Solid catalyst component and preparation method thereof, olefin polymerization catalyst and application thereof

Abstract

The present invention relates to a solid catalyst component and an olefin polymerization catalyst and their application. The solid catalyst component is obtained by reacting a magnesium halide, an organic epoxy compound, an organic phosphorus compound, an organic alcohol compound, a silicon ester compound, a titanium halide or its derivative and a compound represented by formula (I), and the olefin polymerization catalyst comprises a catalyst solid component and a co-catalyst component. The olefin polymerization catalyst obtained by the present invention can not only show good activity, but also show high polymerization activity and high polymer melt index under polymerization conditions of a high hydrogen-to-ethylene ratio; and show low polymer melt index under polymerization conditions of a low hydrogen-to-ethylene ratio. Moreover, the catalyst preparation process is simple, and is very suitable for ethylene slurry polymerization processes and catalyst combination polymerization processes with excellent hydrogen regulation performance.

Description

Technical Field

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

[0002] At present, Ziegler-Natta polyethylene catalysts have made great progress in terms of activity, bulk density of powder, fine powder content, oligomers, etc., and basically meet the requirements of existing process production. With the continuous upgrading of the polyolefin industry structure, a large number of new process technologies have been built and put into production, as well as the development of new products, high-performance catalysts are needed to meet production needs. When producing bimodal resin products, a large amount of hydrogen needs to be added during the high melt index polymerization of existing domestic catalysts, which can easily cause problems such as decreased catalyst activity, increased ethylene ethane reaction, and short safe operation cycle of the device. The hydrogen adjustment of imported catalysts is too sensitive during the low melt index polymerization, the production equipment fluctuates greatly, the product quality is unstable, and it is difficult to produce high-value-added resins such as bimodal pipe materials for a long period of time. There are also problems such as short device operation cycle when producing bimodal film materials, especially the pipe products have flow lines and pitting. In order to better meet the needs of industrial production and produce resin products with better performance, it is necessary to provide catalyst products with better hydrogen adjustment performance while ensuring the basic performance of existing catalysts.

[0003] In the prior art, introducing some electron donors into olefin polymerization catalysts can improve the hydrogen regulation performance of the catalyst, such as the Chinese patents with publication numbers CN1958620A and CN103772536A, which respectively introduce silane electron donors and benzoate electron donors. Introducing other electron donors can improve the copolymerization performance of the catalyst, such as the Chinese patents with publication numbers CN1726230A, CN1798774A and CN101050248A, which respectively introduce electron donors such as alcohols, ketones, amines, amides, nitrile, alkoxysilane, aliphatic ethers and aliphatic carboxylates. Introducing certain electron donors into the catalyst can improve the activity of the catalyst, such as the Chinese patent with publication number CN102977232A, which introduces halogenated alkanes.

[0004] The electron donors mentioned above can only improve the performance of olefin polymerization catalysts in a certain aspect and can no longer meet the needs of industrial production. It is necessary to find a type of electron donor that can give the catalyst the characteristics of high hydrogen and high melt index, and low hydrogen and low melt index, so as to meet the needs of industrial production equipment to produce single-peak high melt index products and multi-peak pipes, membrane materials and other products. Summary of the invention

[0005] In order to solve the above problems existing in the prior art, the present invention proposes a solid catalyst component and a preparation method thereof, an olefin polymerization catalyst and application thereof. The present inventors have found through research that when a silicon ester compound and a compound of the general formula (I) are introduced as internal electron donors in the preparation process of the catalyst, the olefin polymerization catalyst can not only show good activity and copolymerization performance, but also show a high polymer melt index under polymerization conditions of a high hydrogen-ethylene ratio (e.g., hydrogen partial pressure: ethylene partial pressure ≥ 3); and show a low polymer melt index under polymerization conditions of a low hydrogen-ethylene ratio (e.g., hydrogen partial pressure: ethylene partial pressure ≤ 1). Based on this finding, the present invention is proposed.

[0006] One of the objects of the present invention is to provide a solid catalyst component obtained by reacting a magnesium halide, an organic epoxy compound, an organic phosphorus compound, an organic alcohol compound, a silicon ester compound, a titanium halide or its derivative and a compound represented by formula (I).

[0007]

[0008] In the general formula (I), any one of R1, R2, R3, R4, and R5 is RO, and the others are the same or different and are independently hydrogen, C1-C 20 A straight chain alkyl or branched chain alkyl, cycloalkyl, aryl, alkaryl, aralkyl, R is selected from C1 to C 20 Preferably, R is selected from C1 to C 20 Straight chain alkyl or branched chain alkyl, C3~C 20 Cycloalkyl, C6~C 10 Aryl, C6~C 10 An alkylaryl or aralkyl group.

[0009] The solid catalyst component of the present invention, wherein:

[0010] The magnesium halide is magnesium dihalide, and the magnesium dihalide is specifically at least one of magnesium dichloride, magnesium dibromide, and magnesium diiodide, among which magnesium dichloride is preferred.

[0011] The organic epoxy compound is selected from at least one of C2-C8 aliphatic olefins, dienes or halogenated aliphatic olefins or dienes oxides, and compounds such as glycidyl ethers and internal ethers. Specific compounds include but are not limited to: at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran, etc. Among them, at least one of ethylene oxide, propylene oxide, epichlorohydrin, and tetrahydrofuran is preferred, and tetrahydrofuran and / or epichlorohydrin are more preferred.

[0012] The organophosphorus compound is selected from at least one of alkyl esters of orthophosphoric acid, alkyl esters of phosphorous acid, halogenated alkyl esters of orthophosphoric acid, and halogenated alkyl esters of phosphorous acid. Specifically, it includes but is not limited to at least one of trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl phosphite, trimethyl phosphite, triethyl phosphite, tributyl phosphite, triphenyl phosphite, and benzyl phosphite. Among them, at least one of trimethyl orthophosphate, triethyl orthophosphate, and tributyl orthophosphate is preferred, and tributyl orthophosphate is most preferred.

[0013] The organic alcohol compound is selected from C1 to C 10 Straight chain or branched chain or cycloalkyl alcohol, C6~C 20 The alcohol containing an aromatic group is preferably selected from C1 to C 10 Aliphatic alcohol compounds. Specifically include but are not limited to: fatty alcohols: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, glycerol, hexanol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, decanol, etc.; cycloalkanols, such as cyclohexanol, methylcyclohexanol, etc.; aromatic alcohols, such as benzyl alcohol, methylbenzyl alcohol, α-methylbenzyl alcohol, α, α-dimethylbenzyl alcohol, etc. Preferred are ethanol, butanol, 2-ethylhexanol, and glycerol. There is no particular restriction on the proportion of each alcohol in the alcohol composition.

[0014] The general formula of the silicone ester compound is R 2 x R 3 y Si(OR 4 ) z , where R 2 and R 3 C1~C 10 The hydrocarbon or halogen, R 4 C1~C 10 A hydrocarbon group, wherein x, y, z are integers, 0≤x≤2, 0≤y≤2 and 0≤z≤4, and x+y+z=4.

[0015] The silicone ester compounds specifically include, but are not limited to, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetra(2-ethylhexyloxy)silane, ethyltrimethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, ,3-Dimethylcyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, tert-butyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, monochlorotrimethoxysilane, monochlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, trimethylphenoxy Silane, methyl triallyloxysilane, vinyl triacetoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, tert-butylmethyldimethoxysilane, tert-butylmethyldiethoxysilane, tert-amylmethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, methylcyclopentyldiethoxysilane, methylcyclopentyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, One or more of methylphenyldiethoxysilane, methylphenyldimethoxysilane, bis-o-tolyldimethoxysilane, bis-o-tolyldiethoxysilane, bis-m-tolyldimethoxysilane, bis-m-tolyldiethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane and cyclopentyldimethylmethoxysilane are used in combination. More preferably, the silicon ester compound is selected from at least one of tetramethoxysilane, tetraethoxysilane or tetrabutoxysilane.

[0016] The general formula of the titanium halide or its derivative is Ti(OR9): d X b , where R9 is C1~C 14The hydrocarbon group is preferably a C1-C8 alkyl group; X is a halogen atom, d and b are each independently an integer of 0-4, and d+b=3 or 4. Specifically, it can be selected from: TiCl3, TiCl4, TiBr4, TiCl4, Ti(OC2H5)Cl3, Ti(OCH3)Cl3, Ti(OC4H9)Cl3, Ti(OC2H5)Br3, Ti(OC2H5)2Cl2, Ti(OCH3)2Cl2, Ti(OCH3)2I2, Ti(OC2H5)3Cl, Ti(OCH3)3Cl, Ti(OC2H5)3I, Ti(OC2H5)4, Ti(OC3H7)4, Ti(OC4H9)4, etc. Preferred are TiCl3, TiCl4, TiBr4, Ti(OC2H5)2Cl2, Ti(OC2H5)Cl3, Ti(OC2H5)3Cl, Ti(OCH3)Cl3, Ti(OC4H9)Cl3, and Ti(OC4H9)4. TiCl4 is the best.

[0017] The compound represented by formula (I) is preferably selected from at least one of p-methoxyphenol, o-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, o-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, o-propoxyphenol, m-propoxyphenol, p-butoxyphenol, o-butoxyphenol, m-butoxyphenol, p-hexyloxyphenol, o-hexyloxyphenol, m-hexyloxyphenol, p-octyloxyphenol, o-octyloxyphenol, m-octyloxyphenol, p-nonyloxyphenol, m-nonyloxyphenol, o-nonyloxyphenol, dodecyloxyphenol, tetradecyloxyphenol, octadecyloxyphenol, phenoxyphenol and hydroxyphenyl benzyl ether.

[0018] The second object of the present invention is to provide a method for preparing the solid catalyst component, comprising the following steps:

[0019] The magnesium halide is reacted with an organic epoxy compound, an organic phosphorus compound and an organic alcohol compound to form a uniform reaction solution; and then mixed with a silicon ester compound, a titanium halide or its derivative, and a compound represented by formula (I) to obtain the solid catalyst component.

[0020] According to a preferred embodiment of the present invention, the preparation method may include the following steps:

[0021] Under stirring, magnesium halide is dissolved in an organic epoxy compound and an organic phosphorus compound to form a uniform transparent solution, and the mixing temperature is 50-90° C., wherein an organic alcohol compound is added during the process of forming the uniform transparent solution or after the uniform transparent solution is formed, and the reaction is continued for a certain time (specifically, the reaction can be 1.5-4 hours) to obtain a reaction solution; the reaction solution is mixed with a silicone ester compound, a transition metal titanium halide or a derivative thereof, and a compound represented by formula (I) at -30° C. to 0° C.; the mixture is slowly heated to 50-120° C., and after the reaction is completed, solid matter is precipitated and forms particles, and the mother liquor is filtered to remove, and the solid matter is washed with an inert solvent to obtain the solid catalyst component.

[0022] Among them, regarding the preparation of the magnesium halide solution: the magnesium halide solution is a uniform solution obtained by dissolving magnesium halide in a solvent system composed of an organic epoxy compound and an organic phosphorus compound, and an organic alcohol compound is added during or after the solution is formed, and the reaction is carried out for a certain period of time to obtain a reaction solution. The solvent system referred to here includes the use or non-use of an inert diluent.

[0023] The magnesium halide used has a particle size that allows it to dissolve under stirring. During the dissolution, an inert diluent such as benzene, toluene, xylene, 1,2-dichloroethane, chlorobenzene and other hydrocarbons or halogenated hydrocarbon compounds may or may not be added. Benzene, toluene and xylene are preferred, and toluene and xylene are more preferred.

[0024] The addition ratio of the magnesium halide, organic epoxy compound, organic phosphorus compound, organic alcohol compound, silicon ester compound, transition metal titanium halide or its derivative, and the compound represented by formula (I) is, based on each mole of magnesium halide, 0.2 to 10 moles of organic epoxy compound, preferably 0.3 to 4.0 moles, more preferably 0.5 to 1.5 moles; 0.1 to 10 moles of organic phosphorus compound, preferably 0.2 to 4.0 moles, more preferably 0.4 to 1.0 moles; 0.1 to 6 moles of organic alcohol compound, preferably 0.6 to 1.5 moles; The present invention relates to an aqueous solution of at least one alkylene oxide, wherein the amount of the aqueous solution ...

[0025] The third object of the present invention is to provide an olefin polymerization catalyst comprising the following components:

[0026] (A) Solid catalyst component:

[0027] The solid catalyst component is the above-mentioned component, which is prepared by the following steps: reacting magnesium halide with an organic epoxy compound, an organic phosphorus compound, and an organic alcohol compound to form a uniform solution, and then mixing it with a silicon ester compound, a transition metal titanium halide or its derivative, and a compound represented by formula (I) to obtain a solid catalyst component;

[0028] (B) Promoter Component:

[0029] The co-catalyst component is an organoaluminum compound, and preferably the general formula of the organoaluminum compound is AlR 1 e X 1 f H g , where R 1 is hydrogen or C l ~C 20 Hydrocarbon, X 1 is a halogen atom, preferably fluorine, chlorine or bromine, e, f, g are each independently a natural number of 0 to 3, and e+f+g=3; preferably AlEt3, Al(iso-Bu)3, Al(n-C6H 13 )3. Al(n-C8H 17 )3. At least one of AlEt2Cl, etc.

[0030] The ratio between the co-catalyst component and the solid catalyst component, calculated as the molar ratio of aluminum in the co-catalyst component to titanium in the solid catalyst component, is (5-500):1, preferably (20-200):1, further preferably (50-200):1, more preferably (100-150:1), for example, it can be 5:1, 10:1, 20:1, 50:1, 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, 400:1, 450:1, 500:1, etc.

[0031] In the catalyst obtained by the present invention, the titanium content is 3 to 10% (weight content), preferably 3 to 7% (weight content).

[0032] A fourth object of the present invention is to provide the use of the solid catalyst component or the catalyst in ethylene homopolymerization or copolymerization.

[0033] The catalyst of the present invention is suitable for homopolymerization of ethylene or copolymerization of ethylene and other α-olefins, wherein the α-olefin is one of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 4-methylpentene-1. The polymerization can be carried out by slurry polymerization or gas phase polymerization, and the polymerization temperature can be 0 to 150° C., preferably 60 to 90° C.

[0034] The slurry polymerization medium includes inert solvents such as isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, xylene and other saturated aliphatic hydrocarbons or aromatic hydrocarbons.

[0035] In order to adjust the molecular weight of the final polymer, hydrogen was used as a molecular weight regulator.

[0036] The present invention is to dissolve magnesium halide in organic epoxy compound and organic phosphorus compound to form a uniform solution, add organic alcohol compound in the process of forming the solution or after the solution is formed, add transition metal titanium halide or its derivative under low temperature conditions to react, add electron donor in the process of titanium loading or after the titanium loading is completed, gradually precipitate components in the system, control a certain temperature rise trend, and thus obtain the solid catalyst component of the present invention. When the catalyst of the present invention is used for ethylene polymerization, it shows high catalytic activity, good hydrogen adjustment sensitivity and good copolymerization performance.

[0037] Due to the addition of the internal electron donor silicon ester compound and the compound represented by the general formula (I), the olefin polymerization catalyst obtained by the present invention can not only show good activity and copolymerization performance, but also show high polymerization activity and high polymer melt index under polymerization conditions of high hydrogen-ethylene ratio (for example, hydrogen partial pressure: ethylene partial pressure ≥ 3); and show low polymer melt index under polymerization conditions of low hydrogen-ethylene ratio (for example, hydrogen partial pressure: ethylene partial pressure ≤ 1). The catalyst preparation process is simple and is very suitable for ethylene slurry polymerization process and catalyst combination polymerization process requiring good hydrogen adjustment sensitivity. DETAILED DESCRIPTION

[0038] The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall within the scope of protection of the present invention.

[0039] The raw materials used in the examples and comparative examples, unless otherwise specified, are disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0040] Experimental test method:

[0041] 1. Relative weight percentage of titanium in the catalyst: using spectrophotometry.

[0042] 2. Polymer melt index (MI): determined according to ASTM D1238-99, load 2.16 kg, 190°C.

[0043] Example 1

[0044] (1) Preparation of solid catalyst component A

[0045] In a reactor fully replaced with high-purity nitrogen, 4.0g of magnesium dichloride, 50mL of toluene, 3mL of epichlorohydrin, 8mL of tributyl phosphate, and 4mL of ethanol were added in sequence, and the reaction mixture was heated to 70°C under stirring. When the solid was completely dissolved to form a uniform solution, it was reacted at 70°C for 2 hours. The system was cooled to -20°C, 40mL of titanium tetrachloride was added dropwise, and 4.0mL of tetraethoxysilane was added after the titanium was loaded. After 30 minutes of constant temperature, 1g of p-methoxyphenol was slowly added, the temperature was raised to 80°C, and the reaction was carried out for 2 hours. Stop stirring, let it stand, the suspension quickly separated, the upper clear liquid was removed, and the solid was washed four times with hexane. Dry with high-purity nitrogen to obtain a solid catalyst component with good fluidity.

[0046] (2) Homopolymerization

[0047] ①Polymerization reaction with low hydrogen / ethylene ratio

[0048] A 2L stainless steel reactor was fully replaced with high-purity nitrogen, and then 1L of hexane and 1.0mL of 1M triethylaluminum were added, and then the solid catalyst component (containing 0.4mg of titanium) prepared by the above method was added. The temperature was raised to 70°C, hydrogen was introduced to make the pressure in the reactor reach 0.28MPa, and then ethylene was introduced to make the total pressure in the reactor reach 0.73MPa. Polymerization was carried out at 80°C for 2 hours. The polymerization results are shown in Table 1.

[0049] ②Polymerization reaction with high hydrogen / ethylene ratio

[0050] A 2L stainless steel reactor was fully replaced with high-purity nitrogen, and then 1L of hexane and 1.0mL of 1M triethylaluminum were added, and then the solid catalyst component (containing 0.4mg of titanium) prepared by the above method was added. The temperature was raised to 75°C, hydrogen was introduced to make the pressure in the reactor reach 0.58MPa, and then ethylene was introduced to make the total pressure in the reactor reach 0.73MPa. Polymerization was carried out at 85°C for 2 hours. The polymerization results are shown in Table 2.

[0051] Example 2

[0052] (1) Same as Example 1, except that p-methoxyphenol was replaced by p-ethoxyphenol.

[0053] (2) Homopolymerization

[0054] Same as Example 1, the polymerization results are shown in Tables 1 and 2.

[0055] Example 3

[0056] (1) Same as Example 1, except that p-methoxyphenol was replaced by p-butoxyphenol.

[0057] (2) Homopolymerization

[0058] Same as Example 1, the polymerization results are shown in Tables 1 and 2.

[0059] Example 4

[0060] (1) Same as Example 1, except that p-methoxyphenol was replaced by o-methoxyphenol.

[0061] (2) Homopolymerization

[0062] Same as Example 1, the polymerization results are shown in Tables 1 and 2.

[0063] Example 5

[0064] (1) The same as Example 1, except that the amount of p-methoxyphenol added was adjusted to 500 mg.

[0065] (2) Homopolymerization

[0066] Same as Example 1, the polymerization results are shown in Tables 1 and 2.

[0067] Example 6

[0068] (1) Same as Example 2, except that the amount of p-ethoxyphenol added was adjusted to 500 mg.

[0069] (2) Homopolymerization

[0070] Same as Example 1, the polymerization results are shown in Tables 1 and 2.

[0071] Example 7

[0072] (1) Same as Example 3, except that the amount of p-butoxyphenol added was adjusted to 500 mg.

[0073] (2) Homopolymerization

[0074] Same as Example 1, the polymerization results are shown in Tables 1 and 2.

[0075] Example 8

[0076] (1) The same as Example 4, except that the amount of o-methoxyphenol added was adjusted to 500 mg.

[0077] (2) Homopolymerization

[0078] Same as Example 1, the polymerization results are shown in Tables 1 and 2.

[0079] Example 9

[0080] (1) The same as Example 1, except that the amount of p-methoxyphenol added was adjusted to 200 mg.

[0081] (2) Homopolymerization

[0082] Same as Example 1, the polymerization results are shown in Tables 1 and 2.

[0083] Example 10

[0084] (1) Same as Example 2, except that the amount of p-ethoxyphenol added was adjusted to 200 mg.

[0085] (2) Homopolymerization

[0086] Same as Example 1, the polymerization results are shown in Tables 1 and 2.

[0087] Embodiment 11

[0088] (1) Same as Example 3, except that the amount of p-butoxyphenol added was adjusted to 200 mg.

[0089] (2) Homopolymerization

[0090] Same as Example 1, the polymerization results are shown in Tables 1 and 2.

[0091] Example 12

[0092] (1) The same as Example 4, except that the amount of o-methoxyphenol added was adjusted to 200 mg.

[0093] (2) Homopolymerization

[0094] Same as Example 1, the polymerization results are shown in Tables 1 and 2.

[0095] Example 13

[0096] (1) Preparation of solid catalyst component B

[0097] In a reactor fully replaced with high-purity nitrogen, 4.0g of magnesium dichloride, 70mL of toluene, 3mL of epichlorohydrin, 7mL of tributyl phosphate, and 3.6mL of ethanol were added in sequence, and the reaction mixture was heated to 70°C under stirring. When the solid was completely dissolved to form a uniform solution, it was reacted at 70°C for 2 hours. The system was cooled to -20°C, 65mL of titanium tetrachloride was added dropwise, and 2.5mL of tetraethoxysilane was added after the titanium was loaded. After 30 minutes of constant temperature, 0.4g of p-methoxyphenol was slowly added, the temperature was raised to 80°C, and the reaction was carried out for 2 hours. Stop stirring, let it stand, the suspension quickly separated, the upper clear liquid was removed, and the solid was washed four times with hexane. Dry with high-purity nitrogen to obtain a solid catalyst component with good fluidity.

[0098] (2) Homopolymerization

[0099] Same as Example 1, the polymerization results are shown in Tables 1 and 2.

[0100] Comparative Example 1

[0101] (1) Preparation of solid catalyst component

[0102] In a reactor fully replaced with high-purity nitrogen, add 4.0g magnesium dichloride, 50mL toluene, 3mL epichlorohydrin, 8mL tributyl phosphate, and 4mL ethanol in sequence, and heat to 70°C under stirring. When the solid is completely dissolved to form a uniform solution, react at 70°C for 2 hours. Cool the system to -20°C, slowly drop 40mL titanium tetrachloride, and then add 4.0mL tetraethoxysilane. Slowly heat to 80°C and react for 2 hours. Stop stirring, let stand, the suspension quickly separates, remove the supernatant, and wash four times with hexane. Dry with high-purity nitrogen to obtain a solid catalyst component with good fluidity.

[0103] (2) Homopolymerization

[0104] Same as Example 1, the polymerization results are shown in Tables 1 and 2.

[0105] Comparative Example 2

[0106] (1) The solid catalyst component is the same as in Example 1, except that tetraethoxysilane is not added.

[0107] (2) Homopolymerization

[0108] Same as Example 1, the polymerization results are shown in Tables 1 and 2.

[0109] Table 1

[0110]

[0111] It can be seen from the data in Table 1 that after adding the internal electron donor silicone ester compound and the compound of general formula (I) for compounding, the catalyst of the present invention has better activity and higher titanium content under low hydrogen polymerization conditions, and the polymer prepared by the catalyst has a lower melt index under low hydrogen conditions.

[0112] Table 2

[0113]

[0114] From the data in Table 2, it can be seen that after adding the internal electron donor silicon ester compound and the compound of general formula (I), the catalyst of the present invention has a higher melt index under high hydrogen polymerization conditions. It can be seen that under the combined action of the compound of general formula (I) and the silicon ester compound, the catalyst has a higher melt index under a higher hydrogen-to-ethylene ratio, and a lower melt index under a lower hydrogen-to-ethylene ratio. This feature is conducive to the production of bimodal polyethylene products in slurry polymerization processes, and the production of high melt index products in gas phase polymerization processes.

[0115] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A solid catalyst component obtained by reacting a magnesium halide, an organic epoxy compound, an organic phosphorus compound, an organic alcohol compound, a silicon ester compound, a titanium halide or its derivative and a compound represented by formula (I), In formula (I), any one of R1, R2, R3, R4, and R5 is RO, and the others are the same or different and are independently hydrogen, C1-C 20 A straight chain alkyl or branched chain alkyl, cycloalkyl, aryl, alkaryl, aralkyl, R is selected from C1 to C 20 A straight-chain alkyl group or a branched-chain alkyl group, a cycloalkyl group, an aryl group, an alkaryl group, or an aralkyl group; The general formula of the silicone ester compound is R 2 x R 3 y Si(OR 4 ) z , where R 2 and R 3 C1~C 10 Hydrocarbon, halogen, R 4 C1~C 10 A hydrocarbon group, x, y, z are integers, 0≤x≤2, 0≤y≤2 and 0≤z≤4, and x+y+z=4; Based on each mole of magnesium halide, the organic epoxy compound is 0.2 to 10 moles, the organic phosphorus compound is 0.1 to 10 moles, the organic alcohol compound is 0.1 to 6 moles, the silicone ester compound is 0.1 to 1 mole, the titanium halide or its derivative is 1 to 20 moles, and the compound represented by formula (I) is 0.01 to 1.5 moles.

2. The solid catalyst component according to claim 1, characterized in that: The magnesium halide is selected from at least one of magnesium dichloride, magnesium dibromide and magnesium diiodide; The organic epoxy compound is selected from at least one of oxides, glycidyl ethers, and internal ethers of C2-C8 aliphatic olefins, dienes, or halogenated aliphatic olefins or dienes; The organic phosphorus compound is selected from at least one of a hydrocarbyl ester of orthophosphoric acid, a hydrocarbyl ester of phosphorous acid, a halogenated hydrocarbyl ester of orthophosphoric acid, and a halogenated hydrocarbyl ester of phosphorous acid; The organic alcohol compound is selected from C1 to C 10 Straight chain or branched chain or cycloalkyl alcohol, C6~C 20 Alcohols containing aromatic groups; The general formula of the titanium halide or its derivative is Ti(OR9) d X b , where R9 is C1~C 14 X is a halogen atom, d and b are each independently an integer of 0 to 4, and d+b=3 or 4.

3. The solid catalyst component according to claim 1, characterized in that: The compound represented by formula (I) is selected from at least one of p-methoxyphenol, o-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, o-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, o-propoxyphenol, m-propoxyphenol, p-butoxyphenol, o-butoxyphenol, m-butoxyphenol, p-hexyloxyphenol, o-hexyloxyphenol, m-hexyloxyphenol, p-octyloxyphenol, o-octyloxyphenol, m-octyloxyphenol, p-nonyloxyphenol, m-nonyloxyphenol, o-nonyloxyphenol, dodecyloxyphenol, tetradecyloxyphenol, octadecyloxyphenol, phenoxyphenol and hydroxyphenyl benzyl ether.

4. The solid catalyst component according to claim 2, characterized in that: The organic alcohol compound is selected from C1 to C 10 aliphatic alcohols; The silicone ester compound is selected from tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetra(2-ethylhexyloxy)silane, ethyltrimethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethoxysilane, 2-methylcyclopentyltrieth ...-methylcyclopentyltrimethoxysilane, 2,3-dimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethoxysilane, 2-methylcyclopentyltriethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2, Methylcyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, tert-butyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, monochlorotrimethoxysilane, monochlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, trimethylphenoxy Silane, methyl triallyloxysilane, vinyl triacetoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, tert-butylmethyldimethoxysilane, tert-butylmethyldiethoxysilane, tert-amylmethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, methylcyclopentyldiethoxysilane, methylcyclopentyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxy At least one of silane, methylphenyldiethoxysilane, methylphenyldimethoxysilane, bis-o-tolyldimethoxysilane, bis-o-tolyldiethoxysilane, bis-m-tolyldimethoxysilane, bis-m-tolyldiethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, and cyclopentyldimethylmethoxysilane; The titanium halide or its derivative is selected from at least one of TiCl3, TiBr4, TiCl4, Ti(OC2H5)Cl3, Ti(OCH3)Cl3, Ti(OC4H9)Cl3, Ti(OC2H5)Br3, Ti(OC2H5)2Cl2, Ti(OCH3)2Cl2, Ti(OCH3)2I2, Ti(OC2H5)3Cl, Ti(OCH3)3Cl, Ti(OC2H5)3I, Ti(OC2H5)4, Ti(OC3H7)4, and Ti(OC4H9)4.

5. The method for preparing the solid catalyst component according to any one of claims 1 to 4, comprising the following steps: The magnesium halide is reacted with an organic epoxy compound, an organic phosphorus compound and an organic alcohol compound to form a uniform reaction solution; and then mixed with a silicon ester compound, a titanium halide or its derivative, and a compound represented by formula (I) to obtain the solid catalyst component.

6. The preparation method according to claim 5, characterized in that: A magnesium halide, an organic epoxy compound, and an organic phosphorus compound are mixed to form a uniform solution at a mixing temperature of 50 to 90° C., wherein an organic alcohol compound is added during or after the uniform solution is formed, followed by reaction to obtain a reaction solution; the reaction solution is mixed with a silicone ester compound, a titanium halide or a derivative thereof, and a compound represented by formula (I) at -30 to 0° C.; the obtained mixture is heated to 50 to 120° C., and solid matter is precipitated after the reaction is completed, and the solid catalyst component is obtained by filtering.

7. The preparation method according to claim 5, characterized in that: Based on each mole of magnesium halide, the organic epoxy compound is 0.2 to 10 moles, the organic phosphorus compound is 0.1 to 10 moles, the organic alcohol compound is 0.1 to 6 moles, the silicone ester compound is 0.1 to 1 mole, the titanium halide or its derivative is 1 to 20 moles, and the compound represented by formula (I) is 0.01 to 1.5 moles.

8. An olefin polymerization catalyst comprising: (A) a solid catalyst component, wherein the solid catalyst component is a component as claimed in any one of claims 1 to 4; (B) a co-catalyst component, wherein the co-catalyst component is an organic aluminum compound.

9. The olefin polymerization catalyst according to claim 8, characterized in that: The general formula of the organoaluminum compound is AlR 1 e X 1 f H g , where R 1 is hydrogen or C l ~C 20 Hydrocarbon, X 1 is a halogen atom, e, f, and g are each independently a natural number of 0 to 3, and e+f+g=3.

10. The olefin polymerization catalyst according to claim 9, characterized in that: The organic aluminum compound is selected from AlEt3, Al(iso-Bu)3, Al(n-C6H 13 )3. Al(n-C8H 17 )3. At least one of AlEt2Cl.

11. The olefin polymerization catalyst according to claim 8, characterized in that: The molar ratio of the co-catalyst component calculated in terms of aluminum to the solid catalyst component calculated in terms of titanium is (5-500):

1.

12. The olefin polymerization catalyst according to claim 11, characterized in that: The molar ratio of the co-catalyst component calculated in terms of aluminum to the solid catalyst component calculated in terms of titanium is (20-200):

1.

13. Use of the solid catalyst component according to any one of claims 1 to 4 and the catalyst according to any one of claims 8 to 12 in ethylene homopolymerization or copolymerization.

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