Catalyst component for olefin polymerization, catalyst for olefin polymerization, and use thereof

Abstract

The application belongs to the field of catalysts, and discloses a catalyst component for olefin polymerization, a catalyst for olefin polymerization and application thereof. The catalyst component for olefin polymerization is a reaction product of the following components: 1) a magnesium-containing solution; the magnesium-containing solution is a homogeneous solution formed by fully reacting magnesium halide with an organic epoxy compound and an organic phosphorus compound in an inert solvent; 2) a silver-containing solution; the silver-containing solution is an ethanol solution of silver carboxylate and / or silver nitrate; 3) a titanium compound; 4) a co-precipitant; optionally, the catalyst component for olefin polymerization further comprises an electron body compound. The catalyst component for olefin polymerization prepared by the application has good particle morphology and good activity, and the polymer prepared by using the catalyst component is substantially free of abnormal shapes.

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, a catalyst for olefin polymerization and its application in olefin polymerization reactions, and an olefin polymerization method. Background Technology

[0002] As is well known, most of the catalysts currently used in the production of polyolefins, especially polypropylene, rely on Ziegler-Natta catalysts. This type of catalyst is generally supported by magnesium chloride, with active titanium dispersed on the magnesium chloride matrix.

[0003] While supported catalysts generally use magnesium chloride as the support, the formation of magnesium chloride varies. For example, some catalysts use magnesium chloride as a raw material, which is chemically activated to form a spherical support of magnesium chloride ethanolate, which is then treated with titanium to ultimately form the catalyst. The spherical shape is chosen because this type of catalyst and the resulting spherical polymer exhibit excellent flowability, which helps reduce or avoid bridging or clogging caused by shape issues during catalyst addition to the reaction system, the reaction process, and polymer transfer. Specifically, patent documents WO99 / 44009 and US4399054 demonstrate the preparation of spherical magnesium chloride ethanolates using an emulsification and rapid cooling process; however, this method requires the prior preparation and drying of the support before catalyst preparation, making the process relatively complex.

[0004] Therefore, it is of great significance to develop a new catalyst component and catalyst for olefin polymerization that can overcome the above-mentioned defects of the existing technology. Summary of the Invention

[0005] The technical problem to be solved by the present invention is that the preparation process of catalyst components for olefin polymerization in the prior art is cumbersome. The present invention provides a catalyst component for olefin polymerization and its preparation method, a catalyst for olefin polymerization and its application in olefin polymerization reaction, and an olefin polymerization method.

[0006] The inventors of this invention unexpectedly discovered that, in preparing catalyst components for olefin polymerization, magnesium halide is dissolved in an epoxide compound and an organophosphorus compound to form a homogeneous solution, and then silver nitrate ethanol solution is added. In the presence of a precipitation aid, the solution reacts with a titanium compound to directly prepare spherical catalyst components with good morphology for olefin polymerization. This method eliminates the need for high-temperature melting and low-temperature cooling of magnesium chloride alcohols, as well as high-shear processes. Furthermore, it requires less energy and produces catalysts with high hydrogen sensitivity and good activity, resulting in polymers with good morphology.

[0007] To address the aforementioned technical problems, a first aspect of the present invention provides a catalyst component for olefin polymerization, wherein the catalyst component for olefin polymerization is a reaction product comprising the following components:

[0008] 1) Magnesium-containing solution; the magnesium-containing solution is a homogeneous solution formed by the reaction of magnesium halide with organic epoxy compounds and organic phosphorus compounds in an inert solvent;

[0009] 2) A silver-containing solution; wherein the silver-containing solution is an ethanolic solution of silver carboxylate and / or silver nitrate;

[0010] 3) Titanium compounds;

[0011] 4) Precipitation aid;

[0012] Optionally, the catalyst component for olefin polymerization further includes an electron donor compound.

[0013] According to some embodiments of the present invention, the catalyst component for olefin polymerization has an average particle size of 1-30 μm and a sphericity >0.85, for example 0.89, 0.91, 0.92.

[0014] According to some embodiments of the present invention, the ratio of silver nitrate and / or silver carboxylate to ethanol in the silver-containing solution is 1g:(4-20)mL, preferably 1g:(6-10)mL.

[0015] According to some embodiments of the present invention, in the catalyst component for olefin polymerization, the amount of the organic epoxy compound is 0.2-10 mol per mole of magnesium halide, the amount of the organic phosphorus compound is 0.1-3 mol, the amount of silver nitrate and / or silver carboxylate is 0.001-2 mol, the amount of the precipitation aid is 0.03-1 mol, the amount of the titanium compound is 0.5-20 mol, and the amount of the electron donor compound is 0-15 mol.

[0016] According to some embodiments of the present invention, in the catalyst component for olefin polymerization, the amount of the organic epoxy compound is 0.5-4 mol per mole of magnesium halide, the amount of the organic phosphorus compound is 0.3-1 mol, the amount of silver nitrate and / or silver carboxylate is 0.1-1 mol, the amount of the precipitation aid is 0.05-0.4 mol, the amount of the titanium compound is 1-15 mol, and the amount of the electron donor compound is 0.06-10 mol.

[0017] In this invention, the use of silver nitrate and / or silver carboxylate can improve the morphology, particle size and particle size distribution of the catalyst component used in olefin polymerization. Furthermore, when the catalyst prepared using this catalyst component for olefin polymerization is used in the olefin polymerization reaction, the catalyst activity and hydrogen sensitivity can be improved, and the resulting polymer morphology is better.

[0018] According to some embodiments of the present invention, in the catalyst component for olefin polymerization, the magnesium halide is a magnesium dihalide and / or a derivative in which one halogen atom in the magnesium dihalide molecule is replaced by a hydrocarbon group or a hydrocarbon oxygen group.

[0019] According to some embodiments of the present invention, the magnesium halide has the general formula MgXY, where X is chlorine or bromine, and Y is selected from chlorine, bromine, and Cl-C. 14 Alkyl, C6-C 14 aryl, C1-C 14 alkoxy groups, C6-C 14 The aryloxy group; preferably, in the general formula of the magnesium halide, X is chlorine or bromine, and Y is selected from chlorine, bromine, C1-C5 alkyl, C1-C5 alkoxy, C6-C 10 aryl or C6-C 10 The aryl group; wherein the C1-C5 alkyl group includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, and isopentyl; the C1-C5 alkoxy group includes, but is not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, and isopentoxy; the C6-C 10 The aryl group includes, but is not limited to, phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and trimethylphenyl; the C6-C 10 The aryl groups include, but are not limited to, phenoxy, methylphenoxy, ethylphenoxy, dimethylphenoxy, and trimethylphenoxy.

[0020] According to some embodiments of the present invention, the magnesium halide is selected from at least one of magnesium chloride, magnesium bromide, magnesium phenoxychloride, magnesium isopropoxychloride, and magnesium n-butoxychloride.

[0021] According to some embodiments of the present invention, the organic epoxy compound is selected from at least one of aliphatic olefin epoxy compounds having 2-18 carbon atoms, aliphatic diene epoxy compounds having 2-18 carbon atoms, halogenated aliphatic olefin epoxy compounds having 2-18 carbon atoms, or halogenated aliphatic diene epoxides having 2-18 carbon atoms, glycidyl ethers, and internal ethers.

[0022] According to some embodiments of the present invention, the organic epoxy compound is selected from at least one of ethylene oxide, propylene oxide, butane oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ester, and butyl glycidyl ester.

[0023] According to some embodiments of the present invention, the organophosphorus compound is selected from hydrocarbon esters or halocarbon esters of phosphoric acid or phosphorous acid.

[0024] According to some embodiments of the present invention, the organophosphorus compound is selected from at least one of trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and benzoyl phosphite.

[0025] 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.

[0026] According to some embodiments of the present invention, the precipitation aid is selected from at least one of organic acids, organic anhydrides, organic ethers, and organic ketones.

[0027] According to some embodiments of the present invention, the precipitation aid is selected from at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, dimethyl ether, diethyl ether, propyl ether, butyl ether, and pentyl ether.

[0028] According to some embodiments of the present invention, the titanium compound has the general formula Ti(OR). 4-n X' n In the formula, R is C1-C 14 aliphatic hydrocarbon groups or C6-C 14 The aromatic hydrocarbon group, where X' is a halogen atom and n is an integer from 1 to 4.

[0029] According to some embodiments of the present invention, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloromonethoxy.

[0030] According to some embodiments of the present invention, the titanium compound is selected from titanium tetrachloride.

[0031] In this invention, "optionally, electron-donating compound" means that the electron-donating compound may or may not be present in the catalyst component for olefin polymerization of this invention. That is, the catalyst component for olefin polymerization of this invention may or may not contain an electron-donating compound.

[0032] According to some embodiments of the present invention, the electron-donating compound is selected from alkyl esters of aliphatic and aromatic monocarboxylic acids, alkyl esters of aliphatic and aromatic polycarboxylic acids, aliphatic ethers, cyclic aliphatic ethers, and aliphatic ketones.

[0033] According to some embodiments of the present invention, the electron-donating compound is selected from at least one of the following: alkyl esters of C1-C4 saturated fatty carboxylic acids, alkyl esters of C7-C8 aromatic carboxylic acids, C2-C6 fatty ethers, C3-C4 cyclic ethers, and C3-C6 saturated fatty ketones.

[0034] According to some embodiments of the present invention, the electron donor compound is selected from at least one of methyl formate, ethyl acetate, butyl acetate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, diethyl ether, hexyl ether, tetrahydrofuran, acetone and methyl isobutyl ketone.

[0035] According to some embodiments of the present invention, the electron donor compound is selected from diisobutyl phthalate and / or di-n-butyl phthalate.

[0036] According to some embodiments of the present invention, the inert solvent is selected from at least one of hexadecane, heptane, octane, decane, benzene, toluene, and xylene.

[0037] A second aspect of the present invention provides a method for preparing the above-mentioned catalyst component for olefin polymerization, comprising the following steps:

[0038] 1) Under stirring conditions, magnesium halide, organic epoxy compound and organic phosphorus compound are reacted in an inert solvent to form a solution;

[0039] 2) Add a silver-containing solution to the solution obtained in step 1) to react and obtain a reaction solution;

[0040] 3) At a temperature of -30℃ to 60℃, add titanium compound dropwise to the reaction solution obtained in step 2) and mix. Then heat the mixture to 60℃ to 110℃ and keep it at that temperature for 0.5 hours to 8 hours. Filter out the mother liquor and wash to obtain spherical particles.

[0041] 4) The spherical particles obtained in step 3) are washed and dried to obtain the catalyst component for olefin polymerization;

[0042] Preferably, step 2) further includes adding a precipitation aid to the reaction solution;

[0043] And / or, step 3) further includes adding an electron donor compound during the heating process;

[0044] And / or, in step 3), the mixture is heated to 85±2.5℃ and held at that temperature for 1 hour to 1.5 hours;

[0045] And / or, step 4) includes: adding a mixture of titanium halide and inert solvent to the spherical particles obtained in step 3), treating at a constant temperature 1-4 times, filtering out the liquid, washing the solid product with an inert solvent, and drying to obtain the catalyst component for olefin polymerization.

[0046] According to some embodiments of the present invention, in step 1), the reaction conditions include: a temperature of 50°C-70°C, preferably 60°C, and a time of 1h-3h, preferably 2h.

[0047] According to some embodiments of the present invention, in step 2), the reaction conditions for adding the silver-containing solution include: a temperature of 50°C-70°C, preferably 60°C, and a time of 1h-3h, preferably 2h.

[0048] According to some embodiments of the present invention, in step 3), the temperature at which the titanium compound is added is preferably -30°C to 0°C.

[0049] According to some embodiments of the present invention, the method for filtering out the mother liquor or the filtered liquid is pressure filtration. The present invention does not particularly limit the conditions for pressure filtration, but aims to achieve the separation of the solid phase and the liquid phase as fully as possible.

[0050] The washing process in this invention can employ methods known to those skilled in the art to wash the obtained solid product. For example, inert hydrocarbon solvents (such as pentane, hexane, heptane, petroleum ether, and gasoline) can be used to wash the obtained solid product.

[0051] The present invention does not particularly limit the drying conditions. For example, the drying temperature can be 20℃-70℃, the drying time can be 0.5 hours-10 hours, and the drying can be carried out under normal pressure or reduced pressure.

[0052] Other parameters not limited in the preparation method of this invention can be conventionally selected according to existing technology.

[0053] A third aspect of the present invention provides a catalyst for olefin polymerization, said catalyst comprising:

[0054] (1) The catalyst component for olefin polymerization described above or the catalyst component for olefin polymerization prepared by the preparation method described above.

[0055] (2) Organoaluminum compounds;

[0056] (3) Organosilicon compounds.

[0057] According to some embodiments of the present invention, the molar ratio of aluminum in the organoaluminum compound to titanium in the catalyst component is 5-5000:1; the molar ratio of the organoaluminum compound to the organosilicon compound is 0.1-300:1.

[0058] According to some embodiments of the present invention, the organoaluminum compound is selected from at least one of triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, and diethylaluminum chloride.

[0059] According to some embodiments of the present invention, the organosilicon compound is selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylcyclohexyldiethoxysilane, methylcyclohexyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, and vinyltrimethoxysilane.

[0060] A fourth aspect of the present invention provides the application of the above-described catalyst for olefin polymerization in an olefin polymerization method.

[0061] A fifth aspect of the present invention provides an olefin polymerization method, the olefin polymerization method comprising: contacting one or more olefins with the catalyst described above for olefin polymerization under olefin polymerization conditions.

[0062] The olefin polymerization method described in this invention does not particularly limit the olefin polymerization conditions or the olefin used. For example, the olefin may be one or more of ethylene, propylene, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-pentene, 2-pentene, 1-hexene, and styrene, preferably at least one of ethylene, propylene, 1-butene, 2-butene, and styrene, and more preferably propylene.

[0063] The olefin polymerization method of the present invention can be carried out according to conventional methods in the art. For example, the olefin polymerization can be bulk polymerization, gas-phase polymerization, or slurry polymerization. The olefin polymerization reaction conditions in the present invention can be conventional conditions in the art; for example, the polymerization temperature can be 0℃-150℃, preferably 60℃-90℃; the polymerization pressure can be atmospheric pressure or pressurized pressure. The medium used for liquid-phase polymerization can be selected from inert solvents such as isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, xylene, etc., such as saturated aliphatic hydrocarbons or aromatic hydrocarbons, preferably toluene, n-hexane, or cyclohexane.

[0064] Furthermore, by using the catalyst of this invention, polymers with well-defined particulate morphologies can be prepared. Hydrogen is used as a molecular weight regulator to adjust the molecular weight of the final polymer.

[0065] The olefin polymerization parameters not specified in this invention are all conventional techniques in the field.

[0066] During extensive experimentation, the inventors of this invention surprisingly discovered that by dissolving magnesium halide in epoxides and organophosphorus compounds to form a homogeneous solution, adding a silver-containing solution, and reacting it with a titanium compound in the presence of a precipitation aid, a spherical catalyst component with good morphology can be obtained. This method eliminates the need for high-temperature melting and low-temperature cooling of magnesium chloride alcohols, as well as high-shear processes. Furthermore, it requires less energy and produces a catalyst with high hydrogen sensitivity and good activity, resulting in a polymer with excellent morphology.

[0067] Beneficial effects:

[0068] In the preparation of catalyst components for olefin polymerization, the present invention adds a silver-containing solution, which can affect the precipitation and accumulation of particles, promote more orderly growth of catalyst particles, and ultimately make the particles spherical. Detailed Implementation

[0069] The present invention will be further described below with reference to embodiments. However, the present invention is not limited to these embodiments.

[0070] Unless otherwise specified, all raw materials used in the following embodiments and comparative examples of the present invention are commercially available.

[0071] In the following examples and comparative examples of the present invention, the average particle size and particle size distribution of the catalyst components used for olefin polymerization were measured using a Masters Sizer 2000 particle size analyzer (manufactured by Malvern Instruments Ltd).

[0072] In the following embodiments and comparative examples of the present invention, the activity of the catalyst used for olefin polymerization is calculated as follows: Catalyst activity = (mass of prepared polyolefin) / (mass of catalyst solid component) g / g;

[0073] In the following examples and comparative examples of the present invention, the polymer melt index (MI) was determined according to ASTM D1238-99, under a load of 2.16 kg and at 190 °C.

[0074] In the following examples and comparative examples of the present invention, the apparent morphology of the catalyst components was observed using an optical microscope, model Eclipse E200, purchased from Nikon Corporation.

[0075] In the following embodiments and comparative examples of the present invention, the test method for sphericity (SPHT) is as follows: SPHT = 4πA / p is determined by a static image particle size analyzer (Camsizer). 2P is the circumference of the projected particle, and A is the area covered by the particle projection. A SPHT value closer to 1 indicates better particle sphericity.

[0076] Example 1

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

[0078] In a reactor that has undergone repeated purging with high-purity nitrogen, 4.8 g of anhydrous magnesium chloride (0.05 mol), 100 mL of toluene, 4.0 mL of epichlorohydrin (0.05 mol), and 12.5 mL of tributyl phosphate (0.046 mol) were added sequentially. The reaction was carried out at 60°C for 2 hours. Then, 7 mL of silver nitrate ethanol solution (silver nitrate:ethanol = 1 g: 7 mL; 0.005887 mol silver nitrate) was added, and the reaction was continued for another 2 hours. Finally, 1.4 g of phthalic anhydride (9.45 mmol) was added, and the reaction was continued for another hour. The temperature was then lowered to -3°C. At 0°C, 80 mL (0.73 mol) of titanium tetrachloride was added dropwise, and the temperature was gradually increased to 85°C. At 80°C, 2.0 mL of di-n-butyl phthalate (DNBP) (7.57 mmol) was added, and the temperature was kept constant at 85°C for 1 hour. The mother liquor was filtered off, and the product was washed twice with toluene. Then, 48 mL of titanium tetrachloride and 72 mL of toluene solution were added, and the temperature was kept constant at 110°C for 0.5 hours. The process was repeated twice after filtration. Finally, the product was washed five times with hexane, and the remaining solid product was dried under vacuum to obtain the catalyst component C1 for olefin polymerization.

[0079] Example 2

[0080] This embodiment illustrates the catalyst components for olefin polymerization and their preparation method provided by the present invention.

[0081] In a reactor that has undergone repeated purging with high-purity nitrogen, 4.8 g of anhydrous magnesium chloride (0.05 mol), 100 mL of toluene, 4.0 mL of epichlorohydrin (0.05 mol), and 12.5 mL of tributyl phosphate (0.046 mol) were added sequentially. The reaction was carried out at 60°C for 2 hours. Then, 4 mL of silver nitrate ethanol solution (silver nitrate:ethanol = 0.5 g: 4 mL; 0.002943 mol silver nitrate) was added, and the reaction was continued for 2 hours. Next, 1.4 g of phthalic anhydride (9.45 mmol) was added, and the reaction was continued for another hour. Finally, the temperature was lowered to - At 30°C, 56 mL (0.51 mol) of titanium tetrachloride was added dropwise, and the temperature was gradually increased to 85°C. At 80°C, 2.0 mL of di-n-butyl phthalate (DNBP) (7.57 mmol) was added, and the temperature was kept constant at 85°C for 1 hour. The mother liquor was filtered off, and the product was washed twice with toluene. Then, 48 mL of titanium tetrachloride and 72 mL of toluene solution were added, and the temperature was kept constant at 110°C for 0.5 hours. The process was repeated twice after filtration. Finally, the product was washed five times with hexane, and the remaining solid product was dried under vacuum to obtain the catalyst component C2 for olefin polymerization.

[0082] Example 3

[0083] This embodiment illustrates the catalyst components for olefin polymerization and their preparation method provided by the present invention.

[0084] In a reactor that has undergone repeated purging with high-purity nitrogen, 4.8 g of anhydrous magnesium chloride (0.05 mol), 100 mL of toluene, 4.0 mL of epichlorohydrin (0.05 mol), and 12.5 mL of tributyl phosphate (0.046 mol) were added sequentially. The reaction was carried out at 60°C for 2 hours. Then, 4 mL of silver acetate ethanol solution (silver acetate:ethanol = 0.5 g: 4 mL; 2.943 mmol silver acetate) was added, and the reaction was continued for another 2 hours. Finally, 1.4 g of phthalic anhydride (9.45 mmol) was added, and the reaction was continued for another hour. The temperature was then lowered to -3°C. At 0°C, 80 mL (0.73 mol) of titanium tetrachloride was added dropwise, and the temperature was gradually increased to 85°C. At 80°C, 2.0 mL of di-n-butyl phthalate (DNBP) (7.57 mmol) was added, and the temperature was kept constant at 85°C for 1 hour. The mother liquor was filtered off, and the product was washed twice with toluene. Then, 48 mL of titanium tetrachloride and 72 mL of toluene solution were added, and the temperature was kept constant at 110°C for 0.5 hours. The process was repeated twice after filtration. Finally, the product was washed five times with hexane, and the remaining solid product was dried under vacuum to obtain the catalyst component C3 for olefin polymerization.

[0085] Comparative Example 1

[0086] This comparative example is used to illustrate the catalyst components for olefin polymerization and their preparation method provided by the present invention.

[0087] In a reactor that has undergone repeated purging with high-purity nitrogen, 4.8 g of anhydrous magnesium chloride (0.05 mol), 100 mL of toluene, 4.0 mL of epichlorohydrin (0.05 mol), and 12.5 mL of tributyl phosphate (0.046 mol) were added sequentially. The reaction was carried out at 60 °C for 2 hours. Then, 1.4 g of phthalic anhydride (9.45 mmol) was added, and the reaction continued for another hour. The temperature was then lowered to -30 °C, and 56 mL of titanium tetrachloride (0.51 mol) was added dropwise. The temperature was raised to 85°C, and 2.0 mL of di-n-butyl phthalate (DNBP) (7.57 mmol) was added at 80°C. The temperature was kept constant at 85°C for 1 hour. The mother liquor was filtered off, and the product was washed twice with toluene. Then, 48 mL of titanium tetrachloride and 72 mL of toluene solution were added, and the temperature was kept constant at 110°C for 0.5 hours. The process was repeated twice after filtration. Finally, the product was washed five times with hexane. The remaining solid product was dried under vacuum to obtain the catalyst component D-Cl for olefin polymerization.

[0088] Comparative Example 2

[0089] This comparative example is used to illustrate the catalyst components for olefin polymerization and their preparation method provided by the present invention.

[0090] The preparation method described in Example 1 was followed, except that 7 mL of ethanol was added to replace 7 mL of silver nitrate ethanol solution (silver nitrate: ethanol = 1 g: 7 mL; 0.005887 mol silver nitrate) to obtain the catalyst component D-C2 for olefin polymerization.

[0091] The average particle size (D50) and particle size distribution ((D90-D10) / D50) of the catalyst components for olefin polymerization prepared in Examples 1-3 and Comparative Examples 1-2 were measured, and their appearance morphology was observed. The results are shown in Table 1 below:

[0092] Table 1

[0093]

[0094] As can be seen from the results in Table 1 above, when preparing the catalyst component for olefin polymerization, the catalyst component for olefin polymerization prepared by adding a precipitation aid and a silver-containing solution in Examples 1-3 can be obtained by the above method. Compared with the catalyst components for olefin polymerization prepared by Comparative Example 1 without adding a silver-containing solution and Comparative Example 2 with only adding ethanol, the catalyst component for olefin polymerization has a smaller average particle size and particle size distribution. Furthermore, the prepared catalyst component for olefin polymerization has a good particle morphology and basically no heterogeneous particles.

[0095] Example 5

[0096] This embodiment illustrates the catalyst of the present invention for olefin polymerization and its application in olefin polymerization methods.

[0097] In a 5L high-pressure reactor, the reactor was purged with a nitrogen stream. Then, 1 mmol of triethylaluminum in 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 (containing 2.7% titanium by mass and 0.0057 mmol titanium) prepared in Example 1 above for olefin polymerization, 1.5 L (standard volume) of hydrogen, and 2.5 L of liquid propylene were introduced into the nitrogen stream. The reactor was heated to 70°C and polymerized at this temperature for 1 hour. After that, the reactor was cooled, depressurized, and dried to obtain polypropylene powder.

[0098] Example 6

[0099] This embodiment illustrates the catalyst of the present invention for olefin polymerization and its application in olefin polymerization methods.

[0100] 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.

[0101] Example 7

[0102] This embodiment illustrates the catalyst of the present invention for olefin polymerization and its application in olefin polymerization methods.

[0103] Propylene polymerization was carried out according to the method of Example 5, except that the catalyst component C1 for olefin polymerization was replaced by the catalyst component C2 for olefin polymerization obtained in Example 2 (with a titanium mass fraction of 2.5% and titanium 1.47 mmol), to obtain polypropylene powder.

[0104] Example 8

[0105] This embodiment illustrates the catalyst of the present invention for olefin polymerization and its application in olefin polymerization methods.

[0106] 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.

[0107] Example 9

[0108] This embodiment illustrates the catalyst of the present invention for olefin polymerization and its application in olefin polymerization methods.

[0109] Propylene polymerization was carried out according to the method of Example 5, except that the catalyst component C1 for olefin polymerization was replaced with the catalyst component C3 for olefin polymerization obtained in Example 3 (with a titanium mass fraction of 2.5% and titanium 1.43 mmol), to obtain polypropylene powder.

[0110] Example 10

[0111] This embodiment illustrates the catalyst of the present invention for olefin polymerization and its application in olefin polymerization methods.

[0112] 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.

[0113] Comparative Example 3

[0114] This comparative example is used to illustrate the catalyst of the present invention for olefin polymerization and its application in olefin polymerization methods.

[0115] Propylene polymerization was carried out according to the method of Example 5, except that the catalyst component C1 for olefin polymerization was replaced by the catalyst component D-C1 for olefin polymerization obtained in Comparative Example 1, and polypropylene powder was obtained.

[0116] Comparative Example 4

[0117] This comparative example is used to illustrate the catalyst of the present invention for olefin polymerization and its application in olefin polymerization methods.

[0118] Propylene polymerization was carried out according to the method of Comparative Example 3, except that the 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.

[0119] Comparative Example 5

[0120] This comparative example is used to illustrate the catalyst of the present invention for olefin polymerization and its application in olefin polymerization methods.

[0121] Propylene polymerization was carried out according to the method of Example 5, except that the catalyst component C1 for olefin polymerization was replaced by the catalyst component D-C2 for olefin polymerization obtained in Comparative Example 1, to obtain polypropylene powder.

[0122] Comparative Example 6

[0123] This comparative example is used to illustrate the catalyst of the present invention for olefin polymerization and its application in olefin polymerization methods.

[0124] Propylene polymerization was carried out according to the method of Comparative Example 3, except that the 1.5L (standard volume) of hydrogen was replaced with 6.5L (standard volume) of hydrogen to obtain polypropylene powder.

[0125] The catalysts for olefin polymerization prepared in Examples 5-10 and Comparative Examples 3-4 were used in propylene polymerization. The catalytic activity of the catalysts for olefin polymerization in Examples 5-10 and Comparative Examples 3-4 was calculated after 1 hour of polymerization. The appearance of the prepared polypropylene powder was observed. The results are shown in Table 2 below.

[0126] Table 2

[0127]

[0128] As can be seen from the results in Table 2, the catalysts containing the catalyst components for olefin polymerization prepared in Examples 5-10 of this invention exhibit good catalytic activity and high hydrogen sensitivity when used for olefin (especially propylene) polymerization. The resulting polypropylene powder particles have good morphology and there are basically no irregularly shaped particles, which shows great promise for industrial application.

[0129] 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, characterized in that, The catalyst component for olefin polymerization is a reaction product comprising the following components: 1) Magnesium-containing solution; the magnesium-containing solution is a solution formed by reacting magnesium halide with organic epoxy compounds and organic phosphorus compounds in an inert solvent; 2) A silver-containing solution; the silver-containing solution is an ethanolic solution of silver carboxylate and / or silver nitrate; 3) Titanium compounds; 4) Precipitation aid; Optionally, the catalyst component for olefin polymerization further includes an electron donor compound; The silver carboxylate is selected from at least one of silver acetate, silver benzoate, silver propionate, silver butyrate, and silver octanoate; The magnesium halide is a magnesium dihalide and / or a derivative in which one halogen atom in the magnesium dihalide molecule is replaced by a hydrocarbon group or a hydrocarbon oxygen group; The organic epoxy compound is selected from at least one of aliphatic olefin epoxy compounds with 2-18 carbon atoms, halogenated aliphatic olefin epoxy compounds with 2-18 carbon atoms, and glycidyl ether. In the catalyst component for olefin polymerization, the amount of the organic epoxy compound is 0.2-10 mol per mole of magnesium halide, the amount of the organic phosphorus compound is 0.1-3 mol, the amount of silver nitrate and / or silver carboxylate is 0.001-2 mol, the amount of the precipitation aid is 0.03-1 mol, the amount of the titanium compound is 0.5-20 mol, and the amount of the electron donor compound is 0-15 mol.

2. The catalyst component for olefin polymerization according to claim 1, characterized in that, The catalyst component used for olefin polymerization has an average particle size of 1-30 μm and a sphericity >0.85; And / or, the ratio of silver nitrate and / or silver carboxylate to ethanol in the silver-containing solution is 1 g: (4-20) mL.

3. The catalyst component for olefin polymerization according to claim 2, characterized in that, The ratio of silver nitrate and / or silver carboxylate to ethanol in the silver-containing solution is 1 g: (6-10) mL.

4. The catalyst component for olefin polymerization according to any one of claims 1-3, characterized in that, In the catalyst component for olefin polymerization, the amount of the organic epoxy compound is 0.5-4 mol per mole of magnesium halide, the amount of the organic phosphorus compound is 0.3-1 mol, the amount of silver nitrate and / or silver carboxylate is 0.1-1 mol, the amount of the precipitation aid is 0.05-0.4 mol, the amount of the titanium compound is 1-15 mol, and the amount of the electron donor compound is 0.06-10 mol.

5. The catalyst component for olefin polymerization according to any one of claims 1-3, characterized in that, The organic epoxy compound is selected from aliphatic diene epoxy compounds with 2-18 carbon atoms and / or halogenated aliphatic diene epoxy compounds with 2-18 carbon atoms.

6. The catalyst component for olefin polymerization according to any one of claims 1-3, characterized in that, In the catalyst component for olefin polymerization, the magnesium halide has the general formula MgXY, where X is chlorine or bromine, and Y is selected from chlorine, bromine, and C1-C4. 14 Alkyl, C6-C 14 aryl, C1-C 14 alkoxy groups, C6-C 14 aryloxy groups; And / or, the organic epoxy compound is selected from at least one of ethylene oxide, propylene oxide, butane oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ester and butyl glycidyl ester; And / or, the organophosphorus compound is selected from hydrocarbon esters or halocarbon esters of phosphoric acid or phosphorous acid; And / or, the precipitation aid is selected from at least one of organic acids, organic anhydrides, organic ethers, and organic ketones; and / or, the titanium compound has the general formula Ti(OR). 4-n X' n In the formula, R is C1-C 14 aliphatic hydrocarbon groups or C6-C 14 The aromatic hydrocarbon group, where X' is a halogen atom and n is an integer from 1 to 4; And / or, the electron-donating compound is selected from alkyl esters of aliphatic and aromatic monocarboxylic acids, alkyl esters of aliphatic and aromatic polycarboxylic acids, aliphatic ethers, cyclic aliphatic ethers, and aliphatic ketones; And / or, the inert solvent is selected from at least one of hexaalkyl, heptane, octane, decane, benzene, toluene, and xylene.

7. The catalyst component for olefin polymerization according to claim 6, characterized in that, In the general formula of the magnesium halide, X is chlorine or bromine, and Y is selected from chlorine, bromine, C1-C5 alkyl groups, C6-C4 alkyl groups. 10 aryl, C1-C5 alkoxy, C6-C 10 aryloxy groups; And / or, the organophosphorus compound is selected from at least one of trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and benzoyl phosphite; And / or, the precipitation aid is selected from at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, dimethyl ether, diethyl ether, propyl ether, butyl ether, and pentyl ether. And / or, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloromonethoxy. And / or, the electron-donating compound is selected from at least one of the following: alkyl esters of C1-C4 saturated fatty carboxylic acids, alkyl esters of C7-C8 aromatic carboxylic acids, C2-C6 fatty ethers, C3-C4 cyclic ethers, and C3-C6 saturated fatty ketones.

8. The catalyst component for olefin polymerization according to claim 7, characterized in that, The magnesium halide is selected from at least one of magnesium chloride, magnesium bromide, magnesium phenoxy chloride, magnesium isopropoxy chloride, and magnesium n-butoxy chloride; And / or, the titanium compound is selected from titanium tetrachloride; And / or, the electron-donating compound is selected from at least one of methyl formate, ethyl acetate, butyl acetate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, diethyl ether, hexyl ether, tetrahydrofuran, acetone, and methyl isobutyl ketone.

9. The catalyst component for olefin polymerization according to claim 8, characterized in that, The electron donor compound is selected from diisobutyl phthalate and / or di-n-butyl phthalate.

10. A method for preparing a catalyst component for olefin polymerization as described in any one of claims 1-9, characterized in that, Includes the following steps: 1) Under stirring conditions, magnesium halide, organic epoxy compound and organic phosphorus compound are reacted in an inert solvent to form a solution; 2) Add a silver-containing solution to the solution obtained in step 1) to react and obtain a reaction solution; 3) Add titanium compound dropwise to the reaction solution obtained in step 2) and mix at a temperature of -30℃ to 60℃. Then heat the mixture to 60℃ to 110℃ and keep it at that temperature for 0.5 hours to 8 hours. Filter out the mother liquor and wash to obtain spherical particles. 4) The spherical particles obtained in step 3) are washed and dried to obtain the catalyst component for olefin polymerization; Step 2) further includes adding a precipitation aid to the reaction solution.

11. The method for preparing the catalyst component for olefin polymerization according to claim 10, characterized in that, Step 3) further includes adding an electron donor compound during the heating process; And / or, in step 3), the mixture is heated to 85±2.5℃ and held at that temperature for 1-1.5 hours.

12. The method for preparing the catalyst component for olefin polymerization according to claim 10, characterized in that, In step 1), the reaction conditions include: a temperature of 50℃-70℃ and a time of 1h-3h; And / or, in step 2), the reaction conditions for adding the silver-containing solution include: a temperature of 50℃-70℃ and a time of 1h-3h; And / or, in step 3), the temperature at which the titanium compound is added is -30°C to 0°C.

13. The method for preparing the catalyst component for olefin polymerization according to claim 12, characterized in that, In step 1), the reaction conditions include: a temperature of 60°C and a time of 2 hours; And / or, in step 2), the reaction conditions for adding the silver-containing solution include: a temperature of 60°C and a time of 1 hour.

14. A catalyst for olefin polymerization, characterized in that, The catalyst for olefin polymerization contains: (1) The catalyst component for olefin polymerization according to any one of claims 1-9 or the catalyst component for olefin polymerization prepared by the preparation method according to any one of claims 10-13; (2) Organoaluminum compounds; (3) Organosilicon compounds.

15. The catalyst for olefin polymerization according to claim 14, characterized in that, The molar ratio of aluminum in the organoaluminum compound to titanium in the catalyst component is 5-5000:1; the molar ratio of the organoaluminum compound to the organosilicon compound is 0.1-300:

1.

16. The catalyst for olefin polymerization according to claim 14, characterized in that, The organoaluminum compound is selected from at least one of triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, and diethylaluminum chloride. And / or, the general formula of the organosilicon compound is R 1 m Si(OR 2 ) 4-m In the formula, 0≤m≤3, R 1 and R 2 They may be the same or different, each independently selected from hydrogen, halogen, alkyl, cycloalkyl, aryl or halogenated alkyl.

17. The catalyst for olefin polymerization according to claim 16, characterized in that, The organosilicon compound is selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylcyclohexyldiethoxysilane, methylcyclohexyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, and phenyltrimethoxysilane.

18. The use of a catalyst for olefin polymerization as described in any one of claims 14-17 in olefin polymerization.

19. A method for olefin polymerization, characterized in that, include: Under olefin polymerization conditions, one or more olefins are contacted with the catalyst for olefin polymerization as described in any one of claims 14-17.

20. The olefin polymerization method according to claim 19, characterized in that, The olefin is selected from at least one of ethylene, propylene, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 1-pentene, 2-pentene, 1-hexene, and styrene.

21. The olefin polymerization method according to claim 20, characterized in that, The olefin is at least one selected from ethylene, propylene, 1-butene, 2-butene, and styrene.

22. The olefin polymerization method according to claim 21, characterized in that, The olefin is propylene.

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