A catalyst component for propylene polymerization, a method for preparing the same, a catalyst and use thereof

Abstract

The application belongs to the technical field of catalysts, and discloses a catalyst component for propylene polymerization, a preparation method, a catalyst and application, the catalyst component comprising magnesium, titanium, halogen and an electron donor, wherein the electron donor contains compound X and compound Y; the general formula of the compound X is R a -O-R b , wherein R a , R b are the same or different and are selected from C1-C 20 substituted or unsubstituted linear alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, olefinic group; R a and R b may be optionally linked into a ring or not; the compound Y is a diol ester compound. The catalyst has good fluidity, good particle morphology and uniform particle size distribution, and when used for propylene polymerization, has high activity, good hydrogen sensitivity, and the obtained polymer does not contain phthalate compounds.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology, specifically relating to a catalyst component for propylene polymerization and its preparation method, a catalyst containing the catalyst component, and the application of the catalyst component and the catalyst. Background Technology

[0002] Olefin polymerization catalysts can be divided into three main categories: traditional Ziegler-Natta catalysts, metallocene catalysts, and non-metallocene catalysts. For traditional Ziegler-Natta catalysts, with the development of electron-donating compounds, polyolefin catalysts have been continuously updated and upgraded. Catalyst development has progressed from the first-generation TiCl3AlCl3 / AlEt2Cl system and the second-generation TiCl3 / AlEt2Cl system to the third-generation TiCl4·ED·MgCl2 / AlR3·ED system, which uses magnesium chloride as a support, monoesters or aromatic diesters as internal electron donors, and silanes as external electron donors. These catalysts have significantly improved the catalytic polymerization activity and the isotacticity of the resulting polypropylene.

[0003] In existing technologies, titanium catalyst systems used for propylene polymerization are mostly composed of magnesium, titanium, halogens, and electron donors (internal electron donors). Among them, electron donors are an essential component of the catalyst and play a crucial role in improving catalyst performance. They are one of the key factors affecting catalyst performance.

[0004] Currently, various electron-donating compounds have been disclosed, such as phthalates, diethers, glycol esters, and succinates, see patent documents US4784983, US4971937, EP0728769, WO98 / 56830, WO98 / 56834, CN1436766A, CN1453298, etc.

[0005] Different electron-donating compounds have their own advantages and disadvantages. For example, glycol esters are highly active internal electron-donating catalysts, producing polymers with a wide molecular weight distribution, but they have poor hydrogen sensitivity, which is not conducive to the production of polymers with high melt index. On the other hand, monoethers have very low internal electron-donating activity as catalysts for propylene polymerization. Summary of the Invention

[0006] In response to the above situation, the inventors of this invention unexpectedly discovered that, in preparing catalyst components for propylene polymerization, using a combination of a monoether and a glycol ester compound can yield a catalyst with high activity, good hydrogen sensitivity, and excellent overall performance, and the polymer does not contain phthalate compounds. Based on this, the object of this invention is to provide a catalyst component for propylene polymerization, its preparation method, the catalyst itself, and its applications.

[0007] A first aspect of the present invention provides a catalyst composition for propylene polymerization, the catalyst composition comprising magnesium, titanium, halogen and an electron donor, said electron donor comprising compound X and compound Y;

[0008] The general formula of compound X is R a -OR b , where R a R b Same or different, selected from C1-C 20 Substituted or unsubstituted straight-chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, olefinic; R a and R b It can be optionally keyed into a loop or not;

[0009] The compound Y is a diol ester compound.

[0010] A second aspect of the present invention provides a method for preparing the above-described catalyst component for propylene polymerization, the method comprising:

[0011] 1) Dissolve a magnesium compound in a system containing compound X, add a precipitation aid and a precipitation agent, and precipitate a solid.

[0012] 2) Treat the solids precipitated in step 1) with titanium compounds, and add compound Y during and / or before the treatment with titanium compounds.

[0013] A third aspect of the present invention provides a catalyst for propylene polymerization, the catalyst comprising the reaction product of the following components:

[0014] a. The catalyst components described above, or the catalyst components prepared by the above preparation method;

[0015] b. Alkyl aluminum compounds, with the general formula AlR' n X' 3-n In the general formula, R' is hydrogen or C1-C 20 The hydrocarbon group, X' is a halogen, 0 < n ≤ 3;

[0016] c. Optionally, external electrons are provided.

[0017] The fourth aspect of the present invention provides the above-described catalyst component, the catalyst component prepared by the above-described preparation method, or the application of the above-described catalyst in propylene polymerization.

[0018] In the preparation of the catalyst components, this invention utilizes a combination of monoethers and glycol esters, exhibiting a good synergistic effect and yielding a catalyst with good flowability, good particle morphology, uniform particle size distribution, and excellent overall performance. Furthermore, by adjusting the addition method and content ratio of electron donors, the performance of the catalyst can be further improved. When used for propylene polymerization, the catalyst of this invention exhibits high activity, good hydrogen sensitivity, and the resulting polymer does not contain phthalate compounds.

[0019] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0020] 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.

[0021] According to a first aspect of the present invention, the present invention provides a catalyst component for propylene polymerization, the catalyst component comprising magnesium, titanium, halogen and an electron donor, said electron donor comprising compound X and compound Y;

[0022] The general formula of compound X is R a -OR b , where R a R b Same or different, selected from C1-C 20 Substituted or unsubstituted straight-chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, olefinic; R a and R b It can be optionally keyed into a loop or not;

[0023] The compound Y is a diol ester compound.

[0024] In the preferred case, R a R b Same or different, selected from C1-C 10 Substituted or unsubstituted straight-chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, olefinic; R a and R b It can be optionally keyed into a ring or not.

[0025] More preferably, R a R b Same or different, selected from C1-C 10 Unsubstituted straight-chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, olefinic; R a and R b It can be optionally keyed into a ring or not.

[0026] The compound X in this invention may be selected from, but is not limited to, at least one of the following compounds: methyl ether, diethyl ether, n-propyl ether, isopropyl ether, n-butyl ether, isobutyl ether, n-pentyl ether, methyl n-pentyl ether, cyclohexyl ether, ethyl cyclohexyl ether, cyclohexyl vinyl ether, n-heptyl ether, n-octyl ether, n-nonyl ether, n-decyl ether, ethylene oxide, propylene oxide, and tetrahydrofuran.

[0027] In this invention, compound Y can be selected from at least one of the compounds shown in general formula (I).

[0028]

[0029] In equation (I), R1 and R2 may be the same or different, and are selected from C1-C 20 The substituted or unsubstituted straight-chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, olefinic, and fused-ring aryl groups; A is a divalent spar group of alkyl, cycloalkyl, or aryl groups having 1 to 20 carbon atoms, and the divalent spar group may optionally be C1-C2. 20 The straight-chain or branched alkyl group is substituted, wherein the carbon atom and / or hydrogen atom in the divalent styrene group and its substituents may optionally be replaced by a heteroatom, which is a nitrogen, oxygen, sulfur, silicon, phosphorus, or halogen atom, and the substituents on the divalent styrene group may optionally be bonded to one or more saturated / unsaturated rings.

[0030] Preferably, R1 and R2 are the same or different, and are selected from C1-C2. 20 Substituted or unsubstituted aryl or alkylaryl groups; A includes formula (III), formula (IV), or formula (V).

[0031]

[0032] In formula (III), R′3-R′8 may be the same or different, and are selected from hydrogen, halogens, and C1-C. 20 The substituted or unsubstituted straight-chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, olefinic, fused-ring aryl, and ester groups, R′7 and R′8 may optionally be cyclic or non-cyclic;

[0033]

[0034] In equation (IV), R 1 -R 4 Same or different, selected from C1-C 20 Straight-chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, olefinic and fused-ring aryl, R 1 -R 4 They can be optionally bonded into one or more saturated / unsaturated rings;

[0035]

[0036] In formula (V), R is selected from hydrogen, halogens, and C1-C. 20 Substituted or unsubstituted straight-chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, olefinic, and fused-ring aryl groups.

[0037] In this invention, compound Y can be selected from 2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 3,5-heptanediol di-p-methylbenzoate, 3,5-heptanediol di-o-methylbenzoate, 3,5-heptanediol di-p-chlorobenzoate, 3,5-heptanediol di-o-chlorobenzoate, 3,5-heptanediol di-p-methoxybenzoate, 3,5-heptanediol di-o-methoxybenzoate, 3,5-heptanediol di-m-methoxybenzoate, 2-methyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-heptanediol dibenzoate, 6-methyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 5-ethyl-3 5-Heptanediol dibenzoate, 4-propyl-3,5-heptanediol dibenzoate, 4-butyl-3,5-heptanediol dibenzoate, 2,4-dimethyl-3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 4,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 2-methyl-4-ethyl-3,5-heptanediol dibenzoate, 4-methyl-4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-4-propyl 4-Methyl-4-propyl-3,5-heptanediol dibenzoate, 6-methyl-2,4-heptanediol di(p-chlorobenzoate), 6-methyl-2,4-heptanediol di(p-methylbenzoate), 6-methyl-2,4-heptanediol di(m-methylbenzoate), 2,2,6,6-tetramethyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-octanediol dibenzoate, 4-ethyl-3,5-octanediol dibenzoate, 4-propyl-3,5-octanediol dibenzoate, 4-butyl-3,5-octanediol dibenzoate, 4,4-dimethyl-3,5-octanediol dibenzoate, 4-methyl-4-ethyl-3,5-octanediol dibenzoate, 2- Methyl-4-ethyl-3,5-octanediol dibenzoate, 2-methyl-6-ethyl-3,5-octanediol dibenzoate, 5-methyl-4,6-nonanediol dibenzoate, 5-ethyl-4,6-nonanediol dibenzoate, 5-propyl-4,6-nonanediol dibenzoate, 5-butyl-4,6-nonanediol dibenzoate, 5,5-dimethyl-4,6-nonanediol dibenzoate, 5-methyl-4-ethyl-4,6-nonanediol dibenzoate, 5-phenyl-4,6-nonanediol dibenzoate, 4,6-nonanediol dibenzoate, 4-butyl-3,5-heptanediol dibenzoate, 1,2-phenylene dibenzoic acid, 3-methyl-5-tert-butyl-1,2-phenylene dibenzoate, 3,5-diisopropyl-1,2-phenylene dibenzoate2-Phenylidene benzoate, 3,6-dimethyl-1,2-phenylene benzoate, 4-tert-butyl-1,2-phenylene benzoate, 1,2-naphthalene benzoate, 2,3-naphthalene benzoate, 1,8-naphthalene dibenzoate, 1,8-naphthalene dibenzoate, 1,8-naphthalene di-4-methylbenzoate, 1,8-naphthalene di-3-methylbenzoate, 1,8-naphthalene di-2-methylbenzoate, 1,8-naphthalene di-4-ethylbenzoate, 1,8-naphthalene di-4- One or more of the following: n-propylbenzoic acid-1,8-naphthyl ester, di-4-isopropylbenzoic acid-1,8-naphthyl ester, di-4-n-butylbenzoic acid-1,8-naphthyl ester, di-4-isobutylbenzoic acid-1,8-naphthyl ester, di-4-tert-butylbenzoic acid-1,8-naphthyl ester, di-4-phenylbenzoic acid-1,8-naphthyl ester, di-4-fluorobenzoic acid-1,8-naphthyl ester, di-3-fluorobenzoic acid-1,8-naphthyl ester, and di-2-fluorobenzoic acid-1,8-naphthyl ester.

[0038] According to the present invention, the molar ratio of compound X and compound Y is r, 0 < r < 5, preferably 0 < r ≤ 3, and more preferably 0 < r ≤ 2.

[0039] According to a second aspect of the present invention, the present invention provides a method for preparing the above-described catalyst component for propylene polymerization, wherein the catalyst component can be obtained by contacting a magnesium compound, a titanium compound, compound X, and compound Y.

[0040] The preparation methods of catalyst components include, but are not limited to, the following methods:

[0041] 1) Dissolve a magnesium compound in a system containing compound X, add a precipitation aid and a precipitation agent, and precipitate a solid.

[0042] 2) Treat the solids precipitated in step 1) with titanium compounds, and add compound Y during and / or before the treatment with titanium compounds.

[0043] According to the present invention, in step 1), "dissolving the magnesium compound in a system containing compound X" can be done by first dissolving the magnesium compound in a solvent system to obtain a solution, and then adding compound X; or it can be done by dissolving the magnesium compound in a system containing both compound X and a solvent system.

[0044] In this invention, the solvent system can be a conventional solvent system used in the prior art for dissolving magnesium compounds. For example, the solvent system can be a solvent system containing an organic epoxy compound, an organophosphorus compound, and optionally an inert diluent, or a solvent system containing an organic alcohol compound and optionally an inert diluent.

[0045] According to the present invention, the organic epoxy compound, organophosphorus compound, etc., can be conventionally selected according to existing technology. For example, the organic epoxy compound can be selected from aliphatic olefins, dienes, or halogenated aliphatic olefins with 2-8 carbon atoms substituted with heteroatoms, specifically epichlorohydrin, epibromopropane, etc. The organophosphorus compound can be selected from hydrocarbon esters or halogenated hydrocarbon esters of orthophosphoric acid or phosphorous acid; specifically, the organophosphorus compound can be selected from at least one of trimethyl orthophosphoric acid, triethyl orthophosphoric acid, tributyl orthophosphoric acid, triphenyl orthophosphoric acid, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and phenyl phosphite.

[0046] In this invention, the general formula of the organic alcohol compound is R8OH, wherein R8 is a substituted or unsubstituted straight-chain or branched C1-C1 compound. 20 Alkyl, C2-C 20 olefin group, C3-C 20 cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl or C7-C 20 Aryl groups, preferably selected from straight-chain or branched C2-C groups. 10 Alkyl groups, more preferably selected from at least one of ethanol, butanol and isooctyl alcohol.

[0047] According to the present invention, the inert diluent can be any solvent conventional in the art for dissolving Ziegler-Natta catalyst components, preferably selected from C6-C. 10 It contains at least one of alkanes or aromatics, more preferably at least one of hexaane, heptane, octane, decane, benzene, toluene, xylene and their derivatives.

[0048] In this invention, the magnesium compound may be selected from magnesium dihalides, magnesium alkoxy compounds, alkyl magnesium compounds, hydrates or alcohols of magnesium dihalides, and derivatives of magnesium dihalides in which one halogen atom in the molecular formula is replaced by an alkoxy or haloalkoxy group; preferably magnesium dihalides or alcohols of magnesium dihalides, such as magnesium dichloride, magnesium dibromide, magnesium diiodide, and their alcohols.

[0049] According to the present invention, the titanium compound may be selected from those with the general formula TiX. m (OR″1) 4-m Compounds, where R″1 is C1-C 20 The hydrocarbon group, where X is a halogen, and 1 ≤ m ≤ 4. Specifically, the titanium compound can be selected from: titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, titanium trichloromonoethoxy, and titanium tetrachloride, preferably titanium tetrachloride.

[0050] In this invention, the precipitant can be a metal halide, such as titanium halide, iron halide, zinc halide, etc., wherein titanium halide, such as titanium tetrachloride or titanium tetrabromide, is preferred; titanium tetrachloride is more preferred.

[0051] According to the present invention, the precipitation aid can be selected from oxygen-containing compounds, preferably from acid anhydrides and diester compounds, and more preferably from acid anhydrides and malonate diester compounds. Specifically, it can be selected from acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, diisobutylmalonate, di-n-butylmalonate, di-tert-butylmalonate, diisobutylmalonate, di-n-butylmalonate, di-tert-butylmalonate, diisobutylmalonate, di-n-butylmalonate, di-tert-butylmalonate, di-dipentyl diisobutylmalonate, di-n-butylmalonate, di-tert-butylmalonate, di-dihexyl diisobutylmalonate, di-n-butylmalonate, di-tert-butylmalonate, etc.

[0052] The solid catalyst component of the present invention can be prepared according to the method described below, but the preparation method of the catalyst component involved in the present invention is not limited thereto.

[0053] First, a magnesium compound is dissolved in a system consisting of compound X, an organic epoxy compound, an organophosphorus compound, and an inert diluent to form a homogeneous solution. Then, in the presence of a precipitation aid, the solution is mixed with a precipitation agent (such as a titanium compound), heated, and a solid is precipitated. This solid is then treated with an electron donor compound Y to attach it to the solid, and then treated with titanium tetrahalide or titanium tetrahalide and an inert diluent.

[0054] According to a third aspect of the present invention, a catalyst for propylene polymerization is provided, the catalyst comprising the reaction product of the following components:

[0055] a. The catalyst components described above, or the catalyst components prepared by the above preparation method;

[0056] b. Alkyl aluminum compounds, with the general formula AlR' n X' 3-n In the general formula, R' is hydrogen or C1-C 20 The hydrocarbon group, X' is a halogen, 0 < n ≤ 3;

[0057] c. Optionally, external electrons are provided.

[0058] In this invention, the alkyl aluminum compound can be specifically selected from triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum hydrogen, diisobutylaluminum hydrogen, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, and dichloroethylaluminum, preferably triethylaluminum and triisobutylaluminum.

[0059] According to the present invention, "optionally, external electron donor" means that an external electron donor may or may not be added as needed. For applications requiring highly stereoregular olefin polymers, an external electron donor must be added. The external electron donor can be conventionally selected according to existing technology, for example, it can be selected from general formula (R3). k Si(OR4) 4-k The organosilicon compounds shown have the formula 0≤k≤3, and R3 is selected from halogens, hydrogen atoms, and C1-C atoms. 20 Alkyl, cycloalkyl, aryl, haloalkyl, or amino, where R4 is C1-C 20 Alkyl, cycloalkyl, aryl, haloalkyl or amino.

[0060] Specific examples of external electron donors include, but are not limited to: trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, and methyltert-butyldimethoxysilane; preferably cyclohexylmethyldimethoxysilane and diphenyldimethoxysilane.

[0061] In this invention, the molar ratio of component a to component b, calculated as titanium:aluminum, is 1:(5-1000), preferably 1:(25-100); the molar ratio of component c to component a, calculated as electron donor:titanium, is 0-500:1, preferably 25-100:1. When the electron donor of component c is the aforementioned organosilicon compound, the molar ratio of component c to component a, calculated as silicon:titanium, is 0-500:1, preferably 25-100:1.

[0062] According to a fourth aspect of the present invention, the present invention provides the above-described catalyst component, the catalyst component prepared by the above-described preparation method, or the application of the above-described catalyst in propylene polymerization.

[0063] The catalyst component or catalyst of the present invention can be used directly in the propylene polymerization reaction, or it can be used in the propylene polymerization reaction after prepolymerization.

[0064] Prepolymerization involves prepolymerizing the above-mentioned catalyst components or catalyst with olefins (propylene) to obtain a prepolymer. The prepolymerization ratio of the prepolymer is 0.1-1000g olefin polymer / g solid catalyst component, preferably 0.2-500g olefin polymer / g solid catalyst component.

[0065] Prepolymerization can be carried out in a liquid or gas phase at temperatures ranging from -20 to 80°C, preferably 0 to 50°C. The prepolymerization step can be performed online as part of a continuous polymerization process or independently in a batch operation.

[0066] The propylene polymerization of the present invention is carried out according to known polymerization methods, which can be carried out in the liquid phase or gas phase, or in a combination of liquid phase and gas phase polymerization stages. Using conventional techniques such as slurry polymerization and gas-phase fluidized bed polymerization, the propylene polymerization includes homopolymerization of propylene or copolymerization of propylene with other olefins. Preferably, the following reaction conditions are used: polymerization temperature 0-150°C, preferably 60-90°C; polymerization pressure 0.01-10 MPa.

[0067] The substances and parameters not limited in this invention can be selected according to existing technology, which is a conventional technical means in this field.

[0068] The present invention will be further described below with reference to embodiments. However, the invention is not limited to these embodiments.

[0069] In the following examples and comparative examples, the data were obtained using the following test methods:

[0070] 1. Melt flow index (MI) of the polymer: determined using a melt flow indexer at 230°C and 2.16 kg pressure, according to ASTM D1238-99, "Standard Test Method for Determination of Melt Flow Rate of Thermoplastics by Extrusion Plasticity".

[0071] 2. Electron-donator content in the catalyst: The electron-donator content in the catalyst was determined using a Waters 600E high-performance liquid chromatograph. First, the sample was pretreated with an ethyl acetate-dilute hydrochloric acid solution to extract the electron-donator compound. The compound was then separated by HPLC, and its peak area was measured. Correction was performed using an external standard curve, and the percentage content of the electron-donator compound in the sample was calculated. This was then converted to the molar ratio of electron donors.

[0072] Examples 1-8

[0073] In a reactor fully purged with high-purity nitrogen, 4.8 g of magnesium chloride, 98 mL of toluene, 4 mL of epichlorohydrin, 12.5 mL of tributyl phosphate, and compound X were added sequentially. The mixture was heated to 50 °C with stirring and maintained for 2.5 h. Then, 1.4 g of phthalic anhydride was added, and the temperature was maintained for another h. The solution was cooled to below -25 °C, and 56 mL of TiCl4 was added dropwise over 1 h. The temperature was slowly raised to 80 °C, and a solid precipitate formed. Compound Y was then added to the solid, and the temperature was maintained for 1 h. After filtration, the solid precipitate was washed twice with 70 mL of toluene to obtain a solid precipitate. A TiCl4 / toluene solution was then added to the precipitate, and the temperature was raised to 110 °C and maintained for 1 h. The mixture was then filtered. This process was repeated four times. The filtered precipitate was washed three times with 70 mL of toluene at 110 °C for 10 min each time, and then washed twice with 60 mL of hexane to obtain the (solid) catalyst component. The specific substances used for compounds X and Y in each example, as well as the molar ratio of compounds X to Y in the catalyst component, are shown in Table 1.

[0074] Propylene polymerization: In a 5L stainless steel reactor, after complete purging with gaseous propylene, 32.5 mmol of AlEt and 0.1 mmol of methylcyclohexyldimethoxysilane (CHMMS) were added, followed by 8-10 mg of the solid catalyst components prepared in each example and 7.2 L of hydrogen gas. 2.3 L of liquid propylene was then introduced, and the temperature was raised to 70°C and maintained for 1 hour. The reactor was then cooled and depressurized to obtain PP powder. Data are shown in Table 1.

[0075] Example 9

[0076] Under nitrogen protection, 4.8 g of anhydrous magnesium chloride, 19.5 g of isooctanol, compound X, and 19.5 g of decane solvent were added to a 500 mL reactor equipped with a stirrer. The mixture was heated to 130 °C and reacted for 1.5 hours until the magnesium chloride was completely dissolved. 2.0 g of diisobutylmalonate was added, and the reaction was continued at 130 °C for another hour to obtain the alcohol. The alcohol was then cooled to room temperature. Under nitrogen protection, the alcohol was added dropwise to 120 mL of titanium tetrachloride solution pre-cooled to -22 °C. The temperature was slowly increased to 100 °C, compound Y was added, and the temperature was increased to 110 °C and maintained for 2 hours. The mixture was filtered while hot, and 120 mL of titanium tetrachloride was added. The reaction was continued at 110 °C for 1 hour, followed by filtration. The solid particles were washed four times with anhydrous hexane and dried to obtain the solid catalyst component. The specific substances used for compounds X and Y, and the molar ratio of compounds X to Y in the catalyst component, are shown in Table 1.

[0077] Propylene polymerization: In a 5L stainless steel reactor, after complete purging with gaseous propylene, 32.5 mmol of AlEt and 0.1 mmol of methylcyclohexyldimethoxysilane (CHMMS) were added, followed by 8-10 mg of the solid catalyst components prepared in each example and 7.2 L of hydrogen gas. 2.3 L of liquid propylene was then introduced, and the temperature was raised to 70°C and maintained for 1 hour. The reactor was then cooled and depressurized to obtain PP powder. Data are shown in Table 1.

[0078] Example 10

[0079] In a reactor fully purged with high-purity nitrogen, 4.8 g of magnesium chloride, 98 mL of toluene, 4 mL of epichlorohydrin, 12.5 mL of tributyl phosphate, and compound X were added sequentially. The mixture was heated to 50 °C with stirring and maintained for 2.5 h. Then, 8 mmol of diisobutylmalonate was added, and the temperature was maintained for another h. The solution was cooled to below -25 °C, and 35 mL of TiCl4 was added dropwise over 1 h. The temperature was slowly raised to 80 °C, and a solid precipitate formed. Compound Y was then added to the solid, and the temperature was maintained for 1 h. After filtration, the solid precipitate was washed twice with 70 mL of toluene to obtain a solid precipitate. A TiCl4 / toluene solution was then added to the precipitate, and the temperature was raised to 110 °C and maintained for 1 h. The mixture was then filtered. This process was repeated four times. The filtered precipitate was washed three times with 70 mL of toluene at 110 °C for 10 min each time, and then washed twice with 60 mL of hexane to obtain the (solid) catalyst components. The specific substances used for compounds X and Y, as well as the molar ratio of compounds X to Y in the catalyst components, are shown in Table 1.

[0080] Propylene polymerization: In a 5L stainless steel reactor, after complete purging with gaseous propylene, 32.5 mmol of AlEt, 0.1 mmol of methylcyclohexyldimethoxysilane (CHMMS), 8-10 mg of the solid catalyst component prepared in this example, and 7.2 L of hydrogen gas were added. 2.3 L of liquid propylene was then introduced, and the temperature was raised to 70°C and maintained at this temperature for 1 hour. The reactor was then cooled and depressurized to obtain PP powder. Data are shown in Table 1.

[0081] Comparative Example 1

[0082] In a reactor fully purged with high-purity nitrogen, 4.8 g of magnesium chloride, 98 mL of toluene, 4 mL of epichlorohydrin, and 12.5 mL of tributyl phosphate were added sequentially. The mixture was heated to 50 °C with stirring and maintained for 2.5 h. Then, 8 mmol of diisobutylmalonate was added, and the temperature was maintained for another 1 h. The solution was cooled to below -25 °C, and 56 mL of TiCl4 was added dropwise over 1 h. The temperature was slowly raised to 80 °C, and a solid precipitate formed. Compound Y was then added to the solid, and the temperature was maintained for 1 h. After filtration, the solid precipitate was washed twice with 70 mL of toluene to obtain a solid precipitate. A TiCl4 / toluene solution was then added to the precipitate, and the temperature was raised to 110 °C and maintained for 1 h. The mixture was then filtered. This process was repeated four times. The filtered precipitate was then washed three times with 70 mL of toluene at 110 °C for 10 min each time, and then washed twice with 60 mL of hexane to obtain the (solid) catalyst component. The specific substances and contents of compound Y were the same as in Example 2.

[0083] Propylene polymerization: In a 5L stainless steel reactor, after complete purging with gaseous propylene, 32.5 mmol of AlEt, 0.1 mmol of methylcyclohexyldimethoxysilane (CHMMS), 8-10 mg of the solid catalyst component prepared in the comparative proportion, and 7.2 L of hydrogen gas were added. 2.3 L of liquid propylene was then introduced, and the temperature was raised to 70°C and maintained at this temperature for 1 hour. The reactor was then cooled and depressurized to obtain PP powder. Data are shown in Table 1.

[0084] Comparative Example 2

[0085] In a reactor fully purged with high-purity nitrogen, 4.8 g of magnesium chloride, 98 mL of toluene, 4 mL of epichlorohydrin, 12.5 mL of tributyl phosphate, and compound X were added sequentially. The mixture was heated to 50 °C with stirring and maintained for 2.5 h. Then, 1.4 g of phthalic anhydride was added, and the temperature was maintained for another h. The solution was cooled to below -25 °C, and 56 mL of TiCl4 was added dropwise over 1 h. The temperature was slowly raised to 80 °C, and a solid precipitate formed. The temperature was maintained for 1 h, and the mixture was filtered. The precipitate was washed twice with 70 mL of toluene to obtain a solid precipitate. A TiCl4 / toluene solution was then added to the precipitate, and the temperature was raised to 110 °C and maintained for 1 h. The mixture was then filtered. This process was repeated four times. The filtered precipitate was then washed three times with 70 mL of toluene at 110 °C for 10 min each time, and then washed twice with 60 mL of hexane to obtain the (solid) catalyst component. The specific substances and contents of compound X were the same as in Example 2.

[0086] Propylene polymerization: In a 5L stainless steel reactor, after complete purging with gaseous propylene, 32.5 mmol of AlEt, 0.1 mmol of methylcyclohexyldimethoxysilane (CHMMS), 8-10 mg of the solid catalyst component prepared in the comparative proportion, and 7.2 L of hydrogen gas were added. 2.3 L of liquid propylene was then introduced, and the temperature was raised to 70°C and maintained at this temperature for 1 hour. The reactor was then cooled and depressurized to obtain PP powder. Data are shown in Table 1.

[0087] Comparative Example 3

[0088] In a reactor fully purged with high-purity nitrogen, 4.8 g of magnesium chloride, 98 mL of toluene, 4 mL of epichlorohydrin, and 12.5 mL of tributyl phosphate were added sequentially. The mixture was heated to 50 °C with stirring and maintained for 2.5 h. Then, 1.4 g of phthalic anhydride was added, and the temperature was maintained for another h. The solution was cooled to below -25 °C, and 56 mL of TiCl4 was added dropwise over 1 h. The temperature was slowly raised to 80 °C, and a solid precipitate formed. Compounds X and Y were then added to the solid, and the temperature was maintained for 1 h. After filtration, the solid was washed twice with 70 mL of toluene to obtain a solid precipitate. A TiCl4 / toluene solution was then added to the precipitate, and the temperature was raised to 110 °C and maintained for 1 h. The mixture was then filtered. This process was repeated four times. The filtered precipitate was washed three times with 70 mL of toluene at 110 °C for 10 min each time, and then washed twice with 60 mL of hexane to obtain the (solid) catalyst component. The specific substances used for compounds X and Y in this comparative example, as well as the molar ratio of compounds X to Y in the catalyst component, are shown in Table 1.

[0089] Propylene polymerization: In a 5L stainless steel reactor, after complete purging with gaseous propylene, 32.5 mmol of AlEt, 0.1 mmol of methylcyclohexyldimethoxysilane (CHMMS), 8-10 mg of the solid catalyst component prepared in the comparative proportion, and 7.2 L of hydrogen gas were added. 2.3 L of liquid propylene was then introduced, and the temperature was raised to 70°C and maintained at this temperature for 1 hour. The reactor was then cooled and depressurized to obtain PP powder. Data are shown in Table 1.

[0090] Table 1

[0091]

[0092] The catalyst prepared in the embodiments of the present invention has good flowability, good particle morphology, and uniform particle size distribution. In addition, as shown in Table 1, the catalyst provided by the present invention has high activity and good hydrogen regulation sensitivity when used for propylene polymerization, and the resulting polymer does not contain phthalate compounds.

[0093] 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.

Claims

1. A catalyst component for propylene polymerization, characterized in that, The catalyst composition includes magnesium, titanium, halogens, and an electron donor, wherein the electron donor contains compounds X and Y; The general formula of compound X is R a -OR b , where R a R b Same or different, selected from C1-C 10 Unsubstituted straight-chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, olefinic; R a and R b It can be optionally keyed into a loop or not; The compound Y is a diol ester compound, selected from at least one of the compounds shown in general formula (I). Equation (I) In equation (Ⅰ), R1 and R2 may be the same or different, and are selected from C1-C 20 Substituted or unsubstituted aryl and alkylaryl groups; A includes formula (III), formula (IV), or formula (V). Formula (III) In formula (Ⅲ), R′3-R′8 may be the same or different, and are selected from hydrogen, halogens and C1-C 20 The substituted or unsubstituted straight-chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, olefinic, fused-ring aryl, and ester groups, R′7 and R′8 may optionally be cyclic or non-cyclic; Equation (Ⅳ) In equation (Ⅳ), R 1 -R 4 Same or different, selected from C1-C 20 Straight-chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, aralkyl, olefinic and fused-ring aryl, R 1 -R 4 They can be optionally bonded into one or more saturated / unsaturated rings; Formula (V) In formula (V), R is selected from hydrogen, halogens, and C1-C. 20 Substituted or unsubstituted straight-chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, aryl, olefinic, fused-ring aryl; The molar ratio of compound X to compound Y is r, 0 <r<5; The preparation method of the catalyst component includes: 1) Dissolve a magnesium compound in a system containing compound X, add a precipitation aid and a precipitation agent, and precipitate a solid. 2) Treat the solids precipitated in step 1) with titanium compounds, and add compound Y during and / or before the treatment of the solids with titanium compounds.

2. The catalyst component for propylene polymerization according to claim 1, wherein, The compound X is selected from at least one of methyl ether, diethyl ether, n-propyl ether, isopropyl ether, n-butyl ether, isobutyl ether, n-pentyl ether, methyl n-pentyl ether, cyclohexyl ether, ethyl cyclohexyl ether, cyclohexyl vinyl ether, n-heptyl ether, n-octyl ether, n-nonyl ether, n-decyl ether, ethylene oxide, propylene oxide, and tetrahydrofuran.

3. The catalyst component for propylene polymerization according to claim 1, wherein, The compound Y is selected from 2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 3,5-heptanediol di-p-methylbenzoate, 3,5-heptanediol di-o-methylbenzoate, 3,5-heptanediol di-p-chlorobenzoate, 3,5-heptanediol di-o-chlorobenzoate, 3,5-heptanediol di-p-methoxybenzoate, 3,5-heptanediol di-o-methoxybenzoate, 3,5-heptanediol di-m-methoxybenzoate, 2-methyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-heptanediol dibenzoate, 6-methyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, and 5-ethyl-3,5-heptanediol dibenzoate. Formate, 4-propyl-3,5-heptanediol dibenzoate, 4-butyl-3,5-heptanediol dibenzoate, 2,4-dimethyl-3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 4,6-dimethyl-3,5-heptanediol dibenzoate, 2-methyl-4-ethyl-3,5-heptanediol dibenzoate, 4-methyl-4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-4-propyl-3,5-heptanediol dibenzoate, 4-methyl-4-propyl-3,5-heptanediol dibenzoate, 6-methyl-2,4-heptanediol dibenzoate (p-chlorobenzoic acid) ester, 6-methyl-2,4-heptanediol di(p-methylbenzoic acid) ester, 6-methyl-2,4-heptanediol di(m-methylbenzoic acid) ester, 2,2,6,6-tetramethyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-octanediol dibenzoate, 4-ethyl-3,5-octanediol dibenzoate, 4-propyl-3,5-octanediol dibenzoate, 4-butyl-3,5-octanediol dibenzoate, 4,4-dimethyl-3,5-octanediol dibenzoate, 4-methyl-4-ethyl-3,5-octanediol dibenzoate, 2-methyl-4-ethyl-3,5-octanediol dibenzoate, 2-methyl-6-ethyl-3,5-octanediol dibenzoate, 5-methyl-4,6 Nonyl glycol dibenzoate, 5-ethyl-4,6-nonyl glycol dibenzoate, 5-propyl-4,6-nonyl glycol dibenzoate, 5-butyl-4,6-nonyl glycol dibenzoate, 5,5-dimethyl-4,6-nonyl glycol dibenzoate, 5-methyl-4-ethyl-4,6-nonyl glycol dibenzoate, 5-phenyl-4,6-nonyl glycol dibenzoate, 4,6-nonyl glycol dibenzoate, 4-butyl-3,5-heptanediol dibenzoate, 1,2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1,2-phenylene dibenzoate, 3,5-diisopropyl-1,2-phenylene dibenzoate, 3,6-dimethyl-1,2-phenylene dibenzoate, 4-tert-butyl-1,2-phenylene dibenzoate, 1,2-Naphthalene dibenzoate, 2,3-Naphthalene dibenzoate, 1,8-naphthalene dibenzoate, 1,8-naphthalene di-4-methylbenzoate, 1,8-naphthalene di-3-methylbenzoate, 1,8-naphthalene di-2-methylbenzoate, 1,8-naphthalene di-4-ethylbenzoate, 1,8-naphthalene di-4-n-propylbenzoate, 1,8-naphthalene di-4-isopropylbenzoate One or more of the following: 8-naphthyl ester, 1,8-naphthyl di-4-n-butylbenzoic acid, 1,8-naphthyl di-4-isobutylbenzoic acid, 1,8-naphthyl di-4-tert-butylbenzoic acid, 1,8-naphthyl di-4-phenylbenzoic acid, 1,8-naphthyl di-4-fluorobenzoic acid, 1,8-naphthyl di-3-fluorobenzoic acid, and 1,8-naphthyl di-2-fluorobenzoic acid.

4. The catalyst component for propylene polymerization according to claim 1, wherein, 0<r≤3。 5. The catalyst component for propylene polymerization according to claim 4, wherein, 0<r≤2。 6. A method for preparing the catalyst component for propylene polymerization according to any one of claims 1-5, characterized in that, The preparation method includes: 1) Dissolve a magnesium compound in a system containing compound X, add a precipitation aid and a precipitation agent, and precipitate a solid. 2) Treat the solids precipitated in step 1) with titanium compounds, and add compound Y during and / or before the treatment with titanium compounds.

7. The method for preparing the catalyst component for propylene polymerization according to claim 6, wherein, The precipitant is a metal halide.

8. The method for preparing the catalyst component for propylene polymerization according to claim 7, wherein, The precipitant is titanium halide.

9. The method for preparing the catalyst component for propylene polymerization according to claim 8, wherein, The precipitant is titanium tetrachloride.

10. The method for preparing the catalyst component for propylene polymerization according to claim 6, wherein, The precipitation aid is an oxygen-containing compound.

11. The method for preparing the catalyst component for propylene polymerization according to claim 10, wherein, The precipitation aid is an acid anhydride and / or a diester compound.

12. The method for preparing the catalyst component for propylene polymerization according to claim 11, wherein, The precipitation aid is an acid anhydride and / or a malondiester compound.

13. A catalyst for propylene polymerization, characterized in that, The catalyst comprises the following reaction products: a. The catalyst component according to any one of claims 1-5, or the catalyst component prepared by the preparation method according to any one of claims 6-12; b. Alkyl aluminum compounds, with the general formula AlR' n X' 3-n In the general formula, R' is hydrogen or C l -C 20 The hydrocarbon group, X' is a halogen, 0 <n≤3; c. Optionally, external electrons are provided.

14. The application of the catalyst component according to any one of claims 1-5, the catalyst component prepared by the preparation method according to any one of claims 6-12, or the catalyst according to claim 13 in propylene polymerization.

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