Catalyst components for the polymerization of olefins, process for their preparation and use

Abstract

The application belongs to the field of catalysts, and discloses a catalyst component for olefin polymerization and a preparation method and application thereof. The catalyst component for olefin polymerization comprises a carrier, a titanium compound and an internal electron donor compound; the carrier is selected from at least one of substances with a structure as shown in formula (I); the structural formula of the internal electron donor compound is as shown in formula (III); the carrier used in the catalyst component for olefin polymerization has the characteristics of narrow particle size distribution, good carrier particle morphology and smaller average particle size, and the catalyst component for olefin polymerization can be used to obtain polymer particles with silver, good morphology, higher elution resistance and higher bulk density through in-situ polymerization.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, specifically to a catalyst component for olefin polymerization and its preparation method, and the application of a catalyst containing the catalyst component for olefin polymerization in olefin polymerization. Background Technology

[0002] With the rapid development of the polypropylene industry and the advancement of polypropylene resin processing technology, its production capacity has increased rapidly, and its proportion in the synthetic resin field has also grown. This industrial development has placed higher demands on the production and processing efficiency of polypropylene, such as requiring polypropylene resins to have higher melt flow rate indices to improve their fluidity, and demanding that polypropylene resins possess more functionalities.

[0003] With the development of modern transportation and the increasing frequency of economic exchanges, the mobility of people has increased significantly, and the rate of virus transmission has also greatly increased, creating a more urgent need to prevent the rapid spread of viruses. At the same time, as people's material lives become increasingly affluent, they also place higher demands on their own health and the hygiene of the environment and goods.

[0004] Modern life is increasingly inseparable from plastic daily necessities, such as storage, preservation, and packaging. However, these products also attract bacteria, fungi, and viruses. Research data shows that the number of bacteria and fungi on the surface of everyday household plastic cutting boards can be as high as 26,000 per square centimeter. This can lead to cross-contamination due to the use of plastics. Therefore, there is a widespread demand for the research, development, and production of antibacterial materials.

[0005] Antibacterial polypropylene (PP) possesses the advantages of polypropylene, giving it significant advantages in applications. Currently, the main production methods for antibacterial PP include melt blending, impregnation, and coating. Melt blending involves heating the antibacterial agent and other components, such as resin, to above their melting point in a mixing plant to obtain a homogeneous eutectic. Impregnation, commonly used for antibacterial PP fibers, involves immersing the prepared PP material in a liquid or gas containing antibacterial active substances, allowing the substances to adhere to the material through deposition and adsorption. Coating involves coating a gel-like antibacterial substance onto a PP matrix. However, these existing production methods for antibacterial PP generally have various drawbacks. For example, coating is simple but has poor antibacterial durability; melt blending requires heating the plastic to its melting point, consuming a large amount of energy and potentially causing compatibility issues; impregnation is not only inefficient but also suffers from problems with antibacterial durability.

[0006] In addition, molecular weight distribution is an important indicator of polymers and has a significant impact on polymer properties. For example, a wider molecular weight distribution can lead to a better balance between rigidity and toughness, but fiber production requires a narrower molecular weight distribution.

[0007] Therefore, it is of great significance to develop a catalyst component for olefin polymerization that can overcome the above-mentioned defects of the existing technology and can be used to produce antibacterial polypropylene with high fluidity and narrow molecular weight distribution. Summary of the Invention

[0008] The technical problem to be solved by the present invention is that the antibacterial properties of antibacterial polypropylene prepared in the prior art are not durable enough, and the polypropylene has poor flowability and a wide molecular weight distribution, which limits its application fields. The present invention provides a catalyst component for olefin polymerization, its preparation method and application.

[0009] The inventors of this invention unexpectedly discovered that the support for olefin polymerization prepared by this invention not only has a good spherical morphology, but also, when the catalyst component prepared from this support and the hydrogen-containing internal electron donor is used for olefin polymerization (especially propylene polymerization), silver-containing antibacterial polypropylene can be prepared online. The antibacterial polypropylene has good flowability, a narrow molecular weight distribution, and good antibacterial durability.

[0010] To address the aforementioned technical problems, the first aspect of this invention provides a catalyst component for olefin polymerization, comprising a support, a titanium compound, and an internal electron donor compound;

[0011] The carrier is selected from at least one of substances having the structure shown in Formula (I);

[0012]

[0013] In the substance with the structure shown in formula (I), R1 is a C1-C8 straight-chain alkyl, C3-C8 branched alkyl, or C3-C8 cycloalkyl; R2, R3, R'2, and R'3 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 groups R2, R3, R'2, and R'3 is optionally substituted with a halogen atom; X is a halogen, preferably chlorine or bromine; R4 is a C1-C8 cycloalkyl group. 10 Straight-chain alkyl, C3-C 10 Branched alkyl or C6-C 10 The aryl group, wherein the hydrogen atom on the R4 alkyl group is optionally substituted with a halogen atom; m is 0.1-1.9, n is 0.1-1.9, m+n+k=2, 0 <q≤0.5,0<k≤0.5。

[0014] According to some embodiments of the present invention, the molar ratio of silver to magnesium in the carrier is (0.0010-0.50):1.

[0015] In this invention, the substance with the structure shown in formula (I) includes the substance with the structural formula:

[0016] Compounds and silver halides.

[0017] According to some embodiments of the present invention, the raw materials for synthesizing the support include silver carboxylate, magnesium halide, alcohol compounds and ethylene oxide compounds; preferably, the general formula of the magnesium halide is MgX1Y1, the general formula of the alcohol compound is R4'OH, and the structural formula of the ethylene oxide compound is shown in formula (II).

[0018]

[0019] According to some embodiments of the present invention, in the general formula MgX1Y1, X1 is a halogen, and Y1 is a halogen, a C1-C5 alkyl group, a C1-C5 alkoxy group, or a C6-C5 alkyl group. 10 aryl or C6-C 10 The aryloxy group; 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 The aryl group; preferably, the C1-C5 alkyl group can be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, or neopentyl, and the C1-C5 alkoxy group can be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, or isobutoxy, and the C6-C 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 MgX1Y1 can be a single magnesium halide or a mixture of multiple magnesium halides; more preferably, the magnesium halide with the general formula MgX1Y1 is selected from at least one of magnesium chloride, magnesium bromide, magnesium phenoxy chloride, magnesium isopropoxy chloride and magnesium n-butoxy chloride.

[0020] According to some embodiments of the present invention, in the general formula R4'OH, R4' is a C1-C8 straight-chain alkyl, a C3-C8 branched alkyl, or a C3-C8 cycloalkyl, wherein all or part of the carbon atoms in the C3-C8 cycloalkyl can participate in cyclization; preferably, in the general formula R4'OH, R4' is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, isohexyl, heptyl, isohexyl, octyl, isooctyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, or cyclohexylmethyl; more preferably, the alcohol compound of the general formula R4'OH is selected from at least one of ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentyl alcohol, n-hexanol, n-octanol, and 2-ethylhexanol.

[0021] According to some embodiments of the present invention, in formula (II), R5 and R6 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 with a halogen atom; preferably, R5 and R6 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, the ethylene oxide compound is selected from at least one of ethylene oxide, propylene oxide, butane oxide, epichlorohydrin, chlorobutane, bromopropane, and bromobutane.

[0022] 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.

[0023] According to some embodiments of the present invention, the titanium compound has the general formula Ti(OR) 9 ) 4－k X k , where R 9 For C1-C 20 hydrocarbon group, R 9 Preferred C1-C 14 The aliphatic hydrocarbon group, where X is a halogen, preferably F, Cl or Br, and n is 0 or an integer selected from 1 to 4; preferably, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium monochlorotributoxy, titanium dichlorodibutoxy, titanium trichlorobutoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, titanium trichloroethoxy, and titanium trichloride.

[0024] According to some embodiments of the present invention, the internal electron donor compound has the structural formula shown in formula (III);

[0025]

[0026] In equation (III), R”'1 and R”'2 may be the same or different, and are each independently selected from hydrogen or C1-C. 14 Straight-chain alkyl or C3-C 14 Branched alkyl, C3-C 10 cycloalkyl, C6-C 10 Aryl, C7-C 10 Alkyl or C7-C 10 Aryl alkyl groups, R”'1 and R”'2 can be bonded to each other to form one or more fused ring structures; R”'3 and R”'4 may be the same or different, and each is independently selected from C1-C2. 10 Straight-chain alkyl or C3-C 10 Branched alkyl, C3-C 10 cycloalkyl, C6-C 20Aryl, C7-C 20 Alkyl or C7-C 20 Aromatic group; in R”'1, R”'2, R”'3, R”'4, the hydrogen on the benzene ring of the aryl or alkylaryl or aromatic group may optionally be replaced by other atoms; preferably, the internal electron donor compound is selected from one or more of 2,3-diisopropyl-2-cyanosuccinate, 3-methyl-2-isopropyl-2-cyanosuccinate, 3-ethyl-2-isopropyl-2-cyanosuccinate, 3-propyl-2-isopropyl-2-cyanosuccinate, 3-butyl-2-isopropyl-2-cyanosuccinate, and 3-phenyl-2-isopropyl-2-cyanosuccinate.

[0027] The average particle size of the support described in this invention can be controlled within a wide range. According to some embodiments of the invention, the average particle size of the support is 10-100 micrometers. Preferably, the average particle size (D50) of the support can be controlled to be less than or equal to 60 micrometers, more preferably 20-50 micrometers, with a particle size distribution <1.2, preferably ≤0.8. In a preferred embodiment, the catalyst prepared from this support can yield olefin polymers with higher bulk density.

[0028] According to the present invention, the carrier may contain water, which is derived from trace amounts of water carried by the synthetic raw materials and reaction medium.

[0029] According to the present invention, the content of the above-mentioned components in the carrier can be selected and varied within a wide range. Preferably, according to some embodiments of the present invention, in the carrier, based on 1 mol of magnesium halide with the general formula MgX1Y1, the amount of silver carboxylate is 0.0001-0.6 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 0.0001-0.5 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.

[0030] According to the present invention, trace amounts of water in the above reactants can also participate in the reaction to form a carrier.

[0031] According to some embodiments of the present invention, the method for preparing the carrier includes the following steps:

[0032] (1) After mixing magnesium halide and alcohol compounds I, react with silver carboxylate I to obtain the first reactant;

[0033] (2) Add an ethylene oxide compound to the first reactant obtained in step (1) and carry out reaction II to obtain the support;

[0034] Optionally, step (1) may further include the addition of an inert liquid medium and a surfactant.

[0035] According to the present invention, in step (1), there are no particular limitations on the conditions for mixing I with silver carboxylate, magnesium halide of general formula MgX1Y1, alcohol compound of general formula R4OH, optionally with an inert liquid medium and / or surfactant, and for carrying out reaction I, as long as the conditions for mixing I and carrying out reaction I are sufficient to allow magnesium halide of general formula MgX1Y1 to melt and react fully with silver carboxylate.

[0036] According to some embodiments of the present invention, in step (1), the conditions for mixing I include: the mixing I temperature is 80-120°C, preferably 80-100°C; the mixing I time is 0.5-5 hours, preferably 0.5-3 hours;

[0037] And / or, the conditions for reaction I include: a temperature of 80-120°C, preferably 80-100°C; and a time of 0.5-5 hours, preferably 0.5-3 hours.

[0038] According to some embodiments of the present invention, the inert liquid medium can be any liquid medium commonly used in the art that does not chemically react 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, petrolatum oil, white oil, methyl silicone oil, ethyl silicone oil, methylethyl silicone oil, phenyl silicone oil, and methylphenyl silicone oil; more 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 0-10 L, preferably 2-8 L.

[0039] According to some embodiments of the present invention, in step (1), a surfactant is used; the surfactant is selected from at least one of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polyacrylic acid, polyacrylate, polyacrylamide, polystyrene sulfonate, naphthalenesulfonic acid formaldehyde condensate, condensed alkylphenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, oxyalkyl acrylate copolymer modified polyethyleneimine, polymer of 1-dodecyl-4-vinylpyridine bromide, polyvinylbenzyltrimethylamine salt, polyethylene oxide propylene oxide block copolymer, polyvinylpyrrolidone vinyl acetate copolymer, alkylphenyl polyoxyethylene ether, and polyalkyl methacrylate; preferably, the amount of the surfactant is 1-20g based on 1mol of magnesium halide with the general formula MgX1Y1.

[0040] According to the present invention, in step (2), the conditions for contacting the first reactant with the ethylene oxide compound can be any of the existing conditions that can form an olefin polymerization catalyst support; according to some embodiments of the present invention, in step (2), the conditions for reaction II include: a temperature of 40-120°C, preferably 60-100°C; and a time of 15-60 minutes, preferably 20-50 minutes.

[0041] According to the present invention, the preparation method may further include solid-liquid separation of the product obtained from reaction II, washing and drying the separated solid product; the solid-liquid separation can be any existing method capable of separating the solid and liquid phases, such as vacuum filtration, pressure filtration, or centrifugation, preferably pressure filtration; the present invention does not particularly limit the conditions of pressure filtration, as long as the separation of the solid and liquid phases is achieved as fully as possible; the washing can be performed using methods known to those skilled in the art, for example, using inert hydrocarbon solvents (e.g., pentane, hexane, heptane, petroleum ether, and gasoline); the present invention does not particularly limit the drying conditions, for example, the drying temperature can be 20-70°C, and the drying time can be 0.5-10 hours. According to the present invention, the drying can be carried out under normal pressure or reduced pressure.

[0042] A second aspect of the present invention provides a method for preparing the catalyst component for olefin polymerization, comprising mixing the titanium compound with a support (II), adding an internal electron donor compound to carry out a reaction (III), and obtaining the catalyst component; preferably, the conditions for the reaction (III) include: a temperature of -30 to 125°C and a time of 1 to 15 hours.

[0043] The mixture II described in this invention includes a heating process, during which an internal electron-donating compound is added; preferably, the reaction III includes a solid-liquid separation step. This invention does not have a special limitation on the solid-liquid separation step, and the same method as the solid-liquid separation of the product obtained in reaction II can be used.

[0044] The method for preparing the catalyst component according to the present invention further includes vacuum drying, wherein the vacuum drying conditions are: a temperature of 40-50°C and a time of 30-60 min. In this invention, the vacuum drying can be carried out using a conventional vacuum pump, and there are no special requirements for it.

[0045] In the present invention, the preparation method of the catalyst components for olefin polymerization does not have special requirements on the amount of each component, and all are conventional amounts in the art.

[0046] A third aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising:

[0047] 1) The catalyst component provided in the first aspect or the catalyst component provided in the second aspect above;

[0048] 2) Alkyl aluminum compounds;

[0049] 3) Selectively use external electron donor compounds.

[0050] This invention does not impose any particular restrictions on the composition of the catalyst, the content of each component, or the preparation method. The composition, content, and method of existing olefin polymerization catalysts in the art can be used. Those skilled in the art can make reasonable adjustments and designs according to actual needs. The embodiments of this invention described below illustrate a specific operation process, which should not be construed as a limitation of this invention.

[0051] The fourth aspect of the present invention provides the application of the catalyst component provided in the first aspect, the catalyst component provided in the second aspect, or the catalyst provided in the third aspect in olefin polymerization.

[0052] The present invention does not impose any particular limitation on the specific operation method of the application, and those skilled in the art can use existing methods for olefin polymerization reactions to operate it.

[0053] A fifth aspect of the present invention provides a method for olefin polymerization, the method comprising contacting at least one olefin with a catalyst provided in the third aspect under olefin polymerization conditions; preferably, the olefin is selected from olefins with the structural formula CH2=CHR, wherein R is hydrogen or a straight-chain alkyl group of C1-C6 or a branched alkyl group of C3-C6; more preferably, the olefin is selected from ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene, and 4-methyl-1-pentene; preferably, the olefin is ethylene, propylene, 1-n-butene, 1-n-hexene, or 4-methyl-1-pentene; more preferably, the olefin is propylene.

[0054] The olefin polymerization method of the present invention can be a homopolymerization of a single olefin or a copolymerization of multiple olefins.

[0055] 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: a temperature of 0-150°C, a time of 0.1-8 hours, and a pressure of 0.01-10 MPa; preferably, the olefin polymerization conditions include: a temperature of 50-100°C, a time of 0.5-3 hours, and a pressure of 0.5-5 MPa. The amount of olefin polymerization catalyst used can be any conventional amount of olefin catalysts in the prior art.

[0056] Beneficial effects:

[0057] The support used in the catalyst component for olefin polymerization described in this invention has the characteristics of narrow particle size distribution, good support particle morphology, and smaller average particle size. Using the catalyst component for olefin polymerization described in this invention, silver-containing polymer particles with good morphology, higher elution resistance, and higher bulk density can be obtained through in-situ polymerization. Detailed Implementation

[0058] The present invention will be further described below with reference to embodiments. However, the present invention is not limited to these embodiments.

[0059] Unless otherwise specified, all raw materials used in the following embodiments and comparative examples of the present invention are commercially available.

[0060] In the examples and comparative examples:

[0061] 1. The average particle size and particle size distribution of the catalyst support for olefin polymerization were determined using a Masters Sizer 2000 particle size analyzer (manufactured by Malvern Instruments Ltd.);

[0062] 2. The morphology of the catalyst support for olefin polymerization was observed using an optical microscope, model Eclipse E200, purchased from Nikon.

[0063] 3. The bulk density of polyolefin powder shall be determined according to the method specified in GB / T 1636-2008.

[0064] 4. Elution test of polyolefin powder: Wash 10g of sample with anhydrous ethanol 10 times, 100ml / time, freeze section, and analyze the silver content of the particles using X-ray fluorescence spectroscopy. The ratio of the silver content after elution to the silver content before elution is defined as the elution resistance.

[0065] 5. Calculation of catalyst activity for olefin polymerization: Catalyst activity = (mass of prepared polyolefin) / (mass of solid catalyst component) g / g.

[0066] 6. The molecular weight distribution width of the polyolefin powder was determined using a PL-GPC220 gel permeation chromatograph from Polymer Laboratories, UK, combined with an IR5 infrared detector. The determination conditions were: temperature 150℃, chromatographic column 3 PLgel 13μm Olexis column, mobile phase 1,2,4-trichlorobenzene (with 0.025% by mass of antioxidant 2,6-dibutyl-p-cresol), flow rate 1.0 mL / min, sample mass concentration approximately 1 mg / mL, and universal standardization was performed using PL's EasiCal PS-1 narrow distribution polystyrene standard.

[0067] 7. The time it takes for all the polymer powder to pass through the powder funnel of the bulk density tester is recorded as the falling time.

[0068] Example 1

[0069] This embodiment illustrates the catalyst support for olefin polymerization and its preparation method provided by the present invention.

[0070] In a 0.6 L reactor, 0.08 mol (8.0 g) of magnesium chloride, 0.96 mol of ethanol, and 0.8 g of PVP (polyvinylpyrrolidone) were added. The mixture was heated to 86 °C under stirring and reacted at 86 °C for 2 hours. Then, 0.03 mol of silver acetate was added, and the reaction was continued at 86 °C for another 2 hours. Next, 0.48 mol (38 ml) of epichlorohydrin was added, and the mixture was reacted at 86 °C for 30 minutes. The mixture was then filtered under pressure. The filtered product was washed five times with hexane and dried under vacuum to obtain catalyst support Z1 for olefin polymerization.

[0071] Based on gas chromatography-mass spectrometry, elemental analysis, and NMR characterization, the support Z1 has the following structure. The molar ratio of silver to Mg is 0.22:1.

[0072] Example 2

[0073] This embodiment illustrates the catalyst support for olefin polymerization and its preparation method provided by the present invention.

[0074] In a 0.6L reactor, 300mL of white oil, 0.08mol (8.0g) of magnesium chloride, 0.48mol (28mL) of ethanol, and 1g of PVP (polyvinylpyrrolidone) were added. The mixture was heated to 100℃ with stirring and reacted at 100℃ for 1 hour. Then, 0.03mol of silver acetate was added, and the reaction was continued at 100℃ for 2 hours. Next, 0.16mol (12.5mL) of epichlorohydrin was added, and the reaction was continued at 100℃ for 20 minutes. The mixture was then filtered under pressure. The filtered product was washed five times with hexane and dried under vacuum to obtain catalyst support Z2 for olefin polymerization.

[0075] Based on gas chromatography-mass spectrometry, elemental analysis, and NMR characterization, the support Z2 has the following structure. The molar ratio of silver to Mg is 0.2:1.

[0076] Example 3

[0077] This embodiment illustrates the catalyst support for olefin polymerization and its preparation method provided by the present invention.

[0078] In a 0.6L reactor, 300mL of white oil, 0.08mol (8.0g) of magnesium chloride, 0.48mol (28mL) of ethanol, and 1g of PVP (polyvinylpyrrolidone) were added. The mixture was heated to 100℃ with stirring and reacted at 100℃ for 1 hour. Then, 0.01mol of silver acetate was added, and the reaction was continued at 100℃ for 2 hours. Next, 0.16mol (12.5mL) of epichlorohydrin was added, and the reaction was continued at 100℃ for 20 minutes. The mixture was then filtered under pressure. The filtered product was washed five times with hexane and dried under vacuum to obtain catalyst support Z3 for olefin polymerization.

[0079] Based on gas chromatography-mass spectrometry, elemental analysis, and NMR characterization, the support Z3 has the following structure. The molar ratio of silver to Mg is 0.12:1.

[0080] Example 4

[0081] This embodiment illustrates the catalyst support for olefin polymerization and its preparation method provided by the present invention.

[0082] In a 0.6 L reactor, 0.08 mol (8.0 g) of magnesium chloride, 0.96 mol (56 mL) of ethanol, and 1 g of PVP (polyvinylpyrrolidone) were added. The mixture was heated to 90 °C with stirring and reacted at 90 °C for 2 hours. Then, 0.01 mol of silver acetate was added, and the reaction was continued at 90 °C for another 2 hours. Next, 0.38 mol of epichlorohydrin was added, and the reaction was continued at 90 °C for another 20 minutes. The mixture was then filtered under pressure. The filtered product was washed five times with hexane and dried under vacuum to obtain catalyst support Z4 for olefin polymerization.

[0083] Based on gas chromatography-mass spectrometry, elemental analysis, and NMR characterization, the support Z4 has the following structure. The molar ratio of silver to Mg is 0.13:1.

[0084] Comparative Example 1

[0085] This comparative example is used to illustrate the catalyst support for olefin polymerization and its preparation method provided by the comparative example of the present invention.

[0086] In a 0.6L reactor, 0.08mol magnesium chloride, 0.96mol ethanol, and 0.8g PVP (polyvinylpyrrolidone) were added. The mixture was heated to 86℃ under stirring and reacted at 86℃ for 2 hours. Then, 0.48mol (38ml) epichlorohydrin was added, and the mixture was reacted at 90℃ for 30 minutes. After pressure filtration, the filtered product was washed five times with hexane and dried under vacuum to obtain catalyst support DZ1 for olefin polymerization.

[0087] Based on gas chromatography-mass spectrometry, elemental analysis, and NMR characterization, the carrier DZ1 contains the structural formula […].

[0088] The carrier DZ1 does not contain silver.

[0089] Comparative Example 2

[0090] This comparative example is used to illustrate the catalyst support for olefin polymerization and its preparation method provided by the comparative example of the present invention.

[0091] In a 0.6 L reactor, 0.08 mol magnesium chloride, 0.96 mol ethanol, and 0.8 g PVP (polyvinylpyrrolidone) were added. The mixture was heated to 86 °C under stirring and reacted at 86 °C for 2 hours. Then, 0.03 mol silver chloride was added, and the reaction was continued at 86 °C for another 2 hours. Next, 0.48 mol (38 ml) epichlorohydrin was added, and the mixture was reacted at 90 °C for 30 minutes. The mixture was then filtered under pressure. The filtered product was washed five times with hexane and dried under vacuum to obtain catalyst support DZ2 for olefin polymerization.

[0092] Based on gas chromatography-mass spectrometry, elemental analysis, and NMR characterization, the carrier DZ2 contains the structural formula […]. The compound and silver, wherein the molar ratio of silver element and compound (in molar amount of Mg) to silver is 0.02:1.

[0093] The average particle size (D50) and particle size distribution ((D90-D10) / D50) of the catalyst supports for olefin polymerization prepared in Examples 1-4 and Comparative Examples 1-2 were measured, and their appearance morphology was observed. The results are shown in Table 1 below:

[0094] Table 1

[0095]

[0096] As can be seen from the results in Table 1 above, the catalyst supports for olefin polymerization prepared in Examples 1-4 of the present invention have narrow particle size distribution, good particle morphology, and smaller average particle size; and the reduction in average particle size is beneficial to expanding the process adaptability of the catalysts prepared using the supports (such as the Unipol polypropylene production process, which generally requires a smaller particle size).

[0097] Example 5

[0098] This example illustrates the use of the catalyst support for olefin polymerization of the present invention in the preparation of polyolefins.

[0099] (1) Preparation of catalyst components for olefin polymerization

[0100] In a 300 mL reaction flask, 100 mL of titanium tetrachloride was added and cooled to -20 °C. Then, 40 g of the catalyst support Z1 for olefin polymerization obtained in Example 1 was added and stirred at -20 °C for 30 min. After that, the temperature was slowly increased to 110 °C, and 6 mmol of diethyl 2,3-diisopropyl-2-cyanosuccinate was added during the heating process. The temperature was then maintained at 110 °C for 30 min, and the liquid was filtered off. Then, titanium tetrachloride was added to wash twice, and finally, hexane was washed three times. After drying, the catalyst component C1 for olefin polymerization was obtained.

[0101] (2) Propylene polymerization reaction

[0102] In a 5L stainless steel high-pressure reactor, nitrogen gas was used for purging. Then, 1 mmol of triethylaluminum hexane solution (concentration of triethylaluminum was 0.5 mmol / mL), 0.05 mmol of methylcyclohexyldimethoxysilane, 10 mL of anhydrous hexane, 10 mg of catalyst component C1 obtained from step (1) above for olefin polymerization, 1.5 L (standard volume) of hydrogen gas, and 2.5 L of liquid propylene were introduced into the nitrogen gas flow. The temperature was raised to 70°C and the polymerization reaction was carried out at this temperature for 1 hour. After that, the temperature was lowered, the pressure was released, and the material was discharged and dried to obtain polypropylene powder.

[0103] Example 6

[0104] This example illustrates the use of the catalyst support for olefin polymerization of the present invention in the preparation of polyolefins.

[0105] Propylene polymerization was carried out according to the method of Example 5, except that the 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.

[0106] Example 7

[0107] This example illustrates the use of the catalyst support for olefin polymerization of the present invention in the preparation of polyolefins.

[0108] 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 Z2 for olefin polymerization obtained in Example 2, to obtain catalyst components and polypropylene powder for olefin polymerization.

[0109] Example 8

[0110] This example illustrates the use of the catalyst support for olefin polymerization of the present invention in the preparation of polyolefins.

[0111] Propylene polymerization was carried out according to the method of Example 7, except that the 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.

[0112] Example 9

[0113] This example illustrates the use of the catalyst support for olefin polymerization of the present invention in the preparation of polyolefins.

[0114] 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 Z3 for olefin polymerization obtained in Example 3, to obtain catalyst components and polypropylene powder for olefin polymerization.

[0115] Example 10

[0116] This example illustrates the use of the catalyst support for olefin polymerization of the present invention in the preparation of polyolefins.

[0117] Propylene polymerization was carried out according to the method of Example 9, except that the 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.

[0118] Example 11

[0119] This example illustrates the use of the catalyst support for olefin polymerization of the present invention in the preparation of polyolefins.

[0120] 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 Z4 for olefin polymerization obtained in Example 4, to obtain catalyst components and polypropylene powder for olefin polymerization.

[0121] Example 12

[0122] This example illustrates the use of the catalyst support for olefin polymerization of the present invention in the preparation of polyolefins.

[0123] Propylene polymerization was carried out according to the method of Example 11, except that the 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.

[0124] Example 13

[0125] This example illustrates the use of the catalyst support for olefin polymerization of the present invention in the preparation of polyolefins.

[0126] Propylene polymerization was carried out according to the method of Example 5, except that 2,3-diisopropyl-2-cyanosuccinate diethyl ester was replaced with 2,3-diisopropyl-2-ylsuccinate diethyl ester to obtain a catalyst component and polypropylene powder for olefin polymerization.

[0127] Comparative Example 3

[0128] This comparative example is used to illustrate the use of the catalyst support for olefin polymerization of the present invention in the preparation of polyolefins.

[0129] 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 and polypropylene powder for olefin polymerization.

[0130] Comparative Example 4

[0131] This comparative example is used to illustrate the use of the catalyst support for olefin polymerization of the present invention in the preparation of polyolefins.

[0132] Propylene polymerization was carried out according to the method of Example 5, except that the 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.

[0133] Comparative Example 5

[0134] This comparative example is used to illustrate the use of the catalyst support for olefin polymerization of the present invention in the preparation of polyolefins.

[0135] 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 and polypropylene powder for olefin polymerization.

[0136] Comparative Example 6

[0137] This comparative example is used to illustrate the use of the catalyst support for olefin polymerization of the present invention in the preparation of polyolefins.

[0138] Propylene polymerization was carried out according to the method of Example 5, except that the 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.

[0139] The catalyst components for olefin polymerization prepared in Examples 5-13 and Comparative Examples 3-6 were used in propylene polymerization. The catalytic activity of the catalysts for olefin polymerization in Examples 5-13 and Comparative Examples 3-6 was calculated after 1 hour of polymerization. The appearance of the prepared polypropylene powder was observed. The results are shown in Table 2 below.

[0140] Table 2

[0141]

[0142]

[0143] In Table 2, * indicates that when testing the experimental data, the prepared polypropylene powder was first soaked in the same amount of silver acetate ethanol solution as in Example 1 for 1 hour, vacuum dried, and then the wash resistance test was performed.

[0144] Comparative Examples 5-6 did not test molecular weight distribution and elution resistance because the polypropylene powder prepared had poor particle shape.

[0145] As can be seen from the results in Tables 1 and 2 above, the spherical support for olefin polymerization catalyst prepared by this invention has good particle morphology, smooth surface, and virtually no irregular particles. Moreover, the catalyst prepared with this support has good activity, and the resulting polymer has a shorter settling time, indicating better polymer flowability. This is beneficial for preventing bridging / clogging problems during polymer transport in industrial production. When this catalyst is used for olefin (especially propylene) polymerization, it can increase the bulk density of the polymerization product and obtain polymers with a narrower molecular weight distribution, which can expand the application of polymers in different application scenarios. Furthermore, there are virtually no irregular particles in the polymerization product, and the silver element in the polymer is not easily eluted, resulting in more durable antibacterial ability. Therefore, the spherical support for olefin polymerization catalyst of this invention has great industrial application prospects.

[0146] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on 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 terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A catalyst component for olefin polymerization, comprising a support, a titanium compound, and an internal electron donor compound; characterized in that, The carrier is selected from at least one of substances having the structure shown in Formula (I); Equation (I) In the substance with the structure shown in formula (I), R1 is a C1-C8 straight-chain alkyl, C3-C8 branched alkyl, or C3-C8 cycloalkyl; R2, R3, R'2, and R'3 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 of R2, R3, R'2, and R'3 is optionally substituted with a halogen atom; X is a halogen; R4 is a C1-C8 cycloalkyl group. 10 Straight-chain alkyl, C3-C 10 Branched alkyl or C6-C 10 The aryl group, wherein the hydrogen atom on the R4 alkyl group is optionally substituted with a halogen atom; m is 0.1-1.9, n is 0.1-1.9, m+n+k=2, 0 <q≤0.5,0<k≤0.5; In the carrier, the molar ratio of silver to magnesium is (0.0010-0.50):1; The method for preparing the carrier includes the following steps: (1) After mixing magnesium halide and alcohol compounds I, react with silver carboxylate I to obtain the first reactant; (2) Add an ethylene oxide compound to the first reactant obtained in step (1) and carry out reaction II to obtain the support; Optionally, step (1) may further include the addition of an inert liquid medium and a surfactant; The silver carboxylate is selected from at least one of silver acetate, silver benzoate, silver propionate, silver butyrate, and silver octanoate; The general formula of the magnesium halide is MgX1Y1, in which X1 is a halogen, Y1 is a halogen, a C1-C5 alkyl group, a C1-C5 alkoxy group, or a C6-C4 group. 10 aryl or C6-C 10 aryloxy groups; The structural formula of the ethylene oxide compounds is shown in formula (II); Equation (II) In formula (II), R5 and R6 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.

2. The catalyst component according to claim 1, characterized in that, In the substance with the structure shown in formula (I), X is chlorine or bromine.

3. The catalyst component according to claim 1, characterized in that, In the general formula MgX1Y1, X1 is chlorine or bromine, and Y1 is chlorine, bromine, C1-C5 alkoxy group, or C6-C5 alkoxy group. 10 aryloxy groups; And / or, the general formula of the alcohol compound is R4'OH, wherein R4' is a C1-C8 straight-chain alkyl, a C3-C8 branched alkyl, or a C3-C8 cycloalkyl; And / or, in formula (II), R5 and R6 are the same or different, and each is independently hydrogen, a C1-C3 straight-chain alkyl or a C1-C3 haloalkyl; And / or, the general formula of the titanium compound is Ti(OR) 9 ) 4－k X k , where R 9 For C1-C 20 The hydrocarbon group, where X is a halogen and k is 0 or an integer selected from 1 to 4; And / or, the structural formula of the internal electron-donating compound is shown in formula (III); Equation (III) In equation (III), R'''1 and R'''2 may be the same or different, and each is independently selected from hydrogen or C1-C. 14 Straight-chain alkyl or C3-C 14 Branched alkyl, C3-C 10 cycloalkyl, C6-C 10 Aryl, C7-C 10 Alkyl or C7-C 10 Aryl alkyl groups, R'''1 and R'''2 can be bonded to each other to form one or more fused ring structures; R'''3 and R'''4 may be the same or different, and each is independently selected from C1-C1. 10 Straight-chain alkyl or C3-C 10 Branched alkyl, C3-C 10 cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl or C7-C 20 In the aryl group; R'''1, R'''2, R'''3, R'''4, the hydrogen atom on the benzene ring of the aryl or alkylaryl or aryl group may optionally be replaced by other atoms.

4. The catalyst component according to claim 3, characterized in that, Magnesium halides with the general formula MgX1Y1 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 the general formula R4'OH, R4' is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, or cyclohexylmethyl; And / or, the ethylene oxide compounds represented by formula (II) are selected from at least one of ethylene oxide, propylene oxide, butane oxide, epichlorohydrin, chlorobutane, bromopropane, and bromobutane; And / or, the general formula of the titanium compound is Ti(OR) 9 ) 4－k X k , where R 9 For C1-C 14 The aliphatic hydrocarbon group, where X is F, Cl or Br, and k is 0 or an integer selected from 1 to 4; And / or, the internal electron-donating compound is selected from one or more of 2,3-diisopropyl-2-cyanosuccinate, 3-methyl-2-isopropyl-2-cyanosuccinate, 3-ethyl-2-isopropyl-2-cyanosuccinate, 3-propyl-2-isopropyl-2-cyanosuccinate, 3-butyl-2-isopropyl-2-cyanosuccinate, and 3-phenyl-2-isopropyl-2-cyanosuccinate.

5. The catalyst component according to claim 4, characterized in that, Alcohols with the general formula R4'OH are selected from at least one of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, n-octanol, and 2-ethylhexanol; And / or, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium monochlorotributoxy, titanium dichlorodibutoxy, titanium trichlorobutoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloroethoxy.

6. The catalyst component according to any one of claims 1-5, characterized in that, The average particle size of the carrier is 10-100 micrometers, and the particle size distribution is <1.

2. And / or, in the carrier, based on 1 mol of magnesium halide with the general formula MgX1Y1, the amount of silver carboxylate is 0.0001-0.6 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.

7. The catalyst component according to claim 6, characterized in that, The average particle size of the carrier is 20-50 micrometers, and the particle size distribution is ≤0.

8. And / or, in the carrier, 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 6-20 mol, and the amount of ethylene oxide compound is 2-6 mol.

8. The catalyst component according to any one of claims 1-5, characterized in that, In step (1), the conditions for mixing I include: the temperature of mixing I is 80-120℃; the mixing time of mixing I is 0.5-5 hours; And / or, the conditions for reaction I include: a temperature of 80-120°C; and a time of 0.5-5 hours; And / or, the inert liquid medium is silicone oil and / or an inert liquid hydrocarbon solvent; And / or, the surfactant is selected from at least one of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polyacrylic acid, polyacrylate, polyacrylamide, polystyrene sulfonate, naphthalenesulfonic acid formaldehyde condensate, condensed alkylphenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, oxyalkyl acrylate copolymer modified polyethyleneimine, polymer of 1-dodecyl-4-vinylpyridine bromide, polyvinylbenzyltrimethylamine salt, polyethylene oxide-propylene oxide block copolymer, polyvinylpyrrolidone vinyl acetate copolymer, alkylphenyl polyoxyethylene ether, and polyalkyl methacrylate.

9. The catalyst component according to claim 8, characterized in that, In step (1), the conditions for mixing I include: the temperature of mixing I is 80-100℃; the mixing time of mixing I is 0.5-3 hours; And / or, the conditions for reaction I include: a temperature of 80-100°C; and a time of 0.5-3 hours; And / or, 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; And / or, based on 1 mol of magnesium halide with the general formula MgX1Y1, the amount of the surfactant is 1-20 g.

10. The catalyst component according to claim 9, characterized in that, Based on 1 mol of magnesium halide with the general formula MgX1Y1, the amount of the inert liquid medium is 0-10 L.

11. The catalyst component according to claim 10, characterized in that, Based on 1 mol of magnesium halide with the general formula MgX1Y1, the amount of the inert liquid medium is 2-8 L.

12. The catalyst component according to any one of claims 1-5, characterized in that, In step (2), the conditions for reaction II include: a temperature of 40-120°C and a time of 15-60 minutes.

13. The catalyst component according to claim 12, characterized in that, In step (2), the conditions for reaction II include: a temperature of 60-100℃ and a time of 20-50 minutes.

14. A method for preparing a catalyst component according to any one of claims 1-13, characterized in that, The process includes mixing the titanium compound with a support (II), adding an internal electron donor compound, and reacting (III) to obtain the catalyst component.

15. The preparation method according to claim 14, characterized in that, The conditions for reaction III include: a temperature of -30 to 125°C and a time of 1 to 15 hours.

16. A catalyst for olefin polymerization, characterized in that, The catalyst includes: 1) The catalyst component according to any one of claims 1-13 or the catalyst component prepared by the preparation method according to claim 14 or 15; 2) Alkyl aluminum compounds; 3) Optional external electron donor compounds.

17. The application of the catalyst component according to any one of claims 1-13, or the catalyst component prepared by the preparation method according to claim 14 or 15, or the catalyst according to claim 16 in olefin polymerization.

18. A method for olefin polymerization, characterized in that, The method includes contacting at least one olefin with the catalyst of claim 16 under olefin polymerization conditions.

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