Catalyst component for olefin polymerization reaction as well as preparation method, catalyst and application thereof

Abstract

The invention belongs to the technical field of olefin polymerization, and discloses a catalyst component for olefin polymerization reaction and a preparation method, a catalyst and application thereof, the method comprises the following steps: (1) reacting a magnesium-containing compound, an organic epoxy compound and an organic phosphorus compound to obtain a magnesium-containing reaction solution; (2) reacting the magnesium-containing reaction liquid with an acyl halide compound; reacting with a first alcohol compound at-55 to 20 DEG C, and reacting with a first titanium-containing compound to obtain a catalyst component; optionally, adding a first electron donor compound before and / or after the reaction with the first titanium-containing compound, and reacting; optionally, the method also comprises the following steps: (3) reacting the catalyst component obtained in the step (2) with a second titanium-containing compound to obtain the catalyst component, optionally, a second electron donor compound is added before and / or after the reaction with the second titanium-containing compound, and the reaction is carried out. The polymer powder obtained by adopting the catalyst provided by the invention has obviously improved bulk density.

Description

Technical Field

[0001] This invention relates to the field of olefin polymerization technology, and more specifically, to a catalyst component for olefin polymerization reactions, its preparation method, the catalyst, and its application. Background Technology

[0002] In the development of polyolefins, catalyst research has always played a crucial role in the synthesis and production of polyethylene. Among them, titanium-magnesium catalysts have gained widespread application and continued to be developed due to their high catalytic efficiency and low cost.

[0003] Titanium-magnesium catalysts generally include basic components such as magnesium, titanium, halogens, and electron donors. For example, CN201210409037.0 discloses a catalyst for ethylene polymerization, which is obtained by reacting magnesium halide with organic epoxy compounds, organic phosphorus compounds, and organic alcohol compounds to form a homogeneous solution, then mixing it with acyl halide compounds, and then reacting it with halides of transition metal titanium or their derivatives. Although this catalyst has good activity, the irregular particle morphology of the catalyst itself, such as being fragmented, leads to irregular morphology of the resulting polymer powder, which in turn affects the improvement of the bulk density of the polymer powder.

[0004] Preparing catalysts with good particle morphology is an effective method to improve the bulk density of polymer powders. For example, CN202011104500.1 discloses a method for preparing an olefin polymerization catalyst component, comprising: S1. contacting a magnesium halide compound with an organic epoxy compound, an organophosphorus compound, and optionally a hydroxyl-containing compound in an organic solvent to form a magnesium-containing solution; S2. contacting the magnesium-containing solution, an inert dispersion medium, and a titanium-containing compound to form a mixture; S3. heating the mixture in the presence of a precipitation aid, a surfactant, and optionally a first electron donor compound to precipitate spherical or near-spherical solids; and optionally, S4. contacting the spherical or near-spherical solids with a second electron donor compound to obtain the olefin polymerization catalyst component, wherein at least one of the first electron donor compound and the second electron donor compound is used; the above catalyst requires the addition of a precipitation aid, phthalic anhydride, and a surfactant, etc., to obtain spherical particles.

[0005] In particular, phthalic anhydride is added as a precipitation aid in the preparation of spherical catalysts for many related dissolution systems. However, the addition of phthalic anhydride will cause the catalyst to lose activity when used for ethylene polymerization. Summary of the Invention

[0006] The purpose of this invention is to provide a catalyst component for olefin polymerization, its preparation method, catalyst, and application. The catalyst component of this invention is spherical. Using the catalyst of this invention, the obtained polymer powder is spherical while having high polymerization activity and hydrogen regulation sensitivity, and has a significantly improved bulk density.

[0007] To achieve the above objectives, a first aspect of the present invention provides a method for preparing a catalyst component for olefin polymerization, the method comprising:

[0008] (1) In the presence of a first inert diluent, a magnesium-containing compound, an organic epoxy compound, and an organic phosphorus compound are reacted to obtain a magnesium-containing reaction solution;

[0009] (2) The magnesium-containing reaction solution is reacted with an acyl halide compound; then reacted with a first alcohol compound at -55 to 20°C, and then reacted again with a first titanium-containing compound to obtain the catalyst component for olefin polymerization; wherein, optionally, a first electron donor compound is added before and / or after reacting with the first titanium-containing compound, and the reaction is carried out; when the first electron donor compound is a second alcohol compound, the reaction is carried out at -55 to 20°C.

[0010] Optionally, the reaction also includes step (3): reacting the catalyst component obtained in step (2) with a second titanium-containing compound in the presence of a second inert diluent to obtain the catalyst component for olefin polymerization; wherein, optionally, a second electron donor compound is added before and / or after reacting with the second titanium-containing compound to carry out the reaction.

[0011] A second aspect of the present invention provides a catalyst component for olefin polymerization prepared by the above preparation method.

[0012] A third aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising the following components:

[0013] Component A: The catalyst components mentioned above;

[0014] Component B: an organoaluminum compound; preferably, the organoaluminum compound has the general formula AlR. n X 3-n In the formula, R is a hydrogen or a hydrocarbon group with 1 to 20 carbon atoms; X is a halogen; n is an integer 0 < n ≤ 3;

[0015] The molar ratio of aluminum in component B to titanium in component A is preferably 1 to 1000:1; more preferably 5 to 500:1.

[0016] The organoaluminum compound is further preferably at least one selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydrogen, diisobutylaluminum hydrogen, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, and diethylaluminum chloride.

[0017] A fourth aspect of the present invention provides the use of the above-described catalyst component or the above-described catalyst in olefin polymerization reactions.

[0018] The technical solution of the present invention has the following beneficial effects:

[0019] The catalyst component of this invention has a better particle morphology than existing irregular catalyst components such as fragments, being spherical, and the resulting polymer powder is also spherical, with a significantly improved bulk density.

[0020] Compared to the spherical catalyst components currently used with phthalic anhydride, this invention exhibits higher activity and better hydrogen regulation sensitivity during ethylene polymerization.

[0021] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description

[0022] Exemplary embodiments of the present invention will be described in more detail with reference to the accompanying drawings.

[0023] Figure 1 A microscope image of catalyst component A according to Example 1 of the present invention is shown.

[0024] Figure 2 A microscopic image of catalyst component A according to Comparative Example 1 of the present invention is shown.

[0025] Figure 3 A microscopic image of catalyst component A according to Comparative Example 2 of the present invention is shown.

[0026] Figure 4 A microscopic image of catalyst component A according to Comparative Example 3 of the present invention is shown.

[0027] Figure 5 A microscope image of catalyst component A according to Example 2 of the present invention is shown.

[0028] Figure 6 A microscopic image of the polymer powder prepared by ethylene polymerization using catalyst component A of Example 2 according to the present invention is shown.

[0029] Figure 7 A microscopic image of catalyst component A according to Comparative Example 4 of the present invention is shown.

[0030] Figure 8A microscopic image of catalyst component A according to Comparative Example 5 of the present invention is shown.

[0031] Figure 9 A microscope image of catalyst component A according to Example 7 of the present invention is shown.

[0032] Figure 10 A microscope image of catalyst component A according to Example 8 of the present invention is shown.

[0033] Figure 11 A microscopic image of catalyst component A according to Comparative Example 6 of the present invention is shown.

[0034] Figure 12 A microscopic image of the polymer powder prepared by ethylene polymerization using catalyst component A of Comparative Example 6 according to the present invention is shown.

[0035] Figure 13 A microscopic image of catalyst component A according to Comparative Example 7 of the present invention is shown.

[0036] Figure 14 A microscope image of catalyst component A according to Example 11 of the present invention is shown.

[0037] Figure 15 A microscopic image of catalyst component A according to Comparative Example 9 of the present invention is shown.

[0038] Figure 16 A microscope image of catalyst component A according to Example 12 of the present invention is shown. Detailed Implementation

[0039] Preferred embodiments of the invention will now be described in more detail. While preferred embodiments of the invention are described below, it should be understood that the invention can be implemented in various forms and should not be limited to the embodiments set forth herein.

[0040] A first aspect of the present invention provides a method for preparing a catalyst component for olefin polymerization, the method comprising:

[0041] (1) In the presence of a first inert diluent, a magnesium-containing compound, an organic epoxy compound, and an organic phosphorus compound are reacted to obtain a magnesium-containing reaction solution;

[0042] (2) The magnesium-containing reaction solution is reacted with an acyl halide compound; then reacted with a first alcohol compound at -55 to 20°C, and then reacted again with a first titanium-containing compound to obtain the catalyst component for olefin polymerization; wherein, optionally, a first electron donor compound is added before and / or after reacting with the first titanium-containing compound, and the reaction is carried out; when the first electron donor compound is a second alcohol compound, the reaction is carried out at -55 to 20°C.

[0043] Optionally, the reaction also includes step (3): reacting the catalyst component obtained in step (2) with a second titanium-containing compound in the presence of a second inert diluent to obtain the catalyst component for olefin polymerization; wherein, optionally, a second electron donor compound is added before and / or after reacting with the second titanium-containing compound to carry out the reaction.

[0044] In this invention, preferably, when a first electron-donating compound is added both before and after the reaction with the first titanium-containing compound, the first electron-donating compound added before the reaction with the first titanium-containing compound and the first electron-donating compound added after the reaction with the first titanium-containing compound can be the same or different.

[0045] In this invention, the inventors, through in-depth research, discovered that the reason why the catalyst components obtained in the system of CN201210409037.0 are not regular and are in a fragmented state is mainly due to the use of organic alcohol compounds when dissolving magnesium halide in that system, which leads to the fragmented precipitation of the catalyst components. Based on this discovery, the inventors, through extensive experiments, creatively and ingeniously solved the above-mentioned problem (through extensive experiments and analysis, it was found that not introducing alcohol compounds during the initial dissolution of magnesium halide, or if alcohol compounds are added, adding them at a lower temperature in the later stages, such as -55 to 20°C, preferably -35 to 0°C, can avoid the adverse effects of alcohols on subsequent precipitation, thus obtaining spherical precipitates). A novel spherical polyolefin catalyst without phthalic anhydride was prepared. Especially when used for ethylene polymerization, the catalyst of this invention exhibits high polymerization activity and hydrogen sensitivity, while the resulting polymer powder is spherical with a significantly improved bulk density.

[0046] In this invention, step (2) is preferably one of the following methods: method one, method two, method three, or method four.

[0047] Method 1: The magnesium-containing reaction solution is reacted with an acyl halide compound; then reacted with a first alcohol compound at -55 to 20°C; and then reacted again with a first titanium-containing compound to obtain the catalyst component for olefin polymerization.

[0048] Method 2: The magnesium-containing reaction solution is reacted with an acyl halide compound; then reacted with a first alcohol compound at -55 to 20°C; a first electron donor compound is added again and reacted; finally, it is reacted with a first titanium-containing compound to obtain the catalyst component for olefin polymerization; wherein, when the first electron donor compound is a second alcohol compound, the reaction is carried out at -55 to 20°C.

[0049] Method 3: The magnesium-containing reaction solution is reacted with an acyl halide compound; then reacted with a first alcohol compound at -55 to 20°C; reacted again with a first titanium-containing compound; finally, a first electron donor compound is added and reacted to obtain the catalyst component for olefin polymerization; wherein, when the first electron donor compound is a second alcohol compound, the reaction is carried out at -55 to 20°C.

[0050] Method 4: The magnesium-containing reaction solution is reacted with an acyl halide compound; then reacted with a first alcohol compound at -55 to 20°C; a first electron donor compound is added and reacted; the reaction is repeated with a first titanium-containing compound; finally, a first electron donor compound is added and reacted to obtain the catalyst component for olefin polymerization; wherein, when the first electron donor compound is a second alcohol compound, the reaction is carried out at -55 to 20°C; the first electron donor compound added before reacting with the first titanium-containing compound and the first electron donor compound added after reacting with the first titanium-containing compound can be the same or different.

[0051] In this invention, in step (2), the acyl halide compound may be added only after the titanium-containing compound or both before and after the titanium-containing compound; when the acyl halide compound is added after the titanium-containing compound, the first electron donor compound optionally added after the titanium-containing compound may be added before or after the acyl halide compound; when the acyl halide compound is added both before and after the titanium-containing compound, the acyl halide compounds added before and after may be the same or different.

[0052] In this invention, preferably, in step (3), when the second electron-donating compound is added before or after the reaction with the second titanium-containing compound, the second electron-donating compound can be added multiple times, and the second electron-donating compounds added multiple times can be the same or different. That is, when the second electron-donating compound is added before the reaction with the second titanium-containing compound, the second electron-donating compound can be added multiple times, and the second electron-donating compounds added multiple times can be the same or different; or, when the second electron-donating compound is added after the reaction with the second titanium-containing compound, the second electron-donating compound can be added multiple times, and the second electron-donating compounds added multiple times can be the same or different.

[0053] In this invention, preferably, each reaction step of the method for preparing the catalyst component for olefin polymerization is carried out under inert gas conditions, and more preferably under high-purity inert gas conditions.

[0054] According to the present invention, preferably, the magnesium-containing compound is dimethyl magnesium, diethyl magnesium, diisopropyl magnesium, isopropylmethyl magnesium, n-butylethyl magnesium, di-n-butyl magnesium, butyloctyl magnesium, dihexyl magnesium, dioctyl magnesium, magnesium dihalide, or MgR. 1 Cl and Mg(OR) 2 At least one of Cl; wherein, R 1 and R 2 Each is independently selected from substituted or unsubstituted C1-C. 10 The hydrocarbon group, wherein the substituent is selected from at least one of hydroxyl, carboxyl, halogen atom and alkoxy group;

[0055] More preferably, the magnesium-containing compound is magnesium dihalide or MgR. 1 Cl and Mg(OR) 2 At least one of Cl; wherein, R 1 and R 2 Each is independently selected from substituted or unsubstituted C1-C. 10 The hydrocarbon group, wherein the substituent is selected from at least one of hydroxyl, carboxyl, halogen, and alkoxy groups. The magnesium-containing compound is more preferably magnesium dichloride.

[0056] According to the present invention, preferably, the organic epoxy compound is selected from at least one of the following: oxides of C2-C8 aliphatic olefins, glycidyl ethers of C2-C8 aliphatic olefins, internal ethers of C2-C8 aliphatic olefins, oxides of C2-C8 halogenated aliphatic olefins, glycidyl ethers of C2-C8 halogenated aliphatic olefins, and internal ethers of C2-C8 halogenated aliphatic olefins.

[0057] More preferably, the organic epoxy compound is selected from at least one of ethylene oxide, propylene oxide, butane oxide, butadiene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, and tetrahydrofuran. More preferably, the organic epoxy compound is selected from at least one of ethylene oxide, propylene oxide, epichlorohydrin, and tetrahydrofuran.

[0058] According to the present invention, preferably, the organophosphorus compound is selected from at least one of trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, triisopropyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate, tri-tert-butyl phosphate, tri-n-pentyl phosphate, triisopentyl phosphate, tri-n-hexyl phosphate, triisohexyl phosphate, tri-n-heptyl phosphate, triisoheptyl phosphate, tri-n-octyl phosphate, triisooctyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, tri-tert-butyl phosphite, tri-n-pentyl phosphite, triisopentyl phosphite, tri-n-hexyl phosphite, triisoheptyl phosphite, tri-n-octyl phosphite, triisooctyl phosphite, triphenyl phosphite, and di-n-butyl phosphite.

[0059] More preferably, the organophosphorus compound is selected from at least one of triethyl phosphate, tributyl phosphate, triisooctyl phosphate, triphenyl phosphate, triethyl phosphite, tributyl phosphite, and di-n-butyl phosphite.

[0060] According to the present invention, preferably, the acyl halide compound has the general formula R(COX). a In this context, R represents a hydrogen atom, an unsubstituted aliphatic hydrocarbon group with 1 to 8 carbon atoms, a substituted aliphatic hydrocarbon group with 1 to 8 carbon atoms, an unsubstituted aromatic hydrocarbon group with 6 to 10 carbon atoms, or a substituted aromatic hydrocarbon group with 6 to 10 carbon atoms, X represents a halogen, and a represents 1 or 2.

[0061] The acyl halide compound is further preferably an acyl chloride compound; even more preferably at least one of benzoyl chloride, substituted benzoyl chloride, phthaloyl chloride, substituted phthaloyl chloride, terephthaloyl chloride and substituted terephthaloyl chloride; and even more preferably benzoyl chloride and / or substituted benzoyl chloride.

[0062] In this invention, preferably, the acyl chloride compound is selected from at least one of benzoyl chloride and its alkyl, nitro, and halogen substituted derivatives, phthaloyl chloride and its alkyl, nitro, and halogen substituted derivatives, and terephthaloyl chloride and its alkyl, nitro, and halogen substituted derivatives. More preferably, at least one of benzoyl chloride and its alkyl, nitro, and halogen substituted derivatives is selected, such as at least one of benzoyl chloride, methylbenzoyl chloride, ethylbenzoyl chloride, propylbenzoyl chloride, isopropylbenzoyl chloride, nitrobenzoyl chloride, and chlorobenzoyl chloride.

[0063] According to the present invention, preferably, the first alcohol compound is an unsubstituted C1-C1 compound. 12 fatty alcohols, substituted C1-C 12 fatty alcohols, unsubstituted C7-C 12 Aromatic alcohols and substituted C7-C 12 At least one of the aromatic alcohols;

[0064] The first alcohol compound is further preferably at least one of methanol, ethanol, propanol, n-butanol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, isooctanol, 2-ethylhexanol, n-decanol, dodecanol, cyclohexanol, methylcyclohexanol, benzyl alcohol, phenethyl alcohol, and haloalcohols derived from the above alcohols.

[0065] According to the present invention, preferably, the general formulas of the first titanium-containing compound and the second titanium-containing compound are each independently Ti(OR). a X b Where R is C1-C 14 The hydrocarbon group is preferably a C1-C8 alkyl group; X is a halogen atom, a and b are each independent integers from 0 to 4, and a+b=3 or 4;

[0066] More preferably, the first titanium-containing compound and the second titanium-containing compound are each independently selected from at least one of TiCl3, TiCl4, TiBr4, TiCl4, Ti(OC2H5)Cl3, Ti(OCH3)Cl3, Ti(OC4H9)Cl3, Ti(OC2H5)Br3, Ti(OC2H5)2Cl2, Ti(OCH3)2Cl2, Ti(OCH3)2I2, Ti(OC2H5)3Cl, Ti(OCH3)3Cl, Ti(OC2H5)3I, Ti(OC2H5)4, Ti(OC3H7)4, and Ti(OC4H9)4. More preferably, the first titanium-containing compound and the second titanium-containing compound are each independently selected from at least one of TiCl3, TiCl4, TiBr4, Ti(OC2H5)Cl3, Ti(OC2H5)2Cl2, Ti(OC2H5)3Cl, Ti(OCH3)Cl3, Ti(OC2H5)4, Ti(OC4H9)Cl3 and Ti(OC4H9)4.

[0067] According to the present invention, preferably, the first electron-donating compound and the second electron-donating compound are each independently selected from at least one of organic acids, second alcohols, organic acid esters, silicon-containing compounds, boron-containing compounds, organic acyl halides, halogenated hydrocarbons, ethers, ketones, amines, phosphate esters, amides, phenols, and pyridine.

[0068] According to the present invention, preferably, the second alcohol compound is an unsubstituted C1-C1 compound. 12 fatty alcohols, substituted C1-C 12 fatty alcohols, unsubstituted C7-C 12 Aromatic alcohols and substituted C7-C 12 At least one of the aromatic alcohols;

[0069] The second alcohol compound is further preferably at least one of methanol, ethanol, propanol, n-butanol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, isooctanol, 2-ethylhexanol, n-decanol, dodecanol, cyclohexanol, methylcyclohexanol, benzyl alcohol, phenethyl alcohol, and haloalcohols derived from the above alcohols.

[0070] According to the present invention, preferably, the silicon-containing compound is of general formula R. 1 x R 2 y Si(OR 3 ) z The silicon-containing compound shown has no active hydrogen atoms, wherein R 1 and R 2 Each is independently a hydrocarbon group or halogen with 1 to 10 carbon atoms, R 3 It is a hydrocarbon group with 1 to 10 carbon atoms, where x, y, and z are positive integers, 0≤x≤4, 0≤y≤4 and 0≤z≤4, and x+y+z=4;

[0071] More preferably, the silicon-containing compound is at least one selected from silicon tetrachloride, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and tetra(2-ethylhexyloxy)silane.

[0072] In this invention, the non-alcohol electron-donating compound is preferably at least one of methyl benzoate, ethyl benzoate, butyl benzoate, ethyl p-methylbenzoate, di-n-butyl phthalate, diisobutyl phthalate, diethyl succinate, dipropyl succinate, diisopropyl succinate, methyl naphtholate, ethyl naphtholate, methyl methyl benzoate, acyl chloride, diethyl ether, butyl ether, tetrahydrofuran, acetone, butanone, cyclohexanone, phenol, silicon tetrachloride, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and tetra(2-ethylhexoxy)silane; more preferably at least one of silicon tetrachloride, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and tetra(2-ethylhexoxy)silane.

[0073] According to the present invention, preferably, the amount of the organic epoxy compound is 0.01 to 4.0 mol per mole of magnesium halide; the amount of the organic phosphorus compound is 0.01 to 4.0 mol; the amount of the acyl halide compound is 0.01 to 3.0 mol; the amount of the first alcohol compound is 0.001 to 4.0 mol; the amount of the first titanium-containing compound is 0.1 to 100 mol; and the amount of the first electron donor compound is 0 to 4.0 mol.

[0074] Preferably, per mole of magnesium halide, the amount of organic epoxy compound is 0.02 to 3.0 moles; the amount of organic phosphorus compound is 0.02 to 2.0 moles; the amount of acyl halide compound is 0.02 to 2.0 moles; the amount of first alcohol compound is 0.02 to 3.0 moles; the amount of first titanium-containing compound is 0.2 to 50 moles; and the amount of first electron donor compound is 0 to 3.0 moles.

[0075] In this invention, the addition of the first alcohol compound should minimize its impact on the dissolution of magnesium-containing compounds; otherwise, clump-like precipitates are easily generated subsequently. Through extensive experiments and analysis, it has been found that adding the first alcohol compound at a lower temperature, such as -55 to 20°C, preferably -35 to 0°C, can avoid the adverse effects of the alcohol on subsequent precipitation, thereby obtaining spherical precipitates.

[0076] According to the present invention, preferably, in step (1), the temperature of the reaction is 0 to 100°C, more preferably 20 to 80°C;

[0077] Preferably, in step (2), the reaction with the first alcohol compound is carried out at -35 to 0°C; optionally, a first electron donor compound is added, and when the first electron donor compound is a second alcohol compound, the reaction is carried out at -35 to 0°C.

[0078] Preferably, in step (2), the reaction with the acyl halide compound is carried out at -55 to 80°C, more preferably at -35 to 60°C; the reaction with the first titanium-containing compound is carried out at -55 to 80°C, more preferably at -35 to 20°C; optionally, a first electron donor compound is added, and when the first electron donor compound is a non-alcohol compound, the reaction is carried out at -55 to 80°C, more preferably at -35 to 80°C.

[0079] Preferably, in step (2), the final reaction mixture is kept at 10-170°C for 1-5 hours to obtain a solid precipitate, which is then filtered, washed, and dried to obtain the catalyst component for olefin polymerization.

[0080] In this invention, in step (2), the reaction temperature and time for reacting with the first titanium-containing compound, the addition of the first electron-donating compound before and / or after reacting with the first titanium-containing compound, and the reaction temperature and time for the reaction are all conventional techniques in the art (e.g., the reaction temperature for reacting with the first titanium-containing compound and the reaction temperature for reacting with the first electron-donating compound are both -55 to 80°C). Those skilled in the art can design these techniques based on common knowledge in the art. Then, the final reaction mixture is kept at 10 to 170°C for 1 to 5 hours to obtain a solid precipitate.

[0081] In this invention, in step (3), the reaction temperature and time for reacting with the second titanium-containing compound, the addition of the second electron-donating compound before and / or after reacting with the second titanium-containing compound, and the reaction temperature and time for the reaction are all conventional techniques in the art (e.g., the reaction temperature with the second titanium-containing compound and the reaction temperature with the second electron-donating compound are both -55 to 130°C). Those skilled in the art can design these techniques based on common knowledge in the art. Then, the final reaction mixture is kept at 10 to 170°C for 1 to 5 hours, filtered, washed, and dried to obtain the catalyst component.

[0082] In this invention, preferably, the first inert diluent and the second inert diluent are each independently at least one of conventional solvents such as aliphatic hydrocarbons and aromatic hydrocarbons; specifically, they can be at least one of halogenated aromatic hydrocarbons, non-halogenated aromatic hydrocarbons, halogenated aliphatic hydrocarbons, and non-halogenated aliphatic hydrocarbons; they are usually selected from benzene and its homologues or halogenated derivatives; more preferably, the first inert diluent and the second inert diluent are each independently at least one of toluene, xylene, trimethylbenzene, tetramethylchlorobenzene, dichlorobenzene, hexane, heptane, decane, kerosene, dichloromethane, dichloroethane, chloroform, and cyclohexane; the first inert diluent and the second inert diluent only need not have an adverse effect on the reaction.

[0083] In this invention, as a specific preferred embodiment, the preparation method of the catalyst component includes: under stirring and in the presence of a first inert diluent, reacting a magnesium-containing compound with an organic epoxy compound and an organic phosphorus compound at 0–100°C (preferably 20–80°C) (the reaction time can vary depending on the actual selected dissolution ratio and dissolution temperature, specifically from several minutes to tens of hours) to form a dissolution mixture; then, at -55–80°C, preferably -35–80°C, reacting it with at least one acyl halide compound and at least one first titanium-containing compound (the reaction time can vary depending on the mixing temperature, and can be maintained at a certain temperature for a certain period of time). Alternatively, no further reaction is required. The acyl halide compound can be added before, after, or in separate additions to the first titanium-containing compound, either in the same or different amounts. At least one alcohol compound is added before reacting with the first titanium-containing compound. (It is particularly important to note that when using a pre-added alcohol compound, its effect on the dissolution of the magnesium-containing compound should be minimized; otherwise, subsequent precipitates are highly likely to form. Preferably, the first alcohol compound is added at -55 to 20°C, more preferably at -35 to 0°C.) Furthermore, optionally, a first electron-donating compound can be added before and / or after the addition of the first titanium-containing compound. The reaction mixture is then treated at 10–170°C for a certain period of time to obtain a solid precipitate. Afterward, the precipitate is filtered, and the solid is washed (the washing solvent can be at least one of conventional solvents such as aliphatic hydrocarbons or aromatic hydrocarbons, specifically at least one of halogenated or non-halogenated aromatic hydrocarbons and / or halogenated or non-halogenated aliphatic hydrocarbons, typically selected from at least one of benzene and its homologues, chlorobenzene, dichlorobenzene, hexane, heptane, decane, kerosene, dichloromethane, dichloroethane, chloroform, and cyclohexane, as long as it does not adversely affect the subsequent catalyst). (Washing can be simple solvent washing, or it can include complex treatments involving titanium-containing compounds and / or internal electron donors). This yields titanium-containing solid catalyst component A. The above describes the basic features of this invention. In actual synthesis, other conventional additives may be optionally added, which will not be detailed here.

[0084] A second aspect of the present invention provides a catalyst component for olefin polymerization prepared by the above preparation method.

[0085] A third aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising the following components:

[0086] Component A: The catalyst components mentioned above;

[0087] Component B: an organoaluminum compound; preferably, the organoaluminum compound has the general formula AlR. n X 3-nIn the formula, R is a hydrogen or a hydrocarbon group with 1 to 20 carbon atoms; X is a halogen; n is an integer 0 < n ≤ 3;

[0088] The molar ratio of aluminum in component B to titanium in component A is preferably 1 to 1000:1; more preferably 5 to 500:1.

[0089] The organoaluminum compound is further preferably at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydrogen, diisobutylaluminum hydrogen, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, and diethylaluminum chloride; and even more preferably triethylaluminum and / or triisobutylaluminum.

[0090] In this invention, the catalyst component A of this invention is obtained through the above steps, and this component can be used in the form of a solid or a suspension.

[0091] The A and B components (organoaluminum compounds) of the catalyst of this invention can be directly applied to the polymerization system, or they can be pre-complexed and then applied to the polymerization system.

[0092] A fourth aspect of the present invention provides the use of the above-described catalyst component or the above-described catalyst in olefin polymerization reactions.

[0093] The olefin polymerization reaction is preferably an ethylene polymerization reaction and / or a propylene polymerization reaction.

[0094] The catalyst component or catalyst of the present invention can be used for homopolymerization of olefins, and can also be used for copolymerization of olefins and α-olefins. The comonomer can be at least one of propylene, butene, pentene, hexene, octene and 4-methyl-1-pentene.

[0095] Polymerization can be performed in either the liquid phase or the gas phase. In liquid phase polymerization, inert solvents such as propane, hexane, heptane, cyclohexane, isobutane, isopentane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, and xylene, or saturated aliphatic or aromatic hydrocarbons, can be used as the reaction medium. Prepolymerization can be performed before polymerization. Polymerization can be carried out in batch, semi-continuous, or continuous processes.

[0096] The polymerization temperature is room temperature to 150°C, preferably 50°C to 100°C. Hydrogen is used as a molecular weight regulator to adjust the polymer's molecular weight.

[0097] The present invention will be described in more detail below through examples, but the present invention is not limited to these examples.

[0098] In the following examples and comparative examples, the data were obtained using the following test methods:

[0099] 1. Morphology of spherical or near-spherical solid catalyst component A / polymer: determined using a Phenix upright trinocular metallographic microscope PH-M2030B.

[0100] 2. Determination of polymer melt index (MI): According to ASTM D1238-99, the test was conducted at 190°C with a load of 2.16 kg.

[0101] 3. Determination of polymer bulk density: The apparent density, volume factor and pourability of plastics are determined using the test method (ASTM D1895).

[0102] (I) Preparation of catalyst component A

[0103] Example 1

[0104] Preparation of solid catalyst component A (1#)

[0105] 4.8 g magnesium chloride, 90 ml toluene, 5.0 ml epichlorohydrin, and 15.0 ml tri-n-butyl phosphate were added to a reactor under high-purity nitrogen protection. The reaction was carried out for 2.5 hours at a stirring speed of 450 rpm and a temperature of 60°C. Then, 1.0 ml benzoyl chloride was added, and the temperature was lowered to -30°C. Maintaining the system temperature at -30±3°C, 1.0 ml ethanol was added dropwise, maintaining this temperature for 0.5 hours. Then, 70 ml titanium tetrachloride was added dropwise. After the addition was complete, the temperature was gradually raised to 90°C and maintained at this temperature for 2 hours. The mother liquor was filtered off, and the sample was washed multiple times with inert diluent toluene and organic solvent hexane, then dried to obtain spherical solid catalyst component A (component #1).

[0106] Comparative Example 1

[0107] Preparation of solid catalyst component A (1b)

[0108] 4.8 g magnesium chloride, 90 ml toluene, 5.0 ml epichlorohydrin, and 15.0 ml tri-n-butyl phosphate were added to a reactor under high-purity nitrogen protection. The reaction was carried out at 60°C and stirred at 450 rpm for 2.5 hours. Then, 1.3 g phthalic anhydride was added and maintained for 1.0 hour. The temperature was lowered to -30°C, and the system temperature was maintained at -30±3°C. First, 1.0 ml ethanol was added dropwise and maintained for 0.5 hours, followed by the addition of 70 ml titanium tetrachloride. After the addition was complete, the temperature was gradually raised to 90°C and maintained for 2 hours. The mother liquor was filtered off, and the sample was washed multiple times with inert diluent toluene and organic solvent hexane, then dried to obtain spherical 1b# solid catalyst component A.

[0109] Comparative Example 2

[0110] Preparation of solid catalyst component A (2b)

[0111] 4.8 g magnesium chloride, 90 ml toluene, 5.0 ml epichlorohydrin, 15.0 ml tri-n-butyl phosphate, and 1.0 ml ethanol were added to a reactor under high-purity nitrogen protection. The reaction was carried out for 2.5 hours at a stirring speed of 450 rpm and a temperature of 60°C. Then, 1.0 ml benzoyl chloride was added, and the temperature was lowered to -30°C. While maintaining the system temperature at -30±3°C, 70 ml titanium tetrachloride was added dropwise. After the addition was complete, the temperature was gradually raised to 90°C and held at this temperature for 2 hours. The mother liquor was filtered off, and the mixture was washed multiple times with inert diluent toluene and organic solvent hexane, then dried to obtain fragmented solid catalyst component A (2b#).

[0112] Example 2

[0113] Preparation of component A of solid catalyst #2

[0114] 4.8 g magnesium chloride, 90 ml toluene, 5.0 ml epichlorohydrin, and 15.0 ml tri-n-butyl phosphate were added to a reactor under high-purity nitrogen protection. The reaction was carried out at 60°C and stirred at 450 rpm for 2.5 hours. Then, 1.0 ml benzoyl chloride was added, and the temperature was lowered to -30°C. Maintaining the system temperature at -30±3°C, 1.0 ml ethanol was added dropwise, maintaining this temperature for 0.5 hours. Next, 70 ml titanium tetrachloride was added dropwise, maintaining this temperature for 0.5 hours. Finally, 1.0 ml n-butanol was added dropwise. After the addition was complete, the temperature was gradually raised to 90°C and maintained for 2 hours. The mother liquor was filtered off, and the sample was washed multiple times with inert diluent toluene and organic solvent hexane, then dried to obtain spherical solid catalyst component A (#2).

[0115] Comparative Example 3

[0116] Preparation of solid catalyst component A (3b)

[0117] 4.8 g magnesium chloride, 90 ml toluene, 5.0 ml epichlorohydrin, and 15.0 ml tri-n-butyl phosphate were added to a reactor under high-purity nitrogen protection. The reaction was carried out at 60°C and stirred at 450 rpm for 2.0 hours. Then, 1.3 g phthalic anhydride was added and maintained for 1.0 hour. The temperature was lowered to -30°C, and the system temperature was maintained at -30±3°C. First, 1.0 ml ethanol was added dropwise and maintained for 0.5 hours, followed by 70 ml titanium tetrachloride and maintained for 0.5 hours. Then, 1.0 ml n-butanol was added dropwise. After the addition was complete, the temperature was gradually raised to 90°C and maintained for 2 hours. The mother liquor was filtered off, and the sample was washed multiple times with inert diluent toluene and organic solvent hexane, then dried to obtain spherical 3b# solid catalyst component A.

[0118] Example 3

[0119] Preparation of component A of solid catalyst #3

[0120] 4.8 g magnesium chloride, 90 ml toluene, 5.0 ml epichlorohydrin, and 15.0 ml tri-n-butyl phosphate were added to a reactor under high-purity nitrogen protection. The reaction was carried out at 60°C and stirred at 450 rpm for 2.5 hours. Then, 2.0 ml benzoyl chloride was added, and the temperature was lowered to -30°C. Maintaining the system temperature at -30±3°C, 1.0 ml ethanol was added dropwise, maintaining this temperature for 0.5 hours. Then, 70 ml titanium tetrachloride was added dropwise, maintaining this temperature for 0.5 hours. Finally, 2.0 ml ethanol was added dropwise, and the temperature was gradually raised to 90°C and held at this temperature for 2 hours. The mother liquor was filtered off, and the sample was washed multiple times with inert diluent toluene and organic solvent hexane, then dried to obtain spherical solid catalyst component A (#3).

[0121] Example 4

[0122] Preparation of component A of solid catalyst #4

[0123] 4.8 g magnesium chloride, 90 ml toluene, 5.0 ml epichlorohydrin, and 15.0 ml tri-n-butyl phosphate were added to a reactor under high-purity nitrogen protection. The reaction was carried out at 60°C and stirred at 450 rpm for 2.5 hours. Then, 2.0 ml benzoyl chloride was added, and the temperature was lowered to -30°C. Maintaining the system temperature at -30±3°C, 1.0 ml ethanol was added dropwise, maintaining this temperature for 0.5 hours. Next, 70 ml titanium tetrachloride was added dropwise, maintaining this temperature for 0.5 hours. Finally, 2.0 ml tetraethoxysilane was added dropwise. After the addition was complete, the temperature was gradually raised to 90°C and maintained for 2 hours. The mother liquor was filtered off, and the sample was washed repeatedly with inert diluent toluene and organic solvent hexane, then dried to obtain spherical solid catalyst component A (#4).

[0124] Comparative Example 4

[0125] Preparation of solid catalyst component A (4b)

[0126] 4.8 g of magnesium chloride, 90 ml of toluene, 5.0 ml of epichlorohydrin, and 15.0 ml of tri-n-butyl phosphate were added to a reactor under high-purity nitrogen protection. The reaction was carried out for 2.5 hours at a stirring speed of 450 rpm and a temperature of 60 °C. The temperature was then lowered to -30 °C, and the system temperature was maintained at -30 ± 3 °C. 70 ml of titanium tetrachloride was added dropwise. After the addition was complete, the temperature was gradually raised to 90 °C and held at that temperature for 2 hours. The mother liquor was filtered off, and the sample was washed multiple times with inert diluent toluene and organic solvent hexane, and then dried to obtain spherical 4b# solid catalyst component A.

[0127] Comparative Example 5

[0128] Preparation of solid catalyst component A (5b#)

[0129] 4.8 g magnesium chloride, 90 ml toluene, 5.0 ml epichlorohydrin, 15.0 ml tri-n-butyl phosphate, and 1.0 ml ethanol were added to a reactor under high-purity nitrogen protection. The reaction was carried out for 2.5 hours at a stirring speed of 450 rpm and a temperature of 60°C. Then, 2.0 ml benzoyl chloride was added, and the temperature was lowered to -30°C. The system temperature was maintained at -30±3°C, and 70 ml titanium tetrachloride was added dropwise, maintaining this temperature for 0.5 hours. Then, 2.0 ml ethanol was added dropwise. After the addition was complete, the temperature was gradually raised to 90°C and maintained at this temperature for 2 hours. The mother liquor was filtered off, and the mixture was washed multiple times with inert diluent toluene and organic solvent hexane, and then dried to obtain fragmented 5b# solid catalyst component A.

[0130] Example 5

[0131] Preparation of component A of solid catalyst #5

[0132] 4.8 g magnesium chloride, 90 ml toluene, 5.0 ml epichlorohydrin, and 15.0 ml tri-n-butyl phosphate were added to a reactor under high-purity nitrogen protection. The reaction was carried out at 60°C and stirred at 450 rpm for 2.5 hours. Then, 1.0 ml benzoyl chloride was added, and the temperature was lowered to -30°C. Maintaining the system temperature at -30±3°C, 2.7 ml isooctyl alcohol was added dropwise, and the mixture was maintained at this temperature for 0.5 hours. Next, 70 ml titanium tetrachloride was added dropwise, followed by 1.0 ml tetraethoxysilane. After the addition was complete, the temperature was gradually raised to 90°C and maintained at this temperature for 2 hours. The mother liquor was filtered off, and the mixture was washed multiple times with inert diluent toluene and organic solvent hexane, then dried to obtain spherical solid catalyst component A (No. 5).

[0133] Example 6

[0134] Preparation of component A of solid catalyst #6

[0135] 4.8 g magnesium chloride, 90 ml toluene, 5.0 ml epichlorohydrin, and 15.0 ml tri-n-butyl phosphate were added to a reactor under high-purity nitrogen protection. The reaction was carried out at 450 rpm and 60 °C for 2.5 hours. Then, 1.0 ml benzoyl chloride was added, and the temperature was lowered to -30 °C. Maintaining the system temperature at -30 ± 3 °C, 2.7 ml isooctyl alcohol was added dropwise, maintaining this temperature for 0.5 hours. Then, 70 ml titanium tetrachloride was added dropwise. After the addition was complete, the temperature was gradually raised to 90 °C and held at this temperature for 2 hours. The mother liquor was filtered off, and the sample was washed multiple times with inert diluent toluene and organic solvent hexane, then dried to obtain spherical solid catalyst component A (component #6).

[0136] Example 7

[0137] Preparation of component A of solid catalyst #7

[0138] 4.8 g magnesium chloride, 70 ml toluene, 4.0 ml epichlorohydrin, and 13.0 ml tri-n-butyl phosphate were added to a reactor under high-purity nitrogen protection. The reaction was carried out at 60°C and stirred at 450 rpm for 2.5 hours. Then, 2.0 ml benzoyl chloride was added, and the temperature was lowered to -30°C. Maintaining the system temperature at -30±3°C, 2.0 ml ethanol was added dropwise, maintaining this temperature for 0.5 hours. Next, 0.5 ml silicon tetrachloride was added dropwise, maintaining this temperature for 0.5 hours. Finally, 40 ml titanium tetrachloride was added dropwise. After the addition was complete, the temperature was gradually raised to 90°C and maintained for 2 hours. The mother liquor was filtered off, and the sample was washed repeatedly with inert diluent toluene and organic solvent hexane, then dried to obtain spherical solid catalyst component A (#7).

[0139] Example 8

[0140] Preparation of component A of solid catalyst #8

[0141] 4.8 g magnesium chloride, 70 ml toluene, 4.0 ml epichlorohydrin, and 13.0 ml tri-n-butyl phosphate were added to a reactor under high-purity nitrogen protection. The reaction was carried out at 60°C and stirred at 450 rpm for 2.5 hours. Then, 2.0 ml benzoyl chloride was added, and the temperature was lowered to -30°C. Maintaining the system temperature at -30±3°C, 1.0 ml ethanol was added dropwise, maintaining the temperature for 0.5 hours. Next, 0.5 ml silicon tetrachloride was added dropwise, maintaining the temperature for 0.5 hours. Then, 40 ml titanium tetrachloride was added dropwise, followed by 2.7 ml isooctyl alcohol. After the addition was complete, the temperature was gradually raised to 90°C and maintained for 2 hours. The mother liquor was filtered off, and the sample was washed repeatedly with inert diluent toluene and organic solvent hexane, then dried to obtain spherical solid catalyst component A (No. 8).

[0142] Comparative Example 6

[0143] Preparation of Component A of Solid Catalyst 6b#

[0144] Example 1 of CN201210409037.0 was used. Fragmented 6b# solid catalyst component A was obtained.

[0145] Comparative Example 7

[0146] Preparation of solid catalyst component A (7b#)

[0147] Comparative Example 1 of CN201210409037.0 was used. Fragmented 7b# solid catalyst component A was obtained.

[0148] Example 9

[0149] Preparation of component A of solid catalyst #9

[0150] Following the method in Example 1, solid catalyst component A (#1) was obtained as a catalyst precursor. Under high-purity nitrogen protection, 40 ml of toluene was added to the precursor, and the temperature was lowered to -10°C. Maintaining the system temperature at -10 ± 1°C, 1.0 ml of ethanol was added dropwise, and the temperature was maintained for 0.5 hours. Then, 40 ml of titanium tetrachloride was added dropwise. After the addition was complete, the temperature was gradually raised to 110°C and held at that temperature for 1 hour. The mother liquor was filtered off, and the product was washed multiple times with inert diluent toluene and organic solvent hexane, and then dried to obtain spherical solid catalyst component A (#9).

[0151] Example 10

[0152] Preparation of component A of solid catalyst #10

[0153] 4.8 g magnesium chloride, 90 ml toluene, 5.0 ml epichlorohydrin, and 15.0 ml tri-n-butyl phosphate were added to a reactor under high-purity nitrogen protection. The reaction was carried out for 2.5 hours at 450 rpm and 60°C. Then, 1.0 ml benzoyl chloride was added, and the system temperature was maintained at -30 ± 3°C. The temperature was then lowered to -30°C, and 1.0 ml ethanol was added dropwise, maintaining the temperature for 0.5 hours. Then, 70 ml titanium tetrachloride was added dropwise. After the addition was complete, the temperature was gradually increased to 90°C and held for 2 hours. The mother liquor was filtered off, and the mixture was washed twice with toluene (an inert diluent). Under high-purity nitrogen protection, 40 ml toluene was added, and the temperature was lowered to -10°C. The system temperature was maintained at -10 ± 1°C, and 1.0 ml ethanol was added dropwise, maintaining the temperature for 0.5 hours. Then, 40 ml titanium tetrachloride was added dropwise. After the addition was complete, the temperature was gradually increased to 110°C and held for 1 hour. After filtering off the mother liquor, the sample was washed multiple times with inert diluent toluene and organic solvent hexane, and then dried to obtain spherical solid catalyst component A of No. 10.

[0154] Comparative Example 8

[0155] Preparation of Component A of Solid Catalyst #8b

[0156] The procedure is the same as in Example 9, except that solid catalyst component A#1 is replaced with solid catalyst component A#1b#. This yields spherical solid catalyst component A#8b#.

[0157] Example 11

[0158] Preparation of component A of solid catalyst #11

[0159] 4.8 g magnesium chloride, 50 ml toluene, 2.0 ml epichlorohydrin, and 20.0 ml tri-n-butyl phosphate were added to a reactor under high-purity nitrogen protection. The reaction was carried out at 50°C and stirred at 250 rpm for 5.0 hours. The temperature was then lowered to 40°C, and 3.0 ml benzoyl chloride was added and maintained for 10 minutes. The temperature was then lowered to -20°C, and the system temperature was maintained at -20±2°C. First, 4.0 ml ethanol was added dropwise and maintained for 20 minutes, followed by 120 ml titanium tetrachloride, which was maintained for 20 minutes after the addition was complete. The temperature was then gradually increased to 110°C and held at this temperature for 2 hours. The mother liquor was filtered off, and the sample was washed multiple times with inert diluent toluene and organic solvent hexane, and then dried to obtain spherical solid catalyst component A, #11.

[0160] Comparative Example 9

[0161] Preparation of Component A of Solid Catalyst #9b

[0162] 4.8 g magnesium chloride, 50 ml toluene, 2.0 ml epichlorohydrin, and 20.0 ml tri-n-butyl phosphate were added to a reactor under high-purity nitrogen protection. The reaction was carried out at 50 °C and stirred at 250 rpm for 5.0 hours. The temperature was then lowered to 40 °C, and 3.0 ml benzoyl chloride was added and maintained for 10 minutes. 4.0 ml ethanol was added dropwise and maintained for 20 minutes. The temperature was then lowered to -20 °C, and the system temperature was maintained at -20 ± 2 °C. 120 ml titanium tetrachloride was added dropwise and maintained for 20 minutes after the addition was complete. The temperature was then gradually increased to 110 °C and held at this temperature for 2 hours. The mother liquor was filtered off, and the sample was washed repeatedly with inert diluent toluene and organic solvent hexane, then dried to obtain non-spherical (fragmented) 9b# solid catalyst component A.

[0163] Example 12

[0164] Preparation of component A of solid catalyst #12

[0165] 4.8 g magnesium chloride, 50 ml toluene, 2.0 ml epichlorohydrin, and 20.0 ml tri-n-butyl phosphate were added to a reactor under high-purity nitrogen protection. The reaction was carried out at 50°C and stirred at 250 rpm for 5.0 hours. The temperature was then lowered to 40°C, and 3.0 ml benzoyl chloride was added and maintained for 10 minutes. The temperature was then lowered to -5°C, and the system temperature was maintained at 0±1°C. First, 4.0 ml ethanol was added dropwise and maintained for 20 minutes, followed by 120 ml titanium tetrachloride, which was maintained for 20 minutes after the addition was complete. The temperature was then gradually increased to 110°C and held at this temperature for 2 hours. The mother liquor was filtered off, and the sample was washed multiple times with inert diluent toluene and organic solvent hexane, and then dried to obtain spherical solid catalyst component A (No. 12).

[0166] Example 13

[0167] Preparation of component A of solid catalyst #13

[0168] 4.8 g magnesium chloride, 70 ml toluene, 8.0 ml epichlorohydrin, and 8.0 ml tri-n-butyl phosphate were added to a reactor under high-purity nitrogen protection. The reaction was carried out at 55°C and stirred at 350 rpm for 4.0 hours. The temperature was then lowered to 20°C, and 0.3 ml benzoyl chloride was added and maintained for 10 minutes. The temperature was then lowered to -10°C, and the system temperature was maintained at -10±1°C. First, 0.5 ml ethanol was added dropwise and maintained for 20 minutes, followed by 20 ml titanium tetrachloride. After the addition was complete, the temperature was maintained for 20 minutes, and then gradually increased to 80°C and held at that temperature for 2 hours. The mother liquor was filtered off, and the sample was washed twice with 100 ml toluene. Under high-purity nitrogen protection, 30 ml toluene and 30 ml titanium tetrachloride were added, and the temperature was increased to 110°C and maintained for 1.0 hour. The sample was filtered, washed repeatedly with inert diluent toluene and organic solvent hexane, and then dried to obtain spherical solid catalyst component A (No. 13).

[0169] (II) Ethylene Polymerization

[0170] A 2-liter stainless steel reactor was fully purged with H2, then 1000 mL of hexane, 1.0 mL of a 1 mol / L triethylaluminum hexane solution, and a measured amount (containing approximately 0.01 mmol of titanium) of the prepared solid catalyst were added. The reactor was heated to 70°C and hydrogen was added at 0.26 MPa (gauge pressure). Ethylene was then introduced to bring the pressure inside the reactor to 0.72 MPa (gauge pressure), and polymerization was carried out at 80°C for 2 hours. The experimental results are shown in the table below:

[0171] Table 1: Experimental Results

[0172]

[0173]

[0174] The morphology of the catalyst component A and polymer powder particles prepared above was observed using the microscope according to the above test method. Some morphology photographs are shown below. Figure 1-16 .

[0175] As can be seen from the above test data, the preparation method of the present invention can obtain spherical catalyst components and spherical polymer powders. The obtained polymer powders have significantly improved bulk density. Compared with the comparative example using phthalic anhydride, the catalyst obtained by this method has better hydrogen sensitivity and polymerization activity.

[0176] 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 process for the preparation of a catalyst component for the polymerization of olefins, characterized in that, The preparation method comprises: (1) reacting a magnesium-containing compound, an organic epoxy compound and an organic phosphorus compound in the presence of a first inert diluent to obtain a magnesium-containing reaction solution; (2) reacting the magnesium-containing reaction solution with an acid halide compound, then with a first alcohol compound at -55 to 20°C, and again with a first titanium-containing compound to obtain the catalyst component for olefin polymerization reaction; optionally, a first electron donor compound is added before and / or after the reaction with the first titanium-containing compound, and the reaction is carried out when the first electron donor compound is a second alcohol compound at -55 to 20°C; Optionally, it further comprises step (3): reacting the catalyst component obtained in step (2) with a second titanium-containing compound in the presence of a second inert diluent to obtain the catalyst component for olefin polymerization reaction; optionally, a second electron donor compound is added before and / or after the reaction with the second titanium-containing compound, and the reaction is carried out.

2. The production method according to claim 1, wherein, The magnesium-containing compound is dimethylmagnesium, diethylmagnesium, diisopropylmagnesium, isopropylmethylmagnesium, n-butylethylmagnesium, di-n-butylmagnesium, butyloctylmagnesium, dihexylmagnesium, dioctylmagnesium, dihalogenated magnesium, MgR 1 Cl and Mg(OR 2 )Cl; wherein R 1 and R 2 are each independently selected from substituted or unsubstituted C1-C 10 hydrocarbyl, the substituents being selected from at least one of a hydroxyl group, a carboxyl group, a halogen atom, and an alkoxy group; Preferably, the magnesium-containing compound is a magnesium dihalide, MgR 1 Cl and Mg(OR 2 )Cl; wherein R 1 and R 2 are each independently selected from a substituted or unsubstituted C1-C 10 hydrocarbon group, the substituents being selected from at least one of a hydroxyl group, a carboxyl group, a halogen atom and an alkoxy group.

3. The production method according to claim 1, wherein The organic epoxy compound is selected from at least one of the group consisting of C2-C8 aliphatic olefin oxide, C2-C8 aliphatic olefin glycidyl ether, C2-C8 aliphatic olefin internal ether, C2-C8 halogenated aliphatic olefin oxide, C2-C8 halogenated aliphatic olefin glycidyl ether and C2-C8 halogenated aliphatic olefin internal ether; Preferably, the organic epoxy compound is selected from at least one of the group consisting of oxirane, oxetane, butylene oxide, butadiene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether and tetrahydrofuran.

4. The production method according to claim 1, wherein The organic phosphorus compound is selected from at least one of the group consisting of trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, triisopropyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate, tri-t-butyl phosphate, tri-n-pentyl phosphate, triisopentyl phosphate, tri-n-hexyl phosphate, triisohexyl phosphate, tri-n-heptyl phosphate, triisohexyl phosphate, tri-n-octyl phosphate, triisooctyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, tri-t-butyl phosphite, tri-n-pentyl phosphite, triisopentyl phosphite, tri-n-hexyl phosphite, triisohexyl phosphite, tri-n-heptyl phosphite, triisohexyl phosphite, tri-n-octyl phosphite, triisooctyl phosphite, triphenyl phosphite and di-n-butyl phosphite; Preferably, the organic phosphorus compound is selected from at least one of the group consisting of triethyl phosphate, tributyl phosphate, triisooctyl phosphate, triphenyl phosphate, triethyl phosphite, tributyl phosphite and di-n-butyl phosphite.

5. The production method according to claim 1, wherein The acyl halide compound has a general formula of R(COX) a wherein R is a hydrogen atom, an unsubstituted aliphatic group having 1 to 8 carbon atoms, a substituted aliphatic group having 1 to 8 carbon atoms, an unsubstituted aromatic group having 6 to 10 carbon atoms, or a substituted aromatic group having 6 to 10 carbon atoms, X is a halogen, and a is 1 or 2; The acid halide compound is preferably an acid chloride compound; further preferably at least one of benzoyl chloride, substituted benzoyl chloride, phthaloyl dichloride, substituted phthaloyl dichloride, terephthaloyl dichloride and substituted terephthaloyl dichloride; and still further preferably benzoyl chloride and / or substituted benzoyl chloride.

6. The production method according to claim 1, wherein said first alcohol compound is at least one of an unsubstituted C1-C 12 aliphatic alcohol, a substituted C1-C 12 aliphatic alcohol, an unsubstituted C7-C 12 aromatic alcohol, and a substituted C7-C 12 aromatic alcohol. The first alcohol compound is preferably at least one of methanol, ethanol, propanol, n-butanol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, iso-octanol, 2-ethylhexanol, n-decanol, dodecanol, cyclohexanol, methylcyclohexanol, benzyl alcohol, phenethyl alcohol, and a halogenated alcohol derived from the above alcohol.

7. The production method according to claim 1, wherein the general formula of the first titanium-containing compound and the second titanium-containing compound are each independently Ti(OR) a X b wherein R is a C1-C 14 hydrocarbon group, preferably a C1-C8alkyl group; X is a halogen atom, a, b are each independently an integer of 0-4, and a+b = 3 or 4; Preferably, the first titanium-containing compound and the second titanium-containing compound are each independently selected from at least one of TiCl3, TiCl4, TiBr4, TiCl4, Ti(OC2H5)Cl3, Ti(OCH3)Cl3, Ti(OC4H9)Cl3, Ti(OC2H5)Br3, Ti(OC2H5)2Cl2, Ti(OCH3)2Cl2, Ti(OCH3)2I2, Ti(OC2H5)3Cl, Ti(OCH3)3Cl, Ti(OC2H5)3I, Ti(OC2H5)4, Ti(OC3H7)4, and Ti(OC4H9)4.

8. The production method according to claim 1, wherein The first electron donor compound and the second electron donor compound are each independently selected from at least one of an organic acid, a second alcohol compound, an organic acid ester, a silicon-containing compound, a boron-containing compound, an organic acyl halide, a halogenated hydrocarbon, an ether, a ketone, an amine, a phosphoric acid ester, an amide, a phenol, and a pyridine.

9. The production method according to claim 8, wherein said second alcohol compound is at least one of an unsubstituted C1-C 12 aliphatic alcohol, a substituted C1-C 12 aliphatic alcohol, an unsubstituted C7-C 12 aromatic alcohol, and a substituted C7-C 12 aromatic alcohol. The second alcohol compound is preferably at least one of methanol, ethanol, propanol, n-butanol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, iso-octanol, 2-ethylhexanol, n-decanol, dodecanol, cyclohexanol, methylcyclohexanol, benzyl alcohol, phenethyl alcohol, and a halogenated alcohol derived from the above alcohol.

10. The production method according to claim 8, wherein The silicon-containing compound is represented by the general formula R 1 x R 2 y Si(OR 3 ) z a silicon-containing compound having no active hydrogen atom, wherein R 1 and R 2 each independently is a hydrocarbon group having 1 to 10 carbon atoms or a halogen, and R 3 is a hydrocarbon group having 1 to 10 carbon atoms, wherein x, y, z are positive integers, 0≤x≤4, 0≤y≤4 and 0≤z≤4, and x+y+z=4. Preferably, the silicon-containing compound is at least one of silicon tetrachloride, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and tetrakis(2-ethylhexyloxy)silane.

11. The method of producing according to claim 1, wherein, The amount of the organic phosphorus compound is 0.01 to 4.0 moles per mole of the magnesium halide; the amount of the acyl halide compound is 0.01 to 3.0 moles per mole of the magnesium halide; the amount of the first alcohol compound is 0.001 to 4.0 moles per mole of the magnesium halide; the amount of the first titanium-containing compound is 0.1 to 100 moles per mole of the magnesium halide; and the amount of the first electron donor compound is 0 to 4.0 moles per mole of the magnesium halide. Preferably, the amount of the organic phosphorus compound is 0.02 to 2.0 moles per mole of the magnesium halide; the amount of the acyl halide compound is 0.02 to 2.0 moles per mole of the magnesium halide; the amount of the first alcohol compound is 0.02 to 3.0 moles per mole of the magnesium halide; the amount of the first titanium-containing compound is 0.2 to 50 moles per mole of the magnesium halide; and the amount of the first electron donor compound is 0 to 3.0 moles per mole of the magnesium halide.

12. The method of producing according to claim 1, wherein, In step (1), the temperature of the reaction is 0 to 100°C, preferably 20 to 80°C. Preferably, in step (2), the reaction with the first alcohol compound is carried out at -35 to 0°C; and the first electron donor compound is optionally added, and when the first electron donor compound is a second alcohol compound, the reaction is carried out at -35 to 0°C. Preferably, in step (2), the reaction with the acyl halide compound is carried out at a temperature of -55 to 80°C, further preferably -35 to 60°C; the reaction with the first titanium-containing compound is carried out at a temperature of -55 to 80°C, further preferably -35 to 20°C; the optional addition of the first electron donor compound is carried out at a temperature of -55 to 80°C, further preferably -35 to 80°C, when the first electron donor compound is a non-alcohol compound; Preferably, in step (2), the resulting final reaction mixture is kept at a temperature of 10 to 170°C for 1 to 5 hours, resulting in the precipitation of a solid, which is filtered, washed, and dried to obtain the catalyst component for the polymerization of olefins.

13. The catalyst component for the polymerization of olefins, prepared according to the process of any one of claims 1 to 12.

14. A catalyst for the polymerization of olefins, characterized in that, The catalyst comprises the following components: Component A: the catalyst component of claim 13; Component B: an organoaluminum compound; preferably, the organoaluminum compound has a general formula of AlR n X 3-n ; in the formula, R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms; X is halogen; and n is an integer satisfying 0 < n < 3. The molar ratio of aluminum in the component B to titanium in the component A is preferably 1 to 1000: 1; further preferably 5 to 500: 1; The organoaluminum compound is further preferably at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, and ethylaluminum dichloride.

15. Use of the catalyst component of claim 13 or the catalyst of claim 14 in the polymerization of olefins.

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