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

Abstract

A spherical support for an olefin polymerization catalyst, its manufacturing method and applications, and a catalyst and its applications are disclosed, wherein the support comprises at least one magnesium-containing compound having a structure represented by formula (1). The spherical support for an olefin polymerization catalyst of the present invention has a relatively good particle morphology and is essentially free of particles with special morphologies. The provided method enables the production of supports with small particle sizes, significantly expanding the particle size range of the supports that can be produced. When a catalyst produced using the resulting support is used in olefin polymerization, it exhibits good polymerization activity, is essentially free of substances with special morphologies, and has good hydrogen adjustment sensitivity. [Formula 1] JPEG2023540543000016.jpg24169

Description

Detailed Description of the Invention

[0001] [Technical Field] The present invention relates to the field of olefin polymerization catalysts, in particular to a spherical support for an olefin polymerization catalyst, a method for producing the same, a spherical support produced by said method, the use of said spherical support in the production of a catalyst for olefin polymerization, a catalyst comprising said spherical support, and the use of said catalyst for catalyzing olefin polymerization.

[0002] [Background technology] When used in olefin polymerization, Ziegler-Natta catalysts prepared from magnesium dichloride-alcohol adducts, especially those prepared from spherical magnesium dichloride-alcohol adducts, generally exhibit significantly better catalytic performance than catalysts supported on other supports. Therefore, most current catalysts for olefin polymerization are prepared by supporting titanium halides on magnesium dichloride-alcohol adducts.

[0003] However, when a catalyst prepared from a magnesium dichloride-alcohol adduct is used in olefin polymerization, the polymer particles are easily destroyed during polymerization, producing a large amount of polymer fines.

[0004] To overcome this drawback, attempts have been made to incorporate an electron donor compound into the preparation of the magnesium dichloride-alcohol adduct support. For example, CN1397568A and CN1563112A teach the introduction of a phthalate compound as an internal electron donor into the synthesis of the magnesium dichloride-alcohol adduct support to obtain a "magnesium dichloride-alcohol-phthalate" spherical support, which is then reacted with titanium tetrachloride to form a catalyst. However, the composite spherical support tends to be sticky during production, and it is difficult to form spherical particles with an appropriate particle size.

[0005] In addition, most of the magnesium dichloride-alcohol adducts mentioned above are produced by low-temperature quenching and solidification of the melt of the high-temperature alcohol adduct. Such a technique not only consumes a large amount of energy and involves a complex production process that requires the combination of multiple reactors, but also produces alcohol adducts with a relatively wide particle size distribution.

[0006] To solve this problem, CN102040683A discloses a method for preparing a support by reacting a magnesium halide-alcohol adduct with an oxirane-type compound. However, this method often requires the addition of a surfactant to prepare a catalyst support, and this method has the disadvantages of an unstable preparation process, easy support aggregation, and poor support formation.

[0007] Thus, there remains a need to develop new methods for producing supports useful for olefin polymerization catalysts.

[0008] DISCLOSURE OF THE INVENTION The object of the present invention is to overcome the drawbacks of the prior art in that olefin polymerization catalyst supports have poor particle morphology, supports with small particle sizes cannot be produced, and catalysts produced from the supports exhibit poor hydrogen modulation sensitivity when used in olefin polymerization.

[0009] The present inventors have unexpectedly found that, in the preparation of a catalyst support, a catalyst support with a novel composition and good particle morphology can be obtained by adding an alcohol compound and a halogenated alcohol compound to form a fluid mixture and then spray-drying the mixture. Therefore, the resulting catalyst support essentially has no particles with a special morphology; a support with a very small particle size can be prepared, thereby significantly expanding the particle size range of the support that can be produced; the support can be directly synthesized without using a surfactant or an inert solvent during preparation, and the preparation process is stable; and the catalyst prepared from the support has high sensitivity to hydrogen modulation when used in olefin polymerization. Based on these findings, the present inventors have made the present invention.

[0010] An object of the present invention is to provide a spherical support for an olefin polymerization catalyst, comprising at least one magnesium-containing compound having a structure represented by formula (1):

[0011] [ka]

[0012] In formula (1), R1 is C 1-10 is alkyl; R2 and R3 are each independently H, C 1-10 C substituted with alkyl groups and 1 to 10 halogen atoms 1-10 alkyl groups; R4 is a C substituted with at least one halogen atom. 1-10 C substituted with alkyl groups and at least one halogen atom 6-20 aryl groups; R5 is C 1-5 is alkyl; X is selected from the group consisting of fluorine, chlorine, bromine and iodine; m is 0.1 to 1.9, n is 0.1 to 1.9, and m+n=2; 0 <q<0.2であり; 0 <a<0.1である。

[0013] Another object of the present invention is to provide a method for producing a spherical support for an olefin polymerization catalyst, which includes the following steps (1) to (4): (1) subjecting a Component A material to a first contact and then applying shear force to the resulting mixture to obtain a first product, wherein Component A comprises a magnesium halide of general formula MgXY and a first alcohol of general formula ROH; (2) subjecting the first product and component B to a second contact to obtain a second product, wherein component B comprises an oxirane-type compound having a structure represented by formula (2): (3) subjecting the second product and component C to a third contact to obtain a third product, wherein component C comprises a halogenated alcohol of general formula ROH and a second alcohol of general formula ROH; (4) spray drying the third product;

[0014] [ka]

[0015] where: In the formula ROH, R is C 1-10 is alkyl; In the formula (2), R2 and R3 each independently represent H, unsubstituted or C substituted with 1 to 10 halogen atoms. 1-10 alkyl groups; In the formula R4OH, R4 is a C substituted with at least one halogen atom. 1-10 C substituted with alkyl groups and at least one halogen atom 6-20 aryl groups; In the formula R5OH, R5 is C 1-5 is alkyl; In the formula MgXY, X is selected from the group consisting of fluorine, chlorine, bromine, and iodine; Y is fluorine, chlorine, bromine, iodine, C 1-6 Alkyl, C1-6 Alkoxy, C 6-14 Aryl and C 6-14 aryloxy; The amounts of the component A, the component B, and the component C used are such that the resulting spherical carrier contains a magnesium-containing compound having a structure represented by formula (1);

[0016] [ka]

[0017] In formula (1), m is 0.1 to 1.9, n is 0.1 to 1.9, and m+n=2; 0 <q<0.2であり; 0 <a<0.1であり;ならびに In the step (3), the amount of the halogenated alcohol used is 0.05 to 6.5 mol, and the amount of the second alcohol used is 5 to 100 mol, relative to 1 mol of the magnesium halide used.

[0018] Another object of the present invention is to provide a spherical carrier produced by the method described above.

[0019] Another object of the present invention is to provide the use of the spherical support in the preparation of a catalyst for olefin polymerization.

[0020] It is yet another object of the present invention to provide a catalyst comprising the above-described spherical support.

[0021] Yet another object of the present invention is to provide the use of the catalyst described above for catalyzing olefin polymerization.

[0022] Compared with the prior art, the present invention has at least the following advantages: (1) The spherical support of the olefin polymerization catalyst provided by the present invention has good particle morphology and basically does not have particles with special shapes; the method provided by the present invention does not require the addition of surfactants or solvents, has a stable production process, and can produce supports with very small particle sizes, thereby greatly expanding the particle size range of the supports that can be produced; (2) When used in olefin polymerization, such as propylene polymerization, the catalyst prepared from the spherical support has high polymerization activity and good hydrogen control sensitivity, showing promising prospects for industrial application.

[0023] Other features and advantages of the present invention are detailed in the detailed description that follows.

[0024] BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an electron microscope photograph of the spherical carrier of Example 1.

[0025] DESCRIPTION OF THE PREFERRED EMBODIMENTS The range endpoints and any values ​​disclosed herein are not limited to the exact ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the individual range endpoints, the individual range endpoints and the individual point values ​​therebetween, 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.

[0026] As used herein, the term "alkyl" refers to a paraffinic hydrocarbon group that may be straight-chained, branched, or cyclic and that can be derived from an alkane by removing one or more hydrogens from its chemical formula. 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.

[0027] As used herein, the term "aryl" refers to an aromatic hydrocarbon group that can be derived from an aromatic hydrocarbon by removing one or more hydrogens from its chemical formula. Examples of aryl groups 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.

[0028] As used herein, the term "halogen" refers to fluorine, chlorine, bromine or iodine.

[0029] As used herein, "C substituted with 1 to 10 halogen atoms" refers to 1-10 "Alkyl" means C 1-10 This refers to a group formed by substituting 1 to 10 hydrogen atoms of an alkyl with halogen atoms. Multiple hydrogen atoms on the same carbon atom may be substituted with halogen atoms, or hydrogen atoms on different carbon atoms may be substituted with halogen 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.

[0030] Similarly, the term "C substituted with at least one (or at least two) halogen atoms" 1-10 "Alkyl" and "C substituted with at least one (or at least two) halogen atom" 6-20 "Aryl," as used herein, refers to any of C 1-10 At least one (or at least two) hydrogen atoms of alkyl, and C 6-20 It refers to a group formed by replacing at least one (or at least two) hydrogen atoms of an aryl with a halogen atom. When multiple hydrogen atoms are replaced with halogen atoms, the hydrogen atoms may be bonded to the same carbon atom or different carbon atoms, and the halogen atoms may be the same or different. C substituted with at least one halogen atom 1-10 Examples of alkyl include, but are not limited to, CF, -CHCF, -CHCFH, -CFCF, -CFCHCFH, -CHCFCFH, -CHCHCHCl, -CHCHCHBr, etc. C substituted with at least one halogen atom 6-20 Examples of aryl 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, 4-trifluoromethylphenyl.

[0031] As noted above, in a first aspect, the present invention provides a spherical support for an olefin polymerization catalyst, comprising at least one magnesium-containing compound having a structure represented by formula (1):

[0032] [ka]

[0033] In formula (1), R1 is a linear, branched, or cyclic C1-10 is alkyl; R2 and R3 are each independently H, a straight-chain or branched C 1-10 C substituted with alkyl groups and 1 to 10 halogen atoms 1-10 alkyl groups; R4 is a linear, branched, or cyclic C 1-10 C substituted with alkyl groups and at least one halogen atom 6-20 aryl groups; R5 is C 1-5 is alkyl; X is selected from the group consisting of fluorine, chlorine, bromine and iodine; m is 0.1 to 1.9, n is 0.1 to 1.9, and m+n=2; 0 <q<0.2であり; 0 <a<0.1である。

[0034] In some embodiments, the carrier of the present invention consists essentially of at least one magnesium-containing compound having a structure according to formula (1).

[0035] In some embodiments, the support of the present invention is comprised of at least one magnesium-containing compound having a structure represented by formula (1).

[0036] Preferably, R1 is a linear, branched or cyclic C 1-8 alkyl; more preferably, R is a linear, branched or cyclic C 1-6 It is alkyl.

[0037] Preferably, R2 and R3 are each independently H, a linear or branched C 1-5 Linear or branched C substituted with alkyl and 1 to 10 halogen atoms 1-5 alkyl.

[0038] Preferably, R4 is a linear, branched or cyclic C 1-10 C substituted with an alkyl group and at least two halogen atoms 6-20 aryl groups, wherein the halogen atom is preferably at least one selected from the group consisting of chlorine, bromine and iodine atoms.

[0039] Preferably, R5 is C 1-2 It is alkyl.

[0040] Preferably, X is selected from the group consisting of chlorine and bromine.

[0041] Preferably, m is 0.3 to 1.7, more preferably 0.6 to 1.4, and even more preferably 0.8 to 1.2.

[0042] Preferably, n is 0.3 to 1.7, more preferably 0.6 to 1.4, and even more preferably 0.8 to 1.2.

[0043] Preferably, 0.001 <q<0.15である。

[0044] Preferably, 0.001 <a<0.08である。

[0045] Preferably, the spherical carrier has an average particle size of 2 to 100 microns and a particle size distribution of less than 2, and more preferably has an average particle size of 2 to 19 microns and a particle size distribution of 0.6 to 1.6.

[0046] When a catalyst produced from a spherical support is used in olefin polymerization, it is more preferable that the spherical support has an average particle size of 2 to 10 microns and a particle size distribution of 0.6 to 1, in order to enable the production of an olefin polymer having a higher bulk density.

[0047] In the present invention, the average particle size means D50.

[0048] In the present invention, the particle size distribution value is defined as (D90-D10) / D50.

[0049] In the present invention, the average particle size and particle size distribution of the catalyst support are measured using a laser particle size analyzer such as a Master Sizer 2000 laser particle size analyzer (manufactured by Malvern Instruments Ltd.) In the measurement, for example, hexane can be used as an inert dispersion medium.

[0050] As described above, in a second aspect, the present invention provides a method for producing a spherical support for an olefin polymerization catalyst, comprising the following steps (1) to (4): (1) subjecting a Component A material to a first contact and then applying shear force to the resulting mixture to obtain a first product, wherein Component A comprises a magnesium halide of general formula MgXY and a first alcohol of general formula ROH; (2) subjecting the first product and component B to a second contact to obtain a second product, wherein component B comprises an oxirane-type compound having a structure represented by formula (2): (3) subjecting the second product and component C to a third contact to obtain a third product, wherein component C comprises a halogenated alcohol of general formula ROH and a second alcohol of general formula ROH; (4) spray drying the third product;

[0051] [ka]

[0052] where: In the formula ROH, R is a linear, branched, or cyclic C 1-10 is alkyl; In the formula (2), R2 and R3 each independently represent H, a linear or cyclic C 1-10 alkyl groups; In the formula R4OH, R4 is a linear, branched or cyclic C 1-10 C substituted with alkyl groups and at least one halogen atom 6-20 aryl groups; In the formula R5OH, R5 is C 1-5 is alkyl; In the formula MgXY, X is selected from the group consisting of fluorine, chlorine, bromine, and iodine; Y is fluorine, chlorine, bromine, iodine, linear or branched C 1-6 Alkyl, linear or branched C 1-6 Alkoxy, C 6-14 Aryl and C 6-14 aryloxy; The amounts of the component A, the component B, and the component C used 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);

[0053] [ka]

[0054] In formula (1), R1 to R5 and X are as defined above, m is 0.1 to 1.9, n is 0.1 to 1.9, and m+n=2; 0 <q<0.2であり; 0 <a<0.1であり;ならびに In the step (3), the amount of the halogenated alcohol used is 0.05 to 6.5 mol, and the amount of the second alcohol used is 5 to 100 mol, relative to 1 mol of the magnesium halide used.

[0055] In the second aspect of the invention, the definitions and preferred forms of the groups R1, R2, R3, R4 and R5 are the same as those defined in the first aspect of the invention.

[0056] According to a preferred embodiment of the present invention, in the formula MgXY, X is selected from the group consisting of chlorine and bromine, and Y is chlorine, bromine, linear or branched C 1-5 Alkyl, linear or branched C 1-5 Alkoxy, C 6-10 Aryl and C 6-10 aryloxy.

[0057] More preferably, the magnesium halide is at least one selected from the group consisting of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride, and more preferably magnesium chloride.

[0058] According to another preferred embodiment of the present invention, in the formula ROH, R is a linear, branched or cyclic C 1-8 It is alkyl.

[0059] More preferably, the first alcohol compound is at least one selected from the group consisting of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol and 2-ethylhexanol.

[0060] According to another preferred embodiment of the present invention, in formula (2), R2 and R3 are each independently H, linear or branched C 1-5 Linear or branched C substituted with alkyl and 1 to 10 halogen atoms 1-5 alkyl.

[0061] More preferably, the oxirane type compound is at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epoxychlorobutane, epoxybromopropane, and epoxybromobutane.

[0062] According to some embodiments of the present invention, the halogenated alcohol may be a monohalogenated alcohol or a polyhalogenated alcohol, preferably a chlorohydrin, bromohydrin, or iodohydrin, such as 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.

[0063] According to a preferred embodiment of the present invention, in the formula R4OH, R4 is a linear, branched or cyclic C 1-10 C substituted with alkyl groups and at least two halogen atoms 6-20 aryl groups, wherein the halogen atom is at least one selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom.

[0064] Preferably, the halogenated alcohol is at least one selected from the group consisting of 2,2,2-trichloroethanol, 2,2-dichloroethanol, 1,2-dichloroethanol, 1,3-dichloropropanol, and 1,4-dichlorobutanol.

[0065] According to the present invention, the second alcohol compound is a C 10 alcohol such as ethanol, methanol, n-propanol, isopropanol, n-butanol or isobutanol. 1-5 According to a preferred embodiment of the present invention, in the formula R5OH, R5 is C 1-2 It is an alkyl, i.e., the second alcohol compound is methanol and / or ethanol.

[0066] The inventors have found that if the amount of halogenated alcohol compound and alcohol compound is too large, the resulting catalyst support becomes sticky and agglomerates, making it impossible to carry out further operations.

[0067] In the method disclosed herein, the amount of the first alcohol compound is 1 to 30 mol, the amount of the oxirane compound is 1 to 10 mol, the amount of the halogenated alcohol is 0.05 to 6.5 mol, and the amount of the second alcohol compound is 5 to 100 mol, relative to 1 mol of magnesium halide.

[0068] Preferably, the amount of the first alcohol compound is 6 to 22 mol, the amount of the oxirane compound is 2 to 6 mol, the amount of the halogenated alcohol is 1 to 5 mol, and the amount of the second alcohol compound is 8 to 80 mol, more preferably 31 to 50 mol, per 1 mol of magnesium halide.

[0069] It should be noted that a trace amount of water contained in the above-mentioned reactants will also participate in the reaction to form the spherical carrier. Therefore, the produced spherical carrier may contain a trace amount of water from the reaction raw materials and reaction solvent, which should not be construed by those skilled in the art as a limitation of the present invention.

[0070] Preferably, in step (1), the first contact is carried out under stirring, and the conditions for the first contact include a temperature of 40 to 130°C, preferably 50 to 130°C, more preferably 80 to 120°C, and a time of 0.3 to 24 hours, preferably 0.5 to 10 hours, more preferably 0.5 to 5 hours.

[0071] More preferably, in step (1), the conditions for the first contact include a temperature of 80 to 100° C. and a time of 0.5 to 3 hours.

[0072] In step (1), the specific method of applying shear force is not particularly limited and can be carried out by methods known to those skilled in the art. For example, low- or high-shear shearing can be used. Preferably, when low-shear shearing is used, the stirring speed is 400 to 800 rpm. High-shear shearing is well known to those skilled in the art, and can be carried out using high-speed stirring, for example, as disclosed in CN1330086A. In addition, the application of shear force can also be carried out according to the following methods disclosed in patent applications: CN1580136A discloses a method in which a solution containing a liquid magnesium halide compound is dispersed through rotation in a supergravity bed (rotation speed: 100 to 3000 rpm); CN1463990A discloses another method in which a solution containing a liquid magnesium halide adduct is output from an emulsifier at a speed of 1500 to 8000 rpm; and US6020279A discloses a method in which shear force is applied to a solution containing a liquid magnesium halide adduct through a spraying process.

[0073] Preferably, in step (2), the conditions for the second contact include a temperature of 30 to 130°C, preferably 50 to 120°C, and a time of 10 to 180 minutes, preferably 20 to 60 minutes.

[0074] More preferably, in step (2), the conditions for the second contact include a time of 80 to 100° C. and a time of 20 to 50 minutes.

[0075] According to a preferred embodiment of the present invention, step (3) further comprises washing the second product with an inert solvent prior to the third contacting of the second product with an individual component of component C. The inert solvent is preferably at least one selected from pentane, hexane, heptane, petroleum ether, and gasoline.

[0076] According to the present invention, the specific conditions for the third contact in step (3) are not particularly limited, as long as the component C and the second product can be completely contacted to form a liquid. However, in order to obtain a catalyst support with better performance, the conditions for the third contact in step (3) preferably include stirring, a temperature of 0 to 120°C, and a time of 0.5 to 6 hours.

[0077] The specific method of the third contact in step (3) is not particularly limited in the present invention, and the halogenated alcohol and the second alcohol compound can be mixed and contacted with the second component simultaneously or successively in any order.

[0078] In the present invention, the spray-drying conditions may be any known conditions capable of forming an olefin polymerization catalyst support. According to a preferred embodiment of the present invention, spray-drying is carried out in an atomizer equipped with a spray nozzle, the spray nozzle comprising a material conduit and a nozzle head, wherein the third product is introduced into the nozzle head through the material conduit and then sprayed into the tower body of the atomizer containing an inert solvent to achieve evaporation and solidification. Preferably, the temperature of the third product in the material conduit is 0°C to 80°C, and the temperature of the third product in the nozzle head is 80°C to 180°C, more preferably 120°C to 180°C.

[0079] In step (4) of the present invention, the conditions for spray drying include a temperature of preferably 60 to 200° C., more preferably 90 to 150° C. In the present invention, the spray drying temperature refers to the temperature of the inert solvent in the atomizer.

[0080] In the present invention, the inert solvent may include a protective gas solvent and / or an inert liquid solvent. The type of the protective gas solvent is not particularly limited. For example, it may be nitrogen, an inert gas solvent such as helium, or another suitable gas such as carbon dioxide. The inert liquid solvent may be any of various liquid solvents commonly used in the art that do not chemically interact with the reactants and reaction products. Preferably, the inert liquid solvent is silicone oil and / or an inert liquid hydrocarbon solvent. More preferably, the inert liquid solvent is at least one selected from kerosene, paraffin oil, Vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil, and methyl phenyl silicone oil, and more preferably white oil.

[0081] In the present invention, the amount of inert liquid solvent used in the sprayer can be selected according to the amount of magnesium halide of the formula MgXY, and is preferably 0.8 to 10 L per mol of magnesium halide, more preferably 2 to 8 L per mol of magnesium halide.

[0082] The method according to the second aspect of the present invention also includes conventional post-treatment methods in the art, such as solid-liquid separation, washing, and drying, but these are not particularly limited in the present invention. Solid-liquid separation can be achieved using various existing methods capable of separating the solid phase from the liquid phase, such as suction filtration, pressure filtration, and centrifugation. Preferably, solid-liquid separation is achieved by pressure filtration. In the present invention, pressure filtration is not particularly limited as long as it separates the solid and liquid phases as completely as possible. Washing can be achieved by methods known to those skilled in the art to wash the resulting solid product. For example, the resulting solid product can be washed with an inert hydrocarbon solvent such as pentane, hexane, heptane, petroleum ether, or gasoline. The specific drying conditions are not particularly limited in the present invention. For example, the drying temperature can be 20 to 70°C, the drying time can be 0.5 to 10 hours, and drying can be performed under atmospheric pressure or reduced pressure.

[0083] The present inventors have found that by combining specific types and amounts of alcohol compounds and halogenated alcohol compounds with components such as magnesium halide and oxirane-type compounds and spray-drying the mixture, a catalyst support having a novel composition, good particle morphology, and particles with essentially no special shape can be obtained, while there is no need to add a surfactant in the production process, and the production process is stable.

[0084] In particular, the method provided by the present invention can produce supports having very small particle sizes, significantly expanding the particle size range of supports that can be produced; and when used in olefin polymerization, catalysts produced from the resulting supports have good hydrogen modulation sensitivity.

[0085] As mentioned above, in a third aspect, the present invention provides a spherical carrier produced by the method described above in the second aspect.

[0086] The present inventors have found that the spherical catalyst carriers produced by the method of the present invention have good particle morphology and are essentially free from particles with abnormal morphology.

[0087] As mentioned above, in a fourth aspect, the present invention provides the use of a spherical support as described in the first or third aspect in the manufacture of an olefin polymerization catalyst.

[0088] As mentioned above, in a fifth aspect, the present invention provides a catalyst comprising a spherical support according to the first or third aspect.

[0089] Methods for preparing olefin polymerization catalysts from spherical supports and the catalysts thus obtained are known to those skilled in the art. In the present invention, the composition of the catalyst is not particularly limited and may be the composition of any olefin polymerization catalyst known in the art. However, to obtain a catalyst suitable for olefin polymerization, particularly propylene polymerization, it is preferred that the catalyst comprises a support, a titanium halide compound, and an electron donor compound. Preferably, the titanium halide is at least one selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetra-n-butoxytitanium, tetraethoxytitanium, tri-n-butoxytitanium chloride, di-n-butoxytitanium dichloride, n-butoxytitanium trichloride, triethoxytitanium chloride, diethoxytitanium dichloride, ethoxytitanium trichloride, and titanium trichloride. Preferably, the electron donor compound is at least one selected from the group consisting of esters of phthalic acid, such as diisobutyl phthalate, diol esters of carboxylic acids, esters of phosphoric acids, ethers such as 1,3-diethers, etc. Furthermore, the contents of individual components in the catalyst are not particularly limited in the present invention, and those skilled in the art can make reasonable adjustments and designs according to actual needs.

[0090] The method for preparing the catalyst is not particularly limited in the present invention, and conventional methods for preparing olefin polymerization catalysts in the art can be used. In one embodiment, the olefin polymerization catalyst is prepared by treating a spherical support with a titanium halide compound prepared in any inert liquid solvent, and optionally, an internal electron donor compound is introduced into the support before, during, or after the treatment. Specific working processes are described in the following examples, and those skilled in the art should not interpret them as limitations of the present invention.

[0091] As mentioned above, in a sixth aspect, the present invention provides the use of a catalyst as described above in the fifth aspect to catalyse an olefin polymerisation reaction.

[0092] The specific operation of the use is not particularly limited in the present invention, and those skilled in the art can operate according to conventional methods for carrying out olefin polymerization in the art, which are not described in detail herein. A specific operation process is described below, but those skilled in the art should not interpret it as a limitation of the present invention.

[0093] Thus, in one embodiment, the present invention provides a process for olefin polymerization comprising contacting at least one C2 to C10 olefin monomer and optionally a comonomer with a catalyst under polymerizable conditions to form an olefin polymer, and recovering said olefin polymer.

[0094] The present inventors have found that when a catalyst prepared from the spherical support provided by the present invention is used in olefin polymerization, particularly propylene polymerization, it has high polymerization activity, does not produce fine particles with a special morphology, and exhibits significantly better hydrogen adjustment sensitivity than that achieved by the prior art, and shows promising prospects for industrial application.

[0095] The present invention will be described in more detail below with reference to examples.

[0096] In the following examples, unless otherwise noted, raw materials are commercially available and used as received.

[0097] 1,3-Dichloropropanol was purchased from J&K Scientific Co.; Epichlorohydrin was purchased from J&K Scientific Co.; Di-isobutyl phthalate was purchased from J&K Scientific Co.; Titanium tetrachloride was purchased from J&K Scientific Co.; Triethylaluminum was purchased from J&K Scientific Co.; Methylcyclohexyldimethoxysilane was purchased from J&K Scientific Co.

[0098] In the following examples, the properties of interest are measured by the following test methods: 1. Average particle size and particle size distribution of catalyst support: measured by Masters Sizer Model 2000 particle size measuring device (manufactured by Malvern Instruments Co. Ltd.), using hexane as a dispersion medium; 2. Morphology of catalyst support: observed by XL-30 field emission electron microscope (FEI, USA); 3. Structure and composition of catalyst support: 1 H NMR spectra are obtained on an AVANCE 300 nuclear magnetic resonance spectrometer (Bruker, Switzerland), and the composition of the support is determined by using a PY-2020iD cracker (Fronteerlab), a TraceGC Ultra chromatograph, and a DSQ model II mass spectrometer (Thermo Fisher); 4. Catalytic activity: It is evaluated by the ratio of the weight of the product obtained after polymerization to the weight of the catalyst; 5. Bulk density of polyolefin powder: determined using the procedure specified in GB / T 1636-2008; 6. Melt flow rate of polyolefin powder: measured according to ISO 1133 at 230°C under a load of 2.16 kg.

[0099] In the following examples, unless otherwise specified, the application of shear force during the preparation of the catalyst support is achieved by stirring at 600 rpm.

[0100] Example 1 (1) 0.08 mol of magnesium dichloride and 1.7 mol of ethanol (first alcohol compound) were added to a 0.6 L reaction vessel, and the temperature was raised to 90°C with stirring. The contents were reacted at that constant temperature for 1 hour to perform a first contact, and a shear force was applied to the resulting mixture to obtain a first product.

[0101] (2) The first product was subjected to a second contact with 0.48 mol of epichlorohydrin to obtain a second product, and the second contact conditions included a temperature of 90°C and a time of 30 minutes.

[0102] (3) After pressure filtration of the second product, the obtained solid was subjected to a third contact by thoroughly mixing and stirring with 2.5 mol of ethanol (second alcohol compound) and 0.35 mol of 1,3-dichloropropanol (halogenated alcohol) to form a liquid, thereby obtaining a third product.

[0103] (4) Using an atomizer B-290 equipped with a nozzle head and a material conduit, the third product was sprayed into circulating nitrogen at 100°C in a spray tower for spray drying to obtain spherical carrier Z1, wherein the temperature of the third product in the material conduit was 15°C, and the temperature of the third product in the nozzle head was 120°C.

[0104] After testing, the structure and composition of the obtained catalyst spherical support Z1 were found to be as follows:

[0105] [ka]

[0106] The catalyst spherical carrier Z1 was tested with an average particle size (D50) of 4 microns and a particle size distribution ((D90-D10) / D50) of 0.9.

[0107] Figure 1 shows a micrograph of the spherical support Z1. From Figure 1, it can be seen that the particles of the spherical support Z1 have a relatively regular shape, a smooth surface, and substantially all particles are spherical. In addition, the spherical support Z1 has a relatively concentrated particle size distribution and does not generally contain particles with special shapes.

[0108] In the manufacturing process of the catalyst spherical carrier Z1, no clogging phenomenon occurred at the nozzle head of the atomizer, and a total of 11.8 g of carrier Z1 was obtained.

[0109] Example 2 (1) 0.08 mol of magnesium dichloride and 1.4 mol of ethanol (first alcohol compound) were added to a 0.6 L reaction vessel, and the temperature was raised to 90°C with stirring. The contents were reacted at that constant temperature for 1.5 hours to perform a first contact, and a shear force was applied to the resulting mixture to obtain a first product.

[0110] (2) The first product was subjected to a second contact with 0.35 mol of epichlorohydrin to obtain a second product, and the second contact conditions included a temperature of 90° C. and a time of 30 minutes.

[0111] (3) After pressure filtration of the second product, the obtained solid was subjected to a third contact by thoroughly mixing and stirring with 2.5 mol of ethanol (second alcohol compound) and 0.25 mol of 1,3-dichloropropanol (halogenated alcohol) to form a liquid, thereby obtaining a third product.

[0112] (4) Using an atomizer B-290 equipped with a nozzle head and a material conduit, the third product was sprayed into circulating nitrogen at 100°C in a spray tower for spray drying to obtain a catalyst spherical support Z2, the temperature of the third product in the material conduit was 15°C, and the temperature of the third product in the nozzle head was 120°C.

[0113] After testing, the structure and composition of the obtained catalyst spherical support Z2 were found to be as follows:

[0114] [ka]

[0115] The catalyst spherical carrier Z2 was tested with an average particle size (D50) of 4 microns and a particle size distribution ((D90-D10) / D50) of 0.8.

[0116] It was observed that the particles of the spherical support Z2 for the olefin polymerization catalyst had a relatively regular shape, a smooth surface, and substantially all particles were spherical. In addition, the spherical support Z2 had a relatively concentrated particle size distribution and essentially did not contain particles with special shapes.

[0117] In the manufacturing process of the catalyst spherical carrier Z2, no clogging occurred at the nozzle head of the atomizer, and a total of 11.9 g of catalyst spherical carrier Z2 was obtained.

[0118] Example 3 (1) 0.08 mol of magnesium dichloride and 1.4 mol of ethanol (first alcohol compound) were added to a 0.6 L reaction vessel, and the temperature was raised to 90°C with stirring. The contents were reacted at that constant temperature for 1.5 hours to perform a first contact, and a shear force was applied to the resulting mixture to obtain a first product.

[0119] (2) The first product was subjected to a second contact with 0.35 mol of epichlorohydrin to obtain a second product, and the second contact conditions included a temperature of 90° C. and a time of 30 minutes.

[0120] (3) After pressure filtration of the second product, the resulting solid was subjected to a third contact by combining and stirring with 2.5 mol of ethanol (second alcohol compound) and 0.1 mol of 1,3-dichloropropanol (halogenated alcohol), thereby obtaining a third product.

[0121] (4) Using an atomizer B-290 equipped with a nozzle head and a material conduit, the third product was sprayed into circulating nitrogen at 100°C in a spray tower for spray drying to obtain spherical carrier Z3, wherein the temperature of the third product in the material conduit was 15°C, and the temperature of the third product in the nozzle head was 120°C.

[0122] After testing, the structure and composition of the obtained catalyst spherical support Z3 were found to be as follows:

[0123] [ka]

[0124] The catalyst spherical carrier Z3 was tested with an average particle size (D50) of 5 microns and a particle size distribution ((D90-D10) / D50) of 0.8.

[0125] The particles of the catalyst spherical support Z3 were observed to have a relatively regular shape, a smooth surface, and substantially all of the particles were spherical. It was also observed that the catalyst spherical support Z3 had a relatively concentrated particle size distribution and essentially did not contain particles with special shapes.

[0126] In the manufacturing process of the catalyst spherical support Z3, no clogging occurred at the nozzle head of the atomizer, and a total of 12.0 g of catalyst spherical support Z3 was obtained.

[0127] Example 4 (1) 0.08 mol of magnesium dichloride and 1.4 mol of ethanol (first alcohol compound) were added to a 0.6 L reaction vessel, and the temperature was raised to 90°C with stirring. The contents were reacted at that constant temperature for 1.5 hours to perform a first contact, and a shear force was applied to the resulting mixture to obtain a first product.

[0128] (2) The first product was subjected to a second contact with 0.35 mol of epichlorohydrin to obtain a second product, and the second contact conditions included a temperature of 90°C and a time of 30 minutes.

[0129] (3) After pressure filtration of the second product, the resulting solid was stirred with 2.5 mol of ethanol (second alcohol compound) and 0.25 mol of 1,3-dichloropropanol (halogenated alcohol), and then sonicated using an ultrasonic probe for a total of 6 times, each time for 30 minutes, to form a liquid, thereby obtaining a third product.

[0130] (4) Using an atomizer B-290 equipped with a nozzle head and a material conduit, the third product was sprayed into circulating nitrogen at 100°C in a spray tower for spray drying to obtain catalyst spherical carrier Z4, the temperature of the third product in the material conduit was 20°C, and the temperature of the third product in the nozzle head was 120°C.

[0131] After testing, the structure and composition of the obtained catalyst spherical support Z4 were found to be as follows:

[0132] [ka]

[0133] The catalyst spherical carrier Z4 was tested with an average particle size (D50) of 5 microns and a particle size distribution ((D90-D10) / D50) of 1.0.

[0134] It was observed that the particles of the spherical support Z4 of the olefin polymerization catalyst have a relatively regular shape, a smooth surface, and substantially all of the particles are spherical. In addition, the spherical support Z4 has a relatively concentrated particle size distribution and basically does not contain particles with special shapes.

[0135] In the manufacturing process of the catalyst spherical carrier Z4, no clogging occurred at the nozzle head of the atomizer, and a total of 12.4 g of catalyst spherical carrier Z4 was obtained.

[0136] Comparative Example 1 (1) 0.08 mol of magnesium dichloride and 1.4 mol of ethanol were added to a 0.6 L reaction vessel, and the temperature was raised to 90°C while stirring. The contents were reacted at that temperature for 1.5 hours. Thereafter, 0.35 mol of epichlorohydrin was added, and the contents were reacted at 90°C for 30 minutes to obtain a liquid mixture.

[0137] (2) Using an atomizer equipped with a nozzle head and a material conduit, the liquid mixture was sprayed into circulating nitrogen at 100°C to obtain the olefin polymerization catalyst support DZ1, where the temperature of the liquid mixture in the material conduit was 90°C and the temperature of the liquid mixture in the nozzle head was 120°C.

[0138] During the spraying process, the liquid mixture from step (1) is prone to settling, which prevents the spray drying from proceeding normally and tends to cause nozzle clogging.

[0139] The olefin polymerization catalyst support DZ1 was tested with an average particle size (D50) of 15 microns and a particle size distribution ((D90-D10) / D50) of 1.3.

[0140] Comparative Example 2 (1) 0.08 mol of magnesium dichloride and 1.7 mol of ethanol were added to a 0.6 L reactor, and the temperature was raised to 90°C with stirring. The contents were reacted at that temperature for 1 hour. Thereafter, 0.48 mol of epichlorohydrin was added, and the contents were reacted at 90°C for 30 minutes to obtain a first product.

[0141] (2) After pressure filtration of the first product, 2.5 mol of ethanol was added to the solid residue and stirred to form a liquid mixture.

[0142] (3) Using an atomizer equipped with a nozzle head and a material conduit, the liquid mixture was sprayed into circulating nitrogen at 100°C to obtain a catalyst support DZ2 for olefin polymerization. The temperature of the third product in the material conduit was 15°C, and the temperature of the third product in the nozzle head was 120°C.

[0143] The support DZ2 of the catalyst for obtaining olefin polymerization has an average particle size (D50) of 3 microns and a particle size distribution ((D90-D10) / D50) of 0.8.

[0144] Comparative Example 3 A catalyst spherical carrier was produced in the same manner as in Example 1, except that in step (3), no second alcohol compound was used, and only the same amount of halogenated alcohol (1,3-dichloropropanol) as in Example 1 was used, and the second product was thoroughly mixed and stirred to perform the third contact, thereby obtaining catalyst carrier DZ3.

[0145] During the manufacturing process of catalyst support DZ3, the support was sticky and agglomerated, making it impossible to carry out further operations.

[0146] In the experimental examples, an olefin polymerization catalyst was prepared using the spherical carrier of the olefin polymerization catalyst provided by the present invention, and polyolefins were prepared using the prepared olefin polymerization catalyst.

[0147] [Experimental Example 1-1] (1) Production of olefin polymerization catalysts 100 ml of titanium tetrachloride was added to a 300 ml reaction flask and cooled to -20°C. Next, 8 g of the catalyst spherical support Z1 obtained in Example 1 was added to the reaction flask, and the contents were stirred at -20°C for 30 minutes, then gradually heated to 110°C. 1.5 ml of diisobutyl phthalate was added during heating. After maintaining at 110°C for 30 minutes, the liquid was filtered off. The remaining solid was then washed twice with titanium tetrachloride and three times with hexane, and then dried to obtain olefin polymerization catalyst C1.

[0148] (2) Propylene polymerization Under a nitrogen atmosphere, a 5 L stainless steel autoclave was charged with 1 mmol of triethylaluminum in hexane (triethylaluminum concentration: 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 gas, and 2.5 L of liquid propylene monomer. The contents were heated to 70 °C, and polymerization was continued at 70 °C for 1 hour. The autoclave was cooled, and then the pressure was vented. The resulting polymer was discharged and dried to obtain a polypropylene powder.

[0149] The catalyst produced in this example had an activity of 36.1 kg PP / g Cat; the resulting polypropylene powder had a bulk density of 0.41 g / cm 3 The melt flow rate was 11.9 g / 10 min. The polypropylene powder had a good particle morphology and was essentially free of particles with unusual shapes. The results are shown in Table 1 below.

[0150] [Experimental Example 1-2] Polypropylene was produced in the same manner as in Experimental Example 1-1, except that the volume of hydrogen used in step (2) was different. Specifically, 1.5 L (standard volume) of hydrogen was replaced with 6.5 L (standard volume) of hydrogen to obtain polypropylene powder.

[0151] The catalyst produced in this experiment had an activity of 36.0 kg PP / g Cat; the resulting polypropylene powder had a bulk density of 0.41 g / cm3 The melt flow rate was 45.8 g / 10 min. The polypropylene powder had a good particle morphology and was essentially free of particles with unusual shapes. The results are shown in Table 1 below.

[0152] [Experimental Example 2-1] Polypropylene was produced in the same manner as in Experimental Example 1-1, except that the type of catalyst support used in step (1) was different. Specifically, the catalyst spherical support Z1 was replaced with the same weight of the catalyst spherical support Z2 produced in Example 2 to obtain an olefin polymerization catalyst C2. Thereafter, polypropylene powder was produced using the olefin polymerization catalyst C2 according to the method described in step (2) of Experimental Example 1-1.

[0153] The catalyst produced in this example had an activity of 37.6 kg PP / g Cat; the resulting polypropylene powder had a bulk density of 0.41 g / cm 3 The melt flow rate was 11.0 g / 10 min. The polypropylene powder had a good particle morphology and was essentially free of particles with unusual shapes. The results are shown in Table 1 below.

[0154] [Experimental Example 2-2] Polypropylene was produced in the same manner as in Experimental Example 2-1, except that the volume of hydrogen used in step (2) was different. Specifically, 1.5 L (standard volume) of hydrogen was replaced with 6.5 L (standard volume) of hydrogen to obtain polypropylene powder.

[0155] The catalyst produced in this example had an activity of 37.2 kg PP / g Cat; the resulting polypropylene powder had a bulk density of 0.41 g / cm 3 The melt flow rate was 41.2 g / 10 min. The polypropylene powder had a good particle morphology and was essentially free of particles with unusual shapes. The results are shown in Table 1 below.

[0156] [Experimental Example 3-1] Polypropylene was produced in the same manner as in Experimental Example 1-1, except that the type of catalyst support used in step (1) was different. Specifically, the catalyst spherical support Z1 was replaced with the same weight of the catalyst spherical support Z3 produced in Example 3 to obtain an olefin polymerization catalyst C3. Thereafter, polypropylene powder was produced using the olefin polymerization catalyst C3 according to the method described in step (2) of Experimental Example 1-1.

[0157] The catalyst produced in this example had an activity of 38.5 kg PP / g Cat; the resulting polypropylene powder had a bulk density of 0.41 g / cm 3 The melt flow rate was 10.0 g / 10 min. The polypropylene powder had a good particle morphology and was essentially free of particles with unusual shapes. The results are shown in Table 1 below.

[0158] [Experimental Example 3-2] Polypropylene was produced in the same manner as in Experimental Example 3-1, except that the volume of hydrogen used in step (2) was different. Specifically, 1.5 L (standard volume) of hydrogen was replaced with 6.5 L (standard volume) of hydrogen to obtain polypropylene powder.

[0159] The catalyst produced in this example had an activity of 38.2 kg PP / g Cat; the resulting polypropylene powder had a bulk density of 0.41 g / cm 3 The melt flow rate was 39.0 g / 10 min. The polypropylene powder had a good particle morphology and was essentially free of particles with unusual shapes. The results are shown in Table 1 below.

[0160] Comparative Experimental Example 1 Polypropylene was produced in the same manner as in Experimental Example 1-1, except that the type of catalyst support used in step (1) was different. Specifically, the catalyst spherical support Z1 was replaced with the same weight of the catalyst spherical support DZ1 produced in Comparative Example 1 to obtain an olefin polymerization catalyst DC1. Thereafter, polypropylene powder was produced using the olefin polymerization catalyst DC1 according to the method described in step (2) of Experimental Example 1-1.

[0161] The catalyst produced in this example had an activity of 34.8 kg PP / g Cat; the resulting polypropylene powder had a bulk density of 0.37 g / cm 3 The melt flow rate was 9.1 g / 10 min. The results are shown in Table 1 below.

[0162] [Comparative Experimental Example 2-1] Polypropylene was produced in the same manner as in Experimental Example 1-1, except that the type of catalyst support used in step (1) was different. Specifically, the catalyst spherical support Z1 was replaced with the same weight of the catalyst spherical support DZ2 produced in Comparative Example 2 to obtain an olefin polymerization catalyst DC2. Thereafter, polypropylene powder was produced using the olefin polymerization catalyst DC2 according to the method described in step (2) of Experimental Example 1-1.

[0163] The catalyst produced in this example had an activity of 39.0 kg PP / g Cat; the resulting polypropylene powder had a bulk density of 0.41 g / cm 3 The melt flow rate was 9.5 g / 10 min. The results are shown in Table 1 below.

[0164] [Comparative Experimental Example 2-2] Polypropylene was produced in the same manner as in Comparative Experimental Example 2-1, except that the volume of hydrogen used in step (2) was different. Specifically, 1.5 L (standard volume) of hydrogen was replaced with 6.5 L (standard volume) of hydrogen to obtain polypropylene powder.

[0165] The catalyst produced in this example had an activity of 37.9 kg PP / g Cat; the resulting polypropylene powder had a bulk density of 0.41 g / cm 3 The melt flow rate was 37.5 g / 10 min. The results are shown in Table 1 below.

[0166] [Table 1]

[0167] From the above, it can be seen that the olefin polymerization catalyst support prepared by the method of the present invention has good particle morphology and is essentially free of particles with special morphology. Furthermore, the method provided by the present invention allows the preparation of catalyst supports with smaller particle sizes, thereby significantly expanding the particle size range of the support that can be produced. At the same time, when the catalyst prepared from the obtained support is used in olefin (particularly propylene) polymerization, the catalyst produces polypropylene powder with high activity, good particle morphology, and essentially free of particles with special morphology, and also exhibits high sensitivity to hydrogen modulation.

[0168] In particular, a comparison between Comparative Example 2 and Example 1 reveals that Comparative Example 2 can obtain a catalyst support with a smaller particle size, but when a catalyst produced from the support produced in Comparative Example 2 is used in olefin polymerization (particularly propylene polymerization), the polymer has a smaller melt index and is less sensitive to hydrogen modulation.

[0169] Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited thereto. Within the technical spirit of the present invention, various simple modifications can be made to the technical solutions of the present invention, including combining various technical features in any other suitable manner. These simple modifications and combinations should be considered as the contents disclosed in the present invention and fall within the protection scope of the present invention. [Brief explanation of the drawings]

[0170] [Figure 1] FIG. 1 is an electron microscope photograph of the spherical carrier of Example 1.

Claims

1. A spherical support for an olefin polymerization catalyst, comprising a magnesium-containing compound having a structure represented by formula (1): 【Chemistry 1】 In formula (1), R １ is C alkyl; R ２ and R ３ are each independently selected from the group consisting of H, a C1-5 alkyl group, and a C1-5 alkyl group substituted with 1 to 10 halogen atoms; R ４ is a C substituted with at least one halogen atom １－１０ C substituted with an alkyl group and at least one halogen atom ６－２０ aryl groups; R ５ is C1-2 alkyl; X is selected from the group consisting of fluorine, chlorine, bromine and iodine; m is 0.1 to 1.9, n is 0.1 to 1.9, and m+n=2; 0<q<0.2; 0<a<0.

1.

2. The spherical carrier according to claim 1, having at least one of the following characteristics: -R １ But C １－６ is alkyl; -R ４ is C substituted with at least two halogen atoms １－１０ C substituted with an alkyl group and at least two halogen atoms ６－２０ aryl groups; and -X is selected from the group consisting of chlorine and bromine.

3. 2. The spherical carrier according to claim 1, wherein the spherical carrier has an average particle size of 2 to 100 microns and a particle size distribution of less than 2.

4. The spherical carrier according to claim 1, wherein the spherical carrier has an average particle size of 2 to 19 microns and a particle size distribution of 0.6 to 1.

6.

5. A method for producing a spherical carrier for an olefin polymerization catalyst, comprising the following steps (1) to (4): (1) subjecting Component A to a first contact and then applying shear force to the resulting mixture to obtain a first product, wherein Component A is a magnesium halide of general formula MgXY and a magnesium halide of general formula R １ OH primary alcohol; (2) subjecting the first product and component B to a second contact to obtain a second product, wherein component B comprises an oxirane-type compound having a structure represented by formula (2): 【Chemistry 2】 (3) subjecting the second product and component C to a third contact to obtain a third product, wherein component C is a compound represented by the general formula R ４ Halogenated alcohols of the general formula R ５ OH secondary alcohol; and (4) spray drying the third product; where: Formula R １ During OH, R １ is C alkyl; In the formula (2), R ２ and R ３ are each independently selected from the group consisting of H, a C1-5 alkyl group, and a C1-5 alkyl group substituted with 1 to 10 halogen atoms; Formula R ４ During OH, R ４ is a C substituted with at least one halogen atom １－１０ C substituted with an alkyl group and at least one halogen atom ６－２０ aryl groups; Formula R ５ During OH, R ５ is C1-2 alkyl; In the formula MgXY, X is selected from the group consisting of fluorine, chlorine, bromine, and iodine; and Y is selected from the group consisting of fluorine, chlorine, bromine, iodine, C １－６ Alkyl, C １－６ Alkoxy, C ６－１４ Aryl and C ６－１４ aryloxy; The amount of the component A, the amount of the component B, and the amount of the component C are such that the resulting spherical carrier contains a magnesium-containing compound having a structure represented by formula (1); 【Transformation 3】 In formula (1), R １ ~R ５ and X is as defined above; m is 0.1 to 1.9, n is 0.1 to 1.9, and m+n=2; 0<q<0.2; 0<a<0.1; and In step (3), the amount of the halogenated alcohol used is 0.05 to 6.5 mol, and the amount of the second alcohol used is 5 to 100 mol, relative to 1 mol of the magnesium halide used.

6. 6. The method of claim 5, having at least one of the following features: In the formula MgXY, X is selected from the group consisting of 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; - the formula R １ During OH, R １ is C1-6 alkyl; The oxirane compound is at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epoxychlorobutane, epoxybromopropane, and epoxybromobutane; - the formula R ４ During OH, R ４ is C substituted with at least two halogen atoms １－１０ C substituted with an alkyl group and at least two halogen atoms ６－２０ aryl groups; - the amount of the first alcohol compound used is 6 to 22 mol, the amount of the oxirane compound used is 2 to 6 mol, the amount of the halogenated alcohol used is 1 to 5 mol, and the amount of the second alcohol compound used is 8 to 80 mol, relative to 1 mol of the magnesium halide used; In step (1), the first contact is carried out under stirring, and the conditions for the first contact include a temperature of 80 to 120°C and a time of 0.5 to 5 hours; In step (2), the conditions for the second contact include a temperature of 50 to 120°C and a time of 20 to 60 minutes; - in step (3), the third contact conditions include stirring, a temperature of 0 to 120°C, and a time of 0.5 to 6 hours; and In step (4), the spray drying conditions include a temperature of 60 to 200°C.

7. The magnesium halide is at least one selected from the group consisting of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride, and n-butoxymagnesium chloride; The first alcohol compound is at least one selected from the group consisting of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, n-octanol, and 2-ethylhexanol; and 6. The method of claim 5, wherein the halogenated alcohol is at least one selected from the group consisting of 2,2,2-trichloroethanol, 2,2-dichloroethanol, 1,2-dichloroethanol, 1,3-dichloropropanol, and 1,4-dichlorobutanol.

8. - In step (1), the conditions of the first contact include a temperature of 80 to 100°C and a time of 0.5 to 3 hours; - in step (2), the conditions of the second contacting include a temperature of 80 to 100°C and a time of 20 to 50 minutes; and The method according to claim 5, wherein in step (4), the conditions of the spray drying include a temperature of 90 to 150°C.

9. A catalyst comprising the spherical support according to claim 1.

10. A process for olefin polymerization comprising contacting a C2 to C10 olefin monomer with the catalyst of claim 9 under polymerizable conditions to form an olefin polymer, and recovering the olefin polymer.

11. The process for olefin polymerization described in claim 10, wherein the step of contacting the C2 to C10 olefin monomer with the catalyst described in claim 9 under polymerizable conditions to form an olefin polymer further comprises introducing a comonomer into the polymerization system.

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