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 a compound X and a 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 alkyl; R a and R b may be optionally linked into a ring or not; the compound Y is a phthalate compound. When the catalyst is used for propylene polymerization, the catalyst has high activity, the isotacticity of the obtained polymer can be adjusted in a large range, and it is beneficial to develop polypropylene products of different grades.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of catalysts, and particularly relates to a catalyst component for propylene polymerization, a preparation method of the catalyst component, a catalyst comprising the catalyst component, and application of the catalyst component and the catalyst. BACKGROUND

[0002] It is known that a solid titanium catalyst component having magnesium, titanium, halogen and an electron donor as basic components can be used in CH2=CHR olefin polymerization, and particularly, a polymer with high yield and high stereoregularity can be obtained in the polymerization of an alpha-olefin having 3 or more carbon atoms, wherein the electron donor compound is one of the indispensable components in the catalyst component.

[0003] Phthalate compounds are the most commonly used internal electron donors for polypropylene catalysts in the industry. When phthalate compounds are used as internal electron donors, the catalyst activity is not high, the catalyst has strong orientation ability, and it is not easy to adjust. It is not conducive to the production of low isotacticity polymers, such as BOPP. The activity of single ether compounds as internal electron donors for propylene polymerization catalysts is very low. SUMMARY

[0004] In view of the above, the inventors of the present application have unexpectedly found that when preparing a catalyst component for propylene polymerization, compounding a single ether with a phthalate compound can obtain a catalyst with high activity and excellent comprehensive performance. By adjusting the amount of external electron donor, the orientation ability of the catalyst can be easily changed, the isotacticity of the obtained polymer can be adjusted in a large range, which is conducive to the development of different grades of polypropylene products, and more conducive to the industrial popularization and application of the catalyst.

[0005] The first aspect of the present application provides a catalyst component for propylene polymerization, which comprises magnesium, titanium, halogen and an electron donor, wherein the electron donor contains a compound X and a compound Y.

[0006] 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;

[0007] The compound Y is a phthalate compound.

[0008] The second aspect of the present application provides the above-mentioned method for preparing the catalyst component for propylene polymerization, which comprises:

[0009] 1) dissolving a magnesium compound in a system containing compound X, adding a co-precipitant and a precipitant, and precipitating a solid;

[0010] 2) treating the solid precipitated in step 1) with a titanium compound, and adding compound Y during the treatment of the solid with the titanium compound and / or before the treatment.

[0011] The third aspect of the present application provides a catalyst for propylene polymerization, which comprises the reaction product of the following components:

[0012] a) the above-mentioned catalyst component, or the catalyst component prepared by the above-mentioned method;

[0013] b) an aluminum alkyl compound with the general formula of AlR' n X' 3-n , wherein R' is hydrogen or a C1-C 20 hydrocarbon group, X' is halogen, and 0

[0014] c) optionally, an external electron donor.

[0015] The fourth aspect of the present application provides the above-mentioned catalyst component, the catalyst component prepared by the above-mentioned method, or the above-mentioned catalyst for use in propylene polymerization.

[0016] In the preparation of the catalyst component, the present application uses a single ether and a phthalate compound in combination, which has a good synergistic effect, and can obtain a catalyst with excellent comprehensive performance. In addition, by adjusting the addition mode, content ratio, etc. of the electron donor, the performance of the catalyst can be further improved. When the catalyst of the present application is used for propylene polymerization, it has high activity, and the isotacticity of the obtained polymer can be adjusted, which is beneficial to the development of different grades of polypropylene products.

[0017] Other features and advantages of the present application will be described in detail in the following specific embodiments. DETAILED DESCRIPTION

[0018] The specific embodiments of the present application are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0019] According to the first aspect of the present application, the present application provides a catalyst component for propylene polymerization, which comprises magnesium, titanium, halogen and an electron donor containing compound X and compound Y;

[0020] The general formula of the compound X is Ra -O-R b wherein R a , R b are the same or different and are selected from substituted or unsubstituted linear alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, olefinic groups having 1 to 20 carbon atoms; R 20 and R a may optionally be linked to form a ring or not; b

[0021] The compound Y is a phthalate compound.

[0022] Preferably, R a , R b are the same or different and are selected from substituted or unsubstituted linear alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, olefinic groups having 1 to 20 carbon atoms; R 10 and R a may optionally be linked to form a ring or not. b

[0023] More preferably, R a , R b are the same or different and are selected from unsubstituted linear alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, olefinic groups having 1 to 20 carbon atoms; R 10 and R a may optionally be linked to form a ring or not. b

[0024] The compound X in the present application can be selected from, but not limited to, at least one of the following compounds: dimethyl 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, oxirane, oxetane, tetrahydrofuran.

[0025] The compound Y in the present application can be selected from one or more of the following: di-n-butyl phthalate, diisobutyl phthalate, diisooctyl phthalate, diisobutyl phthalate, diisononyl phthalate, diisobutyl phthalate, di(2-ethyl)hexyl phthalate.

[0026] According to the present application, the molar ratio of the compound X and the compound Y is r, 0

[0027] According to a second aspect of the present application, the present application provides a method for preparing the above-mentioned catalyst component for propylene polymerization, which can be obtained by contacting a magnesium compound, a titanium compound, a compound X and a compound Y.

[0028] The method for preparing the catalyst component includes, but is not limited to, the following methods:​​​

[0029] 1) dissolving a magnesium compound in a system containing compound X, adding a co-precipitant and a precipitant, and precipitating a solid;

[0030] 2) treating the solid precipitated in step 1) with a titanium compound, and adding compound Y during and / or before the treatment of the solid with the titanium compound.

[0031] According to the present application, the "dissolving a magnesium compound in a system containing compound X" in step 1) can be dissolving a magnesium compound in a solvent system to obtain a solution, and then adding compound X; or dissolving a magnesium compound in a system containing compound X and a solvent system together.

[0032] In the present application, the solvent system can be a solvent system conventionally used for dissolving a magnesium compound in the prior art, such as a solvent system containing an organic epoxy compound, an organic phosphorus compound, and optionally an inert diluent, or a solvent system containing an organic alcohol compound and optionally an inert diluent.

[0033] According to the present application, the organic epoxy compound, the organic phosphorus compound, etc. can be conventionally selected according to the prior art. For example, the organic epoxy compound can be selected from aliphatic olefins, dienes or halogenated aliphatic olefins having 2 to 8 carbon atoms substituted with heteroatoms, and specifically can be selected from epichlorohydrin, epibromohydrin, etc. The organic phosphorus compound can be selected from hydrocarbyl esters or halogenated hydrocarbyl esters of orthophosphoric acid or phosphorous acid; specifically, the organic phosphorus compound can be selected from at least one of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and phenyl methyl phosphite.

[0034] In the present application, the organic alcohol compound has a general formula of R8OH, wherein R8 is a substituted or unsubstituted linear or branched C1-C 20 alkyl, C2-C 20 alkenyl, C3-C 20 cycloalkyl, C6-C 20 aryl, C7-C 20 alkylaryl, or C7-C 20 aralkyl, preferably selected from at least one of linear or branched C2-C 10 alkyl, and further preferably selected from at least one of ethanol, butanol, and isooctanol.

[0035] According to the present application, the inert diluent can be various solvents conventionally used in the art for dissolving a Ziegler-Natta catalyst component, and preferably selected from at least one of C6-C 10 alkanes or aromatic hydrocarbons, and more preferably selected from at least one of hexane, heptane, octane, decane, benzene, toluene, xylene, and derivatives thereof.

[0036] In the present application, the magnesium compound can be selected from the group consisting of magnesium dihalides, magnesium alkoxides, magnesium alkyls, hydrates or alcoholates of magnesium dihalides, and derivatives of magnesium dihalides in which one of the halogen atoms in the molecular formula is replaced by an alkoxy group or a haloalkoxy group; preferably magnesium dihalides or alcoholates of magnesium dihalides, such as magnesium dichloride, magnesium dibromide, magnesium diiodide, and alcoholates thereof.

[0037] According to the present application, the titanium compound can be selected from the group consisting of compounds of the general formula TiX m (OR"1) 4-m wherein R"1 is a C1-C4 hydrocarbon group, X is halogen, and 1≤m≤4. In particular, the titanium compound can be selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium trichloroethoxide, titanium dichlorodiethoxide, titanium chloroethoxide, and preferably titanium tetrachloride. 20

[0038] In the present application, the precipitant can be a metal halide, such as titanium halide, iron halide, zinc halide, and the like, wherein titanium halide, such as titanium tetrachloride or titanium tetrabromide, and the like, is preferred, and titanium tetrachloride is more preferred.

[0039] According to the present application, the co-precipitant can be selected from oxygen-containing compounds, preferably from acid anhydrides and diester compounds, and further preferably from acid anhydrides and malonic acid diester compounds. In particular, the co-precipitant can be selected from the group consisting of acetic anhydride, phthalic anhydride (phthalic anhydride), succinic anhydride, maleic anhydride, pyromellitic dianhydride, diisobutyl malonic acid diethyl ester, di-n-butyl malonic acid diethyl ester, di-t-butyl malonic acid diethyl ester, diisobutyl malonic acid dipropyl ester, di-n-butyl malonic acid dipropyl ester, di-t-butyl malonic acid dipropyl ester, diisobutyl malonic acid dibutyl ester, di-n-butyl malonic acid dibutyl ester, di-t-butyl malonic acid dibutyl ester, diisobutyl malonic acid dipentyl ester, di-n-butyl malonic acid dipentyl ester, di-t-butyl malonic acid dipentyl ester, diisobutyl malonic acid dihexyl ester, di-n-butyl malonic acid dihexyl ester, di-t-butyl malonic acid dihexyl ester, and the like.

[0040] The solid catalyst component of the present application can be prepared according to the following described method, but the method for preparing the catalyst component according to the present application is not limited thereto.

[0041] First, the magnesium compound is dissolved in a system consisting of compound X, an organic epoxide compound, an organic phosphorus compound, and an inert diluent to form a homogeneous solution, and then mixed with a precipitant (such as a titanium compound) in the presence of a co-precipitant, heated, and precipitated as a solid; this solid is then treated with an electron donor compound Y to be supported on the solid, and then treated with titanium tetrachloride or titanium tetrachloride and an inert diluent.

[0042] ​According to a third aspect of the present application, there is provided a catalyst for the polymerization of propylene, the catalyst comprising the reaction product of:

[0043] a. the catalyst component described above, or the catalyst component prepared by the method described above;

[0044] b. an aluminum alkyl compound having the general formula AlR' n X' 3-n wherein R' is hydrogen or a C1-C 20 hydrocarbon group, X' is a halogen, and 0 < n < 3;

[0045] c. optionally, an external donor.

[0046] In the present application, the aluminum alkyl compound can be selected from the group consisting of triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, and dichloroethylaluminum, preferably triethylaluminum and triisobutylaluminum.

[0047] According to the present application, the "optionally, an external donor" means that an external donor is selected to be added or not added as needed. For the application of an olefin polymer having a high stereoregularity, the external donor is added, and the external donor can be selected conventionally according to the prior art, for example, can be selected from the group consisting of organosilicon compounds represented by the general formula (R3) k Si(OR4) 4-k wherein 0 < k < 3, and R3 is selected from the group consisting of halogen, a hydrogen atom, and a C1-C 20 alkyl group, a cycloalkyl group, an aryl group, a halogenated alkyl group, or an amino group, and R4 is a C1-C 20 alkyl group, a cycloalkyl group, an aryl group, a halogenated alkyl group, or an amino group.

[0048] Specific examples of the external donor include, but are not limited to, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, methyl-tert-butyldimethoxysilane, and the like. Preferably, cyclohexylmethyldimethoxysilane and diphenyldimethoxysilane are used.

[0049] In the present application, the molar ratio of component a to component b is 1 : (5-1000), preferably 1 : (25-100), based on titanium : aluminum; and the molar ratio of component c to component a is 0-500 : 1, preferably 25-100 : 1, based on electron donor : titanium. When component c is the above-mentioned organosilicon compound, the molar ratio of component c to component a is 0-500 : 1, preferably 25-100 : 1, based on silicon : titanium.

[0050] According to a fourth aspect of the present application, the present application provides a catalyst component prepared by the above-mentioned preparation method, or the use of the above-mentioned catalyst component or catalyst in the polymerization of propylene.

[0051] The catalyst component or catalyst of the present application can be directly used in the polymerization of propylene, or can be used in the polymerization of propylene after pre-polymerization.

[0052] Pre-polymerization is the pre-polymerization of the above-mentioned catalyst component or catalyst with olefins (propylene) to obtain a pre-polymer, and the pre-polymerization multiple of the pre-polymer is 0.1-1000 g of olefin polymer / g of solid catalyst component, preferably the pre-polymerization multiple is 0.2-500 g of olefin polymer / g of solid catalyst component.

[0053] Pre-polymerization can be carried out in a liquid or in a gas phase at a temperature of -20 to 80°C, preferably 0-50°C. The step of pre-polymerization can be carried out in-line as part of a continuous polymerization process, or independently in a batch operation.

[0054] The polymerization of propylene according to the present application is carried out according to known polymerization methods, and can be carried out in a liquid phase or in a gas phase, or can be carried out under the operation of a combination of liquid phase and gas phase polymerization stages. The polymerization of propylene includes the homo-polymerization of propylene or the co-polymerization of propylene with other olefins, using conventional techniques such as slurry method, gas phase fluidized bed, etc. Preferably, the following reaction conditions are used: polymerization temperature 0-150°C, preferably 60-90°C; polymerization pressure 0.01-10 MPa.

[0055] The substances and parameters not defined in the present application can be selected according to the prior art, which are conventional technical means in the art.

[0056] The present application will be further described below in conjunction with examples, but is not limited by these examples.

[0057] In the following examples and comparative examples, the relevant data are obtained according to the following test methods:

[0058] 1. Isotacticity of polymer: The isotacticity of polymer was determined by heptane extraction method (heptane boiling extraction for 6 hours): 2 grams of dried polymer sample was placed in an extractor and extracted with boiling heptane for 6 hours. The residue was then dried to constant weight. The ratio of the weight of the polymer obtained (g) to 2 was the isotacticity.

[0059] 2. Content of electron donor in catalyst: The content of electron donor in catalyst was determined by using a Waters 600E high performance liquid chromatograph. First, the sample was pretreated using an ethyl acetate-dilute hydrochloric acid solution system to extract the electron donor compound. The electron donor compound was separated and its peak area was determined by high performance liquid chromatography. The percentage content of the electron donor compound in the sample was calculated by using an external standard curve for correction. Then it was converted into the molar ratio of the electron donor.

[0060] Examples 1-4

[0061] In a reactor which was sufficiently replaced with high-purity nitrogen, magnesium chloride 4.8 g, toluene 98 mL, epichlorohydrin 4 mL, tributyl phosphate 12.5 mL, compound X (isopropyl ether), were sequentially added, and the temperature was raised to 50°C under stirring for 2.5 h. Then phthalic anhydride 1.4 g was added, and the temperature was maintained for 1 h. The solution was cooled to below -25°C, and TiCl4 56 mL was added dropwise within 1 h. The temperature was slowly raised to 80°C, and solid matter was precipitated. Then compound Y (di-n-butyl phthalate) was added to the solid matter, and the temperature was maintained for 1 h. After filtration, the precipitate was washed twice with toluene 70 mL to obtain a solid precipitate. Then TiCl4 / toluene solution was added to the precipitate, and the temperature was raised to 110°C, and maintained for 1 h. The filtration was repeated four times in the same manner. The precipitate after filtration was washed three times with toluene 70 mL at 110°C for 10 min each time, and twice with hexane 60 mL to obtain a (solid) catalyst component. The molar ratio of compound X to compound Y in the catalyst component obtained in each example is shown in Table 1.

[0062] Propylene polymerization: A 5 L stainless steel reactor was sufficiently replaced with gaseous propylene, and then AlEt3 2.5 mmol, methylcyclohexyldimethoxysilane (CHMMS) 0.1 mmol, solid catalyst component obtained in each example 8-10 mg, and 1.2 L of hydrogen gas were sequentially added. Then 2.3 L of liquid propylene was introduced, and the temperature was raised to 70°C, and maintained for 1 h. The temperature was lowered, and the pressure was released to obtain a PP powder. The data are shown in Table 1.

[0063] Example 5

[0064] In a reactor purged with high purity nitrogen, magnesium chloride 4.8 g, toluene 98 mL, epichlorohydrin 4 mL, tributyl phosphate 12.5 mL, compound X (diisopropyl ether), were added successively, heated to 50°C with stirring for 2.5 h, added benzenic anhydride 1.4 g, maintained for 1 h. The solution was cooled to below -25°C, TiCl4 56 mL was added dropwise in 1 h, slowly heated to 80°C, solid precipitated. To the solid was added compound Y (diisobutyl phthalate), maintained for 1 h, filtered, washed twice with toluene 70 mL each, to obtain a precipitate in solid form. To the precipitate was added TiCl4 / toluene solution, heated to 110°C, maintained for 1 h, filtered; the same procedure was repeated four times. The filtered precipitate was washed three times with toluene 70 mL each at 110°C for 10 min each, washed twice with hexane 60 mL, to obtain a (solid) catalyst component, the molar ratio of compound X to compound Y in the catalyst component was 0.1.

[0065] Propylene polymerization: a 5 L stainless steel autoclave was purged with gaseous propylene, AlEt3 2.5 mmol, methylcyclohexyldimethoxysilane (CHMMS) 0.1 mmol, solid catalyst component prepared in each example 8-10 mg, and 1.2 L hydrogen were added successively, liquid propylene 2.3 L was introduced, heated to 70°C, maintained at this temperature for 1 h. The temperature was decreased, the pressure was released, to obtain PP powder. The data are shown in Table 1.

[0066] Example 6

[0067] In a reactor purged with high purity nitrogen, magnesium chloride 4.8 g, toluene 98 mL, epichlorohydrin 4 mL, tributyl phosphate 12.5 mL, compound X (diisopropyl ether), were added successively, heated to 50°C with stirring for 2.5 h, added benzenic anhydride 1.4 g, maintained for 1 h. The solution was cooled to below -25°C, TiCl4 56 mL was added dropwise in 1 h, slowly heated to 80°C, solid precipitated. To the solid was added compound Y (diisobutyl phthalate), maintained for 1 h, filtered, washed twice with toluene 70 mL each, to obtain a precipitate in solid form. To the precipitate was added TiCl4 / toluene solution, heated to 110°C, maintained for 1 h, filtered; the same procedure was repeated four times. The filtered precipitate was washed three times with toluene 70 mL each at 110°C for 10 min each, washed twice with hexane 60 mL, to obtain a (solid) catalyst component, the molar ratio of compound X to compound Y in the catalyst component was 0.1.

[0068] Propylene polymerization: A 5L stainless steel reactor was thoroughly purged with gaseous propylene, then AlEt3 2.5mmol, methylcyclohexyldimethoxysilane (CHMMS) 0.1 mmol, solid catalyst component of each example 8-10 mg and 1.2L hydrogen were added, then 2.3L liquid propylene was introduced, and the temperature was raised to 70°C, and maintained for 1 hour. The temperature was lowered, and the pressure was released, to obtain PP powder. The data are shown in Table 1.

[0069] Example 7

[0070] In a reactor purged with high purity nitrogen, magnesium chloride 4.8g, toluene 98ml, epichlorohydrin 4ml, tributyl phosphate 12.5ml, compound X (cyclohexyl ether) were added successively, and the temperature was raised to 50°C with stirring, and maintained for 2.5h, then phthalic anhydride 1.4g was added, and the temperature was maintained for 1h. The solution was cooled to below -25°C, and TiCl4 56ml was added dropwise within 1h, and the temperature was slowly raised to 80°C, and solid matter was precipitated. Then compound Y (di-n-butyl phthalate) was added to the solid matter, and the temperature was maintained for 1h, and the precipitate was obtained in the form of a solid after filtration, and washing with toluene 70ml twice. Then TiCl4 / toluene solution was added to the precipitate, and the temperature was raised to 110°C, and maintained for 1h, and filtration was performed, and the same operation was repeated four times. The precipitate after filtration was washed with toluene 70ml at 110°C for 10min, and washed with hexane 60ml twice, to obtain a (solid) catalyst component, and the molar ratio of compound X to compound Y in the catalyst component was 0.2.

[0071] Propylene polymerization: A 5L stainless steel reactor was thoroughly purged with gaseous propylene, then AlEt3 2.5mmol, methylcyclohexyldimethoxysilane (CHMMS) 0.1 mmol, solid catalyst component of each example 8-10 mg and 1.2L hydrogen were added, then 2.3L liquid propylene was introduced, and the temperature was raised to 70°C, and maintained for 1 hour. The temperature was lowered, and the pressure was released, to obtain PP powder. The data are shown in Table 1.

[0072] Example 8

[0073] In a reactor purged with high purity nitrogen, magnesium chloride 4.8 g, toluene 98 mL, epichlorohydrin 4 mL, tributyl phosphate 12.5 mL, compound X (tetrahydrofuran), were added successively, heated to 50°C with stirring for 2.5 h, then phthalic anhydride 1.4 g was added and the temperature was maintained for 1 h. The solution was cooled to below -25°C, and TiCl4 56 mL was added dropwise over 1 h, and the temperature was slowly increased to 80°C. Solid material was precipitated. Then compound Y (di-n-butyl phthalate) was added to the solid material, and the temperature was maintained for 1 h. After filtration, the solid was washed twice with toluene 70 mL to obtain a precipitate in solid form. Then TiCl4 / toluene solution was added to the precipitate, and the temperature was increased to 110°C and maintained for 1 h. The filtration was repeated four times. The precipitate was washed with toluene 70 mL at 110°C for 10 min, and then with hexane 60 mL for 2 times to obtain a solid catalyst component, in which the molar ratio of compound X to compound Y was 0.5.

[0074] Propylene polymerization: A 5 L stainless steel reactor was purged with gaseous propylene, and then AlEt3 2.5 mmol, methylcyclohexyldimethoxysilane (CHMMS) 0.1 mmol, solid catalyst component prepared in each example 8-10 mg, and 1.2 L hydrogen were added successively. Liquid propylene 2.3 L was introduced, and the temperature was increased to 70°C and maintained for 1 h. The temperature was decreased, and the pressure was released to obtain PP powder. The 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 (isopropyl ether), and 19.5 g of decane solvent were added to a 500 mL reactor equipped with a stirrer, heated to 130°C, and reacted for 1.5 h until the magnesium chloride was completely dissolved. Then 2.0 g of diisobutyl malonic acid diethyl ester was added, and the temperature was maintained at 130°C for 1 h to obtain an alcohol compound. The alcohol compound was cooled to room temperature. Under nitrogen protection, the alcohol compound was added dropwise to a 120 mL titanium tetrachloride solution pre-cooled to -22°C, and the temperature was slowly increased to 100°C. Compound Y (di-n-butyl phthalate) was added, and the temperature was increased to 110°C and maintained for 2 h. The hot filtration was performed, and then 120 mL of titanium tetrachloride was added, the temperature was increased to 110°C and reacted for 1 h, and then filtered. The solid particles were washed with anhydrous hexane 4 times, and then dried to obtain a solid catalyst component, in which the molar ratio of compound X to compound Y was 0.8.

[0077] Propylene polymerization: A 5 L stainless steel reactor was thoroughly purged with gaseous propylene, then AlEt3 2.5 mmol, methylcyclohexyldimethoxysilane (CHMMS) 0.1 mmol, the solid catalyst component prepared in this example 8-10 mg and 1.2 L of hydrogen were added, then 2.3 L of liquid propylene were introduced, and the temperature was raised to 70°C, maintaining this temperature for 1 hour. The temperature was lowered, and the pressure was released, obtaining a PP powder. The data are reported in Table 1.

[0078] Example 10

[0079] In a reactor purged with high purity nitrogen, magnesium chloride 4.8 g, toluene 98 mL, epichlorohydrin 4 mL, tributyl phosphate 12.5 mL, compound X (isopropyl ether), were sequentially added, and the temperature was raised to 50°C, maintaining this temperature for 2.5 h, while stirring. Diisobutyl malonate 8 mmol was added, and the temperature was maintained for a further hour. The solution was cooled to below -25°C, and TiCl4 35 mL was added dropwise in 1 h, slowly raising the temperature to 80°C, and the solid was precipitated. Then, compound Y (di-n-butyl phthalate) was added to the solid, maintaining the temperature for 1 h, and the precipitate was filtered, washing it twice with toluene 70 mL, obtaining a solid precipitate. Then, the precipitate was treated with a solution of TiCl4 in toluene, raising the temperature to 110°C, maintaining this temperature for 1 h, and filtering. The same operation was repeated four times. The filtered precipitate was washed three times with toluene 70 mL at 110°C for 10 min each time, and twice with hexane 60 mL, obtaining the (solid) catalyst component, in which the molar ratio of compound X to compound Y was 0.3.

[0080] Propylene polymerization: A 5 L stainless steel reactor was thoroughly purged with gaseous propylene, then AlEt3 2.5 mmol, methylcyclohexyldimethoxysilane (CHMMS) 0.1 mmol, the solid catalyst component prepared in this example 8-10 mg and 1.2 L of hydrogen were added, then 2.3 L of liquid propylene were introduced, and the temperature was raised to 70°C, maintaining this temperature for 1 hour. The temperature was lowered, and the pressure was released, obtaining a PP powder. The data are reported in Table 1.

[0081] Example 11

[0082] The catalyst component was prepared as in Example 5.

[0083] Propylene polymerization: A 5 L stainless steel reactor was thoroughly purged with gaseous propylene, then AlEt3 2.5 mmol, methylcyclohexyldimethoxysilane (CHMMS) 0.1 mmol, the solid catalyst component prepared in this example 8-10 mg and 1.2 L of hydrogen were added, then 2.3 L of liquid propylene were introduced, and the temperature was raised to 70°C, maintaining this temperature for 1 hour. The temperature was lowered, and the pressure was released, obtaining a PP powder. The data are reported in Table 1.

[0084] Comparative Example 1

[0085] In a reactor purged with high purity nitrogen, magnesium chloride 4.8 g, toluene 98 mL, epichlorohydrin 4 mL, tributyl phosphate 12.5 mL were added successively, heated to 50°C with stirring for 2.5 h, added phthalic anhydride 1.4 g, maintained for 1 h. The solution was cooled to below -25°C, TiCl4 56 mL was added dropwise in 1 h, slowly heated to 80°C, solid precipitated. Then to the solid was added compound Y (diisobutyl phthalate), maintained for 1 h, after filtration, washed twice with toluene 70 mL each, to obtain a precipitate in solid form. Then to the precipitate was added TiCl4 / toluene solution, heated to 110°C, maintained for 1 h, filtered; the same procedure was repeated four times. The filtered precipitate was washed with toluene 70 mL at 110°C for 10 min each, washed twice with hexane 60 mL, to obtain a (solid) catalyst component, the content of compound Y in the catalyst component was the same as in Example 5.

[0086] Propylene polymerization: a 5 L stainless steel autoclave was purged with gaseous propylene, then AlEt3 2.5 mmol, methylcyclohexyldimethoxysilane (CHMMS) 0.1 mmol, the solid catalyst component prepared in the comparative example 8-10 mg and 1.2 L hydrogen were added, liquid propylene 2.3 L was introduced, heated to 70°C, maintained at this temperature for 1 h. The temperature was decreased, the pressure was released, to obtain a PP powder. The data are shown in Table 1.

[0087] Comparative example 2

[0088] In a reactor purged with high purity nitrogen, magnesium chloride 4.8 g, toluene 98 mL, epichlorohydrin 4 mL, tributyl phosphate 12.5 mL, compound X (diisopropyl ether) were added successively, heated to 50°C with stirring for 2.5 h, added diisobutyl malonate diethyl ester 8 mmol, maintained for 1 h. The solution was cooled to below -25°C, TiCl4 56 mL was added dropwise in 1 h, slowly heated to 80°C, solid precipitated. Maintained for 1 h, after filtration, washed twice with toluene 70 mL each, to obtain a precipitate in solid form. Then to the precipitate was added TiCl4 / toluene solution, heated to 110°C, maintained for 1 h, filtered; the same procedure was repeated four times. The filtered precipitate was washed with toluene 70 mL at 110°C for 10 min each, washed twice with hexane 60 mL, to obtain a (solid) catalyst component, the content of compound X in the catalyst component was the same as in Example 5.

[0089] Propylene polymerization: A 5 L stainless steel reactor was thoroughly purged with gaseous propylene, then AlEt3 2.5 mmol, methylcyclohexyldimethoxysilane (CHMMS) 0.1 mmol, the solid catalyst component prepared in this example 8-10 mg and 1.2 L of hydrogen were added, then 2.3 L of liquid propylene were introduced, and the temperature was raised to 70°C, maintaining this temperature for 1 hour. The temperature was lowered, and the pressure was released, obtaining a PP powder. The data are reported in Table 1.

[0090] Example 3

[0091] In a reactor purged with high purity nitrogen, magnesium chloride 4.8 g, toluene 98 mL, epichlorohydrin 4 mL, tributyl phosphate 12.5 mL were added, the temperature was raised to 50°C, maintaining this temperature for 2.5 h, then phthalic anhydride 1.4 g was added, maintaining for 1 h. The solution was cooled to -25°C, TiCl4 56 mL was added dropwise in 1 h, the temperature was slowly raised to 80°C, and solid material precipitated. Then compound X (isopropyl ether) and compound Y (di-n-butyl phthalate) were added to the solid material, maintaining the temperature for 1 h, then the solid was filtered and washed twice with toluene 70 mL, obtaining a precipitate in the form of a solid. Then a solution of TiCl4 in toluene was added to the precipitate, the temperature was raised to 110°C, maintaining this temperature for 1 h, then the solid was filtered. The same operation was repeated four times. The precipitate was washed three times with toluene 70 mL at 110°C for 10 min each time, then twice with hexane 60 mL, obtaining the (solid) catalyst component, in which the molar ratio of compound X to compound Y was 0.6.

[0092] Propylene polymerization: A 5 L stainless steel reactor was thoroughly purged with gaseous propylene, then AlEt3 2.5 mmol, methylcyclohexyldimethoxysilane (CHMMS) 0.1 mmol, the solid catalyst component prepared in this example 8-10 mg and 1.2 L of hydrogen were added, then 2.3 L of liquid propylene were introduced, and the temperature was raised to 70°C, maintaining this temperature for 1 hour. The temperature was lowered, and the pressure was released, obtaining a PP powder. The data are reported in Table 1.

[0093] Example 4

[0094] The catalyst component was prepared as in Example 1.

[0095] Propylene polymerization: A 5 L stainless steel reactor was thoroughly purged with gaseous propylene, then AlEt3 2.5 mmol, methylcyclohexyldimethoxysilane (CHMMS) 0.1 mmol, the solid catalyst component prepared in this example 8-10 mg and 1.2 L of hydrogen were added, then 2.3 L of liquid propylene were introduced, and the temperature was raised to 70°C, maintaining this temperature for 1 hour. The temperature was lowered, and the pressure was released, obtaining a PP powder. The data are reported in Table 1.

[0096] Table 1

[0097]

[0098]

[0099] From Table 1, it can be seen that the catalyst provided by the application has high activity for propylene polymerization, and the catalyst's stereoregulating ability can be easily changed by adjusting the amount of external electron donor, and the isotacticity of the obtained polymer can be adjusted in a large range, which is beneficial to the development of different grades of polypropylene products.

[0100] Embodiments of the application have been described above, the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes are obvious to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A catalyst component for the polymerization of propylene, characterized in that, The catalyst component comprises magnesium, titanium, halogen and an electron donor, the electron donor containing a compound X and a compound 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 phthalate compound, the phthalate compound being selected from one or more of di-n-butyl phthalate, di-isobutyl phthalate, di-isooctyl phthalate, di-isononyl phthalate, di-(2-ethyl)hexyl phthalate; The molar ratio of the compound X and the compound Y is r, 0.1≤r<5; The preparation method of the catalyst component comprises: 1) dissolving a magnesium compound in a system containing a compound X, adding a co-precipitant and a precipitant, and precipitating a solid; 2) treating the solid precipitated in step 1) with a titanium compound, and adding a compound Y during and / or before the treatment of the solid with the titanium compound.

2. The catalyst component for the polymerization of propylene according to claim 1 wherein, The compound X is at least one selected from methyl ether, ethyl 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, oxirane, oxetane and tetrahydrofuran.

3. The catalyst component for the polymerization of propylene according to claim 1 wherein, The molar ratio of the compound X and the compound Y is r, 0.1≤r≤3.

4. Process for the preparation of a catalyst component for the polymerization of propylene according to any of claims 1-3, characterized in that, The preparation method comprises: 1) dissolving a magnesium compound in a system containing a compound X, adding a co-precipitant and a precipitant, and precipitating a solid; 2) treating the solid precipitated in step 1) with a titanium compound, and adding a compound Y during and / or before the treatment of the solid with the titanium compound.

5. The process for the preparation of a catalyst component for the polymerization of propylene according to claim 4 wherein, The precipitant is a metal halide.

6. The process for the preparation of a catalyst component for the polymerization of propylene according to claim 5 wherein, The precipitant is titanium halide.

7. The process for the preparation of a catalyst component for the polymerization of propylene according to claim 6 wherein, The precipitant is titanium tetrachloride.

8. The process for the preparation of a catalyst component for the polymerization of propylene according to claim 4 wherein, The co-precipitant is an oxygen-containing compound.

9. The process for the preparation of a catalyst component for the polymerization of propylene according to claim 8 wherein, The co-precipitant is an acid anhydride and / or a diester compound.

10. The process for the preparation of a catalyst component for the polymerization of propylene according to claim 9 wherein, The co-precipitant is an acid anhydride and / or a malonate diester compound.

11. A catalyst for the polymerization of propylene, characterized in that, The catalyst comprises a reaction product of the following components: a. the catalyst component of any one of claims 1-3, or the catalyst component prepared by the preparation method of any one of claims 4-10; b. an aluminum alkyl compound of the general formula AlR' n X' 3-n , wherein R' is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, X' is a halogen, and 0 < n < 3. l -C 20 , wherein R' is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, X' is a halogen, and 0 < n < 3. c. optionally, an external electron donor.

12. Use of the catalyst component of any one of claims 1-3, the catalyst component prepared by the preparation method of any one of claims 4-10, or the catalyst of claim 11 in propylene polymerization.

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