Olefin polymerization catalyst component, olefin polymerization catalyst and application thereof

Abstract

The invention discloses an olefin polymerization catalyst component, an olefin polymerization catalyst and application of the olefin polymerization catalyst component, the olefin polymerization catalyst component comprises Mg, Ti, halogen, at least one internal electron donor a compound and at least one internal electron donor b compound, and the internal electron donor a compound is selected from 2, 4, 6-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1, 3, 5-trimethyl-1 the internal electron donor b compound is selected from a Lewis base compound, and the internal electron donor b compound is selected from a Lewis base compound; the olefin polymerization catalyst containing the catalyst component can be used for preparing polyolefin with high melt flow rate.

Description

Technical Field

[0001] The present invention relates to a catalyst component for olefin polymerization, a catalyst containing the solid catalyst component and application of the catalyst in olefin polymerization reaction, in particular to application of propylene polymerization reaction. Background Art

[0002] Polyolefins are a type of polymer material with the largest output and widest application due to their abundant raw materials, low prices, easy processing and excellent comprehensive performance. At present, Ziegler-Natta catalysts (ZN catalysts) still occupy a dominant position in polyolefin production. The development of most ZN catalysts focuses on the development of high-activity and highly stereospecific catalysts and improving the copolymerization ability of catalysts. In addition, due to the high catalytic efficiency of traditional ZN catalysts (transition metal compounds such as titanium chemically bonded to magnesium-containing carriers), the polymers produced have good comprehensive performance and low cost. At present, most catalysts for the production of polyolefins in the world are still based on ZN catalytic systems, which are characterized by high activity, high stereoregularity, long life and customized product structure. It can be seen from the development process of ZN catalysts that as early as the emergence of the first generation of catalysts, it was found that the addition of a third component (mostly an electron donor, also known as a Lewis base, in which the one added during the catalyst preparation process becomes an internal electron donor, and the one added during the polymerization process becomes an external electron donor) will have a great influence on the polymerization behavior of olefins and the properties of polymers. Changing the internal electron donor in the catalyst can change the properties of the catalyst active center to the greatest extent possible, thereby changing the performance of the catalyst to the greatest extent. Therefore, the development of new electron donors has always been a hot topic in the research and development of polyolefin catalysts.

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

[0004] Polypropylene with high melt flow rate has better processing performance and can be made into short fibers, filaments, non-woven fabrics and other forms. It is widely used in packaging, geotechnical engineering, building materials, clothing, medical and sanitary products, injection molding and many other fields, and has great development potential. Due to the limited hydrogen adjustment ability of the commonly used catalyst system in industrial production, polypropylene with high melt flow rate (MFR) is mainly produced by adding peroxide. However, the high-yield high melt flow rate polypropylene produced by the peroxide degradation method has poor melt flow rate stability, high yellow index and strong odor, which limits its application range. The use of catalysts with high hydrogen adjustment sensitivity can realize the direct preparation of high melt flow rate polypropylene using the hydrogen adjustment method.

[0005] The preparation of polyolefin catalysts with high activity, high isotacticity and high hydrogen sensitivity is an important research direction in the industry. Summary of the invention

[0006] In order to solve the problems existing in the prior art, the present invention provides an olefin polymerization catalyst component. The olefin polymerization catalyst containing the catalyst component can prepare polyolefin with a high melt flow rate.

[0007] The object of the present invention is to provide an olefin polymerization catalyst component.

[0008] Another object of the present invention is to provide a method for preparing the olefin polymerization catalyst component.

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

[0010] Another object of the present invention is to provide application of the catalyst in olefin polymerization.

[0011] In order to achieve the object of the present invention, the present invention provides an olefin polymerization catalyst component, which comprises Mg, Ti, 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 the 2,6-dimethoxy-substituted-4-pyrone compound in the general formula (I), and the internal electron donor b compound is selected from the Lewis base compound;

[0012]

[0013] Among them, R in the general formula (I) 1 , R 2 , R 3 and R 4 are the same or different, each independently selected from H, halogen, C1-C 20 The hydrocarbon group, R 1 and R 2 The group connected to the O atom in the 2,6-dimethoxy group is not a carbonyl group; preferably, R 1 , R 2 , R 3 and R 4 may also contain at least one heteroatom selected from N, O, S, P, Si and halogen; preferably, R 1 , R 2 , R 3 and R 4 Two or more of them may be bonded to each other to form a ring.

[0014] Preferably, R in the general formula (I) 1 , R 2 , R 3 and R 4 the same or different, each independently selected from H, halogen, the following substituents with less than 20 carbon atoms: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or substituted with N, O, S, P, Si heteroatom alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or each independently selected from heterocyclic aromatic substituents.

[0015] Preferably, R in the general formula (I) 1 , R 2 , R 3 and R 4 are the same or different and are each 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, C11 ~C 20 a straight-chain or branched alkyl group, or the following substituents having less than 20 carbon atoms: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, substituted benzyl, substituted phenethyl, furanyl, pyrrolyl, thienyl, propenyl, butenyl, pentenyl, hexenyl, and indenyl.

[0016] Preferably, the 2,6-dimethoxy-substituted-4-pyrone compound of general formula (I) is selected from 2,6-dimethoxymethyl-4-pyrone, 2,6-dimethoxyethyl-4-pyrone, 2,6-dimethoxypropyl-4-pyrone, 2,6-dimethoxybutyl-4-pyrone, 2,6-dimethoxypentyl-4-pyrone, 2,6-dimethoxyhexyl-4-pyrone, 2,6- 2,6-dimethoxyheptyl-4-pyrone, 2,6-dimethoxyoctyl-4-pyrone, 2,6-dimethoxydodecyl-4-pyrone, 2,6-dimethoxytetradecyl-4-pyrone, 2,6-dimethoxyhexadecyl-4-pyrone, 2,6-dimethoxyphenyl-4-pyrone, 2,6-dimethoxybenzyl-4-pyrone, 2,6-dimethoxy-m-chlorophenyl-4-pyrone, At least one of 2,6-dimethoxy-o-chlorophenyl-4-pyrone, 2,6-dimethoxy-p-chlorophenyl-4-pyrone, 2,6-dimethoxy-p-methylphenyl-4-pyrone, 2,6-dimethoxy-p-methoxymethyl-4-pyrone, 2,6-dimethoxyfuranyl-4-pyrone, 2,6-dimethoxypropylene-4-pyrone, 2,6-dimethoxymethyl-3,5-dimethyl-4-pyrone, 2,6-dimethoxymethyl-3-methyl-5-ethyl-4-pyrone, 2,6-dimethoxymethyl-3,5-diethyl-4-pyrone, 2,6-dimethoxymethyl-3,5-dibutyl-4-pyrone, 2,6-dimethoxymethyl-3-ethyl-5-butyl-4-pyrone, and 2,6-dimethoxymethyl-3-methyl-5-butyl-4-pyrone.

[0017] Preferably, the 2,6-dimethoxy-substituted-4-pyrone compound of general formula (I) can be synthesized by the following preparation methods including but not limited to:

[0018]

[0019] R 1 and R 2 Same or Different, R 3 and R 4 One of the synthetic routes of the same or different 2,6-dimethoxy-substituted-4-pyrone compounds of general formula (I) is shown below:

[0020]

[0021] The synthetic route specifically comprises the following steps: diethyl oxalate is reacted with the corresponding ketone and then reduced to obtain a substituted 2,6-dimethanol-4-pyrone compound, which is then reacted with an alcohol to obtain a pure (substituted) 2,6-dimethoxy-substituted-4-pyrone compound, or reacted with a mixture of two alcohols to obtain a mixture of three (substituted) 2,6-dimethoxy-substituted-4-pyrones, which is directly used as a mixture as an internal electron donor without separation, and the ratio of each component in the mixture can be adjusted by the addition ratio of the two acyl chlorides as reactants, and the ratio of each component can be characterized and determined by analytical means such as chromatography-mass spectrometry technology and nuclear magnetic resonance.

[0022] Preferably, the molar ratio of the internal electron donor compound a to the internal electron donor compound b is greater than or equal to 2:8.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] Preferably, the molar ratio of the internal electron donor compound a to the internal electron donor compound b is 7:3.

[0027] Preferably, the Lewis base compound contains one or more electronegative groups, wherein the electron donating atom is selected from N, O, S, P, As or Sn.

[0028] Preferably, the Lewis base compound is selected from electron donor compounds of diethers, esters, diketones, diamines, monocarboxylates and polycarboxylates. When the 2,6-dimethoxy-substituted-4-pyrone compound of general formula (I) is used together with the Lewis base compound, a catalyst with adjustable performance can be obtained, especially the activity of the catalyst is significantly improved.

[0029] Preferably, the Lewis base compound is selected from 1,3-diether compounds represented by general formula (II):

[0030]

[0031] In the general formula (II), R 7 -R 12are the same or different and are each independently selected from H, or are each independently selected from a linear or branched alkyl, cycloalkyl, aryl, alkaryl or aralkyl group containing 1 to 18 carbon atoms; R 13 and R 14 are the same or different and are each independently selected from a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms, an alkaryl group having 7 to 20 carbon atoms and an aralkyl group; R 7 -R 14 One or more groups in the group may be linked to form a ring structure, and each may further contain at least one heteroatom selected from halogen, N, O, S, P and Si.

[0032] Specifically, the 1,3-diether compound includes, but is not limited to, 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-decalinyl)-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 Oxypropane, 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 )-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-dimethoxy__ylpropane, 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- Methylindene; 1,1-bis(methoxymethyl)-7-cyclopentylindene; 1,1-bis(methoxymethyl)-7-isopropylindene; 1,1-bis(methoxymethyl)-7-cyclohexylindene; 1,1-bis(methoxymethyl)-7-tert-butylindene; 1,1-bis(methoxymethyl)-7-tert-butyl-2-methylindene; 1,1-bis(methoxymethyl)-7-phenylindene; 1,1-bis(methoxymethyl)-2-phenylindene; 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 )-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)-2,3,6,7-dibenzofluorene; 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,At least one of 4,5,6,7,8-octahydrofluorene and 9,9-bis(methoxymethyl)-4-tert-butylfluorene.

[0033] Preferably, the diether electron donor compound is further selected from the diether compound represented by general formula (III):

[0034]

[0035] In the general formula (III), R 21 -R 28 R is the same or different, each independently selected from hydrogen, halogen, linear or branched alkyl with 1 to 20 carbon atoms, cycloalkyl with 3 to 20 carbon atoms, aryl with 6 to 20 carbon atoms, alkylaryl with 7 to 20 carbon atoms and arylalkyl with 7 to 20 carbon atoms, optionally containing at least one heteroatom selected from N, O, S, P, Si and halogen as a substituent for carbon atoms or hydrogen atoms or both; 15 -R 18 are the same or different and are each independently selected from H, or are each independently selected from a linear or branched alkyl, cycloalkyl, aryl, alkaryl or aralkyl group containing 1 to 18 carbon atoms; R 19 and R 20 are the same or different and are each independently selected from a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms, an alkaryl group having 7 to 20 carbon atoms and an aralkyl group; R 15 -R 28 One or more groups in the group may be linked to form a ring structure, and each may further contain at least one heteroatom selected from halogen, N, O, S, P and Si.

[0036] Preferably, the diether compound includes but is not limited to: 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- 2,2-dibutyl-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 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-di-neopentyl-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- trimethylsilylindene; 1,1-bis(methoxymethyl)-7-trifluoromethylindene; 1,1-bis(methoxymethyl)-4,7-dimethyl-4,5,6,7-tetrahydroindene; 1,1-bis(methoxymethyl)-7-methylindene; 1,1-bis(methoxymethyl)-7-cyclopentylindene; 1,1-bis(methoxymethyl)-7-isopropylindene; 1,1-bis(methoxymethyl)-7-cyclohexylindene; 1,1-bis(methoxymethyl)-7-tert-butylindene; 1,1-bis(methoxymethyl)-7-tert-butyl-2-methylindene; 1,1-bis(methoxymethyl)-7-phenylindene; 1,1-bis(methoxymethyl)-2-phenylindene; 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)- 9,9-bis(methoxymethyl)-2,3,6,7-dibenzofluorene; 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; 9,9-bis(methoxymethyl)-4-tert-butylfluorene.

[0037] Preferably, the polycarboxylic acid ester compound is an aromatic dicarboxylic acid compound or an aliphatic chain dicarboxylic acid ester compound;

[0038] The aromatic dicarboxylic acid compound may be a diester compound of an aromatic dicarboxylic acid, such as phthalic acid diesters or terephthalic acid diesters, wherein the phthalic acid diesters may include but are not limited to: dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, dipropyl butyl phthalate, di-n-butyl phthalate, diisopropyl ... Butyl phthalate, ethyl methyl phthalate, isopropyl methyl phthalate, n-propyl methyl phthalate, n-butyl ethyl phthalate, isobutyl ethyl phthalate, di-n-pentyl phthalate, di-isopentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, di-isooctyl phthalate, (2,2-dimethylhexyl) phthalate, Phthalic acid (2-ethylhexyl) diester, di-n-nonyl phthalate, di-isodecyl phthalate, phthalic acid (2,2-dimethylheptyl) diester, n-butyl phthalate isohexyl ester, n-butyl phthalate (2-ethylhexyl) ester, n-pentyl phthalate n-hexyl ester, n-pentyl phthalate isononyl phthalate, isopentyl phthalate n-decyl ester, n-pentyl phthalate undecyl ester, phthalic acid Isoamyl isohexyl dicarboxylate, n-hexyl phthalate (2-methylhexyl ester), n-hexyl phthalate (2-ethylhexyl ester), n-hexyl phthalate (isononyl ester), n-hexyl phthalate (n-decyl ester), n-heptyl phthalate (2-ethylhexyl ester), n-heptyl phthalate (isononyl ester), n-heptyl phthalate (neonyl ester), n-heptyl phthalate (neonyl ester) and 2-ethylhexyl phthalate (isononyl ester). These esters can be used alone or in combination.The terephthalic acid diesters include but are not limited to: dimethyl terephthalate, diethyl terephthalate, di-n-propyl terephthalate, diisopropyl terephthalate, di-n-butyl terephthalate, diisobutyl terephthalate, ethyl terephthalate methyl ester, methyl terephthalate isopropyl terephthalate, ethyl terephthalate (n-propyl ester), ethyl terephthalate (n-butyl ester), ethyl terephthalate (isobutyl ester), di-n-butyl terephthalate, diisobutyl terephthalate, di-n-butyl terephthalate, diisobutyl terephthalate, diisobutyl terephthalate, diisopropyl ... di-n-pentyl terephthalate, di-isopentyl terephthalate, di-hexyl terephthalate, di-n-heptyl terephthalate, di-n-octyl terephthalate, di-iso-n-octyl terephthalate, di-(2,2-dimethylhexyl) terephthalate, di-(2-ethylhexyl) terephthalate, di-n-nonyl terephthalate, di-isononyl terephthalate, di-isodecyl terephthalate, di-(2,2-dimethylhexyl) terephthalate methyl ethyl heptyl) ester, n-butyl terephthalate isohexyl ester, n-butyl terephthalate (2-ethylhexyl) ester, n-pentyl terephthalate n-hexyl ester, n-pentyl terephthalate isohexyl ester, isopentyl terephthalate (heptyl ester), terephthalic acid, n-pentyl terephthalate (2-ethylhexyl) ester, n-pentyl terephthalate (isononyl ester), isopentyl terephthalate (n-decyl ester), n-pentyl terephthalate At least one of undecyl ester, isopentyl terephthalate, isohexyl terephthalate, n-hexyl terephthalate (2-ethylhexyl ester), n-hexyl terephthalate (isononyl ester), n-hexyl terephthalate (n-decyl ester), n-heptyl terephthalate (2-ethylhexyl ester), n-heptyl terephthalate (isononyl ester), n-heptyl terephthalate (neodecanyl ester), and 2-ethylhexyl terephthalate (isononyl ester).

[0039] Among the diester compounds of the above-mentioned aromatic dicarboxylic acids, it is preferred to use at least one of diethyl phthalate, dipropyl butyl phthalate, diisopropyl terephthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, di-isooctyl phthalate, di-n-butyl terephthalate, diisobutyl terephthalate, di-n-octyl terephthalate, di-iso-octyl terephthalate, di(2-ethylhexyl) terephthalate and diisodecyl phthalate.

[0040] Preferably, the ester compound of the Lewis base compound is a diol ester compound of general formula (IV):

[0041]

[0042] In the general formula (IV), R 29 -R 36 The same or different, each independently selected from hydrogen, halogen or substituted or unsubstituted straight or branched C1-C 20 Alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C20 Alkyl, C7-C 20 Aralkyl, C2-C 10 Olefin or C 10 -C 20 Fused ring aromatic group; but R 31 and R 32 Not hydrogen, R 29 -R 36 One or more of are optionally cyclic or non-cyclic.

[0043] Preferably, the diol ester compound is selected from, but not limited to: 1,3-propylene glycol dibenzoate, 2-methyl-1,3-propylene glycol dibenzoate, 2-ethyl-1,3-propylene glycol dibenzoate, 2-propyl-1,3-propylene glycol dibenzoate, 2-butyl-1,3-propylene glycol dibenzoate, 2,2-dimethyl-1,3-propylene glycol dibenzoate, 2-ethyl-2-butyl-1,3-propylene glycol dibenzoate, 2,2-diethyl-1,3-propylene glycol dibenzoate. Acid ester, 2-methyl-2-propyl-1,3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzoate, 2,4-pentanediol dibenzoate, 3-methyl-2,4-pentanediol dibenzoate, 3-ethyl-2,4-pentanediol dibenzoate, 3-propyl-2,4-pentanediol dibenzoate, 3-butyl-2,4-pentanediol dibenzoate, 3,3-dimethyl-2,4-pentanediol dibenzoate, 2-methyl-1,3-pentanediol dibenzoate 2,2-dimethyl-1,3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2-methyl-1,3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-propyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2-methyl-1,3-pentanediol dibenzoate, At least one of pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2,2,4-trimethyl-1,3-pentanediol dibenzoate, 3-methyl-3-butyl-2,4-pentanediol dibenzoate, 2,2-dimethyl-1,5-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate. Pentanediol esters and heptanediol esters are preferred.

[0044] Preferably, the ester compound of the Lewis base compound is an ortho-phenylene diester of general formula (V):

[0045]

[0046] In the general formula (V), R 37 and R 38 The same or different, each independently selected from substituted or unsubstituted straight or branched C1-C 20 Alkyl, C3-C 20 Cycloalkyl, C6-C 20 Substituted or unsubstituted aryl, C7-C 20 Substituted or unsubstituted aralkyl, C2-C 10 The olefin group, C 10 -C 20 A fused-ring aromatic group or an ester group, and R 37 and R 38 Not hydrogen; R 39 -R 42 are the same or different, each independently selected from hydrogen, substituted or unsubstituted C1-C 20 The hydrocarbon group, including C1-C 20 Alkoxy groups, heteroatoms, and combinations thereof.

[0047] Preferably, the ester compound of the Lewis base compound is a compound represented by general formula (VI):

[0048]

[0049] In the general formula (VI), R 43 -R 56 The same or different, each independently selected from hydrogen, a substituted hydrocarbyl group containing 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms, a heteroatom and combinations thereof.

[0050] Preferably, in the general formula (VI), R 43 -R 46 At least one of the following is selected from a substituted hydrocarbyl group containing 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group containing 1 to 20 carbon atoms, and a combination thereof.

[0051] Preferably, in the general formula (VI), R 47 -R 56 At least one of the following is selected from a substituted hydrocarbyl group containing 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms, a heteroatom and a combination thereof.

[0052] Preferably, the compound represented by general formula (VI) includes but is not limited to:

[0053] 1,2-Benzenediol-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0054] 1,2-benzenediol-3-methyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0055] 1,2-benzenediol-3-methoxy-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0056] 1,2-benzenediol-3-ethyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0057] 1,2-benzenediol-3-propyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0058] 1,2-benzenediol-3-isobutyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0059] 1,2-benzenediol-3-n-butyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0060] 1,2-Benzenediol-3-ethoxy-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0061] 1,2-Benzenediol-4-methyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0062] 1,2-benzenediol-4-ethyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0063] 1,2-benzenediol-4-propyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0064] 1,2-benzenediol-4-tert-butyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0065] 1,2-benzenediol-4-isopentyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0066] 1,2-Benzenediol-4-formyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0067] 1,2-Benzenediol-4-acetyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0068] 1,2-benzenediol-4-hydroxy-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0069] 1,2-benzenediol-4-chloro-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0070] 1,2-Benzenediol-4-bromo-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0071] 1,2-Benzenediol-3,4-dimethyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0072] 1,2-benzenediol-3,4-dimethoxy-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0073] 1,2-Benzenediol-3,4-dichloro-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0074] 1,2-benzenediol-3-methyl-5-tert-butyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0075] 1,2-benzenediol-3,5-di-tert-butyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0076] 1,2-benzenediol-3,5-diisopropyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0077] 1,2-Benzenediol-3,5-dimethoxy-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0078] 1,2-Benzenediol-3,6-dimethyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0079] 1,2-benzenediol-3,6-di-tert-butyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0080] 1,2-benzenediol-3,6-dimethyl-4-isopropyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0081] 1,2-Benzenediol-3-isopropyl-4,5-dimethyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0082] 1,2-benzenediol-4-ethyl-5-isobutyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0083] 1,2-benzenediol-4-ethyl-5-tert-butyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0084] 1,2-benzenediol-3-methoxy-5-methyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0085] 1,2-Benzenediol-3,4,6-trimethyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0086] 1,2-Benzenediol-3,4,6-triisopropyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate].

[0087] The above compound is further preferably:

[0088] 1,2-Benzenediol-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0089] 1,2-benzenediol-3-methyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0090] 1,2-benzenediol-3-n-butyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0091] 1,2-Benzenediol-4-methyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0092] 1,2-benzenediol-4-tert-butyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0093] 1,2-benzenediol-3-methyl-5-tert-butyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0094] 1,2-Benzenediol-3,6-dimethyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0095] 1,2-benzenediol-3,6-di-tert-butyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

[0096] 1,2-Benzenediol-3,4,6-trimethyl-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-tert-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate].

[0097] According to a specific embodiment of the present invention, preferably, the composition of the catalyst component comprises a titanium compound, a magnesium compound, the 2,6-dimethoxy-substituted-4-pyrone compound and a Lewis base compound;

[0098] The precursor of the magnesium compound is selected from X n Mg(OR a ) 2-n 、MgCl2·mR a OH, R a 2-n MgX n , MgCl2 / SiO2, MgCl2 / Al2O3, a mixture of magnesium halide and titanium alkoxide, wherein m is 0.1-6, 0≤n≤2, X is a halogen, R a C1-C 20 The hydrocarbon group;

[0099] The general formula of the titanium compound is TiXN (OR b ) 4-N , where R b C1-C 20 The hydrocarbon group is: X is halogen, and N is 1-4.

[0100] Preferably, the magnesium compound is an alcoholate of magnesium dihalide;

[0101] Alternatively, the magnesium compound is a liquid magnesium compound;

[0102] Alternatively, the magnesium compound is a derivative in which at least one halogen atom in the magnesium dihalide molecule is replaced by a hydrocarbonoxy group or a halogenated hydrocarbonoxy group; preferably a hydrocarbonoxy magnesium compound; more preferably an alkoxy magnesium and / or an aryloxy magnesium. Preferably, the titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and alkoxy titanium halide;

[0103] Preferably, the alkyl titanium halide includes at least one of methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, and tri-n-butoxytitanium chloride;

[0104] Preferably, the titanium compound is titanium tetrachloride.

[0105] Preferably, the molar ratio of the sum of the internal electron donor a compound and the internal electron donor b compound to the magnesium compound is 0.01-5.0, preferably 0.05-3.0, and the magnesium compound is calculated as magnesium element.

[0106] The present invention does not particularly limit the preparation method of the olefin polymerization catalyst component, which can be prepared according to the following preparation methods:

[0107] Method 1: A titanium compound (such as TiCl4 or alkoxytitanium) in an aromatic hydrocarbon (such as toluene, xylene, etc.) solution is reacted with a magnesium compound (such as a dialkoxy magnesium compound such as a dialkoxy magnesium or a diaryloxy magnesium) at -25-0°C, and halogenated at 80-130°C. The treatment with the aromatic hydrocarbon solution of TiCl4 can be repeated once or multiple times, and at least one 2,6-dimethoxy-substituted-4-pyrone compound selected from the general formula (I) and at least one Lewis base compound. For example, the preparation method of the titanium-containing solid catalyst component disclosed in US5077357A can be referred to: ethoxymagnesium, tetraethoxytitanium, o-cresol, ethanol and chlorobenzene are added in sequence, and stirred; TiCl4 / chlorobenzene solution is quickly added to the above liquid, and the temperature is raised until it is completely dissolved, and then the temperature is further raised to 80-130°C; the ethanol reactant is taken away by bubbling with N2, and then the stirring is continued for a certain period of time, and then hot chlorobenzene is used to wash once, isooctane is washed twice, and then N2 is blown dry to obtain the carrier. Or according to another example: TiCl4, tetraethoxytitanium, ethoxymagnesium and o-cresol are added to chlorobenzene in sequence and stirred; ethanol is added and stirring is continued for 3 hours at high temperature after the ethoxymagnesium is dissolved; hot filtering is then washed once with warm chlorobenzene and once with isooctane, and finally dried with N2.

[0108] Method 2: A magnesium compound (such as a magnesium alcoholate or chloroalcoholate) is reacted with an excess of TiCl4 containing at least one 2,6-dimethoxy-substituted-4-pyrone compound selected from the general formula (I) and at least one Lewis base compound at a temperature of 80-135°C. According to a preferred method, a compound of the general formula TiX N (OR b ) 4-N Titanium compounds (where R b C1-C 20 A hydrocarbon group, X is a halogen, N is 1-4; preferably TiCl4) and a general formula of MgCl2·mR a OH (wherein m is a number of 0.1-6, preferably 2-4, and R a C1-C 20 The solid catalyst component is prepared by reacting an adduct of an alcohol with an alkyl group of an isocyanate (a hydrocarbon group). The adduct can be suitably made into a spherical shape by the following method: in the presence of an inert hydrocarbon that is immiscible with the adduct, an alcohol and magnesium chloride are mixed, and the emulsion is rapidly quenched, thereby solidifying the adduct in the form of spherical particles. Spherical MgCl2·mR prepared according to this process aExamples of OH adducts are described in US Pat. No. 4,399,054 A and US Pat. No. 4,469,648 A. The adduct thus obtained can be reacted directly with the titanium compound, or it can be previously subjected to a thermally controlled dealcoholation (80-130° C.) to obtain an adduct in which the number of moles of 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 (dealcoholated or as such) in cold TiCl4 (generally -25-0° C.); the mixture is heated to 80-130° C. and maintained at this temperature for 0.5-2 hours. The treatment with TiCl4 can be carried out once or more. At least one 2,6-dimethoxy-substituted-4-pyrone compound selected from the general formula (I) and at least one Lewis base compound can be added during the treatment with TiCl4, and this treatment can be repeated once or more.

[0109] Method 3: Anhydrous magnesium chloride and at least one 2,6-dimethoxy-substituted-4-pyrone compound selected from the general formula (I) and at least one Lewis base compound are ground together under conditions where magnesium dichloride is activated. The product thus obtained 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 it is free of chloride ions. According to a further method, the product obtained by grinding anhydrous magnesium dichloride, a titanium compound and at least one 2,6-dimethoxy-substituted-4-pyrone compound selected from the general formula (I) and at least one Lewis base compound is treated with a halogenated hydrocarbon such as 1,2-dichloroethane, chlorobenzene, dichloromethane. The treatment is carried out at a temperature between 40°C and the boiling point of the halogenated hydrocarbon for 1-4 hours. The product is then usually washed with an inert hydrocarbon volume such as hexane.

[0110] Method 4: Magnesium dichloride can be preactivated according to known methods and then treated with an excess of TiCl4 at a temperature of about 80-135°C, wherein the solution contains at least one 2,6-dimethoxy-substituted-4-pyrone compound selected from the general formula (I) and at least one Lewis base compound. The TiCl4 treatment is repeated multiple times and the solid is washed with hexane to remove any unreacted TiCl4.

[0111] Method 5: The preparation method of the titanium-containing solid catalyst component disclosed in CN1208045A can also be referred to: first, a liquid magnesium compound and a liquid titanium compound are contacted at low temperature in the presence of a compound selected from alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and esters to precipitate a solid. The contact temperature is generally -70-200°C, preferably -30-130°C. During the contact process, at least one 2,6-dimethoxy-substituted-4-pyrone compound selected from the general formula (I) and at least one Lewis base compound are used for treatment.

[0112] Method 6: dissolving a magnesium compound in a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and an inert diluent to form a uniform solution, mixing with a titanium compound, washing out a solid in the presence of a precipitation aid; treating the solid with at least one 2,6-dimethoxy-substituted-4-pyrone compound selected from the general formula (I) and at least one Lewis base compound to load it on the solid, and if necessary, treating with titanium tetrahalide and an inert diluent to obtain the solid, wherein the precipitation aid is one of an organic anhydride, an organic acid, an ether and a ketone. The components are calculated per mole of magnesium halide, and the organic epoxy compound is 0.2-10 moles, the organic phosphorus compound is 0.1-3 moles, the precipitation aid is 0.03-1.0 moles, and the halide of transition metal Ti and its derivatives are 0.5-150 moles.

[0113] Method 7: A magnesium compound supported on an inorganic oxide such as SiO2, alumina or a porous resin is used as a carrier, and then activated by a known method, and then treated with an excess of TiCl4 at a temperature of about 80-135°C, during which at least one 2,6-dimethoxy-substituted-4-pyrone compound selected from the general formula (I) and at least one Lewis base compound are added.

[0114] The reactions discussed above lead to the formation of magnesium halide in an active form (generally, crystalline magnesium halide has a regular structure and can carry very little Ti, so the catalytic activity is low. To prepare a highly active supported catalyst, the magnesium halide must be activated. The activation treatment method includes using physical and / or chemical methods to make it into microcrystals so that the active center is supported on the surface, edge and defects of the magnesium halide. The treated magnesium halide microcrystals suitable for supporting Ti are "active magnesium halide"). In addition to these reactions, there are other well-known methods in the literature to form magnesium halide in an active form from compound starting materials other than magnesium halide.

[0115] In any of the above-mentioned preparation methods, the internal electron donor compound can be added directly or prepared in an alternative manner, such as in situ by using a suitable precursor, which can be converted into the desired internal electron donor compound by known chemical reactions such as esterification, transesterification, etc. Generally, the internal electron donor compound is used in a molar ratio of 0.01-5, preferably 0.05-3.0, relative to MgCl2.

[0116] In any of the preparation methods described above, the internal electron donor compound (at least one 2,6-dimethoxy-substituted-4-pyrone compound selected from the general formula (I) and at least one Lewis base compound) can be added simultaneously or separately in the preparation process in batches or in any order and combination.

[0117] The present invention also provides an olefin polymerization catalyst, which comprises the above catalyst component.

[0118] The present invention also provides a catalyst for olefin polymerization, the raw material composition of which includes the above catalyst component and an organic aluminum compound.

[0119] According to a specific embodiment of the present invention, preferably, the general formula of the organoaluminum compound is AlR c p X (3-p) , where R c is hydrogen or C1-C 20 wherein X is a halogen and p is an integer of 0≤p≤3.

[0120] According to a specific embodiment of the present invention, preferably, the organic aluminum compound includes at least one of a trialkyl aluminum compound, an alkyl aluminum halide, an alkyl aluminum hydride, an alkyl aluminum sesquichloride, and an alkyl aluminumoxane.

[0121] According to a specific embodiment of the present invention, preferably, the trialkylaluminum compound includes at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and trioctylaluminum; the alkylaluminum halide includes AlEt2Cl; and the alkylaluminum sesquichloride includes Al2Et3Cl3.

[0122] According to a specific embodiment of the present invention, preferably, the molar ratio of the organic aluminum compound to the titanium atom in the catalyst component is 1-1000:1, more preferably 50-800.

[0123] According to a specific embodiment of the present invention, preferably, the raw material composition of the catalyst also includes an external electron donor.

[0124] According to a specific embodiment of the present invention, preferably, the external electron donor is a siloxane compound.

[0125] According to a specific embodiment of the present invention, preferably, the general formula of the siloxane compound is R' t Si(OR”) 4-t , wherein R' and R" are each independently selected from C1-C 18A hydrocarbon group, t is an integer of 0≤t≤3; more preferably, said R' and R" respectively contain heteroatoms; more preferably, said heteroatoms include at least one of N, O, S, P, and Si.

[0126] According to a specific embodiment of the present invention, preferably, the siloxane compound includes trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, triisobutylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane silane, di-tert-butyldiethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, di(2-ethylhexyl)dimethoxysilane, di(2-ethylhexyl)diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldiethoxysilane, cyclopentylisopropyldiethoxysilane, cyclopentylisobutyldimethoxysilane, cyclohexyl-n-propyl Dimethoxysilane, cyclohexyl-n-propyldiethoxysilane, cyclohexyl-n-butyldiethoxysilane, amylmethyldimethoxysilane, amylmethyldiethoxysilane, amylethyldimethoxysilane, amylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, cyclohexyldimethoxysilane, cyclohexyldiethoxysilane, 2-ethylhexyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyl trimethoxysilane, isobutyltrimethoxysilane, tert-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,At least one of 5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, bis(3-methylcyclohexyl)dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, bis(4-methylcyclohexyl)dimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, bis(3,5-dimethylcyclohexyl)dimethoxysilane, tetrapropoxysilane and tetrabutoxysilane;

[0127] The siloxane compound more preferably includes at least one of di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldiethoxysilane, tert-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane and 3,5-dimethylcyclopentyldimethoxysilane.

[0128] 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 further preferably 0.01-5.

[0129] The invention also provides application of the catalyst in olefin polymerization.

[0130] According to a specific embodiment of the present invention, preferably, the olefin includes at least one of a linear or branched olefin, such as 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.

[0131] According to a specific embodiment of the present invention, preferably, the polymerization comprises ethylene and / or propylene polymerization.

[0132] According to a specific embodiment of the present invention, preferably, the polymerization includes homopolymerization or copolymerization.

[0133] According to a specific embodiment of the present invention, preferably, during the catalytic process, the order of adding the components in the catalyst is arbitrary, preferably the organoaluminum compound is first added to the polymerization system, then the external electron donor is added, and finally the catalyst component is added.

[0134] According to a specific embodiment of the present invention, preferably, in the above application, the polymerization process can be carried out with or without a solvent; the olefin monomer can be in gas phase or liquid phase; more preferably, hydrogen can be further added as a molecular weight regulator (polymerization can also be carried out without a molecular weight regulator); continuous polymerization or batch polymerization process can be applied, and the polymerization reaction can be carried out in one step, two steps or multiple steps.

[0135] According to a specific embodiment of the present invention, preferably, the polymerization temperature is ≤200°C, more preferably 20-100°C, and further preferably 40-80°C; the polymerization pressure is ≤10MPa, preferably 0.3-5MPa.

[0136] The catalyst component of the present invention adopts 2,6-dimethoxy-substituted-4-pyrone compound as internal electron donor and is compounded with Lewis base compound, and the activity can be significantly improved, and the high activity can be maintained as the polymerization time increases. The polyolefin obtained by the catalyst has high isotacticity, and high isotacticity polyolefin can be obtained even without adding external electron donor. The obtained catalyst has good hydrogen adjustment sensitivity and is suitable for preparing polyolefin with high melt flow rate. DETAILED DESCRIPTION

[0137] The technical solution of the present invention is described in detail below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the implementation of the present invention, rather than all the embodiments.

[0138] The catalyst preparation operations in the examples were all carried out under the protection of high-purity nitrogen. Determination of polymer isotacticity: Determination by heptane extraction method (6 hours of boiling heptane extraction). Two grams of dry polymer sample are placed in an extractor and extracted with boiling heptane for 6 hours. The ratio of the polymer weight (g) obtained by drying the residue to constant weight to 2 is the isotacticity.

[0139] The bulk density of the polymer was determined using the JB / T 2412-2008 method.

[0140] The molecular weight distribution of the polymer was determined by a PL-220 gel permeation chromatograph using trichlorobenzene as solvent at 150°C (standard sample: polystyrene, flow rate 1.0 mL / min, column: 3xPlgel 10um M1Xed-B 300x7.5nm).

[0141] Sources of other Lewis base compounds: 9,9-bis(methoxymethyl)fluorene, commercially available, CAS No. 182121-12-6; 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, synthesized with reference to CN1041752A; di-n-butyl phthalate, commercially available, CAS No. 84-74-2; diethyl 2,3-diisopropylsuccinate, synthesized with reference to CN1313869A; diethyl 2,3-diisopropyl-2-cyanosuccinate, synthesized with reference to CN106608935A; 2,4-Pentanediol dibenzoate, synthesized with reference to CN1580038; 1,2-benzenediol-4-tert-butyl-1,2-diacetate, 1,2-benzenediol-4-tert-butyl-1,2-di-n-hexanoate, 1,2-benzenediol-1,2-dibenzoate, 1,2-benzenediol-4-tert-butyl-1,2-dibenzoate, 1,2-benzenediol-4-tert-butyl-1,2-di(m-chlorobenzoate), synthesized with reference to CN102325808A; ethyl benzoate, commercially available, CAS No. 93-89-0.

[0142] Synthesis of 2,6-dimethoxy-substituted-4-pyrone compounds represented by general formula (I)

[0143] Preparation Example 1: Synthesis of 2,6-dimethoxymethyl-4-pyrone

[0144] 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 was 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. Then a mixture of water (170 mL) and HCl (aq. 37%, 30 mL) was added to the mixture and stirred until silica gel TLC (eluent: 3 / 7 (v / v) 10% NaCl aqueous solution / ethanol) showed only one spot. After cooling to room temperature, the crystals were filtered out and washed with water and then with cold acetone. The crude product was recrystallized to obtain 4-pyrone-2,6-dicarboxylic acid as a white powder.

[0145] In a 1L three-necked flask, add 4-pyrone-2,6-dicarboxylic acid (6.6g), ethanol (120mL), and concentrated sulfuric acid (0.72mL); heat and reflux for 2 hours; cool to room temperature; pour the reaction solution into a saturated sodium bicarbonate solution, extract twice with ethyl acetate (120mL*2), combine the organic phases, wash with saturated brine (120mL*1), concentrate and recrystallize, dissolve in 120mL of anhydrous methanol, gradually add sodium borohydride (3.8g), cool to -20°C in an ice-salt bath, and stir for 1 hour. After that, remove the solvent, dissolve the orange residue with water (120ml), and then neutralize with 10% H2SO4 aqueous solution. Evaporate to dryness to obtain an orange solid product, dissolve it in ethanol / ethyl acetate (9:1, 170ml) and filter the reaction mixture. Recrystallize from ethanol / petroleum ether (2:1) to obtain a light brown powder 2,6-dimethanol-4-pyrone.

[0146] Add 2,6-dimethylol-4-pyrone (7.8g, 0.05mol), toluene (90ml), tetrabutylammonium hydrogen sulfate (0.283g, 0.8335mmol), 50% NaOH aqueous solution (45.5g, 0.57mol) to a 250mL three-necked flask, cool to 0℃ in an ice-salt bath, add dimethyl sulfate / toluene (8.5g / 20ml) dropwise, add for 0.5h, warm to 10℃, and stir for 5h. Warm to room temperature and stir overnight. Add water (80ml), stir for 20min, extract and separate. Wash the organic phase with water twice (50ml*2), filter the organic phase, evaporate the filtrate to dryness, pump dry with an oil pump to obtain a solid, and recrystallize from ethanol. See Table 1 for NMR data.

[0147] Preparation Example 2-13: Synthesis of other 2,6-dimethoxy-substituted-4-pyrone compounds

[0148] One of the aforementioned routes is adopted, the starting material is selected from oxalic acid or diethyl oxalate, and after addition reaction with acetone or other ketones, reduction is carried out, and then etherification reaction is carried out with one or two alcohols to obtain the corresponding substituted 2,6-dimethoxy-substituted-4-pyrone product. When reacting with two alcohols, a mixture of three products is obtained, which is directly used as an internal electron donor composition without separation. The structures and NMR results of other 2,6-dimethoxy-substituted-4-pyrone compounds are shown in Table 1.

[0149]

[0150] Table 1 2,6-dimethoxy-substituted-4-pyrone compounds prepared in Preparation Examples 1-13

[0151]

[0152]

[0153]

[0154] Catalyst preparation

[0155] Example 1

[0156] In a 500mL 5-necked flask with nitrogen fully replaced and stirred, 10gMgCl2·2.5C2H5OH microspheres and 150mL titanium tetrachloride were added to prepare a suspension, then maintained at -15°C for 1 hour, slowly heated to 80°C, 7mmol 2,6-dimethoxymethyl-4-pyrone and 3mmol 9,9-bis(methoxymethyl)fluorene were added, and then the temperature was continued to rise to 110°C and kept constant for 1 hour, and then the liquid was filtered clean, the liquid was filtered off, and the obtained solid was washed 3 times with 120mL titanium tetrachloride at 125°C. The obtained solid was washed 4 times with 150mL hexane at 60°C, the liquid was filtered off and dried to obtain the solid catalyst component Cat-1.

[0157] Example 2-13

[0158] The solid catalyst component preparation process is as shown in Example 1, except that 2,6-dimethoxymethyl-4-pyrone is replaced with 7 mmol of compounds a2-a13 in Table 1 in sequence.

[0159] Examples 14-25

[0160] The solid catalyst component preparation process is as shown in Example 1, except that 7 mmol of type a internal electron donor and 3 mmol of type b internal electron donor are added respectively according to the internal electron donor numbers shown in Table 2.

[0161] Embodiment 26

[0162] The solid catalyst component preparation process is as shown in Example 1, except that 5 mmol 2,6-dimethoxymethyl-4-pyrone and 5 mmol 9,9-bis(methoxymethyl)fluorene are added.

[0163] Embodiment 27

[0164] The solid catalyst component preparation process is as shown in Example 1, except that 3 mmol 2,6-dimethoxymethyl-4-pyrone and 7 mmol 9,9-bis(methoxymethyl)fluorene are added.

[0165] Embodiment 28

[0166] The solid catalyst component preparation process is as shown in Example 1, except that 2 mmol 2,6-dimethoxymethyl-4-pyrone and 8 mmol 9,9-bis(methoxymethyl)fluorene are added.

[0167] Examples 29-40

[0168] The solid catalyst component preparation process is as shown in Example 1, except that 5 mmol / 3 mmol / 2 mmol of three internal electron donor compounds are added respectively according to the internal electron donor numbers shown in Table 2.

[0169] Examples 41-44

[0170] The solid catalyst component preparation process is as shown in Example 1, except that the internal electron donor compounds a1, b1, and b6 are added respectively according to the molar ratio shown in Table 2 (total feed amount is 10 mmol).

[0171] Comparative Example 1

[0172] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compound are replaced by 10 mmol of 2,6-dimethoxymethyl-4-pyrone (a1).

[0173] Comparative Example 2

[0174] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compound are replaced by 10 mmol of 2,6-dimethoxybenzyl-4-pyrone (a5).

[0175] Comparative Example 3

[0176] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compounds are replaced by 10 mmol of 9,9-bis(methoxymethyl)fluorene (b1).

[0177] Comparative Example 4

[0178] The catalyst component preparation process is the same as Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compound are replaced by 10 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (b2).

[0179] Comparative Example 5

[0180] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compound are replaced by 10 mmol of di-n-butyl phthalate (b3).

[0181] Comparative Example 6

[0182] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compound are replaced by 7 mmol of b1 and 3 mmol of b3.

[0183] Comparative Example 7

[0184] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compound are replaced by 7 mmol of b1 and 3 mmol of b7.

[0185] Comparative Example 8

[0186] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compound are replaced by 4 mmol of b1, 3 mmol of b2 and 3 mmol of b3.

[0187] Comparative Example 9

[0188] The catalyst component preparation process is the same as Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compound are replaced by 4 mmol of b1, 3 mmol of b2 and 3 mmol of b7.

[0189] Comparative Example 10

[0190] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compounds are replaced by 4 mmol of b1, 3 mmol of b2 and 3 mmol of b3 electron donors.

[0191] Comparative Example 11

[0192] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compounds are replaced by 4 mmol of b1, 3 mmol of b3 and 3 mmol of b12 electron donors.

[0193] polymerization:

[0194] After nitrogen is fully replaced in a 5L stainless steel reactor, 5mL of 0.5mol / L triethylaluminum hexane solution and 1mL of 0.1mol / L cyclohexylmethyldimethoxysilane hexane solution and 10mg of the prepared solid catalyst component are added, and then 10mL of hexane is added to flush the feed line, and then 2L (under standard conditions) of hydrogen and 2.5L of refined propylene are added, and the reaction is controlled to prepolymerize at 25°C for 5 minutes, and the temperature is raised to 70°C, and the polymerization reaction is carried out at this temperature for 1 hour. After the reaction is completed, the reactor is cooled and the stirring is stopped to discharge the reaction product, and the polymer is obtained by drying. The polymerization data is shown in Table 2.

[0195] Table 2 Different compounding results under the same polymerization conditions

[0196]

[0197]

[0198]

[0199]

[0200]

[0201] [Note] b1: 9,9-bis(methoxymethyl)fluorene;

[0202] b2: 2-isopropyl-2-isopentyl-1,3-dimethoxypropane;

[0203] b3: di-n-butyl phthalate;

[0204] b4: 2,4-pentanediol dibenzoate;

[0205] b5: 1,2-benzenediol-4-tert-butyl-1,2-diacetate;

[0206] b6: 1,2-benzenediol-4-tert-butyl-1,2-dibenzoate;

[0207] b7: ethyl benzoate.

[0208] As can be seen from Table 2, the activity of 2,6-dicarboxylic acid ester-4-pyrone compound as an internal electron donor compound can be significantly improved after being compounded with a variety of Lewis base compounds, which is higher than the catalyst of a single internal electron donor without compounding (Comparative Examples 1 to 5), and also higher than the catalyst of a compounded internal electron donor without containing 2,6-dicarboxylic acid ester-4-pyrone compound (Comparative Examples 6 to 9). It can be seen that 2,6-dicarboxylic acid ester-4-pyrone compound can produce a synergistic effect with a variety of Lewis base compounds to obtain an activity higher than that of a single internal electron donor (or a catalyst without 2,6-dicarboxylic acid ester-4-pyrone compound internal electron donor). The polypropylene obtained by the catalyst has high isotacticity, regular particle shape and high bulk density.

[0209] Examples 45-53

[0210] After nitrogen is fully replaced in a 5L stainless steel reactor, 5mL of 0.5mol / L triethylaluminum hexane solution and 1mL of 0.1mol / L hexane solution of the external electron donor shown in Table 3 and 10mg of catalyst Cat-1 are added, and then 10mL of hexane is added to flush the feed line, and hydrogen and 2.5L of refined propylene are introduced according to the partial pressure in Table 3, respectively, and the reaction is controlled to prepolymerize at 25°C for 5 minutes, and the temperature is raised to 70°C, and the polymerization reaction is carried out at this temperature for 1 hour. After the reaction is completed, the reactor is cooled and the stirring is stopped to discharge the reaction product, and the polymer is obtained by drying. The polymerization data is shown in Table 3.

[0211] Examples 54-62

[0212] After nitrogen is fully replaced in a 5L stainless steel reactor, 5mL of 0.5mol / L triethylaluminum hexane solution and 1mL of 0.1mol / L hexane solution of the external electron donor shown in Table 3 and 10mg of catalyst Cat-33 are added, and then 10mL of hexane is added to flush the feed line, and hydrogen and 2.5L of refined propylene are introduced according to the partial pressure in Table 3, respectively, and the reaction is controlled to prepolymerize at 25°C for 5 minutes, and the temperature is raised to 70°C, and the polymerization reaction is carried out at this temperature for 1 hour. After the reaction is completed, the reactor is cooled and the stirring is stopped to discharge the reaction product, and the polymer is obtained by drying. The polymerization data is shown in Table 3.

[0213] Table 3 Different external electron donors

[0214]

[0215] [Note] CMMS: methylcyclohexyldimethoxysilane;

[0216] DPDMS: dicyclopentyldimethoxysilane;

[0217] PETS: phenyltrimethoxysilane;

[0218] NPTMS: n-propyltrimethoxysilane.

[0219] Examples 63-70

[0220] After nitrogen is fully replaced in a 5L stainless steel reactor, a 0.5mol / L triethylaluminum hexane solution (the amount of triethylaluminum is shown in Al / Ti in Table 4) and the corresponding catalyst in Table 4 are added, and then 10mL of hexane is added to flush the feed line, and then 2L (under standard conditions) of hydrogen and 2.5L of refined propylene are added, and the reaction is controlled to prepolymerize at 20°C for 5 minutes, and the temperature is raised to 70°C, and the polymerization reaction is carried out at this temperature for the corresponding time (see Table 4). After the reaction is completed, the reactor is cooled and stirring is stopped to discharge the reaction product, and the polymer is obtained by drying. The results are shown in Table 4.

[0221] Comparative Examples 10-13

[0222] The polymerization steps are the same as those in Example 64, except that the catalysts are the catalysts listed in Table 4.

[0223] Table 4 (without using external electron donor)

[0224]

[0225] As can be seen from Table 3, the catalysts CAT-1 and CAT-33 prepared by compounding two or more internal electron donor compounds, when polymerized with different external electron donors, all showed high activity, high isotacticity, high bulk density, and good polymerization compatibility. With the increase of hydrogen, the melt index increased significantly, indicating that the catalyst has good hydrogen adjustment sensitivity and is suitable for the preparation of polypropylene with a high melt flow rate.

[0226] As can be seen from Table 4, even without adding an external electron donor, highly isotactic polypropylene can still be obtained, and the activity is further improved, showing ultra-high activity, which is much higher than the catalysts that are not compounded or do not contain 2,6-dimethoxy-substituted-4-pyrone compounds as internal electron donors (Comparative Examples 10-13). The polymerization time is extended from 60 minutes to 120 minutes, and the catalyst can maintain ultra-high activity without attenuation. When using low Al / Ti, the ash content of the obtained polypropylene is lower, which can be reduced to 21ppm.

[0227] The present invention is not limited to the aforementioned specific embodiments, and any changes or modifications made by any technician in the field of the present invention are all covered by the patent scope of the present invention.

Claims

1. An olefin polymerization catalyst component, characterized in that Containing Mg, Ti, 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 the 2,6-dimethoxy-substituted-4-pyrone compound in the general formula (I), and the internal electron donor b compound is selected from the Lewis base compound; Among them, R in the general formula (I) 1 , R 2 , R 3 and R 4 are the same or different, each independently selected from H, halogen, C1-C 20 The hydrocarbon group; R 1 and R 2 The group attached to the O atom in the 2,6-dimethoxy group is not a carbonyl group.

2. The olefin polymerization catalyst component according to claim 1, characterized in that R 1 , R 2 , R 3 and R 4 They also each contain at least one heteroatom selected from N, O, S, P, Si and halogen.

3. The olefin polymerization catalyst component according to claim 1, characterized in that R 1 , R 2 , R 3 and R 4 Two or more of them are bonded to each other to form a ring.

4. The olefin polymerization catalyst component according to claim 1, characterized in that R in the general formula (I) 1 , R 2 , R 3 and R 4 the same or different, each independently selected from H, halogen, the following substituents with less than 20 carbon atoms: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or substituted with N, O, S, P, Si heteroatom alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or each independently selected from heterocyclic aromatic substituents.

5. The olefin polymerization catalyst component according to claim 1, characterized in that R in the general formula (I) 1 , R 2 , R 3 and R 4 are the same or different and are each 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 a straight-chain or branched alkyl group, or the following substituents having less than 20 carbon atoms: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, substituted benzyl, substituted phenethyl, furanyl, pyrrolyl, thienyl, propenyl, butenyl, pentenyl, hexenyl, and indenyl.

6. The olefin polymerization catalyst component according to claim 1, characterized in that The 2,6-dimethoxy-substituted-4-pyrone compound of general formula (I) is selected from 2,6-dimethoxymethyl-4-pyrone, 2,6-dimethoxyethyl-4-pyrone, 2,6-dimethoxypropyl-4-pyrone, 2,6-dimethoxybutyl-4-pyrone, 2,6-dimethoxypentyl-4-pyrone, 2,6-dimethoxyhexyl-4-pyrone, 2,6-dimethoxy Heptyl-4-pyrone, 2,6-dimethoxyoctyl-4-pyrone, 2,6-dimethoxydodecyl-4-pyrone, 2,6-dimethoxytetradecyl-4-pyrone, 2,6-dimethoxyhexadecyl-4-pyrone, 2,6-dimethoxyphenyl-4-pyrone, 2,6-dimethoxybenzyl-4-pyrone, 2,6-dimethoxy-m-chlorophenyl-4-pyrone, 2, At least one of 6-dimethoxy-o-chlorophenyl-4-pyrone, 2,6-dimethoxy-p-chlorophenyl-4-pyrone, 2,6-dimethoxy-p-methylphenyl-4-pyrone, 2,6-dimethoxy-p-methoxymethyl-4-pyrone, 2,6-dimethoxyfuranyl-4-pyrone, 2,6-dimethoxypropylene-4-pyrone, 2,6-dimethoxymethyl-3,5-dimethyl-4-pyrone, 2,6-dimethoxymethyl-3-methyl-5-ethyl-4-pyrone, 2,6-dimethoxymethyl-3,5-diethyl-4-pyrone, 2,6-dimethoxymethyl-3,5-dibutyl-4-pyrone, 2,6-dimethoxymethyl-3-ethyl-5-butyl-4-pyrone, and 2,6-dimethoxymethyl-3-methyl-5-butyl-4-pyrone.

7. The olefin polymerization catalyst component according to claim 1, characterized in that The feeding molar ratio of the internal electron donor compound a to the internal electron donor compound b is greater than or equal to 2:

8.

8. The olefin polymerization catalyst component according to claim 1, characterized in that The Lewis base compound contains one or more electronegative groups, wherein the electron-donating atom is selected from N, O, S, P, As or Sn.

9. The olefin polymerization catalyst component according to claim 1, characterized in that The Lewis base compound is an electron donor compound selected from diethers, esters, diketones, diamines, monocarboxylates and polycarboxylates.

10. The olefin polymerization catalyst component according to claim 9, characterized in that The Lewis base compound is selected from 1,3-diether compounds represented by general formula (II): In the general formula (II), R 7 -R 12 are the same or different and are each independently selected from H, or are each independently selected from a linear or branched alkyl, cycloalkyl, aryl, alkaryl or aralkyl group containing 1 to 18 carbon atoms; R 13 and R 14 The same or different, each independently selected from a straight chain or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms, an alkaryl group having 7 to 20 carbon atoms and an aralkyl group.

11. The olefin polymerization catalyst component according to claim 10, characterized in that R 7 -R 14 One or more groups in the ring are linked to form a ring structure.

12. The olefin polymerization catalyst component according to claim 10, characterized in that R 7 -R 14 Each of them further comprises at least one heteroatom selected from halogen, N, O, S, P and Si.

13. The olefin polymerization catalyst component according to claim 10, characterized in that The diether electron donor compound is selected from the diether compound represented by general formula (III): In the general formula (III), R 21 -R 28 R is the same as R, each independently selected from hydrogen, halogen, linear or branched alkyl of 1 to 20 carbon atoms, cycloalkyl of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms and arylalkyl of 7 to 20 carbon atoms, optionally containing at least one heteroatom selected from N, O, S, P, Si and halogen as a substituent for carbon atoms or hydrogen atoms or both; 15 -R 18 are the same or different and are each independently selected from H, or are each independently selected from a linear or branched alkyl, cycloalkyl, aryl, alkaryl or aralkyl group containing 1 to 18 carbon atoms; R 19 and R 20 The same or different, each independently selected from a straight chain or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms, an alkaryl group having 7 to 20 carbon atoms and an aralkyl group.

14. The olefin polymerization catalyst component according to claim 13, characterized in that R 15 -R 28 One or more groups in the ring are linked to form a ring structure.

15. The olefin polymerization catalyst component according to claim 13, characterized in that R 15 -R 28 Each of them further comprises at least one heteroatom selected from halogen, N, O, S, P and Si.

16. The olefin polymerization catalyst component according to claim 9, characterized in that The polycarboxylic acid ester compound is an aromatic dicarboxylic acid compound or an aliphatic chain dicarboxylic acid ester compound.

17. The olefin polymerization catalyst component according to claim 9, characterized in that The ester compound is a diol ester compound of general formula (IV): In the general formula (IV), R 29 -R 36 The same or different, each independently selected from hydrogen, halogen or substituted or unsubstituted straight or branched C1-C 20 Alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl, C7-C 20 Aralkyl, C2-C 10 Olefin or C 10 -C 20 Fused ring aromatic group; but R 31 and R 32 Not hydrogen, R 29 -R 36 One or more of are optionally cyclic or non-cyclic.

18. The olefin polymerization catalyst component according to claim 9, characterized in that The ester compound is an ortho-phenylene diester of general formula (V): In the general formula (V), R 37 and R 38 The same or different, each independently selected from substituted or unsubstituted straight or branched C1-C 20 Alkyl, C3-C 20 Cycloalkyl, C6-C 20 Substituted or unsubstituted aryl, C7-C 20 Substituted or unsubstituted aralkyl, C2-C 10 The olefin group, C 10 -C 20 A fused-ring aromatic group or an ester group, and R 37 and R 38 Not hydrogen; R 39 -R 42 are the same or different, each independently selected from hydrogen, substituted or unsubstituted C1-C 20 The hydrocarbon group, including C1-C 20 Alkoxy groups, heteroatoms, and combinations thereof.

19. The olefin polymerization catalyst component according to claim 9, characterized in that The ester compound is a compound represented by the general formula (VI): In the general formula (VI), R 43 -R 56 The same or different, each independently selected from hydrogen, a substituted hydrocarbyl group containing 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms, a heteroatom and combinations thereof.

20. The olefin polymerization catalyst component according to claim 19, characterized in that In the general formula (VI), R 43 -R 46 At least one of the following is selected from a substituted hydrocarbon group containing 1 to 20 carbon atoms, an unsubstituted hydrocarbon group containing 1 to 20 carbon atoms, and a combination thereof; R 47 -R 56 At least one of the following is selected from a substituted hydrocarbyl group containing 1 to 20 carbon atoms, an unsubstituted hydrocarbyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms, a heteroatom and a combination thereof.

21. The olefin polymerization catalyst component according to claim 1, characterized in that The catalyst component comprises a titanium compound, a magnesium compound, the 2,6-dimethoxy-substituted-4-pyrone compound and a Lewis base 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 , MgCl2 / SiO2, MgCl2 / Al2O3, a mixture of magnesium halide and titanium alkoxide, wherein m is 0.1-6, 0≤n≤2, X is a halogen, R a C1-C 20 The hydrocarbon group; The general formula of the titanium compound is TiX N (OR b ) 4-N , where R b C1-C 20 The hydrocarbon group is: X is halogen, and N is 1-4.

22. The olefin polymerization catalyst component according to claim 21, characterized in that The magnesium compound is an alcoholate of magnesium dihalide; Alternatively, the magnesium compound is a liquid magnesium compound; Alternatively, the magnesium compound is a derivative in which at least one halogen atom in a magnesium dihalide molecule is replaced by a hydrocarbonoxy group or a halogenated hydrocarbonoxy group.

23. The olefin polymerization catalyst component according to claim 21, characterized in that The titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and alkoxy titanium halide; The alkyl titanium halide includes at least one of methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, and tri-n-butoxytitanium chloride.

24. The olefin polymerization catalyst component according to claim 21, 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.

25. A catalyst for olefin polymerization, wherein the raw material composition comprises the catalyst component according to any one of claims 1 to 24 and an organic aluminum compound.

26. The catalyst according to claim 25, characterized in that The general formula of the organoaluminum compound is AlR c p X (3-p) , where R c is hydrogen or C1-C 20 wherein X is a halogen and p is an integer of 0≤p≤3.

27. The catalyst according to claim 26, characterized in that The organoaluminum compound includes at least one of trialkylaluminum compounds, alkylaluminum halides, alkylaluminum hydrides, alkylaluminum sesquichlorides, and alkylaluminoxanes.

28. The catalyst according to claim 25, characterized in that The molar ratio of the organic aluminum compound to the titanium atom in the catalyst component is 1-1000:

1.

29. The catalyst according to claim 25, characterized in that The raw material composition of the catalyst also includes an external electron donor; The external electron donor is a siloxane compound; The general formula of the siloxane compound is R' t Si(OR”) 4-t , wherein R' and R" are each independently selected from C1-C 18 A hydrocarbon group, t is an integer of 0≤t≤3.

30. The catalyst according to claim 29, characterized in that R' and R" each contain a heteroatom.

31. The catalyst according to claim 30, characterized in that The heteroatom includes at least one of N, O, S, P, and Si.

32. The catalyst according to claim 29, characterized in that The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100.

33. Use of the catalyst according to any one of claims 25 to 32 in olefin polymerization.

34. The use according to claim 33, 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.

35. The use according to claim 33, characterized in that The polymerization temperature is ≤ 200°C, The polymerization pressure is ≤10 MPa.

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