Solid catalyst component for the polymerization of olefins, catalyst for the polymerization of olefins and use thereof

Abstract

The application discloses a solid catalyst component for olefin polymerization, an olefin polymerization catalyst and application thereof. The solid catalyst component for olefin polymerization comprises Mg, Ti, halogen, an internal electron donor a compound and an internal electron donor b compound. The internal electron donor a compound is selected from substituted 2,6-diformate-4-pyrone compounds of general formula (I), and the internal electron donor b compound is selected from tetrahydro-ortho-substituted phenyl compounds of general formula (II). The solid catalyst component of the application uses substituted 2,6-diformate-4-pyrone compounds as internal electron donors of polyolefin catalysts. After being compounded with tetrahydro-ortho-substituted phenyl compounds, the solid catalyst component has high polymerization activity, high polymer melt index and good hydrogen regulation sensitivity.

Description

Technical Field

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

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

[0003] The most distinctive high-performance internal electron donor compounds in the prior art include: 1) fatty acid esters and aromatic esters, mainly phthalates; 2) diethers (e.g., EP0361493, EP0728724); 3) succinates (e.g., WO9856834, WO0063261, WO03022894); 4) glycol esters (e.g., WO9856834, WO0063261, WO03022894); and 5) compounds with other functional groups (CN1105671, CN1242780, US20060128558), etc. However, in practical applications, the aforementioned compounds all present certain problems when used as internal electron donors in olefin polymerization catalysts. While catalysts using 1,3-diethers as internal electron donors exhibit high activity and good hydrogen-modulated sensitivity, the resulting PP has a narrow molecular weight distribution, hindering the development of different PP grades. Succinate compounds, as internal electron donors, offer the advantage of a wider molecular weight distribution in the synthesized PP, but their stereoregularity and hydrogen-modulated sensitivity require improvement. Diol ester catalytic systems generally exhibit less ideal activity than diether systems. Chinese patent CN102325808 discloses a precatalyst composition containing a phenylene aromatic diester as an internal electron donor, but its activity is low, and even with the use of silane external electron donors, the resulting polymer still has a high xylene-soluble content, indicating poor stereoselectivity for propylene.

[0004] When catalysts prepared using a single internal electron donor cannot meet the specific requirements of polypropylene products, such as the requirement for high activity, high stereoregulation, and high hydrogen sensitivity, the combined use of multiple internal electron donors is an effective solution. This involves using two or more internal electron donors simultaneously during the preparation of Zn catalysts, and adjusting the overall performance of the Zn catalyst by varying the content of different internal electron donors. Chinese patent CN101724102 discloses a catalyst component prepared by combining an internal electron donor diol ester compound and a 1,3-diether compound using a magnesium chloride alcohol adduct support. This catalyst exhibits high activity, but it is only comparable to 1,3-diether-based electron donor catalysts, and silane-based external electron donors are still required to maintain a high isotacticity.

[0005] Currently, phthalate compounds are the most widely used internal electron donors in polyolefin industry. Catalysts prepared from phthalates exhibit moderate activity, good stereoselectivity, and low cost. However, as commonly used plasticizers, phthalates pose significant risks to human reproductive health and the environment, creating a substantial demand for alternatives. Europe has already restricted the use of most phthalate substances. Therefore, developing novel electron donors with excellent activity, good stereoselectivity, superior overall performance, and low cost to replace the widely used phthalate-based electron donor compounds and applying them to the preparation of highly efficient Ziegler-Natta catalysts has been a common research goal in the field of polyolefin catalysts in recent years. Summary of the Invention

[0006] To address the problems existing in the prior art, the present invention provides an internal electron donor compound with excellent basic performance and good compatibility with other internal electron donor compounds. When this internal electron donor compound is compounded with various other types of internal electron donor compounds, it can significantly improve catalytic activity and still obtain a high isotactic polymer without the addition of an external electron donor.

[0007] The purpose of this invention is to provide a solid catalyst component CH2 for olefin polymerization.

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

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

[0010] Another object of the present invention is to provide the application of the catalyst in the polymerization of CH2 olefins.

[0011] To achieve the objectives of this invention, a solid catalyst component for olefin polymerization is provided, comprising Mg, Ti, halogen, an internal electron donor a compound and an internal electron donor b compound, wherein the internal electron donor a compound is selected from substituted 2,6-dicarboxylate-4-pyranone compounds of general formula (I).

[0012]

[0013] In general formula (I), R 1 R 2 R 3 and R 4 Whether the elements are the same or different, they are each independently selected from H, halogens, and C1-C. 20 The hydrocarbon group; preferably, R 1 R 2 R 3 and R 4It may also contain at least one heteroatom selected from N, O, S, P, Si and halogens; preferably, R 1 R 2 R 3 and R 4 Two or more of them can bond together to form a ring;

[0014] The internal electron donor b compound is selected from tetrahydro-ophthalic substituents of general formula (II):

[0015]

[0016] In general formula (II), R 5 -R 8 Whether the two are the same or different, they are each independently selected from H, C1-C. 20 Alkyl group; R 9 and R 10 The substituents, whether identical or different, are independently selected from oxygen- or nitrogen-containing functional groups; preferably R 9 and R 10 They are interconnected to form rings containing oxygen or nitrogen functional groups.

[0017] Preferably, R in general formula (I) 1 R 2 R 3 and R 4 Whether identical or different, each is independently selected from H, halogen, and the following substituents with 20 or fewer carbon atoms: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indene, benzyl, halogenated or substituted with N, O, S, P, or Si heteroatoms, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indene, benzyl; or each is independently selected from heterocyclic aryl substituents.

[0018] Preferably, R in general formula (I) 1 R 2 R 3 and R 4 Whether the groups are the same or different, each is independently selected from H, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 ~C 20 The following substituents with 20 or fewer carbon atoms, whether straight-chain or branched alkyl groups: 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, pyrroleyl, thiophenyl, propenyl, butenyl, pentenyl, hexenyl, indene.

[0019] Preferably, the substituted 2,6-dicarboxylate-4-pyranone compound of general formula (I) is selected from di-n-butyl 2,6-dicarboxylate-4-pyranone, diethyl 2,6-dicarboxylate-4-pyranone, diisobutyl 2,6-dicarboxylate-4-pyranone, dicyclohexyl 2,6-dicarboxylate-4-pyranone, di(tetradecyl) 2,6-dicarboxylate-4-pyranone, diphenyl 2,6-dicarboxylate-4-pyranone, diphenylethyl 2,6-dicarboxylate-4-pyranone, di-m-chlorophenyl 2,6-dicarboxylate-4-pyranone, di-p-chlorophenyl 2,6-dicarboxylate-4-pyranone, di-o-chlorophenyl 2,6-dicarboxylate-4-pyranone, di-p-methylphenyl 2,6-dicarboxylate-4-pyranone, and dimethylphenyl 2,6-dicarboxylate-4-pyranone. At least one of the following: di-m-methoxyphenyl 2,6-dicarboxylate-4-pyranone, di-p-methoxyphenyl 2,6-dicarboxylate-4-pyranone, di-o-methoxyphenyl 2,6-dicarboxylate-4-pyranone, difuranmethyl 2,6-dicarboxylate-4-pyranone, dipentenyl 2,6-dicarboxylate-4-pyranone, di-p-nitrophenyl 2,6-dicarboxylate-4-pyranone, di-n-butyl 2,6-dicarboxylate-4-pyranone, di-n-butyl 2,6-dicarboxylate-3,5-dimethyl-4-pyranone, diethyl 2,6-dicarboxylate-3-phenyl-4-pyranone, diethyl 2,6-dicarboxylate-3-chloro-4-pyranone, and diethyl 2,6-dicarboxylate-3-bromo-4-pyranone.

[0020] Preferably, the substituted 2,6-dicarboxylate-4-pyranone compound of general formula (I) can be synthesized by methods including but not limited to the following:

[0021] R 1 and R 2 The synthetic route for the same general formula (I) compounds is shown below. Esterification of oxalic acid yields the corresponding oxalate diester (some oxalate diesters can be purchased directly), which is then reacted with acetone or other substituted ketones to obtain the corresponding products.

[0022]

[0023] R 1 and R 2 The second synthetic route for the same general formula (I) compound is shown below. This route uses inexpensive diethyl oxalate and acetone or other substituted ketones as starting materials, and requires only two steps to obtain the target product. A wide variety of alcohols R can be used. 1 OH is used to enrich the product structure. Alternatively, the product from the first step, 2,6-dicarboxylic acid-4-pyranone (R), can also be purchased directly. 1 and R 2 The same and of the same type (CAS No.: 99-32-1) was used to obtain 2,6-dicarboxylate-4-pyranone through a one-step esterification reaction.

[0024]

[0025] R 1 and R 2 Same or different, R 3 and R 4 The synthetic routes for compounds of the same or different general formula (I) are shown in the following formula: diethyl oxalate reacts with the corresponding ketone, and then reacts with an alcohol to obtain a pure substituted 2,6-dicarboxylate-4-pyranone compound, or reacts with a mixture of two alcohols to obtain a mixture of three substituted 2,6-dicarboxylate-4-pyranone compounds. Without separation, the mixture is used directly as an internal electron donor. The proportion of each component in the mixture can be adjusted by the addition ratio of the two alcohols in the reactants. The proportion of each component can be determined by characterization using analytical methods such as chromatography-mass spectrometry and nuclear magnetic resonance.

[0026]

[0027] Preferably, R in the tetrahydro-ophthalic substituent of the internal electron donor b compound of general formula (II) 9 and R 10 Preferably, it has a formate substituent; R 9 and R 10 Another preferred option is to connect it into an acid anhydride or a formimide.

[0028] Preferably, the tetrahydro-ophthalic substituent compound of general formula (II) is selected from dimethyl trans-4-cyclohexene-1,2-dicarboxylate, diethyl trans-4-cyclohexene-1,2-dicarboxylate, di-n-propyl trans-4-cyclohexene-1,2-dicarboxylate, diisopropyl trans-4-cyclohexene-1,2-dicarboxylate, di-n-butyl trans-4-cyclohexene-1,2-dicarboxylate, diisobutyl trans-4-cyclohexene-1,2-dicarboxylate, dipentyl trans-4-cyclohexene-1,2-dicarboxylate, and trans-4-cyclohexene-1,2-dicarboxylate. At least one of the following: dihexyl 2-dicarboxylate, diheptyl trans-4-cyclohexene-1,2-dicarboxylate, dioctyl trans-4-cyclohexene-1,2-dicarboxylate, diphenyl trans-4-cyclohexene-1,2-dicarboxylate, dibenzyl trans-4-cyclohexene-1,2-dicarboxylate, diglycidyl tetrahydrophthalic acid, tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, and 1,2,3,6-tetrahydrophthalimide.

[0029] 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.

[0030] Preferably, the molar ratio of the internal electron donor compound a to the internal electron donor compound b is greater than or equal to 4:6.

[0031] Preferably, the molar ratio of the internal electron donor compound a to the internal electron donor compound b is greater than or equal to 5:5.

[0032] Preferably, the molar ratio of the internal electron donor compound a to the internal electron donor compound b is greater than or equal to 8:2.

[0033] Preferably, to further improve the polymerization activity of the solid catalyst component, the solid catalyst component may also contain an internal electron donor compound c, wherein the internal electron donor compound c is selected from 1,3-diether compounds represented by general formula (III):

[0034]

[0035] In general formula (III), R 11 -R 16 Whether the same or different, each is independently selected from H, and each is independently selected from straight-chain or branched alkyl, cycloalkyl, aryl, alkylaryl, or aralkyl groups containing 1-18 carbon atoms; R 17 -R 18 They may be the same or different, each independently selected from straight-chain or branched alkyl groups with 1-20 carbon atoms, cycloalkyl groups with 3-20 carbon atoms, aryl groups with 5-20 carbon atoms, alkylaryl groups with 7-20 carbon atoms, and arylalkyl groups; R 11 -R 18 One or more groups in the structure can be linked to form a ring structure, and each group may also contain at least one heteroatom selected from halogens, N, O, S, P and Si.

[0036] Specifically, the 1,3-diether compounds include, but are not limited to, those selected from: 2-(2-ethylhexyl)1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-tert-butyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2 (1-Naphthyl)-1,3-dimethoxypropane, 2-(p-fluorophenyl)-1,3-dimethoxypropane, 2-(1-decahydronaphthyl)-1,3-dimethoxypropane, 2-(p-tert-butylphenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-diethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-diethoxypropane, 2,2-dibutyl-1,3-diethoxypropane, 2-methyl-2-ethyl-1,3-dimethyl 2-Methyl-2-propyl-1,3-dimethoxypropane, 2-Methyl-2-benzyl-1,3-dimethoxypropane, 2-Methyl-2-phenyl-1,3-dimethoxypropane, 2-Methyl-2-cyclohexyl-1,3-dimethoxypropane, 2-Methyl-2-methylcyclohexyl-1,3-dimethoxypropane, 2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane, 2,2-bis(2-phenylethyl)-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-Methyl-2-isobutyl-1,3-dimethoxypropane, 2-Methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-bis(2-ethylhexyl) )-1,3-dimethoxypropane, 2,2-bis(p-methylphenyl)-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-di-sec-butyl-1,3-dimethoxypropane, 2,2-Di-tert-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-iso-propyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane. 1,1-bis(methoxymethyl)-cyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetramethylcyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetraphenylcyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetrafluorocyclopentadiene; 1,1-bis(methoxymethyl)-3,4-dicyclopentylcyclopentadiene; 1,1-bis(methoxymethyl)indene; 1,1-bis(methoxymethyl)-2,3-dimethylindene; 1,1-bis(methoxymethyl)-4,5,6,7-tetrahydroindene; 1,1-bis(methoxymethyl)-2,3,6,7-tetrafluoroindene; 1,1-bis( 1,1-bis(methoxymethyl)-4,7-dimethylindene; 1,1-bis(methoxymethyl)-3,6-dimethylindene; 1,1-bis(methoxymethyl)-4-phenylindene; 1,1-bis(methoxymethyl)-4-phenyl-2-methylindene; 1,1-bis(methoxymethyl)-4-cyclohexylindene; 1,1-bis(methoxymethyl)-7-(3,3,3-trifluoropropyl)indene; 1,1-bis(methoxymethyl)-7-trimethylsilylindene; 1,1-bis(methoxymethyl)-7-trifluoromethylindene; 1,1-bis(methoxymethyl)-4,7-dimethyl-4,5,6,7-tetrahydroindene; 1,1-bis(methoxymethyl)-7- Methyl indene; 1,1-bis(methoxymethyl)-7-cyclopentyl indene; 1,1-bis(methoxymethyl)-7-isopropyl indene; 1,1-bis(methoxymethyl)-7-cyclohexyl indene; 1,1-bis(methoxymethyl)-7-tert-butyl indene; 1,1-bis(methoxymethyl)-7-tert-butyl-2-methyl indene; 1,1-bis(methoxymethyl)-7-phenyl indene; 1,1-bis(methoxymethyl)-2-phenyl indene; 1,1-bis(methoxymethyl)-1H-benzo[e]indene; 1,1-bis(methoxymethyl)-1H-2-methylbenzo[e]indene; 9,9-bis(methoxymethyl)fluorene; 9,9-bis(methoxymethyl)fluorene 9,9-Bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene; 9,9-Bis(methoxymethyl)-2,3-benzo[a]fluorene; 9,9-Bis(methoxymethyl)-2,3,6,7-dibenzo[a]fluorene; 9,9-Bis(methoxymethyl)-2,7-diisopropylfluorene; 9,9-Bis(methoxymethyl)-1,8-dichlorofluorene; 9,9-Bis(methoxymethyl)-2,7-dicyclopentylfluorene; 9,9-Bis(methoxymethyl)-1,8-difluorofluorene; 9,9-Bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene; 9,9-Bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene; 9,9-Bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene;At least one of 4,5,6,7,8-octahydrofluorene; 9,9-bis(methoxymethyl)-4-tert-butylfluorene.

[0037] Preferably, the diether compound is further selected from diether compounds represented by general formula (IV):

[0038]

[0039] In general formula (IV), R 25 -R 32 Whether identical or different, each independently selected from hydrogen, halogen, straight-chain or branched alkyl, cycloalkyl, aryl, alkylaryl, and arylalkyl groups with 1-20 carbon atoms, 3-20 carbon atoms, aryl, alkylaryl, and arylalkyl groups with 7-20 carbon atoms, optionally containing at least one heteroatom selected from N, O, S, P, Si, and halogen as a substituent for a carbon atom, a hydrogen atom, or both; R 19 -R 22 Whether the groups are the same or different, each is independently selected from H, or each is independently selected from straight-chain or branched alkyl, cycloalkyl, aryl, alkylaryl, or aralkyl groups containing 1-18 carbon atoms; R 23 and R 24 They may be the same or different, each independently selected from straight-chain or branched alkyl groups with 1-20 carbon atoms, cycloalkyl groups with 3-20 carbon atoms, aryl groups with 5-20 carbon atoms, alkylaryl groups with 7-20 carbon atoms, and arylalkyl groups; R 19 -R 32 One or more groups in the structure can be linked to form a ring structure, and each group may also contain at least one heteroatom selected from halogens, N, O, S, P and Si.

[0040] Preferably, the diether compounds include, but are not limited to, those selected from: 2-(2-ethylhexyl)1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-tert-butyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2(1- Naphthyl)-1,3-dimethoxypropane, 2(p-fluorophenyl)-1,3-dimethoxypropane, 2(1-decahydronaphthyl)-1,3-dimethoxypropane, 2(p-tert-butylphenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-diethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-diethoxypropane, 2,2-dibutyl-1,3-diethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane Alkane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2-methyl-2-methylcyclohexyl-1,3-dimethoxypropane, 2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane, 2,2-bis(2-phenylethyl)-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-bis(2-ethylhexyl)-1 3-Dimethoxypropane, 2,2-bis(p-methylphenyl)-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-Di-sec-butyl-1,3-dimethoxypropane, 2,2-di-tert-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-iso-propyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 1,1-bis(methoxymethyl)-cyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetramethylcyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetraphenylcyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetrafluorocyclopentadiene; 1,1-bis(methoxymethyl)-3 4-Dicyclopentylcyclopentadiene; 1,1-bis(methoxymethyl)indene; 1,1-bis(methoxymethyl)-2,3-dimethylindene; 1,1-bis(methoxymethyl)-4,5,6,7-tetrahydroindene; 1,1-bis(methoxymethyl)-2,3,6,7-tetrafluoroindene; 1,1-bis(methoxymethyl)-4,7-dimethylindene; 1,1-bis(methoxymethyl)-3,6-dimethylindene; 1,1-bis(methoxymethyl)-4-phenylindene; 1,1-bis(methoxymethyl)-4-phenyl-2-methylindene; 1,1-bis(methoxymethyl)-4-cyclohexylindene; 1,1-bis(methoxymethyl)-7-(3,3,3-trifluoropropyl)indene; 1,1-bis(methoxymethyl)-7- Trimethylsilyl indene; 1,1-bis(methoxymethyl)-7-trifluoromethyl indene; 1,1-bis(methoxymethyl)-4,7-dimethyl-4,5,6,7-tetrahydro indene; 1,1-bis(methoxymethyl)-7-methyl indene; 1,1-bis(methoxymethyl)-7-cyclopentyl indene; 1,1-bis(methoxymethyl)-7-isopropyl indene; 1,1-bis(methoxymethyl)-7-cyclohexyl indene; 1,1-bis(methoxymethyl)-7-tert-butyl indene; 1,1-bis(methoxymethyl)-7-tert-butyl-2-methyl indene; 1,1-bis(methoxymethyl)-7-phenyl indene; 1,1-bis(methoxymethyl)-2-phenyl indene; 1,1-bis(methoxymethyl)-1H-benzo[e]indene; 1 1-Bis(methoxymethyl)-1H-2-methylbenzo[e]indene; 9,9-bis(methoxymethyl)fluorene; 9,9-bis(methoxymethyl)-2,3,6,7-tetramethylfluorene; 9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene; 9,9-bis(methoxymethyl)-2,3-benzofluorene; 9,9-bis(methoxymethyl)-2,3-benzofluorene 9,9-bis(methoxymethyl)-2,3,6,7-dibenzo[a]fluorene; 9,9-bis(methoxymethyl)-2,7-diisopropylfluorene; 9,9-bis(methoxymethyl)-1,8-dichlorofluorene; 9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorene; 9,9-bis(methoxymethyl)-1,8-difluorofluorene; 9,9-bis(methoxymethyl)-1,2,3,At least one of 4-tetrahydrofluorene; 9,9-bis(methoxymethyl)-1,2,3,4,5,6,7,8-octahydrofluorene; and 9,9-bis(methoxymethyl)-4-tert-butylfluorene.

[0041] Preferably, the internal electron donor c compound is further preferably 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 9,9-bis(methoxymethyl)fluorene.

[0042] Preferably, the molar ratio of the internal electron donor compounds a, b, and c (a+b):c ≥ 2:8.

[0043] Preferably, the molar ratio of the internal electron donor compounds a, b, and c is (a+b):c ≥ 5:5.

[0044] Preferably, the molar ratio of the internal electron donor compounds a, b, and c (a+b):c ≥ 8:2.

[0045] According to a specific embodiment of the present invention, preferably, the catalyst component comprises a titanium compound, a magnesium compound, and the internal electron donor compound;

[0046] The precursor of the magnesium compound is selected from X. n Mg(OR a ) 2-n MgCl2·mR a OH, R a 2-n MgX n At least one of the following: a mixture of MgCl2 / SiO2, MgCl2 / Al2O3, magnesium halide, and titanium alkoxide, wherein m is 0.1-6, 0≤n≤2, X is a halogen, and R a For C1-C 20 hydrocarbon group;

[0047] The general formula of the titanium compound is TiX. N (OR b ) 4-N In the formula, R b For C1-C 20 The hydrocarbon group, where X is a halogen and N is 1-4.

[0048] Preferably, the magnesium compound is an alkoxide of magnesium dihalide;

[0049] Alternatively, the magnesium compound may be a liquid magnesium compound;

[0050] Alternatively, the magnesium compound is a derivative in which at least one halogen atom in a magnesium dihalide molecule is replaced by a hydrocarbon or halohydroxyl group; preferably a hydrocarbon-oxyl magnesium compound; more preferably an alkoxyl magnesium and / or aryloxyl magnesium.

[0051] Preferably, the titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and titanium alkoxyhalide;

[0052] Preferably, the alkyl titanium halide includes at least one of methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, and tri-n-butoxy titanium chloride.

[0053] Preferably, the titanium compound is titanium tetrachloride.

[0054] Preferably, the molar ratio of the total amount of the internal electron-donating compounds to the magnesium compound is 0.01-5.0, more preferably 0.05-3.0, and the magnesium compound is calculated in terms of magnesium element.

[0055] This invention does not specifically limit the preparation method of the olefin polymerization catalyst component, which can be carried out according to the following methods:

[0056] Method 1: A solution of titanium compounds (such as TiCl4 or hydroxyl titanium) in aromatic hydrocarbons (e.g., toluene, xylene, etc.) is reacted with magnesium compounds (such as dialkoxy magnesium or diaryloxy magnesium compounds) at -25 to 0 °C, followed by halogenation at 80 to 130 °C. The treatment with the aromatic hydrocarbon solution of TiCl4 can be repeated once or multiple times, with the addition of an internal electron donor. For example, the preparation method of the titanium-containing solid catalyst component disclosed in US5077357A can be used: ethoxy magnesium, tetraethoxy titanium, o-cresol, ethanol, and chlorobenzene are added sequentially, and the mixture is stirred; a TiCl4 / chlorobenzene solution is rapidly added to the above liquid, and the temperature is raised until complete dissolution, then the temperature is further raised to 80 to 130 °C; the ethanol reactants are removed by bubbling with N2, and the mixture is stirred for a certain period of time, then washed once with hot chlorobenzene, twice with isooctane, and finally dried with N2 to obtain the support. Alternatively, follow another example: add TiCl4, tetraethoxytitanium, ethoxymagnesium, and o-cresol to chlorobenzene in sequence and stir; add ethanol, and continue stirring for 3 hours after the ethoxymagnesium dissolves at high temperature; filter while hot, then wash once with warm chlorobenzene, wash once with isooctane, and finally dry with N2.

[0057] Method 2: React a magnesium compound (such as an alkoxide or chloroalkoxide of magnesium) with excess TiCl4 containing an internal electron donor in solution at a temperature of 80-135°C. According to the preferred method, the general formula TiX can be reacted. N (OR b ) 4-N Titanium compounds (where R) b For C1-C 20The hydrocarbon group, where X is a halogen and N is 1-4; preferably TiCl4) and the general formula MgCl2·mR a OH (where m is a number from 0.1 to 6, preferably 2 to 4, and R) a For C1-C 20 Solid catalyst components are prepared by reacting adducts of hydrocarbon groups. The adducts can be suitably sphericalized by mixing an alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, followed by rapid quenching of the emulsion, thereby solidifying the adduct into spherical particles. Spherical MgCl2·mR particles prepared according to this process... a Examples of OH adducts can be described in US4399054A and US4469648A. The adducts thus obtained can react directly with titanium compounds, or they can be pre-treated with a thermally controlled dealcoholization process (80-130°C) to yield an adduct, wherein the molar number of the alcohol is generally less than 3, preferably between 0.1 and 2.5. The reaction with titanium compounds can be carried out by suspending the adduct (dealcoholized or the adduct itself) in cold TiCl4 (generally -25 to 0°C); the mixture is then heated to 80-130°C and held at this temperature for 0.5-2 hours. The treatment with TiCl4 can be performed once or multiple times. An internal electron donor can be added during the TiCl4 treatment, and this treatment can be repeated once or multiple times.

[0058] Method 3: Anhydrous magnesium chloride and an internal electron donor are ground together under conditions where magnesium dichloride is activated. The resulting product can be treated once or multiple times with an excess of TiCl4 at a temperature of 80-130°C. After treatment, it is washed with a hydrocarbon volume until no chloride ions are present. According to a further method, the product obtained by co-grinding anhydrous magnesium dichloride, a titanium compound, and an internal electron donor is treated with a haloalkane such as 1,2-dichloroethane, chlorobenzene, or dichloromethane. This treatment is carried out at a temperature between 40°C and the boiling point of the haloalkane for 1-4 hours. The product is then washed with an inert hydrocarbon volume, typically hexane.

[0059] Method 4: Magnesium dichloride can be pre-activated using known methods, and then treated with an excess of TiCl4 at a temperature of approximately 80-135°C, where the solution contains an internal electron donor. The solid is treated with TiCl4 multiple times and then washed with hexane to remove any unreacted TiCl4.

[0060] Method 5: Alternatively, the preparation method of the titanium-containing solid catalyst component disclosed in CN1208045A can be used: First, at low temperature, liquid magnesium compound and liquid titanium compound are contacted in the presence of a compound selected from alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and esters to precipitate solids. The contact temperature is generally -70 to 200°C, preferably -30 to 130°C, and an internal electron donor is used during the contact process.

[0061] Method Six: Dissolve a magnesium compound in a solvent system consisting of an organic epoxy compound, an organophosphorus compound, and an inert diluent to form a homogeneous solution. Mix this solution with a titanium compound and wash out the solid in the presence of a precipitation aid. Treat this solid with an internal electron donor to load it onto the solid. If necessary, further treat with titanium tetrahalide and an inert diluent to obtain the final product. The precipitation aid is one of an organic acid anhydride, organic acid, ether, or ketone. The components, per mole of magnesium halide, are: organic epoxy compound 0.2-10 mol, organophosphorus compound 0.1-3 mol, precipitation aid 0.03-1.0 mol, and transition metal Ti halide and its derivatives 0.5-150 mol.

[0062] Method 7: Magnesium compounds supported on inorganic oxides such as SiO2 and alumina or porous resins are used as carriers to prepare the product. The product is then activated by a known method and treated with an excess of TiCl4 at a temperature of about 80-135°C. An internal electron donor is added during the treatment process.

[0063] The reactions discussed above lead to the formation of magnesium halides in an active form (typical crystalline magnesium halides have a regular structure and can support very little Ti, resulting in low catalytic activity; to prepare highly active supported catalysts, magnesium halides must undergo activation treatment. Activation methods include using physical and / or chemical methods to prepare them into microcrystals so that active centers are supported on the surface, edges, and defects of the magnesium halide; these treated magnesium halide microcrystals suitable for supporting Ti are called "active magnesium halides"). In addition to these reactions, other methods are known in the literature for forming active magnesium halides from starting materials different from magnesium halides.

[0064] In any of the preparation methods described above, the internal electron donor compound can be added directly or optionally prepared in situ using a suitable precursor that can be converted in the desired internal electron donor compound via known chemical reactions such as esterification or transesterification. Typically, the internal electron donor compound is used in a molar ratio of 0.01-5, preferably 0.05-3.0, relative to MgCl2.

[0065] In any of the preparation methods described above, the internal electron donor compound can be added simultaneously or separately during the preparation process in batches or in any order or combination.

[0066] The present invention also provides a catalyst for olefin polymerization, the raw material composition of which includes the above-mentioned catalyst components and organoaluminum compounds.

[0067] According to a specific embodiment of the present invention, preferably, the organoaluminum compound has the general formula AlR c p X (3-p) , where R c It is hydrogen or C1-C 20 The hydrocarbon group, X is a halogen, and p is an integer 0 ≤ p ≤ 3.

[0068] According to a specific embodiment of the present invention, preferably, the organoaluminum compound includes at least one of trialkylaluminum compound, alkylaluminum halide, alkylaluminum hydride, alkylaluminum sesquichloride, and alkylaluminoxane.

[0069] According to a specific embodiment of the present invention, preferably, the trialkylaluminum compound includes at least one selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and trioctylaluminum; the alkylaluminum halide includes AlEt2Cl; and the alkylaluminum sesquichloride includes Al2Et3Cl3.

[0070] According to a specific embodiment of the present invention, preferably, the molar ratio of the organoaluminum compound to the titanium atoms in the catalyst component is 1-1000:1, more preferably 50-800.

[0071] According to a specific embodiment of the present invention, preferably, the raw material composition of the catalyst further includes an external electron donor.

[0072] According to a specific embodiment of the present invention, preferably, the external electron donor is a siloxane compound.

[0073] According to a specific embodiment of the present invention, preferably, the general formula of the siloxane compound is R'. t Si(OR”) 4-t In this context, R' and R” are each independently selected from C1-C 18 The hydrocarbon group, where t is an integer of 0 ≤ t ≤ 3; more preferably, R' and R” respectively contain heteroatoms; more preferably, the heteroatoms include at least one of N, O, S, P, and Si.

[0074] According to a specific embodiment of the present invention, preferably, the siloxane compound includes trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, triisobutylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diisobutyldimethoxysilane, di-tert- ... Silane, di-tert-butyldiethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, di(2-ethylhexyl)dimethoxysilane, di(2-ethylhexyl)diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldiethoxysilane, cyclopentylisopropyldiethoxysilane, cyclopentylisobutyldimethoxysilane, cyclohexyl-n-propyl Dimethoxysilane, cyclohexyl-n-propyldiethoxysilane, cyclohexyl-n-butyldiethoxysilane, pentylmethyldimethoxysilane, pentylmethyldiethoxysilane, pentylethyldimethoxysilane, pentylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, cyclohexyldimethoxysilane, cyclohexyldiethoxysilane, 2-ethylhexyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyl 2-Ethylhexyltrimethoxysilane, isobutyltrimethoxysilane, tert-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,At least one of the following: 5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, di(3-methylcyclohexyl)dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, di(4-methylcyclohexyl)dimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, di(3,5-dimethylcyclohexyl)dimethoxysilane, tetrapropoxysilane, and tetrabutoxysilane;

[0075] The siloxane compound more preferably includes at least one of di-n-propyl dimethoxysilane, diisopropyl dimethoxysilane, di-n-butyl dimethoxysilane, diisobutyl dimethoxysilane, di-tert-butyl dimethoxysilane, di-n-butyl diethoxysilane, tert-butyl trimethoxysilane, dicyclohexyl dimethoxysilane, dicyclohexyl diethoxysilane, cyclohexyl methyl dimethoxysilane, cyclohexyl ethyl diethoxysilane, cyclohexyl ethyl dimethoxysilane, cyclohexyl ethyl diethoxysilane, cyclopentyl methyl dimethoxysilane, cyclopentyl methyl diethoxysilane, cyclopentyl ethyl dimethoxysilane, cyclohexylcyclopentyl dimethoxysilane, cyclohexylcyclopentyl diethoxysilane, 3-methylcyclohexylcyclopentyl dimethoxysilane, 4-methylcyclohexylcyclopentyl dimethoxysilane, and 3,5-dimethylcyclopentyl dimethoxysilane.

[0076] According to a specific embodiment of the present invention, preferably, the molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100, more preferably 0.01-20, and even more preferably 0.01-5.

[0077] The present invention also provides the application of the above-mentioned catalyst in olefin polymerization.

[0078] According to a specific embodiment of the present invention, preferably, the olefin includes straight-chain or branched olefins, such as at least one of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, butadiene, vinylcyclopentene, and vinylcyclohexene.

[0079] According to a specific embodiment of the present invention, preferably, the polymerization includes ethylene and / or propylene polymerization.

[0080] According to a specific embodiment of the present invention, preferably, the polymerization includes homopolymerization or copolymerization.

[0081] According to a specific embodiment of the present invention, preferably, the order of adding the components in the catalyst during the catalytic process is arbitrary, with the organoaluminum compound being added to the polymerization system first, followed by the external electron donor, and finally the catalyst components.

[0082] According to a specific embodiment of the present invention, preferably, in the above applications, the polymerization process can be carried out with or without a solvent; the olefin monomer can be in the gas phase or liquid phase; more preferably, hydrogen can be further added as a molecular weight regulator (polymerization can also be carried out without a molecular weight regulator); continuous polymerization or batch polymerization processes can be applied, and the polymerization reaction can be carried out in one step, two steps or multiple steps.

[0083] According to a specific embodiment of the present invention, preferably, the polymerization temperature is ≤200℃, more preferably 20-100℃, and even more preferably 40-80℃; the polymerization pressure is ≤10MPa, preferably 0.3-5MPa.

[0084] The solid catalyst component of this invention uses a substituted 2,6-dicarboxylate-4-pyranone compound as the internal electron donor of the polyolefin catalyst. After being compounded with a tetrahydrophthalic acid substituent compound, it exhibits high polymerization activity, a high polymer melt index, and good hydrogen-modified sensitivity. The tetrahydrophthalic acid substituent compound can be selected from a variety of commercially available products, and its price is relatively low. By compounding it with the substituted 2,6-dicarboxylate-4-pyranone compound, the catalyst's hydrogen-modified sensitivity can be improved while simultaneously reducing raw material costs to some extent. Furthermore, ternary compounding of the substituted 2,6-dicarboxylate-4-pyranone compound with a tetrahydrophthalic acid substituent compound and a diether compound can further enhance the catalyst's polymerization activity. Detailed Implementation

[0085] The technical solution of the present invention will now be described in detail with reference to embodiments thereof. Obviously, the described embodiments are only a part of the implementation of the present invention, and not all of them.

[0086] In the examples, the catalyst preparation operations were all carried out under the protection of high-purity nitrogen.

[0087] Polymer isotacticity determination: The heptane extraction method was used (boiling heptane extraction for 6 hours). Two grams of dried polymer sample were placed in an extractor and extracted with boiling heptane for 6 hours. The residue was dried to constant weight. The ratio of the polymer weight (g) obtained to 2 is the isotacticity.

[0088] The melt index of the polymer was determined using the GB / T 3682-2000 method.

[0089] The bulk density of the polymer was determined using the method specified in GB / T 1636-2008.

[0090] Synthesis of substituted 2,6-dicarboxylate-4-pyranone compounds represented by general formula (I)

[0091] Preparation Example 1: Synthesis of di-n-butyl 2,6-dicarboxylate-4-pyranone

[0092] Sodium (11.8 g, 0.5 mol, 2.04 eq.) was dissolved in anhydrous ethanol (180 mL). A mixture of anhydrous acetone (14.5 g, 19 mL, 0.25 mol, 1 eq.) and diethyl oxalate (77.5 g, 72 mL, 0.53 mol, 2.12 eq.) was added to the previous solution over 15 minutes. A yellow precipitate formed. The reaction mixture was kept at 60 °C for one hour. Then, HCl (aq. 37%, 100 mL) and water (50 mL) were added, and the solution was stirred at 50 °C for 20 hours. The mixture of water and ethanol (approximately 230 mL) was removed under reduced pressure. A mixture of water (150 mL) and HCl (aq. 37%, 25 mL) was then added to this mixture, and stirring was continued until silica gel TLC (elution buffer: 3 / 7 (v / v) 10% NaCl aqueous solution / ethanol) showed only one spot. After cooling to room temperature, the crystals were filtered out, washed first with water, and then with cold acetone. The crude product was recrystallized to give a white powder, 4-pyranone-2,6-dicarboxylic acid (35.0 g, yield: 76%).

[0093] In a 1L three-necked flask, add 5.5g of 4-pyranone-2,6-dicarboxylic acid, 100mL of n-butanol, and 0.6mL of concentrated sulfuric acid; heat under reflux for 2 hours; cool to room temperature; pour the reaction solution into a saturated sodium bicarbonate solution, extract twice with ethyl acetate (100mL*2), combine the organic phases, wash with saturated brine (100mL*2), concentrate and recrystallize to give the product (7.1g, yield 79%). 1 H NMR (500MHz, Chloroform-d) δ / ppm: 6.81 (s, 2H), 4.14 (t, J = 8.7Hz, 4H), 1.77 (p, J = 8.9Hz, 4H), 1.52–1.41 (m, 4H), 0.97 (t, J = 5.6Hz, 6H).

[0094] Preparation Examples 2-9: Synthesis of substituted 2,6-dicarboxylate-4-pyranone compounds

[0095] Using one of the aforementioned routes, the starting material is selected from oxalic acid or diethyl oxalate, which undergoes an addition reaction with acetone or other ketones, followed by esterification with one or two alcohols to obtain the corresponding substituted 2,6-dicarboxylate-4-pyranone products. The structures and NMR results of other compounds are shown in Table 1.

[0096]

[0097] Table 1. Preparation Examples 1-9: Substituted 2,6-dicarboxylate-4-pyranone compounds

[0098]

[0099]

[0100] Tetrahydro-o-phenyl substituents of formula (II) are derived from commercially available products. :

[0101] b1: Dimethyl trans-4-cyclohexene-1,2-dicarboxylate (CAS No. 4841-84-3);

[0102] b2: Diethyl trans-4-cyclohexene-1,2-dicarboxylate (CAS No. 5048-50-0);

[0103] b3: Diglycidyl tetrahydrophthalate (CAS No. 21544-03-6);

[0104] b4: Tetrahydrophthalic anhydride (CAS No. 85-43-8);

[0105] b5: cis-1,2,3,6-tetrahydrophthalic anhydride (CAS No. 935-79-5);

[0106] b6: Methyltetrahydrophthalic anhydride (CAS No. 11070-44-3);

[0107] b7: 4-Methyltetrahydrophthalic anhydride (CAS No. 3425-89-6);

[0108] b8: 1,2,3,6-Tetrahydrophthalimide (CAS No. 85-40-5).

[0109] The following tetrahydro-ophthalic substituents of general formula (II) are prepared by a one-step esterification reaction of trans-4-cyclohexene-1,2-dicarboxylic acid:

[0110] b9: di-n-butyl trans-4-cyclohexene-1,2-dicarboxylate;

[0111] b10: trans-4-cyclohexene-1,2-dicarboxylic acid diphenyl ester;

[0112] b11: trans-4-cyclohexene-1,2-dicarboxylic acid dibenzyl ester.

[0113] Internal electron donor C compounds:

[0114] c1: 2-Isopropyl-2-isopentyl-1,3-dimethoxypropane;

[0115] c2: 9,9-bis(methoxymethyl)fluorene.

[0116] DNBP It is di-n-butyl phthalate.

[0117] Catalyst preparation

[0118] Example 1

[0119] In a 500 mL stirred flask fully purged with nitrogen, 10 g of MgCl2·2.5C2H5OH microspheres and 150 mL of titanium tetrachloride were added to prepare a suspension. The suspension was then maintained at -15 °C for 1 hour, and slowly heated to 80 °C. 7 mmol of di-n-butyl 2,6-dicarboxylate-4-pyranone (a1) and 3 mmol of trans-4-cyclohexene-1,2-dicarboxylate (b2) were added, and the temperature was further increased to 110 °C and held constant for 1 hour. The liquid was then filtered off, and the resulting solid was washed three times with 120 mL of titanium tetrachloride at 125 °C. The resulting solid was then washed four times with 150 mL of hexane at 60 °C, the liquid was filtered off, and the solid was dried to obtain the solid catalyst component Cat-1.

[0120] Example 2-38

[0121] The preparation process of the solid catalyst components is as shown in Example 1, except that the internal electron donors are fed according to the internal electron donor compound numbers and feed ratios in Table 2.

[0122] Comparative Examples 1-6

[0123] The solid catalyst component preparation process is the same as in Example 1, except that the internal electron donor is fed according to the internal electron donor compound number and feed ratio in Table 2.

[0124] polymerization:

[0125] After purging the 5L stainless steel reactor with nitrogen, 5mL of a 0.5mol / L triethylaluminum hexane solution, 1mL of a 0.1mol / L methylcyclohexyldimethoxysilane hexane solution, and 10mg of the prepared catalyst were added. Then, 10mL of hexane was added to flush the feed line, followed by 5L (under standard conditions) of hydrogen and 2.5L of purified propylene. The reaction was prepolymerized at 25℃ for 5 minutes, then the temperature was raised to 70℃, and polymerization was carried out at this temperature for 1 hour. After the reaction, the reactor was cooled and stirring was stopped, and the reaction product was discharged and dried to obtain the polymer. Polymerization data are shown in Table 1.

[0126] Table 2 Results of different compound formulations under the same polymerization conditions

[0127]

[0128]

[0129]

[0130] As can be seen from Table 2, the activity of catalysts prepared by combining two or more internal electron donor compounds is significantly improved during polymerization.

[0131] This invention is not limited to the specific embodiments described above. Any changes or modifications made by those skilled in the art within the scope of this invention are covered by the patent scope of this invention.

Claims

1. A solid catalyst component for olefin polymerization, characterized in that, The mixture comprises Mg, Ti, halogens, an internal electron donor a compound, and an internal electron donor b compound, wherein the molar ratio of internal electron donor a compound to internal electron donor b compound is greater than or equal to 2:8; the internal electron donor a compound is selected from compounds of general formula (I). General Formula (I) In general formula (I), R 1 R 2 R 3 and R 4 Whether the elements are the same or different, they are each independently selected from H, halogens, and C1-C. 20 Hydrocarbon group, or C1-C containing at least one heteroatom selected from N, O and halogen. 20 Group; Alternatively, R in general formula (I) can be chosen as follows: 1 R 2 R 3 and R 4 Two or more of them form a ring through mutual bonding; The internal electron donor b compound is selected from tetrahydro-ophthalic substituents of general formula (II): General Formula (II) In general formula (II), R 5 -R 8 Whether the two are the same or different, they are each independently selected from H, C1-C. 20 Alkyl group; R 9 and R 10 Whether the substituents are the same or different, they are each independently selected from substituents containing oxygen or nitrogen functional groups.

2. The solid catalyst component for olefin polymerization according to claim 1, characterized in that, R in general formula (II) 9 and R 10 They are interconnected to form rings containing oxygen or nitrogen functional groups.

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

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

5. The solid catalyst component for olefin polymerization according to claim 1, characterized in that, R in general formula (I) 1 R 2 R 3 and R 4 Whether the groups are the same or different, each is independently selected from H, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 ~C 20 The following substituents with 20 or fewer carbon atoms, whether straight-chain or branched alkyl groups: 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, pyrroleyl, indene.

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

7. The solid catalyst component for olefin polymerization according to claim 1, characterized in that, The internal electron donor compound a is selected from di-n-butyl 2,6-dicarboxylate-4-pyranone, diethyl 2,6-dicarboxylate-4-pyranone, diisobutyl 2,6-dicarboxylate-4-pyranone, dicyclohexyl 2,6-dicarboxylate-4-pyranone, di(tetradecyl) 2,6-dicarboxylate-4-pyranone, diphenyl 2,6-dicarboxylate-4-pyranone, diphenylethyl 2,6-dicarboxylate-4-pyranone, di-m-chlorophenyl 2,6-dicarboxylate-4-pyranone, di-p-chlorophenyl 2,6-dicarboxylate-4-pyranone, di-o-chlorophenyl 2,6-dicarboxylate-4-pyranone, and di-p-methylphenyl 2,6-dicarboxylate-4-pyranone. At least one of the following: di-m-methoxyphenyl 2,6-dicarboxylate-4-pyranone, di-p-methoxyphenyl 2,6-dicarboxylate-4-pyranone, di-o-methoxyphenyl 2,6-dicarboxylate-4-pyranone, difuranmethyl 2,6-dicarboxylate-4-pyranone, dipentenyl 2,6-dicarboxylate-4-pyranone, di-p-nitrophenyl 2,6-dicarboxylate-4-pyranone, di-n-butyl 2,6-dicarboxylate-3,5-dimethyl-4-pyranone, diethyl 2,6-dicarboxylate-3-phenyl-4-pyranone, diethyl 2,6-dicarboxylate-3-chloro-4-pyranone, and diethyl 2,6-dicarboxylate-3-bromo-4-pyranone.

8. The solid catalyst component for olefin polymerization according to claim 1, characterized in that, R in the tetrahydro-ophthalic substituent compound of the internal electron donor b compound of general formula (II) 9 and R 10 It can be a formate ester substituent or linked to an acid anhydride or formimide.

9. The solid catalyst component for olefin polymerization according to claim 1, characterized in that, The tetrahydro-ophthalic substituent compound of general formula (II) is selected from dimethyl trans-4-cyclohexene-1,2-dicarboxylate, diethyl trans-4-cyclohexene-1,2-dicarboxylate, di-n-propyl trans-4-cyclohexene-1,2-dicarboxylate, diisopropyl trans-4-cyclohexene-1,2-dicarboxylate, di-n-butyl trans-4-cyclohexene-1,2-dicarboxylate, diisobutyl trans-4-cyclohexene-1,2-dicarboxylate, dipentyl trans-4-cyclohexene-1,2-dicarboxylate, and trans-4-cyclohexene-1,2-dicarboxylate. - At least one of the following: di-n-hexyl dicarboxylate, trans-4-cyclohexene-1,2-dicarboxylate, trans-4-cyclohexene-1,2-dicarboxylate, trans-4-cyclohexene-1,2-dicarboxylate, trans-4-cyclohexene-1,2-dicarboxylate, dibenzyl trans-4-cyclohexene-1,2-dicarboxylate, diglycidyl tetrahydrophthalic acid, tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, and 1,2,3,6-tetrahydrophthalimide.

10. The solid catalyst component for olefin polymerization according to claim 1, characterized in that, The solid catalyst component also contains an internal electron donor compound c, which is selected from 1,3-diether compounds of general formula (III): General Formula (III) In general formula (III), R 11 -R 16 Whether the same or different, each is independently selected from H, and each is independently selected from straight-chain or branched alkyl, cycloalkyl, aryl, alkylaryl, or aralkyl groups containing 1-18 carbon atoms; R 17 -R 18 They may be the same or different, each independently selected from straight-chain or branched alkyl groups of 1-20 carbon atoms, cycloalkyl groups of 3-20 carbon atoms, phenyl groups, alkylaryl and aralkyl groups of 7-20 carbon atoms, or R 11 -R 18 One or more groups in the compound link together to form a cyclic structure.

11. The solid catalyst component for olefin polymerization according to claim 10, characterized in that, The diether compounds are selected from the diether compounds represented by general formula (IV): General Formula (IV) In general formula (IV), R 25 -R 32 They may be the same or different, each independently selected from hydrogen, halogen, straight-chain or branched alkyl groups of 1-20 carbon atoms, cycloalkyl groups of 3-20 carbon atoms, aryl groups of 6-20 carbon atoms, alkylaryl groups of 7-20 carbon atoms, and arylalkyl groups of 7-20 carbon atoms; R 19 -R 22 Whether the groups are the same or different, each is independently selected from H, or each is independently selected from straight-chain or branched alkyl, cycloalkyl, aryl, alkylaryl, or aralkyl groups containing 1-18 carbon atoms; R 23 and R 24 Whether identical or different, each independently selected from straight-chain or branched alkyl groups of 1-20 carbon atoms, cycloalkyl groups of 3-20 carbon atoms, aryl groups of 5-20 carbon atoms, alkylaryl and aralkyl groups of 7-20 carbon atoms, or R 19 -R 32 One or more groups in the compound link together to form a cyclic structure.

12. The solid catalyst component for olefin polymerization according to claim 10, characterized in that, The molar ratio of the internal electron donor compound a, internal electron donor compound b, and internal electron donor compound c is (internal electron donor compound a + internal electron donor compound b): internal electron donor compound c ≥ 2:

8.

13. The solid catalyst component for olefin polymerization according to claim 12, characterized in that, The molar ratio of the internal electron donor compound a, internal electron donor compound b, and internal electron donor compound c is (internal electron donor compound a + internal electron donor compound b): internal electron donor compound c ≥ 5:

5.

14. The solid catalyst component for olefin polymerization according to claim 13, characterized in that, The molar ratio of the internal electron donor compound a, internal electron donor compound b, and internal electron donor compound c is (internal electron donor compound a + internal electron donor compound b): internal electron donor compound c ≥ 8:

2.

15. The solid catalyst component for olefin polymerization according to claim 1, characterized in that, The catalyst components comprise titanium compounds, magnesium compounds, and internal electron donor compounds; The precursor of the magnesium compound is selected from X. n Mg(OR a ) 2-n MgCl2·mR a OH, R a 2-n MgX n At least one of the following: a mixture of MgCl2 / SiO2, MgCl2 / Al2O3, magnesium halide, and titanium alkoxide, wherein m is 0.1-6, 0≤n≤2, X is a halogen, and R a For C1-C 20 hydrocarbon group; The general formula of the titanium compound is TiX. N (OR b ) 4-N In the formula, R b For C1-C 20 The hydrocarbon group, where X is a halogen and N is 1-4.

16. The solid catalyst component for olefin polymerization according to claim 15, characterized in that, The magnesium compound is an alkoxide of magnesium dihalide; Alternatively, the magnesium compound may be a liquid magnesium compound; Alternatively, the magnesium compound is a derivative in which at least one halogen atom in a magnesium dihalide molecule is replaced by an alkyl or haloalkyl group.

17. The solid catalyst component for olefin polymerization according to claim 15, characterized in that, The titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and titanium alkoxyhalide.

18. The solid catalyst component for olefin polymerization according to claim 17, characterized in that, The alkoxy titanium halide includes at least one of methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, and tri-n-butoxy titanium chloride.

19. The solid catalyst component for olefin polymerization according to claim 15, characterized in that, The total amount of the internal electron-donating compounds and the molar ratio of the magnesium compounds are 0.01-5.0, and the magnesium compounds are calculated in terms of magnesium element.

20. A catalyst for olefin polymerization, wherein the feedstock comprises the catalyst component as described in any one of claims 1-19 and an organoaluminum compound.

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

22. The catalyst according to claim 20, characterized in that, The organoaluminum compounds include at least one of trialkylaluminum compounds, alkylaluminum halides, alkylaluminum hydrides, alkylaluminum sesquichlorides, and alkylaluminoxanes.

23. The catalyst according to claim 20, characterized in that, The molar ratio of the organoaluminum compound to the titanium atoms in the catalyst component is 1-1000:

1.

24. The catalyst according to claim 20, characterized in that, The catalyst's raw material composition also includes an external electron donor; the external electron donor is a siloxane compound.

25. The catalyst according to claim 24, characterized in that, The general formula of the siloxane compound is R' t Si(OR'') 4-t Where R' and R'' are each independently selected from C1-C 18 The hydrocarbon group, where t is an integer 0 ≤ t ≤ 3.

26. The catalyst according to claim 24, characterized in that, The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100.

27. The use of the catalyst according to any one of claims 20-26 in olefin polymerization.

28. The application according to claim 27, characterized in that, The olefins include at least one of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, butadiene, vinylcyclopentene, and vinylcyclohexene. The polymerization includes homopolymerization or copolymerization; The polymerization temperature is ≤200℃; the polymerization pressure is ≤10MPa.

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