A catalyst component for olefin polymerization, an olefin polymerization catalyst and its application.

Abstract

This invention discloses a catalyst component for olefin polymerization, an olefin polymerization catalyst, and their applications. The catalyst component comprises Mg, Ti, a halogen, at least one internal electron donor compound a, and at least one internal electron donor compound b. The internal electron donor compound a is selected from at least one of 2,6-dicarboxylate-4-pyridinium ether compounds of general formula (I) or N-substituted 2,6-dicarboxylate-4-pyridinone compounds of general formula (II). The internal electron donor compound b is selected from a diether compound. The internal electron donor of the catalyst component of this invention is at least one compound selected from 2,6-dicarboxylate-4-pyridinium ether of general formula (I) or N-substituted 2,6-dicarboxylate-4-pyridinone of general formula (II), as well as a diether compound. The activity can be significantly improved by combining multiple internal electron donors.

Description

Technical Field

[0001] This invention relates to a catalyst component for olefin polymerization, 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 above-mentioned compounds all have certain problems as internal electron donors for olefin polymerization catalysts. Although catalysts using 1,3-diether compounds as internal electron donors have high activity and good hydrogen-modulated sensitivity, the relative molecular mass distribution of the synthesized PP is narrow, which is not conducive to the development of different grades of PP. Succinate compounds as internal electron donors have the advantage of producing PP with a wider relative molecular mass distribution, but the stereoregularity of PP and the hydrogen-modulated sensitivity of the catalyst need to be improved. The activity of glycol ester catalytic systems is generally 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 an internal electron donor compound with excellent basic performance and good compatibility with other internal electron donor compounds. When this internal electron donor compound is compounded with various other types of internal electron donor compounds, it can significantly improve catalytic activity and still obtain a high isotactic polymer without the addition of an external electron donor.

[0006] The purpose of this invention is to provide a catalyst component for the polymerization of olefins.

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

[0008] Another object of the present invention is to provide a catalyst for the polymerization of olefins.

[0009] Another object of the present invention is to provide the application of the polymerization catalyst in olefin polymerization.

[0010] To achieve the objectives of this invention, a polymerization catalyst component for olefins is provided, comprising Mg, Ti, a halogen, at least one internal electron donor compound a, and at least one internal electron donor compound b. The internal electron donor compound a is selected from at least one of 2,6-dicarboxylate-4-pyridinium ether compounds of general formula (I) or N-substituted 2,6-dicarboxylate-4-pyridone compounds of general formula (II), and the internal electron donor compound b is selected from diether compounds.

[0011]

[0012] In general formula (I) or general formula (II), R 1 -R 10 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 10 It may also contain at least one heteroatom selected from N, O, S, P, Si and halogens.

[0013] Preferably, in formula (I) or formula (II), R 1 -R 10 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.

[0014] Preferably, in formula (I) or formula (II), R 1 -R 10 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.

[0015] Preferably, the 2,6-dicarboxylate-4-pyridine ether compound in general formula (I) is selected from di-n-butyl 2,6-dicarboxylate-4-methoxypyridine, diisopropyl 2,6-dicarboxylate-4-isopropyloxypyridine, di(dodecyl) 2,6-dicarboxylate-4-butoxypyridine, diphenyl 2,6-dicarboxylate-4-methoxypyridine, di-m-chlorophenyl 2,6-dicarboxylate-4-methoxypyridine, di-p-toluene 2,6-dicarboxylate-4-methoxypyridine, and di-p-methoxyphenyl 2,6-dicarboxylate-4-benzyloxypyridine. At least one of the following: difuran methyl 2,6-dicarboxylate-4-methoxypyridine, dipentenyl 2,6-dicarboxylate-3-methyl-5-ethyl-4-methoxypyridine, di-p-nitrophenyl 2,6-dicarboxylate-3,5-diethyl-4-methoxypyridine, dimethyl 2,6-dicarboxylate-3-methyl-5-n-butyl-4-methoxypyridine, dibenzyl 2,6-dicarboxylate-4-ethoxypyridine, ethyl 2-6-butyl 2-carboxylate-4-methoxypyridine, and ethyl 2-6-phenyl 2-carboxylate-4-methoxypyridine.

[0016] Preferably, the N-substituted 2,6-dicarboxylate-4-pyridone compound in general formula (II) is 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.

[0017] Preferably, the 2,6-dicarboxylate-4-pyridine ether compound of general formula (I) can be synthesized by methods including but not limited to the following routes 1-3:

[0018]

[0019] Route 1 can be used to synthesize R 1 =R 2 =R 5 The compound; in route 2, when an alcohol is selected in the second step (R 1 With R 2 (same) yields a single product; when two alcohols are used in the second 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 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 analysis methods such as chromatography-mass spectrometry and nuclear magnetic resonance. Route 3 uses oxalic acid as a raw material to synthesize 2,6-dicarboxylate-4-pyranone and then obtains the final product.

[0020] Preferably, the N-substituted 2,6-dicarboxylate-4-pyridone compound of general formula (II) can be synthesized by methods including, but not limited to, those shown in routes 4 and 5:

[0021]

[0022] In route 4, 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 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.

[0023] Preferably, the diether compound is selected from 1,3-diether compounds represented by general formula (III):

[0024]

[0025] In general formula (III), R 11 -R 16 Whether the same or different, each is independently selected from H, and each is independently selected from straight-chain or branched alkyl, cycloalkyl, aryl, alkylaryl, or aralkyl groups containing 1-18 carbon atoms; R 17 -R 18They may be the same or different, each independently selected from straight-chain or branched alkyl groups with 1-20 carbon atoms, cycloalkyl groups with 3-20 carbon atoms, aryl groups with 5-20 carbon atoms, alkylaryl groups with 7-20 carbon atoms, and arylalkyl groups; R 11 -R 18 One or more groups in the structure can be linked to form a ring structure, and each group may also contain at least one heteroatom selected from halogens, N, O, S, P and Si.

[0026] Specifically, the 1,3-diether compounds include, but are not limited to, those selected from: 2-(2-ethylhexyl)1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-tert-butyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2 (1-Naphthyl)-1,3-dimethoxypropane, 2-(p-fluorophenyl)-1,3-dimethoxypropane, 2-(1-decahydronaphthyl)-1,3-dimethoxypropane, 2-(p-tert-butylphenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-diethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-diethoxypropane, 2,2-dibutyl-1,3-diethoxypropane, 2-methyl-2-ethyl-1,3-dimethyl 2-Methyl-2-propyl-1,3-dimethoxypropane, 2-Methyl-2-benzyl-1,3-dimethoxypropane, 2-Methyl-2-phenyl-1,3-dimethoxypropane, 2-Methyl-2-cyclohexyl-1,3-dimethoxypropane, 2-Methyl-2-methylcyclohexyl-1,3-dimethoxypropane, 2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane, 2,2-bis(2-phenylethyl)-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-Methyl-2-isobutyl-1,3-dimethoxypropane, 2-Methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-bis(2-ethylhexyl) )-1,3-dimethoxypropane, 2,2-bis(p-methylphenyl)-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-di-sec-butyl-1,3-dimethoxypropane, 2,2-Di-tert-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-iso-propyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane. 1,1-bis(methoxymethyl)-cyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetramethylcyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetraphenylcyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetrafluorocyclopentadiene; 1,1-bis(methoxymethyl)-3,4-dicyclopentylcyclopentadiene; 1,1-bis(methoxymethyl)indene; 1,1-bis(methoxymethyl)-2,3-dimethylindene; 1,1-bis(methoxymethyl)-4,5,6,7-tetrahydroindene; 1,1-bis(methoxymethyl)-2,3,6,7-tetrafluoroindene; 1,1-bis( 1,1-bis(methoxymethyl)-4,7-dimethylindene; 1,1-bis(methoxymethyl)-3,6-dimethylindene; 1,1-bis(methoxymethyl)-4-phenylindene; 1,1-bis(methoxymethyl)-4-phenyl-2-methylindene; 1,1-bis(methoxymethyl)-4-cyclohexylindene; 1,1-bis(methoxymethyl)-7-(3,3,3-trifluoropropyl)indene; 1,1-bis(methoxymethyl)-7-trimethylsilylindene; 1,1-bis(methoxymethyl)-7-trifluoromethylindene; 1,1-bis(methoxymethyl)-4,7-dimethyl-4,5,6,7-tetrahydroindene; 1,1-bis(methoxymethyl)-7- Methyl indene; 1,1-bis(methoxymethyl)-7-cyclopentyl indene; 1,1-bis(methoxymethyl)-7-isopropyl indene; 1,1-bis(methoxymethyl)-7-cyclohexyl indene; 1,1-bis(methoxymethyl)-7-tert-butyl indene; 1,1-bis(methoxymethyl)-7-tert-butyl-2-methyl indene; 1,1-bis(methoxymethyl)-7-phenyl indene; 1,1-bis(methoxymethyl)-2-phenyl indene; 1,1-bis(methoxymethyl)-1H-benzo[e]indene; 1,1-bis(methoxymethyl)-1H-2-methylbenzo[e]indene; 9,9-bis(methoxymethyl)fluorene; 9,9-bis(methoxymethyl)fluorene 9,9-Bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene; 9,9-Bis(methoxymethyl)-2,3-benzo[a]fluorene; 9,9-Bis(methoxymethyl)-2,3,6,7-dibenzo[a]fluorene; 9,9-Bis(methoxymethyl)-2,7-diisopropylfluorene; 9,9-Bis(methoxymethyl)-1,8-dichlorofluorene; 9,9-Bis(methoxymethyl)-2,7-dicyclopentylfluorene; 9,9-Bis(methoxymethyl)-1,8-difluorofluorene; 9,9-Bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene; 9,9-Bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene; 9,9-Bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene;At least one of 4,5,6,7,8-octahydrofluorene; 9,9-bis(methoxymethyl)-4-tert-butylfluorene.

[0027] Preferably, the diether compound is further selected from compounds represented by general formula (IV):

[0028]

[0029] In general formula (IV), R 25 -R 32 Whether identical or different, each independently selected from hydrogen, halogen, straight-chain or branched alkyl, cycloalkyl, aryl, alkylaryl, and arylalkyl groups with 1-20 carbon atoms, 3-20 carbon atoms, aryl, alkylaryl, and arylalkyl groups with 7-20 carbon atoms, optionally containing at least one heteroatom selected from N, O, S, P, Si, and halogens as a substituent for a carbon atom, a hydrogen atom, or both; R 19 -R 22 Whether the groups are the same or different, each is independently selected from H, or each is independently selected from straight-chain or branched alkyl, cycloalkyl, aryl, alkylaryl, or aralkyl groups containing 1-18 carbon atoms; R 23 and R 24 They may be the same or different, each independently selected from straight-chain or branched alkyl groups with 1-20 carbon atoms, cycloalkyl groups with 3-20 carbon atoms, aryl groups with 5-20 carbon atoms, alkylaryl groups with 7-20 carbon atoms, and arylalkyl groups; R 19 -R 32 One or more groups in the structure can be linked to form a ring structure, and each group may also contain at least one heteroatom selected from halogens, N, O, S, P and Si.

[0030] Preferably, the diether compounds include, but are not limited to, those selected from: 2-(2-ethylhexyl)1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-tert-butyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2(1- Naphthyl)-1,3-dimethoxypropane, 2(p-fluorophenyl)-1,3-dimethoxypropane, 2(1-decahydronaphthyl)-1,3-dimethoxypropane, 2(p-tert-butylphenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-diethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-diethoxypropane, 2,2-dibutyl-1,3-diethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane Alkane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2-methyl-2-methylcyclohexyl-1,3-dimethoxypropane, 2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane, 2,2-bis(2-phenylethyl)-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-bis(2-ethylhexyl)-1 3-Dimethoxypropane, 2,2-bis(p-methylphenyl)-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-Di-sec-butyl-1,3-dimethoxypropane, 2,2-di-tert-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-iso-propyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 1,1-bis(methoxymethyl)-cyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetramethylcyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetraphenylcyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetrafluorocyclopentadiene; 1,1-bis(methoxymethyl)-3 4-Dicyclopentylcyclopentadiene; 1,1-bis(methoxymethyl)indene; 1,1-bis(methoxymethyl)-2,3-dimethylindene; 1,1-bis(methoxymethyl)-4,5,6,7-tetrahydroindene; 1,1-bis(methoxymethyl)-2,3,6,7-tetrafluoroindene; 1,1-bis(methoxymethyl)-4,7-dimethylindene; 1,1-bis(methoxymethyl)-3,6-dimethylindene; 1,1-bis(methoxymethyl)-4-phenylindene; 1,1-bis(methoxymethyl)-4-phenyl-2-methylindene; 1,1-bis(methoxymethyl)-4-cyclohexylindene; 1,1-bis(methoxymethyl)-7-(3,3,3-trifluoropropyl)indene; 1,1-bis(methoxymethyl)-7- Trimethylsilyl indene; 1,1-bis(methoxymethyl)-7-trifluoromethyl indene; 1,1-bis(methoxymethyl)-4,7-dimethyl-4,5,6,7-tetrahydro indene; 1,1-bis(methoxymethyl)-7-methyl indene; 1,1-bis(methoxymethyl)-7-cyclopentyl indene; 1,1-bis(methoxymethyl)-7-isopropyl indene; 1,1-bis(methoxymethyl)-7-cyclohexyl indene; 1,1-bis(methoxymethyl)-7-tert-butyl indene; 1,1-bis(methoxymethyl)-7-tert-butyl-2-methyl indene; 1,1-bis(methoxymethyl)-7-phenyl indene; 1,1-bis(methoxymethyl)-2-phenyl indene; 1,1-bis(methoxymethyl)-1H-benzo[e]indene; 1 1-Bis(methoxymethyl)-1H-2-methylbenzo[e]indene; 9,9-bis(methoxymethyl)fluorene; 9,9-bis(methoxymethyl)-2,3,6,7-tetramethylfluorene; 9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene; 9,9-bis(methoxymethyl)-2,3-benzofluorene; 9,9-bis(methoxymethyl)-2,3-benzofluorene 9,9-bis(methoxymethyl)-2,3,6,7-dibenzo[a]fluorene; 9,9-bis(methoxymethyl)-2,7-diisopropylfluorene; 9,9-bis(methoxymethyl)-1,8-dichlorofluorene; 9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorene; 9,9-bis(methoxymethyl)-1,8-difluorofluorene; 9,9-bis(methoxymethyl)-1,2,3,At least one of 4-tetrahydrofluorene; 9,9-bis(methoxymethyl)-1,2,3,4,5,6,7,8-octahydrofluorene; and 9,9-bis(methoxymethyl)-4-tert-butylfluorene.

[0031] Preferably, the molar ratio of the internal electron donor compound a to the internal electron donor compound b is greater than or equal to 3:7.

[0032] Preferably, the molar ratio of the internal electron donor compound a to the internal electron donor compound b is greater than or equal to 5:5.

[0033] Preferably, the molar ratio of the internal electron donor compound a to the internal electron donor compound b is greater than or equal to 6:4.

[0034] Preferably, the molar ratio of the internal electron donor compound a to the internal electron donor compound b is greater than or equal to 7:3.

[0035] Preferably, the molar ratio of the internal electron donor compound a to the internal electron donor compound b is 7:3.

[0036] According to a specific embodiment of the present invention, preferably, the catalyst component comprises a titanium compound, a magnesium compound, the internal electron donor a compound, and the internal electron donor b compound;

[0037] 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;

[0038] 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.

[0039] Preferably, the magnesium compound is an alkoxide of magnesium dihalide;

[0040] Alternatively, the magnesium compound may be a liquid magnesium compound;

[0041] 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.

[0042] Preferably, the titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and titanium alkoxyhalide;

[0043] 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.

[0044] Preferably, the titanium compound is titanium tetrachloride.

[0045] Preferably, the molar ratio of the sum of the internal electron donor compound a and the internal electron donor compound b to the magnesium compound is 0.01-5.0, more preferably 0.05-3.0, and the magnesium compound is calculated in terms of magnesium element.

[0046] This invention does not specifically limit the preparation method of the olefin polymerization catalyst component, which can be carried out according to the following methods:

[0047] Method 1: A solution of titanium compounds (such as TiCl4 or hydroxyl titanium) in aromatic hydrocarbons (e.g., toluene, xylene, etc.) is reacted with magnesium compounds (such as dialkoxy magnesium or diaryloxy magnesium compounds) at -25 to 0 °C, followed by halogenation at 80 to 130 °C. The treatment with the aromatic hydrocarbon solution of TiCl4 can be repeated once or multiple times, with the addition of an internal electron donor. For example, the preparation method of the titanium-containing solid catalyst component disclosed in US5077357A can be used: ethoxy magnesium, tetraethoxy titanium, o-cresol, ethanol, and chlorobenzene are added sequentially, and the mixture is stirred; a TiCl4 / chlorobenzene solution is rapidly added to the above liquid, and the temperature is raised until complete dissolution, then the temperature is further raised to 80 to 130 °C; 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, twice with isooctane, and finally 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.

[0048] Method 2: React a magnesium compound (such as an alkoxide or chloroalkoxide of magnesium) with excess TiCl4 containing an internal electron donor in solution at a temperature of 80-135°C. According to the preferred method, the general formula TiX can be reacted. 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 3.5, 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 titanium compounds can be carried out by suspending the adduct (dealcoholized or the adduct itself) 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. An internal electron donor can be added during the TiCl4 treatment, and this treatment can be repeated once or multiple times.

[0049] Method 3: Anhydrous magnesium chloride and an internal electron donor are ground together under conditions where magnesium dichloride is activated. The resulting product can be treated once or multiple times with an excess of TiCl4 at a temperature of 80-130°C. After treatment, it is washed with a hydrocarbon volume until no chloride ions are present. According to a further method, the product obtained by co-grinding anhydrous magnesium dichloride, a titanium compound, and an internal electron donor 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 washed with an inert hydrocarbon volume, typically hexane.

[0050] Method 4: Magnesium dichloride can be pre-activated using known methods, and then treated with an excess of TiCl4 at a temperature of approximately 80-135°C, where the solution contains an internal electron donor. The solid is treated with TiCl4 multiple times and then washed with hexane to remove any unreacted TiCl4.

[0051] Method 5: 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, and an internal electron donor is used during the contact process.

[0052] Method Six: Dissolve a magnesium compound in a solvent system consisting of an organic epoxy compound, an organophosphorus compound, and an inert diluent to form a homogeneous solution. Mix this solution with a titanium compound and wash out the solid in the presence of a precipitation aid. Treat this solid with an internal electron donor to load it onto the solid. If necessary, further treat with titanium tetrahalide and an inert diluent to obtain the final product. The precipitation aid is one of an organic acid anhydride, organic acid, ether, or ketone. The components, per mole of magnesium halide, are: organic epoxy compound 0.2-10 mol, organophosphorus compound 0.1-3 mol, precipitation aid 0.03-1.0 mol, and transition metal Ti halide and its derivatives 0.5-150 mol.

[0053] Method 7: Magnesium compounds supported on inorganic oxides such as SiO2 and alumina or porous resins are used as carriers to prepare the product. The product is then activated by a known method and treated with an excess of TiCl4 at a temperature of about 80-135°C. An internal electron donor is added during the treatment process.

[0054] The reactions discussed above 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.

[0055] In any of the preparation methods described above, the internal electron donor compound can be added directly or optionally prepared in situ using a suitable precursor that can be converted in the desired internal electron donor compound via known chemical reactions such as esterification or transesterification. Typically, the internal electron donor compound is used in a molar ratio of 0.01-5, preferably 0.05-3.0, relative to MgCl2.

[0056] In any of the preparation methods described above, the internal electron donor compound can be added simultaneously or separately during the preparation process in batches or in any order or combination.

[0057] The present invention also provides an olefin polymerization catalyst, wherein the olefin polymerization catalyst comprises the above-described catalyst components.

[0058] 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.

[0059] 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 20 The hydrocarbon group, X is a halogen, and p is an integer 0 ≤ p ≤ 3.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] According to a specific embodiment of the present invention, preferably, the raw material composition of the catalyst further includes an external electron donor.

[0064] According to a specific embodiment of the present invention, preferably, the external electron donor is a siloxane compound.

[0065] 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.

[0066] 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, diisobutyldimethoxysilane, di-tert- ... Silane, di-tert-butyldiethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, di(2-ethylhexyl)dimethoxysilane, di(2-ethylhexyl)diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclohexyldimethoxysilane, 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 2-Ethylhexyltrimethoxysilane, 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,At least one of the following: 5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, di(3-methylcyclohexyl)dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, di(4-methylcyclohexyl)dimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, di(3,5-dimethylcyclohexyl)dimethoxysilane, tetrapropoxysilane, and tetrabutoxysilane;

[0067] The siloxane compound more preferably includes at least one of 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, cyclohexyl methyl dimethoxysilane, cyclohexyl ethyl diethoxysilane, cyclohexyl ethyl dimethoxysilane, cyclohexyl ethyl diethoxysilane, cyclopentyl methyl dimethoxysilane, cyclopentyl methyl diethoxysilane, cyclopentyl ethyl dimethoxysilane, cyclohexylcyclopentyl dimethoxysilane, cyclohexylcyclopentyl diethoxysilane, 3-methylcyclohexylcyclopentyl dimethoxysilane, 4-methylcyclohexylcyclopentyl dimethoxysilane, and 3,5-dimethylcyclopentyl dimethoxysilane.

[0068] 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.

[0069] The present invention also provides the application of the above-mentioned catalyst in olefin polymerization.

[0070] 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.

[0071] According to a specific embodiment of the present invention, preferably, the polymerization includes ethylene and / or propylene polymerization.

[0072] According to a specific embodiment of the present invention, preferably, the polymerization includes homopolymerization or copolymerization.

[0073] 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.

[0074] 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.

[0075] 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, preferably 0.3-5MPa.

[0076] The internal electron donor of the catalyst component of this invention is at least one compound selected from 2,6-dicarboxylate-4-pyridinium ether of general formula (I) or N-substituted 2,6-dicarboxylate-4-pyridinone of general formula (II), as well as a diether compound. The activity can be significantly improved by combining multiple internal electron donors, generally exceeding that of phthalate-based internal electron donor catalysts commonly used in industry today, and also exceeding that of diether catalysts. The resulting polymer exhibits high isotacticity, high bulk density, and a moderate molecular weight distribution. Even without using external electron donors, the polymer maintains high isotacticity, further enhancing polymerization activity and exhibiting ultra-high activity, far exceeding that of non-combined catalysts. The resulting polymer has low ash content. Detailed Implementation

[0077] 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.

[0078] 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.

[0079] The bulk density of the polymer was determined using the method specified in JB / T 2412-2008.

[0080] 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).

[0081] Determination of polymer ash content: determined in accordance with GB / T 9345.1-2008.

[0082] 9,9-Bis(methoxymethyl)fluorene, commercially available, CAS No. 182121-12-6.

[0083] 2-Isopropyl-2-isopentyl-1,3-dimethoxypropane was synthesized according to CN1041752A.

[0084] Synthesis of the 2,6-dicarboxylate-4-pyridine ether compound represented by general formula (I)

[0085] Preparation Example 1: Synthesis of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine

[0086] Sodium (23.6 g, 1 mol, 2.04 eq.) was dissolved in anhydrous ethanol (350 mL). A mixture of anhydrous acetone (29 g, 38 mL, 0.5 mol, 1 eq.) and diethyl oxalate (155 g, 144 mL, 1.06 mol, 2.12 eq.) 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%, 200 mL) and water (100 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 (300 mL) and HCl (aq. 37%, 50 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 a white powder, 2,6-dicarboxylic acid-4-pyranone.

[0087] In a 1L three-necked flask, add 11g of 2,6-dicarboxylic acid-4-pyranone, 200mL of n-butanol, and 1mL of concentrated sulfuric acid; 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 (150mL*2), combine the organic phases, wash with saturated brine (150mL*2), concentrate and recrystallize to obtain the product 2,6-dicarboxylic acid di-n-butyl ester-4-pyranone.

[0088] Dibutyl 2,6-dicarboxylate-4-hydroxypyridine (7.4 g, 25 mmol) was added dropwise to an ammonia solution (aq. 25%, 50 mL) 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 dibutyl 2,6-dicarboxylate-4-hydroxypyridine.

[0089] Sodium methoxide (4 g, 74 mmol) was gradually added to a solution of di-n-butyl 2,6-dicarboxylate-4-hydroxypyridine (10.5 g, 35.7 mmol) and anhydrous MeOH (500 ml). The reaction mixture was stirred at room temperature for 1 hour.

[0090] Dimethyl ether (10 mL) was then added. The mixture was heated to 60 °C, stirred for 12 hours, and filtered to obtain di-n-butyl 2,6-dicarboxylate-4-methoxypyridine. 1 H NMR (500MHz, Chloroform-d) δ / ppm: 7.65 (s, 2H), 4.30 (t, J = 8.4Hz, 4H), 3.82 (s, 3H), 1.80-1.69 (m, 4H), 1.52-1.41 (m, 4H), 0.97 (t, J = 5.6Hz, 6H).

[0091] Preparation Example 2-14: Synthesis of other 2,6-dicarboxylate-4-pyridine ether compounds

[0092] The compounds were synthesized using routes 1-3 as described above. The structures and NMR results of the compounds are shown in Table 1.

[0093] Synthesis of N-substituted 2,6-dicarboxylate-4-pyridone compounds represented by general formula (II)

[0094] Preparation Example 15: Synthesis of N-isopropyl-2,6-dicarboxylic acid ethyl ester-4-pyridone

[0095] 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.

[0096] 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.

[0097] 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).

[0098] Preparation Examples 16-26: Synthesis of Other N-Substituted-2,6-Dicarboxylate-4-pyridone Compounds

[0099] The compounds were synthesized using routes 4 and 5 mentioned above. The structures and NMR results of the compounds are shown in Table 2.

[0100]

[0101] Table 1. 2,6-Dicarboxylate-4-pyridine ether compounds prepared in Examples 1-14

[0102]

[0103]

[0104]

[0105]

[0106]

[0107] Table 2. N-substituted 2,6-dicarboxylate-4-pyridone compounds prepared in Examples 15-26

[0108]

[0109]

[0110]

[0111]

[0112] Catalyst preparation

[0113] Example 1

[0114] 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. 7 mmol of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine and 3 mmol of 9,9-bis(methoxymethyl)fluorene were 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 resulting solid was then washed four times with 150 mL of hexane at 60 °C, the liquid was filtered off, and the solid catalyst component Cat-1 was obtained.

[0115] Example 2-26

[0116] The preparation process of the solid catalyst components is as shown in Example 1, except that 2,6-dibutyl 2,6-dicarboxylate-4-methoxypyridine is replaced with 7 mmol of compounds 2-26 in Tables 1 and 2 respectively.

[0117] Example 27

[0118] The solid catalyst component was prepared as in Example 1, except that 6 mmol of 2,6-dibutyl 2,6-dicarboxylate-4-methoxypyridine and 4 mmol of 9,9-bis(methoxymethyl)fluorene were added.

[0119] Example 28

[0120] The solid catalyst component was prepared as in Example 1, except that 5 mmol of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine and 5 mmol of 9,9-bis(methoxymethyl)fluorene were added.

[0121] Example 29

[0122] The solid catalyst component was prepared as in Example 1, except that 4 mmol of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine and 6 mmol of 9,9-bis(methoxymethyl)fluorene were added.

[0123] Example 30

[0124] The solid catalyst component was prepared as shown in Example 1, except that 3 mmol of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine and 7 mmol of 9,9-bis(methoxymethyl)fluorene were added.

[0125] Examples 31-56

[0126] The solid catalyst components were prepared as in Example 1, except that 7 mmol of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine and 3 mmol of 9,9-bis(methoxymethyl)fluorene were replaced with 7 mmol of compounds 1-26 in Tables 1 and 2 and 3 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane.

[0127] Example 57

[0128] The solid catalyst component was prepared as shown in Example 1, except that 6 mmol of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine and 4 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were added.

[0129] Example 58

[0130] The solid catalyst component was prepared as in Example 1, except that 5 mmol of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine and 5 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were added.

[0131] Example 59

[0132] The solid catalyst component was prepared as shown in Example 1, except that 4 mmol of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine and 6 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were added.

[0133] Example 60

[0134] The solid catalyst component was prepared as in Example 1, except that 3 mmol of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine and 7 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were added.

[0135] Example 61

[0136] The solid catalyst component was prepared as shown in Example 1, except that 3 mmol of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine, 3 mmol of N-isopropyl-2,6-diethyl 2,6-dicarboxylate-4-pyridone, and 4 mmol of 9,9-bis(methoxymethyl)fluorene were added.

[0137] Example 62

[0138] The solid catalyst component was prepared as in Example 1, except that 3 mmol of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine, 3 mmol of N-isopropyl-2,6-diethyl 2,6-dicarboxylate-4-pyridone, and 4 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were added.

[0139] Comparative Example 1

[0140] The catalyst component was prepared as in Example 1, except that 7 mmol of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine and 3 mmol of 9,9-bis(methoxymethyl)fluorene internal electron donor compound were replaced with 10 mmol of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine (a1).

[0141] Comparative Example 2

[0142] The catalyst component was prepared as in Example 1, except that 7 mmol of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine and 3 mmol of 9,9-bis(methoxymethyl)fluorene internal electron donor compound were replaced with 10 mmol of diisopropyl 2,6-dicarboxylate-4-isopropyloxypyridine (a2).

[0143] Comparative Example 3

[0144] The catalyst component was prepared as in Example 1, except that 7 mmol of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine and 3 mmol of 9,9-bis(methoxymethyl)fluorene internal electron donor compound were replaced with 10 mmol of N-n-butyl-2,6-dicarboxylate-4-pyridone (a17).

[0145] Comparative Example 4

[0146] The catalyst component was prepared as in Example 1, except that 7 mmol of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine and 3 mmol of 9,9-bis(methoxymethyl)fluorene internal electron donor compound were replaced with 10 mmol of N-phenyl-2,6-diphenyl 2,6-dicarboxylate-4-pyridone (a18).

[0147] Comparative Example 5

[0148] The catalyst component was prepared as described in Example 1, except that 7 mmol of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine and 3 mmol of 9,9-bis(methoxymethyl)fluorene internal electron donor compound were replaced with 5 mmol of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine and 5 mmol of N-isopropyl-2,6-diethyl-4-pyridone.

[0149] Comparative Example 6

[0150] The catalyst component was prepared as in Example 1, except that 7 mmol of di-n-butyl 2,6-dicarboxylate-4-methoxypyridine and 3 mmol of 9,9-bis(methoxymethyl)fluorene internal electron donor compound were replaced with 10 mmol of 9,9-bis(methoxymethyl)fluorene (FLU).

[0151] Comparative Example 7

[0152] The catalyst component was prepared as in Example 1, except that 7 mmol of 2,6-dibutyl 2,6-dicarboxylate-4-methoxypyridine and 3 mmol of 9,9-bis(methoxymethyl)fluorene internal electron donor compound were replaced with 10 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (E2).

[0153] polymerization:

[0154] 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 solid catalyst component 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, the reactor was cooled and stirring was stopped, and the reaction product was discharged and dried to obtain the polymer. Polymerization data are shown in Table 3.

[0155] Table 3 Results of different compound formulations under the same polymerization conditions

[0156]

[0157]

[0158]

[0159]

[0160]

[0161] [Note] FLU: 9,9-bis(methoxymethyl)fluorene;

[0162] E2: 2-Isopropyl-2-isopentyl-1,3-dimethoxypropane.

[0163] Examples 63-77

[0164] After the 5L stainless steel reactor was fully purged with nitrogen, a 0.5mol / L triethylaluminum hexane solution (the amount of triethylaluminum is shown in Table 4 for Al / Ti) and the corresponding catalyst from Table 3 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 refined propylene. The reaction was prepolymerized at 20℃ for 5 minutes, then the temperature was raised to 70℃, and the polymerization reaction was carried out at this temperature for the corresponding time (see Table 4). 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. The results are shown in Table 4.

[0165] Comparative Examples 8-13

[0166] The polymerization steps are the same as in Example 64, except that the catalysts are Cat-D1 to Cat-D4 and Cat-D6 to Cat-D7, respectively.

[0167] Table 4 (Without external electron donors)

[0168]

[0169]

[0170] As can be seen from Table 3, the activity of 2,6-dicarboxylate-4-pyridine ether compound and / or N-substituted-2,6-dicarboxylate-4-pyridone compound as internal electron donors combined with diether compounds can be significantly improved, which is higher than that of uncombined single internal electron donor catalysts (Comparative Examples 1-7). The polymer has high isotacticity, high bulk density and moderate molecular weight distribution.

[0171] As shown in Table 4, the polymer maintained a high isotacticity even without the use of an external electron donor, and the polymerization activity was further improved, exhibiting ultra-high activity, far exceeding that of the non-composite catalysts (Comparative Examples 8-13). The polymerization time was extended from 60 minutes to 120 minutes, and the catalyst maintained its ultra-high activity without decay. The polypropylene obtained using a low Al / Ti ratio had a lower ash content, which could be reduced to 22 ppm.

[0172] 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 polymerization catalyst component for olefins, characterized in that, The compound comprises Mg, Ti, a halogen, at least one internal electron donor a compound and at least one internal electron donor b compound, wherein the internal electron donor a compound is selected from at least one of 2,6-dicarboxylate-4-pyridinium ether compounds of general formula (I) or N-substituted 2,6-dicarboxylate-4-pyridinone compounds of general formula (II), and the internal electron donor b compound is selected from diether compounds. General Formula (I) General Formula (II) In general formula (I), R 1 -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; In general formula (II), R 6 -R 10 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; The diether compound is selected from 1,3-diether compounds represented by general formula (III): General Formula (III) In general formula (III), R 11 -R 16 Whether the groups are the same or different, each is independently selected from H, or each is independently selected from straight-chain or branched alkyl, cycloalkyl, aryl, alkylaryl, or aralkyl groups containing 1-18 carbon atoms; R 17 -R 18 They may be the same or different, each independently selected from straight-chain or branched alkyl groups with 1-20 carbon atoms, cycloalkyl groups with 3-20 carbon atoms, aryl groups with 5-20 carbon atoms, alkylaryl groups with 7-20 carbon atoms, and arylalkyl groups; R 11 -R 18 One or more groups in the compound link together to form a cyclic structure.

2. The olefin polymerization catalyst component according to claim 1, characterized in that, In general formula (I) or general formula (II), R 1 -R 10 The substituents may be the same or different, and are each independently selected from H, halogens, and the following substituents with 20 or fewer carbon atoms: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indene, benzyl, halogenated or substituted with N or O heteroatoms, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indene, benzyl; or each independently selected from heterocyclic aryl substituents.

3. The olefin polymerization catalyst component according to claim 1, characterized in that, In general formula (I) or general formula (II), R 1 -R 10 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, propenyl, butenyl, pentenyl, hexenyl, indene.

4. The olefin polymerization catalyst component according to claim 1, characterized in that, The 2,6-dicarboxylate-4-pyridine ether compound of general formula (I) is selected from di-n-butyl 2,6-dicarboxylate-4-methoxypyridine, diisopropyl 2,6-dicarboxylate-4-isopropyloxypyridine, di(dodecyl) 2,6-dicarboxylate-4-butoxypyridine, diphenyl 2,6-dicarboxylate-4-methoxypyridine, di-m-chlorophenyl 2,6-dicarboxylate-4-methoxypyridine, di-p-toluene 2,6-dicarboxylate-4-methoxypyridine, di-p-methoxyphenyl 2,6-dicarboxylate-4-benzyloxypyridine, 2 At least one of the following: difuran methyl 6-dicarboxylate-4-methoxypyridine, dipentenyl 2,6-dicarboxylate-3-methyl-5-ethyl-4-methoxypyridine, di-p-nitrophenyl 2,6-dicarboxylate-3,5-diethyl-4-methoxypyridine, dimethyl 2,6-dicarboxylate-3-methyl-5-n-butyl-4-methoxypyridine, dibenzyl 2,6-dicarboxylate-4-ethoxypyridine, ethyl 2-formate-6-butyl 4-methoxypyridine, and ethyl 2-formate-6-phenyl 4-methoxypyridine.

5. The olefin polymerization catalyst component according to claim 1, characterized in that, The N-substituted 2,6-dicarboxylate-4-pyridone compound in general formula (II) is selected from diethyl 2,6-dicarboxylate-4-pyridone, di(dodecyl) 2,6-dicarboxylate-4-pyridone, dibutyl 2,6-dicarboxylate-4-pyridone, diphenyl 2,6-dicarboxylate-4-pyridone, di-m-chlorophenyl 2,6-dicarboxylate-4-pyridone, di-p-chlorophenyl 2,6-dicarboxylate-4-pyridone, di-p-chlorophenyl 2,6-dicarboxylate-4-pyridone, di-p-chlorophenyl 2,6-dicarboxylate-4-pyridone, di-p-methoxyphenyl 2,6-dicarboxylate-4-pyridone, di-p-methoxyphenyl 2,6-dicarboxylate-4-pyridone, dipentenyl 2,6-dicarboxylate-4-pyridone, and dimethyl 2,6-dicarboxylate-4-pyridone. 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.

6. The olefin polymerization catalyst component according to claim 1, characterized in that, The diether compound is selected from compounds represented by general formula (IV): General Formula (IV) In general formula (IV), R 25 -R 32 They may be the same or different, each independently selected from hydrogen, halogen, straight-chain or branched alkyl groups of 1-20 carbon atoms, cycloalkyl groups of 3-20 carbon atoms, aryl groups of 6-20 carbon atoms, alkylaryl groups of 7-20 carbon atoms, and arylalkyl groups of 7-20 carbon atoms; R 19 -R 22 Whether the groups are the same or different, each is independently selected from H, or each is independently selected from straight-chain or branched alkyl, cycloalkyl, aryl, alkylaryl, or aralkyl groups containing 1-18 carbon atoms; R 23 and R 24 They may be the same or different, each independently selected from straight-chain or branched alkyl groups with 1-20 carbon atoms, cycloalkyl groups with 3-20 carbon atoms, aryl groups with 5-20 carbon atoms, alkylaryl groups with 7-20 carbon atoms, and arylalkyl groups; R 19 -R 32 One or more groups in the compound link together to form a cyclic structure.

7. The catalyst component for olefin polymerization according to claim 1, characterized in that, The molar ratio of the internal electron donor compound a to the internal electron donor compound b is greater than or equal to 3:

7.

8. The olefin polymerization catalyst component according to claim 1, characterized in that, The catalyst component comprises a titanium compound, a magnesium compound, the internal electron donor a compound, and the internal electron donor b 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.

9. The olefin polymerization catalyst component according to claim 8, 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.

10. The olefin polymerization catalyst component according to claim 8, characterized in that, The titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and titanium alkoxyhalide.

11. The olefin polymerization catalyst component according to claim 10, 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.

12. The olefin polymerization catalyst component according to claim 8, characterized in that, The molar ratio of the sum of the internal electron donor compound a and the internal electron donor compound b to the magnesium compound is 0.01-5.0, and the magnesium compound is calculated as magnesium element.

13. A catalyst for olefin polymerization, wherein the feedstock comprises the polymerization catalyst component as described in any one of claims 1-12 and an organoaluminum compound.

14. The catalyst according to claim 13, 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.

15. The catalyst according to claim 13, characterized in that, The organoaluminum compounds include at least one of trialkylaluminum compounds, alkylaluminum halides, alkylaluminum hydrides, alkylaluminum sesquichlorides, and alkylaluminoxanes.

16. The catalyst according to claim 13, characterized in that, The molar ratio of the organoaluminum compound to the titanium atoms in the catalyst component is 1-1000:

1.

17. The catalyst according to claim 13, characterized in that, The catalyst's raw material composition also includes an external electron donor; The external electron donor is a siloxane compound.

18. The catalyst according to claim 17, 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 a catalyst according to any one of claims 13-18 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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