Process for the preparation of an olefin polymerization catalyst component, catalyst system and use thereof

Abstract

The application provides a preparation method of a spherical catalyst component, a catalyst system and application thereof, and belongs to the technical field of olefin polymerization. The preparation method of the spherical catalyst component comprises the following steps: S1, contacting a magnesium compound, an organic epoxy compound, an organic phosphorus compound and an inert dispersion medium in an organic solvent to form a magnesium-containing solution; S2, contacting the magnesium-containing solution with a titanium-containing compound in the presence of an assistant precipitant and optionally a surfactant to form a mixture; S3, performing a temperature rising treatment on the mixture to precipitate a spherical solid, and performing filtration, washing and drying to obtain the spherical catalyst component; wherein a long-chain alpha-olefin compound represented by the formula CH2=CHRa is added before the spherical solid is precipitated; wherein Ra is selected from linear or branched alkyl with 8-30 carbon atoms or cycloalkyl with 8-30 carbon atoms. The spherical olefin polymerization catalyst component has high polymerization activity, and the obtained polymer has a higher bulk density.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of olefin polymerization catalyst, in particular to a preparation method of an olefin polymerization catalyst component, a catalyst system and application thereof. BACKGROUND

[0002] The dissolution precipitation method is one of the main preparation methods of polyolefin Ziegler-Natta catalyst. This method usually needs to prepare a homogeneous solution containing a magnesium compound, and then reacts with a chlorinating agent to precipitate a solid titanium / magnesium complex, and loads an internal electron donor compound to form a catalyst component. The feature of this method is that the preparation of the catalyst no longer needs to separately prepare the carrier, but precipitates the titanium / magnesium catalyst or catalyst intermediate from the solution through co-crystallization. Since the morphology and particle size distribution of this type of catalyst are controlled by the crystallization precipitation process, there are many influencing factors, so the catalyst particle morphology is not easy to control. Early patent documents such as CN85100997A and CN1097597C precipitate granular catalysts with wide particle size distribution and poor particle shape. In recent years, the preparation of spherical catalysts by emulsification molding process has attracted more and more attention. Patent documents CN103619475B and CN107207657A control the crystallization process through emulsification technology, and precipitate spherical solid materials, which have greatly improved morphology. However, when preparing catalysts with large average particle size, this technology often has the problems of low catalyst activity and low polymer bulk density. The methods described in patent documents CN114426597A, CN116041578A and CN116041579A often need to use white oil as an inert dispersion medium, which increases the difficulty of solvent recovery and treatment. When using hexane or decane as an inert dispersion medium, the inert dispersion medium needs to be mixed with a titanium-containing compound first, and then contacted with a magnesium-containing solution, which is a complex preparation process and is not conducive to industrial scale-up. The method described in patent document CN116041584A needs to consume a large amount of toluene and titanium tetrachloride when preparing large particle size catalysts, which has a high production cost. SUMMARY

[0003] In view of the problems existing in the prior art, the inventors have found through a large number of experiments that the addition of a long-chain α-olefin compound before the precipitation of spherical solid materials can obtain catalyst particles with large average particle size, which have excellent activity when used for propylene polymerization and high polymer bulk density.

[0004] One of the purposes of the present application is to provide a preparation method of a spherical catalyst component, which comprises the following steps:

[0005] S1. Contacting a magnesium compound, an organic epoxy compound, an organic phosphorus compound and an inert dispersion medium in an organic solvent to form a magnesium-containing solution;

[0006] S2. Contacting the magnesium-containing solution with a titanium-containing compound in the presence of an aid-precipitant and optionally a surfactant to form a mixture;

[0007] S3. Subjecting the mixture to a temperature raising treatment to precipitate a spherical solid, and obtaining a spherical catalyst component by filtering, washing and drying;

[0008] wherein a long-chain α-olefin compound as shown in formula (I) is added before the precipitation of the spherical solid;

[0009] CH2=CHR a Formula (I)

[0010] wherein R a is selected from linear or branched alkyl of 8-30 carbon atoms, and cycloalkyl of 8-30 carbon atoms.

[0011] Optionally, the long-chain α-olefin compound is selected from one or more of 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-docosene, 1-tetracosene, 1-hexacosene.

[0012] In the preparation method of the present application, the long-chain α-olefin compound can be added at any position before the precipitation of the spherical solid, and can be added in one whole or in multiple parts. Specifically, it can be added in whole or in part before or after the formation of the magnesium-containing solution, and can be added in whole or in part before the temperature of the mixture is raised to 50°C.

[0013] Optionally, the magnesium compound of the present application has a general formula of MgX2, wherein X is halogen, preferably bromine, chlorine or iodine; specifically, it can be at least one of magnesium dichloride, magnesium dibromide and magnesium diiodide, and preferably magnesium dichloride.

[0014] Optionally, the organic epoxy compound of the present application is selected from one or more of oxirane, oxetane, epichlorohydrin, epichloropropane, butylene oxide, butadiene oxide, butadiene dioxide, methyl glycidyl ether and diglycidyl ether, and preferably epichlorohydrin.

[0015] Optionally, the organic phosphorus compound of the present application is selected from one or more of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triamyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, benzyl phosphite, and preferably tributyl phosphate.

[0016] Optionally, the inert dispersion medium of the present application is selected from one or more of hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, and preferably one or more of hexane and decane.

[0017] Optionally, the organic solvent is aromatic hydrocarbon, and specifically, one or more of toluene, ethylbenzene, benzene, xylene, and preferably toluene.

[0018] Optionally, the titanium-containing compound is at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, chlorotriethoxy titanium, dichlorodiethoxy titanium, and chloroethoxy titanium, and preferably titanium tetrachloride.

[0019] Optionally, the co-precipitant is one or more of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, amyl ether, and preferably phthalic anhydride.

[0020] Optionally, the surfactant is at least one of alkyl (meth)acrylate polymer and alkyl (meth)acrylate copolymer, and can be a surfactant product with a trademark of T602 purchased from any additive company.

[0021] Optionally, in the step S1, the contact method for forming the magnesium-containing solution is not particularly limited, and the purpose of the contact is to form a uniform magnesium-containing solution. The contact conditions include a contact temperature of 10-100°C, preferably 20-80°C, and a contact time of 0.05-10 hours, preferably 0.1-6 hours.

[0022] Optionally, in the step S2, the method for contacting the magnesium-containing solution with the titanium-containing compound to form a mixture is preferably dropping the titanium-containing compound into the magnesium-containing solution.

[0023] Optionally, in the step S2, the contact temperature for contacting the titanium-containing compound and the magnesium-containing solution is -35-60°C, preferably -20-40°C, and the contact time is 1 minute-10 hours, preferably 3 minutes-7 hours.

[0024] Optionally, in the step S2, the mixture formed is in a form of colloid, two-phase solution, emulsion, or other forms.

[0025] Optionally, in the step S2, the preparation method further includes using one or more of vibration, stirring, atomization, and shearing to promote the uniform dispersion of the mixture.

[0026] Optionally, in the step S3, the temperature raising process comprises: raising the temperature of the mixture to 50-110℃, solidifying and precipitating the spherical solid, obtaining a suspension, and then stirring the suspension at this temperature or at a higher temperature (not higher than 130℃) for 10 minutes to 24 hours.

[0027] According to the present application, the temperature raising process of the mixture is not specifically limited, and any known method can be used, such as slow, step-by-step, fast or programmed temperature raising, and the specific temperature raising method is adjusted according to the specific formula, contact temperature, etc.; and the present inventors have found that, in the preparation method of the present application, under the condition that other conditions are the same, different temperature raising processes will affect the particle morphology and particle size distribution of the final catalyst; specifically, a slower temperature raising process can obtain a better particle morphology, and conversely, a too fast temperature raising speed will lead to a poor particle morphology; therefore, the time of the temperature raising process of the mixture can be 1 minute to 36 hours, preferably 3 minutes to 24 hours.

[0028] According to the present application, the purpose of stirring the suspension at a certain temperature for 10 minutes to 24 hours after the mixture precipitates the spherical solid is to make the crystal morphology more stable and improve the particle strength.

[0029] According to the present application, the spherical solid can be washed and dried by using the technical means known in the art.

[0030] In the preparation method of the present application, the addition position of the surfactant can be any position before the temperature raising process in the preparation method, and the surfactant can be added in one time or in multiple times.

[0031] Optionally, in the preparation method of the present application, the addition temperature of the surfactant is 10-100℃, preferably 10-80℃, and further preferably 10-60℃.

[0032] In the preparation method of the present application, an internal electron donor compound is also added, and optionally, the addition position of the internal electron donor compound can be any position after the temperature raising process starts in the preparation method, including that the internal electron donor compound can be added in whole or in part during the solidification and temperature raising precipitation of the mixture; the internal electron donor compound can be contacted after the precipitation of the spherical solid or after the precipitation of the spherical solid and the filtration and washing.

[0033] Optionally, the internal electron donor compound is at least one selected from the group consisting of di-n-butyl phthalate, di-isobutyl phthalate, 2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, diethyl 2,3-diisopropyl succinate, diisobutyl 2,3-diisopropyl succinate, di-n-butyl 2,3-diisopropyl succinate, dimethyl 2,3-diisopropyl succinate, diisobutyl 2,2-dimethyl succinate, diisobutyl 2-ethyl-2-methyl succinate, diethyl 2-ethyl-2-methyl succinate, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and 9,9-dimethoxymethylfluorene.

[0034] Optionally, in the preparation method of the present application, the internal electron donor compound is added at a temperature of 10-150°C, preferably 10-100°C.

[0035] Optionally, in the preparation method of the present application, the contact time of the spherical solid with the internal electron donor compound is 0.05-8 hours, preferably 1-6 hours.

[0036] Optionally, in the preparation method of the present application, the amount of the organic epoxy compound is 0.1-10 moles, the amount of the organic phosphorus compound is 0.1-10 moles, the amount of the organic solvent is 0.5-40 moles, the amount of the titanium-containing compound is 0.5-25 moles, the amount of the co-precipitant is 0.01-1 moles, the amount of the internal electron donor compound is 0.01-1 moles, and the amount of the long-chain α-olefin compound is 0.01-1 moles, per mole of the magnesium compound; preferably, the amount of the organic epoxy compound is 0.4-4 moles, the amount of the organic phosphorus compound is 0.8-4 moles, the amount of the organic solvent is 2-30 moles, the amount of the titanium-containing compound is 1-20 moles, the amount of the co-precipitant is 0.04-0.4 moles, the amount of the internal electron donor compound is 0.03-0.8 moles, and the amount of the long-chain α-olefin compound is 0.05-0.5 moles, per mole of the magnesium compound.

[0037] Optionally, in the preparation method of the present application, the amount of the surfactant is 0.01-1 g, and the amount of the inert dispersion medium is 1-150 g, per gram of the magnesium compound.

[0038] The second object of the present application is to provide a spherical catalyst component prepared by the above preparation method.

[0039] The third object of the present application is to provide a catalyst system for olefin polymerization reaction corresponding to the above objects, which comprises:

[0040] (1) at least one selected from the group consisting of the spherical catalyst components prepared by the above preparation method;

[0041] (2) an aluminum alkyl compound; and

[0042] (3) optionally, an external electron donor compound.

[0043] Optionally, according to the present application, the alkylaluminum compound has a general formula of AlR' n X" 3-n wherein R' is selected from hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, particularly an alkyl group, an aralkyl group, an aryl group, and the like; X" is a halogen; and n is an integer of 1 to 3.

[0044] Optionally, the alkylaluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, and ethylaluminum dichloride, preferably triethylaluminum and / or triisobutylaluminum.

[0045] According to the present application, the amount of the alkylaluminum compound can be a conventional amount in the art. Preferably, the molar ratio of the aluminum element in the alkylaluminum compound to the titanium element in the catalyst component is 5 to 5000:1, more preferably 20 to 800:1.

[0046] Optionally, according to the present application, the external electron donor compound is an organosilicon compound having a general formula of R" n' Si(OR y ) 4-n' wherein n' is an integer of 0 to 3, R" is selected from one of an alkyl group, a cycloalkyl group, an aryl group, a halogenated alkyl group, a halogen, and a hydrogen atom, and R y is selected from one of an alkyl group, a cycloalkyl group, an aryl group, and a halogenated alkyl group.

[0047] Optionally, the external electron donor compound is selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl tert-butyl dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dicyclohexyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, methylcyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyl dimethoxysilane, (1,1,1-trifluoro-2-propyl)-methyl dimethoxysilane, preferably methylcyclohexyldimethoxysilane.

[0048] According to the present application, the amount of the external electron donor compound is not particularly limited. Preferably, the molar ratio of the alkylaluminum compound to the external electron donor compound, based on the aluminum element content, is 0.1 to 500:1, preferably 1 to 300:1, more preferably 3 to 100:1.

[0049] The fourth object of the present application is to provide an olefin polymerization method corresponding to the above-mentioned objects, the method comprising: contacting one or more olefins with the above-mentioned catalyst system under olefin polymerization conditions.

[0050] Optionally, at least one of the olefins is an olefin represented by the formula CH2=CHR, wherein R is hydrogen or a C1-C6 linear or branched alkyl group.

[0051] Optionally, the olefin represented by the formula CH2=CHR is one or more of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene, and 4-methyl-1-pentene.

[0052] Optionally, the olefin is propylene or a copolymer of propylene and other olefins.

[0053] According to the present application, the polymerization of the olefins is carried out according to known methods, in liquid monomer or in liquid phase of the monomer in an inert solvent, or in gas phase, or by a combined polymerization process in gas-liquid phase.

[0054] Optionally, the conditions for the polymerization of the olefins include a polymerization temperature of 0-150°C, preferably 60-100°C, and a polymerization reaction pressure of 0.1-10 MPa, preferably 0.1-5 MPa.

[0055] Compared with the prior art, the present application has at least the following beneficial effects:

[0056] The present application adds a long-chain α-olefin compound before the precipitation of spherical solid particles, so that spherical catalyst particles with a larger average particle size can be prepared, which have excellent activity when used for propylene polymerization and have a higher polymer bulk density. In addition, the method of the present application does not need to use high-viscosity white oil as an inert dispersion medium, which is beneficial for solvent recovery; it does not need to use the inert dispersion medium and titanium tetrachloride together, which simplifies the process flow; and it can reduce the consumption of solvent and titanium tetrachloride, thereby reducing production costs. BRIEF DESCRIPTION OF DRAWINGS

[0057] The accompanying drawings are included to provide a further understanding of the present application and are incorporated in and constitute a part of the specification, illustrate embodiments of the present application and serve to explain the present application and do not limit the present application. In the drawings:

[0058] Figure 1 Microscope image of catalyst component A1. DETAILED DESCRIPTION

[0059] The present application is described in detail below by way of examples, but the scope of protection of the present application is not limited to the following description.

[0060] Unless otherwise indicated, conventional conditions or manufacturer's recommended conditions were used in the examples. Unless otherwise indicated, the reagents or instruments used were conventional products available commercially.

[0061] The test method involved in the embodiments of the present application:

[0062] 1. Catalyst particle size distribution: measured according to Malvern 2000 n-hexane dispersant laser diffraction method;

[0063] 2. The determination of polymer bulk density (BD) refers to the standard of ASTM D1895-96;

[0064] 3. The isotacticity index (II) of propylene polymer is determined by heptane extraction method: 2 grams of dried polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours, then the remaining material is dried to constant weight, and the ratio of the obtained polymer weight (g) to 2 (g) is the isotacticity.

[0065] Example 1

[0066] (1) Preparation of catalyst component

[0067] In a 1L reactor purged repeatedly with high-purity nitrogen, 10.8g of anhydrous magnesium chloride, 75.3g of toluene, 10.6g of epichlorohydrin, 46.9g of tributyl phosphate, and 116.8g of decane were sequentially added, and stirring was maintained at 300RPM for 2 hours at 60°C to obtain a magnesium-containing solution. Then 3.6g of phthalic anhydride and 5.7g of T602 were added, and stirring was maintained at 60°C for another 1 hour. The magnesium-containing solution was cooled to 0°C, and the stirring speed was increased to 400RPM. 190g of titanium tetrachloride was added dropwise, and stirring was continued for 1 hour after the addition was completed. The temperature was gradually increased to 80°C over 3 hours and maintained for 1 hour. During the temperature increase to 40°C, 3.0mL of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 3.0mL of 1-octadecene were added. After filtering the mother liquor, the solid was washed twice with 200mL of toluene. 120mL of toluene and 80mL of titanium tetrachloride were added, and the mixture was treated at 110°C for 0.5 hours to remove the filtrate. 120mL of toluene and 80mL of titanium tetrachloride were added, and the mixture was treated at 110°C for 0.5 hours to remove the filtrate. After repeating the washing with 200mL of hexane for 4 times, the catalyst component A1 was obtained by drying, and the average particle size D50 was 46.5μm. The morphology of the catalyst component A1 is shown in Figure 1

[0068] (2) Propylene polymerization

[0069] ​In a 5 liter autoclave, after sufficient replacement by nitrogen, 5 mL of triethylaluminum hexane solution (the concentration of triethylaluminum is 0.5 mmol / mL), 1 mL of cyclohexylmethyldimethoxysilane (CHMMS) hexane solution (the concentration of CHMMS is 0.1 mmol / mL), 10 mL of anhydrous hexane and 10 mg of solid catalyst component A1 were added at room temperature. The autoclave was closed, 1.0 L of hydrogen and 2.3 L of liquid propylene were added. The temperature was raised to 70°C, and the polymerization reaction was carried out at 70°C for 1 hour. After the reaction was completed, the reaction kettle was cooled and the stirring was stopped, and the reaction product was discharged to obtain an olefin polymer.

[0070] Example 2

[0071] (1) Preparation of catalyst component

[0072] Solid catalyst component A2 was prepared by the method of Example 1, except that the addition position of 1-octadecene was changed to addition in the magnesium-containing solution, and the average particle size D50 was 43.1 μm.

[0073] (2) Propylene polymerization

[0074] The polymerization conditions were the same as in Example 1, solid catalyst component A2 was used, and the polymerization data and olefin polymer data are shown in Table 1.

[0075] Example 3

[0076] (1) Preparation of catalyst component

[0077] Solid catalyst component A3 was prepared by the method of Example 1, except that the amount of 1-octadecene added was 6.0 mL, and the average particle size D50 was 50.3 μm.

[0078] (2) Propylene polymerization

[0079] The polymerization conditions were the same as in Example 1, solid catalyst component A3 was used, and the polymerization data and olefin polymer data are shown in Table 1.

[0080] Example 4

[0081] (1) Preparation of catalyst component

[0082] Solid catalyst component A4 was prepared by the method of Example 1, except that 5.0 mL of 1-dodecene was used instead of 1-octadecene, and the average particle size D50 was 41.6 μm.

[0083] (2) Propylene polymerization

[0084] The polymerization conditions were the same as in Example 1, solid catalyst component A4 was used, and the polymerization data and olefin polymer data are shown in Table 1.

[0085] Example 5

[0086] (1) Preparation of the catalyst component

[0087] The solid catalyst component A5 was prepared according to the procedure of Example 1, except that 158.2 g of hexane was used instead of decane, and the average particle size D50 was 58.1 μm.

[0088] (2) Propylene polymerization

[0089] The polymerization conditions were the same as in Example 1, using the solid catalyst component A5, and the polymerization data and the data of the olefin polymer are reported in Table 1.

[0090] Comparative Example 1

[0091] (1) Preparation of the catalyst component

[0092] The solid catalyst component D1 was prepared according to the procedure of Example 1, except that no 1-octadecene was added, and the average particle size D50 was 43.7 μm.

[0093] (2) Propylene polymerization

[0094] The polymerization conditions were the same as in Example 1, using the solid catalyst component D1, and the polymerization data and the data of the olefin polymer are reported in Table 1.

[0095] Comparative Example 2

[0096] (1) Preparation of the catalyst component

[0097] The solid catalyst component D2 was prepared according to the procedure of Example 5, except that no 1-octadecene was added, and the average particle size D50 was 55.2 μm.

[0098] (2) Propylene polymerization

[0099] The polymerization conditions were the same as in Example 1, using the solid catalyst component D2, and the polymerization data and the data of the olefin polymer are reported in Table 1.

[0100] Comparative Example 3

[0101] (1) Preparation of the catalyst component

[0102] The solid catalyst component D3 was prepared according to the procedure of Example 1, except that the addition of 1-octadecene was moved to the first titanium treatment, and the average particle size D50 was 44.6 μm.

[0103] (2) Propylene polymerization

[0104] The polymerization conditions were the same as in Example 1, using the solid catalyst component D3, and the polymerization data and the data of the olefin polymer are reported in Table 1.

[0105] Table 1.

[0106]

[0107]

[0108] As can be seen from the above examples and comparative examples, by adding long-chain α-olefins before the precipitation of spherical solids, the prepared spherical olefin polymerization catalyst components can have higher polymerization activity and higher polymer packing density.

[0109] Any numerical value mentioned in this invention, if there is only a two-unit interval between any minimum and any maximum value, includes all values ​​that increase by one unit each time from the minimum to the maximum value. For example, if the amount of a component, or the value of a process variable such as temperature, pressure, or time, is stated as 50-90, in this specification it means specifically listing values ​​such as 51-89, 52-88… and 69-71 and 70-71, etc. For non-integer values, it may be appropriately considered that a unit is 0.1, 0.01, 0.001, or 0.0001. These are merely some specifically specified examples. In this application, in a similar manner, all possible combinations of numerical values ​​between the listed minimum and maximum values ​​are considered to have been disclosed.

[0110] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A process for the preparation of a spherical catalyst component, characterized in that, Comprising the following steps: S1. Contacting a magnesium compound, an organic epoxy compound, an organic phosphorus compound and an inert dispersion medium in an organic solvent to form a magnesium-containing solution; S2. Contacting the magnesium-containing solution with a titanium-containing compound in the presence of a co-precipitant and optionally a surfactant to form a mixture; S3. Subjecting the mixture to a temperature raising treatment to precipitate spherical solid, and obtaining the spherical catalyst component by filtering, washing and drying; wherein a long-chain α-olefin compound as shown in formula (I) is added before the precipitation of the spherical solid; CH2=CHR a formula (I) wherein R a a straight or branched chain alkyl group of from 8 to 24 carbon atoms; The amount of the organic epoxy compound is 0.1-10 moles, the amount of the organic phosphorus compound is 0.1-10 moles, the amount of the organic solvent is 0.5-40 moles, the amount of the titanium-containing compound is 0.5-25 moles, the amount of the co-precipitant is 0.01-1 moles, the amount of the internal electron donor compound is 0.01-1 moles, and the amount of the long-chain α-olefin compound is 0.01-1 moles, all based on per mole of the magnesium compound.

2. The production method according to claim 1, characterized by, The long-chain α-olefin compound can be added at any position before the precipitation of the spherical solid, and the long-chain α-olefin compound can be added as a whole at one time or in multiple times in parts; And / or, the long-chain α-olefin compound is selected from one or more of 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-docosene, 1-tetracosene and 1-hexacosene.

3. The production method according to claim 1 or 2, characterized by, The magnesium compound has a general formula of MgX2, wherein X is halogen; And / or, the organic epoxy compound is selected from one or more of oxirane, oxetane, epichlorohydrin, epichloropropane, butylene oxide, butadiene oxide, butadiene dioxide, methyl glycidyl ether and diglycidyl ether; And / or, the organic phosphorus compound is selected from one or more of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triamyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite and benzyl phosphite; And / or, the inert dispersion medium is selected from one or more of hexane, heptane, octane, nonane, decane, dodecane and cyclohexane; And / or, the organic solvent is an aromatic hydrocarbon compound; And / or, the titanium-containing compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, chlorotriethoxy titanium, dichlorodiethoxy titanium and chloroethoxy titanium; And / or, the co-precipitant is selected from at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether and dipentyl ether; And / or, the surfactant is selected from at least one of (meth)acrylic alkyl ester polymer and (meth)acrylic alkyl ester copolymer.

4. The production method according to claim 3, characterized by, X is bromine, chlorine or iodine; And / or, the organic solvent is one or more of toluene, ethylbenzene, benzene and xylene.

5. The production method according to claim 4, characterized by, The magnesium compound is at least one of magnesium dichloride, magnesium dibromide and magnesium diiodide.

6. The production method according to claim 1 or 2, characterized by, In the step S1, the contacting condition includes that the contacting temperature is 10-100℃ and the contacting time is 0.05-10 hours. In the step S2, the way of contacting the magnesium-containing solution with the titanium-containing compound to form the mixture is dropping the titanium-containing compound into the magnesium-containing solution. In the step S2, the contacting temperature of the titanium-containing compound and the magnesium-containing solution is -35-60℃ and the contacting time is 1 minute-10 hours. In the step S2, the adding temperature of the surfactant is 10-100℃. In the step S3, the temperature raising treatment includes raising the mixture to 50-110℃, solidifying and precipitating spherical solid, obtaining a suspension, and stirring the suspension at 50-130℃ for 10 minutes-24 hours; the temperature raising treatment time is 1 minute-36 hours.

7. The production method according to claim 6, wherein In the step S1, the contacting condition includes that the contacting temperature is 20-80℃ and the contacting time is 0.1-6 hours. In the step S2, the contacting temperature of the titanium-containing compound and the magnesium-containing solution is -20-40℃ and the contacting time is 3 minutes-7 hours. In the step S2, the adding temperature of the surfactant is 10-80℃. In the step S3, the temperature raising treatment time is 3 minutes-24 hours.

8. The preparation method according to claim 7, characterized in that, In the step S2, the adding temperature of the surfactant is 10-60℃.

9. The production method according to claim 1 or 2, characterized by, The preparation method further includes adding an internal electron donor compound, and the adding position of the internal electron donor compound is any position after the temperature raising treatment starts. In the step S2, the adding temperature of the surfactant is 10-60℃. In the step S2, the adding temperature of the surfactant is 10-60℃.

10. The method of claim 9, wherein, The internal electron donor compound is at least one of di-n-butyl phthalate, diisobutyl phthalate, 2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, diethyl 2,3-diisopropyl succinate, diisobutyl 2,3-diisopropyl succinate, di-n-butyl 2,3-diisopropyl succinate, dimethyl 2,3-diisopropyl succinate, diisobutyl 2,2-dimethyl succinate, diisobutyl 2-ethyl-2-methyl succinate, diethyl 2-ethyl-2-methyl succinate, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 9,9-dimethoxymethyl fluorene.

11. The preparation method according to claim 9, characterized in that, The adding temperature of the internal electron donor compound is 10-150℃.

12. The method of claim 11, wherein, The adding temperature of the internal electron donor compound is 10-100℃.

13. The preparation method according to claim 9, characterized in that, The contact time of the spherical solid with the internal electron donor compound is 0.05-8 hours.

14. The method of claim 13, wherein, The contact time of the spherical solid with the internal electron donor compound is 1-6 hours.

15. A spherical catalyst component prepared by the preparation method of any one of claims 1-14.

16. A catalyst system for the polymerization of olefins, characterized in that, The catalyst system comprises: (1) the catalyst component of claim 15; (2) an alkyl aluminum compound; and (3) optionally, an external electron donor compound.

17. The catalyst system of claim 16, wherein, The alkyl aluminum compound is of the general formula AlR' n X" 3-n The compound is shown below, wherein R' is selected from hydrogen or a hydrocarbon group having 1 to 20 carbon atoms; X" is a halogen, and n is an integer from 1 to 3. The molar ratio of aluminum element in the alkyl aluminum compound to titanium element in the catalyst component is 5-5000:1; and / or the external electron donor compound is an organosilicon compound having the general formula R n' Si(OR y ) 4-n' wherein n' is an integer from 0 to 3, R" is selected from one of an alkyl group, a cycloalkyl group, an aryl group, a halogenated alkyl group, a halogen, and a hydrogen atom, and R y is selected from one of an alkyl group, a cycloalkyl group, an aryl group, and a halogenated alkyl group; The molar ratio of aluminum element in the alkyl aluminum compound to titanium element in the catalyst component is 20-800:1; 18. The catalyst system of claim 17, wherein, R' is an alkyl group, an aralkyl group, or an aryl group; The molar ratio of aluminum element in the alkyl aluminum compound to titanium element in the catalyst component is 20-800:1; The molar ratio of aluminum element in the alkyl aluminum compound to titanium element in the catalyst component is 20-800:1; 19. The catalyst system of claim 17, wherein, The alkyl aluminum compound is selected from at least one of trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum, diethyl aluminum hydride, diisobutyl aluminum hydride, diethyl aluminum chloride, diisobutyl aluminum chloride, ethyl aluminum sesquichloride, and ethyl aluminum dichloride; The molar ratio of aluminum element in the alkyl aluminum compound to titanium element in the catalyst component is 20-800:1; 20. The catalyst system of claim 17, wherein, The external electron donor compound is selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl tert-butyl dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dicyclohexyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, methylcyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyl dimethoxysilane, (1,1,1-trifluoro-2-propyl)-methyl dimethoxysilane.

21. A process for the polymerization of olefins, characterized in that, The method comprises: contacting one or more olefins with the catalyst system of any one of claims 16-20 under olefin polymerization conditions.

22. The method of claim 21, wherein, At least one of the olefins is an olefin represented by the formula CH2=CHR, wherein R is hydrogen or a C1-C6 linear or branched alkyl group; The olefin polymerization conditions comprise: a polymerization reaction temperature of 0-150°C, and a polymerization reaction pressure of 0.1-10 MPa.

23. The method of claim 22, wherein, The olefin represented by the formula CH2=CHR is one or more of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene, and 4-methyl-1-pentene.

24. The method of claim 23, wherein, The olefin is propylene or a copolymer of propylene and other olefins.

25. The method of claim 22, wherein, The olefin polymerization conditions comprise: a polymerization reaction temperature of 60-100°C, and a polymerization reaction pressure of 0.1-5 MPa.

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