Catalyst carrier for olefin polymerization and preparation method and application thereof

Abstract

The invention belongs to the field of catalysts, and discloses a catalyst carrier for olefin polymerization and a preparation method and application thereof. The preparation method of the catalyst carrier for olefin polymerization comprises the following steps: (1) mixing magnesium halide and an alcohol compound, and reacting with an ethylene oxide compound to obtain a first reactant; (2) dissolving the first reactant obtained in the step (1) in a solvent to obtain a first mixture; and (3) adding a silver carboxylate ethanol solution into the first mixture obtained in the step (2) to obtain a second mixture, and curing to obtain the catalyst carrier for olefin polymerization, optionally, the step (1) further comprises the step of adding an inert liquid solvent; the olefin polymerization catalyst carrier prepared by the method provided by the invention is not easy to adhere and has good morphology; the catalyst prepared from the catalyst carrier for olefin polymerization has the advantage of high catalytic activity.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, and in particular to a catalyst carrier for olefin polymerization and a preparation method thereof, as well as application of the catalyst carrier for olefin polymerization in preparing a catalyst for olefin polymerization or in olefin polymerization. Background Art

[0002] The spherical catalysts widely used in industry at present are based on magnesium chloride alcoholate. This is because the catalysts supported by them have good performance when used for olefin (especially propylene) polymerization, and their sources are relatively convenient.

[0003] This spherical magnesium chloride alcoholate carrier is generally by high temperature melting after magnesium chloride and alcohol mixed reaction, preparing a melt with good dispersibility by methods such as high pressure extrusion, high-speed stirring, emulsifier method and supergravity rotating bed method, and then rapidly cooling the melt to obtain a spherical carrier, as patent documents WO1999044009A1 and US4399054 etc. all disclose that spherical magnesium chloride alcoholate can be formed by high-speed stirring emulsified magnesium chloride alcoholate system under high temperature and then quenching. The carrier production carried out by this method requires high temperature reaction and quenching process, which causes its production process to consume energy larger and the technical process is longer, multiple reactors are required to be prepared jointly, and the particle size distribution of the carrier finally obtained is wider.

[0004] In order to solve this problem, Chinese patent document CN102040683A discloses a method for preparing a carrier by reacting a magnesium halide alcoholate with an ethylene oxide compound, that is, after the magnesium halide alcoholate is melt-dispersed, the ethylene oxide compound is added; or after the magnesium halide alcoholate is melt-dispersed, it is directly added to a reactor containing an ethylene oxide compound; however, the use of this patented method to prepare a catalyst carrier has the problems of unstable preparation process, easy carrier adhesion, and poor carrier molding effect.

[0005] Therefore, it is of great significance to develop a new catalyst support for olefin polymerization that can overcome the above-mentioned defects of the prior art. Summary of the invention

[0006] The technical problem to be solved by the present invention is to provide a catalyst carrier for olefin polymerization and its preparation method and application in view of the problems that the catalyst carrier for olefin polymerization in the prior art is unstable in the preparation process, easy to cause carrier adhesion, and poor molding effect.

[0007] The inventors of the present invention unexpectedly discovered that when preparing a catalyst carrier for olefin polymerization, after a magnesium halide, an alcohol compound and an ethylene oxide compound react to form a solid, the solid is separated into a solid and the mother liquor is removed, and the solid is dissolved in ethanol to form a fluidized substance, and a silver carboxylate ethanol solution is added for spray solidification. The obtained catalyst carrier for olefin polymerization 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 invention has better hydrogen adjustment sensitivity and good activity, and the prepared polymerization reaction product has a higher bulk density and excellent elution resistance.

[0008] In order to solve the above technical problems, the first aspect of the present invention provides a method for preparing a catalyst carrier for olefin polymerization, comprising the following steps:

[0009] (1) mixing a magnesium halide and an alcohol compound, and reacting the mixture with an ethylene oxide compound to obtain a first reactant;

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

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

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

[0013] According to some embodiments of the present invention, 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 as shown in formula (I).

[0014]

[0015] According to some embodiments of the present invention, in the general formula MgXY, X is a halogen, Y is a halogen, a C1-C 14 Alkyl, C1-C 14 Alkoxy, C6-C 14 Aryl or C6-C 14 Further preferably, in the general formula MgXY, X is fluorine, chlorine or bromine, and Y is fluorine, chlorine, bromine, C1-C5 alkyl, C1-C5 alkoxy, C6-C 10 Aryl or C6-C 10 The C1-C5 alkyl group 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 group may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy; the C6-C10 The aryl group may be, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl or naphthyl. 10 The aryloxy group may be, for example, a phenoxy group or a naphthoxy group; the magnesium halide of the general formula MgXY may be a single magnesium halide or a mixture of multiple magnesium halides; further preferably, the magnesium halide of the general formula MgXY is selected from at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride.

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

[0017] According to some embodiments of the present invention, in formula (I), R2 and R3 are the same or different, and are 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 are the same or different, and are independently hydrogen, a C1-C3 straight-chain alkyl group or a C1-C3 haloalkyl group; more preferably, R2 and R3 are the same or different, and are independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, chloromethyl, bromomethyl, chloroethyl, chloropropyl, bromopropyl; further preferably, the oxirane compound is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epichlorohydrin, epibromohydrin and epibromohydrin.

[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 the present invention, the phrase "optionally, the step (1) further comprises adding an inert liquid solvent" means that the inert liquid solvent may or may not be involved in the mixing. That is, the method of the present invention may or may not require an inert liquid solvent.

[0020] In the present invention, the halogen elements include fluorine, chlorine, bromine and iodine.

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

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

[0023] In the present invention, the C6-C 14 The aryl group refers to an aryl group having 6 to 14 carbon atoms, including a phenyl group, the C6-C 14 The aryl group may include an aryl group in which a hydrogen atom is substituted by a halogen element or the like.

[0024] In the present invention, the C6-C 14 The aryloxy group refers to an aryloxy group having 6 to 14 carbon atoms, including a phenoxy group, the C6-C 14 The aryloxy group may include an aryloxy group in which a hydrogen atom is substituted by a halogen element or the like.

[0025] In the present invention, the C1-C5 alkyl group includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl and isopentyl.

[0026] In the present invention, there is no particular limitation on the conditions for reacting the mixture of the magnesium halide of the general formula MgXY and the compound of the general formula R1OH with the ethylene oxide compound of the structure shown in formula (I) and the optional inert liquid solvent, as long as the mixing and reaction conditions allow the mixture of the magnesium halide of the general formula MgXY, the compound of the general formula R1OH and the ethylene oxide compound of the structure shown in formula (I) to form a solid substance (first reactant).

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

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

[0029] According to some embodiments of the present invention, in step (1), the inert liquid solvent is silicone oil and / or an inert liquid hydrocarbon solvent; preferably, the inert liquid solvent is selected from at least one of kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methylethyl silicone oil, phenyl silicone oil and methylphenyl silicone oil.

[0030] In the present invention, the amounts of the components 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 invention, in step (1), based on 1 mol of magnesium halide of the general formula MgXY, the amount of the alcohol compound of the general formula R1OH is 4-30 mol, preferably 6-22 mol; the amount of the ethylene oxide compound represented by 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 invention, there is no particular limitation on the mixing conditions of the solid substance (first reactant) and the solvent, as long as the mixing conditions allow the solid substance (first reactant) and the solvent to form a fluid mixed substance (first mixture), a silver carboxylate ethanol solution is added to the fluid mixed substance (first mixture) to obtain a second mixture, and then the second mixture can be solidified when entering the inert medium in the sprayer.

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

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

[0035] According to some embodiments of the present invention, in step (3), the curing is carried out in a sprayer; preferably, the sprayer is provided with an atomizing nozzle, the atomizing nozzle comprises a material conduit and a nozzle head, the second mixture is introduced into the nozzle head through the material conduit, and is sprayed into a tower body containing an inert medium of the sprayer through the nozzle head for curing; more preferably, 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, preferably 120-180°C.

[0036] According to some embodiments of the present invention, the sprayer includes an inert medium; preferably, the temperature of the inert medium is 60-200°C, preferably 90-150°C; more preferably, the amount of the inert medium can be selected according to the amount of magnesium halide with the general formula MgXY; generally, based on 1 mol of magnesium halide with the general formula MgXY, the amount of the inert medium is 0.8-10L, preferably 2-8L.

[0037] According to some embodiments of the present invention, the inert medium is an inert gas medium or an inert liquid medium, and there is no particular limitation on the type of the inert medium; preferably, the inert gas medium is selected from at least one of nitrogen, helium, and carbon dioxide; the inert liquid medium is silicone oil and / or an inert liquid hydrocarbon solvent; more preferably, the inert liquid medium can be various liquid media commonly used in the art that do not chemically interact with the reactants and reaction products, for example, at least one selected from kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methylethyl silicone oil, phenyl silicone oil and methylphenyl silicone oil.

[0038] In the present invention, the conditions for solidifying the fluid mixed substance (second mixture) by spraying can be various existing conditions that can form a catalyst carrier for olefin polymerization, for example, the fluid mixed substance (second mixture) is sprayed into a sprayer so that the fluid mixed substance (second mixture) can contact the inert medium in the sprayer.

[0039] In the present invention, the fluid mixed substance (second mixture) can be emulsified by various methods known to those skilled in the art. For example, the fluid mixed substance (second mixture) can be subjected to high-speed shearing to emulsify it. The method of high-speed shearing is well known to those skilled in the art, for example, the fluid mixed substance (second mixture) is stirred at a speed of 2000-5000 rpm. In addition, the fluid mixed substance can also be emulsified by referring to the methods disclosed in the following prior art: CN1267508C discloses that a solution containing a liquid magnesium halide adduct is rotated and dispersed in a supergravity bed (the rotation speed can be 100-3000 rpm); CN1463990A discloses that a solution containing a liquid magnesium halide adduct is output in an emulsifier at a speed of 1500-8000 rpm; US6020279 discloses that a solution containing a liquid magnesium halide adduct is emulsified by a spray method.

[0040] According to the present invention, the preparation method of the catalyst carrier for olefin polymerization may further include: performing solid-liquid separation on the product obtained after spray solidification, washing the solid phase product and drying it. The solid-liquid separation may be any existing method capable of achieving solid-liquid separation, such as suction filtration, filter pressing or centrifugal separation. Preferably, the solid-liquid separation method is filter pressing. The present invention does not particularly limit the conditions for filter pressing, and the separation of the solid phase and the liquid phase is achieved as fully as possible. The washing may be performed by washing the obtained solid phase product using methods known to those skilled in the art, for example, the obtained solid phase product may be washed using an inert hydrocarbon solvent (for example, pentane, hexane, heptane, petroleum ether and gasoline). The present invention does not particularly limit the drying conditions, for example, the drying temperature may be 20-70°C, and the drying time may be 0.5-10 hours. According to the present invention, the drying may be performed under normal pressure or reduced pressure.

[0041] According to the preparation method of the present invention, a trace amount of water in the above-mentioned reactants can also participate in the reaction of forming the catalyst carrier for olefin polymerization.

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

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

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

[0045] The inventors of the present invention unexpectedly discovered that during the preparation process of the catalyst carrier for olefin polymerization, after a magnesium halide of the general formula MgXY, an alcohol compound of the general formula R1OH and an ethylene oxide compound of the structural formula shown in formula (I) react to form a solid, the solid obtained by removing the mother liquor through solid-liquid separation is dissolved in ethanol to form a fluidized substance, and the addition of a silver carboxylate ethanol solution can affect the crystallization and accumulation of the carrier particles, thereby finally obtaining a carrier with good morphology.

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

[0047] The present invention does not particularly limit the conditions for the application of the catalyst carrier for olefin polymerization in the preparation of the catalyst for olefin polymerization, and those skilled in the art can prepare the catalyst for olefin polymerization of the present invention by conventional technical means. In the embodiments of the present invention, the catalyst is prepared by contacting the carrier prepared by the present invention with a titanium source and an internal electron donor compound, and there is no particular limitation on the temperature and time of the contact reaction, which should not be understood by those skilled in the art as limiting the technical solution of the present invention.

[0048] Beneficial effects:

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

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

[0051] (3) When the method of the present invention is used to prepare a catalyst carrier for olefin polymerization, it is not necessary to use a surfactant that is required in the prior art method, thereby reducing production costs;

[0052] (4) When the olefin polymerization catalyst prepared by using the olefin polymerization catalyst carrier of the present invention is used in olefin polymerization reaction, the bulk density and 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 elution resistance. DETAILED DESCRIPTION

[0053] The present invention will be further described below in conjunction with the embodiments, but the present invention is not limited by these embodiments.

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

[0055] In the Examples and Comparative Examples:

[0056] 1. The average particle size and particle size distribution of the catalyst support for olefin polymerization were measured using a Masters Sizer 2000 particle size analyzer (manufactured by Malvern Instruments Ltd);

[0057] 2. The surface morphology of the catalyst support for olefin polymerization was observed by an optical microscope of model Eclipse E200 purchased from Nikon Corporation;

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

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

[0060] 5. Calculation of the activity of the catalyst used for olefin polymerization: Catalyst activity = (mass of polyolefin prepared) / (mass of catalyst solid component) g / g.

[0061] 6. Determination of melt index (MI) of polyolefin powder: According to ASTM D1238-99, measured at a load of 2.16 kg and 190°C.

[0062] Example 1

[0063] This embodiment is used to illustrate the catalyst support for olefin polymerization provided by the present invention and its preparation method.

[0064] In a 0.6L reactor, 0.08mol (8.0g) of magnesium chloride and 1.7mol of ethanol were added, and the temperature was raised to 90°C under stirring. After isothermal reaction at 90°C for 1 hour, 0.48mol of epichlorohydrin was added, and the reaction was continued at 90°C for 30 minutes, followed by filter pressing. 2.5mol of ethanol was added to the filter press product, and the mixture was stirred to form a fluidized mixture. Then, silver acetate ethanol solution (silver acetate: ethanol = 0.2g: 100mL; silver acetate 0.0012mol) was added, and the fluidized mixture was sprayed into the circulating nitrogen using a sprayer containing a nozzle head and a material conduit, and the nozzle head was heated to 140°C to obtain a catalyst carrier Z1 for olefin polymerization.

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

[0066] Example 2

[0067] This embodiment is used to illustrate the catalyst support for olefin polymerization provided by the present invention and its preparation method.

[0068] In a 0.6L reactor, 0.08mol (8.0g) of magnesium chloride and 1.7mol of ethanol were added, and the temperature was raised to 90°C under stirring. After isothermal reaction at 90°C for 1 hour, 0.48mol of epichlorohydrin was added, and the reaction was continued at 90°C for 30 minutes, followed by filter pressing. 2.5mol of ethanol was added to the filter press product, and the mixture was stirred to form a fluidized mixture. Then, silver acetate ethanol solution (silver acetate: ethanol = 0.1g: 100mL; silver acetate 0.0006mol) was added, and the fluidized mixture was sprayed into the circulating nitrogen using a sprayer containing a nozzle head and a material conduit, and the nozzle head was heated to 140°C to obtain a catalyst carrier Z2 for olefin polymerization.

[0069] The molar ratio of silver element to magnesium element in the above-mentioned olefin polymerization catalyst carrier Z2 is 0.007:1.

[0070] Example 3

[0071] This embodiment is used to illustrate the catalyst support for olefin polymerization provided by the present invention and its preparation method.

[0072] In a 0.6L reactor, 0.08mol (8.0g) of magnesium chloride and 1.7mol of ethanol were added, and the temperature was raised to 90°C under stirring. After isothermal reaction at 90°C for 1 hour, 0.48mol of epichlorohydrin was added, and the reaction was continued at 90°C for 30 minutes, followed by filter pressing. 2.5mol of ethanol was added to the filter press product, and the mixture was stirred to form a fluidized mixture. Then, a silver propionate ethanol solution (silver propionate: ethanol = 0.2g: 100mL; silver propionate 0.0012mol) was added, and the fluidized mixture was sprayed into the circulating nitrogen using a sprayer containing a nozzle head and a material conduit. The nozzle head was heated to 140°C to obtain a catalyst carrier Z3 for olefin polymerization.

[0073] The molar ratio of the silver element to the magnesium element in the above-mentioned olefin polymerization catalyst carrier Z3 is 0.012:1.

[0074] Example 4

[0075] This embodiment is used to illustrate the catalyst support for olefin polymerization provided by the present invention and its preparation method.

[0076] In a 0.6L reactor, 0.08mol (8.0g) of magnesium chloride and 1.7mol of ethanol were added, and the temperature was raised to 90°C under stirring. After isothermal reaction at 90°C for 1 hour, 0.48mol of epichlorohydrin was added, and the reaction was continued at 90°C for 30 minutes, followed by filter pressing. 2.5mol of ethanol was added to the filter press product, and the mixture was stirred to form a fluidized mixture. Then, a silver propionate ethanol solution (silver propionate: ethanol = 0.1g: 100mL; silver propionate 0.0006mol) was added, and the fluidized mixed substance was sprayed into the circulating nitrogen using a sprayer containing a nozzle head and a material conduit, and the nozzle head was heated to 140°C to obtain a catalyst carrier Z3 for olefin polymerization.

[0077] The molar ratio of silver element to magnesium element in the above-mentioned olefin polymerization catalyst carrier Z3 is 0.006:1.

[0078] Comparative Example 1

[0079] This comparative example is used to illustrate the catalyst support for olefin polymerization provided by the comparative example of the present invention and its preparation method.

[0080] In a 0.6L reactor, 0.08mol of magnesium chloride and 1.7mol of ethanol were added, and the temperature was raised to 90°C under stirring conditions. After constant temperature reaction at 90°C for 1 hour, 0.48mol of epichlorohydrin was added, and the reaction was carried out at 90°C for 30 minutes, followed by filter pressing. 2.5mol of ethanol was added to the filter press product, and stirred to form a fluid mixture. Then, 100mL of ethanol was added, and the fluid mixture was sprayed into the circulating nitrogen using a sprayer containing a nozzle head and a material conduit. The heating temperature of the nozzle head was 160°C, and finally the catalyst carrier DZ1 for olefin polymerization was obtained.

[0081] According to elemental analysis, the carrier DZ1 does not contain the element silver.

[0082] Comparative Example 2

[0083] This comparative example is used to illustrate the catalyst support for olefin polymerization provided by the comparative example of the present invention and its preparation method.

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

[0085] The average particle size (D50) and particle size distribution ((D90-D10) / D50) of the catalyst carrier for olefin polymerization prepared in the above Examples 1-4 and Comparative Examples 1-2 were measured and their surface morphologies were observed. The results are shown in Table 1 below:

[0086] Table 1

[0087]

[0088]

[0089] Example 5

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

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

[0092] In a 300mL reaction bottle, add 100mL of titanium tetrachloride, cool to -20°C, then add 8g of the catalyst carrier Z1 for olefin polymerization obtained in Example 1, and stir at -20°C for 30min. Then, slowly heat up to 110°C, add 1.5mL of diisobutyl phthalate during the heating process, maintain the temperature at 110°C for 30min, filter out the liquid, then add titanium tetrachloride and wash twice, finally wash three times with hexane, and obtain the catalyst component C1 for olefin polymerization after drying.

[0093] (2) Propylene polymerization

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

[0095] Example 6

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

[0097] 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 olefin polymerization of the present invention in the preparation of polyolefins.

[0100] Propylene polymerization was carried out according to the method of Example 5, except that the olefin polymerization catalyst carrier Z1 was replaced by the olefin polymerization catalyst carrier Z2 obtained in Example 2, to obtain catalyst components for olefin polymerization and polypropylene powder.

[0101] Example 8

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

[0103] Propylene polymerization 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 olefin polymerization of the present invention in the preparation of polyolefins.

[0106] Propylene polymerization was carried out according to the method of Example 5, except that the olefin polymerization catalyst carrier Z1 was replaced by the olefin polymerization catalyst carrier Z3 obtained in Example 3, to obtain catalyst components for olefin polymerization and polypropylene powder.

[0107] Example 10

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

[0109] Propylene polymerization 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] Embodiment 11

[0111] This example is used to illustrate that the catalyst support for olefin polymerization of the present invention is used for the preparation of polyolefin.

[0112] Propylene polymerization was carried out according to the method of Example 5, except that the olefin polymerization catalyst carrier Z1 was replaced by the olefin polymerization catalyst carrier Z4 obtained in Example 4, to obtain catalyst components for olefin polymerization and polypropylene powder.

[0113] Example 12

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

[0115] Propylene polymerization was carried out according to the method of Example 11, except that the 1.5 L (standard volume) of hydrogen was replaced by 6.5 L (standard volume) of hydrogen.

[0116] Comparative Example 3

[0117] This comparative example is used to illustrate that the catalyst support for olefin polymerization of the present invention is used for the preparation of polyolefin.

[0118] Propylene polymerization was carried out according to the method of Example 5, except that the catalyst support Z1 for olefin polymerization was replaced by the catalyst support DZ1 for olefin polymerization obtained in Comparative Example 1, to obtain catalyst components for olefin polymerization and polypropylene powder.

[0119] Comparative Example 4

[0120] This comparative example is used to illustrate that the catalyst support for olefin polymerization of the present invention is used for the preparation of polyolefin.

[0121] 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.

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

[0123] Table 2

[0124]

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

[0126] From the above results, it can be seen that the particle morphology of the olefin polymerization catalyst carrier prepared by the method of the present invention is good, and basically no irregular particles appear. Moreover, when the catalyst prepared with the obtained carrier is used for olefin (especially propylene) polymerization, the polymerization activity is good, and basically no irregular materials appear. The bulk density and melt index of the prepared polymer product are significantly higher than those of the prior art, and it has excellent elution resistance, and has great industrial application prospects.

[0127] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A method for preparing a catalyst carrier for olefin polymerization, characterized in that: The steps include: (1) mixing a magnesium halide and an alcohol compound, and reacting the mixture with an ethylene oxide 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 a silver carboxylate ethanol solution to the first mixture obtained in step (2) to obtain a second mixture, and solidifying the mixture to obtain the catalyst support for olefin polymerization; Optionally, the step (1) further comprises adding an inert liquid solvent.

2. The preparation method according to claim 1, characterized in that: 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 as shown in formula (I); Preferably, in the general formula MgXY, X is halogen, Y is halogen, C1-C 14 Alkyl, C1-C 14 Alkoxy, C6-C 14 Aryl or C6-C 14 Further preferably, in the general formula MgXY, X is fluorine, chlorine or bromine, and Y is fluorine, chlorine, bromine, C1-C5 alkyl, C1-C5 alkoxy, C6-C 10 Aryl or C6-C 10 More preferably, the magnesium halide of the general formula MgXY is selected from at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride; and / or, in the general formula R1OH, R1 is a C1-C8 straight chain alkyl group, a C3-C8 branched chain alkyl group or a C3-C8 cycloalkyl group; preferably, in the general formula R1OH, R1 is a C1-C6 straight chain alkyl group, a C3-C6 branched chain alkyl group or a C3-C8 cycloalkyl group; more preferably, in the general formula R1OH, R1 is a C1-C5 straight chain alkyl group, a C3-C5 branched chain alkyl group or a C3-C6 cycloalkyl group; further Preferably, in the general formula R1OH, R1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, cyclopropyl, cyclopentyl, methylcyclopropyl, dimethylcyclopropyl, cyclohexyl, methylcyclopentyl; further preferably, the alcohol compound of the general formula R1OH is at least one selected from ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol and 2-ethylhexanol; And / or, in formula (I), R2 and R3 are the same or different, and are 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 are the same or different, and are independently hydrogen, a C1-C3 straight-chain alkyl group or a C1-C3 haloalkyl group; more preferably, R2 and R3 are the same or different, and are independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, chloromethyl, bromomethyl, chloroethyl, chloropropyl, bromopropyl; further preferably, the oxirane compound is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epichlorohydrin, epibromohydrin and epibromohydrin; And / or, 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.

3. The preparation method according to claim 1 or 2, characterized in that: In step (1), the mixing temperature is 70-90° C. and 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; preferably, the inert liquid medium is selected from at least one of kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methylethyl silicone oil, phenyl silicone oil and methylphenyl silicone oil; And / or, based on 1 mol of magnesium halide with the general formula MgXY, the amount of the alcohol compound with the general formula R1OH is 4-30 mol, preferably 6-22 mol; the amount of the ethylene oxide compound shown in formula (I) is 1-10 mol, preferably 2-6 mol; the amount of the inert liquid solvent is 0-10 L, preferably 2-8 L.

4. The preparation method according to any one of claims 1 to 3, characterized in that In step (2), the solvent is an alcohol; preferably, 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 of the general formula MgXY, the amount of silver carboxylate used is 0.001-100 mol, preferably 0.001-10 mol; the amount of solvent used is 8-80 mol, preferably 30-50 mol.

5. The preparation method according to any one of claims 1 to 4, characterized in that: In step (3), the curing is carried out in a sprayer; preferably, the sprayer is provided with an atomizing nozzle, and the atomizing nozzle comprises a material conduit and a nozzle head; more preferably, 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, preferably 120-180°C.

6. The preparation method according to claim 5, characterized in that: The sprayer comprises an inert medium; preferably, the temperature of the inert medium is 60-200°C, preferably 90-150°C; more preferably, based on 1 mol of magnesium halide with the general formula MgXY, the amount of the inert medium is 0.8-10L, preferably 2-8L.

7. The preparation method according to claim 6, characterized in that: The inert medium is an inert gas medium or an inert liquid medium; preferably, the inert gas medium is selected from at least one of nitrogen, helium, and carbon dioxide; the inert liquid medium is silicone oil and / or an inert liquid hydrocarbon solvent; more preferably, the inert liquid medium is selected from at least one of kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methylethyl silicone oil, phenyl silicone oil, and methylphenyl silicone oil.

8. A catalyst support for olefin polymerization prepared by the preparation method according to any one of claims 1 to 7, characterized in that: The molar ratio of silver element to magnesium element in the catalyst carrier for olefin polymerization is (0.001-0.5):

1.

9. The catalyst carrier for olefin polymerization according to claim 8, characterized in that The average particle size of the olefin polymerization catalyst carrier is 1-100 microns, preferably 1-80 microns; and / or the particle size distribution of the olefin polymerization catalyst carrier is less than 1.5, preferably less than 1.

2.

10. Use of the catalyst carrier for olefin polymerization prepared by the preparation method according to any one of claims 1 to 7 or the catalyst carrier for olefin polymerization according to claim 8 or 9 in preparing a catalyst for olefin polymerization or in olefin polymerization.

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