Catalyst component for olefin polymerization, catalyst for olefin polymerization and application of catalyst component and catalyst

Abstract

The invention belongs to the field of catalysts, and discloses a catalyst component for olefin polymerization, a catalyst for olefin polymerization and application of the catalyst component and the catalyst. 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 uniform 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) an assistant precipitation agent; optionally, the catalyst component for olefin polymerization also comprises an electron compound; the prepared catalyst component for olefin polymerization is good in particle morphology and good in activity, and a polymer prepared from the catalyst component is basically free of special shapes.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, and in particular to a catalyst component for olefin polymerization and a preparation method thereof, a catalyst for olefin polymerization and application thereof in olefin polymerization reactions, and an olefin polymerization method. Background Art

[0002] As is known to all, most of the catalysts currently used in the production of polyolefins, especially polypropylene, rely on Ziegler-Natta catalysts. This type of catalyst is generally based on magnesium chloride as a carrier, and active titanium is dispersed on the magnesium chloride matrix.

[0003] Although the supported catalyst is generally only magnesium chloride as a carrier, the formation form of magnesium chloride is not quite the same. If magnesium chloride is used as a raw material, a spherical carrier of magnesium chloride alcoholate is formed by chemical activation and then titanium treatment is performed to finally form a catalyst. The reason why it is made into a spherical form is that the catalyst of this form and the spherical polymer formed by it have good fluidity, and the catalyst is added to the reaction system and the reaction process and the polymer transfer process to help reduce or avoid the appearance of bridging or blocking caused by morphological problems. Specifically, the preparation of spherical magnesium chloride alcoholate is carried out by the process of emulsification and quenching such as patent documents WO99 / 44009 and US4399054; However, this preparation method needs to prepare a carrier first, and then the catalyst is prepared after the carrier is dried, and the process is more complicated.

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

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

[0006] The inventors of the present invention unexpectedly discovered that, when preparing a catalyst component for olefin polymerization, the present invention dissolves magnesium halide in an epoxy compound and an organic phosphorus compound to form a uniform solution, adds a silver nitrate ethanol solution, and reacts with a titanium compound in the presence of a precipitation aid, so that a spherical catalyst component for olefin polymerization with good morphology can be directly prepared; the method does not require high-temperature melting and low-temperature cooling of magnesium chloride alcoholate and high-shear process, and does not require high and low temperatures, and has relatively low energy requirements; the catalyst obtained thereby has high hydrogen adjustment sensitivity and good activity, and the prepared polymer has good morphology.

[0007] In order to solve the above technical problems, the 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) a magnesium-containing solution; the magnesium-containing solution is a uniform solution formed by the reaction of magnesium halide with an organic epoxy compound and an organic phosphorus compound in an inert solvent;

[0009] 2) a silver-containing solution; the silver-containing solution is an ethanol 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 comprises 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, such as 0.89, 0.91, or 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 1 g: (4-20) mL, preferably 1 g: (6-10) mL.

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

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

[0017] In the present invention, the use of silver nitrate and / or silver carboxylate can make the catalyst component for olefin polymerization have a better morphology, smaller particle size and smaller particle size distribution. Moreover, when the catalyst prepared by using the catalyst component for olefin polymerization is used in an olefin polymerization reaction, the activity and hydrogen regulation sensitivity of the catalyst can be improved, and the morphology of the prepared polymer is better.

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

[0019] According to some embodiments of the present invention, the general formula of the magnesium halide is MgXY, X is chlorine or bromine, and Y is selected from chlorine, bromine, C1-C 14 Alkyl, C6-C 14 Aryl, C1-C 14 Alkoxy, C6-C 14 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 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-pentyl, and isopentyl; the C6-C 10 The aryl group includes but is not limited to phenyl, methylphenyl, ethylphenyl, dimethylphenyl, trimethylphenyl; the C6-C 10 The aryloxy group includes, but is not limited to, phenoxy, methylphenoxy, ethylphenoxy, dimethylphenoxy, trimethylphenoxy.

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

[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, butylene oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ester and butyl glycidyl ester.

[0023] According to some embodiments of the present invention, the organic phosphorus compound is selected from a hydrocarbyl ester or a halogenated hydrocarbyl ester of orthophosphoric 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 benzyl 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 an organic acid, an organic acid anhydride, an organic ether and an organic ketone.

[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 anhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether and pentyl ether.

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

[0029] According to some embodiments of the present invention, the titanium compound is at least one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, triethoxytitanium monochloride, diethoxytitanium dichloride and triethoxytitanium monochloride.

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

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

[0032] According to some embodiments of the invention, the electron donor compound is selected from the group consisting of alkyl esters of aliphatic and aromatic monocarboxylic acids, alkyl esters of aliphatic and aromatic polycarboxylic acids, aliphatic ethers, cycloaliphatic ethers and aliphatic ketones.

[0033] According to some embodiments of the present invention, the electron donor compound is selected from at least one of 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, ethyl 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 at least one selected from hexane, heptane, octane, decane, benzene, toluene and xylene.

[0037] The 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) reacting a magnesium halide, an organic epoxy compound and an organic phosphorus compound in an inert solvent to form a solution under stirring;

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

[0040] 3) adding the titanium compound dropwise to the reaction solution obtained in step 2) at a temperature of -30°C to 60°C and mixing, then heating the mixture to 60°C to 110°C and keeping the temperature constant for 0.5 hour to 8 hours, filtering off the mother liquor and washing to obtain spherical particles;

[0041] 4) washing and drying the spherical particles obtained in step 3) to obtain the catalyst component for olefin polymerization;

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

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

[0044] And / or, in step 3), the mixture is heated to 85±2.5° C. and kept at this temperature for 1 hour to 1.5 hours;

[0045] And / or, the step 4) comprises: adding a mixture of titanium halide and an inert solvent to the spherical particles obtained in step 3), treating at a constant temperature for 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: temperature of 50°C-70°C, preferably 60°C, and 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: temperature of 50° C.-70° C., preferably 60° C., and time of 1 h-3 h, preferably 2 h.

[0048] According to some embodiments of the present invention, in step 3), the temperature for adding the titanium compound 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 filtering out the liquid is a filter press method. The present invention does not particularly limit the conditions of the filter press, so as to achieve the separation of the solid phase and the liquid phase as fully as possible.

[0050] The washing in the present invention can be carried out by methods known to those skilled in the art to wash the obtained solid phase product, for example, the obtained solid phase product can be washed by using an inert hydrocarbon solvent (such as pentane, hexane, heptane, petroleum ether and gasoline).

[0051] The present invention has no particular limitation on the drying conditions. For example, the drying temperature may be 20° C. to 70° C., the drying time may be 0.5 hour to 10 hours, and the drying may be performed under normal pressure or reduced pressure.

[0052] Other parameters not limited in the preparation method of the present invention can be conventionally selected according to the prior art.

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

[0054] (1) the above-mentioned catalyst component for olefin polymerization or the catalyst component for olefin polymerization prepared by the above-mentioned preparation method;

[0055] (2) Organic aluminum compounds;

[0056] (3) Organic silicon 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; and 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 at least one selected from triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride and diethylaluminum dichloride.

[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 use of the above catalyst for olefin polymerization in an olefin polymerization method.

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

[0062] The olefin polymerization method of the present invention is not particularly limited to olefin polymerization conditions and the olefin used. For example, the olefin can 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, 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°C-150°C, preferably 60°C-90°C; the polymerization pressure can be normal pressure or pressurized. The medium used for liquid phase polymerization can be selected from saturated aliphatic hydrocarbons such as isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, xylene, or aromatic hydrocarbons, and is preferably toluene, n-hexane or cyclohexane.

[0064] In addition, by using the catalyst of the present invention, a polymer with good particle morphology can be prepared. In order to adjust the molecular weight of the final polymer, hydrogen is used as a molecular weight regulator.

[0065] The olefin polymerization parameters not limited in the present invention are all conventional technical means in the art.

[0066] The inventors of the present invention surprisingly found in a large number of experiments that a spherical catalyst component with good morphology can be obtained by dissolving magnesium halide in epoxy compounds and organic phosphorus compounds to form a uniform solution, adding a silver-containing solution, and reacting with a titanium compound in the presence of a precipitation aid. The method does not require high-temperature melting and low-temperature cooling of magnesium chloride alcoholate and high-shear process, and does not require high and low temperatures, and requires less energy. Moreover, the obtained catalyst has high hydrogen adjustment sensitivity and good activity, and the obtained polymer has good morphology.

[0067] Beneficial effects:

[0068] The invention adds a silver-containing solution during the preparation process of the catalyst component for olefin polymerization, which can affect the precipitation and accumulation of particles, promote the growth of catalyst particles to be more orderly, and finally the particles present a spherical shape. DETAILED DESCRIPTION

[0069] The present invention will be further described below in conjunction with the embodiments, but the present invention is not limited by these embodiments.

[0070] In the following examples and comparative examples of the present invention, unless otherwise specified, all raw materials used 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 component for olefin polymerization were measured using a Masters Sizer 2000 particle size analyzer (manufactured by Malvern Instruments Ltd);

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

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

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

[0075] In the following examples and comparative examples of the present invention, the sphericity (SPHT) is measured by a static image particle size analyzer (Camsizer), SPHT = 4πA / p 2, P is the measured circumference of the particle projection, and A is the measured area covered by the particle projection. The closer the SPHT value is to 1, the better the particle sphericity.

[0076] Example 1

[0077] This example is used to illustrate the catalyst component for olefin polymerization and the preparation method thereof provided by the present invention.

[0078] In a reactor that has been repeatedly replaced 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 in sequence, and the reaction was carried out at a temperature of 60°C for 2 hours. 7 mL of silver nitrate ethanol solution (silver nitrate: ethanol is 1 g: 7 mL; 0.005887 mol of silver nitrate) was added and the reaction was carried out for 2 hours. 1.4 g of phthalic anhydride (9.45 mmol) was added and the reaction was continued for 1 hour, and then the temperature was lowered to -3 0 ℃, add 80mL (0.73mol) of titanium tetrachloride dropwise, gradually raise the temperature to 85 ℃, and add 2.0mL of di-n-butyl phthalate DNBP (7.57mmol) at 80 ℃, keep the temperature at 85 ℃ for 1 hour, filter out the mother liquor, wash twice with toluene, then add 48mL of titanium tetrachloride and 72mL of toluene solution, keep the temperature at 110 ℃ for 0.5 hour, filter and repeat the process twice, finally wash 5 times with hexane, and the remaining solid product is dried in vacuo to obtain the catalyst component C1 for olefin polymerization.

[0079] Example 2

[0080] This example is used to illustrate the catalyst component for olefin polymerization and the preparation method thereof provided by the present invention.

[0081] In a reaction kettle that has been repeatedly replaced 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 in sequence, and the reaction was carried out at a temperature of 60°C for 2 hours. 4 mL of silver nitrate ethanol solution (silver nitrate: ethanol is 0.5 g: 4 mL; 0.002943 mol of silver nitrate) was added and the reaction was carried out for 2 hours. 1.4 g of phthalic anhydride (9.45 mmol) was added and the reaction was continued for 1 hour, and then the temperature was lowered to - 30 ℃, after adding 56mL (0.51mol) of titanium tetrachloride dropwise, gradually raise the temperature to 85 ℃, and add 2.0mL of di-n-butyl phthalate DNBP (7.57mmol) at 80 ℃, keep the temperature at 85 ℃ for 1 hour, filter out the mother liquor, wash twice with toluene, then add 48mL of titanium tetrachloride and 72mL of toluene solution, keep the temperature at 110 ℃ for 0.5 hour, filter and repeat the process twice, finally wash 5 times with hexane, and the remaining solid product is dried in vacuo to obtain the catalyst component C2 for olefin polymerization.

[0082] Example 3

[0083] This example is used to illustrate the catalyst component for olefin polymerization and the preparation method thereof provided by the present invention.

[0084] In a reactor that has been repeatedly replaced 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 in sequence, and the reaction was carried out at a temperature of 60°C for 2 hours. 4 mL of silver acetate ethanol solution (silver acetate: ethanol is 0.5 g: 4 mL; 2.943 mmol of silver acetate) was added and the reaction was carried out for 2 hours. 1.4 g of phthalic anhydride (9.45 mmol) was added and the reaction was continued for 1 hour, and then the temperature was lowered to -3 0 ℃, add 80mL (0.73mol) of titanium tetrachloride dropwise, gradually raise the temperature to 85 ℃, and add 2.0mL of di-n-butyl phthalate DNBP (7.57mmol) at 80 ℃, keep the temperature at 85 ℃ for 1 hour, filter out the mother liquor, wash twice with toluene, then add 48mL of titanium tetrachloride and 72mL of toluene solution, keep the temperature at 110 ℃ for 0.5 hour, filter and repeat the process twice, finally wash 5 times with hexane, and the remaining solid product is dried in vacuo to obtain the catalyst component C3 for olefin polymerization.

[0085] Comparative Example 1

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

[0087] In a reactor that has been repeatedly replaced 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 in sequence, and the reaction was carried out at a temperature of 60°C for 2 hours. 1.4 g of phthalic anhydride (9.45 mmol) 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, and then the mixture was gradually heated to 40°C. 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, and the mixture was kept at a constant temperature of 85°C for 1 hour. The mother liquor was filtered out, and the mixture was washed twice with toluene. Then, 48 mL of titanium tetrachloride and 72 mL of toluene solution were added, and the mixture was kept at a constant temperature of 110°C for 0.5 hour. After filtering, the treatment was repeated twice, and the mixture was washed 5 times with hexane. The remaining solid product was dried in vacuo to obtain the catalyst component D-C1 for olefin polymerization.

[0088] Comparative Example 2

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

[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 was 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 the above Examples 1-3 and Comparative Examples 1-2 were measured and their apparent morphologies were observed. The results are shown in Table 1:

[0092] Table 1

[0093]

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

[0095] Example 5

[0096] This example is used to illustrate the catalyst for olefin polymerization of the present invention and its application in an olefin polymerization method.

[0097] In a 5L autoclave, a nitrogen stream was used for purging, and then 1mmol of a hexane solution of triethylaluminum (the concentration of triethylaluminum was 0.5mmol / mL), 0.05mmol of methylcyclohexyldimethoxysilane, 10mL of anhydrous hexane and 10mg of the catalyst component C1 for olefin polymerization prepared in the above Example 1 (the mass fraction of titanium was 2.7%, titanium was 0.0057mmol), 1.5L (standard volume) of hydrogen and 2.5L of liquid propylene were introduced into the nitrogen stream. The temperature was raised to 70°C, and polymerization reaction was carried out at this temperature for 1 hour. The temperature was then lowered, the pressure was released, and the discharged material was dried to obtain a polypropylene powder.

[0098] Example 6

[0099] This example is used to illustrate the catalyst for olefin polymerization of the present invention and its application in an olefin polymerization method.

[0100] Propylene polymerization was carried out according to the method of Example 5, except that the 1.5 L (standard volume) of hydrogen was replaced by 6.5 L (standard volume) of hydrogen to obtain polypropylene powder.

[0101] Example 7

[0102] This example is used to illustrate the catalyst for olefin polymerization of the present invention and its application in an olefin polymerization method.

[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 (mass fraction of titanium was 2.5%, titanium was 1.47 mmol), to obtain polypropylene powder.

[0104] Example 8

[0105] This example is used to illustrate the catalyst for olefin polymerization of the present invention and its application in an olefin polymerization method.

[0106] Propylene polymerization was carried out according to the method of Example 7, except that the 1.5 L (standard volume) of hydrogen was replaced by 6.5 L (standard volume) of hydrogen to obtain polypropylene powder.

[0107] Example 9

[0108] This example is used to illustrate the catalyst for olefin polymerization of the present invention and its application in an olefin polymerization method.

[0109] 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 C3 for olefin polymerization obtained in Example 3 (mass fraction of titanium was 2.5%, titanium was 1.43 mmol), to obtain polypropylene powder.

[0110] Example 10

[0111] This example is used to illustrate the catalyst for olefin polymerization of the present invention and its application in an olefin polymerization method.

[0112] Propylene polymerization was carried out according to the method of Example 9, except that the 1.5 L (standard volume) of hydrogen was replaced by 6.5 L (standard volume) of hydrogen to obtain polypropylene powder.

[0113] Comparative Example 3

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

[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, to obtain polypropylene powder.

[0116] Comparative Example 4

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

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

[0119] Comparative Example 5

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

[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 for olefin polymerization of the present invention and its application in an olefin polymerization method.

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

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

[0126] Table 2

[0127]

[0128] It can be seen from the results in Table 2 that when the catalysts containing the catalyst components for olefin polymerization prepared in Examples 5 to 10 of the present invention are used for olefin (especially propylene) polymerization, the catalytic activity is good, the hydrogen adjustment sensitivity is high, the particle morphology of the prepared polypropylene powder is good, and there is basically no irregular shape, which has great industrial application prospects.

[0129] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

Claims

1. A catalyst component for olefin polymerization, characterized in that 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 solution formed by reacting a 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) Titanium compounds; 4) precipitation aid; Optionally, the catalyst component for olefin polymerization further comprises an electron donor compound.

2. The catalyst component for olefin polymerization according to claim 1, characterized in that The catalyst component for olefin polymerization has an average particle size of 1-30 μm and a sphericity of >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, preferably 1 g: (6-10) mL.

3. The catalyst component for olefin polymerization according to claim 1 or 2, characterized in that In the catalyst component for olefin polymerization, per mole of magnesium halide, the amount of the organic epoxy compound is 0.2-10 moles, the amount of the organic phosphorus compound is 0.1-3 moles, the amount of the silver nitrate and / or silver carboxylate is 0.001-2 moles, the amount of the precipitation aid is 0.03-1 mole, the amount of the titanium compound is 0.5-20 moles, and the amount of the electron donor compound is 0-15 moles; Preferably, in the catalyst component for olefin polymerization, per mole of magnesium halide, the amount of the organic epoxy compound is 0.5-4 moles, the amount of the organic phosphorus compound is 0.3-1 mole, the amount of the silver nitrate and / or silver carboxylate is 0.1-1 mole, the amount of the precipitation aid is 0.05-0.4 mole, the amount of the titanium compound is 1-15 moles, and the amount of the electron donor compound is 0.06-10 moles.

4. The catalyst component for olefin polymerization according to any one of claims 1 to 3, characterized in that In the catalyst component for olefin polymerization, the magnesium halide is a magnesium dihalide and / or a derivative in which a halogen atom in the magnesium dihalide molecule is replaced by a hydrocarbon group or a hydrocarbon oxygen group; preferably, the general formula of the magnesium halide is MgXY, X is chlorine or bromine, and Y is selected from chlorine, bromine, C1-C 14 Alkyl, C6-C 14 Aryl, C1-C 14 Alkoxy, C6-C 14 Further preferably, in the general formula of the magnesium halide, X is chlorine or bromine, and Y is selected from chlorine, bromine, C1-C5 alkyl, C6-C 10 Aryl, C1-C5 alkoxy, C6-C 10 More preferably, the magnesium halide is selected from at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride; And / or, 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 epoxy compounds having 2-18 carbon atoms, glycidyl ethers and internal ethers; preferably, the organic epoxy compound is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ester and butyl glycidyl ester; And / or, the organophosphorus compound is selected from the group consisting of hydrocarbon esters or halogenated hydrocarbon esters of orthophosphoric acid or phosphorous acid; preferably, 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 benzyl phosphite; And / or, the silver carboxylate is selected from at least one of silver acetate, silver benzoate, silver propionate, silver butyrate, and silver octanoate; And / or, the precipitation aid is selected from at least one of organic acids, organic anhydrides, organic ethers and organic ketones; preferably, the precipitation aid is selected from at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic anhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether and pentyl ether; And / or, the general formula of the titanium compound is Ti(OR) 4-n X' n , where R is C1-C 14 Aliphatic hydrocarbon or C6-C 14 An aromatic hydrocarbon group, X' is a halogen atom, and n is an integer of 1-4; preferably, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, triethoxytitanium monochloride, diethoxytitanium dichloride and triethoxytitanium trichloride; more preferably, the titanium compound is selected from titanium tetrachloride; And / or, the electron donor compound is selected from the group consisting of alkyl esters of aliphatic and aromatic monocarboxylic acids, alkyl esters of aliphatic and aromatic polycarboxylic acids, aliphatic ethers, cycloaliphatic ethers and aliphatic ketones; preferably, the electron donor compound is selected from at least one of 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; more preferably, 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, ethyl ether, hexyl ether, tetrahydrofuran, acetone and methyl isobutyl ketone, and most preferably, the electron donor compound is selected from diisobutyl phthalate and / or di-n-butyl phthalate; And / or, the inert solvent is at least one selected from hexane, heptane, octane, decane, benzene, toluene and xylene.

5. A method for preparing a catalyst component for olefin polymerization as claimed in any one of claims 1 to 4, characterized in that: The following steps are involved: 1) reacting a magnesium halide, an organic epoxy compound and an organic phosphorus compound in an inert solvent to form a solution under stirring; 2) adding a silver-containing solution to the solution obtained in step 1) to react to obtain a reaction solution; 3) adding a titanium compound dropwise to the reaction solution obtained in step 2) at a temperature of -30°C to 60°C and mixing, then heating the mixture to 60°C to 110°C and keeping the temperature constant for 0.5 to 8 hours, filtering off the mother liquor and washing to obtain spherical particles; 4) washing and drying the spherical particles obtained in step 3) to obtain the catalyst component for olefin polymerization; Preferably, the step 2) further comprises adding a precipitation aid to the reaction solution; And / or, the step 3) further comprises adding an electron donor compound during the heating process; And / or, in step 3), the mixture is heated to 85±2.5° C. and kept at this temperature for 1 hour to 1.5 hours.

6. The method for preparing a catalyst component for olefin polymerization according to claim 5, characterized in that: In step 1), the reaction conditions include: temperature of 50°C-70°C, preferably 60°C, time of 1h-3h, preferably 2h; And / or, in step 2), the reaction conditions of adding the silver-containing solution include: temperature of 50° C.-70° C., preferably 60° C., time of 1 h-3 h, preferably 1 h; And / or, in step 3), the temperature for adding the titanium compound is -30°C to 0°C.

7. 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 to 4 or the catalyst component for olefin polymerization prepared by the preparation method provided by claim 5 or 6; (2) Organic aluminum compounds; (3) Organic silicon compounds.

8. The catalyst for olefin polymerization according to claim 7, characterized in that The molar ratio of aluminum in the organic aluminum compound to titanium in the catalyst component is 5-5000:1; the molar ratio of the organic aluminum compound to the organic silicon compound is 0.1-300:

1.

9. The catalyst for olefin polymerization according to claim 7 or 8, characterized in that The organoaluminum compound is at least one selected from triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride and diethylaluminum dichloride; And / or, the general formula of the organosilicon compound is R 1 m Si(OR 2 ) 4-m , where 0≤m≤3, R 1 and R 2 the same or different, each independently selected from hydrogen, halogen, alkyl, cycloalkyl, aryl or halogenated alkyl; preferably, the organosilicon compound is selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylcyclohexyldiethoxysilane, methylcyclohexyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane and vinyltrimethoxysilane.

10. Use of the catalyst for olefin polymerization according to any one of claims 7 to 9 in olefin polymerization.

11. An olefin polymerization method, characterized in that: include: Under olefin polymerization conditions, one or more olefins are contacted with the catalyst for olefin polymerization described in any one of claims 7 to 9; preferably, 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, preferably at least one of ethylene, propylene, 1-butene, 2-butene and styrene, more preferably propylene.

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