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

Abstract

The present invention discloses a solid catalyst component for olefin polymerization, an olefin polymerization catalyst and applications thereof, the solid catalyst component for olefin polymerization comprises Mg, Ti, halogen, an internal electron donor a compound and an internal electron donor b compound, the internal electron donor a compound is selected from substituted 2, 6-diformate 4-pyrone compounds represented by a general formula (I), the internal electron donor b compound is selected from substituted 2, 6-diformate 4-pyrone compounds represented by a general formula (II), and the internal electron donor b compound is selected from substituted 2, 6-diformate 4-pyrone compounds represented by a general formula (II). And the internal electron donor b compound is selected from a tetrahydroo-phenyl substituent compound in a general formula (II). According to the solid catalyst component disclosed by the invention, the substituted 2, 6-diformic acid-4-pyrone compound is adopted as an internal electron donor of a polyolefin catalyst, and after the substituted 2, 6-diformic acid-4-pyrone compound is compounded with the tetrahydrophthalic substituent compound, the polymerization activity is relatively high, the melt index of a polymer is high, and the hydrogen regulation sensitivity is good.

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 catalyst using 1,3-diether compounds as internal electron donors has high activity and good catalyst hydrogen adjustment sensitivity, the relative molecular mass distribution of the prepared PP is narrow, which is not conducive to the development of different grades of PP; the advantage of using succinate compounds as internal electron donors is that the relative molecular mass distribution of the synthesized PP is relatively wide, but the disadvantage is that the stereoregularity of PP and the hydrogen adjustment sensitivity of the catalyst need to be improved; and the overall activity of the diol ester catalyst system is not as ideal as the diether system. Chinese patent CN102325808 discloses a precatalyst composition containing a phenylene aromatic diester internal electron donor, which has low activity, and the xylene soluble content of the obtained polymer is still high when a silane external electron donor is used, indicating that the catalyst has poor stereoselectivity for propylene.

[0004] When the catalyst prepared by a single internal electron donor cannot meet the specific requirements of polypropylene products, such as requiring the catalyst to have the characteristics of high activity, high stereospecificity and high hydrogen sensitivity, the compound use of multiple internal electron donors is an effective method to solve this problem, that is, when preparing the ZN catalyst, two or more internal electron donors are used at the same time, and the comprehensive performance of the ZN catalyst is adjusted by adjusting the content of different internal electron donors in the ZN catalyst. Chinese patent CN101724102 discloses a catalyst component prepared by compounding an internal electron donor diol ester compound and a 1,3-diether compound and using a magnesium chloride alcohol adduct carrier. The catalyst has high activity, but is only equivalent to a 1,3-diether electron donor catalyst, and in order to maintain a high isotacticity, a silane external electron donor is still required.

[0005] At present, the most widely used polyolefin internal electron donor in industry is phthalate compounds, which have medium catalyst activity, good stereoselectivity and low price. However, phthalate compounds, as commonly used plasticizers, have great harm to human reproductive health and the environment, and there is a great demand for replacement. Europe has restricted the use of most phthalate substances. 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 phthalate electron donor compounds widely used in the prior art and apply them to the preparation of efficient Ziegler-Natta catalysts. Summary of the invention

[0006] 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.

[0007] The object of the present invention is to provide a solid catalyst component CH2 for olefin polymerization.

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

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

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

[0011] In order to achieve the object of the present invention, the present invention provides a solid catalyst component for olefin polymerization, which comprises Mg, Ti, halogen, an internal electron donor a compound and an internal electron donor b compound, wherein the internal electron donor a compound is selected from substituted 2,6-dicarboxylate-4-pyrone compounds of general formula (I):

[0012]

[0013] Among them, R in the general formula (I) 1 , R 2 , R 3 and R 4 are the same or different, each independently selected from H, halogen, C1-C 20 Preferably, R 1 , R 2 , R 3 and R 4may also contain at least one heteroatom selected from N, O, S, P, Si and halogen; preferably, R 1 , R 2 , R 3 and R 4 Two or more of them may be bonded to each other to form a ring;

[0014] The internal electron donor b compound is selected from tetrahydro-o-phenyl substituted compounds of general formula (II):

[0015]

[0016] Among them, R in the general formula (II) 5 -R 8 The same or different, each independently selected from H, C1-C 20 Alkyl; R 9 and R 10 The same or different, each independently selected from substituents containing oxygen or nitrogen functional groups; preferably R 9 and R 10 They are connected to each other to form rings containing oxygen or nitrogen functional groups.

[0017] Preferably, R in the general formula (I) 1 , R 2 , R 3 and R 4 the same or different, each independently selected from H, halogen, the following substituents with less than 20 carbon atoms: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or substituted by N, O, S, P, Si heteroatom, alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or each independently selected from heterocyclic aromatic substituents.

[0018] Preferably, R in the general formula (I) 1 , R 2 , R 3 and R 4 are the same or different and are each independently selected from H, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 ~C 20 a straight-chain or branched alkyl group, or the following substituents having less than 20 carbon atoms: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, substituted benzyl, substituted phenethyl, furanyl, pyrrolyl, thienyl, propenyl, butenyl, pentenyl, hexenyl, and indenyl.

[0019] Preferably, the substituted 2,6-dicarboxylate-4-pyrone compound of general formula (I) is selected from 2,6-di-n-butyl-4-pyrone, 2,6-diethyl-4-pyrone, 2,6-dicarboxylic acid diisobutyl-4-pyrone, 2,6-dicyclohexyl-4-pyrone, 2,6-dicarboxylic acid di-tetradecyl-4-pyrone, 2,6-dicarboxylic acid diphenyl-4-pyrone, 2,6-diphenylethyl-4-pyrone, 2,6-dicarboxylic acid di-m-chlorophenyl-4-pyrone, 2,6-di-p-chlorophenyl-4-pyrone, 2,6-di-o-chlorophenyl-4-pyrone, 2,6-di-p-methylphenyl-4-pyrone. The invention relates to at least one of pyrone, di-m-methoxyphenyl 2,6-dicarboxylate-4-pyrone, di-p-methoxyphenyl 2,6-dicarboxylate-4-pyrone, di-o-methoxyphenyl 2,6-dicarboxylate-4-pyrone, difuranmethyl 2,6-dicarboxylate-4-pyrone, dipentenyl 2,6-dicarboxylate-4-pyrone, di-p-nitrophenyl 2,6-dicarboxylate-4-pyrone, di-n-butyl 2,6-dicarboxylate-4-pyrone, di-n-butyl 2,6-dicarboxylate-3,5-dimethyl-4-pyrone, diethyl 2,6-dicarboxylate-3-phenyl-4-pyrone, diethyl 2,6-dicarboxylate-3-chloro-4-pyrone, and diethyl 2,6-dicarboxylate-3-bromo-4-pyrone.

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

[0021] R 1 and R 2 The synthetic route of the compound of the same general formula (I) is shown in the following formula: oxalic acid is esterified to obtain the corresponding oxalic acid diester (part of the oxalic acid diester can be purchased directly), and then reacted with acetone or other substituted ketones to obtain the corresponding product.

[0022]

[0023] R 1 and R 2 The second synthetic route of the compound of the same general formula (I) is shown in the following formula. The raw materials used in this route are cheap diethyl oxalate and acetone or other substituted ketones. The target product can be obtained in only two steps. A variety of alcohols R can be selected. 1 OH to enrich the product structure. In addition, the product of the first step, 2,6-dicarboxylic acid-4-pyrone (R 1 and R 2 The same and H, CAS number: 99-32-1), after a one-step esterification reaction to obtain 2,6-dicarboxylic acid ester-4-pyrone.

[0024]

[0025] R 1 and R 2 Same or Different, R 3 and R 4 The synthesis route three of the same or different compounds of general formula (I) is shown in the following formula: diethyl oxalate reacts with the corresponding ketone, and then reacts with an alcohol to obtain a pure substituted 2,6-dicarboxylate-4-pyrone compound, or reacts with a mixture of two alcohols to obtain a mixture of three substituted 2,6-dicarboxylate-4-pyrones, which is directly used as a mixture as an internal electron donor without separation. The ratio of each component in the mixture can be adjusted by the addition ratio of the two alcohols as reactants, and the ratio of each component can be characterized and determined by analytical means such as chromatography-mass spectrometry technology and nuclear magnetic resonance.

[0026]

[0027] Preferably, R 9 and R 10 Preferably, it is a formate substituent; R 9 and R 10 Another preferred embodiment is to link to form an anhydride or carboximide.

[0028] Preferably, the tetrahydrobenzene substituted compound of general formula (II) is selected from trans-4-cyclohexene-1,2-dicarboxylic acid dimethyl ester, trans-4-cyclohexene-1,2-dicarboxylic acid diethyl ester, trans-4-cyclohexene-1,2-dicarboxylic acid di-n-propyl ester, trans-4-cyclohexene-1,2-dicarboxylic acid diisopropyl ester, trans-4-cyclohexene-1,2-dicarboxylic acid di-n-butyl ester, trans-4-cyclohexene-1,2-dicarboxylic acid diisobutyl ester, trans-4-cyclohexene-1,2-dipentyl ester, trans-4-cyclohexene-1,2-dicarboxylic acid dibutyl ... , at least one of di-n-hexyl 2-dicarboxylate, diheptyl trans-4-cyclohexene-1,2-dicarboxylate, dioctyl trans-4-cyclohexene-1,2-dicarboxylate, diphenyl trans-4-cyclohexene-1,2-dicarboxylate, dibenzyl trans-4-cyclohexene-1,2-dicarboxylate, diglycidyl tetrahydrophthalate, tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, and 1,2,3,6-tetrahydrophthalimide.

[0029] Preferably, the molar ratio of the internal electron donor compound a to the internal electron donor compound b is greater than or equal to 2:8.

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

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

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

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

[0034]

[0035] 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 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.

[0036] 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.

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

[0038]

[0039] 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.

[0040] 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.

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

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

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

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

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

[0046] The precursor of the magnesium compound is selected from X n Mg(OR a ) 2-n 、MgCl2·mR a OH, R a 2-n MgX n , 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;

[0047] 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.

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

[0049] Alternatively, the magnesium compound is a liquid magnesium compound;

[0050] 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.

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

[0052] 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;

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

[0054] Preferably, the molar ratio of the sum of the internal electron donor compounds to the magnesium compound is 0.01-5.0, preferably 0.05-3.0, and the magnesium compound is calculated as magnesium element.

[0055] 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:

[0056] 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 dialkoxy magnesium compound such as a dialkoxy magnesium or a diaryloxy magnesium) at -25-0°C, and halogenated at 80-130°C. The treatment with the aromatic hydrocarbon solution of TiCl4 can be repeated once or multiple times, and an internal electron donor is added. For example, the preparation method of the titanium-containing solid catalyst component disclosed in US5077357A can be referred to: ethoxy magnesium, tetraethoxy titanium, o-cresol, ethanol and chlorobenzene are added in sequence, and stirred; 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.

[0057] 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 20A hydrocarbon group, X is a halogen, N is 1-4; preferably TiCl4) and a general formula of MgCl2·mR a OH (wherein m is a number of 0.1-6, preferably 2-4, and R a C1-C 20 The solid catalyst component is prepared by reacting an adduct of an alcohol with an alkyl group of an isocyanate (a hydrocarbon group). The adduct can be suitably made into a spherical shape by the following method: in the presence of an inert hydrocarbon that is immiscible with the adduct, an alcohol and magnesium chloride are mixed, and the emulsion is rapidly quenched, thereby solidifying the adduct in the form of spherical particles. Spherical MgCl2·mR prepared according to this process 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

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

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

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

[0074] According to a specific embodiment of the present invention, preferably, the siloxane compound includes trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, triisobutylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane 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;

[0075] 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.

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

[0077] The invention also provides application of the catalyst in olefin polymerization.

[0078] 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.

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

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

[0081] According to a specific embodiment of the present invention, preferably, 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.

[0082] 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.

[0083] 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.

[0084] The solid catalyst component of the present invention adopts a substituted 2,6-dicarboxylic acid ester-4-pyrone compound as an internal electron donor of a polyolefin catalyst, and after compounding with a tetrahydro-o-phenylene substituent compound, the polymerization activity is high, the polymer melt index is high, and the hydrogen adjustment sensitivity is good; the tetrahydro-o-phenylene substituent compound can be selected from a variety of commercially available products, and the price is low. By compounding with the substituted 2,6-dicarboxylic acid ester-4-pyrone compound, the catalyst hydrogen adjustment sensitivity can be improved while the raw material cost can be reduced to a certain extent. The substituted 2,6-dicarboxylic acid ester-4-pyrone, the tetrahydro-o-phenylene substituent compound and the diether compound are ternary compounded to further improve the polymerization activity of the catalyst. DETAILED DESCRIPTION

[0085] 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.

[0086] The operations for preparing the catalyst in the examples were all carried out under the protection of high-purity nitrogen.

[0087] 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 residue is dried to constant weight. The ratio of the polymer weight (g) to 2 is the isotacticity.

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

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

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

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

[0092] Sodium (11.8 g, 0.5 mol, 2.04 eq.) was dissolved in anhydrous ethanol (180 mL). A mixture of anhydrous acetone (14.5 g, 19 mL, 0.25 mol, 1 eq.) and diethyl oxalate (77.5 g, 72 mL, 0.53 mol, 2.12 eq.) was added to the previous solution over 15 minutes. A yellow precipitate was formed. The reaction mixture was kept at 60°C for one hour. Then, HCl (aq. 37%, 100 mL) and water (50 mL) were added, and the solution was stirred at 50°C for 20 hours. The mixture of water and ethanol (about 230 mL) was removed under reduced pressure. Then a mixture of water (150 mL) and HCl (aq. 37%, 25 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 off, washed with water and then with cold acetone. The crude product was recrystallized to obtain white powder 4-pyrone-2,6-dicarboxylic acid (35.0 g, yield: 76%).

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

[0094] Preparation Example 2-9: Synthesis of Substituted 2,6-Dicarboxylate-4-pyrone Compounds

[0095] Using one of the aforementioned routes, the starting material is selected from oxalic acid or diethyl oxalate, and reacts with acetone or other ketones, and then reacts with one or two alcohols for esterification to obtain the corresponding substituted 2,6-dicarboxylate-4-pyrone product. The structures and NMR results of other compounds are shown in Table 1.

[0096]

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

[0098]

[0099]

[0100] The tetrahydrobenzene substituted compound of general formula (II) is a commercially available product :

[0101] b1: trans-4-cyclohexene-1,2-dicarboxylic acid dimethyl ester (CAS No. 4841-84-3);

[0102] b2: trans-4-cyclohexene-1,2-dicarboxylic acid diethyl ester (CAS No. 5048-50-0);

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

[0104] B4: Tetrahydrophthalic anhydride (CAS No. 85-43-8);

[0105] B5: cis-1,2,3,6-tetrahydrophthalic anhydride (CAS No. 935-79-5);

[0106] B6: methyltetrahydrophthalic anhydride (CAS No. 11070-44-3);

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

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

[0109] The following tetrahydro-o-phenyl substituted compound of general formula (II) is prepared from trans-4-cyclohexene-1,2-dicarboxylic acid by a one-step esterification reaction:

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

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

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

[0113] Internal electron donor c compound:

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

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

[0116] DNBP : Di-n-butyl phthalate

[0117] Catalyst preparation

[0118] Example 1

[0119] In a 500mL 5-necked flask with nitrogen fully replaced and stirred, 10gMgCl2·2.5C2H5OH microspheres and 150mL titanium tetrachloride were added to prepare a suspension, then maintained at -15°C for 1 hour, slowly heated to 80°C, 7mmol 2,6-di-n-butyl dicarboxylate-4-pyrone (a1) and 3mmol trans-4-cyclohexene-1,2-dicarboxylic acid diethyl ester (b2) 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.

[0120] Example 2-38

[0121] The solid catalyst component preparation process is as shown in Example 1, except that the internal electron donor is fed according to the internal electron donor compound number and feeding ratio in Table 2.

[0122] Comparative Examples 1-6

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

[0124] polymerization:

[0125] After nitrogen is fully replaced in a 5L stainless steel reactor, 5mL of 0.5mol / L triethylaluminum hexane solution and 1mL of 0.1mol / L methylcyclohexyldimethoxysilane hexane solution and 10mg of the prepared catalyst are added, and then 10mL of hexane is added to flush the feed line, and then 5L (under standard conditions) of hydrogen and 2.5L of refined propylene are added, and the reaction is controlled to prepolymerize at 25°C for 5 minutes, and the temperature is raised to 70°C, and the polymerization reaction is carried out at this temperature for 1 hour. After the reaction is completed, the reactor is cooled and the stirring is stopped to discharge the reaction product, and the polymer is obtained by drying. The polymerization data is shown in Table 1.

[0126] Table 2 Different compounding results under the same polymerization conditions

[0127]

[0128]

[0129]

[0130] It can be seen from Table 2 that the activity of the catalyst prepared by compounding two or more internal electron donor compounds is significantly improved when polymerization is carried out.

[0131] The present invention is not limited to the aforementioned specific embodiments, and any changes or modifications made by any technician in the field of the present invention are all covered by the patent scope of the present invention.

Claims

1. A solid catalyst component for olefin polymerization, characterized in that The invention comprises Mg, Ti, halogen, an internal electron donor a compound and an internal electron donor b compound, wherein the internal electron donor a compound is selected from substituted 2,6-dicarboxylate-4-pyrone compounds of the general formula (I): Among them, R in the general formula (I) 1 , R 2 , R 3 and R 4 are the same or different, each independently selected from H, halogen, C1-C 20 The hydrocarbon group; The internal electron donor b compound is selected from tetrahydro-o-phenyl substituted compounds of general formula (II): Among them, R in the general formula (II) 5 -R 8 The same or different, each independently selected from H, C1-C 20 Alkyl; R 9 and R 10 The same or different substituents are each independently selected from substituents containing oxygen or nitrogen functional groups.

2. The solid catalyst component for olefin polymerization according to claim 1, characterized in that R in the general formula (I) 1 , R 2 , R 3 and R 4 They also each contain at least one heteroatom selected from N, O, S, P, Si and halogen.

3. The solid catalyst component for olefin polymerization according to claim 1, characterized in that R in the general formula (I) 1 , R 2 , R 3 and R 4 Two or more of them are bonded to each other to form a ring.

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

5. The solid catalyst component for olefin polymerization according to claim 1, characterized in that R in the general formula (I) 1 , R 2 , R 3 and R 4 the same or different, each independently selected from H, halogen, the following substituents with less than 20 carbon atoms: straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl, halogenated or substituted by N, O, S, P, Si heteroatom, alkyl, cycloalkyl, phenyl, alkylphenyl, phenylalkyl, indenyl, benzyl; or each independently selected from heterocyclic aromatic substituents.

6. The solid catalyst component for olefin polymerization according to claim 1, characterized in that R in the general formula (I) 1 , R 2 , R 3 and R 4 are the same or different and are each independently selected from H, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 ~C 20 a straight-chain or branched alkyl group, or the following substituents having less than 20 carbon atoms: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, substituted benzyl, substituted phenethyl, furanyl, pyrrolyl, thienyl, propenyl, butenyl, pentenyl, hexenyl, and indenyl.

7. The solid catalyst component for olefin polymerization according to claim 1, characterized in that The substituted 2,6-dicarboxylate-4-pyrone compound of general formula (I) is selected from 2,6-di-n-butyl-4-pyrone, 2,6-diethyl-4-pyrone, 2,6-dicarboxylic acid diisobutyl-4-pyrone, 2,6-dicyclohexyl-4-pyrone, 2,6-dicarboxylic acid di-tetradecyl-4-pyrone, 2,6-dicarboxylic acid diphenyl-4-pyrone, 2,6-diphenylethyl-4-pyrone, 2,6-dicarboxylic acid di-m-chlorophenyl-4-pyrone, 2,6-di-p-chlorophenyl-4-pyrone, 2,6-di-o-chlorophenyl-4-pyrone, 2,6-dicarboxylic acid di-p-methylphenyl-4-pyrone , at least one of 2,6-dicarboxylic acid di-m-methoxyphenyl-4-pyrone, 2,6-dicarboxylic acid di-p-methoxyphenyl-4-pyrone, 2,6-dicarboxylic acid di-o-methoxyphenyl-4-pyrone, 2,6-dicarboxylic acid difuranmethyl-4-pyrone, 2,6-dipentenyl-4-pyrone, 2,6-dicarboxylic acid di-p-nitrophenyl-4-pyrone, 2,6-dicarboxylic acid di-n-butyl-4-pyrone, 2,6-dicarboxylic acid di-n-butyl-3,5-dimethyl-4-pyrone, 2,6-dicarboxylic acid diethyl-3-phenyl-4-pyrone, 2,6-dicarboxylic acid diethyl-3-chloro-4-pyrone, and 2,6-dicarboxylic acid diethyl-3-bromo-4-pyrone.

8. The solid catalyst component for olefin polymerization according to claim 1, characterized in that R in the tetrahydro-o-phenyl substituted compound of the internal electron donor b compound of the general formula (II) is 9 and R 10 It is a formate substituent or is linked to form an anhydride or a carboximide.

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

10. The solid catalyst component for olefin polymerization according to claim 1, characterized in that The molar ratio of the internal electron donor compound a to the internal electron donor compound b is greater than or equal to 2:

8.

11. The solid catalyst component for olefin polymerization according to claim 1, characterized in that The solid catalyst component further contains an internal electron donor c compound, and the internal electron donor c 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.

12. The solid catalyst component for olefin polymerization according to claim 11, characterized in that The diether compound is selected from the diether compound 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.

13. The solid catalyst component for olefin polymerization according to claim 11, characterized in that The molar ratio of the internal electron donor compounds a, b and c is (a+b):c≥2:

8.

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

5.

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

2.

16. The solid catalyst component for olefin polymerization according to claim 1, characterized in that The catalyst component comprises a titanium compound, a magnesium compound, and the internal electron donor 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.

17. The solid catalyst component for olefin polymerization according to claim 16, 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.

18. The solid catalyst component for olefin polymerization according to claim 16, characterized in that The titanium compound includes at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and alkoxy titanium halide.

19. The solid catalyst component for olefin polymerization according to claim 18, 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.

20. The solid catalyst component for olefin polymerization according to claim 16, characterized in that The molar ratio of the sum of the internal electron donor compounds to the magnesium compound is 0.01-5.0, and the magnesium compound is calculated as magnesium element.

21. A catalyst for olefin polymerization, wherein the raw material composition comprises the catalyst component according to any one of claims 1 to 20 and an organic aluminum compound.

22. The catalyst according to claim 21, 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.

23. The solid catalyst component for olefin polymerization according to claim 21, characterized in that The organic aluminum compound includes at least one of a trialkyl aluminum compound, an alkyl aluminum halide, an alkyl aluminum hydride, an alkyl aluminum sesquichloride, and an alkyl aluminumoxane.

24. The catalyst according to claim 21, characterized in that The molar ratio of the organic aluminum compound to the titanium atom in the catalyst component is 1-1000:

1.

25. The catalyst according to claim 21, characterized in that The raw material composition of the catalyst also includes an external electron donor; the external electron donor is a siloxane compound.

26. The solid catalyst component for olefin polymerization according to claim 25, 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.

27. The solid catalyst component for olefin polymerization according to claim 26, characterized in that R' and R" each contain a heteroatom.

28. The solid catalyst component for olefin polymerization according to claim 27, characterized in that The heteroatom includes at least one of N, O, S, P, and Si.

29. The catalyst according to claim 25, characterized in that The molar ratio of silicon in the external electron donor to titanium in the catalyst component is 0.002-100.

30. Use of the catalyst according to any one of claims 21 to 29 in olefin polymerization.

31. The use according to claim 30, 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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