Olefin polymerization catalyst component, olefin polymerization catalyst and application thereof

Abstract

The present invention discloses an olefin polymerization catalyst component, an olefin polymerization catalyst and applications thereof, the olefin polymerization catalyst component comprises Mg, Ti, halogen, at least one internal electron donor a compound and at least one internal electron donor b compound, and the internal electron donor a compound is selected from 2, 3, 4, 5, 6-tetramethyl-1, 3, 4, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5-tetramethyl-1, 3, 5 the compound of the internal electron donor b is selected from at least one of an N-substituent-2, 6-diformate 4-pyridine ether compound as shown in a general formula (I) or an N-substituent-2, 6-diformate 4-pyridine ketone compound as shown in a general formula (II), and the compound of the internal electron donor b is selected from a diether compound. The internal electron donor of the catalyst component is at least one compound selected from 2, 6-diformate 4-pyridine ether in the general formula (I) or N-substituent-2, 6-diformate 4-pyridine ketone in the general formula (II) and a diether compound, and the activity can be remarkably improved after multiple internal electron donors are compounded.

Description

Technical Field

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

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

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

[0004] At present, the most widely used polyolefin internal electron donor in industry is phthalate compounds, which have medium activity, good stereoselectivity and low price for the catalysts prepared by them. However, phthalate compounds, as commonly used plasticizers, are very harmful to human reproductive health and the environment, and there is a great demand for replacement. Europe has restricted the use of most phthalate substances; at the same time, the new phthalate restriction policy is bound to affect its use in China. Therefore, it is one of the common research and development goals in the field of polyolefin catalysts in recent years to develop new electron donors with excellent activity, good stereospecificity, good comprehensive performance and low cost to replace the widely used phthalate electron donor compounds in the prior art, and use them to prepare efficient Ziegler-Natta catalysts. Summary of the invention

[0005] In order to solve the problems existing in the prior art, the present invention provides an internal electron donor compound with excellent basic performance and good compatibility with various other internal electron donor compounds. After the internal electron donor compound is compounded with various other types of internal electron donor compounds, the catalytic activity can be significantly improved, and a highly isotactic polymer can still be obtained without adding an external electron donor.

[0006] The object of the present invention is to provide a catalyst component for the polymerization of olefins.

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

[0008] Another object of the present invention is to provide a catalyst for the polymerization of olefins.

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

[0010] In order to achieve the object of the present invention, the present invention provides an olefin polymerization catalyst component, which comprises Mg, Ti, halogen, at least one internal electron donor a compound and at least one internal electron donor b compound, wherein the internal electron donor a compound is selected from at least one of a 2,6-dicarboxylic acid ester-4-pyridyl ether compound of general formula (I) or an N-substituted-2,6-dicarboxylic acid ester-4-pyridinone compound of general formula (II), and the internal electron donor b compound is selected from a diether compound.

[0011]

[0012] Wherein, R in the general formula (I) or the general formula (II) 1 -R 10 are the same or different, each independently selected from H, halogen, C1-C 20 Preferably, R 1 -R 10 They may further contain at least one heteroatom selected from N, O, S, P, Si and halogen.

[0013] Preferably, in the general formula (I) or (II), R 1 -R 10 the same or different, each independently selected from H, halogen, the following substituents with less than 20 carbon atoms: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or substituted with N, O, S, P, Si heteroatom alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or each independently selected from heterocyclic aromatic substituents.

[0014] Preferably, in the general formula (I) or (II), R 1 -R 10 are the same or different and are each independently selected from H, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 ~C 20a linear or branched or cyclic alkyl group, or the following substituents having up to 20 carbon atoms: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, m-methylphenyl, o-methylphenyl, m-trimethylphenyl, p-nitrophenyl, m-nitrophenyl, substituted benzyl, substituted phenethyl, furanyl, pyrrolyl, thienyl, propenyl, butenyl, pentenyl, hexenyl, and indenyl.

[0015] Preferably, the 2,6-dicarboxylate-4-pyridine ether compound in the general formula (I) is selected from 2,6-di-n-butyl dicarboxylate-4-methoxypyridine, 2,6-diisopropyl dicarboxylate-4-isopropyloxypyridine, 2,6-di(dodecyl) dicarboxylate-4-n-butoxypyridine, 2,6-diphenyl dicarboxylate-4-methoxypyridine, 2,6-dichlorophenyl dicarboxylate-4-methoxypyridine, 2,6-di-p-tolyl dicarboxylate-4-methoxypyridine, 2,6-di-p-methoxyphenyl dicarboxylate-4-benzyloxypyridine. , at least one of 2,6-dicarboxylic acid difuranyl methyl ester-4-methoxypyridine, 2,6-dipentenyl dicarboxylate-3-methyl-5-ethyl-4-methoxypyridine, 2,6-di-p-nitrophenyl dicarboxylate-3,5-diethyl-4-methoxypyridine, 2,6-dimethyl dicarboxylate-3-methyl-5-n-butyl-4-methoxypyridine, 2,6-dicarboxylic acid dibenzyl ester-4-ethoxypyridine, 2-ethyl formate-6-n-butyl formate 4-methoxypyridine, and 2-ethyl formate-6-phenyl formate-4-methoxypyridine.

[0016] Preferably, the N-substituted-2,6-dicarboxylate-4-pyridone compound in the general formula (II) is selected from N-isopropyl-2,6-diethyl dicarboxylate-4-pyridone, N-tert-butyl-2,6-dicarboxylic acid didodecyl ester-4-pyridone, N-n-butyl-2,6-dicarboxylic acid di-n-butyl ester-4-pyridone, N-phenyl-2,6-dicarboxylic acid diphenyl ester-4-pyridone, N-m-chlorophenyl-2,6-dicarboxylic acid di-m-chlorophenyl ester-4-pyridone, N-p-chlorophenyl-2,6-dicarboxylic acid di-p-tolyl ester-4 -pyridone, N-o-chlorophenyl-2,6-dicarboxylic acid di-p-methoxyphenyl-4-pyridone, N-p-methoxyphenyl-2,6-dicarboxylic acid difuranyl ester-4-pyridone, N-methyl-2,6-dicarboxylic acid dipentenyl ester-4-pyridone, N-methyl-2,6-dicarboxylic acid di-p-nitrophenyl ester-3-methyl-5-ethyl-4-pyridone, N-benzyl-2,6-dicarboxylic acid dibenzyl ester-3,5-diethyl-4-pyridone, N-methyl-2-ethyl-6-phenyl-4-pyridone.

[0017] Preferably, the 2,6-dicarboxylate-4-pyridine ether compound of general formula (I) can be synthesized by the preparation methods including but not limited to the following routes 1-3:

[0018]

[0019] Route 1 can be used to synthesize R 1 =R 2 =R 5 In route 2, when an alcohol is selected in the second step (R 1 With R 2 same) to obtain a single product; when two alcohols are selected in the second step (R 1 With R 2 The final mixture can be used as an internal electron donor directly as a mixture without separation. The ratio of each component in the mixture can be adjusted by the addition ratio of the two alcohols as reactants. The ratio of each component can be determined by characterization by chromatography-mass spectrometry, nuclear magnetic resonance and other analytical methods; Route 3 uses oxalic acid as a raw material to synthesize 2,6-dicarboxylic acid ester-4-pyrone, and then obtain the final product.

[0020] Preferably, the N-substituted-2,6-dicarboxylate-4-pyridone compound of general formula (II) can be synthesized by the preparation methods including but not limited to those shown in Scheme 4 and Scheme 5:

[0021]

[0022] In route 4, when an alcohol is selected in the third step (R 1 With R 2 The same) gives a single product. When two alcohols are selected in the third step (R 1 With R 2 The final mixture can be used as an internal electron donor directly as a mixture without separation. The ratio of each component in the mixture can be adjusted by the addition ratio of the two alcohols as reactants. The ratio of each component can be determined by chromatography-mass spectrometry, nuclear magnetic resonance and other analytical methods.

[0023] Preferably, the diether compound is selected from 1,3-diether compounds represented by general formula (III):

[0024]

[0025] In the general formula (III), R 11 -R 16 are the same or different, each independently selected from H, each independently selected from a linear or branched alkyl, cycloalkyl, aryl, alkaryl or aralkyl group containing 1 to 18 carbon atoms; R 17 -R 18are the same or different and are each independently selected from a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms, an alkaryl group having 7 to 20 carbon atoms and an aralkyl group; R 11 -R 18 One or more groups in the group may be linked to form a ring structure, and each may further contain at least one heteroatom selected from halogen, N, O, S, P and Si.

[0026] Specifically, the 1,3-diether compound includes, but is not limited to, 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-tert-butyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2 (1-naphthyl)-1,3-dimethoxypropane, 2(p-fluorophenyl)-1,3-dimethoxypropane, 2(1-decalinyl)-1,3-dimethoxypropane, 2(p-tert-butylphenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-diethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-diethoxypropane, 2,2-dibutyl-1,3-diethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane Oxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2-methyl-2-methylcyclohexyl-1,3-dimethoxypropane, 2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane, 2,2-bis(2-phenylethyl)-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-bis(2-ethylhexyl)-1,3-dimethoxypropane )-1,3-dimethoxypropane, 2,2-bis(p-methylphenyl)-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-di-sec-butyl-1,3-dimethoxypropane, 2,2-di-tert-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-iso-propyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxy__ylpropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane. 1,1-Bis(methoxymethyl)-cyclopentadiene; 1,1-Bis(methoxymethyl)-2,3,4,5-tetramethylcyclopentadiene; 1,1-Bis(methoxymethyl)-2,3,4,5-tetraphenylcyclopentadiene; 1,1-Bis(methoxymethyl)-2,3,4,5-tetrafluorocyclopentadiene; 1,1-Bis(methoxymethyl)-3,4-dicyclopentylcyclopentadiene; 1,1-Bis(methoxymethyl)-indene; 1,1-Bis(methoxymethyl)-2,3-dimethylindene; 1,1-Bis(methoxymethyl)-4,5,6,7-tetrahydroindene; 1,1-Bis(methoxymethyl)-2,3,6,7-tetrafluoroindene; 1,1-Bis( 1,1-bis(methoxymethyl)-4,7-dimethylindene; 1,1-bis(methoxymethyl)-3,6-dimethylindene; 1,1-bis(methoxymethyl)-4-phenylindene; 1,1-bis(methoxymethyl)-4-phenyl-2-methylindene; 1,1-bis(methoxymethyl)-4-cyclohexylindene; 1,1-bis(methoxymethyl)-7-(3,3,3-trifluoropropyl)indene; 1,1-bis(methoxymethyl)-7-trimethylsilylindene; 1,1-bis(methoxymethyl)-7-trifluoromethylindene; 1,1-bis(methoxymethyl)-4,7-dimethyl-4,5,6,7-tetrahydroindene; 1,1-bis(methoxymethyl)-7- Methylindene; 1,1-bis(methoxymethyl)-7-cyclopentylindene; 1,1-bis(methoxymethyl)-7-isopropylindene; 1,1-bis(methoxymethyl)-7-cyclohexylindene; 1,1-bis(methoxymethyl)-7-tert-butylindene; 1,1-bis(methoxymethyl)-7-tert-butyl-2-methylindene; 1,1-bis(methoxymethyl)-7-phenylindene; 1,1-bis(methoxymethyl)-2-phenylindene; 1,1-bis(methoxymethyl)-1H-benzo[e]indene; 1,1-bis(methoxymethyl)-1H-2-methylbenzo[e]indene; 9,9-bis(methoxymethyl)fluorene; 9,9-bis(methoxymethyl)fluorene )-2,3,6,7-tetramethylfluorene; 9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene; 9,9-bis(methoxymethyl)-2,3-benzofluorene; 9,9-bis(methoxymethyl)-2,3,6,7-dibenzofluorene; 9,9-bis(methoxymethyl)-2,7-diisopropylfluorene; 9,9-bis(methoxymethyl)-1,8-dichlorofluorene; 9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorene; 9,9-bis(methoxymethyl)-1,8-difluorofluorene; 9,9-bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene; 9,9-bis(methoxymethyl)-1,2,3,At least one of 4,5,6,7,8-octahydrofluorene and 9,9-bis(methoxymethyl)-4-tert-butylfluorene.

[0027] Preferably, the diether compound is further selected from the compound represented by general formula (IV):

[0028]

[0029] In the general formula (IV), R 25 -R 32 R is the same or different, each independently selected from hydrogen, halogen, linear or branched alkyl with 1 to 20 carbon atoms, cycloalkyl with 3 to 20 carbon atoms, aryl with 6 to 20 carbon atoms, alkylaryl with 7 to 20 carbon atoms and arylalkyl with 7 to 20 carbon atoms, optionally containing at least one heteroatom selected from N, O, S, P, Si and halogen as a substituent for carbon atoms or hydrogen atoms or both; 19 -R 22 are the same or different and are each independently selected from H, or are each independently selected from a linear or branched alkyl, cycloalkyl, aryl, alkaryl or aralkyl group containing 1 to 18 carbon atoms; R 23 and R 24 are the same or different and are each independently selected from a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms, an alkaryl group having 7 to 20 carbon atoms and an aralkyl group; R 19 -R 32 One or more groups in the group may be linked to form a ring structure, and each may further contain at least one heteroatom selected from halogen, N, O, S, P and Si.

[0030] Preferably, the diether compound includes but is not limited to: 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-tert-butyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2-(1- 2,2-dibutyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-diethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-diethoxypropane, 2,2-dibutyl-1,3-diethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane 2-Methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2-methyl-2-methylcyclohexyl-1,3-dimethoxypropane, 2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane, 2,2-bis(2-phenylethyl)-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-bis(2-ethylhexyl)-1 ,3-dimethoxypropane, 2,2-bis(p-methylphenyl)-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-di-sec-butyl-1,3-dimethoxypropane, 2,2-di-tert-butyl-1,3-dimethoxypropane, 2,2-di-neopentyl-1,3-dimethoxypropane, 2-iso-propyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 1,1-bis(methoxymethyl)-cyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetramethylcyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetraphenylcyclopentadiene; 1,1-bis(methoxymethyl)-2,3,4,5-tetrafluorocyclopentadiene; 1,1-bis(methoxymethyl)-3 ,4-dicyclopentylcyclopentadiene; 1,1-bis(methoxymethyl)indene; 1,1-bis(methoxymethyl)-2,3-dimethylindene; 1,1-bis(methoxymethyl)-4,5,6,7-tetrahydroindene; 1,1-bis(methoxymethyl)-2,3,6,7-tetrafluoroindene; 1,1-bis(methoxymethyl)-4,7-dimethylindene; 1,1-bis(methoxymethyl)-3,6-dimethylindene; 1,1-bis(methoxymethyl)-4-phenylindene; 1,1-bis(methoxymethyl)-4-phenyl-2-methylindene; 1,1-bis(methoxymethyl)-4-cyclohexylindene; 1,1-bis(methoxymethyl)-7-(3,3,3-trifluoropropyl)indene; 1,1-bis(methoxymethyl)-7- trimethylsilylindene; 1,1-bis(methoxymethyl)-7-trifluoromethylindene; 1,1-bis(methoxymethyl)-4,7-dimethyl-4,5,6,7-tetrahydroindene; 1,1-bis(methoxymethyl)-7-methylindene; 1,1-bis(methoxymethyl)-7-cyclopentylindene; 1,1-bis(methoxymethyl)-7-isopropylindene; 1,1-bis(methoxymethyl)-7-cyclohexylindene; 1,1-bis(methoxymethyl)-7-tert-butylindene; 1,1-bis(methoxymethyl)-7-tert-butyl-2-methylindene; 1,1-bis(methoxymethyl)-7-phenylindene; 1,1-bis(methoxymethyl)-2-phenylindene; 1,1-bis(methoxymethyl)-1H-benzo[e]indene; 1 ,1-bis(methoxymethyl)-1H-2-methylbenzo[e]indene; 9,9-bis(methoxymethyl)fluorene; 9,9-bis(methoxymethyl)-2,3,6,7-tetramethylfluorene; 9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene; 9,9-bis(methoxymethyl)-2,3-benzofluorene; 9,9-bis(methoxymethyl)- 9,9-bis(methoxymethyl)-2,3,6,7-dibenzofluorene; 9,9-bis(methoxymethyl)-2,7-diisopropylfluorene; 9,9-bis(methoxymethyl)-1,8-dichlorofluorene; 9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorene; 9,9-bis(methoxymethyl)-1,8-difluorofluorene; 9,9-bis(methoxymethyl)-1,2,3,At least one of 4-tetrahydrofluorene; 9,9-bis(methoxymethyl)-1,2,3,4,5,6,7,8-octahydrofluorene; 9,9-bis(methoxymethyl)-4-tert-butylfluorene.

[0031] Preferably, the molar ratio of the internal electron donor compound a to the internal electron donor compound b is greater than or equal to 3:7.

[0032] Preferably, the molar ratio of the internal electron donor compound a to the internal electron donor compound b is greater than or equal to 5:5.

[0033] Preferably, the molar ratio of the internal electron donor compound a to the internal electron donor compound b is greater than or equal to 6:4.

[0034] Preferably, the molar ratio of the internal electron donor compound a to the internal electron donor compound b is greater than or equal to 7:3.

[0035] Preferably, the molar ratio of the internal electron donor compound a to the internal electron donor compound b is 7:3.

[0036] According to a specific embodiment of the present invention, preferably, the composition of the catalyst component comprises a titanium compound, a magnesium compound, the internal electron donor a compound and the internal electron donor b compound;

[0037] The precursor of the magnesium compound is selected from X n Mg(OR a ) 2-n 、MgCl2·mR a OH, R a 2-n MgX n , MgCl2 / SiO2, MgCl2 / Al2O3, a mixture of magnesium halide and titanium alkoxide, wherein m is 0.1-6, 0≤n≤2, X is a halogen, R a C1-C 20 The hydrocarbon group;

[0038] The general formula of the titanium compound is TiX N (OR b ) 4-N , where R b C1-C 20 The hydrocarbon group is: X is halogen, and N is 1-4.

[0039] Preferably, the magnesium compound is an alcoholate of magnesium dihalide;

[0040] Alternatively, the magnesium compound is a liquid magnesium compound;

[0041] Alternatively, the magnesium compound is a derivative of a magnesium dihalide molecule in which at least one halogen atom is replaced by a hydrocarbonoxy group or a halogenated hydrocarbonoxy group; preferably, it is a hydrocarbonoxy magnesium compound; more preferably, it is an alkoxy magnesium and / or an aryloxy magnesium.

[0042] Preferably, the titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and alkoxy titanium halide;

[0043] Preferably, the alkyl titanium halide includes at least one of methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, and tri-n-butoxytitanium chloride;

[0044] Preferably, the titanium compound is titanium tetrachloride.

[0045] Preferably, the molar ratio of the sum of the internal electron donor a compound and the internal electron donor b compound to the magnesium compound is 0.01-5.0, preferably 0.05-3.0, and the magnesium compound is calculated as magnesium element.

[0046] The present invention does not particularly limit the preparation method of the olefin polymerization catalyst component, which can be prepared according to the following preparation methods:

[0047] Method 1: A solution of a titanium compound (such as TiCl4 or titanium alkoxide) in an aromatic hydrocarbon (such as toluene, xylene, etc.) is reacted with a magnesium compound (such as a dihydrocarbyl magnesium compound such as a magnesium dialkoxide or a magnesium diaryloxide) at -25-0°C, and halogenated at 80-130°C. The treatment with the aromatic hydrocarbon solution of TiCl4 can be repeated once or multiple times, and an internal electron donor can be added. For example, the preparation method of the titanium-containing solid catalyst component disclosed in US5077357A can be referred to: ethoxymagnesium, tetraethoxytitanium, o-cresol, ethanol and chlorobenzene are added in sequence, and stirred; the TiCl4 / chlorobenzene solution is quickly added to the above liquid, and the temperature is raised until it is completely dissolved, and then the temperature is further raised to 80-130°C; the ethanol reactant is taken away by bubbling with N2, and then the stirring is continued for a certain period of time, and then hot chlorobenzene is used to wash once, isooctane is washed twice, and then N2 is blown dry to obtain the carrier. Or according to another example: TiCl4, tetraethoxytitanium, ethoxymagnesium and o-cresol are added to chlorobenzene in sequence and stirred; ethanol is added and stirring is continued for 3 hours at high temperature after the ethoxymagnesium is dissolved; hot filtering is then washed once with warm chlorobenzene and once with isooctane, and finally dried with N2.

[0048] Method 2: A magnesium compound (such as magnesium alcoholate or chloroalcoholate) is reacted with an excess of TiCl4 containing an internal electron donor in a solution at a temperature of 80-135°C. According to a preferred method, a general formula of TiX N (OR b ) 4-N Titanium compounds (where R b C1-C 20 A hydrocarbon group, X is a halogen, N is 1-4; preferably TiCl4) and a general formula of MgCl2·mR a OH (wherein m is a number of 0.1-6, preferably 2-3.5, and R a C1-C 20 The solid catalyst component is prepared by reacting an adduct of an alcohol with an alkyl group of an isocyanate (a hydrocarbon group). The adduct can be suitably made into a spherical shape by the following method: in the presence of an inert hydrocarbon that is immiscible with the adduct, an alcohol and magnesium chloride are mixed, and the emulsion is rapidly quenched, thereby solidifying the adduct in the form of spherical particles. Spherical MgCl2·mR prepared according to this process a Examples of OH adducts are described in US Pat. No. 4,399,054 A and US Pat. No. 4,469,648 A. The adduct thus obtained can be reacted directly with the titanium compound, or it can be previously subjected to a thermally controlled dealcoholation (80-130° C.) to obtain an adduct in which the number of moles of alcohol is generally less than 3, preferably between 0.1 and 2.5. The reaction with the titanium compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCl4 (generally -25-0° C.); the mixture is heated to 80-130° C. and kept at this temperature for 0.5-2 hours. The treatment with TiCl4 can be carried out once or more. An internal electron donor can be added during the treatment with TiCl4, and this treatment can be repeated once or more.

[0049] Method 3: Anhydrous magnesium chloride and an internal electron donor are ground together under conditions where magnesium dichloride is activated. The product thus obtained can be treated one or more times with an excess of TiCl4 at a temperature of 80-130°C. After treatment, it is washed with a hydrocarbon volume until it is free of chloride ions. According to a further method, the product obtained by grinding magnesium dichloride, a titanium compound and an internal electron donor in an anhydrous state is treated with a halogenated hydrocarbon such as 1,2-dichloroethane, chlorobenzene, dichloromethane. The treatment is carried out at a temperature between 40°C and the boiling point of the halogenated hydrocarbon for 1-4 hours. The product is then usually washed with an inert hydrocarbon volume such as hexane.

[0050] Method 4: Magnesium dichloride can be preactivated according to known methods and then treated with excess TiCl4 at a temperature of about 80-135° C., wherein the internal electron donor is contained in the solution. The TiCl4 treatment is repeated multiple times and the solid is washed with hexane to remove any unreacted TiCl4.

[0051] Method 5: The preparation method of the titanium-containing solid catalyst component disclosed in CN1208045A can also be referred to for preparation: first, a liquid magnesium compound and a liquid titanium compound are contacted at low temperature in the presence of a compound selected from alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and esters to precipitate a solid. The contact temperature is generally -70-200°C, preferably -30-130°C, and an internal electron donor is used during the contact process.

[0052] Method 6: dissolving a magnesium compound in a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and an inert diluent to form a uniform solution, mixing with a titanium compound, washing out a solid in the presence of a precipitation aid; treating the solid with an internal electron donor to load it on the solid, and if necessary, treating it with titanium tetrahalide and an inert diluent to obtain the solid, wherein the precipitation aid is one of an organic anhydride, an organic acid, an ether and a ketone. The components are calculated per mole of magnesium halide, and the organic epoxy compound is 0.2-10 moles, the organic phosphorus compound is 0.1-3 moles, the precipitation aid is 0.03-1.0 moles, and the halide of transition metal Ti and its derivatives are 0.5-150 moles.

[0053] Method 7: A magnesium compound supported on an inorganic oxide such as SiO2, alumina or a porous resin is used as a carrier, activated by a known method, and then treated with an excess of TiCl4 at a temperature of about 80-135°C, and an internal electron donor is added during the treatment process.

[0054] The reactions discussed above lead to the formation of magnesium halide in an active form (generally, crystalline magnesium halide has a regular structure and can carry very little Ti, so the catalytic activity is low. To prepare a highly active supported catalyst, the magnesium halide must be activated. The activation treatment method includes using physical and / or chemical methods to make it into microcrystals so that the active center is supported on the surface, edge and defects of the magnesium halide. The treated magnesium halide microcrystals suitable for supporting Ti are "active magnesium halide"). In addition to these reactions, there are other well-known methods in the literature to form magnesium halide in an active form from compound starting materials other than magnesium halide.

[0055] In any of the above-mentioned preparation methods, the internal electron donor compound can be added directly or prepared in an alternative manner, such as in situ by using a suitable precursor, which can be converted into the desired internal electron donor compound by known chemical reactions such as esterification, transesterification, etc. Generally, the internal electron donor compound is used in a molar ratio of 0.01-5, preferably 0.05-3.0, relative to MgCl2.

[0056] In any of the above preparation methods, the internal electron donor compound can be added simultaneously or separately in the preparation process in one batch or in several batches, in any order and in any combination.

[0057] The present invention also provides an olefin polymerization catalyst, which comprises the above catalyst component.

[0058] The present invention also provides a catalyst for olefin polymerization, the raw material composition of which includes the above catalyst component and an organic aluminum compound.

[0059] According to a specific embodiment of the present invention, preferably, the general formula of the organoaluminum compound is AlR c p X (3-p) , where R c is hydrogen or C1-C 20 wherein X is a halogen and p is an integer of 0≤p≤3.

[0060] According to a specific embodiment of the present invention, preferably, the organic aluminum compound includes at least one of a trialkyl aluminum compound, an alkyl aluminum halide, an alkyl aluminum hydride, an alkyl aluminum sesquichloride, and an alkyl aluminumoxane.

[0061] According to a specific embodiment of the present invention, preferably, the trialkylaluminum compound includes at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and trioctylaluminum; the alkylaluminum halide includes AlEt2Cl; and the alkylaluminum sesquichloride includes Al2Et3Cl3.

[0062] According to a specific embodiment of the present invention, preferably, the molar ratio of the organic aluminum compound to the titanium atom in the catalyst component is 1-1000:1, more preferably 50-800.

[0063] According to a specific embodiment of the present invention, preferably, the raw material composition of the catalyst also includes an external electron donor.

[0064] According to a specific embodiment of the present invention, preferably, the external electron donor is a siloxane compound.

[0065] According to a specific embodiment of the present invention, preferably, the general formula of the siloxane compound is R' t Si(OR”) 4-t , wherein R' and R" are each independently selected from C1-C 18 A hydrocarbon group, t is an integer of 0≤t≤3; more preferably, said R' and R" respectively contain heteroatoms; more preferably, said heteroatoms include at least one of N, O, S, P, and Si.

[0066] According to a specific embodiment of the present invention, preferably, the siloxane compound includes trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, triisobutylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane silane, di-tert-butyldiethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, di(2-ethylhexyl)dimethoxysilane, di(2-ethylhexyl)diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldiethoxysilane, cyclopentylisopropyldiethoxysilane, cyclopentylisobutyldimethoxysilane, cyclohexyl-n-propyl Dimethoxysilane, cyclohexyl-n-propyldiethoxysilane, cyclohexyl-n-butyldiethoxysilane, amylmethyldimethoxysilane, amylmethyldiethoxysilane, amylethyldimethoxysilane, amylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, cyclohexyldimethoxysilane, cyclohexyldiethoxysilane, 2-ethylhexyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyl trimethoxysilane, isobutyltrimethoxysilane, tert-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,At least one of 5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, bis(3-methylcyclohexyl)dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, bis(4-methylcyclohexyl)dimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, bis(3,5-dimethylcyclohexyl)dimethoxysilane, tetrapropoxysilane and tetrabutoxysilane;

[0067] The siloxane compound more preferably includes at least one of di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldiethoxysilane, tert-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane and 3,5-dimethylcyclopentyldimethoxysilane.

[0068] According to a specific embodiment of the present invention, preferably, the molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100, more preferably 0.01-20, and further preferably 0.01-5.

[0069] The invention also provides application of the catalyst in olefin polymerization.

[0070] According to a specific embodiment of the present invention, preferably, the olefin includes at least one of a linear or branched olefin, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, butadiene, vinylcyclopentene, and vinylcyclohexene.

[0071] According to a specific embodiment of the present invention, preferably, the polymerization comprises ethylene and / or propylene polymerization.

[0072] According to a specific embodiment of the present invention, preferably, the polymerization includes homopolymerization or copolymerization.

[0073] According to a specific embodiment of the present invention, preferably, during the catalytic process, the order of adding the components in the catalyst is arbitrary, preferably the organoaluminum compound is first added to the polymerization system, then the external electron donor is added, and finally the catalyst component is added.

[0074] According to a specific embodiment of the present invention, preferably, in the above application, the polymerization process can be carried out with or without a solvent; the olefin monomer can be in gas phase or liquid phase; more preferably, hydrogen can be further added as a molecular weight regulator (polymerization can also be carried out without a molecular weight regulator); continuous polymerization or batch polymerization process can be applied, and the polymerization reaction can be carried out in one step, two steps or multiple steps.

[0075] According to a specific embodiment of the present invention, preferably, the polymerization temperature is ≤200°C, more preferably 20-100°C, and further preferably 40-80°C; the polymerization pressure is ≤10MPa, preferably 0.3-5MPa.

[0076] The internal electron donor of the catalyst component of the present invention is at least one compound selected from 2,6-dicarboxylic acid ester-4-pyridyl ether of general formula (I) or N-substituted-2,6-dicarboxylic acid ester-4-pyridone of general formula (II) and a diether compound. The activity of multiple internal electron donors can be significantly improved after compounding, which is generally higher than the catalyst of phthalic acid ester internal electron donor commonly used in industry today, and higher than the diether catalyst. The obtained polymer has high isotacticity, high bulk density and moderate molecular weight distribution. When the external electron donor is not used, the polymer can still maintain a high isotacticity, the polymerization activity is further improved, and super high activity is shown, which is much higher than that of the non-compounded catalyst, and the obtained polymer has low ash content. DETAILED DESCRIPTION

[0077] The technical solution of the present invention is described in detail below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the implementation of the present invention, rather than all the embodiments.

[0078] The catalyst preparation operations in the examples were all carried out under the protection of high-purity nitrogen. Determination of polymer isotacticity: Determination by heptane extraction method (6 hours of boiling heptane extraction). Two grams of dry polymer sample are placed in an extractor and extracted with boiling heptane for 6 hours. The ratio of the polymer weight (g) obtained by drying the residue to constant weight to 2 is the isotacticity.

[0079] The bulk density of the polymer was determined using the JB / T 2412-2008 method.

[0080] The molecular weight distribution of the polymer was determined by a PL-220 gel permeation chromatograph using trichlorobenzene as solvent at 150°C (standard sample: polystyrene, flow rate 1.0 mL / min, column: 3xPlgel 10um M1Xed-B 300x7.5nm).

[0081] Determination of polymer ash content: Determined in accordance with GBT9345.1-2008.

[0082] 9,9-Bis(methoxymethyl)fluorene, commercially available, CAS No. 182121-12-6.

[0083] 2-Isopropyl-2-isopentyl-1,3-dimethoxypropane was synthesized according to CN1041752A.

[0084] Synthesis of 2,6-dicarboxylate-4-pyridyl ether compound represented by general formula (I)

[0085] Preparation Example 1: Synthesis of 2,6-di-n-butyl dicarboxylate-4-methoxypyridine

[0086] Sodium (23.6 g, 1 mol, 2.04 eq.) was dissolved in anhydrous ethanol (350 mL). A mixture of anhydrous acetone (29 g, 38 mL, 0.5 mol, 1 eq.) and diethyl oxalate (155 g, 144 mL, 1.06 mol, 2.12 eq.) was added to the previous solution over 15 minutes. A yellow precipitate was formed. The reaction mixture was kept at 60°C for one hour. Then, HCl (aq. 37%, 200 mL) and water (100 mL) were added, and the solution was stirred at 50°C for 20 hours. The mixture of water and ethanol was removed under reduced pressure. Then a mixture of water (300 mL) and HCl (aq. 37%, 50 mL) was added to the mixture and stirred until silica gel TLC (eluent: 3 / 7 (v / v) 10% NaCl aqueous solution / ethanol) showed only one spot. After cooling to room temperature, the crystals were filtered out and washed with water first and then with cold acetone. The crude product was recrystallized to obtain 2,6-dicarboxylic acid-4-pyrone as a white powder.

[0087] In a 1L three-necked flask, add 2,6-dicarboxylic acid-4-pyrone (11 g), n-butanol (200 mL), and concentrated sulfuric acid (1 mL); heat to reflux for 2 hours; cool to room temperature; pour the reaction solution into a saturated sodium bicarbonate solution, extract twice with ethyl acetate (150 mL*2), combine the organic phases, wash with saturated brine (150 mL*2), concentrate and recrystallize to obtain the product 2,6-di-n-butyl dicarboxylate-4-pyrone.

[0088] 2,6-di-n-butyl-4-pyrone dicarboxylate (7.4 g, 25 mmol) was added dropwise to an aqueous ammonia solution (aq. 25%, 50 mL) at 0°C. Stir at room temperature for two days. The solvent was removed by rotary evaporation, and the residue was boiled after adding water (50 mL) and activated carbon (1 g). The solution was filtered and then cooled to 5°C. The cold solution was acidified to pH = 1 with HCl (aq. 37%). The solid was filtered, washed three times with ice water, and dried under vacuum at 150°C for 24 hours to obtain 2,6-di-n-butyl-4-hydroxypyridine dicarboxylate.

[0089] To a solution of di-n-butyl 2,6-dicarboxylate-4-hydroxypyridine (10.5 g, 35.7 mmoles) and anhydrous MeOH (500 ml) was gradually added sodium methoxide (4 g, 74 mmoles), and the reaction mixture was stirred at room temperature for 1 hour.

[0090] Dimethyl ether (10 mL) was then added, the mixture was heated to 60°C, stirred for 12 hours, and filtered to obtain di-n-butyl 2,6-dicarboxylate-4-methoxypyridine. 1 H NMR (500MHz, Chloroform-d) δ / ppm: 7.65 (s, 2H), 4.30 (t, J = 8.4Hz, 4H), 3.82 (s, 3H), 1.80-1.69 (m, 4H), 1.52-1.41 (m, 4H), 0.97 (t, J = 5.6Hz, 6H).

[0091] Preparation Example 2-14: Synthesis of other 2,6-dicarboxylate-4-pyridyl ether compounds

[0092] The compounds were synthesized using routes including but not limited to the aforementioned routes 1-3. The structures and NMR results of the compounds are shown in Table 1.

[0093] Synthesis of N-substituted-2,6-dicarboxylate-4-pyridone compounds represented by general formula (II)

[0094] Preparation Example 15: Synthesis of N-isopropyl-2,6-dicarboxylic acid ethyl ester-4-pyridone

[0095] Sodium (14.2 g, 0.6 mol) was dissolved in anhydrous ethanol (200 mL). A mixture of anhydrous acetone (17.4 g, 22.8 mL, 0.3 mol) and diethyl oxalate (93 g, 86.5 mL, 0.64 mol) was added to the previous solution over 15 minutes. A yellow precipitate was formed. The reaction mixture was kept at 60 ° C for one hour. Then, HCl (aq. 37%, 120 mL) and water (60 mL) were added, and the solution was stirred at 50 ° C for 20 hours. The mixture of water and ethanol was removed under reduced pressure. Then a mixture of water (170 mL) and HCl (aq. 37%, 30 mL) was added to the mixture and stirred until silica gel TLC (eluent: 3 / 7 (v / v) 10% NaCl aqueous solution / ethanol) showed only one spot. After cooling to room temperature, the crystals were filtered out and washed with water and then with cold acetone. The crude product was recrystallized to give 2,6-dicarboxylic acid-4-pyrone.

[0096] 2,6-dicarboxylic acid-4-pyrone (4.6 g, 25 mmol) was added dropwise to 100 mL of isopropylamine-dichloromethane solution (isopropylamine 1.8 g, 30 mmol) at 0°C. Stir at room temperature for two days. The solvent was removed by rotary evaporation, and the residue was boiled after adding water (50 mL) and activated carbon (1 g). The solution was filtered and then cooled to 5°C. The cold solution was acidified to pH = 1 with HCl (aq. 37%). The solid was filtered, washed three times with ice water, and vacuum dried at 150°C for 24 hours to obtain N-isopropyl-2,6-dicarboxylic acid-4-pyridone.

[0097] In a 1L three-necked flask, add N-isopropyl-2,6-dicarboxylic acid-4-pyridone (4.5 g, 20 mmol), ethanol (50 mL), and concentrated sulfuric acid (0.3 mL); heat to reflux for 2 hours; cool to room temperature; pour the reaction solution into a saturated sodium bicarbonate solution, extract twice with ethyl acetate (100 mL*2), combine the organic phases, wash with saturated brine (100 mL*2), concentrate and recrystallize to obtain the product N-isopropyl-2,6-dicarboxylic acid ethyl ester-4-pyridone. 1 H NMR (500MHz, Chloroform-d) δ / ppm: 6.89 (s, 2H), 4.69 (p, J = 4.3Hz, 1H), 4.30 (q, J = 5.1Hz, 4H), 1.35-1.27 (m, 12H).

[0098] Preparation Examples 16-26: Synthesis of other N-substituted-2,6-dicarboxylate-4-pyridone compounds

[0099] The compounds were synthesized using routes including but not limited to the aforementioned routes 4 and 5. The structures and NMR results of the compounds are shown in Table 2.

[0100]

[0101] Table 1 2,6-dicarboxylate-4-pyridine ether compounds prepared in Examples 1-14

[0102]

[0103]

[0104]

[0105]

[0106]

[0107] Table 2 N-substituted-2,6-dicarboxylate-4-pyridone compounds prepared in Examples 15-26

[0108]

[0109]

[0110]

[0111]

[0112] Catalyst preparation

[0113] Example 1

[0114] In a 500ml 5-necked flask with nitrogen fully replaced and stirred, 10g MgCl2·2.5C2H5OH microspheres and 150mL titanium tetrachloride were added to prepare a suspension, then maintained at -15°C for 1 hour, slowly heated to 80°C, 7mmol 2,6-di-n-butyl dicarboxylate-4-methoxypyridine and 3mmol 9,9-bis(methoxymethyl)fluorene were added, and then the temperature was continued to rise to 110°C and kept constant for 1 hour, and then the liquid was filtered clean, the liquid was filtered off, and the obtained solid was washed 3 times with 120mL titanium tetrachloride at 125°C. The obtained solid was washed 4 times with 150mL hexane at 60°C, the liquid was filtered off and dried to obtain the solid catalyst component Cat-1.

[0115] Example 2-26

[0116] The solid catalyst component preparation process is as shown in Example 1, except that 2,6-di-n-butyl dicarboxylate-4-methoxypyridine is replaced by 7 mmol of compounds No. 2 to 26 in Table 1 and Table 2 in sequence.

[0117] Embodiment 27

[0118] The solid catalyst component preparation process is as shown in Example 1, except that 6 mmol of 2,6-di-n-butyl dicarboxylate-4-methoxypyridine and 4 mmol of 9,9-bis(methoxymethyl)fluorene are added.

[0119] Embodiment 28

[0120] The solid catalyst component preparation process is as shown in Example 1, except that 5 mmol of 2,6-di-n-butyl dicarboxylate-4-methoxypyridine and 5 mmol of 9,9-bis(methoxymethyl)fluorene are added.

[0121] Embodiment 29

[0122] The solid catalyst component preparation process is as shown in Example 1, except that 4 mmol of 2,6-di-n-butyl dicarboxylate-4-methoxypyridine and 6 mmol of 9,9-bis(methoxymethyl)fluorene are added.

[0123] Embodiment 30

[0124] The solid catalyst component preparation process is as shown in Example 1, except that 3 mmol of 2,6-di-n-butyl dicarboxylate-4-methoxypyridine and 7 mmol of 9,9-bis(methoxymethyl)fluorene are added.

[0125] Examples 31-56

[0126] The solid catalyst component preparation process is as shown in Example 1, except that 7mmol of 2,6-di-n-butyl dicarboxylate-4-methoxypyridine and 3mmol of 9,9-bis(methoxymethyl)fluorene are replaced by 7mmol of compounds No. 1-26 in Table 1 and Table 2 and 3mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane.

[0127] Embodiment 57

[0128] The preparation process of the solid catalyst component is as shown in Example 1, except that 6 mmol of 2,6-di-n-butyl dicarboxylate-4-methoxypyridine and 4 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane are added.

[0129] Embodiment 58

[0130] The solid catalyst component preparation process is as shown in Example 1, except that 5 mmol of 2,6-di-n-butyl dicarboxylate-4-methoxypyridine and 5 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane are added.

[0131] Embodiment 59

[0132] The preparation process of the solid catalyst component is as shown in Example 1, except that 4 mmol of 2,6-di-n-butyl dicarboxylate-4-methoxypyridine and 6 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane are added.

[0133] Embodiment 60

[0134] The solid catalyst component preparation process is as shown in Example 1, except that 3 mmol of 2,6-di-n-butyl dicarboxylate-4-methoxypyridine and 7 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane are added.

[0135] Embodiment 61

[0136] The solid catalyst component preparation process is as shown in Example 1, except that 3 mmol 2,6-di-n-butyl-4-methoxypyridine, 3 mmol N-isopropyl-2,6-diethyl-4-pyridone and 4 mmol 9,9-bis(methoxymethyl)fluorene are added.

[0137] Embodiment 62

[0138] The solid catalyst component preparation process is as shown in Example 1, except that 3 mmol 2,6-di-n-butyl dicarboxylate-4-methoxypyridine, 3 mmol N-isopropyl-2,6-diethyl dicarboxylate-4-pyridone and 4 mmol 2-isopropyl-2-isopentyl-1,3-dimethoxypropane are added.

[0139] Comparative Example 1

[0140] The catalyst component preparation process is the same as Example 1, except that 7 mmol of 2,6-di-n-butyl-4-methoxypyridine dicarboxylate and 3 mmol of 9,9-bis(methoxymethyl)fluorene internal electron donor compound are replaced by 10 mmol of 2,6-di-n-butyl-4-methoxypyridine dicarboxylate (a1).

[0141] Comparative Example 2

[0142] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of 2,6-di-n-butyl-4-methoxypyridine dicarboxylate and 3 mmol of 9,9-bis(methoxymethyl)fluorene internal electron donor compound are replaced by 10 mmol of 2,6-diisopropyl-4-isopropyloxypyridine (a2).

[0143] Comparative Example 3

[0144] The catalyst component preparation process is the same as that in Example 1, except that 7 mmol of 2,6-di-n-butyl-4-methoxypyridine dicarboxylate and 3 mmol of 9,9-bis(methoxymethyl)fluorene internal electron donor compound are replaced by 10 mmol of N-n-butyl-2,6-dicarboxylate-4-pyridone (a17).

[0145] Comparative Example 4

[0146] The catalyst component preparation process is the same as in Example 1, except that 7 mmol of 2,6-di-n-butyl-4-methoxypyridine dicarboxylate and 3 mmol of 9,9-bis(methoxymethyl)fluorene internal electron donor compound are replaced by 10 mmol of N-phenyl-2,6-dicarboxylic acid diphenyl ester-4-pyridone (a18).

[0147] Comparative Example 5

[0148] The catalyst component preparation process is as shown in Example 1, except that 7 mmol of 2,6-di-n-butyl dicarboxylate-4-methoxypyridine and 3 mmol of 9,9-bis(methoxymethyl)fluorene internal electron donor compound are replaced by 5 mmol of 2,6-di-n-butyl dicarboxylate-4-methoxypyridine and 5 mmol of N-isopropyl-2,6-diethyl dicarboxylate-4-pyridone.

[0149] Comparative Example 6

[0150] The catalyst component preparation process is the same as Example 1, except that 7 mmol of 2,6-di-n-butyl-4-methoxypyridine dicarboxylate and 3 mmol of 9,9-bis(methoxymethyl)fluorene internal electron donor compound are replaced by 10 mmol of 9,9-bis(methoxymethyl)fluorene (FLU).

[0151] Comparative Example 7

[0152] The catalyst component preparation process is the same as Example 1, except that 7 mmol of 2,6-di-n-butyl dicarboxylate-4-methoxypyridine and 3 mmol of 9,9-bis(methoxymethyl)fluorene internal electron donor compound are replaced by 10 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (E2).

[0153] polymerization:

[0154] After nitrogen is fully replaced in a 5L stainless steel reactor, 5mL of 0.5mol / L triethylaluminum hexane solution and 1mL of 0.1mol / L methylcyclohexyldimethoxysilane hexane solution and 10mg of the prepared solid catalyst component are added, and then 10mL of hexane is added to flush the feed line, and then 2L (under standard conditions) of hydrogen and 2.5L of refined propylene are added, and the reaction is controlled to prepolymerize at 25°C for 5 minutes, and the temperature is raised to 70°C, and the polymerization reaction is carried out at this temperature for 1 hour. After the reaction is completed, the reactor is cooled and the stirring is stopped to discharge the reaction product, and the polymer is obtained by drying. The polymerization data is shown in Table 3.

[0155] Table 3 Different compounding results under the same polymerization conditions

[0156]

[0157]

[0158]

[0159]

[0160]

[0161] [Note] FLU: 9,9-bis(methoxymethyl)fluorene;

[0162] E2: 2-isopropyl-2-isopentyl-1,3-dimethoxypropane.

[0163] Examples 63-77

[0164] After nitrogen is fully replaced in a 5L stainless steel reactor, a 0.5mol / L triethylaluminum hexane solution (the amount of triethylaluminum is shown in Al / Ti in Table 4) and the corresponding catalyst in Table 3 are added, and then 10mL of hexane is added to flush the feed line, and then 2L (under standard conditions) of hydrogen and 2.5L of refined propylene are added, and the reaction is controlled to prepolymerize at 20°C for 5 minutes, and the temperature is raised to 70°C, and the polymerization reaction is carried out at this temperature for the corresponding time (see Table 4). After the reaction is completed, the reactor is cooled and stirring is stopped to discharge the reaction product, and the polymer is obtained by drying. The results are shown in Table 4.

[0165] Comparative Examples 8-13

[0166] The polymerization steps are the same as those in Example 64, except that the catalysts are Cat-D1 to Cat-D4 and Cat-D6 to Cat-D7, respectively.

[0167] Table 4 (without using external electron donor)

[0168]

[0169]

[0170] As can be seen from Table 3, when 2,6-dicarboxylate-4-pyridyl ether compound and / or N-substituted-2,6-dicarboxylate-4-pyridone compound are compounded with diether compound as internal electron donor, the activity can be significantly improved, which is higher than that of the single internal electron donor catalyst (Comparative Examples 1 to 7) that is not compounded, and the polymer has high isotacticity, high bulk density and moderate molecular weight distribution.

[0171] As can be seen from Table 4, when no external electron donor is used, the polymer can still maintain a high isotacticity, and the polymerization activity is further improved, showing ultra-high activity, which is much higher than that of non-compounded catalysts (Comparative Examples 8-13). The polymerization time is extended from 60 minutes to 120 minutes, and the catalyst can maintain ultra-high activity without attenuation. When low Al / Ti is used, the ash content of the obtained polypropylene is low, which can be reduced to 22ppm.

[0172] The present invention is not limited to the aforementioned specific embodiments, and any changes or modifications made by any technician in the field of the present invention are all covered by the patent scope of the present invention.

Claims

1. An olefin polymerization catalyst component, characterized in that: The invention comprises Mg, Ti, halogen, at least one internal electron donor a compound and at least one internal electron donor b compound, wherein the internal electron donor a compound is selected from at least one of a 2,6-dicarboxylate-4-pyridyl ether compound of the general formula (I) or an N-substituted-2,6-dicarboxylate-4-pyridone compound of the general formula (II), and the internal electron donor b compound is selected from a diether compound. Among them, R in the general formula (I) 1 -R 5 are the same or different, each independently selected from H, halogen, C1-C 20 The hydrocarbon group; Among them, R in the general formula (II) 6 -R 10 are the same or different, each independently selected from H, halogen, C1-C 20 of hydrocarbon groups.

2. The olefin polymerization catalyst component according to claim 1, characterized in that R 1 -R 10 They also each contain at least one heteroatom selected from N, O, S, P, Si and halogen.

3. The olefin polymerization catalyst component according to claim 1, characterized in that In the general formula (I) or (II), R 1 -R 10 the same or different, each independently selected from H, halogen, the following substituents with less than 20 carbon atoms: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or substituted with N, O, S, P, Si heteroatom alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or each independently selected from heterocyclic aromatic substituents.

4. The olefin polymerization catalyst component according to claim 1, characterized in that In the general formula (I) or (II), R 1 -R 10 are the same or different and are each independently selected from H, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 ~C 20 a linear or branched or cyclic alkyl group, or the following substituents having up to 20 carbon atoms: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, m-methylphenyl, o-methylphenyl, m-trimethylphenyl, p-nitrophenyl, m-nitrophenyl, substituted benzyl, substituted phenethyl, furanyl, pyrrolyl, thienyl, propenyl, butenyl, pentenyl, hexenyl, and indenyl.

5. The olefin polymerization catalyst component according to claim 1, characterized in that The 2,6-dicarboxylic acid ester-4-pyridine ether compound in the general formula (I) is selected from 2,6-di-n-butyl dicarboxylate-4-methoxypyridine, 2,6-diisopropyl dicarboxylate-4-isopropyloxypyridine, 2,6-di(dodecyl) dicarboxylate-4-n-butoxypyridine, 2,6-diphenyl dicarboxylate-4-methoxypyridine, 2,6-dichlorophenyl dicarboxylate-4-methoxypyridine, 2,6-di-p-tolyl dicarboxylate-4-methoxypyridine, 2,6-di-p-methoxyphenyl dicarboxylate-4-benzyloxypyridine, 2 , at least one of 2,6-dicarboxylic acid difuranyl methyl ester-4-methoxypyridine, 2,6-dipentenyl dicarboxylate-3-methyl-5-ethyl-4-methoxypyridine, 2,6-di-p-nitrophenyl dicarboxylate-3,5-diethyl-4-methoxypyridine, 2,6-dimethyl dicarboxylate-3-methyl-5-n-butyl-4-methoxypyridine, 2,6-dibenzyl dicarboxylate-4-ethoxypyridine, 2-ethyl formate-6-n-butyl formate 4-methoxypyridine, and 2-ethyl formate-6-phenyl formate-4-methoxypyridine.

6. The olefin polymerization catalyst component according to claim 1, characterized in that The N-substituted-2,6-dicarboxylate-4-pyridone compound in the general formula (II) is selected from N-isopropyl-2,6-dicarboxylic acid diethyl ester-4-pyridone, N-tert-butyl-2,6-dicarboxylic acid didodecyl ester-4-pyridone, N-n-butyl-2,6-dicarboxylic acid di-n-butyl ester-4-pyridone, N-phenyl-2,6-dicarboxylic acid diphenyl ester-4-pyridone, N-m-chlorophenyl-2,6-dicarboxylic acid di-m-chlorophenyl ester-4-pyridone, N-p-chlorophenyl-2,6-dicarboxylic acid di-p-tolyl ester-4-pyridone. At least one of pyridone, N-o-chlorophenyl-2,6-dicarboxylic acid di-p-methoxyphenyl-4-pyridone, N-p-methoxyphenyl-2,6-dicarboxylic acid difuranyl ester-4-pyridone, N-methyl-2,6-dicarboxylic acid dipentenyl ester-4-pyridone, N-methyl-2,6-dicarboxylic acid di-p-nitrophenyl ester-3-methyl-5-ethyl-4-pyridone, N-benzyl-2,6-dicarboxylic acid dibenzyl ester-3,5-diethyl-4-pyridone, and N-methyl-2-ethyl-6-carboxylic acid phenyl ester-4-pyridone.

7. The olefin polymerization catalyst component according to claim 1, characterized in that The diether compound is selected from 1,3-diether compounds represented by general formula (III): In the general formula (III), R 11 -R 16 are the same or different, each independently selected from H, each independently selected from a linear or branched alkyl, cycloalkyl, aryl, alkaryl or aralkyl group containing 1 to 18 carbon atoms; R 17 -R 18 are the same or different and are each independently selected from a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms, an alkaryl group having 7 to 20 carbon atoms and an aralkyl group; R 11 -R 18 One or more groups in the are linked to form a ring structure, and each further contains at least one heteroatom selected from halogen, N, O, S, P and Si.

8. The olefin polymerization catalyst component according to claim 1, characterized in that The diether compound is selected from the compounds represented by general formula (IV): In the general formula (IV), R 25 -R 32 R is the same or different, each independently selected from hydrogen, halogen, linear or branched alkyl with 1 to 20 carbon atoms, cycloalkyl with 3 to 20 carbon atoms, aryl with 6 to 20 carbon atoms, alkylaryl with 7 to 20 carbon atoms and arylalkyl with 7 to 20 carbon atoms, optionally containing at least one heteroatom selected from N, O, S, P, Si and halogen as a substituent for carbon atoms or hydrogen atoms or both; 19 -R 22 are the same or different and are each independently selected from H, or are each independently selected from a linear or branched alkyl, cycloalkyl, aryl, alkaryl or aralkyl group containing 1 to 18 carbon atoms; R 23 and R 24 are the same or different and are each independently selected from a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms, an alkaryl group having 7 to 20 carbon atoms and an aralkyl group; R 19 -R 32 One or more groups in the are linked to form a ring structure, and each further contains at least one heteroatom selected from halogen, N, O, S, P and Si.

9. The catalyst component for olefin polymerization according to claim 1, characterized in that The molar ratio of the internal electron donor compound a to the internal electron donor compound b is greater than or equal to 3:

7.

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

11. The olefin polymerization catalyst component according to claim 10, characterized in that The magnesium compound is an alcoholate of magnesium dihalide; Alternatively, the magnesium compound is a liquid magnesium compound; Alternatively, the magnesium compound is a derivative in which at least one halogen atom in a magnesium dihalide molecule is replaced by a hydrocarbonoxy group or a halogenated hydrocarbonoxy group.

12. The olefin polymerization catalyst component according to claim 10, characterized in that The titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and alkoxy titanium halide.

13. The olefin polymerization catalyst component according to claim 12, characterized in that The alkyl titanium halide includes at least one of methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, and tri-n-butoxytitanium chloride.

14. The olefin polymerization catalyst component according to claim 10, characterized in that The molar ratio of the sum of the internal electron donor compound a and the internal electron donor compound b to the magnesium compound is 0.01-5.0, and the magnesium compound is calculated as magnesium element.

15. A catalyst for olefin polymerization, wherein the raw material composition comprises the catalyst component according to any one of claims 1 to 14 and an organic aluminum compound.

16. The catalyst according to claim 15, characterized in that The general formula of the organoaluminum compound is AlR c p X (3-p) , where R c is hydrogen or C1-C 20 wherein X is a halogen and p is an integer of 0≤p≤3.

17. The catalyst according to claim 15, characterized in that The organoaluminum compound includes at least one of trialkylaluminum compounds, alkylaluminum halides, alkylaluminum hydrides, alkylaluminum sesquichlorides, and alkylaluminoxanes.

18. The catalyst according to claim 15, characterized in that The molar ratio of the organic aluminum compound to the titanium atom in the catalyst component is 1-1000:

1.

19. The catalyst according to claim 15, characterized in that The raw material composition of the catalyst also includes an external electron donor; The external electron donor is a siloxane compound.

20. The catalyst according to claim 19, characterized in that The general formula of the siloxane compound is R' t Si(OR”) 4-t , wherein R' and R" are each independently selected from C1-C 18 A hydrocarbon group, t is an integer of 0≤t≤3.

21. The catalyst according to claim 20, characterized in that R' and R" each contain a heteroatom.

22. The catalyst according to claim 21, characterized in that The heteroatom includes at least one of N, O, S, P, and Si.

23. The catalyst according to claim 19, characterized in that The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100.

24. Use of the catalyst according to any one of claims 15 to 23 in olefin polymerization.

25. The use according to claim 24, characterized in that The olefins include at least one of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, butadiene, vinylcyclopentene, and vinylcyclohexene; The polymerization includes homopolymerization or copolymerization; The polymerization temperature is ≤200°C; the polymerization pressure is ≤10MPa.

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