Catalyst component for olefin polymerization, catalyst and application thereof

Abstract

The invention provides a catalyst component for olefin polymerization, a catalyst and application thereof. The catalyst component is prepared from the following components: Mg, Ti, halogen, a 2, 6-dicarboxylate-4-pyrone internal electron donor and a Lewis alkali internal electron donor, wherein the 2, 6-diformic acid-4-pyrone internal electron donor has a structure as shown in a formula I: # imgabs0 #, the catalyst component and the catalyst have high catalytic activity, and polypropylene obtained through catalytic polymerization has relatively high bulk density and high isotacticity; when the catalyst is used for propylene polymerization, low-ash polymers can be obtained when the Al / Ti ratio is reduced.

Description

Technical Field

[0001] The 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 in propylene polymerization reaction, and belongs to the field of polyolefin catalysts. Background Art

[0002] At present, Ziegler-Natta catalysts (ZN catalysts) still occupy a dominant position in polyolefin production. The development focus of most ZN catalysts is on the development of highly active 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 a magnesium-containing carrier), the polymer produced has good comprehensive performance and low cost. At present, most catalysts for producing polypropylene in the world are still based on ZN catalytic systems, which are characterized by high activity, high stereoregularity, long life and customized product structure. From the development process of ZN catalysts, it can be seen that as early as the emergence of the first generation of catalysts, it was found that adding a third component (mostly electron donors, also known as Lewis bases, among which those added during the catalyst preparation process are called internal electron donors, and those added during the polymerization process are called external electron donors) 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 spot in the research and development of ZN polypropylene 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, compounds disclosed in EP0361493 and EP0728724); (3) succinate compounds (for example, compounds disclosed in WO9856834, WO0063261, and WO03022894); (4) glycol ester compounds (for example, compounds disclosed in WO9856834, WO0063261, and WO03022894); (5) compounds with other functional groups (for example, compounds disclosed in CN1105671, CN1242780, and US20060128558), etc. However, in practical applications, the above compounds have certain problems as internal electron donors for olefin polymerization catalysts. Although the catalyst using 1,3-diether compounds as internal electron donors has high activity and good catalyst hydrogen adjustment sensitivity, the relative molecular mass distribution of the prepared 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 adjustment 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. CN102325808 discloses a precatalyst composition containing a phenylene aromatic diester internal electron donor, which has low activity, and the xylene soluble content of the obtained polymer is still high when a silane external electron donor is used, indicating that the catalyst has poor stereoselectivity for propylene.

[0004] At present, the most widely used polyolefin internal electron donor in industry is phthalate compounds, which have medium catalyst activity, good stereoselectivity and low price. However, phthalate compounds, as commonly used plasticizers, have great harm to human reproductive health and the environment, and there is a great demand for replacement. At present, the use of most phthalate substances has been restricted. Therefore, it is one of the common research and development goals in the field of polyolefin catalysts in recent years to develop a new electron donor with excellent activity, good stereospecificity, good comprehensive performance and low cost to replace the phthalate electron donor compounds widely used in the prior art and apply them to the preparation of efficient Ziegler-Natta catalysts.

[0005] When the catalyst prepared by a single internal electron donor cannot meet the specific requirements of polypropylene products, such as requiring the catalyst to have the characteristics of high activity, high stereospecificity and high hydrogen sensitivity, the compounding of multiple internal electron donors is an effective method to solve this problem, that is, when preparing the ZN catalyst, two or more internal electron donors are used at the same time, and the comprehensive performance of the ZN catalyst is adjusted by adjusting the content of different internal electron donors in the ZN catalyst. CN101724102 discloses a catalyst component prepared by compounding an internal electron donor diol ester compound and a 1,3-diether compound and using a magnesium chloride alcohol adduct carrier. The catalyst has high activity, but is only equivalent to a 1,3-diether electron donor catalyst, and in order to maintain a high isotacticity, a silane external electron donor is still required. Summary of the invention

[0006] In order to solve the above problems, the purpose of the present invention is to provide a catalyst component, a catalyst and its application for olefin polymerization, the catalyst component and the catalyst have high catalytic activity, and the polypropylene obtained by catalytic polymerization has a high bulk density and high isotacticity; when used for propylene polymerization, when the Al / Ti ratio is reduced, a low ash polymer can be obtained.

[0007] In order to achieve the above object, the present invention provides a catalyst component for olefin polymerization, which comprises: Mg, Ti, halogen, 2,6-dicarboxylic acid ester-4-pyrone internal electron donor and Lewis base internal electron donor; wherein the 2,6-dicarboxylic acid ester-4-pyrone internal electron donor has a structure shown in formula I:

[0008]

[0009] In Formula I, R 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 Each of the above mentioned heteroatoms contains one or more heteroatoms selected from N, O, S, P, Si and halogen; more preferably, R 1 , R 2 , R 3 and R 4 Two or more of them are bonded to each other to form a ring;

[0010] The Lewis base internal electron donor comprises one or more electronegative groups, and the electron donating atom of the Lewis base internal electron donor is selected from one or a combination of two or more of N, O, S, P, As or Sn; preferably, the Lewis base internal electron donor comprises one or a combination of two or more of a diether electron donor compound, an ester electron donor compound, a diketone electron donor compound and a diamine electron donor compound.

[0011] According to a specific embodiment of the present invention, preferably, in Formula I, R 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 alkyl, alkyl containing heteroatoms, halogenated cycloalkyl, cycloalkyl containing heteroatoms, halogenated phenyl, phenyl containing heteroatoms, halogenated alkylphenyl, alkylphenyl containing heteroatoms, halogenated phenylalkyl, phenylalkyl containing heteroatoms, halogenated indenyl, indenyl containing heteroatoms, halogenated benzyl, benzyl containing heteroatoms, heterocyclic aromatic substituents; the heteroatoms include one or a combination of two or more of N, O, S, P, and Si.

[0012] According to a specific embodiment of the present invention, preferably, in Formula I, R 1 , R 2 , R 3 and R 4 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 The straight chain or branched alkyl group of 20 carbon atoms or the following substituents within 20 carbon atoms: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, benzyl and its derivatives, phenethyl and its derivatives, furyl, pyrrolyl, thienyl and indenyl; more preferably, the alkenyl group includes propenyl, butenyl, pentenyl and hexenyl.

[0013] According to a specific embodiment of the present invention, preferably, the 2,6-dicarboxylic acid ester-4-pyrone internal electron donor includes 2,6-dicarboxylic acid di-n-butyl ester-4-pyrone, 2,6-dicarboxylic acid diethyl ester-4-pyrone, 2,6-dicarboxylic acid diisobutyl ester-4-pyrone, 2,6-dicarboxylic acid dicyclohexyl ester-4-pyrone, 2,6-dicarboxylic acid di (tetradecyl) ester-4-pyrone, 2,6-dicarboxylic acid diphenyl ester-4-pyrone, 2,6- 2,6-dicarboxylic acid diphenyl ethyl ester-4-pyrone, 2,6-dicarboxylic acid di-m-chlorophenyl ester-4-pyrone, 2,6-dicarboxylic acid di-p-chlorophenyl ester-4-pyrone, 2,6-dicarboxylic acid di-o-chlorophenyl ester-4-pyrone, 2,6-dicarboxylic acid di-p-methylphenyl ester-4-pyrone, 2,6-dicarboxylic acid di-m-methoxyphenyl ester-4-pyrone, 2,6-dicarboxylic acid di-p-methoxyphenyl ester-4-pyrone, 2,6-dicarboxylic acid di-o-methoxyphenyl ester-4-pyrone, 2, 2,6-dicarboxylic acid di(α-furanylmethyl)-4-pyrone, 2,6-dicarboxylic acid di(5-pentenyl)-4-pyrone, 2,6-dicarboxylic acid di-p-nitrophenyl-4-pyrone, 2,6-dicarboxylic acid di-n-butyl-4-pyrone, 2,6-dicarboxylic acid di-n-butyl-3,5-dimethyl-4-pyrone, 2,6-dicarboxylic acid diethyl-3-phenyl-4-pyrone, 2,6-dicarboxylic acid diethyl-3-chloro ... One or a combination of two or more of diethyl 2,6-dicarboxylate-3-bromo-4-pyrone, diisopropyl 2,6-dicarboxylate-4-pyrone, dibenzyl 2,6-dicarboxylate-4-pyrone, ethyl 2-carboxylate-6-n-butyl carboxylate-4-pyrone, ethyl 2-carboxylate-6-phenyl carboxylate-4-pyrone, di-n-butyl 2,6-dicarboxylate-3-methyl-4-pyrone, and di-n-butyl 2,6-dicarboxylate-3-methyl-5-ethyl-4-pyrone.

[0014] The 2,6-dicarboxylate-4-pyrone compound shown in Formula I can be synthesized by the following preparation methods including but not limited to:

[0015] The synthetic route is shown in Reaction Formula I. Esterification of oxalic acid is performed to obtain the corresponding oxalic acid diester (part of the oxalic acid diester can be purchased directly), and then the corresponding product can be obtained by reacting with acetone or other substituted ketones.

[0016] Reaction formula Ⅰ:

[0017]

[0018] It can also be prepared by a synthetic route as shown in reaction formula II. The raw materials used in this route are cheap diethyl oxalate and acetone or other substituted ketones, which are then reacted with an alcohol to obtain a substituted 2,6-dicarboxylate-4-pyrone compound. Only two steps are required to obtain the target product, and a variety of alcohols R can be selected. 1OH to enrich the product structure; or react with a mixture of two alcohols (the synthesis route is shown in Reaction Formula III) to obtain a mixture of three substituted 2,6-dicarboxylic acid ester-4-pyrone, which can be directly used as an internal electron donor without separation. The ratio of each component in the mixture can be adjusted by the addition ratio of the two alcohols in the reactants, and the ratio of each component can be characterized and determined by analytical methods such as chromatography-mass spectrometry technology and nuclear magnetic resonance. In addition, the product of the first step, 2,6-dicarboxylic acid-4-pyrone (CAS No.: 99-32-1), can also be directly purchased, and 2,6-dicarboxylic acid ester-4-pyrone can be obtained through a one-step esterification reaction;

[0019] Reaction formula II:

[0020]

[0021] Reaction formula III:

[0022]

[0023] According to a specific embodiment of the present invention, preferably, the Lewis base internal electron donor comprises a 1,3-diether compound, and the 1,3-diether compound has a structure shown in Formula II:

[0024]

[0025] In formula II, R 5 , R 6 , R 7 , R 8 , R 9 and R 10 The same or different, each independently selected from H, C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C5-C 20 Aryl, C7-C 20 Alkyl or C7-C 20 Aralkyl; R 11 and R 12 The same or different, each independently selected from C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C5-C 20 Aryl, C7-C 20 Alkyl and C7-C 20 Preferably, R 5 -R 12 One or more groups in the ring are linked to form a ring structure; preferably, R 5 -R 12 Each of the heteroatoms contains one or a combination of two or more selected from halogen, N, O, S, P and Si.

[0026] According to a specific embodiment of the present invention, preferably, the 1,3-diether compound has a structure shown in Formula III:

[0027]

[0028] In formula III, the eight R 19 are the same or different, each independently selected from hydrogen, halogen, C1-C 14 Straight or branched alkyl, C3-C 14 Cycloalkyl, C6-C 14 Aryl, C7-C 14 Alkyl aryl, C7-C 14 of arylalkyl.

[0029] According to a specific embodiment of the present invention, preferably, eight R 19 Each of the heteroatoms contains one or a combination of two or more selected from N, O, S, P, Si and halogen.

[0030] According to a specific embodiment of the present invention, preferably, R 13 , R 14 , R 15 and R 16 The same or different, each independently selected from H, C1-C 18 Straight or branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl or C7-C 20 Aralkyl; R 17 and R 18 The same or different, each independently selected from C1-C 20 Straight chain or branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl and C7-C 20 Preferably, R 13 -R 18 One or more groups in the ring are linked to form a ring structure.

[0031] According to a specific embodiment of the present invention, preferably, R 13 -R 18 Each of the heteroatoms contains one or a combination of two or more selected from halogen, N, O, S, P and Si.

[0032] According to a specific embodiment of the present invention, preferably, the 1,3-diether compound includes 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 Methoxypropane, 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, 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-isopropyl-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)- 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)- 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)- (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)-1,2,3,4,5,6,7,8-octahydrofluorene, 9,9-bis(methoxymethyl)-4-tert-butylfluorene, or a combination of two or more thereof.

[0033] According to a specific embodiment of the present invention, preferably, the Lewis base internal electron donor includes a carboxylate compound, and the carboxylate compound includes a monocarboxylate compound and / or a polycarboxylate compound; more preferably, the polycarboxylate compound includes an aromatic dicarboxylate compound and / or an aliphatic chain dicarboxylate compound.

[0034] According to a specific embodiment of the present invention, preferably, the aromatic dicarboxylic acid ester compound includes a phthalic acid diester compound and / or a terephthalic acid diester compound; the phthalic acid diester compound includes dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, methyl phthalate phthalate, ethyl ester, methyl isopropyl phthalate, methyl n-propyl phthalate, ethyl n-butyl phthalate, ethyl isobutyl phthalate, di-n-pentyl phthalate, di-isopentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, di-isooctyl phthalate, di(2,2-dimethylhexyl) phthalate, di(2- phthalate, di-n-nonyl phthalate, di-isodecyl phthalate, di(2,2-dimethylheptyl) phthalate, n-butyl isohexyl phthalate, n-butyl (2-ethylhexyl) phthalate, n-pentyl-n-hexyl phthalate, n-pentyl isononyl phthalate, isopentyl-n-decyl phthalate, n-pentyl undecyl phthalate, isopentyl isononyl phthalate, Hexyl ester, n-hexyl (2-methylhexyl) phthalate, n-hexyl (2-ethylhexyl) phthalate, n-hexyl isononyl phthalate, n-hexyl n-decyl phthalate, n-heptyl (2-ethylhexyl) phthalate, n-heptyl isononyl phthalate, n-heptyl neononyl phthalate, and (2-ethylhexyl) isononyl phthalate, or a combination of two or more thereof;The terephthalic acid diester compounds include dimethyl terephthalate, diethyl terephthalate, di-n-propyl terephthalate, diisopropyl terephthalate, di-n-butyl terephthalate, diisobutyl terephthalate, ethyl methyl terephthalate, methyl isopropyl terephthalate, ethyl n-propyl terephthalate, ethyl n-butyl terephthalate, ethyl isobutyl terephthalate, di-n-pentyl terephthalate, diisopentyl terephthalate, dihexyl terephthalate, di-n-heptyl terephthalate, Di-n-octyl terephthalate, di-isooctyl terephthalate, bis (2,2-dimethylhexyl) terephthalate, bis (2-ethylhexyl) terephthalate, di-n-nonyl terephthalate, di-isononyl terephthalate, di-isodecyl terephthalate, bis (2,2-dimethylethylheptyl) terephthalate, n-butyl isohexyl terephthalate, n-butyl (2-ethylhexyl) terephthalate, n-pentyl-n-hexyl terephthalate, n-pentyl isohexyl terephthalate, isopentylheptyl terephthalate, n-butyl terephthalate One or two of amyl (2-ethylhexyl) ester, n-amyl isononyl terephthalate, isopentyl n-decyl terephthalate, n-amyl undecyl terephthalate, isopentyl isohexyl terephthalate, n-hexyl (2-ethylhexyl) terephthalate, n-hexyl isononyl terephthalate, n-hexyl n-decyl terephthalate, n-heptyl (2-ethylhexyl) terephthalate, n-heptyl isononyl terephthalate, n-heptyl neodecyl terephthalate, and (2-ethylhexyl) isononyl terephthalate More preferably, the aromatic dicarboxylic acid ester compound includes one or a combination of two or more of diethyl phthalate, propyl 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-isooctyl terephthalate, di(2-ethylhexyl) terephthalate and diisodecyl phthalate. ;

[0035] According to a specific embodiment of the present invention, preferably, the Lewis base internal electron donor comprises a succinate compound, and the succinate compound has a structure shown in Formula IV:

[0036]

[0037] In Formula IV, R 20 and R 21 The same or different, each independently selected from C1-C 20 Straight or branched alkyl, C2-C 20 Alkenyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C20 Aralkyl, C7-C 20 Preferably, R 20 and R 21 Each contains a heteroatom; R 22 -R 25 Each independently selected from hydrogen, C1-C 20 Straight or branched alkyl, C2-C 20 Alkenyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Aralkyl, C7-C 20 Preferably, R 22 -R 25 bonded to each other to form a ring; preferably, R 22 -R 25 Each of the heteroatoms contains heteroatoms; preferably, the heteroatoms include one or a combination of two or more of N, O, S, P, Si, and halogen.

[0038] According to a specific embodiment of the present invention, preferably, R 20 and R 21 Each is independently selected from C1-C8 alkyl, C3-C8 cycloalkyl, C6-C8 aryl, C7-C8 aralkyl, C7-C8 alkaryl; preferably, R 20 and R 21 Each is independently selected from a linear primary alkyl group or a branched primary alkyl group; preferably, R 20 and R 21 Each is independently selected from methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, and 2-ethylhexyl, and more preferably selected from ethyl, isobutyl, and neopentyl.

[0039] According to a specific embodiment of the present invention, preferably, in Formula IV, R 22 -R 24 is hydrogen, R 25 Selected from C3-C 10 Branched alkyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Aralkyl, C7-C 10 The alkylaryl group, R 25 Preferably selected from C3-C 10 Branched primary alkyl, C3-C 10 of a cycloalkyl group.

[0040] According to a specific embodiment of the present invention, preferably, the monosubstituted succinate compound includes diethyl sec-butyl succinate, diethyl hexyl succinate, diethyl cyclopropyl succinate, diethyl norbornyl succinate, diethyl methoxy succinate, diethyl p-methoxyphenyl succinate, diethyl p-chlorophenyl succinate, diethyl phenyl succinate, diethyl cyclohexyl succinate, diethyl benzyl succinate, diethyl tert-butyl succinate, diethyl isobutyl succinate, diethyl isopropyl succinate, diethyl methoxy succinate, diethyl p-methoxyphenyl succinate, diethyl p-chlorophenyl succinate, diethyl phenyl succinate, diethyl cyclohexyl succinate, diethyl benzyl succinate, diethyl tert-butyl succinate, diethyl isobutyl succinate, diethyl isopropyl diethyl succinate, diethyl neopentyl succinate, diethyl isopentyl succinate, diethyl (1-trifluoromethylethyl) succinate, diethyl fluorenyl succinate, diisobutyl sec-butyl succinate, diisobutyl hexyl succinate, diisobutyl cyclopropyl succinate, diisobutyl norbornyl succinate, diisobutyl trimethylsilyl succinate, diisobutyl methoxy succinate, diisobutyl p-methoxyphenyl succinate, diisobutyl p-chlorophenoxy succinate, cyclohexyl Diisobutyl succinate, diisobutyl benzyl succinate, diisobutyl tert-butyl succinate, diisobutyl isobutyl succinate, diisobutyl isopropyl succinate, diisobutyl neopentyl succinate, diisobutyl isopentyl succinate, diisobutyl (1-trifluoromethylethyl) succinate, diisobutyl fluorenyl succinate, dineopentyl sec-butyl succinate, dineopentyl hexyl succinate, dineopentyl cyclopropyl succinate, dineopentyl norbornyl succinate, trimethylsilyl succinate The invention can be selected from the group consisting of dineopentyl succinate, dineopentyl methoxysuccinate, dineopentyl p-chlorophenylsuccinate, dineopentyl phenylsuccinate, dineopentyl cyclohexylsuccinate, dineopentyl benzylsuccinate, dineopentyl tert-butylsuccinate, dineopentyl isobutylsuccinate, dineopentyl isopropylsuccinate, dineopentyl neopentylsuccinate, dineopentyl isopentylsuccinate, dineopentyl (1-trifluoromethylethyl)succinate, and dineopentyl fluorenylsuccinate, or a combination of two or more thereof.

[0041] According to a specific embodiment of the present invention, preferably, in Formula IV, R 22 -R 25 At least two of the groups are different from hydrogen and are each independently selected from C1-C 20 Straight or branched alkyl, C2-C 20 Alkenyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Aralkyl, C7-C 20 Preferably, R 22 -R 25 Contain heteroatoms.

[0042] According to a specific embodiment of the present invention, preferably, R 22 -R 25 The two non-hydrogen groups in a compound are attached to the same carbon atom.

[0043] According to a specific embodiment of the present invention, preferably, the disubstituted succinate compounds include diethyl 2,2-dimethylsuccinate, diethyl 2-ethyl-2-methylsuccinate, diethyl 2-benzyl-2-isopropylsuccinate, diethyl 2-cyclohexylmethyl-2-isobutylsuccinate, diethyl 2-cyclopentyl-2-n-butylsuccinate, diethyl 2,2-diisobutylsuccinate, diethyl 2-cyclohexyl-2-ethylsuccinate, diethyl 2-isopropyl-2-methylsuccinate, diethyl 2-tetradecyl-2-ethylsuccinate, diethyl 2-isobutyl- Diethyl 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 2,2-diisobutylsuccinate, 2-cyclohexyl-2-ethylsuccinate 2-isobutyl succinate, diisobutyl 2-isopropyl-2-methylsuccinate, diisobutyl 2-tetradecyl-2-ethylsuccinate, diisobutyl 2-isobutyl-2-ethylsuccinate, diisobutyl 2-(1-trifluoromethylethyl)-2-methylsuccinate, diisobutyl 2-isopentyl-2-isobutylsuccinate, diisobutyl 2-phenyl-2-n-butylsuccinate, dineopentyl 2,2-dimethylsuccinate, dineopentyl 2-ethyl-2-methylsuccinate, dineopentyl 2-benzyl-2-isopropylsuccinate, 2-cyclohexylmethyl-2-isobutylsuccinate The invention can be selected from the group consisting of 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.

[0044] According to a specific embodiment of the present invention, preferably, in Formula IV, R 22 -R 25 The two non-hydrogen groups in the compound are attached to different carbon atoms.

[0045] According to a specific embodiment of the present invention, preferably, the disubstituted succinate compounds include diethyl 2,3-bis(trimethylsilyl)succinate, diethyl 2-sec-butyl-3-methylsuccinate, diethyl 2-(3,3,3-trifluoropropyl)-3-methylsuccinate, diethyl 2,3-bis(2-ethylbutyl)succinate, diethyl 2,3-dibenzylsuccinate, diethyl 2,3-diisopropylsuccinate, diethyl 2,3-bis(cyclohexylmethyl)succinate, diethyl 2,3-di-tert-butylsuccinate, diethyl 2,3-diisobutylsuccinate, diethyl 2,3-dineopentylsuccinate, diethyl 2,3-diisopentylsuccinate, diethyl 2,3-bis(1-trifluoromethylethyl)succinate, 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, 2,3-bis(trimethylsilyl)succinic acid diisobutyl ester, 2-sec-butyl-3-methylsuccinic acid diisobutyl ester, 2-(3,3,3-trifluoropropyl)-3-methylsuccinic acid diisobutyl ester, 2,3-bis(2-ethylbutyl)succinic acid diisobutyl ester, 2,3-dibenzylsuccinic acid diisobutyl ester, 2,3-diisobutyl Diisobutyl propyl succinate, diisobutyl 2,3-di(cyclohexylmethyl)succinate, diisobutyl 2,3-di-tert-butyl succinate, diisobutyl 2,3-diisobutyl succinate, diisobutyl 2,3-dineopentyl succinate, diisobutyl 2,3-diisopentyl succinate, diisobutyl 2,3-di(1-trifluoromethylethyl)succinate, diisobutyl 2,3-di(tetradecyl)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-cyclohexylmethyl succinate Ester, diisobutyl 2-cyclohexyl-3-cyclopentylsuccinate, dineopentyl 2,3-bis(trimethylsilyl)succinate, dineopentyl 2-sec-butyl-3-methylsuccinate, dineopentyl 2-(3,3,3-trifluoropropyl)-3-methylsuccinate, dineopentyl 2,3-bis(2-ethylbutyl)succinate, dineopentyl 2,3-dibenzylsuccinate, dineopentyl 2,3-diisopropylsuccinate, dineopentyl 2,3-bis(cyclohexylmethyl)succinate, dineopentyl 2,3-di-tert-butylsuccinate, dineopentyl 2,3-diisobutylsuccinate, dineopentyl 2,3-dineopentylsuccinate, dineopentyl 2,3-diisopentylsuccinate, dineopentyl 2,3-(1-trifluoromethylethyl)succinate, 2,3-di(tetradecyl)succinic acid dineopentyl ester, 2,3-difluorenylsuccinic acid dineopentyl ester, 2-isopropyl-3-isobutylsuccinic acid dineopentyl ester, 2-tert-butyl-3-isopropylsuccinic acid dineopentyl ester, 2-isopropyl-3-cyclohexylsuccinic acid dineopentyl ester, 2-isopentyl-3-cyclohexylsuccinic acid dineopentyl ester, 2-tetradecyl-3-cyclohexylmethylsuccinic acid dineopentyl ester, 2-cyclohexyl-3-cyclopentylsuccinic acid dineopentyl ester, or a combination of two or more thereof.

[0046] According to a specific embodiment of the present invention, preferably, in Formula IV, R 22 -R 25 Two or four of them are connected into a ring.

[0047] According to a specific embodiment of the present invention, preferably, the succinate compound includes one or a combination of two or more 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.

[0048] According to a specific embodiment of the present invention, preferably, the succinate ester compound includes diethyl perhydrosuccinate, diethyl trimethylsuccinate, diethyl cyclohexyl methylsuccinate, 1-ethoxycarbonyl diisobutyl phenylsuccinate, diisobutyl perhydrosuccinate, diisobutyl cyclohexyl methylsuccinate, dineopentyl perhydrosuccinate, dineopentyl p-methoxyphenylsuccinate, dineopentyl cyclohexyl methylsuccinate, diethyl 2,3-diethyl-2-isopropylsuccinate, diethyl 2,3-diisopropyl-2-methylsuccinate, diethyl 2,3-dicyclohexyl-2-methylsuccinate, 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-diethyl-2,3-diisopropylsuccinic acid diethyl ester, 2,2,3,3-tetrafluorosuccinic acid diethyl ester, 2,3-diethyl-2-isopropylsuccinic acid diisobutyl ester, 2,3-diisopropyl-2-methylsuccinic acid diisobutyl ester, 2,3-dicyclohexyl -2-methylsuccinic acid diisobutyl ester, 2,2,3,3-tetramethylsuccinic acid diisobutyl ester, 2,2,3,3-tetraethylsuccinic acid diisobutyl ester, 2,2,3,3-tetrapropylsuccinic acid diisobutyl ester, 2,3-diethyl-2,3-dipropylsuccinic acid diisobutyl ester, 2,2,3,3-tetrafluorosuccinic acid diisobutyl ester, 2,3-diethyl-2-isopropylsuccinic acid dineopentyl ester, 2,3-diisopropyl-2- One or a combination of two or more of dineopentyl methylsuccinate, dineopentyl 2,3-dicyclohexyl-2-methylsuccinate, dineopentyl 2,2,3,3-tetramethylsuccinate, dineopentyl 2,2,3,3-tetraethylsuccinate, dineopentyl 2,2,3,3-tetrapropylsuccinate, dineopentyl 2,3-diethyl-2,3-diisopropylsuccinate, and dineopentyl 2,2,3,3-tetrafluorosuccinate.

[0049] Each compound as listed above can be used in the form of pure isomers 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 separated 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 as a mixture of these two forms.

[0050] According to a specific embodiment of the present invention, preferably, the Lewis base internal electron donor comprises a diol ester compound, and the diol ester compound has a structure shown in Formula V:

[0051]

[0052] In Formula V, R 26-R 31 are the same or different, each independently selected from hydrogen, halogen, C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl, C7-C 20 Aralkyl, C2-C 10 The alkenyl group, C 10 -C 20 More preferably, R 26 -R 31 Two or more of them are bonded to form a ring; 32 -R 33 the same or different, each independently selected from halogen, C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl, C7-C 20 Aralkyl, C2-C 10 The olefin group, C 10 -C 20 A fused ring aromatic group.

[0053] According to a specific embodiment of the present invention, preferably, the glycol ester compound includes 1,3-propylene glycol dibenzoate, 2-methyl-1,3-propylene glycol dibenzoate, 2-ethyl-1,3-propylene glycol dibenzoate, 2-propyl-1,3-propylene glycol dibenzoate, 2-butyl-1,3-propylene glycol dibenzoate, 2,2-dimethyl-1,3-propylene glycol dibenzoate, 2-ethyl-2-butyl-1,3-propylene glycol dibenzoate, 2,2-diethyl-1,3-propylene glycol dibenzoate. dibenzoate, 2-methyl-2-propyl-1,3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1,3-propanediol dibenzoate, 2,4-pentanediol dibenzoate, 3-methyl-2,4-pentanediol dibenzoate, 3-ethyl-2,4-pentanediol dibenzoate, 3-propyl-2,4-pentanediol dibenzoate, 3-butyl-2,4-pentanediol dibenzoate, 3,3-dimethyl-2,4-pentanediol dibenzoate, 2-methyl-1,3-pentanediol dibenzoate 2,2-dimethyl-1,3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2-methyl-1,3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-propyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2-methyl-1,3-pentanediol dibenzoate Benzoate, 2,2-dimethyl-1,3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-butyl-1,3-pentanediol dibenzoate, 2,2,4-trimethyl-1,3-pentanediol dibenzoate, 3-methyl-3-butyl-2,4-pentanediol dibenzoate, 2,2-dimethyl-3,5-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, or a combination of two or more thereof.

[0054] According to a specific embodiment of the present invention, preferably, the Lewis base internal electron donor comprises an ortho-phenylene diester compound; wherein the ortho-phenylene diester compound has a structure shown in Formula VI:

[0055]

[0056] In Formula VI, R 38 and R 39 The same or different, each independently selected from C1-C 20 Straight-chain or branched alkyl and its derivatives, C3-C 20 Cycloalkyl, C6-C 20 Aryl and its derivatives, C7-C 20Arylalkyl and its derivatives, C2-C 10 The olefin group, C 10 -C 20 The condensed aromatic ring, C 10 -C 20 The ester group, R 38 and R 39 Not hydrogen; R 34 -R 37 the same or different, each independently selected from hydrogen, C1-C 20 Hydrocarbon groups and their derivatives, including C1-C 20 Alkoxy groups, heteroatom-containing groups, C1-C 20 The present invention relates to a group of alkoxy and heteroatoms; more preferably, the heteroatoms include one or a combination of two or more of N, O, S, P, Si and halogen.

[0057] According to a specific embodiment of the present invention, preferably, the ortho-phenylene diester compound has a structure shown in Formula VII:

[0058]

[0059] In formula VII, R 40 -R 53 the same or different, each independently selected from hydrogen, C1-C 20 Hydrocarbon groups and their derivatives, including C1-C 20 Alkoxy groups, heteroatom-containing groups, C1-C 20 More preferably, in formula VII, R 40 -R 43 At least one selected from C1-C 20 More preferably, in formula VII, R 44 -R 53 At least one selected from C1-C 20 Hydrocarbon groups and their derivatives, including C1-C 20 Alkoxy groups, heteroatom-containing groups, C1-C 20 Alkoxy and heteroatom groups.

[0060] According to a specific embodiment of the present invention, preferably, the ortho-phenylene diester compound is selected from 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];

[0061] 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];

[0062] 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];

[0063] 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];

[0064] 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];

[0065] 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];

[0066] 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];

[0067] 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];

[0068] 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];

[0069] 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];

[0070] 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];

[0071] 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];

[0072] 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];

[0073] 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];

[0074] 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];

[0075] 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];

[0076] 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];

[0077] 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];

[0078] 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];

[0079] 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];

[0080] 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];

[0081] 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];

[0082] 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];

[0083] 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];

[0084] 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];

[0085] 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];

[0086] 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];

[0087] 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];

[0088] 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];

[0089] 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];

[0090] 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];

[0091] 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];

[0092] 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];

[0093] 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] or a combination of two or more thereof;

[0094] The ortho-phenylene diester internal electron donor is more preferably selected from:

[0095] 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];

[0096] 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];

[0097] 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];

[0098] 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];

[0099] 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];

[0100] 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];

[0101] 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];

[0102] 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];

[0103] One or a combination of two or more of 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, and 4-methoxybenzoate].

[0104] According to a specific embodiment of the present invention, preferably, the feeding molar ratio of the 2,6-dicarboxylate-4-pyrone internal electron donor to the Lewis base internal electron donor is ≥1:9; more preferably ≥4:6; more preferably ≥5:5; and further preferably ≥7:3.

[0105] According to a specific embodiment of the present invention, preferably, the catalyst component comprises a titanium compound, a magnesium compound, the 2,6-dicarboxylate-4-pyrone internal electron donor and a Lewis base internal electron donor; 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, or a combination of two or more thereof, wherein m is 0.1-6, 0≤n≤2, X is a halogen, R a C1-C 20 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.

[0106] According to a specific embodiment of the present invention, preferably, the magnesium compound is an alcoholate of magnesium dihalide; or, the magnesium compound is a liquid magnesium compound (a magnesium compound dissolved in a liquid); or, the magnesium compound is a derivative of the magnesium dihalide molecule in which at least one halogen atom is replaced by a hydrocarbonoxy group or a halogenated hydrocarbonoxy group; preferably, it is a hydrocarbonoxy magnesium compound; more preferably, it is an alkoxy magnesium and / or an aryloxy magnesium.

[0107] According to a specific embodiment of the present invention, preferably, the titanium compound includes one or a combination of two or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and alkoxy titanium halide.

[0108] According to a specific embodiment of the present invention, preferably, the alkyl titanium halide includes one or a combination of two or more 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.

[0109] According to a specific embodiment of the present invention, preferably, the titanium compound is titanium tetrachloride.

[0110] According to a specific embodiment of the present invention, preferably, the molar ratio of the sum of the internal electron donors to the magnesium compound calculated as magnesium element is 0.01-5.0:1, preferably 0.05-3.0:1.

[0111] The present invention does not particularly limit the preparation method of the above-mentioned solid catalyst component, which can be carried out according to the following methods:

[0112] Method 1: A magnesium alcoholate or a magnesium chloroalcoholate is reacted with an excess of TiCl4 and an internal electron donor compound at a temperature of 80°C to 135°C; preferably, a compound of the general formula TiX N (OR b ) 4-N Titanium compounds (where R bC1-C 20 A hydrocarbon group, X is a halogen, N = 1-4; preferably TiCl4) and a general formula of MgCl2·mR a OH adduct (wherein m is a number of 0.1-6, preferably 2-3.5, and R a C1-C 20 The solid catalyst component is prepared by reacting an internal electron donor with a hydrocarbon group; wherein the general formula is MgCl2·mR a The adduct of OH can be suitably made into spherical shape by the following method: in the presence of an inert hydrocarbon immiscible with the adduct, alcohol and magnesium chloride are mixed, and the emulsion is rapidly quenched, thereby solidifying the adduct in the form of spherical particles (refer to the disclosures of US4399054 and US4469648). The spherical adduct obtained in this way can be directly reacted with the titanium compound, or it can be previously subjected to heat-controlled dealcoholation (80°C-130°C) to obtain a dealcoholated adduct (wherein the molar number of alcohol is generally less than 3, preferably between 0.1-2.5), and then subjected to the subsequent reaction;

[0113] For example, the adduct or dealcohol adduct is suspended in cold TiCl4 (generally -25°C-0°C) to react with the titanium compound, and the mixture of the two is heated to 80°C-130°C and maintained at this temperature for 0.5-2 hours, wherein the treatment with TiCl4 can be carried out once or more, and an internal electron donor compound can be added during the treatment with TiCl4, and this treatment can be repeated once or more;

[0114] Method 2: Dissolve the magnesium compound in a solvent system consisting of an organic epoxy compound, an organic phosphine compound and an inert diluent to form a uniform solution, and then mix it with a titanium compound, and precipitate a solid in the presence of a precipitation aid; the solid is treated with an internal electron donor compound to load the internal electron donor compound on the solid, and if necessary, further treated with titanium tetrahalide and an inert diluent; 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 mol, the organic phosphine compound is 0.1-3 mol, the precipitation aid is 0.03-1.0 mol, and the titanium compound is 0.5-150 mol (calculated as mole of titanium element);

[0115] Method 3: react a titanium compound (e.g., TiCl4) or an aromatic hydrocarbon solution of titanium alkoxide (e.g., toluene, xylene, etc.) with a magnesium compound, such as a dialkoxy magnesium compound such as a dialkoxy magnesium compound or a diaryloxy magnesium compound at -25-0°C, and halogenate at 80°C-130°C. The treatment with the aromatic hydrocarbon solution of TiCl4 can be repeated once or multiple times, and the internal electron donor compound is added once or in batches during multiple such treatments. For example, the preparation method of the titanium-containing solid catalyst component disclosed in US5077357 can be used for preparation: 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, heated to be completely dissolved, and then continued to be heated to 80°C-130°C; N2 is used to bubble away the ethanol reactant and then continue to stir for a certain period of time, then washed once with hot chlorobenzene, washed twice with isooctane, and then dried with N2 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 stirred for 3 hours at high temperature after the ethoxymagnesium is dissolved; hot filtering is performed and then washed once with warm chlorobenzene and once with isooctane, and finally dried with N2;

[0116] Method 4: Magnesium dichloride is preactivated according to existing methods and then treated with excess TiCl4 at a temperature of about 80°C to 135°C, wherein an internal electron donor compound is contained in the solution. The TiCl4 is treated multiple times and the solid is washed with hexane to remove any unreacted TiCl4;

[0117] Method 5: Prepare with reference to the preparation method of titanium-containing solid catalyst component disclosed in CN1208045: 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°C to 200°C, preferably -30°C to 130°C, and an internal electron donor compound is used during the contact process;

[0118] Method 6: Grind anhydrous magnesium chloride and an internal electron donor compound together under conditions where magnesium dichloride is activated, and the product obtained in this way can be treated once or multiple times with excess TiCl4 at a temperature of 80°C-130°C, and then washed with a hydrocarbon solvent until it is free of chloride ions. A further detailed method is: the product obtained by co-grinding anhydrous magnesium dichloride, a titanium compound and an internal electron donor compound is treated with a halogenated hydrocarbon such as 1,2-dichloroethane, chlorobenzene, dichloromethane, etc., the treatment being carried out at a temperature between 40°C and the boiling point of the halogenated hydrocarbon for 1-4 hours, and then the product is usually washed with an inert hydrocarbon solvent such as hexane;

[0119] Method 7: A magnesium compound supported on an inorganic oxide such as SiO2, alumina or a porous resin is used as a carrier for preparation, and then activated by a well-known method, and then treated with an excess of TiCl4 at a temperature of about 80°C-135°C, and an internal electron donor compound is added during the treatment process.

[0120] The reaction of the above catalyst components leads to the formation of magnesium halide in an active form; general 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 loaded on the surface, edge and defect of the magnesium halide. The treated magnesium halide microcrystal suitable for loading Ti is "active magnesium halide". In addition to these reactions, other methods are also known in the literature to make compound starting materials other than magnesium halide form magnesium halide in an active form.

[0121] In any of the methods for preparing the catalyst components, the internal electron donor compound can be added directly as such or in an alternative manner, such as by preparing it in situ using a suitable precursor that can be converted in the desired internal electron donor compound, such as by known chemical reactions such as esterification, transesterification, etc. Typically, the internal electron donor compound is used in a molar ratio of 0.01-5:1, preferably 0.05-3.0:1, relative to the molar number of MgCl2; in addition, the internal electron donor compound can be added simultaneously or separately during the preparation process in batches or in parts, in any order and in any combination.

[0122] The present invention also provides a catalyst for olefin polymerization, which comprises the above catalyst component and an organic aluminum compound.

[0123] 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.

[0124] According to a specific embodiment of the present invention, preferably, the organoaluminum compound includes one or a combination of two or more of trialkylaluminum compounds, alkylaluminum halides, alkylaluminum hydrides, alkylaluminum sesquichlorides, and alkylaluminoxanes.

[0125] According to a specific embodiment of the present invention, preferably, the trialkylaluminum compound includes one or a combination of two or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and trioctylaluminum; the alkylaluminum halide includes AlEt2Cl; the alkylaluminum sesquichloride includes Al2Et3Cl3; more preferably, the organoaluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

[0126] 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 50-800:1; in terms of reducing the ash content of the polymer, the Al / Ti molar ratio in the catalyst is less than 500, preferably less than 200, and further preferably less than 100.

[0127] According to a specific embodiment of the present invention, preferably, the raw material composition of the catalyst also includes an external electron donor.

[0128] According to a specific embodiment of the present invention, preferably, the external electron donor is a siloxane compound.

[0129] 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, R' and R" each contain a heteroatom; more preferably, the heteroatom includes one or a combination of two or more of N, O, S, P, and Si.

[0130] 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, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, bis(3-methylcyclohexyl)dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, bis(4-methylcyclohexyl)dimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, bis(3,5-dimethylcyclohexyl)dimethoxysilane, tetrapropoxysilane, tetrabutoxysilane, or a combination of two or more thereof;

[0131] The siloxane compound more preferably includes one or a combination of two or more 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.

[0132] 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 0.002-100:1, more preferably 0.01-20:1, and further preferably 0.01-5:1.

[0133] The invention also provides application of the catalyst in olefin polymerization.

[0134] According to a specific embodiment of the present invention, preferably, the olefin includes 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, vinylcyclohexene, one or a combination of two or more thereof.

[0135] According to a specific embodiment of the present invention, preferably, the polymerization comprises ethylene and / or propylene polymerization.

[0136] According to a specific embodiment of the present invention, preferably, the polymerization includes homopolymerization or copolymerization.

[0137] 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.

[0138] 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.

[0139] 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.

[0140] The present invention has the following beneficial effects:

[0141] The present invention adopts 2,6-dicarboxylic acid ester-4-pyrone compounds as internal electron donors of polyolefin catalysts, and has good compounding tolerance. Compounding with various Lewis base compounds can make the catalyst show optimized performance, especially the activity can be significantly improved after compounding, and is significantly higher than the activity of any compounded internal electron donor when used alone. The activity of some embodiments after compounding can reach more than twice that before compounding. The polypropylene obtained by the catalyst has high isotacticity, and a high isotactic polymer can be obtained even without adding an external electron donor. At the same time, the catalyst has ultra-high activity, and the activity decays slowly as the polymerization reaction time is prolonged, and a high level of activity is maintained for a long time. When used for propylene polymerization, when the Al / Ti ratio is reduced, a low-ash polymer can be obtained. DETAILED DESCRIPTION

[0142] In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be construed as limiting the applicable scope of the present invention.

[0143] The operations for preparing the catalysts in the following examples were all carried out under the protection of high-purity nitrogen.

[0144] The isotacticity of a polymer is determined by the heptane extraction method (extraction with boiling heptane for 6 hours): two grams of a dry polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours. The residue is then dried to a constant weight, and the ratio of the obtained polymer weight (g) to 2 is the isotacticity.

[0145] The bulk density of the polymer was determined using the JB / T 2412-2008 method.

[0146] 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: 3×Plgel 10um M1Xed-B 300×7.5 nm).

[0147] Other sources of Lewis base compounds:

[0148] 9,9-Bismethoxymethylfluorene, commercially available, CAS No. 182121-12-6;

[0149] 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, synthesized according to CN1041752A;

[0150] Di-n-butyl phthalate, commercially available, CAS No. 84-74-2;

[0151] 2,3-Diisopropyl succinate, synthesized according to CN1313869A;

[0152] 2,3-Diisopropyl-2-cyanosuccinic acid diethyl ester, synthesized according to CN106608935A;

[0153] 2,4-Pentanediol dibenzoate, synthesized according to CN1580038A;

[0154] 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;

[0155] Ethyl benzoate, commercially available, CAS number 93-89-0.

[0156] Preparation Example: Synthesis of 2,6-dicarboxylate-4-pyrone compounds shown in Formula I

[0157] 1. The synthesis of 2,6-di-n-butyl dicarboxylate-4-pyrone is as follows:

[0158] (1) Sodium (11.8 g, 0.5 mol, 2.04 eq.) was dissolved in anhydrous ethanol (180 mL) to obtain a solution for use; 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.) were added to the solution obtained above within 15 minutes to form a yellow precipitate; the reaction mixture was maintained at 60° C. for one hour, and HCl (aq. 37%, 100 mL) and water (50 mL) were added. The solution was stirred at 50°C for 20 hours, after which water and ethanol (about 230 mL) were removed under reduced pressure, and then water (150 mL) and HCl (aq. 37%, 25 mL) were added to the mixture and stirred until silica gel TLC (eluent: 3 / 7 (v / v), 10% NaCl aqueous solution / ethanol) showed only one point. After cooling to room temperature, the crystals were filtered out, washed with water, and then washed with cold acetone, and the crude product was recrystallized to obtain white powder 4-pyrone-2,6-dicarboxylic acid (35.0 g, yield: 76%);

[0159] (2) In a 1 L three-necked flask, 4-pyrone-2,6-dicarboxylic acid (5.5 g), n-butanol (100 mL), and concentrated sulfuric acid (0.6 mL) were added, heated to reflux for 2 hours, and cooled to room temperature; the reaction solution was poured into a saturated sodium bicarbonate solution, extracted twice with ethyl acetate (100 mL×2), the organic phases were combined, washed with saturated brine (100 mL×2), concentrated and recrystallized to obtain the product 2,6-di-n-butyl dicarboxylate-4-pyrone (a1, 7.1 g, yield 79%). 1 H NMR (500 MHz, Chloroform-d) δ / ppm: 6.81 (s, 2H), 4.14 (t, J = 8.7 Hz, 4H), 1.77 (p, J = 8.9 Hz, 4H), 1.52–1.41 (m, 4H), 0.97 (t, J = 5.6 Hz, 6H). The specific structural information is shown in Table 1.

[0160] 2. Other 2,6-dicarboxylic acid ester-4-pyrone compounds (a2-a25) are synthesized by the above-mentioned route (other existing synthetic routes may also be used), the starting material is selected from oxalic acid or diethyl oxalate, and is subjected to addition reaction with acetone or other ketones, and then esterified with one or two alcohols to obtain the corresponding 2,6-dicarboxylic acid ester-4-pyrone products. When reacting with two alcohols, a mixture of three products is obtained, which can be directly used as an internal electron donor composition without separation. The structures and NMR results of other 2,6-dicarboxylic acid ester-4-pyrone compounds (a2-a25) are shown in Table 1.

[0161]

[0162] Table 1 2,6-dicarboxylate-4-pyrone compounds shown in formula I

[0163]

[0164]

[0165]

[0166] Preparation of catalyst components

[0167] Example 1

[0168] This embodiment provides a catalyst component, and the preparation method thereof is as follows:

[0169] In a 500 ml 5-necked flask with nitrogen fully replaced and stirred, 10 g of MgCl2·2.5C2H5OH microspheres and 150 mL of titanium tetrachloride were added to prepare a suspension, then maintained at -15°C for 1 hour, slowly heated to 80°C, 2.1 g (7 mmol) of 2,6-di-n-butyl-4-pyrone and 0.76 g (3 mmol) of 9,9-bis-methoxymethylfluorene were added, and the temperature was continued to rise to 110°C and kept constant for 1 hour, then the liquid was filtered clean, the liquid was filtered off, and the obtained solid was washed 3 times with 120 mL of titanium tetrachloride at 125°C, and then washed 4 times with 150 mL of hexane at 60°C, the liquid was filtered off and dried to obtain a solid catalyst component E1. The titanium content, internal electron donor content and polymerization data of the solid catalyst component are shown in Table 2.

[0170] Example 2-25

[0171] Examples 2-25 each provide a catalyst component E2-E25, the preparation process of which is as shown in Example 1, except that 2,6-di-n-butyl dicarboxylate-4-pyrone is replaced with 7 mmol of compounds a2-a25 in Table 1 in sequence.

[0172] Embodiment 26

[0173] This embodiment provides a solid catalyst component E26, and its preparation process is as shown in Example 1, except that 5 mmol of 2,6-di-n-butyl-4-pyrone and 5 mmol of 9,9-bismethoxymethylfluorene are added.

[0174] Embodiment 27

[0175] This embodiment provides a solid catalyst component E27, and its preparation process is as shown in Example 1, except that 2 mmol 2,6-di-n-butyl dicarboxylate-4-pyrone and 8 mmol 9,9-bismethoxymethylfluorene are added.

[0176] Embodiment 28-67

[0177] Examples 28-67 each provide a catalyst component E28-E67, the preparation process of which is as shown in Example 1, except that 7 mmol of a type a internal electron donor (2,6-dicarboxylic acid ester-4-pyrone compound) and 3 mmol of a type b internal electron donor (Lewis base internal electron donor) are added respectively according to the internal electron donor numbers shown in Table 2.

[0178] Examples 68-75

[0179] Examples 68-75 each provide a catalyst component E68-E75, the preparation process of which is as shown in Example 1, except that 5mmol / 3mmol / 2mmol of three electron donor compounds are added respectively according to the internal electron donor numbers shown in Table 2.

[0180] Examples 76-78

[0181] Examples 76-78 each provide a catalyst component E76-E78, the preparation process of which is as shown in Example 1, except that electron donors a1, b1, and b10 are added respectively according to the molar ratio shown in Table 2 (total feed amount is 10 mmol).

[0182] Embodiment 79

[0183] This embodiment provides a solid catalyst component E79, and its preparation process is as shown in Example 1, except that 5 mmol of a1, 3 mmol of b1 and 2 mmol of b12 electron donors are added respectively.

[0184] Comparative Example 1

[0185] This comparative example provides a catalyst component D1, which is prepared in the same manner as in Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compounds are replaced with 10 mmol of di-n-butyl phthalate (b3).

[0186] Comparative Example 2

[0187] This comparative example provides a catalyst component D2, which is prepared in the same manner as in Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compounds are replaced with 10 mmol of 9,9-dimethoxyfluorene (b1).

[0188] Comparative Example 3

[0189] This comparative example provides a catalyst component D3, which is prepared in the same manner as in Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compounds are replaced with 10 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (b2).

[0190] Comparative Example 4

[0191] This comparative example provides a catalyst component D4, which is prepared in the same manner as in Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compounds are replaced with 10 mmol of 2,6-di-n-butyl-4-pyrone (a1).

[0192] Comparative Example 5

[0193] This comparative example provides a catalyst component D5, which is prepared in the same manner as in Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compounds are replaced with 10 mmol of 2,6-diethyl dicarboxylate-4-pyrone (a2).

[0194] Comparative Example 6

[0195] This comparative example provides a catalyst component D6, which is prepared in the same manner as in Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compounds are replaced with 10 mmol of 2,6-diphenyl dicarboxylate-4-pyrone (a6).

[0196] Comparative Example 7

[0197] This comparative example provides a catalyst component D7, which is prepared in the same manner as in Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compounds are replaced with 10 mmol of 2,6-di-m-chlorophenyl dicarboxylate-4-pyrone (a9).

[0198] Comparative Example 8

[0199] This comparative example provides a catalyst component D8, and its preparation process is the same as that of Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compound are replaced by 7 mmol of b1 and 3 mmol of b3.

[0200] Comparative Example 9

[0201] This comparative example provides a catalyst component D9, which is prepared in the same manner as in Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compound are replaced by 7 mmol of b1 and 3 mmol of b12.

[0202] Comparative Example 10

[0203] This comparative example provides a catalyst component D10, which is prepared in the same manner as in Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compounds are replaced with 4 mmol of b1, 3 mmol of b2 and 3 mmol of b3 electron donors.

[0204] Comparative Example 11

[0205] This comparative example provides a catalyst component D11, which is prepared in the same manner as in Example 1, except that 7 mmol of a1 and 3 mmol of b1 internal electron donor compounds are replaced with 4 mmol of b1, 3 mmol of b3 and 3 mmol of b12 electron donors.

[0206] Aggregation condition 1:

[0207] 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 methylcyclohexyldimethoxysilane hexane solution and 10mg of the prepared catalyst component are added, and then 10mL of hexane is added to flush the feed line, and then 2L (under standard conditions) of hydrogen and 2.5L of refined propylene are added, and the reaction is controlled to prepolymerize at 25°C for 5 minutes, and the temperature is raised to 70°C, and the polymerization reaction is carried out at this temperature for 1 hour. After the reaction is completed, the reactor is cooled and stirring is stopped, the reaction product is discharged, and the polymer is obtained by drying. The polymerization data is shown in Table 2.

[0208] Table 2 Different compounding results under the same polymerization conditions

[0209]

[0210]

[0211]

[0212]

[0213]

Note

[0214] b1: 9,9-bis(methoxymethyl)fluorene;

[0215] b2: 2-isopropyl-2-isopentyl-1,3-dimethoxypropane;

[0216] b3: di-n-butyl phthalate;

[0217] b4: diethyl 2,3-diisopropylsuccinate;

[0218] b5: diethyl 2,3-diisopropyl-2-cyanosuccinate;

[0219] b6: 2,4-pentanediol dibenzoate;

[0220] b7: 1,2-benzenediol-4-tert-butyl-1,2-diacetate;

[0221] b8: 1,2-benzenediol-4-tert-butyl-1,2-di-n-hexanoate;

[0222] b9: 1,2-benzenediol-1,2-dibenzoate;

[0223] b10: 1,2-benzenediol-4-tert-butyl-1,2-dibenzoate;

[0224] b11: 1,2-benzenediol-4-tert-butyl-1,2-di(m-chlorobenzoate); b12: ethyl benzoate.

[0225] As can be seen from Table 2, the 2,6-dicarboxylate-4-pyrone compound was compounded with a diether compound, a succinate compound, a diol ester compound, an orthophenylene diester compound, a monocarboxylic acid ester, and an aromatic dicarboxylic acid ester compound in two-component (polymerization number 1-67) and three-component (polymerization number 68-79) combinations. The results showed that the compounding compatibility was good, and the polymerization activity was significantly improved, which was higher than the activity of any compound internal electron donor when used alone (polymerization number 80-86). Compared with the compounded catalyst without the 2,6-dicarboxylate-4-pyrone compound (polymerization number 87-90), the activity was significantly improved. The obtained polymer has high isotacticity, regular particle shape, and high bulk density.

[0226] Polymerization condition 2

[0227] 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 component E1 (corresponding catalyst is 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.

[0228] Polymerization condition 3

[0229] 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 component E68 (corresponding catalyst is Cat-68) 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 stirring is stopped, the reaction product is discharged, and the polymer is obtained by drying. The polymerization data is shown in Table 3.

[0230] Table 3 Different external electron donors

[0231]

[0232]

Note

[0233] CMMS: methylcyclohexyldimethoxysilane;

[0234] DPDMS: dicyclopentyldimethoxysilane;

[0235] PETS: phenyltrimethoxysilane;

[0236] NPTMS: n-propyltrimethoxysilane.

[0237] Polymerization Condition 4

[0238] 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, the reaction product is discharged, and the polymer is obtained by drying. The results are shown in Table 4.

[0239] The steps of polymerization No. 109-115 are the same as those of polymerization No. 98, except that the catalysts are Cat-D1 to Cat-D7, respectively.

[0240] Table 4 (without using external electron donor)

[0241]

[0242]

[0243] From the data in Table 2, it can be seen that the activity of the three internal electron donors is higher overall (E68-E79, i.e., the combination of "2,6-dicarboxylate-4-pyrone + diether + other internal electron donors"); from Table 3, it can be seen that the catalysts Cat-1 and Cat-68 prepared by compounding two or more internal electron donors, when polymerized with different external electron donors, all show high activity, high isotacticity, high bulk density, and good polymerization compatibility. From Table 4, it can be seen that 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 that of non-compounded catalysts (Cat-D1 to Cat-D7). When the polymerization time of Cat-1 and Cat-68 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 20ppm.

Claims

1. A catalyst component for olefin polymerization, comprising: Mg, Ti, halogens, 2,6-dicarboxylate-4-pyrone internal electron donors and Lewis base internal electron donors; in, The 2,6-dicarboxylate-4-pyrone internal electron donor has a structure shown in Formula I: In Formula I, R 1 , R 2 , R 3 and R 4 are the same or different, each independently selected from H, halogen, C1-C 20 The hydrocarbon group; Preferably, R 1 , R 2 , R 3 and R 4 Each of the heteroatoms comprises one or a combination of two or more selected from N, O, S, P, Si and halogen; Preferably, R 1 , R 2 , R 3 and R 4 Two or more of them are bonded to each other to form a ring; The Lewis base internal electron donor comprises one or more electronegative groups, and the electron donating atom of the Lewis base internal electron donor is selected from one or a combination of two or more of N, O, S, P, As or Sn; Preferably, the Lewis base internal electron donor includes one or a combination of two or more of a diether electron donor compound, an ester electron donor compound, a diketone electron donor compound and a diamine electron donor compound.

2. The catalyst component according to claim 1, wherein In Formula I, R 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 alkyl, alkyl containing heteroatoms, halogenated cycloalkyl, cycloalkyl containing heteroatoms, halogenated phenyl, phenyl containing heteroatoms, halogenated alkylphenyl, alkylphenyl containing heteroatoms, halogenated phenylalkyl, phenylalkyl containing heteroatoms, halogenated indenyl, indenyl containing heteroatoms, halogenated benzyl, benzyl containing heteroatoms, heterocyclic aromatic substituents; the heteroatoms include one or a combination of two or more of N, O, S, P, and Si.

3. The catalyst component according to claim 2, wherein In Formula I, R 1 , R 2 , R 3 and R 4 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 The straight-chain or branched alkyl group of 20 carbon atoms or the following substituents within 20 carbon atoms: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, benzyl and its derivatives, phenethyl and its derivatives, furyl, pyrrolyl, thienyl and indenyl.

4. The catalyst component according to claim 1, wherein The 2,6-dicarboxylate-4-pyrone internal electron donor includes 2,6-dicarboxylic acid di-n-butyl ester-4-pyrone, 2,6-dicarboxylic acid diethyl ester-4-pyrone, 2,6-dicarboxylic acid diisobutyl ester-4-pyrone, 2,6-dicarboxylic acid dicyclohexyl ester-4-pyrone, 2,6-dicarboxylic acid di(tetradecyl) ester-4-pyrone, 2,6-dicarboxylic acid diphenyl ester-4-pyrone, 2,6-dicarboxylic acid diphenylethyl ester-4-pyrone. , 2,6-dicarboxylic acid di-m-chlorophenyl ester-4-pyrone, 2,6-dicarboxylic acid di-p-chlorophenyl ester-4-pyrone, 2,6-dicarboxylic acid di-o-chlorophenyl ester-4-pyrone, 2,6-dicarboxylic acid di-p-methylphenyl ester-4-pyrone, 2,6-dicarboxylic acid di-m-methoxyphenyl ester-4-pyrone, 2,6-dicarboxylic acid di-p-methoxyphenyl ester-4-pyrone, 2,6-dicarboxylic acid di-o-methoxyphenyl ester-4-pyrone, 2,6-dicarboxylic acid di-(α- Furan methyl ester)-4-pyrone, 2,6-dicarboxylic acid di (5-pentenyl)-4-pyrone, 2,6-dicarboxylic acid di-p-nitrophenyl ester-4-pyrone, 2,6-dicarboxylic acid di-n-butyl ester-4-pyrone, 2,6-dicarboxylic acid di-n-butyl ester-3,5-dimethyl-4-pyrone, 2,6-dicarboxylic acid diethyl ester-3-phenyl-4-pyrone, 2,6-dicarboxylic acid diethyl ester-3-chloro-4-pyrone, 2,6-dicarboxylic acid diethyl ester- 3-bromo-4-pyrone, 2,6-diisopropyl dicarboxylate-4-pyrone, 2,6-dibenzyl dicarboxylate-4-pyrone, 2-ethyl carboxylate-6-n-butyl carboxylate-4-pyrone, 2-n-butyl ethyl carboxylate-6-phenyl carboxylate-4-pyrone, 2,6-dicarboxylate-3-methyl-4-pyrone, 2,6-dicarboxylate-di-n-butyl-3-methyl-5-ethyl-4-pyrone, or a combination of two or more thereof.

5. The catalyst component according to claim 1, wherein The Lewis base internal electron donor includes a 1,3-diether compound, and the 1,3-diether compound has a structure shown in Formula II: In formula II, R 5 , R 6 , R 7 , R 8 , R 9 and R 10 The same or different, each independently selected from H, C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C5-C 20 Aryl, C7-C 20 Alkyl or C7-C 20 Aralkyl; R 11 and R 12 The same or different, each independently selected from C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C5-C 20 Aryl, C7-C 20 Alkyl and C7-C 20 Preferably, R 5 -R 12 One or more groups in the molecule are linked to form a ring structure; Preferably, R 5 -R 12 Each of the heteroatoms comprises one or a combination of two or more selected from halogen, N, O, S, P and Si; Preferably, the 1,3-diether compound has a structure shown in Formula III: In formula III, the eight R 19 are the same or different, each independently selected from hydrogen, halogen, C1-C 14 Straight or branched alkyl, C3-C 14 Cycloalkyl, C6-C 14 Aryl, C7-C 14 Alkyl aryl, C7-C 14 Arylalkyl; Preferably, eight R 19 Each of the heteroatoms contains one or a combination of two or more selected from N, O, S, P, Si and halogen; R 13 , R 14 , R 15 and R 16 The same or different, each independently selected from H, C1-C 18 Straight or branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl or C7-C 20 Aralkyl; R 17 and R 18 The same or different, each independently selected from C1-C 20 Straight chain or branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl and C7-C 20 Preferably, R 13 -R 18 One or more groups in the molecule are linked to form a ring structure; Preferably, R 13 -R 18 Each of the heteroatoms contains one or a combination of two or more selected from halogen, N, O, S, P and Si.

6. The catalyst component according to claim 1, wherein The Lewis base internal electron donor includes a carboxylate compound, and the carboxylate compound includes a monocarboxylate compound and / or a polycarboxylate compound; Preferably, the polycarboxylic acid ester compounds include aromatic dicarboxylic acid ester compounds and / or fatty chain dicarboxylic acid ester compounds.

7. The catalyst component according to claim 1, wherein The Lewis base internal electron donor includes a succinate compound, and the succinate compound has a structure shown in Formula IV: In Formula IV, R 20 and R 21 The same or different, each independently selected from C1-C 20 Straight or branched alkyl, C2-C 20 Alkenyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Aralkyl, C7-C 20 Preferably, R 20 and R 21 Each contains a heteroatom; R 22 -R 25 Each independently selected from hydrogen, C1-C 20 Straight or branched alkyl, C2-C 20 Alkenyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Aralkyl, C7-C 20 Alkaryl; Preferably, R 22 -R 25 Bond to each other to form a ring; Preferably, R 22 -R 25 respectively contain heteroatoms; preferably, the heteroatoms include one or a combination of two or more of N, O, S, P, Si, and halogen; Preferably, R 20 and R 21 Each is independently selected from C1-C8 alkyl, C3-C8 cycloalkyl, C6-C8 aryl, C7-C8 aralkyl, C7-C8 alkaryl; Preferably, R 20 and R 21 Each is independently selected from a straight chain primary alkyl group or a branched chain primary alkyl group; Preferably, R 20 and R 21 Each is independently selected from methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, and 2-ethylhexyl, and more preferably selected from ethyl, isobutyl, and neopentyl.

8. The catalyst component according to claim 7, wherein In Formula IV, R 22 -R 24 is hydrogen, R 25 Selected from C3-C 10 Branched alkyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Aralkyl, C7-C 10 The alkylaryl group, R 25 Preferably selected from C3-C 10 Branched primary alkyl, C3-C 10 of a cycloalkyl group.

9. The catalyst component according to claim 7, wherein In Formula IV, R 22 -R 25 At least two of the groups are different from hydrogen and are each independently selected from C1-C 20 Straight or branched alkyl, C2-C 20 Alkenyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Aralkyl, C7-C 20 Preferably, R 22 -R 25 Contain heteroatoms.

10. The catalyst component according to claim 9, wherein In Formula IV, R 22 -R 25 The two non-hydrogen groups in the R 22 -R 25 The two non-hydrogen groups in the compound are attached to different carbon atoms.

11. The catalyst component according to claim 7, wherein In Formula IV, R 22 -R 25 Two or four of them are connected into a ring.

12. The catalyst component according to claim 1, wherein The Lewis base internal electron donor includes a diol ester compound, and the diol ester compound has a structure shown in Formula V: In Formula V, R 26 -R 31 are the same or different, each independently selected from hydrogen, halogen, C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl, C7-C 20 Aralkyl, C2-C 10 The alkenyl group, C 10 -C 20 Preferably, R 26 -R 31 Two or more of them are bonded to form a ring; 32 -R 33 the same or different, each independently selected from halogen, C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl, C7-C 20 Aralkyl, C2-C 10 The olefin group, C 10 -C 20 A fused ring aromatic group.

13. The catalyst component according to claim 1, wherein The Lewis base internal electron donor includes an ortho-phenylene diester compound; Wherein, the ortho-phenylene diester compound has a structure shown in Formula VI: In Formula VI, R 38 and R 39 The same or different, each independently selected from C1-C 20 Straight-chain or branched alkyl and its derivatives, C3-C 20 Cycloalkyl, C6-C 20 Aryl and its derivatives, C7-C 20 Arylalkyl and its derivatives, C2-C 10 The olefin group, C 10 -C 20 The condensed aromatic ring, C 10 -C 20 The ester group, R 38 and R 39 Not hydrogen; R 34 -R 37 the same or different, each independently selected from hydrogen, C1-C 20 Hydrocarbon groups and their derivatives, including C1-C 20 Alkoxy groups, heteroatom-containing groups, C1-C 20 An alkoxy group and a heteroatom group; preferably, the heteroatom includes one or a combination of two or more of N, O, S, P, Si, and halogen.

14. The catalyst component according to claim 13, wherein The ortho-phenylene diester compound has a structure shown in Formula VII: In formula VII, R 40 -R 53 the same or different, each independently selected from hydrogen, C1-C 20 Hydrocarbon groups and their derivatives, including C1-C 20 Alkoxy groups, heteroatom-containing groups, C1-C 20 Alkoxy and heteroatom groups; Preferably, in Formula VII, R 40 -R 43 At least one selected from C1-C 20 Hydrocarbons and their derivatives; Preferably, in Formula VII, R 44 -R 53 At least one selected from C1-C 20 Hydrocarbon groups and their derivatives, including C1-C 20 Alkoxy groups, heteroatom-containing groups, C1-C 20 Alkoxy and heteroatom groups.

15. The catalyst component according to claim 1, wherein The molar ratio of the 2,6-dicarboxylate-4-pyrone internal electron donor to the Lewis base internal electron donor is ≥1:9; Preferably, the molar ratio of the 2,6-dicarboxylate-4-pyrone internal electron donor to the Lewis base internal electron donor is ≥4:6; Preferably, the molar ratio of the 2,6-dicarboxylate-4-pyrone internal electron donor to the Lewis base internal electron donor is ≥5:5; Preferably, the feeding molar ratio of the 2,6-dicarboxylate-4-pyrone internal electron donor to the Lewis base internal electron donor is ≥7:

3.

16. The catalyst component according to any one of claims 1 to 15, wherein The catalyst component comprises a titanium compound, a magnesium compound, the 2,6-dicarboxylate-4-pyrone internal electron donor and a Lewis base internal electron donor; 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, or a combination of two or more thereof, 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.

17. The catalyst component according to claim 16, wherein 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 of a magnesium dihalide molecule in which at least one halogen atom is replaced by a hydrocarbonoxy group or a halogenated hydrocarbonoxy group; preferably, it is a hydrocarbonoxy magnesium compound; more preferably, it is an alkoxy magnesium and / or an aryloxy magnesium.

18. The catalyst component according to claim 16, wherein The titanium compound includes one or a combination of two or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and alkoxy titanium halide; Preferably, the alkyl titanium halide includes one or a combination of two or more 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; Preferably, the titanium compound is titanium tetrachloride.

19. The catalyst component according to claim 16, wherein The molar ratio of the total internal electron donor to the magnesium compound is 0.01-5.0:1, preferably 0.05-3.0:1, and the magnesium compound is calculated as magnesium element.

20. A catalyst for olefin polymerization, comprising the catalyst component according to any one of claims 1 to 19 and an organic aluminum compound.

21. The catalyst according to claim 20, wherein The general formula of the organoaluminum compound is AlR c p X (3-p) , where R c is hydrogen or C1-C 20 A hydrocarbon group, X is a halogen, and p is an integer of 0≤p≤3; Preferably, the organoaluminum compound comprises one or a combination of two or more of trialkylaluminum compounds, alkylaluminum halides, alkylaluminum hydrides, alkylaluminum sesquichlorides, and alkylaluminoxanes; Preferably, the trialkylaluminum compound includes one or a combination of two or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and trioctylaluminum; the alkylaluminum halide includes AlEt2Cl; the alkylaluminum sesquichloride includes Al2Et3Cl3; Preferably, the organoaluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

22. The catalyst according to claim 20, wherein The molar ratio of the organic aluminum compound to the titanium atom in the catalyst component is 1-1000:1, preferably 50-800:

1.

23. The catalyst according to claim 20, wherein The raw material composition of the catalyst also includes an external electron donor.

24. The catalyst according to claim 23, wherein The external electron donor is a siloxane compound; 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; Preferably, R' and R" each contain a heteroatom; Preferably, the heteroatom includes one or a combination of two or more of N, O, S, P and Si.

25. The catalyst according to claim 23, wherein The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100:1, preferably 0.01-20:1, and more preferably 0.01-5:

1.

26. Use of the catalyst according to any one of claims 20 to 25 in olefin polymerization; Preferably, the olefin includes one or a combination of two or more 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; Preferably, the polymerization comprises ethylene and / or propylene polymerization; Preferably, the polymerization comprises homopolymerization or copolymerization.

27. The use according to claim 26, wherein: The polymerization temperature is ≤200°C, preferably 20-100°C, more preferably 40-80°C; The polymerization pressure is ≤10 MPa, preferably 0.3-5 MPa.

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