Catalyst component for olefin polymerization, catalyst for olefin polymerization, and use thereof

Abstract

The application discloses an olefin polymerization catalyst component, an olefin polymerization catalyst and application thereof. The olefin polymerization catalyst component comprises Mg, Ti, halogen and an internal electron donor compound, and the internal electron donor compound is selected from N-substituted-2,6-dicarboxylate-4-pyridone compounds of general formula (I). The internal electron donor compound of the catalyst component is at least one selected from N-substituted-2,6-dicarboxylate-4-pyridone compounds of general formula (I), and the prepared catalyst has the characteristics of high activity, and the obtained polymer has high isotacticity and wide overall molecular weight distribution.

Description

Technical Field

[0001] This invention relates to a solid catalyst component for olefin polymerization, and more specifically, to a solid catalyst component of a compound, a catalyst containing the solid catalyst component, and the application of the catalyst in olefin polymerization reactions, particularly in propylene polymerization reactions. Background Technology

[0002] Polyolefins are a class of polymer materials with the largest production volume and widest application due to their abundant raw materials, low price, ease of processing and molding, and excellent comprehensive properties. Currently, Ziegler-Natta catalysts (ZN catalysts) still dominate polyolefin production. Most ZN catalyst development focuses on the development of highly active and stereoregular catalysts and improving the copolymerization ability of catalysts. Moreover, because traditional ZN catalysts (transition metal compounds such as titanium chemically bonded to a magnesium support) have high catalytic efficiency, produce polymers with good comprehensive performance, and are low in cost, the vast majority of catalysts used in polyolefin production worldwide are still based on ZN catalytic systems, characterized by high activity, high stereoregularity, long lifespan, and customizable product structures. The development process of ZN catalysts shows that as early as after the emergence of the first generation of catalysts, it was discovered that the addition of a third component (mostly an electron donor, also known as a Lewis base; those added during catalyst preparation are called internal electron donors, while those added during polymerization are called external electron donors) has a significant impact on olefin polymerization behavior and polymer properties. Modifying the internal electron donor in a catalyst can maximally alter the properties of the catalyst's active center, thereby maximizing the change in catalyst performance. Therefore, the development of novel electron donors has always been a hot topic in polyolefin catalyst research and development.

[0003] The most distinctive high-performance internal electron donor compounds in the prior art include: 1) fatty acid esters and aromatic esters, mainly phthalates; 2) diethers (e.g., EP0361493, EP0728724); 3) succinates (e.g., WO9856834, WO0063261, WO03022894); 4) glycol esters (e.g., WO9856834, WO0063261, WO03022894); and 5) compounds with other functional groups (CN1105671, CN1242780, US20060128558), etc. However, in practical applications, the aforementioned compounds all have certain problems when used as internal electron donors in olefin polymerization catalysts. For example, catalysts using diaromatic carboxylic acid esters as internal electron donors have low activity, and the resulting polypropylene (PP) has a narrow molecular weight distribution. Furthermore, phthalic acid esters, as commonly used plasticizers, pose significant risks to human reproductive health and the environment. While catalysts using 1,3-diethers as internal electron donors exhibit high activity and good hydrogen-modulated sensitivity, the resulting PP has a narrow molecular weight distribution, which is not conducive to developing different grades of PP. Succinate esters, as internal electron donors, have the advantage of producing PP with a wider molecular weight distribution, but their stereoregularity and hydrogen-modulated sensitivity need improvement. The overall activity of diol ester catalytic systems is not as ideal as that of diether systems.

[0004] Currently, phthalate compounds are the most widely used internal electron donors in polyolefin industry. Catalysts prepared from phthalates exhibit moderate activity, good stereoselectivity, and low cost. However, as commonly used plasticizers, phthalates pose significant risks to human reproductive health and the environment, creating a substantial demand for alternatives. Europe has already restricted the use of most phthalates; furthermore, new phthalate restrictions will inevitably impact their use in China. Therefore, developing novel electron donors with excellent activity, good stereoselectivity, superior overall performance, and low cost to replace the widely used phthalate-based electron donor compounds and applying them to the preparation of highly efficient Ziegler-Natta catalysts has been a common research goal in the field of polyolefin catalysts in recent years. Summary of the Invention

[0005] To address the problems existing in the prior art, the present invention provides a catalyst component for olefin polymerization, which adopts an internal electron donor compound of N-substituted-2,6-dicarboxylate-4-pyridone, which can improve the activity of the catalyst and obtain olefin polymers with higher isotacticity.

[0006] Another object of the present invention is to provide a method for preparing the catalyst component for olefin polymerization.

[0007] Another object of the present invention is to provide a catalyst for olefin polymerization.

[0008] Another object of the present invention is to provide the application of the catalyst for olefin polymerization in olefin polymerization.

[0009] To achieve the objectives of this invention, a catalyst component for olefin polymerization is provided, comprising Mg, Ti, a halogen, and an internal electron donor compound, wherein the internal electron donor compound is selected from N-substituted-2,6-dicarboxylate-4-pyridone compounds of general formula (I):

[0010]

[0011] In general formula (I), R 1 R 2 R 3 R 4 and R 5’ Whether the elements are the same or different, they are each independently selected from H, halogens, and C1-C. 20 The hydrocarbon group; preferably, R 1 R 2 R 3 R 4 and R 5’ It may also contain at least one heteroatom selected from N, O, S, P, Si and halogens.

[0012] Preferably, R in general formula (I) 1 R 2 R 3 R 4 R 5’ The substituents, whether identical or different, are independently selected from H, halogens, and the following substituents with up to 20 carbon atoms: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indene, benzyl, halogenated or substituted with N, O, S, P, or Si heteroatoms, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indene, benzyl; or are independently selected from heterocyclic aryl substituents.

[0013] Preferably, R in general formula (I) 1 R 2 R 3 R 4 R 5’ Whether the groups are the same or different, 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 20The following substituents with 20 or fewer carbon atoms, whether linear, branched, or cyclic alkyl groups: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, m-methylphenyl, o-methylphenyl, m-trimethylphenyl, p-nitrophenyl, m-nitrophenyl, substituted benzyl, substituted phenethyl, furanyl, pyrroleyl, thiophenyl, propenyl, butenyl, pentenyl, hexenyl, indene.

[0014] Preferably, the N-substituted 2,6-dicarboxylate-4-pyridone compound in general formula (I) is preferably selected from N-isopropyl-2,6-dicarboxylate-4-pyridone, N-tert-butyl-2,6-dicarboxylate-4-pyridone, N-n-butyl-2,6-dicarboxylate-4-pyridone, N-phenyl-2,6-dicarboxylate-4-pyridone, N-m-chlorophenyl-2,6-dicarboxylate-4-pyridone, and N-p-chlorophenyl-2,6-dicarboxylate-4-pyridone. At least one of the following: pyridinone, N-o-chlorophenyl-2,6-dicarboxylic acid di-p-methoxyphenyl-4-pyridinone, N-p-methoxyphenyl-2,6-dicarboxylic acid difuran methyl ester-4-pyridinone, N-methyl-2,6-dicarboxylic acid dipentenyl ester-4-pyridinone, N-methyl-2,6-dicarboxylic acid di-p-nitrophenyl ester-3-methyl-5-ethyl-4-pyridinone, N-benzyl-2,6-dicarboxylic acid dibenzyl ester-3,5-diethyl-4-pyridinone, and N-methyl-2-carboxylic acid ethyl ester-6-phenyl ester-4-pyridinone.

[0015] Preferably, the N-substituted 2,6-dicarboxylate-4-pyridone compound of general formula (I) can be synthesized by methods including but not limited to those shown in Route 1 and Route 2 below:

[0016]

[0017] In route 1, when an alcohol is selected in the third step (R) 1 With R 2 (same) yields a single product, when two alcohols are used in the third step (R) 1 With R 2 (Different) A mixture of three products is obtained. This final mixture can be used directly as an internal electron donor compound without separation. The proportion of each component in the mixture can be adjusted by the addition ratio of the two alcohols in the reactants. The proportion of each component can be determined by analytical methods such as chromatography-mass spectrometry and nuclear magnetic resonance.

[0018] Preferably, the catalyst component comprises a titanium compound, a magnesium compound, and the N-substituted-2,6-dicarboxylate-4-pyridone compound;

[0019] 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 At least one of the following: a mixture of MgCl2 / SiO2, MgCl2 / Al2O3, magnesium halide, and titanium alkoxide, wherein m is 0.1-6, 0≤n≤2, X is a halogen, and R a For C1-C 20 hydrocarbon group;

[0020] The general formula of the titanium compound is TiX. N (OR b ) 4-N In the formula, R b For C1-C 20 The hydrocarbon group, where X is a halogen and N is 1-4.

[0021] Preferably, the magnesium compound is an alkoxide of magnesium dihalide;

[0022] Alternatively, the magnesium compound may be a liquid magnesium compound;

[0023] Alternatively, the magnesium compound is a derivative in which at least one halogen atom in a magnesium dihalide molecule is replaced by a hydrocarbon or halohydroxyl group; preferably a hydrocarbon-oxyl magnesium compound; more preferably an alkoxyl magnesium and / or aryloxyl magnesium.

[0024] Preferably, the titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and titanium alkoxyhalide;

[0025] Preferably, the alkyl titanium halide includes at least one of methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, and tri-n-butoxy titanium chloride.

[0026] Preferably, the titanium compound is titanium tetrachloride.

[0027] Preferably, the molar ratio of the N-substituted-2,6-dicarboxylate-4-pyridone compound to the magnesium compound is 0.01-5.0, more preferably 0.05-3.0, and the magnesium compound is calculated as magnesium element.

[0028] This invention does not specifically limit the preparation method of the catalyst component for olefin polymerization, which can be carried out according to the following preparation methods:

[0029] Method 1: An excess of TiCl4 containing an alkoxide or chloroalkoxide of magnesium and at least one N-substituted 2,6-dicarboxylate-4-pyridone compound of general formula (I) in solution is reacted at a temperature of 80-135°C. According to the preferred method, TiX can be used... N (OR b ) 4-N Titanium compounds (where R) b For C1-C 20 The hydrocarbon group, where X is a halogen and N is 1-4; preferably TiCl4) and the general formula MgCl2·mR a OH (where m is a number from 0.1 to 6, preferably 2 to 4, and R) a For C1-C 20 Solid catalyst components are prepared by reacting adducts of hydrocarbon groups. The adducts can be suitably sphericalized by mixing an alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, followed by rapid quenching of the emulsion, thereby solidifying the adduct into spherical particles. Spherical MgCl2·mR particles prepared according to this process... a Examples of OH adducts can be described in US4399054A and US4469648A. The adducts thus obtained can react directly with titanium compounds, or they can be pre-treated with a thermally controlled dealcoholization process (80-130°C) to yield an adduct, wherein the molar number of the alcohol is generally less than 3, preferably between 0.1 and 2.5. The reaction with the titanium compound can be carried out by suspending the adduct (dealcoholized or otherwise) in cold TiCl4 (generally -25 to 0°C); the mixture is then heated to 80-130°C and held at this temperature for 0.5-2 hours. The treatment with TiCl4 can be performed once or multiple times. During the TiCl4 treatment, at least one compound of general formula (I) can be added, and this treatment can be repeated once or multiple times.

[0030] Method 2: A magnesium compound is dissolved in a solvent system consisting of an organic epoxy compound, an organophosphorus compound, and an inert diluent to form a homogeneous solution. This solution is then mixed with a titanium compound, and a solid is precipitated in the presence of a precipitation aid. This solid is treated with at least one compound of general formula (I) to load it onto the solid. If necessary, it is further treated with titanium tetrahalide and an inert diluent. The precipitation aid is one of organic anhydrides, organic acids, ethers, and ketones. The components, per mole of magnesium halide, are: 0.2-10 mol of organic epoxy compound, 0.1-3 mol of organophosphorus compound, 0-1.0 mol of precipitation aid, and 0.5-150 mol of Ti compound.

[0031] Method 3: A solution of TiCl4 or alkyloxytitanium aromatics (e.g., toluene, xylene, etc.) can be used to react with dialkyloxymagnesium compounds such as dialkoxymagnesium or diaryloxymagnesium at -25 to 0 °C, followed by halogenation at 80 to 130 °C. The treatment with the TiCl4 aromatic solution can be repeated once or multiple times, with at least one compound of general formula (I) added once or in batches during these multiple treatments. For example, the preparation method of the titanium-containing solid catalyst component disclosed in US5077357A can be used: magnesium ethoxy, tetraethoxytitanium, o-cresol, ethanol, and chlorobenzene are added sequentially and stirred; a TiCl4 / chlorobenzene solution is rapidly added to the above liquid, and the temperature is raised until complete dissolution, and then the temperature is further raised to a specific temperature; the ethanol reactants are removed by bubbling with N2, and the mixture is stirred for a certain period of time, then washed once with hot chlorobenzene, washed twice with isooctane, and then dried with N2 to obtain the support. Alternatively, follow another example: add TiCl4, tetraethoxytitanium, ethoxymagnesium, and o-cresol to chlorobenzene in sequence and stir; add ethanol, and continue stirring for 3 hours after the ethoxymagnesium dissolves at high temperature; filter while hot, then wash once with warm chlorobenzene, wash once with isooctane, and finally dry with N2.

[0032] Method 4: Anhydrous magnesium chloride and at least one N-substituted 2,6-dicarboxylate-4-pyridone compound of general formula (I) are co-milled under conditions where magnesium chloride is activated. The product thus obtained can be treated once or multiple times with excess TiCl4 at a temperature of 80-130°C. After treatment, it is washed with a hydrocarbon solvent until chloride ions are removed. According to a further method, the product obtained by co-milling anhydrous magnesium chloride, a titanium compound, and at least one N-substituted 2,6-dicarboxylate-4-pyridone compound of general formula (I) is treated with a haloalkane such as 1,2-dichloroethane, chlorobenzene, or dichloromethane. This treatment is carried out at a temperature between 40°C and the boiling point of the haloalkane for 1-4 hours. The product is then typically washed with an inert hydrocarbon solvent such as hexane.

[0033] Method 5: Magnesium dichloride is pre-activated using a well-known method, and then treated with an excess of TiCl4 at a temperature of approximately 80-135°C, wherein the solution contains at least one compound of general formula (I). The solid is treated with TiCl4 multiple times and washed with hexane to remove any unreacted TiCl4.

[0034] Method Six: Alternatively, the preparation method of the titanium-containing solid catalyst component disclosed in CN1208045A can be used: First, at low temperature, liquid magnesium compound and liquid titanium compound are contacted in the presence of a compound selected from alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and esters to precipitate solids. The contact temperature is generally -70 to 200°C, preferably -30 to 130°C. During the contact process, at least one compound of general formula (I) is used for treatment.

[0035] Method 7: Magnesium compounds supported on inorganic oxides such as SiO2 and alumina or porous resins can also be used as carriers to prepare the product. The product is then activated by a well-known method and treated with an excess of TiCl4 at a temperature of about 80-135°C. During the treatment, at least one N-substituent-2,6-dicarboxylate-4-pyridone compound of general formula (I) is added.

[0036] The above reactions lead to the formation of magnesium halides in an active form (typical crystalline magnesium halides have a regular structure and can support very little Ti, resulting in low catalytic activity. To prepare highly active supported catalysts, magnesium halides must undergo activation treatment. Activation methods include using physical and / or chemical methods to prepare them into microcrystals so that active centers are supported on the surface, edges, and defects of the magnesium halide. These treated magnesium halide microcrystals suitable for supporting Ti are called "active magnesium halides"). In addition to these reactions, other methods are known in the literature for forming active magnesium halides from starting materials different from magnesium halides.

[0037] In any preparation method, the aforementioned internal electron-donating compound can be added directly or optionally prepared in situ using a suitable precursor that can be converted in the desired internal electron-donating compound via known chemical reactions such as esterification or transesterification. Typically, the aforementioned internal electron-donating compound is used in a molar ratio of 0.01-5, preferably 0.05-3.0, relative to MgCl2.

[0038] In any preparation method, at least one compound of general formula (I) may be added simultaneously or separately during the preparation process in batches or in any order or combination.

[0039] The present invention also provides a catalyst for olefin polymerization, the raw material composition of which includes the above-mentioned catalyst components and organoaluminum compounds.

[0040] According to a specific embodiment of the present invention, preferably, the organoaluminum compound has the general formula AlR c p X (3-p) , where R c It is hydrogen or C1-C 20The hydrocarbon group, X is a halogen, and p is an integer 0 ≤ p ≤ 3.

[0041] According to a specific embodiment of the present invention, preferably, the organoaluminum compound includes at least one of trialkylaluminum compound, alkylaluminum halide, alkylaluminum hydride, alkylaluminum sesquichloride, and alkylaluminoxane.

[0042] According to a specific embodiment of the present invention, preferably, the trialkylaluminum compound includes at least one selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and trioctylaluminum; the alkylaluminum halide includes AlEt2Cl; and the alkylaluminum sesquichloride includes Al2Et3Cl3.

[0043] According to a specific embodiment of the present invention, preferably, the molar ratio of the organoaluminum compound to the titanium atoms in the catalyst component is 1-1000:1, more preferably 50-800.

[0044] According to a specific embodiment of the present invention, preferably, the raw material composition of the catalyst further includes an external electron donor.

[0045] According to a specific embodiment of the present invention, preferably, the external electron donor is a siloxane compound.

[0046] According to a specific embodiment of the present invention, preferably, the general formula of the siloxane compound is R'. t Si(OR”) 4-t In this context, R' and R” are each independently selected from C1-C 18 The hydrocarbon group, where t is an integer of 0 ≤ t ≤ 3; more preferably, R' and R” respectively contain heteroatoms; more preferably, the heteroatoms include at least one of N, O, S, P, and Si.

[0047] Preferably, the siloxane compound is selected from: trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, triisobutylethoxysilane, tricyclohexylmethylsilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldiethoxysilane, n-butylmethyldimethoxysilane , bis(2-ethylhexyl)dimethoxysilane, bis(2-ethylhexyl)diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentylisopropyldiethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclohexyl-n-propyldimethoxysilane, cyclohexyl-n-propyldimethoxysilane oxysilanes, 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-butyltrimethoxysilane, 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, 3,5-Dimethylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, di(3-methylcyclohexyl)dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, di(4-methylcyclohexyl)dimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, di(3,5-dimethylcyclohexyl)dimethoxysilane, tetrapropoxysilane, tetrabutoxysilane. Preferred organosilicon compounds include: di-n-propyl dimethoxysilane, diisopropyl dimethoxysilane, di-n-butyl dimethoxysilane, diisobutyl dimethoxysilane, di-tert-butyl dimethoxysilane, di-n-butyl diethoxysilane, tert-butyl trimethoxysilane, dicyclohexyl dimethoxysilane, dicyclohexyl diethoxysilane, cyclohexylmethyl dimethoxysilane, cyclohexylethyl diethoxysilane, cyclohexylethyl dimethoxysilane, cyclohexylethyl diethoxysilane, cyclopentylmethyl dimethoxysilane, cyclopentylmethyl diethoxysilane, cyclopentylethyl dimethoxysilane, and cyclohexyl... The silane is selected from at least one of the following: cyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclopentyldimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, methyl tert-butyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane, and tert-hexyltrimethoxysilane.

[0048] Preferably, the siloxane compound is selected from at least one of cyclohexylmethyldimethoxysilane; diisopropyldimethoxysilane; di-n-butyldimethoxysilane; diisobutyldimethoxysilane; diphenyldimethoxysilane; phenyltriethoxysilane; methyl tert-butyldimethoxysilane; dicyclopentyldimethoxysilane; 2-ethylpiperidinyl-2-tert-butyldimethoxysilane and (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane and (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane, cyclohexyltrimethoxysilane; tert-butyltrimethoxysilane and tert-hexyltrimethoxysilane.

[0049] 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, more preferably 0.01-20, and even more preferably 0.01-5.

[0050] The present invention also provides the application of the above-mentioned catalyst in olefin polymerization.

[0051] According to a specific embodiment of the present invention, preferably, the olefin includes straight-chain or branched olefins, such as at least one 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.

[0052] According to a specific embodiment of the present invention, preferably, the polymerization includes ethylene and / or propylene polymerization.

[0053] According to a specific embodiment of the present invention, preferably, the polymerization includes homopolymerization or copolymerization.

[0054] According to a specific embodiment of the present invention, preferably, the order of adding the components in the catalyst during the catalytic process is arbitrary, with the organoaluminum compound being added to the polymerization system first, followed by the external electron donor, and finally the catalyst components.

[0055] According to a specific embodiment of the present invention, preferably, in the above applications, the polymerization process can be carried out with or without a solvent; the olefin monomer can be in the 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 processes can be applied, and the polymerization reaction can be carried out in one step, two steps or multiple steps.

[0056] According to a specific embodiment of the present invention, preferably, the polymerization temperature is ≤200℃, more preferably 20-100℃, and even more preferably 40-80℃; the polymerization pressure is ≤10MPa, more preferably 0.3-5MPa.

[0057] The internal electron donor compound of the catalyst component of this invention is at least one selected from N-substituted 2,6-dicarboxylate-4-pyridone compounds of general formula (I). The internal electron donor compound contains various functional groups such as aza, ester, ether, or ketone in its six-membered ring structure, and its stereoconfiguration and steric hindrance are conducive to the participation of these functional groups in the formation of active centers. Catalysts prepared from internal electron donor compounds of various different substituents in the same series generally exhibit higher activity than phthalate-based internal electron donor catalysts commonly used in industry today, and also higher activity than diether catalysts. Furthermore, they show good stereoselectivity, high isotacticity of the resulting polymers, and a broad overall molecular weight distribution. Detailed Implementation

[0058] The technical solution of the present invention will now be described in detail with reference to embodiments thereof. Obviously, the described embodiments are only a part of the implementation of the present invention, and not all of them.

[0059] In all examples, the catalyst preparation operations were carried out under high-purity nitrogen protection. Polymer isotacticity was determined using the heptane extraction method (boiling heptane extraction for 6 hours). Two grams of dried polymer sample were placed in an extractor and extracted with boiling heptane for 6 hours. The residue was dried to constant weight. The ratio of the polymer weight (g) obtained to 2 is the isotacticity.

[0060] The bulk density of the polymer was determined using the method specified in JB / T 2412-2008.

[0061] The molecular weight distribution of the polymer was determined by PL-220 gel permeation chromatography at 150 °C with trichlorobenzene as solvent (standard: polystyrene, flow rate 1.0 mL / min, column: 3xPlgel 10um M1Xed-B 300x7.5nm).

[0062] Synthesis of N-substituted 2,6-dicarboxylate-4-pyridone compounds represented by general formula (I)

[0063] Preparation Example 1: Synthesis of N-isopropyl-2,6-dicarboxylic acid ethyl ester-4-pyridone

[0064] Sodium (14.2 g, 0.6 mol) was dissolved in anhydrous ethanol (200 mL). A mixture of anhydrous acetone (17.4 g, 22.8 mL, 0.3 mol) and diethyl oxalate (93 g, 86.5 mL, 0.64 mol) was added to the previous solution over 15 minutes. A yellow precipitate formed. The reaction mixture was kept at 60 °C for one hour. Then, HCl (aq. 37%, 120 mL) and water (60 mL) were added, and the solution was stirred at 50 °C for 20 hours. The mixture of water and ethanol was removed under reduced pressure. A mixture of water (170 mL) and HCl (aq. 37%, 30 mL) was then added to this mixture and stirred until silica gel TLC (elution buffer: 3 / 7 (v / v) 10% NaCl aqueous solution / ethanol) showed only one spot. After cooling to room temperature, the crystals were filtered off, washed first with water, then with cold acetone. The crude product was recrystallized to give 2,6-dicarboxylic acid-4-pyranone.

[0065] 4,6-Dicarboxylic acid-4-pyridone (4.6 g, 25 mmol) was added dropwise to 100 mL of isopropylamine-dichloromethane solution (isopropylamine 1.8 g, 30 mmol) at 0 °C. The mixture was stirred at room temperature for two days. The solvent was removed by rotary evaporation, and the residue was boiled after the addition of water (50 mL) and activated charcoal (1 g). The solution was filtered and then cooled to 5 °C. The cold solution was acidified to pH 1 with HCl (aq. 37%). The solid was filtered, washed three times with ice water, and dried under vacuum at 150 °C for 24 h to give N-isopropyl-2,6-dicarboxylic acid-4-pyridone.

[0066] In a 1L three-necked flask, add N-isopropyl-2,6-dicarboxylic acid-4-pyridone (4.5g, 20mmol), ethanol (50mL), and concentrated sulfuric acid (0.3mL); heat under reflux for 2 hours; cool to room temperature; pour the reaction solution into a saturated sodium bicarbonate solution, extract twice with ethyl acetate (100mL*2), combine the organic phases, wash with saturated brine (100mL*2), concentrate and recrystallize to obtain the product N-isopropyl-2,6-dicarboxylic acid ethyl ester-4-pyridone. 1 H NMR (500MHz, Chloroform-d) δ / ppm: 6.89 (s, 2H), 4.69 (p, J = 4.3Hz, 1H), 4.30 (q, J = 5.1Hz, 4H), 1.35–1.27 (m, 12H).

[0067] Preparation 2-12: Synthesis of other N-substituted 2,6-dicarboxylate-4-pyridone compounds

[0068] Compound 1, prepared according to Example 1, was synthesized using routes 1 and 2 as described above. The structure and NMR results of the compound are shown in Table 1.

[0069]

[0070] Table 1. N-substituted 2,6-dicarboxylate-4-pyridone compounds prepared in Examples 1-12

[0071]

[0072]

[0073]

[0074] Catalyst preparation

[0075] Example 1

[0076] In a 500 mL stirred flask fully purged with nitrogen, 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, and slowly heated to 80 °C. N-Isopropyl-2,6-diethyl-4-pyridone (3.1 g, 10 mmol) was added, and the temperature was further increased to 110 °C and held constant for 1 hour. The liquid was then filtered off, and the resulting solid was washed three times with 120 mL of titanium tetrachloride at 125 °C. The solid was then washed four times with 150 mL of hexane at 60 °C. The liquid was filtered off and the solid was dried to obtain the solid catalyst component. The titanium content, internal electron donor content, and polymerization data of this solid catalyst component are shown in Table 2.

[0077] Example 2-12

[0078] The preparation process of the solid catalyst components is as shown in Example 1, except that N-isopropyl-2,6-diethyl 2,6-dicarboxylate-4-pyridone is replaced in sequence with 10 mmol of compounds 2-12 prepared in Examples 2-12 of Table 1.

[0079] Example 13

[0080] In a 500 mL stirred flask fully purged with nitrogen, 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 mixture was heated to 50 °C with stirring and maintained for 2 hours until the solid was completely dissolved. Then, 2.40 g of phthalic anhydride was added, and the mixture was maintained for another hour. The solution was cooled to -25 °C, and 110 mL of titanium tetrachloride was added dropwise over 1 hour. The temperature was slowly raised to 80 °C, and the solid was gradually washed away during the heating process. 10 mmol of N-isopropyl-2,6-diethyl-4-pyridone was added, and the mixture was maintained at 80 °C for 1 hour. After filtration, the solution was washed twice with 200 mL of toluene. Then, 120 mL of toluene and 80 mL of titanium tetrachloride were added, and the temperature was raised to 110 °C and maintained for 2 hours. The liquid was then filtered clean, and the process was repeated once more. 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 was obtained. The titanium content, internal electron donor content, and polymerization data of this solid catalyst component are shown in Table 2.

[0081] Example 14

[0082] In a 500 mL stirred flask fully purged with nitrogen, 8 g of magnesium diethoxy 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, and then 50 mL of titanium tetrachloride was added dropwise. The temperature was then slowly raised to 80 °C, and 10 mmol of N-isopropyl-2,6-dicarboxylic acid diethyl ester-4-pyridone was added. The temperature was then raised to 110 °C and held constant for 2 hours. The liquid was then filtered off, and the resulting solid was washed three times with 100 mL of titanium tetrachloride at 125 °C. The resulting solid was then washed four times with 120 mL of hexane at 60 °C. The liquid was filtered off and the solid was dried to obtain the solid catalyst component.

[0083] Comparative Example 1

[0084] The catalyst component was prepared as in Example 1, except that N-isopropyl-2,6-diethyl-4-pyridone was replaced with 10 mmol of di-n-butyl phthalate (DN).

[0085] Comparative Example 2

[0086] The catalyst component was prepared as in Example 1, except that N-isopropyl-2,6-diethyl 2,6-dicarboxylate-4-pyridone was replaced with 10 mmol of 9,9-dimethoxyfluorene (FLU).

[0087] polymerization

[0088] Polymerization evaluation was conducted using solid catalysts as components of catalysts for olefin polymerization.

[0089] After purging the 5L stainless steel reactor with nitrogen, 5mL of a 0.5mol / L triethylaluminum hexane solution, 1mL of a 0.1mol / L methylcyclohexyldimethoxysilane hexane solution, and 10mg of the prepared catalyst were added. Then, 10mL of hexane was added to flush the feed line, followed by 2L (under standard conditions) of hydrogen and 2.5L of purified propylene. The reaction was prepolymerized at 25℃ for 5 minutes, then the temperature was raised to 70℃, and polymerization was carried out at this temperature for 1 hour. After the reaction was completed, the reactor was cooled and stirring was stopped, and the reaction product was discharged and dried to obtain the polymer.

[0090] Table 2

[0091]

[0092]

[0093] As shown in Table 2, the catalysts containing internal electron donors of N-substituted 2,6-dicarboxylate-4-pyridone compounds in Examples 1-12, under the same preparation conditions, exhibited higher activity than the phthalate-based internal electron donor catalyst of Comparative Example 1, and higher activity than the diether catalyst of Comparative Example 2. They also showed good stereoselectivity and high isotacticity of the resulting polymers. The catalysts had regular particle size and high packing density. Examples 13-14, prepared using different methods with N-isopropyl-2,6-dicarboxylate-4-pyridone, also demonstrated excellent performance with high activity and high stereoselectivity.

[0094] This invention is not limited to the specific embodiments described above. Any changes or modifications made by those skilled in the art within the scope of this invention are covered by the patent scope of this invention.

Claims

1. A catalyst component for olefin polymerization, characterized in that, It comprises Mg, Ti, halogens, and an internal electron donor compound, wherein the internal electron donor compound is selected from compounds of general formula (I): General Formula (I) In general formula (I), R 1 R 2 R 3 R 4 and R 5’ Whether the elements are the same or different, they are each independently selected from H, halogens, and C1-C. 20 Hydrocarbon group, or C1-C containing at least one heteroatom selected from N, O and halogen. 20 Group.

2. The catalyst component for olefin polymerization according to claim 1, characterized in that, R in general formula (I) 1 R 2 R 3 R 4 R 5’ The substituents, whether identical or different, are each independently selected from H, halogens, and the following substituents with up to 20 carbon atoms: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, halogenated or substituted with N or O heteroatoms, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl; or each independently selected from heterocyclic aryl substituents.

3. The catalyst component for olefin polymerization according to claim 2, characterized in that, The phenylalkyl group includes benzyl.

4. The catalyst component for olefin polymerization according to claim 1, characterized in that, R in general formula (I) 1 R 2 R 3 R 4 R 5’ Whether the groups are the same or different, 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 following substituents with 20 or fewer carbon atoms, whether linear, branched, or cyclic alkyl groups: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, m-methylphenyl, o-methylphenyl, m-trimethylphenyl, p-nitrophenyl, m-nitrophenyl, substituted benzyl, substituted phenethyl, furanyl, pyrroleyl, indene.

5. The catalyst component for olefin polymerization according to claim 4, characterized in that, The alkenyl group includes at least one of propenyl, butenyl, pentenyl, and hexenyl.

6. The catalyst component for olefin polymerization according to claim 1, characterized in that, The internal electron-donating compound is selected from N-isopropyl-2,6-diethyl-4-pyridone, N-tert-butyl-2,6-dicarboxylate di(dodecyl)-4-pyridone, N-n-butyl-2,6-dicarboxylate di-n-butyl-4-pyridone, N-phenyl-2,6-dicarboxylate diphenyl-4-pyridone, N-m-chlorophenyl-2,6-dicarboxylate di-m-chlorophenyl-4-pyridone, N-p-chlorophenyl-2,6-dicarboxylate di-p-toluene-4-pyridone, N-o-chlorophenyl-2,6-dicarboxylate di-p-methoxyphenyl-4-pyridone, N-p-methoxyphenyl-2,6-dicarboxylate difuranmethyl ester-4-pyridone, and N-methyl-2,6-dicarboxylate dipentenyl ester- At least one of 4-pyridone, di-p-nitrophenyl N-methyl-2,6-dicarboxylate-3-methyl-5-ethyl-4-pyridone, dibenzyl N-benzyl-2,6-dicarboxylate-3,5-diethyl-4-pyridone, and ethyl N-methyl-2-carboxylate-6-phenyl 4-pyridone.

7. The catalyst component for olefin polymerization according to any one of claims 1-6, characterized in that, The catalyst component comprises a titanium compound, a magnesium compound, and the internal electron donor compound; 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 At least one of the following: a mixture of MgCl2 / SiO2, MgCl2 / Al2O3, magnesium halide, and titanium alkoxide, wherein m is 0.1-6, 0≤n≤2, X is a halogen, and R a For C1-C 20 hydrocarbon group; The general formula of the titanium compound is TiX. N (OR b ) 4-N In the formula, R b For C1-C 20 The hydrocarbon group, where X is a halogen and N is 1-4.

8. The catalyst component for olefin polymerization according to claim 7, characterized in that, The magnesium compound is an alkoxide of magnesium dihalide; Alternatively, the magnesium compound may be a liquid magnesium compound; Alternatively, the magnesium compound is a derivative in which at least one halogen atom in a magnesium dihalide molecule is replaced by an alkyl or haloalkyl group.

9. The catalyst component for olefin polymerization according to claim 7, characterized in that, The titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and titanium alkoxyhalide.

10. The catalyst component for olefin polymerization according to claim 9, characterized in that, The alkoxy titanium halide includes at least one of methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, and tri-n-butoxy titanium chloride.

11. The catalyst component for olefin polymerization according to claim 7, characterized in that, The molar ratio of the internal electron donor compound to the magnesium compound is 0.01-5.0, and the magnesium compound is calculated based on magnesium element.

12. A catalyst for olefin polymerization, comprising the catalyst component according to any one of claims 1-11 and an organoaluminum compound.

13. The catalyst according to claim 12, characterized in that, The general formula of the organoaluminum compound is AlR c p X (3-p) , where R c It is hydrogen or C1-C 20 The hydrocarbon group, X is a halogen, and p is an integer 0 ≤ p ≤ 3.

14. The catalyst according to claim 12, characterized in that, The organoaluminum compounds include at least one of trialkylaluminum compounds, alkylaluminum halides, alkylaluminum hydrides, alkylaluminum sesquichlorides, and alkylaluminoxanes.

15. The catalyst according to claim 12, characterized in that, The molar ratio of the organoaluminum compound to the titanium atoms in the catalyst component is 1-1000:

1.

16. The catalyst according to claim 12, characterized in that, The catalyst's raw material composition also includes an external electron donor; The external electron donor is a siloxane compound.

17. The catalyst according to claim 16, characterized in that, The general formula of the siloxane compound is R' t Si(OR'') 4-t Where R' and R'' are each independently selected from C1-C 18 The hydrocarbon group, where t is an integer 0 ≤ t ≤ 3.

18. The catalyst according to claim 16, characterized in that, The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100.

19. The use of the catalyst according to any one of claims 12-18 in olefin polymerization.

20. The application according to claim 19, characterized in that, The olefins include at least one 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. The polymerization includes homopolymerization or copolymerization; The polymerization temperature is ≤200℃; the polymerization pressure is ≤10MPa.

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