Carrier, supported metallocene catalyst, and preparation method and application of supported metallocene catalyst

Abstract

The invention relates to the technical field of olefin polymerization, and discloses a carrier, a supported metallocene catalyst and a preparation method and application of the supported metallocene catalyst, the carrier comprises 1-35wt% of mesoporous silica, 1-35wt% of silica gel and 1-35wt% of cordierite clay mineral, and the total weight of the carrier is taken as a reference. The content of the silica gel is 1-35 wt%, and the content of the cordierite clay mineral is 30-98 wt%. The supported metallocene catalyst has a stable structure, and has high catalytic activity when used for olefin polymerization.

Description

Technical Field

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

[0002] The development and application of metallocene catalysts represents another major breakthrough in the field of olefin polymerization catalysts, following the traditional Ziegler-Natta catalyst. In particular, the development of the highly efficient co-catalyst methylaluminoxane (MAO) by Kaminsky and Sinn et al. in the 1980s propelled the research of metallocene catalysts into a period of rapid development. However, homogeneous metallocene catalysts require large amounts of MAO to achieve high activity, resulting in high production costs and the absence of particulate polymers, making them unsuitable for widely used slurry or gas-phase polymerization processes. An effective solution to these problems is to support soluble metallocene catalysts. Currently, there are numerous reports on metallocene support studies, with the most extensive research using SiO2, such as 955 silica gel, as a support. CN1095474C, CN1049439C, CN1157419C, US4808561, US5026797, US5763543, and US5661098 all disclose supported metallocene catalysts using SiO2 as a support. To conduct in-depth research on new support / catalyst / co-catalyst systems, it is necessary to try different supports in order to promote the further development of supported catalysts and the polyolefin industry.

[0003] Supporting olefin polymerization catalysts on molecular sieves has the following advantages:

[0004] (1) Artificially synthesized molecular sieves do not contain impurities that can easily degrade polymers, which will improve the anti-aging properties of polyolefin materials;

[0005] (2) Molecular sieve nanopores have the dual functions of carrier and reactor, with high catalyst loading efficiency, easy control of polymerization process, and can introduce active centers into the framework of polymerization reactor to accelerate reaction process and improve yield.

[0006] (3) It has a stereoselective effect on monomer insertion and polymerization reactions, which can increase the molecular weight and melting point of polyolefins.

[0007] Therefore, the emergence of molecular sieve-supported olefin polymerization catalysts has opened up a new field for olefin coordination polymerization.

[0008] Current literature reports the use of MAO-treated MCM-41 mesoporous materials to support metallocene catalysts for olefin polymerization, but the activity for ethylene polymerization is only 10. 6g PE / (mol Zr h) (Chen ST, Guo CY, Lei L, et al. Polymer, 2005, 46: 11093).

[0009] CN1923862 discloses a mesoporous molecular sieve-supported olefin polymerization catalyst, which is obtained by supporting a semi-sandwich metallocene compound of the following formula on MAO-treated SBA-15.

[0010]

[0011] However, the catalyst disclosed in CN1923862 has a maximum catalytic activity of only 10. 6 g PE / (mol Zr h).

[0012] Therefore, how to obtain supported metallocene catalysts with high catalytic activity remains a technical problem that urgently needs to be solved. Summary of the Invention

[0013] The purpose of this invention is to overcome the problem of low catalytic activity of existing supported metallocene catalysts, and to provide a support, a supported metallocene catalyst, a preparation method thereof, and its application. This supported metallocene catalyst has a stable structure and exhibits high catalytic activity when used for olefin polymerization.

[0014] To achieve the above objectives, a first aspect of the present invention provides a carrier comprising mesoporous silica, silica gel, and cordierite clay mineral, wherein, based on the total weight of the carrier, the content of mesoporous silica is 1-35% by weight, the content of silica gel is 1-35% by weight, and the content of cordierite clay mineral is 30-98% by weight.

[0015] A second aspect of the present invention provides a method for preparing the aforementioned carrier, wherein the method comprises: ball milling, slurry preparation and spray drying of mesoporous silica, silica gel and cordierite clay minerals to obtain the carrier.

[0016] A third aspect of the present invention provides a supported metallocene catalyst, the supported metallocene catalyst comprising a support and a metallocene compound and an alkylaluminoxane supported on the support, wherein the support is the aforementioned support.

[0017] A fourth aspect of the present invention provides a method for preparing the aforementioned supported metallocene catalyst, wherein the preparation method includes:

[0018] (1) Under the protection of an inert gas, the aforementioned support and alkylaluminoxane are first contacted in a solvent, and then the solvent is removed to obtain a support loaded with alkylaluminoxane.

[0019] (2) Under the protection of an inert gas, the support of the alkylaluminoxane is brought into a second contact with the metallocene compound in a solvent, and the solvent is removed to obtain a supported metallocene catalyst.

[0020] The fifth aspect of this invention provides an application of the aforementioned supported metallocene catalyst in olefin polymerization.

[0021] Through the above technical solution, the present invention has the following beneficial effects:

[0022] The supported metallocene catalyst of the present invention uses a stable mesoporous support with a well-dispersed, complete spherical microstructure. The resulting supported metallocene catalyst has a stable structure and exhibits high catalytic activity when used for olefin polymerization.

[0023] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description

[0024] Figure 1 A scanning electron microscope image of the carrier prepared in Example 1 of this invention;

[0025] Figure 2 The X-ray diffraction pattern of the carrier prepared in Example 1 of this invention. Detailed Implementation

[0026] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0027] As previously stated, the first aspect of the present invention provides a carrier comprising mesoporous silica, silica gel, and cordierite clay mineral, wherein, based on the total weight of the carrier, the content of mesoporous silica is 1-35% by weight, the content of silica gel is 1-35% by weight, and the content of cordierite clay mineral is 30-98% by weight.

[0028] According to the present invention, preferably, based on the total weight of the carrier, the content of mesoporous silica is 15-35% by weight, the content of silica gel is 15-35% by weight, and the content of cordierite clay mineral is 30-70% by weight.

[0029] In this invention, it should be noted that the total content of mesoporous silica, silica gel and cordierite clay minerals is 100%.

[0030] The inventors of this invention discovered that the low activity of the mesoporous material MCM-41 in ethylene polymerization after loading with metallocene is mainly due to the poor thermal and hydrothermal stability of the pore wall structure of MCM-41. During the loading process, some pore walls collapse, affecting the loading effect and consequently the catalytic activity. Therefore, this invention seeks a support with a stable mesoporous structure that can maintain an ordered mesoporous structure after loading.

[0031] The geometric shape of spherical mesoporous materials has obvious advantages in reducing powder agglomeration and improving their flowability. Therefore, making mesoporous materials into spherical shapes can not only retain the characteristics of high specific surface area, large pore volume, large pore size and narrow distribution of mesoporous materials, but also reduce the agglomeration of mesoporous materials and increase their flowability.

[0032] Cordierite has been studied for over a century, but it remains a treasure in the eyes of scientists and is widely used in various industrial fields, greatly promoting the development of human materials science. This is thanks to the many excellent properties brought about by the unique crystal structure of cordierite, which has always made it an important part of industrial production.

[0033] As industrial production gradually becomes more large-scale and specialized, high-performance cordierite materials are beginning to emerge. With their extremely low coefficient of thermal expansion, excellent thermal shock resistance, good high-temperature stability, and good oxidation resistance, cordierite can be widely used in metallurgy, automotive, catalysis, environmental protection, electronic packaging, and infrared emission fields. Cordierite is chemically very stable, does not readily react with acids or alkalis, and is not easily corroded. It is often used as a catalyst carrier or as a matrix material in composites with other substances to meet the working requirements of various harsh environments and extreme conditions. Typical examples include cordierite-based SiC / SiN composite materials, cordierite-based catalyst materials, mullite-cordierite, and alumina-cordierite composite materials.

[0034] Based on the above findings, the inventors of this invention combined cordierite with mesoporous materials (mesoporous silica and silica gel) to obtain the supported metallocene catalyst support of this invention. This support has a dual-pore distribution structure, a stable mesoporous structure, and a well-dispersed, complete spherical microstructure. The dual-pore distribution structure is provided by mesoporous silica and silica gel, and the use of cordierite clay minerals contributes to improved catalyst activity.

[0035] According to the present invention, the average particle size of the carrier is 30-60 micrometers, the specific surface area is 150-600 square meters / gram, the pore volume is 0.5-1.5 milliliters / gram, and the most probable pore size is 2-4 and 10-40 nanometers; preferably, the average particle size of the carrier is 30-60 micrometers, the specific surface area is 400-520 square meters / gram, the pore volume is 1.2-1.3 milliliters / gram, and the most probable pore size is 2.5-3.1 and 25-30 nanometers.

[0036] A second aspect of the present invention provides a method for preparing the aforementioned carrier, wherein the method comprises: ball milling, slurry preparation and spray drying of mesoporous silica, silica gel and cordierite clay minerals to obtain the carrier.

[0037] According to the present invention, relative to 100 parts by weight of the mesoporous silica, the amount of the silica gel is 20-150 parts by weight, and the amount of the cordierite clay mineral is 20-150 parts by weight; preferably, relative to 100 parts by weight of the mesoporous silica, the amount of the silica gel is 20-100 parts by weight, and the amount of the cordierite clay mineral is 20-100 parts by weight.

[0038] According to a preferred embodiment of the present invention, a method for preparing a carrier includes:

[0039] (S1) Hexadecyltrimethylammonium bromide, tetraethyl orthosilicate and ammonia water are contacted and the product after contact is filtered to obtain mesoporous silica filter cake;

[0040] (S2) Contact water glass with inorganic acid and filter the product obtained after contact to obtain silica gel filter cake;

[0041] (S3) The mesoporous silica filter cake, silica gel filter cake and cordierite clay mineral powder are mixed and ball-milled;

[0042] (S4) The solid powder obtained after ball milling is slurried with water and then spray-dried. The template agent in the obtained product is then removed to obtain the carrier.

[0043] According to the present invention, in step (S1), there is no particular limitation on the type of template agent, as long as it can make the obtained carrier have the above-mentioned pore structure. In the present invention, the template agent is hexadecyltrimethylammonium bromide and tetraethyl orthosilicate.

[0044] According to the present invention, the molar ratio of ammonia and water in the tetraethyl orthosilicate, hexadecyltrimethylammonium bromide, and ammonia water can be 1:(0.1-1):(0.1-5):(100-200), preferably 1:(0.1-0.5):(2-4):(120-160).

[0045] According to the present invention, in step (S1), the conditions for contacting hexadecyltrimethylammonium bromide, tetraethyl orthosilicate, and ammonia may include: a temperature of 25-100°C and a contact time of 1-10 hours. Preferably, the contact temperature is 50-100°C and the contact time is 2-6 hours.

[0046] According to the present invention, in step (S2), the conditions for contacting the water glass with the inorganic acid may include: a temperature of 10-60°C, a time of 1-5 hours, and a pH value of 2-4. Preferably, the temperature is 20-40°C and the time is 1.5-3 hours.

[0047] According to the present invention, in step (S2), the amount of water glass and inorganic acid used is in a weight ratio of 5:1.

[0048] According to the present invention, in step (S3), based on a total amount of 100 parts by weight of the mesoporous silica filter cake, the amount of the silica filter cake is 20-150 parts by weight, and the amount of the cordierite clay mineral powder is 20-500 parts by weight; preferably, based on a total amount of 100 parts by weight of the mesoporous silica filter cake, the amount of the silica filter cake is 100-120 parts by weight, and the amount of the cordierite clay mineral powder is 100-400 parts by weight.

[0049] According to the present invention, there are no particular limitations on the specific operation methods and conditions of ball milling, as long as the structure of the carrier is not damaged or substantially not damaged. Those skilled in the art can select various suitable conditions to implement the present invention based on the above principles. Specifically, the ball milling is carried out in a ball mill, wherein the diameter of the grinding balls in the ball mill can be 2-3 mm; the number of grinding balls can be reasonably selected according to the size of the grinding jar; for a grinding jar of 50-150 mL, usually one grinding ball can be used; the material of the grinding balls can be agate, polytetrafluoroethylene, etc., preferably agate. The ball milling conditions include: the rotational speed of the grinding balls can be 300-500 r / min, the temperature inside the grinding jar can be 15-100℃, and the ball milling time can be 0.1-100 hours.

[0050] According to the present invention, the specific operation method and conditions of the spray drying are well known to those skilled in the art. Specifically, a slurry composed of the solid powder and water is added into an atomizer and rotated at high speed to achieve spray drying. The spray drying conditions include: a temperature of 100-300°C and a rotation speed of 10000-15000 r / min; preferably, the spray drying conditions include: a temperature of 150-250°C and a rotation speed of 11000-13000 r / min; and most preferably, the spray drying conditions include: a temperature of 200°C and a rotation speed of 12000 r / min.

[0051] According to the present invention, in step (S4), the method for removing the template agent can be calcination, and the calcination conditions include: the temperature can be 500-700℃, preferably 500-600℃; the time can be 10-40 hours, preferably 20-30 hours, and most preferably 24 hours.

[0052] A third aspect of the present invention provides a supported metallocene catalyst, the supported metallocene catalyst comprising a support and a metallocene compound and an alkylaluminoxane supported on the support, wherein the support is the aforementioned support.

[0053] According to the present invention, the metallocene compound has the structure shown in formula (1):

[0054]

[0055] In formula (1), R1, R2, R3, R4, R5, R1', R2', R3', R4' and R5' are the same or different, and each is independently at least one of hydrogen and C1-C5 alkyl, and at least one of R1, R2, R3, R4 and R5 is a C1-C5 alkyl, at least one of R1', R2', R3', R4' and R5' is a C1-C5 alkyl, M is one or more of titanium, zirconium and hafnium, and X is a halogen.

[0056] According to the present invention, in a preferred embodiment, in formula (1), R1 and R1' are each independently C1-C5 alkyl groups, and R2, R3, R4, R5, R2', R3', R4' and R5' are all hydrogen; more preferably, R1 and R1' are each independently n-butyl and / or tert-butyl, more preferably n-butyl; M is zirconium; X is chlorine and / or bromine, preferably chlorine.

[0057] Specific examples of cyclopentadienyl groups include: methylcyclopentadienyl, 1,2-dimethyl-cyclopentadienyl, 1,3-dimethyl-cyclopentadienyl, 1,2,3-trimethyl-cyclopentadienyl, 1,2,4-trimethyl-cyclopentadienyl, 1,2,3,4-tetramethyl-cyclopentadienyl, pentamethyl-cyclopentadienyl, ethyl-cyclopentadienyl, 1,2-diethyl-cyclopentadienyl, 1,3-diethyl-cyclopentadienyl, 1,2,4-triethyl-cyclopentadienyl Pentadienyl, 1,3,5-triethyl-cyclopentadienyl, 1-methyl-2-ethyl-cyclopentadienyl, 1-methyl-3-ethyl-cyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl, 1,3-di-n-propyl-cyclopentadienyl, 1-methyl-3-n-propyl-cyclopentadienyl, 1,3-diisopropyl-cyclopentadienyl, 1-methyl-3-isopropyl-cyclopentadienyl, n-butylcyclopentadienyl, sec-butylcyclopentadienyl, isobutyl Cyclopentadienyl, tert-butylcyclopentadienyl, 1,3-di-n-butyl-cyclopentadienyl, 1-methyl-3-n-butyl-cyclopentadienyl, 1,3-di-sec-butyl-cyclopentadienyl, 1-methyl-3-sec-butyl-cyclopentadienyl, 1,3-diisobutyl-cyclopentadienyl, 1-methyl-3-isobutyl-cyclopentadienyl, 1,3-di-tert-butyl-cyclopentadienyl, 1-methyl-3-tert-butyl-cyclopentadienyl, n-pentylcyclopentadienyl, isopentylcyclopentadienyl One or more of the following: alkenyl, tert-pentylcyclopentadienyl, neopentylcyclopentadienyl, 1,3-di-n-pentyl-cyclopentadienyl, 1-methyl-3-n-pentyl-cyclopentadienyl, 1,3-diisopentyl-cyclopentadienyl, 1-methyl-3-isopentyl-cyclopentadienyl, 1,3-di-tert-pentyl-cyclopentadienyl, 1-methyl-3-tert-pentyl-cyclopentadienyl, 1,3-di-neoplyl-cyclopentadienyl and 1-methyl-3-neoplyl-cyclopentadienyl.

[0058] In a preferred embodiment, R1 and R1' are each independently a C1-C5 alkyl group, and R2, R3, R4, R5, R2', R3', R4' and R5' are all hydrogen.

[0059] Specific examples of cyclopentadienyl include one or more of the following: methylcyclopentadienyl, ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec-butylcyclopentadienyl, isobutylcyclopentadienyl, tert-butylcyclopentadienyl, n-pentylcyclopentadienyl, isopentylcyclopentadienyl, tert-pentylcyclopentadienyl, and neopentylcyclopentadienyl.

[0060] More preferably, R1 and R1' are each independently n-butyl and / or tert-butyl; more preferably, R1 and R1' are both n-butyl.

[0061] According to the present invention, M in different metallocene compound molecules can be the same or different. Preferably, M is zirconium.

[0062] According to the present invention, X in formula (1) can be one or more of fluorine, chlorine, bromine, and iodine. X in different metallocene compound molecules can be the same or different. Preferably, X in formula (1) is chlorine or bromine. More preferably, X in formula (1) is chlorine.

[0063] In a preferred embodiment, the metallocene compound is bis(n-butylcyclopentadienyl)zirconium dichloride.

[0064] According to the present invention, the alkylaluminoxane can be any of the various alkylaluminoxanes commonly used in the field of metallocene catalysts. Generally, the alkyl group in the alkylaluminoxane is a C1-C5 alkyl group, and the C1-C5 alkyl group can be any of the aforementioned C1-C5 alkyl groups. Preferably, the alkylaluminoxane is a methylaluminoxane.

[0065] According to the present invention, the amounts of metallocene compounds and alkylaluminoxanes supported on the support can vary within a wide range. The inventors of the present invention have found that, based on the total weight of the supported metallocene catalyst, when the total amount of the metallocene compounds and alkylaluminoxanes is 10-60% by weight and the content of the support is 40-90% by weight, not only can satisfactory catalytic effects be obtained, but costs can also be reduced. More preferably, based on the total weight of the supported metallocene catalyst, the total amount of the metallocene compounds and alkylaluminoxanes is 45-55% by weight and the content of the support is 45-55% by weight. It should be noted that the content of the metallocene compounds, alkylaluminoxanes, and support in the catalyst is calculated based on the weight of each component's raw material before loading.

[0066] In this invention, the ratio between the alkylaluminoxane and the metallocene compound can be a ratio known to those skilled in the art of olefin polymerization. Specifically, the molar ratio of aluminum in the alkylaluminoxane to M in the metallocene compound can be (10-300):1, preferably (15-250):1, and more preferably (15-200):1.

[0067] A fourth aspect of the present invention provides a method for preparing the aforementioned supported metallocene catalyst, wherein the preparation method includes:

[0068] (1) Under the protection of an inert gas, the aforementioned support and alkylaluminoxane are first contacted in a solvent, and then the solvent is removed to obtain a support loaded with alkylaluminoxane.

[0069] (2) Under the protection of an inert gas, the support of the alkylaluminoxane is brought into a second contact with the metallocene compound in a solvent, and the solvent is removed to obtain a supported metallocene catalyst.

[0070] According to the present invention, the methods for the first and second contacts are not particularly limited, and can be various methods known to those skilled in the art, such as dipping and / or spraying. Dipping allows the solution to penetrate more fully into the pores of the carrier; therefore, dipping is preferred in the present invention.

[0071] In this invention, in step (1), the conditions for the first contact include: a contact time of 1-10 hours, preferably 2-6 hours, more preferably 4 hours; and a contact temperature of 25-80°C, preferably 30-60°C, more preferably 50°C.

[0072] According to the present invention, in step (2), the conditions for the second contact include: a contact time of 0.3-2 hours, preferably 0.4-1 hour, more preferably 0.5 hours; and a contact temperature of 25-80°C, preferably 25-50°C, more preferably 30°C.

[0073] In this invention, the amounts of the support, alkylaluminoxane, and metallocene compound can be adjusted and determined based on the content of each component in the catalyst described above.

[0074] According to the present invention, the solvent can be a conventional solvent, such as toluene, and is preferably purified by methods known to those skilled in the art to remove water and the like before use.

[0075] The preparation method of the present invention may further include heating the support at a temperature of 300-900°C for 7-36 hours under an inert gas protection before loading the alkylaluminoxane and the metallocene compound, so as to remove the hydroxyl groups on the surface of the support and the volatile substances (e.g., water) contained in the support.

[0076] According to the present invention, the inert gas can be any gas that does not chemically interact with the support, alkylaluminoxane, or metallocene compound. For example, the inert gas can be nitrogen or argon, preferably nitrogen.

[0077] The fifth aspect of this invention provides an application of the aforementioned supported metallocene catalyst in olefin polymerization.

[0078] The supported metallocene catalyst of the present invention is a structurally stable catalyst with high catalytic activity. When used in the homopolymerization and copolymerization of ethylene, it exhibits high activity.

[0079] The substances and parameters not specified in this invention can be selected according to existing technology and are conventional techniques in the field. Unless otherwise specified, the operations and processing methods involved in this invention are conventional methods in the field, the instruments used are conventional instruments in the field, and the raw materials used are commercially available.

[0080] The present invention will be further described below with reference to embodiments. However, the invention is not limited to these embodiments.

[0081] The present invention will be described in detail below through embodiments.

[0082] In the following examples and comparative examples, the sources of raw materials and the methods for determining the data are as follows:

[0083] Methylaluminoxane: purchased from Albemarle, USA, with an average molecular weight (Mn) of 5800;

[0084] Bis(n-butylcyclopentadienyl)zirconium dichloride: purchased from Alfa Aesar, product number H27576;

[0085] Triethylaluminum: TEA, purchased from Zhejiang Furui Chemical Co., Ltd.;

[0086] ES955 silicone: purchased from GRACE.

[0087] 1. X-ray diffraction analysis was performed on an X-ray diffractometer, model D8 Advance, purchased from Bruker AXS, Germany.

[0088] 2. Scanning electron microscopy analysis was performed on a scanning electron microscope, model XL-30, purchased from FEI Corporation, USA.

[0089] 3. Nitrogen adsorption-desorption experimental conditions included: using an Autosorb-1 nitrogen adsorption-desorption apparatus from Quanta Computer (USA), and degassing the sample at 200℃ for 4 hours. All raw materials were chemically pure.

[0090] Example 1

[0091] This embodiment is intended to illustrate the support and supported metallocene catalyst prepared using the method of the present invention.

[0092] Carrier preparation:

[0093] (S1) Add hexadecyltrimethylammonium bromide and tetraethyl orthosilicate to an ammonia solution. The molar ratio of tetraethyl orthosilicate, hexadecyltrimethylammonium bromide, ammonia (25 wt%), and water is 1:0.37:2.8:142. Stir at 50°C until dissolved. Filter the solution to obtain a mesoporous clay filter cake. Wash the filter cake until the pH is 7 to obtain a mesoporous silica filter cake.

[0094] (S2) A water glass solution with a concentration of 15% by weight and a sulfuric acid solution with a concentration of 12% by weight are reacted at a water glass: sulfuric acid weight ratio of 5:1 for 1.5 hours. The pH is adjusted to 3 with sulfuric acid with a concentration of 98% by weight. The reaction material is then filtered and washed with distilled water until the sodium ion content is 0.02% by weight to obtain a silica gel filter cake.

[0095] (S3) 10 g of the mesoporous silica filter cake, 10 g of silica gel filter cake, and 10 g of cordierite clay mineral powder prepared above were placed together in a 100 mL ball mill jar. The ball mill jar was made of polytetrafluoroethylene, and the grinding balls were made of agate with a diameter of 3 mm. There was one grinding ball, and the rotation speed was 400 r / min. The ball mill jar was sealed and ball milled at 60 °C for 1 hour to obtain 26 g of solid powder. The solid powder was dissolved in 30 g of deionized water and spray-dried at 200 °C and 12000 r / min. The product obtained after spray drying was calcined in a muffle furnace at 500 °C for 24 hours to remove the template agent, and 24 g of the target product carrier with the template agent removed was obtained, named JKGJJQ.

[0096] Based on the total weight of the carrier, the content of mesoporous silica is 33.33% by weight, the content of silica gel is 33.33% by weight, and the content of cordierite clay mineral is 33.33% by weight.

[0097] Scanning electron microscope images of the carrier are as follows: Figure 1 As shown, the X-ray diffraction pattern is as follows: Figure 2 As shown, the structural parameters are listed in Table 1.

[0098] Supported metallocene catalysts prepared using the above-mentioned supports:

[0099] (1) 0.3407 g of activated JKGJJQ (the above-prepared support JKGJJQ was heated at 500 °C for 24 hours under nitrogen protection) was transferred to a 250 mL glass reactor that had been fully purged with nitrogen. 20 mL of purified toluene (refluxed with sodium for 24 hours) and 0.4 g of methylaluminoxane were added, and the mixture was stirred at 50 °C for 4 hours. After the reaction was complete, the mixture was allowed to stand, and after separation, the liquid was filtered off. The solid was washed three times with 20 mL of hexane, and finally the solid was dried with nitrogen to obtain JKGJJQ loaded with methylaluminoxane (named MAO / JKGJJQ).

[0100] (2) Under nitrogen protection, MAO / JKGJJQ was added to a 250 mL glass reactor, along with 20 mL of purified toluene (refluxed with sodium for 24 hours). At 30 °C, 15.6 mg of bis(n-butylcyclopentadienyl)zirconium dichloride was added dropwise, and the reaction was stirred for 0.5 hours. After the reaction was complete, the mixture was allowed to stand, and the layers were separated. The liquid was filtered off, and the solid was washed three times with 10 mL of toluene, followed by two washes with 40 mL of hexane. The solid was then dried under nitrogen to obtain the supported metallocene catalyst (named JKGJJQ-BU).

[0101] Specifically, based on the total weight of the supported metallocene catalyst, the total amount of the metallocene compound and alkylaluminoxane is 60% by weight, and the content of the support is 40% by weight; the molar ratio of aluminum in the alkylaluminoxane to M in the metallocene compound is 35:1.

[0102] The structural parameters of the catalyst are shown in Table 1.

[0103] Table 1

[0104]

[0105] As can be seen from the data in Table 1, the pore structure parameters of JKGJJQ-BU are lower than those of JKGJJQ, indicating that methylaluminoxane and metallocene compounds have indeed entered the pores of JKGJJQ.

[0106] Figure 1 The scanning electron microscope image of the carrier prepared in Example 1 of this invention is shown below. Figure 1 The scanning electron microscope images show that JKGJJQ has a spherical microstructure.

[0107] Figure 2 The X-ray diffraction pattern of the carrier prepared in Example 1 of this invention, wherein the horizontal axis represents 2θ (°), from Figure 2 The XRD pattern clearly shows that JKGJJQ exhibits diffraction peaks in the small-angle region.

[0108] Application Example 1

[0109] This application example 1 is intended to illustrate the use of the supported metallocene catalyst (named JKGJJQ-BU) prepared in Example 1 to catalyze the homopolymerization of ethylene.

[0110] In a 2-liter stainless steel high-pressure polymerization reactor, the reactor was purged three times each with nitrogen and ethylene. Then, 200 mL of hexane was added, and the reactor temperature was raised to 80°C. Another 800 mL of hexane was added, followed by 2 mL of a 1 mol / L triethylaluminum hexane solution. Next, 43.3 mg of JKGJJQ-BU prepared in Example 1 was added. Ethylene was introduced to raise the pressure to 1.0 MPa and maintain it at 1.0 MPa. The reaction was carried out at 70°C for 1 hour. The catalyst efficiency was calculated to be 3100 g PE / gcat·h.

[0111] Application Example 2

[0112] This application example 1 is intended to illustrate the use of the supported metallocene catalyst (named JKGJJQ-BU) prepared in Example 1 to catalyze ethylene copolymerization.

[0113] In a 2-liter stainless steel high-pressure polymerization reactor, the reactor was purged three times each with nitrogen and ethylene. Then, 200 mL of hexane was added, and the reactor temperature was raised to 80°C. Another 800 mL of hexane was added, followed by 2 mL of a 1 mol / L triethylaluminum (TEA) hexane solution and 10 mL of hexene. Next, 40.3 mg of JKGJJQ-BU prepared in Example 1 was added. Ethylene was introduced to raise the pressure to 1.0 MPa and maintain it at 1.0 MPa. The reaction was carried out at 70°C for 1 hour. The catalyst efficiency was calculated to be 3500 gPE / gat·h.

[0114] Example 2

[0115] This embodiment is intended to illustrate the support and supported metallocene catalyst prepared using the method of the present invention.

[0116] (S1) Add hexadecyltrimethylammonium bromide and tetraethyl orthosilicate to an ammonia solution. The molar ratio of tetraethyl orthosilicate, hexadecyltrimethylammonium bromide, ammonia (25 wt%), and water is 1:0.37:2.8:142. Stir at 50°C until dissolved. Filter the solution to obtain a mesoporous clay filter cake. Wash the filter cake until the pH is 7 to obtain a mesoporous silica filter cake.

[0117] (S2) A water glass solution with a concentration of 15% by weight and a sulfuric acid solution with a concentration of 12% by weight are reacted at a water glass: sulfuric acid weight ratio of 5:1 for 1.5 hours. The pH is adjusted to 3 with sulfuric acid with a concentration of 98% by weight. The reaction material is then filtered and washed with distilled water until the sodium ion content is 0.02% by weight to obtain a silica gel filter cake.

[0118] (S3) 10 g of the mesoporous silica filter cake, 10 g of silica gel filter cake, and 20 g of cordierite clay mineral powder prepared above were placed together in a 100 mL ball mill jar. The ball mill jar was made of polytetrafluoroethylene, and the grinding balls were made of agate with a diameter of 3 mm. There was one grinding ball, and the rotation speed was 400 r / min. The ball mill jar was sealed and ball milled at 60 °C for 1 hour to obtain 26 g of solid powder. The solid powder was dissolved in 30 g of deionized water and spray-dried at 200 °C and 12000 r / min. The product obtained after spray drying was calcined in a muffle furnace at 500 °C for 24 hours to remove the template agent, and 24 g of the target product carrier with the template agent removed was obtained, named JKGJJQ-1.

[0119] Of which, based on the total weight of the carrier, the content of mesoporous silica is 25% by weight, the content of silica gel is 25% by weight, and the content of cordierite clay mineral is 50% by weight.

[0120] The supported metallocene catalyst was prepared using the same method as in Example 1, wherein the support was JKGJJQ-1.

[0121] The resulting supported metallocene catalyst, named JKGJJQ-1-BU, wherein, based on the total weight of the supported metallocene catalyst, the total amount of the metallocene compound and alkylaluminoxane is 60% by weight, and the content of the support is 40% by weight; the molar ratio of aluminum in the alkylaluminoxane to M in the metallocene compound is 35:1.

[0122] The structural parameters of the catalyst are shown in Table 2.

[0123] Table 2

[0124]

[0125] As can be seen from the data in Table 2, the pore structure parameters of JKGJJQ-1-BU are lower than those of JKGJJQ-1, indicating that methylaluminoxane and metallocene compounds have indeed entered the pores of JKGJJQ-1.

[0126] Application Example 3

[0127] This application example 3 is intended to illustrate the use of the supported metallocene catalyst (named JKGJJQ-2-BU) prepared in Example 2 to catalyze the homopolymerization of ethylene.

[0128] The homopolymerization of ethylene was carried out using the same method as in "Application Example 1", except that the supported metallocene catalyst (named JKGJJQ-1-BU) prepared in Example 2 was used to catalyze the homopolymerization of ethylene. That is, "JKGJJQ-BU prepared in Example 1" was replaced with "JKGJJQ-1-BU prepared in Example 2".

[0129] The results showed that the catalyst efficiency was 2900 gPE / gcat·h.

[0130] Application Example 4

[0131] This application example 3 is intended to illustrate the use of the supported metallocene catalyst (named JKGJJQ-2-BU) prepared in Example 2 to catalyze ethylene copolymerization.

[0132] The ethylene copolymerization was carried out using the same method as in "Application Example 2", except that the supported metallocene catalyst (named JKGJJQ-1-BU) prepared in Example 2 was used to catalyze the ethylene copolymerization. That is, "JKGJJQ-BU prepared in Example 1" was replaced with "JKGJJQ-1-BU prepared in Example 2" in Application Example 1.

[0133] The results showed that the catalyst efficiency was 2850 gPE / gcat·h.

[0134] Example 3

[0135] This embodiment is intended to illustrate the support and supported metallocene catalyst prepared using the method of the present invention.

[0136] (S1) Add hexadecyltrimethylammonium bromide and tetraethyl orthosilicate to an ammonia solution. The molar ratio of tetraethyl orthosilicate, hexadecyltrimethylammonium bromide, ammonia (25 wt%), and water is 1:0.37:2.8:142. Stir at 50°C until dissolved. Filter the solution to obtain a mesoporous clay filter cake. Wash the filter cake until the pH is 7 to obtain a mesoporous silica filter cake.

[0137] (S2) A water glass solution with a concentration of 15% by weight and a sulfuric acid solution with a concentration of 12% by weight are reacted at a water glass: sulfuric acid weight ratio of 5:1 for 1.5 hours. The pH is adjusted to 3 with sulfuric acid with a concentration of 98% by weight. The reaction material is then filtered and washed with distilled water until the sodium ion content is 0.02% by weight to obtain a silica gel filter cake.

[0138] (S3) 10 g of the mesoporous silica filter cake, 10 g of silica gel filter cake, and 40 g of cordierite clay mineral powder prepared above were placed together in a 100 mL ball mill jar. The ball mill jar was made of polytetrafluoroethylene, and the grinding balls were made of agate with a diameter of 3 mm. There was one grinding ball, and the rotation speed was 400 r / min. The ball mill jar was sealed and ball milled at 60 °C for 1 hour to obtain 26 g of solid powder. The solid powder was dissolved in 30 g of deionized water and spray-dried at 200 °C and 12000 r / min. The product obtained after spray drying was calcined in a muffle furnace at 500 °C for 24 hours to remove the template agent, and 24 g of the target product carrier with the template agent removed was obtained, named JKGJJQ-2.

[0139] Based on the total weight of the carrier, the content of mesoporous silica is 16.67% by weight, the content of silica gel is 16.67% by weight, and the content of cordierite clay mineral is 66.67% by weight.

[0140] The supported metallocene catalyst was prepared using the same method as in Example 1, wherein the support was JKGJJQ-2.

[0141] The resulting supported metallocene catalyst, named JKGJJQ-2-BU, wherein, based on the total weight of the supported metallocene catalyst, the total amount of the metallocene compound and alkylaluminoxane is 60% by weight, and the content of the support is 40% by weight; the molar ratio of aluminum in the alkylaluminoxane to M in the metallocene compound is 35:1.

[0142] The structural parameters of the catalyst are shown in Table 3.

[0143] Table 3

[0144]

[0145] As can be seen from the data in Table 3, the pore structure parameters of JKGJJQ-2-BU are lower than those of JKGJJQ-2, indicating that methylaluminoxane and metallocene compounds have indeed entered the pores of JKGJJQ-2.

[0146] Application Example 5

[0147] This application example 5 illustrates the use of the supported metallocene catalyst (named JKGJJQ-3-BU) prepared in Example 3 to catalyze the homopolymerization of ethylene.

[0148] The homopolymerization of ethylene was carried out using the same method as in "Application Example 1", except that the supported metallocene catalyst (named JKGJJQ-2-BU) prepared in Example 3 was used to catalyze the homopolymerization of ethylene. That is, "JKGJJQ-BU prepared in Example 1" was replaced with "JKGJJQ-2-BU prepared in Example 3".

[0149] The results showed that the catalyst efficiency was 2770 gPE / gcat·h.

[0150] Application Example 6

[0151] This application example 6 illustrates the use of the supported metallocene catalyst (named JKGJJQ-3-BU) prepared in Example 3 to catalyze ethylene copolymerization.

[0152] The ethylene copolymerization was carried out using the same method as in "Application Example 2", except that the supported metallocene catalyst (named JKGJJQ-2-BU) prepared in Example 3 was used to catalyze the ethylene copolymerization. That is, "JKGJJQ-BU prepared in Example 1" was replaced with "JKGJJQ-2-BU prepared in Example 3" in Application Example 1.

[0153] The results showed that the catalyst efficiency was 2650 gPE / gcat·h.

[0154] Comparative Example 1

[0155] ES955 silicone was calcined at 400°C for 10 hours under nitrogen protection to remove hydroxyl groups and residual moisture, thereby obtaining thermally activated ES955 silicone.

[0156] Under nitrogen protection, 0.9 g of ES955 silica gel, 1.0 g of methylaluminoxane, and 10 mL of toluene (refluxed with sodium for 24 hours) were stirred and reacted at 50 °C for 4 hours. The solid was washed three times with toluene, then washed three times with 20 mL of hexane, and finally dried with nitrogen to obtain ES955 loaded with methylaluminoxane (named MAO / ES955).

[0157] Under nitrogen protection, MAO / ES955 was added to a 250 mL glass reactor, along with 20 mL of purified toluene (refluxed with sodium for 24 hours). At 30 °C, 49 mg of the metallocene catalyst precursor bis(n-butylcyclopentadienyl)zirconium dichloride was added dropwise, and the reaction was stirred for 0.5 hours. After the reaction was complete, the mixture was allowed to stand, the liquid was filtered off, and the solid was washed three times with 10 mL of toluene, followed by two washes with 40 mL of hexane. The solid was then dried under nitrogen to obtain the supported metallocene catalyst (named ES955-BU).

[0158] Application Comparative Example 1

[0159] The homopolymerization of ethylene was carried out using the same method as in Application Example 1, except that the catalyst used was ES955-BU prepared in Comparative Example 1. The catalyst efficiency was calculated to be 694 g PE / gcat·h.

[0160] Application Comparative Example 2

[0161] Ethylene and hexene were copolymerized using the same method as in Application Example 2, except that the catalyst used was ES955-BU prepared in Comparative Example 1. The catalyst efficiency was calculated to be 1361 g PE / gcat·h.

[0162] Comparative Example 2

[0163] The support and catalyst were prepared using the same method as in Example 1, except that the support did not contain cordierite clay mineral powder, and no cordierite clay mineral powder was added during ball milling. Otherwise, the process was the same as in Example 1.

[0164] In the resulting carrier, based on the total weight of the carrier, the content of mesoporous silica is 50% by weight and the content of silica gel is 50% by weight.

[0165] In addition, the catalyst obtained is JKGJ-BU, wherein, based on the total weight of the supported metallocene catalyst, the total amount of the metallocene compound and alkylaluminoxane is 6% by weight, and the content of the support is 40% by weight; the molar ratio of aluminum in the alkylaluminoxane to M in the metallocene compound is 35:1.

[0166] Application Comparative Example 3

[0167] The homopolymerization of ethylene was carried out using the same method as in Application Example 1, except that the catalyst used was JKGJ-BU prepared in Comparative Example 2. The catalyst efficiency was calculated to be 1200 g PE / gcat·h.

[0168] Application Comparative Example 4

[0169] Ethylene and hexene were copolymerized using the same method as in Application Example 2, except that the catalyst used was JKGJ-BU prepared in Comparative Example 2. The catalyst efficiency was calculated to be 1000 g PE / gcat·h.

[0170] Comparative Example 3

[0171] The support and catalyst were prepared using the same method as in Example 1, except that the support did not contain silica gel and cordierite clay mineral powder, and silica gel and cordierite clay mineral powder were not added during ball milling. Otherwise, the process was the same as in Example 1.

[0172] The resulting carrier was mainly composed of mesoporous silica.

[0173] In addition, the obtained catalyst is JK-BU, wherein, based on the total weight of the supported metallocene catalyst, the total amount of the metallocene compound and alkylaluminoxane is 60% by weight, and the content of the support is 40% by weight; the molar ratio of aluminum in the alkylaluminoxane to M in the metallocene compound is 35:1.

[0174] Application Comparative Example 5

[0175] The homopolymerization of ethylene was carried out using the same method as in Application Example 1, except that the catalyst used was JK-BU prepared in Comparative Example 3. The catalyst efficiency was calculated to be 1300 g PE / gcat·h.

[0176] Application Comparative Example 6

[0177] Ethylene and hexene were copolymerized using the same method as in Application Example 2, except that the catalyst used was JK-BU prepared in Comparative Example 3. The catalyst efficiency was calculated to be 1100 g PE / gcat·h.

[0178] Data from the application examples and comparative examples show that the supported metallocene catalyst prepared in Example 1 of this invention exhibits activities of 3100 g PE / gcat·h and 3500 g PE / gcat·h for ethylene homopolymerization and copolymerization, respectively. In contrast, the activities of the same active component supported on industrially common 955 silica gel for ethylene homopolymerization and copolymerization are 694 g PE / gcat·h and 1361 g PE / gcat·h, respectively. Therefore, the catalyst of this invention has higher activity.

[0179] Furthermore, the catalyst of the present invention exhibits higher catalytic activity compared to supports using materials without added cordierite clay mineral powder. The catalyst of the present invention also exhibits higher catalytic activity compared to supports using materials without added silica gel and cordierite clay mineral powder.

[0180] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A carrier, characterized in that, The carrier comprises mesoporous silica, silica gel, and cordierite clay mineral, and based on the total weight of the carrier, the content of mesoporous silica is 1-35% by weight, the content of silica gel is 1-35% by weight, and the content of cordierite clay mineral is 30-98% by weight.

2. The carrier according to claim 1, wherein, Based on the total weight of the carrier, the content of mesoporous silica is 15-35% by weight, the content of silica gel is 15-35% by weight, and the content of cordierite clay mineral is 30-70% by weight.

3. The carrier according to claim 1 or 2, wherein, The carrier has a particle size of 30-60 micrometers, a specific surface area of ​​150-600 square meters / gram, a pore volume of 0.5-1.5 milliliters / gram, and most probable pore sizes of 2-4 and 10-40 nanometers.

4. A method for preparing a carrier according to any one of claims 1-3, characterized in that, The preparation method includes: ball milling, slurry preparation and spray drying of mesoporous silica, silica gel and cordierite clay minerals to prepare a carrier.

5. The preparation method according to claim 4, wherein, The amount of silica gel is 20-150 parts by weight relative to 100 parts by weight of the mesoporous silica, and the amount of cordierite clay mineral is 20-500 parts by weight. Preferably, relative to 100 parts by weight of the mesoporous silica, the amount of the silica gel is 100-120 parts by weight, and the amount of the cordierite clay mineral is 100-400 parts by weight.

6. A supported metallocene catalyst, said supported metallocene catalyst comprising a support and a metallocene compound and an alkylaluminoxane supported on said support, characterized in that, The carrier is the carrier described in any one of claims 1-3.

7. The supported metallocene catalyst according to claim 6, wherein, The metallocene compound has the structure shown in formula (1). In formula (1), R1, R2, R3, R4, R5, R1', R2', R3', R4' and R5' are the same or different, and each is independently at least one of hydrogen and C1-C5 alkyl, and at least one of R1, R2, R3, R4 and R5 is a C1-C5 alkyl, at least one of R1', R2', R3', R4' and R5' is a C1-C5 alkyl, M is one or more of titanium, zirconium and hafnium, and X is a halogen; And / or, the alkyl group in the alkylaluminoxane is a C1-C5 alkyl group, preferably, the alkylaluminoxane is a methylaluminoxane.

8. The supported metallocene catalyst according to claim 6 or 7, wherein, Based on the total weight of the supported metallocene catalyst, the total amount of the metallocene compound and alkylaluminoxane is 10-60% by weight, preferably 45-55% by weight, and the content of the support is 40-90% by weight, preferably 45-55% by weight. And / or, the molar ratio of aluminum in the alkylaluminoxane to M in the metallocene compound is (10-300):1, preferably (15-250):1, more preferably (15-200):

1.

9. A method for preparing a supported metallocene catalyst according to any one of claims 6-8, characterized in that, The preparation method includes: (1) Under inert gas protection, the support described in any one of claims 1-3 is reacted with alkane 1240342. I94937BHY The alkylaluminoxane undergoes a first contact in a solvent, followed by solvent removal, to obtain a support for the alkylaluminoxane. (2) Under the protection of an inert gas, the support of the alkylaluminoxane is brought into a second contact with the metallocene compound in a solvent, and the solvent is removed to obtain a supported metallocene catalyst.

10. The application of a supported metallocene catalyst according to any one of claims 6-8 in olefin polymerization.

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