A catalyst component for the polymerization of olefins, a catalyst and use thereof

Abstract

The application provides a catalyst component for olefin polymerization, a catalyst and application thereof; the composition of the catalyst component comprises: Mg, Ti, halogen, 2,6-dicarboxylate-4-pyrone internal electron donor and Lewis base internal electron donor; wherein the 2,6-dicarboxylate-4-pyrone internal electron donor has a structure shown in formula I: the catalyst component and the catalyst have high catalytic activity, and the polypropylene obtained by catalytic polymerization has high bulk density and high isotacticity; for propylene polymerization, when the Al / Ti ratio is reduced, a polymer with low ash content can be obtained.

Description

TECHNICAL FIELD

[0001] The present application relates to a catalyst component for olefin polymerization, a catalyst containing the solid catalyst component and the application of the catalyst in olefin polymerization, especially in propylene polymerization, belonging to the field of polyolefin catalysts. BACKGROUND

[0002] At present, Ziegler-Natta catalyst (Z-N catalyst) still occupies a dominant position in the production of polyolefins. The development of most Z-N catalysts focuses on the development of high activity and high stereospecific catalysts and the improvement of the copolymerization ability of the catalyst. Moreover, due to the high catalytic efficiency of traditional Z-N catalysts (transition metal compounds such as titanium chemically bonded on a magnesium-containing carrier), the comprehensive performance of the produced polymers is good, and the cost is low. At present, most of the catalysts for producing polypropylene in the world are still based on Z-N catalyst system, and the characteristics are high activity, high stereoregularity, long service life and product structure customization. From the development process of Z-N catalysts, it can be seen that as early as the first generation of catalysts appeared, it was found that the addition of the third component (mostly electron donors, also known as Lewis bases, among which, the addition in the catalyst preparation process is called internal electron donor, and the addition in the polymerization process is called external electron donor) will have a great influence on the behavior of olefin polymerization and the performance of the polymer. Changing the internal electron donor in the catalyst can change the properties of the active center of the catalyst to the greatest extent, 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 Z-N polypropylene catalysts.

[0003] The high-performance internal electron donor compounds with distinctive features in the prior art mainly include: (1) fatty acid ester and aromatic acid ester compounds, mainly represented by phthalate compounds; (2) diether compounds (such as the compounds disclosed in EP0361493 and EP0728724); (3) succinate compounds (such as the compounds disclosed in WO9856834, WO0063261 and WO03022894); (4) diol ester compounds (such as the compounds disclosed in WO9856834, WO0063261 and WO03022894); (5) other functional group compounds (such as the compounds disclosed in CN1105671, CN1242780 and US20060128558); and the like. However, in actual application, the above-mentioned compounds as internal electron donors for olefin polymerization catalysts all have certain problems. Although the catalysts using 1,3-diether compounds as internal electron donors have high activity and good hydrogen regulation 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 succinate compounds as internal electron donors have the advantages of wide relative molecular mass distribution of the synthesized PP, but the stereoregularity of the PP and the hydrogen regulation sensitivity of the catalyst need to be improved. The activity of the diol ester catalyst system as a whole is not as ideal as the diether system. CN102325808 discloses a procatalyst 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] The most widely used polyolefin internal electron donor in the industry is phthalate compounds, which have moderate activity, good stereoselectivity and low price. However, phthalate compounds are commonly used as plasticizers, which have great harm to human reproductive health and the environment, and there is a great demand for replacement. The use of most phthalate compounds has been restricted. Therefore, it is one of the common research and development goals in the field of polyolefin catalysts to develop new electron donors with excellent activity, good stereodirecting property, good comprehensive performance and low cost to replace the widely used phthalate electron donor compounds in the prior art and apply them to the preparation of high-efficiency Ziegler-Natta catalysts.

[0005] When the catalyst prepared by using a single internal electron donor cannot meet the specific requirements of the polypropylene product, such as the requirement that the catalyst has high activity, high stereospecificity and high hydrogen sensitivity, the use of multiple internal electron donors is an effective method to solve this problem, that is, two or more internal electron donors are used in the preparation of the Z-N catalyst, and the comprehensive performance of the Z-N catalyst is adjusted by adjusting the content of the different internal electron donors in the Z-N catalyst. CN101724102 discloses a catalyst component prepared by compounding an internal electron donor diol ester compound and a 1,3-dioxane compound and using a magnesium chloride alcohol adduct carrier, which has relatively high activity, but is only comparable to a 1,3-dioxane electron donor catalyst, and a silane external electron donor is still needed to maintain high isotacticity. SUMMARY

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

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

[0008]

[0009] In formula I, R 1 , R 2 , R 3 and R 4 are the same or different, and each is independently selected from H, halogen, C1-C 20 hydrocarbon group; preferably, R 1 , R 2 , R 3 and R 4 each contain one or more than two combinations of heteroatoms selected from N, O, S, P, Si and halogen; more preferably, two or more of R 1 , R 2 , R 3 and R 4 are bonded to each other to form a ring;

[0010] The Lewis base internal donor comprises one or more electronegative groups, the electron donating atoms of the Lewis base internal donor are selected from one or a combination of more than one of N, O, S, P, As, or Sn; preferably, the Lewis base internal donor includes one or a combination of more than one of diether internal donor compounds, ester internal donor compounds, diketone internal donor compounds, and diamine internal donor compounds.

[0011] According to a specific embodiment of the present application, preferably, in Formula I, R 1 , R 2 , R 3 , and R 4 are the same or different, each independently selected from H, halogen, the following substituents within 20 carbon atoms: straight chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, haloalkyl, heteroatom-containing alkyl, halocycloalkyl, heteroatom-containing cycloalkyl, halophenyl, heteroatom-containing phenyl, haloalkylphenyl, heteroatom-containing alkylphenyl, halophenylalkyl, heteroatom-containing phenylalkyl, haloindenyl, heteroatom-containing indenyl, halobenzyl, heteroatom-containing benzyl, heterocyclic aryl substituents; the heteroatoms include one or a combination of more than one of N, O, S, P, Si.

[0012] According to a specific embodiment of the present application, preferably, in Formula I, R 1 , R 2 , R 3 , and R 4 are the same or different, each independently selected from H, halogen, the following substituents within 20 carbon atoms: straight chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, haloalkyl, heteroatom-containing alkyl, halocycloalkyl, heteroatom-containing cycloalkyl, halophenyl, heteroatom-containing phenyl, haloalkylphenyl, heteroatom-containing alkylphenyl, halophenylalkyl, heteroatom-containing phenylalkyl, haloindenyl, heteroatom-containing indenyl, halobenzyl, heteroatom-containing benzyl, heterocyclic aryl substituents; the heteroatoms include one or a combination of more than one of N, O, S, P, Si. 11 20 According to a specific embodiment of the present application, preferably, in Formula I, R 1 , R 2 , R 3 , and R 4 are the same or different, each independently selected from H, halogen, the following substituents within 20 carbon atoms: straight chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, haloalkyl, heteroatom-containing alkyl, halocycloalkyl, heteroatom-containing cycloalkyl, halophenyl, heteroatom-containing phenyl, haloalkylphenyl, heteroatom-containing alkylphenyl, halophenylalkyl, heteroatom-containing phenylalkyl, haloindenyl, heteroatom-containing indenyl, halobenzyl, heteroatom-containing benzyl, heterocyclic aryl substituents; the heteroatoms include one or a combination of more than one of N, O, S, P, Si.

[0013] According to a specific embodiment of the present application, preferably, the 2,6-dicarboxylate-4-pyrone internal electron donor includes one or more than two combinations of 2,6-dicarboxylic di-n-butyl ester-4-pyrone, 2,6-dicarboxylic diethyl ester-4-pyrone, 2,6-dicarboxylic diisobutyl ester-4-pyrone, 2,6-dicarboxylic dicyclohexyl ester-4-pyrone, 2,6-dicarboxylic ditetradecyl ester-4-pyrone, 2,6-dicarboxylic diphenyl ester-4-pyrone, 2,6-dicarboxylic diphenethyl ester-4-pyrone, 2,6-dicarboxylic di-m-chlorophenyl ester-4-pyrone, 2,6-dicarboxylic di-p-chlorophenyl ester-4-pyrone, 2,6-dicarboxylic di-o-chlorophenyl ester-4-pyrone, 2,6-dicarboxylic di-p-methylphenyl ester-4-pyrone, 2,6-dicarboxylic di-m-methoxyphenyl ester-4-pyrone, 2,6-dicarboxylic di-p-methoxyphenyl ester-4-pyrone, 2,6-dicarboxylic di-o-methoxyphenyl ester-4-pyrone, 2,6-dicarboxylic di-(a-furancarboxylate)-4-pyrone, 2,6-dicarboxylic di-(5-pentenyl ester)-4-pyrone, 2,6-dicarboxylic di-p-nitrophenyl ester-4-pyrone, 2,6-dicarboxylic di-n-butyl ester-4-pyrone, 2,6-dicarboxylic di-n-butyl ester-3,5-dimethyl-4-pyrone, 2,6-dicarboxylic diethyl ester-3-phenyl-4-pyrone, 2,6-dicarboxylic diethyl ester-3-chloro-4-pyrone, 2,6-dicarboxylic diethyl ester-3-bromo-4-pyrone, 2,6-dicarboxylic diisopropyl ester-4-pyrone, 2,6-dicarboxylic dibenzyl ester-4-pyrone, 2-ethyl carboxylate-6-n-butyl carboxylate-4-pyrone, 2-n-butyl ethyl carboxylate-6-phenyl carboxylate-4-pyrone, 2,6-dicarboxylic di-n-butyl ester-3-methyl-4-pyrone, 2,6-dicarboxylic di-n-butyl ester-3-methyl-5-ethyl-4-pyrone.

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

[0015] The synthesis route is shown in reaction formula I. Esterification is performed on ethanedioic acid to obtain the corresponding oxalic acid diester (some oxalic acid diesters can be directly purchased), and then reacted with acetone or other substituted ketones to obtain the corresponding product;

[0016] Reaction formula I:

[0017]

[0018] The synthesis route shown in reaction formula II can also be used for preparation. This route selects oxalic acid diethyl ester and acetone or other substituted ketones as raw materials, and then reacts with an alcohol to obtain a substituted 2,6-dicarboxylate-4-pyrone compound. Only two steps are needed to obtain the target product. A large number of alcohols R 1OH to enrich the product structure; or reacting with a mixture of two alcohols (synthesis route as shown in Reaction Formula III) to obtain a mixture of three substituted 2,6-diformyl-4-pyrone esters, which can be directly used as internal electron donors without separation, the proportion of each component in the mixture can be adjusted by the addition proportion of the two alcohols in the reactants, and the proportion of each component can be determined by chromatography-mass spectrometry technology, nuclear magnetic resonance and other analytical means. In addition, the product 2,6-diformyl-4-pyrone (CAS number: 99-32-1) of the first step can also be directly purchased, and 2,6-diformyl-4-pyrone ester can be obtained through one-step esterification reaction;

[0019] Reaction Formula II:

[0020]

[0021] Reaction Formula III:

[0022]

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

[0024]

[0025] In Formula II, R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are the same or different, each independently selected from H, a linear or branched C1-C 20 alkyl group, a C3-C 20 cycloalkyl group, a C5-C 20 aryl group, a C7-C 20 alkylaryl group or a C7-C 20 arylalkyl group; R 11 and R 12 are the same or different, each independently selected from a linear or branched C1-C 20 alkyl group, a C3-C 20 cycloalkyl group, a C5-C 20 aryl group, a C7-C 20 alkylaryl group and a C7-C 20 arylalkyl group; preferably, one or more groups in R 5 -R 12 are linked to form a cyclic structure; preferably, R 5 -R 12 respectively comprises one or more than two heteroatoms selected from the group consisting of halogen, N, O, S, P and Si.

[0026] According to a specific embodiment of the present application, preferably, the 1,3-dioxetane compound has a structure represented by Formula III:

[0027]

[0028] In Formula III, eight R 19 are the same or different, each independently selected from hydrogen, halogen, C1-C 14 linear or branched alkyl, C3-C 14 cycloalkyl, C6-C 14 aryl, C7-C 14 alkylaryl, C7-C 14 arylalkyl.

[0029] According to a specific embodiment of the present application, preferably, eight R 19 each contain one or more than two heteroatoms selected from the group consisting of N, O, S, P, Si and halogen.

[0030] According to a specific embodiment of the present application, preferably, R 13 , R 14 , R 15 and R 16 are the same or different, each independently selected from H, C1-C 18 linear or branched alkyl, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 alkylaryl or C7-C 20 arylalkyl; R 17 and R 18 are the same or different, each independently selected from C1-C 20 linear or branched alkyl, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 alkylaryl and C7-C 20 arylalkyl; preferably, one or more groups in R 13 -R 18 are linked to form a cyclic structure.

[0031] According to a specific embodiment of the present application, preferably, R 13 -R 18 each contain one or more than two heteroatoms selected from the group consisting of 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-di ... 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 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-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3- dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexyl- methyl-1,3-dimethoxypropane, 1,1 -bis(methoxymethyl)-cyclopentadiene, 1,1 -bis(methoxymethyl)-2,3,4,5-tetramethylcyclopentadiene, 1,1 -bis(methoxymethyl)-2,3,4,5- tetraphenylcyclopentadiene, 1,1 -bis(methoxymethyl)-2,3,4,5-tetrafluorocyclopentadiene, 1,1 -bis(methoxymethyl)-3,4-dicyclopentylcyclopentadiene, 1,1 -bis(methoxymethyl)indene, 1,1 -bis(methoxymethyl)-2,3-dimethylindene, 1,1 -bis(methoxymethyl)-4,5,6,7- tetrahydroindene, 1,1 -bis(methoxymethyl)-2,3,6,7-tetrafluoroindene, 1,1 -bis(methoxymethyl)- 4,7-dimethylindene, 1,1 -bis(methoxymethyl)-3,6-dimethylindene, 1,1 -bis(methoxymethyl)- 4-phenylindene, 1,1 -bis(methoxymethyl)-4-phenyl-2-methylindene, 1,1 -bis(methoxymethyl)- 4-cyclohexylindene, 1,1 -bis(methoxymethyl)-7-(3,3,3-trifluoropropyl)indene, 1,1 -bis(methoxymethyl)-7-trimethylsilylindene, 1,1 -bis(methoxymethyl)-7- trifluoromethylindene, 1,1 -bis(methoxymethyl)-4,7-dimethyl-4,5,6,7-tetrahydroindene, 1,1 -bis(methoxymethyl)-7-methylindene, 1,1 -bis(methoxymethyl)-7-cyclopentylindene, 1,1 -bis(methoxymethyl)-7-isopropylindene, 1,1 -bis(methoxymethyl)-7- cyclohexylindene, 1,1 -bis(methoxymethyl)-7-tert-butylindene, 1,1 -bis(methoxymethyl)-7- tert-butyl-2-methylindene, 1,1 -bis(methoxymethyl)-7-phenylindene, 1,1 -bis(methoxymethyl)- 2-phenylindene, 1,1 -bis(methoxymethyl)-1 H-benzo[e]indene, 1,1 -bis(methoxymethyl)- 1 H-2-methylbenzo[e]indene, 9,9-bis(methoxymethyl)fluorene, 9,9-bis(methoxymethyl)- 2,3,6,7-tetramethylfluorene, 9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene, 9,9- bis(methoxymethyl)-2,3-benzofluorene, 9,9-bis(methoxymethyl)-2,3,6,7- 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 application, preferably, the Lewis base internal donor comprises a carboxylic acid ester compound, which comprises a mono-carboxylic acid ester compound and / or a poly-carboxylic acid ester compound; more preferably, the poly-carboxylic acid ester compound comprises an aromatic di-carboxylic acid ester compound and / or a fatty chain di-carboxylic acid ester compound.

[0034] According to a specific embodiment of the present application, 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 one or a combination of two or more of dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, methyl ethyl phthalate, methyl isopropyl phthalate, methyl n-propyl phthalate, ethyl n-butyl phthalate, ethyl isobutyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, di(2,2-dimethylhexyl) phthalate, di(2-ethylhexyl) phthalate, di-n-nonyl phthalate, diisodecyl phthalate, di(2,2-dimethylheptyl) phthalate, n-butyl isohexyl phthalate, n-butyl(2-ethylhexyl) phthalate, n-pentyl n-hexyl phthalate, n-pentyl isononyl phthalate, iso-pentyl n-decyl phthalate, n-pentyl undecyl phthalate, iso-pentyl isohexyl phthalate, 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 neoisnonyl phthalate, (2-ethylhexyl) isononyl phthalate.The terephthalic acid diester compound includes one or a combination of two or more of 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, diisooctyl terephthalate, di(2,2-dimethylhexyl) terephthalate, di(2-ethylhexyl) terephthalate, di-n-nonyl terephthalate, diisooctyl terephthalate, diisodecyl terephthalate, di(2,2-dimethyl ethyl heptyl) terephthalate, n-butyl isohexyl terephthalate, n-butyl(2-ethylhexyl) terephthalate, n-pentyl n-hexyl terephthalate, n-pentyl isohexyl terephthalate, iso-pentyl heptyl terephthalate, n-pentyl(2-ethylhexyl) terephthalate, n-pentyl isononyl terephthalate, iso-pentyl n-decyl terephthalate, n-pentyl undecyl terephthalate, iso-pentyl 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, diisooctyl phthalate, di-n-butyl terephthalate, diisobutyl terephthalate, di-n-octyl terephthalate, diisooctyl terephthalate, di(2-ethylhexyl) terephthalate, and diisodecyl phthalate.

[0035] According to a specific embodiment of the present application, preferably, the Lewis base internal electron donor includes a succinate compound having a structure shown in Formula IV:

[0036]

[0037] In Formula IV, R 20 and R 21 are the same or different, each independently selected from a linear or branched C1-C 20 alkyl group, a C2-C 20 alkenyl group, a C3-C 20 cycloalkyl group, a C6-C 20 aryl group, a C7-C20 Aryl groups, C7-C 20 The alkylaryl group; preferably, R 20 and R 21 Each contains heteroatoms; R 22 -R 25 Each is independently selected from hydrogen, C1-C 20 Straight-chain or branched alkyl groups, C2-C 20 alkenyl, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 Aryl groups, C7-C 20 alkylaryl; preferably, R 22 -R 25 Mutually bonded to form a ring; preferably, R 22 -R 25 Each contains heteroatoms; preferably, the heteroatoms include one or more combinations of N, O, S, P, Si, and halogens.

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

[0039] According to a specific embodiment of the present invention, preferably, in formula IV, R 22 -R 24 For hydrogen, R 25 Selected from C3-C 10 Branched alkyl groups, C3-C 10 cycloalkyl, C6-C 10 aryl, C7-C 10 Aryl groups, C7-C 10 alkylaryl groups, R 25 Preferred selection from C3-C 10 Branched primary alkyl groups, C3-C 10 cycloalkyl groups.

[0040] According to a specific embodiment of the present application, preferably, the mono-substituted succinate compound comprises one or more than two combinations of sec-butyl diethyl succinate, hexyl diethyl succinate, cyclopropyl diethyl succinate, norbornyl diethyl succinate, methoxy diethyl succinate, p-methoxyphenyl diethyl succinate, p-chlorophenyl diethyl succinate, phenyl diethyl succinate, cyclohexyl diethyl succinate, benzyl diethyl succinate, t-butyl diethyl succinate, isobutyl diethyl succinate, isopropyl diethyl succinate, neopentyl diethyl succinate, isoamyl diethyl succinate, (1-trifluoromethylethyl) diethyl succinate, fluorenyl diethyl succinate, sec-butyl diisobutyl succinate, hexyl diisobutyl succinate, cyclopropyl diisobutyl succinate, norbornyl diisobutyl succinate, trimethylsilyl diisobutyl succinate, methoxy diisobutyl succinate, p-methoxyphenyl diisobutyl succinate, p-chlorophenoxy diisobutyl succinate, cyclohexyl diisobutyl succinate, benzyl diisobutyl succinate, t-butyl diisobutyl succinate, isobutyl diisobutyl succinate, isopropyl diisobutyl succinate, neopentyl diisobutyl succinate, isoamyl diisobutyl succinate, (1-trifluoromethylethyl) diisobutyl succinate, fluorenyl diisobutyl succinate, sec-butyl dinopentyl succinate, hexyl dinopentyl succinate, cyclopropyl dinopentyl succinate, norbornyl dinopentyl succinate, trimethylsilyl dinopentyl succinate, methoxy dinopentyl succinate, p-chlorophenyl dinopentyl succinate, phenyl dinopentyl succinate, cyclohexyl dinopentyl succinate, benzyl dinopentyl succinate, t-butyl dinopentyl succinate, isobutyl dinopentyl succinate, isopropyl dinopentyl succinate, neopentyl dinopentyl succinate, isoamyl dinopentyl succinate, (1-trifluoromethylethyl) dinopentyl succinate, fluorenyl dinopentyl succinate.

[0041] According to a specific embodiment of the present application, preferably, in formula IV, R 22 -R 25 are different from hydrogen and each independently selected from the group consisting of linear or branched C1-C 20 alkyl, C2-C 20 alkenyl, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 aralkyl, C7-C 20 alkylaryl; preferably, R 22 -R 25 each contain a heteroatom.

[0042] According to a specific embodiment of the present application, preferably, two non-hydrogen groups in R 22 -R 25 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, and diethyl 2-isobutyl- Diethyl 2-ethylsuccinate, 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, diisobutyl 2-cyclohexyl-2-ethylsuccinate Diisobutyl succinate, 2-isopropyl-2-methylsuccinate, 2-tetradecyl-2-ethylsuccinate, 2-isobutyl-2-ethylsuccinate, 2-(1-trifluoromethylethyl)-2-methylsuccinate, 2-isopentyl-2-isobutylsuccinate, 2-phenyl-2-n-butylsuccinate, 2,2-dimethylsuccinate, 2-ethyl-2-methylsuccinate, 2-benzyl-2-isopropylsuccinate, 2-cyclohexylmethyl-2-isobutylsuccinate Dipentyl succinate, 2-cyclopentyl-2-n-butylsuccinate, 2,2-diisobutylsuccinate, 2-cyclohexyl-2-ethylsuccinate, 2-isopropyl-2-methylsuccinate, 2-tetradecyl-2-ethylsuccinate, 2-isobutyl-2-ethylsuccinate, 2-(1-trifluoromethylethyl)-2-methylsuccinate, 2-isopentyl-2-isobutylsuccinate, and 2-phenyl-2-n-butylsuccinate are selected as one or a combination of two or more of these.

[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 structure are attached to different carbon atoms.

[0045] According to specific embodiments of the present invention, preferably, the disubstituted succinate compounds include diethyl 2,3-di(trimethylsilyl)succinate, diethyl 2-sec-butyl-3-methylsuccinate, diethyl 2-(3,3,3-trifluoropropyl)-3-methylsuccinate, diethyl 2,3-di(2-ethylbutyl)succinate, diethyl 2,3-dibenzylsuccinate, diethyl 2,3-diisopropylsuccinate, diethyl 2,3-di(cyclohexylmethyl)succinate, diethyl 2,3-di-tert-butylsuccinate, diethyl 2,3-diisobutylsuccinate, diethyl 2,3-dineopentylsuccinate, diethyl 2,3-diisopentylsuccinate, diethyl 2,3-di(1-trifluoromethylethyl)succinate, diethyl 2,3 Diethyl bis(tetradecyl)succinate, diethyl 2,3-difluorenylsuccinate, diethyl 2-isopropyl-3-isobutylsuccinate, diethyl 2-tert-butyl-3-isopropylsuccinate, diethyl 2-isopropyl-3-cyclohexylsuccinate, diethyl 2-isopentyl-3-cyclohexylsuccinate, diethyl 2-tetradecyl-3-cyclohexylsuccinate, diethyl 2-cyclohexyl-3-cyclopentylsuccinate, diisobutyl 2,3-di(trimethylsilyl)succinate, diisobutyl 2-sec-butyl-3-methylsuccinate, diisobutyl 2-(3,3,3-trifluoropropyl)-3-methylsuccinate, diisobutyl 2,3-di(2-ethylbutyl)succinate, diisobutyl 2,3-dibenzylsuccinate, diisobutyl 2,3-diisobutyl Diisobutyl propyl succinate, 2,3-di(cyclohexylmethyl)succinate, 2,3-di-tert-butylsuccinate, 2,3-diisobutylsuccinate, 2,3-dineopentylsuccinate, 2,3-diisopentylsuccinate, 2,3-diisopentylsuccinate, 2,3-di(1-trifluoromethylethyl)succinate, 2,3-di(tetradecyl)succinate, 2,3-difluorenylsuccinate, 2-isopropyl-3-isobutylsuccinate, 2-tert-butyl-3-isopropylsuccinate, 2-isopropyl-3-cyclohexylsuccinate, 2-isopentyl-3-cyclohexylsuccinate, 2-tetradecyl-3-cyclohexylmethylsuccinate Ester, 2-cyclohexyl-3-cyclopentylsuccinate diisobutyl ester, 2,3-di(trimethylsilyl)succinate dineopentyl ester, 2-sec-butyl-3-methylsuccinate dineopentyl ester, 2-(3,3,3-trifluoropropyl)-3-methylsuccinate dineopentyl ester, 2,3-di(2-ethylbutyl)succinate dineopentyl ester, 2,3-dibenzylsuccinate dineopentyl ester, 2,3-diisopropylsuccinate dineopentyl ester, 2,3-di(cyclohexylmethyl)succinate dineopentyl ester, 2,3-di-tert-butylsuccinate dineopentyl ester, 2,3-diisobutylsuccinate dineopentyl ester, 2,3-dineopentylsuccinate dineopentyl ester, 2,3-ditetradecylsuccinic 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, one or two or more combinations thereof.

[0046] According to a specific embodiment of the present application, preferably, in formula IV, R 22 two or four of -R 25 are linked to form a ring.

[0047] According to a specific embodiment of the present application, preferably, the succinate compound includes one or two or more combinations of 1-(ethoxycarbonyl)-1-(ethoxyacetyl)-2,6-dimethylcyclohexane, 1-(ethoxycarbonyl)-1-(ethoxyacetyl)-2,5-dimethylcyclopentane, 1-(ethoxycarbonyl)-1-(ethoxyacetylmethyl)-2-methylcyclohexane, 1-(ethoxycarbonyl)-1-(ethoxyacetylcyclohexyl)cyclohexane.

[0048] According to a specific embodiment of the present invention, preferably, the succinate compounds include diethyl perhydrogenated succinate, diethyl trimethylsuccinate, diethyl cyclohexylmethylsuccinate, phenylsuccinate (1-ethoxycarbo diisobutyl phenylsuccinate), diisobutyl perhydrogenated succinate, diisobutyl cyclohexylmethylsuccinate, dipentyl perhydrogenated succinate, dipentyl p-methoxyphenylsuccinate, dipentyl cyclohexylmethylsuccinate, 2,3-diethyl-2-isopropylsuccinate, diethyl 2,3-diisopropyl-2-methylsuccinate, diethyl 2,3-dicyclohexyl-2-methylsuccinate, 2, Diethyl 2,3,3-tetramethylsuccinate, diethyl 2,2,3,3-tetraethylsuccinate, diethyl 2,2,3,3-tetrapropylsuccinate, diethyl 2,3-diethyl-2,3-diisopropylsuccinate, diethyl 2,2,3,3-tetrafluorosuccinate, diisobutyl 2,3-diethyl-2-isopropylsuccinate, diisobutyl 2,3-diisopropyl-2-methylsuccinate, 2,3-dicyclohexyl 2-Methylsuccinate diisobutyl ester, 2,2,3,3-tetramethylsuccinate diisobutyl ester, 2,2,3,3-tetraethylsuccinate diisobutyl ester, 2,2,3,3-tetrapropylsuccinate diisobutyl ester, 2,3-diethyl-2,3-dipropylsuccinate diisobutyl ester, 2,2,3,3-tetrafluorosuccinate diisobutyl ester, 2,3-diethyl-2-isopropylsuccinate dinepentyl ester, 2,3-diisopropyl-2- Dipentyl methylsuccinate, 2,3-dicyclohexyl-2-methylsuccinate, 2,2,3,3-tetramethylsuccinate, 2,2,3,3-tetraethylsuccinate, 2,2,3,3-tetrapropylsuccinate, 2,3-diethyl-2,3-diisopropylsuccinate, and 2,2,3,3-tetrafluorosuccinate, or a combination of two or more of these.

[0049] The compounds listed above can be used as pure isomers, mixtures of enantiomers, or mixtures 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 mixtures of both.

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

[0051]

[0052] In Equation V, R 26-R 31 identically or differently, are each independently selected from the group consisting of hydrogen, halogen, Ci-C 20 straight-chain or branched alkyl, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 alkylaryl, C7-C 20 aralkyl, C2-C 10 alkenyl, C 10 -C 20 fused-ring aryl; more preferably, R 26 -R 31 two or more of which are bonded to one another to form a ring; R 32 -R 33 identically or differently, are each independently selected from the group consisting of halogen, Ci-C 20 straight-chain or branched alkyl, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 alkylaryl, C7-C 20 aralkyl, C2-C 10 alkenyl, C 10 -C 20 fused-ring aryl.

[0053] According to a specific embodiment of the present application, preferably, the diol ester compound includes one or a combination of two or more of 1,3-propanediol dibenzoate, 2-methyl-1,3-propanediol dibenzoate, 2-ethyl-1,3-propanediol dibenzoate, 2-propyl-1,3-propanediol dibenzoate, 2-butyl-1,3-propanediol dibenzoate, 2,2-dimethyl-1,3-propanediol dibenzoate, 2-ethyl-2-butyl-1,3-propanediol dibenzoate, 2,2-diethyl-1,3-propanediol 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, 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.

[0054] According to a specific embodiment of the present application, preferably, the Lewis base internal donor includes 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 are the same or different, each independently selected from a linear or branched alkyl group of C1-C 20 , a cycloalkyl group of C3-C 20 , an aryl group of C6-C 20 , and a derivative thereof, and a derivative thereof. 20aralkyl and derivatives thereof, C2-C 10 olefinic group, C 10 -C 20 fused ring aryl, C 10 -C 20 ester group, R 38 and R 39 is not hydrogen; R 34 -R 37 are the same or different, each independently selected from the group consisting of hydrogen, C1-C 20 hydrocarbon group and derivatives thereof, a group comprising C1-C 20 alkoxy group, a group comprising a heteroatom, a group comprising C1-C 20 alkoxy group and a heteroatom; more preferably, the heteroatom comprises one or a combination of two or more of N, O, S, P, Si, halogen.

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

[0058]

[0059] In Formula VII, R 40 -R 53 are the same or different, each independently selected from the group consisting of hydrogen, C1-C 20 hydrocarbon group and derivatives thereof, a group comprising C1-C 20 alkoxy group, a group comprising a heteroatom, a group comprising C1-C 20 alkoxy group and a heteroatom; more preferably, in Formula VII, R 40 -R 43 at least one is selected from the group consisting of C1-C 20 hydrocarbon group and derivatives thereof; more preferably, in Formula VII, R 44 -R 53 at least one is selected from the group consisting of C1-C 20 hydrocarbon group and derivatives thereof, a group comprising C1-C 20 alkoxy group, a group comprising a heteroatom, a group comprising C1-C 20 alkoxy group and a heteroatom.

[0060] According to a specific embodiment of the present application, preferably, the ortho-phenylene diester compound is selected from the group consisting of 1,2-dihydroxybenzene-1,2-di[benzoate, 2-methylbenzoate, 2-isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n-butylbenzoate, 4-t-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2-chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3-methoxybenzoate, 4-methoxybenzoate];

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

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

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

[0064] 1,2-Dihydroxy-3-ethyl-1,2-bis[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-Dihydroxy-3-ethyl-1,2-bis[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-Dihydroxy-3-ethyl-1,2-bis[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-Dihydroxy-3-ethyl-1,2-bis[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-Dihydroxybenzene-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-Dihydroxybenzene-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-Dihydroxybenzene-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-Dihydroxybenzene-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-Ceramide-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-Ceramide-4-formyl-1,2-di[benzoic acid ester, 2-methylbenzoic acid ester, 2-isopropylbenzoic acid ester, 4-methylbenzoic acid ester, 4-n-propylbenzoic acid ester, 4-isopropylbenzoic acid ester, 4-n-butylbenzoic acid ester, 4-tert-butylbenzoic acid ester, 4-isobutylbenzoic acid ester, 4-aminobenzoic acid ester, 4-fluorobenzoic acid ester, 2-chlorobenzoic acid ester, 3-chlorobenzoic acid ester, 4-chlorobenzoic acid ester, 2,4,6-trimethylbenzoic acid ester, 3-methoxybenzoic acid ester, 4-methoxybenzoic acid ester];

[0074] 1,2-Ceramide-4-acetyl-1,2-di[benzoic acid ester, 2-methylbenzoic acid ester, 2-isopropylbenzoic acid ester, 4-methylbenzoic acid ester, 4-n-propylbenzoic acid ester, 4-isopropylbenzoic acid ester, 4-n-butylbenzoic acid ester, 4-tert-butylbenzoic acid ester, 4-isobutylbenzoic acid ester, 4-aminobenzoic acid ester, 4-fluorobenzoic acid ester, 2-chlorobenzoic acid ester, 3-chlorobenzoic acid ester, 4-chlorobenzoic acid ester, 2,4,6-trimethylbenzoic acid ester, 3-methoxybenzoic acid ester, 4-methoxybenzoic acid ester];

[0075] 1,2-Ceramide-4-hydroxy-1,2-di[benzoic acid ester, 2-methylbenzoic acid ester, 2-isopropylbenzoic acid ester, 4-methylbenzoic acid ester, 4-n-propylbenzoic acid ester, 4-isopropylbenzoic acid ester, 4-n-butylbenzoic acid ester, 4-tert-butylbenzoic acid ester, 4-isobutylbenzoic acid ester, 4-aminobenzoic acid ester, 4-fluorobenzoic acid ester, 2-chlorobenzoic acid ester, 3-chlorobenzoic acid ester, 4-chlorobenzoic acid ester, 2,4,6-trimethylbenzoic acid ester, 3-methoxybenzoic acid ester, 4-methoxybenzoic acid ester];

[0076] 1,2-Cephedrol-4-chloro-1,2-di[benzoic acid ester, 2-methylbenzoic acid ester, 2-isopropylbenzoic acid ester, 4-methylbenzoic acid ester, 4-n-propylbenzoic acid ester, 4-isopropylbenzoic acid ester, 4-n-butylbenzoic acid ester, 4-tert-butylbenzoic acid ester, 4-isobutylbenzoic acid ester, 4-aminobenzoic acid ester, 4-fluorobenzoic acid ester, 2-chlorobenzoic acid ester, 3-chlorobenzoic acid ester, 4-chlorobenzoic acid ester, 2,4,6-trimethylbenzoic acid ester, 3-methoxybenzoic acid ester, 4-methoxybenzoic acid ester];

[0077] 1,2-Ceramide-4-bromo-1,2-di[benzoic acid ester, 2-methylbenzoic acid ester, 2-isopropylbenzoic acid ester, 4-methylbenzoic acid ester, 4-n-propylbenzoic acid ester, 4-isopropylbenzoic acid ester, 4-n-butylbenzoic acid ester, 4-tert-butylbenzoic acid ester, 4-isobutylbenzoic acid ester, 4-aminobenzoic acid ester, 4-fluorobenzoic acid ester, 2-chlorobenzoic acid ester, 3-chlorobenzoic acid ester, 4-chlorobenzoic acid ester, 2,4,6-trimethylbenzoic acid ester, 3-methoxybenzoic acid ester, 4-methoxybenzoic acid ester];

[0078] 1,2-Cephedrol-3,4-dimethyl-1,2-di[benzoic acid ester, 2-methylbenzoic acid ester, 2-isopropylbenzoic acid ester, 4-methylbenzoic acid ester, 4-n-propylbenzoic acid ester, 4-isopropylbenzoic acid ester, 4-n-butylbenzoic acid ester, 4-tert-butylbenzoic acid ester, 4-isobutylbenzoic acid ester, 4-aminobenzoic acid ester, 4-fluorobenzoic acid ester, 2-chlorobenzoic acid ester, 3-chlorobenzoic acid ester, 4-chlorobenzoic acid ester, 2,4,6-trimethylbenzoic acid ester, 3-methoxybenzoic acid ester, 4-methoxybenzoic acid ester];

[0079] 1,2-Cephedrol-3,4-dimethoxy-1,2-di[benzoic acid ester, 2-methylbenzoic acid ester, 2-isopropylbenzoic acid ester, 4-methylbenzoic acid ester, 4-n-propylbenzoic acid ester, 4-isopropylbenzoic acid ester, 4-n-butylbenzoic acid ester, 4-tert-butylbenzoic acid ester, 4-isobutylbenzoic acid ester, 4-aminobenzoic acid ester, 4-fluorobenzoic acid ester, 2-chlorobenzoic acid ester, 3-chlorobenzoic acid ester, 4-chlorobenzoic acid ester, 2,4,6-trimethylbenzoic acid ester, 3-methoxybenzoic acid ester, 4-methoxybenzoic acid ester];

[0080] 1,2-Dihydroxybenzene-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];

[0081] 1,2-Dihydroxybenzene-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-Dihydroxybenzene-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-Dihydroxybenzene-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];

[0084] 1,2-Dihydroxybenzene-3,5-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];

[0085] 1,2-Dihydroxybenzene-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-Dihydroxybenzene-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];

[0087] 1,2-Dihydroxybenzene-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-methoxy-5-methyl-1,2-di[benzoate, 2-methylbenzoate, 2- isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n- butylbenzoate, 4-t-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2- chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3- methoxybenzoate, 4-methoxybenzoate];

[0089] 1,2-Benzenediol-3-methoxy-5-methyl-1,2-di[benzoate, 2-methylbenzoate, 2- isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n- butylbenzoate, 4-t-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2- chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3- methoxybenzoate, 4-methoxybenzoate];

[0090] 1,2-Benzenediol-3-methoxy-5-methyl-1,2-di[benzoate, 2-methylbenzoate, 2- isopropylbenzoate, 4-methylbenzoate, 4-n-propylbenzoate, 4-isopropylbenzoate, 4-n- butylbenzoate, 4-t-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-t-butylbenzoate, 4-isobutylbenzoate, 4-aminobenzoate, 4-fluorobenzoate, 2- chlorobenzoate, 3-chlorobenzoate, 4-chlorobenzoate, 2,4,6-trimethylbenzoate, 3- methoxybenzoate, 4-methoxybenzoate];

[0092] 1,2-dihydroxybenzene-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-dihydroxybenzene-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];

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

[0095] 1,2-dihydroxybenzene-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];

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

[0097] 1,2-Dihydroxybenzene-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];

[0098] 1,2-Dihydroxybenzene-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-Dihydroxybenzene-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-Dihydroxybenzene-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-dihydroxybenzene-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];

[0102] 1,2-dihydroxybenzene-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] 1,2-dihydroxybenzene-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];

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

[0105] According to a specific embodiment of the present application, preferably, the composition of the catalyst component comprises a titanium compound, a magnesium compound, the 2,6-dicarboxylate-4-pyrone internal electron donor and Lewis base internal electron donor; the precursor of the magnesium compound is selected from the group consisting of X n Mg(OR a ) 2-n , MgCl2.mR a OH, R a 2-n MgX none or more combinations of the above-mentioned magnesium compounds and the above-mentioned titanium compounds, wherein m is 0.1-6, 0 a 0 20 n is 0-2, R is a C1-C6 hydrocarbon group, and X is a halogen. N b 4-N b 20

[0106] According to a specific embodiment of the present application, preferably, the magnesium compound is an alcoholate of a 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 a magnesium dihalide molecule in which at least one halogen atom is replaced by a hydrocarbyloxy group or a halocarbyloxy group; preferably, a hydrocarbyloxymagnesium compound; more preferably, an alkoxy magnesium and / or an aryloxy magnesium.

[0107] According to a specific embodiment of the present application, preferably, the titanium compound comprises one or more combinations of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and an alkoxy halide of titanium.

[0108] According to a specific embodiment of the present application, preferably, the alky halide of titanium comprises one or more combinations of methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, and tri-n-butoxy titanium chloride.

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

[0110] According to a specific embodiment of the present application, preferably, the total amount of the internal electron donor is in a molar ratio of 0.01-5.0:1, preferably 0.05-3.0:1, to the magnesium compound calculated as magnesium element.

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

[0112] Method 1: reaction of an alcoholate of magnesium or a chlorohydrate of magnesium and excess TiCl4 and an internal electron donor compound at a temperature of 80-135°C; preferably, a titanium compound of the general formula TiX N (OR b ) 4-N , wherein R is a C1-C6 hydrocarbon group, and X is a halogen. b ​​​​​For C1-C 20 The hydrocarbon group, where X is a halogen and N = 1-4; preferably TiCl4) and the general formula MgCl2·mR a The adduct of OH (where m is a number from 0.1 to 6, preferably 2 to 3.5, and R...) a For C1-C 20 Solid catalyst components are prepared by reacting hydrocarbon groups (or internal electron donors); wherein the general formula is MgCl2·mR a OH adducts can be suitably prepared into spherical form by mixing an alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, followed by rapid quenching of the emulsion, thereby solidifying the adduct into spherical particles (see disclosures in US4399054 and US4469648). The spherical adducts obtained by this method can react directly with titanium compounds, or they can be pre-treated with a thermally controlled dealcoholization process (80°C–130°C) to obtain a dealcoholization adduct (wherein the molar number of alcohol is generally less than 3, preferably between 0.1 and 2.5), before proceeding with subsequent reactions.

[0113] For example, the adduct or dealcohol adduct is suspended in cold TiCl4 (typically -25°C to 0°C) to react with a titanium compound, and the mixture is heated to 80°C to 130°C and held at this temperature for 0.5 to 2 hours. The treatment with TiCl4 can be performed once or multiple times, and an internal electron donor compound can be added during the TiCl4 treatment. This treatment can be repeated once or multiple times.

[0114] Method 2: A magnesium compound is dissolved in a solvent system consisting of an organic epoxy compound, an organophosphorus compound, and an inert diluent to form a homogeneous solution. This solution is then mixed with a titanium compound, and a solid is precipitated in the presence of a precipitation aid. This solid is treated with an internal electron-donating compound to load the compound onto the solid. If necessary, further treatment with titanium tetrahalide and an inert diluent is performed. The precipitation aid is one of organic anhydrides, organic acids, ethers, or ketones. The components, per mole of magnesium halide, are: organic epoxy compound 0.2-10 mol, organophosphorus compound 0.1-3 mol, precipitation aid 0.03-1.0 mol, and titanium compound 0.5-150 mol (based on moles of titanium).

[0115] Method three: reaction of a titanium compound (e.g. TiCl4) or an aromatic hydrocarbon solution (e.g. toluene, xylene, etc.) of a titanium alkoxide with a magnesium compound, such as a dialkoxymagnesium or a diaryloxymagnesium compound, at -25 to 0°C, halogenation at 80 to 130°C, the treatment with the aromatic hydrocarbon solution of TiCl4may be repeated one or more times, and the internal electron donor compound can be added in one or more portions during the course of the treatment. For example, the preparation of a titanium-containing solid catalyst component can be carried out according to the procedure disclosed in US 5 077 357: ethylmagnesium, titanium tetraethoxide, o-cresol, ethanol and chlorobenzene are added in this order, stirring; the TiCl4 / chlorobenzene solution is quickly added to the above liquid, after complete dissolution by heating, the temperature is increased to 80 to 130°C; after the ethanol reactant is removed by bubbling N2, the stirring is continued for a certain time, then a washing with hot chlorobenzene is carried out once, a washing with isooctane is carried out twice, then N2drying is carried out;

[0116] Method four: the dichloromagnesium is pre-activated according to the known methods, then it is treated with an excess of TiCl4at a temperature of about 80 to 135°C, wherein the internal electron donor compound is contained in the solution. The treatment with TiCl4is carried out several times and the solid is washed with hexane to remove any unreacted TiCl4;

[0117] Method five: the preparation of a titanium-containing solid catalyst component can be carried out according to the procedure disclosed in CN 1208045: a liquid magnesium compound and a liquid titanium compound are contacted in the presence of a compound selected from the group consisting of alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and esters at a temperature of -70 to 200°C, preferably -30 to 130°C, the contacting is carried out in the presence of an internal electron donor compound;

[0118] Method six: anhydrous magnesium chloride and an internal electron donor compound are ground together under the conditions of the activation of the dichloromagnesium, the product thus obtained can be treated with an excess of TiCl4at a temperature of 80 to 130°C, one or more times, after the treatment the product is washed with a hydrocarbon solvent until it is free from chloride ions. In further detail: the product obtained by the co-grinding of anhydrous dichloromagnesium, 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 is carried out at a temperature of 40°C to the boiling point of the halogenated hydrocarbon for 1 to 4 hours, then the product is washed with an inert hydrocarbon solvent, such as hexane, etc.;

[0119] Method seven: the catalyst component is prepared using a magnesium compound supported on inorganic oxides such as SiO2, alumina or porous resins, then activated by well-known methods and treated with an excess of TiCl4 at temperatures of from about 80°C to about 135°C, adding an internal donor compound during the treatment.

[0120] The reactions of the above catalyst components result in the formation of magnesium halides in an active form; the crystalline magnesium halides are generally regular and have a low capacity for Ti, thus having a low catalytic activity; to prepare supported catalysts with high activity, the magnesium halide must be subjected to an activation treatment; the activation treatment consists in making it microcrystalline by physical and / or chemical methods, so that the active centres are available on the surface, edges and defects of the magnesium halide; the microcrystalline magnesium halide thus treated, which is suitable for supporting Ti, is the "active magnesium halide". In addition to these reactions, other methods are known from the literature for obtaining active magnesium halides starting from compounds different from magnesium halides.

[0121] In any of the preparation methods of the catalyst components, the above internal donor compound can be added directly as such or by alternative means, for example by using a suitable precursor which is able to be converted in situ in the desired internal donor compound, for example by means of known chemical reactions such as esterification, transesterification and the like. Generally, the above internal donor compound is used in a molar ratio of from 0.01 to 5:1, preferably from 0.05 to 3.0:1, with respect to the number of moles of MgCl2; furthermore, the internal donor compound can be added in one batch or in several batches, simultaneously or separately, in any order and in any combination.

[0122] The present application also provides a catalyst for the polymerization of olefins, which comprises the above catalyst component and an organic aluminium compound.

[0123] According to a specific embodiment of the present application, preferably, the organic aluminium compound has the general formula AlR c p X (3-p) wherein R c is hydrogen or a C1-C 20 hydrocarbon group, X is halogen and p is an integer of from 0 to 3.

[0124] According to a specific embodiment of the present application, preferably, the organic aluminium compound comprises one or a combination of two or more of a trialkyl aluminium compound, an alkyl aluminium halide, an alkyl aluminium hydride, an alkyl aluminium sesquichloride, an alkyl aluminium oxide.

[0125] According to the specific embodiments of the present application, preferably, the trialkyl aluminum compound comprises one or more than two combinations of trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, trioctyl aluminum; the alkyl aluminum halide comprises AlEt2Cl; the alkyl aluminum sesquichloride comprises Al2Et3Cl3; more preferably, the organoaluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

[0126] According to the specific embodiments of the present application, preferably, the molar ratio of the organoaluminum compound to the titanium atom in the catalyst component is 1-1000:1, more preferably 50-800:1; in terms of reducing the polymer ash content, the molar ratio of Al / Ti in the catalyst is less than 500, preferably less than 200, further preferably less than 100.

[0127] According to the specific embodiments of the present application, preferably, the raw material composition of the catalyst further comprises an external electron donor.

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

[0129] According to the specific embodiments of the present application, 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 hydrocarbon groups, and t is an integer of 0≤t≤3; more preferably, R’ and R” each comprises one or more than two combinations of N, O, S, P, Si.

[0130] According to a particular embodiment of the application, preferably, the siloxane compound comprises 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-t-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-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-propyldimethoxysilane, cyclohexyl-n-propyldiethoxysilane, cyclohexyl-n-butyldiethoxysilane, pentylmethyldimethoxysilane, pentylmethyldiethoxysilane, pentylethyldimethoxysilane, pentylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethyl-ethoxysilane, 2-ethylhexyltrimethoxysilane, cyclohexyldimethoxysilane, cyclohexyldiethoxysilane, 2-ethylhexyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, t-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,one or more than two kinds of a combination of 5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, di(3-methylcyclohexyl)dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, di(4-methylcyclohexyl)dimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, di(3,5-dimethylcyclohexyl)dimethoxysilane, tetrapropoxysilane, tetrabutoxysilane,

[0131] The siloxane compound more preferably includes one or more than two kinds of a combination of di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, t-butytrimethoxysilane, 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 application, 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 present application also provides the use of the above-mentioned catalyst in the polymerization of olefins.

[0134] According to a specific embodiment of the present application, preferably, the olefin includes one or more than two kinds of a combination of linear or branched olefins, 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.

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

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

[0137] According to a specific embodiment of the present application, preferably, in the catalytic process, the order of adding each component in the catalyst is arbitrary, and it is preferable that the organic aluminum compound is added first into the polymerization system, then the external electron donor is added, and finally the catalyst component is added.

[0138] According to the specific embodiments of the present application, preferably, in the above-mentioned applications, the polymerization process can be carried out with or without solvent; the olefin monomer can be in gas phase or liquid phase; more preferably, hydrogen can be further added as a molecular weight regulator (the polymerization can also be carried out without molecular weight regulator); both continuous polymerization and 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 the specific embodiments of the present application, preferably, the temperature of the polymerization is ≤200℃, more preferably 20-100℃, and further preferably 40-80℃; the pressure of the polymerization is ≤10MPa, preferably 0.3-5MPa.

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

[0141] The present application uses 2,6-dicarboxylate-4-pyrone compound as an internal electron donor of polyolefin catalyst, which has good complexing property, and can be complexed with various Lewis base compounds to make the catalyst exhibit optimal performance, especially the activity can be significantly improved after complexing, and is significantly higher than the activity when any one of the complexed internal electron donors is used alone, and the activity of some embodiments after complexing can be more than twice that before complexing. The polypropylene obtained by using the catalyst has high isotacticity, and even without external electron donor, high isotacticity polymer can still be obtained, and the catalyst has ultra-high activity, and the activity decays slowly with the extension of the polymerization reaction time, and remains at a high level for a long time. When used for propylene polymerization, low-ash polymer can be obtained when the Al / Ti ratio is reduced. DETAILED DESCRIPTION

[0142] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the present application, the technical solutions of the present application are described in detail as follows, but it should not be understood as a limitation on the implementable scope of the present application.

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

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

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

[0146] The determination of the molecular weight distribution of the polymers was carried out by means of gel permeation chromatography PL-220, with trichlorobenzene as solvent at 150°C (standard: polystyrene, flow rate 1.0 mL / min, column: 3 x Plgel 10um M1Xed-B 300 x 7.5 nm).

[0147] Other Lewis base compound sources:

[0148] 9,9-bis-methoxymethylfluorene, commercially available, CAS number 182121-12-6;

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

[0150] di-n-butyl phthalate, commercially available, CAS number 84-74-2;

[0151] diethyl 2,3-diisopropylsuccinate, synthesized according to CN1313869A;

[0152] diethyl 2,3-diisopropyl-2-cyanosuccinate, synthesized according to CN106608935A;

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

[0154] 1,2-dihydroxybenzene-4-tert-butyl-1,2-diethyl acetate, 1,2-dihydroxybenzene-4-tert-butyl-1,2-di-n-hexanoate, 1,2-dihydroxybenzene-1,2-dibenzoate, 1,2-dihydroxybenzene-4-tert-butyl-1,2-dibenzoate, 1,2-dihydroxybenzene-4-tert-butyl-1,2-di(m-chlorobenzoate), synthesized according to CN102325808A;

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

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

[0157] 1,2,6-di-n-butyl-4-pyrone dicarboxylate synthesis, the procedure is as follows:

[0158] (1) Dissolve sodium (11.8 g, 0.5 mol, 2.04 eq.) in absolute ethanol (180 mL) to obtain a solution ready for use; add absolute 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.) to the solution obtained previously in 15 minutes, forming a yellow precipitate; keep the reaction mixture at 60°C for one hour, add HCl (aq. 37%, 100 mL) and water (50 mL), and stir the solution at 50°C for 20 hours, after which remove water and ethanol (about 230 mL) under reduced pressure, then add water (150 mL) and HCl (aq. 37%, 25 mL) to the mixture and stir until the silica gel TLC (eluent: 3 / 7 (v / v), 10% NaCl aqueous solution / ethanol) shows only one spot, after cooling to room temperature, filter the crystals, wash with water, then with cold acetone, recrystallize the crude product to obtain 4-pyrone-2,6-dicarboxylic acid as a white powder (35.0 g, yield: 76%);

[0159] (2) In a 1 L three-necked flask, add 4-pyrone-2,6-dicarboxylic acid (5.5 g), n-butanol (100 mL), concentrated sulfuric acid (0.6 mL), heat to reflux for 2 hours, cool to room temperature; pour the reaction solution into saturated sodium bicarbonate solution, extract twice with ethyl acetate (100 mL x 2), combine the organic phases, wash with saturated brine (100 mL x 2), concentrate and recrystallize to obtain the product 2,6-dibutyl ester-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). See Table 1 for specific structural information.

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

[0161]

[0162] Table 1 2,6-dicarboxylate-4-pyrone compounds of Formula I

[0163]

[0164]

[0165]

[0166] Preparation of catalyst components

[0167] Example 1

[0168] This example provides a catalyst component prepared as follows:

[0169] In a 500 mL 5-necked flask with stirring, fitted with a nitrogen inlet, was placed 10 g of MgCl2-2.5 C2H5OH microspheres and 150 mL of titanium tetrachloride to make a suspension. The suspension was then maintained at -15 °C for 1 hour, slowly warmed to 80 °C, and 2.1 g (7 mmol) of 2,6-dicarbonyl di-n-butyl ester-4-pyrone and 0.76 g (3 mmol) of 9,9-bis-methoxymethyl fluorene were added. The temperature was then increased to 110 °C and held for 1 hour. The liquid was then filtered off and the resulting solid was washed with 120 mL of titanium tetrachloride at 125 °C for 3 times and then with 150 mL of hexane at 60 °C for 4 times. The liquid was filtered off and the resulting solid was dried to give a solid catalyst component E1. The titanium content, internal electron donor content, and polymerization data for this solid catalyst component are shown in Table 2.

[0170] Examples 2-25

[0171] Examples 2-25 each provide a catalyst component E2-E25 prepared as shown in Example 1 except that 2,6-dicarbonyl di-n-butyl ester-4-pyrone is replaced in order by 7 mmol of the compound a2-a25 in Table 1.

[0172] Example 26

[0173] This example provides a solid catalyst component E26 prepared as shown in Example 1 except that 5 mmol of 2,6-dicarbonyl di-n-butyl ester-4-pyrone and 5 mmol of 9,9-bis-methoxymethyl fluorene are added.

[0174] Example 27

[0175] This example provides a solid catalyst component E27 prepared as shown in Example 1 except that 2 mmol of 2,6-dicarbonyl di-n-butyl ester-4-pyrone and 8 mmol of 9,9-bis-methoxymethyl fluorene are added.

[0176] Examples 28-67

[0177] Each of Examples 28-67 provides a catalyst component E28-E67, which is prepared as shown in Example 1, except that 7 mmol of the internal donor of class a (2,6-dicarboxylate-4-pyrone compounds) and 3 mmol of the internal donor of class b (Lewis base internal donors) are added according to the internal donor numbers shown in Table 2, respectively.

[0178] Examples 68-75

[0179] Each of Examples 68-75 provides a catalyst component E68-E75, which is prepared as shown in Example 1, except that 5 mmol / 3 mmol / 2 mmol of the three donor compounds are added according to the molar ratios shown in Table 2 (total amount of feed is 10 mmol), respectively.

[0180] Examples 76-78

[0181] Each of Examples 76-78 provides a catalyst component E76-E78, which is prepared as shown in Example 1, except that al, bl, blO donors are added according to the molar ratios shown in Table 2 (total amount of feed is 10 mmol), respectively.

[0182] Example 79

[0183] This example provides a solid catalyst component E79, which is prepared as shown in Example 1, except that 5 mmol of al, 3 mmol of bl, and 2 mmol of b12 donors are added, respectively.

[0184] Comparative Example 1

[0185] This comparative example provides a catalyst component D1, which is prepared as in Example 1, except that 7 mmol of al and 3 mmol of bl internal 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 as in Example 1, except that 7 mmol of al and 3 mmol of bl internal donor compounds are replaced with 10 mmol of 9,9-dimethoxyfluorene (bl).

[0188] Comparative Example 3

[0189] This comparative example provides a catalyst component D3 which is prepared according to Example 1 except that 7 mmol of a1 and 3 mmol of the internal donor compound b1 are replaced by 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 according to Example 1 except that 7 mmol of a1 and 3 mmol of the internal donor compound b1 are replaced by 10 mmol of 2,6-di-n-butylate-4-pyrone (a1).

[0192] Comparative Example 5

[0193] This comparative example provides a catalyst component D5 which is prepared according to Example 1 except that 7 mmol of a1 and 3 mmol of the internal donor compound b1 are replaced by 10 mmol of 2,6-diethylate-4-pyrone (a2).

[0194] Comparative Example 6

[0195] This comparative example provides a catalyst component D6 which is prepared according to Example 1 except that 7 mmol of a1 and 3 mmol of the internal donor compound b1 are replaced by 10 mmol of 2,6-diphenylate-4-pyrone (a6).

[0196] Comparative Example 7

[0197] This comparative example provides a catalyst component D7 which is prepared according to Example 1 except that 7 mmol of a1 and 3 mmol of the internal donor compound b1 are replaced by 10 mmol of 2,6-di-m-chlorophenylate-4-pyrone (a9).

[0198] Comparative Example 8

[0199] This comparative example provides a catalyst component D8 which is prepared according to Example 1 except that 7 mmol of a1 and 3 mmol of the internal donor compound b1 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 according to Example 1 except that 7 mmol of a1 and 3 mmol of the internal donor compound b1 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 according to Example 1, except that 7 mmol of a1 and 3 mmol of the internal electron donor compound b1 are replaced by 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 according to Example 1, except that 7 mmol of a1 and 3 mmol of the internal electron donor compound b1 are replaced by 4 mmol of b1, 3 mmol of b3 and 3 mmol of b12 electron donors.

[0206] Polymerization condition 1

[0207] After the 5 L stainless steel autoclave was sufficiently replaced with nitrogen, 5 mL of a triethylaluminum hexane solution with a concentration of 0.5 mol / L and 1 mL of a methylcyclohexyldimethoxysilane hexane solution with a concentration of 0.1 mol / L and 10 mg of the prepared catalyst component were added, then 10 mL of hexane was added to flush the feeding line, 2 L (standard state) of hydrogen and 2.5 L of refined propylene were added, and the reaction was pre-polymerized at 25°C for 5 minutes, and then the temperature was raised to 70°C, and the polymerization reaction was carried out at this temperature for 1 hour. After the reaction was completed, the reactor was cooled and stirring was stopped, and the reaction product was discharged and dried to obtain a polymer. The polymerization data are shown in Table 2.

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

[0209]

[0210]

[0211]

[0212]

[0213]

Note

[0214] b1 : 9,9-bis-methoxymethylfluorene;

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

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

[0217] b4: 2,3-diisopropyl succinic acid diethyl ester;

[0218] b5: 2,3-diisopropyl-2-cyanosuccinic acid diethyl ester;

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

[0220] b7: 1,2-dihydroxybenzene-4-tert-butyl-1,2-diethyl acetate;

[0221] b8: 1,2-dihydroxybenzene-4-tert-butyl-1,2-di-n-hexyl acetate;

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

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

[0224] b11: 1,2-dihydroxybenzene-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 is respectively compounded with diether compound, succinate compound, diol ester compound, ortho-phenylene diester compound, monobasic carboxylic acid ester, aromatic dicarboxylic acid ester compound to form two-component (polymerization numbers 1-67) and three-component (polymerization numbers 68-79), and the results show that the compounding compatibility is good, the polymerization activity is significantly improved, and is higher than that of any one of the electron donor used alone (polymerization numbers 80-86). And compared with the compounding catalysts without 2,6-dicarboxylate-4-pyrone compound (polymerization numbers 87-90), the activity is significantly improved. The obtained polymers have high isotacticity, regular particle shape and high bulk density.

[0226] Polymerization condition 2

[0227] After the 5L stainless steel reaction kettle was sufficiently replaced with nitrogen, 5mL of triethylaluminum hexane solution with a concentration of 0.5mol / L and 1mL of hexane solution of external electron donor shown in Table 3 with a concentration of 0.1mol / L and 10mg of catalyst component E1 (correspondingly, the catalyst is Cat-1) were added, then 10mL of hexane was added to flush the feeding pipeline, 2L (standard state) of hydrogen and 2.5L of refined propylene were added, and the reaction was controlled at 25°C for 5 minutes of pre-polymerization, and then the temperature was increased to 70°C, and the polymerization reaction was carried out at this temperature for 1 hour. After the reaction was completed, the reaction kettle was cooled and the stirring was stopped to discharge the reaction product, and the polymer was obtained after drying. The polymerization data is shown in Table 3.

[0228] Polymerization condition 3

[0229] Into a 5-L stainless steel autoclave, which was thoroughly purged with nitrogen, was added 5 mL of a 0.5 M triethylaluminum solution in hexane and 1 mL of a 0.1 M solution of the external donor shown in Table 3 in hexane and 10 mg of catalyst component E68 (corresponding catalyst Cat-68). The line was then flushed with 10 mL of hexane, and the reactor was charged with 2 L (standard state) of hydrogen and 2.5 L of purified propylene. The reaction was allowed to pre-polymerize at 25 °C for 5 minutes, and then the temperature was increased to 70 °C. The polymerization was allowed to proceed at this temperature for 1 hour. After the reaction was complete, the reactor was cooled and the stirring was stopped, and the reaction product was discharged and dried to obtain the polymer. The polymerization data are shown in Table 3.

[0230] Table 3 Different External Donors

[0231]

[0232] Notes

[0233] CMMS: methylcyclohexyldimethoxysilane;

[0234] DPDMS: dicyclopentyldimethoxysilane;

[0235] PETS: phenyltrimethoxysilane;

[0236] NPTMS: n-propyltrimethoxysilane.

[0237] Polymerization condition 4

[0238] Into a 5-L stainless steel autoclave, which was thoroughly purged with nitrogen, was added 5 mL of a 0.5 M triethylaluminum solution in hexane and 1 mL of a 0.1 M solution of the external donor shown in Table 3 in hexane and 10 mg of catalyst component E68 (corresponding catalyst Cat-68). The line was then flushed with 10 mL of hexane, and the reactor was charged with 2 L (standard state) of hydrogen and 2.5 L of purified propylene. The reaction was allowed to pre-polymerize at 25 °C for 5 minutes, and then the temperature was increased to 70 °C. The polymerization was allowed to proceed at this temperature for 1 hour. After the reaction was complete, the reactor was cooled and the stirring was stopped, and the reaction product was discharged and dried to obtain the polymer. The polymerization data are shown in Table 3.

[0239] The procedure for polymerization Nos. 109-115 was the same as for polymerization No. 98, except that the catalysts were Cat-D1 to Cat-D7, respectively.

[0240] Table 4 (without external donor)

[0241]

[0242]

[0243] As can be seen from the data in Table 2, the activity of the three internal electron donors complex is higher overall (E68-E79, i.e. the combination of "2,6-dicarboxylate-4-pyrone + diether + other internal electron donor"); as can be seen from Table 3, the catalysts Cat-1 and Cat-68 prepared by complexing two or more internal electron donors, when polymerized with different external electron donors, all show high activity, the polymers have high isotacticity, high bulk density, and have good polymerization matching degree. As can be seen from Table 4, when no external electron donor is used, the polymer can still maintain a relatively high isotacticity, the polymerization activity is further improved, showing super-high activity, which is much higher than that of the non-complex catalysts (Cat-D1 to Cat-D7), and when the polymerization time of Cat-1 and Cat-68 is extended from 60 minutes to 120 minutes, the catalyst can maintain super-high activity without attenuation. When low Al / Ti is used, the ash content of the obtained polypropylene is low, which can be reduced to 20 ppm.

Claims

1. A catalyst component for olefin polymerization, comprising: Mg, Ti, halogens, 2,6-dicarboxylate-4-pyranone internal electron donors and Lewis base internal electron donors; in, The 2,6-dicarboxylate-4-pyranone internal electron donor has the structure shown in Formula I: Formula I, In Equation I, R 1 R 2 R 3 and R 4 Whether the elements are the same or different, they are each independently selected from H, halogens, and C1-C. 20 Hydrocarbon group, or C1-C containing one or more heteroatoms selected from N, O and halogens. 20 group; Optional, R 1 R 2 R 3 and R 4 Two or more interdependent bonds in a ring are formed; The Lewis base internal electron donor includes one or more of the following: diether electron donor compounds, ester electron donor compounds, and diketone electron donor compounds.

2. The catalyst component according to claim 1, wherein, In Equation I, R 1 R 2 R 3 and R 4 The substituents, whether identical or different, are independently selected from H, halogens, and the following substituents with up to 20 carbon atoms: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indene, benzyl, haloalkyl, heteroatom-containing alkyl, halocycloalkyl, heteroatom-containing cycloalkyl, halophenyl, heteroatom-containing phenyl, haloalkylphenyl, heteroatom-containing alkylphenyl, halophenylalkyl, heteroatom-containing phenylalkyl, haloindenyl, heteroatom-containing indene, halobenzyl, heteroatom-containing benzyl, heterocyclic aryl substituents; wherein the heteroatom includes one or both of N and O.

3. The catalyst component according to claim 2, wherein, In Equation I, R 1 R 2 R 3 and R 4 Each is independently selected from H, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20 Straight-chain or branched alkyl groups, and the following substituents with 20 or fewer 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, furanyl, pyrroleyl, indene.

4. The catalyst component according to claim 1, wherein, The internal electron donors of the 2,6-dicarboxylate-4-pyranone class include di-n-butyl 2,6-dicarboxylate-4-pyranone, diethyl 2,6-dicarboxylate-4-pyranone, diisobutyl 2,6-dicarboxylate-4-pyranone, dicyclohexyl 2,6-dicarboxylate-4-pyranone, di(tetradecyl) 2,6-dicarboxylate-4-pyranone, diphenyl 2,6-dicarboxylate-4-pyranone, and diphenyl 2,6-dicarboxylate. 4-Pyranone, di-m-chlorophenyl 2,6-dicarboxylate-4-pyranone, di-p-chlorophenyl 2,6-dicarboxylate-4-pyranone, di-o-chlorophenyl 2,6-dicarboxylate-4-pyranone, di-p-methylphenyl 2,6-dicarboxylate-4-pyranone, di-m-methoxyphenyl 2,6-dicarboxylate-4-pyranone, di-p-methoxyphenyl 2,6-dicarboxylate-4-pyranone, di-o-methoxyphenyl 2,6-dicarboxylate-4-pyranone 2,6-Dicarboxylic acid di(α-furanyl ester)-4-pyranone, 2,6-dicarboxylic acid di(5-pentenyl ester)-4-pyranone, 2,6-dicarboxylic acid di-p-nitrobenzene ester-4-pyranone, 2,6-dicarboxylic acid di-n-butyl ester-4-pyranone, 2,6-dicarboxylic acid di-n-butyl ester-3,5-dimethyl-4-pyranone, 2,6-dicarboxylic acid diethyl ester-3-phenyl-4-pyranone, 2,6-dicarboxylic acid diethyl ester-3-chloro- One or more of the following: 4-pyranone, diethyl 2,6-dicarboxylate-3-bromo-4-pyranone, diisopropyl 2,6-dicarboxylate-4-pyranone, dibenzyl 2,6-dicarboxylate-4-pyranone, ethyl 2-carboxylate-6-butyl 2-carboxylate-4-pyranone, dibutyl 2,6-dicarboxylate-3-methyl-4-pyranone, and dibutyl 2,6-dicarboxylate-3-methyl-5-ethyl-4-pyranone.

5. The catalyst component according to claim 1, wherein, The Lewis base internal electron donors include 1,3-diether compounds having the structure shown in Formula II: Formula II, In formula II, R 5 R 6 R 7 R 8 R 9 and R 10 Whether the two are the same or different, they are each independently selected from H, C1-C. 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C5-C 20 aryl, C7-C 20 alkylaryl or C7-C 20 Aryl groups; R 11 and R 12 Whether the two are the same or different, they are each independently selected from C1-C. 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C5-C 20 aryl, C7-C 20 alkylaryl and C7-C 20 Aryl alkyl group; optionally, R 5 -R 12 One or more groups in the compound link together to form a cyclic structure.

6. The catalyst component according to claim 5, wherein, The 1,3-diether compounds have the structure shown in Formula III: Formula III, In Equation III, there are eight R 19 Whether the same or different, each is independently selected from hydrogen, halogen, C1-C 14 Straight-chain or branched alkyl groups, C3-C 14 cycloalkyl, C6-C 14 aryl, C7-C 14 alkylaryl, C7-C 14 arylalkyl groups; R 13 R 14 R 15 and R 16 Whether the two are the same or different, they are each independently selected from H, C1-C. 18 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 alkylaryl or C7-C 20 Aryl groups; R 17 and R 18 Whether the two are the same or different, they are each independently selected from C1-C. 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 alkylaryl and C7-C 20 Aryl alkyl group; optionally, R 13 -R 18 One or more groups in the compound link together to form a cyclic structure.

7. The catalyst component according to claim 1, wherein, The internal electron donors of the Lewis bases include carboxylic acid esters, which include monocarboxylic acid esters and / or polycarboxylic acid esters.

8. The catalyst component according to claim 7, wherein, The polycarboxylic acid esters include aromatic dicarboxylic acid esters and / or aliphatic dicarboxylic acid esters.

9. The catalyst component according to claim 1, wherein, The Lewis base internal electron donors include succinate compounds having the structure shown in Formula IV: Formula IV, In Equation IV, R 20 and R 21 Whether the two are the same or different, they are each independently selected from C1-C. 20 Straight-chain or branched alkyl groups, C2-C 20 alkenyl, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 Aryl groups, C7-C 20 alkylaryl groups;; R 22 -R 25 Each is independently selected from hydrogen, C1-C 20 Straight-chain or branched alkyl groups, C2-C 20 alkenyl, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 Aryl groups, C7-C 20 alkylaryl groups; Optional, R 22 -R 25 They bond to each other to form a ring.

10. The catalyst component according to claim 9, wherein, R 20 and R 21 Each group is independently selected from C1-C8 alkyl, C3-C8 cycloalkyl, C6-C8 aryl, C7-C8 aralkyl, and C7-C8 alkylaryl groups.

11. The catalyst component according to claim 10, wherein, R 20 and R 21 Each is independently selected from straight-chain primary alkyl or branched primary alkyl.

12. The catalyst component according to claim 11, wherein, R 20 and R 21 Each is independently selected from methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, and 2-ethylhexyl.

13. The catalyst component according to claim 12, wherein, R 20 and R 21 Each is independently selected from ethyl, isobutyl, and neopentyl.

14. The catalyst component according to claim 9, wherein, In Equation IV, R 22 -R 24 For hydrogen, R 25 Selected from C3-C 10 Branched alkyl groups, C3-C 10 cycloalkyl, C6-C 10 aryl, C7-C 10 Aryl groups, C7-C 10 alkylaryl groups.

15. The catalyst component according to claim 14, wherein, R 25 Selected from C3-C 10 Branched primary alkyl groups, C3-C 10 cycloalkyl groups.

16. The catalyst component according to claim 9, wherein, In Equation IV, R 22 -R 25 At least two groups are different from hydrogen, and each is independently selected from C1-C2. 20 Straight-chain or branched alkyl groups, C2-C 20 alkenyl, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 Aryl groups, C7-C 20 alkylaryl groups.

17. The catalyst component according to claim 16, wherein, In Equation IV, R 22 -R 25 In the case where two non-hydrogen groups are attached to the same carbon atom, or, R 22 -R 25 The two non-hydrogen groups in the structure are attached to different carbon atoms.

18. The catalyst component according to claim 9, wherein, In Equation IV, R 22 -R 25 Two or four of them are connected to form a loop.

19. The catalyst component according to claim 1, wherein, The Lewis base internal electron donor includes a glycol ester compound having the structure shown in Formula V: Formula V, In Equation V, R 26 -R 31 Whether the same or different, each is independently selected from hydrogen, halogen, C1-C 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 alkylaryl, C7-C 20 Aryl groups, C2-C 10 alkenyl, C 10 -C 20 Fused ring aryl; optionally, R 26 -R 31 Two or more interdependent bonds in R form a ring; 32 -R 33 Whether the two are the same or different, they are each independently selected from halogens, C1-C. 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 alkylaryl, C7-C 20 Aryl groups, C2-C 10 olefin group, C 10 -C 20 Fused ring aryl groups.

20. The catalyst component according to claim 1, wherein, The Lewis base internal electron donors include ortho-phenylene diesters; The ortho-phenylene diester compound has the structure shown in Formula VI: Formula VI, In Equation VI, R 38 and R 39 Whether the two are the same or different, they are each independently selected from C1-C. 20 Straight-chain or branched alkyl groups and their derivatives, C3-C 20 cycloalkyl, C6-C 20 aryl groups and their derivatives, C7-C 20 Araneyl groups and their derivatives, C2-C 10 olefin group, C 10 -C 20 Fused ring aryl, C 10 -C 20 ester group, R 38 and R 39 Not hydrogen; R 34 -R 37 Whether the two are the same or different, they are each independently selected from hydrogen, C1-C 20 hydrocarbon groups and their derivatives, including C1-C 20 Alkoxy groups, groups containing heteroatoms, groups containing C1-C 20 An alkoxy group and a heteroatom group; the heteroatom is a halogen.

21. The catalyst component according to claim 20, wherein, The ortho-phenylene diester compound has the structure shown in Formula VII: Formula VII In equation Ⅶ, R 40 -R 53 Whether the two are the same or different, they are each independently selected from hydrogen, C1-C 20 hydrocarbon groups and their derivatives, including C1-C 20 An alkoxy group.

22. The catalyst component according to claim 21, wherein, In equation Ⅶ, R 40 -R 43 At least one of them is selected from C1-C 20 hydrocarbon groups and their derivatives.

23. The catalyst component according to claim 21, wherein, In equation Ⅶ, R 44 -R 53 At least one of them is selected from C1-C 20 hydrocarbon groups and their derivatives, including C1-C 20 An alkoxy group.

24. The catalyst component according to claim 1, wherein, The molar ratio of the 2,6-dicarboxylate-4-pyranone internal electron donor to the Lewis base internal electron donor is ≥1:

9.

25. The catalyst component according to claim 24, wherein, The molar ratio of the 2,6-dicarboxylate-4-pyranone internal electron donor to the Lewis base internal electron donor is ≥4:

6.

26. The catalyst component according to claim 25, wherein, The molar ratio of the 2,6-dicarboxylate-4-pyranone internal electron donor to the Lewis base internal electron donor is ≥5:

5.

27. The catalyst component according to claim 26, wherein, The molar ratio of the 2,6-dicarboxylate-4-pyranone internal electron donor to the Lewis base internal electron donor is ≥7:

3.

28. The catalyst component according to any one of claims 1-27, wherein, The catalyst component comprises titanium compounds, magnesium compounds, the 2,6-dicarboxylate-4-pyranone internal electron donor and the 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 One or more combinations of MgCl2 / SiO2, MgCl2 / Al2O3, magnesium halides, and titanium alkoxides, wherein m is 0.1-6, 0≤n≤2, X is a halogen, and R a For C1-C 20 hydrocarbon group; The general formula of the titanium compound is TiX. N (OR b ) 4-N In the formula, R b For C1-C 20 The hydrocarbon group, where X is a halogen and N is 1-4.

29. The catalyst component according to claim 28, wherein, The magnesium compound is an alkoxide of magnesium dihalide; Alternatively, the magnesium compound may be a liquid magnesium compound; Alternatively, the magnesium compound is a derivative in which at least one halogen atom in a magnesium dihalide molecule is replaced by an alkyl or haloalkyl group.

30. The catalyst component according to claim 29, wherein, The magnesium compound is an alkyl oxymagnesium compound.

31. The catalyst component according to claim 30, wherein, The magnesium compound is alkoxymagnesium and / or aryloxymagnesium.

32. The catalyst component according to claim 28, wherein, The titanium compound includes one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and titanium alkoxyhalides.

33. The catalyst component according to claim 32, wherein, The alkoxy titanium halide includes one or more combinations of methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, and tri-n-butoxy titanium chloride.

34. The catalyst component according to claim 32, wherein, The titanium compound is titanium tetrachloride.

35. The catalyst component according to claim 28, wherein, The total molar ratio of internal electron donors to the magnesium compound is 0.01-5.0:1, and the magnesium compound is calculated based on magnesium element.

36. The catalyst component according to claim 35, wherein, The total molar ratio of internal electron donors to the magnesium compound is 0.05-3.0:

1.

37. A catalyst for olefin polymerization, comprising the catalyst component as described in any one of claims 1-36 and an organoaluminum compound.

38. The catalyst according to claim 37, wherein, The general formula of the organoaluminum compound is AlR c p X (3-p) , where R c It is hydrogen or C1-C 20 The hydrocarbon group, X is a halogen, and p is an integer 0 ≤ p ≤ 3.

39. The catalyst according to claim 38, wherein, The organoaluminum compounds include one or more of the following: trialkylaluminum compounds, alkylaluminum halides, alkylaluminum hydrides, alkylaluminum sesquichlorides, and alkylaluminoxanes.

40. The catalyst according to claim 39, wherein, The trialkylaluminum compound includes one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and trioctylaluminum; the alkylaluminum halide includes AlEt2Cl; and the alkylaluminum sesquichloride includes Al2Et3Cl3.

41. The catalyst according to claim 39, wherein, The organoaluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

42. The catalyst according to claim 37, wherein, The molar ratio of the organoaluminum compound to the titanium atoms in the catalyst component is 1-1000:

1.

43. The catalyst according to claim 42, wherein, The molar ratio of the organoaluminum compound to the titanium atoms in the catalyst component is 50-800:

1.

44. The catalyst according to claim 37, wherein, The catalyst's feedstock composition also includes an external electron donor.

45. The catalyst according to claim 44, wherein, The external electron donor is a siloxane compound; The general formula of the siloxane compound is R' t Si(OR'') 4-t Where R' and R'' are each independently selected from C1-C 18 The hydrocarbon group, where t is an integer 0 ≤ t ≤ 3.

46. ​​The catalyst according to claim 44, wherein, The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100:

1.

47. The catalyst according to claim 46, wherein, The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.01-20:

1.

48. The catalyst according to claim 47, wherein, The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.01-5:

1.

49. The use of the catalyst according to any one of claims 37-48 in olefin polymerization, wherein the olefin comprises one or more combinations 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.

50. The application according to claim 49, wherein, The polymerization includes the polymerization of ethylene and / or propylene.

51. The application according to claim 50, wherein, The polymerization includes homopolymerization or copolymerization.

52. The application according to claim 49, wherein, The polymerization temperature is ≤200℃ and the polymerization pressure is ≤10MPa.

53. The application according to claim 52, wherein, The polymerization temperature is 20-100℃, and the polymerization pressure is 0.3-5MPa.

54. The application according to claim 53, wherein, The polymerization temperature is 40-80℃.

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