Solid catalyst component for the polymerization of olefins, process for its preparation, catalyst and use thereof

Abstract

This invention belongs to the field of olefin polymerization technology, and relates to a solid catalyst component for olefin polymerization, its preparation method, the catalyst, and its applications. The solid catalyst component contains a magnesium source, a titanium source, and a product obtained from the reaction of an internal electron donor; the internal electron donor comprises phosphate esters, furans, and diethers. The preparation method includes the following steps: contacting a magnesium source with a titanium source, and adding an internal electron donor before, during, and after the contact reaction. Advantages of this invention: it does not use phthalate compounds, thus the catalyst is a non-plasticizing catalyst; the catalyst has the advantages of stable activity release and high hydrogen sensitivity, which can meet the application requirements of multi-reactor process equipment and is beneficial for developing various high-performance polyolefin products.

Description

Technical Field

[0001] This invention belongs to the field of olefin polymerization technology, and more specifically, relates to a solid catalyst component for olefin polymerization, a method for preparing the solid catalyst component, a catalyst comprising the solid catalyst component, and the application of the catalyst in olefin polymerization reactions. Background Technology

[0002] As is well known, Zn catalysts, primarily composed of titanium, magnesium, halogens, and electron donors, can be used in olefin polymerization reactions. Existing continuous processes for preparing polyolefins often employ a series of two or more reactors, such as two liquid-phase bulk polymerization reactors in series, a liquid-phase bulk polymerization reactor and a gas-phase polymerization reactor in series, or two gas-phase reactors in series. During production, the residence time and other parameters in each reactor are controlled according to the specific product performance requirements and process conditions. The total residence time in each reactor is generally controlled between 2 and 4 hours, which necessitates that the catalyst releases its activity smoothly and uniformly throughout the polymerization process. Otherwise, problems will arise such as excessively high activity in the early stages, making the reaction difficult to control, and insufficient activity in the later stages. This will directly lead to a decline in product quality or even failure to meet performance requirements. Therefore, a smooth and uniform release of catalyst activity is beneficial for both the stability and controllability of the polymerization process and the adjustment of various parameters during polymerization to produce products with superior performance.

[0003] As internal electron donors driving the development of Zn catalysts, the use of monoester compounds, such as ethyl benzoate and ethyl p-ethoxybenzoate, in third-generation Zn catalysts has evolved into diester compounds, such as di(iso)butyl phthalate in fourth-generation Zn catalysts. Phthalate compounds (plasticizers) are currently the most commonly used internal electron donors in polypropylene catalysts. However, studies have found that they can cause serious damage to the growth, development, and reproductive systems of animals, and may also have similar effects on humans. The United States, the European Union, and other countries and regions have successively listed these compounds as toxic chemicals, and their uses (especially in infant toys) are strictly restricted.

[0004] Therefore, it is of great significance to develop high-performance catalysts with stable release of active material and free of plasticizers. Summary of the Invention

[0005] During their research, the inventors unexpectedly discovered that a catalyst using a combination of phosphate esters, furans, and diethers as internal electron donors exhibits advantages such as stable activity release and high hydrogen sensitivity, meeting the application requirements of multi-reactor process units and facilitating the development of various high-performance polyolefin products. Based on this discovery, this invention is proposed.

[0006] To achieve the objectives of this invention, a first aspect of this invention provides a solid catalyst component for olefin polymerization, said solid catalyst component containing a magnesium source, a titanium source, and a product obtained from the reaction of an internal electron donor; The internal electron donor includes phosphate esters, furans, and diethers.

[0007] A second aspect of the present invention provides a method for preparing the solid catalyst component for olefin polymerization, comprising the following steps: A magnesium source and a titanium source are brought into contact and reacted, and an internal electron donor is added before, during and after the contact and reaction of the magnesium source and the titanium source.

[0008] A third aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising: (i) the solid catalyst components described above; (ii) at least one alkylaluminum compound; and (iii) Optional external electron donor compounds.

[0009] A fourth aspect of the invention provides the application of the catalyst described above for olefin polymerization in olefin polymerization reactions.

[0010] The present invention has the following advantages: (1) The present invention uses an internal electron donor containing phosphate esters, furans and diethers, and does not use phthalates, thus the catalyst is a non-plasticizing catalyst.

[0011] (2) The catalyst has the advantages of stable release of activity and high sensitivity to hydrogen regulation, 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.

[0012] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0013] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0014] To achieve the objectives of this invention, a first aspect of this invention provides a solid catalyst component for olefin polymerization, said solid catalyst component containing a magnesium source, a titanium source, and a product obtained from the reaction of an internal electron donor; The internal electron donor includes phosphate esters, furans, and diethers.

[0015] According to the present invention, preferably, the total amount of phosphate ester compound, furan compound and diether compound is 70-100% by weight, more preferably 80-100% by weight, based on the total weight of the internal electron donor.

[0016] The present invention does not particularly limit the type of phosphate ester compound, and it can be any existing phosphate ester compound that can serve as an internal electron donor in a catalyst for olefin polymerization. Preferably, the phosphate ester compound is selected from at least one of the phosphate ester compounds shown in formula (1). Equation (1) In equation (1), R 13 R 14 and R 15 Each is independently selected from C1-C4 straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 alkylaryl and C7-C 20 One of the aryl, alkylaryl, and aryl groups, wherein the hydrogen atom on the benzene ring is optionally substituted with a halogen atom; further preferably R 13 R 14 and R 15 Each is independently selected from C1-C4 straight-chain or branched alkyl groups, C3-C 12 cycloalkyl, C6-C 12 aryl, C7-C 12 alkylaryl and C7-C 12 One of the aryl, alkylaryl, and aryl groups, wherein the hydrogen atom on the benzene ring is optionally substituted with a halogen atom; more preferably R 13 R 14 and R 15 Each is independently selected from one of C1-C4 straight-chain or branched alkyl groups, C3-C6 cycloalkyl groups, C6-C8 aryl groups, C7-C8 alkylaryl groups, and C7-C8 aralkyl groups, wherein the hydrogen atom on the benzene ring in the aryl, alkylaryl, and aralkyl groups is optionally substituted with a halogen atom; 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.

[0017] According to the present invention, preferably, the phosphate ester compound is selected from at least one of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, triisopropylphenyl phosphate, trimethoxyphenyl phosphate, dimethyl phosphate, toluene dibutyl phosphate, isopropylphenyl dimethyl phosphate, isopropylphenyl diethyl phosphate, isopropylphenyl dibutyl phosphate, phenylxyl phosphate, diisopropylphenyl diisopropyl phosphate, p-toluene dibutyl phosphate, m-toluene dibutyl phosphate, p-isopropylphenyl dimethyl phosphate, p-isopropylphenyl diethyl phosphate, p-tert-butylphenyl dimethyl phosphate, and o-toluene-p-di-tert-butylphenyl phosphate.

[0018] Most preferably, the phosphate ester compound is tributyl phosphate.

[0019] In this invention, the furan compound can be any furan compound capable of being used as an electron donor in an olefin polymerization catalyst. Preferably, the furan compound is selected from at least one of the furan compounds shown in formula (2): Equation (2) In equation (2), R1 and R3 are each independently selected from hydrogen, C1-C 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 Aryl groups and C7-C 20 One of the alkylaryl groups; R2 and R4 are each independently selected from C1-C1. 10 Straight-chain or branched alkyl groups, C3-C 10 cycloalkyl, C6-C 10 aryl, C7-C 10 Aryl or C7-C 10 alkylaryl groups.

[0020] Preferably, R1 and R3 are each independently selected from hydrogen, C1-C 10 Straight-chain or branched alkyl groups, C3-C 10 cycloalkyl, C6-C 10 aryl, C7-C 10 Aryl groups and C7-C 10 One of the alkylaryl groups; R2 and R4 are each independently selected from C1-C4 straight-chain or branched alkyl groups, C3-C8 cycloalkyl groups, C6-C4 cycloalkyl groups, and C4-C4 cycloalkyl groups. 10 It is an aryl, C7-C8 aralkyl or C7-C8 alkylaryl group.

[0021] 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, and (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofurano[3,2-b]furan. At least one of (3R,3aR,6S,6aR)-3,6-diethoxyhexahydrofuran[3,2-b]furan and (3R,3aR,6S,6aR)-3,6-dipropoxyhexahydrofuran[3,2-b]furan; more preferably, the furan-containing compound is (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofuran[3,2-b]furan.

[0022] According to the present invention, the diether compound can be any diether compound capable of being 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 shown in formula (3): Equation (3) In equation (3), R Ⅰ R Ⅱ R Ⅲ R Ⅳ R Ⅴ and R Ⅵ Whether they are the same or different, they are each independently selected from hydrogen, halogen atoms, and C1-C atoms. 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 Aryl groups and C7-C 20 One of the alkylaryl groups, R Ⅰ -R Ⅵ The groups can be bonded together to form a ring; while R Ⅶ and R Ⅷ Whether the two are the same or different, they are each independently selected from C1-C. 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl and C7-C 20 One of the aryl 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 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-methyl-2-cyclohexyl-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.

[0023] Preferably, the diether compound is 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and / or 9,9-dimethoxymethylfluorene.

[0024] According to the present invention, the phosphate ester compound, furan compound, and diether compound in the internal electron donor can produce a synergistic effect. According to a preferred embodiment of the present invention, the amount of phosphate ester compound relative to each mole of diether compound can be 0.08-0.45 mol, preferably 0.12-0.35 mol, more preferably 0.14-0.26 mol; the amount of furan compound can be 0.10-0.70 mol, preferably 0.15-0.65 mol, more preferably 0.40-0.60 mol. The above-mentioned preferred amounts of the three compounds can achieve better synergistic formulation, more stable release of catalyst polymerization activity, and good hydrogen regulation sensitivity.

[0025] In this invention, the magnesium source can be a magnesium-containing compound that can be used as a catalyst for olefin polymerization. For example, the magnesium source can be magnesium halide, magnesium alcohol, magnesium halohydride, or magnesium halide adduct support. The magnesium halide can be, for example, magnesium chloride and / or magnesium bromide. The magnesium alcohol can be, for example, magnesium diethoxy. The magnesium halohydride can be, for example, magnesium ethoxychloride. The types of magnesium halide adduct supports are well known to those skilled in the art. For example, magnesium halide adduct supports disclosed in patent documents CN1091748, CN101050245, CN101486722, CN102796132B, CN102796129B, and CN102796128B are included in this invention for reference.

[0026] According to the present invention, the titanium source can be a conventional choice in the art; for example, the titanium source can be of the general formula Ti(OR′). 3-a Z a And / or Ti(OR′) 4-b Z b Titanium compounds, wherein R′ is C1-C 20 The alkyl group, Z is F, Cl, Br or I, a is an integer from 1 to 3, and b is an integer from 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.

[0027] In this invention, the amounts of magnesium source, titanium source, and internal electron donor can be those commonly used in the prior art. For example, the molar ratio of magnesium source (calculated as magnesium element), titanium source (calculated as titanium element), and internal electron donor can be 1:20-190:0.1-2. Preferably, the molar ratio of magnesium source (calculated as magnesium element), titanium source (calculated as titanium element), and internal electron donor is 1:25-170:0.15-1.5.

[0028] The second aspect of the present invention provides a method for preparing the solid catalyst component for olefin polymerization, comprising the following steps: 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.

[0029] 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 the temperature is raised to the reaction temperature (i.e., about 60 - 130 °C), and maintained at this reaction temperature for 0.5 - 10 hours.

[0030] 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 furan compound are added at 5 - 35 °C, and the diether compound is added at 36 - 60 °C.

[0031] The third aspect of the present invention provides a catalyst for olefin polymerization, which catalyst comprises: (i) the solid catalyst component as described above; (ii) at least one alkylaluminum compound; and (iii) an optional external electron donor compound.

[0032] 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 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.

[0033] Specific examples of the alkyl group having 1 to 8 carbon atoms 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.

[0034] Specifically, the alkylaluminum compound can be selected from one or more of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, diethylaluminum chloride, diisobutylaluminum chloride, di-n-butylaluminum chloride, di-n-hexylaluminum chloride, ethylaluminum dichloride, isobutylaluminum dichloride, n-butylaluminum dichloride, and n-hexylaluminum dichloride.

[0035] According to the present invention, the amount of the alkylaluminum compound can be a conventional amount in the art. The molar ratio of aluminum in the alkylaluminum compound to titanium in the catalyst component can be 1-2000:1, preferably 20-500:1, and more preferably 30-300:1.

[0036] In this invention, the external electron donor can be any of the 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.

[0037] Preferably, the external electron donor is selected from those containing at least one Si-OR. 19 The key and the general formula is (R) 17 ) x (R 18 ) y Si(OR 19 ) z Silicon compounds, wherein R 17 R 18 and R 19 For C1-C 18 The hydrocarbon group, optionally containing heteroatoms, has x and y as independent integers from 0 to 2, z as integers from 1 to 3, and the sum of x, y, and z is 4. R 17 R 18 Preferably C3-C 10 Alkyl or cycloalkyl groups, optionally containing heteroatoms; R 19 Preferably C1-C 10 Alkyl groups, optionally containing heteroatoms.

[0038] Specifically, the external electron donor may 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.

[0039] 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 aluminum in the alkylaluminum compound can be 1:1-300, preferably 1:2-100.

[0040] A fourth aspect of the invention provides the application of the catalyst described above for olefin polymerization in olefin polymerization reactions.

[0041] When the catalyst of the present invention is used in olefin polymerization, the catalyst component, alkylaluminum compound, and optional external electron donor can be added to the polymerization reactor separately, or they can be mixed before being added to the polymerization reactor. Alternatively, the olefin can be prepolymerized using a prepolymerization method known in the art before being added to the polymerization reactor. According to a preferred embodiment of the present invention, after the pre-contact reaction of the catalyst component, alkylaluminum compound, and optional external electron donor, and before the polymerization reaction, the catalyst is preferably reacted with propylene and / or other [components]. - The olefin monomer undergoes a prepolymerization reaction. The prepolymerization reaction temperature can be 5-40℃, preferably 10-30℃.

[0042] In this invention, the specific type of olefin, the polymerization reaction method and conditions of the olefin can all be conventionally selected based on existing technology.

[0043] The catalyst of the present invention is particularly suitable for the general formula CH2=CHR 1 The homopolymerization and copolymerization reactions of olefins, wherein R 1 It is hydrogen, C1-C6 alkyl or C6-C 12 Aryl groups.

[0044] According to the present invention, the polymerization reaction of the olefin can be carried out according to existing methods, specifically, under the protection of an inert gas, in a liquid monomer or an inert solvent containing the monomer, or in the gas phase, or through a combined gas-liquid phase polymerization process. The polymerization temperature is generally 0-150°C, preferably 60-90°C. The polymerization pressure can be atmospheric pressure or higher, for example 0.01-10 MPa, preferably 0.01-5 MPa, more preferably 0.1-4 MPa; all pressures in this invention refer to gauge pressure. During the polymerization process, hydrogen can be added to the reaction system as a polymer molecular weight regulator to adjust the polymer's molecular weight and melt index. Furthermore, the types and amounts of the inert gas and solvent used in the olefin polymerization reaction are well known to those skilled in the art and will not be described further here.

[0045] Parameters not specified in this invention are all conventional techniques in the field.

[0046] The present invention will be further described below with reference to the embodiments, but the scope of the present invention is not limited to these embodiments.

[0047] The polymer melt index in this invention was determined according to GB3682-2000 at 230°C and a load of 2.16 kg.

[0048] Examples 1-9 illustrate the catalyst components, catalysts, and applications of the present invention for olefin polymerization.

[0049] Example 1

[0050] (1) Preparation of catalyst components

[0051] In a 300 mL glass reaction flask, 90 mL of titanium tetrachloride was added and cooled to -20 °C. 35 mmol of magnesium halide support (based on elemental magnesium) was added, and the temperature was raised to 115 °C. During the heating process, 1.5 mmol of tributyl phosphate was added at 10 °C, 3 mmol of (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofuran[3,2-b]furan was added at 20 °C, and 7 mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was added at 40 °C. After maintaining the temperature at 115 °C for 30 min, the liquid was filtered off, washed with titanium tetrachloride, then washed with hexane, and dried under vacuum to obtain the catalyst component Cat-1 for olefin polymerization.

[0052] (2) Propylene liquid-phase bulk polymerization

[0053] Propylene liquid-phase bulk polymerization was carried out in a 5L stainless steel high-pressure reactor. Under nitrogen protection, 1 mmol of triethylaluminum, 0.04 mmol of cyclohexylmethyldimethoxysilane (CHMMS), and 8.5 mg of the above-mentioned catalyst component Cat-1 for olefin polymerization were added sequentially to the reactor. The high-pressure reactor was closed, and hydrogen and 2.3L of liquid propylene were added. The temperature was raised to 70°C, and after reacting for a certain time, the temperature was lowered, the pressure was released, and the product was discharged. The resulting propylene homopolymer was dried, weighed, and analyzed. The results are shown in Table 1.

[0054] Example 2

[0055] 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, but 9,9-dimethoxymethylfluorene was added to obtain the catalyst component Cat-2 for olefin polymerization.

[0056] The obtained propylene homopolymer was dried, weighed, and analyzed. The results are shown in Table 1.

[0057] Example 3

[0058] 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 the catalyst component Cat-3 for olefin polymerization.

[0059] The obtained propylene homopolymer was dried, weighed, and analyzed. The results are shown in Table 1.

[0060] Example 4

[0061] 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-dimethoxyhexahydrofurano[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 the catalyst component Cat-4 for olefin polymerization.

[0062] The obtained propylene homopolymer was dried, weighed, and analyzed. The results are shown in Table 1.

[0063] Example 5

[0064] 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-dimethoxyhexahydrofurano[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 the catalyst component Cat-5 for olefin polymerization.

[0065] The obtained propylene homopolymer was dried, weighed, and analyzed. The results are shown in Table 1.

[0066] Example 6

[0067] 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-dimethoxyhexahydrofurano[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 the catalyst component Cat-6 for olefin polymerization.

[0068] The obtained propylene homopolymer was dried, weighed, and analyzed. The results are shown in Table 1.

[0069] Example 7

[0070] 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-dimethoxyhexahydrofurano[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 the catalyst component Cat-7 for olefin polymerization.

[0071] The obtained propylene homopolymer was dried, weighed, and analyzed. The results are shown in Table 1.

[0072] Example 8

[0073] 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-dimethoxyhexahydrofurano[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 the catalyst component Cat-8 for olefin polymerization.

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

[0075] Example 9

[0076] 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 simultaneously at 20°C to obtain the catalyst component Cat-9 for olefin polymerization. The obtained propylene homopolymer was dried, weighed, and analyzed, and the results are shown in Table 1.

[0077] Comparative Example 1

[0078] The catalyst component was prepared and propylene liquid-phase bulk polymerization was carried out according to the method of Example 1. The difference was that in the preparation of the catalyst component, tributyl phosphate and (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofurano[3,2-b]furan were not added. Instead, 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.

[0079] Comparative Example 2

[0080] The catalyst component was prepared and propylene liquid-phase bulk polymerization was carried out according to the method of Example 1. The difference was that in the preparation of the catalyst component, tributyl phosphate and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane were not added. Instead, 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.

[0081] Table 1

[0082] Note: In the table, AC2h / A.C1h represents the ratio of the activity of polymerization after 2 hours to that after 1 hour, with a hydrogenation amount of 1.5NL. The melt index in the table is the melt index of the polymer with a hydrogenation amount of 6.5 NL and a polymerization time of 1 hour.

[0083] As can be seen from Table 1, compared with Comparative Examples 1-2, the catalysts obtained by using phosphate esters, furans, and diethers as internal electron donors in Examples 1-9 of the present invention exhibit slower polymerization activity decay, higher hydrogen sensitivity, and the absence of phthalate esters (plasticizers) in the catalyst composition, which is of great significance.

[0084] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

[0085] The endpoints and any values ​​of the ranges disclosed herein 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 the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

Claims

1. A solid catalyst component for olefin polymerization, characterized in that, The solid catalyst component contains a magnesium source, a titanium source, and a product obtained from the reaction of an internal electron donor. The internal electron donor includes phosphate esters, furans, and diethers. The furan compound is selected from at least one of the furan compounds shown in formula (2): Equation (2) In equation (2), R1 and R3 are each independently selected from hydrogen, C1-C 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 Aryl groups and C7-C 20 One of the alkylaryl groups; R2 and R4 are each independently selected from C1-C1. 10 Straight-chain or branched alkyl groups, C3-C 10 cycloalkyl, C6-C 10 aryl, C7-C 10 Aryl or C7-C 10 alkylaryl groups.

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 phosphate esters, furans and diethers is 70-100% by weight.

3. The solid catalyst component for olefin polymerization according to claim 2, wherein, Based on the content of the internal electron donor, the total content of phosphate esters, furans and diethers is 80-100% by weight.

4. The solid catalyst component for olefin polymerization according to claim 1, wherein, The phosphate ester compound is selected from at least one of the phosphate ester compounds shown in formula (1). Equation (1) In equation (1), R 13 R 14 and R 15 Each is independently selected from C1-C4 straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 alkylaryl and C7-C 20 One of the aryl, alkylaryl and aryl groups, wherein the hydrogen atoms on the benzene ring in the aryl, alkylaryl and aryl groups are optionally replaced by halogen atoms.

5. The solid catalyst component for olefin polymerization according to claim 4, wherein, R 13 R 14 and R 15 Each is independently selected from C1-C4 straight-chain or branched alkyl groups, C3-C 12 cycloalkyl, C6-C 12 aryl, C7-C 12 alkylaryl and C7-C 12 One of the aryl, alkylaryl and aryl groups, wherein the hydrogen atoms on the benzene ring in the aryl, alkylaryl and aryl groups are optionally replaced by halogen atoms.

6. The solid catalyst component for olefin polymerization according to claim 5, wherein, R 13 R 14 and R 15 Each of the following is independently selected from one of C1-C4 straight-chain or branched alkyl, C3-C6 cycloalkyl, C6-C8 aryl, C7-C8 alkylaryl, and C7-C8 aralkyl, wherein the hydrogen atom on the benzene ring in the aryl, alkylaryl, and aralkyl groups is optionally substituted with a halogen atom.

7. The solid catalyst component for olefin polymerization according to claim 6, wherein, The phosphate ester compound is selected from at least one of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, triisopropylphenyl phosphate, trimethoxyphenyl phosphate, dimethyl phosphate, toluene dibutyl phosphate, isopropylphenyl dimethyl phosphate, isopropylphenyl diethyl phosphate, isopropylphenyl dibutyl phosphate, phenylxyl phosphate, phenylxyl diisopropylphenyl phosphate, p-toluene dibutyl phosphate, m-toluene dibutyl phosphate, p-isopropylphenyl dimethyl phosphate, p-isopropylphenyl diethyl phosphate, p-tert-butylphenyl dimethyl phosphate, and o-toluene p-di-tert-butylphenyl phosphate.

8. The solid catalyst component for olefin polymerization according to claim 1, wherein, R1 and R3 are each independently selected from hydrogen, C1-C 10 Straight-chain or branched alkyl groups, C3-C 10 cycloalkyl, C6-C 10 aryl, C7-C 10 Aryl groups and C7-C 10 One of the alkylaryl groups; R2 and R4 are each independently selected from C1-C4 straight-chain or branched alkyl groups, C3-C8 cycloalkyl groups, C6-C4 cycloalkyl groups, and C4-C4 cycloalkyl groups. 10 It is an aryl, C7-C8 aralkyl or C7-C8 alkylaryl group.

9. The solid catalyst component for olefin polymerization according to claim 8, wherein, The furan compounds are selected from at least one of (3R,3aR,6S,6aR)-3-methoxy-6-propoxyhexahydrofuran[3,2-b]furan, (3R,3aR,6S,6aR)-3-methoxy-6-ethoxyhexahydrofuran[3,2-b]furan, (3R,3aR,6S,6aR)-3,6-dimethoxyhexahydrofuran[3,2-b]furan, (3R,3aR,6S,6aR)-3,6-diethoxyhexahydrofuran[3,2-b]furan, and (3R,3aR,6S,6aR)-3,6-dipropoxyhexahydrofuran[3,2-b]furan.

10. 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 shown in formula (3): Equation (3) In equation (3), R Ⅰ R Ⅱ R Ⅲ R Ⅳ R Ⅴ and R Ⅵ Whether they are the same or different, they are each independently selected from hydrogen, halogen atoms, and C1-C atoms. 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 Aryl groups and C7-C 20 One of the alkylaryl groups, R Ⅰ -R Ⅵ The groups can be bonded together to form a ring; R Ⅶ and R Ⅷ Whether the two are the same or different, they are each independently selected from C1-C. 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl and C7-C 20 One of the aryl groups.

11. The solid catalyst component for olefin polymerization according to claim 10, wherein, The diether compounds are 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, 2,2- 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-methyl-2-cyclohexyl-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-dimethoxypropane At least one of the following: alkyl, 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.

12. The solid catalyst component for olefin polymerization according to claim 11, wherein, The diether compound is 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and / or 9,9-dimethoxymethylfluorene.

13. The solid catalyst component for olefin polymerization according to claim 1, wherein, The amount of phosphate esters used per mole of diether compounds is 0.08-0.45 mol; the amount of furan compounds used per mole is 0.10-0.70 mol.

14. The solid catalyst component for olefin polymerization according to claim 13, wherein, The amount of phosphate esters used per mole of diether compounds is 0.12-0.35 moles; the amount of furan compounds used per mole is 0.15-0.65 moles.

15. The solid catalyst component for olefin polymerization according to claim 14, wherein, The amount of phosphate esters used per mole of diether compounds is 0.14-0.26 mol; the amount of furan compounds used per mole is 0.40-0.60 mol.

16. The solid catalyst component for olefin polymerization according to claim 1, wherein, The magnesium source is at least one of magnesium halide, magnesium alcohol or haloalkanes and 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 Alkyl group, Z is halogen, a is an integer from 1 to 3, and b is an integer from 1 to 4.

17. The solid catalyst component for olefin polymerization according to claim 16, wherein, R′ is C1-C 12 Alkyl groups.

18. The solid catalyst component for olefin polymerization according to claim 17, wherein, R′ is a C1-C6 alkyl group.

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

20. The solid catalyst component for olefin polymerization according to claim 19, wherein, In the solid catalyst composition, the molar ratio of magnesium source (calculated as magnesium element), titanium source (calculated as titanium element), and internal electron donor is 1:25-170:0.15-1.

5.

21. The method for preparing the solid catalyst component for olefin polymerization according to any one of claims 1-20, characterized in that, Includes the following steps: A magnesium source and a titanium source are brought into contact and reacted, and an internal electron donor is added before, during and after the contact and reaction of the magnesium source and the titanium source.

22. The preparation method according to claim 21, wherein, The process also includes the following steps: cooling the titanium source to below 0°C, adding the magnesium source, and stirring and mixing at this temperature for 10-60 minutes, then raising the temperature to 60-130°C and maintaining it at this reaction temperature for 0.5-10 hours.

23. The preparation method according to claim 22, wherein, The titanium source was cooled to -5 to -30°C.

24. The preparation method according to claim 22, wherein, Phosphate esters, furans, and diethers are added to the internal electron donor, respectively.

25. The preparation method according to claim 24, wherein, Phosphate esters and furans are added at 5-35°C, while diethers are added at 36-60°C.

26. A catalyst for olefin polymerization, characterized in that, The catalyst contains: (i) The solid catalyst component according to any one of claims 1-20; (ii) at least one alkylaluminum compound; as well as (iii) Optional external electron donor compounds.

27. The catalyst for olefin polymerization according to claim 26, wherein, The alkylaluminum compound is selected from at least one of the compounds represented by AlR n X 3-n , where 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; The external electron donor is selected from at least one of carboxylic acids, carboxylic anhydrides, carboxylic esters, ketones, ethers, alcohols, lactones, organophosphorus compounds, and organosilicon compounds.

28. The catalyst for olefin polymerization according to claim 27, wherein, The alkylaluminum compound is selected from at least one of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, diethylaluminum chloride, diisobutylaluminum chloride, di-n-butylaluminum chloride, di-n-hexylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, di-n-butylaluminum chloride, and di-n-hexylaluminum chloride.

29. The catalyst for olefin polymerization according to claim 27, wherein, The external electron donor is selected from those containing at least one Si-OR 19 The key and the general formula is (R) 17 ) x (R 18 ) y Si(OR 19 ) z Silicon compounds, wherein R 17 R 18 and R 19 For C1-C 18 The hydrocarbon group, optionally containing heteroatoms, x and y are each independent integers from 0 to 2, z is an integer from 1 to 3, and the sum of x, y, and z is 4.

30. The catalyst for olefin polymerization according to claim 29, wherein, R 17 R 18 For C3-C 10 Alkyl or cycloalkyl groups, optionally containing heteroatoms.

31. The catalyst for olefin polymerization according to claim 29, wherein, R 19 For C1-C 10 Alkyl groups, optionally containing heteroatoms.

32. The catalyst for olefin polymerization according to claim 26, wherein, The molar ratio of the solid catalyst component (calculated as titanium) to the alkylaluminum compound (calculated as aluminum) is 1:1-2000; the molar ratio of the external electron donor to the alkylaluminum compound (calculated as aluminum) is 1:1-300.

33. The catalyst for olefin polymerization according to claim 32, wherein, The molar ratio of the solid catalyst component (calculated as titanium) to the alkylaluminum compound (calculated as aluminum) is 1:20-500.

34. The catalyst for olefin polymerization according to claim 33, wherein, The molar ratio of the solid catalyst component (calculated as titanium) to the alkylaluminum compound (calculated as aluminum) is 1:30-300.

35. The catalyst for olefin polymerization according to claim 32, wherein, The molar ratio of the external electron donor to the alkylaluminum compound (calculated as aluminum) is 1:2-100.

36. The use of the catalyst for olefin polymerization according to any one of claims 26-35 in an olefin polymerization reaction.

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