Asymmetric diimine zinc complex as well as preparation method and application thereof

Abstract

The invention discloses an asymmetric diimine zinc complex and a preparation method and application thereof.The preparation method of the asymmetric diimine zinc complex comprises the steps that acenaphthequinone, a first dehydrating agent, a first catalyst, first substituted aniline and a solvent are subjected to a first reaction, and a monoimine ketone compound is obtained; and performing a second reaction on the monoimine ketone compound, a zinc salt, a second dehydrating agent, second substituted aniline and a second catalyst to obtain the asymmetric diimine zinc compound. According to the preparation method of the asymmetric diimine zinc compound, zinc salt is added in the reaction process, generated unstable large-steric-hindrance groups are used for replacing diimine for stable complexation, a corresponding zinc complex is generated and can be separated from a reaction system in time in the reaction process, the reaction equilibrium can be effectively promoted to be carried out to a positive reaction, and the yield of the asymmetric diimine zinc compound is improved. And the large-steric-hindrance group substituted diimine zinc complex can be synthesized with high selectivity and high yield.

Description

Technical Field

[0001] The present application relates to the technical field of catalysis and olefin polymerization, and in particular to an asymmetric diimine zinc complex and a preparation method and application thereof. Background Art

[0002] Polyolefins have the characteristics of good chemical resistance, low price, simple preparation, low density, and good mechanical properties. They are indispensable and important materials in photovoltaic cells, automotive parts, aerospace, 5G / 6G communications, etc. In recent years, the scale of my country's polyolefin imports has been increasing year by year, but the high dependence on imported products has seriously restricted the development of my country's petrochemical industry. Therefore, various research institutions have increased their research and development efforts on POE special catalysts and production processes year by year, which is of great significance to the early realization of POE domestic substitution.

[0003] The traditional process of POE uses metallocene-catalyzed copolymerization of ethylene and α-olefins. In the late 1990s, late transition metal (Fe / Co / Ni / Pd, etc.) catalysts were widely studied by chemists due to their stable chemical properties and polymerization catalytic activity. Among them, imine metal complexes are one of the most widely studied late transition metal catalysts in the field of olefin polymerization catalysis, and diimine compounds are the key raw materials for the synthesis of this catalyst. The most classic method is to synthesize imines using weak acids as catalysts. For structures with less steric hindrance, using acids as catalysts can obtain good yields, while for ligands with larger steric hindrance, the yields are lower.

[0004] The inventors have found that in the related art, imines can be synthesized from ketones and amine compounds through condensation reaction and removal of a molecule of water. The reaction is reversible. Diimines with large steric hindrance are unstable in the reaction system and are easily decomposed to undergo reverse reaction, and then condense with small sterically hindered substituted amines to form symmetrical by-products, resulting in a low synthesis yield of asymmetric diimines substituted with large steric hindrance groups.

[0005] At the same time, the inventors also found that the existing asymmetric diimine compound synthesis method has the following defects: multiple synthesis steps, complex post-processing, and difficulty in separation and purification after the reaction is completed. In addition, the existing asymmetric diimine compound is not easy to decomplex to generate imine under the action of alkali, and the yield of synthesizing asymmetric diimine needs to be improved. Summary of the invention

[0006] In view of this, an object of the present application is to provide an asymmetric zinc diimide compound, which is very easy to decomplex to generate imine under the action of a base, and can achieve the effect of synthesizing asymmetric diimine in high yield.

[0007] Another object of the present application is to provide an asymmetric diimine zinc compound.

[0008] Another object of the present application is to provide a catalyst.

[0009] Another object of the present application relates to the use of asymmetric diimine zinc compounds.

[0010] To achieve the above-mentioned purpose, the first aspect of the present application provides an asymmetric zinc diimide compound, wherein the asymmetric zinc diimide compound has a structure shown in Formula I:

[0011]

[0012] In Formula I, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Each is independently selected from one of H, F, Cl, Br, I, NO2, trifluoromethyl, nitrile, benzyl, diphenylmethyl, C1-6 alkyl, C1-6 alkoxy, a functional group having a structure of formula II, and a functional group having a structure of formula III; X1 and X2 are each independently selected from one of F, Cl, Br, and I;

[0013]

[0014] Among them, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 Each is independently selected from one of H, F, Cl, Br, I, NO2, trifluoromethyl, nitrile, C1-6 alkyl, and C1-6 alkoxy.

[0015] In some embodiments, in the asymmetric zinc diimide compound in Formula I, R1, R2, R3, R4, and R5 are each independently selected from one of H, C1-6 alkyl, or C1-6 alkoxy.

[0016] In some embodiments, R6, R7, R8, R9, R 10 Each is independently selected from one of H, F, Cl, Br, I, NO2, trifluoromethyl, nitrile, the functional group having the structure of formula II, and the functional group having the structure of formula III.

[0017] In some embodiments, the asymmetric zinc diimide compound includes but is not limited to at least one of compounds 1-5, etc.:

[0018]

[0019] In the compound 3, X3 and X4 are each independently selected from one of F, Cl, Br and I.

[0020] The asymmetric zinc diimine compound described in the present application can at least bring about the following beneficial effects: it is very easy to decomplex and generate imine under the action of a base, and can achieve the effect of synthesizing asymmetric diimine in high yield.

[0021] The second aspect of the present application provides a method for preparing an asymmetric diimine zinc compound, comprising:

[0022] The acenaphthenequinone, the first dehydrating agent, the first catalyst, the first substituted aniline and the solvent are subjected to a first reaction to obtain a monoimine ketone compound;

[0023] The monoimine ketone compound, zinc salt, a second dehydrating agent, a second substituted aniline, and a second catalyst are subjected to a second reaction to obtain the asymmetric diimine zinc compound;

[0024] The first substituted aniline and the second substituted aniline are different anilines.

[0025] In some embodiments, the first substituted aniline and the second substituted aniline both include compounds having a structure of Formula IV:

[0026]

[0027] In Formula I, R1', R2', R3', R4', and R5' are each independently selected from one of H, F, Cl, Br, I, NO2, trifluoromethyl, cyano, C1-6 alkyl, C1-6 alkoxy, a functional group having a structure of Formula V, and a functional group having a structure of Formula VI,

[0028]

[0029] Among them, R6', R7', R8', R9', R 10 '、R 11 '、R 12 '、R 13 '、R 14 '、R 15 '、R 16 '、R 17 '、R 18 '、R 19 '、R 20 ' are each independently selected from one of H, F, Cl, Br, I, NO2, trifluoromethyl, nitrile, C1-6 alkyl, and C1-6 alkoxy.

[0030] In some embodiments, the first dehydrating agent and the second dehydrating agent both include, but are not limited to, at least one of molecular sieves, anhydrous sodium sulfate, anhydrous magnesium sulfate, calcium chloride, orthoesters, and the like.

[0031] In some embodiments, the orthoester includes but is not limited to at least one of trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, and the like.

[0032] Preferably, the first dehydrating agent includes but is not limited to at least one of molecular sieves, anhydrous sodium sulfate, anhydrous magnesium sulfate, calcium chloride, orthoesters, and the like.

[0033] Preferably, the second dehydrating agent includes but is not limited to at least one of molecular sieves, anhydrous sodium sulfate, anhydrous magnesium sulfate, calcium chloride, orthoesters, and the like.

[0034] In some embodiments, both the first catalyst and the second catalyst include, but are not limited to, at least one of a proton acid, a Lewis acid, and the like.

[0035] In some embodiments, the protonic acid includes but is not limited to at least one of formic acid, acetic acid, trifluoroacetic acid, difluoroacetic acid, oxalic acid, benzenesulfonic acid, p-toluenesulfonic acid, hydrogen chloride, hydrogen bromide, and the like.

[0036] In some embodiments, the Lewis acid includes but is not limited to at least one of ferric chloride, zinc chloride, titanium tetrachloride, aluminum trichloride, boron trifluoride, and the like.

[0037] Preferably, the first catalyst includes but is not limited to at least one of formic acid, acetic acid, trifluoroacetic acid, difluoroacetic acid, oxalic acid, benzenesulfonic acid, p-toluenesulfonic acid, hydrogen chloride, hydrogen bromide and the like.

[0038] Preferably, the second catalyst includes but is not limited to at least one of formic acid, acetic acid, trifluoroacetic acid, difluoroacetic acid, oxalic acid, benzenesulfonic acid, p-toluenesulfonic acid, hydrogen chloride, hydrogen bromide and the like.

[0039] In some embodiments, the zinc salt includes but is not limited to at least one of zinc chloride, zinc bromide, zinc iodide, zinc fluoride, and the like.

[0040] In some embodiments, the solvent includes but is not limited to at least one of C8-12 alkanes, alkylbenzenes, halogenated benzenes, ethers, esters, alcohols, halogenated alkanes, nitriles, and the like.

[0041] In some embodiments, the solvent includes but is not limited to at least one of octane, nonane, decane, dichloromethane, chloroform, dichloroethane, trichloroethane, benzene, toluene, chlorobenzene, fluorobenzene, tetrahydrofuran, methyltetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, methanol, ethanol, propanol, butanol, cyclohexanol, ethyl acetate, butyl acetate, butyl butyrate, acetonitrile, propionitrile, butyronitrile, benzonitrile, etc.

[0042] In some embodiments, the mass of the solvent is 0-60 times the mass of the acenaphthenequinone.

[0043] In some embodiments, the molar ratio of the acenaphthenequinone, the first dehydrating agent, the first catalyst, the first substituted aniline, the zinc salt, the second dehydrating agent, the second substituted aniline, and the second catalyst is 1: (0.5-10.0): (0.5-5.0): (0.8-1.5): (1.0-3.0): (0.5-10.0): (0.8-1.5): (0.5-5.0).

[0044] In some embodiments, the first reaction and the second reaction are performed in the same reaction vessel.

[0045] In some embodiments, both the first reaction and the second reaction are performed under stirring conditions.

[0046] In some embodiments, the reaction temperature of the first reaction and the reaction temperature of the second reaction are both 20-120°C.

[0047] In some embodiments, the reaction temperatures of the first reaction and the second reaction are different.

[0048] In some embodiments, the reaction time of the first reaction and the second reaction is 2-24 hours.

[0049] In some embodiments, the method for preparing the asymmetric zinc diimide compound further comprises the steps of filtering and crystallizing after the second reaction.

[0050] The preparation method of the asymmetric zinc diimide compound described in the present application can at least bring the following beneficial effects: the synthesis method is simple to operate, mild in conditions, easy to separate and purify, and has a high yield. The obtained asymmetric zinc diimide complex is very easy to decomplex to generate imine under the action of a base, which can achieve the effect of synthesizing asymmetric diimide with high yield. Specifically:

[0051] 1. A complexing agent zinc salt is added during the reaction process, and the generated unstable large steric hindrance group-substituted diimine is stably complexed with the zinc salt to generate a corresponding zinc complex, and the zinc complex can be separated from the reaction system in time during the reaction process, effectively promoting the reaction equilibrium to the forward reaction, and the large steric hindrance group-substituted diimine zinc complex can be synthesized with high selectivity and high yield, and the synthesis process steps are short and the operation is simple.

[0052] 2. Using orthoesters, sodium sulfate, etc. as the first dehydrating agent and the second dehydrating agent can timely adsorb the water generated by the reaction, effectively inhibit the reverse reaction, greatly improve the raw material conversion rate, and have high reaction selectivity.

[0053] 3. The synthesis of asymmetric diimine zinc complexes substituted with large steric hindrance groups is carried out in the same reactor, which can realize the one-pot synthesis of asymmetric structures. It can be purified by simple stirring and filtration, with a short process flow and simple post-treatment.

[0054] The third aspect of the present application relates to the use of the asymmetric diimine zinc compound described in the present application or the asymmetric diimine zinc compound prepared by the preparation method of the asymmetric diimine zinc compound described in the present application in catalyst preparation and polyolefin production.

[0055] The third aspect of the present application provides a catalyst, which is prepared using the asymmetric diimine zinc compound described in the present application or the asymmetric diimine zinc compound prepared by the preparation method of the asymmetric diimine zinc compound described in the present application as a raw material.

[0056] The fourth aspect of the present application relates to the use of the asymmetric diimine zinc compound described in the present application or the asymmetric diimine zinc compound prepared by the preparation method of the asymmetric diimine zinc compound described in the present application or the catalyst described in the present application in the production of polyolefins.

[0057] Additional aspects and advantages of the present application will be given in part in the description below, and in part will become apparent from the description below, or will be learned through the practice of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0058] The above and / or additional aspects and advantages of the present application will become apparent and easily understood from the following description of the embodiments in conjunction with the accompanying drawings.

[0059] in:

[0060] Figure 1 This is the NMR spectrum of the asymmetric diimine zinc bromide prepared in Example 1. DETAILED DESCRIPTION

[0061] The embodiments of the present application are described in detail below, and examples of the embodiments are shown in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present application, but cannot be understood as limiting the present application.

[0062] In this application, the disclosure of numerical ranges includes all values ​​within the entire range and the disclosure of further subdivided ranges, including the endpoints and sub-ranges given in these ranges.

[0063] In this application, the raw materials, equipment, etc. involved, unless otherwise specified, are all raw materials and equipment that can be made through commercial channels or known methods; the methods involved, unless otherwise specified, are all conventional methods.

[0064] The term "and / or", when used in a list of two or more items, means that any of the listed items can be used alone or in combination with any one or more of the listed items. For example, the expression "A and / or B" is intended to mean A or B or A and B, that is, only A, only B, or a combination of A and B.

[0065] The term "alkyl" refers to a -C n H 2n+1 The alkyl group may be a straight chain or branched chain. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, and the like.

[0066] The term "alkoxy" refers to a group of the formula -O-alkyl. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, and the like.

[0067] The prefix "Cu-v" means that the following group has from u to v carbon atoms. For example, "C1-6 alkyl" means that the alkyl group has 1 to 6 carbon atoms.

[0068] <Asymmetric zinc diimide compound>

[0069] To achieve the above purpose, the asymmetric zinc diimide compound of the embodiment of the present application has a structure shown in Formula I:

[0070]

[0071] In Formula I, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10Each is independently selected from one of H, F, Cl, Br, I, NO2, trifluoromethyl, nitrile, benzyl, diphenylmethyl, C1-6 alkyl, C1-6 alkoxy, a functional group having a structure of formula II, and a functional group having a structure of formula III; X1 and X2 are each independently selected from one of F, Cl, Br, and I;

[0072]

[0073] Among them, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 Each is independently selected from one of H, F, Cl, Br, I, NO2, trifluoromethyl, nitrile, C1-6 alkyl, and C1-6 alkoxy.

[0074] In some embodiments, R1, R2, R3, R4, and R5 are each independently selected from one of H, C1-6 alkyl, or C1-6 alkoxy.

[0075] In some embodiments, R6, R7, R8, R9, R 10 Each is independently selected from one of H, F, Cl, Br, I, NO2, trifluoromethyl, nitrile, the functional group having the structure of formula II, the functional group having the structure of formula III, etc.

[0076] In some embodiments, the asymmetric zinc diimide compound includes but is not limited to at least one of compounds 1-5, etc.:

[0077]

[0078] In the compound 3, X3 and X4 are each independently selected from one of F, Cl, Br and I.

[0079] The asymmetric zinc diimide compound of the embodiment of the present application is an asymmetric zinc diimide complex substituted with a large steric hindered group, which is very easy to decomplex to generate imine under the action of a base, and can achieve the effect of synthesizing asymmetric diimide in high yield.

[0080] <Method for preparing asymmetric zinc diimide compound>

[0081] The preparation method of the asymmetric zinc diimide compound of the embodiment of the present application can be used to prepare the asymmetric zinc diimide compound of the embodiment of the present application.

[0082] The inventors have found that the prior art has a reversible reaction in which amines and dicarbonyl compounds undergo condensation reactions to generate diimines. For the synthesis of some diimines substituted with large steric hindrance groups, there are problems such as poor product stability and insufficient driving force for the positive reaction, resulting in low reaction yields. Therefore, the present application embodiment aims to provide a stable large steric hindrance group substituted asymmetric diimine zinc compound, mild reaction conditions, simple post-treatment, and a high yield preparation method. The compound is easily decomplexed and converted into diimine under certain conditions.

[0083] Specifically, zinc salt is added as a complexing agent to the reaction system for synthesizing diimine, and the diimine is complexed and separated from the reaction system in time during the reaction process, thereby effectively promoting the reaction in the forward direction. At the same time, a certain amount of a first dehydrating agent and a second dehydrating agent (including chemical dehydration and physical dehydration principles) such as molecular sieves, anhydrous magnesium sulfate, orthoesters are added to the reaction system to timely adsorb the generated water in the reaction process, which can effectively avoid the occurrence of reverse reactions, further inhibit the occurrence of side reactions, effectively promote the equilibrium to the forward reaction, and improve the reaction conversion rate, yield and selectivity.

[0084] The preparation method of the asymmetric zinc diimide compound of the embodiment of the present application is described in detail below.

[0085] The preparation method of the asymmetric zinc diimide compound of the embodiment of the present application comprises the following steps:

[0086] S101, subjecting acenaphthenequinone, a first dehydrating agent, a first catalyst, a first substituted aniline and a solvent to a first reaction to obtain a monoimine ketone compound.

[0087] S102, subjecting the monoimine ketone compound, zinc salt, a second dehydrating agent, a second substituted aniline, and a second catalyst to a second reaction to obtain the asymmetric diimine zinc compound.

[0088] In some embodiments, the first substituted aniline and the second substituted aniline are different anilines.

[0089] In some embodiments, the first substituted aniline and the second substituted aniline both include compounds having a structure of Formula IV:

[0090]

[0091] In Formula I, R1', R2', R3 ’ 、R4 ’ 、R5 ’Each is independently selected from one of H, F, Cl, Br, I, NO2, trifluoromethyl, cyano, C1-6 alkyl, C1-6 alkoxy, a functional group having a structure of formula V, and a functional group having a structure of formula VI,

[0092]

[0093] Among them, R6 ’ , R7', R8', R9 ’ , R 10 '、R 11 '、R 12 '、R 13 '、R 14 '、R 15 '、R 16 '、R 17 '、R 18 '、R 19 '、R 20 ' are each independently selected from one of H, F, Cl, Br, I, NO2, trifluoromethyl, nitrile, C1-6 alkyl, and C1-6 alkoxy.

[0094] As a preferred example, the first substituted aniline includes at least one of 2-di(p-cyanophenyl)methyl-4,6-dimethylaniline, 2-di(p-trifluoromethylphenyl)methyl-4,6-dimethylaniline, 2-di(p-nitrophenyl)methyl-4,6-dimethylaniline, 2-di(p-fluorophenyl)methyl-4,6-dimethylaniline, 2-di(p-chlorophenyl)methyl-4,6-dimethylaniline, 2-di(p-bromophenyl)methyl-4,6-dimethylaniline, etc.

[0095] As a preferred example, the second substituted aniline includes at least one of 2,4,6-trimethylaniline, 3,4,5-trimethylaniline, aniline, 2,4-dimethylaniline, 2,6-dimethyl-4-ethylaniline and the like.

[0096] In some embodiments, the first dehydrating agent and the second dehydrating agent both include, but are not limited to, at least one of a chemical dehydrating agent and a physical dehydrating agent.

[0097] In some embodiments, the chemical dehydrating agent includes but is not limited to orthoesters and the like.

[0098] Exemplarily, the orthoester includes but is not limited to at least one of trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, etc., preferably trimethyl orthoacetate or triethyl orthoacetate.

[0099] In some embodiments, the physical dehydrating agent includes but is not limited to at least one of molecular sieves, anhydrous sodium sulfate, anhydrous magnesium sulfate, calcium chloride, etc., preferably molecular sieves.

[0100] It should be noted that, in the embodiments of the present application, the first dehydrating agent and the second dehydrating agent may be the same or different.

[0101] As a preferred example, the first dehydrating agent includes but is not limited to at least one of molecular sieves, anhydrous sodium sulfate, anhydrous magnesium sulfate, calcium chloride, orthoesters, and the like.

[0102] As a preferred example, the second dehydrating agent includes but is not limited to at least one of molecular sieves, anhydrous sodium sulfate, anhydrous magnesium sulfate, calcium chloride, orthoesters, and the like.

[0103] In some embodiments, both the first catalyst and the second catalyst include, but are not limited to, at least one of a proton acid, a Lewis acid, and the like.

[0104] In some embodiments, the protonic acid includes but is not limited to at least one of formic acid, acetic acid, trifluoroacetic acid, difluoroacetic acid, oxalic acid, benzenesulfonic acid, p-toluenesulfonic acid, hydrogen chloride, hydrogen bromide, and the like.

[0105] In some embodiments, the Lewis acid includes but is not limited to at least one of ferric chloride, zinc chloride, titanium tetrachloride, aluminum trichloride, boron trifluoride, and the like.

[0106] It should be noted that, in the embodiments of the present application, the first catalyst and the second catalyst may be the same or different.

[0107] As a preferred example, the first catalyst includes but is not limited to at least one of formic acid, acetic acid, trifluoroacetic acid, difluoroacetic acid, oxalic acid, benzenesulfonic acid, p-toluenesulfonic acid, hydrogen chloride, hydrogen bromide and the like.

[0108] As a preferred example, the second catalyst includes but is not limited to at least one of formic acid, acetic acid, trifluoroacetic acid, difluoroacetic acid, oxalic acid, benzenesulfonic acid, p-toluenesulfonic acid, hydrogen chloride, hydrogen bromide and the like.

[0109] In some embodiments, the zinc salt includes but is not limited to at least one of zinc chloride, zinc bromide, zinc iodide, zinc carbonate, and the like.

[0110] As a preferred example, the zinc salt is zinc chloride or zinc carbonate.

[0111] In some embodiments, the solvent includes but is not limited to at least one of C8-12 alkanes, alkylbenzenes, halogenated benzenes, ethers, esters, alcohols, halogenated alkanes, nitriles, and the like.

[0112] As an optional example, the solvent includes but is not limited to at least one of octane, nonane, decane, dichloromethane, chloroform, dichloroethane, trichloroethane, benzene, toluene, chlorobenzene, fluorobenzene, tetrahydrofuran, methyltetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, methanol, ethanol, propanol, butanol, cyclohexanol, ethyl acetate, butyl acetate, butyl butyrate, acetonitrile, propionitrile, butyronitrile, benzonitrile, etc.

[0113] In some embodiments, the mass of the solvent is 0-60 times the mass of the acenaphthenequinone, including but not limited to 0 times, 5 times, 10 times, 15 times, 20 times, 25 times, 30 times, 35 times, 40 times, 45 times, 50 times or 55 times, etc.

[0114] It is understandable that when the mass of the solvent is 0 times the mass of the acenaphthenequinone, there is no solvent in the preparation method of the asymmetric zinc diimide compound of the embodiment of the present application, that is, the first reaction is carried out without a solvent.

[0115] In the examples of the present application, a large amount of solvent is used, the raw material solubility is good, and the reaction speed is fast, but too much is not economical. Therefore, in a preferred case, the mass of the solvent is 1 / 3-40 times the mass of the acenaphthenequinone.

[0116] In some embodiments, the molar ratio of the acenaphthenequinone, the first dehydrating agent, the first catalyst, the first substituted aniline, the zinc salt, the second dehydrating agent, the second substituted aniline, and the second catalyst is 1: (0.5-10.0): (0.5-5.0): (0.8-1.5): (1.0-3.0): (0.5-10.0): (0.8-1.5): (0.5-5.0).

[0117] Exemplarily, the molar ratio of the acenaphthenequinone, the first dehydrating agent, the first catalyst, the first substituted aniline, the zinc salt, the second dehydrating agent, the second substituted aniline, and the second catalyst (acenaphthenequinone: the first dehydrating agent: the first catalyst: the first substituted aniline: the zinc salt: the second dehydrating agent: the second substituted aniline: the second catalyst) includes but is not limited to 1:1.0:1.0:1.15:2.0:1.0:1.15:1.0, 1:1.0:2.0:1:2.0:1.5:1.15 :1.6, 1:1.8:2.0:1.3:2.0:0.9:1.15:2.0, 1:2.5:2.0:1.15:1.5:1.7:1.15:2.6, 1:1.3:1.6:1.15:2.5:2.0:1.15:2.0, 1:2.2:1.5:1.15:2.0:3.3:1:3.0 or 1:3.4:2.0:1.15:2.0:1.5:1.4:2.0, etc.

[0118] In the embodiment of the present application, the molar ratio of the acenaphthenequinone, the first dehydrating agent, the first catalyst, the first substituted aniline, the zinc salt, the second dehydrating agent, the second substituted aniline, and the second catalyst is more suitable within the above range, at which time the raw material conversion rate is high, and the yield and selectivity of the asymmetric diimine zinc complex are high. If the molar ratio of the dehydrating agent (the first dehydrating agent and / or the second dehydrating agent) to the acenaphthenequinone is too small, the dehydration is incomplete, the reaction selectivity is reduced, and the yield is low; if the molar ratio is too large, the reaction is complete, the reaction yield is high, but it is not economical. If the molar ratio of substituted aniline (the first substituted aniline and / or the second substituted aniline) to acenaphthenequinone is too small, the acenaphthenequinone reaction is incomplete and the reaction conversion rate is low; if the molar ratio of substituted aniline (the first substituted aniline and / or the second substituted aniline) is too large, the acenaphthenequinone reaction is complete and the reaction yield is high; if the molar ratio of zinc salt to substituted aniline (the first substituted aniline and / or the second substituted aniline) is too large, the byproduct of symmetrical diimine zinc complex increases and the selectivity of the target product decreases; if the molar ratio of zinc salt to acenaphthenequinone is too small, the diimine complex is incomplete and the reaction selectivity is low; if the molar ratio is large, a large amount of zinc salt remains and is easily left in the product. If the amount of catalyst (the first catalyst and / or the second catalyst) is too much, both the main and side reactions are promoted, resulting in an increase in byproducts and a decrease in yield; if the amount of catalyst (the first catalyst and / or the second catalyst) is too little, the reaction speed is too slow, the reaction time is extended, the product decomposes, and the yield decreases.

[0119] It should be noted that in the embodiments of the present application, when the first catalyst and / or the second catalyst is a weak acid such as acetic acid or oxalic acid, the amount of the first catalyst and / or the second catalyst can be appropriately increased within the above-mentioned amount ratio.

[0120] In some embodiments, both the first reaction and the second reaction are reflux reactions.

[0121] In some embodiments, the first reaction and the second reaction are performed in the same reaction vessel.

[0122] Exemplarily, the reaction vessel includes, but is not limited to, a four-necked flask, a round-bottomed flask, an eggplant-shaped flask, and the like.

[0123] In some embodiments, both the first reaction and the second reaction are performed under stirring conditions.

[0124] In the embodiments of the present application, the reaction of acenaphthenequinone with a dehydrating agent (a first dehydrating agent and / or a second dehydrating agent), a substituted aniline (a first substituted aniline and / or a second substituted aniline), and a zinc salt to synthesize diimine is performed at a high temperature, and the reaction rate is fast. However, too high a temperature will lead to an increase in side reactions and a decrease in the reaction selectivity. The reaction temperature required for the substituted aniline (the first substituted aniline and / or the second substituted aniline) with a lower molecular weight is also lower.

[0125] Therefore, in some embodiments, the reaction temperature of the first reaction and the second reaction is 20-120°C, including but not limited to 25°C, 35°C, 50°C, 65°C, 80°C, 95°C, 110°C or 115°C, etc.

[0126] In some embodiments, the reaction temperatures of the first reaction and the second reaction are different.

[0127] In some embodiments, the reaction time of the first reaction and the second reaction is 2-24 hours, including but not limited to 3 hours, 6 hours, 9 hours, 12 hours, 15 hours, 18 hours, 21 hours or 23 hours, etc.

[0128] In some embodiments, the method for preparing the asymmetric zinc diimide compound further comprises the steps of filtering and crystallizing after the second reaction.

[0129] In some embodiments, the method for preparing the asymmetric zinc diimide compound further comprises the step of slurrying the product of the second reaction before filtering.

[0130] Exemplarily, the pulping process includes: washing with sodium carbonate solution and solvent pulping.

[0131] In the embodiments of the present application, separation and purification of the asymmetric zinc diimide compound can be achieved by slurrying and filtering.

[0132] The preparation method of the asymmetric zinc diimide compound of the embodiment of the present application can at least bring the following beneficial effects: the synthesis method is simple to operate, the conditions are mild, it is easy to separate and purify, and the yield is high. The obtained asymmetric zinc diimide complex is very easy to decomplex to generate imine under the action of a base, which can achieve the effect of synthesizing asymmetric diimide with high yield. Specifically:

[0133] 1. A complexing agent zinc salt is added during the reaction process, and the generated unstable large steric hindrance group-substituted diimine is stably complexed with the zinc salt to generate a corresponding zinc complex, and the zinc complex can be separated from the reaction system in time during the reaction process, effectively promoting the reaction equilibrium to the forward reaction, and the large steric hindrance group-substituted diimine zinc complex can be synthesized with high selectivity and high yield, and the synthesis process steps are short and the operation is simple.

[0134] 2. Using orthoesters, sodium sulfate, etc. as the first dehydrating agent and the second dehydrating agent can timely adsorb the water generated by the reaction, effectively inhibit the reverse reaction, greatly improve the raw material conversion rate, and have high reaction selectivity.

[0135] 3. The synthesis of asymmetric diimine zinc complexes substituted with large steric hindrance groups is carried out in the same reactor, which can realize the one-pot synthesis of asymmetric structures. It can be purified by simple stirring and filtration, with a short process flow and simple post-treatment.

[0136] The asymmetric zinc diimide compound of the embodiment of the present application, or the asymmetric zinc diimide compound prepared by the method for preparing the asymmetric zinc diimide compound of the embodiment of the present application can be used in the production of polyolefins, especially as a raw material for the preparation of catalysts for the production of polyolefins.

[0137] <Catalyst>

[0138] The catalyst of the embodiment of the present application is prepared using the asymmetric zinc diimide compound of the embodiment of the present application as a raw material, or is prepared using the asymmetric zinc diimide compound prepared by the preparation method of the asymmetric zinc diimide compound of the embodiment of the present application as a raw material.

[0139] In some embodiments, the catalyst is an imine metal complex, which can be used in the synthesis of polyolefins and the like.

[0140] Certain features of the present technology are further illustrated in the following non-limiting examples.

[0141] Example 1

[0142] The asymmetric diimine zinc complex of this embodiment is asymmetric diimine zinc bromide, and its structural formula is The preparation method is:

[0143] In a 500 ml four-necked flask with a condenser, add acenaphthenequinone (3.6 g, 20 mmol), 10 g of anhydrous sodium sulfate, p-toluenesulfonic acid (3.8 g, 22 mmol), 2-di(p-cyanophenyl)methyl-4,6-dimethylaniline (6.7 g, 20 mmol), 180 g of butyl acetate, stir and reflux at 130 ° C for 4 h (to obtain a monoimine ketone compound), then the reaction liquid temperature is reduced to 40 ° C, zinc bromide (5.6 g, 25 mmol) is added, Trimethyl orthoacetate (2.4 g, 20 mmol), 3,4,5-trimethylaniline (2.8 g, 21 mmol), formic acid (1.01 g, 22 mmol), continue stirring for 6 h, cool with ice water, filter, add 100 g petroleum ether to the filter cake, stir for 3 h, filter to obtain 16.03 g of asymmetric diimine zinc bromide solid substituted by one molecule of 2-di(p-cyanophenyl)methyl-4,6-dimethyl and one molecule of 3,4,5-trimethyl. Its nuclear magnetic hydrogen spectrum test diagram is as follows Figure 1 shown.

[0144] According to the test, the yield of the asymmetric diimine zinc bromide solid prepared in this example is 95%.

[0145] The asymmetric diimine zinc bromide solid was washed with a saturated sodium carbonate solution and slurried with ethyl acetate solvent, and filtered to separate and obtain 10.58 g of asymmetric diimine substituted with a large steric group, with a yield of 86%.

[0146] Example 2 (Compared with Example 1, the zinc salt is different)

[0147] This embodiment is basically the same as Embodiment 1, except that:

[0148] The asymmetric diimine zinc complex of this embodiment is an asymmetric diimine zinc chloride, and its structural formula is

[0149]

[0150] In the preparation method, zinc bromide was replaced with zinc chloride (3.41 g, 25 mmol); 13.74 g of asymmetric diimine zinc chloride solid was obtained.

[0151] According to the test, the yield of the asymmetric diimine zinc chloride solid prepared in this example is 91%.

[0152] Example 3 (Compared with Example 1, the dehydrating agents of the first reaction and the second reaction are interchanged)

[0153] This embodiment is basically the same as Embodiment 1, except that:

[0154] 10 g of anhydrous sodium sulfate was replaced by 10 g of trimethyl orthoacetate, and trimethyl orthoacetate (2.4 g, 20 mmol) was replaced by anhydrous sodium sulfate (2.84 g, 20 mmol); 8.95 g of asymmetric diimine zinc bromide solid was obtained.

[0155] According to the test, the yield of the asymmetric diimine zinc bromide solid prepared in this example is 53%.

[0156] Example 4 (Compared with Example 1, the catalysts of the first reaction and the second reaction are interchanged)

[0157] This embodiment is basically the same as Embodiment 1, except that:

[0158] p-Toluenesulfonic acid (3.8 g, 22 mmol) was replaced by formic acid (1.01 g, 22 mmol), and formic acid (1.01 g, 22 mmol) was replaced by p-toluenesulfonic acid (3.8 g, 22 mmol); 9.8 g of asymmetric diimine zinc bromide solid was obtained.

[0159] The yield of the asymmetric diimine zinc bromide solid prepared in this example is 58%.

[0160] Example 5 (Compared with Example 1, the dehydrating agent in the first reaction and the second reaction is the same)

[0161] This embodiment is basically the same as Embodiment 1, except that:

[0162] 10 g of anhydrous sodium sulfate was replaced with 10 g of trimethyl orthoacetate; 9.62 g of asymmetric diimine zinc bromide solid was obtained.

[0163] The yield of the asymmetric diimine zinc bromide solid prepared in this example is 57%.

[0164] Example 6 (Compared with Example 1, the catalysts for the first reaction and the second reaction are the same)

[0165] This embodiment is basically the same as Embodiment 1, except that:

[0166] Formic acid (1.01 g, 22 mmol) was replaced with p-toluenesulfonic acid (3.8 g, 22 mmol); 7.94 g of asymmetric diimine zinc bromide solid was obtained.

[0167] The yield of the asymmetric diimine zinc bromide solid prepared in this example is 47%.

[0168] Example 7 (Compared with Example 1, the first substituted aniline is different)

[0169] This embodiment is basically the same as Embodiment 1, except that:

[0170] The asymmetric diimine zinc complex of this embodiment is asymmetric diimine zinc bromide, and its structural formula is

[0171]

[0172] In the preparation method, 2-di(p-cyanophenyl)methyl-4,6-dimethylaniline (6.7 g, 20 mmol) was replaced with 2-di(p-chlorophenyl)methyl-4,6-dimethylaniline (7.13 g, 20 mmol); 16.05 g of asymmetric diimine zinc bromide solid was obtained.

[0173] The yield of the asymmetric diimine zinc bromide solid prepared in this example is 93%.

[0174] Example 8 (Compared with Example 1, the second substituted aniline is different)

[0175] This embodiment is basically the same as Embodiment 1, except that:

[0176] In the preparation method, 3,4,5-trimethylaniline (2.8 g, 21 mmol) was replaced with 2,4,6-trimethylaniline (2.8 g, 21 mmol); 16.2 g of asymmetric diimine zinc bromide solid was obtained.

[0177] The yield of the asymmetric diimine zinc bromide solid prepared in this example is 96%.

[0178] Example 9 (Compared with Example 1, the first substituted aniline and the second substituted aniline are different)

[0179] This embodiment is basically the same as Embodiment 1, except that:

[0180] In the preparation method, 2-di(p-cyanophenyl)methyl-4,6-dimethylaniline (6.7 g, 20 mmol) was replaced by 2-di(p-chlorophenyl)methyl-4,6-dimethylaniline (7.13 g, 20 mmol), and 3,4,5-trimethylaniline (2.8 g, 21 mmol) was replaced by 2,4,6-trimethylaniline (2.8 g, 21 mmol); 15.02 g of asymmetric diimine zinc bromide solid was obtained.

[0181] According to the test, the yield of the asymmetric diimine zinc bromide solid prepared in this example is 87%.

[0182] Comparative Example 1

[0183] In a 500 ml four-necked flask, add acenaphthenequinone (3.6 g, 20 mmol), p-toluenesulfonic acid (3.8 g, 22 mmol), 2-di(p-cyanophenyl)methyl-4,6-dimethylaniline (6.7 g, 20 mmol) and 180 g of dichloromethane, and stir at room temperature (25°C) for 5 h. After the reaction is completed, distill under reduced pressure. The obtained solid crude product is further subjected to column chromatography. The eluent is petroleum ether: ethyl acetate 10:1 (v / v). 3.51 g of a monoimine ketone compound substituted by one molecule of 2-di(p-cyanophenyl)methyl-4,6-dimethyl is separated, and the yield is 35%.

[0184] In a 500 ml four-necked flask with a condenser and a water separator, the above-mentioned monoimine ketone compound (10.0 g, 20 mmol), p-toluenesulfonic acid (3.5 g, 20 mmol), 3,4,5-trimethylaniline (2.7 g, 20 mmol) and 200 g of toluene were added, and stirred at 115°C for 7 h. After the reaction was completed, the mixture was distilled under reduced pressure. The obtained solid crude product was further subjected to column chromatography. The eluent was petroleum ether: ethyl acetate 10:1 (v / v). 3.71 g of asymmetric diimine substituted by one molecule of 2-di(p-cyanophenyl)methyl-4,6-dimethyl and one molecule of 3,4,5-trimethyl was separated, and the yield was 30%.

[0185] In summary, the synthesis of asymmetric diimine from acenaphthenequinone requires two-step synthesis and two column chromatography separation and purification steps, with a comprehensive yield of 10.5%.

[0186] Comparative Example 2 (Compared with Example 1, without zinc salt)

[0187] This comparative example is basically the same as Example 1, except that:

[0188] The step of "adding zinc bromide (5.6 g, 25 mmol)" was removed. After the reaction was completed, the solid crude product was further subjected to column chromatography using a ratio of petroleum ether to ethyl acetate (10:1 (v / v) as the eluent to obtain 6.07 g of an asymmetric diimine substituted by one molecule of 2-di(p-cyanophenyl)methyl-4,6-dimethyl and one molecule of 3,4,5-trimethyl.

[0189] According to the test, the yield of the asymmetric diimine solid prepared in this comparative example is 49%.

[0190] Comparative Example 3 (Compared with Example 1, the first dehydrating agent was removed)

[0191] This comparative example is basically the same as Example 1, except that:

[0192] Remove “10g of anhydrous sodium sulfate”.

[0193] According to the test, the yield of the asymmetric diimine zinc bromide solid prepared in this comparative example is 71%.

[0194] Comparative Example 4 (Compared with Example 1, the second dehydrating agent was removed)

[0195] This comparative example is basically the same as Example 1, except that:

[0196] Remove "10g of trimethyl orthoacetate".

[0197] According to the test, the yield of the asymmetric diimine zinc bromide solid prepared in this comparative example is 75%.

[0198] Comparative Example 5 (Compared with Example 1, zinc salt was replaced by zinc oxide)

[0199] This comparative example is basically the same as Example 1, except that:

[0200] Zinc bromide was replaced with zinc oxide (2.04 g, 25 mmol); after the reaction was completed, the product was distilled under reduced pressure, and the obtained solid crude product was further subjected to column chromatography with the eluent being petroleum ether:ethyl acetate 10:1 (v / v), to separate 2.48 g of asymmetric diimine solid.

[0201] According to the test, the yield of the asymmetric diimine solid prepared in this comparative example is 20%.

[0202] It can be seen from the above examples and comparative examples that the method provided by the present application can achieve high selectivity and high yield synthesis by adding the first dehydrating agent when synthesizing the monoimine ketone compound, and the synthesis of the asymmetric diimine zinc complex can be directly carried out without separation. By further adding the second dehydrating agent and the complexing agent zinc salt to the reaction solution, the reaction is effectively promoted in the forward direction, and the reverse reaction is avoided, and the asymmetric diimine zinc complex substituted with a large steric hindering group can be synthesized with a high yield (95%). The above asymmetric diimine zinc complex is a key intermediate for preparing asymmetric diimine. After washing with sodium carbonate solution and solvent beating, 10.58g of asymmetric diimine substituted with a large steric hindering group was obtained by filtration and separation, with a yield of 86%.

[0203] In summary, the present application adds zinc salt as a complexing agent to the reaction system for synthesizing diimine, separates the diimine from the reaction system in time during the reaction, thereby promoting the reaction to proceed in the forward direction, and at the same time, adds a certain amount of anhydrous magnesium sulfate, orthoester and other dehydrating agents (first dehydrating agent and / or second dehydrating agent) to the reaction system, and timely adsorbs the generated water during the reaction, which can further inhibit the occurrence of side reactions and effectively promote the equilibrium to proceed to the forward reaction. Through this strategy, a large sterically hindered group-substituted diimine zinc complex can be synthesized with high selectivity and high yield. The diimine zinc complex is very easy to decomplex under certain conditions to obtain diimine.

[0204] In the present application, the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the described specific features, structures, materials or characteristics may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0205] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In the description of this application, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0206] Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limitations on the present application. Ordinary technicians in this field can change, modify, replace and modify the above embodiments within the scope of the present application.

Claims

1. An asymmetric zinc diimide compound, characterized in that The asymmetric zinc diimide compound has a structure shown in Formula I: In Formula I, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 Each is independently selected from one of H, F, Cl, Br, I, NO2, trifluoromethyl, nitrile, benzyl, diphenylmethyl, C1-6 alkyl, C1-6 alkoxy, a functional group having a structure of formula II, and a functional group having a structure of formula III; X1 and X2 are each independently selected from one of F, Cl, Br, and I; Among them, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 Each is independently selected from one of H, F, Cl, Br, I, NO2, trifluoromethyl, nitrile, C1-6 alkyl, and C1-6 alkoxy.

2. The asymmetric zinc diimide compound according to claim 1, characterized in that The R1, R2, R3, R4, and R5 are each independently selected from one of H, C1-6 alkyl or C1-6 alkoxy; and / or, R6, R7, R8, R9, R 10 Each is independently selected from one of H, F, Cl, Br, I, NO2, trifluoromethyl, nitrile, the functional group having the structure of formula II, and the functional group having the structure of formula III.

3. The asymmetric zinc diimide compound according to claim 1, characterized in that The asymmetric zinc diimide compound comprises at least one of compounds 1-5: In the compound 3, X3 and X4 are each independently selected from one of F, Cl, Br and I.

4. A method for preparing an asymmetric zinc diimide compound, characterized in that: include: The acenaphthenequinone, the first dehydrating agent, the first catalyst, the first substituted aniline and the solvent are subjected to a first reaction to obtain a monoimine ketone compound; The monoimine ketone compound, zinc salt, a second dehydrating agent, a second substituted aniline, and a second catalyst are subjected to a second reaction to obtain the asymmetric diimine zinc compound; The first substituted aniline and the second substituted aniline are different anilines.

5. The preparation method according to claim 4, characterized in that: The first substituted aniline and the second substituted aniline both include compounds having a structure of Formula IV: In Formula I, R1', R2', R3', R4', and R5' are each independently selected from one of H, F, Cl, Br, I, NO2, trifluoromethyl, cyano, C1-6 alkyl, C1-6 alkoxy, a functional group having a structure of Formula V, and a functional group having a structure of Formula VI, Among them, R6', R7', R8', R9', R 10 '、R 11 '、R 12 '、R 13 '、R 14 '、R 15 '、R 16 '、R 17 '、R 18 '、R 19 '、R 20 ' are each independently selected from one of H, F, Cl, Br, I, NO2, trifluoromethyl, nitrile, C1-6 alkyl, and C1-6 alkoxy.

6. The preparation method according to claim 4, characterized in that: The first dehydrating agent and the second dehydrating agent both include at least one of molecular sieves, anhydrous sodium sulfate, anhydrous magnesium sulfate, calcium chloride, and orthoesters; and / or, The first catalyst and the second catalyst both include at least one of a protonic acid and a Lewis acid; and / or, The zinc salt comprises at least one of zinc chloride, zinc bromide, zinc iodide and zinc carbonate; and / or, The solvent includes at least one of C8-12 alkanes, alkylbenzenes, halogenated benzenes, ethers, esters, alcohols, halogenated alkanes, and nitriles.

7. The preparation method according to claim 6, characterized in that: The orthoester includes at least one of trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, and triethyl orthoacetate; and / or, The protonic acid includes at least one of formic acid, acetic acid, trifluoroacetic acid, difluoroacetic acid, oxalic acid, benzenesulfonic acid, p-toluenesulfonic acid, hydrogen chloride and hydrogen bromide; and / or, The Lewis acid comprises at least one of ferric chloride, zinc chloride, titanium tetrachloride, aluminum trichloride, and boron trifluoride; and / or, The solvent includes at least one of octane, nonane, decane, dichloromethane, chloroform, dichloroethane, trichloroethane, benzene, toluene, chlorobenzene, fluorobenzene, tetrahydrofuran, methyltetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, methanol, ethanol, propanol, butanol, cyclohexanol, ethyl acetate, butyl acetate, butyl butyrate, acetonitrile, propionitrile, butyronitrile, and benzonitrile.

8. The preparation method according to claim 4, characterized in that: The molar ratio of the acenaphthenequinone, the first dehydrating agent, the first catalyst, the first substituted aniline, the zinc salt, the second dehydrating agent, the second substituted aniline, and the second catalyst is 1: (0.5-10.0): (0.5-5.0): (0.8-1.5): (1.0-3.0): (0.5-10.0): (0.8-1.5): (0.5-5.0); and / or, The mass of the solvent is 0-60 times the mass of the acenaphthenequinone; and / or, The first reaction and the second reaction are carried out in the same reaction vessel; and / or, The first reaction and the second reaction are both carried out under stirring conditions; and / or, The reaction temperature of the first reaction and the reaction temperature of the second reaction are both 20-120° C.; and / or, The reaction temperatures of the first reaction and the second reaction are different; and / or, The reaction time of the first reaction and the second reaction is 2-24h; and / or, The method for preparing the asymmetric zinc diimide compound further comprises the steps of filtering and crystallizing after the second reaction.

9. A catalyst, characterized in that The method is prepared using the asymmetric zinc diimide compound as claimed in any one of claims 1 to 3 or the asymmetric zinc diimide compound prepared by the preparation method as claimed in any one of claims 4 to 9 as a raw material.

10. Use of the asymmetric zinc diimide compound according to any one of claims 1 to 3, or the asymmetric zinc diimide compound prepared by the preparation method according to any one of claims 4 to 8, or the catalyst according to claim 9 in the production of polyolefins.

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