Metal complexes containing silicon-containing heterofluorene groups, olefin polymerization catalysts, and preparation and use thereof

Abstract

The present application discloses a metal complex containing silicon-containing heterofluorene group, an olefin polymerization catalyst containing the metal complex, and a preparation method and application thereof. The metal complex contains a main complex which is a metal compound containing silicon-containing heterofluorene group, the metal compound is a mixture of metal halide, dialkyl silicon-containing heterofluorene compound, electron donor compound and / or reaction product of the above components, and the silicon-containing heterofluorene group contained therein makes the catalyst containing the same have higher activity. The above main complex is loaded on an inorganic oxide carrier with a specific particle size range to obtain a high-dispersity catalyst, and the catalyst can be used in olefin polymerization reaction, and the polymer obtained by polymerization has higher melt index and lower oligomer content.

Description

Technical Field

[0001] This invention belongs to the field of olefin polymerization catalysts, specifically relating to a metal complex containing a silane fluorene group, an olefin polymerization catalyst containing the metal complex, its preparation method, and its application. Background Technology

[0002] The Univation company's Unipol process for producing polyethylene initially used the M-1 catalyst (UCAT-A) with silica gel as the primary catalyst. Because of the silica gel support, the catalyst exhibited high fluidity and mechanical strength, performing well in direct application to gas-phase fluidized beds and providing some control over polymer particle properties. However, with continued production experience, the M-1 catalyst revealed problems with solid feed stability, leading to issues like tube blockage and bridging. Furthermore, the catalyst was highly sensitive to electrostatic discharge caused by impurities in the reaction system, resulting in reactor agglomeration and clumping. Moreover, the M-1 catalyst had low efficiency, resulting in high ash content in the resin product, leading to higher catalyst costs per unit and impacting film quality. In the 1990s, Univation developed the slurry catalyst—the J catalyst (UCAT-J)—to replace the original M-1 catalyst and promoted its application both domestically and internationally. Currently, the UCAT-J catalyst has replaced the M-1 catalyst, becoming a new direction for the Unipol process.

[0003] Chinese Patent CN106543303A relates to a catalyst component, a catalyst, and a method for preparing the same for olefin polymerization. The catalyst component comprises: 1) an ultrafine inorganic oxide support, and 2) reaction products of magnesium halide, halogenated hydrocarbons, titanium halide, and electron-donating compounds. The catalyst comprises reaction products of the following components: (A) the catalyst component described in this invention; and (B) a catalyst of the general formula AlR. n X 3-n The present invention relates to organoaluminum compounds, wherein R is a hydrogen or a hydrocarbon group having 1-20 carbon atoms, X is a halogen, preferably chlorine, bromine, or iodine, and 0 < n ≤ 3. The catalyst of this invention exhibits high activity, resulting in a polymer with higher bulk density and a higher melt index. However, the catalyst prepared by this method has a high hexane extractable content in the polymer powder generated from ethylene homopolymerization, which has an adverse effect on industrial production.

[0004] Chinese patent CN100389134A discloses a catalyst component for ethylene polymerization or copolymerization. It comprises a magnesium / titanium-containing solid with at least one transition metal titanium compound supported on it, at least one suitable electron donor, and at least one hydrogen modifier. The catalyst containing this component exhibits excellent hydrogen sensitivity, high catalytic activity, good catalyst-polymer particle morphology, and low fine powder content. It is highly suitable for ethylene slurry and gas-phase polymerization processes, especially for the production of ethylene polymers with a wide molecular weight distribution using a dual-reactor system. Its key feature is that it comprises a catalyst component obtained by supporting at least one transition metal titanium compound, at least one electron donor, and at least one hydrogen modifier on a titanium / magnesium-containing solid; the electron donor is an aliphatic ether, aromatic ether, cyclic aliphatic ether, or aliphatic ketone; the general formula of the transition metal titanium compound is Ti(OR). a X b In the formula, R is a C1-C14 aliphatic or aromatic hydrocarbon group, X is a halogen atom, a is an integer from 0 to 2, b is an integer from 0 to 4, and a+b=3 or 4; the hydrogen-modified performance improver is silicon tetrachloride. This scheme reduces the oligomer content in the polymer, but the catalyst activity is not high enough.

[0005] Chinese patent CN1493599A discloses an improved catalyst for ethylene polymerization, which improves catalyst activity and reduces oligomer content in the polymer by adding alkyl silicate to the mother liquor preparation of the main catalytic component of the catalyst. However, the activity of this catalyst is not high enough.

[0006] Therefore, there is an urgent need to develop a catalyst for olefin polymerization that has higher activity and melt index, and low oligomer content in the polymer. Summary of the Invention

[0007] To address the technical problems existing in the prior art, this invention provides a metal complex containing silane fluorene groups and an olefin polymerization catalyst employing this complex. The metal complex containing silane fluorene groups comprises an ultrafine inorganic oxide support and a host compound. The host compound contains a metal catalytic component and silane fluorene groups, resulting in a catalyst with higher activity. By loading the aforementioned host compound onto an inorganic oxide support with a specific particle size range, a highly dispersed catalyst is obtained, which can be used in olefin polymerization reactions.

[0008] One objective of this invention is to provide a metal composite containing silicon-fluorene groups, comprising: an ultrafine carrier, and a metal compound containing silicon-fluorene groups loaded on the ultrafine carrier, wherein the ultrafine carrier is selected from at least one of ultrafine silica and ultrafine alumina, preferably ultrafine silica; and the metal contains magnesium and titanium.

[0009] According to the present invention, in the metal composite containing silicon-containing heterofluorene groups:

[0010] Based on a total weight of 100 parts of the metal composite containing silicon fluorene groups, the ultrafine carrier comprises 10-55 parts, and the metal compound containing silicon fluorene groups comprises 45-90 parts; preferably, based on a total weight of 100 parts of the metal composite containing silicon fluorene groups, the ultrafine carrier comprises 10-35 parts, and the metal compound containing silicon fluorene groups comprises 65-90 parts; more preferably, based on a total weight of 100 parts of the metal composite containing silicon fluorene groups, the ultrafine carrier comprises 15-30 parts, and the metal compound containing silicon fluorene groups comprises 70-85 parts.

[0011] In the metal composite containing silicon fluorene groups, the content of titanium is 0.2 to 3.5 wt%, for example, it can be 0.2, 0.5, 1, 1.5, 2, 2.5, 3 or 3.5 wt%, or any value or range between any two of the above values; preferably, the content of titanium in the metal composite containing silicon fluorene groups is 0.8 to 2.8 wt%, more preferably, the content of titanium in the metal composite containing silicon fluorene groups is 1.9 to 2.5 wt%;

[0012] The particle size of the ultrafine carrier can be selected within a wide range. Preferably, the particle size of the ultrafine carrier is 0.5 nm to 8 μm, more preferably 1 nm to 3 μm, and even more preferably 15 nm to 1.5 μm. Inorganic oxides within this particle size range result in catalysts with good particle size distribution, high strength, and resistance to breakage after loading dialkylsilane fluorene compounds. The ultrafine inorganic oxide carrier of this invention can be used in solid or dispersion form, such as commercially available silica gel.

[0013] According to the present invention, in the metal complex containing silane groups, the metal compound containing silane groups is a mixture of metal halides, dialkylsilane compounds, electron donor compounds, and / or reaction products of the above components.

[0014] According to an embodiment of the present invention, in the metal compound containing the silicon-containing heterofluorene group:

[0015] The metal halide includes magnesium halide and titanium halide; wherein the magnesium halide is selected from at least one of magnesium chloride, magnesium bromide, and magnesium iodide, and the titanium halide is selected from at least one of titanium trichloride, titanium tetrachloride, titanium tribromide, and titanium tetrabromide, preferably at least one of titanium trichloride and titanium tetrachloride;

[0016] The general formula of the dialkylsilane fluorene compound is R 1 R 2Silafluorene, where Silafluorene is a silanefluorene group; R 1 R 2 The compounds are selected independently from C1-C10 saturated or unsaturated hydrocarbon groups, C3-C10 cycloalkyl groups, or C6-C18 aryl groups, preferably from C1-C6 saturated alkyl groups, C3-C8 cycloalkyl groups, or C6-C12 aryl groups; specifically, the dialkylsilane fluorene compounds are selected from at least one of 9,9-dimethyl-9H-9-silane fluorene and 9,9-diphenyl-9H-9-silane fluorene.

[0017] The electron-donating compound is selected from at least one of esters, ethers, and ketones, preferably from at least one of alkyl esters of C1-C8 saturated fatty carboxylic acids, alkyl esters of C7-C12 aromatic carboxylic acids, C2-C8 fatty ethers, C3-C8 cyclic ethers, and C3-C10 saturated fatty ketones; specifically, the electron-donating compound is selected from at least one of methyl formate, ethyl formate, isopropyl formate, n-propyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, diethyl ether, propyl ether, hexyl ether, tetrahydrofuran, acetone, and methyl isobutyl ketone, preferably from at least one of methyl formate, ethyl acetate, n-butyl acetate, diethyl ether, hexyl ether, tetrahydrofuran, acetone, and methyl isobutyl ketone.

[0018] A second objective of this invention is to provide a method for preparing the aforementioned metal composite containing silicon fluorene groups, comprising: uniformly mixing a slurry containing the ultrafine carrier and the metal compound containing silicon fluorene groups, followed by drying to obtain the metal composite containing silicon fluorene groups. Specifically, the preparation method includes the following steps:

[0019] (1) React components including magnesium halide, titanium halide, dialkylsilane fluorene compounds and electron donor compounds to obtain a mother liquor of metal compounds containing silane fluorene groups;

[0020] (2) Then, an ultrafine carrier is added and mixed to obtain a slurry;

[0021] (3) After spray drying the obtained slurry, the metal complex containing silicon fluorene groups is obtained.

[0022] According to the present invention, in the method for preparing the metal composite containing silicon heterofluorene groups:

[0023] Based on 1 mol of titanium halide, the magnesium halide is 0.4–20 mol, preferably 1–12 mol, more preferably 2–10 mol; the dialkylsilane fluorene compound is 0.02–12 mol, preferably 0.05–8 mol, more preferably 0.1–5 mol; the electron donor compound is 1–450 mol, preferably 35–250 mol, more preferably 110–200 mol.

[0024] The reaction conditions in step (1) are: reaction temperature of 65-85℃ and reaction time of 2-5h;

[0025] In step (2), the amount of ultrafine carrier in the slurry is such that the carrier and mother liquor can be mixed to form a slurry suitable for spray drying. Preferably, the content of ultrafine carrier in the slurry is 0.5-50 wt%, and more preferably 1-30 wt%.

[0026] In step (3), spray drying can be performed using spray drying equipment and drying process conditions commonly used in the art. Preferably, the spray drying conditions include: an inlet temperature of 90-240°C, preferably 110-200°C; and an outlet temperature of 70-130°C, preferably 95-110°C.

[0027] A third objective of this invention is to provide an olefin polymerization catalyst, comprising:

[0028] Component (A): Organoaluminum compound;

[0029] Component (B): The above-mentioned metal complex containing silicon fluorene groups or the metal complex containing silicon fluorene groups obtained by the above preparation method.

[0030] According to the present invention, in the olefin polymerization catalyst:

[0031] The general formula of the organoaluminum compound in component (A) is AlR. n X 3-n Wherein, R is a C1-C18 hydrocarbon group, X is chlorine, bromine or iodine, and 0 < n ≤ 3; preferably, the organoaluminum compound is selected from at least one of triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethylaluminum chloride;

[0032] The molar ratio of component (A) to component (B) is (5-450):1, preferably (15-250):1, wherein component (A) is calculated based on the aluminum element contained therein, and component (B) is calculated based on the titanium element contained therein.

[0033] The fourth objective of this invention is to provide a method for preparing the above-mentioned olefin polymerization catalyst, comprising: mixing the components including the organoaluminum compound and the metal complex containing the silicon fluorene group to obtain the olefin polymerization catalyst.

[0034] The fifth objective of this invention is to provide the above-mentioned olefin polymerization catalyst or the olefin polymerization catalyst obtained by the above preparation method for use in olefin polymerization reactions.

[0035] Specifically, the olefin polymerization catalyst is activated before being used in the olefin polymerization reaction. For example, the olefin polymerization catalyst is added to an activator for activation to initiate the olefin polymerization reaction. Preferably, the activator is selected from hydrocarbon organic solvents, and more preferably from at least one of isopentane, hexane, heptane, toluene, xylene, naphtha, and mineral oil.

[0036] The catalyst of this invention is suitable for olefin polymerization reactions, especially ethylene-containing olefin polymerization reactions. It can be a homopolymerization of various ethylene groups or a copolymerization of ethylene and α-olefins, wherein the α-olefins can be selected from propylene, butene, pentene, hexene, octene, and 4-methylpentene-1. The polymerization process can employ gas-phase, slurry, and solution methods, with gas-phase fluidized bed polymerization being more suitable. The conditions for olefin polymerization can be conventionally selected according to existing technologies and will not be elaborated here. To make the solid catalyst component obtained after spray drying suitable for the production of ethylene polymers, an organoaluminum compound must be added as an activator component to reduce the titanium atoms in the catalyst component to a state that allows for effective polymerization of ethylene. Generally, the above-mentioned catalyst component and activator component are reacted in a hydrocarbon solvent to obtain a catalyst for olefin polymerization; alternatively, the above-mentioned catalyst component and activator component can be added to a hydrocarbon solvent during the polymerization process to initiate the olefin polymerization reaction.

[0037] The catalyst for olefin polymerization of the present invention comprises an organoaluminum compound and a metal complex containing silane fluorene groups. The metal complex containing silane fluorene groups is supported on an ultrafine inorganic oxide as a carrier. In this invention, magnesium halide is dissolved using an electron-donating compound, and a mother liquor is prepared by adding a dialkylsilane fluorene compound and titanium halide. After adding an ultrafine carrier, the metal complex containing silane fluorene groups is obtained by spray molding. The polymer prepared using the catalyst containing the metal complex containing silane fluorene groups of the present invention has a high melt index, low hexane extract, and low oligomer content. The multi-ringed cyclic ladder π-conjugated molecular structure contained in the dialkylsilane fluorene compound has a strong electron-donating effect, which allows silicon atoms to coordinate with the active center, effectively improving the polymerization efficiency of the catalyst's active center. Detailed Implementation

[0038] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0039] The testing instruments and conditions used in this embodiment are as follows:

[0040] 1. Catalyst activity: expressed as the weight of polymer obtained per gram of catalyst;

[0041] 2. Polymer melt index (MI): Model 6932 melt indexer, CEAST, Italy;

[0042] 3. Hexane extractable content (wt%) in polymer powder: The dried polymer powder is extracted with hexane. Specifically, the polymer is washed with hexane for 4 hours. The percentage of the weight difference of the polymer powder before and after extraction relative to the weight of the polymer powder before extraction is the hexane extractable content in the polymer powder.

[0043] 4. Determination of titanium content in catalyst components: Dissolve the catalyst sample in 1M sulfuric acid, measure the solution using a spectrophotometer, and calculate the titanium content using the working curve;

[0044] 5. The content of ultrafine inorganic oxides can be obtained by calculating the ratio of the feed amount to the mass of the produced catalyst.

[0045] All raw materials used in the examples are commercially available products.

[0046] Example 1

[0047] (1) Preparation of metal complexes containing silane groups

[0048] 1.8 g TiCl4, 4.8 g anhydrous MgCl2, 1.7 g 9,9-dimethyl-9H-9-silazanefluorene, and 120 mL tetrahydrofuran were added sequentially to a 250 mL three-necked flask purged with nitrogen. The mixture was stirred and heated to 65 °C, and reacted at this temperature for 3 hours. The mixture was then cooled to 35 °C to obtain the mother liquor.

[0049] 7 g of silica gel (Cabot Corporation TS-610, particle size 0.02-0.1 μm) was added to a 250 mL three-necked flask purged with nitrogen. The cooled mother liquor was then added, and the temperature was maintained at 35 °C. After stirring for 1 hour, the mother liquor mixed with silica gel was spray-dried using a spray dryer under the following conditions: inlet temperature 195 °C and outlet temperature 110 °C. The resulting catalyst composition contained 2.24 wt% titanium and 25 wt% silica.

[0050] (2) Ethylene slurry polymerization

[0051] 1L of hexane was added to a 2L polymerization reactor purged with nitrogen, along with 1mL of 1M triethylaluminum / hexane and 0.02g of catalyst. The temperature was raised to 75℃, and hydrogen gas at 0.18MPa was added. After hydrogenation, ethylene gas at 0.75MPa was added, and the temperature was raised to 85℃. After reacting for 2 hours, the mixture was cooled and discharged. The polymerization results are shown in Table 1.

[0052] Example 2

[0053] (1) Preparation of catalyst system

[0054] Same as Example 1, except that the reaction temperature was adjusted to 85°C, the reaction time was adjusted to 4 hours, and the titanium content of the obtained catalyst component was 2.26 wt% and the silicon dioxide content was 23 wt%.

[0055] (2) Ethylene slurry polymerization

[0056] Same as Example 1, the polymerization results are shown in Table 1.

[0057] Example 3

[0058] (1) Preparation of catalyst system

[0059] Same as Example 1, except that: the spray inlet temperature is adjusted to 170°C, the outlet temperature is 100°C, and the titanium content of the obtained catalyst component is 2.15 wt% and the silica content is 22 wt%.

[0060] (2) Ethylene slurry polymerization

[0061] Same as Example 1, the polymerization results are shown in Table 1.

[0062] Example 4

[0063] (1) Preparation of catalyst components

[0064] Same as Example 1, except that: the amount of 9,9-dimethyl-9H-9-silicon fluorene used is 3.4 g, the titanium content of the obtained catalyst component is 2.27 wt%, and the silicon dioxide content is 23 wt%.

[0065] (2) Ethylene slurry polymerization

[0066] Same as Example 1, except that the metal complex containing silicon fluorene groups obtained in step (1) above is added. The polymerization results are shown in Table 1.

[0067] Example 5

[0068] (1) Preparation of catalyst components

[0069] Same as Example 1, except that the amount of 9,9-dimethyl-9H-9-silicon fluorene used is 0.8 g, and the titanium content of the obtained catalyst component is 2.09 wt% and the silicon dioxide content is 24 wt%.

[0070] (2) Ethylene slurry polymerization

[0071] Same as Example 1, except that the metal complex containing silicon fluorene groups obtained in step (1) above is added. The polymerization results are shown in Table 1.

[0072] Example 6

[0073] (1) Preparation of catalyst components

[0074] Same as Example 1, except that 9,9-dimethyl-9H-9-silicon fluorene is replaced with 9,9-diphenyl-9H-9-silicon fluorene, and the amount used is 1.4g. The resulting catalyst component has a titanium content of 2.19wt% and a silicon dioxide content of 22wt%.

[0075] (2) Ethylene slurry polymerization

[0076] Same as Example 1, except that the metal complex containing silicon fluorene groups obtained in step (1) above is added. The polymerization results are shown in Table 1.

[0077] Comparative Example 1

[0078] (1) Preparation of catalyst components

[0079] 1.8 g TiCl4, 4.8 g anhydrous MgCl2 and 120 mL tetrahydrofuran were added to a 250 mL three-necked flask purged with nitrogen. The mixture was stirred and heated to 65 °C. The mixture was then kept at this temperature for 3 hours and cooled to 35 °C to obtain the mother liquor.

[0080] 7g of silica gel (Cabot Corporation TS-610, particle size 0.02-0.1 μm) was added to a 250mL three-necked flask purged with nitrogen. The cooled mother liquor was then added, and the temperature was maintained at 35℃. After stirring for 1 hour, the mother liquor mixed with silica gel was spray-dried using a spray dryer under the following conditions: inlet temperature 195℃ and outlet temperature 110℃. The resulting catalyst composition contained 2.2wt% titanium and 25wt% silica.

[0081] (2) Ethylene slurry polymerization

[0082] 1L of hexane was added to a 2L polymerization reactor purged with nitrogen, along with 2mL of 1M triethylaluminum / hexane and 0.01g of catalyst. The temperature was raised to 75℃, and hydrogen gas was added at 0.18MPa. After hydrogenation, ethylene gas at 0.75MPa was added, and the temperature was raised to 85℃. After reacting for 2 hours, the mixture was cooled and discharged. The polymerization results are shown in Table 1.

[0083] Table 1. Catalyst performance obtained from examples and comparative examples

[0084]

[0085] As can be seen from the polymerization data in Table 1, under the same polymerization conditions, compared with Comparative Example 1, the multi-ringed cyclic ladder π-conjugated molecular structure contained in the silane fluorene group of the catalyst in the examples enables the coordination of silicon atoms with the active center to effectively improve the polymerization efficiency of the active center of the catalyst, resulting in a catalyst with higher activity, a polymer with a higher melt index, and a lower hexane extractable content.

[0086] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A metal composite containing a silicon-containing heterofluorene group, comprising: An ultrafine support and a metal compound containing a silicon-fluorene group loaded on the ultrafine support, wherein the ultrafine support is selected from at least one of ultrafine silica and ultrafine alumina, and the metal contains magnesium and titanium; the metal compound containing the silicon-fluorene group is a mixture of metal halides, dialkylsilane-fluorene compounds, electron-donating compounds, and / or reaction products of the above components, wherein the metal halide includes magnesium halides and titanium halides, and the electron-donating compound is selected from at least one of esters, ethers, and ketones.

2. The metal composite according to claim 1, characterized in that, Based on a total weight of 100 parts of the silicon-containing fluorene group-based metal composite, the ultrafine carrier comprises 10-55 parts, and the silicon-containing fluorene group-based metal compound comprises 45-90 parts; and / or, In the metal composite containing silicon-containing heterofluorene groups, the titanium content is 0.2~3.5 wt%; and / or, The particle size of the ultrafine carrier is 0.5 nm to 8 μm.

3. The metal composite according to claim 2, characterized in that, Based on a total weight of 100 parts of the silicon-containing fluorene group-based metal composite, the ultrafine carrier comprises 10-35 parts, and the silicon-containing fluorene group-based metal compound comprises 65-90 parts; and / or, In the metal composite containing silicon-containing heterofluorene groups, the titanium content is 0.8~2.8 wt%; and / or, The particle size of the ultrafine carrier is 1 nm to 3 μm.

4. The metal composite according to claim 1, characterized in that, The ultrafine carrier is ultrafine silicon dioxide.

5. The metal composite according to claim 1, characterized in that, The general formula of the dialkylsilane fluorene compound is R 1 R 2 Silafluorene, where Silafluorene is a silanefluorene group; R 1 R 2 The group, whether identical or different, is independently selected from C1-C10 saturated or unsaturated hydrocarbon groups, C3-C10 cycloalkyl groups, or C6-C18 aryl groups; and / or, The electron-donating compound is selected from at least one of the following: alkyl esters of C1-C8 saturated fatty carboxylic acids, alkyl esters of C7-C12 aromatic carboxylic acids, C2-C8 fatty ethers, C3-C8 cyclic ethers, and C3-C10 saturated fatty ketones.

6. The metal composite according to claim 5, characterized in that, The general formula of the dialkylsilane fluorene compound is R 1 R 2 Silafluorene, where Silafluorene is a silanefluorene group; R 1 R 2 They may be the same or different, and are independently selected from C1-C6 saturated alkyl, C3-C8 cycloalkyl or C6-C12 aryl.

7. The metal composite according to claim 6, characterized in that, The magnesium halide is selected from at least one of magnesium chloride, magnesium bromide, and magnesium iodide; and / or, The titanium halide is selected from at least one of titanium trichloride, titanium tetrachloride, titanium tribromide, and titanium tetrabromide; and / or, The dialkylsilane fluorene compound is selected from at least one of 9,9-dimethyl-9H-9-silane fluorene and 9,9-diphenyl-9H-9-silane fluorene; and / or, The electron-donating compound is selected from at least one of methyl formate, ethyl formate, isopropyl formate, n-propyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, diethyl ether, propyl ether, hexyl ether, tetrahydrofuran, acetone, and methyl isobutyl ketone.

8. The metal composite according to claim 7, characterized in that, The titanium halide is selected from at least one of titanium trichloride and titanium tetrachloride; and / or, The electron-donating compound is selected from at least one of methyl formate, ethyl acetate, n-butyl acetate, diethyl ether, hexyl ether, tetrahydrofuran, acetone, and methyl isobutyl ketone.

9. A method for preparing a silicon-containing heterofluorene group-based metal composite according to any one of claims 1 to 8, comprising: The slurry containing the ultrafine carrier and the metal compound containing silicon fluorene groups is mixed evenly and then dried to obtain the metal composite containing silicon fluorene groups.

10. The preparation method according to claim 9, characterized in that, The preparation method specifically includes the following steps: (1) Reacting the components including magnesium halide, titanium halide, dialkylsilane fluorene compounds and electron donor compounds to obtain a mother liquor of metal compounds containing silane fluorene groups; (2) Then add an ultrafine carrier and mix to obtain a slurry; (3) After spray drying the obtained slurry, the metal complex containing silicon fluorene groups is obtained.

11. The preparation method according to claim 10, characterized in that, Based on 1 mol of the titanium halide, the magnesium halide comprises 0.4-20 mol, the dialkylsilane fluorene compound comprises 0.02-12 mol, and the electron donor compound comprises 1-450 mol; and / or, The reaction conditions in step (1) are: a reaction temperature of 65~85℃, and / or a reaction time of 2~5h; and / or, In step (2), the content of ultrafine carriers in the slurry is 0.5~50wt%; and / or, The spray drying conditions in step (3) include: an inlet temperature of 90~240℃ and / or an outlet temperature of 70~130℃.

12. The preparation method according to claim 11, characterized in that, Based on 1 mol of the titanium halide, the magnesium halide is 1-12 mol, the dialkylsilane fluorene compound is 0.05-8 mol, and the electron donor compound is 35-250 mol; and / or, In step (2), the content of ultrafine carriers in the slurry is 1~30wt%; and / or, The conditions for spray drying in step (3) include: an inlet temperature of 110~200℃ and / or an outlet temperature of 95~110℃.

13. An olefin polymerization catalyst, comprising: Component (A): Organoaluminum compound; Component (B): The metal complex containing silicon fluorene groups as described in any one of claims 1 to 8 or the metal complex containing silicon fluorene groups obtained by the preparation method described in any one of claims 9 to 12.

14. The olefin polymerization catalyst according to claim 13, characterized in that, The general formula of the organoaluminum compound in component (A) is AlR. n X 3-n Where R is a C1-C18 hydrocarbon group, X is chlorine, bromine, or iodine, 0 < n ≤ 3; and / or, The molar ratio of component (A) to component (B) is (5~450):1, wherein component (A) is calculated based on the aluminum element contained therein, and component (B) is calculated based on the titanium element contained therein.

15. The olefin polymerization catalyst according to claim 14, characterized in that, The organoaluminum compound is selected from at least one of triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethylaluminum chloride; and / or, The molar ratio of component (A) to component (B) is (15~250):1, wherein component (A) is calculated based on the aluminum element contained therein, and component (B) is calculated based on the titanium element contained therein.

16. A method for preparing the olefin polymerization catalyst according to any one of claims 13 to 15, comprising: The olefin polymerization catalyst is obtained by mixing the components including the organoaluminum compound and the metal complex containing the silane group.

17. An olefin polymerization catalyst according to any one of claims 13 to 15 or an olefin polymerization catalyst obtained by the preparation method according to claim 16, for use in an olefin polymerization reaction.

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