Catalyst support for olefin polymerization and its preparation method and application

Abstract

The application belongs to the field of catalysts, and discloses an olefin polymerization catalyst carrier and a preparation method and application thereof. The preparation method of the olefin polymerization catalyst carrier comprises the following steps: (1) mixing magnesium halide and an alcohol compound, and then reacting with an oxirane compound to obtain a first reactant; (2) dissolving the first reactant obtained in step (1) in a solvent to obtain a first mixture; (3) adding an ethanol silver carboxylate solution to the first mixture obtained in step (2) to obtain a second mixture, and solidifying to obtain the olefin polymerization catalyst carrier; optionally, the step (1) further comprises adding an inert liquid solvent. The olefin polymerization catalyst carrier prepared by the method has the advantages of not being prone to adhesion and good morphology. The catalyst prepared by using the olefin polymerization catalyst carrier prepared by the application has the advantage of high catalytic activity.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of catalyst technology, in particular to an olefin polymerization catalyst carrier and a preparation method thereof, and application of the olefin polymerization catalyst carrier in preparing a catalyst for olefin polymerization or in olefin polymerization. BACKGROUND

[0002] Currently, the spherical catalyst widely used in industry is based on magnesium chloride alcoholates, because the catalyst supported thereon has good performance when used in olefin (especially propylene) polymerization, and the source thereof is relatively convenient.

[0003] The spherical magnesium chloride alcoholate carrier is generally prepared by mixing magnesium chloride with alcohol, then melting at high temperature, and then preparing a melt with good dispersibility through high-pressure extrusion, high-speed stirring, emulsification machine method, supergravity rotating bed method, and the like, and then rapidly cooling the melt to obtain a spherical carrier. Patent documents WO1999044009A1 and US4399054 disclose that a spherical magnesium chloride alcoholate can be formed by high-temperature high-speed stirring emulsification of a magnesium chloride alcoholate system, followed by rapid cooling. The carrier production by this method requires high-temperature reaction and rapid cooling process, which results in large energy consumption in the production process and a long process flow, and requires multiple reactors for joint preparation, and the final obtained carrier has a wide particle size distribution.

[0004] In order to solve the problem, Chinese patent document CN102040683A discloses a method for preparing a carrier by reacting a magnesium halide alcoholate with an oxirane compound, i.e. melting and dispersing the magnesium halide alcoholate, and then adding the oxirane compound; or melting and dispersing the magnesium halide alcoholate, and then directly adding to a reactor containing the oxirane compound. However, the catalyst carrier prepared by the method of the patent has the problems of unstable preparation process, easy carrier adhesion, and poor carrier forming effect.

[0005] Therefore, it is of great significance to develop a new olefin polymerization catalyst carrier which can overcome the above-mentioned defects of the prior art. SUMMARY

[0006] The technical problem to be solved by the present application is to provide an olefin polymerization catalyst carrier and a preparation method and application thereof, in order to solve the problems of unstable preparation process, easy carrier adhesion, and poor forming effect of the olefin polymerization catalyst carrier in the prior art.

[0007] The inventors of the present application have unexpectedly found that, in the preparation of the catalyst carrier for olefin polymerization, after the reaction of the magnesium halide, the alcohol compound and the ethylene oxide compound to form a solid, the solid obtained by removing the mother liquor is dissolved in ethanol to form a fluid material, and the silver carboxylate ethanol solution is added for spray solidification, so that the catalyst carrier for olefin polymerization obtained is not prone to adhesion and has a good morphology; the catalyst prepared by using the catalyst carrier for olefin polymerization prepared by the present application has better hydrogen regulation sensitivity and good activity, and the polymerization reaction product prepared has high bulk density and excellent elution resistance.

[0008] To solve the above technical problems, the present application provides a preparation method of a catalyst carrier for olefin polymerization, comprising the following steps:

[0009] (1) mixing the magnesium halide and the alcohol compound, and then reacting with the ethylene oxide compound to obtain a first reaction product;

[0010] (2) dissolving the first reaction product obtained in step (1) in a solvent to obtain a first mixture;

[0011] (3) adding the silver carboxylate ethanol solution to the first mixture obtained in step (2) to obtain a second mixture, and solidifying to obtain the catalyst carrier for olefin polymerization;

[0012] Optionally, step (1) further comprises adding an inert liquid solvent.

[0013] According to some embodiments of the present application, in step (1), the general formula of the magnesium halide is MgXY, the general formula of the alcohol compound is R1OH, and the structural formula of the ethylene oxide compound is shown as formula (I).

[0014]

[0015] According to some embodiments of the present application, in the general formula MgXY, X is halogen, Y is halogen, C1-C5 alkyl, C1-C5 alkoxy, C6-C10 aryl or C6-C10 aryloxy; further preferably, in the general formula MgXY, X is fluorine, chlorine or bromine, Y is fluorine, chlorine, bromine, C1-C5 alkyl, C1-C5 alkoxy, C6-C10 aryl or C6-C10 aryloxy; the C1-C5 alkyl may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or neopentyl, the C1-C5 alkoxy may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, and the C6-C10 aryl may be, for example, phenyl, naphthyl or biphenyl. 14 14 14 14 10 10 ​​​​​​10 The aryl group can be, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, or naphthyl, wherein the C6-C 10 The aryloxy group can be, for example, phenoxy or naphthoxy; the magnesium halide with the general formula MgXY can be a single magnesium halide or a mixture of multiple magnesium halides; more preferably, the magnesium halide with the general formula MgXY is selected from at least one of magnesium chloride, magnesium bromide, magnesium phenoxy chloride, magnesium isopropoxy chloride and magnesium n-butoxy chloride.

[0016] According to some embodiments of the present invention, in the general formula R1OH, R1 is a C1-C8 straight-chain alkyl, a C3-C8 branched-chain alkyl, or a C3-C8 cycloalkyl; preferably, in the general formula R1OH, R1 is a C1-C6 straight-chain alkyl, a C3-C6 branched-chain alkyl, or a C3-C8 cycloalkyl; more preferably, in the general formula R1OH, R1 is a C1-C5 straight-chain alkyl, a C3-C5 branched-chain alkyl, or a C3-C6 cycloalkyl. More preferably, in the general formula R1OH, R1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, cyclopropyl, cyclopentyl, methylcyclopropyl, dimethylcyclopropyl, cyclohexyl, or methylcyclopentyl; even more preferably, the alcohol compound of the general formula R1OH is selected from at least one of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentyl alcohol, n-hexanol, n-octanol, and 2-ethylhexanol.

[0017] According to some embodiments of the present invention, in formula (I), R2 and R3 may be the same or different, each being independently hydrogen, a C1-C5 straight-chain alkyl group, or a C3-C5 branched alkyl group, wherein the hydrogen on the alkyl group is optionally substituted by a halogen atom; preferably, R2 and R3 may be the same or different, each being independently hydrogen, a C1-C3 straight-chain alkyl group, or a C1-C3 haloalkyl group; more preferably, R2 and R3 may be the same or different, each being independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, chloromethyl, bromomethyl, chloroethyl, chloropropyl, or bromopropyl; even more preferably, the ethylene oxide compound is selected from at least one of ethylene oxide, propylene oxide, epibutylene oxide, epichlorohydrin, epichlorobutylene oxide, epibromopropane, and epibromobutane.

[0018] According to some embodiments of the present invention, the silver carboxylate in the ethanol solution is selected from at least one of silver acetate, silver propionate, silver butyrate, and silver octanoate.

[0019] In this invention, the phrase "optionally, step (1) further includes adding an inert liquid solvent" means that the inert liquid solvent may or may not participate in the mixing. That is, the method of this invention may or may not require an inert liquid solvent.

[0020] In the present application, the halogen element includes fluorine, chlorine, bromine and iodine elements.

[0021] In the present application, the C1-C 14 alkyl group refers to an alkyl group having 1 to 14 carbon elements, including branched alkyl groups and branched alkyl groups, including unsubstituted alkyl groups and substituted alkyl groups in which hydrogen atoms are selectively substituted with halogen elements and the like.

[0022] In the present application, the C1-C 14 alkoxy group refers to an alkoxy group having 1 to 14 carbon elements, including branched alkoxy groups and branched alkoxy groups, including unsubstituted alkoxy groups and substituted alkoxy groups in which hydrogen atoms are selectively substituted with halogen elements and the like.

[0023] In the present application, the C6-C 14 aryl group refers to an aryl group having 6 to 14 carbon atoms, including a phenyl group, and the C6-C 14 aryl group can include an aryl group in which hydrogen atoms are substituted with halogen elements and the like.

[0024] In the present application, the C6-C 14 aryloxy group refers to an aryloxy group having 6 to 14 carbon atoms, including a phenoxy group, and the C6-C 14 aryloxy group can include an aryloxy group in which hydrogen atoms are substituted with halogen elements and the like.

[0025] In the present application, the C1-C5 alkyl group includes a methyl group, an ethyl group, a n-propyl group, an iso-propyl group, a n-butyl group, an iso-butyl group, a n-pentyl group, and an iso-pentyl group.

[0026] In the present application, the conditions for the reaction of the mixture of the magnesium halide of the general formula MgXY and the compound of the general formula R1OH with the oxirane compound having the structure as shown in formula (I) and the optional inert liquid solvent are not particularly limited, as long as the conditions for the mixing and the reaction allow the mixture of the magnesium halide of the general formula MgXY, the compound of the general formula R1OH and the oxirane compound having the structure as shown in formula (I) to form a solid-state material (the first reaction product).

[0027] According to some embodiments of the present application, in step (1), the temperature of the mixing is 70-90°C; and the time of the mixing is 0.5-2 hours.

[0028] According to some embodiments of the present application, in step (1), the temperature of the reaction is 70-90°C; and the time of the reaction is 0.5-2 hours.

[0029] According to some embodiments of the present application, in step (1), the inert liquid solvent is a silicone oil and / or an inert liquid hydrocarbon solvent; 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.

[0030] In the present application, the amount of the component used in the preparation of the catalyst carrier for olefin polymerization can be selected and varied within a wide range.

[0031] According to some embodiments of the present application, in step (1), the amount of the alcohol compound of the general formula R1OH is 4-30 mol, preferably 6-22 mol, based on 1 mol of the magnesium halide of the general formula MgXY; the amount of the oxirane compound of the formula (I) is 1-10 mol, preferably 2-6 mol; and the amount of the inert liquid solvent is 0-10 L, preferably 2-8 L.

[0032] In the present application, the conditions for mixing the solid substance (the first reactant) and the solvent are not particularly limited, as long as the mixed conditions allow the solid substance (the first reactant) and the solvent to form a fluidized mixed substance (the first mixture), and the fluidized mixed substance (the first mixture) can be solidified when added with the silver carboxylate ethanol solution to obtain a second mixture, and then introduced into the inert medium in the spray machine.

[0033] According to some embodiments of the present application, in step (2), the solvent is an alcohol; preferably, the solvent is at least one selected from methanol, ethanol, isopropanol, n-butanol and isobutanol.

[0034] According to some embodiments of the present application, in step (2), the amount of the silver carboxylate is 0.001-100 mol, preferably 0.001-10 mol, based on 1 mol of the magnesium halide of the general formula MgXY; and the amount of the solvent is 8-80 mol, preferably 30-50 mol.

[0035] According to some embodiments of the present application, in step (3), the solidification is performed in a spray machine; preferably, the spray machine is provided with an atomizing nozzle, which comprises a material guide pipe and a nozzle head, the second mixture is introduced into the nozzle head through the material guide pipe, and is sprayed into the tower body containing the inert medium in the spray machine for solidification; more preferably, the temperature of the second mixture in the material guide pipe is 0-80℃, and the temperature of the second mixture in the nozzle head is 80-180℃, preferably 120-180℃.

[0036] According to some embodiments of the present application, the inert medium in the atomizer is preferably at a temperature of 60-200°C, more preferably 90-150°C; the amount of the inert medium can be selected according to the amount of the magnesium halide of the general formula MgXY, and is preferably 0.8-10 L, more preferably 2-8 L, based on 1 mol of the magnesium halide of the general formula MgXY.

[0037] According to some embodiments of the present application, the inert medium can be an inert gas medium or an inert liquid medium, and the type of the inert medium is not particularly limited; the inert gas medium is preferably at least one selected from the group consisting of nitrogen, helium and carbon dioxide; the inert liquid medium is preferably a silicon oil and / or an inert liquid hydrocarbon solvent; more preferably, the inert liquid medium can be any liquid medium commonly used in the art that does not chemically interact with the reactants and the reaction products, such as at least one selected from the group consisting of kerosene, paraffin oil, vaseline oil, white oil, methyl silicon oil, ethyl silicon oil, methyl ethyl silicon oil, phenyl silicon oil and methyl phenyl silicon oil.

[0038] According to the present application, the conditions for solidifying the fluidized mixture (the second mixture) by atomization can be any conditions that can form a catalyst carrier for olefin polymerization, such as by injecting the fluidized mixture (the second mixture) into an atomizer so that the fluidized mixture (the second mixture) can contact the inert medium in the atomizer.

[0039] According to the present application, the fluidized mixture (the second mixture) can be emulsified by any method known to those skilled in the art. For example, the fluidized mixture (the second mixture) can be subjected to high-speed shearing to emulsify it. The method of high-speed shearing is known to those skilled in the art, such as by stirring the fluidized mixture (the second mixture) at a speed of 2000-5000 rpm. In addition, the fluidized mixture can be emulsified by any method disclosed in the prior art, such as by rotating the solution containing the liquid magnesium halide adduct in a high-gravity bed at a speed of 100-3000 rpm as disclosed in CN1267508C, by outputting the solution containing the liquid magnesium halide adduct in an emulsifier at a speed of 1500-8000 rpm as disclosed in CN1463990A, or by emulsifying the solution containing the liquid magnesium halide adduct by the spray method as disclosed in US6020279.

[0040] According to the present application, the method for preparing the catalyst carrier for olefin polymerization can further comprise solid-liquid separation of the product obtained after spray solidification, washing of the solid product and drying. The solid-liquid separation can be any method known in the art that can achieve separation of solid phase from liquid phase, such as suction filtration, pressure filtration or centrifugal separation, and preferably the method for solid-liquid separation is pressure filtration. The present application does not particularly limit the conditions for pressure filtration, and the conditions are determined so as to achieve separation of solid phase from liquid phase as fully as possible. The washing can be performed by any method known to those skilled in the art, such as washing the obtained solid product with inert hydrocarbon solvents (e.g. pentane, hexane, heptane, petroleum ether and gasoline). The present application does not particularly limit the conditions for drying, such as the temperature for drying can be 20-70°C and the time for drying can be 0.5-10 hours. According to the present application, the drying can be performed under normal pressure or reduced pressure.

[0041] According to the method for preparation of the present application, trace amounts of water in each of the above-mentioned reactants can also participate in the reaction to form the catalyst carrier for olefin polymerization.

[0042] According to the method for preparation of the present application, the possible water contained in the catalyst carrier for olefin polymerization comes from trace amounts of water carried by the synthetic raw materials and reaction medium.

[0043] The second aspect of the present application provides a catalyst carrier for olefin polymerization prepared by the above-mentioned method for preparing a catalyst carrier for olefin polymerization, and the molar ratio of silver element to magnesium element in the catalyst carrier for olefin polymerization is (0.001-0.5):1.

[0044] According to some embodiments of the present application, the average particle size of the catalyst carrier for olefin polymerization is 1-100 microns, preferably 1-80 microns; and / or, the particle size distribution of the catalyst carrier for olefin polymerization is less than 1.5, preferably less than 1.2. In this preferred embodiment, the catalyst for olefin polymerization prepared from the catalyst carrier for olefin polymerization can obtain olefin polymers with higher bulk density.

[0045] The inventors of the present application have unexpectedly found that, in the preparation of the catalyst carrier for olefin polymerization, after the reaction of magnesium halide with general formula MgXY, alcohol compound with general formula R1OH and oxirane compound with structural formula as shown in formula (I) to form a solid, the solid obtained by removing the mother liquor through solid-liquid separation is dissolved in ethanol to form a fluid substance, and the addition of silver carboxylate ethanol solution can affect the crystallization and packing of the carrier particles, and finally a carrier with good morphology is obtained.

[0046] The third aspect of the present application provides application of the above-mentioned olefin polymerization catalyst carrier or the olefin polymerization catalyst carrier prepared by the above-mentioned preparation method in preparation of a catalyst for olefin polymerization or in olefin polymerization.

[0047] The present application does not have a particular limitation on the conditions for application of the above-mentioned olefin polymerization catalyst carrier in preparation of a catalyst for olefin polymerization, and a person skilled in the art can prepare the catalyst for olefin polymerization according to the present application by using conventional technical means. In the examples of the present application, the catalyst is prepared by contacting the carrier prepared according to the present application with a titanium source and an internal electron donor compound, and the temperature and time for the contacting reaction are not particularly limited, which should not be understood as a limitation on the technical solution of the present application.

[0048] Advantages:

[0049] (1) The olefin polymerization catalyst carrier prepared by the method according to the present application is not prone to adhesion and has a good morphology;

[0050] (2) The catalyst prepared by using the olefin polymerization catalyst carrier prepared according to the present application has the advantage of high catalytic activity;

[0051] (3) When the olefin polymerization catalyst carrier is prepared by the method according to the present application, it is not necessary to use the surfactant that must be used in the prior art, thereby reducing the production cost;

[0052] (4) When the olefin polymerization catalyst prepared by using the olefin polymerization catalyst carrier according to the present application is used in an olefin polymerization reaction, the bulk density and the melt index of the obtained polymerization reaction product can be significantly improved compared with the prior art, and the obtained polymerization reaction product has excellent resistance to elution. DETAILED DESCRIPTION

[0053] The present application will be further described below in conjunction with examples. However, the present application is not limited by these examples.

[0054] In the following examples and comparative examples of the present application, the various raw materials used are commercially available, unless otherwise specified.

[0055] In the examples and comparative examples:

[0056] 1. The average particle size and particle size distribution of the olefin polymerization catalyst carrier are determined by using a Masters Sizer 2000 particle size instrument (manufactured by Malvern Instruments Ltd).

[0057] 2. The apparent morphology of the olefin polymerization catalyst carrier is observed by using an optical microscope of the Eclipse E200 type (commercially available from Nikon Corporation).

[0058] 3. The bulk density of the polyolefin powder is determined according to the method specified in GB / T 1636-2008.

[0059] 4. Elution test of the polyolefin powder: 10 g of the sample is washed 10 times with anhydrous ethanol, 100 ml each time, and is subjected to frozen sectioning. The silver content of the particles is analyzed by X-ray fluorescence spectroscopy. The ratio of the silver content after elution to the silver content before elution is defined as the elution resistance.

[0060] 5. The activity of the catalyst for olefin polymerization is calculated as follows: catalyst activity = (mass of the prepared polyolefin) / (mass of the solid component of the catalyst) g / g.

[0061] 6. The determination of the melt index (MI) of the polyolefin powder: determined according to ASTM D1238-99, under a load of 2.16 kg at 190°C.

[0062] Example 1

[0063] This example is used to illustrate the catalyst carrier for olefin polymerization and the preparation method thereof provided by the present application.

[0064] In a 0.6 L reaction kettle, 0.08 mol (8.0 g) of magnesium chloride, 1.7 mol of ethanol were added, and the temperature was raised to 90°C under stirring. After constant temperature reaction at 90°C for 1 hour, 0.48 mol of epichlorohydrin was added. After continuous reaction at 90°C for 30 minutes, pressure filtration was performed. In the pressure filtration product, 2.5 mol of ethanol was added, and stirring was performed until a fluidized mixture was formed. Then, silver acetate ethanol solution (silver acetate: ethanol = 0.2 g: 100 mL; silver acetate 0.0012 mol) was added, and the fluidized mixture was sprayed into circulating nitrogen using a sprayer with a nozzle head and a material conduit. The heating temperature of the nozzle head was 140°C, and the catalyst carrier for olefin polymerization Z1 was obtained.

[0065] The molar ratio of silver element to magnesium element in the above catalyst carrier for olefin polymerization Z1 is 0.014:1.

[0066] Example 2

[0067] This example is used to illustrate the catalyst carrier for olefin polymerization and the preparation method thereof provided by the present application.

[0068] In a 0.6 L reaction vessel, 0.08 mol (8.0 g) of magnesium chloride, 1.7 mol of ethanol were added, and the temperature was raised to 90°C under stirring, and after the reaction was carried out at the temperature of 90°C for 1 hour, 0.48 mol of epichlorohydrin was added, and the reaction was carried out at the temperature of 90°C for 30 minutes, and then the product was pressure-filtered, 2.5 mol of ethanol was added to the pressure-filtered product, and the mixture was stirred to form a fluidized mixture, and then silver acetate ethanol solution (silver acetate: ethanol = 0.1 g: 100 mL; silver acetate 0.0006 mol) was added, and the fluidized mixture was sprayed into circulating nitrogen using a spray machine equipped with a nozzle head and a material pipe, and the nozzle head was heated at a temperature of 140°C, to obtain a catalyst support Z2 for olefin polymerization.

[0069] The molar ratio of the silver element to the magnesium element in the catalyst support Z2 for olefin polymerization described above was 0.007: 1.

[0070] Example 3

[0071] This example is intended to illustrate the catalyst support for olefin polymerization and the method for producing the same according to the present application.

[0072] In a 0.6 L reaction vessel, 0.08 mol (8.0 g) of magnesium chloride, 1.7 mol of ethanol were added, and the temperature was raised to 90°C under stirring, and after the reaction was carried out at the temperature of 90°C for 1 hour, 0.48 mol of epichlorohydrin was added, and the reaction was carried out at the temperature of 90°C for 30 minutes, and then the product was pressure-filtered, 2.5 mol of ethanol was added to the pressure-filtered product, and the mixture was stirred to form a fluidized mixture, and then silver acetate ethanol solution (silver acetate: ethanol = 0.1 g: 100 mL; silver acetate 0.0006 mol) was added, and the fluidized mixture was sprayed into circulating nitrogen using a spray machine equipped with a nozzle head and a material pipe, and the nozzle head was heated at a temperature of 140°C, to obtain a catalyst support Z2 for olefin polymerization.

[0073] The molar ratio of the silver element to the magnesium element in the catalyst support Z3 for olefin polymerization described above was 0.012: 1.

[0074] Example 4

[0075] This example is intended to illustrate the catalyst support for olefin polymerization and the method for producing the same according to the present application.

[0076] In a 0.6 L reaction vessel, 0.08 mol (8.0 g) of magnesium chloride, 1.7 mol of ethanol were added, and the temperature was raised to 90°C under stirring, and after the reaction was kept at 90°C for 1 hour, 0.48 mol of epichlorohydrin was added, and the reaction was continued at 90°C for 30 minutes, and then filtered under pressure. To the filtered product, 2.5 mol of ethanol was added, and the mixture was stirred to form a fluidized mixture, and then 100 mL of ethanol was added, and the fluidized mixture was sprayed into circulating nitrogen using a spray machine equipped with a nozzle head and a material conduit, and the nozzle head was heated at 140°C to obtain a catalyst support Z3 for olefin polymerization.

[0077] The molar ratio of silver element to magnesium element in the catalyst support Z3 for olefin polymerization described above was 0.006:1.

[0078] Comparative Example 1

[0079] This comparative example was used to illustrate the catalyst support for olefin polymerization and the method for preparing the same according to the present application.

[0080] In a 0.6 L reaction vessel, 0.08 mol of magnesium chloride, 1.7 mol of ethanol were added, and the temperature was raised to 90°C under stirring, and after the reaction was kept at 90°C for 1 hour, 0.48 mol of epichlorohydrin was added, and the reaction was continued at 90°C for 30 minutes, and then filtered under pressure. To the filtered product, 2.5 mol of ethanol was added, and the mixture was stirred to form a fluidized mixture, and then 100 mL of ethanol was added, and the fluidized mixture was sprayed into circulating nitrogen using a spray machine equipped with a nozzle head and a material conduit, and the nozzle head was heated at 140°C to obtain a catalyst support Z3 for olefin polymerization.

[0081] The catalyst support DZ1 did not contain silver element according to elemental analysis.

[0082] Comparative Example 2

[0083] This comparative example was used to illustrate the catalyst support for olefin polymerization and the method for preparing the same according to the present application.

[0084] The preparation method of Example 1 was used, except that 2.5 mol of ethanol was not added to the filtered product, and 0.2 g of silver acetate was used instead of silver acetate ethanol solution (silver acetate: ethanol = 0.2 g: 100 mL; silver acetate 0.0012 mol), and finally, the nozzle was clogged during spraying, and the catalyst support DZ2 for olefin polymerization could not be obtained.

[0085] The average particle diameter (D50), the particle diameter distribution ((D90-D10) / D50) and the apparent morphology of the catalyst support for olefin polymerization prepared in the above Examples 1-4 and Comparative Examples 1-2 were measured and observed, and the results are shown in Table 1 below.

[0086] Table 1

[0087]

[0088]

[0089] Example 5

[0090] This example is used to illustrate the use of the catalyst support for olefin polymerization of the present application for the preparation of polyolefin.

[0091] (1) Preparation of catalyst component for olefin polymerization

[0092] In a 300 mL reaction bottle, 100 mL of titanium tetrachloride was added, cooled to -20°C, then 8 grams of the catalyst support for olefin polymerization Z1 obtained in Example 1 was added, and stirred at a temperature of -20°C for 30 min, then slowly warmed up to 110°C, and 1.5 mL of diisobutyl phthalate was added during the warming up, then maintained at a temperature of 110°C for 30 min, then the liquid was filtered out, then washed with titanium tetrachloride for 2 times, and finally washed with hexane for 3 times, dried to obtain the catalyst component C1 for olefin polymerization.

[0093] (2) Propylene polymerization reaction

[0094] In a 5 L stainless steel autoclave, purged with nitrogen gas flow, then 1 mmol of triethylaluminum hexane solution (concentration of triethylaluminum is 0.5 mmol / mL), 0.05 mmol of methylcyclohexyldimethoxysilane, 10 mL of anhydrous hexane and 10 mg of the catalyst component C1 for olefin polymerization obtained in the above step (1), 1.5 L (standard volume) of hydrogen and 2.5 L of liquid propylene were introduced into the nitrogen gas flow, warmed up to 70°C, and the polymerization reaction was carried out at this temperature for 1 hour, then cooled down, released the pressure, and the polypropylene powder was obtained after drying.

[0095] Example 6

[0096] This example is used to illustrate the use of the catalyst support for olefin polymerization of the present application for the preparation of polyolefin.

[0097] The propylene polymerization was carried out according to the method of Example 5, except that the 1.5 L (standard volume) of hydrogen was replaced by 6.5 L (standard volume) of hydrogen.

[0098] Example 7

[0099] This example is used to illustrate the use of the catalyst support for the polymerization of olefins of the present application for the preparation of polyolefins.

[0100] The polymerization of propylene was carried out according to the method of Example 5, except that the catalyst support for the polymerization of olefins Z1 was replaced by the catalyst support for the polymerization of olefins Z2 obtained in Example 2, to obtain the catalyst component for the polymerization of olefins and polypropylene powder.

[0101] Example 8

[0102] This example is used to illustrate the use of the catalyst support for the polymerization of olefins of the present application for the preparation of polyolefins.

[0103] The polymerization of propylene was carried out according to the method of Example 7, except that the 1.5 L (standard volume) of hydrogen was replaced by 6.5 L (standard volume) of hydrogen.

[0104] Example 9

[0105] This example is used to illustrate the use of the catalyst support for the polymerization of olefins of the present application for the preparation of polyolefins.

[0106] The polymerization of propylene was carried out according to the method of Example 5, except that the catalyst support for the polymerization of olefins Z1 was replaced by the catalyst support for the polymerization of olefins Z3 obtained in Example 3, to obtain the catalyst component for the polymerization of olefins and polypropylene powder.

[0107] Example 10

[0108] This example is used to illustrate the use of the catalyst support for the polymerization of olefins of the present application for the preparation of polyolefins.

[0109] The polymerization of propylene was carried out according to the method of Example 9, except that the 1.5 L (standard volume) of hydrogen was replaced by 6.5 L (standard volume) of hydrogen.

[0110] Example 11

[0111] This example is used to illustrate the use of the catalyst support for the polymerization of olefins of the present application for the preparation of polyolefins.

[0112] The polymerization of propylene was carried out according to the method of Example 5, except that the catalyst support for the polymerization of olefins Z1 was replaced by the catalyst support for the polymerization of olefins Z4 obtained in Example 4, to obtain the catalyst component for the polymerization of olefins and polypropylene powder.

[0113] Example 12

[0114] This example is used to illustrate the use of the catalyst support for the polymerization of olefins of the present application for the preparation of polyolefins.

[0115] The propylene polymerization was carried out according to the method of Example 11, except that 6.5 L (standard volume) of hydrogen was used instead of 1.5 L (standard volume) of hydrogen.

[0116] Comparative Example 3

[0117] This comparative example is used to illustrate the preparation of polyolefins using the catalyst support for olefin polymerization according to the present application.

[0118] The propylene polymerization was carried out according to the method of Example 5, except that the catalyst support for olefin polymerization Zl was replaced by the catalyst support for olefin polymerization DZl obtained in Comparative Example 1 to obtain the catalyst component for olefin polymerization and polypropylene powder.

[0119] Comparative Example 4

[0120] This comparative example is used to illustrate the preparation of polyolefins using the catalyst support for olefin polymerization according to the present application.

[0121] The propylene polymerization was carried out according to the method of Example 5, except that 6.5 L (standard volume) of hydrogen was used instead of 1.5 L (standard volume) of hydrogen.

[0122] The catalyst components for olefin polymerization obtained in Examples 5-12 and Comparative Examples 3-4 above were used in the propylene polymerization reaction, the catalytic activity of the catalyst for olefin polymerization in Examples 5-12 and Comparative Examples 3-4 was calculated at 1 hour of polymerization reaction, and the appearance of the prepared polypropylene powder was observed, and the results are shown in Table 2 below:

[0123] Table 2

[0124]

[0125] In Table 2, * indicates that the prepared polypropylene powder was first immersed in the same amount of silver acetate ethanol solution as in Example 1 for 1 h, vacuum dried, and then subjected to the washing resistance test.

[0126] From the above results, it can be seen that the particle morphology of the catalyst support for olefin polymerization prepared by the method of the present application is good, and no abnormal particles are present, and the catalyst prepared using the obtained support has good polymerization activity and no abnormal particles are present when used in olefin (particularly propylene) polymerization, the bulk density and melt index of the prepared polymer product are obviously higher than those of the prior art, and the washing resistance is excellent, which has great industrial application prospects.

[0127] It should be noted that the foregoing examples have been provided merely for the purposes of illustration and are not intended to limit the application in any way. Descriptions and examples of materials and processes of the application are intended to be illustrative not limiting. Any modifications of the application and other applications of the application will occur to those skilled in the art to which the application pertains and many options for modification of the application will suggest themselves. The application lies in the broadest aspects of the technological concepts involved. Descriptions and examples of specific chemical materials and processes are intended to be illustrative of the application and it is intended that requests for patent protection be limited to one of the specific embodiments described above, described in the following claims, and any equivalents thereof.

Claims

1. A method for preparing a catalyst support for olefin polymerization, characterized in that, Includes the following steps: (1) After mixing magnesium halide and alcohol compounds, react with ethylene oxide compounds to obtain the first reactant; (2) Dissolve the first reactant obtained in step (1) in a solvent to obtain a first mixture; (3) Add silver carboxylate ethanol solution to the first mixture obtained in step (2) to obtain a second mixture, and solidify it to obtain the catalyst support for olefin polymerization; Optionally, step (1) may further include adding an inert liquid solvent; In step (1), the general formula of the magnesium halide is MgXY; In the general formula MgXY, X is a halogen, Y is a halogen, and C1-C 14 Alkyl, C1-C 14 alkoxy groups, C6-C 14 aryl or C6-C 14 aryloxy groups; The structural formula of the ethylene oxide compounds is shown in formula (I); Formula (I); In formula (I), R2 and R3 may be the same or different, and each is independently hydrogen, a C1-C5 straight-chain alkyl or a C3-C5 branched alkyl, wherein the hydrogen on the alkyl group is optionally replaced by a halogen atom; The silver carboxylate in the silver carboxylate ethanol solution is selected from at least one of silver acetate, silver propionate, silver butyrate, and silver octanoate. Based on 1 mol of magnesium halide with the general formula MgXY, the amount of silver carboxylate used is 0.001-100 mol.

2. The preparation method according to claim 1, characterized in that, In step (1), the general formula of the alcohol compound is R1OH; In the general formula R1OH, R1 is a C1-C8 straight-chain alkyl, a C3-C8 branched alkyl, or a C3-C8 cycloalkyl.

3. The preparation method according to claim 2, characterized in that, In the general formula R1OH, R1 is a straight-chain alkyl group of C1-C6, a branched alkyl group of C3-C6, or a cycloalkyl group of C3-C8.

4. The preparation method according to claim 3, characterized in that, In the general formula R1OH, R1 is a straight-chain alkyl group of C1-C5, a branched alkyl group of C3-C5, or a cycloalkyl group of C3-C6.

5. The preparation method according to claim 4, characterized in that, In the general formula R1OH, R1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, cyclopropyl, cyclopentyl, methylcyclopropyl, dimethylcyclopropyl, cyclohexyl, or methylcyclopentyl.

6. The preparation method according to claim 2, characterized in that, Alcohols with the general formula R1OH are selected from at least one of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isoamyl alcohol, n-hexanol, n-octanol, and 2-ethylhexanol.

7. The preparation method according to any one of claims 1-6, characterized in that, In the general formula MgXY, X is fluorine, chlorine, or bromine, and Y is fluorine, chlorine, bromine, C1-C5 alkyl, C1-C5 alkoxy, or C6-C5 alkyl. 10 aryl or C6-C 10 aryloxy groups; And / or, in formula (I), R2 and R3 may be the same or different, and each may be hydrogen, a C1-C3 straight-chain alkyl or a C1-C3 haloalkyl.

8. The preparation method according to claim 1, characterized in that, Magnesium halides with the general formula MgXY are selected from at least one of magnesium chloride, magnesium bromide, magnesium phenoxy chloride, magnesium isopropoxy chloride, and magnesium n-butoxy chloride. And / or, in formula (I), R2 and R3 may be the same or different, and each may be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, chloromethyl, bromomethyl, chloroethyl, chloropropyl, or bromopropyl.

9. The preparation method according to any one of claims 1-6, characterized in that, The ethylene oxide compounds are selected from at least one of ethylene oxide, propylene oxide, butane oxide, epichlorohydrin, chlorobutane, bromopropane, and bromobutane.

10. The preparation method according to any one of claims 1-6, characterized in that, In step (1), the mixing temperature is 70-90℃; the mixing time is 0.5-2 hours; And / or, the reaction temperature is 70-90°C; the reaction time is 0.5-2 hours; And / or, the inert liquid solvent is silicone oil and / or an inert liquid hydrocarbon solvent; And / or, based on 1 mol of magnesium halide with the general formula MgXY, the amount of alcohol compound with the general formula R1OH is 4-30 mol; the amount of ethylene oxide compound shown in formula (I) is 1-10 mol; and the amount of the inert liquid solvent is 0-10 L.

11. The preparation method according to claim 10, characterized in that, The inert liquid solvent is selected from at least one of kerosene, paraffin oil, petrolatum oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil, and methyl phenyl silicone oil; And / or, based on 1 mol of magnesium halide with the general formula MgXY, the amount of alcohol compound with the general formula R1OH is 6-22 mol; the amount of ethylene oxide compound shown in formula (I) is 2-6 mol; and the amount of the inert liquid solvent is 2-8 L.

12. The preparation method according to any one of claims 1-6, characterized in that, In step (2), the solvent is an alcohol; And / or, based on 1 mol of magnesium halide with the general formula MgXY, the amount of silver carboxylate is 0.001-10 mol; the amount of solvent is 8-80 mol.

13. The preparation method according to claim 12, characterized in that, In step (2), the solvent is selected from at least one of methanol, ethanol, isopropanol, n-butanol, and isobutanol; And / or, based on 1 mol of magnesium halide with the general formula MgXY, the amount of solvent used is 30-50 mol.

14. The preparation method according to any one of claims 1-6, characterized in that, In step (3), the curing is carried out in a sprayer.

15. The preparation method according to claim 14, characterized in that, The sprayer is equipped with an atomizing nozzle, which includes a material conduit and a nozzle head.

16. The preparation method according to claim 15, characterized in that, The temperature of the second mixture in the material conduit is 0-80°C, and the temperature in the nozzle head is 80-180°C.

17. The preparation method according to claim 16, characterized in that, The temperature of the second mixture in the material conduit is 0-80°C, and the temperature in the nozzle head is 120-180°C.

18. The preparation method according to claim 14, characterized in that, The sprayer includes an inert medium.

19. The preparation method according to claim 18, characterized in that, The temperature of the inert medium is 60-200℃.

20. The preparation method according to claim 19, characterized in that, The temperature of the inert medium is 90-150℃.

21. The preparation method according to claim 18, characterized in that, Based on 1 mol of magnesium halide with the general formula MgXY, the amount of the inert medium is 0.8-10 L.

22. The preparation method according to claim 21, characterized in that, Based on 1 mol of magnesium halide with the general formula MgXY, the amount of the inert medium is 2-8 L.

23. The preparation method according to claim 18, characterized in that, The inert medium is an inert gas medium or an inert liquid medium.

24. The preparation method according to claim 23, characterized in that, The inert gas medium is selected from at least one of nitrogen, helium, and carbon dioxide; and / or, the inert liquid medium is silicone oil and / or an inert liquid hydrocarbon solvent.

25. The preparation method according to claim 24, characterized in that, The inert liquid medium is selected from at least one of kerosene, paraffin oil, petrolatum oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil, and methyl phenyl silicone oil.

26. A catalyst support for olefin polymerization prepared by the method according to any one of claims 1-25, characterized in that, The molar ratio of silver to magnesium in the catalyst support for olefin polymerization is (0.001-0.5):

1.

27. The catalyst support for olefin polymerization according to claim 26, characterized in that, The average particle size of the catalyst support for olefin polymerization is 1-100 micrometers; and / or, the particle size distribution of the catalyst support for olefin polymerization is less than 1.

5.

28. The catalyst support for olefin polymerization according to claim 27, characterized in that, The average particle size of the catalyst support for olefin polymerization is 1-80 micrometers; and / or, the particle size distribution of the catalyst support for olefin polymerization is less than 1.

2.

29. The catalyst support for olefin polymerization prepared by the preparation method according to any one of claims 1-25 or the catalyst support for olefin polymerization according to any one of claims 26-28, in the preparation of catalysts for olefin polymerization or in olefin polymerization.

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