An olefin polymerization catalyst component, a method for preparing the same, a catalyst system and an application thereof

Abstract

The application provides a spherical catalyst component for olefin polymerization and a preparation method, a catalyst system and application thereof, and belongs to the technical field of olefin polymerization.The spherical catalyst component comprises a spherical solid and a long-chain alpha-olefin compound shown as CH2=CHR a wherein R a is selected from linear or branched alkyl with 14-30 carbon atoms, and cycloalkyl with 14-30 carbon atoms; and the spherical solid comprises magnesium elements, titanium elements, halogen and an internal electron donor compound.The application uses the long-chain alpha-olefin compound to treat the spherical solid, so that the catalyst component has higher activity and stereospecificity, the obtained polymer powder has higher sphericity and bulk density, the powder D 10 is larger, the fine particles are reduced, the particle size distribution is narrower, and the phenomenon of cracking, breaking and opening is almost eliminated, and the application is suitable for industrial device operation.

Description

Technical Field

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

[0002] Since the particle morphology and size distribution of polyolefin powder can replicate that of catalyst particles, and a good polymer particle morphology can increase powder flowability, reduce fine powder content, lower the risk of equipment blockage, and extend the stable operation time of the equipment, catalysts with good particle morphology and narrow particle size distribution are a key research and development direction in the polyolefin industry. Patent documents such as US4421674, US4469648, WO8707620, WO9311166, US5100849, US6020279, US4399054, EP0395383, US6127304, and US6323152 disclose magnesium chloride-alcohol adducts, which are prepared into spherical catalyst supports through methods such as spray drying, spray cooling, high-pressure extrusion, or high-speed stirring. However, these technologies are typically energy-intensive and complex, and cannot continuously produce catalyst components. Patents CN85100997A, CN1097597C, US4952649, and US6323150 employ a solution-elution method to prepare particulate catalysts. A key feature of this method is that the support is no longer prepared separately during catalyst preparation; instead, titanium / magnesium catalysts or catalyst intermediates are precipitated from solution via co-crystallization. Because the morphology and particle size distribution of these catalysts are controlled by the crystallization process, which is influenced by numerous factors, the catalyst particle morphology is difficult to control.

[0003] In recent years, the preparation of spherical catalysts using emulsification molding processes has attracted increasing attention. Patent documents CN1537118, CN101454357, CN103619475, CN107207657, and CN114426597, among others, utilize emulsification technology to control the crystallization process, resulting in precipitated spherical solids with significantly improved morphology. However, some shortcomings remain. Specifically, the resulting polymer particles often fail to replicate the particle morphology of spherical catalysts effectively, frequently exhibiting cracking, breakage, and opening, leading to an increase in fine powder. This, in turn, causes equipment blockage and pipeline contamination, hindering the stable operation of the polymerization unit. Patent document CN202211326173.3 uses mineral oil to treat the catalyst, which improves polymer particle morphology, but significantly reduces catalyst activity. Summary of the Invention

[0004] In view of the problems existing in the prior art, the present invention, through experimental exploration, discovered that using long-chain α-olefins to treat the solid catalyst component can achieve the required results. Compared with the prior art, the catalyst component described in the present invention exhibits higher activity when used for olefin polymerization, producing polymer particles with higher sphericity, bulk density, and isotactic index, narrower particle size distribution, and intact particle shape, with almost no cracking, breakage, or opening.

[0005] One object of the present invention is to provide a spherical catalyst component for olefin polymerization, the spherical catalyst component comprising a spherical solid and a long-chain α-olefin compound of formula (I); said spherical solid comprising magnesium, titanium, halogen and an internal electron donor compound;

[0006] CH2=CHR a Formula (I)

[0007] Among them, R a Selected from straight-chain or branched alkyl groups with 14 to 30 carbon atoms, and cycloalkyl groups with 14 to 30 carbon atoms.

[0008] Optionally, the long-chain α-olefin compound may be selected from one or more of the following compounds: 1-tetradecene, 1-pentadene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadene, 1-eicosene, 1-docosahexadecene, and 1-hexadecene.

[0009] Optionally, the internal electron-donating compound in the spherical solid of the present invention is selected from one or more of 2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, diethyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, di-n-butyl 2,3-diisopropylsuccinate, dimethyl 2,3-diisopropylsuccinate, diisobutyl 2,2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl 2-ethyl-2-methylsuccinate, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and 9,9-dimethoxymethylfluorene.

[0010] Optionally, the magnesium element in this invention is derived from a magnesium compound with the general formula MgX2, wherein X is a halogen, preferably bromine, chlorine or iodine; specifically, it can be at least one of magnesium dichloride, magnesium dibromide and magnesium diiodide, preferably magnesium dichloride.

[0011] Optionally, the titanium element in this invention is derived from titanium compounds, which have the structure TiX'. m (OR7) 4-mThe expression indicates that X' is a halogen, R7 is a hydrocarbon group with 1 to 20 carbon atoms, and m is an integer from 1 to 4; preferably at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloromonoethoxy, more preferably titanium tetrachloride.

[0012] Optionally, the spherical catalyst component of the present invention, based on a total weight of 100wt%, contains 1wt% to 5wt% titanium, 10wt% to 30wt% magnesium, 40wt% to 60wt% halogen, 5wt% to 20wt% internal electron donor compound, and 1wt% to 25wt% long-chain α-olefin compound.

[0013] A second objective of this invention is to provide a method for preparing a spherical catalyst component corresponding to one objective, comprising the following steps:

[0014] S1. To bring magnesium compounds, organic epoxy compounds, and organic phosphorus compounds into contact in an organic solvent to form a magnesium-containing solution;

[0015] S2. In the presence of a precipitation aid and optionally a surfactant, a magnesium-containing solution is contacted with a titanium compound and an inert dispersion medium to form a mixture, the mixture is heated, and then filtered and washed to obtain spherical solids;

[0016] S3. Disperse the long-chain α-olefin compound and spherical solid as shown in formula (I) in an inert diluent and contact them, then evaporate the inert diluent to obtain the spherical catalyst component;

[0017] CH2=CHR a Formula (I)

[0018] Among them, R a Selected from straight-chain or branched alkyl groups with 14 to 30 carbon atoms, and cycloalkyl groups with 14 to 30 carbon atoms.

[0019] Optionally, the long-chain α-olefin compound may be selected from one or more of the following compounds: 1-tetradecene, 1-pentadene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadene, 1-eicosene, 1-docosahexadecene, and 1-hexadecene.

[0020] Optionally, the contact conditions in step S3 include: a contact temperature of 0 to 100°C, preferably 20 to 80°C, and a contact time of 0.1 minutes to 5 hours, preferably 0.2 minutes to 2 hours.

[0021] Optionally, the volume of the long-chain α-olefin compound added per gram of spherical solid does not exceed 1.5 times the pore volume of the spherical solid, preferably 0.3 to 1.0 times. The pore volume can be determined using BET technology.

[0022] Optionally, the inert diluent is selected from one or more of pentane, isopentane, hexane, heptane, and toluene.

[0023] Optionally, there is no particular limitation on the amount of the inert diluent added. Preferably, the amount of the inert diluent added is 0.1 mL to 100 mL per gram of spherical solids, and more preferably 0.5 mL to 50 mL.

[0024] Optionally, evaporation can be carried out under normal pressure, reduced pressure or vacuum conditions; the evaporation temperature is 10℃ to 100℃, preferably 20℃ to 80℃.

[0025] Optionally, the organic epoxy compound of the present invention is selected from one or more of ethylene oxide, propylene oxide, epichlorohydrin, epichlorohydrin, epichlorohydrin, butane oxide, butadiene oxide, butadiene dioxide, methyl glycidyl ether, and diglycidyl ether, preferably epichlorohydrin.

[0026] Optionally, the organophosphorus compound of the present invention is selected from one or more of trimethyl phosphate, triethyl phosphate, tributyl phosphate, tripentyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and benzyl phosphite, preferably tributyl phosphate.

[0027] Optionally, the organic solvent of the present invention is an aromatic hydrocarbon compound, specifically one or more of toluene, ethylbenzene, benzene, and xylene, with toluene being preferred.

[0028] Optionally, the inert dispersion medium of the present invention is selected from one or more of white oil, hexane, heptane, octane, nonane, decane, dodecane, and cyclohexane, preferably one or more of white oil, hexane, and decane.

[0029] Optionally, the precipitation aid of the present invention is selected from one or more 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, preferably phthalic anhydride.

[0030] Optionally, the surfactant of the present invention includes one or more selected from the alcoholysis products of maleic anhydride polymers and maleic anhydride copolymers, preferably one or more selected from the alcoholysis products of polymaleic anhydride, maleic anhydride-styrene copolymers, maleic anhydride-styrene-(meth)acrylate terpolymers, and maleic anhydride-(meth)acrylate alkyl copolymers.

[0031] Wherein, the alkyl ester side chains in the maleic anhydride-styrene-(meth)acrylate terpolymer and the maleic anhydride-(meth)acrylate terpolymer are independently selected from at least one of straight-chain or branched alkane groups with 1 to 30 carbon atoms, cycloalkane groups with 1 to 30 carbon atoms, and aromatic hydrocarbon groups with 1 to 30 carbon atoms, preferably the above-mentioned substituents with 1 to 20 carbon atoms.

[0032] In this invention, the alcoholysis product refers to the polymer product obtained by reacting the product with an organic alcohol compound, such as the organic alcohol compound with the structure R. a OH, where R a It is selected from straight-chain or branched alkane groups with 2 to 20 carbon atoms, cycloalkane groups with 2 to 20 carbon atoms, or aromatic hydrocarbon groups with 2 to 20 carbon atoms.

[0033] Optionally, the surfactant of the present invention further includes at least one of (meth)acrylate alkyl ester polymers and (meth)acrylate alkyl ester copolymers, such as at least one of poly(meth)acrylate alkyl ester, (meth)acrylate alkyl-maleic anhydride copolymer, and (meth)acrylate alkyl-maleic anhydride-styrene copolymer; wherein the alkyl ester side chains in the (meth)acrylate alkyl ester polymers and (meth)acrylate alkyl ester copolymers are independently selected from straight-chain or branched alkane groups of 1 to 30 carbon atoms, cycloalkane groups of 1 to 30 carbon atoms, or aromatic groups, preferably the above-mentioned substituents of 1 to 20 carbon atoms.

[0034] The poly(meth)acrylate polymer surfactant described in this invention can be a surfactant product with the trademark name T602 purchased from any additive company.

[0035] Optionally, in step S1 of the present invention, there is no particular limitation on the contact method for forming the magnesium-containing solution. The purpose of the contact is to form a homogeneous magnesium-containing solution. The contact conditions include: a contact temperature of 10℃ to 100℃, preferably 20℃ to 80℃, and a contact time of 0.05 to 10 hours, preferably 0.1 to 6 hours.

[0036] Optionally, in step S2 of the present invention, the contact method between the inert dispersion medium, the titanium compound, and the homogeneous solution containing magnesium can be any method. Specifically, it can be that the inert dispersion medium is contacted with the homogeneous solution containing magnesium to form a solution, and then the titanium compound is contacted with the solution to form a mixture; it can be that the titanium compound is contacted with the homogeneous solution containing magnesium to form a solution, and then the inert dispersion medium is contacted with the solution to form a mixture; it can also be that the inert dispersion medium and the titanium compound are mixed evenly and then dripped into the homogeneous solution containing magnesium, or the inert dispersion medium and the titanium compound are dripped separately into the homogeneous solution containing magnesium to form a mixture.

[0037] Optionally, in step S2 of the present invention, the contact temperature between the inert dispersion medium, the titanium compound, and the magnesium-containing solution is -35 to 60°C, preferably -20 to 40°C; the contact time is 1 minute to 10 hours, preferably 3 minutes to 7 hours.

[0038] Optionally, the mixture formed in step S2 of the present invention comprises colloids, two-phase solutions, emulsions, and other forms.

[0039] Optionally, the preparation method of step S2 of the present invention further includes using one or more methods such as vibration, stirring, atomization, and shearing to promote uniform dispersion of the mixture, further heating the mixture to 50-110°C to solidify and precipitate solids to obtain a suspension, and then stirring the suspension at this temperature or a higher temperature (not higher than 130°C) for 10 minutes to 24 hours.

[0040] According to the present invention, the heating process of the mixture is not specifically limited, and any known method can be used for heating, such as slow, stepwise, rapid, or programmed heating. The specific heating method should be adjusted according to the specific formulation, contact temperature, etc. The heating time of the mixture can be from 1 minute to 36 hours, preferably from 3 minutes to 24 hours.

[0041] Optionally, in the preparation method of the present invention, the surfactant can be added at any position in the preparation method, and can be added all at once or in multiple parts. According to the present invention, the surfactant can be added entirely or partially during or after the formation of a homogeneous magnesium-containing solution; it can be added entirely to an inert dispersion medium; or it can be partially added to an inert dispersion medium and another part added to a homogeneous magnesium-containing solution.

[0042] Optionally, in the preparation method of the present invention, the temperature at which the surfactant is added is 0℃~100℃, preferably 0℃~80℃, and more preferably 0℃~60℃.

[0043] Optionally, the preparation method of the present invention further includes the addition of an internal electron donor compound. The addition position can be any position before step S3, and it can be added all at once or in multiple parts. This includes adding it all or partly to a homogeneous solution containing magnesium; adding it all or partly after the mixture is formed and during the solidification and heating precipitation process; or contacting it with the internal electron donor compound all or partly after the spherical solid precipitates or after the solid precipitates and is filtered and washed.

[0044] Optionally, in the preparation method of the present invention, the temperature at which the internal electron donor compound is added is 10℃ to 150℃, preferably 10℃ to 100℃.

[0045] Optionally, in the preparation method of the present invention, the contact time between the spherical solid and the internal electron donor compound is 0.05 to 8 hours, preferably 1 to 6 hours.

[0046] Optionally, in the preparation method of the present invention, the amount of each component added, calculated per mole of magnesium halide compound, is as follows: organic epoxy compound 0.1-10 moles, organophosphorus compound 0.1-10 moles, organic solvent 0.5-40 moles, titanium compound 0.5-25 moles, precipitation aid 0.01-1 moles, and internal electron donor compound 0.01-1 moles; preferably, organic epoxy compound 0.4-4 moles, organophosphorus compound 0.8-4 moles, organic solvent 2-30 moles, titanium compound 1-20 moles, and precipitation aid 0.04-0.4 moles.

[0047] Optionally, the amount of the inert dispersion medium added per gram of magnesium halide compound is 0.1g to 300g, preferably 1g to 150g, and the amount of the surfactant added is 0.05g to 1g.

[0048] A third objective of this invention is to provide a catalyst system for olefin polymerization corresponding to the above-mentioned objective, the catalyst system comprising:

[0049] (1) Catalyst component; selected from at least one of the above-mentioned spherical catalyst components;

[0050] (2) Alkyl aluminum compounds; and

[0051] (3)Optionally, external electron-donating compounds.

[0052] Optionally, according to the present invention, the alkylaluminum compound has the general formula AlR'. n The compounds shown in X"3-n are: R' is selected from hydrogen or hydrocarbon groups having 1 to 20 carbon atoms, especially alkyl, aralkyl, aryl, etc.; X" is a halogen; and n is an integer from 1 to 3.

[0053] Optionally, the alkylaluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydrogen, diisobutylaluminum hydrogen, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, and diethylaluminum chloride, preferably triethylaluminum and / or triisobutylaluminum.

[0054] According to the present invention, the amount of the alkylaluminum compound can be a conventional amount in the art. Preferably, the molar ratio of aluminum in the alkylaluminum compound to titanium in the catalyst component is 5 to 5000:1, more preferably 20 to 800:1.

[0055] Optionally, according to the present invention, the external electron donor compound is an organosilicon compound with the general formula R". n' Si(OR y ) 4-n' In the formula, n' is an integer from 0 to 3, and R" is selected from one of alkyl, cycloalkyl, aryl, haloalkyl, halogen, and hydrogen atoms. y It is selected from one of alkyl, cycloalkyl, aryl and haloalkyl groups.

[0056] Optionally, the external electron donor compound is selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl tert-butyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dicyclohexyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, methylcyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, and (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane, preferably methylcyclohexyldimethoxysilane.

[0057] According to the present invention, the amount of the external electron-donating compound is not particularly limited. Preferably, the molar ratio of the alkylaluminum compound to the external electron-donating compound is 0.1 to 500:1, more preferably 1 to 300:1, and more preferably 3 to 100:1, based on the aluminum content.

[0058] A fourth objective of the present invention is to provide an olefin polymerization method corresponding to the above objective, the method comprising: contacting one or more olefins with the above-described catalyst system under olefin polymerization conditions.

[0059] Optionally, at least one of the olefins is an olefin represented by the formula CH2=CHR, wherein R is hydrogen or a straight-chain or branched alkyl group of C1 to C6.

[0060] Optionally, the olefin represented by the formula CH2=CHR is one or more of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene, and 4-methyl-1-pentene.

[0061] Optionally, the olefin is propylene or a copolymer of propylene and other olefins.

[0062] According to the present invention, the polymerization of olefins is carried out according to known methods, in a liquid phase monomer or monomer in an inert solvent in a liquid phase, or in a gas phase, or by a combined polymerization process in a gas-liquid phase.

[0063] Optionally, the conditions for olefin polymerization include: a polymerization temperature of 0℃ to 150℃, preferably 60℃ to 100℃, and a polymerization reaction pressure of 0.1MPa to 10MPa, preferably 0.1MPa to 5MPa.

[0064] Compared with the prior art, the present invention has at least the following beneficial effects:

[0065] The spherical catalyst component described in this invention exhibits higher activity and stereotactic orientation when used in propylene polymerization, resulting in polymer particles with high sphericity, high packing density, narrow particle size distribution, and intact particle shape, making them less prone to fine fragmentation. Attached Figure Description

[0066] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the following detailed description to explain the invention, but do not constitute a limitation thereof. In the drawings:

[0067] Figure 1 This is a photograph of the olefin polymer produced by polymerization in Example 1.

[0068] Figure 2 The image shows the physical product of the olefin polymer produced by polymerization in Comparative Example 1. Detailed Implementation

[0069] The present invention will be described in detail below through embodiments, but the scope of protection of the present invention is not limited to the following description.

[0070] Unless otherwise specified in the examples, the procedures should be performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0071] The testing methods involved in the embodiments of this invention are as follows:

[0072] 1. Determination of titanium content in catalyst: Colorimetric determination was performed using a UV-Vis spectrophotometer (model 722).

[0073] 2. The magnesium content was determined by complexometric titration of magnesium ions and EDTA.

[0074] 3. Determination of the content of internal electron donor compounds in the catalyst: The catalyst dry powder is decomposed with dilute acid, and the internal electron donor compounds are extracted with an extractant and then determined by liquid chromatography.

[0075] 4. The content of long-chain α-olefins in the catalyst is calculated based on the dosage and product weight: long-chain α-olefin content = (catalyst product weight - spherical solid weight) / catalyst product weight × 100wt%.

[0076] 5. The determination of polymer bulk density (BD) shall be in accordance with ASTM D1895-96 standard.

[0077] 6. The isotacticity index (II) of propylene polymer is determined by the heptane extraction method: 2 grams of dry polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours. The residue is then dried to constant weight. The ratio of the obtained polymer weight (g) to 2 (g) is the isotacticity.

[0078] 7. The particle size of the polymer was determined using a Camsizer instrument, D 10 This indicates that 10% of the particles are smaller than the particle size (diameter) specified in D. 50 This indicates that 50% of the particles are smaller than this particle size, D 90 This indicates that 90% of the particles are smaller than this size. SPAN represents the particle size distribution. SPAN = (D 90 -D 10 ) / D 50 .

[0079] 8. The sphericity SPHT of the polymer (ISO 9276-6) is determined using a Camsizer instrument. SPHT = 4πA / p 2 P is the circumference of the projected particle, and A is the area covered by the particle's projection. For an ideal sphere, the SPHT value is 1. If it is not an ideal sphere, the SPHT value is less than 1. The closer the SPHT value is to 1, the closer the particle is to a sphere.

[0080] 9. The symmetry (Symm) of the polymer is determined using a Camsizer instrument. Symmm = (1 + min(r1 / r2)) / 2, where r1 and r2 are the distances from the center of the region to the boundary in the measurement direction. For asymmetric particles, Symmm is less than 1. If the center of the region is outside the particle, Symmm is less than 0.5. "Symm" represents the minimum of a set of symmetry values ​​measured from different directions.

[0081] 10. The aspect ratio (B / L) of the polymer is determined using a Camsizer instrument. B / L = X c min / X Fe max , where X c min and X Fe max Value in X c and X Fe Outside of the value measurement set.

[0082] Example 1

[0083] (1) Preparation of catalyst components

[0084] In a 1L reactor that has been repeatedly purged with high-purity nitrogen, 10.8g of anhydrous magnesium chloride, 75mL of toluene, 9.6mL of epichlorohydrin, and 42mL of tributyl phosphate were added sequentially. The mixture was stirred at 300 rpm for 2 hours at 60°C. Then, 3.3g of phthalic anhydride was added, and the mixture was maintained at 60°C for another hour. The temperature was lowered to 40°C, and a mixture of 129mL of decane and 5.7g of T602 was added. The mixture was stirred at 400 rpm for another hour. The solution was then cooled to 10°C, and 114mL of titanium tetrachloride was added dropwise. The mixture was maintained for another hour after the addition was complete. The temperature was gradually increased to 80°C over 3 hours and maintained for 1 hour. During the heating process, 1.4mL of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was added. After filtering the mother liquor, the solid was washed twice with 200mL of toluene. Add 120 mL of toluene and 80 mL of titanium tetrachloride, treat at 110 °C for 0.5 hours, and remove the filtrate. Wash four times with 200 mL of hexane, and then dry to obtain spherical solid a1. The obtained spherical solid a1 contains 2.0 wt% titanium, 18.5 wt% magnesium, and 10.8 wt% 2-isopropyl-2-isopentyl-1,3-dimethoxypropane. The specific surface area of ​​spherical solid a1 is 420.2 m². 2 / g, pore volume is 0.287cm3 / g.

[0085] 5.0 g of spherical solid a1, 1.4 mL of 1-octadecene, and 5 mL of hexane were placed in a 240 mL reactor and the mixture was stirred thoroughly. The hexane was removed by evaporation under a nitrogen atmosphere to obtain catalyst component A1. The 1-octadecene content in the obtained catalyst component A1 was 18.0 wt%.

[0086] (2) Propylene polymerization

[0087] In a 5-liter high-pressure reactor, after complete purging with nitrogen, 5 mL of a triethylaluminum hexane solution (0.5 mmol / mL), 1 mL of a cyclohexylmethyldimethoxysilane (CHMMS) hexane solution (0.1 mmol / mL), 10 mL of anhydrous hexane, and 10 mg of solid catalyst component A1 were added at room temperature. The high-pressure reactor was closed, and 4.5 L of hydrogen and 2.3 L of liquid propylene were added. The temperature was raised to 70 °C, and polymerization was carried out at 70 °C for 1 hour. After the reaction was completed, the reactor was cooled and stirring was stopped. The reaction product was discharged to obtain an olefin polymer, as shown in the figure. Figure 1 As shown, catalyst polymerization data and olefin polymer data are presented in Table 1.

[0088] Example 2

[0089] (1) Preparation of catalyst components

[0090] 5.0 g of the spherical solid a1 prepared in Example 1, 0.7 mL of 1-octadecene, and 5 mL of hexane were placed in a 240 mL reactor and the mixture was stirred thoroughly. The hexane was removed by evaporation under a nitrogen atmosphere to obtain catalyst component A2. The 1-octadecene content in the obtained catalyst component A2 was 10.0 wt%.

[0091] (2) Propylene polymerization

[0092] The polymerization conditions were the same as in Example 1, using solid catalyst component A2. The polymerization data and olefin polymer data are shown in Table 1.

[0093] Example 3

[0094] (1) Preparation of catalyst components

[0095] 5.0 g of the spherical solid a1 prepared in Example 1, 1.4 mL of 1-hexadecene, and 10 mL of hexane were placed in a 240 mL reactor and the mixture was stirred thoroughly. Hexane was removed by evaporation under a nitrogen atmosphere to obtain solid catalyst component A3. The 1-hexadecene content in the obtained catalyst component A3 was 17.5 wt%.

[0096] (2) Propylene polymerization

[0097] The polymerization conditions were the same as in Example 1, using solid catalyst component A3. The polymerization data and olefin polymer data are shown in Table 1.

[0098] Example 4

[0099] (1) Preparation of catalyst components

[0100] 5.0 g of the spherical solid a1 prepared in Example 1, 1.4 mL of 1-eicosene, and 5 mL of hexane were placed in a 240 mL reactor and the mixture was stirred thoroughly. The hexane was removed by evaporation under a nitrogen atmosphere to obtain solid catalyst component A4. The 1-eicosene content in the obtained catalyst component A4 was 18.0 wt%.

[0101] (2) Propylene polymerization

[0102] The polymerization conditions were the same as in Example 1, using solid catalyst component A4. The polymerization data and olefin polymer data are shown in Table 1.

[0103] Example 5

[0104] (1) Preparation of catalyst components

[0105] 5.0 g of the spherical solid a1 prepared in Example 1, 1.4 mL of 1-tetradecene, and 5 mL of hexane were placed in a 240 mL reactor and the mixture was stirred thoroughly. The hexane was removed by evaporation under a nitrogen atmosphere to obtain solid catalyst component A5. The 1-tetradecene content in the obtained catalyst component A5 was 16.4 wt%.

[0106] (2) Propylene polymerization

[0107] The polymerization conditions were the same as in Example 1, using solid catalyst component A5. The polymerization data and olefin polymer data are shown in Table 1.

[0108] Comparative Example 1

[0109] The spherical solid a1 prepared in Example 1 was directly subjected to propylene polymerization under the same polymerization conditions as in Example 1. Polymerization data and olefin polymer data are shown in Table 1. Actual olefin polymer samples are shown below. Figure 2 As shown.

[0110] Comparative Example 2

[0111] (1) Preparation of catalyst components

[0112] 5.0 g of the spherical solid a1 prepared in Example 1, 1.4 mL of octadecane, and 5 mL of hexane were placed in a 240 mL reactor and the mixture was stirred thoroughly. Hexane was removed by evaporation under a nitrogen atmosphere to obtain 6.1 g of solid catalyst component D1. The octadecane content in the obtained catalyst component D1 was 18.0 wt%.

[0113] (2) Propylene polymerization

[0114] The polymerization conditions were the same as in Example 1, using solid catalyst component D1. The polymerization data and olefin polymer data are shown in Table 1.

[0115] Comparative Example 3

[0116] (1) Preparation of catalyst components

[0117] 5.0 g of the spherical solid a1 prepared in Example 1, 1.4 mL of 1-hexene, and 5 mL of hexane were placed in a 240 mL reactor and the mixture was stirred thoroughly. The hexane was removed by evaporation under a nitrogen atmosphere to obtain 5.0 g of solid catalyst component D2. The 1-hexene content in the obtained catalyst component D2 was 0.9 wt%.

[0118] (2) Propylene polymerization

[0119] The polymerization conditions were the same as in Example 1, using solid catalyst component D2. The polymerization data and olefin polymer data are shown in Table 1.

[0120] Table 1.

[0121]

[0122] As can be seen from the above embodiments and comparative examples, in the preparation method of the present invention, by using long-chain α-olefin compounds to treat spherical solids, the catalyst component has higher activity and stereotactic orientation, and the resulting polymer powder has higher sphericity and packing density, and the powder D... 10 It becomes larger, with fewer fine particles, a narrower particle size distribution, and almost no cracking, breakage, or opening, making it suitable for industrial equipment operation.

[0123] Any numerical value mentioned in this invention, if there is only a two-unit interval between any minimum and any maximum value, includes all values ​​that increase by one unit each time from the minimum to the maximum value. For example, if the amount of a component, or the value of a process variable such as temperature, pressure, or time, is stated as 50-90, in this specification it means specifically listing values ​​such as 51-89, 52-88… and 69-71 and 70-71, etc. For non-integer values, it may be appropriately considered that a unit is 0.1, 0.01, 0.001, or 0.0001. These are merely some specifically specified examples. In this application, in a similar manner, all possible combinations of numerical values ​​between the listed minimum and maximum values ​​are considered to have been disclosed.

[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 spherical catalyst component for olefin polymerization, characterized in that, The spherical catalyst component comprises a spherical solid and a long-chain α-olefin compound as shown in formula (I); the spherical solid comprises magnesium, titanium, halogens, and an internal electron donor compound; CH2=CHR a Formula (I) Among them, R a Selected from straight-chain or branched alkyl groups with 14 to 30 carbon atoms, and straight-chain alkyl groups with 12 carbon atoms; Based on the total weight of the spherical catalyst components of 100wt%, the content of titanium is 1wt%~5wt%, the content of magnesium is 10wt%~30wt%, the content of halogen is 40wt%~60wt%, the content of internal electron donor compound is 5wt%~20wt%, and the content of long-chain α-olefin compound is 1wt%~25wt%.

2. The spherical catalyst component according to claim 1, characterized in that, The long-chain α-olefin compound is selected from at least one of 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadene, 1-eicosene, 1-docosahexadecene, 1-tetradecene, and 1-hexadecene. And / or, the internal electron-donating compound is selected from at least one of 2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, diethyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, di-n-butyl 2,3-diisopropylsuccinate, dimethyl 2,3-diisopropylsuccinate, diisobutyl 2,2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl 2-ethyl-2-methylsuccinate, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and 9,9-dimethoxymethylfluorene; And / or, the magnesium element is derived from a magnesium compound with the general formula MgX2, wherein X is a halogen; And / or, the titanium element is derived from a titanium compound with the general formula TiX'. m (OR7) 4-m , where X' is a halogen, R7 is a hydrocarbon group with 1 to 20 carbon atoms, and m is an integer from 1 to 4.

3. The spherical catalyst component according to claim 2, characterized in that, X is bromine, chlorine, or iodine; And / or, the titanium compound is at least one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloroethoxy.

4. The spherical catalyst component according to claim 3, characterized in that, The magnesium compound is at least one of magnesium dichloride, magnesium dibromide, and magnesium diiodide.

5. A method for preparing a spherical catalyst component, characterized in that, Includes the following steps: S1. To bring magnesium compounds, organic epoxy compounds, and organic phosphorus compounds into contact in an organic solvent to form a magnesium-containing solution; S2. In the presence of a precipitation aid and optionally a surfactant, a magnesium-containing solution is contacted with a titanium compound and an inert dispersion medium to form a mixture, the mixture is heated, and then filtered and washed to obtain spherical solids; S3. Disperse the long-chain α-olefin compound and spherical solid as shown in formula (I) in an inert diluent and contact them, then evaporate the inert diluent to obtain the spherical catalyst component; CH2=CHR a Formula (I) Among them, R a Selected from straight-chain or branched alkyl groups with 14 to 30 carbon atoms, and straight-chain alkyl groups with 12 carbon atoms; The volume of the long-chain α-olefin compound added per gram of spherical solid does not exceed 1.5 times the pore volume of the spherical solid.

6. The preparation method according to claim 5, characterized in that, The long-chain α-olefin compound is selected from at least one of 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadene, 1-eicosene, 1-docosahexadecene, 1-tetradecene, and 1-hexadecene. And / or, per gram of spherical solids, the volume of the added long-chain α-olefin compound does not exceed 0.3 to 1.0 times the pore volume of the spherical solids; And / or, the inert diluent is selected from at least one of pentane, isopentane, hexane, heptane, and toluene; And / or, the amount of the inert diluent added is 0.1 mL to 100 mL per gram of spherical solids; And / or, the evaporation is carried out under normal pressure, reduced pressure or vacuum conditions, and the evaporation temperature is 10°C to 100°C; And / or, the organic epoxy compound is selected from at least one of ethylene oxide, propylene oxide, epichlorohydrin, epichlorohydrin, epichlorohydrin, butane oxide, butadiene oxide, butadiene dioxide, methyl glycidyl ether, and diglycidyl ether; And / or, the organophosphorus compound is selected from at least one of trimethyl phosphate, triethyl phosphate, tributyl phosphate, tripentyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and benzoyl phosphite; And / or, the organic solvent is an aromatic hydrocarbon compound; And / or, the inert dispersion medium is selected from at least one of white oil, hexane, heptane, octane, nonane, decane, dodecane, and cyclohexane; 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 surfactant includes one or more selected from the alcoholysis products of maleic anhydride polymers and maleic anhydride copolymers.

7. The preparation method according to claim 6, characterized in that, The amount of the inert diluent added is 0.5 mL to 50 mL per gram of spherical solids; And / or, the evaporation temperature is 20°C to 80°C; And / or, the organic solvent is at least one of toluene, ethylbenzene, benzene, and xylene; And / or, the surfactant is selected from at least one of the following: alcoholysis product of polymaleic anhydride, alcoholysis product of maleic anhydride-styrene copolymer, alcoholysis product of maleic anhydride-styrene-(meth)acrylate terpolymer, and alcoholysis product of maleic anhydride-(meth)acrylate alkyl copolymer. Wherein, the alkyl ester side chains in the maleic anhydride-styrene-(meth)acrylate terpolymer and the maleic anhydride-(meth)acrylate terpolymer are independently selected from at least one of straight-chain or branched alkane groups of 1 to 30 carbon atoms, cycloalkane groups of 1 to 30 carbon atoms, and aromatic hydrocarbon groups of 1 to 30 carbon atoms.

8. The preparation method according to claim 7, characterized in that, The alkyl ester side chains in the maleic anhydride-styrene-(meth)acrylate terpolymer and the maleic anhydride-(meth)acrylate terpolymer are independently at least one of a straight-chain or branched alkane group of 1 to 20 carbon atoms, a cycloalkane group of 1 to 20 carbon atoms, and an aromatic hydrocarbon group of 1 to 20 carbon atoms.

9. The preparation method according to claim 7, characterized in that, The surfactant also includes at least one of (meth)acrylate alkyl ester polymers and (meth)acrylate alkyl ester copolymers.

10. The preparation method according to claim 7, characterized in that, The surfactant further includes at least one of poly(meth)acrylate alkyl ester, (meth)acrylate alkyl ester-maleic anhydride copolymer, and (meth)acrylate alkyl ester-maleic anhydride-styrene copolymer; wherein the alkyl ester side chains in the (meth)acrylate alkyl ester polymer and the (meth)acrylate alkyl ester copolymer are independently selected from straight-chain or branched alkane groups of 1 to 30 carbon atoms, cycloalkane groups of 1 to 30 carbon atoms, or aromatic hydrocarbon groups.

11. The preparation method according to claim 10, characterized in that, in, The alkyl ester side chains in the (meth)acrylate alkyl ester polymers and (meth)acrylate alkyl ester copolymers are independently selected from at least one of a straight-chain or branched alkane group of 1 to 20 carbon atoms, a cycloalkane group of 1 to 20 carbon atoms, and an aromatic hydrocarbon group of 1 to 20 carbon atoms.

12. The preparation method according to any one of claims 5-11, characterized in that, In step S1, the contact conditions include: a contact temperature of 10℃ to 100℃ and a contact time of 0.05 to 10 hours. And / or, in step S2, the contact temperature between the inert dispersion medium, the titanium compound, and the magnesium-containing solution is -35 to 60°C; the contact time is 1 minute to 10 hours. And / or, in step S2, the heating treatment includes: heating the mixture to 50~110℃, solidifying and precipitating spherical solids to obtain a suspension, and stirring the suspension at 50~130℃ for 10 minutes to 24 hours; the heating treatment time is 1 minute to 36 hours. And / or, the surfactant is added at a temperature of 0°C to 100°C; And / or, in step S3, the contact conditions include: a contact temperature of 0~100℃ and a contact time of 0.1 minutes~5 hours; And / or, the preparation method further includes the addition of an internal electron donor compound, wherein the internal electron donor compound is added at any position before step S3; And / or, the addition temperature of the internal electron donor compound is 10°C to 150°C; And / or, the contact time between the spherical solid and the internal electron-donating compound is 0.05~8h; And / or, the amount of each component added is calculated per mole of magnesium halide compound: 0.1 to 10 moles of organic epoxy compound, 0.1 to 10 moles of organic phosphorus compound, 0.5 to 40 moles of organic solvent, 0.5 to 25 moles of titanium compound, 0.01 to 1 mole of precipitation aid, and 0.01 to 1 mole of internal electron donor compound; And / or, based on each gram of magnesium halide compound, the amount of the inert dispersion medium added is 0.1 g to 300 g, and the amount of the surfactant added is 0.05 g to 1 g.

13. The preparation method according to claim 12, characterized in that, In step S1, the contact conditions include: a contact temperature of 20°C to 80°C and a contact time of 0.1 to 6 hours. And / or, in step S2, the contact temperature between the inert dispersion medium, the titanium compound, and the magnesium-containing solution is -20 to 40°C; the contact time is 3 minutes to 7 hours. And / or, in step S2, the heating process takes 3 minutes to 24 hours; And / or, the surfactant is added at a temperature of 0°C to 80°C; And / or, in step S3, the contact conditions include: a contact temperature of 20~80℃ and a contact time of 0.2 minutes~2 hours; And / or, the addition temperature of the internal electron-donating compound is 10°C to 100°C; And / or, the contact time between the spherical solid and the internal electron-donating compound is 1 to 6 hours; And / or, the organic epoxy compound is 0.4 to 4 mol, the organophosphorus compound is 0.8 to 4 mol, the organic solvent is 2 to 30 mol, the titanium compound is 1 to 20 mol, and the precipitation aid is 0.04 to 0.4 mol; And / or, the amount of the inert dispersion medium added is 1 g to 150 g per gram of magnesium halide compound.

14. The preparation method according to claim 13, characterized in that, The surfactant is added at a temperature of 0℃ to 60℃.

15. A catalyst system for olefin polymerization, characterized in that, The catalyst system includes: (1) Catalyst component; selected from at least one of the spherical catalyst components described in any one of claims 1 to 4 and the spherical catalyst components prepared by the preparation method described in any one of claims 5 to 14; (2) Alkyl aluminum compounds; and (3)Optionally, external electron donor compounds.

16. The catalyst system according to claim 15, characterized in that, The alkylaluminum compound has the general formula AlR' n X" 3-n The compounds shown are in which R' is selected from hydrogen or hydrocarbon groups having 1 to 20 carbon atoms; X" is a halogen; and n is an integer from 1 to 3. And / or, the molar ratio of aluminum in the alkylaluminum compound to titanium in the catalyst component is 5~5000:1; And / or, the external electron donor compound is an organosilicon compound with the general formula R". n' Si(OR y ) 4-n' In the formula, n' is an integer from 0 to 3, and R" is selected from one of alkyl, cycloalkyl, aryl, haloalkyl, halogen, and hydrogen atoms. y Selected from one of alkyl, cycloalkyl, aryl, and halogenated alkyl groups; And / or, based on the aluminum content, the molar ratio of the alkylaluminum compound to the external electron donor compound is 0.1 to 500:

1.

17. The catalyst system according to claim 16, characterized in that, R' is alkyl, aralkyl, or aryl; And / or, the molar ratio of aluminum in the alkylaluminum compound to titanium in the catalyst component is 20~800:1; And / or, based on the aluminum content, the molar ratio of the alkylaluminum compound to the external electron donor compound is 1~300:

1.

18. The catalyst system according to claim 17, characterized in that, The alkylaluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloro, diisobutylaluminum monochloro, sesquiethylaluminum chloride, and diethylaluminum dichloro. And / or, the external electron donor compound is selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl tert-butyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dicyclohexyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, methylcyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, and (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane; And / or, based on the aluminum content, the molar ratio of the alkylaluminum compound to the external electron donor compound is 3~100:

1.

19. A method for olefin polymerization, characterized in that, The method includes contacting one or more olefins with the catalyst system of any one of claims 15-18 under olefin polymerization conditions.

20. The method according to claim 19, characterized in that, At least one of the olefins is an olefin represented by the formula CH2=CHR, wherein R is hydrogen or a straight-chain or branched alkyl group of C1 to C6. And / or, the conditions for the polymerization of the olefin include: a polymerization temperature of 0°C to 150°C and a polymerization pressure of 0.1 MPa to 10 MPa.

21. The method according to claim 20, characterized in that, The olefin represented by the formula CH2=CHR is at least one of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene, and 4-methyl-1-pentene.

22. The method according to claim 21, characterized in that, The olefin is propylene or a copolymer of propylene and other olefins.

23. The method according to claim 20, characterized in that, The conditions for the olefin polymerization include: polymerization temperature of 60℃~100℃ and polymerization pressure of 0.1MPa~5MPa.

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