3.0 ml of a 1.6% solution of TEA in nonane was added in order to neutralize the poisons in the ethylene feed. The reactor was closed and ethylene supply was stopped until the temperature in the reactor reached the required temperature, for example, 90 ^° C. The ethylene pressure in the reactor was raised to 38.5 atm (550 psi), the reaction time was 30 minutes, while according to need served ethylene. At the end of the reaction, a small sample of the liquid reaction mixture was taken and analyzed by gas chromatography. The resulting reaction mixture was evaporated and the amount of solid product was determined. Ethylene flow rate was determined using a calibrated flow meter.

 The results are presented below in table.3.

Cycle 3003. The methodology of cycle 3002 was followed except that CrEG _{3 was} used as the chromium source, and the aromatic solvent was not used in the preparation of the catalytic system. In addition, a supported catalyst system was prepared in an in situ reactor.

A solution of CrEG ₃ / PyH was prepared by mixing 0.33 g (0.69 mmol) of CrEG ₃ with 0.26 ml (3.75 mmol) of PyH in 16 ml of pentane and kept before use for 4 days in a dry nitrogen atmosphere at room temperature and atmospheric pressure. 0.40 g of an aluminophosphate support (molar ratio P / Al 0.9, activated at 700 ^° C) was prepared in a 2 L autoclave at room temperature and countercurrent of ethylene, which was prepared in accordance with Pat. USA 4364855 (1982) and 2.0 ml of a 1M solution (2.0 mmol) of TEA in hexane. Then, 1 L of cyclohexane, 2.1 ml (4.32 mg, 0.083 mmol of Cr) of a CrEG ₃ / PyH solution and hydrogen (H ₂ ) under a pressure of 3.5 atm (50 psi) were loaded into the reactor.

 The results are shown below in table 3.

 Example IV

Cycle 4001. In a 100 ml thick-walled tube, 3.5 g (10 mmol of Cracac ₃ ) were weighed. A mixing bar was placed in the tube and closed with a self-locking lid. 40 ml of toluene and 2.1 ml (30 mmol) of PyH were added by syringe. Then 12 ml of a 2.5 M solution (30.0 mmol) of n-butyllithium in hexane were slowly added. The resulting precipitate was isolated, washed with toluene (2 x 10 ml) and cyclohexane (2 x 10 ml) to an unpainted wash filtrate. A total of 5.59 g of solid product was obtained. Under the conditions described in cycle 1001, 0.5 ml of a 1.1 M solution (0.55 mmol) of TEA in heptane and a suspension of 38 mg of a solid product in cyclohexane were used.

 The results are presented below in table 4.

Cycle 4002. The procedure for Cycle 4001 was followed, except that a solid catalyst was prepared (88 g total) in a 25 ml thick-walled tube using 0.349 g (1 mmol) Cracac ₃ , to ml toluene, 0.14 ml (2 mmol) PyH and 0.8 ml of a 2.5 M solution (2.0 mmol) of n-butyllithium in hexane.

 Under the conditions described in cycle 1001, 0.5 ml of a 1.1 M solution (0.55 mmol) of TEA and a suspension of 16 g of a solid product in cyclohexane were used.

 The results are presented below in table 4.

Cycle 4003. In a thick-walled tube, 1.0 g of an aluminophosphate support was weighed per 25 ml (molar ratio P / Al 0.4, activated at 700 ^o C), obtained by the method of Pat. USA 4364855 (1982), and 93 mg of the solid product described in cycle 4001. The tube was closed, 5 ml of toluene and 3 ml of a 1.9 M solution (5.7 mmol) of TEA in toluene were added with a syringe. The resulting suspension was kept for a day. The solid product was isolated, washed with toluene and cyclohexane in 10 ml portions until the wash solution ceased to stain.

 Under conditions of cycle 1001, 0.5 ml of a 1.1 M solution (0.55 mmol) of a solution of TEA in heptane and a suspension of 80 mg of a solid product in cyclohexane were used.

 The results are presented below in table 4.

Cycle 4004. In a thick-walled tube, 0.7 g of an aluminophosphate support (molar ratio P / Al 0.4, activated at 700 ^° C) obtained by the method of US Pat. No. 4,364,855 (1982) and 53 mg of the solid product described in cycle 4002 were weighed into a 25 ml tube. The tube was closed, 3.5 ml of toluene and 2 ml of a 1.9 M solution (3.8 mmol) of TEA in toluene were added with a syringe. The resulting suspension was kept for a day. The solid product was isolated, washed with toluene and cyclohexane in 10 ml portions until the wash solution ceased to stain.

 Under conditions of cycle 1001, 0.5 ml of a 1.1 M solution (0.55 mmol) of TEA in heptane and a suspension of 78 mg of a solid product in cyclohexane were used.

 The results are presented in table 4.

 Example V.

Cycle 5001. In a thick-walled tube, 0.17 g of chromium (III) 2,2,6,6-tetramethyl-3,5-heptadionate (Cr (III) TMHD) (0.28 mmol) was weighed into 25 ml. The tube was closed with a self-locking round lid. Syringe was added 0.06 ml of pyrrole (0.89 mmol) and 0.17 mmol (0.87 mmol) of pure diisobutylaluminium chloride (DuBAlCl), a Cr (III) TMHD / DuBAlCl / Py solution was obtained, which was diluted with cyclohexane to a total volume of 8 ml. 0.25 ml of a 1.1 M solution (0.28 mmol) of TEA in heptane and 0.75 ml of a solution of Cr (III) NVUL / DuBAlCl / Py were added to a glass vessel containing 100 ml of cyclohexane and 10 g of butadiene. A glass vessel was placed in a thermostatic bath at a temperature of 70 ^° C. at atmospheric pressure and stirred for 16 hours. After 16 hours, a small sample of the liquid reaction mixture was taken and analyzed by gas chromatography. The remaining liquid reaction mixture was evaporated and the amount of solid product was determined. The results are presented below in table 5.

 Cycle 5002. The procedure for Cycle 5001 was followed except that there was no excess aluminum alkyl compound in the reactor and the catalyst was prepared using the procedure described in Cycle 3001 as follows.

0.21 g (0.601 mmol) of Cracac _{3 were} mixed with 0.12 ml (1.73 mmol) of pure pyrrole and 15 ml of toluene. The resulting solution was stirred in an atmosphere of dry nitrogen at room temperature and atmospheric pressure for 5 minutes. Then 6.0 ml of a 1.9 M solution (11.4 mmol) of TEA in toluene was added. The resulting dark brown reaction mixture was stirred for 5 min in an atmosphere of dry nitrogen at room temperature and atmospheric pressure. Then added 2 g of aluminophosphate support (molar ratio P / Al 0.4, activated at 700 ^o C), obtained by the method of Pat. US 4364855 (1982), and the resulting suspension was stirred for approximately 12 hours. The product was filtered off, washed at least twice with 10 ml portions of toluene and pentane until the wash solution ceased to stain, and dried in vacuo. The dried product was used as a supported catalyst system.

 A 0.28 g catalyst loading was used in the butadiene reaction.

 Example VI

 In the following cycles, all catalytic systems were prepared in a box, in an atmosphere of dry nitrogen, at room temperature and atmospheric pressure. The transition metal compounds were weighed and mixed with three equivalents (0.062 ml) of pyrrole, 2 ml of cyclohexane as a solvent, and 6 ml of a 1.1 M solution of triethylaluminum (TEA) in heptane. The resulting product was shaken for 5 minutes to 16 hours

All cycles were carried out in a 1 L autoclave containing 300 ml of cyclohexane. Dilute 1 ml of liquid catalyst systems with cyclohexane and add countercurrent ethylene (chemically pure) to the reactor. The reactor was shut down and ethylene supply was stopped until the temperature in the reactor rose to a reaction temperature of 80 ^° C. Then, the ethylene pressure in the reactor was raised to 550 psi. Ethylene was supplied as needed for 30 minutes. If necessary, the reactor was heated so that the temperature remained unchanged, that is, 80 ^o C.

At the end of the cycle, a sample of the liquid reaction mixture was taken and analyzed using capillary gas chromatography on an HP-5880 gas chromatograph equipped with a flame ionization detector and a DV-1 column (60 m, internal diameter 0.25 mm, film thickness 0.25 μm). The gas chromatograph was gradually heated from 40 to 272 ^o C at a heating rate of 10 ^o / min for 20 minutes Cyclohexane was used as an internal standard. The remaining reaction mixture was evaporated and the amount of solid product was determined.

 The results are presented below in table.6.

The data in the table. show that compounds of other metals can be used in the trimerization, oligomerization and / or polymerization of 1-olefins. Of these metal compounds IINiacac ₂ , cycle 6001 showed the best trimerization activity and selectivity.

 Example VII

 In the following example, cycles 7001 to 7005 illustrate the effects of hydrolysis of metal alkyls prior to use, as well as the effects of the presence or absence of a pyrrole-containing compound. Cycles 7006-7009 in comparison with cycles 7010-7013, show the effect of using unsaturated hydrocarbon in the preparation of the catalytic system.

 Cycles 7001-7005.

In cycles 7001 to 7005, the molar ratio of elemental chromium to elemental aluminum and to the ligand (Cr: Al: L) of the catalyst components added to the reactor is 1:30:10. In cycles 7001 - 7003, Cr (EG) _{3 was} used as the chromium compound, and in cycles 7004 and 7005, Cr (Py) ₃ . As an aluminum compound, triisobutylaluminum (Al (iso-Bu) ₃ ) was used, which was subjected to the following treatment. To a approximately 10% (wt.) Solution of triisobutylaluminum in hexane was added 1.0 molar equivalent of distilled water, slowly but in one portion, while cooling the flask containing the solution with ice-water so that the temperature was in the range from about 10 ^o C to about 20 ^o C. The solution was vigorously stirred before and after adding water until gas evolution ceased. Dimethoxyethane (DME) was used as a ligand.

Cycles 7001 - 7005 were carried out in a 2 L autoclave. The chromium compound was dissolved in 400-500 ml of anhydrous n-heptane and added to the reactor in an atmosphere of dry nitrogen. Then, the required volume of a stirred, treated as described above, 0.31 C solution of Al (iso-Bu) ₃ in heptane was added. Then, the required volume of DME was added along with 5 ml of nonane (internal standard of the reactor). The reactor was closed and the temperature was raised to 80 ^o C in a cycle of 7001 and to 95 ^o C in cycles of 7002 - 7005. The ethylene pressure was raised to 38.5 atm (550 psi). If necessary, ethylene was fed into the reactor during the whole cycle - 25 min in the cycle 7001, 30 min in the cycle 7002 and 45 min in the cycles 7003 - 7005.

At the end of each cycle, a sample of the liquid reaction mixture was taken and analyzed using capillary gas chromatography on an HP-5880 gas chromatograph equipped with a flame-conization detector and a DV-1 column (60 m, internal diameter 0.25 mm, film thickness 0.25 μm). The gas chromatograph was gradually heated from 40 to 272 ^o C at a heating rate of 10 ^o / min for 20 minutes Cyclohexane was used as an internal standard. The remaining reaction mass was evaporated and the amount of solid product was determined.

 The catalyst systems used in cycles 7006 - 7013 were prepared in accordance with the following procedures. Catalytic systems in cycles 7006–7009 were prepared in the presence of toluene, an unsaturated aromatic hydrocarbon. Catalytic systems in cycles 7010 - 7013 were prepared in the presence of 1-hexene, an unsaturated aliphatic hydrocarbon.

Cycle 7006. 3.72 g / Na (DME ₂ / / CrCl (Py) _{3 was} mixed with 50 ml of toluene. 26.4 ml of pure (93%) TEA was slowly added and stirred for 30 minutes, a dark brown suspension was obtained. The excess solvent was removed. under vacuum, a dark tan oil and solid were obtained, approximately 70 ml of cyclohexane was added, the resulting product was filtered, the filtrate was diluted with 200 ml of cyclohexane and 8 ml of the solution was charged into the reactor. The product contained 1.67 mg Cr / ml.

Cycle 7007. 0.35 g of chromium (III) ethylhexanoate (CrEG ₃ ) was mixed with approximately 15 ml of toluene, and an intensely colored green solution was obtained. 0.22 ml of 2,5-dimethylpyrrole (2,5-DPM) and 0.20 ml of 1-bromobutane were added. 5.7 ml of a 1.9 M TEA in toluene solution was slowly added and stirred for 30 min to obtain a greenish-brown solution and a solid product. Excess solvent was removed in vacuo and the liquid was extracted with approximately 15 ml of cyclohexane. The resulting product was filtered, the filtrate was diluted with 25 ml of cyclohexane and a golden solution was obtained, 7.0 ml of which was loaded into the reactor. The product contained 0.014 CrEG ₃ / ml.

Cycle 7008. The procedure described in cycle 7007 was followed, except that 0.22 g of CrEG ₃ and 0.13 ml of 2,5-DMP were used. In addition, instead of 1-bromobutane, 0.10 ml of GeCl _{4 was used} . 3.4 ml of a 1.9 M TEA in toluene solution was added and a brown to tan solution and a precipitate were obtained. The final product, after filtration and dilution with 25 ml of cyclohexane, had a bright golden green color and contained 0.0088 g of CrEG ₃ / ml. 3.0 ml of solution was charged into the reactor.

Cycle 7009. 2.070 g of CrPy ₃ Cl and 70 ml of toluene and 62 ml of a 1.9 M TEA in toluene solution were added, mixed and filtered. The filtrate volume was reduced to approximately 20 ml by evaporation in vacuo. The viscous brown solution was filtered again, then approximately 30 ml of pentane was added to the filtrate. After a day, excess solvent was removed from the solution in vacuo. Then 38.1 g of aluminophosphate support was added. (molar ratio P / Al 0.9, activated at 700 ^o C) obtained by the method of Pat. U.S. 4,364,855 (1982). The suspension was stirred for approximately 30 hours. The solid product was filtered off, washed with toluene, cyclohexane and then pentane. 0.4388 g of solid catalyst system was charged into the reactor.

Cycle 7010. 0.21 g of [Na (DME) ₂ ] [CrCl (Py) ₃ DME] was mixed with approximately 15 ml of 1-hexene. 0.75 ml of pure (93%) TEA was slowly added, a brown solution and a subtle precipitate were obtained, the mixture was stirred for 30 minutes. Excess solvent was removed in vacuo. The residue was extracted with approximately 15 ml of cyclohexane, filtered, the filtrate was diluted with cyclohexane to 25 ml. 0.8 ml (0.067 g) of the solution was charged into the reactor.

 Cycle 7011. The procedure for Cycle 7010 was followed except that the catalyst system prepared in cyclohexane was held for approximately 24 hours before use. 0.8 ml (0.067 g) of the solution was charged to the reactor.

Cycle 7012. 0.26 g of CrEG _{3 was} dissolved in approximately 15 ml of 1-hexene. 0.15 ml of 2,5-DMP and 0.13 ml of 1-bromobutane were added. 1.0 pure (93% / TEA) was added slowly and stirred for 30 minutes. The excess solvent was removed in vacuo and the liquid was extracted with approximately 15 ml of cyclohexane. The resulting product was filtered, the filtrate was diluted with cyclohexane to 25 ml, 7.0 ml of solution was charged into the reactor.

Cycle 7013. 0.21 g of [Na (DME) ₂ ] [CrCl (Py) ₃ DME] was mixed with 15 ml of 1-hexene. 1.0 ml of pure (93%) TEA was slowly added, a dark brown solution was obtained and a precipitate was stirred for approximately 1 hour. The solution was decanted and added to 1.5 g of aluminophosphate (P / Al molar ratio 0.4, activated at 700 ^° C) obtained by the method of Pat. U.S. 4,364,855 (1982).

 The supported catalyst system was filtered off, washed with 1-hexane and dried under a nitrogen atmosphere. 0.6328 g of solid catalyst system was charged into the reactor.

Cycles 7006-7013 were carried out in a 1.2 L autoclave containing cyclohexane. The supported heterogeneous dried catalyst system (cycles 7009 and 7013) was suspended in cyclohexane to facilitate addition to the polymerization reactor, and the suspension was added to the polymerization reactor under countercurrent ethylene (chemically pure). Homogeneous liquid catalyst systems (without being supported on a carrier) (cycles 7006-7008 and 7010-7012) were diluted with cyclohexane and added to a polymerization reactor in countercurrent flow of ethylene (chemically pure). The reactor was closed, and ethylene supply was stopped until the temperature in the reactor rose to a temperature of 80 ^° C. Then, the ethylene pressure in the reactor was raised to 38.5 atm (550 psi). Ethylene was supplied as needed for 30 minutes.

At the end of the cycle, a sample of the liquid reaction mixture was taken and analyzed using capillary gas chromatography on an HP-5880 gas chromatograph equipped with a flame-iodination detector and a DV-1 column (60 m, internal diameter 0.25 mm, film thickness 0.25 μm). The gas chromatograph was gradually heated from 40 to 275 ^o C at a heating rate of 10 ^o / min, for 20 minutes The remaining reaction mixture was evaporated and the amount of solid product was determined.

 The results are presented below in table.7.

 The data in the table. 7 show that the presence of water (cycles 7001 to 7005) has a negative effect on the formation of liquid products, such as, for example, 1-hexene. In fact, the presence of water in the reactor leads to the formation of a large number of solid products. Cycles 7006-7013 show that a catalyst system prepared in the presence of any unsaturated hydrocarbon effectively facilitates the trimerization process. However, a comparison of the catalyst systems of cycles 7006-7009 prepared in toluene with cycles 7010-7013 prepared in 1-hexene shows that an unsaturated aromatic hydrocarbon is the preferred medium for preparing the catalyst system.

 Example VIII

 In the following example, cycles 8001-8017, the effect of the pyrrole-containing compound, halogen and metal additives used is illustrated.

 All catalyst systems used in cycles 8001-8017 were prepared using the same general procedure. In accordance with this procedure, chromium (III) 2-ethylhexanoate was dissolved in toluene, then 3 equivalents of 2,5-dimethylpyrrole (or hydrogen pyrrolide in the case of cycles 8014-8017) were added to the solution. The required amount of halide (2 to 3 molar equivalents) was added, followed by 15 molar equivalents of triethylaluminium (TEA). The reaction mixture was stirred for 5-10 minutes, toluene was removed in vacuo. The liquid residue was diluted with cyclohexane to a total volume of 10 ml and the corresponding aliquot was loaded into the reactor as a catalytic system.

Trimerization experiments were carried out in a 2 L autoclave containing 1.2 L of 85% cyclohexane as diluent. The catalyst system was charged to the reactor after cyclohexane was added. The temperature of the reactor was raised to 80 ^° C. and ethylene was introduced. The pressure in the reactor was maintained at 38.5 atm 550 psi, supplying, if necessary, ethylene. Each cycle was continued for 30 minutes before etching. At the end of the cycle, samples were taken and analyzed by gas chromatography, as described in other examples. The results of the cycles and analysis data are given in table.8.

The data in table 8 show that the selectivity for 1-hexene increases in the following order I <Cl <B. Bromine-containing additives consistently have the highest selectivity for the formation of 1-hexene in comparison with the corresponding chlorides and iodides. An increase in the formation of 1-hexane also means a decrease in the formation of organic products (C ₄ =, C ₈ =, C ₁₀ =). The ratio of 1-hexene to hexenes with a non-terminal olefinic bond also tends to increase in the order I <Cl <B.

Thus, the use of halides not only leads to a large amount of product, but also to a cleaner trimer. The activity of the catalytic system increases in the order I <Cl <Br. However, differences in activity between the Br and Cl analogues, as it turned out, are unpredictable. In the case of some additives (SnX ₄ or AlX ₃ SiX), the bromides are more active.

 The data in the table. 8 also show that the tendency of 1-hexene selectivity and activity of the catalyst system can be transferred to catalyst systems containing other pyrroles, as shown in cycles 8014-8017.

In general, the best combination of activity and selectivity is obtained when GeCl ₄ or SnCl ₄ halide is used as additives. However, it was shown that the ratio of halide to triethyl aluminum also affects the selectivity for 1-hexene, which makes it possible to obtain high selectivity when using additives of other halides.

 Example IX

 In the following example, cycles 9001 to 9004 show that excess unsaturated aromatic hydrocarbon can adversely affect the trimerization and / or oligomerization process. Therefore, when the catalyst system is prepared in the presence of an aromatic hydrocarbon, such as, for example, toluene, the excess aromatic hydrocarbon should preferably be removed. The resulting liquid was then extracted or dissolved in a suitable solvent, for example, such as cyclohexane or heptane. Although theoretically an aromatic hydrocarbon does not enter into a chemical reaction, it is believed that it can compete with a monomer that undergoes trimerization and / or oligomerization, for example, ethylene, for the active sites of the catalytic system. It is believed that such competition can lead to a decrease in the activity of the catalytic system.

 The catalyst system used in cycles 9001 to 9004 was prepared using solutions of 1.35 g of chromium (III) 2-ethylhexanoate in toluene. 0.86 ml (3.2 mmol equivalents) of 2,5-dimethylpyrrole was added to the solution. Then, 0.90 ml (3.2 molar equivalents) of n-butyl bromide was added, followed by 7.60 ml (21 molar equivalents) of 93% triethylaluminium. The mixture was stirred for 5-10 minutes and toluene was removed in vacuo. The liquid residue was dissolved in 30 ml of cyclohexane, filtered and then diluted with cyclohexane to a total volume of 50 ml. 4 ml of the resulting solution was charged into the reactor together with the required amount of anhydrous, gas-free toluene (0.5, 10 or 15 ml).

The trimerization reaction was carried out in a 2 L autoclave containing 1.2 L of 85% cyclohexane as a diluent. The catalyst system was charged to the reactor after cyclohexane was added. The temperature of the reactor was raised to 80 ^° C. and ethylene was introduced. The pressure in the reactor was raised to 38.5 atm (550 psi) and maintained at that level, supplying ethylene as needed. Each cycle lasted 30 minutes before etching. The total consumption of ethylene was measured.

 The results of cycles 9001-9004 are given in table.9.

 The data in Table 9 show that the presence of an aromatic hydrocarbon, i.e. toluene, can lead to a significant decrease in the activity of the catalytic system, as evidenced by the measured consumption of ethylene. This decrease is proportional to the amount of aromatic hydrocarbon added to the reactor.

Claims (32)

 1. A method of obtaining a catalytic system for the trimerization, oligomerization or polymerization of olefins, comprising the step of mixing a metal source, a pyrrole-containing compound and metal alkyl in a common solvent, characterized in that the mixing of the metal source, pyrrole-containing compound and metal alkyl is carried out without prior interaction between the metal source and the pyrrole-containing compound in the presence of an electron donor solvent.  2. The method according to p. 1, characterized in that it further admixes an unsaturated hydrocarbon, which may be a common solvent.  3. The method according to p. 2, characterized in that the unsaturated hydrocarbon is an aromatic or aliphatic hydrocarbon containing in the molecule less than about 70 carbon atoms.  4. The method according to p. 3, characterized in that said unsaturated hydrocarbon is an aromatic hydrocarbon containing in the molecule less than about 20 carbon atoms.  5. The method according to p. 4, characterized in that said aromatic unsaturated hydrocarbon is toluene, benzene, xylene, mesitylene or hexamethylbenzene.  6. The method according to any one of paragraphs. 2 to 5, characterized in that the excess aromatic hydrocarbon is desorbed from the resulting catalyst system.  7. The method according to p. 3, characterized in that the unsaturated hydrocarbon is ethylene.  8. The method according to any one of paragraphs. 1 to 7, characterized in that the metal source is a compound of chromium, nickel, cobalt, iron, molybdenum or copper.  9. The method according to p. 8, characterized in that the metal source is a chromium compound.  10. The method according to any one of paragraphs. 1 to 9, characterized in that the pyrrole-containing compound is pyrrole or 2,5-dimethylpyrrolide.  11. The method according to any one of paragraphs. 1 to 10, characterized in that the metal in the metal alkyl is aluminum, lithium, magnesium or zinc.  12. The method according to p. 11, characterized in that said metallkyl is an alkylaluminum.  13. The method according to p. 12, characterized in that said alkylaluminum is a trialkylaluminum compound, for example triethylaluminum.  14. The method according to any one of paragraphs. 1 to 13, characterized in that the carrier is introduced into the catalytic system.  15. The method according to p. 14, characterized in that the carrier is an inorganic oxide.  16. The method of claim 15, wherein said inorganic oxide is silica, aluminosilicate, alumina, fluorinated alumina, silylated alumina, thorium oxide, aluminophosphate, aluminum phosphate, phosphated silica, phosphated alumina, titanosilicate , coprecipitated silica (titanium dioxide fluorinated), silylated alumina or mixtures thereof.  17. The method according to any one of paragraphs. 1 16, characterized in that the source of the halide is added.  18. The method according to p. 17, characterized in that the halide is a chloride or bromide, or a mixture thereof. 19. The method according to p. 17 or 18, characterized in that the halide is a compound of the formula
R _m X _n
where R is an organic or inorganic residue;
X is halogen;
m + n> 0.  20. The method according to p. 19, wherein R is aluminum, silicon, germanium, hydrogen, boron, lithium, tin, gallium, indium, lead, or a mixture thereof.  21. The method according to p. 20, characterized in that R tin, germanium or a mixture thereof.  22. The method according to PP. 1 21, characterized in that the resulting catalytic system has a molar ratio of: a) approximately 1 mol of metal in the metal source; b) from about 1 to about 15 mol of a pyrrole-containing compound; c) from about 5 to about 40 mol of metalalkyl; and, if present, d) from about 1 to about 30 mol of halide.  23. The method according to any one of paragraphs. 1 22, characterized in that it is carried out in the absence of oxygen and water.  24. The method according to any one of paragraphs. 1 to 23, characterized in that the metal source and the pyrrole-containing compound are mixed prior to the addition of metal alkyl.  25. A method of obtaining a catalytic system for the trimerization, oligomerization or polymerization of olefins, comprising the step of reacting the mixture: a) a metal salt, preferably a chromium salt; b) a metal amide; and c) an electron donor solvent, wherein the amide is pyrrole or substituted pyrrole, and, if desired, the process includes an additional step of reacting the resulting reaction product with an unsaturated hydrocarbon, which is an aliphatic or aromatic hydrocarbon, preferably ethylene or ethylbenzene and toluene.  26. A method of obtaining a catalytic system for the trimerization, oligomerization or polymerization of olefins, comprising the step of reacting a mixture consisting of: a) a metal salt other than chromium, preferably a salt of nickel, cobalt, iron, molybdenum, copper; b) a metal amide, preferably pyrrole, substituted pyrrole, pyrrolidine or substituted pyrrolidine, for example Na, Li, K, Cs, and c) an electron-donating solvent, and, if desired, comprising an additional step of reacting the obtained product with an unsaturated hydrocarbon, which is an aliphatic or an aromatic hydrocarbon, preferably ethylene or ethylbenzene and toluene.  27. The method according to any one of paragraphs. 1 26, characterized in that it comprises mixing a catalyst system prepared as a cocatalyst system with a catalyst system for polymerization.  28. The method according to p. 27, characterized in that the catalytic system for polymerization includes chromium, titanium, zirconium and / or vanadium-containing catalyst.  29. The method of trimerization, oligomerization or polymerization of an olefin compound containing 2 30 carbon atoms per molecule and at least one double olefin bond, comprising the step of trimerization, oligomerization or polymerization in the presence of a catalytic system or catalytic / cocatalytic system, characterized in that the catalytic or the catalytic / cocatalytic system is obtained by the method according to any claims. 1 29.  30. The method according to p. 29, wherein the olefin compound is ethylene, 1-butene, 1-hexene, 1,3-butadiene, or a mixture thereof.  31. The method according to p. 29 or 30, characterized in that the unsaturated hydrocarbon is used to prepare the catalytic system, but is introduced during the process of trimerization, oligomerization or polymerization.  32. The method according to p. 31, wherein the unsaturated hydrocarbon used to prepare the catalyst system is an unsaturated aliphatic hydrocarbon, which is also an olefin compound that is subjected to trimerization, oligomerization or polymerization.

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