Solid catalyst component for olefin polymerization as well as preparation method, catalyst and application of solid catalyst component

Abstract

The invention belongs to the technical field of olefin polymerization, and relates to a solid catalyst component for olefin polymerization, and a preparation method, a catalyst and application thereof. The solid catalyst component contains a product obtained by reaction of a magnesium source, a titanium source and an internal electron donor; the internal electron donor comprises a phosphate ester compound, a furan compound and a diether compound. The preparation method comprises the following steps: carrying out contact reaction on a magnesium source and a titanium source, and adding an internal electron donor in one or more time periods before, during and after the contact reaction of the magnesium source and the titanium source. The method has the advantages that a phthalate compound is not used, so that the catalyst is a non-plasticized catalyst; the catalyst has the advantages of stable activity release and high hydrogen regulation sensitivity, can meet the application requirements of a multi-kettle flow process device, and is beneficial to development of various high-performance polyolefin products.

Description

Technical Field

[0001] The present invention belongs to the technical field of olefin polymerization, and more specifically, relates to a solid catalyst component for olefin polymerization, a preparation method of the solid catalyst component, a catalyst containing the solid catalyst component, and application of the catalyst in olefin polymerization reactions. Background Art

[0002] As is known to all, ZN catalysts with titanium, magnesium, halogen and electron donor as main components can be used for olefin polymerization. The existing continuous process for preparing polyolefins often adopts a process flow of two or more reactors in series, such as two liquid bulk polymerization reactors in series, liquid bulk polymerization reactor and gas phase polymerization reactor in series, two gas phase reactors in series, etc. In the production process, the reaction residence time and other parameters in each reactor are controlled according to the performance requirements and process conditions of the specific product. The total residence time in each reactor is generally controlled at 2-4 hours, which requires the catalyst used to release activity steadily and evenly throughout the polymerization process. Otherwise, there will be problems such as excessive activity in the early stage, the reaction is difficult to control, and insufficient activity in the later stage. This will directly lead to a decrease in product quality or even failure to meet its performance requirements. It can be seen that the steady and uniform release of catalyst activity is conducive to the stability and controllability of the polymerization process on the one hand; on the other hand, it is conducive to the adjustment of various parameters in the polymerization process to produce products with better performance.

[0003] As the internal electron donor that promotes the development of ZN catalysts, it has developed from the monobasic acid ester compounds of the third-generation ZN catalysts, such as ethyl benzoate and ethyl p-ethoxybenzoate, to dibasic acid ester compounds, such as di(iso)butyl phthalate of the fourth-generation ZN catalysts. Phthalate ester compounds (plasticizers) are currently the most commonly used internal electron donors in polypropylene catalysts. According to research, they can cause serious damage to the growth and development and reproductive system of animals, and may also have similar effects on humans. The United States, the European Union and other countries and regions have successively listed such compounds as toxic chemicals, and their use (especially in infant toys, etc.) is strictly restricted.

[0004] Therefore, it is of great significance to develop high-performance catalysts with smooth activity release and without plasticizers. Summary of the invention

[0005] The inventors unexpectedly discovered during their research that a catalyst using a phosphate compound, a furan compound and a diether compound as an internal electron donor has the advantages of stable activity release and high hydrogen adjustment sensitivity, which can meet the application requirements of a multi-reactor process device and is conducive to the development of a variety of high-performance polyolefin products. Based on this discovery, the present invention is proposed.

[0006] In order to achieve the purpose of the present invention, the first aspect of the present invention provides a solid catalyst component for olefin polymerization, wherein the solid catalyst component contains a product obtained by the reaction of a magnesium source, a titanium source and an internal electron donor;

[0007] Wherein, the internal electron donor comprises phosphate compounds, furan compounds and diether compounds.

[0008] The second aspect of the present invention provides a method for preparing the solid catalyst component for olefin polymerization, comprising the following steps:

[0009] A magnesium source is contacted with a titanium source for reaction, and an internal electron donor is added at one or more time periods before, during and after the magnesium source is contacted with the titanium source for reaction.

[0010] The third aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising:

[0011] (i) the solid catalyst component;

[0012] (ii) at least one alkylaluminum compound; and

[0013] (iii) Optional external electron donor compound.

[0014] The fourth aspect of the present invention provides use of the catalyst for olefin polymerization in olefin polymerization reactions.

[0015] The present invention has the following advantages:

[0016] (1) The present invention uses an internal electron donor comprising a phosphate compound, a furan compound and a diether compound, and does not use a phthalate compound, so the catalyst is a non-plasticizer catalyst.

[0017] (2) The catalyst has the advantages of stable activity release and high hydrogen regulation sensitivity, which can meet the application requirements of multi-reactor process equipment and is conducive to the development of a variety of high-performance polyolefin products.

[0018] Other features and advantages of the present invention will be described in detail in the following detailed description. DETAILED DESCRIPTION

[0019] The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0020] In order to achieve the purpose of the present invention, the first aspect of the present invention provides a solid catalyst component for olefin polymerization, wherein the solid catalyst component contains a product obtained by the reaction of a magnesium source, a titanium source and an internal electron donor;

[0021] Wherein, the internal electron donor comprises phosphate compounds, furan compounds and diether compounds.

[0022] According to the present invention, preferably, based on the total weight of the internal electron donor, the total amount of the phosphate compound, the furan compound and the diether compound is 70-100 wt %, preferably 80-100 wt %.

[0023] The present invention does not particularly limit the type of the phosphate compound, and can be any existing phosphate compound that can be used as an electron donor in a catalyst for olefin polymerization. Preferably, the phosphate compound is selected from at least one of the phosphate compounds represented by formula (1):

[0024]

[0025] In formula (1), R 13 , R 14 and R 15 Each independently selected from a C1-C4 straight chain or branched alkyl group, a C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl and C7-C 20 The hydrogen atoms on the benzene ring in the aryl, alkaryl and aralkyl groups are optionally substituted by halogen atoms; further preferably R 13 , R 14 and R 15 Each independently selected from a C1-C4 straight chain or branched alkyl group, a C3-C 12 Cycloalkyl, C6-C 12 Aryl, C7-C 12 Alkyl and C7-C 12 The hydrogen atoms on the benzene ring in the aryl, alkaryl and aralkyl groups are optionally substituted by halogen atoms; further preferably R 13 , R 14 and R 15 Each is independently selected from one of a C1-C4 straight or branched alkyl group, a C3-C6 cycloalkyl group, a C6-C8 aryl group, a C7-C8 alkaryl group and a C7-C8 aralkyl group, wherein the hydrogen atoms on the benzene ring in the aryl group, alkaryl group and aralkyl group are optionally substituted by halogen atoms; for example, R 13 , R 14 and R 15 Each is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, dimethylphenyl, ethylphenyl, benzyl, methylbenzyl or phenethyl.

[0026] According to the present invention, preferably, the phosphate compound is selected from at least one of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, triisopropylphenyl phosphate, trimethoxyphenyl phosphate, phenyl dimethyl phosphate, cresyl dibutyl phosphate, isopropylphenyl dimethyl phosphate, isopropylphenyl diethyl phosphate, isopropylphenyl dibutyl phosphate, phenyl ditolyl phosphate, phenyl diisopropylphenyl phosphate, p-cresyl dibutyl phosphate, m-cresyl dibutyl phosphate, p-cumyl dimethyl phosphate, p-cumyl diethyl phosphate, p-tert-butylphenyl dimethyl phosphate and o-cresyl p-di-tert-butylphenyl phosphate.

[0027] Most preferably, the phosphate compound is tributyl phosphate.

[0028] In the present invention, the furan compound may be any furan compound that can be used as an electron donor in an olefin polymerization catalyst. Preferably, the furan compound is selected from at least one of the furan compounds represented by formula (2):

[0029]

[0030] In formula (2), R1 and R3 are each independently selected from hydrogen, C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Arylalkyl and C7-C 20 R2 and R4 are each independently selected from C1-C 10 Straight or branched alkyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Arylalkyl or C7-C 10 of alkylaryl.

[0031] Preferably, R1 and R3 are each independently selected from hydrogen, C1-C 10 Straight or branched alkyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Arylalkyl and C7-C 10 R2 and R4 are each independently selected from a C1-C4 straight chain or branched chain alkyl, a C3-C8 cycloalkyl, a C6-C 10 The present invention can be selected from the group consisting of a C7-C8 aryl group, a C7-C8 aralkyl group or a C7-C8 alkaryl group.

[0032] Preferably, the furan compound is selected from (3R,3aR,6S,6aR)-3-methoxy-6-propoxyhexahydrofurano[3,2-b]furan, (3R,3aR,6S,6aR)-3-methoxy-6-ethoxyhexahydrofurano[3,2-b]furan, (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofurano[3,2-b]furan, ( At least one of (3R,3aR,6S,6aR)-3,6-diethoxyhexahydrofuro[3,2-b]furan and (3R,3aR,6S,6aR)-3,6-dipropoxyhexahydrofuro[3,2-b]furan; more preferably, the furan-containing compound is (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofuro[3,2-b]furan.

[0033] According to the present invention, the diether compound may be any diether compound that can be used as an electron donor in a catalyst for olefin polymerization. Preferably, the diether compound is selected from at least one of the diether compounds represented by formula (3):

[0034]

[0035] In formula (3), R Ⅰ , R Ⅱ , R Ⅲ , R Ⅳ , R Ⅴ and R Ⅵ The same or different, each independently selected from hydrogen, halogen atoms, C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Arylalkyl and C7-C 20 One of the alkylaryl groups, R Ⅰ -R Ⅵ The groups of R Ⅶ and R Ⅷ The same or different, each independently selected from C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkaryl and C7-C 20 One of the aralkyl groups;

[0036] Preferably, the diether compound is selected from 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, ,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-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-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxy At least one of propane, 2-phenyl-2-isopropyl-1,3-dimethoxypropane, 2-phenyl-2-sec-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane and 9,9-dimethoxymethylfluorene.

[0037] Preferably, the diether compound is 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and / or 9,9-dimethoxymethylfluorene.

[0038] According to the present invention, the phosphate compound, the furan compound and the diether compound in the internal electron donor can produce a synergistic effect. According to a preferred embodiment of the present invention, the amount of the phosphate compound can be 0.08-0.45 mol, preferably 0.12-0.35 mol, and more preferably 0.14-0.26 mol per mol of the diether compound; the amount of the furan compound can be 0.10-0.70 mol, preferably 0.15-0.65 mol, and more preferably 0.40-0.60 mol. The three can be better synergistically formulated by using the above preferred amounts, the catalyst polymerization activity is released more smoothly, and has good hydrogen adjustment sensitivity.

[0039] In the present invention, the magnesium source can be various magnesium-containing compounds that can be used as catalysts for olefin polymerization, for example, the magnesium source can be a magnesium halide, an alcoholate of magnesium, a halogenated alcoholate of magnesium, or a magnesium halide adduct carrier, etc. The magnesium halide can be, for example, magnesium chloride and / or magnesium bromide. The alcoholate of magnesium can be, for example, diethoxymagnesium. The halogenated alcoholate of magnesium can be, for example, ethoxymagnesium chloride. The types of the magnesium halide adduct carrier are well known to those skilled in the art, for example, the magnesium halide adduct carriers disclosed in patent documents CN1091748, CN101050245, CN101486722, CN102796132B, CN102796129B and CN102796128B, and the relevant contents disclosed in these patent documents are all introduced into the present invention as a reference.

[0040] According to the present invention, the titanium source can be a conventional choice in the art, for example, the titanium source can be a titanium source having a general formula of Ti(OR′) 3-a Z a and / or Ti(OR′) 4-b Z b A titanium compound wherein R′ is C1-C 20 alkyl, Z is F, Cl, Br or I, a is an integer of 1 to 3, and b is an integer of 1 to 4. Preferably, the titanium source is one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tributoxytitanium chloride, dibutoxytitanium dichloride, butoxytitanium trichloride, triethoxytitanium chloride, diethoxytitanium dichloride, ethoxytitanium trichloride and titanium trichloride.

[0041] In the present invention, the amounts of the magnesium source, the titanium source and the internal electron donor can be conventional amounts in the prior art, for example, the molar ratio of the amount of the magnesium source calculated as magnesium element, the amount of the titanium source calculated as titanium element and the amount of the internal electron donor can be 1:20-190:0.1-2. Preferably, the molar ratio of the amount of the magnesium source calculated as magnesium element, the amount of the titanium source calculated as titanium element and the amount of the internal electron donor is 1:25-170:0.15-1.5.

[0042] The second aspect of the present invention provides a method for preparing the solid catalyst component for olefin polymerization, comprising the following steps:

[0043] Contact the magnesium source with the titanium source, and add an internal electron donor during one or more time periods before, during, and after the contact reaction between the magnesium source and the titanium source.

[0044] Specifically, the reaction between the magnesium source and the titanium source can be carried out in the same manner as in the prior art. For example, the titanium source can be cooled to below 0 °C (preferably -5 to -30 °C), then the magnesium source is added, and the mixture is stirred at this temperature for 10 - 60 minutes, and then heated to the reaction temperature (i.e., about 60 - 130 °C) and maintained at this reaction temperature for 0.5 - 10 hours.

[0045] According to a preferred embodiment of the present invention, the phosphate ester compound, furan compound, and diether compound in the internal electron donor are added separately. Preferably, the phosphate ester compound and the furan compound are added at 5 - 35 °C, and the diether compound is added at 36 - 60 °C.

[0046] The third aspect of the present invention provides a catalyst for olefin polymerization, which catalyst contains:

[0047] (i) the solid catalyst component as described above;

[0048] (ii) at least one alkylaluminum compound; and

[0049] (iii) an optional external electron donor compound.

[0050] In the present invention, the alkylaluminum compound can be various alkylaluminum compounds conventionally used in the art. For example, the general formula of the alkylaluminum can be AlR n X 3-n , where R is an alkyl group of C1 - C8, the hydrogen on the alkyl group is optionally substituted by a halogen atom, X is a halogen, and n is an integer of 0 < n ≤ 3.

[0051] Specific examples of the alkyl group of C1 - C8 may include, but are not limited to: methyl, ethyl, propyl, n-butyl, isobutyl, pentyl, hexyl, n-heptyl, n-octyl, and the halogen may be fluorine, chlorine, bromine, or iodine.

[0052] Specifically, the alkylaluminum compound can be selected from one or more of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, monochlorodiethylaluminum, monochlorodiisobutylaluminum, monochlorodi-n-butylaluminum, monochlorodi-n-hexylaluminum, dichloroethylaluminum, dichloroisobutylaluminum, dichloro-n-butylaluminum, and dichloro-n-hexylaluminum.

[0053] According to the present invention, the amount of the alkyl aluminum compound can be the conventional amount in the art. The molar ratio of aluminum in the alkyl aluminum compound to titanium in the catalyst component can be 1-2000:1, preferably 20-500:1, more preferably 30-300:1.

[0054] In the present invention, the external electron donor can be any of various external electron donors commonly used in the art. For example, the external electron donor can be selected from at least one of carboxylic acids, carboxylic anhydrides, carboxylic esters, ketones, ethers, alcohols, lactones, organophosphorus compounds and organosilicon compounds.

[0055] Preferably, the external electron donor is selected from a group containing at least one Si-OR 19 bond, and the general formula is (R 17 ) x (R 18 ) y Si(OR 19 ) z Silicon compounds, where R 17 , R 18 and R 19 C1-C 18 The hydrocarbon group optionally contains heteroatoms, x and y are each independently an integer of 0-2, z is an integer of 1-3, and the sum of x, y, and z is 4. 17 , R 18 Preferably C3-C 10 The alkyl or cycloalkyl group may contain heteroatoms; R 19 Preferably C1-C 10 The alkyl group may contain heteroatoms.

[0056] Specifically, the external electron donor can be selected from at least one of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane and (1,1,1-, trifluoro-2-propyl)-methyldimethoxysilane.

[0057] According to the present invention, the amount of the external electron donor can be a conventional amount in the art. The molar ratio of the external electron donor to the aluminum in the alkyl aluminum compound can be 1:1-300, preferably 1:2-100.

[0058] The fourth aspect of the present invention provides use of the catalyst for olefin polymerization in olefin polymerization reactions.

[0059] When the catalyst of the present invention is used for olefin polymerization, the catalyst component, the alkyl aluminum compound, and the optional external electron donor can be added to the polymerization reactor separately, or mixed and added to the polymerization reactor, or the olefin can be prepolymerized by a prepolymerization method known in the industry and then added to the polymerization reactor. According to a preferred embodiment of the present invention, after the catalyst component, the alkyl aluminum compound, and the optional external electron donor are pre-contacted and reacted, the catalyst is preferably prepolymerized with propylene and / or other α-olefin monomers before the polymerization reaction. The prepolymerization reaction temperature can be 5-40°C, preferably 10-30°C.

[0060] In the present invention, the specific type of olefin, the polymerization reaction method and conditions of olefin can be conventionally selected according to the prior art.

[0061] The catalyst of the present invention is particularly suitable for the general formula CH2=CHR 1 Homopolymerization and copolymerization of olefins, wherein R 1 is hydrogen, C1-C6 alkyl or C6-C 12 The aromatic group.

[0062] According to the present invention, the polymerization reaction of the olefin can be carried out according to the existing method, specifically, under the protection of an inert gas, in a liquid phase monomer or an inert solvent containing a polymerizable monomer, or in a gas phase, or by a combined polymerization process in a gas-liquid phase. The temperature of the polymerization reaction can generally be 0-150°C, preferably 60-90°C. The pressure of the polymerization reaction can be normal pressure or higher, for example, 0.01-10MPa, preferably 0.01-5MPa, more preferably 0.1-4Mpa, and the pressure of the present invention refers to the gauge pressure. In the polymerization process, hydrogen can be used as a polymer molecular weight regulator and added to the reaction system to adjust the molecular weight and melt index of the polymer. In addition, in the polymerization process of the olefin, the type and amount of the inert gas and solvent are well known to those skilled in the art and will not be repeated here.

[0063] Parameters not limited in the present invention are all conventional technical means in the art.

[0064] The present invention will be further described below in conjunction with embodiments, but the scope of the present invention is not limited to these embodiments.

[0065] The polymer melt index in the present invention is measured according to GB3682-2000 at 230°C and a load of 2.16 kg.

[0066] Examples 1 to 9 are used to illustrate the catalyst component and catalyst for olefin polymerization and their application according to the present invention.

[0067] Example 1

[0068] (1) Preparation of catalyst components

[0069] In a 300 mL glass reaction bottle, add 90 mL of titanium tetrachloride and cool to -20°C, add 35 mmol of a magnesium halide carrier in terms of magnesium element, and then heat to 115°C. During the heating process, add 1.5 mmol of tributyl phosphate at 10°C, add 3 mmol of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofuran[3,2-b]furan at 20°C, and add 7 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane at 40°C. After maintaining at 115°C for 30 minutes, filter out the liquid, wash with titanium tetrachloride, then wash with hexane, and vacuum dry to obtain a catalyst component Cat-1 for olefin polymerization.

[0070] (2) Propylene liquid phase bulk polymerization

[0071] The bulk polymerization of propylene in liquid phase was carried out in a 5L stainless steel autoclave. 1mmol of triethylaluminum, 0.04mmol of cyclohexylmethyldimethoxysilane (CHMMS) and 8.5mg of the above-mentioned catalyst component Cat-1 for olefin polymerization were added to the autoclave in sequence under nitrogen protection. The autoclave was closed, and hydrogen and 2.3L of liquid propylene were added. The temperature was raised to 70°C, and after a certain reaction time, the temperature was lowered, the pressure was released, and the material was discharged. The obtained propylene homopolymer was dried, weighed and analyzed. The results are shown in Table 1.

[0072] Example 2

[0073] The catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1, except that 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was not added during the heating process, and 9,9-dimethoxymethylfluorene was added to obtain a catalyst component Cat-2 for olefin polymerization.

[0074] The obtained propylene homopolymer was dried, weighed and analyzed. The results are shown in Table 1.

[0075] Example 3

[0076] The catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1, except that during the heating process, 1 mmol of tributyl phosphate was added at 20°C, 4 mmol of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofuran[3,2-b]furan was added at 30°C, and 6.8 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was added at 50°C to obtain a catalyst component Cat-3 for olefin polymerization.

[0077] The obtained propylene homopolymer was dried, weighed and analyzed. The results are shown in Table 1.

[0078] Example 4

[0079] The catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1, except that the amounts of tributyl phosphate, (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofuran[3,2-b]furan and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane added during the heating process were 2 mmol, 4.5 mmol and 8 mmol, respectively, to obtain catalyst component Cat-4 for olefin polymerization.

[0080] The obtained propylene homopolymer was dried, weighed and analyzed. The results are shown in Table 1.

[0081] Example 5

[0082] The catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1, except that the amounts of tributyl phosphate, (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofuran[3,2-b]furan and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane added during the heating process were 1.8 mmol, 3.2 mmol and 6.2 mmol, respectively, to obtain a catalyst component Cat-5 for olefin polymerization.

[0083] The obtained propylene homopolymer was dried, weighed and analyzed. The results are shown in Table 1.

[0084] Example 6

[0085] The catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1, except that the amounts of tributyl phosphate, (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofuran[3,2-b]furan and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane added during the heating process were 0.8 mmol, 1.9 mmol and 6.8 mmol, respectively, to obtain a catalyst component Cat-6 for olefin polymerization.

[0086] The obtained propylene homopolymer was dried, weighed and analyzed. The results are shown in Table 1.

[0087] Example 7

[0088] The catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 2, except that the amounts of tributyl phosphate, (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofuran[3,2-b]furan and 9,9-dimethoxymethylfluorene added during the heating process were 1.5 mmol, 2.1 mmol and 7 mmol, respectively, to obtain a catalyst component Cat-7 for olefin polymerization.

[0089] The obtained propylene homopolymer was dried, weighed and analyzed. The results are shown in Table 1.

[0090] Example 8

[0091] The catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1, except that the amounts of tributyl phosphate, (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofuran[3,2-b]furan and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane added during the heating process were 2.5 mmol, 5 mmol and 6 mmol, respectively, to obtain a catalyst component Cat-8 for olefin polymerization.

[0092] The obtained propylene homopolymer was dried, weighed and analyzed. The results are shown in Table 1.

[0093] Example 9

[0094] The catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1, except that tributyl phosphate, (3R, 3aR, 6S, 6aR)-3,6-dimethoxyhexahydrofurano[3,2-b]furan and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were added at 20° C. to obtain a catalyst component Cat-9 for olefin polymerization. The obtained propylene homopolymer was dried, weighed and analyzed, and the results are shown in Table 1.

[0095] Comparative Example 1

[0096] The catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1, except that, during the preparation of the catalyst component, tributyl phosphate and (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofuran[3,2-b]furan were not added, and only 11.5 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was added at 20°C to obtain the catalyst component DCat-1 for olefin polymerization; the obtained propylene homopolymer was dried, weighed and analyzed. The results are shown in Table 1.

[0097] Comparative Example 2

[0098] The catalyst component was prepared and propylene liquid phase bulk polymerization was carried out according to the method of Example 1, except that, during the preparation of the catalyst component, tributyl phosphate and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were not added, and only 11.5 mmol of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofuran[3,2-b]furan was added at 20°C to obtain the catalyst component DCat-2 for olefin polymerization; the obtained propylene homopolymer was dried, weighed and analyzed. The results are shown in Table 1.

[0099] Table 1

[0100]

[0101] Note: AC2h / A.C1h in the table is the ratio of activity after 2 hours of polymerization with a hydrogenation amount of 1.5NL to that after 1 hour of polymerization; the melt index in the table is the melt index of the polymer after 1 hour of polymerization with a hydrogenation amount of 6.5NL.

[0102] It can be seen from Table 1 that, relative to Comparative Examples 1-2, in Examples 1-9 of the present invention, the phosphate compounds, furan compounds and diether compounds are used as the internal electron donors, and the obtained catalyst polymerization activity decays slowly, has high hydrogen regulation sensitivity, and does not contain phthalate compounds (plasticizers) in the catalyst components, which is of great significance.

[0103] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

[0104] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

Claims

1. A solid catalyst component for olefin polymerization, characterized in that: The solid catalyst component contains a product obtained by the reaction of a magnesium source, a titanium source and an internal electron donor; Wherein, the internal electron donor comprises phosphate compounds, furan compounds and diether compounds.

2. The solid catalyst component for olefin polymerization according to claim 1, wherein Based on the content of the internal electron donor, the total content of the phosphate compound, the furan compound and the diether compound is 70-100% by weight, preferably 80-100% by weight.

3. The solid catalyst component for olefin polymerization according to claim 1, wherein The phosphate compound is selected from at least one of the phosphate compounds represented by formula (1), In formula (1), R 13 , R 14 and R 15 Each independently selected from a C1-C4 straight chain or branched alkyl group, a C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl and C7-C 20 The hydrogen atoms on the benzene ring in the aryl, alkaryl and aralkyl groups are optionally substituted by halogen atoms; further preferably R 13 , R 14 and R 15 Each independently selected from a C1-C4 straight chain or branched alkyl group, a C3-C 12 Cycloalkyl, C6-C 12 Aryl, C7-C 12 Alkyl and C7-C 12 The hydrogen atoms on the benzene ring in the aryl, alkaryl and aralkyl groups are optionally substituted by halogen atoms; further preferably R 13 , R 14 and R 15 Each is independently selected from one of a C1-C4 straight or branched alkyl group, a C3-C6 cycloalkyl group, a C6-C8 aryl group, a C7-C8 alkaryl group and a C7-C8 aralkyl group, wherein the hydrogen atoms on the benzene rings in the aryl group, the alkaryl group and the aralkyl group are optionally substituted by halogen atoms; Preferably, the phosphate compound is selected from at least one of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, triisopropylphenyl phosphate, trimethoxyphenyl phosphate, phenyl dimethyl phosphate, cresyl dibutyl phosphate, isopropylphenyl dimethyl phosphate, isopropylphenyl diethyl phosphate, isopropylphenyl dibutyl phosphate, phenyl ditolyl phosphate, phenyl diisopropylphenyl phosphate, p-cresyl dibutyl phosphate, m-cresyl dibutyl phosphate, p-cumyl dimethyl phosphate, p-cumyl diethyl phosphate, p-tert-butylphenyl dimethyl phosphate and o-cresyl p-di-tert-butylphenyl phosphate.

4. The solid catalyst component for olefin polymerization according to claim 1, wherein The furan compound is selected from at least one of the furan compounds represented by formula (2): In formula (2), R1 and R3 are each independently selected from hydrogen, C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Arylalkyl and C7-C 20 R2 and R4 are each independently selected from C1-C 10 Straight or branched alkyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Arylalkyl or C7-C 10 Alkaryl; Preferably, R1 and R3 are each independently selected from hydrogen, C1-C 10 Straight or branched alkyl, C3-C 10 Cycloalkyl, C6-C 10 Aryl, C7-C 10 Arylalkyl and C7-C 10 R2 and R4 are each independently selected from a C1-C4 straight chain or branched chain alkyl, a C3-C8 cycloalkyl, a C6-C 10 aryl, C7-C8 aralkyl or C7-C8 alkaryl; More preferably, the furan compound is selected from at least one of (3R,3aR,6S,6aR)-3-methoxy-6-propoxyhexahydrofuro[3,2-b]furan, (3R,3aR,6S,6aR)-3-methoxy-6-ethoxyhexahydrofuro[3,2-b]furan, (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofuro[3,2-b]furan, (3R,3aR,6S,6aR)-3,6-diethoxyhexahydrofuro[3,2-b]furan and (3R,3aR,6S,6aR)-3,6-dipropoxyhexahydrofuro[3,2-b]furan.

5. The solid catalyst component for olefin polymerization according to claim 1, wherein The diether compound is selected from at least one of the diether compounds represented by formula (3): In formula (3), R Ⅰ , R Ⅱ , R Ⅲ , R Ⅳ , R Ⅴ and R Ⅵ The same or different, each independently selected from hydrogen, halogen atoms, C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Arylalkyl and C7-C 20 One of the alkylaryl groups, R Ⅰ -R Ⅵ The groups of R can be bonded to form a ring; Ⅶ and R Ⅷ The same or different, each independently selected from C1-C 20 Straight or branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkaryl and C7-C 20 One of the aralkyl groups; Preferably, the diether compound is selected from 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, ,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-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-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxy at least one of propane, 2-phenyl-2-isopropyl-1,3-dimethoxypropane, 2-phenyl-2-sec-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane and 9,9-dimethoxymethylfluorene; Preferably, the diether compound is 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and / or 9,9-dimethoxymethylfluorene.

6. The solid catalyst component for olefin polymerization according to claim 1, wherein Relative to each mole of diether compound, the amount of phosphate compound used is 0.08-0.45 mole, preferably 0.12-0.35 mole, more preferably 0.14-0.26 mole; the amount of furan compound used is 0.10-0.70 mole, preferably 0.15-0.65 mole, more preferably 0.40-0.60 mole.

7. The solid catalyst component for olefin polymerization according to claim 1, wherein The magnesium source is at least one of a magnesium halide, a magnesium alcoholate or a halogenated alcoholate and a magnesium halide adduct carrier; The titanium source is of the general formula Ti(OR′) 3-a Z a and Ti(OR′) 4-b Z b At least one of the compounds shown, wherein R′ is C1-C 20 The alkyl group is preferably C1-C 12 The alkyl group is preferably a C1-C6 alkyl group, Z is a halogen, a is an integer of 1-3, and b is an integer of 1-4.

8. The solid catalyst component for olefin polymerization according to claim 1, wherein In the solid catalyst component, the molar ratio of the magnesium source calculated as magnesium element, the titanium source calculated as titanium element and the internal electron donor is 1:20-190:0.1-2, preferably 1:25-170:0.15-1.

5.

9. The method for preparing a solid catalyst component for olefin polymerization according to any one of claims 1 to 8, characterized in that: The steps include: A magnesium source is contacted with a titanium source for reaction, and an internal electron donor is added at one or more time periods before, during and after the magnesium source is contacted with the titanium source for reaction.

10. The preparation method according to claim 9, wherein: The method further comprises the following steps: cooling the titanium source to below 0°C, preferably to -5 to -30°C, adding a magnesium source, and stirring and mixing at the temperature for 10 to 60 minutes, then heating to 60 to 130°C, and maintaining the reaction temperature for 0.5 to 10 hours; Preferably, the phosphate compound, furan compound and diether compound in the internal electron donor are added separately; more preferably, the phosphate compound and furan compound are added at 5-35°C, and the diether compound is added at 36-60°C.

11. A catalyst for olefin polymerization, characterized in that: The catalyst contains: (i) the solid catalyst component according to any one of claims 1 to 8; (ii) at least one alkylaluminum compound; as well as (iii) Optional external electron donor compound.

12. The catalyst for olefin polymerization according to claim 11, wherein The alkylaluminum compound is selected from at least one of the compounds represented by AlR n X 3-n , wherein R is an alkyl group having 1 to 8 carbon atoms, the hydrogen on the alkyl group is optionally substituted by a halogen atom, X is a halogen, and n is an integer of 0 < n ≤ 3; preferably, the alkylaluminum compound is selected from at least one of triethylaluminum, triisobutylaluminum, tributylaluminum, trihexylaluminum, chloro-diethylaluminum, chloro-diisobutylaluminum, chloro-dibutylaluminum, chloro-dihexylaluminum, dichloro-ethylaluminum, dichloro-isobutylaluminum, dichloro-butylaluminum, and dichloro-hexylaluminum; The external electron donor is selected from at least one of carboxylic acid, carboxylic anhydride, carboxylic ester, ketone, ether, alcohol, lactone, organophosphorus compound and organosilicon compound; preferably, the external electron donor is selected from at least one Si-OR 19 bond, and the general formula is (R 17 ) x (R 18 ) y Si(OR 19 ) z Silicon compounds, where R 17 , R 18 and R 19 C1-C 18 The hydrocarbon group optionally contains heteroatoms, x and y are each independently an integer of 0-2, z is an integer of 1-3, and the sum of x, y, and z is 4, R 17 , R 18 Preferably C3-C 10 The alkyl or cycloalkyl group may contain heteroatoms; R 19 Preferably C1-C 10 The alkyl group may contain a heteroatom.

13. The catalyst for olefin polymerization according to claim 11, wherein The molar ratio of the solid catalyst component calculated as titanium element to the alkyl aluminum compound calculated as aluminum element is 1:1-2000, preferably 1:20-500, more preferably 1:30-300; the molar ratio of the external electron donor to the alkyl aluminum compound calculated as aluminum element is 1:1-300, preferably 1:2-100.

14. Use of the catalyst for olefin polymerization according to any one of claims 11 to 13 in olefin polymerization reactions.

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