Carrier for olefin polymerization catalyst and application thereof, catalyst for olefin polymerization and application thereof, and olefin polymerization method

Abstract

Disclosed are a spherical carrier for olefin polymerization catalysts, a preparation method therefor and an application thereof, a catalyst and an application thereof, the carrier comprising at least one magnesium-containing compound having a structure represented by formula (1). The spherical carrier for olefin polymerization catalysts of the present invention has a relatively good particle morphology, and substantially no abnormally morphological particles will appear. The provided method may prepare a carrier having a small particle size and greatly expands the particle size range of the preparable carrier. When the catalyst prepared by using the obtained carrier is used for olefin polymerization, polymerization activity is good, substantially no abnormally morphological material is present, and hydrogen response is good. (FORMULA 1)

Description

Catalyst carrier for olefin polymerization and use thereof, catalyst for olefin polymerization and use thereof, and olefin polymerization method Technical Field

[0001] The present invention relates to the field of olefin polymerization catalysts, and in particular to a spherical catalyst carrier for olefin polymerization, a method for preparing a spherical catalyst carrier for olefin polymerization, a spherical carrier prepared by the method, use of the spherical carrier in preparing a catalyst for olefin polymerization, a catalyst containing the spherical carrier, and use of the catalyst in catalyzing olefin polymerization reactions. Background Art

[0002] Ziegler-Natta catalysts prepared from magnesium chloride alcoholates, particularly those prepared from spherical magnesium chloride alcoholates, typically exhibit significantly better catalytic performance than other supported catalysts when used in olefin polymerization. Therefore, most catalysts currently used in olefin polymerization are prepared by loading titanium halides onto magnesium chloride alcoholates.

[0003] However, when the catalyst prepared from the magnesium chloride alcoholate is used for olefin polymerization, the polymer particles are easily broken during the polymerization process, resulting in a large amount of polymer fine powder.

[0004] To overcome this shortcoming, attempts have been made to introduce electron donor compounds into the preparation of magnesium chloride alcoholate supports. For example, CN1397568A and CN1563112A teach the introduction of internal electron donor phthalate compounds into the synthesis of magnesium chloride alcoholate supports, thereby producing a spherical "magnesium chloride-alcohol-phthalate" support. This support is then reacted with titanium tetrachloride to form a catalyst. However, these composite spherical supports tend to become sticky during the preparation process, making it difficult to form spherical particles of an appropriate particle size.

[0005] Furthermore, most of the magnesium chloride alcoholates are produced by rapidly cooling and solidifying a high-temperature alcoholate melt at low temperatures. This technology consumes a lot of energy, is complex, and requires multiple reactors for preparation. Furthermore, the resulting alcoholate has a wide particle size distribution.

[0006] To address this issue, CN102040683A discloses a method for preparing a catalyst support by reacting a magnesium halide alcoholate with an ethylene oxide compound. However, this method often requires the addition of a surfactant and suffers from the disadvantages of unstable preparation process, prone to carrier adhesion, and poor carrier formation.

[0007] Therefore, there is still a need to develop a new method for preparing an olefin polymerization catalyst carrier.

[0008] Summary of the Invention

[0009] The purpose of the present invention is to overcome the defects of the prior art olefin polymerization catalyst carrier in that the particle morphology is poor, small-particle size carrier cannot be prepared, and the catalyst prepared from the carrier has low hydrogen adjustment sensitivity when used in olefin polymerization reaction.

[0010] The inventors unexpectedly discovered that by adding an alcohol compound and a halohydrin compound to the catalyst support during preparation to form a fluidized mixture, spray drying the mixture yields a catalyst support with a novel composition and excellent particle morphology, essentially free of irregularly shaped particles. Furthermore, the catalyst support can be prepared with very small particle sizes, broadening the range of particle sizes that can be prepared. Furthermore, the preparation process does not require the use of surfactants or inert solvents, allowing for direct synthesis of the support, resulting in a stable preparation process. Furthermore, the catalyst prepared from the support exhibits high sensitivity to hydrogen regulation when used in olefin polymerization. Based on these findings, the inventors completed the present invention.

[0011] An object of the present invention is to provide a spherical catalyst carrier for olefin polymerization, the carrier comprising at least one magnesium-containing compound having a structure represented by formula (1);

[0012]

[0013] in,

[0014] R1 is C 1-10 Alkyl;

[0015] R2 and R3 are each independently selected from H, C 1-10 and C substituted by 1-10 halogen atoms 1-10 Alkyl;

[0016] R4 is selected from C 1-10 and an alkyl group substituted with at least one halogen atom. 6-20 aromatic groups;

[0017] R5 is C 1-5 Alkyl;

[0018] X is selected from fluorine, chlorine, bromine and iodine;

[0019] m is 0.1-1.9, n is 0.1-1.9, and m+n=2; 0 <q<0.2;0<a<0.1。

[0020] Another object of the present invention is to provide a method for preparing a spherical catalyst carrier for olefin polymerization, the method comprising:

[0021] (1) first contacting the materials of component A and then applying shear force to the resulting mixture to obtain a first product, wherein component A contains a magnesium halide of the general formula MgXY and a first alcohol compound of the general formula R1OH;

[0022] (2) contacting the first product with component B for a second time to obtain a second product, wherein component B contains an oxirane compound having a structure represented by formula (2);

[0023] (3) contacting the second product with component C for a third time to obtain a third product, wherein component C contains a halohydrin of the general formula R4OH and a second alcohol compound of the general formula R5OH;

[0024] (4) spray drying the third product;

[0025]

[0026] Wherein, in the formula R1OH, R1 is C 1-10 Alkyl;

[0027] In formula (2), R2 and R3 are each independently selected from H, C 1-10 and C substituted by 1-10 halogen atoms 1-10 Alkyl;

[0028] In the formula R4OH, R4 is selected from C 1-10 and an alkyl group substituted with at least one halogen atom. 6-20 aromatic groups;

[0029] In the formula R5OH, R5 is C 1-5 Alkyl;

[0030] In the formula MgXY, X is selected from fluorine, chlorine, bromine and iodine; Y is selected from fluorine, chlorine, bromine, iodine, C 1-6 Alkyl, C 1-6 Alkoxy, C 6-14 The aryl and C 6-14 aryloxy;

[0031] The amounts of component A, component B and component C are such that the obtained spherical carrier contains a magnesium-containing compound having a structure represented by formula (1):

[0032]

[0033] Wherein, m is 0.1-1.9, n is 0.1-1.9, and m+n=2; 0 <q<0.2;0<a<0.1;

[0034] Wherein, in step (3), relative to 1 mol of the magnesium halide, the amount of the halohydrin used is 0.05-6.5 mol, and the amount of the second alcohol compound used is 5-100 mol.

[0035] Another object of the present invention is to provide a spherical carrier prepared by the above method.

[0036] Another object of the present invention is to provide use of the spherical carrier in preparing a catalyst for olefin polymerization.

[0037] Another object of the present invention is to provide a catalyst containing the above-mentioned spherical carrier.

[0038] Another object of the present invention is to provide use of the above catalyst in catalyzing olefin polymerization.

[0039] Compared with the prior art, the present invention has at least the following advantages:

[0040] (1) The spherical catalyst carrier for olefin polymerization provided by the present invention has a good particle morphology and basically no irregular particles. The method provided by the present invention does not require the addition of surfactants or solvents, the preparation process is stable, and a carrier with very small particle size can be prepared, which greatly broadens the range of particle size that can be prepared for the carrier.

[0041] (2) The catalyst prepared using the spherical carrier is used for olefin polymerization, such as propylene polymerization, and has good polymerization activity and high hydrogen regulation sensitivity, and has great industrial application prospects.

[0042] Other features and advantages of the present invention will be described in detail in the following detailed description.

[0043] BRIEF DESCRIPTION OF THE DRAWINGS

[0044] FIG1 is an electron micrograph of the spherical carrier obtained from Example 1.

[0045] DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0046] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0047] As used herein, the term "alkyl" refers to a paraffinic hydrocarbon group that can be derived from an alkane by removing one or more hydrogen atoms from the chemical formula and can be linear, branched, or cyclic. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, and the like.

[0048] The term "aryl" as used herein refers to an aromatic hydrocarbon radical that can be derived from an aromatic hydrocarbon by removing one or more hydrogen atoms from the chemical formula. Examples of aryl radicals include, but are not limited to, phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, naphthyl, benzyl, phenethyl, and the like.

[0049] The term "halogen" as used herein refers to fluorine, chlorine, bromine or iodine.

[0050] The term "C substituted by 1 to 10 halogen atoms" as used herein 1-10 "Alkyl" refers to C 1-10 A group formed by replacing 1-10 hydrogen atoms in an alkyl group with halogen atoms. Multiple hydrogen atoms may be replaced by halogen atoms on the same carbon atom or on different carbon atoms. When multiple halogen atoms are substituted, the halogen atoms may be the same or different. Examples include, but are not limited to, -CF3, -CH2CF3, -CH2CF2H, -CF2CF3, -CF2CH2CF2H, -CH2CF2CF2H, -CH2CH2CH2Cl, and -CH2CH2CH2Br.

[0051] Similarly, the term "C substituted by at least one (or at least two) halogen atoms" as used herein 1-10 "alkyl" and "C substituted by at least one (or at least two) halogen atoms 6-20 The aryl groups are C 1-10 The alkyl group and C 6-20 A group formed by replacing at least one (or at least two) hydrogen atoms in an aryl group with a halogen atom. When more than one hydrogen atom is replaced by a halogen atom, the hydrogen atoms may be hydrogen atoms on one carbon or on different carbons, and the halogen atoms may be the same or different. 1-10 Examples of alkyl groups include, but are not limited to, CF3, -CH2CF3, -CH2CF2H, -CF2CF3, -CF2CH2CF2H, -CH2CF2CF2H, -CH2CH2CH2Cl, -CH2CH2CH2Br, and the like. C substituted by at least one halogen atom6-20 Examples of aryl groups include, but are not limited to, 2-, 3-, or 4-chlorophenyl, 2-, 3-, or 4-bromophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-dichlorophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-dibromophenyl, and 4-trifluoromethylphenyl.

[0052] As mentioned above, in a first aspect, the present invention provides a spherical catalyst carrier for olefin polymerization, the carrier comprising at least one magnesium-containing compound having a structure represented by formula (1);

[0053]

[0054] in,

[0055] R1 is C 1-10 a linear, branched or cyclic alkyl group;

[0056] R2 and R3 are each independently selected from H, C 1-10 A linear or branched alkyl group and a C 1-10 a straight-chain or branched-chain alkyl group;

[0057] R4 is selected from C 1-10 a linear, branched or cyclic alkyl group and a C 6-20 aromatic groups;

[0058] R5 is C 1-5 Alkyl;

[0059] X is selected from fluorine, chlorine, bromine and iodine;

[0060] m is 0.1-1.9, n is 0.1-1.9, and m+n=2; 0 <q<0.2;0<a<0.1。

[0061] In some embodiments, the support of the present invention consists essentially of the at least one magnesium-containing compound having the structure represented by formula (1).

[0062] In some embodiments, the carrier of the present invention is composed of the at least one magnesium-containing compound having a structure represented by formula (1).

[0063] Preferably, R1 is C 1-8 More preferably, R1 is C 1-6 a linear, branched or cyclic alkyl group.

[0064] Preferably, R2 and R3 are each independently selected from H, C 1-5A linear or branched alkyl group and a C 1-5 A straight-chain or branched-chain alkyl group.

[0065] Preferably, R4 is selected from C 1-10 a linear, branched or cyclic alkyl group and a C 6-20 The halogen atom is preferably at least one selected from a chlorine atom, a bromine atom and an iodine atom.

[0066] Preferably, R5 is C 1-2 of alkyl.

[0067] Preferably, X is selected from chlorine and bromine.

[0068] Preferably, m is 0.3-1.7, more preferably m is 0.6-1.4, still more preferably m is 0.8-1.2.

[0069] Preferably, n is 0.3-1.7, more preferably n is 0.6-1.4, still more preferably n is 0.8-1.2.

[0070] Preferably, 0.001 <q<0.15。

[0071] Preferably, 0.001 <a<0.08。

[0072] Preferably, the average particle diameter of the spherical carrier is 2-100 microns, and the particle size distribution is less than 2. More preferably, the average particle diameter of the spherical carrier is 2-19 microns, and the particle size distribution is 0.6-1.6.

[0073] In order to enable the catalyst prepared by using the spherical carrier to obtain olefin polymers with higher bulk density when used for olefin polymerization, it is further preferred that the average particle diameter of the spherical carrier is 2-10 microns and the particle size distribution is 0.6-1.

[0074] In the present invention, the average particle diameter refers to D50.

[0075] In the present invention, the size of the particle size distribution is defined as (D90-D10) / D50.

[0076] In the present invention, the average particle diameter and particle size distribution of the catalyst support are measured using a laser particle size analyzer such as Master Sizer 2000 (manufactured by Malvern Instruments Ltd). In the test, hexane, for example, can be used as an inert dispersion medium.

[0077] As mentioned above, in a second aspect, the present invention provides a method for preparing a spherical catalyst carrier for olefin polymerization, the method comprising:

[0078] (1) first contacting the materials of component A and then applying shear force to the resulting mixture to obtain a first product, wherein component A contains a magnesium halide of the general formula MgXY and a first alcohol compound of the general formula R1OH;

[0079] (2) contacting the first product with component B for a second time to obtain a second product, wherein component B contains an oxirane compound having a structure represented by formula (2);

[0080] (3) contacting the second product with component C for a third time to obtain a third product, wherein component C contains a halohydrin of the general formula R4OH and a second alcohol compound of the general formula R5OH;

[0081] (4) spray drying the third product;

[0082]

[0083] Wherein, in the formula R1OH, R1 is C 1-10 a linear, branched or cyclic alkyl group;

[0084] In formula (2), R2 and R3 are each independently selected from H, C 1-10 A linear or branched alkyl group and a C substituted by 1 to 10 halogen atoms 1-10 A straight-chain or branched alkyl group;

[0085] In the formula R4OH, R4 is selected from C 1-10 a linear, branched or cyclic alkyl group and a C 6-20 aromatic groups;

[0086] In the formula R5OH, R5 is C 1-5 Alkyl;

[0087] In the formula MgXY, X is selected from fluorine, chlorine, bromine and iodine; Y is selected from fluorine, chlorine, bromine, iodine, C 1-6 Straight or branched alkyl, C 1-6 Straight-chain or branched alkoxy, C 6-14 The aryl and C 6-14 aryloxy;

[0088] The amounts of component A, component B, and component C are such that the resulting spherical carrier comprises, consists essentially of, or consists of a magnesium-containing compound having a structure represented by formula (1):

[0089]

[0090] In formula (1), R1-R5 and X are as defined above, m is 0.1-1.9, n is 0.1-1.9, and m+n=2; <q<0.2;0<a<0.1;

[0091] Wherein, in step (3), relative to 1 mol of the magnesium halide, the amount of the halohydrin used is 0.05-6.5 mol, and the amount of the second alcohol compound used is 5-100 mol.

[0092] In the second aspect of the present invention, the definitions and preferences of the R1, R2, R3, R4 and R5 groups are the same as those in the first aspect of the present invention.

[0093] According to a preferred embodiment of the present invention, in the formula MgXY, X is selected from chlorine and bromine, and Y is selected from chlorine, bromine, C 1-5 Straight or branched alkyl, C 1-5 Straight-chain or branched alkoxy, C 6-10 The aryl and C 6-10 of aryloxy.

[0094] More preferably, the magnesium halide is selected from at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride, and further preferably is magnesium chloride.

[0095] According to another preferred embodiment of the present invention, in the formula R1OH, R1 is C 1-8 a linear, branched or cyclic alkyl group.

[0096] More preferably, the first alcohol compound is at least one selected from ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol and 2-ethylhexanol.

[0097] According to another preferred embodiment of the present invention, in formula (2), R2 and R3 are each independently selected from H, C 1-5 A linear or branched alkyl group and a C 1-5 A straight-chain or branched-chain alkyl group.

[0098] More preferably, the oxirane compound is at least one selected from ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epichlorohydrin, epibromohydrin and epibromobutylene oxide.

[0099] According to some embodiments of the present invention, the halohydrin may be a monohalohydrin or a polyhalohydrin, preferably a chlorohydrin, a bromohydrin or an iodohydrin, for example, 2,2,2-trichloroethanol, 2,2-dichloroethanol, 2-chloroethanol, 3-chloro-1-propanol, 6-chloro-1-hexanol, 3-bromo-1-propanol, 5-chloro-1-pentanol, 4-chloro-1-butanol, 2-chlorocyclohexanol, 1,2-dichloroethanol, 1,3-dichloropropanol, 1,4-dichlorobutanol or 2-iodoethanol, etc.

[0100] According to a preferred embodiment of the present invention, in the formula R4OH, R4 is selected from C 1-10 a linear, branched or cyclic alkyl group and a C 6-20 The halogen atom is selected from at least one of a chlorine atom, a bromine atom and an iodine atom.

[0101] Preferably, the halogenated alcohol is selected from at least one of 2,2,2-trichloroethanol, 2,2-dichloroethanol, 1,2-dichloroethanol, 1,3-dichloropropanol and 1,4-dichlorobutanol.

[0102] According to the present invention, the second alcohol compound is C 1-5 At least one of the alcohol compounds, for example, ethanol, methanol, n-propanol, isopropanol, n-butanol or isobutanol. According to a preferred embodiment of the present invention, in the formula R5OH, R5 is C 1-2 The alkyl group, that is, the second alcohol compound is methanol and / or ethanol.

[0103] The inventors have found that when the amount of the halohydrin compound and the alcohol compound used is too large, the resulting catalyst support forms lumps and cannot be subjected to subsequent operations.

[0104] In the method disclosed in the present invention, relative to 1 mol of the magnesium halide, the amount of the first alcohol compound is 1-30 mol, the amount of the ethylene oxide compound is 1-10 mol, the amount of the halohydrin is 0.05-6.5 mol, and the amount of the second alcohol compound is 5-100 mol.

[0105] Preferably, relative to 1 mol of the magnesium halide, the amount of the first alcohol compound is 6-22 mol, the amount of the ethylene oxide compound is 2-6 mol, the amount of the halohydrin is 1-5 mol, and the amount of the second alcohol compound is 8-80 mol, more preferably 31-50 mol.

[0106] It should be noted that the trace amount of water carried by the above-mentioned reactants will also participate in the reaction to form the spherical carrier. Therefore, the prepared spherical carrier may contain trace amounts of water from the reaction raw materials and the reaction medium, which should not be understood by those skilled in the art as a limitation of the present invention.

[0107] Preferably, in step (1), the first contact is carried out under stirring conditions, and the conditions for the first contact include: temperature of 40-130°C, preferably 50-130°C, more preferably 80-120°C, time of 0.3-24h, preferably 0.5-10h, more preferably 0.5-5h.

[0108] More preferably, in step (1), the conditions for the first contact include: temperature of 80-100° C., and time of 0.5-3 h.

[0109] In step (1), the present invention does not particularly limit the specific operation method of applying shear force, and it can be carried out by methods known to those skilled in the art. For example, low-speed shearing or high-speed shearing is used. Preferably, when low-speed shearing is used, the stirring rate of the low-speed shearing is 400-800 rpm. The high-speed shearing method is well known to those skilled in the art, for example, it is carried out by using the high stirring speed disclosed in CN1330086A. In addition, the shear force application operation can also be carried out with reference to the methods disclosed in the following patent applications, such as CN1580136A discloses that a solution containing a liquid magnesium halide compound is subjected to rotational dispersion in a supergravity bed (the rotation speed is 100-3000 rpm); CN1463990A discloses that a solution containing a liquid magnesium halide adduct is output in an emulsifier at a speed of 1500-8000 rpm; and US6020279A discloses that a shear force is applied to a solution containing a liquid magnesium halide adduct by spraying.

[0110] Preferably, in step (2), the conditions for the second contact include: a temperature of 30-130°C, preferably 50-120°C, and a time of 10-180 min, preferably 20-60 min;

[0111] More preferably, in step (2), the conditions for the second contact include: a temperature of 80-100° C. and a time of 20-50 min.

[0112] According to a preferred embodiment of the present invention, step (3) further includes washing the second product with an inert solvent and then contacting it with the components in component C for the third time. Preferably, the inert solvent is selected from at least one of pentane, hexane, heptane, petroleum ether and gasoline.

[0113] The present invention has no particular restrictions on the specific conditions of the third contact in step (3), as long as the component C and the second product can be fully contacted to form a fluid. However, in order to obtain a catalyst support with better performance, preferably, in step (3), the conditions of the third contact include: carrying out under stirring conditions, a temperature of 0-120°C, and a time of 0.5-6h.

[0114] The present invention has no particular limitation on the specific manner of the third contact in step (3). The halohydrin and the second alcohol compound may be mixed and contacted with the second component simultaneously, or the halohydrin and the second alcohol compound may be contacted with the second component successively in any order.

[0115] In the present invention, the spray drying conditions can be based on existing conditions for forming catalyst supports for olefin polymerization. According to a preferred embodiment of the present invention, the spray drying is carried out in a sprayer equipped with an atomizing nozzle, the atomizing nozzle comprising a material conduit and a nozzle head. The third product is introduced into the nozzle head through the material conduit and sprayed into the sprayer's tower containing an inert medium for evaporation and solidification. Preferably, the temperature of the third product in the material conduit is between 0°C and 80°C, and the temperature of the third product in the nozzle head is between 80°C and 180°C; more preferably, the temperature of the third product in the nozzle head is between 120°C and 180°C.

[0116] In the present invention, in step (4), preferably, the spray drying conditions include: a temperature of 60-200° C., more preferably 90-150° C. In the present invention, the spray drying temperature refers to the temperature of the inert medium in the sprayer.

[0117] In the present invention, the inert medium may include a protective gas medium and / or an inert liquid medium. There is no particular limitation on the type of the protective gas medium. For example, it may be nitrogen, an inert gas medium such as helium, or other suitable gases such as carbon dioxide. The inert liquid medium is any liquid medium commonly used in the art that does not chemically react with the reactants and reaction products. Preferably, the inert liquid medium is silicone oil and / or an inert liquid hydrocarbon solvent. More preferably, the inert liquid medium is selected from at least one of kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methylethyl silicone oil, phenyl silicone oil and methylphenyl silicone oil, and is further preferably white oil.

[0118] In the present invention, the amount of the inert liquid medium in the sprayer can be selected according to the amount of the magnesium halide of the general formula MgXY, preferably 0.8-10 L / mole of magnesium halide, more preferably 2-8 L / mole of magnesium halide.

[0119] In the method described in the second aspect of the present invention, conventional post-processing means such as solid-liquid separation, washing, drying, etc. in the art are also included, and the present invention has no particular restrictions on this. The solid-liquid separation can adopt various existing methods that can achieve separation of solid and liquid phases, such as suction filtration, filter press or centrifugal separation, etc. Preferably, the method of solid-liquid separation is filter press. The present invention does not particularly limit the conditions for filter press, and the separation of solid and liquid phases is achieved as fully as possible. The washing can be carried out by washing the obtained solid phase product using methods well known to those skilled in the art, for example, the obtained solid phase product can be washed using inert hydrocarbon solvents (such as pentane, hexane, heptane, petroleum ether and gasoline). The present invention has no particular restrictions on the specific conditions of the drying, for example, the drying temperature can be 20-70°C, the drying time can be 0.5-10h, and the drying can be carried out under normal pressure or reduced pressure.

[0120] The inventors discovered that by using specific types and amounts of alcohol compounds and halohydrin compounds in combination with components such as magnesium halide and ethylene oxide compounds, and matching them with a spray drying method, a catalyst carrier with a novel composition and good particle morphology can be obtained. The catalyst carrier basically does not contain irregularly shaped particles; and the preparation process does not require the addition of surfactants, and the process is stable.

[0121] In particular, the method provided by the present invention can prepare a carrier with a very small particle size, greatly expanding the range of particle sizes that can be prepared for the carrier; and the catalyst prepared from the carrier has a high hydrogen regulation sensitivity when used for olefin polymerization.

[0122] As mentioned above, in the third aspect, the present invention provides a spherical carrier prepared by the method described in the second aspect.

[0123] The inventors have found that the spherical catalyst carrier prepared by the method of the present invention has a good particle morphology and basically no irregular-shaped particles appear.

[0124] As mentioned above, in a fourth aspect, the present invention provides use of the spherical carrier described in the first or third aspect in preparing a catalyst for olefin polymerization.

[0125] As mentioned above, in the fifth aspect, the present invention provides a catalyst containing the spherical carrier described in the first aspect or the third aspect.

[0126] The method for preparing a catalyst for olefin polymerization from a spherical carrier and the catalyst obtained therefrom are known to those skilled in the art. In the present invention, there is no particular restriction on the composition of the catalyst, and it can be the composition of the catalyst for olefin polymerization existing in the art. However, in order to obtain a catalyst suitable for olefin polymerization, especially propylene polymerization, preferably, the catalyst contains the carrier, a titanium halide compound and an electron donor compound. Preferably, the titanium halide is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetra-n-butoxytitanium, tetraethoxytitanium, tri-n-butoxytitanium monochloride, di-n-butoxytitanium dichloride, trichloro-n-butoxytitanium, triethoxytitanium monochloride, diethoxytitanium dichloride, trichloro-ethoxytitanium and titanium trichloride. Preferably, the electron donor compound is selected from at least one of phthalates such as diisobutyl phthalate, carboxylic acid glycol esters, phosphates, and ethers such as 1,3-diethers. At the same time, the present invention does not particularly limit the content of each component in the catalyst, and those skilled in the art can make reasonable adjustments and designs according to actual needs.

[0127] The present invention is not particularly limited to the preparation method of the catalyst; existing methods for preparing olefin polymerization catalysts in the art can be employed. In one embodiment, the olefin polymerization catalyst is prepared by treating the spherical support with a titanium halide compound, optionally in an inert liquid medium, and optionally introducing an internal electron donor compound into the support before, during, or after the treatment. A specific operating process is described in the examples below, which should not be construed as limiting the present invention by those skilled in the art.

[0128] As mentioned above, in the sixth aspect, the present invention provides the use of the catalyst described in the fifth aspect in catalyzing olefin polymerization reactions.

[0129] The present invention does not particularly limit the specific operating method of the application. Those skilled in the art can use conventional methods for olefin polymerization in the art to carry out the operation, and the present invention will not be described in detail here. The present invention hereinafter lists a specific operating process, which should not be understood by those skilled in the art as limiting the present invention.

[0130] Thus, in one embodiment, the present invention provides an olefin polymerization process comprising contacting at least one C2-C10 olefin monomer and optional comonomer with the catalyst under polymerizable conditions to form an olefin polymer, and recovering the olefin polymer.

[0131] The inventors have found that the catalyst prepared from the spherical carrier provided by the present invention has good polymerization activity, basically no irregular materials appear, and significantly higher hydrogen adjustment sensitivity than the existing technology when used for olefin polymerization, especially propylene polymerization, and has great industrial application prospects.

[0132] The present invention will be described in detail below with reference to examples.

[0133] In the following examples, unless otherwise specified, all raw materials used were commercially available and were used as received.

[0134] 1,3-Dichloropropanol was purchased from J&K Company;

[0135] Epichlorohydrin was purchased from J&K Company;

[0136] Diisobutyl phthalate was purchased from J&K Company;

[0137] Titanium tetrachloride was purchased from J&K;

[0138] Triethylaluminum was purchased from J&K;

[0139] Methylcyclohexyldimethoxysilane was purchased from J&K Company.

[0140] In the following examples, the performance involved is obtained by testing in the following ways:

[0141] 1. Average particle diameter and particle size distribution of the catalyst support: measured using a Masters Sizer 2000 particle size analyzer manufactured by Malvern Instruments, using hexane as the dispersion medium;

[0142] 2. Morphology of catalyst support: observed using an XL-30 field emission electron microscope produced by FEI Company, USA;

[0143] 3. Structure and composition of the catalyst support: The support was tested by 1H-NMR using an AVANCE 300 nuclear magnetic resonance spectrometer from Bruker, Switzerland, and by a PY-2020iD pyrolyzer from Fronteerlab, a TraceGC Ultra chromatograph from Thermo Fisher, and a DSQⅡ mass spectrometer from Thermo Fisher.

[0144] 4. Catalyst activity: evaluated by the ratio of the weight of the product obtained after polymerization to the weight of the catalyst used;

[0145] 5. Bulk density of polyolefin powder: measured using the method specified in GB / T 1636-2008;

[0146] 6. Melt flow rate index of polyolefin powder: measured in accordance with ISO 1133, 230°C, under a load of 2.16 kg.

[0147] In the following examples, unless otherwise specified, the application of shear force during the preparation of the catalyst support was carried out by stirring at 600 rpm.

[0148] Example 1

[0149] (1) In a 0.6 L reactor, 0.08 mol of magnesium chloride and 1.7 mol of ethanol (a first alcohol compound) were added, and the temperature was raised to 90° C. under stirring. The reaction was carried out at this temperature for 1 hour to perform a first contact, and then a shear force was applied to the resulting mixture to obtain a first product;

[0150] (2) contacting the first product with 0.48 mol of epichlorohydrin for a second time to obtain a second product, wherein the conditions of the second contact include: temperature of 90° C. and time of 30 min;

[0151] (3) After the second product is filtered, the resulting solid is thoroughly mixed with 2.5 mol of ethanol (the second alcohol compound) and 0.35 mol of 1,3-dichloropropanol (halohydrin) by stirring to form a fluid, thereby obtaining a third product;

[0152] (4) Using a sprayer B-290 having a nozzle head and a material conduit, the third product was sprayed into a 100° C. circulating nitrogen gas in a sprayer tower for spray drying. The temperature of the third product in the material conduit was 15° C., and the temperature in the nozzle head was 120° C., to obtain a spherical carrier Z1.

[0153] After testing, the structure and composition of the obtained catalyst spherical carrier Z1 are as follows:

[0154]

[0155] According to tests, the average particle diameter (D50) of the catalyst spherical carrier Z1 is 4 microns, and the particle size distribution ((D90-D10) / D50) is 0.9.

[0156] FIG1 shows a micrograph of the spherical carrier Z1. As can be seen from FIG1, the catalyst spherical carrier Z1 has a relatively regular particle morphology, a smooth surface, is substantially spherical, has a relatively concentrated particle size distribution, and has substantially no irregularly shaped particles.

[0157] During the preparation of the catalyst spherical carrier Z1, no clogging occurred at the nozzle head of the sprayer, and a total of 11.8 g of the carrier Z1 was obtained.

[0158] Example 2

[0159] (1) In a 0.6 L reactor, 0.08 mol of magnesium chloride and 1.4 mol of ethanol (a first alcohol compound) were added, the temperature was raised to 90° C. under stirring, and the reaction was carried out at a constant temperature for 1.5 hours to perform a first contact, and then a shear force was applied to the resulting mixture to obtain a first product;

[0160] (2) contacting the first product with 0.35 mol of epichlorohydrin for a second time to obtain a second product, wherein the conditions of the second contact include: temperature of 90° C. and time of 30 minutes;

[0161] (3) After the second product is filtered, the resulting solid is thoroughly mixed with 2.5 mol of ethanol (the second alcohol compound) and 0.25 mol of 1,3-dichloropropanol (halohydrin) by stirring to perform a third contact to form a fluid, thereby obtaining a third product;

[0162] (4) Using a sprayer B-290 containing a nozzle head and a material conduit, the third product is sprayed into the circulating nitrogen at 100°C in the sprayer tower for spray drying. The temperature of the third product in the material conduit is 15°C, and the temperature in the nozzle head is 120°C, to obtain a catalyst spherical carrier Z2.

[0163] After testing, the structure and composition of the obtained catalyst spherical carrier Z2 are as follows:

[0164]

[0165] According to tests, the average particle diameter (D50) of the catalyst spherical carrier Z2 is 4 microns, and the particle size distribution ((D90-D10) / D50) is 0.8.

[0166] Observation shows that the particles of the spherical carrier Z2 for olefin polymerization are relatively regular in shape, smooth in surface, and are basically spherical. The particle size distribution is relatively concentrated, and there are basically no irregular particles.

[0167] During the preparation of the catalyst spherical carrier Z2, no clogging occurred at the nozzle head of the sprayer, and a total of 11.9 g of the catalyst spherical carrier Z2 was obtained.

[0168] Example 3

[0169] (1) In a 0.6 L reactor, 0.08 mol of magnesium chloride and 1.4 mol of ethanol (a first alcohol compound) were added, and the temperature was raised to 90° C. under stirring. The reaction was carried out at a constant temperature for 1.5 hours to perform a first contact, and then a shear force was applied to the resulting mixture to obtain a first product;

[0170] (2) contacting the first product with 0.35 mol of epichlorohydrin for a second time to obtain a second product, wherein the conditions of the second contact include: temperature of 90° C. and time of 30 min;

[0171] (3) combining the solid obtained after pressure filtration of the second product with 2.5 mol of ethanol (a second alcohol compound) and 0.1 mol of 1,3-dichloropropanol (a halohydrin), stirring and performing a third contact until a fluid is formed to obtain a third product;

[0172] (4) Using a sprayer B-290 having a nozzle head and a material conduit, the third product was sprayed into the circulating nitrogen at 100° C. in the sprayer tower. The temperature of the third product in the material conduit was 15° C., and the temperature in the nozzle head was 120° C., to obtain a spherical carrier Z3.

[0173] After testing, the structure and composition of the obtained catalyst spherical carrier Z3 are as follows:

[0174]

[0175] According to tests, the average particle diameter (D50) of the catalyst spherical carrier Z3 is 5 microns, and the particle size distribution ((D90-D10) / D50) is 0.8.

[0176] Observation shows that the particles of the catalyst spherical carrier Z3 are relatively regular in shape, smooth in surface, and are basically spherical. The particle size distribution is relatively concentrated, and there are basically no irregular particles.

[0177] During the preparation of the catalyst spherical carrier Z3, no clogging occurred at the nozzle head of the sprayer, and a total of 12.0 g of the catalyst spherical carrier Z3 was obtained.

[0178] Example 4

[0179] (1) In a 0.6 L reactor, 0.08 mol of magnesium chloride and 1.4 mol of ethanol (a first alcohol compound) were added, and the temperature was raised to 90° C. under stirring, and the reaction was carried out at a constant temperature for 1.5 hours to perform a first contact, and then a shear force was applied to the resulting mixture to obtain a first product;

[0180] (2) contacting the first product with 0.35 mol of epichlorohydrin for a second time to obtain a second product, wherein the conditions of the second contact include: temperature of 90° C. and time of 30 minutes;

[0181] (3) After the second product is filtered, the resulting solid is mixed with 2.5 mol of ethanol (the second alcohol compound) and 0.25 mol of 1,3-dichloropropanol (halohydrin) and stirred, and ultrasonicated using an ultrasonic probe for a total of 6 times, each time for 30 minutes, to form a fluid to obtain a third product;

[0182] (4) Using a sprayer B-290 having a nozzle head and a material conduit, the third product is sprayed into the circulating nitrogen at 100° C. in the sprayer tower for spray drying. The temperature of the third product in the material conduit is 20° C., and the temperature in the nozzle head is 120° C., to obtain a catalyst spherical carrier Z4.

[0183] After testing, the structure and composition of the obtained catalyst spherical carrier Z4 are as follows:

[0184]

[0185] According to tests, the average particle diameter (D50) of the catalyst spherical carrier Z4 is 5 microns, and the particle size distribution ((D90-D10) / D50) is 1.0.

[0186] Observation shows that the particles of the spherical carrier Z4 for olefin polymerization are relatively regular in shape, smooth in surface, and are basically spherical. The particle size distribution is relatively concentrated, and there are basically no irregular particles.

[0187] During the preparation of the catalyst spherical carrier Z4, no clogging occurred at the nozzle head of the sprayer, and a total of 12.4 g of the catalyst spherical carrier Z4 was obtained.

[0188] Comparative Example 1

[0189] (1) In a 0.6 L reactor, 0.08 mol of magnesium chloride and 1.4 mol of ethanol were added, and the temperature was raised to 90°C with stirring. The reaction was carried out at this temperature for 1.5 hours. Then, 0.35 mol of epichlorohydrin was added and the reaction was carried out at 90°C for 30 minutes to obtain a fluidized mixed substance.

[0190] (2) Using a sprayer containing a nozzle head and a material conduit, the fluidized mixed substance is sprayed into circulating nitrogen at 100° C., and the temperature of the fluidized mixed substance in the material conduit is 90° C. and the temperature in the nozzle head is 120° C., to obtain a catalyst carrier DZ1 for olefin polymerization.

[0191] During the spraying process, the fluid mixed material obtained in step (1) is very easy to precipitate, which may cause the spray drying to fail to proceed normally and may also cause the nozzle to be blocked.

[0192] The average particle diameter (D50) of the olefin polymerization catalyst support DZ1 is 15 μm, and the particle size distribution ((D90-D10) / D50) is 1.3.

[0193] Comparative Example 2

[0194] (1) In a 0.6 L reactor, 0.08 mol of magnesium chloride and 1.7 mol of ethanol were added, and the temperature was raised to 90°C under stirring. After the reaction was kept at this temperature for 1 hour, 0.48 mol of epichlorohydrin was added and the reaction was continued at 90°C for 30 minutes to obtain the first product;

[0195] (2) After filtering the first product, 2.5 mol of ethanol was added to the solid residue and stirred until a fluid mixture was formed;

[0196] (3) Using a sprayer containing a nozzle head and a material conduit, the fluidized mixture is sprayed into circulating nitrogen at 100° C., and the temperature of the third product in the material conduit is 15° C. and the temperature in the nozzle head is 120° C., to obtain a catalyst support DZ2 for olefin polymerization.

[0197] The average particle diameter (D50) of the olefin polymerization catalyst carrier DZ2 is 3 μm, and the particle size distribution ((D90-D10) / D50) is 0.8.

[0198] Comparative Example 3

[0199] The catalyst spherical support was prepared in a manner similar to that of Example 1, except that in step (3), no second alcohol compound was used, and only a halohydrin (1,3-dichloropropanol) was used to fully mix and stir with the second product for the third contact, and the amount of the halohydrin used was the same as that of Example 1, to obtain a catalyst support DZ3.

[0200] During the preparation of catalyst carrier DZ3, the carrier formed lumps and subsequent operations could not be performed.

[0201] Test Example The spherical catalyst carrier for olefin polymerization provided by the present invention is used to prepare a catalyst for olefin polymerization, and the prepared catalyst for olefin polymerization is used to prepare olefins.

[0202] Test Example 1-1

[0203] (1) Preparation of olefin polymerization catalyst

[0204] In a 300 mL reaction flask, add 100 mL of titanium tetrachloride, cool to -20°C, add 8 g of the spherical catalyst carrier Z1 obtained in Example 1, and stir at -20°C for 30 minutes. Then, slowly raise the temperature to 110°C. During this heating process, add 1.5 mL of diisobutyl phthalate. After maintaining the temperature at 110°C for 30 minutes, filter out the liquid. Wash twice with titanium tetrachloride and finally three times with hexane, then dry to obtain Catalyst C1 for olefin polymerization.

[0205] (2) Propylene polymerization

[0206] In a 5 L stainless steel autoclave, under a nitrogen atmosphere, were added 1 mmol of a hexane solution of triethylaluminum (the concentration of triethylaluminum was 0.5 mmol / mL), 0.05 mmol of methylcyclohexyldimethoxysilane, 10 mL of anhydrous hexane, 10 mg of the olefin polymerization catalyst C1 obtained in step (1), 1.5 L (standard volume) of hydrogen, and 2.5 L of liquid propylene monomer. The reaction was heated to 70° C., reacted at this temperature for 1 h, then cooled, depressurized, discharged, and dried to obtain a polypropylene powder.

[0207] The catalyst activity prepared in this test example was 36.1 KgPP / g·Cat;

[0208] The bulk density of the obtained polypropylene powder is 0.41 g / cm 3 The melt flow rate index is 11.9 g / 10 min. The polypropylene powder has good particle morphology and basically no irregular shapes exist. The details can be seen in Table 1.

[0209] Test Example 1-2

[0210] Polypropylene was prepared in a manner similar to that of Test Example 1-1, except that in step (2), the volume of hydrogen used was different, and the rest was the same as that of Test Example 1-1.

[0211] Specifically: 1.5 L (standard volume) of hydrogen is replaced with 6.5 L (standard volume) of hydrogen to obtain polypropylene powder.

[0212] The catalyst activity prepared in this test example was 36.0 KgPP / g·Cat;

[0213] The bulk density of the obtained polypropylene powder is 0.41 g / cm 3 The melt flow rate index is 45.8g / 10min. The polypropylene powder has good particle morphology and basically no irregular shapes exist. The details can be seen in Table 1.

[0214] Test Example 2-1

[0215] Polypropylene was prepared in a manner similar to that of Test Example 1-1, except that in step (1), the type of catalyst carrier used was different, and the rest was the same as that of Test Example 1-1.

[0216] Specifically: the catalyst spherical carrier Z2 prepared in Example 2 of the same weight is used to replace the catalyst spherical carrier Z1 to obtain olefin polymerization catalyst C2; then the olefin polymerization catalyst C2 is used to prepare polypropylene powder according to step (2) of Test Example 1-1.

[0217] The catalyst activity prepared in this test example was 37.6KgPP / g·Cat;

[0218] The bulk density of the obtained polypropylene powder is 0.41 g / cm 3 The melt flow rate index is 11.0 g / 10 min. The polypropylene powder has good particle morphology and basically no irregular shapes exist. The details can be seen in Table 1.

[0219] Test Example 2-2

[0220] Polypropylene was prepared in a manner similar to that of Test Example 2-1, except that in step (2), the volume of hydrogen used was different, and the rest was the same as that of Test Example 2-1.

[0221] Specifically: 1.5 L (standard volume) of hydrogen is replaced with 6.5 L (standard volume) of hydrogen to obtain polypropylene powder.

[0222] The catalyst activity prepared in this test example was 37.2 KgPP / g·Cat;

[0223] The bulk density of the obtained polypropylene powder is 0.41 g / cm 3 The melt flow rate index is 41.2 g / 10 min. The polypropylene powder has good particle morphology and basically no irregular shapes exist. The details can be seen in Table 1.

[0224] Test Example 3-1

[0225] Polypropylene was prepared in a manner similar to that of Test Example 1-1, except that in step (1), the type of catalyst carrier used was different, and the rest was the same as that of Test Example 1-1.

[0226] Specifically: the catalyst spherical carrier Z3 prepared in Example 3 of the same weight is used to replace the catalyst spherical carrier Z1 to obtain olefin polymerization catalyst C3; then, the olefin polymerization catalyst C3 is used to prepare polypropylene powder according to step (2) of Test Example 1-1.

[0227] The catalyst activity prepared in this test example was 38.5KgPP / g·Cat;

[0228] The bulk density of the obtained polypropylene powder is 0.41 g / cm 3 The melt flow rate index is 10.0 g / 10 min. The polypropylene powder has good particle morphology and basically no irregular shapes exist. The details can be seen in Table 1.

[0229] Test Example 3-2

[0230] Polypropylene was prepared in a manner similar to that of Test Example 3-1, except that in step (2), the volume of hydrogen used was different, and the rest was the same as that of Test Example 3-1.

[0231] Specifically: 1.5 L (standard volume) of hydrogen is replaced with 6.5 L (standard volume) of hydrogen to obtain polypropylene powder.

[0232] The catalyst activity prepared in this test example was 38.2 KgPP / g·Cat;

[0233] The bulk density of the obtained polypropylene powder is 0.41 g / cm 3 The melt flow rate index is 39.0 g / 10 min. The polypropylene powder has good particle morphology and basically no irregular shapes exist. The details can be seen in Table 1.

[0234] Comparative test example 1

[0235] Polypropylene was prepared in a manner similar to that of Test Example 1-1, except that in step (1), the type of catalyst carrier used was different, and the rest was the same as that of Test Example 1-1.

[0236] Specifically: the catalyst spherical carrier DZ1 prepared in Comparative Example 1 with the same weight was used to replace the catalyst spherical carrier Z1 to obtain olefin polymerization catalyst DC1, and then the olefin polymerization catalyst DC1 was used to prepare polypropylene powder according to step (2) of Test Example 1-1.

[0237] The catalyst activity prepared in this test example was 34.8KgPP / g·Cat;

[0238] The bulk density of the obtained polypropylene powder is 0.37 g / cm 3 , the melt flow rate index is 9.1g / 10min, as shown in Table 1.

[0239] Comparative Test Example 2-1

[0240] Polypropylene was prepared in a manner similar to that of Test Example 1-1, except that in step (1), the type of catalyst carrier used was different. The rest was the same as that of Test Example 1-1.

[0241] Specifically: the catalyst spherical carrier DZ2 prepared in Comparative Example 2 of the same weight was used to replace the catalyst spherical carrier Z1 to obtain olefin polymerization catalyst DC2, and then the olefin polymerization catalyst DC2 was used to prepare polypropylene powder according to step (2) of Test Example 1-1.

[0242] The catalyst activity prepared in this test example was 39.0 KgPP / g·Cat;

[0243] The bulk density of the obtained polypropylene powder is 0.41 g / cm 3 , the melt flow rate index is 9.5g / 10min, as shown in Table 1.

[0244] Comparative Test Example 2-2

[0245] Polypropylene was prepared in a manner similar to that of Comparative Test Example 2-1, except that in step (2), the volume of hydrogen used was different. The rest was the same as that of Comparative Test Example 2-1.

[0246] Specifically: 1.5 L (standard volume) of hydrogen is replaced with 6.5 L (standard volume) of hydrogen to obtain polypropylene powder.

[0247] The catalyst activity prepared in this test example was 37.9KgPP / g·Cat;

[0248] The bulk density of the obtained polypropylene powder is 0.41 g / cm 3 , the melt flow rate index is 37.5g / 10min, as shown in Table 1.

[0249] Table 1

[0250]

[0251] The above results demonstrate that the olefin polymerization catalyst support prepared using the method of the present invention exhibits excellent particle morphology, with virtually no irregularly shaped particles. Furthermore, the method provided by the present invention enables the preparation of catalyst supports with smaller particle sizes, significantly expanding the range of particle sizes that can be prepared. Furthermore, when used in olefin (particularly propylene) polymerization, catalysts prepared using the resulting supports exhibit excellent catalytic activity, good polypropylene powder morphology, virtually no irregular particles, and high sensitivity to hydrogen regulation.

[0252] In particular, by comparing Comparative Example 2 with Example 1, it can be seen that although Comparative Example 2 can obtain a catalyst support with a smaller particle size, when the catalyst prepared from the catalyst support is used for olefin (especially propylene) polymerization reaction, the polymer melt index is small and the corresponding hydrogen adjustment sensitivity is low.

[0253] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A spherical carrier for olefin polymerization, the carrier comprising a magnesium-containing compound having the structure shown in formula (1); Wherein, R1 is an alkyl group of C 1-10 ; R2 and R3 are each independently selected from H, C 1-10 alkyl groups and C 1-10 alkyl groups substituted by 1 to 10 halogen atoms; R4 is selected from an alkyl group having C substituted by at least one halogen atom and an aryl group having C substituted by at least one halogen atom; 1-10 6-20 ​​ R5 is an alkyl group of C 1-5 ; X is selected from fluorine, chlorine, bromine and iodine; m is 0.1 - 1.9, n is 0.1 - 1.9, and m + n = 2; 0 < q < 0.2; 0 < a < 0.

1.

2. The spherical carrier according to claim 1, which has at least one of the following characteristics - R1 is an alkyl group of C 1-8 ; Preferably, R1 is an alkyl group of C 1-6 ; - R2 and R3 are each independently selected from H, an alkyl group of C 1-5 and an alkyl group of C 1-5 substituted by 1 - 10 halogen atoms; - R4 is selected from an alkyl group of C 1-10 substituted by at least two halogen atoms and an aryl group of C 6-20 substituted by at least two halogen atoms; - R5 is an alkyl group of C 1-2 ; - X is selected from chlorine and bromine.

3. The spherical carrier according to claim 1 or 2, wherein, The average particle diameter of the spherical carrier is 2 - 100 μm, and the particle size distribution is less than 2; Preferably, the average particle diameter of the spherical carrier is 2 - 19 μm, and the particle size distribution is 0.6 - 1.

6.

4. A method for preparing a spherical carrier for olefin polymerization, the method comprising: (1) Component A is subjected to a first contact and then a shear force is applied to the resulting mixture to obtain a first product, where Component A contains a magnesium halide of the general formula MgXY and a first alcohol compound of the general formula R1OH; (2) The first product is subjected to a second contact with Component B to obtain a second product, where Component B contains an ethylene oxide compound having the structure shown in formula (2); (3) The second product is subjected to a third contact with Component C to obtain a third product, where Component C contains a halogenated alcohol of the general formula R4OH and a second alcohol compound of the general formula R5OH; (4) The third product is spray-dried; Among them, in the formula R1OH, R1 is an alkyl group of C 1-10 ; In formula (2), R2 and R3 are each independently selected from H, C 1-10 alkyl groups and C 1-10 alkyl groups substituted by 1-10 halogen atoms; In the formula R4OH, R4 is selected from an alkyl group of C substituted by at least one halogen atom and an aryl group of C substituted by at least one halogen atom; 1-10 and an aryl group of C substituted by at least one halogen atom; 6-20 ; In the formula R5OH, R5 is an alkyl group of C 1-5 ; In the formula MgXY, X is selected from fluorine, chlorine, bromine, and iodine; Y is selected from fluorine, chlorine, bromine, iodine, C 1-6 alkyl, C 1-6 alkoxy, C 6-14 aryl, and C 6-14 aryloxy; The amounts of Component A, Component B, and Component C are such that the resulting spherical carrier contains a magnesium-containing compound having the structure shown in formula (1): In formula (1), R1 - R5 and X are defined as above, m is 0.1 - 1.9, n is 0.1 - 1.9, and m + n = 2; 0 < q < 0.2; 0 < a < 0.1; Wherein, in step (3), relative to 1 mol of the magnesium halide, the amount of the halogenated alcohol is 0.05 - 6.5 mol, and the amount of the second alcohol compound is 5 - 100 mol.

5. The method according to claim 4 has at least one of the following features: - In the formula MgXY, X is selected from chlorine and bromine, and Y is selected from chlorine, bromine, C 1-5 alkyl, C 1-5 alkoxy, C 6-10 aryl and C 6-10 aryloxy; Or the magnesium halide is selected from at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride; - In the formula R1OH, R1 is C 1-8 alkyl; Or the first alcohol compound is selected from at least one of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, n-octanol and 2-ethylhexanol; - In the formula (2), R2 and R3 are each independently selected from H, C 1-5 alkyl and C substituted by 1-10 halogen atoms 1-5 alkyl; Or the ethylene oxide compound is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epichlorobutane, epibromopropane and epibromobutane; - In the formula R4OH, R4 is selected from C substituted by at least two halogen atoms 1-10 alkyl and C substituted by at least two halogen atoms 6-20 aryl; Or the halogenated alcohol is selected from at least one of 2,2,2-trichloroethanol, 2,2-dichloroethanol, 1,2-dichloroethanol, 1,3-dichloropropanol and 1,4-dichlorobutanol; - In the formula R5OH, R5 is C 1-2 alkyl; - Relative to 1 mol of the magnesium halide, the dosage of the first alcohol compound is 6-22 mol, the dosage of the ethylene oxide compound is 2-6 mol, the dosage of the halogenated alcohol is 1-5 mol, and the dosage of the second alcohol compound is 8-80 mol; - In step (1), the first contact is carried out under stirring, and the conditions of the first contact include: The temperature is 80 - 120 °C, and the time is 0.5 - 5 h; Or in step (1), the conditions of the first contact include: the temperature is 80 - 100 °C, and the time is 0.5 - 3 h; - In step (2), the conditions of the second contact include: the temperature is 50 - 120 °C, and the time is 20 - 60 min; Or in step (2), the conditions of the second contact include: the temperature is 80 - 100 °C, and the time is 20 - 50 min. - In step (3), the conditions of the third contact include: carried out under stirring, the temperature is 0 - 120 °C, and the time is 0.5 - 6 h; - In step (4), the conditions of the spray drying include: the temperature is 60 - 200 °C, preferably 90 - 150 °C.

6. A spherical carrier prepared by the method according to any one of claims 4-5.

7. Use of the spherical carrier according to any one of claims 1-3 and 6 in the preparation of a catalyst for olefin polymerization.

8. A catalyst comprising the spherical carrier according to any one of claims 1-3 and 6.

9. Use of the catalyst according to claim 8 in the catalytic olefin polymerization reaction.