TW379237B - Preparing catalyst for trimerization oligomerization or polymerization of olefinic compounds - Google Patents

Abstract

Improvements or modifications of earlier process for preparing chromium-containing compounds, such as, for example, chromium pyrrolides, by forming a mixture of a chromium salt, a metal amide, particularly a pyrrolide, and an electron pair donor solvent, such as, for example, an ether, and reaction with an unsaturated hydrocarbon are disclosed, including use of pyrrole or derivatives thereof as the pyrrolide and an aliphatic as the unsaturated hydrocarbon. A new process for preparing a catalyst system comprises combining a metal source, a pyrrole-containing compound and a metal alkyl without a preliminary reaction step between the metal source and the pyrrole-containing compound in the presence of an electron donor solvent. These catalyst systems and chromium-containing compounds either unsupported or supported on an inorganic oxide support, if desired functioning as a cocatalyst in combination with another polymerization catalyst, such as containing chromium or titanium, can be used to trimerize, oligomerize, and/or polymerize olefins.

Description

Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs on the patent No. S2 101 3 46 by the patent case, and the description is given in February (3 Γ) February A7 B7 V. Description of the invention ().;: 1.- ί "The present invention relates to chromium catalysts or co-catalysts for trimerization, oligomerization, and / or polymerization of olefins. The present invention also relates to methods for trimerization, oligomerization, and / or polymerization of olefins. Supported oxidation complex catalysts have The main factor in the preparation of olefin polymers such as polyethylene or copolymers of ethylene and hexene. This catalyst can be used in various polymerization processes. However, most of the known chromium compounds must support the catalytic action of K. In addition, most The supported chromium compounds can only be used for ene smoke polymerization. If an olefin copolymer is required, the polymerization process becomes complicated by having to feed two different monomers to the polymerization reactor. Olefin trimerization and oligomerization catalysts are known This technique, but usually lacks selectivity to the desired product * and also has low product yields. However, if done efficiently, trimerization and / or oligomerization of olefins is a method to provide usable olefins. Some olefins The product can be trimerized, oligomerized, and / or added to the polymerization process as appropriate. According to my patent application No. 7 9 1 0 β 5 3 2 filed on August 7, 1990, it is described that the following formula has Chromium-containing compounds: C r 5 (C ^ Η 4 Ν) 1 〇 (C 4 Η 3 0) Λ; [C rf C 4 Η 4 Ν) 4 j [N a] a 2 (0 ί; AH 3); [C r (C 4 H a H) 5 (0 C 4 H ai J [N a] 2 4 (0 C ^ H 3 i; C r (N “H 4) 3 C 1 (fU C 2 H 4 ( CH 3) 2) 3 N a. According to one aspect of the application on M, the chromium-containing compound of this novel compound is prepared from a reaction mixture containing an acrylamide, amidine, and an electron-to-supplier solvent such as ether. I ratio catalyst system can be used with or without support, and trimer and / or polymer M welding. 錤 翱 can be more organic and organic. No chrome rhyme, the chloride state of the road -------- 1 Pack ------ Order ------ For one reason (please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) Α4 specification (21〇 × 297 mm) Economy Printed by the Consumer Standards Cooperative of the Ministry of Standards of the People's Republic of China on Patent No. S2 101 3 46 The description is based on the description of Xi Xiubai (3 Γ) February 丨 A7 B7 V. Description of the invention (). ： "1.-丨" The present invention relates to trimerization, oligomerization, and / or polymerization of olefins Chromium catalyst or co-catalyst used. This invention also relates to a method for trimerization, oligomerization, and / or polymerization of olefins. Supported oxide complex catalysts have been a major factor in the preparation of olefin polymers such as polyethylene or copolymers of ethylene and hexene. This catalyst can be used in various polymerization processes. However, most of the known chromium compounds must support K to act catalytically. In addition, most of the supported chromium compounds can only be used for diene polymerization. If an olefin copolymer is required, the polymerization process becomes complicated by having to feed two different monomers to the polymerization reactor. Olefin trimerization and oligomerization catalysts are known in the art, but often lack selectivity to the desired product * and also have low product yields. However, if done efficiently, olefin trimerization and / or oligomerization is a method to provide useful olefins. Some olefin products may be trimerized, oligomerized, and / or optionally added to the polymerization process. According to my patent application No. 7 9 1 0 β 5 3 2 filed on August 7, 1990, a description of a chromium-containing compound having the formula: C r 5 (C ^ Η 4 Ν) 1 〇 (C 4 Η 3 0) Λ; [C rf C 4 Η 4 Ν) 4 j [N a] a 2 (0 ί; AH 3); [C r (C 4 H a H) 5 (0 C 4 H ai J [N a] 2 4 (0 C ^ H 3 i; C r (N “H 4) 3 C 1 (fU C 2 H 4 (CH 3) 2) 3 N a. According to one aspect of the application on M, The chromium-containing compound of this new compound is prepared from a reaction mixture containing Ming compound, ammonium amine, and electrons such as ether to the supplier's solvent. I ratio catalyst system can be supported or unsupported and trimered and / or polymerized. Welding. I can be a more organic Rong Wu Yi. Organic chrome rhyme, the chlorination state of the road -------- 1 installed -------- order ---- one reason ( Please read the precautions on the back before filling in this page) This paper size applies Chinese National Standard (CNS) Α4 specification (21〇 × 297 mm) No. 82101346 Patent Application A 7 Chinese Manual Correction Page (April 1987) β7 D / V. Description of the invention (), .., ;;, potassium pyrrole salt, and pyrrole Substituted pyrrole salts include, but are not limited to, sodium 2,5-dimethylpyrrole salts and / or 3,4-dimethylpyrrole salts. When metal amines are the pyrrole salt ligands, the chromium compound produced is Mingpyr The acid of the reaction mixture may be one of the reactions between the chromium salt and the amidine. »Or more ether compounds, although not wishing to be bound by theory, it is believed that the ether may be the reaction solvent and may be Reactant. The ether can be any aliphatic and / or aromatic compound containing R-0-R functional groups, where the R groups can be the same or different, but is not preferably hydrogen. Because of the safety reasons that aromatic ethers are toxic to humans The preferred ether is a fatty ether. In addition, the preferred ether is one that facilitates the reaction between the chromium halide and the Group IA or Group IIA metal pyrrole salt and is also easily removed from the reaction mixture. Exemplary compounds include, but are not limited to, tetrahydrofuran , Dihenane, diethyl ether, dimethoxyethane (glyme), diglyme, triglyme, and mixtures of two or more of them. Reasons > And the reason why the preferred salts of amines are soluble in these ethers | Ether is selected from tetrahydrofuran, tetra Furan derivatives, dimethoxyethane, dimethoxyethane derivatives, and mixtures thereof are the best. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ------------ Clothing --- order (please read the notes on the back before filling this page) The three reactants can be mixed by any method under conditions suitable for forming a solution containing one or more chromium compounds of the present invention. The reaction takes place in the absence of oxygen and moisture • and therefore in an inert atmosphere such as nitrogen and / or argon. The reaction pressure may be any pressure sufficient to maintain the reactants in a liquid state. Generally speaking, pressures ranging from about atmospheric pressure to about three atmospheres are acceptable. For this paper size, the Chinese National Standard (CNS) A4 specification (210 × 297 mm) applies to the staff consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. A7 _ B7 V. Description of the invention () is from 0 to 6. As used in this disclosure, 'Ming Jin' is included in this definition of Ming salt. In general, complex salts have the formula OX, where X can be the same or different and can be any organic or inorganic radical • and η is an integer from 1 to 6. Exemplary organic radicals are at every 1Θ radical It may have about 1 to about 30 carbon atoms, and is selected from the group consisting of hexyl, oxy, ketone, and / or amidine radicals. Organic radicals may be straight or branched, cyclic, and acyclic , Aromatic or aliphatic, and may be composed of aliphatic, aromatic, and / or cycloaliphatic groups of the mixture. Exemplary inorganic free radicals include, but are not limited to, halides, sulfates, and / or oxides. Salts are halides Preferably, for example, chromium fluoride, fluoride fluoride, chlorinated chloride, chromite, chromium bromide, bromide, chromium iodide, chromium iodide, and mixtures thereof. Chromium salts are the most common odorants. Good, such as chlorinated chloride and / or oxidative pathway, because the separation of reaction by-products such as oxidized sodium is simple and the cost is relatively low. Auridamine can react with chromium salts to form chromium-fluorenamine complexes. Any metal amides. In a broad sense, amidoamines can be any heterolipids or complexes or salts with oligoamines, of which amidines The radical may be any nitrogen-containing organic free radical. Amidoamine may be added to the reaction indefinitely * or generated in situ. Generally speaking, amidoamine has about 1 to about 20 carbon atoms. Examples are preferred. Ammonium amines include, but are not limited to, lithium dimethyl ammonium amine, lithium diethyl ammonium amine, lithium diisopropyl ammonium amine, lithium dicyclohexyl ammonium amine, lithium bis (triethylsilyl) ammonium amine, lithium indole , Private gold tincture and tertium gold pyrrole salt, and mixtures of two or more thereof. Because of its high reactivity and activity with other reactants, the best is the gold pyrrole salt on K, such as lithium pyrrole Salt, nalpyrrole salt (please read the notes on the back before filling out this page) Water --- Order ---- Line-4-This paper size is applicable to Chinese National Standard (〇 奶) 8 4% ^ (210 > < 297 mm) 83. 3. 10,000 Patent Application No. 32101346 A 7 Revised Chinese Manual (δ7, April B7 V. Description of the Invention) (-) Revised to supplement easy operation, usually using atmospheric pressure The precipitated hafnium compound of the present invention can be recovered by any method known in the art. The simplest way to remove the precipitated chromium compound The step is extinction. The chromium compounds prepared by the above method can be used in olefin trimerization, oligomerization, or polymerization, whether as a supported and / or unsupported catalyst system. Supported chromium catalyst systems can be used Prepared from any support that supports a chromium catalyst. Example catalyst supports include, but are not limited to, zeolites, inorganic oxides, whether alone or in combination, phosphorylated inorganic oxides, and mixtures thereof. Particularly preferred are selected from the group consisting of silica, oxidation Silica-alumina, alumina, fluorided alumina, silylated alumina, hafnium oxide, aluminophosphate, aluminum phosphate, phosphorylated silica, silica-titanium oxide, co-precipitated silica / titanium oxide, fluorinated / Silicated alumina, and mixtures thereof, and one or more of these may contain chromium are currently preferred. Currently the best catalyst support is aluminophosphate because of its maximum trimerization activity, as disclosed in U.S. Patent 4,364,855 (1982). The amount of chromium pyrrole salt compound per gram of support can be expressed by different but synonymous terms, for example, the chromium moles per gram of support. In general, less than about 8.6 X 10-3 moles of chromium per gram of support is sufficient. For reasons of M, use about 1.7 X 10_β to about 1.7 X 10-5 to about 1 gram of support (please read the precautions on the back before filling out this page). Printed by the Ministry of Economic Affairs Central Standard Bureau employee consumer cooperative. Paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) No. 82101346 Patent Application A 7 Chinese Manual Correction Page (April 1987) β7 D / V. Description of the invention (), .., ;; Potassium pyrrole salt and shaved pyrrole salt. Substituted pyrrole salts include, but are not limited to, sodium 2,5-dimethylpyrrole salts and / or 3,4-dimethylpyrrole salts. When the metal sulfonium amine is a pyrrole salt ligand, the resulting chromium compound is the salt of pyracal. The acid of the reaction mixture may be one of the reactions between the chromium salt and haptenamine. Although one or more ether compounds are not intended to be bound by theory, it is believed that the ether may be the reaction solvent and may be the reactant. The ether may be any aliphatic and / or aromatic compound containing a R-0-R functional group, where the R groups may be the same or different, but is preferably not hydrogen. For safety reasons that aryl ethers are toxic to humans, the preferred ethers are fatty ethers. In addition, preferred ethers are those which facilitate the reaction between chromium halides and Group IA or Group IIA metal pyrrole salts and are also easily removed from the reaction mixture. Exemplary compounds include, but are not limited to, tetrahydrofuran, dihumane, diethyl ether, dimethoxyethane (glyme), diglyme, triglyme, and two or more thereof Of a mixture. For reasons on M > and the reason why preferred salts of amines are soluble in these ethers | ethers are selected from tetrahydrofuran, derivatives of tetrahydrofuran, dimethoxyethane, derivatives of dimethoxyethane, And their mixtures are the best. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ---------- Taxi-Cloths ---- Order (please read the precautions on the back before filling this page) Mix by any method while forming a solution containing one or more chromium compounds of the invention. The reaction takes place in the absence of oxygen and moisture • and therefore in an inert atmosphere such as nitrogen and / or argon. The reaction pressure may be any pressure sufficient to maintain the reactants in a liquid state. Generally speaking, pressures ranging from about atmospheric pressure to about three atmospheres are acceptable. For this paper size, apply Chinese National Standard (CNS) A4 specification (210 × 297 mm) A7 B7 Patent Application No. 82101346 Chinese manual amendment page (April S7)

V. Description of the invention ((Please read the notes on the back before filling out this page) Any amount of activated compounds, such as amidinyl and / or Lewis acid, is sufficient to activate and / or react with the chromium pyrrole salt catalyst. Each Gram chromium usually uses about 200 grams of activated compound, that is, metal alkyl and / or Lewis acid. About 1 to about 100 grams of activated compound is used per gram of chromium pyrrole salt, such as amidinyl and / or Lewis acid. And about 5 to about 30 grams of activating compound, such as amidinoyl and / or Lewis acid, is used per gram of chromium pyrrole salt, because the catalyst activity is the best. However, the amount of activating compound used, such as metal alkane Base and / or Lewis acid, may vary depending on the catalyst support used. For example, if the support is silica and / or alumina * too many activating compounds | such as metal alkyl and / or Lewis acid, the catalyst will be reduced Activity. However, similar amounts of activating compounds used for aluminophosphate supports, such as metal alkyls and / or Lewis acids, will not sufficiently reduce catalyst activity. Printed here by the Central Standards Bureau Offshore Consumers Cooperative, Ministry of Economic Affairs Wider When explained> The hydrocarbon compound used as the solvent may be any combination of one or more aromatic or aliphatic unsaturated hydrocarbon compounds. Although not wishing to be bound by any theory, it is believed that the unsaturated hydrocarbon compound acts not only as a solvent, And is a stable component during or after the formation of the reactant and / or the catalyst system of the present invention. Exemplary unsaturated hydrocarbon compounds, such as solvents, may be any unsaturated hydrocarbon compound that can dissolve the activated compound, that is, where the activated compound is amidinoalkyl And / or Lewis acid. According to one aspect of the present invention, in addition to aromatic compounds having about 6 to about 50 carbon atoms per mole molecule as the solvent described above in the present case, it is also possible to use less than Unsaturated aliphatic hydrocarbons of about 20 carbon atoms. Specific examples of unsaturated aliphatic compounds include ethylene, 1-hexene, 1,3-butadiene, and mixtures thereof. Because of the elimination of the catalyst system's preparation step , The best unsaturated aliphatic cigarette is ethylene, and the paper can be applied to Chinese National Standard (CNS) A4 specification (210X297 mm) No. 32101346 patent application A7 The revised page of the manual (δ7, April B7 V. Description of the invention () --- Revision ί supplements easy operation, usually using atmospheric pressure. Precipitated rhenium compounds of the invention can be recovered by any method known in the art. The simplest step to remove the precipitated chromium compounds is extinction. The chromium compounds prepared by the above method can be used for olefin trimerization, oligomerization, or polymerization, whether as a supported and / or unsupported catalyst system. Supported chromium catalyst systems can be prepared using any support that supports a chromium catalyst. Example catalyst supports include, but are not limited to, zeolites, inorganic oxides, whether alone or in combination, phosphorylated inorganic oxides, and mixtures thereof. It is selected from the group consisting of silica, silica-alumina, alumina, fluorinated alumina, silylated alumina, hafnium oxide, aluminophosphate, aluminum phosphate, phosphorylated silica, silica-titanium oxide, and co-precipitated Supports of silicon oxide / titanium oxide, fluorinated / silicated alumina, and mixtures thereof, and one or more of these supports which may contain chromium are currently preferred. Currently the best catalyst support is aluminophosphate because of its maximum trimerization activity, as disclosed in U.S. Patent 4,364,855 (1982). The amount of chromium pyrrole salt compound per gram of support can be expressed by different but synonymous terms, for example, the chromium moles per gram of support. In general, less than about 8.6 X 10-3 moles of chromium per gram of support is sufficient. For reasons of M, use about 1.7 X 10_β to about 1.7 X 10-5 to about 1 gram of support (please read the precautions on the back before filling out this page). Printed by the Ministry of Economic Affairs Central Standard Bureau employee consumer cooperative. Paper size applies to Chinese National Standard (CNS) Α4 specification (210 × 297 mm) No. 82101346 Patent Application Hei A7 Chinese manual revision page (April 1987) β7 V. Description of invention ()

Triethylaluminum. According to another aspect of the present invention, the catalyst system can be used in the preparatory reaction step (for the reaction between the sulphur-containing compound and the pyrrole-containing compound as described above) without an electron donor solvent and an unsaturated liquid hydrocarbon compound. It is prepared by mixing a metal source, a pyrrole-containing compound, and a metal alkylate in the presence. The unsaturated smoke, such as toluene, can be used as a miscible solvent. These catalyst systems may further include a catalyst support. The metal source is preferably a chromium source, but it can also be any other metal as described above. Similar to the chromium salts discussed on K, the source of chromium can be one or more organic or inorganic complexes, where the oxidation state of chromium is from 0 to 6. As used herein, chromium salts are included in the definition of chromium salts. Generally speaking, chromium sources have the formula OX, where X is the same or different, and can be any organic or inorganic radical * and η is an integer from 1 to 6. Exemplary organic radicals can each have about 1 Up to about 20 carbon atoms • and selected from alkyl, alkoxy, ester, amidine, and / or amidine radicals. Organic radicals may be linear or branched, cyclic or acyclic, aromatic or wax Family, which can be mixed aliphatic, aromatic, and / or cycloaliphatic radicals. Exemplary inorganic free radicals include, but are not limited to, halides, sulfates, and / or oxides. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (Please Read the notes on the back before filling this page.) The source of chromium is preferably complex compounds containing II (II)-and / or chromium (III)-, which can produce a catalyst system with improved trimerization activity. The source of chromium is Chromium (III) compounds are best because of their ease of use, availability, and enhanced catalyst system activity. Exemplary chromium (III) compounds include, but are not limited to, carboxylic acid salts, chromium naphthalate, chromium halides, chromium pyrrole salts, And / or chromium diketonates. Specific exemplary complex (III) compounds include but are not Limited to acid (111) 2,2,2,6-4-10-This paper size is applicable to Chinese National Standard (CNS) A4 size (210 X 297 mm) A7 Printed by Brigade Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of the invention () 8. 6 X ΙΟ-4 mol of chromium. After the support is added and completely mixed with the chromium pyrrole salt, it can be collected by filtration, dried under vacuum, and then activated by adding the support / chrome pyrrole salt mixture. The compound is usually a solution of one or more Lewis acid and / or amidinoalkyl, preferably in a hydrocarbon compound solvent. The activated and supported catalyst system can then be collected by quenching. The Lewis acid used in this disclosure Any compound that is defined as an electron acceptor. Activated compounds are compounds that can be considered as Lewis acid and amidinoalkyl. When this case is more broadly described, activated compounds can have any number of carbons. However, due to commercial availability And easy to use, the activating compound usually contains less than about 70 carbon atoms per mole of metal alkyl molecules, and preferably less than about 20 carbon atoms per molecule. It is a Lewis acid and is a preferred activation of metal alkyl groups. Turn into Substances include, but are not limited to, aluminum alkyl compounds, alkyl boron compounds, alkyl magnesium, fluorenyl zinc, and / or alkyl lithium compounds. Examples of fluorinated alkyl groups include, but are not limited to, n-butyllithium, dioxetane Lithium, tributyllithium, diethylmagnesium, dibutylmagnesium, diethylzinc, triethylaluminum, trimethylaluminum, triisobutylaluminum, and mixtures thereof. Products of activated compounds due to improvement Selectivity, and improved reactivity, activity, and / or productivity of the catalyst system are selected from alkylaluminum compounds, derivatives of alkylaluminum compounds, halogenated alkylaluminum compounds, non-hydrolyzed, that is, without first contact with water, And their mixtures are optimal. Because of the best catalyst system activity and product selectivity, exemplary compounds include, but are not limited to, triethylaluminum, tripropylaluminum, tributylaluminum, diethylaluminum chloride, diethylbromide Aluminium oxide, diethyl alumina, ethyl sesquichloride, and lean mixtures. The most basic aluminum alkyl compound is triethylaluminum * because of its best catalyst system activity and product selectivity. Loading-: --- ^-Order ------ · I line i (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297) Cents) 83. 3. 10,000

Patent Application No. 32 1 0 1 346 Chinese Revised Page (July 88) A7 B7 V. Description of Invention () Any unsaturated aromatic or aliphatic hydrocarbon can be used. Unsaturated hydrocarbons are preferably present in the reaction mixture at first, and denier aromatic hydrocarbons and / or ethylene are present at first, and it is best to produce catalysts with regard to activity and selectivity, and stable catalyst systems that are highly active. Unsaturated hydrocarbons can have any number of carbon atoms per molecule. Generally, because of commercial availability and ease of use, unsaturated hydrocarbons contain less than about 70 carbon atoms per molecule, and preferably less than about 20 carbon atoms per molecule. The unsaturated hydrocarbon is in a liquid state. In order to completely contact and mix the chromium salt, the compound containing lazier, and the metal base, it is preferable that the unsaturated smoke is liquid and / or dissolved. Exemplary unsaturated aliphatic hydrocarbons include, but are not limited to, ethylene, 1-hexane, 1,3-butadiene, and mixtures thereof. Exemplary unsaturated aromatic hydrocarbons include, but are not limited to, toluene, benzene, xylene, hexamethylbenzene, and mixtures thereof. In order to improve the stability of the catalyst system and the activity of the catalyst system, unsaturated hydrocarbons are better and the best unsaturated aromatic smoke is methylbenzyl, because it has the best stability and activity of the catalyst system. If unsaturated aromatic hydrocarbons are added to the gfj from the introduction of chromium compounds to trimerization, oligomerization and / or polymerization reactions, 'removal or removal of compounds in the introduction path to the reactor may improve catalyst + system activity and / or Product selectivity. The removal of unsaturated aromatic hydrocarbons can be accomplished by any method known in the art, such as flash evaporation or evaporation. The resulting product is a concentrated or saturated solution of the catalyst system of the present invention. When unsaturated aromatic hydrocarbons are removed before introduction into the reactor, the concentrated or saturated solution of the catalyst system of the present invention is soluble in trimerization, oligomerization, and _ 1 4 _ This paper standard applies to China National Standards (CNS) Α4 Specification (210X2S »7mm) IIII IJ— Seed clothing n ~~ Orders (please read the precautions on the back before filling this page) Printed by A7 B7 No. 82101346 Patent Application by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Case Chinese Manual Revision Sheet (April S7)

V. Description of the invention ((Please read the notes on the back before filling out this page) Any amount of activated compounds, such as amidinyl and / or Lewis acid, is sufficient to activate and / or react with the chromium pyrrole salt catalyst. Each Gram chromium usually uses about 200 grams of activated compound, that is, metal alkyl and / or Lewis acid. About 1 to about 100 grams of activated compound is used per gram of chromium pyrrole salt, such as amidinyl and / or Lewis acid. And about 5 to about 30 grams of activating compound, such as amidinoyl and / or Lewis acid, is used per gram of chromium pyrrole salt, because the catalyst activity is the best. However, the amount of activating compound used, such as metal alkane Base and / or Lewis acid, may vary depending on the catalyst support used. For example, if the support is silica and / or alumina * too many activating compounds | such as metal alkyl and / or Lewis acid, the catalyst will be reduced Activity. However, similar amounts of activating compounds used for aluminophosphate supports, such as metal alkyls and / or Lewis acids, will not sufficiently reduce catalyst activity. Printed here by the Central Standards Bureau Offshore Consumers Cooperative, Ministry of Economic Affairs Wider When explained> The hydrocarbon compound used as the solvent may be any combination of one or more aromatic or aliphatic unsaturated hydrocarbon compounds. Although not wishing to be bound by any theory, it is believed that the unsaturated hydrocarbon compound acts not only as a solvent, And is a stable component during or after the formation of the reactant and / or the catalyst system of the present invention. Exemplary unsaturated hydrocarbon compounds, such as solvents, may be any unsaturated hydrocarbon compound that can dissolve the activated compound, that is, where the activated compound is amidinoalkyl And / or Lewis acid. According to one aspect of the present invention, in addition to aromatic compounds having about 6 to about 50 carbon atoms per mole molecule as the solvent described above in the present case, it is also possible to use less than Unsaturated aliphatic hydrocarbons of about 20 carbon atoms. Specific examples of unsaturated aliphatic compounds include ethylene, 1-hexene, 1,3-butadiene, and mixtures thereof. Because of the elimination of the catalyst system's preparation step , The best unsaturated aliphatic cigarette is ethylene, and the paper can be applied to Chinese National Standard (CNS) A4 specification (210X297 mm). Printed by Zhuosha A7 ___B7 V. Description of the invention () is a trimerization and / or oligomerization reactant. Specific unsaturated aromatic hydrocarbon compounds include, but are not limited to, methylbenzyl, benzene, xylene, benzene, hexamethyl Benzene, and mixtures thereof. As described in this case, the best unsaturated aromatic hydrocarbon compound solvent is methylbenzene, because it is easy to remove and has minimal catalyst system interference. Unsaturated hydrocarbon compounds can be present in chromium pyrrole salts Upon initial contact with the activated compound, just before the trimerization, oligomerization, and / or polymerization reactor is introduced, or unsaturated hydrocarbon compounds may be introduced directly into the reactor. As mentioned above, one or more olefin reactants may be It is regarded as unsaturated hydrocarbon. Unsaturated hydrocarbon and hydrocarbon exist in the initial contact between lupyrrole salt and activated compound to form a stable catalyst system. If there are no unsaturated hydrocarbons, the generated catalyst system is deactivated and lost over time. active. Although any halogenated unsaturated hydrocarbon compound can be used, too much or too little will negatively affect the catalyst system activity. Therefore, the resulting catalyst systematically removes any excess unsaturated aromatic hydrocarbons. Removal of excess unsaturated aromatic hydrocarbons can be accomplished by any method known in the art, such as solvent removal. Examples Removal methods include, but are not limited to, extinction, vacuum drying, drying in an inert atmosphere, and their sisters. Although not wishing to be bound by theory, it is believed that the remaining unsaturated hydrocarbons can be stabilized to form catalyst systems. If unsaturated hydrocarbons are not present, the catalyst system is believed to be deactivated. A variation or preferred method of generating a supported catalyst system in accordance with the present case is to mix one or more solid, chromium pyrrole salt compounds of the present invention with an unsaturated hydrocarbon solvent, as disclosed herein in a broader sense, including, for example, methylbenzyl and / or ethylene , And activating compounds, as shown previously, such as amidinoalkyl and / or Lewis acid, such as one pack 1 | two swallow I 1 line-(Please read the note of the back-matters before filling this page) This Paper size applies to National Standard (CNS) A4 specifications (210 × 297 mm) 83. 3. 10,000 Patent Application No. 82101346 Patent Application A7 Chinese Manual Correction Page (April 1987) β7 V. Description of Invention ()

Triethylaluminum. According to another aspect of the present invention, the catalyst system can be used in the preparatory reaction step (for the reaction between the sulphur-containing compound and the pyrrole-containing compound as described above) without an electron donor solvent and an unsaturated liquid hydrocarbon compound. It is prepared by mixing a metal source, a pyrrole-containing compound, and a metal alkylate in the presence. The unsaturated smoke, such as toluene, can be used as a miscible solvent. These catalyst systems may further include a catalyst support. The metal source is preferably a chromium source, but it can also be any other metal as described above. Similar to the chromium salts discussed on K, the source of chromium can be one or more organic or inorganic complexes, where the oxidation state of chromium is from 0 to 6. As used herein, chromium salts are included in the definition of chromium salts. Generally speaking, chromium sources have the formula OX, where X is the same or different, and can be any organic or inorganic radical * and η is an integer from 1 to 6. Exemplary organic radicals can each have about 1 Up to about 20 carbon atoms • and selected from alkyl, alkoxy, ester, amidine, and / or amidine radicals. Organic radicals may be linear or branched, cyclic or acyclic, aromatic or wax Family, which can be mixed aliphatic, aromatic, and / or cycloaliphatic radicals. Exemplary inorganic free radicals include, but are not limited to, halides, sulfates, and / or oxides. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (Please Read the notes on the back before filling this page.) The source of chromium is preferably complex compounds containing II (II)-and / or chromium (III)-, which can produce a catalyst system with improved trimerization activity. The source of chromium is Chromium (III) compounds are best because of their ease of use, availability, and enhanced catalyst system activity. Exemplary chromium (III) compounds include, but are not limited to, carboxylic acid salts, chromium naphthalate, chromium halides, chromium pyrrole salts, And / or chromium diketonates. Specific exemplary complex (III) compounds include but are not Limited to acid (111) 2,2,2,6 -4-10-This paper size is applicable to China National Standard (CNS) Α4 size (210 X 297 mm) Printed by A7 ___ B7 five Description of the invention () Methylpimelate [Cr (TMHD) 3], Chromium (111) 2-ethylhexanone [Cr (DH) 3], Complex (III) Naphthate [CrUp) 3], chromium (III) chloride, complex (III) tris (2-ethylhexanone), n-chromium bromide, n-chromium chloride, n-fluoride, and chromium (III) chloride- 2-Ethylhexanoate. Chloro (III) chloride, dichloroethylhexanone, chromium (III) chloride, ethynylpyruvate, acetate (III), butyric acid (III), Chromium (III) pivalate, lauric acid (III), chromium (III) stearate, chromium (III) pyrrole salt, and / or oxalic acid (III). Specific examples_examples (11) compounds include but Not limited to Cr (II) fluoride, Cr (II) chloride, Cr (II) bromide, Cr (II) iodide, (II) bis (2-ethylhexanone), osmium (II) acetate, chromium (II) butyrate , Pivalic acid complex (II), chromium (II) laurate, chromium (II) stearate, chromium (II) pyrrole salt, and / or chromium (II) oxalate. A pyrrole-containing compound can be any pyrrole-containing compound that forms a chrome-pyrrole complex by a complex salt reaction. As used in this disclosure, the term "pyrrole-containing compound" refers to a hydrogen pyrrole salt, that is, a derivative of pyrrole (CaHsN), a hydrogen pyrrole salt , And gold pyrrole salt complex. &Quot; Pyrrole salt "(or" pyrrole "in the first state of the present invention) may be any compound containing a 5-ring, nitrogen-containing heterocyclic ring, such as a derivative of pyrrole, Materials, and mixtures thereof. Broadly speaking, the pyrrole-containing compound may be pyrrole and / or any heterolipid or homolipidic metal complex or salt, containing a pyrrole salt radical or a ligand. The pyrrole salt-containing compound can be definitely added to the reaction or generated in situ. In other words, the pyrrole salt-containing compound has 1 to about 20 carbon atoms in ruthenium per molecule. Examples of pyrrole salts (or pyrrole) include hydropyrrole salts (pyrrolates), derivatives of pyrrole, substituted pyrrole salts (or pyrrole I) * ^^^ (Please read the precautions on the back before filling out this page ) -11-The size of this paper method is applicable to the Chinese National Standard (CNS) A4il (210X297 mm) 83.3. 10,000 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention () slightly), lithium pyrrole salt , Sodium pyrrole salt, potassium pyrrole salt, pyrrole salt, and / or substituted pyrrole salt 'because of its higher reactivity and activity than other reactants. Exemplary substituted pyrrole salts (or pyrrole) include, but are not limited to, pyrrole-2-carboxylic acid, 2-ethynylpyrrole, pyrrole-2-carboxaldehyde, 2,4-dimethyl-3-ethylpyrrole, 3-acetylene -2,4-dimethylpyrrole, ethyl-2,4-dimethyl-5- (ethoxycarbonyl) -3 -pyrrole-propionate, ethyl-3,5-dimethyl- 2-Pyrrole-hydrochloride. When the pyrrole-containing compound contains chromium, the resulting complex compound may be referred to as a "chrome pyrrole salt". The best pyrrole-containing compounds for use in the triple-action catalyst system are selected from hydropyrrole salts, that is, pyrrole (C4H5N), and / or 2,5-dimethylpyrrole. Although pyrrole-containing compounds can produce catalysts with high activity and productivity, the use of pyrrole and / or 2,5-dimethylpyrrole can also produce catalyst systems with enhanced activity and selectivity for desired trimerization products, such as ethylene To '1 — trimerization of hexene * and reduced polymer production. The amidinoalkyl group, which was also earlier referred to as the activated compound, can be any heterolipid or isolipidaninoalkyl compound. One or more amidinoalkyl groups can be used. The ligands of the gold tincture may be aliphatic and / or aromatic. The ligand is preferably any saturated or unsaturated aliphatic radical. The amidinoalkyl group may have any number of carbon atoms. However, due to commercial availability and ease of rejection, metal alkyl groups generally contain less than about 70 carbon atoms per metal alkyl molecule, and preferably less than about 20 carbon atoms per molecule. Preferred aluminoalkyl groups include, but are not limited to, alkylaluminum compounds, alkylboron compounds, alkylmagnesium compounds, alkylzinc compounds, and / or lithium alkyl compounds. Exemplary gold alkyl groups include, but are not limited to, n-butyllithium, secondary butyllithium, triisobutyllithium, dimethylmagnesium, diethylzinc, triethylaluminum, -12-This paper size applies to Chinese national standards ( CNS) A4 specification (210X297 mm) 83. 3. 10,000 One 丨 installed-^ ---_-- order ----- ^ —line I (Please read the precautions on the back before filling this page) Economy The Ministry of Central Standards Bureau staff consumer cooperatives India policy A7 B7 V. Description of invention () Trimethyl aluminum, tertiary butyl aluminum, and mixtures thereof. The activating compound is selected from the group consisting of alkylaluminum compounds, derivatives of alkylaluminum compounds, halogenated alkylaluminum compounds, and mixtures thereof that do not hydrolyze * that is, without first contact with water, because of improved product selectivity, and improved .Good catalyst system reactivity, activity counter / or productivity. Exemplary compounds include, but are not limited to, triethylaluminum, tripropylaluminum, tributylaluminum, diethylaluminum chloride, diethylaluminum bromide, diethylethylaluminum, ethylsesquichloride, And their mixtures because of their optimal catalyst system activity and product selectivity. The best alkyl aluminum jb compound is triethylaluminum because of its catalyst system activity, product selectivity, and commercial availability. When the trimerization catalyst system is the desired product, at least one of the activated compounds must be a non-hydrolyzable alkyl aluminum compound, represented by the general formula A1R3, AU2X, AUX2, iUR2OR, AIRXOR, and / or AUR3X3, where R Is an alkyl group and X is a halogen atom. Exemplary compounds include, but are not limited to, triethylaluminum, tripropylaluminum, tributylaluminum, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum ethoxide, aluminum diethylbenzoate, ethyl Ethoxy aluminum chloride, and / or ethyl sesquialumina. For the above reasons, it is preferred that the activation compound of the trimerization catalyst system is a trialkylaluminum compound A 1R3. For these reasons, the most preferred trialkylaluminum compound is triethylaluminum. The formation of stable and active catalyst systems can occur in the presence of unsaturated hydrocarbons. As discussed in the specific examples above, unsaturated hydrocarbons may be present when chromium sources, the initial contact of the pika compounds and aurantyl groups, or when direct introduction of trimerization, low r, and / or polymerization reactors . In addition, one or more olefin reactants may be considered as unsaturated hydrocarbons. I--without winter; ,, order f. '纟 i (Please read the notes on the back before filling this page) -13-This paper size applies the Chinese national standard. ^) 8 4 specifications (210 乂 297 mm ) 83: 3.10,000

Patent Application No. 32 1 0 1 346 Chinese Revised Page (July 88) A7 B7 V. Description of Invention () Any unsaturated aromatic or aliphatic hydrocarbon can be used. Unsaturated hydrocarbons are preferably present in the reaction mixture at first, and denier aromatic hydrocarbons and / or ethylene are present at first, and it is best to produce catalysts with regard to activity and selectivity, and stable catalyst systems that are highly active. Unsaturated hydrocarbons can have any number of carbon atoms per molecule. Generally, because of commercial availability and ease of use, unsaturated hydrocarbons contain less than about 70 carbon atoms per molecule, and preferably less than about 20 carbon atoms per molecule. The unsaturated hydrocarbon is in a liquid state. In order to completely contact and mix the chromium salt, the compound containing lazier, and the metal base, it is preferable that the unsaturated smoke is liquid and / or dissolved. Exemplary unsaturated aliphatic hydrocarbons include, but are not limited to, ethylene, 1-hexane, 1,3-butadiene, and mixtures thereof. Exemplary unsaturated aromatic hydrocarbons include, but are not limited to, toluene, benzene, xylene, hexamethylbenzene, and mixtures thereof. In order to improve the stability of the catalyst system and the activity of the catalyst system, unsaturated hydrocarbons are better and the best unsaturated aromatic smoke is methylbenzyl, because it has the best stability and activity of the catalyst system. If unsaturated aromatic hydrocarbons are added to the gfj from the introduction of chromium compounds to trimerization, oligomerization and / or polymerization reactions, 'removal or removal of compounds in the introduction path to the reactor may improve catalyst + system activity and / or Product selectivity. The removal of unsaturated aromatic hydrocarbons can be accomplished by any method known in the art, such as flash evaporation or evaporation. The resulting product is a concentrated or saturated solution of the catalyst system of the present invention. When unsaturated aromatic hydrocarbons are removed before introduction into the reactor, the concentrated or saturated solution of the catalyst system of the present invention is soluble in trimerization, oligomerization, and _ 1 4 _ This paper size applies to Chinese National Standards (CNS) Α4 Specification (210X2S »7mm) IIII IJ— Seed clothing n ~~ Order ί (Please read the precautions on the back before filling this page) Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Α7 Β7 Central Standard of the Ministry of Economic Affairs Printing by Bureau staff consumer cooperatives V. Description of the invention () / or a solvent compatible with the co-processing process to improve the ease of processing the catalyst system of the present invention. In general, this solvent is the same as the reactor diluent. Preferred solvents include, but are not limited to, cyclohexane, isobutane, hexane, pentane, and mixtures thereof. The I reaction may also occur in the presence of a halide source, as the case may be. The presence of halide sources in the reaction mixture can increase the activity and productivity of the biocide system and increase product selectivity. Exemplary halides include, but are not limited to, gaseous, chloride, bromide, and / or iodide. Because of the ease of use and availability 1 Chloride. Better halide. Based on improved activity, productivity, and / or selectivity, bromide is the best halide. The halide source can be any halogen-containing compound. Fan Wang compounds include, but are not limited to, compounds of the general formula R »X„ t, where R is any fluorene and / or inorganic radical, X is a halide selected from fluoride, chloride, bromide, and / or Iodide, and m + η is any number greater than 0. If R is an organic radical, R has preferably about 1 to about 70 carbon atoms per radical, and most preferably has 1 to 20 carbon atoms per radical, Because of the best compatibility and catalyst system activity. If R is an inorganic radical, R is selected from the group consisting of aluminum, silicon, silicon, hydrogen, boron, lithium, tin, gallium, indium, lead, and mixtures thereof. Hold example compounds Including, but not limited to, dichloromethane, chloroform, benzyl nitrogen, tetra-silicon, tetra-tin (11), tetra-tin (IV), tetrachloride, boron trichloride, aluminum tribromide, trichloride Aluminium, 1,4-dibromobutene, and / or 1-bromobutene. In addition, chromium sources, amidino, and / or unsaturated hydrocarbons may be included and provide a halide * to the reaction mixture. Because Simple and compatible to use, and improved catalyst system activity and product selectivity, halide source is alkyl aluminum halide -15-Applicable to this paper size National Standard (CNS) A4 Specification (210X297 mm) 83. 3.! 0, 〇〇〇 (please read the note on the back and fill in the ft? Page) Central Bureau of Standards, Ministry of Economic Affairs, Shellfish Consumer Cooperative Printing A7 B7 V. Description of the invention () compounds and K alkyl aluminum compounds are preferred. Range M alkyl aluminum halides include, but are not limited to, diisobutyl aluminum chloride, diethyl aluminum chloride, ethyl Aluminum sesquichloride, ethyl aluminum dichloride, diethyl aluminum bromide, diethyl aluminum iodide, and mixtures thereof. When the trimerization catalyst system is the desired product, the reaction mixture contains a halide The source is better. In addition, the halide source is preferably selected from tin (IV) halide, halide, and mixtures thereof. The halide source is best mixed with the complex source and the pyrrole-containing compound before the metal alkyl group is added, that is, M The halide source pretreats the JS source and the pyrrole-containing compound to increase the productivity of the catalyst system. The children of each reactant used in the preparation of the trimerization catalyst system can be sufficient. The amount of trimerization as defined above. Usually In other words, in order to prepare a trimerization catalyst system, about 1 mole of chromium and chromium (Cr) may be in excess with about 1 to about 50 moles of a pyrrole-containing compound and about 1 to about 75 moles of aluminum. Unsaturated hydrocarbons are mixed. If a source of selective halide is present, usually about 1 to about 75 moles of halide element is present. Calculated by Cr element (Cr), about 1 mole and about 1 to about 15 moles Compounds containing pyrrole and about 5 to about 40 mols of aluminum, calculated as aluminum element U1), preferably mixed with the amount of unsaturated hydrocarbons. If a source of selective halide is present, it is calculated as halide element (X). About 1 to about 30 moles of halides are preferred. Calculated by the chromium element (Cr), about 1 mole of chromium and 2 to 4 moles of pyrrole-containing compounds and 10 to 20 moles of aluminum are used. Element (A1) calculations • Best in excess unsaturated hydrocarbon mixtures. If there is a source of selective halide, K halide element (X) is calculated to be 2--pack. ： Order | I line i (Please read the note on the back before filling this page) -16-This paper Α Applicable to China National Standards (CNS) Α4 specifications (210X297 gong) '~' 83. 3.10,000 A7 Consumption cooperation by employees of the Central Standards Bureau of the Ministry of Economic Affairs _B7_ V. Description of the invention () to 15 mol halogenated The best thing. An excess of the pyrrole-containing compound M does not improve catalyst system activity, productivity, and / or selectivity. Unsaturated hydrocarbons can improve catalyst system stability, activity, and / or selectivity. Excessive unsaturated hydrocarbons are harmful catalysts. System selectivity and / or activity. Too much aluminum alkyl can reduce catalyst system activity and product selectivity. Too little alkyl aluminum can cause incomplete formation of the catalyst system, which in turn results in low catalyst system activity * and increases formation of undesired polymerization by-products. Excess halide sources deactivate the catalyst system and thus cause reduced catalyst system activity. As mentioned earlier, the presence of a source of compounds increases catalyst system activity and product selectivity. According to the fourth aspect of the present invention, it is preferred that the pyrrole-containing compound and the metal source are present in the reaction mixture before the metal alkyl group is introduced. If this order of addition is followed, product selectivity and catalyst system activity and productivity can be produced1. In the absence of oxygen, it can deactivate the catalyst, and under anhydrous conditions, i.e. initially without water, the reaction occurs better. Generally, pressures ranging from about atmospheric pressure to about 3 atmospheres are acceptable. For ease of operation, atmospheric pressure is generally used. The reaction temperature may be any temperature. In order to carry out a more effective reaction, it is better to maintain the temperature of the reaction mixture in a liquid state for reasons of M. The reaction time may be any time required for the reaction to occur. The reaction can be viewed as a dissolution process; any time that can dissolve substantially all reactants is sufficient. The reaction time varies depending on the reaction temperature and pressure of the reactants. Generally speaking • Less than about ^ 1 day is not enough. Generally speaking, the reaction time is less than about 60 minutes. Under the optimal conditions, the response time can be from about 1 second to about -------- ji equipment ---- ^-order ----- 1 1 line- (Please read the note I on the back first (Fill in this page again.) -17-This paper size is applicable to China National Standard (0 Yang) 8 4 specifications (210 father 297 mm) 83. 3. 10,000 A7 B7 The invention description () 15 minutes. Longer times usually do not provide additional advantages and shorter times do not allow sufficient time for complete retort. The unevenness, that is, the supported catalyst system can be prepared in situ in the reactor by directly adding a solid support to the reactor according to the fourth state of the present invention. As mentioned earlier, Fan's catalyst supports include, but are not limited to, zeolites, inorganic oxides, either alone or in combination, phosphorylated inorganic oxides, and mixtures thereof. Particularly preferred are selected from the group consisting of silicon oxide, silicon oxide-alumina, vaporized aluminum, fluorinated aluminum oxide, silicified alumina, hafnium oxide, aluminophosphate, aluminum phosphate, phosphoric oxide sand, silicon oxide-titanium oxide, Co-precipitated supports of silicon oxide / titanium oxide, fluorinated / silicated alumina, and mixtures thereof, and one or more of these supports that may contain chromium are currently preferred. Currently the best catalyst support is aluminate salt because of its maximum trimerization activity • as disclosed in U.S. Patent Nos. 4, 3, 6, 4, 8 and 5. The in-situ preparation of heterogeneous catalysts for trimerization or oligomerization processes can reduce the formation of unwanted polymers. The heterogeneous trimerization, oligomerization, and / or polymerization catalyst system can also be used in accordance with this state of the present invention to form a catalyst system containing a source, a pyrrole-containing compound, an amidinoalkyl group, an unsaturated hydrocarbon, and an inorganic oxide. The reaction mixture was prepared as disclosed earlier. Optionally, as revealed earlier, halide sources can be added. The reaction stoichiometry and reaction conditions are the same as those disclosed in the second embodiment of the present invention. Regarding the inorganic oxide catalyst support * Any amount of chromium source is sufficient. However, usually about 5 grams less chromium pyrrole salt compound per gram of catalytic support is / sufficient. Use about 0.001 to about 0.01 to 0.5 grams of chromium pyrrole salt compound or source of chromium per gram of support to get the best support minus -18-This paper size applies to China National Standard Liang (CNS) A4 (210X297 mm) 81 3. 10,000 (please read the note I on the back before filling out this page) • Install --r ---- Order ----- ~. Line, Α7 Β7 Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs i 2. Description of the invention () The most effective use of the load and test m. The amount of the chromium pyrrole salt compound or the chromium source per gram of the support may be different but equivalent, such as the number of moles per gram of the support. In general, less than about 8.6 X 10-3 moles per gram of support is sufficient. For reasons of K, the use of about 1.7 X 10-β to about 1.7 X 10- 5 to about 8.6 X 10-4 moles of chromium per gram of support. And collected to recover the solid catalyst system product. The solid catalyst is generally kept under a dry, inert atmosphere to maintain stability and reactivity. My application 79106776, filed on August 14, 1990, describes polymerization catalysts and co-catalyst systems. * The co-catalyst includes the inventive compound of application 79106532, filed on August 7, 990. In general • Polymerization catalyst systems are considered to be chromium catalysts (also known as "Phillips catalysts") or titanium, zirconium, and / or vanadium catalysts. Any chromium catalyst system known in the art can be used. Commercially available chromium catalyst systems generally include chromium, at least a portion of which is hexavalent and supported on an inorganic oxide. Optionally, the polymerization catalyst system may further include a gold alkyl co-catalyst. Example chromium catalyst systems include, but are not limited to, those disclosed in U.S. Patents 3,837,494, 3,900,457, 4,053,436, 4,151,122, 4,294,724, 4,392,990, and 4,405,50 1. Any titanium-, hafnium-, and / or vanadium-containing catalyst system known in the art can also be used. Commercially available titanium-, rhenium-, and / or vanadium-based catalyst systems typically include transition gold 'rhenium halides, composites, and organic gold rhenium compounds. Example magnesium / neodymium catalysts include, but are not limited to, U.S. patents 4,394,29 1, 4,326, 988, -19-This paper size applies to the Chinese National Standard (CNS} M specifications (210 × 297 mm) 83. 3. 10,000 ----- -丨 Installation ------- Order ----- II line- (Please read the precautions on the back before filling out this page) Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Seal A7 B7 V. Invention Description ( ) And 4,347,158. The amount of novel trimerization and / or oligomerization co-catalyst system, including the chromium compound used as a co-catalyst in the present invention, may be any sufficient to produce a co-monomer that can be added to the polymer product. The chromium catalyst system prepared in various states of the present invention can be used as a co-catalyst with the titanium, junction, and / or vanadium catalysts discussed above. The metal source of the fourth compound of the present invention, and the pyrrole-containing compound, and Metal alkyl and unsaturated hydrocarbons are preferred methods to avoid isolating the first reaction product according to the method described in my above application .. In addition, the catalyst system produced by the method of the fourth aspect of the present invention has improved productivity and Desire Three Selectivity of the reaction product * For example, 1-hexene is prepared from ethylene. The polymerization reaction reactant can be used in the M catalyst system and the co-catalyst system and the polymerization reaction of the method of the present invention is a polymerizable olefin compound, that is, > Reacts with the same or other olefin compounds. The catalyst system of the present invention can be used to polymerize at least one straight or branched mono-1 -olefin having from about 2 to about 8 carbon atoms. Exemplary compounds include, but are not limited to, ethylene, propylene, 1 -Butene, 1-pentene, 1-hexene, 1-octene, and mixtures thereof. The catalyst system of the present invention can also be used to use about 2 to about 30 carbon atoms per molecule and have at least one fluorene. Oligomerization of difluorene olefins. Exemplary mono-olefin compounds include, but are not limited to, acyclic olefins, such as ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene , 1-hexene. *, 2-hexene, 3-hexene, 1-heptene, 2-heptene, 3-heptene, four n-octene, four n-nonene, and any of them-- ----- I 丨 Installation-- ·-^-Order ---- One-line- (Please read the precautions on the back before filling Page) -20-This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 83. 3.! 〇, 〇〇〇〇A7 B7 V. Description of the invention () What is a mixture of two or more. Exemplary olefins Compounds include, but are not limited to, 3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene. If branched and / or cyclopentadiene is used as the reactant, although it is not desired to be The theory is limited, but it is believed that the steric hindrance will hinder the trimerization. Therefore, the branch and / or the bark portion of the dilute hydrocarbon should be kept away from the carbon-carbon double hydrazone. As used in this disclosure, trimerization is defined as any combination of two, three, or more olefins, in which the number of olefins, ie, double bonds, is reduced by two. The reactants used in the trimerization method of the present invention are a) self-reaction, that is, trimerization, of olefinized foods to obtain useful products, such as ethylene, which can react with hexene and 1,3-butane 1,5 -cyclooctanediene by self reaction: and / or b) olefin compounds that can react with other olefin compounds, i.e. co-trimerization, to obtain useful products such as ethylene plus hexene One decene and / or 1-tetradecene can be obtained, and tri-polymerization of ethylene and 1-butene can be obtained by octene, and 1-tetradecene and / or can be obtained by tri-polymerization of 1-decene and ethylene. The co-trimerization of 1-icosadiene, or 1,3-butadiene and 1,5-hexadiene can give 1,5-cyclooctadecadiene. For example, three ethylene bills are printed on carbon-reducing polymers in the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. 3 three s in 1 bond number "using 30 chemistry, hydrocarbon suffix as the name of the alkene olefin polymerized to allylic olefin 3 2 single, olefin use covenant example, hexamethylation" Have vanene-sister here And with. The existence of B 1-The child is Yuan. Use the example of separation and combination to form a single bond for each compound,, the olefin poly- is a hydrocarbon diene diene pinene minus butyl combination _ mesh-olefination cyclic / 21 number, 3 diene olefin, and bond 1 octadiene is dilute by two I, including 5 oligocyclics. Three as for it, the meaning of 1 is limited, and the combined example is the intended one, but the other is the proper one, and the other two are used as the original package. (Please read the notes on the back before filling this page) This paper size applies to China National Standards (CNS) Α4 size (2 丨 0X297 male 4) 83. 3. 10,000 Ministry of Economic Affairs Central Standards Bureau, labor and consumer cooperation Du Yin Policy A7 ______. B7__, V. Description of the invention () Butan, 2-butene, isobutene, ι_pentene, 2-pentene, 1 ~ hexene, 2-hexene, 3-hexene, 1-heptene Ene, 2-heptene, 3 ~ heptene, four n-octene, four n-nonene, and any two or more mixtures thereof. Exemplary olefin compounds include, but are not limited to, 3-butadiene., Isoprene '1,4-pentane-dilute, and ι, 5-hexanedilute. If branched and / or cyclic dilute hydrocarbons are used as reactants, although not wishing to be limited by theory, it is believed that steric hindrance will hinder Trimerization. Therefore, the branched and / or cyclic parts of the olefin should be kept away from the carbon-carbon difluorene. The catalyst strips prepared according to the present invention are used as trimerization for trimerization. The system is preferred. Anti-membrane strip # The reaction product, that is, the terpolymer and / or polymer, can be used by the catalyst system of the present invention for solution reaction, slurry reaction, and / or gas phase reaction techniques. Using conventional devices and contact methods For preparation, the contact of the monomer with the catalyst system or with the polymerization catalyst system and the trimerization / oligomerization co-catalyst system can be achieved by any method known in the art of homogeneous (liquid) or heterogeneous (solid) catalyst systems. A convenient method is to suspend the catalyst in an organic medium and mix the mixture, and M will maintain the catalyst to a floating liquid during all trimerization, oligomerization, and / or polymerization processes. Other already used catalysts can also be used. Known contact methods, such as fluid bed, gravity suction bed, and fixed bed. A convenient method for the catalyst / co-catalyst system is to float the polymerization catalyst in an organic medium and mix the mixture. / Use and / or polymerization process to maintain the polymerization catalyst system into a suspension. Then add the co-catalyst system of the present invention. Polymerization | Packing: .-- Order ---- One—Line I (Please read the notes on the back before filling this page) -22-This paper size applies to China National Standard (CNS) Α4 size (210X297 mm) ~ ~ '83, 3. 10,000 A7 B7 V. Description of the invention () The chemical agent system and the co-catalyst system of the present invention can also be simultaneously fed to the polymerization reactor via one or more catalyst and / or co-catalyst feed streams. Better. In all of these catalyst systems, other contact methods can also be used, such as fluid bed, gravity suction bed, and fixed bed. The reaction temperature and pressure can be trimerized, oligomerized, and / or polymerized olefin reaction Any temperature and pressure. Generally, the reaction temperature is about zero. To about 250 t. The reaction temperature used is about 60. To about 200 t: The range is better, and the range from 80 ° to 1501 is better. In general, the reaction pressure is in the range of from about atmospheric pressure to about 2500 ps. The reaction pressure used is preferably in the range of about atmospheric pressure to about 1000 pSU, and most preferably in the range of 300 to 700 ps ig. Too low a reaction temperature produces too many undesired insoluble products, and too high a temperature causes decomposition of the catalyst system and reaction products. Too low a reaction pressure results in low catalyst system activity. Too high a pressure causes too many undesired products to be produced. Hydrogen may be added to the reactor as appropriate to accelerate the reaction and / or increase catalyst system activity. Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page). The catalyst system of the present invention is particularly suitable for trimerization and / or oligomerization. The slurry method is generally carried out in an inert diluent (medium), such as stone butterfly, cycloparaffin, or aromatic hydrocarbon. Exemplary reactor diluents include, but are not limited to, isobutane and cyclohexane. Isobutane reduces swelling of polymer products. However, the homotrimerization / oligomerization co-catalyzed II system is more stable in cyclohexane. Therefore, the preferred diluent for the homotrimerization or oligomerization method is cyclohexane and the heterotrimerization or oligomerization method is isobutane. When the reactant is mainly ethylene-23-This paper is scaled to the Chinese National Standard (CNS) A4 (2IOX297 mm) 83.3. 10,000 A7 B7 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs , Generally can be used in the range of about 0. To a temperature of about 300 =. When the reactant is mainly ethylene, a temperature in the range of about 60 ° to about 150 ° is preferred. Any amount of polymerization catalyst system and co-catalyst system can exist in the polymerization reactor, and M produces a polymer with desired optimum properties, such as density, high load melting index, and molecular weight. Generally speaking, up to about 40 parts by weight of support can be present for each part by weight of the polymerization catalyst system, that is, a heterogeneous co-catalyst system. Each part of the polymerization catalyst system is preferably about 1 to 25 parts, and each part of the polymerization catalyst system is preferably 3 to 15 parts by weight. M produces a polymer having the desired physical and processing characteristics. The olefins and / or polymerization products of the present invention have established applications in a wide range of applications, for example, as monomers for the production of homopolymers, copolymers, and / or terpolymers for use in cooking. The polymerized products of the present invention have established uses in a wide range of applications, such as polyethylene. A further understanding of the present invention and its advantages will be realized by referring to the following examples. Various abbreviations are used in the present disclosure and examples. Some of them include triethyl aluminum TEA, A1 (C2H5) 2; diethyl aluminized aluminum DEAC, (AUC2H5) 2C1); chromium 2-ethylhexanoate (II) is Cr (EH) 3, CrEH, CrEH3; Hydropyrrole salts are pyrrole, py, pyH, (C4H5H +); Acetyl propyl " acetic acid path (III4 is Cr (acac) 3, Cracac3, Cracac, Cr (C5H7〇2) 3; Chromium ( 111) Pyrrole salt gCrPy2, 24 -I n I-(n -I 士 K-In-nn IT _______ I ·, i ^ Business (please read the notes on the back * before filling out this page) The paper scale is applicable China National Standard (CNS) A4 Specification (210X297 mm) 83. 3. 10,000 Employees' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs printed A7 B7 V. Invention Description () [Na (C4Hlo〇2) 2] [Cr (C4H4N) 3Ci (C4H1002)], [Na (DME)] [Cr ("fUN) 3CI (DME)], [Na (DME) 2] [Cr (Py) 3Cl (DME)], product V, compound V; Tritetrahydrofuran chromated chromium (III) is CrCUTHF3, CrCl (THF) 3 ;. 2,5-dimethylpyrrole salt is hydrogen 2,5-dimethylpyrrole salt, (: 8 [^, 2,5-01 ^; Butene is C4 =; 1-hexene is Ce =; hexene is Ce =; octene is Ca =; decene is C1〇 =; dodecene is (: 12 =; tetradecene is Cl4 =. Officer Example T — 100th: 0.14 grams (0.29 millitorles) of 2-ethylhexanoic acid complex (III) (CrEH3), [Cr (CaH15〇2) 3], weighed in a 25b1 pressure tube. Tube M Self-sealing crown cap seal. 0.062 ml (0.89 mmol) of PyH [C4NH5] and cyclohexane as a diluent are added via a syringe to form a solution. Its volume is approximately 8 ml. 0.9 ml Triethylaluminum (TEA), [A1 (C2H5) 3] in heptane 1.1 > 4 solution (0.99 mmol), and 0.9 1111 equal parts of £ 113 / 卩 7 [1 solution in countercurrent ethylene ( Under CP grade), a one-liter hot-pressurized reactor containing 300 mL of cyclohexane was added to form a catalyst system. The reactor was sealed and ethylene addition was stopped * until the reactor temperature reached a reaction temperature of 80t. The ethylene pressure was increased to 550 psig The total reactor pressure. Ethylene was then fed for 30 minutes. At the end of the process, a sample of the liquid reverse product mixture was taken and analyzed by capillary gas phase layer analysis. The remaining reaction product mixture was evaporated and the amount of solid product was determined. The results are summarized in Table I below. ------- 1 I Pack-«----- Order ----- ^ —Line- (Please read the note on the back before filling this page) -2 5-This paper Α Degree applies to China National Standard (CNS) A4 specification (210X297 mm) 83.3.! 〇, 〇〇〇 _____ B7 V. Description of the invention () No. 100? [5 {Follow the steps described in No. 1001, except for 8 mi Add TEA to a 1.1 »solution of heptane (8.8 millimoles) and directly add 〇 £ 3 / 卩 7 (^ solution to form a solution (缌 volume 10ml) instead of to the reactor. 0.7 ml aliquot, CrElfU / The pyH / TEA solution was added to the autoclaved reactor. No additional TEA was introduced into the reactor. The results are summarized in Table I below. The 100th round was performed according to the procedure described in the 1002th round, except that 0.10g (0.29 mmol) was used. The acetylene-propionate (II) is (C racac 3), [Cr (C5H7〇2) 3] is substituted for CrEH3, and 6 ml of Cracac3 / PyH / TEA solution is used to form a Crac3 / PyH / TEA solution (absolute volume 8 ml). 1.1 ml (6.6 millimolars) of TEA in heptane. An 1.4 ml aliquot of Cracac3 / PyH / TEA solution was added to the autoclave reactor. The results are summarized in Table I below. The first 004 side is described in the first 1001 session. Except for 0.9 ml of diethyl chloride (DEAC), [iUCl (C2H5) 2] was added to CrEH3 / PyH solution M in hexane 11 < solution (0.9 millimolar) to form a CrEH3 / PyH / DEAC solution. 0.65ml aliquots of CrEH3 / PyH / DEAC solution and 0.9 TEA in ml was added to the autoclave reactor in a 1.1 M solution of heptane (0.99 mmol). The results are summarized in the table below. It is printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. Page) I. m 1 ο 〇b rsi According to the procedure described in the first 1001 round, except that 0.9 ml of a 1M solution of DEAC in hexane (0.9 mmol) was added to a CrEH3 / PyH solution, and the resulting C "EH3 / The PyH / DEAC solution is aged at ambient temperature and pressure for 1 day. -26- This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 83. 3. 10,000 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 Five 'invention description () 0.65ml aging CrEH3 / PyH / DEAC solution + 0.9 ml of TEA in heptane 1.1M solution (0.99 millimolar) was added to the autoclave reactor. The results are summarized in Table I below. No. 100fi 制备. Follow the steps described in No. 1001 to prepare a solution except 0.13 ml of pyrrole. In addition, a 1.0 M solution of DEAC in hexane in 0.1 M (0.1 mmol) and TEA were added to the reactor. Use 0.9 ml aliquots of the C "EH3 / PyH solution. The results are summarized in Table I below. Section 1007: Follow the procedure described in Section 1003, except for using 3 m of TEA in Mebenzine's 1.9M solution (5.7 mmol) Ear), and M toluene replaced the cyclohexane diluent when a CrEH3PyH / TEA solution was formed. Therefore * there was an excess of toluene in the reactor. Use 0.9 ml aliquots of CrEH3 / PyH / TEA solution. The results are summarized in Table I below 1008 冋 According to the procedure described in the 1002th round, except that K (0.10s) chromium (III) pyrrole salt (Cr / Py3), [Cr (C4H4N) 3ClHa (C4H1〇02) 3] (0.17 mmol) are replaced 〇 £ 113, and the solution was prepared using 0.041111 (0.52 mmol) and 7 [1 and 3.5 ml of TEA in 1.1 ml (3.85 mmol) of heptane. The final solution volume was about 5 ml. Use 1.0 ml aliquots CrPy3 / PyH / TEA solution. The results are summarized in the following table I. W, 1 QQC) [6! Follow the steps described in Chapter 1008, except that 1.8 ml of TEA is used in a benzyl 1. ^ solution (3.85 Millions of moles), and the formation of 〇 73 /? ^ / Has been 8-27 -27- This paper A degree applies the Chinese National Standard (CNS) A4 specifications (210X297 mm) * 83, 3. 10,000

In 1 ^ 1 In n if -IJ ^ in ^ J.-n ^ i--. 1 mw I one i (please read the precautions on the back before filling in this copy) A, 7 ______ ^ 7___ — V. Description of the invention () M toluene replaces the cyclohexane diluent in the solution. Therefore • Excess toluene in the reactor. Use 1.4 ml aliquots of CrPya / PyH / TEA solution. The results are summarized in Table I below. No. 10 1 Please-Follow the steps described in No. 1008. • Except that no pure PyH was added during the preparation of the CrP ^ / TEA solution. A 1.4 ml aliquot of CrPys / TEA in cyclohexane was used. The results are summarized in Table I below. Side 1011 Follow the procedure described in Step 1009, except that no pure PyH was added during the preparation of the CrPy3 / TEA solution. Use a 1.4 ml aliquot of CrPys / TEA in toluene. As a result, the reactor was in excess. The results are summarized in Table I below. ------- y I installed -------- Order ----- 1 — line (Please read the precautions on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs The size of the paper is applicable to the Chinese standard (CNS) A4 (210X297 mm) 83.3.10,000 V. Description of the invention (S0 ^ ski 谳 ^ 7 ^^ 03 A7 B7 τ > τ Ην τ Ην τ > Ην Ην Τ τ & gt τν-τ > τ > τ > τ > ι > ι > τ > τ > τ Ην τ > ~ ι "ς 9 9 8 ε ε τ > 9 9 Η τ τ τ > η τ 9 τ τ 2: 9 π ”Δ6 -26 5 as s ~ · 8 s, s' 98. I 88 18 Z.9 ·, αυ, Ηΐ Ην Ην Η Η Ην Ην Ην Zn Η 1Μα Swallowing & swallowing-1M ^ .s ° 1 door τ τ > S ζ ε 9 door ζτ 9 86 LS 66 66 < 0 ^ 86 S6 86 S Β8 τ 6 9 0 6 8 τ 8 ° s ° T 68 one-p inch-ω- ------ --- Packing :: ----- Order ----- One: Line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 垲 ο 0-1 ϊ »〇ΟΟ S: One (δ)-" οοεη οοτ, Δ οοτ, acridine οε, 8 00Sη οοο'ετ 000, 9 (ν OO ^ ST 'orsa: 0〇8β-^-0〇0 -ττ 9 96 τ Μ s τ Η τ Η 2: ο Η ττοτ οτοτ 60s 8001 /.οοτ SS ςοοτ SOT SOI ss Vboi: i. -29 The paper's wave scales are in accordance with Chinese national standards ( CNS) A4 specification (210X297 mm) 83. 3. 10,000 Α7 Β7 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention () All the rounds mentioned above were performed using different chromium compounds against different aluminum alkoxides. These reactions are performed in a single step. S_ @ LL1 It should be noted that the results from Table I of Example I and the results from Table II of Example tt are not directly compared because the reactions are in different reactors and in different Under the conditions, the use of different ethylene and cyclohexane feeds and the use of different diluents. However, direct comparison within each example can be performed. 箪 2001 to 0. 30 g_ (0.62 mmol) 2- Ethylhexanoic acid complex (III) (C r E Η 3) (10.15% by weight C r) and 0.1 2 m 1 (1. 73 mmol) pure pyrrole (PyH) in 10 ml Toluene was mixed. Add 2.8 m of a 1.9 M triethylaluminum (butadiene) solution (5.32 mmol) to toluene, and the [113 /? 7 [1 / butylene 4 solution under dry nitrogen at ambient temperature and pressure Stir for 30 minutes. "Dark brown CrEH3 / PyH / TEA was filtered and vacuum removed to remove excess toluene, which formed 1.0 ml of a dark brown oil * as a catalyst system. 0.5 ml (0.15g CrEH3; 5.2mgCr) of the catalyst system, and 4.0 The nonane of π 丨 (the standard in the reactor) was added to a 2 liter autoclaved reactor containing 1.2 liters of cyclohexane under countercurrent ethylene. The reactor was then pressurized with ethylene to 550 psig and fed with ethylene. The reaction was allowed to proceed for 30 minutes. The results are summarized in Table E below. In 2002, the procedure described in 2001 was followed: in addition to the CrEH3 / PyH / TEA solution M, Λ was added; diethylaluminum chloride. 0.53 g (1.10 mmol) Moore) of 0 £ 113 (10.15% by weight (: 1 ') and -30- This paper size applies to China National Standard (CNS) A4 (210X297 mm) 83. 3. 10,000 (Please read first Note for the back to fill in this page) -7 —Packing ------ Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description () 0.52ml (7.5 millimoles) pure PyH in 15ml of toluene was mixed and stirred for 5 minutes. 0ml of 1.9M TEA (1,1 mmol) was added to the solution of methylbenzyl, and CrEH3 / PyH / TEi was dissolved. Under dry nitrogen, search and stir at ambient temperature and pressure overnight. Excess toluene was removed by vacuum to form a dark brown. The color solution was removed, and it was 2.5 ml of dark brown oil, 0.5 ml (10.8 mg; 0.21 mmol) Ear dark brown oil mixed with 1.0 ml of 0.87M (0.87 mmol) diethylaluminum chloride (DE AC) solution in nonane, and

The CrEH3 / PyH / TEA / DEAC solution was stirred under dry nitrogen at ambient temperature and pressure overnight. The resulting product was used as a catalyst system and 4.0 m I of nonane (standard in the reactor) was directly charged into a 80 2 liter autoclaved reactor containing 1.2 liters of cyclohexane. The reactor was then pressurized to 550 psig with ethylene, and the reaction was carried out for 30 minutes. The results are summarized in Table I below. 2003 冋 0.33 g (0.68 mmol) of CrEH3 (10.15 wt% Cr) was mixed with 0.13 ml (1.87 mmol) of pure PyH in 10 ml of methylbenzine and mixed for 5 minutes. Add 1.9 ml of a solution of 1M DEAC (1.9 mmol) in hexane, and stir the CrEH3 / PyH / DE / \ C solution under dry nitrogen at ambient temperature and pressure for 30 minutes to form a light / green solution. . Add 5.1 m [of 1.9M diethylaluminum chloride (DEACM9.7 millirales) to methylbenzyl solution and stir the CrElU / PyH / TEA / DEAC solution for 0.5 hours to form a dark yellow / brown solution. Excess toluene and hexane are removed under vacuum and removed from dark yellow / brown CrEfU / P / H / TEA / DEAC solution, leaving dark yellow / brown oil. Dark yellow / brown oil is dissolved in cyclohexane and added to a volume of 25 ml, and used as -31- This paper size applies to China National Standard (CNS) A4 (210X297 mm) 83.3.! 〇, 〇〇〇I— I 1. Λ— fl ^ i 11-1 — ^ n ^ J- [I ----.. Ί f hair tf, please read the note of back xenon before filling this page) A7 Economy Printed by the Central Standards Bureau of the Ministry of Labor and Consumer Cooperatives B7_V. Description of the invention () is the catalyst system (.32mgCr / ml). Under countercurrent ethylene, 7.0 ml (9.2ragCr; 0.178 millimolar Cr) of the catalyst system and 4.0 ml of nonane (standard product in the reactor) were directly charged into a 80t: 2 liter autoclaved reactor containing 1 . 2 liters of cyclohexane. The reactor was then added with ethylene to 5 50 Psis, and the reaction was carried out by feeding ethylene. The results are summarized in Table I below. ^ 2Q04 151 Follow the steps described in 2002. • Except for diluting pr E Η 3 / P y H / TEA / DE i \ C solution * in K cyclohexane before loading into the reactor and before the M ethylene pressurized reactor Hydrogen (H2) (50 psig) was added to the reactor. 0.30 g (0.62 mmol) of CrEH3 (10.15% Cr) was mixed with 0.12 ml (1.73 mmol) of pure PyH in 15 ml of toluene. Add 1.7 ml of a 1M solution of DEAC (1.7 mils) in hexane, and the 'CrEH3 / PyH / DEAC solution was stirred under dry nitrogen at ambient temperature and pressure for 5 minutes. Add 1.8 ml of a 1.9M TEA (3.42 mmol) solution in toluene, and stir the CrEH3 / PyH / DEAC / TEA solution under dry nitrogen at ambient temperature and pressure for 30 minutes. The dark brown solution formed was filtered and excess methylbenzyl-hexane was removed by vacuum removal. It produced 0.8 nl of a dark yellow / brown oil and was used as a catalyst system. Under countercurrent ethylene, 0.4 ml (15.2 mgCr; 0.29 millimolar Cr) of the catalyst system and 4.0 ml of nonane (standard in the reactor) were directly charged into a 2 liter autoclaved reactor of δOP, which Contains 1.2 liters of cyclohexane. 50 psig of hydrogen (H2) was added to the reactor, and then MZ / ene was added to 55 ipsig. Feed ethylene and perform reverse g for 30 minutes ------- ^ 1 pack -----: --- order ----- ^. Line I (read first read the back &-note of the "item again (Fill in this page) -32- This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297mm) 83. 3. 10,000 V. Description of invention () A7 B7 Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs The results are summarized in Table I below. The 2.0 side was in a 500 ml Schlenk flask, 1.98 g (3.4 mmol) of CrPy3 (11.1 wt% Cr), 40 ml of methylbenzyl and 54 ml of 1.9M TEA (1.026 mmol) in nail Mix the stupid solution. The resulting dark brown reaction mixture was stirred under dry nitrogen 'for 1 hour at ambient temperature and pressure. The excess toluene was removed under vacuum, which resulted in 13 ml of a dark yellow / brown oil and a small amount of light colored precipitate. The dark yellow / brown oil was separated, collected from the precipitate with a syringe, and used as a catalyst system. 2.0 m 1 of catalyst system K 2 7 m 1 of cyclohexane was diluted, and before use, it was aged for 3 days at ambient temperature and history under dry refining nitrogen. Under countercurrent ethylene, 8.0 ml (9.3 ms; 0.18 millimolar Cr) of the catalyst system / cyclohexane solution and 4.0 ml of nonane (standard in the reactor) were directly charged into 80X: 2 liters of autoclaved reaction Device containing 1.2 liters of cyclohexane. The reactor was then pressurized to 550 psig and fed with ethylene for 30 minutes. The results are summarized in Table I below. Side 200R Follow the steps described in chapter 2005, except that fewer reactants are used and shorter aging times are used. In a 500 ml Schlenk flask, 0,25 g (0.432 mmol) of 0? 3 (11.1% by weight) with 1'1111 methylbenzyl and 3,4 1111 1. ^^ TEA (6 45 millimoles) and mixed with a stupid solution. The resulting dark brown reaction mixture was stirred under dry nitrogen at ambient temperature and pressure for 30 minutes. Pass 33- This paper is suitable for Chinese National Standards (CNS) (21 {) > < 297 Publication 83. 3. 10,000 (read the necessary precautions before filling in this page) -° Line A7 B7 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the Invention () The amount of Jiaben was removed by vacuum removal, which produced a dark brown oil. All dark brown oil, M cyclohexane, was diluted to 25 ml of stilbene, resulting in a solution containing 1.11 msCr / ml, which was used as a catalyst system. Under countercurrent ethylene, a catalyst system of 8.0 m 1 (8.88 mg; 0.11 mmol, mole Cr) / cyclohexane solution and 4.0 ml of nonane (standard in the reactor) Product) directly into 80t: 2 liter autoclave reactor • It contains 1.2 liters of cyclohexane. The reactor was then pressurized with K ethylene to 550 psig and fed with ethylene for 30 minutes. The results are summarized in Table I below. No. 2007 is the same as the procedure described at No. 2005, except that Jiaben exists in the trimerization reactor. In a 500 ml Schlenk flask * 1.98 g (3-4 millitorles): CrPy3 (11.1 wt% Cr) was mixed with 40 mL of methylbenzyl and 54 ml of 1.9MTEA (102.6 milliers) in methylbenzyl solution. The resulting dark brown reaction mixture was stirred under dry nitrogen at ambient temperature and pressure for 1 hour. Excessive methylbenzyl was removed by vacuum removal, which produced 13 ml of dark yellow / brown oil and a small amount of light-colored precipitate. Separated dark yellow / brown oil. M syringe was collected from the precipitate and used as a catalyst system. 2.0 ml of the catalyst system M27inl was diluted in cyclohexane and aged for 3 days at ambient temperature and pressure under dry nitrogen before use. Under countercurrent ethylene, 0.5 ml '(8.5ms; 0.163 millimoles) of the catalyst system / cyclohexane solution, 4.5 ml of toluene and 4.0 ml of nonane (standard product in the reactor) were directly charged into 80t : 2 liter autoclave reactor, -34- This paper size adopts China National Standard (CNS) A4 specification (210X297 mm) 83. 3.10,000 H-nnn-| ~ II— —I ----- (Please read the notes on the back * before filling out this page) —Order ----- {line description instructions issued, five

A B

Ethylene M is added to the pressure. After the clock, the splitter 30 should be reversed. Ethane into hexane and ethylcyclohexene in liters and feed 2 1: 1 --- 8 containing i

Under the MI table, Nagui 31 / knot 0.28 g (0.802 mmol) of Cracac3 and 0.17 ml (2.45 mmol) of pure pyrrole were mixed in 10 ml of methylbenzyl and stirred under dry nitrogen at ambient temperature and pressure. 5 minutes. Then add 6.3 ml of 1.9M TEA (12.0 mmol) to methylbenzyl solution. The resulting dark brown reaction mixture was dried under dry nitrogen: F, and stirred at ambient temperature and M force for 30 minutes. However, Jiaben was removed by vacuum removal, which produced a dark yellow / brown oil. All dark yellow / brown oil M cyclohexane was diluted to a total volume of 25 ral to produce a solution containing 0.0112 g Cracac3 / ml, which was used as a catalyst system. Under countercurrent ethylene * 7.0 ml (15.2 mg; 0.293 millimolar Cr) of catalyst system / cyclohexane solution and 4.0 π > of nonane (standard product in the reactor) was directly charged into 80t of 2 Litre autoclave reactor * which contains 1.2 liters of cyclohexane. The reactor was then pressurized with ethylene to 550 psig * and fed with ethylene for 30 minutes. The results are summarized in Table E below. Flute 2009 follows the procedure described in 2008 * except that chromium (III) naphthalate is the source of chromium. 0.33 g (0.508 mil) of CrNaoth3 (8,0% by weight Cr) was mixed with 0.112 ml of pure pyrrole to 10 ml of toluene, and under dry nitrogen at ambient temperature and pressure Stir for 5 minutes. Then add 4.6 -3 5-^ [^^ using China National Standard (CNS) A4 specifications (210X297 ^ * 1 83: 3: 10,000 ------- Calling-installing-;-.-Ordering- ---- j Line I (Please read the argon note on the back before filling out this page) Printed by the Consumers 'Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economics Printed A7 ___B7 V. Description of Invention () ml Solution of 1.9M TEA (8.74 millitorles) in methylbenzyl. The resulting dark brown reaction mixture was stirred at ambient temperature and pressure for 30 minutes under dry nitrogen. The excess toluene was removed by vacuum removal, which resulted in a dark yellow / Brown oil. All dark yellow / brown oil K cyclohexane was diluted to 25 ml of carcass. The product was produced as a solution containing 1.056 mgCr / ml, which was used as a catalyst system. Under countercurrent ethylene, 7.0 ml (7.39 mg ; 0.142 millimolar C ") of the chemist system / cyclohexane solution and 4.0 π» 丨 nonane (standard product in the reactor) directly into a 30T: 2 liter autoclaved reactor, which contains 1.2 liters The "cyclohexane" reactor was then pressurized to 550 psig of ethylene and fed with ethylene for 30 minutes. The results are summarized below Table 2. The steps from 2010 to 2010 according to the 200δ round, except that the chloride (III) chloride was used as the source. 0.4 1 g (1.09 mmol) of C r CI 3 THF 4 and 0.2 3 in i (3.3 2 millimoles) of pure pyridine 10πιΙ toluene was mixed and stirred under dry nitrogen at ambient temperature and pressure for 5 minutes. Then 8.6 ml of 1.9MTEA (16.3 millimoles) was added. Solution in methylbenzyl. The resulting dark brown reaction mixture was stirred under ambient nitrogen at 30 ° C and ambient temperature for 30 minutes. Excess methylbenzyl was removed by vacuum removal, which produced a dark yellow / brown oil. Add 7.5 of nonane Dark yellow / brown oil and the resulting solution was diluted with cyclohexane to a volume of 25 nii to produce a solution containing O.OlSAgCrCUTHF ^ ml. The solution was passed through and the passivation was used as a catalyst system. Next, 5.0 ml (11.38 rag; 0.219 milliohms) I * Package-'Order I' line t (Please read the note of the descendants before filling in this page) -36- This paper is a standard of ϋ 财 S ® Furniture Standards (CNS) A4 * i # · (published by 2ΙΟχ297) 83. 3. 10,000 Α7 Β7 Staff Consumer Cooperation of Central Bureau of Standards, Ministry of Economic Affairs Newsletter of the Fifth, the description of the invention () catalyst system / cyclohexane / nonane solution and 2.5 ml of nonane (standard product in the reactor) is directly charged into a 2 liter autoclaved reactor at 80 = C, which contains 1.2 liters of cyclohexane. The reactor was then pressurized to 550 psig and fed with ethylene for 30 minutes. · Results are summarized in Table I below. Section 201 1 冋 Follow the procedure described in Section 2005 except that M excess hexane was stored in the trimerization reactor. In a 500 jl marinated cold gram flask * 1.98 g (3.4 mmol) of C r P y 3 (11.1% by weight C r) with 40 m 1 of toluene and 54 m 1 of 1.9 TEA ( 102.6 mTorr) in toluene solution. The resulting dark brown reaction mixture was stirred under dry nitrogen for 1 hour at ambient temperature and pressure. The excess toluene was removed by vacuum removal, which produced 13m 丨 dark yellow / grass oil 1 and a small amount of light color sedimentation * 2. The dark yellow / brown oil was separated, and the M needle was collected from the sinking forging and used as a catalyst system. The 2.0 ml catalyst system was diluted with 27 ml of cyclohexane and aged for 3 days at ambient temperature and pressure under dry nitrogen before use. Under countercurrent ethylene, 1.0 ml (16.9 mg; 0.325 millitorr Cr) of the catalyst system / cyclohexane solution, 55 ml of 1-hexane and 4.0 ml of nonane (standard product in the reactor) were directly charged The 801 2 liter autoclave reactor contains 1.2 liters of cyclohexane. The reactor was then pressurized to 550 psig with ethylene and fed with ethylene for 30 minutes. The results are summarized in Table I · below. flute? 0 1 2 冋 -37- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 83. 3. 10,000 I------I »1 ·-I • Mc / v-I-. 1 I! I-II]. \ —R--II!, 1 _ I-(Please read the note on the back first, and then complete this education) A7 B7 V. Description of the invention () According to the 2005 report Except that K complex (11) pyrrole salt (compound I) is chromium source 3 0.30 g (0.85 mmol) of compound I (CrPy10THFA) and 10 ml of methylbenzyl and 6.7 ml of 1.9H (12.7 mmol) Ear) TEA. Mix in methylbenzyl solution. The resulting dark brown reaction mixture was stirred at ambient temperature and pressure for 30 minutes under dry nitrogen. Excessive methylbenzyl was removed by vacuum removal, which produced a dark yellow / brown oil and a small amount of light-colored precipitate. Separate the dark yellow / brown oil from filtration and dilute the cyclohexane to a volume of 25 nl to produce a solution containing 0.012 g of compound I (CrPy10THF4), which is used as a catalyst system. Under countercurrent ethylene, 7.0 ml The catalyst system / cyclohexane solution and 4.0 m of nonane (standard product in the reactor) were directly charged into a 2 liter autoclaved reactor at δ0 ° C, which contained 1.2 liters of hexane. The reactor was then pressurized to 550 psis with ethylene, and reacted with ethylene for 30 minutes. The results are summarized in the following table ϋ. ------- j --install --Γ ----- order ----- 1 -line I (please read the note t on the back before filling in this page) Staff Consumption of Central Bureau of Standards, Ministry of Economic Affairs Printed by the cooperative-38- 83. 3.10,000 This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7B7 V. Description of the invention () til of, αϋΤ οτ Ην Ην τ > τ > τ > τ > τ > Ην τ > ς τ > 9 ς 9 π Γ LC ς c 6 ττ ζ τ τ c τ es τ 6

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Is. 008, B0: 5.8τ: ζ: τ 0 00Ί ο: 〇: οε: τ; δ 000, a ο: ςτ: ε: ooi's !; ο .000, Δτ ο οοττο 008οτ 〇00901 ο: οε: ε : τ 1 .-. 00 6, π ΓΓ: 9: ε: τ '-00' " ε: ςΗ: ε: τ--οοϋβϋτ: /.:-! ° 00-0: 6: ε ”τ ST on on OH NTS Η ct ττο01 ττ οτοε Γ 60ο01 ττ SON ^ SOS Γ 9002 Γ SON ς τ SS ^ ηοοζ 6, SOZ / ς τ τοοζ -3 9-This paper size applies the Chinese National Standard (CNS) A4 (210X297 mm) 83. 3. 10,000 ^ —install ------- order ----- j ·, line- (Please read the cautions on the back before filling in this page) A7 B7 V. Description of the invention () The 2000 The series is carried out using different chromium compounds and different aluminum alkyls, but in different reactors. The performers are also aware of the preferred aspect of the present invention, that is, the methyl group is removed at least before polymerization.

The Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs printed 0.21 grams (0.601 mmol) of Cracac3 with 0.12 ml (1.73 mmol) of pure pyrrole (PyH) and 15m of methylbenzyl. Stir for 5 minutes at ambient temperature and pressure. Then add 6.0 b 1 to 1. 9 M TEAU (1.4 mmol) to methylbenzyl solution. The resulting dark brown reaction mixture was stirred under dry nitrogen at ambient temperature and pressure for 5 minutes. Then, add 2.0 g of aluminum phosphate support (0.4 P / A1 mole ratio, activated at 70 (Π)) in accordance with U.S. Patent 4,364, 855 (1982), which is hereby incorporated by reference. And the resulting slurry was stirred for about 12 hours. Produced by filtration and collected, M 10ml aliquots of toluene-pentane were washed at least twice until no color was observed in the filtrate and dried in vacuo. The dried product was used as Solid weight supported catalyst system. 2.1022s of equal weight solid catalyst system under countercurrent ethylene was added to a 1 liter autoclave containing 1 liter of isobutane. Before loading the catalyst, 0.25ml of 16.5% by weight TEA in The nonane solution is added to the reactor, and M neutralizes any ethylene feed toxins that may be present. The reactor is sealed and the ethylene addition is stopped until the reactor temperature reaches the desired process temperature, such as 90 ° C. The ethylene pressure is then increased To 550 psU, feed ethylene for a reaction time of 30 minutes. At the end of the process, a sample of the liquid reaction product mixture was collected and analyzed by gas chromatography. The remaining reactor mixture was evaporated and the amount of solid product was determined.涑 The scale is applicable to China National Standard (CNS) A4g (210X297mm) 83.3. 10,000 (Please read the precautions on the back before filling this page) —Installation ------- Order ----- 1, line- ---- Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, printed A7 B7 V. Description of the invention () The results are summarized in the following table BI. Question 3002 Q According to the steps described in the 3001 round, except for aluminum phosphate-free Diethylaluminum chloride and TEA were added to Craca3 / PyH dissolved @ d 0.21 g (0.60 mmol) and Cracac3 was screwed in a 30ml screw cap before oxygen was added; ^, j, bottle weighed. Add 0.12ml (1.73 milli-ears) PyH and 15 ml methylbenzyl, and a solution was formed. # Cover and soak for 5 minutes. Then, while stirring continuously, add 6.0 ml of 1.9M TEA (11.4 mmol) to Jiabenzhi Solution. 〇3〇3 < 3 /? 7 [1 / 了 £ & solution stirred for 5 minutes, add 2.4111 丨 1 «DEAC (2.4 mmol) in hexane solution and C" acaC3 / PyH / TEA / DEAC toluene solution was stirred for 5 minutes. Add Ren Yi according to US Patent 4,364,355 (1982), incorporated herein by reference, and prepared 2.0 grams of aluminate support (0.4 P / A1 mole ratio , Activated at 7001) and The slurry was stirred for about 12 hours. It was collected by filtration, washed with 10 ml aliquots of methylbenzyl and pentane at least twice until the color was not observed in the filtrate, and dried under vacuum. The dried product was used as Solid-state, supported catalyst systems. 0.50 48 s equal-weight solid-state catalyst systems are fed with a 2 liter autoclave containing 1 liter of isobutane under countercurrent ethylene. Prior to loading the catalyst, '3.0 ml of a 1.6 wt% TEA in oxane solution was added to the reactor' to neutralize any ethylene feed toxins that may be present *. The reactor is sealed and the & M addition is stopped until the reactor temperature reaches the desired process temperature, such as 90 ° c ° -41 "-一 I 装 --.--.-- Order ----- 1 ' Line {(read the cautions on the back first and then fill out this page) This paper wave is again applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 5. Description of the invention () The ethylene pressure was then increased to 550 psig and the ethylene was fed for a reaction time of 30 minutes. At the end of the process * a sample of the liquid reaction product mixture was collected and analyzed by gas chromatography. The remaining reactor mixture was evaporated and Measure the amount of solid products. The ethylene consumption is determined by calibrating the flow meter. The results are summarized in the following table m. W. η Ο. Η 3 is used as the source of chromium, and no aromatic solvent is used in the preparation of the catalyst system. The support catalyst system is also prepared in situ in the reactor. 0.33 g (0.69 mmol) of 16 ml of pentane is mixed. CrEH3 with 0.26ml (3.75 mmol) PyH and dried before use. Aging under ambient temperature and pressure for 4 days. Under countercurrent ethylene, the ambient temperature will be in accordance with US Patent 4,364,855 (1982), incorporated herein by reference, and 0.49 g of aluminate support ( 0.9 P / A ratio, at 700 t: activated) A solution of TEA in hexane was charged into a 2 liter autoclave reactor. Then 1 liter of hexane, 2.1 ml (4.32 μg; 0.083 milliliter) Mol (Cr), CrEH3 / PyH solution, and 50 psig of hydrogen (H2) into the reactor. The results are summarized in the following table m. In this 3000 series, the catalyst is supported on the inorganic oxide support, but The catalysts for the 1000 and 2000 series are unsupported. -42- This paper is suitable for the China National Standards (CNS) Congxie (21Qx297 Public Manager 83. 3.10,000 -------,-installed -.. (Please read the precautions below and fill out this page)

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T9 s 9L 16fir ~ w After one system, "19J% 1M more-¢ 1 ^ /-^ .: ετ Η 8Τ Employee consumption cooperation of the Central Standards Bureau of the Ministry of Economy Du Yin 褽 (" s_ υ, ι ^ ίit '¥ _n 3 ) si molybdenum _-s5 〇ςς '0: 9 ·: 5 · S: T 1,92s · cooc 5 < ^ C ^ >: 6T: C: T: sss_o SOC ε (Ν < Ν_, οτΙΝ '---CNsrH- 二 οοε ^ 1¾ ^ ¾¾to g ^ l ^^ KsaK-^^ · N and §2 3 ref. 1 & 7 -------- f I 装- , ----- Order ----- 1-Line i (Please read the precautions on the back before filling out this page) -43 This paper size applies to China National Standard (CNS) Α4 specification (210X297 mm) 83.3 10,000 A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the Invention () Example IV Pen 4001 times _ 3.0 grams (10 millimoles) of Craca3 is filled into a 100 ml pressure tube. Place it in a tube and seal the tube with a self-sealing crown cap. 40 ml of toluene and 2.1 ml (30 millijoules) of PyH are added via syringe. Slowly add 12ml of 2.5M (30.0 millimoles) of n-butyl Solution of lithium in hexane. A precipitate was formed, collected and washed twice with 10 ml aliquots of methylbenzene and twice with 10 ml aliquots of cyclohexane. No color was observed until the cleaning solution. A solid law of 5.59 grams was obtained. The reaction under the conditions described in the first 1001 reaction was performed using a 0.5 η 丨 1.1M (0.55 millimolar) solution of TEA in heptane and 38nu solid with Cyclohexane slurry. The results are summarized in Table IV below. M 400215] Follow the procedure described in section 4001, except that the solid catalyst component (collected 88 mg) was used in a pressure tube of 25ral using 0.349 g (1 milliohm). 3〇3 <: 3, 5 1111 toluene, 0.1141111 (2 millimoles) of yala [{, and 0.8 ml of a 2.5M (2.0 millimoles) n-butyllithium solution in hexane to separate The reaction under the conditions described at 1001 times used a 0.5 ml solution of 1.1 M (0.55 mmol) of TEA in heptane and a cyclohexyl slurry containing 80 mg of solid. The results are summarized in Table IV below. ^ m 400-iini ^. · In accordance with US Patent 4,364,855 (1982), incorporated herein by reference, -44-This paper size applies the Chinese National Standard (CNS) A4 wash (2 丨 0X297 mm) 83. 3.10,000 I | —Equipment · 11 Orders {Line-(Please read the note r on the back before filling out this page) Member of the Central Bureau of Prospecting, Ministry of Economic Affairs Consumption cooperation Du printed A7 ____B7 V. Description of the invention () 1.0 g of aluminophosphate water product (0.4 P / A1 ears ratio, at 700 t: activation) for cooking, and 93rag equivalent of 4001 The solid was weighed in a 25 ml pressure tube. The tube is capped. A solution of 5 nl of methylbenzene and 3 ml of 1.9M (5.7 mmol) TEA toluene was added via a needle to a slurry generated in a human tube and stirred for 1 day. Isolate the solids and wash with 10 ml aliquots of toluene and cyclohexane until no color is observed in the washing solution. The reaction under the conditions described in No. 1001 was performed using 0.5 ml of a 1.1 M (0.55 millimolar) solution of TEA in heptane and a slurry of cyclohexane containing 16 w of solid. _ Results are summarized in Table IV below. No. 4004 冋 According to US Patent 4, 364, δ55 (1 982) > incorporated herein by reference, and prepared 0.7 g of aluminophosphate support (0.4 P / A [Ear ratio ', activated at 700¾), The inverse aliquot (53 mg) of the solid described in 4002 was weighed in a 25 ml pressure tube. The tube is capped. A 3.5 ml solution of methylbenzyl and 2 mi of 1.9M (3.8 millimolars) of TEA methylben was added to the tube via a syringe. The resulting slurry was stirred for 1 day. Isolate the solids and wash aliquots of methylbenzene and cyclohexane until the cleaning solution does not detect color. The reaction under the conditions described at number 1001 used 0.5 ml of a 1.1 M (0.55 mmol) TEA in heptane solution and a 80 ms solid cyclohexane slurry. The results are summarized in Table IV below. ------- 一-装 -------- Order ----- \ .line i (Please read the notes on the back before filling this page) -45-This paper is suitable for China National Standard (CNS) A4 specification (210X297 mm) 83.3. 10,000 V. Description of the invention () A7 B7 τ τ 8π9 τ ^ ς ς τ > τ > 々ε ^ τ > η ς — 丨-: = 7 π υ π υ Μ »ο Μη υ = υ SL 6Z. S τα ίΜΗ τ τ ε inch, ηυΤ swallow two s% 1Α \ S0 ^^^ 1 im --- 1 1 ^ 1 ^ 1 > —a—» aar -xs士. 一 &i; (Please read the precautions of the back ¾ and then fill in {; e this page) 9Τ ττ 3 inch 'inch 8 68 s 98

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iUJ -46- οτε οττ ο inch 1 ° lat 3 '. COZ.0.0 35 0000 · 0 S5 9IH0.0 S3 8S, 0 τ05 ^ ------------ This paper size applies to the Chinese National Standard (CNS ) Α4 specification (210 × 297 mm) 83. 3.10,000 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention () Rich cases V Leather 5 0 01 冋 0.17 grams 2,2,6,6- Tetramethyl-3,5-heptanedioic acid complex (III) (Cr (III) TMHD) (0.28 mmol) was weighed in a 25 ml pressure tube. Tube; 乂 Self-sealing crown cap closure. 0.06ra 1 of pyrrole (0.89 millimolar) and 0.17m of pure (0.87 millimolar) diisobutylaluminum chloride (DiB / UCl) are formed by needle addition (Cr (III) TMHD / DiBAlCl / Py) solution, its W cyclohexane was diluted to a knot of about 8 ml! volume. 1.1M (0.28 mmol) of 0.25ra TEA solution in heptyl and Cr (III) TMHD / D 丨 B / UCl / Py solution of 0.75ral added to glass containing 100 ml of cyclohexane and 10 g of butadiene bottle. The temperature of the glass bottle was set at 70 t: the temperature control bath, and stirred for 16 hours. After 16 hours • Collect a sample of the children's liquid reaction product mixture and analyze by gas chromatography. The remaining reaction product mixture was evaporated and the amount of solid product was determined. The results are summarized in Table V below. Flute 5 0 0 2 冏 According to the procedure described in the 5001 cycle, except that the alkyl aluminum compound is not present in the reactor, and the procedure described in the 3001 cycle is used to derive the halogenating agent, as follows. 0.21 g (0.601 mmol) of Cracac3 was mixed with 0.12 ml (1.73 mmol) of pure pyrrole and 15 nl of methylbenzyl. The resulting solution was stirred under dry nitrogen * at ambient temperature and pressure for 5 minutes and then 6.0 ml of 1.9M TEA (1.4 mmol) was added to the solution. The resulting dark brown reaction mixture was stirred under dry nitrogen at ambient temperature and pressure for 5 minutes. Then '-47- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 83. 3. 10,000 ------- 『-pack—— I (Please read the notes on the back before filling This page),-& line A7 B7 V. Description of the invention () Added in accordance with US Patent 4,364, 855 (1982), which is hereby incorporated by reference, and a 2.0 g aluminum phosphate support (0.4 P / A 1 mole ratio (at 700 t: activation) and the resulting slurry is stirred for approximately 12 hours. The product was collected by filtration. K10 ml aliquots of methylbenzyl and pentane were washed at least twice until no color was observed in the mash, and dried under vacuum. The dried product was used as a solid supported catalyst system. A 0.28 g catalyst was used in the butadiene reaction. The results are summarized in Table V below. In the 5000 series, the treated olefin compound is butadiene but not a single olefin. Table V Butadiene repellent 艉 'to the product% product distribution weight% m butadiene total 5-pinzadiene Other liquid solids 5001 97 91.9 0.3 7.8 5002 68 60.8 2.5 36.7 One pack _. Order J-line I (please read the note f on the back first and then fill out this page) The Central Government Bureau of the Ministry of Economic Affairs and the Consumer Cooperatives printed the g case VT (I: Bu.'S) Each time under M, all catalyst systems are made in a glove box under dry nitrogen at ambient temperature and pressure. The transition Au compound was weighed and mixed with three (3) equivalents of 0.062 Hi pyrrole; 2 ml of hexane as a solvent; and 6 ml of a 1.1 M solution of triethylaluminum (TEA) in heptane. Generated -48- The standard of this paper is applicable to China Solid State Standard (CNS) A4 (210X297mm) 83. 3. 10,000 A7 B7 V. Description of the invention () The product is shaken for 5 minutes to 16 hours. Each time a Q liter of liquid catalyst in a 1 liter autoclaved reactor containing 300 ml of hexane was diluted in cyclohexane and added to the reactor under countercurrent ethylene (CPS). The reactor was sealed and ethylene addition was stopped until the reactor temperature reached a reaction temperature of 80 t. The ethylene pressure was increased to a reactor pressure of 55 ° psig, and if necessary, heated to maintain a reactor temperature of 80 ° C. At the end of each round, take a sample of the liquid reaction product mixture and use capillary gas chromatography. "On HP-5380 gas chromatography equipped with a FID detector and a 60-meter DB-1 column, 0.25 mm ID and 0.25 μ 瞑仪 分析。 Instrument analysis. The gas phase decanter was increased from 40t to 275C at a rate of 101 / min and held for 20 minutes. Cyclohexane was used as the internal standard. The remaining reaction product mixture was evaporated and the amount of solid product was determined. The results are shown in Table VI below. (--Installation-- (Please read the note r on the back before filling out this page) ..-- Order ----- First-line printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy Chinese national standard f (CNS) A4 specification (210X297 mm) 83.3.1, 0.005. Description of the invention (111 · -111-0

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(Please read the precautions on the back and fill in this page first) 83.3. 10,000 Binding-Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention () In the 6000 series, the method of the present invention is used, in which the metal compound Not a compound. The data in Table VI shows the better results obtained with chromium.

Example V Ι In the following examples, the 7001-7005 times prove the effect of hydrolyzing metal alkyl groups before use and the effect of the presence or absence of pyrrole-containing compounds. The comparison between the 7006-7009 and 7010-70 13 cycles proved the effect of the catalyst system in the preparation of unsaturated hydrocarbons. Flute 7001-700 5 冏 In the 7001-7005 rounds, the ratio of the element chromium to the element aluminum to the ligand (Cr: Al: L) added to the reactor's catalyst ratio is 1:10:30. At 7001-7003, the chromium compound was Cr (EH) 3, and at 7004-7005, the chromium compound was Cr (Py) 3. The aluminum compound was triisobutylaluminum (Al (I-Bu) 3), and it was tested using the following method. Approximately 10 weights of triisobutylaluminum in heptane solution was spiked, but 1.0 mol equivalent of distilled water was added at one time, while the flask containing the solution was cooled with ice water to maintain a temperature of about 10 to about 20 t: . The solution was stirred vigorously after adding water and continued until no further gas evolution was observed. The ligand is dimethoxyethane (DME). In the 7001-7005 cycles, the chromium compound was dissolved in a 2-liter hot-pressed reactor. 400-500 ml of anhydrous n-heptane was added, and the reactor was added under a nitrogen purge. Then add an appropriate volume of a 0.31M solution of i-Al (Bu) 3 in heptane as described above, stirred and treated. Then, add an appropriate volume of D M E, 'and 5 1111. Synthesize (in-reactor standard). The reactor was sealed and wells were 80 to 7001 rounds. (: And the 7002-7005 is the temperature of 95¾ 'and -52- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 83. 3.10,000 i lull i--I m -SI n I mi HI-- I ^ «--1 n ^ i--I-二 i-< I 0¾.. Ί I business I (Please read the precautions on the back before filling this page) Staff Consumption of the Central Bureau of Standards, Ministry of Economic Affairs Cooperative printed A7 B7 i. Description of the invention (M) The pressure of ethylene is increased to 550 psig; the time for feeding ethylene in the 7001th round is 25 minutes, the 7002th round is 30 minutes and the 7003th-7005th is 45 minutes. At the end, take a sample of the liquid reaction product mixture and use capillary gas chromatography on a HP-5880 gas chromatography equipped with a FID detector and a 60-meter DB-1 column, 0.25mm ID and 0.25w membrane. 'Instrument analysis. The rate of the gas chromatograph M 10 ° C / min was increased from 40 ° C to 275 ° C for 20 minutes. The remaining reaction product mixture was evaporated and the amount of solid products was determined. The catalysts from 7 0 06 to 7013 were prepared according to the following steps. The catalyst system from 7006 to 7009 was used in Jiaben, unsaturated aromatic smoke. It is prepared below. The catalysts in the 70th to 7013th cycles are prepared in the presence of 1-hexene and unsaturated aliphatic hydrocarbons. H 700R 151 3. 72 g of [N a (D M E) 2] [C r C Η P y 0 3 D Μ Ε] is mixed with 50 m 1 of toluene. Slowly add 26.4 m 1 of pure (93%) TEA and stir for 30 minutes. The slurry turns dark brown. Excess solvent Remove by vacuum to produce dark yellow / brown oil and solid. Add about 70m of cyclohexane. The resulting product is destroyed and the mash is diluted to 200ml with cyclohexane, 8.0m into the reactor. The product contains 1.67 mg C r / m 1 ° No. 7007 冏 0.35 grams of chromium (III) ethylhexanoate (CrEH3) is mixed with about 15 ml of toluene to form a dark green solution. Add 2,5-dimethyl at 0'.22m 丨Pyrrole (2, 5-D M P / and 0.20 m 1 .1-bromobutane. Slowly add 5.7 m 1 of 1 · 9M TEA in toluene solution and stir for 30 minutes. Excess solvent in vacuo Excluding -53- n ^ n Βϋ Λ ^^ 1 · 1 ^ 1 It— ^ > CTV ^ 1 I ^, V6 i 乡 i '(Please read the precautions on the back before filling this page ·) This paper size applies China National Standard (CNS) A4 Specification 210X297 mm) 83.3. 10,000 A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention () and liquid extraction to about 15 ml of cyclohexane = the product is produced and the liquid M cyclohexane is diluted to 25 ml Instead, a golden solution was formed | 7.0 ml was charged into the reactor. The product contains 0.014 g of "EH3 / ml. Same as 7008. Follow the steps described in 7007, except that 0.22 g of CrEH3 and 0.13 ml of 2,5-DMP are used. In addition, MOCU of 10 ml replaces 1-bromobutane. Add 3.4 ml of 1.9MTEA solution in methylbenzyl to obtain a brown to yellow / yellow solution and precipitate. After filtering and diluting to 25m with cyclohexane, the final product is #gold yellow and contains 0.0%. 〇888 (: "£ [{3/1111. 3.0.111 was loaded into the reactor. 7070q 2.070g of CrPy3Cl was added with 70ml of toluene and 62ml of 1.9HTEA in methylbenzyl solution, mixed and killed. The volume of the filtrate was reduced by dynamic vacuum to as little as about 20 ml. The viscous brown solution was filtered again. Then, about 30 ral of pentane was added to the filtrate. After about 1 day, the solution was removed in vacuo by excess solvent. Then added in accordance with US Patent 4,364,855 (1982 ), Incorporated here as a reference, and prepared 38.1 g of aluminophosphate support (0.9P / A1 Molar ratio, activated at 700t). The slurry was stirred for about 30 hours. Solids were collected by quenching, and were separately Washed with water, cyclohexane and pentane. 0.4388 g of a solid supported catalyst system was loaded into the reactor. 7010 冏 0,21 grams of [Na (DME) 2] [CrCUPy) 3DME] is mixed with about 15m of 1-hexene ^ Slowly add 4). 75 ml of pure (93%) TEA to form a brown Solution and seemingly sticky precipitate, and stir for 30 minutes. Excess solvent by vacuum -54- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 83. 3. 10,000 ------ -· '1 Pack --r --.-- Order ----- 1 -line (please read the notes on the back 顼 before filling out this page) Α7 Β7 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The description of the invention () is removed. The residue is extracted to about 15ml of cyclohexane * filtered and the filtrate is diluted to 25m with cyclohexane. 8.0ml (0.067g) is installed in the reactor. Section 701 1 冋 According to the description in Section 7010 Steps, except that the catalyst system of cyclohexanone is aged for about 24 hours before use. 8.0ml (0.067g) is packed into the reactor. 堃 7012 dissolves 0.26g of C r E Η 3 in about 1 5 m 1 2 -hexene mixed. Add 0.1 15 m 1?, 5-D MP and 0.1 13 m 1-bromobutane. Slowly add 1.0 ml of pure (93%) TEA and mix for 30 minutes. Excess solvent It was removed, and the liquid was extracted into about 15ml of cyclohexane. The resulting product was filtered and the filtrate was diluted to 25 ml with cyclohexane. 7.0 m 丨 installed human reactor. m 7 Q 1 151 '0.21 grams of [Na (DME) 2] [CrCl (Py) 3DME] was mixed with about 15 inl of 1-hexene. Slowly add 1.0 ml of pure (93%) TEA to form a dark brown solution and precipitate * and mix for about 1 hour. The solution was decanted and added in accordance with U.S. Patent No. 4,364,855 (1982), incorporated herein by reference, and 1.5 g of aluminophosphate support (0.4 P / Al mole ratio, activated at 700 C). The collection support by filtration included the system, K 1 -hexene was washed and dried under a nitrogen purge. A solid catalyst of 0.628 g was installed in a human reactor. The 7006-7013 rounds were performed in a 2-liter autoclaved reactor containing cyclohexanone. Heterogeneous, dry, dry, supported catalyst systems (No. 7009 and 7013) are slurried in cyclohexane to facilitate the addition of polymerization reactors | and countercurrent ethylene (: C PF-55-)-This paper size applies to Chinese national standards (CNS) Α4 specification (210X297 mm) 83. 3. 10,000 (Please read the precautions on the back before filling out this page) — Installation --- I. Order-line A7 Β7 5. Add the description under ()) Polymerization reactor. Heterogeneous, liquid, unsupported catalyst systems (Nos. 7006-7003 and 7010-7012) are diluted in cyclohexane and a polymerization reactor is added under the flow of ethylene (CP grade). The reactor was sealed and the ethylene addition was stopped until the reaction temperature reached a reaction temperature of 30 t. The pressure of ethylene was increased to a reactor pressure of 550 psig. The feeding time of ethylene was 30 minutes. At the end of each round, a sample of the liquid reaction product mixture was taken and subjected to capillary gas chromatography in a HP-5880 gas phase layer equipped with a FID detector and a 60-meter DB-1 column '0.25® m ID and 0.25ii 瞑. Analyzer analysis. The rate of gas chromatograph M 10 C / min was increased from 401 to 2751 and maintained for 20 minutes. The remaining reaction product mixture is evaporated and the amount of solid product is determined. The results are summarized in the following table VI ° (Please read the note on the back Ϋ 'before filling this page) tj ____ 一 ^ ifl ^ i 11 »% 1 ffn # in 0¾ Printed by Beige Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs-56- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X: 297 mm) 83.3. 10,000 V. Description of the invention () V6 A7 B7 T > 56 9 s 9 Z * 7 o ^ z wz- \ l- \ ο / οε / ε / ιoi / oe / o / ΐ '· 2 / oc / o / t ~ 〆οι / οε / ο / ΐοΐ / οε / ο / ι OI / S / O / T-(5s——), i / IV / N-/ ^ l 1 ^-^ ¾ "0 9_0 Jz ei 9n1 躞 画, • ss

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• J-line-58- This paper size is in accordance with Chinese National Standard (CNS) A4 (210X29 * 7mm) 83. 3. 10,000 A7 B7 printed by Shelley Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Data from VI indicate the presence of water (7001-7005) formation of harmful liquids, such as 1-hexene. In fact, the water in the reactor causes a high solids formation. The 7006-7013 times show that the catalyst system prepared in the presence of any unsaturated hydrocarbon is effective for trimerization. However, a comparison of the 7006 to 7009 cycles with the 7010 to 7013 cycles of the 1-hexene preparation shows that unsaturated aromatic hydrocarbons are the better catalyst system preparation media.

Tube 剜 Γ Γ 卞 卞 JI, 800 1-80 17th time, prove the effect of changing the pyrrole compound, halogen, and gold tincture additive. The catalyst systems used at 8001-δ017 were all prepared by the same general procedure. In a typical system of osmium, chromium (III) 2-ethylhexanoate is soluble in methylbenzyl. Second, 3 equivalents of 2,5-dimethylpyrrole (or hydropyrrole salt 8014-8017) were added to the solution. The required amount of halide additive (2 to 3 mole equivalents) is then added, followed by 15 mole equivalents of triethylaluminum (TEA). The reaction mixture was stirred for 5-10 minutes and the toluene was removed under vacuum. The liquid residue was diluted with cyclohexane to a total volume of 10 ml, and an equal portion was charged to the reactor as a catalyst. System 3 The trimerization reaction was carried out at 1.2 liters with 85% cyclohexane as the reactor diluent. 2 A liter hot-press polymerization reactor was performed. The catalyst system was installed in the reactor and cyclohexane was added. The reactor temperature rose to 80t: ethylene was introduced at this time. Pressure M feed ethylene was held at 550 pSig. Each reaction was performed for 30 minutes before shutting down ethylene. Samples were taken at the end of each round and analyzed by gas phase analysis as described in other examples. -59- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 83. 3.10,000 (Please read the precautions on the back before filling this page), II ---- I --- ^- Equipment-, J line A7 B7 V. Description of the invention () The results and analysis of each time are shown in Table B.

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Employees' Cooperation of the Central Standards Bureau of the Ministry of Economy Du Yin 5L

-¾ ° zi Iti 9ΐ0Β rays ςίοβ υν3α is-° csmi '1 zi -¾ ° έτ-3χso · 0 GTS &quot; 3160s I3m—U goo® sng 丨 u ^ 00 «Jang—U 9 °° &quot; snq-u SOH ifly3a ^ 00® rasa ss uv3a SOMocoz loo®-!-8 .nm ^ i-n ^ i-.. i II m I---1--I 1 J. I: -I--n ^ i ---I---I-ί li I-^^^ 1---I--1_. ...... i nn li-I ^ 0¾. Ί I i (Please read the back first * Please note this page and fill in this page again): _ 弑 弑 遛 衾 珣 赵 衾 珣 衾 珣 1} The two paper sizes are applicable to the Chinese National Standard (CNS) A4 Washing (210X297 mm) 83. 3. 10,000 Central Bureau of Standards Printed by employee consumer cooperative A7 B7 V. Description of the invention () The data in Table V01 shows that the order of selectivity M 1 <Cl <Br for 1-hexene increases. The formation of 1-hexene with bromine-containing additives is consistently more selective than the corresponding chloride or iodide additives. The increased productivity of 1-hexene also indicates the formation of fewer by-products (C4 =, c8 =., And c10 =>). The ratio of 1-hexene to endohexene also tends to M I (C 1 (B The order of r increases. Therefore, the use of halides not only results in more products, but also results in cleaner terpolymers. The order of the activity M I &lt; C1 <Br of the catalyst system increases. However, the order between Br and Cl congeners The activity seems to be unpredictable. In some additives (Snx4 & AlX3SiX), bromine is more active. The data in Table VII also shows that the selectivity and activity trend for 1-hexene can be extended to other pyrrole-containing catalysts | As shown in Nos. 3014-8017. Overall, the best combination of activity and selectivity is obtained by using GeCU or SnCU as a halide additive. However, the selectivity to 1-Ihexene is also shown. Influenced by the ratio of halide additives to triethylaluminum, it can obtain high selectivity from other halide additives.

Take the example of X in the following example, Nos. 9001-9004 prove that excess unsaturated aromatic hydrocarbons are harmful to trimerization and / or oligomerization. Therefore, when the catalyst system is prepared in the presence of, for example, methylbenzene aromatic hydrocarbons, it is preferred to remove excess aromatic hydrocarbons. The resulting liquid is then extracted or dissolved in a desired solvent, such as cyclohexane or heptane. Although not wishing to be bound by theory, it is believed that aromatic hydrocarbons can compete with trimeric and / or oligomeric monomers such as ethylene, competing for the active site of the catalyst system. Therefore, it is believed that this competition will inhibit the catalyst system. Activity; The catalyst used for the 90th 0 〇 1-9 0 0 4 times is the use of 1. 3.5 grams of soluble in A-61- This paper size applies to Chinese national standards (〇15> 六 4 ^^ (210/297 Mm) 83. 3. 10,000 ϋ ^ — m ^ ......--I n a. Γ ^^ 1-m ^ i --- ^ I (Fill in this page again) Α7 Β7 V. Description of the invention () Stupid 2-ethylhexanoic acid complex (III) for cooking. Second, 0.86ml (3.2 (equivalent) of 2,5-dimethylpyrrole was added Solution. Then 0.91 ^ (3.2 mole equivalents) of n-butyl bromide was added, followed by 7.60 ^ (21 mole equivalents) of 93% triethylaluminum. The mixture was stirred for 5-10 minutes · min and methylbenzyl Remove under vacuum. The liquid residue is dissolved in 30 ml of cyclohexane, filtered, and then diluted with additional cyclohexane to a volume of 50 ml. Four (4) mL of this solution and the required amount of anhydrous, Degassed toluene (0, 5, 10 or 15 mL) The trimerization reaction was performed in a 2 liter autoclave polymerization reactor containing 1.2 liters of 85% cyclohexane as a reactor diluent. The catalyst was installed in the reactor and then cyclohexane was added. The reactor temperature rose to 80 ° C, at which time ethylene was fed into the bow. The pressure was maintained at 550 ps U with the ethylene fed. Each reaction was performed for 30 minutes before the ethylene was shut down. The amount of ethylene consumed was measured, that is, charged. The results of the material quantity 0 9001-9004 times are shown in Table IX. Table IX If the family 惮 惮 彳 彳 剂 剂 剂 鸵 is the traditional living osteoplastic-(Please read the notes on the back * before filling this page) __ 丁__ ..., τ .1 Consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs, Du Yinchai, Jiaoquan.m 1, 穑% toluene (a), which is consumed after 30 minutes;? ( b) 900 1 0 0.00 184 9002 5 0.42 160 9003 10 ϋ.83 127 9004 15 1.25 / 109 -62- This paper size applies the Chinese National Standard (CNS) Α4 specification (210X297 mm) 83. 3. 10,000 ο 'ί Α · 7 Β7 V. Description of the invention () Absolute solution of alkane agent, which has a solution value of ab, has a release ring that is thinner than that of organene. The inversion is equal to that of the benzene methylbenzene which is not consumed in the tuning base., Quantitative examples of hydrocarbons are found to be aromatic, and the amount of IX, which is a low-significant and significant-reduced quantity, is the opposite of the hydrocarbon-based aromatics. Addition and reduction of device injection agent can be done here (please read the note at the back of f before filling out this page)-install '

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Claims (1)

ABCD No. 821.01346 Patent Application Chinese Patent Application Amendment (July 88) VI. Patent Application Range 丨 m, i. 2S &quot; .. j ^-"(Please read the notes on the back before filling in this贳) 1 · A method for preparing a catalyst system, which comprises reacting Mingyuan, a pyrrole-containing compound, and a non-hydrolyzable alkylaluminum compound in the presence of unsaturated liquid hydrocarbons, but without the presence of an electron donor solvent (such as ether) A preliminary reaction, wherein the non-hydrolyzable alkyl aluminum compound is not in contact with water first, the chromium source is selected from compounds containing chromium I [and Ming E [, and the pyrrole-containing compound is selected from pyrrole, pyrrole salt, 2, 5- Dimethylpyrrole and 2,5-Dimethylpyrrole salt, the reaction is carried out under anhydrous and anaerobic conditions, and the pressure is maintained at atmospheric pressure to 3 atmospheres and temperature so that the reaction mixture is maintained in a liquid state. 2. The method according to item 1 of the scope of application, wherein the unsaturated hydrocarbon is used as a miscible solvent for the reaction. 3'The method according to item 2 of the scope of patent application, wherein the unsaturated hydrocarbon is an aromatic or aliphatic hydrocarbon having less than 70 carbon atoms per molecule. 4. The method according to item 3 of the scope of patent application, wherein the unsaturated hydrocarbon is an aromatic hydrocarbon having less than 20 carbon atoms per molecule. 5. The method according to item 4 of the scope of patent application, wherein the aromatic hydrocarbon is methylbenzyl, benzene, xylene, copper, or hexamethylbenzene. β. The method according to any one of claims 2 to 5 of the patent application scope ', which comprises removing excess unsaturated aromatic hydrocarbons from the generated catalyst system. Printed by the Central Bureau of Standards of the Ministry of Economic Affairs, which belongs to the Industrial and Consumer Cooperatives. 7. The method according to any one of items 1 to 5 of the scope of patent application, wherein the susceptible compound is pyrrole or 2,5-dimethylpyrrole salt. δ: The method according to item 1 of the scope of patent application, wherein the alkylaluminum is a dialkylaluminum compound, such as triethylaluminum. 9. The method according to any one of the scope of claims 1 to 1 above, wherein a support is added to the catalyst system. -1-Chinese paper standard (CNS) A4 size (210X 297 mm) ABCD No. 821.01346 Patent Application Amendment of Chinese Patent Application Range (July 88) VI. Patent Application Range 丨 m, i. 2S &quot; .. j ^-"(Please read the notes on the back before filling in this section) 1 · A method for preparing catalyst systems, including ordering Mingyuan, pyrrole-containing compounds and other compounds in the presence of unsaturated liquid hydrocarbons Hydrolysis of aluminum alkyl compounds, but no preliminary reaction in the presence of an electron donor solvent (such as ether) occurs, wherein the non-hydrolyzed alkyl aluminum compound is not in contact with water first, and the chromium source is selected from chromium-containing I [and The compound containing E [, the pyrrole-containing compound is selected from the group consisting of pyrrole, pyrrole salt, 2,5-dimethylpyrrole and 2,5-dimethylproprole salt. The reaction is performed under anhydrous and oxygen-free conditions, and pressure Maintain one atmosphere to three atmospheres and temperature so that the reaction mixture is maintained in a liquid state. 2. The method according to item 1 of the scope of application, wherein the unsaturated hydrocarbon is used as a miscible solvent for the reaction. 3'The method according to item 2 of the scope of patent application, wherein the unsaturated hydrocarbon is an aromatic or aliphatic hydrocarbon having less than 70 carbon atoms per molecule. 4. The method according to item 3 of the scope of patent application, wherein the unsaturated hydrocarbon is an aromatic hydrocarbon having less than 20 carbon atoms per molecule. 5. The method according to item 4 of the scope of patent application, wherein the aromatic hydrocarbon is methylbenzyl, benzene, xylene, copper, or hexamethylbenzene. β. The method according to any one of claims 2 to 5 of the patent application scope ', which comprises removing excess unsaturated aromatic hydrocarbons from the generated catalyst system. Printed by the Central Bureau of Standards of the Ministry of Economic Affairs, which belongs to the Industrial and Consumer Cooperatives. 7. The method according to any one of items 1 to 5 of the scope of patent application, wherein the susceptible compound is pyrrole or 2,5-dimethylpyrrole salt. δ: The method according to item 1 of the scope of patent application, wherein the alkylaluminum is a dialkylaluminum compound, such as triethylaluminum. 9. The method according to any one of the scope of claims 1 to 1 above, wherein a support is added to the catalyst system. -1-This paper size adopts Chinese National Standard (CNS) A4 specification (210X 297 mm) Ί 'am Α δ D8 6. Application scope of patent I 0. Method according to item 8 of the scope of patent application &gt; where the support The substance is an inorganic oxide. II. The method according to item 10 of the scope of patent application, wherein the inorganic oxide is oxidized sand, oxidized sand-oxidized oxide, oxidized oxide, fluorinated oxidized oxide, sand-acidified alumina, hafnium oxide, aluminophosphate, aluminum phosphate , Phosphorylated silica, silica-titanium oxide, co-precipitated silica / titanium oxide, fluorinated / silicified alumina, and mixtures thereof. 12. A method according to any one of claims 1 to 5 of the scope of patent application, which comprises adding a halide source. 13. The method according to item 12 of the scope of patent application, wherein the halide is a chloride or a bromide or a mixture thereof. 14. The method according to item 12 of the scope of patent application, wherein the halide source is provided by a compound having the formula RX n, where R is an organic or inorganic chromium radical, X is a halide, and the sum of m plus η is greater than Any number of 0. 15. The method according to item 14 of the scope of the patent application, wherein R is aluminum, silicon, germanium, hydrogen, 5 pentium, lithium, tin, gallium, thallium, lead, or a mixture thereof. Printed by the Employees' Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the notes on the back before filling out this page) 1 6. According to the method of item 15 of the scope of patent application, where R is tin, gallium, or a mixture thereof. 17. The method according to any one of items 1 to 5 of the scope of patent application, wherein the catalyst system produced has a relative ratio of M: (a) 1 mol of chromium source; (b) 1 to 15 mol of Pyrrole-containing compounds; (c) 5 to 40 moles of aluminum alkyl; and, if present, this paper size applies to China National Standard (CNS) A4 (210X297 mm) A8 B8 C8 D8 VI. Patent Application Range (d) 1 to 30 moles of halide. 1 δ. The method according to any one of claims 1 to 5 of the scope of the patent application, wherein the 'complex source and the pyrrole-containing compound are mixed before adding the aluminum alkyl. 19. A method for terpolymerizing an olefin compound, which comprises performing the trimerization in the presence of a catalyst system prepared by a method according to any one of claims 1 to 5, wherein the method is 80 ° t: to 150 ° C and 300-700 psig. 20. The method according to item 9 of the scope of patent application, wherein the olefin compound has 2 to 30 carbon atoms and at least 1 olefin difluorene per molecule. 21. A method according to item 20 of the scope of patent application, wherein the olefin compound is ethylene, 1-butene, 1-hexene, 3-butadiene, or a mixture thereof. 2 2. The method according to item 19 of the scope of patent application, in which a catalyst system is prepared by mixing an unsaturated diameter M, but 0 2 3 is first introduced during the trimerization. The method according to item 22 of the scope of patent application, wherein The unsaturated hydrocarbons used to prepare the catalyst system are unsaturated aliphatic hydrocarbons, which are also used as trimerized olefin compounds. -------- ^ -Packing— (Please read the notes on the back before filling out this page) Graded paper printed on paper by the Consumer Standards Cooperative of the Central Bureau of Standardization of the Ministry of Economic Affairs Applicable to Chinese National Standard (CNS) A4 specifications (210X297 mm)