Catalyst component for olefin polymerization, catalyst and application thereof

Abstract

The present invention provides a catalyst component, a catalyst and applications thereof for olefin polymerization. The catalyst component comprises: Mg, Ti, a halogen, and a chlorendic acid ester internal electron donor. The chlorendic acid ester internal electron donor has a structure shown in Formula I: #imgabs0#. The catalyst component and the catalyst have high catalytic activity, and the polypropylene obtained by catalytic polymerization has a regular particle size, a high bulk density, and a high isotacticity. Compared with the polypropylene obtained by phthalate ester and diether catalysts, the molecular weight distribution is wider, and the overall performance is better.

Description

Technical Field

[0001] The invention relates to a solid catalyst component for olefin polymerization, a catalyst, a preparation method and application thereof, and belongs to the field of polyolefin catalysts. Background Art

[0002] Currently, Ziegler-Natta (ZN) catalysts still dominate polyolefin production. Most ZN catalyst development focuses on developing highly active and stereospecific catalysts and improving their copolymerization ability. Furthermore, due to the high catalytic efficiency, excellent overall polymer properties, and low cost of traditional ZN catalysts (transition metal compounds such as titanium chemically bonded to a magnesium-containing support), the vast majority of catalysts used in polypropylene production worldwide are still based on ZN catalytic systems, characterized by high activity, high stereoregularity, long life, and customizable product structures. The development of ZN catalysts reveals that, even after the emergence of the first generation of catalysts, the addition of a third component (mostly an electron donor, also known as a Lewis base, added during catalyst preparation as an internal electron donor and during polymerization as an external electron donor) has been found to significantly influence olefin polymerization behavior and polymer properties. Modifying the internal electron donor in the catalyst can significantly alter the properties of the catalyst's active sites, thereby maximizing catalyst performance. Therefore, the development of new electron donors has been a hot topic in ZN polypropylene catalyst research and development.

[0003] The relatively distinctive high-performance internal electron donor compounds in the prior art mainly include: (1) fatty acid esters and aromatic acid ester compounds, mainly represented by phthalate compounds; (2) diether compounds (for example, the compounds disclosed in EP0361493 and EP0728724); (3) succinate compounds (for example, the compounds disclosed in WO9856834, WO0063261, and WO03022894); (4) glycol ester compounds (for example, the compounds disclosed in WO9856834, WO0063261, and WO03022894); (5) compounds with other functional groups (for example, the compounds disclosed in CN1105671, CN1242780, and US20060128558), etc. However, in practical applications, the above-mentioned compounds all have certain problems when used as internal electron donors in olefin polymerization catalysts. Although the catalysts using 1,3-diether compounds as internal electron donors have higher activity and better hydrogen modulation sensitivity, the relative molecular weight distribution of the produced PP is narrow, which is not conducive to the development of different grades of PP; the advantage of using succinate compounds as internal electron donors is that the relative molecular weight distribution of the synthesized PP is relatively wide, but the disadvantage is that the stereoregularity of PP and the hydrogen modulation sensitivity of the catalyst need to be improved; and the overall activity of the diol ester catalytic system is not as ideal as the diether system.

[0004] Phthalate compounds are currently the most widely used internal electron donors for polyolefins in industry. These compounds offer moderate catalyst activity, good stereoselectivity, and are inexpensive. However, as commonly used plasticizers, phthalate compounds pose significant risks to human reproductive health and the environment, creating a significant demand for alternatives. Currently, the use of most phthalate compounds has been limited. Therefore, developing novel electron donors with excellent activity, good stereospecificity, good overall performance, and low cost to replace the widely used phthalate electron donor compounds in the prior art and to apply them to the preparation of efficient Ziegler-Natta catalysts has been a common research and development goal in the field of polyolefin catalysts in recent years. Summary of the Invention

[0005] In order to solve the above problems, the purpose of the present invention is to provide a catalyst component, catalyst and application thereof for olefin polymerization. The catalyst component and catalyst have high catalytic activity, and the polypropylene obtained by catalytic polymerization has regular particle size, high bulk density, high isotacticity, and a wider molecular weight distribution than that of polypropylene obtained by phthalate ester and diether catalysts, thereby having better overall performance.

[0006] In order to achieve the above object, the present invention provides a catalyst component for olefin polymerization, which comprises: Mg, Ti, halogen, and a chloranilate internal electron donor; wherein the chloranilate internal electron donor has a structure shown in Formula I:

[0007]

[0008] In Formula I, R 1 and R 2 the same or different, each independently selected from hydrogen, halogen, C1-C 20 Preferably, R 1 and R 2 Each of the heteroatoms comprises one or a combination of two or more selected from halogen, N, O, S, P and Si; More preferably, R 1 and R 2 Bonded to each other to form a ring.

[0009] According to a specific embodiment of the present invention, preferably, in Formula I, R 1 and R 2the same or different, each independently selected from H, halogen, the following substituents with less than 20 carbon atoms: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, haloalkyl, alkyl containing heteroatoms, halocycloalkyl, cycloalkyl containing heteroatoms, halophenyl, phenyl containing heteroatoms, haloalkylphenyl, alkylphenyl containing heteroatoms, halophenylalkyl, phenylalkyl containing heteroatoms, haloindenyl, indenyl containing heteroatoms, halobenzyl, benzyl containing heteroatoms, and heterocyclic aromatic substituents; the heteroatoms include one or a combination of two or more of N, O, S, P, and Si.

[0010] According to a specific embodiment of the present invention, preferably, in Formula I, R 1 and R 2 Each is independently selected from H, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20 The straight-chain or branched alkyl group of 20 carbon atoms or the following substituents within 20 carbon atoms: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, benzyl and its derivatives, phenethyl and its derivatives, furyl, pyrrolyl, thienyl, indenyl; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

[0011] According to a specific embodiment of the present invention, preferably, the chlorendic acid ester internal electron donor includes dimethyl chlorendic acid, diethyl chlorendic acid, di-n-propyl chlorendic acid, diisopropyl chlorendic acid, di-n-butyl chlorendic acid, diisobutyl chlorendic acid, di-tert-butyl chlorendic acid, di-n-pentyl chlorendic acid, diisopentyl chlorendic acid, dicyclopentyl chlorendic acid, di-n-hexyl chlorendic acid, dicyclohexyl chlorendic acid, diheptyl chlorendic acid, dioctyl chlorendic acid, dinonyl chlorendic acid, didecyl chlorendic acid, diundecyl chlorendic acid, didodecyl chlorendic acid, didodecyl chlorendic acid, didedecyl chlorendic acid, didetradecyl chlorendic acid, didopentadecyl chlorendic acid, didedecyl chlorendic acid, didecapdecyl chlorendic acid, didedecyl chlorendic acid, didetradecyl chlorendic acid, didedecyl chlorendic acid, didedecyl chlorendic acid, didecapdecyl chlorendic acid, dide ... chlorendic acid di(octadecyl) ester, chlorendic acid di(nonadecyl) ester, chlorendic acid di(eicosyl) ester, chlorendic acid diphenyl ester, chlorendic acid di-m-chlorophenyl ester, chlorendic acid di-p-chlorophenyl ester, chlorendic acid di-o-chlorophenyl ester, chlorendic acid di-p-tolyl ester, chlorendic acid di-m-tolyl ester, chlorendic acid di-o-tolyl ester, chlorendic acid di(mesitylene) ester, chlorendic acid di-p-methoxyphenyl ester, chlorendic acid di-m-methoxyphenyl ester, chlorendic acid di-o-methoxyphenyl ester, chlorendic acid di-p-nitrophenyl ester, chlorendic acid di(α-furan)methyl ester, chlorendic acid di(5-pentene) ester, chlorendic acid di(α-thiophene) ester, chlorendic acid dibenzyl ester, chlorendic acid diphenylethyl ester, chlorendic acid dicinnamyl ester, chlorendic acid ditetrahydrofurfuryl ester, and chlorendic acid di(1-indenyl) alcohol ester, or a combination of two or more thereof.

[0012] The chlorendic acid ester compound shown in formula I can be obtained by esterification reaction using chlorendic acid as a raw material, as shown in the following reaction formula I. Only one step of reaction is required, the synthesis is simple, and the yield is high; when performing the esterification reaction, the raw material alcohol can be an alcohol (R 1 and R 2 Same situation) or two alcohols (R 1 and R 2 Different situations), when two alcohols are used, a mixture of three chlorendic acid esters can be obtained, which can be directly used as an internal electron donor without separation. The ratio of each component in the mixture can be adjusted by the addition ratio of the two alcohols in the reaction raw materials, and the ratio of each component can be characterized and determined by analytical methods such as chromatography-mass spectrometry and nuclear magnetic resonance;

[0013]

[0014] According to a specific embodiment of the present invention, preferably, the catalyst component comprises a titanium compound, a magnesium compound, and an internal electron donor represented by formula I; the precursor of the magnesium compound is selected from X n Mg(OR a ) 2-n 、MgCl2·mR a OH, R a 2- n MgXn , MgCl2 / SiO2, MgCl2 / Al2O3, a mixture of magnesium halide and titanium alkoxide, or a combination of two or more thereof, wherein m is 0.1-6, 0≤n≤2, X is a halogen, R a C1-C 20 The general formula of the titanium compound is TiX N (OR b ) 4-N , where R b C1-C 20 The hydrocarbon group, X is halogen, and N is 1-4.

[0015] According to a specific embodiment of the present invention, preferably, the magnesium compound is an alcoholate of magnesium dihalide; or, the magnesium compound is a liquid magnesium compound (a magnesium compound dissolved in a liquid); or, the magnesium compound is a derivative of a magnesium dihalide molecule in which at least one halogen atom is replaced by a hydrocarbonoxy group or a halogenated hydrocarbonoxy group; more preferably, it is a hydrocarbonoxy magnesium compound, and further preferably, it is an alkoxy magnesium and / or an aryloxy magnesium.

[0016] According to a specific embodiment of the present invention, preferably, the titanium compound includes one or a combination of two or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and alkoxy titanium halide.

[0017] According to a specific embodiment of the present invention, preferably, the alkyl titanium halide includes one or a combination of two or more of methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, and tri-n-butoxytitanium chloride.

[0018] According to a specific embodiment of the present invention, preferably, the titanium compound is titanium tetrachloride.

[0019] According to a specific embodiment of the present invention, preferably, the molar ratio of the internal electron donor represented by formula I to the magnesium compound calculated as magnesium element is 0.01-5.0:1, preferably 0.05-3.0:1.

[0020] The present invention does not particularly limit the preparation method of the above-mentioned solid catalyst component, which can be carried out according to the following methods:

[0021] Method 1: Magnesium alcoholate or magnesium chloroalcoholate and excess TiCl4 and internal electron donor compound are reacted at a temperature of 80°C-135°C; preferably, the general formula TiX N (OR b ) 4-NTitanium compounds (where R b C1-C 20 A hydrocarbon group, X is a halogen, N = 1-4; preferably TiCl4) and a general formula of MgCl2·mR a OH adduct (wherein m is a number from 0.1 to 6, preferably from 2 to 4, and R a C1-C 20 The solid catalyst component is prepared by reacting an internal electron donor; wherein the general formula is MgCl2·mR a The OH adduct can be conveniently prepared into spherical form by mixing an alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, and rapidly quenching the emulsion to solidify the adduct in the form of spherical particles (see the disclosures of US Pat. No. 4,399,054 and US Pat. No. 4,469,648). The spherical adduct obtained in this way can be reacted directly with the titanium compound, or it can be pre-treated by thermally controlled dealcoholation (80° C. to 130° C.) to obtain a dealcoholated adduct (wherein the molar number of alcohol is generally less than 3, preferably between 0.1 and 2.5), before being subjected to the subsequent reaction.

[0022] For example, the adduct or dealcoholated adduct is suspended in cold TiCl4 (generally -25°C to 0°C) to react with the titanium compound, and the mixture is heated to 80°C to 130°C and maintained at this temperature for 0.5 to 2 hours, wherein the treatment with TiCl4 can be carried out once or multiple times, and an internal electron donor compound can be added during the treatment with TiCl4, and this treatment can be repeated once or multiple times;

[0023] Method 2: A magnesium compound is dissolved in a solvent system consisting of an organic epoxy compound, an organic phosphine compound, and an inert diluent to form a uniform solution, which is then mixed with a titanium compound and, in the presence of a precipitation aid, a solid is precipitated. This solid is treated with an internal electron donor compound to load the internal electron donor compound onto the solid, and, if necessary, further treated with titanium tetrahalide and an inert diluent. The precipitation aid is selected from the group consisting of an organic anhydride, an organic acid, an ether, and a ketone. The components, calculated per mole of magnesium halide, include 0.2-10 moles of the organic epoxy compound, 0.1-3 moles of the organic phosphine compound, 0-1.0 moles of the precipitation aid, and 0.5-150 moles of the titanium compound (calculated as moles of titanium element).

[0024] Method 3: TiCl4 or an aromatic hydrocarbon solution of titanium alkoxide (e.g., toluene, dimethylbenzene, etc.) is reacted with a dihydrocarbyl magnesium compound such as magnesium dialkoxide (preferably magnesium diethoxide) or magnesium diaryloxide at -25-0°C and halogenated at 80-130°C. The treatment with the aromatic hydrocarbon solution of TiCl4 can be repeated one or more times, and an internal electron donor compound is added once or in batches during multiple such treatments. For example, the preparation method of the titanium-containing solid catalyst component disclosed in US Pat. No. 5,077,357 can be used for preparation: magnesium ethoxide, titanium tetraethoxide, o-cresol, ethanol, and chlorobenzene are sequentially added and stirred; the TiCl4 / chlorobenzene solution is quickly added to the liquid, heated until completely dissolved, and then continued to be heated to a specific temperature; stirring is continued for a certain period of time after bubbling with N2 to remove the ethanol reactant, followed by washing once with hot chlorobenzene, twice with isooctane, and then drying with N2 to obtain the carrier. Or according to another example: TiCl4, tetraethoxytitanium, ethoxymagnesium and o-cresol are added to chlorobenzene in sequence and stirred; ethanol is added and stirred at high temperature for 3 hours after the ethoxymagnesium is dissolved; the mixture is filtered while hot and then washed once with warm chlorobenzene and once with isooctane, and finally dried with nitrogen;

[0025] Method 4: Magnesium dichloride is preactivated according to existing methods and then treated with an excess of TiCl4 at a temperature of about 80°C to 135°C, wherein the solution contains an internal electron donor compound. The TiCl4 treatment is repeated multiple times and the solid is washed with hexane to remove any unreacted TiCl4.

[0026] Method 5: Prepared with reference to the preparation method of the titanium-containing solid catalyst component disclosed in CN1208045: first, a liquid magnesium compound and a liquid titanium compound are contacted at low temperature in the presence of a compound selected from alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and esters to precipitate a solid. The temperature during contact is generally -70°C to 200°C, preferably -30°C to 130°C, and the internal electron donor compound is used during the contact process;

[0027] Method 6: Anhydrous magnesium chloride and an internal electron donor compound are ground together under conditions where magnesium dichloride is activated. The resulting product can be treated one or more times with an excess of TiCl4 at a temperature of 80°C to 130°C and then washed with a hydrocarbon solvent until it is free of chloride ions. A further detailed method is as follows: the product obtained by co-grinding anhydrous magnesium dichloride, a titanium compound, and an internal electron donor compound is treated with a halogenated hydrocarbon such as 1,2-dichloroethane, chlorobenzene, or dichloromethane at a temperature between 40°C and the boiling point of the halogenated hydrocarbon for 1-4 hours, and then the product is typically washed with an inert hydrocarbon solvent such as hexane.

[0028] Method 7: A magnesium compound supported on an inorganic oxide such as SiO2, alumina or porous silica gel is used as a carrier for preparation, which is then activated by a well-known method and then treated with an excess of TiCl4 at a temperature of about 80°C-135°C, with an internal electron donor compound added during the treatment process.

[0029] The reaction of the above-mentioned catalyst components results in the formation of magnesium halide in an active form. Typical crystalline magnesium halide has a regular structure and can only support a small amount of Ti, resulting in low catalytic activity. To prepare a highly active supported catalyst, the magnesium halide must be activated. Activation methods include physical and / or chemical methods to convert it into microcrystals so that the active centers are supported on the surface, edges, and defects of the magnesium halide. These treated magnesium halide microcrystals suitable for supporting Ti are referred to as "active magnesium halide." In addition to these reactions, other methods are known in the literature for converting compound starting materials other than magnesium halide into an active form of magnesium halide.

[0030] In any of the catalyst component preparation methods, the internal electron donor compound can be added directly or prepared in situ using an alternative method, such as an appropriate precursor that can be converted into the desired internal electron donor compound by known chemical reactions such as esterification, transesterification, etc. Typically, the internal electron donor compound is used in a molar ratio of 0.01-5:1, preferably 0.05-3.0:1, relative to the moles of MgCl2. Furthermore, the internal electron donor compound can be added simultaneously or separately during the preparation process, in batches or in any order and combination.

[0031] The present invention also provides a catalyst for olefin polymerization, which comprises the above catalyst component and an organic aluminum compound.

[0032] According to a specific embodiment of the present invention, preferably, the general formula of the organoaluminum compound is AlR c p X (3-p) , where R c is hydrogen or C1-C 20 wherein X is a halogen, and p is an integer of 0≤p≤3.

[0033] According to a specific embodiment of the present invention, preferably, the organoaluminum compound includes one or a combination of two or more of a trialkylaluminum compound, an alkylaluminum halide, an alkylaluminum hydride, an alkylaluminum sesquichloride, and an alkylaluminoxane.

[0034] According to a specific embodiment of the present invention, preferably, the trialkylaluminum compound includes one or a combination of two or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and trioctylaluminum; the alkylaluminum halide includes AlEt2Cl; the alkylaluminum sesquichloride includes Al2Et3Cl3, and more preferably, the organoaluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

[0035] According to a specific embodiment of the present invention, preferably, the molar ratio of the organoaluminum compound to the titanium atom in the catalyst component is 1-1000:1, more preferably 50-800:1.

[0036] According to a specific embodiment of the present invention, preferably, the raw material composition of the catalyst further includes an external electron donor.

[0037] According to a specific embodiment of the present invention, preferably, the external electron donor is a siloxane compound.

[0038] According to a specific embodiment of the present invention, preferably, the general formula of the siloxane compound is R' t Si(OR”) 4-t , wherein R' and R" are each independently selected from C1-C 18 wherein t is an integer of 0≤t≤3.

[0039] According to a specific embodiment of the present invention, preferably, R' and R" each contain a heteroatom; more preferably, the heteroatom includes one or a combination of two or more of N, O, S, P, and Si.

[0040] According to a specific embodiment of the present invention, preferably, the siloxane compound includes trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, triisobutylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane silane, di-tert-butyldiethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, di(2-ethylhexyl)dimethoxysilane, di(2-ethylhexyl)diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldiethoxysilane, cyclopentylisopropyldiethoxysilane, cyclopentylisobutyldimethoxysilane, cyclohexyl-n-propyl Dimethoxysilane, cyclohexyl-n-propyldiethoxysilane, cyclohexyl-n-butyldiethoxysilane, pentylmethyldimethoxysilane, pentylmethyldiethoxysilane, pentylethyldimethoxysilane, pentylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, cyclohexyldimethoxysilane, cyclohexyldiethoxysilane, 2-ethylhexyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyl trimethoxysilane, isobutyltrimethoxysilane, tert-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, bis(3-methylcyclohexyl)dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, bis(4-methylcyclohexyl)dimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, bis(3,5-dimethylcyclohexyl)dimethoxysilane, tetrapropoxysilane, tetrabutoxysilane, or a combination of two or more thereof.

[0041] According to a specific embodiment of the present invention, preferably, the siloxane compound includes di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldiethoxysilane, tert-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldiethoxysilane, One or a combination of two or more of cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane and 3,5-dimethylcyclopentyldimethoxysilane.

[0042] According to a specific embodiment of the present invention, preferably, the siloxane compound includes one or a combination of two or more of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, methyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-methyl-methoxysilane, cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane, and tert-hexyltrimethoxysilane.

[0043] According to a specific embodiment of the present invention, preferably, the molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100:1, more preferably 0.01-20:1, and further preferably 0.01-5:1.

[0044] The present invention also provides application of the catalyst in olefin polymerization.

[0045] According to a specific embodiment of the present invention, preferably, the olefin includes a linear or branched olefin, such as one or a combination of two or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, butadiene, vinylcyclopentene, and vinylcyclohexene.

[0046] According to a specific embodiment of the present invention, preferably, the polymerization comprises ethylene and / or propylene polymerization.

[0047] According to a specific embodiment of the present invention, preferably, the polymerization includes homopolymerization or copolymerization.

[0048] According to a specific embodiment of the present invention, preferably, during the catalytic process, the order of adding the components in the catalyst is arbitrary, and it is best to add the organoaluminum compound to the polymerization system first, then add the external electron donor, and finally add the catalyst component.

[0049] According to a specific embodiment of the present invention, preferably, in the above application, the polymerization process can be carried out with or without a solvent; the olefin monomer can be in gas phase or liquid phase; more preferably, hydrogen can be further added as a molecular weight regulator (polymerization can also be carried out without a molecular weight regulator); continuous polymerization or batch polymerization process can be applied, and the polymerization reaction can be carried out in one step, two steps or multiple steps.

[0050] According to a specific embodiment of the present invention, preferably, the polymerization temperature is ≤200°C, more preferably 20-100°C, and further preferably 40-80°C; the polymerization pressure is ≤10 MPa, more preferably 0.3-5 MPa.

[0051] The present invention has the following beneficial effects:

[0052] The present invention provides a catalyst component using chloranil as an internal electron donor. Chloranil is prepared by esterifying chloranil with alcohol under acidic conditions to obtain chloranil. The final product can be obtained in a single step, resulting in simple synthesis, high yield, and low cost, making it suitable for industrial production applications. Chloranil compounds have a variety of ester substituents, and the activity of the catalysts prepared is generally higher than that of phthalate catalysts commonly used in industry today, and higher than that of diether catalysts. Polypropylene obtained by catalytic polymerization using the catalyst of the present invention has high isotacticity and a wider molecular weight distribution than polypropylene obtained using phthalate and diether catalysts. Polyolefin catalysts prepared using chloranil internal electron donors avoid the use of phthalate internal electron donors, which are reproductively and environmentally toxic, and have better overall performance. This has broader industrial application prospects in countries and regions where the use of phthalate plasticizers is restricted. DETAILED DESCRIPTION

[0053] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be understood as limiting the scope of implementation of the present invention.

[0054] The operations for preparing the catalysts in the following examples were all carried out under the protection of high-purity nitrogen.

[0055] The isotacticity of polymers is determined by the heptane extraction method (extraction with boiling heptane for 6 hours): two grams of dry polymer sample are placed in an extractor and extracted with boiling heptane for 6 hours. The residue is then dried to a constant weight. The ratio of the obtained polymer weight (g) to 2 is the isotacticity.

[0056] The bulk density of the polymer was determined using the JB / T 2412-2008 method.

[0057] The molecular weight distribution of the polymer was determined using a PL-220 gel permeation chromatograph using trichlorobenzene as solvent at 150°C (standard: polystyrene, flow rate 1.0 mL / min, column: 3×Plgel 10 μm M1Xed-B 300×7.5 nm).

[0058] Preparation Example Synthesis of Chlorotolic Acid Compounds Shown in Formula I

[0059] 1. The synthesis of dimethyl chlorendic acid is as follows:

[0060] Chlorendic acid (3.9 g), methanol (100 mL), and concentrated sulfuric acid (0.6 mL) were added to a 500 L three-necked flask; heated under reflux for 2 h; cooled to room temperature; the reaction solution was poured into a saturated sodium bicarbonate solution and extracted twice with ethyl acetate (100 mL × 2). The organic phases were combined, washed with saturated brine (100 mL × 2), concentrated and recrystallized to obtain the product, chlorendic acid dimethyl ester (a1). The structure and H NMR spectrum results are shown in Table 1.

[0061] 2. Other chlorendic acid ester compounds (a2-a22) were prepared using the same synthetic method described above. Chlorendic acid was used as the starting material and esterified with the corresponding alcohol under acidic conditions to yield the corresponding chlorendic acid esters. The structures and H NMR spectra of compounds a2-a22 are shown in Table 1.

[0062]

[0063] Table 1

[0064]

[0065]

[0066]

[0067] Preparation of catalyst components Example 1

[0068] This embodiment provides a catalyst component, and its preparation method is as follows:

[0069] In a 500 ml, nitrogen-purged, stirred, five-necked flask, 10 g of MgCl2·2.5C2H5OH microspheres and 150 mL of titanium tetrachloride were added to prepare a suspension. The suspension was then maintained at -15°C for 1 hour, slowly heated to 80°C, and 4.2 g (10 mmol) of dimethyl chlorendonate was added. The temperature was then raised to 110°C and held there for 1 hour. The suspension was then filtered clean. The resulting solid was washed three times with 120 mL of titanium tetrachloride at 110°C and four times with 150 mL of hexane at 60°C. The suspension was then filtered off and dried to obtain solid catalyst component E1. The titanium content, internal electron donor content, and polymerization data of this solid catalyst component are shown in Table 2.

[0070] Example 2-22

[0071] Examples 2-22 each provide a catalyst component E2-E22, the preparation process of which is as shown in Example 1, except that dimethyl chlorendic acid is replaced by 10 mmol of compounds a2-a22 in Table 1 in sequence.

[0072] Example 23

[0073] This embodiment provides a catalyst component, and its preparation method is as follows:

[0074] In a 500 ml, nitrogen-purged, stirred, 5-necked flask, 10 g of anhydrous magnesium chloride, 150 mL of toluene, 17 mL of epichlorohydrin, and 16 mL of tributyl phosphate were added at room temperature. The temperature was raised to 50° C. with stirring and maintained for 2 hours until the solid was completely dissolved. 2.40 g of phthalic anhydride was then added and maintained for another hour. The solution was cooled to −25° C., 110 mL of titanium tetrachloride was added dropwise over 1 hour, and the temperature was slowly raised to 80° C. During the heating process, the solid was gradually washed out. 4.4 g of diethyl chlorendate was added, and the temperature was maintained at 80° C. for 1 hour. After filtration, the solution was washed twice with 200 mL of toluene. 120 mL of toluene and 80 mL of titanium tetrachloride were then added, and the temperature was continued to rise to 110° C. and maintained at this temperature for 2 hours. The liquid was then filter-pressed and the process was repeated once. The liquid was filtered off, and the resulting solid was washed once with 100 mL of dichloroethane and four times with hexane. After drying, the solid catalyst component E23 was obtained. The titanium content, internal electron donor content and polymerization data of the solid catalyst component are shown in Table 2.

[0075] Example 24

[0076] This embodiment provides a catalyst component, and its preparation method is as follows:

[0077] In a 500-ml, nitrogen-purged, stirred, five-necked flask, 8 g of diethoxymagnesium and 100 mL of toluene were added to prepare a suspension. 25 mL of titanium tetrachloride was added dropwise at -15°C. After the addition was complete, the temperature was slowly raised to 0°C, followed by the dropwise addition of 50 mL of titanium tetrachloride. The temperature was then slowly raised to 80°C, 4.4 g of diethyl chlorendate was added, and the temperature was continued to rise to 110°C and held constant for 2 hours. The liquid was then filtered clean and the liquid was removed. The resulting solid was washed three times with 100 mL of titanium tetrachloride at 125°C and four times with 120 mL of hexane at 60°C. The liquid was removed by filtration and the solid was dried to obtain solid catalyst component E24. The titanium content, internal electron donor content, and polymerization data of this solid catalyst component are shown in Table 2.

[0078] Comparative Example 1

[0079] This comparative example provides a catalyst component D1, the preparation process of which is the same as that of Example 1, except that dimethyl chlorendic acid is replaced by 10 mmol of di-n-butyl phthalate (DN).

[0080] Comparative Example 2

[0081] This comparative example provides a catalyst component D2, the preparation process of which is the same as that of Example 1, except that dimethyl chlorendic acid is replaced by 10 mmol of 9,9-dimethoxyfluorene (FLU).

[0082] polymerization

[0083] The above-obtained catalyst component was used as a component of an olefin polymerization catalyst to carry out polymerization evaluation:

[0084] After fully purging the atmosphere with nitrogen, a 5L stainless steel reactor was charged with 5mL of a 0.5mol / L triethylaluminum hexane solution, 1mL of a 0.1mol / L methylcyclohexyldimethoxysilane hexane solution, and 10mg of the prepared catalyst component. The feed line was then flushed with 10mL of hexane. 2L of hydrogen (under standard conditions) and 2.5L of purified propylene were then added. The reaction was prepolymerized at 25°C for 5 minutes, then heated to 70°C and allowed to polymerize for 1 hour. After the reaction, the reactor was cooled and stirring was stopped. The reaction product was discharged and dried to obtain a polymer. Polymerization data are shown in Table 2.

[0085] Table 2

[0086]

[0087]

[0088] The catalyst components containing chlorendic acid ester compounds as internal electron donors with different substituents in Examples 1-22, under the same preparation conditions, all exhibited higher activity than the most commonly used internal electron donor catalyst in industry (the phthalate-based internal electron donor catalyst component in Comparative Example 1), and higher activity than the diether-based catalyst in Comparative Example 2. Furthermore, they exhibited excellent stereoselectivity, high isotacticity, and a wider molecular weight distribution for the resulting polymers compared to those produced using phthalate-based and diether-based catalysts. Furthermore, the polymers exhibited regular particle size and high bulk density. Examples 23 and 24, catalyst components prepared using chlorendic acid ester compounds using different preparation methods, also exhibited excellent performance with high activity and stereoselectivity.

Claims

1. A catalyst component for olefin polymerization, comprising: Mg, Ti, halogens, chloranilates as internal electron donors; in, The chlorendic acid ester internal electron donor has the structure shown in Formula I: In Formula I, R 1 and R 2 The substituents are the same or different and are each independently selected from the following substituents with less than 20 carbon atoms: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated alkyl, alkyl containing heteroatoms, halogenated cycloalkyl, cycloalkyl containing heteroatoms, halogenated phenyl, phenyl containing heteroatoms, halogenated alkylphenyl, alkylphenyl containing heteroatoms, halogenated phenylalkyl, phenylalkyl containing heteroatoms, halogenated indenyl, indenyl containing heteroatoms, halogenated benzyl, benzyl containing heteroatoms, and heterocyclic aromatic substituents; the heteroatoms include one or a combination of two or more of N, O, S, P, and Si.

2. The catalyst component according to claim 1, wherein In Formula I, R 1 and R 2 Each is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20 a straight-chain or branched-chain alkyl group having less than 20 carbon atoms, or the following substituents: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, benzyl, phenethyl, furyl, pyrrolyl, thienyl, and indenyl.

3. The catalyst component according to claim 1, wherein The chlorendic acid ester internal electron donor includes dimethyl chlorendic acid, diethyl chlorendic acid, di-n-propyl chlorendic acid, diisopropyl chlorendic acid, di-n-butyl chlorendic acid, diisobutyl chlorendic acid, di-tert-butyl chlorendic acid, di-n-pentyl chlorendic acid, diisopentyl chlorendic acid, dicyclopentyl chlorendic acid, di-n-hexyl chlorendic acid, dicyclohexyl chlorendic acid, diheptyl chlorendic acid, dioctyl chlorendic acid, dinonyl chlorendic acid, didecyl chlorendic acid, diundecyl chlorendic acid, didodecyl chlorendic acid, didodecyl chlorendic acid, didedecyl chlorendic acid, didetradecyl chlorendic acid, didopentadecyl chlorendic acid, didecapdecyl chlorendic acid, dihexadecyl chlorendic acid, didephedecyl chlorendic acid, dideoctadecyl chlorendic acid, ... Chlorendic acid di(nonadecyl) ester, chlorendic acid di(eicosyl) ester, chlorendic acid diphenyl ester, chlorendic acid di-m-chlorophenyl ester, chlorendic acid di-p-chlorophenyl ester, chlorendic acid di-o-chlorophenyl ester, chlorendic acid di-p-tolyl ester, chlorendic acid di-m-tolyl ester, chlorendic acid di-o-tolyl ester, chlorendic acid di(mesitylene) ester, chlorendic acid di-p-methoxyphenyl ester, chlorendic acid di-m-methoxyphenyl ester, chlorendic acid di-o-methoxyphenyl ester, chlorendic acid di-p-nitrophenyl ester, chlorendic acid di(α-furan)methyl ester, chlorendic acid di(5-pentenyl) ester, chlorendic acid di(α-thiophene) ester, chlorendic acid dibenzyl ester, chlorendic acid diphenylethyl ester, chlorendic acid dicinnamyl ester, chlorendic acid ditetrahydrofurfuryl ester, and chlorendic acid di(1-indenyl) alcohol ester, or a combination of two or more thereof.

4. The catalyst component according to any one of claims 1 to 3, wherein The catalyst component comprises a titanium compound, a magnesium compound, and an internal electron donor represented by formula I; The precursor of the magnesium compound is selected from X n Mg(OR a ) 2-n 、MgCl2·mR a OH, R a 2-n MgX n , MgCl2 / SiO2, MgCl2 / Al2O3, a mixture of magnesium halide and titanium alkoxide, or a combination of two or more thereof, wherein m is 0.1-6, 0≤n≤2, X is a halogen, R a C1-C 20 of hydrocarbon groups; The general formula of the titanium compound is TiX N (OR b ) 4-N , where R b C1-C 20 The hydrocarbon group, X is halogen, and N is 1-4.

5. The catalyst component according to claim 4, wherein The magnesium compound is an alcoholate of magnesium dihalide; Alternatively, the magnesium compound is a liquid magnesium compound; Alternatively, the magnesium compound is a derivative of magnesium dihalide in which at least one halogen atom in the molecule is replaced by a hydrocarbyloxy group or a halogenated hydrocarbyloxy group.

6. The catalyst component according to claim 4, wherein The titanium compound includes one or a combination of two or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and alkoxy titanium halide.

7. The catalyst component according to claim 6, wherein The alkoxy titanium halide includes one or a combination of two or more of methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, and tri-n-butoxytitanium chloride.

8. The catalyst component according to claim 4, wherein The titanium compound is titanium tetrachloride.

9. The catalyst component according to claim 4, wherein The molar ratio of the internal electron donor represented by formula I to the magnesium compound is 0.01-5.0:1, and the magnesium compound is calculated as magnesium element.

10. A catalyst for olefin polymerization, comprising the catalyst component according to any one of claims 1 to 9 and an organoaluminum compound. The catalyst according to claim 10 , wherein The general formula of the organoaluminum compound is AlR c p X (3-p) , where R c is hydrogen or C1-C 20 wherein X is a halogen, and p is an integer of 0≤p≤3.

12. The catalyst according to claim 10, wherein The organoaluminum compound includes one or a combination of two or more of trialkylaluminum compounds, alkylaluminum halides, alkylaluminum hydrides, alkylaluminum sesquichlorides, and alkylaluminoxanes.

13. The catalyst according to claim 12, wherein The trialkylaluminum compound includes one or a combination of two or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and trioctylaluminum; the alkylaluminum halide includes AlEt2Cl; and the alkylaluminum sesquichloride includes Al2Et3Cl3.

14. The catalyst according to claim 10, wherein The organoaluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

15. The catalyst according to claim 10, wherein The molar ratio of the organic aluminum compound to the titanium atom in the catalyst component is 1-1000:

1.

16. The catalyst according to claim 10, wherein The raw material composition of the catalyst also includes an external electron donor.

17. The catalyst according to claim 16, wherein The external electron donor is a siloxane compound.

18. The catalyst according to claim 17, wherein The general formula of the siloxane compound is R' t Si(OR”) 4-t , wherein R' and R" are each independently selected from C1-C 18 wherein t is an integer of 0≤t≤3.

19. The catalyst according to claim 18, wherein R' and R" each contain a heteroatom; The heteroatom includes one or a combination of two or more of N, O, S, P, and Si.

20. The catalyst according to claim 16, wherein The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100:

1.

21. Use of the catalyst according to any one of claims 10 to 20 in olefin polymerization.

22. The use according to claim 21, wherein The olefins include one or a combination of two or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, butadiene, vinylcyclopentene, and vinylcyclohexene.

23. The use according to claim 21, wherein: The polymerization comprises ethylene and / or propylene polymerization.

24. The use according to claim 21, wherein The polymerization includes homopolymerization or copolymerization.

25. The use according to claim 21, wherein The polymerization temperature is ≤200°C; The polymerization pressure is ≤10 MPa.

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