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 catalyst carrier for olefin polymerization comprises a compound as shown in a structural formula (I) and a silver element, in the catalyst carrier for olefin polymerization, the molar ratio of the silver element to the compound shown in the formula (I) is (0.10-0.50): 1; wherein the compound shown in the formula (I) is metered by the molar weight of Mg; the catalyst carrier for olefin polymerization has better morphology, and polypropylene particles with higher bulk density, higher melt index and higher elution resistance can be obtained through online polymerization.

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, a catalyst component containing the catalyst carrier for olefin polymerization, and an application of the olefin polymerization catalyst in olefin polymerization. Background Art

[0002] In recent years, the production capacity of polypropylene has increased rapidly, the proportion of polypropylene output in plastics has continued to rise, its application areas have even expanded to special plastics, and its application scope is constantly expanding.

[0003] As people's living standards improve, the requirements for hygiene and health are also increasing rapidly. Since a variety of pathogens may remain on the surface of plastic products, research, development and production of antibacterial materials can reduce cross-contamination caused by the use of plastics. Therefore, the demand for antibacterial plastic products continues to increase, and various antibacterial agents and antibacterial plastics are also developing. Antibacterial polypropylene has great advantages in application because it combines the advantages of polypropylene.

[0004] At present, the production of antibacterial polypropylene mainly includes melt blending, impregnation, coating and other methods. In the melt blending method, the antibacterial agent and other components such as resin are heated to above the melting temperature in the mixing equipment to obtain a uniform eutectic. The impregnation method is usually used for antibacterial polypropylene fiber. It is to put the prepared polypropylene material into a liquid or gas containing antibacterial active substances, and achieve the combination of antibacterial substances and materials through deposition and adsorption. The coating method is to coat the gel antibacterial substance on the polypropylene material matrix. However, these existing antibacterial polypropylene production methods all have some disadvantages. For example, the coating method has a simple process, but poor antibacterial durability; the melt blending method requires heating the plastic to the melting point, consumes a lot of energy, and there may be compatibility problems; the impregnation method is not only inefficient, but also has the problem of antibacterial durability.

[0005] Therefore, it is of great significance to develop a new catalyst carrier for olefin polymerization suitable for preparing antibacterial polypropylene 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 a preparation method and application thereof in view of the poor antibacterial durability of the antibacterial polypropylene produced in the prior art and the inability to prepare the antibacterial polypropylene by in-situ polymerization.

[0007] The inventors of the present invention unexpectedly discovered that the catalyst carrier for olefin polymerization comprising the compound as shown in structural formula (I) and silver element prepared by the present invention not only has a good spherical morphology, but also the hydrogen regulation sensitivity and activity of the catalyst for olefin polymerization prepared from the carrier are good, and antibacterial polypropylene containing silver element can be prepared by in-situ polymerization. The antibacterial polypropylene has a high bulk density, excellent elution resistance, and long-lasting antibacterial performance.

[0008] In order to solve the above technical problems, the first aspect of the present invention provides a catalyst carrier for olefin polymerization, wherein the catalyst carrier for olefin polymerization comprises a compound as shown in structural formula (I) and silver element;

[0009]

[0010] In the compound represented by formula (I), R1 is a C1-C8 straight-chain alkyl, a C3-C8 branched-chain alkyl or a C3-C8 cycloalkyl; R2 and R3 are the same or different and are independently hydrogen, a C1-C5 straight-chain alkyl or a C3-C5 branched-chain alkyl, wherein the hydrogen on the R2 and R3 alkyl groups is optionally replaced by a halogen atom; X is a halogen, preferably chlorine or bromine; m is 0.1-1.9, n is 0.1-1.9, and m+n=2;

[0011] In the catalyst carrier for olefin polymerization, the molar ratio of silver element to the compound represented by formula (I) is (0.0010-0.50):1; wherein the compound represented by formula (I) is calculated based on the molar amount of Mg.

[0012] According to some embodiments of the present invention, the synthetic raw materials of the catalyst carrier for olefin polymerization include silver carboxylate, magnesium halide, alcohol compound and ethylene oxide compound; preferably, the general formula of the magnesium halide is MgX1Y1, the general formula of the alcohol compound is R4OH, and the structural formula of the ethylene oxide compound is as shown in formula (II).

[0013]

[0014] According to some embodiments of the present invention, in the general formula MgX1Y1, X1 is chlorine or bromine, and Y1 is chlorine, bromine, C1-C5 alkyl, C1-C5 alkoxy, C6-C 10 Aryl or C6-C 10 Preferably, 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-C 10The 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 with the general formula MgX1Y1 may be a single magnesium halide or a mixture of multiple magnesium halides; further preferably, the magnesium halide with the general formula MgX1Y1 is selected from at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride.

[0015] According to some embodiments of the present invention, in the general formula R4OH, R4 is a straight-chain alkyl group of C1-C8, a branched alkyl group of C3-C8 or a cycloalkyl group of C3-C8, wherein the carbon atoms in the cycloalkyl group of C3-C8 may all or partly participate in the ring formation; preferably, in the general formula R4OH, R4 is a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group, an isooctyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexyl group or a cyclohexylmethyl group; further preferably, the alcohol compound of the general formula R4OH is selected from at least one of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, n-hexanol, n-octanol and 2-ethylhexanol.

[0016] According to some embodiments of the present invention, in formula (II), R5 and R6 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, R5 and R6 are the same or different, and are independently hydrogen, a C1-C3 straight-chain alkyl group, or a C1-C3 halogenated alkyl group; more preferably, the oxirane compound is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epichlorohydrin, epibromohydrin and epibromobutylene oxide.

[0017] According to some embodiments of the present invention, the silver carboxylate is selected from at least one of silver acetate, silver benzoate, silver propionate, silver butyrate, and silver octanoate.

[0018] The average particle size of the spherical carrier of the catalyst for olefin polymerization of the present invention can be controlled within a wide range. According to some embodiments of the present invention, the average particle size of the catalyst carrier for olefin polymerization is 10-100 microns. Preferably, the average particle size (D50) of the spherical carrier of the catalyst for olefin polymerization can be controlled to be less than or equal to 60 microns, preferably 20-50 microns, and the particle size distribution is <1.2, preferably ≦0.8. In a preferred embodiment, the catalyst prepared from the spherical carrier of the catalyst for olefin polymerization can obtain an olefin polymer with a higher bulk density.

[0019] According to the present invention, the spherical carrier of the catalyst for olefin polymerization may contain water, and the contained water comes from trace amounts of water in the synthetic raw materials and the reaction medium.

[0020] According to the present invention, the contents of the above-mentioned components in the spherical carrier of the catalyst for olefin polymerization can be selected and varied within a large range. Preferably, according to some embodiments of the present invention, in the catalyst carrier for olefin polymerization, based on 1 mol of magnesium halide with the general formula MgX1Y1, the amount of silver carboxylate is 0.0001-0.5 mol, the amount of the compound with the general formula R4OH is 4-30 mol, and the amount of ethylene oxide compound is 1-10 mol; preferably, based on 1 mol of magnesium halide with the general formula MgX1Y1, the amount of silver carboxylate is 0.0001-0.5 mol, the amount of the compound with the general formula R4OH is 6-20 mol, and the amount of ethylene oxide compound is 2-6 mol.

[0021] According to the present invention, a trace amount of water in the above-mentioned reactants can also participate in the reaction of forming the spherical catalyst carrier for olefin polymerization.

[0022] The second aspect of the present invention provides a method for preparing the above-mentioned catalyst carrier for olefin polymerization, comprising the following steps:

[0023] (1) mixing a magnesium halide and an alcohol compound, and reacting the mixture with a silver carboxylate to obtain a first reactant;

[0024] (2) adding an ethylene oxide compound to the first reactant obtained in step (1) to carry out reaction II to obtain the catalyst support for olefin polymerization;

[0025] Optionally, the step (1) further comprises adding an inert liquid medium and a surfactant.

[0026] According to the present invention, in step (1), the conditions for mixing the silver carboxylate, the magnesium halide of the general formula MgX1Y1, the alcohol compound of the general formula R4OH, and optionally the mixture with the inert liquid medium and / or the surfactant, and carrying out the reaction I are not particularly limited, as long as the conditions for the mixing and carrying out the reaction I can make the magnesium halide of the general formula MgX1Y1 melt and fully react with the silver carboxylate.

[0027] According to some embodiments of the present invention, in step (1), the mixing conditions include: a mixing temperature of 80-120° C., preferably 80-100° C.; a mixing time of 0.5-5 hours, preferably 0.5-3 hours;

[0028] And / or, the conditions of the reaction I include: temperature of 80-120° C., preferably 80-100° C.; time of 0.5-5 hours, preferably 0.5-3 hours.

[0029] According to some embodiments of the present invention, the inert liquid medium can be various liquid media commonly used in the art that do not react chemically with reactants and reaction products; the inert liquid medium 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; further preferably, according to the present invention, the amount of the inert liquid medium can be determined according to the amount of magnesium halide with the general formula MgX1Y1, and based on 1 mol of magnesium halide with the general formula MgX1Y1, the amount of the inert liquid medium is 0-10L, preferably 2-8L.

[0030] According to some embodiments of the present invention, in step (1), a surfactant is used; the surfactant is selected from at least one of polyvinyl pyrrolidone, polyethylene glycol, polyvinyl alcohol, polyacrylic acid, polyacrylic acid salt, polyacrylamide, polystyrene sulfonate, naphthalenesulfonic acid formaldehyde condensate, condensed alkyl phenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, oxyalkyl acrylate copolymer modified polyethyleneimine, 1-dodeca-4-vinylpyridinium bromide polymer, polyvinyl benzyltrimethylamine salt, polyethylene oxide propylene oxide block copolymer, polyvinyl pyrrolidone vinyl acetate copolymer, alkylphenyl polyoxyethylene ether and polyalkyl methacrylate; preferably, the amount of the surfactant used is 1-20g based on 1 mol of magnesium halide with the general formula MgX1Y1.

[0031] According to the present invention, in step (2), the conditions for contacting the first reactant with the ethylene oxide compound can be various existing conditions that can form an olefin polymerization catalyst carrier; according to some embodiments of the present invention, in step (2), the conditions of reaction II include: temperature of 40-120°C, preferably 60-100°C; time of 15-60 minutes, preferably 20-50 minutes.

[0032] According to the present invention, the preparation method may further include solid-liquid separation of the product obtained by reaction II, washing the separated 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 is subject to achieving the separation of the solid phase and the liquid phase as fully as possible; the washing may be performed by a method known to those skilled in the art to wash the obtained solid phase product, for example, an inert hydrocarbon solvent (for example: pentane, hexane, heptane, petroleum ether and gasoline) may be used to wash the obtained solid phase product; 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.

[0033] The third aspect of the present invention provides a catalyst component for olefin polymerization, wherein the catalyst component comprises a product obtained by reacting the above catalyst support for olefin polymerization, a titanium compound and an optional internal electron donor compound.

[0034] The present invention has no particular restrictions on the composition of the catalyst components, the content of each component, the preparation method, etc. The composition, content and method of the olefin polymerization catalyst components currently available in the art can be used. Those skilled in the art can make reasonable adjustments and designs according to actual needs. The present invention lists a specific operation process in the embodiments hereinafter, which should not be construed by those skilled in the art as a limitation of the present invention.

[0035] A fourth aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising:

[0036] 1) the above catalyst components;

[0037] 2) Alkyl aluminum compounds;

[0038] 3) Optionally an external electron donor compound.

[0039] The present invention has no particular limitation on the composition of the catalyst, the content of each component, the preparation method, etc. The composition, content and method of the existing olefin polymerization catalyst in the art can be used. Those skilled in the art can make reasonable adjustments and designs according to actual needs. The present invention lists a specific operation process in the embodiments hereinafter, which should not be construed by those skilled in the art as a limitation of the present invention.

[0040] The fifth aspect of the present invention provides an olefin polymerization method, which comprises contacting at least one olefin with the above-mentioned catalyst under olefin polymerization conditions; preferably, the olefin is selected from an olefin with the structural formula CH2=CHR, wherein R is hydrogen or a straight-chain alkyl group of C1-C6 or a branched-chain alkyl group of C3-C6; further preferably, the olefin is selected from ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene, 4-methyl-1-pentene; preferably, the olefin is ethylene, propylene, 1-n-butene, 1-n-hexene, 4-methyl-1-pentene; more preferably, the olefin is propylene.

[0041] The olefin polymerization method of the present invention may be the homopolymerization of a single olefin or the copolymerization of multiple olefins.

[0042] According to the olefin polymerization method of the present invention, the olefin polymerization conditions can be conventional conditions in the art. Generally, the olefin polymerization conditions include: temperature of 0-150°C, time of 0.1-8 hours, and pressure of 0.01-10MPa; preferably, the olefin polymerization conditions include: temperature of 50-100°C, time of 0.5-3 hours, and pressure of 0.5-5MPa. The amount of the olefin polymerization catalyst can be various conventional amounts of olefin catalysts in the prior art.

[0043] Beneficial effects:

[0044] The catalyst carrier for olefin polymerization of the present invention has a good morphology, and can obtain polypropylene particles with higher bulk density, higher melt index and higher elution resistance through online polymerization. DETAILED DESCRIPTION

[0045] The present invention will be further described below in conjunction with the embodiments, but the present invention is not limited by these embodiments.

[0046] In the following examples and comparative examples of the present invention, unless otherwise specified, all raw materials used are commercially available.

[0047] In the Examples and Comparative Examples:

[0048] 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);

[0049] 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;

[0050] 3. Melt flow rate (MFR) of polyolefin powder: measured according to ISO1133 at 230°C and 2.16 kg load.

[0051] 4. The bulk density of polyolefin powder is determined by the method specified in GB / T 1636-2008.

[0052] 5. 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.

[0053] 6. Calculation of the activity of the catalyst used for olefin polymerization: Catalyst activity = (mass of polyolefin prepared) / (mass of catalyst solid component) g / g.

[0054] Example 1

[0055] This embodiment is used to illustrate the catalyst support for olefin polymerization provided by the present invention and its preparation method.

[0056] In a 0.6L reactor, add 0.08mol (8.0g) of magnesium chloride, 0.96mol of ethanol, and 0.8g of PVP (polyvinyl pyrrolidone), raise the temperature to 86°C under stirring conditions, and react at a constant temperature of 86°C for 2 hours, then add 0.03mol of silver acetate and continue to react at a constant temperature for 2 hours; then add 0.48mol (38ml) of epichlorohydrin, react at a temperature of 86°C for 30 minutes, then filter, wash the filter product with hexane 5 times, and vacuum dry to obtain the catalyst carrier Z1 for olefin polymerization.

[0057] According to the characterization of gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic resonance, the carrier Z1 contains the structural formula

[0058] The compound and the silver element, wherein the molar ratio of the silver element to the compound (based on the molar amount of Mg) is 0.22:1.

[0059] Example 2

[0060] This embodiment is used to illustrate the catalyst support for olefin polymerization provided by the present invention and its preparation method.

[0061] In a 0.6L reactor, add 300mL of white oil, 0.08mol (8.0g) of magnesium chloride, 0.48mol (28mL) of ethanol, and 1g of PVP (polyvinyl pyrrolidone), heat to 100°C under stirring conditions, and react at a constant temperature of 100°C for 1 hour, then add 0.03mol of silver acetate and continue the constant temperature reaction for 2 hours; then add 0.16mol (12.5mL) of epichlorohydrin, continue to react at 100°C for 20 minutes, then filter, wash the filter product with hexane 5 times, and vacuum dry to obtain the catalyst carrier Z2 for olefin polymerization.

[0062] According to GC-MS, elemental analysis and NMR characterization, the carrier Z2 contains the structural formula

[0063] The compound and the silver element, wherein the molar ratio of the silver element to the compound (based on the molar amount of Mg) is 0.20:1.

[0064] Example 3

[0065] This embodiment is used to illustrate the catalyst support for olefin polymerization provided by the present invention and its preparation method.

[0066] In a 0.6L reactor, add 300mL of white oil, 0.08mol (8.0g) of magnesium chloride, 0.48mol (28mL) of ethanol, and 1g of PVP (polyvinyl pyrrolidone), raise the temperature to 100°C under stirring conditions, and react at a constant temperature of 100°C for 1 hour, then add 0.01mol of silver acetate and continue the constant temperature reaction for 2 hours; then add 0.16mol (12.5mL) of epichlorohydrin, continue to react at a temperature of 100°C for 20 minutes, then filter, wash the filter product with hexane 5 times, and vacuum dry to obtain the catalyst carrier Z3 for olefin polymerization.

[0067] According to the characterization of gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic resonance, the carrier Z3 contains the structural formula

[0068] The compound and the silver element, wherein the molar ratio of the silver element to the compound (based on the molar amount of Mg) is 0.12:1.

[0069] Example 4

[0070] This embodiment is used to illustrate the catalyst support for olefin polymerization provided by the present invention and its preparation method.

[0071] In a 0.6L reactor, add 0.08mol (8.0g) magnesium chloride, 0.96mol (56mL) ethanol, and 1g PVP (polyvinyl pyrrolidone), raise the temperature to 90°C under stirring conditions, and react at a constant temperature of 90°C for 2 hours, then add 0.01mol silver acetate and continue to react at a constant temperature for 2 hours; then add 0.38mol epichlorohydrin, continue to react at 90°C for 20 minutes, then filter, wash the filter product with hexane 5 times, and vacuum dry to obtain the catalyst carrier Z4 for olefin polymerization.

[0072] According to GC-MS, elemental analysis and NMR characterization, the carrier Z4 contains the structural formula

[0073] The compound and the silver element, wherein the molar ratio of the silver element to the compound (based on the molar amount of Mg) is 0.13:1.

[0074] Comparative Example 1

[0075] 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.

[0076] In a 0.6L reactor, add 0.08mol magnesium chloride, 0.96mol ethanol, and 0.8g PVP (polyvinyl pyrrolidone), raise the temperature to 86°C under stirring conditions, and react at a constant temperature of 86°C for 2 hours, then add 0.48mol (38ml) of epichlorohydrin, react at 90°C for 30 minutes, and filter press. Wash the filtered product with hexane 5 times, and vacuum dry to finally obtain the catalyst carrier DZ1 for olefin polymerization.

[0077] According to GC-MS, elemental analysis and NMR characterization, the carrier DZ1 contains the structural formula

[0078] The compound contains no silver in the carrier DZ1.

[0079] Comparative Example 2

[0080] 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.

[0081] In a 0.6L reactor, 0.08mol magnesium chloride, 0.96mol ethanol and 0.8g PVP (polyvinyl pyrrolidone) were added, and the temperature was raised to 86°C under stirring conditions. After isothermal reaction at 86°C for 2 hours, 0.03mol silver chloride was added and the isothermal reaction was continued for 2 hours. Then 0.48mol (38ml) of epichlorohydrin was added, and the reaction was carried out at 90°C for 30 minutes and then filtered. The filtered product was washed with hexane 5 times and dried in vacuo to finally obtain the catalyst carrier DZ2 for olefin polymerization.

[0082] According to GC-MS, elemental analysis and NMR characterization, the carrier DZ2 contains the structural formula The compound comprises a molar ratio of the silver element and the compound (based on the molar amount of Mg) to silver of 0.02:1.

[0083] 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:

[0084] Table 1

[0085]

[0086]

[0087] It can be seen from the results in Table 1 above that the catalyst carriers for olefin polymerization prepared in Examples 1-4 of the present invention have narrow particle size distribution, good carrier particle morphology, and smaller average particle size; and the reduction in average particle size is conducive to expanding the process adaptability of the catalyst prepared using the carrier (for example, the Unipol polypropylene production process generally requires a smaller particle size).

[0088] Example 5

[0089] This example is used to illustrate that the catalyst support for olefin polymerization of the present invention is used for the preparation of polyolefin.

[0090] (1) Preparation of catalyst components for olefin polymerization

[0091] In a 300mL reaction bottle, add 100mL of titanium tetrachloride, cool to -20°C, then add 40g 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.

[0092] (2) Propylene polymerization

[0093] 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.

[0094] Example 6

[0095] This example is used to illustrate that the catalyst support for olefin polymerization of the present invention is used for the preparation of polyolefin.

[0096] 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 to obtain polypropylene powder.

[0097] Example 7

[0098] This example is used to illustrate that the catalyst support for olefin polymerization of the present invention is used for the preparation of polyolefin.

[0099] 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.

[0100] Example 8

[0101] This example is used to illustrate that the catalyst support for olefin polymerization of the present invention is used for the preparation of polyolefin.

[0102] 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 to obtain polypropylene powder.

[0103] Example 9

[0104] This example is used to illustrate that the catalyst support for olefin polymerization of the present invention is used for the preparation of polyolefin.

[0105] 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.

[0106] Example 10

[0107] This example is used to illustrate that the catalyst support for olefin polymerization of the present invention is used for the preparation of polyolefin.

[0108] 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 to obtain polypropylene powder.

[0109] Embodiment 11

[0110] This example is used to illustrate that the catalyst support for olefin polymerization of the present invention is used for the preparation of polyolefin.

[0111] 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.

[0112] Example 12

[0113] This example is used to illustrate that the catalyst support for olefin polymerization of the present invention is used for the preparation of polyolefin.

[0114] 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 to obtain polypropylene powder.

[0115] Comparative Example 3

[0116] 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.

[0117] 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.

[0118] Comparative Example 4

[0119] 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.

[0120] 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 to obtain polypropylene powder.

[0121] Comparative Example 5

[0122] 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.

[0123] 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 DZ2 for olefin polymerization obtained in Comparative Example 2, to obtain catalyst components for olefin polymerization and polypropylene powder.

[0124] Comparative Example 6

[0125] 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.

[0126] 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 to obtain polypropylene powder.

[0127] The catalyst components for olefin polymerization prepared in the above Examples 5-12 and Comparative Examples 3-6 were used for propylene polymerization, and the catalytic activity of the catalysts for olefin polymerization in Examples 5-12 and Comparative Examples 3-6 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:

[0128] Table 2

[0129]

[0130] 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 before the wash resistance test;

[0131] Since the particle shape of the prepared polypropylene powder in Comparative Example 5-6 was not good, the washout resistance was not tested.

[0132] From the results in Table 1 and Table 2 above, it can be seen that the particle morphology of the catalyst carrier for olefin polymerization prepared by the present invention is good, the surface is smooth, and there are basically no irregular particles. Moreover, the catalyst prepared by using the catalyst carrier for olefin polymerization has better activity and better hydrogen adjustment sensitivity. When the catalyst is used for olefin (especially propylene) polymerization, the bulk density of the polymerization product can be increased, and there is basically no irregular material in the polymerization product. At the same time, the silver element in the prepared polymer is not easily eluted, and has a more lasting antibacterial ability. Therefore, the spherical carrier of the olefin polymerization catalyst described in the present invention has great industrial application prospects.

[0133] 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 catalyst carrier for olefin polymerization, characterized in that The olefin polymerization catalyst carrier comprises a compound as shown in structural formula (I) and silver element; In the compound represented by formula (I), R1 is a C1-C8 straight-chain alkyl, a C3-C8 branched-chain alkyl or a C3-C8 cycloalkyl; R2 and R3 are the same or different and are independently hydrogen, a C1-C5 straight-chain alkyl or a C3-C5 branched-chain alkyl, wherein the hydrogen on the R2 and R3 alkyl groups is optionally replaced by a halogen atom; X is a halogen, preferably chlorine or bromine; m is 0.1-1.9, n is 0.1-1.9, and m+n=2; In the catalyst carrier for olefin polymerization, the molar ratio of silver element to the compound represented by formula (I) is (0.0010-0.50):1; wherein the compound represented by formula (I) is calculated based on the molar amount of Mg.

2. The catalyst carrier for olefin polymerization according to claim 1, characterized in that The synthetic raw materials of the catalyst carrier for olefin polymerization include silver carboxylate, magnesium halide, alcohol compound and ethylene oxide compound; Preferably, the general formula of the magnesium halide is MgX1Y1, the general formula of the alcohol compound is R4OH, and the structural formula of the ethylene oxide compound is as shown in formula (II); Preferably, in the general formula MgX1Y1, X1 is chlorine or bromine, and Y1 is chlorine, bromine, C1-C5 alkyl, C1-C5 alkoxy, C6-C 10 Aryl or C6-C 10 Further preferably, the magnesium halide of the general formula MgX1Y1 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 R4OH, R4 is a C1-C8 straight-chain alkyl group, a C3-C8 branched alkyl group or a C3-C8 cycloalkyl group; preferably, in the general formula R4OH, R4 is a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group, an isooctyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexyl group or a cyclohexylmethyl group; further preferably, the alcohol compound of the general formula R4OH is selected from at least one of ethanol, propanol, isopropanol, n-butanol, isobutanol, amyl alcohol, isopentanol, n-hexanol, n-octanol and 2-ethylhexanol; And / or, in formula (II), R5 and R6 are the same or different, and are independently hydrogen, a C1-C5 straight-chain alkyl group or a C3-C5 branched-chain alkyl group, wherein the hydrogen on the alkyl group is optionally substituted by a halogen atom; preferably, R5 and R6 are the same or different, and are independently hydrogen, a C1-C3 straight-chain alkyl group or a C1-C3 haloalkyl group; more preferably, the oxirane compound is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epichlorohydrin, epibromohydrin and epibromobutylene oxide; And / or, the silver carboxylate is selected from at least one of silver acetate, silver benzoate, silver propionate, silver butyrate and silver octanoate.

3. The catalyst support for olefin polymerization according to claim 1 or 2, characterized in that The average particle size of the catalyst carrier for olefin polymerization is 10-100 microns, preferably 20-50 microns, and the particle size distribution is <1.2, preferably ≦0.

8.

4. The catalyst support for olefin polymerization according to any one of claims 1 to 3, characterized in that In the catalyst carrier for olefin polymerization, based on 1 mol of magnesium halide with the general formula MgX1Y1, the amount of silver carboxylate is 0.0001-0.5 mol, the amount of compound with the general formula R4OH is 4-30 mol, and the amount of ethylene oxide compound is 1-10 mol; preferably, based on 1 mol of magnesium halide with the general formula MgX1Y1, the amount of silver carboxylate is 0.01-0.5 mol, the amount of compound with the general formula R4OH is 6-20 mol, and the amount of ethylene oxide compound is 2-6 mol.

5. A method for preparing a catalyst carrier for olefin polymerization according to any one of claims 1 to 4, characterized in that: The steps include: (1) mixing a magnesium halide and an alcohol compound, and reacting the mixture with a silver carboxylate to obtain a first reactant; (2) adding an ethylene oxide compound to the first reactant obtained in step (1) to carry out reaction II to obtain the olefin polymer and the catalyst carrier; Optionally, the step (1) further comprises adding an inert liquid medium and a surfactant.

6. The preparation method according to claim 5, characterized in that: In step (1), the mixing conditions include: a mixing temperature of 80-120° C., preferably 80-100° C.; a mixing time of 0.5-5 hours, preferably 0.5-3 hours; And / or, the conditions of the reaction I include: temperature of 80-120°C, preferably 80-100°C; time of 0.5-5 hours, preferably 0.5-3 hours; And / or, the inert liquid medium 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; further preferably, based on 1 mol of magnesium halide with the general formula MgX1Y1, the amount of the inert liquid medium is 0-10L, preferably 2-8L; And / or, the surfactant is selected from at least one of polyvinyl pyrrolidone, polyethylene glycol, polyvinyl alcohol, polyacrylic acid, polyacrylic acid salt, polyacrylamide, polystyrene sulfonate, naphthalenesulfonic acid formaldehyde condensate, condensed alkyl phenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, oxyalkyl acrylate copolymer modified polyethyleneimine, 1-dodeca-4-vinylpyridinium bromide polymer, polyvinyl benzyltrimethylamine salt, polyethylene oxide propylene oxide block copolymer, polyvinyl pyrrolidone vinyl acetate copolymer, alkylphenyl polyoxyethylene ether and polyalkyl methacrylate; preferably, the amount of the surfactant used is 1-20g based on 1 mol of magnesium halide with the general formula MgX1Y1.

7. The preparation method according to claim 5 or 6, characterized in that: In step (2), the conditions of reaction II include: temperature of 40-120°C, preferably 60-100°C; time of 15-60 minutes, preferably 20-50 minutes.

8. A catalyst component for olefin polymerization, characterized in that The catalyst component comprises a product obtained by reacting the catalyst support for olefin polymerization according to any one of claims 1 to 4 or the catalyst support for olefin polymerization prepared by the preparation method according to any one of claims 5 to 7, a titanium compound and an optional internal electron donor compound.

9. A catalyst for olefin polymerization, characterized in that: The catalyst comprises: 1) The catalyst component according to claim 8; 2) Alkyl aluminum compounds; 3) Optionally an external electron donor compound.

10. Use of the catalyst carrier for olefin polymerization according to any one of claims 1 to 4, or the catalyst carrier for olefin polymerization prepared by the preparation method according to any one of claims 5 to 7, or the catalyst component according to claim 8, or the catalyst according to claim 9 in preparing a catalyst for olefin polymerization.

11. An olefin polymerization method, characterized in that: The process comprises contacting at least one olefin with the catalyst of claim 9 under olefin polymerization conditions.

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