Catalyst components for the polymerization of olefins, catalysts and use thereof

Abstract

This invention belongs to the field of catalysts, and discloses a catalyst component for olefin polymerization, a catalyst for olefin polymerization, and their applications. The catalyst component for olefin polymerization is a reaction product comprising the following components: 1) a magnesium-containing solution; the magnesium-containing solution is a homogeneous solution formed by the complete reaction of magnesium halide with an organic epoxy compound and an organophosphorus compound in an inert solvent; 2) a bismuth compound; 3) a titanium compound; preferably, the catalyst component for olefin polymerization further includes a precipitation aid and / or an electron carrier compound; the catalyst component for olefin polymerization prepared by this invention has good particle morphology and activity, and the polymers prepared using it are essentially free of anomalies.

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 industrially produced Ziegler-Natta catalysts are based on activated magnesium chloride supports. These catalyst components can be divided into two categories according to their preparation methods: supported catalysts, where the support is prepared first and then the catalyst is prepared, as disclosed in US4399054; and precipitated catalysts, which use a magnesium-containing solution and a precipitant to form the catalyst component, as disclosed in patents such as CN85100997A. Generally, catalysts prepared by the former method have better morphology, typically spherical or near-spherical, while catalysts prepared by the latter method are often particulate with poor sphericity. The former has better fluidity, which is beneficial to the stable operation of the polymer polymerization and transportation processes. However, its strength is poor and it is often easily broken into finer particles. The latter is a catalyst prepared by direct crystallization from solution, so the catalyst particles have higher strength. Therefore, the probability of the catalyst breaking into finer particles during polymerization is relatively low. It can be applied directly to polymerization without prepolymerization and has good adaptability to gas-phase fluidized bed and stirred bed processes. However, due to the poor sphericity of the catalyst, its fluidity is not ideal.

[0003] Therefore, it is of great significance to develop a new catalyst support for olefin polymerization that can overcome the above-mentioned defects of the existing technology. Summary of the Invention

[0004] The technical problem to be solved by the present invention is that the catalyst components used for olefin polymerization in the prior art have large particle sizes and poor strength of the prepared spherical catalyst components. 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.

[0005] 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:

[0006] 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;

[0007] 2) Bismuth compounds;

[0008] 3) Titanium compounds;

[0009] Preferably, the catalyst component for olefin polymerization further includes a co-precipitant and / or an electron donor compound.

[0010] According to some embodiments of the present invention, the average particle size of the catalyst component for olefin polymerization is 4 μm to 40 μm.

[0011] 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 mol to 10 mol per mole of magnesium halide, the amount of the organic phosphorus compound is 0.1 mol to 3 mol, the amount of the bismuth compound is 0.1 mol to 2 mol, the amount of the precipitation aid is 0 to 1 mol, the amount of the titanium compound is 0.5 mol to 20 mol, and the amount of the electron donor compound is 0 to 15 mol.

[0012] 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 mol to 4 mol per mole of magnesium halide, the amount of the organic phosphorus compound is 0.3 mol to 1 mol, the amount of the bismuth compound is 0.1 mol to 1 mol, the amount of the precipitation aid is 0.05 mol to 0.4 mol, the amount of the titanium compound is 1 mol to 15 mol, and the amount of the electron donor compound is 0.06 mol to 10 mol.

[0013] According to some embodiments of the present invention, in the catalyst component for olefin polymerization, the amount of the organic epoxy compound is 1 mole per mole of magnesium halide, the amount of the organic phosphorus compound is 0.92 moles per mole, the amount of the bismuth compound is 0.2 to 0.6 moles, for example 0.2, 0.3, 0.4, 0.5, and 0.6 moles per mole of magnesium halide, the amount of the co-precipitant is 0.189 moles, the amount of the titanium compound is 10.2 moles, and the amount of the electron donor compound is 0.1514 moles per mole.

[0014] In this invention, the use of bismuth compounds can improve the morphology, particle size and particle size distribution of catalyst components used in olefin polymerization. Furthermore, when catalysts prepared using this catalyst component for olefin polymerization are used in olefin polymerization reactions, the activity and hydrogen sensitivity of the catalyst can be improved, and the resulting polymers have better morphology.

[0015] 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.

[0016] 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, 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.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] According to some embodiments of the present invention, the bismuth compound is selected from bismuth halides.

[0023] 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.

[0024] 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.

[0025] According to some embodiments of the present invention, the titanium compound has the general formula Ti(OR)4-nX' 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.

[0026] 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 tetrabutoxy, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloroethoxy.

[0027] According to some embodiments of the present invention, the titanium compound is selected from titanium tetrachloride.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] According to some embodiments of the present invention, the electron donor compound is selected from diisobutyl phthalate and / or di-n-butyl phthalate.

[0032] 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.

[0033] A second aspect of the present invention provides a method for preparing the above-mentioned catalyst component for olefin polymerization, comprising the following steps:

[0034] 1) Under stirring conditions, magnesium halide, organic epoxy compound and organic phosphorus compound are reacted in an inert solvent to form a solution;

[0035] 2) Add a bismuth compound to the solution obtained in step 1) to react and obtain a reaction solution;

[0036] 3) After lowering the temperature to -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.

[0037] 4) The spherical particles obtained in step 3) are washed and dried to obtain the catalyst component for olefin polymerization.

[0038] According to some embodiments of the present invention, step 1) further includes adding a precipitation aid to the solution and continuing the reaction for 1 hour to 1.5 hours, preferably 1 hour.

[0039] According to some embodiments of the present invention, step 3) further includes adding an electron donor compound during the heating process.

[0040] According to some embodiments of the present invention, the washing in step 3) includes: washing the obtained spherical particles with an inert solvent 1 to 2 times, preferably 2 times, then adding a mixture of titanium halide and inert solvent, and treating at a constant temperature 1 to 4 times, preferably 3 times, and finally washing with an inert solvent 3 to 5 times, preferably 5 times.

[0041] According to some embodiments of the present invention, the isothermal treatment specifically involves maintaining a constant temperature of 90°C to 120°C for 0.5 hours to 1 hour.

[0042] According to some embodiments of the present invention, in step 1), the reaction conditions include: a temperature of 50°C to 70°C, preferably 60°C, and a time of 1h to 3h, preferably 2h.

[0043] According to some embodiments of the present invention, in step 2), the reaction conditions for adding the bismuth compound include: a temperature of 50°C to 70°C, preferably 60°C, and a time of 1h to 3h, preferably 1h.

[0044] 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, and more preferably -30°C.

[0045] According to some embodiments of the present invention, in step 3), the mixture is heated to 85±2.5℃ and held at that temperature for 1 hour to 1.5 hours.

[0046] 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.

[0047] 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.

[0048] The present invention does not particularly limit the drying conditions. For example, the drying temperature can be 20℃ to 70℃, the drying time can be 0.5 hours to 10 hours, and the drying can be carried out under normal pressure or reduced pressure.

[0049] Other parameters not limited in the preparation method of this invention can be conventionally selected according to existing technology.

[0050] A third aspect of the present invention provides a catalyst for olefin polymerization, said catalyst comprising:

[0051] (1) The catalyst component for olefin polymerization described above or the catalyst component for olefin polymerization prepared by the preparation method described above.

[0052] (2) Organoaluminum compounds;

[0053] (3) Organosilicon compounds.

[0054] 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 to 5000:1, preferably 50 to 600:1, and most preferably 50 to 160:1, for example 154.4:1, 159.6:1, and 149.6:1; the molar ratio of the organoaluminum compound to the organosilicon compound is 0.1 to 300:1, preferably 1 to 50:1, and most preferably 20:1.

[0055] 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.

[0056] 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.

[0057] A fourth aspect of the present invention provides the application of the above-described catalyst for olefin polymerization in an olefin polymerization method.

[0058] 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.

[0059] 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.

[0060] 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℃ to 150℃, preferably 60℃ to 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.

[0061] 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.

[0062] The olefin polymerization parameters not specified in this invention are all conventional techniques in the field.

[0063] Beneficial effects:

[0064] This invention incorporates a bismuth compound and selectively adds a precipitation aid during the preparation of a catalyst component for olefin polymerization. On one hand, the bismuth compound acts as a particle size regulator, reducing the particle size of the precipitated catalyst component for olefin polymerization. This results in a smaller particle size catalyst component with a well-defined morphology and virtually no irregular particles. On the other hand, even without the addition of a precipitation aid, the presence of the bismuth compound still produces a smaller particle size catalyst component for olefin polymerization with a well-defined morphology and virtually no irregular particles. More importantly, the catalyst containing this catalyst component for olefin polymerization exhibits high strength and good activity when used for olefin polymerization. Detailed Implementation

[0065] The present invention will be further described below with reference to embodiments. However, the present invention is not limited to these embodiments.

[0066] In the examples and comparative examples:

[0067] 1. The average particle size and particle size distribution of the catalyst components used in olefin polymerization were determined using a Masters Sizer 2000 particle size analyzer (manufactured by Malvern Instruments Ltd).

[0068] 2. Calculation of catalyst activity for olefin polymerization: Catalyst activity = (mass of polyolefin prepared) / (mass of solid catalyst component) g / g;

[0069] 3. Determination of polymer melt index (MI): According to ASTM D1238-99, the MI was determined at a load of 2.16 kg and a temperature of 190 °C.

[0070] Example 1

[0071] This embodiment illustrates the catalyst components for olefin polymerization and their preparation method provided by the present invention.

[0072] 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. Next, 0.03 mol of bismuth chloride was added, and the reaction continued for another hour. The temperature was then lowered to -30°C, and 56 mL of titanium tetrachloride was added dropwise. After adding 0.51 mol of the solution, the temperature was gradually increased 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 C1 for olefin polymerization.

[0073] Example 2

[0074] This embodiment illustrates the catalyst components for olefin polymerization and their preparation method provided by the present invention.

[0075] In a reactor that has been repeatedly purged 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. Next, 0.01 mol of bismuth chloride was added, and the reaction continued for another hour. The temperature was then lowered to -30°C, and 56 mL of titanium tetrachloride was added dropwise. After adding 0.51 mol of the solution, the temperature was gradually increased 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 C2 for olefin polymerization.

[0076] Example 3

[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, 0.03 mol of bismuth chloride was added, and the reaction was continued for 1 hour. The temperature was lowered to -30 °C, and 56 mL of titanium tetrachloride (0.51 mol) was added dropwise. The temperature was gradually 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 maintained 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 maintained at 110 °C for 0.5 hours. The reaction 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 C3 for olefin polymerization.

[0079] Example 4

[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, 0.01 mol of bismuth chloride was added, and the reaction was continued for 1 hour. The temperature was lowered to -30 °C, and 56 mL of titanium tetrachloride (0.51 mol) was added dropwise. The temperature was gradually 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 maintained 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 maintained at 110 °C for 0.5 hours. The reaction 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 C4 for olefin polymerization.

[0082] Comparative Example 1

[0083] 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.

[0084] Comparative Example 2

[0085] The preparation method described in Comparative Example 1 was followed, except that phthalic anhydride was not added. The final results showed that a catalyst component for olefin polymerization could not be obtained.

[0086] The average particle size (D50) and particle size distribution ((D90-D10) / D50) of the catalyst components for olefin polymerization prepared in Examples 1-4 and Comparative Example 1 were measured, and their appearance morphology was observed. The results are shown in Table 1 below:

[0087] Table 1

[0088]

[0089]

[0090] As can be seen from the results in Table 1 above, in preparing catalysts for olefin polymerization, Examples 1 and 2 added a precipitant and a bismuth compound, while Examples 3 and 4 only added a bismuth compound. The above methods can prepare catalyst components for olefin polymerization that have smaller average particle size and particle size distribution compared to the catalyst component for olefin polymerization in Comparative Example 1, which does not contain a bismuth compound. Furthermore, the prepared catalyst component for olefin polymerization has good particle morphology and is basically free of heterogeneous particles. In contrast, Comparative Example 2 did not add a bismuth compound and did not add phthalic anhydride (a precipitant), so a solid catalyst component could not be obtained. This indicates that the bismuth compound added in Examples 3 and 4 can be used as a precipitant, and catalyst components for olefin polymerization with smaller average particle size can be obtained.

[0091] Example 5

[0092] This embodiment illustrates the catalyst of the present invention for olefin polymerization and its application in olefin polymerization methods.

[0093] In a 5L stainless steel high-pressure reactor, the reactor was purged with a nitrogen stream. Then, 1 mmol of triethylaluminum in hexane solution (triethylaluminum concentration was 0.5 mmol / mL), 0.05 mmol of methylcyclohexyldimethoxysilane, 10 mL of anhydrous hexane, 10 mg of catalyst component C1 (titanium mass fraction of 3.1%, titanium 0.006476 mmol) 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.

[0094] Example 6

[0095] This embodiment illustrates the catalyst of the present invention for olefin polymerization and its application in olefin polymerization methods.

[0096] 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.

[0097] Example 7

[0098] This embodiment illustrates the catalyst of the present invention for olefin polymerization and its application in olefin polymerization methods.

[0099] 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 3.0% and titanium 0.006267 mmol), to obtain polypropylene powder.

[0100] Example 8

[0101] This embodiment illustrates the catalyst of the present invention for olefin polymerization and its application in olefin polymerization methods.

[0102] 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.

[0103] Example 9

[0104] This embodiment illustrates the catalyst of the present invention for olefin polymerization and its application in olefin polymerization methods.

[0105] 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 3.2% and titanium 0.006685 mmol), to obtain polypropylene powder.

[0106] Example 10

[0107] This embodiment illustrates the catalyst of the present invention for olefin polymerization and its application in olefin polymerization methods.

[0108] 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.

[0109] Example 11

[0110] This embodiment illustrates the catalyst of the present invention for olefin polymerization and its application in olefin polymerization methods.

[0111] 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 C4 for olefin polymerization obtained in Example 4 (with a titanium mass fraction of 3.2% and titanium 0.006685 mmol), to obtain polypropylene powder.

[0112] Example 12

[0113] This embodiment illustrates the catalyst of the present invention for olefin polymerization and its application in olefin polymerization methods.

[0114] 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.

[0115] Comparative Example 3

[0116] 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.

[0117] Comparative Example 4

[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] The catalysts for olefin polymerization prepared in Examples 5-12 and Comparative Examples 3-4 were used in propylene polymerization. The catalytic activity of the catalysts for olefin polymerization in Examples 5-12 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.

[0120] Table 2

[0121]

[0122]

[0123] As can be seen from the results in Table 2, the catalysts containing the catalyst components for olefin polymerization prepared in this invention in Examples 5-8 and 9-12 exhibit good catalytic activity and high hydrogen sensitivity when used for olefin (especially propylene) polymerization. The resulting polypropylene powder particles have good morphology and are basically free of irregular shapes. Furthermore, it can be seen that the catalysts containing the catalyst components for olefin polymerization prepared in this invention (without adding a precipitation aid) in Examples 9-12 exhibit even better catalytic activity when used for olefin (especially propylene) polymerization.

[0124] 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 the polymerization of olefins, characterized by, The catalyst component for olefin polymerization is a reaction product comprising the following components: 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; 2) Bismuth compounds; 3) Titanium compounds; The catalyst component for olefin polymerization also includes an electron donor compound and an optional precipitation aid; 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 the following: aliphatic olefin epoxy compounds with 2-18 carbon atoms, aliphatic diene epoxy compounds with 2-18 carbon atoms, halogenated aliphatic olefin epoxy compounds with 2-18 carbon atoms, halogenated aliphatic diene epoxy compounds with 2-18 carbon atoms, glycidyl ether, and internal ether. The organophosphorus compound is selected from hydrocarbon esters or halocarbon esters of phosphoric acid or phosphorous acid. The bismuth compound is selected from bismuth halides; The general formula of the titanium compound is 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; In the catalyst component for olefin polymerization, the amount of the organic epoxy compound is 0.2 mol to 10 mol per mole of magnesium halide, the amount of the organic phosphorus compound is 0.1 mol to 3 mol, the amount of the bismuth compound is 0.1 mol to 2 mol, the amount of the precipitation aid is 0 to 1 mol, the amount of the titanium compound is 0.5 mol to 20 mol, and the amount of the electron donor compound is 0.06 to 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 4 μm to 40 μm.

3. The catalyst component for the polymerization of olefins according to claim 1, characterized in that, In the catalyst component for olefin polymerization, the amount of the organic epoxy compound is 0.5 mol to 4 mol per mole of magnesium halide, and / or the amount of the organic phosphorus compound is 0.3 mol to 1 mol, and / or the amount of the bismuth compound is 0.1 mol to 1 mol, and / or the amount of the precipitation aid is 0.05 mol to 0.4 mol, and / or the amount of the titanium compound is 1 mol to 15 mol.

4. The catalyst component for the polymerization of olefins according to claim 3, characterized in that, In the catalyst component for olefin polymerization, the amount of the organic epoxy compound is 1 mole per mole of magnesium halide, and / or the amount of the organic phosphorus compound is 0.92 moles, and / or the amount of the bismuth compound is 0.2 to 0.6 moles, and / or the amount of the co-precipitant is 0.189 moles, and / or the amount of the titanium compound is 10.2 moles, and / or the amount of the electron donor compound is 0.1514 moles.

5. Catalyst component for the polymerization of olefins according to any one of claims 1-4, characterized by the fact that, In the catalyst component for olefin polymerization, the precipitant is selected from at least one of organic acids, organic anhydrides, organic ethers, and organic ketones; 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.

6. Catalyst component for the polymerization of olefins according to any one of claims 1-4, characterized by the fact that, The magnesium halide has the general formula MgXY, X is chlorine or bromine, Y is selected from chlorine, bromine, C1-C5 alkyl, C1-C5 alkoxy, C6-C 10 aryl or C6-C 10 aryloxy; And / or, the organic epoxy compound is selected from at least one of ethylene oxide, propylene oxide, epibutylene oxide, and epichlorohydrin; 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 tetrabutoxy, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloroethoxy. 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.

7. The catalyst component for the polymerization of olefins according to claim 6, 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.

8. The catalyst component for the polymerization of olefins according to claim 7, characterized in that, The electron donor compound is selected from diisobutyl phthalate and / or di-n-butyl phthalate.

9. A process for the preparation of a catalyst component for the polymerization of olefins as claimed in any one of claims 1-8, 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 bismuth compound to the solution obtained in step 1) to react and obtain a reaction solution; 3) After lowering the temperature to -30℃ to 0℃, 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. 4) The spherical particles obtained in step 3) are washed and dried to obtain the catalyst component for olefin polymerization.

10. The process for the preparation of a catalyst component for the polymerization of olefins according to claim 9, characterized in that, Step 1) also includes adding a precipitation aid to the solution and continuing the reaction for 1 to 1.5 hours.

11. The process for the preparation of a catalyst component for the polymerization of olefins according to claim 10, characterized in that, Step 1) also includes adding a precipitation aid to the solution and continuing the reaction for 1 hour.

12. The process for the preparation of a catalyst component for the polymerization of olefins according to claim 9, characterized in that, Step 3) also includes adding an electron donor compound during the heating process.

13. The method for preparing the catalyst component for olefin polymerization according to any one of claims 9-12, 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 bismuth compound include: a temperature of 50°C to 70°C and a time of 1 h to 3 h; And / or, in step 3), the temperature at which the titanium compound is added is -30°C; 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.

14. The process for the preparation of a catalyst component for the polymerization of olefins according to claim 13, 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 bismuth compound include: a temperature of 60°C and a time of 1 hour.

15. A catalyst for the polymerization of olefins, characterized in that, The catalyst for olefin polymerization contains: (1) The catalyst component for olefin polymerization according to any one of claims 1-8 or the catalyst component for olefin polymerization prepared by the preparation method provided in any one of claims 9-14; (2) Organoaluminum compounds; (3) Organosilicon compounds.

16. The catalyst for the polymerization of olefins according to claim 15, characterized by the fact that, The molar ratio of aluminum in the organoaluminum compound to titanium in the catalyst component is 5 to 5000:1, and the molar ratio of the organoaluminum compound to the organosilicon compound is 0.1 to 300:

1.

17. The catalyst for the polymerization of olefins according to claim 16, characterized by the fact that, The molar ratio of aluminum in the organoaluminum compound to titanium in the catalyst component is 50-600:1, and the molar ratio of the organoaluminum compound to the organosilicon compound is 1-50:

1.

18. The catalyst for the polymerization of olefins according to claim 17, characterized by the fact that, The molar ratio of aluminum in the organoaluminum compound to titanium in the catalyst component is 50-160:1, and the molar ratio of the organoaluminum compound to the organosilicon compound is 20:

1.

19. The catalyst for the polymerization of olefins according to any one of claims 15-18, characterized by the fact 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 organosilicon compound is selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylcyclohexyldiethoxysilane, methylcyclohexyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, and vinyltrimethoxysilane.

20. The use of a catalyst for olefin polymerization as described in any one of claims 15-19 in olefin polymerization.

21. A method for olefin polymerization, characterized in that, include: Under olefin polymerization conditions, one or more olefins are contacted with a catalyst for olefin polymerization as described in any one of claims 15-19.

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