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

Abstract

The present invention discloses an olefin polymerization catalyst component, an olefin polymerization catalyst and applications thereof, 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, 3, 4, 5, 6-tetramethyl-1, 3-pentanediol in a general formula (I). The compound A is 2, 6-dimethoxycarbonyl substituent-4-pyrone, and the internal electron donor b is selected from a Lewis alkali compound. According to the catalyst component disclosed by the invention, after the 2, 6-dimethoxycarbonyl substituent-4-pyrone is adopted as an internal electron donor and compounded with the Lewis alkali compound, the activity can be remarkably improved, polypropylene obtained by the catalyst is high in isotacticity, and high-isotacticity polyolefin can still be obtained even if an external electron donor is not added.

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] High-rigidity polypropylene has the characteristics of high strength, high modulus, high surface hardness, good scratch resistance and creep resistance, high heat deformation resistance, chemical corrosion resistance, good melt fluidity, and short molding cycle. It has been widely used in domestic and foreign markets. Improving the rigidity of polypropylene can be divided into two methods: external reactor rigidification and internal reactor rigidification. The external reactor rigidification method refers to adding fillers, nucleating agents or rigidification agents to polypropylene by blending. The internal reactor rigidification method refers to preparing high-rigidity polypropylene by improving the polymerization process, or selecting a suitable catalyst system, or modifying the catalyst, or adding a nucleating agent to the reactor, or combining the above methods. The internal reactor rigidification polypropylene has the characteristics of low raw material loss, low energy consumption, low cost, and uniform product quality. Therefore, the internal reactor rigidification polypropylene has a good development prospect. The internal reactor rigidification method generally requires the use of catalysts with high activity, high stereoselectivity, and the ability to effectively control the relative molecular mass and distribution of polypropylene.

[0005] The preparation of polyolefin catalysts with high activity, high isotacticity and wide molecular weight distribution 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 a catalyst component for olefin polymerization, wherein the olefin polymerization catalyst has high activity, and the polyolefin obtained by catalysis has the characteristics of high isotacticity, wide molecular weight distribution, etc.

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

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

[0009] Another object of the present invention is to provide the 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 purpose of the present invention, the present invention provides a catalyst component for olefin polymerization, 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-dimethoxycarbonyl substituted-4-pyrone 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 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 4are 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.

[0016] Preferably, the 2,6-dimethoxycarbonyl substituent-4-pyrone of general formula (I) is selected from 2,6-dimethoxycarbonylethyl-4-pyrone, 2,6-dimethoxycarbonylpropyl-4-pyrone, 2,6-dimethoxycarbonylbutyl-4-pyrone, 2,6-dimethoxycarbonylpentyl-4-pyrone, 2,6-dimethoxycarbonylcyclohexyl-4-pyrone, 2,6-dimethoxycarbonylbutyl-4-pyrone, 2,6-dimethoxycarbonyl hexadecyl-4-pyrone, 2,6-dimethoxycarbonyl phenyl-4-pyrone, 2,6-dimethoxycarbonyl m-chlorophenyl-4-pyrone, 2,6-dimethoxycarbonyl o-chlorophenyl-4-pyrone ketone, 2,6-dimethoxycarbonyl-4-chlorophenyl-4-pyrone, 2,6-dimethoxycarbonyl-4-methoxyphenyl-4-pyrone, 2,6-dimethoxycarbonyl-4-nitrophenyl-4-pyrone, 2,6-dimethoxycarbonylphenyl-3,5-dimethyl-4-pyrone, 2,6-dimethoxycarbonylphenyl-3,5-diethyl-4-pyrone, 2,6-dimethoxycarbonylphenyl-3,5-dipropyl-4-pyrone, 2,6-dimethoxycarbonylphenyl-3,5-dibutyl-4-pyrone, 2,6-dimethoxycarbonylphenyl-3-methyl-5-ethyl-4-pyrone, 2,6-dimethoxycarbonylphenyl-3-ethyl-5-butyl-4-pyrone, 2,6-dimethoxycarbonylphenyl-3-methyl-5-butyl-4-pyrone.

[0017] Preferably, the 2,6-dimethoxycarbonyl-substituted-4-pyrone 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 4One of the synthetic routes of the same or different 2,6-dimethoxycarbonyl-substituted-4-pyrone 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 acyl chloride to obtain a pure (substituted) 2,6-dimethoxycarbonyl-substituted-4-pyrone compound, or reacted with a mixture of two acyl chlorides to obtain a mixture of three (substituted) 2,6-dimethoxycarbonyl-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 5:5.

[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 6:4.

[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 an electron donor compound selected from diethers, esters, diketones, diamines, monocarboxylates or polycarboxylates. When the 2,6-dimethoxycarbonyl-substituted-4-pyrone 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 5 -R 10 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 11 and R 2 are the same or different, and are 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; preferably, R 5 -R 12 One or more groups in are linked to form a ring structure, and preferably, each further contains 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 19 -R 26 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; 13 -R 16 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 17 and R 18 are the same or different, and are 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; preferably, R 13 -R 18 One or more groups in are linked to form a ring structure, and preferably, each further contains 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 polycarboxylic acid ester compound of the Lewis base compound is selected from succinate ester compounds represented by general formula (IV):

[0041]

[0042] In the general formula (IV), R 27 and R 28 The same or different, each independently selected from C1-C 20 a linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl group, optionally containing heteroatoms; R 29 -R32 At least two of the groups are different from hydrogen and are selected from C1-C 20 A linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl group, optionally containing heteroatoms; preferably, R 29 -R 32 connected together to form a ring; preferably, R 27 and R 28 are the same or different and are independently selected from C1-C8 alkyl, cycloalkyl, aryl, aralkyl and alkaryl groups; preferably, R 27 and R 28 is selected from primary alkyl groups, in particular branched primary alkyl groups; preferably, R 27 and R 28 Selected from methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl.

[0043] Preferably, the general formula (IV) is such a compound: R 29 -R 31 is hydrogen and R 32 is a branched alkyl, cycloalkyl, aryl, aralkyl and alkaryl group having 3 to 10 carbon atoms; preferably, R 32It is a branched primary alkyl group or a cycloalkyl group having 3 to 10 carbon atoms. Specifically, the succinate compound is a monosubstituted succinate compound, which may include but is not limited to: diethyl sec-butyl succinate, diethyl hexyl succinate, diethyl cyclopropyl succinate, diethyl norbornyl succinate, diethyl perhydrosuccinate, diethyl trimethyl succinate, diethyl methoxy succinate, diethyl p-methoxyphenyl succinate, diethyl p-chlorophenyl succinate, diethyl phenyl succinate, cyclohexyl succinate diethyl succinate, diethyl benzyl succinate, diethyl cyclohexyl methyl succinate, diethyl tert-butyl succinate, diethyl isobutyl succinate, diethyl isopropyl succinate, diethyl neopentyl succinate, diethyl isopentyl succinate, diethyl (1-trifluoromethylethyl) succinate, diethyl fluorenyl succinate, 1-ethoxycarbonyl diisobutyl phenyl succinate phenylsuccinate), diisobutyl sec-butylsuccinate, diisobutyl hexylsuccinate, diisobutyl cyclopropylsuccinate, diisobutyl norbornylsuccinate, diisobutyl perhydrosuccinate, diisobutyl trimethylsilylsuccinate, diisobutyl methoxysuccinate, diisobutyl p-methoxyphenylsuccinate, diisobutyl p-chlorophenoxysuccinate, diisobutyl cyclohexylsuccinate, diisobutyl benzylsuccinate, diisobutyl cyclohexylmethylsuccinate, diisobutyl tert-butylsuccinate, diisobutyl isobutylsuccinate, diisobutyl isopropylsuccinate, diisobutyl neopentylsuccinate, diisobutyl isopentylsuccinate, diisobutyl (1-trifluoromethylethyl)succinate, diisobutyl fluorenylsuccinate , dineopentyl sec-butylsuccinate, dineopentyl hexylsuccinate, dineopentyl cyclopropylsuccinate, dineopentyl norbornylsuccinate, dineopentyl perhydrosuccinate, dineopentyl trimethylsilylsuccinate, dineopentyl methoxysuccinate, dineopentyl p-methoxyphenylsuccinate, dineopentyl p-chlorophenylsuccinate, dineopentyl phenylsuccinate, dineopentyl cyclohexylsuccinate, dineopentyl benzylsuccinate, dineopentyl cyclohexylmethylsuccinate, dineopentyl tert-butylsuccinate, dineopentyl isobutylsuccinate, dineopentyl isopropylsuccinate, dineopentyl neopentylsuccinate, dineopentyl isopentylsuccinate, dineopentyl (1-trifluoromethylethyl)succinate, and dineopentyl fluorenylsuccinate.

[0044] As another preferred embodiment, the compound represented by the general formula (IV) may be a compound: wherein R 29 -R 32 At least two of the groups are different from hydrogen and are selected from C1-C 20A linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl group, optionally containing heteroatoms; preferably, two non-hydrogen groups are connected to the same carbon atom; specifically, the succinate compound is a disubstituted succinate compound, which may include but is not limited to: 2,2-dimethylsuccinic acid diethyl ester, 2-ethyl-2-methylsuccinic acid diethyl ester, 2-benzyl-2-isopropylsuccinic acid diethyl ester, 2-cyclohexylmethyl-2-isobutylsuccinic acid diethyl ester, 2-cyclopentyl-2-n-butylsuccinic acid diethyl ester, 2,2-diisobutyl ... diethyl 2-isopropyl-2-methylsuccinate, diethyl 2-tetradecyl-2-ethylsuccinate, diethyl 2-isobutyl-2-ethylsuccinate, diethyl 2-(1-trifluoromethylethyl)-2-methylsuccinate, diethyl 2-isopentyl-2-isobutylsuccinate, diethyl 2-phenyl-2-n-butylsuccinate, diisobutyl 2,2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diisobutyl 2-benzyl-2-isopropylsuccinate, diisobutyl 2-cyclohexylmethyl-2-isobutylsuccinate, diisobutyl 2-cyclopentyl-2-n-butylsuccinate Diisobutyl butyl succinate, diisobutyl 2,2-diisobutyl succinate, diisobutyl 2-cyclohexyl-2-ethyl succinate, diisobutyl 2-isopropyl-2-methyl succinate, diisobutyl 2-tetradecyl-2-ethyl succinate, diisobutyl 2-isobutyl-2-ethyl succinate, diisobutyl 2-(1-trifluoromethylethyl)-2-methyl succinate, diisobutyl 2-isopentyl-2-isobutyl succinate, diisobutyl 2-phenyl-2-n-butyl succinate, dineopentyl 2,2-dimethyl succinate, dineopentyl 2-ethyl-2-methyl succinate, 2-benzyl-2-isopropyl succinate At least one of dineopentyl succinate, dineopentyl 2-cyclohexylmethyl-2-isobutylsuccinate, dineopentyl 2-cyclopentyl-2-n-butylsuccinate, dineopentyl 2,2-diisobutylsuccinate, dineopentyl 2-cyclohexyl-2-ethylsuccinate, dineopentyl 2-isopropyl-2-methylsuccinate, dineopentyl 2-tetradecyl-2-ethylsuccinate, dineopentyl 2-isobutyl-2-ethylsuccinate, dineopentyl 2-(1-trifluoromethylethyl)-2-methylsuccinate, dineopentyl 2-isopentyl-2-isobutylsuccinate, and dineopentyl 2-phenyl-2-n-butylsuccinate.

[0045] In addition, according to another embodiment of the present invention, in the compound represented by general formula (IV), at least two non-hydrogen groups are connected to different carbon atoms; preferably, at least two non-hydrogen groups are connected to R 29 and R 31 , or R 30 and R 32Specifically, the succinate compounds may include, but are not limited to: 2,3-bis(trimethylsilyl)succinic acid diethyl ester, 2-sec-butyl-3-methylsuccinic acid diethyl ester, 2-(3,3,3-trifluoropropyl)-3-methylsuccinic acid diethyl ester, 2,3-bis(2-ethylbutyl)succinic acid diethyl ester, 2,3-diethyl-2-isopropylsuccinic acid diethyl ester, 2,3-diisopropyl-2-methylsuccinic acid diethyl ester, 2,3-dicyclohexyl-2-methylsuccinic acid diethyl ester, 2,3-dibenzylsuccinic acid diethyl ester, 2,3-diisopropylsuccinic acid diethyl ester, 2,3-bis(cyclohexylmethyl)succinic acid diethyl ester, 2,3-di-tert-butylsuccinic acid diethyl ester, 2,3-diisobutylsuccinic acid diethyl ester, 2, 3-dineopentylsuccinic acid diethyl ester, 2,3-diisopentylsuccinic acid diethyl ester, 2,3-bis(1-trifluoromethylethyl)succinic acid diethyl ester, 2,3-di(tetradecyl)succinic acid diethyl ester, 2,3-difluorenylsuccinic acid diethyl ester, 2-isopropyl-3-isobutylsuccinic acid diethyl ester, 2-tert-butyl-3-isopropylsuccinic acid diethyl ester, 2-isopropyl-3-cyclohexylsuccinic acid diethyl ester, 2-isopentyl-3-cyclohexylsuccinic acid diethyl ester, 2-tetradecyl-3-cyclohexylsuccinic acid diethyl ester, 2-cyclohexyl-3-cyclopentylsuccinic acid diethyl ester, 2,2,3,3-tetramethylsuccinic acid diethyl ester, 2,2,3,3-tetraethylsuccinic acid diethyl ester, 2,2,3,3-tetrapropylsuccinic acid diethyl ester, 2,3-di ethyl-2,3-diisopropylsuccinate, diethyl 2,2,3,3-tetrafluorosuccinate, diisobutyl 2,3-bis(trimethylsilyl)succinate, diisobutyl 2-sec-butyl-3-methylsuccinate, diisobutyl 2-(3,3,3-trifluoropropyl)-3-methylsuccinate, diisobutyl 2,3-bis(2-ethylbutyl)succinate, diisobutyl 2,3-diethyl-2-isopropylsuccinate, diisobutyl 2,3-diisopropyl-2-methylsuccinate, diisobutyl 2,3-dicyclohexyl-2-methylsuccinate, diisobutyl 2,3-dibenzylsuccinate, diisobutyl 2,3-diisopropylsuccinate, diisobutyl 2,3-bis(cyclohexylmethyl)succinate, diisobutyl 2,3-di-tert-butylsuccinate 2,3-diisobutyl succinate, diisobutyl 2,3-dineopentyl succinate, diisobutyl 2,3-diisopentyl succinate, diisobutyl 2,3-bis(1-trifluoromethylethyl) succinate, diisobutyl 2,3-ditetradecyl succinate, diisobutyl 2,3-difluorenyl succinate, diisobutyl 2-isopropyl-3-isobutyl succinate, diisobutyl 2-tert-butyl-3-isopropyl succinate, diisobutyl 2-isopropyl-3-cyclohexyl succinate, diisobutyl 2-isopentyl-3-cyclohexyl succinate, diisobutyl 2-tetradecyl-3-cyclohexyl methyl succinate, diisobutyl 2-cyclohexyl-3-cyclopentyl succinate, diisobutyl 2,2,3,3-tetramethyl succinate, diisobutyl 2,2,3,3-Tetraethylsuccinate diisobutyl ester, 2,2,3,3-tetrapropylsuccinate diisobutyl ester, 2,3-diethyl-2,3-dipropylsuccinate, 2,2,3,3-tetrafluorosuccinate diisobutyl ester, 2,3-bis(trimethylsilyl)succinate dineopentyl ester, 2-sec-butyl-3-methylsuccinate dineopentyl ester, 2-(3,3,3-trifluoropropyl)-3-methylsuccinate dineopentyl ester, 2,3-bis(2-ethylbutyl)succinate dineopentyl succinate, dineopentyl 2,3-diethyl-2-isopropylsuccinate, dineopentyl 2,3-diisopropyl-2-methylsuccinate, dineopentyl 2,3-dicyclohexyl-2-methylsuccinate, dineopentyl 2,3-dibenzylsuccinate, dineopentyl 2,3-diisopropylsuccinate, dineopentyl 2,3-di(cyclohexylmethyl)succinate, dineopentyl 2,3-di-tert-butylsuccinate, dineopentyl 2,3-diisobutylsuccinate, 2 , dineopentyl succinate, dineopentyl 2,3-diisopentyl succinate, dineopentyl 2,3-(1-trifluoromethylethyl) succinate, dineopentyl 2,3-di(tetradecyl) succinate, dineopentyl 2,3-difluorenyl succinate, dineopentyl 2-isopropyl-3-isobutyl succinate, dineopentyl 2-tert-butyl-3-isopropyl succinate, dineopentyl 2-isopropyl-3-cyclohexyl succinate, dineopentyl 2-isopentyl ... At least one of dineopentyl succinate, dineopentyl 2-tetradecyl-3-cyclohexylmethyl succinate, dineopentyl 2-cyclohexyl-3-cyclopentyl succinate, dineopentyl 2,2,3,3-tetramethyl succinate, dineopentyl 2,2,3,3-tetraethyl succinate, dineopentyl 2,2,3,3-tetrapropyl succinate, dineopentyl 2,3-diethyl-2,3-diisopropyl succinate, and dineopentyl 2,2,3,3-tetrafluorosuccinate.

[0046] Preferably, in the compound of general formula (IV), the groups R attached to the same carbon atom 29 -R 32 Two or four of them are connected together to form a ring. Such succinate compounds may include, but are not limited to, at least one of 1-(ethoxycarbonyl)-1-(ethoxyacetyl)-2,6-dimethylcyclohexane, 1-(ethoxycarbonyl)-1-(ethoxyacetyl)-2,5-dimethylcyclopentane, 1-(ethoxycarbonyl)-1-(ethoxyacetylmethyl)-2-methylcyclohexane, and 1-(ethoxycarbonyl)-1-(ethoxyacetylcyclohexyl)cyclohexane.

[0047] As discussed above, each compound can be used in the form of a pure isomer or in the form of a mixture of enantiomers, or in the form of a mixture of positional isomers and enantiomers. When pure isomers are to be used, they are generally isolated and purified using separation techniques known in the art. In particular, some of the succinate compounds of the present invention can be used as pure racemic or meso forms, or alternatively as a mixture of these two forms.

[0048] Preferably, the ester compound of the Lewis base compound is an ortho-phenylene diester of general formula (V):

[0049]

[0050] In the general formula (V), R 33 and R 34 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 33 and R 34 Not hydrogen; R 35 -R 38 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.

[0051] Preferably, the ester compound of the Lewis base compound is a compound represented by general formula (VI):

[0052]

[0053] In the general formula (VI), R 39 -R 52 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.

[0054] Preferably, in the general formula (VI), R 39 -R 42 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.

[0055] Preferably, in the general formula (VI), R 43 -R 52 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.

[0056] Preferably, the compound represented by general formula (VI) includes but is not limited to:

[0057] 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];

[0058] 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];

[0059] 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];

[0060] 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];

[0061] 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];

[0062] 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];

[0063] 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];

[0064] 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];

[0065] 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];

[0066] 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];

[0067] 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];

[0068] 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];

[0069] 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];

[0070] 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];

[0071] 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];

[0072] 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];

[0073] 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];

[0074] 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];

[0075] 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];

[0076] 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];

[0077] 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];

[0078] 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];

[0079] 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];

[0080] 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];

[0081] 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];

[0082] 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];

[0083] 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];

[0084] 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];

[0085] 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];

[0086] 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];

[0087] 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];

[0088] 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];

[0089] 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];

[0090] 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].

[0091] The above compound is further preferably:

[0092] 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];

[0093] 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];

[0094] 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];

[0095] 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];

[0096] 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];

[0097] 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];

[0098] 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];

[0099] 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];

[0100] 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].

[0101] Preferably, the catalyst component comprises a titanium compound, a magnesium compound, the 2,6-dimethoxycarbonyl-substituted-4-pyrone and a Lewis base compound;

[0102] The precursor of the magnesium compound is selected from X n Mg(OR a ) 2-n 、MgCl2·mRa 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;

[0103] 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.

[0104] Preferably, the magnesium compound is an alcoholate of magnesium dihalide;

[0105] Alternatively, the magnesium compound is a liquid magnesium compound;

[0106] Alternatively, the magnesium compound is a derivative of a magnesium dihalide molecule in which at least one halogen atom is replaced by a hydrocarbonoxy group or a halogenated hydrocarbonoxy group; preferably, a hydrocarbonoxy magnesium compound; more preferably, an alkoxy magnesium and / or an aryloxy magnesium

[0107] Preferably, the titanium compound includes titanium tetrachloride, titanium tetrabromide, titanium tetraiodide or alkyl titanium halide, wherein the alkyl titanium halide includes but is not limited to at least one of methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride and tri-n-butoxy titanium chloride; wherein these alkyl titanium halides can be used in combination of one or more. The titanium compound of the present invention preferably uses titanium tetrachloride.

[0108] According to a specific embodiment of the present invention, 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.

[0109] 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:

[0110] Method 1: A titanium compound (such as TiCl4 or titanium alkoxide) 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-dimethoxycarbonyl-substituted-4-pyrone compound and at least one Lewis base compound are selected from the general formula (I). For example, the preparation method of the titanium-containing solid catalyst component disclosed in US5077357A can be referred to: ethoxy magnesium, tetraethoxy titanium, 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.

[0111] 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-dimethoxycarbonyl-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-dimethoxycarbonyl-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.

[0112] Method 3: Anhydrous magnesium chloride and at least one 2,6-dimethoxycarbonyl-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-dimethoxycarbonyl-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.

[0113] 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-dimethoxycarbonyl-substituted-4-pyrone compound selected from the general formula (I) and at least one Lewis base compound. The treatment with TiCl4 is repeated multiple times and the solid is washed with hexane to remove any unreacted TiCl4.

[0114] Method 5: The preparation method of the titanium-containing solid catalyst component disclosed in CN1208045A can also be referred to for preparation: 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-dimethoxycarbonyl-substituted-4-pyrone compound selected from the general formula (I) and at least one Lewis base compound are used for treatment.

[0115] Method 6: Dissolve the 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, and then mix it with a titanium compound. In the presence of a precipitation aid, wash out the solid; the solid is treated with at least one 2,6-dimethoxycarbonyl 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, it is treated 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.

[0116] 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 the treatment process, at least one 2,6-dimethoxycarbonyl-substituted-4-pyrone compound selected from the general formula (I) and at least one Lewis base compound are added.

[0117] 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.

[0118] 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.

[0119] In any of the above-mentioned preparation methods, the internal electron donor compound (at least one selected from the 2,6-dimethoxycarbonyl-substituted-4-pyrone compound of 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.

[0120] The present invention also provides an olefin polymerization catalyst, which comprises the above catalyst component.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] According to a specific embodiment of the present invention, preferably, the raw material composition of the catalyst also includes an external electron donor.

[0127] According to a specific embodiment of the present invention, preferably, the external electron donor is a siloxane compound.

[0128] According to a specific embodiment of the present invention, preferably, the general formula of the siloxane compound is R' t Si(OR”) 4-t , wherein R' and R" are each independently selected from C1-C 18 A 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.

[0129] 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;

[0130] 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.

[0131] 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.

[0132] The invention also provides application of the catalyst in olefin polymerization.

[0133] 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.

[0134] According to a specific embodiment of the present invention, preferably, the polymerization comprises ethylene and / or propylene polymerization.

[0135] According to a specific embodiment of the present invention, preferably, the polymerization includes homopolymerization or copolymerization.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] The catalyst component of the present invention adopts 2,6-dimethoxycarbonyl substituted-4-pyrone as an internal electron donor and is compounded with a Lewis base compound to significantly improve its activity. The polypropylene obtained by the catalyst has high isotacticity, and even without adding an external electron donor, a high isotactic polyolefin can still be obtained. The polyolefin obtained by polymerization of the catalyst of the present invention has a wide molecular weight distribution, especially the catalyst prepared by compounding with succinate has a significantly widened molecular weight distribution, and is suitable for preparing high-rigidity polyolefin. DETAILED DESCRIPTION

[0140] 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.

[0141] 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.

[0142] The bulk density of the polymer was determined using the JB / T 2412-2008 method.

[0143] 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).

[0144] 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.

[0145] Synthesis of 2,6-dimethoxycarbonyl-substituted-4-pyrone compounds represented by general formula (I)

[0146] Preparation Example 1: 1. Synthesis of 2,6-dimethoxycarbonylpropyl-4-pyrone

[0147] 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.

[0148] 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.

[0149] In a 250mL five-necked flask, add 2,6-dimethylol-4-pyrone (15.5g, 0.1mol), lutidine (4.9g), triethylamine (36mL), THF (100mL), and stir to form a homogeneous solution. Cool to 10℃, control the temperature at 10-20℃, and drop a solution of propionyl chloride (20mL) in THF (50mL). After the addition is complete, stir for 10min, then heat to reflux and react overnight. Cool to room temperature, filter, concentrate the filtrate to near dryness, and add dichloromethane (200mL) solution to the residue. Add aqueous solution to the filter cake, combine the aqueous solution and dichloromethane phase, and separate the layers. The organic phase is washed with HCl solution (100mL, 1moL / L), saturated sodium bicarbonate solution (100mL), and saturated brine (100mL), respectively. Dry the organic phase with anhydrous Na2SO4 and filter. Concentrate to dryness to obtain the crude product by recrystallization.

[0150] Preparation Example 2-13: Synthesis of other 2,6-dimethoxycarbonyl-substituted-4-pyrone compounds

[0151] 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, it is reduced, and then reacted with one or two acid chlorides for esterification to obtain the corresponding substituted 2,6-dimethoxycarbonyl-substituted-4-pyrone product. When reacting with two acid chlorides, a mixture of three products is obtained, which is directly used as an internal electron donor composition without separation. The structures of other 2,6-dimethoxycarbonyl-substituted-4-pyrone compounds are shown in Table 1.

[0152]

[0153] General formula (I)

[0154] Table 1 2,6-dimethoxycarbonyl-substituted-4-pyrone compounds prepared in Preparation Examples 1-13

[0155]

[0156]

[0157]

[0158] Catalyst preparation

[0159] Example 1

[0160] 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-dimethoxycarbonylethyl-4-pyrone and 3mmol 2,3-diisopropylsuccinic acid diethyl ester 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.

[0161] Polymerization: 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 catalyst 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 1.

[0162] Example 2-13

[0163] The solid catalyst component preparation process is as shown in Example 1, except that 2,6-dimethoxycarbonylethyl-4-pyrone is replaced with 7 mmol of compounds a2-a13 in Table 1 in sequence.

[0164] Embodiment 14

[0165] The solid catalyst component preparation process is as shown in Example 1, except that 5 mmol 2,6-dimethoxycarbonylethyl-4-pyrone and 5 mmol 2,3-diisopropyl diethyl succinate are added.

[0166] Embodiment 15

[0167] The solid catalyst component preparation process is as shown in Example 1, except that 2 mmol 2,6-dimethoxycarbonylethyl-4-pyrone and 8 mmol 2,3-diisopropyl diethyl succinate are added.

[0168] Example 16

[0169] The solid catalyst component preparation process is as shown in Example 1, except that 6 mmol 2,6-dimethoxycarbonylethyl-4-pyrone and 4 mmol 2,3-diisopropyl diethyl succinate are added.

[0170] Examples 17-37

[0171] 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 according to the internal electron donor numbers shown in Table 2.

[0172] Examples 38-45

[0173] 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.

[0174] Examples 46-48

[0175] The solid catalyst component preparation process is as shown in Example 1, except that the internal electron donor compounds a1, b4 and b7 are added respectively according to the molar ratio shown in Table 2 (total feed amount is 10 mmol).

[0176] Comparative Example 1

[0177] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b4 internal electron donor compound are replaced by 10 mmol of 2,6-dimethoxycarbonylethyl-4-pyrone (a1).

[0178] Comparative Example 2

[0179] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b4 internal electron donor compound are replaced by 10 mmol of 2,6-dimethoxycarbonylphenyl-4-pyrone (a5).

[0180] Comparative Example 3

[0181] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b4 internal electron donor compound are replaced by 10 mmol of 2,6-dimethoxycarbonyl-m-chlorophenyl-4-pyrone (a6).

[0182] Comparative Example 4

[0183] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b4 internal electron donor compound are replaced by 10 mmol of 9,9-bis(methoxymethyl)fluorene (b1).

[0184] Comparative Example 5

[0185] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b4 internal electron donor compound are replaced by 10 mmol of di-n-butyl phthalate (b3).

[0186] Comparative Example 6

[0187] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b4 internal electron donor compound are replaced by 10 mmol of 2,3-diisopropyl diethyl succinate (b4).

[0188] Comparative Example 7

[0189] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b4 internal electron donor compound are replaced by 10 mmol of 1,2-benzenediol-4-tert-butyl-1,2-dibenzoate (b7).

[0190] Comparative Example 8

[0191] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b4 internal electron donor compound are replaced by 7 mmol of b1 and 3 mmol of b4.

[0192] Comparative Example 9

[0193] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b4 internal electron donor compound are replaced by 7 mmol of b3 and 3 mmol of b4.

[0194] Comparative Example 10

[0195] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b4 internal electron donor compound are replaced by 5 mmol of b1, 3 mmol of b3 and 2 mmol of b4 electron donor.

[0196] Comparative Example 11

[0197] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of a1 and 3 mmol of b4 internal electron donor compound are replaced by 5 mmol of b1, 3 mmol of b4 and 2 mmol of b6 electron donor.

[0198] Table 2 Different compounding results under the same polymerization conditions

[0199]

[0200]

[0201]

[0202]

[0203]

[0204] [Note] b1: 9,9-bis(methoxymethyl)fluorene;

[0205] b2: 2-isopropyl-2-isopentyl-1,3-dimethoxypropane;

[0206] b3: di-n-butyl phthalate;

[0207] b4: diethyl 2,3-diisopropylsuccinate;

[0208] b5: diethyl 2,3-diisopropyl-2-cyanosuccinate;

[0209] b6: 1,2-benzenediol-4-tert-butyl-1,2-di-n-hexanoate;

[0210] b7: 1,2-benzenediol-4-tert-butyl-1,2-dibenzoate;

[0211] b8: ethyl benzoate.

[0212] As can be seen from Table 2, the activity of 2,6-dimethoxycarbonyl-substituted-4-pyrone 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 single internal electron donor catalyst without compounding (Comparative Examples 1 to 7), and also higher than the catalyst of the compounded internal electron donor without 2,6-dimethoxycarbonyl-substituted-4-pyrone (Comparative Examples 8 to 11), and the molecular weight distribution is relatively wide. The molecular weight distribution of the catalyst prepared by compounding 2,6-dimethoxycarbonyl-substituted-4-pyrone with succinate is significantly broadened compared with that of 2,6-dimethoxycarbonyl-substituted-4-pyrone, and is suitable for the preparation of high-rigidity polypropylene. The polypropylene obtained by the catalyst has high isotacticity, regular particle shape and high bulk density.

[0213] Examples 49-52

[0214] 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 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 3.

[0215] Examples 53-56

[0216] 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-48 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 3.

[0217] Table 3 Different external electron donors

[0218]

[0219] [Note] CMMS: methylcyclohexyldimethoxysilane;

[0220] DPDMS: dicyclopentyldimethoxysilane;

[0221] PETS: phenyltrimethoxysilane;

[0222] NPTMS: n-propyltrimethoxysilane.

[0223] Examples 57-68

[0224] 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.

[0225] Comparative Examples 12-18

[0226] The polymerization steps are the same as those in Example 58, except that the catalysts are the catalysts listed in Table 4.

[0227] Table 4 (without using external electron donor)

[0228]

[0229] As can be seen from Table 3, the catalysts CAT-1 and CAT-48 prepared by compounding two or more internal electron donor compounds, when polymerized with different external electron donors, all showed high activity, high isotacticity and high bulk density of the polymers, good polymerization compatibility, and wide molecular weight distribution.

[0230] As can be seen from Table 4, when no external electron donor is used, the polymer can still maintain a high isotacticity, and the polymerization activity is further improved, showing ultra-high activity, which is much higher than the non-compounded catalyst and the compounded internal electron donor catalyst without 2,6-dimethoxycarbonyl substituent-4-pyrone (Comparative Examples 12-16). When the polymerization time of Cat-1 and Cat-48 is extended from 60 minutes to 120 minutes, the catalyst can maintain ultra-high activity without attenuation. When low Al / Ti is used, the ash content of the obtained polypropylene is low, which can be reduced to 23ppm. The molecular weight distribution is wide.

[0231] 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. A catalyst component for olefin polymerization, 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-dimethoxycarbonyl substituted-4-pyrone 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 of hydrocarbon groups.

2. The catalyst component for olefin polymerization 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 catalyst component for olefin polymerization 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 catalyst component for olefin polymerization 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 by N, O, S, P, Si heteroatom alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or each independently selected from heterocyclic aromatic substituents.

5. The catalyst component for olefin polymerization 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 catalyst component for olefin polymerization according to claim 1, characterized in that The 2,6-dimethoxycarbonyl substituent-4-pyrone of general formula (I) is selected from 2,6-dimethoxycarbonylethyl-4-pyrone, 2,6-dimethoxycarbonylpropyl-4-pyrone, 2,6-dimethoxycarbonylbutyl-4-pyrone, 2,6-dimethoxycarbonylpentyl-4-pyrone, 2,6-dimethoxycarbonylcyclohexyl-4-pyrone, 2,6-dimethoxycarbonyloctyl-4-pyrone, 2,6-dimethoxycarbonyl dodecyl-4-pyrone, 2,6-dimethoxycarbonyl tetradecyl-4-pyrone, 2,6-dimethoxycarbonyl hexadecyl-4-pyrone, 2,6-dimethoxycarbonyl phenyl-4-pyrone, 2,6-dimethoxycarbonyl m-chlorophenyl-p-tolyl-4-pyrone, 2,6-dimethoxycarbonyl o-chlorophenyl-4-pyrone, At least one of 2,6-dimethoxycarbonyl-4-chlorophenyl-4-pyrone, 2,6-dimethoxycarbonyl-4-methoxyphenyl-4-pyrone, 2,6-dimethoxycarbonyl-4-nitrophenyl-4-pyrone, 2,6-dimethoxycarbonylphenyl-3,5-dimethyl-4-pyrone, 2,6-dimethoxycarbonylphenyl-3,5-diethyl-4-pyrone, 2,6-dimethoxycarbonylphenyl-3,5-dipropyl-4-pyrone, 2,6-dimethoxycarbonylphenyl-3,5-dibutyl-4-pyrone, 2,6-dimethoxycarbonylphenyl-3-methyl-5-ethyl-4-pyrone, 2,6-dimethoxycarbonylphenyl-3-ethyl-5-butyl-4-pyrone and 2,6-dimethoxycarbonylphenyl-3-methyl-5-butyl-4-pyrone.

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

10. The catalyst component for olefin polymerization 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 5 -R 10 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 11 and R 12 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 catalyst component for olefin polymerization according to claim 10, characterized in that R 5 -R 12 One or more groups in the ring are linked to form a ring structure.

12. The catalyst component for olefin polymerization according to claim 10, characterized in that R 5 -R 12 Each of them further comprises at least one heteroatom selected from halogen, N, O, S, P and Si.

13. The catalyst component for olefin polymerization 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 19 -R 26 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; 13 -R 16 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 17 and R 18 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 catalyst component for olefin polymerization according to claim 13, characterized in that R 13 -R 18 One or more groups in the ring are linked to form a ring structure.

15. The catalyst component for olefin polymerization according to claim 13, characterized in that R 13 -R 18 Each of them further comprises at least one heteroatom selected from halogen, N, O, S, P and Si.

16. The catalyst component for olefin polymerization 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 catalyst component for olefin polymerization according to claim 9, characterized in that The polycarboxylic acid ester compound is a succinate compound represented by the general formula (IV): In the general formula (IV), R 27 and R 28 The same or different, each independently selected from C1-C 20 a linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl group, optionally containing heteroatoms; R 29 -R 32 At least two of the groups are different from hydrogen and are selected from C1-C 20 Linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl groups, optionally containing heteroatoms.

18. The catalyst component for olefin polymerization according to claim 17, characterized in that R 29 -R 32 Connect together to form a ring.

19. The catalyst component for olefin polymerization according to claim 17, characterized in that R 27 and R 28 The same or different, each independently selected from C1-C8 alkyl, cycloalkyl, aryl, aralkyl and alkaryl groups.

20. The catalyst component for olefin polymerization according to claim 17, characterized in that R 27 and R 28 Selected from primary alkyl groups.

21. The catalyst component for olefin polymerization according to claim 17, characterized in that R 27 and R 28 Selected from methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl.

22. The catalyst component for olefin polymerization according to claim 17, characterized in that In the general formula (IV), R 29 -R 31 is hydrogen and R 32 are branched alkyl, cycloalkyl, aryl, aralkyl and alkaryl groups having 3 to 10 carbon atoms.

23. The catalyst component for olefin polymerization according to claim 17, characterized in that R 32 is a branched primary alkyl group or a cycloalkyl group having 3 to 10 carbon atoms.

24. The catalyst component for olefin polymerization according to claim 17, characterized in that In the general formula (IV), R 29 -R 32 At least two of the groups are different from hydrogen and are selected from C1-C 20 Linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl groups, optionally containing heteroatoms.

25. The catalyst component for olefin polymerization according to claim 24, characterized in that R 29 -R 32 Two non-hydrogen groups are attached to the same carbon atom.

26. The catalyst component for olefin polymerization according to claim 17, characterized in that The succinate compound is a disubstituted succinate compound.

27. The catalyst component for olefin polymerization according to claim 24, characterized in that In the general formula (IV), at least two non-hydrogen groups are bonded to different carbon atoms.

28. The catalyst component for olefin polymerization according to claim 24, characterized in that In the general formula (IV), at least two non-hydrogen groups are connected to R 29 and R 31 , or R 30 and R 32 superior.

29. The catalyst component for olefin polymerization according to claim 17, characterized in that In the general formula (IV), the groups R connected to the same carbon atom 29 -R 32 Two or four of them are connected together to form a ring.

30. The catalyst component for olefin polymerization 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 33 and R 34 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 33 and R 34 Not hydrogen; R 35 -R 38 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.

31. The catalyst component for olefin polymerization 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 39 -R 52 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.

32. The catalyst component for olefin polymerization according to claim 31, characterized in that In the general formula (VI), R 39 -R 42 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.

33. The catalyst component for olefin polymerization according to claim 31, characterized in that In the general formula (VI), R 43 -R 52 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.

34. The catalyst component for olefin polymerization according to claim 1, characterized in that The catalyst component comprises a titanium compound, a magnesium compound, the 2,6-dimethoxycarbonyl-substituted-4-pyrone 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.

35. The catalyst component for olefin polymerization according to claim 34, 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.

36. The catalyst component for olefin polymerization according to claim 34, characterized in that The titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and alkoxy titanium halide.

37. The catalyst component for olefin polymerization according to claim 36, characterized in that 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.

38. The catalyst component for olefin polymerization according to claim 34, 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.

39. A catalyst for olefin polymerization, wherein the raw material composition comprises the catalyst component according to any one of claims 1 to 38 and an organic aluminum compound.

40. The catalyst according to claim 39, 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.

41. The catalyst component according to claim 40, characterized in that 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.

42. The catalyst according to claim 39, characterized in that The molar ratio of the organic aluminum compound to the titanium atom in the catalyst component is 1-1000:

1.

43. The catalyst according to claim 39, characterized in that ,, the raw material composition of the catalyst also includes an external electron donor; The external electron donor is a siloxane compound.

44. The catalyst component according to claim 43, characterized in that 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.

45. The catalyst component according to claim 44, characterized in that R' and R" each contain a heteroatom.

46. ​​The catalyst component according to claim 45, characterized in that The heteroatom includes at least one of N, O, S, P, and Si.

47. The catalyst according to claim 43, characterized in that The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100.

48. Use of the catalyst according to any one of claims 39 to 47 in olefin polymerization.

49. The use according to claim 48, characterized in that The olefins include at least one of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, butadiene, vinylcyclopentene, and vinylcyclohexene; The polymerization includes homopolymerization or copolymerization; The polymerization temperature is ≤200°C; the polymerization pressure is ≤10MPa.

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