Olefin polymerization catalyst, catalyst composition, preparation method and application thereof

Abstract

The present invention provides an olefin polymerization catalyst, a catalyst composition, a preparation method thereof, and an application thereof. The preparation method of the olefin polymerization catalyst comprises the following steps: (1) dissolving a magnesium compound in an alcohol to carry out a first reaction to obtain a first reaction liquid; (2) adding a sulfonamide silane compound to the first reaction liquid to carry out a second reaction to obtain a second reaction liquid; (3) adding the second reaction liquid to a titanium compound to carry out a third reaction to obtain a third reaction liquid; and (4) heating the third reaction liquid and maintaining the temperature to generate a solid to obtain the olefin polymerization catalyst. The olefin polymerization catalyst of the present invention has the advantages of uniform particle size distribution, narrow particle size distribution, low polymer fine powder content, and good hydrogen adjustment sensitivity.

Description

Technical Field

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

[0002] As we all know, in recent years, single-site catalysts, such as metallocene and non-metallocene catalysts, have become a hot topic in polyolefin catalyst research and development. The industrial application of single-site catalysts has also gradually increased, but Ziegler-Natta catalysts still dominate the industrial production of polyolefins. Since the 1980s, a large number of Ziegler-Natta catalyst products have been introduced both domestically and internationally, with catalyst stability and polymerization activity continuously improving. However, currently used catalysts are prone to producing relatively fine polymer particles during the polymerization process. The presence of these fine particles often leads to low bulk density of the polymer, causing blockage of equipment or pipelines, and affecting the long-term operation of the equipment.

[0003] Patent CN101891849B dissolves a magnesium halide compound in an organic solvent to form a homogeneous solution, then drips a transition metal halide to slowly precipitate a solid catalyst. However, the direct dripping of a transition metal halide into a homogeneous magnesium halide solution results in a violent reaction, releasing a large amount of hydrogen chloride gas. This results in poor morphology and uneven particle size distribution of the resulting solid catalyst particles, and easily causes catalyst sticking to the wall. Patent CN102358761B reports a method for preparing an olefin polymerization catalyst. The method first involves dripping a silicon halide compound into a homogeneous organic solvent containing a magnesium halide to obtain a support, and then dripping a transition metal halide into the organic solvent containing the support to obtain a solid polyolefin catalyst component. The catalyst obtained by this method results in a high content of fines in the resulting polymer, making it unsuitable for industrial production.

[0004] Furthermore, in the industrial production of polyolefins, in addition to requiring high catalytic activity and good particle size distribution, catalysts must also exhibit good hydrogen sensitivity in order to produce high-performance polyolefin homopolymers or copolymers. This means that the melt index of the final polymer can be easily adjusted by adjusting the hydrogen partial pressure during polymerization to obtain polyolefin resins with varying properties. However, the hydrogen sensitivity of the aforementioned catalyst systems remains unsatisfactory. Summary of the Invention

[0005] To address the above technical problems, the inventors unexpectedly discovered that adding a novel silane compound to the preparation of an olefin polymerization catalyst improves the catalytic system's hydrogen sensitivity and polymerization activity. Based on this discovery, the present invention provides an olefin polymerization catalyst, a catalyst composition, and methods for preparing and applying the same.

[0006] To achieve the above object, the present invention provides a first aspect of a method for preparing an olefin polymerization catalyst, comprising the following steps:

[0007] (1) dissolving a magnesium compound in alcohol to perform a first reaction to obtain a first reaction solution;

[0008] (2) adding a sulfonamide silane compound to the first reaction solution to carry out a second reaction to obtain a second reaction solution;

[0009] (3) adding the second reaction liquid to the titanium compound to carry out a third reaction to obtain a third reaction liquid;

[0010] (4) heating the third reaction liquid and maintaining the temperature to generate a solid, thereby obtaining the olefin polymerization catalyst;

[0011] The sulfonamide silane compound is selected from at least one compound represented by general formula (I),

[0012]

[0013] Wherein, R1 and R2 are the same or different, R1 and R2 are each independently selected from a hydrogen atom, a halogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted heteroatom-containing ring; R3, R4, and R5 are each independently selected from a C1-C8 straight chain or branched alkyl group, a C1-C8 straight chain or branched alkoxy group.

[0014] According to a specific embodiment of the present invention, preferably, in general formula (I), R1 and R2 are each independently selected from a fluorine atom, a bromine atom, a methyl group, an ethyl group, a phenylsulfonylmethyl group, a difluoromethyl group, a dibromomethyl group, a trifluoromethyl group or a tribromomethyl group.

[0015] According to a specific embodiment of the present invention, preferably, in the general formula (I), at least one of R3, R4, and R5 is a straight or branched alkoxy group selected from C1-C8.

[0016] According to a specific embodiment of the present invention, preferably, in the general formula (I), R3, R4, and R5 are each independently selected from methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, or 3-propoxy.

[0017] According to a specific embodiment of the present invention, preferably, in the general formula (I), at least one of R3, R4, and R5 is selected from methoxy, ethoxy, or 3-propoxy.

[0018] According to a specific embodiment of the present invention, preferably, in the above preparation method, the sulfonamide silane compound is selected from [bis(trifluoromethanesulfonyl)amino]trimethoxysilane, [bis(trifluoromethanesulfonyl)amino]triethoxysilane, [bis(trifluoromethanesulfonyl)amino]tri(3-propoxy)silane, [bis(trifluoromethanesulfonyl)amino]methyldimethoxysilane, [bis(trifluoromethanesulfonyl)amino]methyldiethoxysilane, [bis(trifluoromethanesulfonyl)amino]methyldi(3-propoxy)silane, [bis(trifluoromethanesulfonyl)amino]dimethylmethoxysilane, [bis(trifluoromethanesulfonyl)amino]dimethylethoxysilane, [bis(trifluoromethanesulfonyl)amino]dimethyl(3-propoxy)silane, [bis(trifluoromethanesulfonyl)amino]ethyldimethoxysilane, [bis(trifluoromethanesulfonyl)amino] ]ethyldiethoxysilane, [bis(trifluoromethanesulfonyl)amino]ethylbis(3-propoxy)silane, [bis(trifluoromethanesulfonyl)amino]diethylmethoxysilane, [bis(trifluoromethanesulfonyl)amino]diethylethoxysilane, [bis(trifluoromethanesulfonyl)amino]diethyl(3-propoxy)silane, [bis(tribromomethanesulfonyl)amino](3-propyl)dimethoxysilane, [bis(tribromomethanesulfonyl)amino]diethyl One or more of [bis(tribromomethanesulfonyl)amino](3-propyl)diethoxysilane, [bis(tribromomethanesulfonyl)amino](3-propyl)bis(3-propoxy)silane, [bis(tribromomethanesulfonyl)amino]bis(3-propyl)methoxysilane, [bis(tribromomethanesulfonyl)amino]bis(3-propyl)ethoxysilane, and [bis(tribromomethanesulfonyl)amino]bis(3-propyl)(3-propoxy)silane.

[0019] According to a specific embodiment of the present invention, the present invention provides several structural formulas of preferred sulfonamide silane compounds (Compounds AE), which are specifically as follows.

[0020]

[0021]

[0022] In the present invention, the sulfonamide silane compound can be prepared by the following method: reacting the compound represented by general formula (II) and alkyl lithium in tetrahydrofuran or toluene under a protective gas atmosphere at -80°C to 30°C for 1-48 hours, adding R3R4R5SiCl to the reaction system without separation, and continuing to react at -80°C to 30°C for 1-48 hours to obtain the silane compound after the reaction is completed; wherein the molar ratio of the compound represented by general formula (II): alkyl lithium: R3R4R5SiCl is 1:(1-5):(1-5).

[0023]

[0024] According to a specific embodiment of the present invention, preferably, in the above preparation method, the first reaction temperature is 100° C.-150° C., and the first reaction time is 2-6 h.

[0025] According to a specific embodiment of the present invention, preferably, in the above preparation method, the second reaction temperature is 30° C.-60° C., and the second reaction time is 1-5 h.

[0026] According to a specific embodiment of the present invention, preferably, in the above preparation method, the third reaction temperature is -25°C to 0°C, and the second reaction time is 0.5-8h.

[0027] According to a specific embodiment of the present invention, preferably, in the above preparation method, the third reaction liquid is heated to 80°C-130°C and maintained for 1-4 hours, and the heating rate of the third reaction liquid is 10°C / h-60°C / h.

[0028] According to a specific embodiment of the present invention, preferably, in the above preparation method, the molar ratio of the silane compound to the magnesium compound is 0.01-10, more preferably 0.05-2.

[0029] According to a specific embodiment of the present invention, preferably, in the above preparation method, the molar ratio of the titanium compound to the magnesium compound is 1-100, more preferably 20-50.

[0030] According to a specific embodiment of the present invention, preferably, in the above preparation method, the molar ratio of the alcohol to the magnesium compound is 1-10, more preferably 2-6.

[0031] According to a specific embodiment of the present invention, preferably, in the above preparation method, the magnesium compound is selected from one or more of magnesium dihalide, hydrate of magnesium dihalide, alcoholate of magnesium dihalide, hydrocarbyl magnesium halide and hydrocarbyloxy magnesium halide, preferably magnesium dichloride.

[0032] According to a specific embodiment of the present invention, preferably, in the above preparation method, the titanium compound is selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, triethoxytitanium monochloride, diethoxytitanium dichloride and trichloromonoethoxytitanium.

[0033] According to a specific embodiment of the present invention, preferably, in the above preparation method, the alcohol is selected from one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, 2-methylpentanol, 2-ethylbutanol, heptanol, 2-ethylhexanol, octanol, decanol, dodecanol, tetradecanol and octadecyl alcohol, more preferably one or more of 2-ethylhexanol, 2-methylpentanol and 2-ethylbutanol.

[0034] According to a specific embodiment of the present invention, preferably, the preparation method further comprises filtering, washing and drying the solid.

[0035] According to a specific embodiment of the present invention, preferably, in the above preparation method, the solid is washed with an inert diluent, and the inert diluent is selected from one or more of hexane, heptane, octane, nonane and decane, preferably hexane and decane.

[0036] According to a specific embodiment of the present invention, preferably, in the above preparation method, the molar ratio of the inert diluent to the magnesium compound is 1-150, preferably 5-30.

[0037] The second aspect of the present invention provides an olefin polymerization catalyst obtained by the above preparation method.

[0038] The third aspect of the present invention provides a catalyst composition comprising the above-mentioned olefin polymerization catalyst and an organoaluminum compound, wherein the molar ratio of aluminum element to titanium element in the catalyst composition is 10-1000, preferably 50-500.

[0039] According to a specific embodiment of the present invention, preferably, in the above catalyst composition, the general formula of the organoaluminum compound is AlR' n X 3-n , wherein R' is an alkyl group, X is a halogen group, and n is 1, 2 or 3.

[0040] According to a specific embodiment of the present invention, preferably, in the above catalyst composition, the organoaluminum compound is selected from one or more of triethylaluminum, triisobutylaluminum, diethylaluminum monochloride, ethylaluminum dichloride and sesquiethylaluminum chloride, preferably triethylaluminum and triisobutylaluminum.

[0041] A fourth aspect of the present invention provides a use of the above-mentioned olefin polymerization catalyst or the above-mentioned catalyst composition in olefin polymerization.

[0042] According to a specific embodiment of the present invention, preferably, in the above application, the olefin polymerization is homopolymerization of ethylene or propylene.

[0043] According to a specific embodiment of the present invention, preferably, in the above application, the olefin polymerization is a copolymerization of ethylene or propylene with an α-olefin, and the α-olefin is selected from propylene, butene, pentene, hexene, octene, 4-methyl-1-pentene, and more preferably propylene.

[0044] According to a specific embodiment of the present invention, preferably, in the above application, the polymerization method adopts a slurry method, a gas phase method or a solution method.

[0045] The olefin polymerization catalyst of the present invention, its preparation method and application have the following beneficial effects:

[0046] The olefin polymerization catalyst of the present invention is suitable for homopolymerization of ethylene or propylene, as well as copolymerization of ethylene with propylene or other α-olefins. Compared with existing catalysts, the olefin polymerization catalyst of the present invention has the advantages of uniform and narrow particle size distribution, low polymer fines content, and good hydrogen regulation sensitivity. DETAILED DESCRIPTION

[0047] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be understood as limiting the scope of implementation of the present invention.

[0048] In a specific embodiment of the present invention, the evaluation and analysis method used includes:

[0049] 1. According to the national standard GB / T 3682-2018, the melt index of the polymer product was measured with a 5 kg weight;

[0050] 2. Determine the bulk density of the polymer product according to the national standard GB / T 1636-2008;

[0051] 3. According to the national standard GB / T 21843-2008, the particle size distribution of the polymer product was determined;

[0052] 4. Catalyst polymerization evaluation: Ethylene slurry polymerization was carried out as described in the examples to obtain polyethylene. The ratio of the mass of polyethylene to the mass of the catalyst was the catalyst polymerization activity, and the unit of activity was kgPE / (gcat.h).

[0053] In a specific embodiment of the present invention, the preparation method of compound AE used in the sulfonamide silane compound is as follows:

[0054] Preparation method of compound A: Take a 200ml Schlenk flask, add 4g of bistrifluoromethylsulfonimide and 40ml of tetrahydrofuran (THF), cool to 0°C, slowly add 30ml of n-butyllithium (1.6M n-hexane solution) dropwise, react for 2h, then add 7g of dimethylmethoxysilyl chloride dropwise, naturally warm to room temperature and react for 24h, remove the solvent in vacuo, add 60ml of n-hexane, filter, then remove the n-hexane in vacuo, and distill under reduced pressure to obtain compound A.

[0055] Preparation method of compound B: Take a 200ml Schlenk flask, add 4g of bistrifluoromethylsulfonimide and 40ml of THF, cool to 0°C, slowly add 30ml of n-butyllithium (1.6M n-hexane solution) dropwise, react for 2h, then add 7g of methyldimethoxysilyl chloride dropwise, naturally warm to room temperature and react for 24h, remove the solvent in vacuo, add 60ml of n-hexane, filter, then remove the n-hexane in vacuo, and distill under reduced pressure to obtain compound B.

[0056] Preparation method of compound C: Take a 200ml Schlenk flask, add 4g of bistrifluoromethylsulfonimide and 40ml of THF, cool to 0°C, slowly add 30ml of n-butyllithium (1.6M n-hexane solution) dropwise, react for 2h, then add 7g of trimethoxysilyl chloride dropwise, naturally warm to room temperature and react for 24h, remove the solvent in vacuo, add 60ml of n-hexane, filter, then remove the n-hexane in vacuo, and distill under reduced pressure to obtain compound C.

[0057] Preparation method of compound D: Take a 200ml Schlenk flask, add 8g of bistrifluoromethylsulfonyl imide and 80ml of THF, cool to 0°C, slowly add 60ml of n-butyl lithium (1.6M n-hexane solution) dropwise, react for 2h, then add 14g of monomethyltrichlorosilane dropwise, naturally warm to room temperature and react for 24h, remove the solvent in vacuo, add 100ml of n-hexane and filter, then remove the n-hexane in vacuo, and distill under reduced pressure to obtain the intermediate [bis(trifluoromethylsulfonyl)amino]methyldichlorosilane; Take a 500ml Schlenk flask, add 5g of the intermediate [bis(trifluoromethylsulfonyl)amino]methyldichlorosilane synthesized above and 100mL of toluene, then add 7.5g of anhydrous ethanol and 15g of triethylamine in toluene solution dropwise, react for 12h, remove the solvent under vacuum, add n-hexane and filter, then remove the n-hexane in vacuo, and distill under reduced pressure to obtain compound D.

[0058] Preparation method of compound E: Take a 200ml Schlenk flask, add 4g of bistrifluoromethylsulfonimide and 40ml of THF, cool to 0°C, slowly add 30ml of n-butyllithium (1.6M n-hexane solution) dropwise, react for 2h, then add 7g of triethoxysilyl chloride dropwise, naturally warm to room temperature and react for 24h, remove the solvent in vacuo, add 60ml of n-hexane, filter, then remove the n-hexane in vacuo, and distill under reduced pressure to obtain compound E.

[0059] The present invention is described in detail below with reference to specific embodiments.

[0060] Example 1

[0061] This embodiment provides a preparation method and application of an olefin polymerization catalyst, which are specifically as follows:

[0062] (1) Preparation of olefin polymerization catalyst:

[0063] In a reactor thoroughly purged with nitrogen, 5g of magnesium dichloride, 50ml of n-decane, and 23ml of isooctyl alcohol were added, stirred, and heated to 130°C. The reaction was then continued at this temperature for 3 hours, until the solid completely dissolved, forming a homogeneous, transparent solution. The temperature was then lowered to 50°C, and 2.8ml of [bis(trifluoromethylsulfonyl)amino]dimethylmethoxysilane (Compound A) was added and allowed to react for 2 hours to obtain a homogeneous solution. The resulting homogeneous solution was cooled to room temperature and then added dropwise over 1 hour to 200ml of titanium tetrachloride maintained at -20°C. Following the addition, the mixture was maintained at -20°C for 1 hour, then heated to 110°C over 3 hours and maintained at this temperature for 2 hours. After the 2-hour reaction, the resulting solid was separated by hot filtration and then thoroughly washed with hexane until no precipitated titanium compound could be detected in the washing solution. After drying, the resulting solid catalyst, a spherical solid catalyst with good fluidity and uniform particle size distribution, was obtained, i.e., an olefin polymerization catalyst.

[0064] (2) Ethylene polymerization:

[0065] A 2 L polymerization kettle was alternately filled with hydrogen and evacuated three times. 1.0 L of hexane, 5 mmol of triethylaluminum, and the olefin polymerization catalyst prepared in this example were added. The reactor was heated to 70° C. Hydrogen was introduced to a pressure of 0.28 MPa, and then ethylene was introduced to a total pressure of 0.73 MPa. Polymerization was then carried out at 80° C. for 2 hours. The polymerization results are shown in Table 1.

[0066] Example 2

[0067] This embodiment provides a preparation method and application of an olefin polymerization catalyst, which are specifically as follows:

[0068] (1) Preparation of olefin polymerization catalyst:

[0069] In a reactor thoroughly purged with nitrogen, 5g of magnesium dichloride, 40ml of n-decane, and 23ml of isooctyl alcohol were added. The mixture was stirred and heated to 130°C. The reaction was continued at this temperature for 3 hours, during which the solid completely dissolved to form a homogeneous, transparent solution. The temperature was then lowered to 50°C, and 2.8ml of [bis(trifluoromethylsulfonyl)amino]dimethylmethoxysilane (Compound A) was added and allowed to react for 2 hours to obtain a homogeneous solution. The homogeneous solution obtained above was cooled to room temperature and then added dropwise over 1 hour to 100ml of titanium tetrachloride maintained at -20°C. After the addition was complete, the mixture was maintained at -20°C for 1 hour, then the system was heated to 110°C over 3 hours and maintained at this temperature for 2 hours. After the 2-hour reaction, the resulting solid was separated by hot filtration and then thoroughly washed with hexane until no precipitated titanium compound could be detected in the washing solution. After drying, the resulting solid catalyst product, an olefin polymerization catalyst, exhibited good fluidity, uniform particle size distribution, and a spherical shape.

[0070] (2) Ethylene polymerization:

[0071] A 2 L polymerization kettle was alternately filled with hydrogen and evacuated three times. 1.0 L of hexane, 5 mmol of triethylaluminum, and the olefin polymerization catalyst prepared in this example were added. The reactor was heated to 70° C. Hydrogen was introduced to a pressure of 0.28 MPa, and then ethylene was introduced to a total pressure of 0.73 MPa. Polymerization was then carried out at 80° C. for 2 hours. The polymerization results are shown in Table 1.

[0072] Example 3

[0073] This embodiment provides a preparation method and application of an olefin polymerization catalyst, which are specifically as follows:

[0074] (1) Preparation of olefin polymerization catalyst:

[0075] In a reactor thoroughly purged with nitrogen, 5g of magnesium dichloride, 50ml of n-decane, and 23ml of isooctyl alcohol were added. The mixture was stirred and heated to 130°C. The reaction was continued at this temperature for 3 hours, during which the solid completely dissolved to form a homogeneous, transparent solution. The temperature was then lowered to 50°C, and 1.4ml of [bis(trifluoromethanesulfonyl)amino]dimethylmethoxysilane (Compound A) was added and allowed to react for 2 hours to obtain a homogeneous solution. The homogeneous solution was cooled to room temperature and then added dropwise over 1 hour to 200ml of titanium tetrachloride maintained at -20°C. After the addition was complete, the mixture was maintained at -20°C for 1 hour, then the system was heated to 110°C over 3 hours and maintained at this temperature for 2 hours. After the 2-hour reaction, the resulting solid was separated by hot filtration and then thoroughly washed with hexane until no precipitated titanium compound could be detected in the washing solution. After drying, the resulting solid catalyst, which had good fluidity, uniform particle size distribution, and a spherical shape, was obtained as a finished olefin polymerization catalyst.

[0076] (2) Ethylene polymerization:

[0077] A 2 L polymerization kettle was alternately filled with hydrogen and evacuated three times. 1.0 L of hexane, 5 mmol of triethylaluminum, and the olefin polymerization catalyst prepared in this example were added. The reactor was heated to 70° C. Hydrogen was introduced to a pressure of 0.28 MPa, and then ethylene was introduced to a total pressure of 0.73 MPa. Polymerization was then carried out at 80° C. for 2 hours. The polymerization results are shown in Table 1.

[0078] Example 4

[0079] This embodiment provides a preparation method and application of an olefin polymerization catalyst, which are specifically as follows:

[0080] The preparation method of the olefin polymerization catalyst is the same as that of Example 1, except that [bis(trifluoromethanesulfonyl)amino]methyldimethoxysilane (Compound B) is used instead of Compound A.

[0081] The ethylene polymerization method was the same as in Example 1. The polymerization results are shown in Table 1.

[0082] Example 5

[0083] This embodiment provides a preparation method and application of an olefin polymerization catalyst, which are specifically as follows:

[0084] The preparation method of the olefin polymerization catalyst is the same as that of Example 1, except that [bis(trifluoromethanesulfonyl)amino]trimethoxysilane (Compound C) is used instead of Compound A.

[0085] The ethylene polymerization method was the same as in Example 1. The polymerization results are shown in Table 1.

[0086] Example 6

[0087] This embodiment provides a preparation method and application of an olefin polymerization catalyst, which are specifically as follows:

[0088] The preparation method of the olefin polymerization catalyst is the same as that of Example 1, except that [bis(trifluoromethanesulfonyl)amino]methyldiethoxysilane (Compound D) is used instead of Compound A.

[0089] The ethylene polymerization method was the same as in Example 1. The polymerization results are shown in Table 1.

[0090] Example 7

[0091] This embodiment provides a preparation method and application of an olefin polymerization catalyst, which are specifically as follows:

[0092] The preparation method of the olefin polymerization catalyst is the same as that of Example 1, except that [bis(trifluoromethanesulfonyl)amino]triethoxysilane (Compound E) replaces Compound A.

[0093] The ethylene polymerization method was the same as in Example 1. The polymerization results are shown in Table 1.

[0094] Example 8

[0095] This embodiment provides a preparation method and application of an olefin polymerization catalyst, which are specifically as follows:

[0096] The preparation method of the olefin polymerization catalyst is the same as that of Example 1, except that the amount of [bis(trifluoromethanesulfonyl)amino]dimethylmethoxysilane (Compound A) added is 3.7 ml.

[0097] The ethylene polymerization method was the same as in Example 1. The polymerization results are shown in Table 1.

[0098] Example 9

[0099] This embodiment provides a preparation method and application of an olefin polymerization catalyst, which are specifically as follows:

[0100] The preparation method of the olefin polymerization catalyst is the same as that of Example 1, except that the amount of [bis(trifluoromethanesulfonyl)amino]dimethylmethoxysilane (Compound A) added is 1.5 ml.

[0101] The ethylene polymerization method was the same as in Example 1. The polymerization results are shown in Table 1.

[0102] Example 10

[0103] This embodiment provides a preparation method and application of an olefin polymerization catalyst, which are specifically as follows:

[0104] (1) Preparation of olefin polymerization catalyst: same as in Example 1.

[0105] (2) Ethylene polymerization:

[0106] A 2 L polymerization kettle was alternately filled with hydrogen and evacuated three times. 1.0 L of hexane, 5 mmol of triethylaluminum, and the above-described solid catalyst components were added. The reactor was heated to 70°C, and hydrogen was introduced to a pressure of 0.73 MPa. Ethylene was then introduced to a total pressure of 1.0 MPa. Polymerization was then carried out at 80°C for 2 hours. The polymerization results are shown in Table 1.

[0107] Example 11

[0108] This embodiment provides a preparation method and application of an olefin polymerization catalyst, which are specifically as follows:

[0109] (1) Preparation of olefin polymerization catalyst: same as in Example 2.

[0110] (2) Ethylene polymerization:

[0111] A 2 L polymerization kettle was alternately filled with hydrogen and evacuated three times. 1.0 L of hexane, 5 mmol of triethylaluminum, and the above-described solid catalyst components were added. The reactor was heated to 70°C, and hydrogen was introduced to a pressure of 0.73 MPa. Ethylene was then introduced to a total pressure of 1.0 MPa. Polymerization was then carried out at 80°C for 2 hours. The polymerization results are shown in Table 1.

[0112] Example 12

[0113] This embodiment provides a preparation method and application of an olefin polymerization catalyst, which are specifically as follows:

[0114] (1) Preparation of olefin polymerization catalyst: same as in Example 1.

[0115] (2) Ethylene copolymerization:

[0116] A 2 L polymerization kettle was alternately filled with hydrogen and evacuated three times. 1.0 L of hexane, 5 mmol of triethylaluminum, and the above-described solid catalyst component were added. 10 mL of 1-hexene was also added. The reactor was heated to 70°C, and hydrogen was introduced to a pressure of 0.28 MPa. Ethylene was then introduced to a total pressure of 0.73 MPa. Polymerization was then carried out at 80°C for 2 hours. The polymerization results are shown in Table 1.

[0117] Comparative Example 1

[0118] This comparative example provides a method for preparing a catalyst, which is as follows:

[0119] The catalyst was prepared in the same manner as in Example 1, with the catalyst component being prepared in the same manner as in Example 1, except that the sulfonamide silane compound was not added. The catalyst was difficult to precipitate, and the solid was difficult to settle, resulting in no catalyst formation.

[0120] Comparative Example 2

[0121] This comparative example provides a preparation method and application of a catalyst, which are as follows:

[0122] The preparation method of the catalyst is the same as that of Example 1, except that tetraethoxysilane is used instead of compound A.

[0123] The ethylene polymerization method was the same as in Example 1. The polymerization results are shown in Table 1.

[0124] Comparative Example 3

[0125] This comparative example provides a preparation method and application of a catalyst, which are as follows:

[0126] (1) Preparation of catalyst: same as Comparative Example 2.

[0127] (2) Ethylene polymerization:

[0128] A 2 L polymerization kettle was alternately filled with hydrogen and evacuated three times. 1.0 L of hexane, 5 mmol of triethylaluminum, and the above-described solid catalyst components were added. The reactor was heated to 70°C, and hydrogen was introduced to a pressure of 0.73 MPa. Ethylene was then introduced to a total pressure of 1.0 MPa. Polymerization was then carried out at 80°C for 2 hours. The polymerization results are shown in Table 1.

[0129] Table 1 Polymerization results of Examples and Comparative Examples

[0130]

[0131] As can be seen from the polymerization data in Table 1, the addition of the sulfonamide silane compound increases the bulk density of the polymer, makes the polymer particle size distribution more uniform, reduces the content of fine powder >200 mesh, and increases the melt index of the obtained polymer. In particular, the melt index of the obtained polymer is greatly improved under high hydrogen polymerization conditions (hydrogen pressure = 0.73 MPa). This indicates that the addition of the sulfonamide silane compound of the present invention significantly improves the hydrogen modulation sensitivity of the catalyst.

Claims

1. A method for preparing an olefin polymerization catalyst, characterized in that: The steps include: (1) dissolving a magnesium compound in alcohol to perform a first reaction to obtain a first reaction solution; (2) adding a sulfonamide silane compound to the first reaction solution to carry out a second reaction to obtain a second reaction solution; (3) adding the second reaction liquid to the titanium compound to carry out a third reaction to obtain a third reaction liquid; (4) heating the third reaction liquid and maintaining the temperature to generate a solid, thereby obtaining the olefin polymerization catalyst; The sulfonamide silane compound is selected from at least one compound represented by general formula (I), Wherein, R1 and R2 are the same or different, R1 and R2 are each independently selected from a hydrogen atom, a halogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted heteroatom-containing ring; R3, R4, and R5 are each independently selected from a C1-C8 straight chain or branched alkyl group, a C1-C8 straight chain or branched alkoxy group, and at least one of R3, R4, and R5 is selected from a C1-C8 straight chain or branched alkoxy group.

2. The preparation method according to claim 1, characterized in that R1 and R2 are each independently selected from a fluorine atom, a bromine atom, a methyl group, an ethyl group, a phenylsulfonylmethyl group, a difluoromethyl group, a dibromomethyl group, a trifluoromethyl group or a tribromomethyl group.

3. The preparation method according to claim 1, characterized in that R3, R4, and R5 are each independently selected from methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, or 3-propoxy, and at least one of R3, R4, and R5 is selected from methoxy, ethoxy, or 3-propoxy.

4. The preparation method according to claim 1, characterized in that The sulfonamide silane compound is selected from [bis(trifluoromethanesulfonyl)amino]trimethoxysilane, [bis(trifluoromethanesulfonyl)amino]triethoxysilane, [bis(trifluoromethanesulfonyl)amino]tri(3-propoxy)silane, [bis(trifluoromethanesulfonyl)amino]methyldimethoxysilane, [bis(trifluoromethanesulfonyl)amino]methyldiethoxysilane, [bis(trifluoromethanesulfonyl)amino]methyldi(3-propoxy)silane, [bis(trifluoromethanesulfonyl)amino]dimethylmethoxysilane, [bis(trifluoromethanesulfonyl)amino]dimethylethoxysilane, [bis(trifluoromethanesulfonyl)amino]dimethyl(3-propoxy)silane, [bis(trifluoromethanesulfonyl)amino]ethyldimethoxysilane, [bis(trifluoromethanesulfonyl)amino]ethyldiethoxysilane, [bis(trifluoromethanesulfonyl)amino]methyldi(3-propoxy)silane. One or more of [bis(trifluoromethanesulfonyl)amino]ethylbis(3-propoxy)silane, [bis(trifluoromethanesulfonyl)amino]diethylmethoxysilane, [bis(trifluoromethanesulfonyl)amino]diethylethoxysilane, [bis(trifluoromethanesulfonyl)amino]diethyl(3-propoxy)silane, [bis(tribromomethanesulfonyl)amino](3-propyl)dimethoxysilane, [bis(tribromomethanesulfonyl)amino](3-propyl)diethoxysilane, [bis(tribromomethanesulfonyl)amino](3-propyl)bis(3-propoxy)silane, [bis(tribromomethanesulfonyl)amino]bis(3-propyl)methoxysilane, [bis(tribromomethanesulfonyl)amino]bis(3-propyl)ethoxysilane, and [bis(tribromomethanesulfonyl)amino]bis(3-propyl)(3-propoxy)silane.

5. The preparation method according to claim 1, characterized in that The first reaction temperature is 100° C.-150° C., and the first reaction time is 2-6 hours.

6. The preparation method according to claim 1, characterized in that The second reaction temperature is 30° C.-60° C., and the second reaction time is 1-5 h.

7. The preparation method according to claim 1, characterized in that The third reaction temperature is -25°C to 0°C, and the third reaction time is 0.5-8h.

8. The preparation method according to claim 1, characterized in that The third reaction liquid is heated to 80° C.-130° C. and maintained at this temperature for 1-4 hours. The heating rate of the third reaction liquid is 10° C. / h-60° C. / h.

9. The preparation method according to claim 1, characterized in that The molar ratio of the silane compound to the magnesium compound is 0.01-10.

10. The preparation method according to claim 9, characterized in that The molar ratio of the silane compound to the magnesium compound is 0.05-2.

11. The preparation method according to claim 1, characterized in that The molar ratio of the titanium compound to the magnesium compound is 1-100.

12. The preparation method according to claim 11, characterized in that The molar ratio of the titanium compound to the magnesium compound is 20-50.

13. The preparation method according to claim 1, characterized in that The molar ratio of the alcohol to the magnesium compound is 1-10.

14. The preparation method according to claim 13, characterized in that The molar ratio of the alcohol to the magnesium compound is 2-6.

15. The preparation method according to claim 1, characterized in that The magnesium compound is selected from one or more of magnesium dihalide, hydrate of magnesium dihalide, alcoholate of magnesium dihalide, hydrocarbyl magnesium halide and hydrocarbyloxy magnesium halide.

16. The preparation method according to claim 1, characterized in that The titanium compound is selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium triethoxide monochloride, titanium diethoxide dichloride and titanium triethoxide monochloride.

17. The preparation method according to claim 1, characterized in that The alcohol is selected from one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, 2-methylpentanol, 2-ethylbutanol, heptanol, 2-ethylhexanol, octanol, decanol, dodecanol, tetradecanol and octadecyl alcohol.

18. The preparation method according to claim 1, characterized in that The preparation method further comprises filtering, washing and drying the solid.

19. The preparation method according to claim 18, characterized in that The solid is washed with an inert diluent, wherein the inert diluent is selected from one or more of hexane, heptane, octane, nonane and decane.

20. The preparation method according to claim 19, characterized in that The molar ratio of the inert diluent to the magnesium compound is 1-150.

21. The preparation method according to claim 20, characterized in that The molar ratio of the inert diluent to the magnesium compound is 5-30.

22. An olefin polymerization catalyst obtained by the preparation method according to any one of claims 1 to 21.

23. A catalyst composition, characterized in that The olefin polymerization catalyst according to claim 22 and an organic aluminum compound are included, wherein the molar ratio of aluminum element to titanium element in the catalyst composition is 10-1000.

24. The catalyst composition according to claim 23, characterized in that The molar ratio of aluminum element to titanium element in the catalyst composition is 50-500.

25. The catalyst composition according to claim 23, characterized in that The general formula of the organoaluminum compound is AlR' n X 3-n , wherein R' is an alkyl group, X is a halogen group, and n is 1, 2 or 3.

26. The catalyst composition according to claim 23, characterized in that The organoaluminum compound is selected from one or more of triethylaluminum, triisobutylaluminum, diethylaluminum monochloride, ethylaluminum dichloride and sesquiethylaluminum chloride.

27. Use of the olefin polymerization catalyst according to claim 22 or the catalyst composition according to any one of claims 23 to 26 in olefin polymerization.

28. The use according to claim 27, characterized in that The olefin polymerization is homopolymerization of ethylene or propylene.

29. The use according to claim 27, characterized in that The olefin polymerization is copolymerization of ethylene or propylene with α-olefin, and the α-olefin is selected from propylene, butene, pentene, hexene, octene, and 4-methyl-1-pentene.

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