Alkoxymagnesium solid supports, solid catalyst components, catalysts and processes for the polymerization of olefins

Abstract

This invention discloses an alkoxymagnesium solid support, a solid catalyst component, a catalyst, a preparation method, and an olefin polymerization method. The alkoxymagnesium solid support is obtained by dispersing alkoxymagnesium in a magnesium-containing composite solution, reacting thoroughly, washing, and drying. The magnesium-containing composite solution contains magnesium halides, organic epoxides, organophosphorus compounds, organic alcohols, and optionally an inert solvent. The alkoxymagnesium solid support of this invention has an adjustable particle size and narrow particle size distribution, and the catalyst exhibits high catalytic activity and good hydrogen sensitivity. Compared with other methods, the preparation method of this invention is simple to operate, highly adjustable, and has greater application prospects.

Description

Technical Field

[0001] This invention relates to the field of olefin polymerization technology, specifically to an alkoxymagnesium solid support, a solid catalyst component, a catalyst, a preparation method, and an olefin polymerization method for olefin polymerization. Background Technology

[0002] Polyolefins, as one of the world's largest industries, play a vital role in various fields of defense technology and people's lives. Ziegler-Natta catalysts are currently the most widely used catalysts in the polyolefin industry. Since their inception in the 1950s, they have undergone years of improvement by researchers and have formed a mature industrial system. They mainly consist of MgCl2-supported TiCl4 and Lewis basic compounds. Currently, most industrial catalysts are synthesized using two main methods: one is the direct dissolution method using MgCl2-supported titanium, and the other is a chemical reaction method using ethoxymagnesium as a precursor. The latter uses ethoxymagnesium as a support, reacting with TiCl4 to convert ethoxymagnesium to MgCl2 while simultaneously supporting titanium. The resulting catalyst exhibits good hydrogen sensitivity and excellent particle morphology. Several inventions, such as CN104592427A, CN101415666A, and CN109890850A, disclose methods for preparing excellent catalysts using alkoxymagnesium as a support.

[0003] In the prior art, a variety of methods for preparing alkoxy magnesium particles have been disclosed, such as patents EP1505084A1 and CN101054424A. Currently, the common preparation method is to use halogen elements or halides as initiators to directly react alcohols and magnesium. The products obtained by this method generally have a large particle size, and it is difficult to significantly adjust the particle size by adjusting the material ratio or changing the reaction conditions.

[0004] The patent with publication number CN108690152A proposes a method for preparing alkoxy magnesium microspheres by spray drying. The method involves mixing alkoxy magnesium solid powder with ethanol, grinding it with a ball mill, and then treating it with a high-speed disperser for a period of time to form a gel-like dispersion. After spray drying, small-sized alkoxy magnesium microspheres are obtained. However, this method has a low yield and the grinding process destroys some of the active centers, which reduces the activity of the catalyst.

[0005] Since the particle size of existing alkoxymagnesium supports is generally too large, their application range is limited. Small-particle-size supports obtained by physical methods such as grinding will cause some active centers to be destroyed. Therefore, post-processing of alkoxymagnesium supports to adjust the particle size can meet different process requirements. Summary of the Invention

[0006] To address the problems existing in the prior art, this invention provides a solid support for an alkoxymagnesium catalyst for olefin polymerization, its preparation method, and the components and catalyst composition for olefin polymerization. The alkoxymagnesium catalyst support obtained by this invention exhibits excellent particle morphology, suitable particle size, and uniform particle distribution. The size is controllable, resulting in high catalyst activity and good hydrogen sensitivity, making it suitable for olefin polymerization.

[0007] One object of the present invention is to provide an alkoxy magnesium solid support for olefin polymerization, comprising the reaction product of alkoxy magnesium with magnesium halide, organic epoxy compound, organophosphorus compound, organic alcohol compound and optionally inert solvent.

[0008] The alkoxymagnesium solid support is obtained by reacting alkoxymagnesium with a magnesium-containing composite solution and then drying it. The magnesium-containing composite solution includes magnesium halides, organic epoxy compounds, organophosphorus compounds, organic alcohol compounds, and optionally, an inert solvent. With the same initial particle size of alkoxymagnesium, alkoxymagnesium solid supports of different particle sizes can be obtained by controlling the molar ratio of alkoxymagnesium to the composite solution or the molar ratio of the components in the composite solution.

[0009] The alkoxymagnesium has the general formula Mg(OR) 1 ) n (OR 2 ) 2-n Where 0≤n≤2, R 1 and R 2 Whether they are the same or different, they are independently classified as C1 to C2. 20 The hydrocarbon group is preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, 2-ethylbutyl, 2-ethylhexyl, 4-methyl-sec-pentyl, 3,3,5-trimethylpentyl, 1-ethyl-2-methylpentyl, benzyl, 2-phenylethyl, 1-phenylpropyl, and more preferably ethyl or isooctyl.

[0010] More preferably, the alkoxy magnesium is dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, ethoxypropoxy magnesium, or butoxyethoxy magnesium; most preferably, the alkoxy magnesium is diethoxy magnesium or dipropoxy magnesium.

[0011] The magnesium halide is selected from magnesium dihalides, complexes of magnesium dihalides with water or alcohol, and derivatives of magnesium dihalides in which one or two halogen atoms are replaced by alkyl halides. Specific compounds include, but are not limited to, magnesium dichloride, magnesium dibromide, magnesium phenoxychloride, magnesium isopropoxychloride, magnesium butoxychloride, etc., with magnesium dichloride being preferred. The magnesium halide compounds can be used alone or in combination.

[0012] The organic epoxy compound may be selected from at least one of the following: oxides of C2-C8 aliphatic olefins, oxides of C2-C8 aliphatic dienes, oxides of C2-C8 halogenated aliphatic olefins, oxides of C2-C8 halogenated aliphatic dienes, glycidyl ethers, and internal ethers. Specifically, the organic epoxy compound may preferably be at least one of the following: ethylene oxide, propylene oxide, epibutane oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether, and butyl glycidyl ether.

[0013] The organophosphorus compound is selected from at least one of the following: hydrocarbon esters of orthophosphoric acid, hydrocarbon esters of phosphorous acid, halohydrocarbon esters of orthophosphoric acid, and halohydrocarbon esters of phosphorous acid. Specifically, the organophosphorus compound is preferably at least one of the following: trimethyl orthophosphoric acid, triethyl orthophosphoric acid, tributyl orthophosphoric acid, triphenyl orthophosphoric acid, trimethyl orthophosphoric acid, triethyl orthophosphoric acid, tributyl orthophosphoric acid, and triphenyl orthophosphoric acid.

[0014] The organic alcohol compound is selected from C1 to C2. 18 fatty alcohols, C6-C 18 At least one of aromatic alcohols, wherein the organic alcohol compound is preferably at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, hexanol, cyclohexanol, octanol, isoooctanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, propylene glycol, butanediol, hexanediol, and isohexanediol.

[0015] To achieve a more uniform dispersion, an inert diluent may be optionally added. This inert diluent typically includes aromatic or alkane compounds. Preferred aromatic compounds include benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, monochlorotoluene, and their derivatives. Alkane compounds are one or a mixture of straight-chain alkanes, branched alkanes, or cycloalkanes with 3 to 20 carbon atoms, such as butane, pentane, hexane, cyclohexane, and heptane. Any solvent that aids in the dispersion of magnesium halides and alkoxymagnesium can be used. The aforementioned inert solvents can be used alone or in combination.

[0016] In the alkoxy magnesium solid support described in this invention, per mole of magnesium: 0.2-4 mol of organic epoxy compound, 0.2-4 mol of organic phosphorus compound, and 0.5-4 mol of organic alcohol compound, wherein the molar amount of magnesium is the total molar amount of magnesium in alkoxy magnesium and magnesium halide.

[0017] Preferably, the organic epoxy compound is 0.3–2 mol, the organic phosphorus compound is 0.3–2 mol, and the organic alcohol compound is 1–2 mol.

[0018] Specifically, in the alkoxy magnesium solid support, per mole of magnesium: the organic epoxy compound can be 0.2 mol, 0.5 mol, 1 mol, 1.5 mol, 2 mol, 2.5 mol, 3 mol, 3.5 mol, 4 mol, etc.; the organic phosphorus compound can be 0.2 mol, 0.5 mol, 1 mol, 1.5 mol, 2 mol, 2.5 mol, 3 mol, 3.5 mol, 4 mol, etc.; and the organic alcohol compound can be 0.5 mol, 1 mol, 1.5 mol, 2 mol, 2.5 mol, 3 mol, 3.5 mol, 4 mol, etc.

[0019] In the alkoxymagnesium solid support of the present invention, the amount of the inert solvent is 0 to 10 L / mol per mole of magnesium, preferably 0.2 to 5 L / mol, wherein the molar amount of magnesium is the total molar amount of magnesium in alkoxymagnesium and magnesium halide.

[0020] In the alkoxymagnesium solid support of the present invention, alkoxymagnesium and magnesium halide can be mixed in any proportion. Preferably, the molar ratio of magnesium halide to alkoxymagnesium is (0.1-3):1, more preferably (0.2-2):1, and even more preferably (0.5-2):1. For example, it can be 0.1:1, 0.3:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, etc.

[0021] A second objective of this invention is to provide a method for preparing the alkoxymagnesium solid support for olefin polymerization as described in one objective of this invention, comprising reacting a component including alkoxymagnesium, magnesium halide, organic epoxy compound, organic phosphorus compound and organic alcohol compound to obtain the alkoxymagnesium solid support for olefin polymerization.

[0022] Specifically, the method for preparing the alkoxymagnesium solid support includes dispersing alkoxymagnesium in a magnesium-containing composite solution, washing and drying the resulting precipitate after the reaction. Preferably, the reaction is carried out at 50–90°C for 0.5–10 h. The magnesium-containing composite solution includes magnesium halide, organic epoxy compounds, organophosphorus compounds, organic alcohol compounds, and optionally an inert solvent.

[0023] According to one embodiment of the present invention, the alkoxymagnesium solid support can be prepared by the following method:

[0024] (1) Disperse magnesium alkoxy in a solvent system containing magnesium halide, organic epoxy compound, organic phosphorus compound and organic alcohol compound, preferably by adding an inert solvent to the solvent system to form a homogeneous suspension.

[0025] (2) At a higher temperature, preferably 50 to 90°C, the surface layer of alkoxy magnesium is partially dissolved under the action of other components.

[0026] (3) After a certain reaction time, unreacted substances and solvents are removed, and the mixture is washed with an inert solvent to obtain the alkoxy magnesium solid support of the present invention.

[0027] In the above technical solution, after the reaction, it is preferred to wash with an inert solvent for washing, and then dry to obtain the alkoxy magnesium solid support for olefin polymerization; the inert solvent for washing is at least one of liquid aromatic hydrocarbons and alkanes at room temperature, the aromatic hydrocarbons include but are not limited to: benzene, toluene, xylene, ethylbenzene, propylbenzene or trimethylbenzene, preferably toluene or xylene; the alkanes include but are not limited to hexane, cyclohexane, heptane, octane or decane.

[0028] In the above technical solution, the reaction product after washing is dried or suspended in a dispersant.

[0029] The present invention provides a method for preparing alkoxymagnesium solid supports with adjustable size. By adjusting the proportion of each component in the magnesium-containing composite solution, alkoxymagnesium catalyst supports of different sizes can be obtained, thus making them suitable for different polymerization processes.

[0030] A third objective of this invention is to provide a solid catalyst component for olefin polymerization, comprising the alkoxymagnesium solid support described in one objective of this invention or the alkoxymagnesium solid support obtained by the preparation method described in another objective of this invention, an electron donor compound, and a reaction product containing a titanium compound.

[0031] The solid catalyst component of the present invention includes the reaction product of the following components: (1) an alkoxy magnesium solid support for olefin polymerization for one of the purposes of the present invention or a solid support for olefin polymerization prepared by the method for another purpose of the present invention; (2) a titanium-containing compound; and (3) an electron donor compound.

[0032] The titanium-containing compound is selected from compounds with the general formula Ti(OR). a X b At least one of the compounds, wherein R is C1 to C2. 14 Aliphatic hydrocarbon group, C6~C 18 Aromatic hydrocarbon group, where X is a halogen, a is an integer from 0 to 4, b is an integer from 0 to 4, and a + b = 3 or 4; where R is a C1 to C2 group. 14 aliphatic hydrocarbon groups or C6~C 18 Aromatic hydrocarbon group, including saturated or unsaturated groups, or straight-chain or branched groups, or cyclic groups, preferably R is C1 to C2. 14The alkyl, alkenyl, cycloalkyl, cycloalkenyl, or aralkyl group, more preferably R is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, allyl, butenyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl, tolyl, benzyl, or phenethyl; X is a halogen atom, preferably a chlorine or bromine atom, more preferably a chlorine atom; when a is 2 or more, the general formula is Ti(OR). a X b Multiple R's in the equation can be the same or different.

[0033] In a preferred embodiment of the present invention,

[0034] The titanium-containing compound is selected from one or more of tetraalkyl titanium, tetraalkoxy titanium, tetrahalide titanium, trihaloalkoxy titanium, dihalodialkoxy titanium, and monohalotrialkoxy titanium compounds; the tetraalkoxy titanium is selected from at least one of tetramethoxy titanium, tetraethoxy titanium, tetran-propoxy titanium, tetraisopropoxy titanium, tetran-butoxy titanium, tetraisobutoxy titanium, tetracyclohexyloxy titanium, and tetraphenoxy titanium; the tetrahalide titanium is selected from at least one of titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide; the trihaloalkoxy titanium is selected from trichloromethoxy titanium, trichloroethoxy titanium, trichloropropoxy titanium, trichloron-butoxy titanium, and tribromoethoxy titanium. At least one of titanium; the dihalodialkoxy titanium is selected from at least one of dichlorodimethoxy titanium, dichlorodiethoxy titanium, dichlorodi-n-propoxy titanium, dichlorodiisopropoxy titanium, and dibromodiethoxy titanium; the monohalotrialkoxy titanium is selected from at least one of monochlorotrimethoxy titanium, monochlorotriethoxy titanium, monochlorotri-n-propoxy titanium, and monochlorotriisopropoxy titanium; more preferably, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraethoxy, titanium monochlorotriethoxy, titanium trichloride, dichlorodiethoxy, and trichloromonethoxy titanium; even more preferably, the titanium compound is selected from titanium tetrachloride.

[0035] The electron-donating compound is selected from at least one of the following: alkyl esters of aliphatic monocarboxylic acids, alkyl esters of aromatic monocarboxylic acids, alkyl esters of aliphatic polycarboxylic acids, alkyl esters of aromatic polycarboxylic acids, aliphatic ethers, cyclic aliphatic ethers, and aliphatic ketones, preferably at least one of the following: alkyl esters of C1-C4 saturated aliphatic carboxylic acids, alkyl esters of C7-C8 aromatic carboxylic acids, C2-C6 aliphatic ethers, C3-C4 cyclic ethers, and C3-C6 saturated aliphatic ketones.

[0036] In a specific example, the electron-donating compound is selected from at least one of methyl formate, ethyl acetate, butyl acetate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, 1,3-dipentyl phthalate, diethyl ether, hexyl ether, tetrahydrofuran (THF), acetone, and methyl isobutyl ketone, preferably from at least one of di-n-butyl phthalate, diisobutyl phthalate, and 1,3-dipentyl phthalate.

[0037] In a preferred embodiment of the present invention, per mole of magnesium in the alkoxymagnesium solid support: the titanium-containing compound is 0.5 to 50 mol, and the electron-donating compound is 0.01 to 1 mol; preferably, the titanium-containing compound is 1 to 10 mol, and the electron-donating compound is 0.1 to 0.6 mol.

[0038] Specifically, in the solid catalyst components, based on each mole of magnesium in the alkoxymagnesium solid support: the titanium-containing compound can be 0.5 mol, 1 mol, 5 mol, 8 mol, 10 mol, 20 mol, 30 mol, 40 mol, 50 mol, etc.; the electron-donating compound can be 0.01 mol, 0.1 mol, 0.2 mol, 0.4 mol, 0.6 mol, 0.8 mol, 1 mol, etc.

[0039] The fourth objective of this invention is to provide a method for preparing a solid catalyst component for olefin polymerization, as described in the third objective of this invention, comprising reacting the alkoxymagnesium solid support with a titanium-containing compound and an electron donor compound in an inert diluent, and washing and drying the mixture after the reaction to obtain the solid catalyst component.

[0040] In a preferred embodiment of the present invention,

[0041] The inert diluent is selected from C6 to C6. 10 It contains at least one of alkanes or aromatics, preferably at least one of hexane, heptane, octane, decane, benzene, toluene, and xylene.

[0042] The method for preparing the solid catalyst component according to the present invention does not particularly limit the reaction conditions. Reaction conditions known to those skilled in the art of olefin polymerization solid catalyst components can be used.

[0043] According to a preferred embodiment of the present invention, the alkoxymagnesium solid support and an inert diluent are added to a reaction vessel, the temperature is lowered to -50 to 10°C, and a titanium-containing compound and an electron donor compound are slowly added dropwise under stirring. After the reaction is completed, the temperature is raised to 50 to 150°C and held at that temperature for 0.1 to 5 hours. The mixture is allowed to settle, the supernatant is decanted, washed with a solvent, separated, and dried to obtain the solid catalyst component.

[0044] A fifth objective of this invention is to provide a catalyst for olefin polymerization, comprising:

[0045] (A) The solid catalyst component described in the third objective of this invention or the solid catalyst component obtained by the preparation method described in the fourth objective of this invention;

[0046] (B) The general formula is AlR 3 m X 3-m Organoaluminum compounds, where R 3 Hydrogen, C1 to C 20 Hydrocarbon group, where X is a halogen, preferably fluorine, chlorine or bromine, and 0 < m ≤ 3.

[0047] In this invention, the organoaluminum compound can be at least one of Al(CH3)3, Al(CH2CH3)3, Al(i-Bu)3, AlH(CH2CH3)2, AlH(i-Bu)2, AlCl(CH2CH3)2, Al2Cl3(CH2CH3)3, AlCl2(CH2CH3), etc., preferably Al(CH2CH3)3 or Al(i-Bu)3.

[0048] The molar ratio of the organoaluminum compound to titanium in the solid catalyst component is (5-500):1, preferably (20-200):1.

[0049] The sixth objective of this invention is to provide a method for olefin polymerization, comprising contacting an olefin and optionally a comonomer with the catalyst described in the fifth objective of this invention under polymerization conditions to carry out a polymerization reaction.

[0050] Specifically, the olefin polymerization method includes:

[0051] (i) Contacting the olefin and optionally the comonomer with the catalyst under polymerization conditions to form a polymer; and

[0052] (ii) Recover the polymer formed in step (i).

[0053] The olefin polymerization method according to the present invention can be used for homopolymerization of olefins and copolymerization with α-olefins. Specific examples of olefins include: ethylene, propylene, butene, pentene, hexene, octene, 4-methyl-1-pentene, etc.

[0054] The olefin polymerization method according to the present invention does not particularly limit the polymerization conditions of the olefins. Polymerization conditions known to those skilled in the art of olefin polymerization can be used.

[0055] The substances and parameters not limited in this invention can be selected according to existing technology, which is a conventional technical means in this field.

[0056] The beneficial effects of this invention are:

[0057] Since the preparation of small-particle-size alkoxy magnesium is relatively difficult, the method of this invention can more easily obtain small-particle-size alkoxy magnesium, and the particle size of the treated alkoxy magnesium can be freely controlled by adjusting the composition ratio of the magnesium-containing composite solution.

[0058] The alkoxymagnesium solid support provided by this invention has the advantages of uniform particle shape, simple operation, and controllable size, and can be used to catalyze olefin polymerization; the catalyst prepared with the above-mentioned alkoxymagnesium as support has high polymerization activity and good hydrogen regulation sensitivity.

[0059] The preparation method of the present invention is simple to operate, highly adjustable, and has greater application prospects. Detailed Implementation

[0060] 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.

[0061] Furthermore, various embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention. The resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0062] Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0063] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0064] In the following embodiments, the testing methods involved are as follows:

[0065] (1) Average particle size (D50): Particle size corresponding to 50% of cumulative weight;

[0066] (2) The particle size distribution of alkoxy magnesium was measured by laser diffraction using a Malvern Mastersizer TM2000 laser particle size analyzer with n-hexane as the dispersant, where SPAN = (D90-D10) / D50.

[0067] (3) The melt flow index of the polymer powder is adopted. The MI-2 melt indexer manufactured by our company measures the mass of molten powder passing through a die per unit time under conditions of 190℃ and 2.16kg pressure. Unit: g / min.

[0068] (4) The relative weight percentage of titanium in the solid catalyst component was characterized by spectrophotometry.

[0069] (5) The pressure inside the reactor mentioned in the polymerization reaction is absolute pressure.

[0070] ① Polymerization reaction with low hydrogen / ethylene ratio

[0071] A 2L stainless steel reactor was fully purged with high-purity nitrogen, then 1L of hexane and 2.0mL of 1M triethylaluminum solution were added, followed by the solid catalyst components (containing 0.6mg titanium) prepared in the examples and comparative examples. The temperature was raised to 70°C, and hydrogen was introduced to bring the pressure inside the reactor to 0.28MPa. Ethylene was then introduced to bring the total pressure inside the reactor to 0.73MPa, and polymerization was carried out at 80°C for 2 hours.

[0072] ② Polymerization reaction with high hydrogen / ethylene ratio

[0073] A 2L stainless steel reactor was fully purged with high-purity nitrogen, then 1L of hexane and 1.0mL of 1M triethylaluminum were added, followed by the solid catalyst components (containing 0.6mg titanium) prepared in the examples and comparative examples. The temperature was raised to 70°C, and hydrogen was introduced to bring the pressure inside the reactor to 0.58MPa. Ethylene was then introduced to bring the total pressure inside the reactor to 0.73MPa, and polymerization was carried out at 80°C for 2 hours.

[0074] The present invention will be further described below with reference to specific embodiments.

[0075] Example 1

[0076] In a reactor thoroughly purged with high-purity nitrogen, 4.00 g (35 mmol) of magnesium diethoxy (40 μm), 0.67 g (7 mmol) of magnesium chloride, 100 mL of toluene, 2.0 mL of epichlorohydrin, 6.0 mL of tributyl phosphate, and 3.4 mL of ethanol were added sequentially. The mixture was heated to 66 °C with stirring to disperse the system and form a homogeneous suspension. The reaction was carried out at 66 °C for 2 hours. After stirring was stopped and the mixture was allowed to stand, the suspension quickly separated into layers. The supernatant was extracted, and the precipitate was washed twice with toluene and hexane, then transferred to a chromatography funnel with hexane and dried with high-purity nitrogen to obtain a white solid powder with good flowability (i.e., alkoxymagnesium support for olefin polymerization).

[0077] In a 300 mL stirred reactor fully purged with nitrogen, 4 g of the alkoxymagnesium support (35 mmol) prepared in Example 1 and 40 mL of toluene were added. The mixture was cooled to -15 °C, and 15 mL of TiCl4 and 1.5 mL of ethyl acetate were slowly added dropwise with stirring. After the reaction was completed, the temperature was raised to 85 °C and held at that temperature for 2 h. The mixture was allowed to settle, and the supernatant was decanted. The supernatant was washed four times with hexane, separated, and dried to obtain a solid catalyst with good flowability.

[0078] The properties of the obtained alkoxymagnesium support and catalyst are shown in Table 1 and Table 2, respectively.

[0079] Example 2

[0080] The same method as in Example 1 was used, except that 3.20 g (28 mmol) magnesium diethoxy (40 μm) and 1.33 g (14 mmol) magnesium chloride were added to the reaction system. After the reaction was complete, the product was washed and dried to obtain a white solid powder with good flowability.

[0081] In a 300 mL stirred reactor fully purged with nitrogen, 4 g of the alkoxymagnesium support prepared in Example 2 and 40 mL of toluene were added. The temperature was lowered to -15 °C, and 15 mL of TiCl4 and 1.5 mL of ethyl acetate were slowly added dropwise with stirring. After the reaction was completed, the temperature was raised to 85 °C and held for 2 h. The mixture was allowed to settle, and the supernatant was decanted. The supernatant was washed four times with hexane, separated, and dried to obtain a solid catalyst with good flowability.

[0082] The properties of the obtained alkoxymagnesium support and catalyst are shown in Table 1 and Table 2, respectively.

[0083] Example 3

[0084] The same method as in Example 1 was used, except that 2.40 g (21 mmol) magnesium diethoxy (40 μm) and 2.00 g (21 mmol) magnesium chloride were added to the reaction system. After the reaction was complete, the product was washed and dried to obtain a white solid powder with good flowability.

[0085] In a 300 mL stirred reactor fully purged with nitrogen, 4 g of the alkoxymagnesium support prepared in Example 3 and 40 mL of toluene were added. The temperature was lowered to -15 °C, and 15 mL of TiCl4 and 1.5 mL of ethyl acetate were slowly added dropwise with stirring. After the reaction was completed, the temperature was raised to 85 °C and held at that temperature for 2 h. The mixture was allowed to settle, and the supernatant was decanted. The supernatant was washed four times with hexane, separated, and dried to obtain a solid catalyst with good flowability.

[0086] The properties of the obtained alkoxymagnesium support and catalyst are shown in Table 1 and Table 2, respectively.

[0087] Example 4

[0088] The same method as in Example 1 was used, except that 1.60 g (14 mmol) magnesium diethoxy (40 μm) and 2.67 g (28 mmol) magnesium chloride were added to the reaction system. After the reaction was complete, the product was washed and dried to obtain a white solid powder with good flowability.

[0089] In a 300 mL stirred reactor fully purged with nitrogen, 4 g of the alkoxymagnesium support prepared in Example 4 and 40 mL of toluene were added. The temperature was lowered to -15 °C, and 15 mL of TiCl4 and 1.5 mL of ethyl acetate were slowly added dropwise with stirring. After the reaction was completed, the temperature was raised to 85 °C and held for 2 h. The mixture was allowed to settle, and the supernatant was decanted. The supernatant was washed four times with hexane, separated, and dried to obtain a solid catalyst with good flowability.

[0090] The properties of the obtained alkoxymagnesium support and catalyst are shown in Table 1 and Table 2, respectively.

[0091] Example 5

[0092] The same method as in Example 3 was used, except that 1.0 mL of epichlorohydrin was added to the reaction system. After the reaction was complete, the product was washed and dried to obtain a white solid powder with good flowability.

[0093] In a 300 mL stirred reactor fully purged with nitrogen, 4 g of the alkoxymagnesium support prepared in Example 5 and 40 mL of toluene were added. The temperature was lowered to -15 °C, and 15 mL of TiCl4 and 1.5 mL of ethyl acetate were slowly added dropwise with stirring. After the reaction was completed, the temperature was raised to 85 °C and held for 2 h. The mixture was allowed to settle, and the supernatant was decanted. The supernatant was washed four times with hexane, separated, and dried to obtain a solid catalyst with good flowability.

[0094] The properties of the obtained alkoxymagnesium support and catalyst are shown in Table 1 and Table 2, respectively.

[0095] Example 6

[0096] The same method as in Example 3 was used, except that 3.0 mL of epichlorohydrin was added to the reaction system. After the reaction was complete, the product was washed and dried to obtain a white solid powder with good flowability.

[0097] In a 300 mL stirred reactor fully purged with nitrogen, 4 g of the alkoxymagnesium support prepared in Example 6 and 40 mL of toluene were added. The temperature was lowered to -15 °C, and 15 mL of TiCl4 and 1.5 mL of ethyl acetate were slowly added dropwise with stirring. After the reaction was completed, the temperature was raised to 85 °C and held at that temperature for 2 h. The mixture was allowed to settle, and the supernatant was decanted. The supernatant was washed four times with hexane, separated, and dried to obtain a solid catalyst with good flowability.

[0098] The properties of the obtained alkoxymagnesium support and catalyst are shown in Table 1 and Table 2, respectively.

[0099] Example 7

[0100] The same method as in Example 3 was used, except that 4.0 mL of tributyl phosphate was added to the reaction system. After the reaction was complete, the product was washed and dried to obtain a white solid powder with good flowability.

[0101] In a 300 mL stirred reactor fully purged with nitrogen, 4 g of the alkoxymagnesium support prepared in Example 7 and 40 mL of toluene were added. The temperature was lowered to -15 °C, and 15 mL of TiCl4 and 1.5 mL of ethyl acetate were slowly added dropwise with stirring. After the reaction was completed, the temperature was raised to 85 °C and held for 2 h. The mixture was allowed to settle, and the supernatant was decanted. The supernatant was washed four times with hexane, separated, and dried to obtain a solid catalyst with good flowability.

[0102] The properties of the obtained alkoxymagnesium support and catalyst are shown in Table 1 and Table 2, respectively.

[0103] Example 8

[0104] The same method as in Example 3 was used, except that 8.0 mL of tributyl phosphate was added to the reaction system. After the reaction was complete, the product was washed and dried to obtain a white solid powder with good flowability.

[0105] In a 300 mL stirred reactor fully purged with nitrogen, 4 g of the alkoxymagnesium support prepared in Example 8 and 40 mL of toluene were added. The temperature was lowered to -15 °C, and 15 mL of TiCl4 and 1.5 mL of ethyl acetate were slowly added dropwise with stirring. After the reaction was completed, the temperature was raised to 85 °C and held at that temperature for 2 h. The mixture was allowed to settle, and the supernatant was decanted. The supernatant was washed four times with hexane, separated, and dried to obtain a solid catalyst with good flowability.

[0106] The properties of the obtained alkoxymagnesium support and catalyst are shown in Table 1 and Table 2, respectively.

[0107] Comparative Example 1

[0108] In a reactor thoroughly purged with high-purity nitrogen, 4.78 g (42 mmol) of magnesium diethoxy (40 μm), 100 mL of toluene, 2 mL of epichlorohydrin, 6 mL of tributyl phosphate, and 3.4 mL of ethanol were added sequentially. The mixture was stirred and heated to 66 °C to disperse the system into a homogeneous suspension. The reaction was carried out at 66 °C for 2 hours. After stirring was stopped and the mixture was allowed to stand, the suspension quickly separated into layers. The supernatant was removed, and the precipitate was washed twice with toluene and hexane, then transferred to a chromatography funnel with hexane and dried with high-purity nitrogen to obtain a white solid powder with good flowability (i.e., magnesium alkoxy support for olefin polymerization).

[0109] In a 300 mL stirred reactor fully purged with nitrogen, 4 g of the alkoxymagnesium support prepared in Example 1 and 40 mL of toluene were added. The temperature was lowered to -15 °C, and 15 mL of TiCl4 and 1.5 mL of ethyl acetate were slowly added dropwise with stirring. After the reaction was completed, the temperature was raised to 85 °C and held for 2 h. The mixture was allowed to settle, and the supernatant was decanted. The supernatant was washed four times with hexane, separated, and dried to obtain a solid catalyst with good flowability.

[0110] The properties of the obtained alkoxymagnesium support and catalyst are shown in Table 1 and Table 2, respectively.

[0111] Comparative Example 2

[0112] In a reactor thoroughly purged with high-purity nitrogen, 4.00 g (42 mmol) of magnesium chloride, 100 mL of toluene, 2 mL of epichlorohydrin, 6 mL of tributyl phosphate, and 3.4 mL of ethanol were added sequentially. The mixture was heated to 66 °C with stirring to disperse the solid and form a homogeneous suspension. The reaction was maintained at 66 °C for 2 hours until the solid completely dissolved, forming a homogeneous solution. The mixture was then cooled to -15 °C, and 70 mL of TiCl4 was slowly added dropwise with stirring. Subsequently, 1.5 mL of ethyl acetate was added. After the reaction was complete, the temperature was raised to 85 °C and maintained for 2 hours. Stirring was stopped, and the mixture was allowed to settle. The supernatant was decanted, washed four times with hexane, separated, and dried to obtain a solid catalyst with good flowability.

[0113] The performance of the obtained catalyst is shown in Table 2.

[0114] Table 1. Performance comparison of alkoxymagnesium carriers

[0115]

[0116] Table 2 Comparison of catalyst performance

[0117]

[0118] As shown in Tables 1 and 2, this invention achieves controllable adjustment of the alkoxymagnesium support by changing the composition ratio of substances in the magnesium-containing composite solution. The alkoxymagnesium support obtained by this method has controllable particle size and a narrow particle size distribution, resulting in high activity in the ethylene polymerization process. Compared with the dissolution-type catalyst of Comparative Example 2, the catalyst prepared by this invention exhibits better hydrogen regulation sensitivity. Therefore, the catalyst components of this invention have superior overall performance.

[0119] Specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above. Without departing from the scope of the present invention, those skilled in the art can make various modifications and variations within the scope of the claims, and can substitute equivalent substances, which does not affect the substantive content of the present invention.

Claims

1. An alkoxymagnesium solid support comprising the reaction product of alkoxymagnesium with magnesium halide, an organic epoxy compound, an organic phosphorus compound, an organic alcohol compound, and optionally an inert solvent.

2. The alkoxymagnesium solid support according to claim 1, characterized in that: The general formula of the alkoxymagnesium is Mg(OR) 1 ) n (OR 2 ) 2-n Where 0≤n≤2, R 1 and R 2 Whether they are the same or different, they are independently classified as C1 to C2. 20 hydrocarbon groups; and / or, The magnesium halide is selected from at least one of magnesium dihalides, complexes of magnesium dihalides with water or alcohol, and derivatives of magnesium dihalides in which one or two halogen atoms are replaced by alkyl halides, preferably from at least one of magnesium dichloride, magnesium dibromide, magnesium phenoxychloride, magnesium isopropoxychloride, and magnesium butoxychloride; and / or, The organic epoxy compound is selected from at least one of the following: oxides of C2-C8 aliphatic olefins, oxides of C2-C8 aliphatic dienes, oxides of C2-C8 haloaliphatic olefins, oxides of C2-C8 haloaliphatic dienes, glycidyl ethers, and internal ethers; preferably from at least one of ethylene oxide, propylene oxide, butane oxide, butadiene oxide, epichlorohydrin, glycidyl methacrylate, ethyl glycidyl ether, and butyl glycidyl ether; and / or, The organophosphorus compound is selected from at least one of the following: alkyl esters of orthophosphoric acid, alkyl esters of phosphorous acid, haloalkyl esters of orthophosphoric acid, and haloalkyl esters of phosphorous acid; preferably from at least one of the following: trimethyl orthophosphoric acid, triethyl orthophosphoric acid, tributyl orthophosphoric acid, triphenyl orthophosphoric acid, trimethyl orthophosphoric acid, triethyl orthophosphoric acid, tributyl orthophosphoric acid, and triphenyl orthophosphoric acid; and / or, The organic alcohol compound is selected from C1 to C2. 18 fatty alcohols, C6-C 18 At least one of the aromatic alcohols, preferably selected from at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, hexanol, cyclohexanol, octanol, isooctanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, propylene glycol, butanediol, hexanediol, and isohexanediol; and / or, The inert solvent is selected from at least one of aromatic compounds and alkane compounds.

3. The alkoxymagnesium solid support according to claim 1, characterized in that: Based on each mole of magnesium, the organic epoxy compound comprises 0.2–4 mol, the organic phosphorus compound comprises 0.2–4 mol, and the organic alcohol compound comprises 0.5–4 mol, wherein the molar amount of magnesium is the total molar amount of magnesium in alkoxy magnesium and magnesium halide; preferably, the organic epoxy compound comprises 0.3–2 mol, the organic phosphorus compound comprises 0.3–2 mol, and the organic alcohol compound comprises 1–2 mol; and / or, The amount of the inert solvent used is 0 to 10 L / mol per mole of magnesium, preferably 0.2 to 5 L / mol.

4. A method for preparing an alkoxymagnesium solid support according to any one of claims 1 to 3, comprising dispersing alkoxymagnesium in a magnesium-containing composite solution, washing and drying the resulting precipitate after the reaction, wherein the magnesium-containing composite solution comprises magnesium halide, organic epoxy compound, organic phosphorus compound, organic alcohol compound and optionally an inert solvent; preferably, the reaction is carried out at 50 to 90°C for 0.5 to 10 h.

5. A solid catalyst component for olefin polymerization, comprising the alkoxymagnesium solid support as described in any one of claims 1 to 3 or the alkoxymagnesium solid support obtained by the preparation method described in claim 4, an electron donor compound, and a reaction product containing a titanium compound.

6. The solid catalyst component according to claim 5, characterized in that: The electron-donating compound is selected from at least one of the following: alkyl esters of aliphatic monocarboxylic acids, alkyl esters of aromatic monocarboxylic acids, alkyl esters of aliphatic polycarboxylic acids, alkyl esters of aromatic polycarboxylic acids, aliphatic ethers, cyclic aliphatic ethers, and aliphatic ketones; preferably at least one of the following: methyl formate, ethyl acetate, butyl acetate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, 1,3-dipentyl phthalate, diethyl ether, hexyl ether, tetrahydrofuran, acetone, and methyl isobutyl ketone; and / or, The general formula of the titanium-containing compound is Ti(OR). a X b Where R is C1 to C 14 Aliphatic hydrocarbon group, C6~C 18 Aromatic hydrocarbon group, X is a halogen, a is an integer from 0 to 4, b is an integer from 0 to 4, and a+b=3 or 4.

7. The solid catalyst component according to claim 5, characterized in that: Based on each mole of magnesium in the alkoxy magnesium solid support: electron-donating compounds are 0.01–1 mol, and titanium-containing compounds are 0.5–50 mol; Preferably, the titanium-containing compound is 1–10 mol and the electron-donating compound is 0.1–0.6 mol.

8. A method for preparing a solid catalyst component according to any one of claims 5 to 7, comprising reacting an alkoxy magnesium solid support with an electron donor compound and a titanium-containing compound in an inert diluent.

9. A catalyst for olefin polymerization, comprising: (A) The solid catalyst component according to any one of claims 5 to 7 or the solid catalyst component obtained by the preparation method according to claim 8; (B) The general formula is AlR 3 m X 3-m Organoaluminum compounds, where R 3 Hydrogen, C1 to C 20 Hydrocarbon group, X is halogen, 0 < m ≤ 3.

10. The catalyst for olefin polymerization according to claim 9, characterized in that: The molar ratio of the organoaluminum compound to titanium in the solid catalyst component is (5-500):1, preferably (20-200):

1.

11. An olefin polymerization method comprising contacting an olefin and optionally a comonomer with the catalyst of claim 9 or 10 under polymerization conditions to carry out a polymerization reaction.

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