Spherical-like ultra-macroporous mesoporous material and polyolefin catalyst containing the same

Abstract

A sphere-like ultra-macroporous mesoporous material, a polyolefin catalyst, a method for preparing the same, and an olefin polymerization process are disclosed. The sphere-like ultra-macroporous material has a two-dimensional hexagonal ordered pore channel structure; the mesoporous material has an average pore diameter of 10 nm to 15 nm, and an average pore diameter of 300 nm. 2 / g~400m 2 The mesoporous material has a specific surface area of ​​1 / g and an average particle size of 1-3 μm; the water content by mass in the mesoporous material is less than 1 ppm, and the oxygen content by mass in the mesoporous material is less than 1 ppm, based on the total mass of the mesoporous material. When polyolefin catalysts prepared using mesoporous materials as supports are used in olefin polymerization reactions, the catalysts exhibit high catalytic efficiency and can produce polyolefin products with narrow molecular weight distributions and good melt indices.

Description

Technical Field

[0001] The present disclosure relates to the technical field of heterogeneous catalytic olefin polymerization reactions, and specifically to spherical-like supermacroporous mesoporous materials and methods for preparing the same, polyolefin catalysts containing the aforementioned spherical-like supermacroporous mesoporous materials and methods for preparing the same, and olefin polymerization methods using the above polyolefin catalysts.

Background Art

[0002] The preparation technology of the carrier is one of the core technologies in the production of polyolefin catalysts. Also, looking at the preparation technologies of various current production processes, the carriers used are mainly silica gel. Ordinary silica gel cannot be used as a carrier for polyolefin catalysts. Carrier silica gel for polyolefin catalysts has high technical requirements such as a certain bulk density, specific surface area, pore structure (pore volume, pore diameter, pore distribution), grinding strength, etc. Therefore, the development of such carrier silica gel is difficult.

[0003] WO2020083386A1 discloses a polyolefin catalyst component containing a mesoporous material, as well as its preparation method and use. The mesoporous material is heat-activated, and the mesoporous material is selected from the group consisting of: a) a mesoporous material having a two-dimensional hexagonal channel structure; b) an eggshell-shaped mesoporous material having a two-dimensional hexagonal channel structure; c) spherical mesoporous silica having a body-centered cubic structure; and d) a hexagonal mesoporous material having a cubic cage-shaped channel structure. The document discloses that when using the above mesoporous material in a polyolefin catalyst and using the polyolefin catalyst in an olefin polymerization reaction, a polyolefin product with higher catalytic efficiency, a narrower molecular weight distribution, and a better melt index can be obtained. However, the catalytic efficiency of the polyolefin catalyst needs to be further improved.

Summary of the Invention

[0004] Through intensive research, the inventors of the present invention have found that a novel spherical-like supermacroporous mesoporous material is particularly suitable for use as a carrier for polyolefin catalysts, and that the spherical-like supermacroporous mesoporous material can be easily prepared. The polyolefin catalyst prepared by using this spherical-like supermacroporous mesoporous material as a carrier has extremely high catalytic efficiency.

[0005] Therefore, an object of the present disclosure is to provide a mesoporous material having a two-dimensional hexagonal regular channel structure, an average pore diameter of 10 nm to 15 nm, a specific surface area of 300 m 2 / g to 400 m 2 / g, and an average particle size of 1 μm to 3 μm; Based on the total mass of the mesoporous material, the mass content of water in the mesoporous material is less than 1 ppm, preferably less than 0.5 ppm, more preferably less than 0.1 ppm, and the mass content of oxygen in the mesoporous material is less than 1 ppm, preferably less than 0.5 ppm, more preferably less than 0.1 ppm.

[0006] Another object of the present disclosure is to provide a method for preparing a mesoporous material, the method comprising the following: (1) Mixing and contacting a silicon source, an acid agent, ammonium fluoride, and heptane in the presence of a templating agent and water, and subjecting the mixture obtained from the mixing and contacting to crystallization, filtration, and drying in that order to obtain a raw material powder of the mesoporous material; (2) Subjecting the raw material powder of the mesoporous material to a templating agent removal treatment, a primary thermal activation treatment, and a secondary thermal activation treatment in that order to obtain the mesoporous material.

[0007] Another object of the present disclosure is to provide a polyolefin catalyst comprising a carrier and a magnesium component, a titanium component, and an optional electron donor component supported on the carrier, wherein the carrier is the aforementioned mesoporous material.

[0008] Still another object of the present disclosure is to provide a method for preparing the above polyolefin catalyst, the method comprising: (i) impregnating the mesoporous material with (ia) a solution containing a magnesium component and then a solution containing a titanium component, (ib) a solution containing a titanium component and then a solution containing a magnesium component, or (ic) a solution containing both a titanium component and a magnesium component under an inert atmosphere to obtain a slurry; and (ii) spray-drying the slurry resulting from step (i) to obtain a polyolefin catalyst.

[0009] Still another object of the present disclosure is to provide an olefin polymerization method comprising: a) polymerizing an olefin monomer in the presence of the above polyolefin catalyst and a cocatalyst under polymerization reaction conditions to obtain a polyolefin; and b) recovering the polyolefin.

[0010] The mesoporous material of the present disclosure has a two-dimensional hexagonal regular channel structure and a spherical-like morphology. Due to its ultra-large and regular channel structure, it has significant advantages in reducing powder aggregation and improving fluidity. By using this spherical-like mesoporous material as a carrier for the polyolefin catalyst, the advantages of microspheres and the mesoporous material can be combined, that is, not only can the characteristics of the high specific surface area, large pore volume, large pore diameter, and narrow pore diameter distribution of the mesoporous material be retained, but also the aggregation of the mesoporous material can be reduced, thereby increasing their fluidity. The resulting polyolefin catalyst particles have a stable structure and high strength, are not easily broken, have a small particle size, a uniform particle size distribution, and a narrow particle size distribution curve, can effectively control the water content of the particles, prevent the carrier particles from deliquescing and binding, avoid the aggregation of the catalyst during use, and improve their fluidity. These advantages bring convenience to the storage, transportation, post-processing, and utilization of the resulting polyolefin catalyst.

[0011] In addition, due to the large average pore diameter of the mesoporous material, the active ingredient of the polyolefin catalyst can not only be supported on the outer surface of the mesoporous material, but also enter the abundant internal pores. In particular, the hexagonal straight-through channels and spherical-like structure of the mesoporous material are also suitable for the entry of the active ingredient of the catalyst, and the obtained catalyst has excellent catalytic performance.

[0012] Furthermore, by using the method for preparing the spherical-like mesoporous material of the present disclosure, a spherical-like mesoporous material with small particle size, narrow particle size distribution, medium specific surface area, large pore volume, large pore diameter, and narrow pore diameter distribution can be obtained without grinding. In addition, the mesoporous material has good fluidity. Therefore, not only the grinding process is omitted, but also the catalytic efficiency of the catalyst prepared from the mesoporous material can be improved.

[0013] In addition, when preparing a polyolefin catalyst using the method of the present disclosure, a spherical-like polyolefin catalyst can be directly obtained by using spray drying technology. The operation is simple, the obtained slurry can be made finer, and the filling amount of the active ingredient can be effectively increased. The obtained polyolefin catalyst particles have a stable structure and high strength, are not easily broken, have a small particle size, a uniform particle size distribution, and a narrow particle size distribution curve, and have excellent catalytic activity. When the polyolefin catalyst is used for olefin polymerization, a significantly improved conversion rate of the raw materials can be obtained.

[0014] In addition, when the polyolefin catalyst according to the present disclosure is used for olefin polymerization, the molecular weight distribution and melt index of the obtained polyolefin product can be improved, and the obtained polyolefin product has a spherical-like and uniform particle size.

[0015] Other features and advantages of the present disclosure will be described in detail below.

[0016] The accompanying drawings are used to provide a further understanding of the present disclosure and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present disclosure, but do not constitute a limitation to the present disclosure.

Brief Description of the Drawings

[0017]

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Modes for Carrying Out the Invention

[0018] Endpoints and any values within the scope disclosed in this specification are not limited to the exact scope or value, and these scopes or values should be understood to include values close to these scopes or values. For numerical ranges, the end values of the individual ranges, the end values of the individual ranges and the individual point values therebetween, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in this specification.

[0019] According to the regulations of the International Union of Pure and Applied Chemistry (IUPAC), mesoporous materials refer to a class of porous materials having pore diameters between 2 nm and 50 nm. The term "mesoporous material" used in this specification has the same meaning as above.

[0020] As used herein, the term "catalyst" refers to a main catalyst component or a catalyst precursor, which, together with conventional cocatalysts such as alkylaluminum and any external electron donor, constitutes a catalyst system for olefin polymerization.

[0021] As used herein, the term "halogen" refers to fluorine, chlorine, bromine, and iodine.

[0022] In this context, unless otherwise specified, the average particle size and SPAN value of the particle size distribution of the material are measured using a laser particle size distribution analyzer, and the specific surface area, pore volume, and average pore diameter are measured through the nitrogen adsorption method. In this context, unless otherwise specified, the particle size refers to the particle size of the particulate material, and the particle size is represented by the diameter of the sphere when the particulate material is spherical, by the side length of the cube when the particulate material is cubic or approximately cubic in shape, or by the mesh size of the sieve that can just sieve the particulate material when the particulate material is irregular in shape.

[0023] In the present disclosure, room temperature means 23°C ± 2°C.

[0024] In a first aspect, the present disclosure provides a mesoporous material having a two-dimensional hexagonal regular channel structure, an average pore diameter of 10 nm to 15 nm, a specific surface area of 300 m 2 / g to 400 m 2 / g, an average particle size of 1 μm to 3 μm; based on the total mass of the mesoporous material, the mass content of water in the mesoporous material is less than 1 ppm, preferably less than 0.5 ppm, more preferably less than 0.1 ppm, and the mass content of oxygen in the mesoporous material is less than 1 ppm, preferably less than 0.5 ppm, more preferably less than 0.1 ppm.

[0025] In the present disclosure, the mesoporous material is a mesoporous silica particle material.

[0026] The "two-dimensional hexagonal regular channel structure" is a term with an exact meaning in the fields of catalysts and catalyst supports. In the present disclosure, the term "two-dimensional hexagonal regular channel structure" has the same meaning as its ordinary meaning known in the prior art, that is, the channels are regularly distributed uniformly, meaning that the channels are in the shape of hexagonal channels.

[0027] The mesoporous material according to the present disclosure has a form of spherical-like (also referred to as subspherical) particles. The "spherical-like mesoporous material" means that the particle shape of the mesoporous material is nearly spherical, that is, the mesoporous material does not have a completely spherical-like appearance (for example, the requirements for the spherical shape are not met at one or more local positions), but generally has an appearance like a sphere.

[0028] The mesoporous material according to the present disclosure is a spherical-like supermacroporous mesoporous material. As used herein, the term "supermacroporous mesoporous material" refers to a mesoporous material having an average pore diameter of 10 nm or more and the number of pores having a pore diameter of 10 nm or more accounting for more than 50% of the total number of pores.

[0029] In the present disclosure, the water content in the mesoporous material is measured by a Karl Fischer moisture meter, and the oxygen content in the mesoporous material is measured by an oxygen and nitrogen analyzer. In the present disclosure, the water content and oxygen content of the mesoporous material include the water content and oxygen content both in the internal pores of the mesoporous material and on the outer surface of the mesoporous material, respectively. In the present disclosure, ppm refers to the ratio of the mass of oxygen gas or water to the total mass of the mesoporous material.

[0030] The spherical-like supermacroporous mesoporous material according to the present disclosure has a specific two-dimensional hexagonal regular channel structure. The mesoporous channel structure of the mesoporous material is uniformly distributed, has a suitable pore diameter, and the mesoporous material has a small particle size, low moisture and low oxygen content, good mechanical strength, and good structural stability, and particularly contributes to the good dispersion of magnesium-based and titanium-based active components on the surface of the carrier. Thereby, the prepared polyolefin catalyst not only has the advantages of supported catalysts such as good dispersion of metal active components, high filling amount, few side reactions, and simple post-treatment, but also has higher catalytic activity, and thereby, when used in the polymerization of olefin monomers, it ensures that the supported catalyst made by using the spherical-like supermacroporous mesoporous material as the carrier has better catalytic activity and significantly improved conversion rate of raw materials.

[0031] Preferably, the mesoporous material according to the present disclosure has an average pore diameter of 10 nm to 15 nm, a specific surface area of 300 m 2 / g to 400 m 2 / g, and an average particle size of 1 μm to 3 μm. When the spherical-like supermacroporous mesoporous material carrier has a specific surface area of less than 300 m 2 / g, a particle size of less than 1 μm, and / or an average pore diameter of less than 10 nm, the supported catalyst made by using it as the carrier has significantly reduced catalytic activity; when the spherical-like supermacroporous mesoporous material carrier has a specific surface area exceeding 400 m / g, a particle size exceeding 3 μm, and / or an average pore diameter exceeding 15 nm, the supported catalyst made by using it as the carrier tends to aggregate during olefin polymerization, thereby affecting the conversion of olefin monomers in olefin polymerization.

[0032] Furthermore, the structural parameters of the spherical-like supermacroporous mesoporous material having a two-dimensional hexagonal channel structure are an average pore diameter of 11 nm to 13 nm, a specific surface area of 310 m 2 / g to 380 m 2By controlling it within the range of / g and an average particle size of 1.1 μm to 2.9 μm, the supported catalyst produced by using it as a carrier can further increase the conversion rate of the reaction raw materials during olefin polymerization.

[0033] According to the present disclosure, the water content in the mesoporous material is controlled to be less than 0.1 ppm, and the oxygen gas content in the mesoporous material is controlled to be less than 0.1 ppm. Thus, the catalyst produced by using it as a carrier has no tendency to aggregate during olefin polymerization and has excellent catalytic activity.

[0034] In some embodiments, the mesoporous material has a contact angle of 101° to 130°, preferably 115° to 125°, more preferably 118° to 124°. When the mesoporous material has a contact angle of 101° to 130°, when used as a carrier for preparing a supported catalyst, it particularly contributes to the good dispersion of magnesium-based and titanium-based active components on the surface of the carrier. As a result, the prepared polyolefin catalyst not only has the advantages of a supported catalyst such as good dispersion of metal active components, high filling amount, few side reactions, and simple post-treatment, but also has higher catalytic activity. Thereby, when used for the polymerization of olefin monomers, it has been found that the supported catalyst produced by using a spherical-like supermacroporous mesoporous material as a carrier ensures better catalytic activity. Mesoporous materials known in the prior art generally have a contact angle much smaller than 100°. For example, the commercially available mesoporous material product SBA-15 has a contact angle of 20°.

[0035] Furthermore, when the contact angle of the mesoporous material is 115° to 125°, preferably 118° to 124°, the catalyst prepared therefrom has more excellent technical effects.

[0036] In the present disclosure, the contact angle of the mesoporous material is measured by RDAX.

[0037] According to the present disclosure, the mesoporous material is obtained by treating a thermally activated mesoporous material with a chlorine-containing silane. Preferably, the chlorine-containing silane is at least one selected from dichlorodimethoxysilane, monochlorotrimethoxysilane, dichlorodiethoxysilane, and monochlorotriethoxysilane.

[0038] In the present disclosure, the chlorine-containing silane treatment may be achieved by stirring the thermally activated mesoporous material together with the chlorine-containing silane in the presence or absence of another solvent such as an inert solvent, and the treatment temperature may be 20 to 150 °C, preferably 30 to 120 °C, more preferably 40 to 100 °C.

[0039] The amount of the chlorine-containing silane used may be 0.2 to 1.5 g per gram of the thermally activated mesoporous material.

[0040] Hereinafter, the thermal activation treatment will be described.

[0041] In a preferred embodiment of the present disclosure, the mesoporous material has a pore volume of 1 mL / g to 2 mL / g, preferably 1.5 mL / g to 1.9 mL / g. If the pore volume is within the above range, the prepared supported catalyst is less likely to aggregate during olefin polymerization and has better catalytic activity.

[0042] In some embodiments, the mesoporous material according to the present disclosure has a crushing strength of 0.001 N / cm to 0.6 N / cm, preferably 0.01 N / cm to 0.55 N / cm, more preferably 0.1 N / cm to 0.45 N / cm, as measured by the GB3635-1983 standard method. When the mesoporous material has a crushing strength within the above range, the particles of the catalyst prepared therefrom have a stable structure and high strength and are not easily crushed.

[0043] In some embodiments, the mesoporous material according to the present disclosure has a particle size distribution of 0.01 to 3, preferably 0.1 to 2.8. When the mesoporous material has a particle size distribution of 0.01 to 3, the supported catalyst prepared by using it as a carrier does not tend to aggregate during olefin polymerization and has higher catalytic activity.

[0044] In a second aspect, the present disclosure provides a method for preparing a spherical-like mesoporous material, the method comprising the following: (1) Mixing and contacting a silicon source, an acid agent, ammonium fluoride, and heptane in the presence of a templating agent and water, and subjecting the mixture obtained from the mixing and contacting to crystallization, filtration, and drying in that order to obtain a raw material powder of the spherical-like mesoporous material; (2) Subjecting the raw material powder of the spherical-like mesoporous material to a templating agent removal treatment, a primary thermal activation treatment, and a secondary thermal activation treatment in that order to obtain a mesoporous material.

[0045] In some embodiments, in step (1), the operation of mixing and contacting includes mixing at a temperature of 25°C to 60°C for at least 4 minutes and then standing for at least 1 hour. To facilitate uniform mixing of the substances, the mixing and contacting are carried out under stirring conditions in the preferred embodiments of the present disclosure. Preferably, the operation of mixing and contacting includes stirring at a temperature of 25°C to 60°C for 10 minutes to 240 minutes and then standing for 4 hours to 24 hours.

[0046] In some embodiments, the molar ratio of the templating agent:silicon source:acid agent:ammonium fluoride:heptane is 1:2 to 500:100 to 2000:0.7 to 200:20 to 1650. Preferably, the molar ratio of the templating agent:silicon source:acid agent:ammonium fluoride:heptane is 1:10 to 250:200 to 500:1 to 180:50 to 1450.

[0047] In the present disclosure, the combined use of the addition of ammonium fluoride, the use of heptane, and the secondary thermal activation treatment is an important factor for obtaining the spherical-like super macroporous mesoporous material of the present disclosure.

[0048] Preferably, the template agent is a triblock copolymer of polyoxyethylene-polyoxypropylene-polyoxyethylene (EO 20 PO 70 EO 20 ). This template agent is commercially available (for example, it can be purchased from Aldrich under the trade name P123, and the molecular formula is EO 20 PO 70 EO 20 ), or it can be prepared by various existing methods. The number of moles of the template agent is calculated based on the average molecular weight of polyoxyethylene-polyoxypropylene-polyoxyethylene.

[0049] In the present disclosure, examples of the silicon source include, but are not limited to, ethyl orthosilicate, methyl orthosilicate, propyl orthosilicate, sodium orthosilicate, and silica sol, and ethyl orthosilicate is more preferred. The acid agent may be a conventional substance known in the art that can provide acidic conditions such as hydrochloric acid and sulfuric acid, and hydrochloric acid is preferred. In the present disclosure, heptane refers to a straight-chain or branched-chain alkane having 7 carbon atoms, preferably n-heptane.

[0050] According to the present disclosure, the crystallization conditions include: the crystallization temperature is 90 °C to 180 °C, and the crystallization time is 10 hours to 40 hours. Preferably, the crystallization temperature is 95 °C to 105 °C, and the crystallization time is 20 hours to 36 hours.

[0051] In the present disclosure, the template agent removal treatment includes calcining the raw material powder of the spherical-like mesoporous material at 300 °C to 600 °C for 8 hours to 20 hours.

[0052] Through the primary thermal activation treatment, the mass content of water in the mesoporous material is controlled to be 100 ppm or less, and the mass content of oxygen in the mesoporous material is controlled to be 100 ppm or less.

[0053] In the present disclosure, the thermal activation treatment is carried out in an inert atmosphere. After the primary thermal activation treatment, the temperature is lowered to the ambient temperature (e.g., room temperature) and then raised again to carry out the secondary thermal activation treatment.

[0054] In the present disclosure, through the secondary thermal activation treatment, the water content in the mesoporous material can be controlled to be 1 ppm or less, preferably 0.5 ppm or less, more preferably 0.1 ppm or less, and the oxygen content in the mesoporous material can be controlled to be 1 ppm or less, preferably 0.5 ppm or less, more preferably 0.1 ppm or less. By using such a mesoporous material as a carrier, the prepared catalyst is less likely to aggregate during handling or olefin polymerization, and the obtained catalyst has excellent catalytic activity.

[0055] According to the present disclosure, the conditions of the primary thermal activation treatment include the following: in an inert atmosphere, the treatment temperature is 250°C to 900°C, preferably 250°C to 700°C, more preferably 250°C to 650°C, and the treatment time is 1 to 48 hours, preferably 4 to 48 hours, more preferably 6 to 24 hours. In the present disclosure, unless otherwise specified, the treatment time refers to the period during which the material being treated is within the above treatment temperature range.

[0056] Preferably, the method of the primary thermal activation treatment includes the following: in an inert atmosphere, the temperature is raised from the ambient temperature at a rate of 0.5 to 10°C per minute, preferably 0.5 to 1.5°C per minute, to 200 to 300°C, maintained for 1 to 10 hours, and then the temperature is further raised at a rate of 0.5 to 10°C per minute, preferably 0.5 to 1.5°C per minute, to 400 to 900°C, preferably 500 to 700°C, more preferably 550 to 650°C, and maintained for 2 to 10 hours.

[0057] According to the present disclosure, the conditions for the secondary thermal activation treatment include the following: in an inert atmosphere, the treatment temperature is 250 to 900 °C, preferably 250 to 700 °C, more preferably 250 to 650 °C, and the treatment time is 1 to 48 hours, preferably 4 to 48 hours, more preferably 6 to 24 hours. In the present disclosure, unless otherwise specified, the treatment time refers to the period during which the material being treated is within the above treatment temperature range.

[0058] Preferably, the method for the secondary thermal activation treatment includes the following: in an inert atmosphere, the temperature is raised from the ambient temperature to 200 to 300 °C at a rate of 0.5 to 10 °C per minute, preferably 0.5 to 1.5 °C per minute, maintained for 1 to 10 hours, and then the temperature is raised to 400 to 900 °C, preferably 500 to 700 °C, more preferably 550 to 650 °C at a rate of 0.5 to 10 °C per minute, preferably 0.5 to 1.5 °C per minute, and maintained for 2 to 10 hours.

[0059] Preferably, the treatment conditions for the primary thermal activation treatment are the same as those for the secondary thermal activation treatment.

[0060] In a preferred embodiment of the present disclosure, the operation of the thermal activation treatment includes the following: Heating from the ambient temperature to 200 to 300 °C at 0.5 to 10 °C per minute, preferably 0.5 to 1.5 °C per minute; maintaining for 1 to 10 hours; further heating to 400 to 900 °C, preferably 500 to 700 °C, more preferably 550 to 650 °C at 0.5 to 10 °C per minute, preferably 0.5 to 1.5 °C per minute; performing the primary thermal activation treatment in a nitrogen atmosphere by maintaining at that temperature for 2 to 10 hours; Then cooling to the ambient temperature (e.g., room temperature); Heating from the ambient temperature to 200 - 300 °C at 0.5 - 10 °C per minute, preferably 0.5 - 1.5 °C per minute; maintaining for 1 - 10 hours; further heating from 400 - 900 °C, preferably 500 - 700 °C, more preferably 550 - 650 °C at 0.5 - 10 °C per minute, preferably 0.5 - 1.5 °C per minute; performing a secondary thermal activation treatment in a nitrogen atmosphere by maintaining at that temperature for 2 - 10 hours; and Cooling to room temperature to obtain a spherical - like super - macroporous mesoporous material.

[0061] The nitrogen atmosphere is always maintained during the primary thermal activation treatment and the secondary thermal activation treatment.

[0062] In the present disclosure, after the filtration process, washing with deionized water (the washing may be performed 2 - 10 times) can be repeated, and suction filtration may be performed.

[0063] In the present disclosure, drying can be carried out in a drying oven. The drying conditions can be a temperature of 110 °C - 150 °C and a time of 3 - 6 hours.

[0064] According to a preferred embodiment of the present disclosure, the method further includes mixing the product obtained by the thermal activation treatment by stirring with a chlorine - containing silane.

[0065] In the present disclosure, the modification of the mesoporous material with a chlorine - containing silane is achieved by mixing the product obtained by the thermal activation treatment by stirring with a chlorine - containing silane, so that the prepared spherical - like super - macroporous mesoporous material has lipophilic properties, thereby further ensuring that the mesoporous material is in a state of low water content and low oxygen content over a long period of time.

[0066] According to the present disclosure, chlorine-containing silanes refer to various substances that contain carbon, chlorine, and silicon, with or without oxygen atoms, and do not contain hydrophilic groups such as hydroxyl groups, amino groups, and carboxyl groups. The chlorine-containing silane may contain one or more chlorine atoms and one or more silicon atoms. When a plurality of chlorine atoms are included in the chlorine-containing silane, the plurality of chlorine atoms can be located on one silicon atom or on a plurality of silicon atoms. The chlorine-containing silane may be at least one selected from dichlorodimethoxysilane, monochlorotrimethoxysilane, dichlorodiethoxysilane, and monochlorotriethoxysilane.

[0067] The mesoporous material obtained by the above method has the characteristics of small particle size and uniform particle size. Therefore, the thermally activated mesoporous material obtained by the method of the present invention does not need to go through the grinding process used in the prior art. In this way, the method of the present invention not only saves the process steps, but also reduces the damage to the structure of the mesoporous material caused by grinding, reduces the loss of the mesoporous material, and can ensure the mechanical strength of the mesoporous material. More importantly, the ball milling used in the prior art directly damages the pores of the mesoporous material support or even causes the pores of the mesoporous material support to be blocked by slag, resulting in a decrease in catalytic activity.

[0068] In a specific embodiment of the present disclosure, the mesoporous material can be prepared by a method comprising the following steps: Step 1: Polyoxyethylene-polyoxypropylene-polyoxyethylene (EO 20 PO 70 EO 20 , abbreviated as P123), ammonium fluoride (NH 4 F) is added to a hydrochloric acid solution at a molar ratio of triblock copolymer: ammonium fluoride: hydrogen chloride = 1:1 to 3:100 to 2000, and stirred at 25 to 60 ° C until the solid dissolves; Step 2: Ethyl orthosilicate and heptane are added to the solution derived from Step 1 in a molar ratio of triblock copolymer:ethyl orthosilicate:heptane = 1:20 - 500:20 - 500, and the mixture is vigorously stirred at a temperature of 25 - 60°C for 10 minutes or more, and then the resulting mixture is allowed to stand at a temperature of 25 - 60°C for 10 hours or more; Step 3: The solution derived from Step 2 is placed in a sealed reaction vessel and crystallized at a temperature of 90 - 180°C for 10 hours - 40 hours; Step 4: The crystallized product derived from Step 3 is diluted with deionized water, filtered, washed, and dried to obtain a raw material powder of a spherical - like super - macroporous mesoporous material; Step 5: The raw material powder of the obtained mesoporous material is calcined at 300 - 600°C for 8 - 20 hours in an oxygen - containing atmosphere such as air to remove the template agent; Step 6: Under a nitrogen gas flow, the material after removing the template agent is heated from ambient temperature to 200 - 300°C at 0.5 - 10°C per minute, preferably 0.5 - 1.5°C per minute; maintained for 1 hour - 10 hours; further heated from 0.5 - 10°C per minute, preferably 0.5 - 1.5°C per minute, to 400 - 900°C, preferably 500 - 700°C, more preferably 550 - 650°C; and the temperature is maintained for 2 hours - 10 hours; Step 7: After cooling the above - mentioned once thermally activated material to room temperature, under a nitrogen gas flow, it is heated from ambient temperature to 200 - 300°C at 0.5 - 10°C per minute, preferably 0.5 - 1.5°C per minute; maintained for 1 - 10 hours; further heated from 0.5 - 10°C per minute, preferably 0.5 - 1.5°C per minute, to 400 - 900°C, preferably 500 - 700°C, more preferably 550 - 650°C; and the temperature is maintained at that temperature for 2 - 10 hours, thereby performing a secondary thermal activation treatment to obtain a spherical - like super - macroporous mesoporous material.

[0069] In a third aspect, the present disclosure provides a spherical - like mesoporous substance prepared by the above - mentioned preparation method.

[0070] In the present disclosure, the spherical - like mesoporous material has a two - dimensional hexagonal regular channel structure. The mesoporous material has an average pore diameter of 10 nm - 15 nm, 300m2 / g~400m 2 It has a specific surface area of / g and an average particle size of 1 μm to 3 μm; based on the total mass of the mesoporous material, the mass content of water in the mesoporous material is less than 1 ppm, preferably less than 0.5 ppm, more preferably less than 0.1 ppm, and the mass content of oxygen in the mesoporous material is less than 1 ppm, preferably less than 0.5 ppm, more preferably less than 0.1 ppm.

[0071] In a fourth aspect, the present disclosure provides a polyolefin catalyst comprising a carrier and a magnesium component, a titanium component, and an optional electron donor component supported on the carrier, wherein the carrier is the aforementioned spherical-like mesoporous material.

[0072] The polyolefin catalyst of the present disclosure includes a spherical-like supermacroporous mesoporous material as a carrier. The spherical-like supermacroporous mesoporous material carrier has a specific two-dimensional hexagonal crystal structure. The mesoporous channel structure of the mesoporous material is uniformly distributed, has a suitable pore size, the mesoporous material has a small particle size, good mechanical strength, and good structural stability, and particularly contributes to the good dispersion of magnesium-based and titanium-based active components on the surface of the carrier. Thereby, the prepared polyolefin catalyst not only has the advantages of supported catalysts such as good dispersion of metal active components, high filling amount, few side reactions, and simple post-treatment, but also has better catalytic activity. As a result, when used in the polymerization of olefin monomers, the supported catalyst made by using the spherical-like supermacroporous mesoporous material as a carrier ensures that it has better catalytic activity and significantly improved conversion rate of raw materials.

[0073] According to the present disclosure, based on the total weight of the polyolefin catalyst, the content of the carrier is 20 wt% to 90 wt%, preferably 30 wt% to 70 wt%; the content of the magnesium component in terms of magnesium element is 1 wt% to 50 wt%, preferably 1 wt% to 30 wt%; the content of the titanium component in terms of titanium element is 1 wt% to 50 wt%, preferably 1 wt% to 30 wt%.

[0074] According to the present disclosure, when the active metal component supported on the carrier in the polyolefin catalyst contains only a magnesium component, based on the total weight of the polyolefin catalyst, the content of the carrier may be 20% by weight to 90% by weight, and the content of the magnesium component may be 1% by weight to 50% by weight, preferably 1% by weight to 30% by weight, more preferably 1% by weight to 20% by weight; when the active metal component supported on the carrier in the polyolefin catalyst contains only a titanium component, based on the total weight of the polyolefin catalyst, the content of the carrier may be 20% by weight to 90% by weight, and the content of the titanium component may be 1% by weight to 50% by weight, preferably 1% by weight to 15% by weight, more preferably 1% by weight to 5% by weight.

[0075] Preferably, in the polyolefin catalyst, the molar ratio of the magnesium component (in terms of magnesium element) to the titanium component (in terms of titanium element) is 0.5 to 50:1, preferably 5 to 18:1.

[0076] According to the present disclosure, the polyolefin catalyst may have a pore volume of 0.5 mL / g to 1 mL / g, a specific surface area of 120 m 2 / g to 300 m 2 / g, a most probable pore diameter of 7 nm to 12 nm, an average particle diameter of 3 μm to 25 μm, and a particle size distribution of 0.85 to 0.95.

[0077] In the present disclosure, the average particle diameter and particle size distribution of the polyolefin catalyst, that is, the SPAN value, are measured by a Malvern laser particle size analyzer, and the specific surface area, pore volume, average pore diameter, and most probable pore diameter are measured by nitrogen adsorption.

[0078] In one embodiment of the present disclosure, the polyolefin catalyst component includes a spherical-like super macroporous mesoporous material, magnesium, titanium, a halogen, and an electron donor. In the present disclosure, the halogen refers to at least one of fluorine, chlorine, bromine, and iodine.

[0079] In a fifth aspect, the present disclosure provides a method for preparing the above polyolefin catalyst, the method comprising: (i) Under an inert atmosphere, impregnating the spherical mesoporous material with (ia) a magnesium component-containing solution and then a titanium component-containing solution, (ib) a titanium component-containing solution and then a magnesium component-containing solution, or (ic) a solution containing both a titanium component and a magnesium component to obtain a slurry; (ii) Spray-drying the slurry resulting from step (i).

[0080] According to the present disclosure, the solution containing a magnesium component and / or a titanium component may be a solution containing a magnesium salt and / or a titanium salt in an organic solvent, and the organic solvent may be an electron-donating solvent. For example, the organic solvent may be selected from the group consisting of alkyl esters of aliphatic or aromatic carboxylic acids, aliphatic ethers, and cyclic ethers, preferably at least one of C 1 -C 4 alkyl esters of saturated aliphatic carboxylic acids, C 1 -C 4 alkyl esters of aromatic carboxylic acids, C 7 -C 8 alkyl ethers of aromatic carboxylic acids, C 1 -C 4 alkyl esters of aromatic carboxylic acids, C 2 -C 6 aliphatic ethers, and at least one of C 3 -C 4 cyclic ethers, more preferably at least one of methyl formate, ethyl formate, methyl acetate, ethyl acetate, butyl acetate, diethyl ether, dihexyl ether, and tetrahydrofuran (THF), even more preferably tetrahydrofuran.

[0081] According to the present disclosure, the loading of the magnesium component and / or titanium component on the mesoporous material can be achieved through impregnation, where the magnesium component and / or titanium component enters the channels of the mesoporous material by the capillary pressure of the channel structure of the carrier, and at the same time, the magnesium component and / or titanium component is also adsorbed on the surface of the mesoporous material until the magnesium component and / or titanium component reaches the adsorption equilibrium on the surface of the mesoporous material. When the mesoporous material supports both the magnesium component and the titanium component, the impregnation treatment may be a co-impregnation treatment or a sequential impregnation treatment. In order to save the preparation cost and simplify the experimental process, the impregnation treatment is preferably a co-impregnation treatment. More preferably, the conditions of the co-impregnation treatment may include: the impregnation temperature is 25 to 100 °C, preferably 40 to 80 °C, and the impregnation time is 0.1 to 5 hours, preferably 1 to 4 hours.

[0082] According to the present disclosure, the amounts of the mesoporous material, magnesium component, and titanium component used are preferably such that in the prepared polyolefin catalyst component, based on the total weight of the polyolefin catalyst component, the content of the mesoporous material is in the range of 20% to 90% by weight, preferably 30% to 70% by weight, the content of the magnesium component in terms of magnesium element is in the range of 1% to 50% by weight, preferably 1% to 30% by weight, more preferably 10% to 30% by weight, and the content of the titanium component in terms of titanium element is in the range of 1 to 50% by weight, preferably 1% to 30% by weight, more preferably 10% to 30% by weight.

[0083] In the present disclosure, when the mesoporous material is impregnated with a solution containing only the magnesium component, the amounts of the mesoporous material and the magnesium component used are preferably such that in the prepared polyolefin catalyst component, based on the total weight of the polyolefin catalyst component, the content of the mesoporous material is in the range of 20% to 90% by weight, and the content of the magnesium component (in terms of magnesium element) is in the range of 1% to 50% by weight, preferably 1% to 30% by weight, more preferably 1% to 20% by weight.

[0084] In a specific embodiment of the present disclosure, the prepared polyolefin catalyst component has a mesoporous material content in the range of 20% to 90% by weight based on the total weight of the polyolefin catalyst component, and the total content of the magnesium component converted to magnesium element and the titanium component converted to titanium element is in the range of 10% to 30% by weight.

[0085] Preferably, in step (i), the weight ratio of the mesoporous material to the solution containing the magnesium component and / or titanium component may be 1:50 to 150, preferably 1:75 to 120.

[0086] Preferably, in step (i), the amounts of the magnesium component and the titanium component used are such that in the prepared polyolefin catalyst component, the molar ratio of the magnesium component converted to magnesium element to the titanium component converted to titanium element is in the range of 0.5 to 50:1, preferably 5 to 18:1.

[0087] In the present disclosure, the magnesium component may be a magnesium compound of the chemical formula Mg(OR 1 ) m X 2-m , where R 1 is a hydrocarbon group having 2 to 20 carbon atoms, such as C 2 -C 10 alkyl, X is a halogen atom, and 0 ≦ m ≦ 2. For example, the magnesium component may be at least one of diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, dioctoxymagnesium, and magnesium dichloride.

[0088] In the present disclosure, the titanium component is a titanium compound of the chemical formula Ti(OR 2 ) n X 4-n , where R 2 is a hydrocarbon group having 1 to 20 carbon atoms, such as C 1 -C 10It may be a titanium compound where R is alkyl, X is a halogen atom, and 0 ≦ n ≦ 4, and / or titanium trichloride. For example, the titanium component may be at least one of tetraethyl titanate, tetramethyl titanate, tetrabutyl titanate, tetraisopropyl titanate, titanium trichloride, and titanium tetrachloride. Preferably, the titanium component is titanium tetrachloride and / or titanium trichloride, and more preferably titanium tetrachloride.

[0089] In the method of the present disclosure, a magnesium component precursor that can be converted to the above magnesium component during the preparation of the catalyst component can be used instead of the magnesium component, and / or a titanium component precursor that can be converted to the above titanium component during the preparation of the catalyst component can be used instead of the titanium component.

[0090] In the present disclosure, there is no particular limitation on the concentrations of the magnesium component and the titanium component in the solution containing the magnesium component and / or the titanium component. For example, the magnesium component and the titanium component may be those conventionally selected in the art. For example, the concentration of the magnesium component may be in the range of 0.1 to 1 mol / L, and the concentration of the titanium component may be in the range of 0.01 to 0.2 mol / L.

[0091] According to the present disclosure, the inert gas used for the impregnation treatment is a gas that does not react with the raw materials or products. For example, it may be at least one of nitrogen and the gases in Group 0 of the periodic table of elements that are conventionally used in the art, preferably nitrogen. In the present disclosure, the impregnation state is such that the impregnation temperature is 25°C to 100°C and the impregnation time is 0.1 hour to 5 hours.

[0092] According to the present disclosure, spray drying can be carried out according to a conventional process. For example, the spray drying method may be at least one selected from a pressure spray drying method, a centrifugal spray drying method, and a gas flow spray drying method. According to a preferred embodiment of the present disclosure, spray drying is achieved through a gas flow spray drying method. Spray drying can be carried out in a sprayer. The spray drying conditions may include: under a protective atmosphere of nitrogen or argon, a gas introduction temperature of 100 to 150 °C, a gas discharge temperature of 100 to 120 °C, and a carrier gas flow rate of 10 to 50 L / s. The above conditions can impart a relatively high viscosity to the slurry to be sprayed, making it suitable for a spray forming operation, and can impart good mechanical strength to the particles obtained by spraying. Preferably, the spray drying conditions are such that the prepared polyolefin catalyst has an average particle size of 3 to 25 μm and a particle size distribution value of 0.85 to 0.95.

[0093] According to a preferred embodiment of the present disclosure, steps (i)-(ii) are performed as follows: In a reactor equipped with a stirrer under an inert atmosphere, an electron-donating solvent tetrahydrofuran (THF) is added, and the reactor temperature is controlled to 25°C to 40°C. After turning on the stirring, magnesium dichloride and titanium tetrachloride are rapidly added. The temperature of the system is adjusted to 60-75°C, and the mixture is reacted at a constant temperature for 1-5 hours until magnesium dichloride and titanium tetrachloride are completely dissolved to obtain an organic solution containing magnesium dichloride and titanium tetrachloride. The organic solution containing magnesium dichloride and titanium tetrachloride is mixed with a spherical-like mesoporous material and controlled so that the amounts of the individual components are as follows: per 1 mol of titanium element, the magnesium element is 0.5-50 mol, preferably 1-10 mol, and the electron-donating solvent tetrahydrofuran (THF) is 0.5-200 mol, preferably 20-200 mol. The resulting mixture is stirred at a reactor temperature controlled to 60-75°C for 0.1-5 hours to obtain a uniform slurry for spraying. The spherical-like mesoporous material should be added in an amount sufficient to form a slurry suitable for spray forming, and the total content of magnesium dichloride and titanium tetrachloride in terms of magnesium element and titanium element is 1-50 wt%, preferably 1-30 wt% respectively. Next, the resulting slurry for spraying is introduced into a spray dryer operating under an N 2 atmosphere, and the gas inlet temperature is controlled to 100-150°C, the gas outlet temperature is controlled to 100-120°C, and the carrier gas flow rate is controlled to 10-50 L / s to obtain spherical-like polyolefin catalyst particles with an average particle size of 3-25 μm, preferably 3-20 μm.

[0094] The polyolefin catalyst prepared by the above method has a spherical-like morphological feature and may be referred to as a spherical-like catalyst component for convenience. The term "spherical-like catalyst component" used herein means that the catalyst component has a particle morphology close to a sphere. The catalyst of the present disclosure has a high packing amount of the magnesium component and the titanium component, as well as a proper channel structure. When the catalyst of the present disclosure is used for the polymerization of olefin monomers, the polymerization activity is higher, and the resulting polymer has good particle morphology, narrow molecular weight distribution, and excellent fluidity.

[0095] In the present disclosure, when the catalyst is used for ethylene polymerization, the catalyst efficiency (gPE / gcat·h) can exceed 25,000, preferably 28,000 - 29,000. In contrast, the catalyst efficiency of the prior art catalysts does not exceed 22,000 and usually does not exceed 20,000.

[0096] In the present disclosure, the mesoporous material as the carrier used in the polyolefin catalyst has a much larger average pore diameter than the conventional mesoporous materials, which helps the polyethylene catalyst to enter its rich internal pores during the loading process rather than simply being supported on the outer surface. The hexagonal straight channels also further promote the entry of the catalyst, and as a result, the resulting catalyst has excellent catalyst efficiency.

[0097] In a sixth aspect, the present disclosure provides an olefin polymerization method comprising: a) a method for polymerizing an olefin monomer in the presence of the above polyolefin catalyst and a cocatalyst under polymerization conditions to obtain a polyolefin; and b) a method for recovering the polyolefin.

[0098] As used herein, the term "polymerization" includes homopolymerization and copolymerization. As used herein, the term "polymer" includes homopolymers, copolymers and terpolymers.

[0099] The polymerization reaction of olefin monomers for preparing polyolefins using the polyolefin catalyst component of the present disclosure includes the homopolymerization of ethylene and the copolymerization of ethylene with other α-olefins, where the α-olefin can be at least one selected from propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, and 4-methyl-1-pentene.

[0100] According to the present disclosure, the reaction conditions for polymerization are not particularly limited and may be conventional reaction conditions for olefin polymerization in the art. For example, the reaction may be carried out under an inert atmosphere, and the conditions for polymerization may include the following: a temperature of 10 to 100 °C, a time of 0.5 to 5 hours, and a pressure of 0.1 to 2 MPa; preferably, the conditions for polymerization may include the following: a temperature of 20 to 95 °C, a time of 1 to 4 hours, and a pressure of 0.5 to 1.5 MPa; more preferably, a temperature of 70 to 85 °C, a time of 1 to 2 hours, and a pressure of 1 to 1.5 MPa.

[0101] The polyethylene particles obtained by the olefin polymerization method according to the present disclosure have good morphology and excellent fluidity, the melt index of the polymer powder is relatively large, and the molecular weight distribution of the polymer powder is narrow. Preferably, the melt index MI2.16 (g / 10 min) of the polyethylene powder is greater than 1.6 g / 10 min, preferably 1.7 g / 10 min to 3 g / 10 min; the molecular weight distribution index (Mw / Mn) of the polyethylene powder is less than 3.5, preferably 2.8 to 3.

[0102] The pressure referred to in this specification refers to gauge pressure.

[0103] In the present disclosure, the polymerization may be carried out in the presence of a solvent. The solvent that can be used for polymerization is not particularly limited, and for example, it may be hexane.

[0104] In a specific embodiment of the present disclosure, the supported polyolefin catalyst component may be a supported polyethylene catalyst component, and the polymerization is ethylene polymerization. The method for polymerizing ethylene includes polymerizing ethylene in the presence of a catalyst and a cocatalyst under ethylene polymerization conditions, and the cocatalyst is preferably an alkylaluminum compound.

[0105] The cocatalyst that can be used in the method of the present disclosure may be any cocatalyst commonly used in the art. For example, the cocatalyst may be an alkylaluminum compound represented by the following formula I: AlRn X (3-n) (Formula I) (wherein each R is C 1 -C 8 alkyl, preferably C 1 -C 5 alkyl; X may each be one of halogen atoms, preferably a chlorine atom; and n is 0, 1, 2 or 3).

[0106] Preferably, C 1 -C 5 alkyl may be one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-amyl, and neopentyl).

[0107] Examples of the alkylaluminum compound include, but are not limited to, trimethylaluminum, dimethylaluminum chloride, triethylaluminum, diethylaluminum chloride, tri-n-propylaluminum, di-n-propylaluminum chloride, tri-n-butylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, di-n-butylaluminum chloride, and diisobutylaluminum chloride. Most preferably, the alkylaluminum compound is triethylaluminum).

[0108] The amount of the alkylaluminum compound used may be a conventional choice in the art. Generally, the molar ratio of the catalyst component to the alkylaluminum compound may be 1:20 to 300).

[0109] In the present disclosure, the olefin polymerization method may further include a step of isolating the final reaction mixture after the polymerization reaction is completed to obtain a powder of polyolefin particles).

[0110] Hereinafter, the present disclosure will be specifically described by way of examples).

[0111] In the following examples and comparative examples: The triblock copolymer of polyoxyethylene-polyoxypropylene-polyoxyethylene, P123, was purchased from Aldrich (abbreviated as P123), with EO 20 PO 70 EO 20 molecular formula, and an average molecular weight Mn of 5800, which is a substance with the registration number 9003-11-6 in the American Chemical Abstracts. Other raw materials used in the examples and comparative examples are commercially available.

[0112] In the following examples and comparative examples, X-ray diffraction analysis was carried out using an X-ray diffractometer model D8 Advance purchased from Bruker AXS (Germany); scanning electron microscope analysis was carried out using a scanning electron microscope model XL-30 purchased from FEI (USA); pore structure parameter analysis was carried out using an adsorption apparatus model ASAP 2020-M+C purchased from Micromeritics Co. (USA); the specific surface area and pore volume of the sample were calculated using the BET method; the particle size distribution value (SPAN) of the sample was obtained using a Malvern laser particle size analyzer (available from Malvin, UK); the rotary evaporator used was a model RV10 digital manufactured by IKA (Germany); the content of each component of the polyolefin catalyst component was determined using a wavelength dispersive X-ray fluorescence spectrometer model Axios-Advanced purchased from Panaco (Netherlands); spray drying was carried out on a spray dryer model B-290 manufactured by Buchi (Switzerland). The water content of the mesoporous material was measured using a MA-30 smart Karl Fischer moisture meter. The oxygen content of the mesoporous material was measured using an ONH-3000 oxygen nitrogen hydrogen analyzer.

[0113] The molecular weight distribution (Mw / Mn) of the polyolefin powder was measured using a PL-GPC220 gel permeation chromatograph manufactured by Polymer Laboratories Ltd. (UK) according to the method specified in ASTM D6474-99.

[0114] The melt index of the polyolefin was determined by the method specified in ASTM D1238-99.

[0115] The average particle size of the particulate matter was measured by a scanning electron microscope. [Example 1] This example is used to illustrate the polyolefin catalyst component and its preparation.

[0116] (I) Support preparation (1) 2.4 g of P123 (substance with CAS number 9003-11-6 having an average molecular weight Mn of 5800) and 0.028 g of ammonium fluoride were added to 80 mL of hydrochloric acid with a concentration of 1.75 mol / L, and stirred at 20 °C until P123 and ammonium fluoride were completely dissolved.

[0117] (2) Then, 17 mL of n-heptane and 5.5 mL of ethyl orthosilicate were added to the above solution, vigorously stirred at 20 °C for 4 minutes, and the resulting reaction mixture was allowed to stand for 1 hour.

[0118] (3) The resulting solution was transferred to a polytetrafluoroethylene-lined reactor and crystallized at 100 °C for 24 hours.

[0119] (4) Through filtration, washing, and drying, a raw material powder of the mesoporous material was obtained.

[0120] (5) The raw material powder of the mesoporous material was calcined in a muffle furnace at 500 °C for 24 hours to remove the template agent. Then, under a nitrogen flow rate of 1.3 m 3 / s, the calcined mesoporous material was heated from room temperature to 250 °C at a rate of 1 °C per minute, held at that temperature for 2 hours, then heated to 550 °C at a rate of 1 °C per minute, and held at that temperature for 8 hours, and subjected to a primary thermal activation treatment. The temperature was lowered to room temperature. Subsequently, the mesoporous material was subjected to a nitrogen flow rate of 13 m 3Under a nitrogen flow of / s, it was heated from room temperature to 250 °C at a rate of 1 °C per minute, held at that temperature for 2 hours, then heated to 550 °C at a rate of 1 °C per minute, and held at that temperature for 8 hours, and subjected to a secondary thermal activation treatment. Then, the temperature was lowered to room temperature to obtain a spherical-like supermacroporous mesoporous material B1. The thermally activated mesoporous material was sampled under a nitrogen atmosphere and then measured with an MA-30 smart Karl Fischer moisture meter. No moisture was detected from the spherical-like supermacroporous mesoporous material. Since the MA-30 smart Karl Fischer moisture meter has a detection limit of 0.1 ppm (mass basis), the spherical-like supermacroporous mesoporous material has a moisture content of less than 0.1 ppm. Furthermore, through measurement with an ONH-3000 oxygen, nitrogen, and hydrogen analyzer, which is an analytical device with a detection limit of 0.1 ppm (mass basis) and is performed under a nitrogen atmosphere, no oxygen gas was detected from the mesoporous material. This suggests that the spherical-like supermacroporous mesoporous material has an oxygen content of less than 0.1 ppm. 10 g of the above thermally activated mesoporous material B1 was placed in a three-necked flask, and 10 mL of toluene and 5 mL of dichlorodimethylsilane were added thereto. After stirring at 30 °C for 10 hours, the contents were evaporated to dryness under a nitrogen flow to obtain a spherical-like supermacroporous mesoporous material support C1 (10 g).

[0121] (II) Preparation of polyolefin catalyst N 2 purified with and maintained under an N 2 atmosphere, 130 mL of tetrahydrofuran as an electron-donating solvent was added to a reactor equipped with a stirrer. At a reactor temperature controlled at 30 °C, 5.3 g of magnesium dichloride and 1 mL of titanium tetrachloride were added to the reactor, the temperature of the system was adjusted to 70 °C, and maintained at that temperature for 4 hours to obtain a solution containing magnesium dichloride and titanium tetrachloride. This solution was cooled to 50 °C, 6 g of the spherical-like supermacroporous mesoporous material support C1 was added thereto, and the resulting mixture was stirred for 2 hours to obtain a uniform slurry for spraying. Next, the resulting spraying slurry was introduced into a spray dryer, and N with a gas introduction temperature of 140 °C, a gas discharge temperature of 105 °C, and a carrier gas flow rate of 30 L / s 2It was spray-dried under an atmosphere to obtain a polyolefin catalyst component designated as Cat-1.

[0122] The properties of the spherical-like supermacroporous mesoporous material A1 and the polyolefin catalyst Cat-1 were investigated through X-ray diffraction, scanning electron microscopy, particle size analyzer, and nitrogen adsorption apparatus model ASAP2020-M+C.

[0123] Through X-ray fluorescence analysis, it was found that in the catalyst component Cat-1 obtained in this example, the magnesium content was 11.17 wt% and the titanium content was 2.55 wt% in terms of elements.

[0124] Figure 1 is the XRD pattern of the spherical-like supermacroporous mesoporous material. It can be seen from the XRD pattern that the mesoporous material has a highly regular channel structure.

[0125] Figure 2 is a scanning electron microscope (SEM) image (magnification 20,000 times) of the spherical-like supermacroporous mesoporous material. It can be seen from the SEM image that the mesoporous material has a spherical-like fine morphology.

[0126] The characteristic parameters of the mesoporous material are shown in Table 1. [Comparative Example 1] This comparative example is used to explain the comparative polyolefin catalyst and its preparation.

[0127] (I) Carrier preparation Commercially available silica gel (TS610 grade available from Cabot Corporation, having a particle size of 0.02 - 0.1 μm) was used as carrier D1. Through measurement with an MA-30 Smart Karl Fischer moisture meter, which is an analytical instrument having a detection limit of 0.1 ppm (mass basis) and was conducted under a nitrogen atmosphere, no moisture was detected from carrier D1. This suggests that carrier D1 has a moisture content of less than 0.1 ppm. Also, through measurement with an ONH-3000 oxygen, nitrogen, hydrogen analyzer, which is an analytical instrument having a detection limit of 0.1 ppm (mass basis) and was conducted under a nitrogen atmosphere, no oxygen gas was detected from carrier D1. This suggests that carrier D1 has an oxygen gas content of less than 0.1 ppm.

[0128] (II) Preparation of polyolefin catalyst A polyolefin catalyst designated as Comparative Catalyst Cat-D-1 was prepared according to the procedure described in Example 1, except that the same weight of the above silica gel carrier D1 was used instead of the spherical-like super macroporous mesoporous material carrier C1.

[0129] In catalyst Cat-D-1, it was found that the content of magnesium in terms of elements is 15.3% by weight, and the content of titanium is 2.5% by weight. [Comparative Example 2] This comparative example is used to explain a comparative polyolefin catalyst and its preparation.

[0130] Carrier D2 and polyolefin catalyst Cat-D-2 were prepared according to the procedure described in Example 1, except that the same weight of an alumina carrier was used instead of the spherical-like super macroporous mesoporous material carrier C1.

[0131] Through X-ray fluorescence analysis, in catalyst Cat-D-2, it was found that the magnesium content in terms of elements is 14.6% by weight, and the titanium content is 1.8% by weight. [Comparative Example 3] This comparative example is used to explain a comparative polyolefin catalyst and its preparation.

[0132] The polyolefin catalyst Cat-D-3 was prepared according to the procedure described in Example 1, except that spray drying and organic modification treatment were not used during the preparation of the polyolefin catalyst Cat-D-3. Instead, after the impregnation treatment, the mixture was directly filtered, washed 4 times with n-hexane, and dried at 75 °C to obtain the polyolefin catalyst Cat-D-3.

[0133] Through X-ray fluorescence analysis, it was found that in the catalyst Cat-D-3, the magnesium content was 11.13 wt% and the titanium content was 1 wt% in terms of elements. [Example 2] (I) Support preparation (1) 2.4 g of P123 (substance with CAS number 9003-11-6 having an average molecular weight Mn of 5800) and 0.01 g of ammonium fluoride were added to 80 mL of hydrochloric acid with a concentration of 1.75 mol / L, and stirred at 20 °C until P123 and ammonium fluoride were completely dissolved.

[0134] (2) Then, 1 mL of n-heptane and 5.5 mL of ethyl orthosilicate were added to the above solution, stirred vigorously at 20 °C for 4 minutes, and the resulting reaction mixture was allowed to stand for 1 hour.

[0135] (3) The resulting solution was transferred to a polytetrafluoroethylene-lined reactor and crystallized at 100 °C for 24 hours.

[0136] (4) Through filtration, washing, and drying, the raw material powder of the mesoporous material was obtained.

[0137] (5) The raw material powder of the mesoporous material was calcined in a muffle furnace at 500 °C for 24 hours to remove the template agent. Then, under a nitrogen flow rate of 1.3 m 3 / s, the calcined mesoporous material was heated from room temperature to 250 °C at a rate of 1 °C per minute, held at that temperature for 2 hours, then heated to 550 °C at a rate of 1 °C per minute, and held at that temperature for 8 hours, and subjected to a primary thermal activation treatment. The temperature was lowered to room temperature. Subsequently, the mesoporous material was under a nitrogen flow rate of 1.3 m 3Under a nitrogen flow of / s, it was heated from room temperature to 250 °C at a rate of 1 °C per minute, held at that temperature for 2 hours, then heated to 550 °C at a rate of 1 °C per minute, and held at that temperature for 8 hours, and subjected to a secondary thermal activation treatment. Then, the temperature was lowered to room temperature to obtain a spherical-like supermacroporous mesoporous material B2. Through measurement with an MA-30 Smart Karl Fischer moisture meter, an analytical instrument with a detection limit of 0.1 ppm (mass basis) conducted under a nitrogen atmosphere, no moisture was detected from the spherical-like supermacroporous mesoporous material. This suggests that the spherical-like supermacroporous mesoporous material has a water content of less than 0.1 ppm. Furthermore, through measurement with an ONH-3000 oxygen, nitrogen, and hydrogen analyzer, an analytical instrument with a detection limit of 0.1 ppm (mass basis) conducted under a nitrogen atmosphere, no oxygen gas was detected from the mesoporous material. This suggests that the spherical-like supermacroporous mesoporous material has an oxygen content of less than 0.1 ppm. 10 g of the above thermally activated mesoporous material B2 was placed in a three-necked flask, and 10 mL of toluene and 5 mL of dichlorodimethylsilane were added thereto. After stirring at 30 °C for 10 hours, the contents were evaporated to dryness under a nitrogen flow to obtain a spherical-like supermacroporous mesoporous material support C2 (10 g).

[0138] (II) Preparation of Polyolefin Catalyst The polyolefin catalyst Cat-2 was prepared according to the procedure described in Example 1. [Example 3] (I) Support Preparation (1) 2.4 g of P123 (substance with CAS number 9003-11-6 having an average molecular weight Mn of 5800) and 3 g of ammonium fluoride were added to 80 mL of 1.75 mol / L hydrochloric acid, and stirred at 20 °C until P123 and ammonium fluoride were completely dissolved.

[0139] (2) Then, 100 mL of n-heptane and 5.5 mL of ethyl orthosilicate were added to the above solution, vigorously stirred at 20 °C for 4 minutes, and the resulting reaction mixture was allowed to stand for 1 hour.

[0140] (3) The resulting solution was transferred to a polytetrafluoroethylene-lined reactor and crystallized at 100 °C for 24 hours.

[0141] (4) Through filtration, washing, and drying, the raw material powder of the mesoporous material was obtained.

[0142] (5) The raw material powder of the mesoporous material was calcined in a muffle furnace at 500 °C for 24 hours to remove the template agent. Subsequently, under a nitrogen flow rate of 1.3 m 3 / s, the calcined mesoporous material was heated from room temperature to 250 °C at a rate of 1 °C per minute, held at that temperature for 2 hours, then heated to 550 °C at a rate of 1 °C per minute, and held at that temperature for 8 hours, and subjected to a primary thermal activation treatment. The temperature was lowered to room temperature. Subsequently, the mesoporous material was heated from room temperature to 250 °C at a rate of 1 °C per minute under a nitrogen flow rate of 1.3 m 3 / s, held at that temperature for 2 hours, then heated to 550 °C at a rate of 1 °C per minute, and held at that temperature for 8 hours, and subjected to a secondary thermal activation treatment. Then, the temperature was lowered to room temperature to obtain a spherical-like super macroporous mesoporous material B3. Through measurement with an MA-30 smart Karl Fischer moisture meter, an analytical apparatus with a detection limit of 0.1 ppm (mass basis) conducted under a nitrogen atmosphere, no moisture was detected from the spherical-like super macroporous mesoporous material. This suggests that the spherical-like super macroporous mesoporous material has a moisture content of less than 0.1 ppm. Furthermore, through measurement with an ONH-3000 oxygen, nitrogen, and hydrogen analyzer, an analytical apparatus with a detection limit of 0.1 ppm (mass basis) conducted under a nitrogen atmosphere, no oxygen gas was detected from the mesoporous material. This suggests that the spherical-like super macroporous mesoporous material has an oxygen content of less than 0.1 ppm. 10 g of the above thermally activated mesoporous material B3 was placed in a three-necked flask, and 10 mL of toluene and 5 mL of dichlorodimethylsilane were added thereto. After stirring at 30 °C for 10 hours, the content was evaporated to dryness under a nitrogen flow to obtain a spherical-like super macroporous mesoporous material support C3 (10 g).

[0143] (II) Preparation of polyolefin catalyst The polyolefin catalyst Cat-3 was prepared according to the procedure described in Example 1. [Example 4] (I) In the step (5) of carrier preparation, the polyolefin catalyst component was prepared according to the procedure described in Example 1, except that the mesoporous material obtained after the heat activation treatment was ball-milled under nitrogen-free conditions, and the spherical-like supermacroporous mesoporous material carrier C4 was obtained. Through measurement with the MA-30 Smart Karl Fischer moisture meter, an analytical instrument with a detection limit of 0.1 ppm (mass basis) performed under a nitrogen atmosphere, no moisture was detected from the spherical-like supermacroporous mesoporous material. This suggests that the spherical-like supermacroporous mesoporous material has a water content of less than 0.1 ppm. Further, through measurement with the ONH-3000 oxygen, nitrogen, and hydrogen analyzer, an analytical instrument with a detection limit of 0.1 ppm (mass basis) performed under a nitrogen atmosphere, no oxygen gas was detected from the mesoporous material. This suggests that the spherical-like supermacroporous mesoporous material has an oxygen content of less than 0.1 ppm.

[0144] (II) Preparation of the polyolefin catalyst The polyolefin catalyst Cat-4 was prepared according to the procedure described in Example 1. [Example 5] (I) In the preparation of the support, except that 0.046 g of ammonium fluoride was used, the polyolefin catalyst component was prepared according to the procedure described in Example 1 to obtain a spherical-like supermacroporous mesoporous material support C5. Through measurement by an MA-30 Smart Karl Fischer moisture meter, an analytical instrument with a detection limit of 0.1 ppm (mass basis) conducted under a nitrogen atmosphere, no moisture was detected from the spherical-like supermacroporous mesoporous material. This suggests that the spherical-like supermacroporous mesoporous material has a moisture content of less than 0.1 ppm. Furthermore, through measurement by an ONH-3000 oxygen, nitrogen, and hydrogen analyzer, an analytical instrument with a detection limit of 0.1 ppm (mass basis) conducted under a nitrogen atmosphere, no oxygen gas was detected from the mesoporous material. This suggests that the spherical-like supermacroporous mesoporous material has an oxygen content of less than 0.1 ppm.

[0145] The polyolefin catalyst Cat-5 was prepared according to the procedure described in Example 1. [Example 6] (I) In the preparation of the support, except that 28 mL of heptane was used, the polyolefin catalyst component was prepared according to the procedure described in Example 1 to obtain a spherical-like supermacroporous mesoporous material support C6. Through measurement by an MA-30 Smart Karl Fischer moisture meter, an analytical instrument with a detection limit of 0.1 ppm (mass basis) conducted under a nitrogen atmosphere, no moisture was detected from the spherical-like supermacroporous mesoporous material. This suggests that the spherical-like supermacroporous mesoporous material has a moisture content of less than 0.1 ppm. Furthermore, through measurement by an ONH-3000 oxygen, nitrogen, and hydrogen analyzer, an analytical instrument with a detection limit of 0.1 ppm (mass basis) conducted under a nitrogen atmosphere, no oxygen gas was detected from the mesoporous material. This suggests that the spherical-like supermacroporous mesoporous material has an oxygen content of less than 0.1 ppm.

[0146] The polyolefin catalyst Cat-6 was prepared according to the procedure described in Example 1. [Comparative Example 4] (I) Support preparation 2 g of the template agent F127 was added to a solution prepared by dissolving 2.9 g of 37 wt% hydrochloric acid in 56 g of water, and the resulting mixture was stirred at 40 °C until F127 was completely dissolved. Subsequently, 8.2 g (0.04 mol) of ethyl orthosilicate was added to the above solution, and the mixture was stirred at 40 °C for 45 minutes. The resulting solution was transferred to a polytetrafluoroethylene-lined reactor and crystallized at 100 °C for 24 hours. Subsequently, through filtration, washing four times with deionized water, suction filtration, and drying, raw material powder of the mesoporous material having a body-centered cubic structure was obtained. Subsequently, the raw material powder of the mesoporous material having a body-centered cubic structure was calcined in a muffle furnace at 400 °C for 10 hours to remove the template agent, and template agent-removed spherical mesoporous silica D4 with an average particle size of 3 - 9 μm was obtained. Next, under a nitrogen atmosphere, the template agent-removed spherical mesoporous silica D4 was thermally activated by calcining at 400 °C for 10 hours to remove hydroxyl groups and residual moisture from the spherical mesoporous silica D4, thereby obtaining thermally activated spherical mesoporous silica. Under a nitrogen atmosphere, the thermally activated mesoporous material was sampled and then measured with an MA-30 smart Karl Fischer moisture meter. The spherical-like super macroporous mesoporous material was found to have a water content of 500 ppm (mass basis). Furthermore, through an ONH-3000 oxygen-nitrogen-hydrogen analyzer, the mesoporous material was found to have an oxygen content of 300 ppm (mass basis).

[0147] 10 g of the above thermally activated spherical mesoporous silica D4 and 1 g of dichlorodimethylsilane were placed in a 100 mL ball mill jar. Here, the material of the ball mill jar was polytetrafluoroethylene, the material of the milling balls was agate, the diameter of the milling balls was in the range of 3 - 15 mm, and the number of milling balls was 30. The ball mill jar was closed, and ball milling was carried out at a temperature of 25 °C inside the ball mill jar and a rotational speed of 400 r / min for 12 hours to obtain spherical mesoporous silica support D4 having a body-centered cubic structure and an average particle size of 3 - 8 μm.

[0148] (II) Preparation of Polyolefin Catalyst The polyolefin catalyst Cat-D-4 was prepared according to the procedure described in Example 1. [Comparative Example 5] (I) Carrier preparation 1 g of a triblock copolymer of polyethylene glycol - polyglycerol - polyethylene glycol, P123, and 1.69 g of ethanol were added to 28 mL of a buffer solution of acetic acid and sodium acetate with a pH of 4.4, and the mixture was stirred at 15°C until the polyethylene glycol - polyglycerol - polyethylene glycol P123 was completely dissolved. Then, 6 g of trimethylpentane was added to the above solution, and the mixture was stirred at 15°C for 8 hours, and 2.13 g of tetramethoxysilane was added thereto. After stirring at 15°C for 20 hours, the resulting solution was transferred to a polytetrafluoroethylene-lined reactor and crystallized at 60°C for 24 hours. Through filtration, washing with pure water, and drying, a raw material powder of an eggshell-shaped mesoporous material was obtained. The raw material powder of the eggshell-shaped mesoporous material was calcined in a muffle furnace at 550°C for 24 hours to remove the template agent, and an eggshell-shaped mesoporous material D5 with a particle size diameter of 3 to 22 μm from which the template agent had been removed was obtained. Then, under a nitrogen atmosphere, the eggshell-shaped mesoporous material D5 from which the template agent had been removed was thermally activated by calcining at 400°C for 10 hours to remove hydroxyl groups and residual moisture from the eggshell-shaped mesoporous material D5, thereby obtaining a thermally activated eggshell-shaped mesoporous material. Under a nitrogen atmosphere, the thermally activated mesoporous material was sampled and then measured with a MA-30 smart Karl Fischer moisture meter. The mesoporous material was found to have a water content of 300 ppm (mass basis). Furthermore, through an ONH-3000 oxygen nitrogen hydrogen analyzer, the mesoporous material was found to have an oxygen content of 280 ppm (mass basis).

[0149] 10 g of the above thermally activated eggshell-like mesoporous material D5 and 1 g of dichlorodimethylsilane were placed in a 100 mL ball mill jar. Here, the material of the ball mill jar was polytetrafluoroethylene, the material of the milling balls was agate, the diameter of the milling balls was in the range of 3 - 15 mm, and the number of milling balls was 30 (including large balls (with a diameter exceeding 10 mm), medium balls (with a diameter of 6 - 10 mm), and small balls (with a diameter less than 6 mm) in a number ratio of approximately 1:2:3). The ball mill jar was closed, and ball milling was carried out at a temperature of 25°C inside the ball mill jar and a rotation speed of 400 r / min for 12 hours to obtain the pulverized eggshell-like mesoporous material carrier D5 (10 g).

[0150] (II) Preparation of Polyolefin Catalyst The polyolefin catalyst Cat-D-5 was prepared according to the procedure described in Example 1. [Comparative Example 6] (I) Carrier Preparation 0.0007 mol of template agent P123 was added to a solution prepared by dissolving 16.4 mL of 37 wt% hydrochloric acid in 128 mL of water, and the mixture was stirred at 40 °C until P123 was completely dissolved. Subsequently, 8.86 g (0.042 mol) of ethyl orthosilicate was added to the above solution, and the mixture was stirred at 40 °C for 24 hours. The resulting solution was transferred to a polytetrafluoroethylene-lined reactor and crystallized at 150 °C for 24 hours. Then, through filtration, washing 4 times with deionized water, suction filtration, and drying, raw material powder of the mesoporous material was obtained. The raw material powder of the mesoporous material was washed with ethanol for 24 hours under reflux conditions to remove the template agent, and mesoporous molecular sieve D6 was obtained. Then, under a nitrogen atmosphere, the product after removing the template agent was thermally activated by calcining at 400 °C for 10 hours to remove hydroxyl groups and residual moisture from the mesoporous material, and thermally activated mesoporous material D6 was obtained. Under a nitrogen atmosphere, the thermally activated mesoporous material was sampled and then measured with an MA-30 smart Karl Fischer moisture meter. The mesoporous material was found to have a water content of 250 ppm (by mass). Furthermore, through an ONH-3000 oxygen, nitrogen, and hydrogen analyzer, the mesoporous material was found to have an oxygen gas content of 390 ppm (by mass).

[0151] 10 g of the above thermally activated mesoporous material D6 and 1 g of dichlorodimethylsilane were placed in a 100 mL ball mill jar. Here, the material of the ball mill jar was polytetrafluoroethylene, the material of the milling balls was agate, the diameter of the milling balls ranged from 3 to 15 mm, and the number of milling balls was 30. The ball mill jar was closed, and ball milling was carried out at a temperature of 25 °C inside the ball mill jar and a rotation speed of 400 r / min for 12 hours to obtain mesoporous material carrier D6 (10 g) with an average particle size of 1 μm to 10 μm.

[0152] Figure 3 is a scanning electron micrograph of the mesoporous material D6 prepared in Comparative Example 6. It can be seen from the SEM image that the mesoporous material is rod-shaped.

[0153] Figures 4 to 5 are scanning electron microscope (SEM) images of the mesoporous material D6 prepared in Comparative Example 6 where ball milling was performed, from a different perspective. From the SEM images, it can be seen that the mesoporous material D6 was completely destroyed after ball milling.

[0154] (II) Preparation of polyolefin catalyst The polyolefin catalyst Cat-D-6 was prepared according to the procedure described in Example 1. [Comparative Example 7] (I) The polyolefin catalyst components were prepared according to the procedure described in Example 1, except that the same weight of cyclohexane was used instead of heptane in the carrier preparation, thereby obtaining the mesoporous material D7.

[0155] Under a nitrogen atmosphere, the thermally activated mesoporous material was sampled and then measured with an MA-30 Smart Karl Fischer moisture meter. The mesoporous material was found to have a water content of 100 ppm (by mass). Furthermore, through an ONH-3000 oxygen nitrogen hydrogen analyzer, the mesoporous material was found to have an oxygen gas content of 130 ppm (by mass).

[0156] The polyolefin catalyst Cat-D-7 was prepared according to the procedure described in Example 1. [Comparative Example 8] (I) The polyolefin catalyst components were prepared according to the procedure described in Example 1, except that ammonium fluoride was not used in the carrier preparation, thereby obtaining the mesoporous material D8. Under a nitrogen atmosphere, the thermally activated mesoporous material was sampled and then measured with an MA-30 Smart Karl Fischer moisture meter. The mesoporous material was found to have a water content of 112 ppm (by mass). Furthermore, through an ONH-3000 oxygen nitrogen hydrogen analyzer, the mesoporous material was found to have an oxygen content of 109 ppm (by mass). The polyolefin catalyst Cat-D-8 was prepared according to the method described in Example 1. [Comparative Example 9] (I) In the preparation of the support, the polyolefin catalyst component was prepared according to the method described in Example 1, except that only the primary thermal activation treatment was used, thereby obtaining the spherical-like supermacroporous mesoporous material support D9. Under a nitrogen atmosphere, the thermally activated mesoporous material was sampled and then measured with an MA-30 Smart Karl Fischer moisture meter. The mesoporous material was found to have a water content of 60 ppm (by mass). Furthermore, through an ONH-3000 oxygen, nitrogen, hydrogen analyzer, the mesoporous material was found to have an oxygen content of 50 ppm (by mass). The polyolefin catalyst Cat-D-9 was prepared according to the procedure described in Example 1.

[0157] [Table 1]

[0158] [Table 2]

[0159] [Example 1] This example is used to illustrate a method for preparing polyethylene by polymerizing ethylene using the polyolefin catalyst Cat-1 of the present disclosure.

[0160] The atmosphere in a 2 L stainless steel polymerization autoclave was replaced with nitrogen three times and then with ethylene three times. To the stirred 2 L stainless steel polymerization autoclave, 1 L of hexane, 1 mmol of triethylaluminum, and 20 mg to 50 mg of catalyst Cat-1 were added, the temperature was raised to 85 °C, hydrogen was added to 0.28 MPa, and then the total pressure of the system was maintained at 1 MPa with ethylene for polymerization. After the reaction was carried out for 2 hours, the addition of ethylene was stopped, the temperature was lowered, and the pressure was released. The polyethylene powder was taken out and weighed, and the catalyst activity was calculated. The molecular weight distribution and the MI of the melt index 2.16 , as well as the productivity of the catalyst, are shown in Table 3.

[0161] Comparative Examples 1 to 9 and Examples 2 to 6 were carried out in the same manner as Example 1.

[0162]

Table 3

[0163] From Tables 1 to 3, it can be seen that the spherical-like supermacroporous mesoporous material C1 as the carrier provided by the present disclosure has the most moderate particle size distribution (1 μm to 3 μm) and specific surface area (350 m 2 / g), and can be directly used as a catalyst carrier without ball milling. The catalyst prepared from the spherical-like supermacroporous mesoporous material C1 has high catalytic activity. Specifically, the catalyst prepared from the spherical-like supermacroporous mesoporous material carrier C1 has the highest catalytic performance of 28,000 gPE / gcat·h in the ethylene polymerization process.

[0164] In contrast, Comparative D4 has an average particle size distribution of 3 μm to 9 μm and a specific surface area of 800 m 2 / g; D5 has an average particle size of 3 μm to 22 μm and a specific surface area of 261 m 2 / g; D6 has an average particle size of 1 μm to 10 μm and a specific surface area of 598 m 2 / g. The mesoporous materials D4 to D5 have a wide particle size distribution. Therefore, these three materials can be used as polyolefin catalyst carriers only after being pulverized. However, ball milling directly damages or even blocks the pores of the mesoporous material carrier (Figs. 3, 4, and 5), resulting in a decrease in catalytic activity. The catalyst made from the mesoporous material D4 shows catalytic efficiency in the ethylene polymerization process of 19,500 gPE / gcat·h, the catalyst made from the mesoporous material D5 shows catalytic efficiency in the ethylene polymerization process of 19,000 gPE / gcat·h, and the catalyst made from the mesoporous material D6 shows catalytic efficiency in the ethylene polymerization process of 17,000 gPE / gcat·h.

[0165] Thus, if the specific surface area is too large (>500 m 2 / g) or too small (<280 m 2 / g), it can be seen that it is not useful for the synthesis of a polyethylene catalyst having high catalytic activity. This is because when the specific surface area is too large (>500 m 2 / g), the filling amount during catalyst synthesis is too much, and explosive polymerization is likely to occur during ethylene polymerization, resulting in a decrease in catalytic activity. On the other hand, when the specific surface area is too small (<280 m 2 / g), the filling amount during catalyst synthesis decreases, the catalytic performance during ethylene polymerization is insufficient, and directly the catalytic activity decreases.

[0166] As a result, these three materials can be used as polyolefin catalyst carriers only after being subjected to ball milling. However, ball milling directly damages the pores of the mesoporous material carrier or leads to the blockage of the pores of the mesoporous material carrier, resulting in a decrease in catalytic activity.

[0167] From Tables 1 to 3, it can also be seen that the spherical-like supermacroporous mesoporous material C1 provided by the present disclosure has an average pore diameter of 12 nm. The average pore diameter of such a material is the most moderate, and this material can be directly used as a catalyst support, and the highest catalytic efficiency of 28,000 gPE / gcat·h can be obtained. Comparative example D4 has an average pore diameter of 3 nm, and the corresponding catalytic efficiency is 19,500 gPE / gcat·h. Comparative example D5 has an average pore diameter of 9.8 nm, and the corresponding catalytic efficiency is 19,000 gPE / gcat·h. Comparative example D6 has an average pore diameter of 4.8 nm, and the corresponding catalytic efficiency is 17,000 gPE / gcat·h. The catalytic efficiency for all three comparative examples is lower than that for the spherical-like support. Therefore, it can be seen that an average pore diameter of less than 10 nm does not contribute to the synthesis of a polyethylene catalyst having high catalytic activity. The reason is that when the average pore diameter is less than 10 nm, it becomes difficult for the polymer catalyst to enter the pores during catalyst synthesis, resulting in insufficient catalytic efficiency during ethylene polymerization and directly causing a decrease in catalytic activity. Therefore, the average pore diameter of the spherical-like mesoporous material C1 is 12 nm, which is the most moderate. This directly leads to the highest catalytic activity of 28,000 gPE / gcat·h in the ethylene polymerization process.

[0168] Also, from Table 3, it can be seen that the polyolefin catalyst component prepared by supporting a titanium component and a magnesium component on the spherical-like supermacroporous mesoporous material support prepared by the present disclosure has high catalytic activity. The polymer particles obtained by catalyzing ethylene polymerization using the polyolefin catalyst component have good morphology and excellent fluidity, the melt index of the polymer powder is relatively large, and the molecular weight distribution of the polymer powder is narrow. These characteristics bring convenience to the storage, transportation, post-treatment, and utilization of the obtained polyolefin catalyst. In addition, when preparing a supported catalyst using the method of the present disclosure, a spherical-like polyolefin catalyst can be directly obtained in one step through a spray drying method, and the operation is simple and convenient.

[0169] As described above, the preferred embodiments of the present disclosure have been described in detail, but the present disclosure is not limited thereto. Within the scope of the technical concept of the present disclosure, various simple modifications can be made to the technical solution of the present disclosure, including combinations of various technical features by any other appropriate method. These simple changes and combinations should be regarded as the disclosure of the present invention, and all of them belong to the scope of application of the present invention.

Claims

1. A mesoporous material, wherein the mesoporous material has a two-dimensional hexagonal regular channel structure, and the mesoporous material has an average pore diameter of 10 nm to 15 nm, a specific surface area of 300 m ２ / g to 400 m / g, and an average particle size of 1 μm to 3 μm; based on the total mass of the mesoporous material, the mass content of water in the mesoporous material is less than 1 ppm, and the mass content of oxygen gas in the mesoporous material is less than 1 ppm, and The mesoporous material is characterized in that it is treated with a chlorine-containing silane, and is a mesoporous material.

2. The mesoporous material according to claim 1, wherein based on the total mass of the mesoporous material, the mass content of water in the mesoporous material is less than 0.5 ppm, and / or the mass content of oxygen gas in the mesoporous material is less than 0.5 ppm.

3. The mesoporous material according to claim 1, wherein based on the total mass of the mesoporous material, the mass content of water in the mesoporous material is less than 0.1 ppm, and / or the mass content of oxygen gas in the mesoporous material is less than 0.1 ppm.

4. The mesoporous material according to claim 1, having at least one of the following characteristics: - The mesoporous material has a water contact angle of 101° to 130°; - The mesoporous material has a crushing strength of 0.001 N / cm to 0.6 N / cm; - The mesoporous material has a pore volume of 1 mL / g to 2 mL / g; and - The mesoporous material has a particle size distribution of 0.01 to 3, and the particle size distribution is the SPAN value measured using a laser particle size distribution analyzer.

5. The mesoporous material according to claim 1, having at least one of the following characteristics: - The mesoporous material has a water contact angle of 115° to 125°; - The mesoporous material has a crushing strength of 0.01 N / cm to 0.55 N / cm; - The mesoporous material has a pore volume of 1.5 mL / g to 1.9 mL / g; and - The mesoporous material has a particle size distribution of 0.1 to 2.8, and the particle size distribution is the SPAN value measured using a laser particle size distribution analyzer.

6. The mesoporous material according to claim 1, having at least one of the following characteristics: - The mesoporous material has a water contact angle of 118° to 124°; - The mesoporous material has a crushing strength of 0.1 N / cm to 0.45 N / cm.

7. The mesoporous material according to any one of claims 1 to 6, wherein the chlorine-containing silane is at least one selected from the group consisting of dichlorodimethoxysilane, monochlorotrimethoxysilane, dichlorodiethoxysilane, and monochlorotriethoxysilane.

8. The mesoporous material has an average pore diameter of 11 nm to 13 nm, 310 m ２ / g to 380 m ２ / g of specific surface area, and an average particle size of 1.1 μm to 2.9 μm. The mesoporous material according to any one of claims 1 to 7.

9. A method for manufacturing the mesoporous material according to claim 1, the method comprising the following: (1) Mix and contact a silicon source, an acid agent, ammonium fluoride, and heptane in the presence of a template agent and water, and subject the mixture obtained from the mixing and contacting to crystallization, filtration, and drying in this order to obtain a raw material powder of the mesoporous material; and (2) Subject the raw material powder of the mesoporous material to a template agent removal treatment, a primary thermal activation treatment, a secondary thermal activation treatment, and a chlorine-containing silane treatment in this order to obtain the mesoporous material.

10. The method according to claim 9, having at least one of the following features: - In step (2), the conditions of the primary thermal activation treatment include the following: in an inert atmosphere, a treatment temperature of 250°C to 900°C, and a treatment time of 1 to 48 hours; - In step (2), the conditions of the secondary thermal activation treatment include the following: under an inert atmosphere, a treatment temperature of 250°C to 900°C, and a treatment time of 1 to 48 hours; and - In step (2), the conditions of the primary thermal activation treatment are the same as those of the secondary thermal activation treatment.

11. The method according to claim 9, having at least one of the following features: - In step (2), the conditions of the primary thermal activation treatment include the following: in an inert atmosphere, a treatment temperature of 250°C to 700°C, and a treatment time of 4 to 48 hours; - In step (2), the conditions of the secondary thermal activation treatment include the following: under an inert atmosphere, a treatment temperature of 250°C to 700°C, and a treatment time of 4 to 48 hours.

12. The method according to claim 9, having at least one of the following features: - In step (2), the conditions of the primary thermal activation treatment include the following: in an inert atmosphere, a treatment temperature of 250°C to 650°C, and a treatment time of 6 to 24 hours; - In step (2), the conditions of the secondary thermal activation treatment include the following: under an inert atmosphere, a treatment temperature of 250°C to 650°C, and a treatment time of 6 to 24 hours.

13. The method according to any one of claims 9 to 12, having at least one of the following features: - In step (1), the mixing and contacting are carried out as follows: the silicon source, the acid agent, the ammonium fluoride, and the heptane are mixed at a temperature of 25°C to 60°C for 4 minutes or more in the presence of the template agent and water, and then left standing for 1 hour or more; - In step (1), the acid agent is at least one of hydrochloric acid, sulfuric acid, nitric acid, and hydrobromic acid; - In step (1), the silicon source is at least one of ethyl orthosilicate, methyl orthosilicate, propyl orthosilicate, sodium orthosilicate, and silica sol; - The molar ratio of the template agent: the silicon source: the acid agent: the ammonium fluoride: the heptane is 1: 2 to 500: 100 to 2000: 0.7 to 200: 20 to 1650; - The template agent is a triblock copolymer of polyoxyethylene - polyoxypropylene - polyoxyethylene, EO ２０ PO ７０ EO ２０ ; - The crystallization conditions include a crystallization temperature of 90 ° C to 180 ° C and a crystallization time of 10 hours to 40 hours; In step (2), the template agent removal treatment includes washing the raw material powder of the mesoporous material with alcohol at 90 to 120 ° C for 10 to 40 hours.

14. The method according to any one of claims 9 to 13, wherein the chlorine-containing silane is at least one selected from the group consisting of dichlorodimethoxysilane, monochlorotrimethoxysilane, dichlorodiethoxysilane, and monochlorotriethoxysilane.

15. The method according to any one of claims 9 to 14, which does not include a pulverization step after the thermal activation treatment.

16. A polyolefin catalyst comprising a carrier and a magnesium component, a titanium component, and an optional electron donor component supported on the carrier, wherein the carrier is the mesoporous material according to any one of claims 1 to 8.

17. The polyolefin catalyst according to claim 16, having at least one of the following characteristics: - The content of the carrier is 20% by weight to 90% by weight based on the total weight of the polyolefin catalyst; - The content of the magnesium component in terms of magnesium element is 1% by weight to 50% by weight based on the total weight of the polyolefin catalyst; - The content of the titanium component in terms of titanium element is 1% by weight to 50% by weight based on the total weight of the polyolefin catalyst; - The polyolefin catalyst has a pore volume of 0.5 mL / g to 1 mL / g; - The polyolefin catalyst has a specific surface area of 120 m ２ / g to 300 m ２ / g; - The polyolefin catalyst has a most probable pore diameter of 7 nm to 12 nm; - The polyolefin catalyst has an average particle size of 3 μm to 25 μm; and - The polyolefin catalyst has a particle size distribution value of 0.85 to 0.95, and the particle size distribution value is SPAN measured using a laser particle size distribution analyzer.

18. The polyolefin catalyst according to claim 16, having at least one of the following features: - The content of the carrier is 30% to 70% by weight based on the total weight of the polyolefin catalyst; - The content of the magnesium component in terms of magnesium element is 1% to 30% by weight based on the total weight of the polyolefin catalyst; - The content of the titanium component in terms of titanium element is 1% to 30% by weight based on the total weight of the polyolefin catalyst.

19. A method for preparing the polyolefin catalyst according to any one of claims 16 to 18, the method comprising: (i) Under an inert atmosphere, (ia) impregnating the mesoporous material according to any one of claims 1 to 8 with a magnesium component-containing solution and then with a titanium component-containing solution, (ib) impregnating the mesoporous material according to any one of claims 1 to 8 with a titanium component-containing solution and then with a magnesium component-containing solution, or (ic) co-impregnating the mesoporous material according to any one of claims 1 to 8 with a solution containing both a titanium component and a magnesium component to obtain a slurry; and (ii) Spray-drying the slurry from step (i) to obtain the polyolefin catalyst.

20. a) Under polymerization reaction conditions, polymerizing an olefin monomer in the presence of the polyolefin catalyst and a co-catalyst according to any one of claims 16 to 18 to obtain a polyolefin; and b) recovering the polyolefin, an olefin polymerization method comprising.

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