A catalyst component for the polymerization of olefins, process for its preparation, catalyst and use thereof

Abstract

The present application belongs to the field of olefin polymerization, and discloses a catalyst component for olefin polymerization, a preparation method of the catalyst component, a catalyst and application of the catalyst component. The catalyst component comprises a reaction product of a magnesium-containing liquid component, a carbonate compound, a titanium compound and an optional other electron donor compound. The magnesium-containing liquid component is prepared by the following method: in the presence of an inert solvent, a magnesium-containing compound, an alcohol compound, an optional organic epoxy compound and an optional organic phosphorus compound are reacted to obtain the magnesium-containing liquid component. The magnesium-containing compound is at least one of magnesium dihalide, MgR 1 Cl and Mg(OR 2 )Cl; the carbonate compound comprises at least one of the compounds of formula I; R1-R6 are each independently C1-C8 hydrocarbyl, C1-C8 halogenated hydrocarbyl, H or halogen. The catalyst of the present application has higher activity, higher polymer powder bulk density and better hydrogen sensitivity, and the obtained polymer has less fine powder.

Description

Technical Field

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

[0002] Since its invention in the 1930s, polyethylene has been widely used in industry, agriculture, packaging and daily consumption due to its abundant raw materials and excellent product performance.

[0003] Catalyst research has always played a crucial role in the synthesis and production of polyethylene. Among them, titanium-magnesium catalysts have gained widespread application and continued to be developed due to their high catalytic efficiency and low cost.

[0004] In polyethylene production, excessive polymer powder can easily generate static electricity, leading to clumping and blockage of equipment and pipelines. Good particle morphology can effectively reduce the generation of polymer powder.

[0005] The dissolution and precipitation method plays an important role in the preparation of titanium-magnesium catalysts. Among them, how to control the precipitation of the catalyst to obtain catalysts with good particle morphology is a key point. For example, CN96106647.4 uses an organosilicon compound without active hydrogen to contact a liquid magnesium compound with a liquid titanium compound to obtain a catalyst; CN200410078279.1 uses organic acids, organic anhydrides, organic ethers, and organic ketones as precipitation aids to obtain catalysts.

[0006] With the development of the polyolefin industry, there is a need to continuously develop more and better high-performance catalysts with good particle morphology to meet the industry's higher requirements for catalysts. Summary of the Invention

[0007] The purpose of this invention is to provide a catalyst component for ethylene polymerization, its preparation method, catalyst, and application. The catalyst of this invention has good overall performance, especially in terms of high activity, high polymer powder packing density, and better hydrogen regulation sensitivity, while the resulting polymer has less fine powder.

[0008] A first aspect of the present invention provides a catalyst composition for olefin polymerization, the catalyst composition comprising a magnesium-containing liquid component, a carbonate compound, a titanium compound, and optionally other electron-donating compounds as reaction products.

[0009] The magnesium-containing liquid component is prepared by reacting a magnesium-containing compound, an alcohol compound, an optional organic epoxy compound, and an optional organic phosphorus compound in the presence of an inert solvent to obtain the magnesium-containing liquid component.

[0010] The magnesium-containing compound is magnesium dihalide or MgR. 1 Cl and Mg(OR) 2 At least one of Cl; R 1 and R 2 Each is independently selected from substituted or unsubstituted C1-C 10 The hydrocarbon group, wherein the substituent is selected from at least one of hydroxyl, carboxyl, halogen atom and alkoxy group;

[0011] The carbonate compounds comprise at least one of the compounds shown in Formula I; wherein R1-R6 are each independently a C1-C8 hydrocarbon group, a C1-C8 halohydrocarbon group, H, or a halogen;

[0012]

[0013] A second aspect of the present invention provides a method for preparing the above-mentioned catalyst component, the method comprising:

[0014] (1) In the presence of an inert solvent, the magnesium-containing compound, alcohol, optional organophosphorus compound and optional organic epoxy compound are reacted to obtain the magnesium-containing liquid component;

[0015] (2) The magnesium-containing liquid component obtained in step (1), carbonate compounds, titanium compounds and optional other electron-donating compounds are contacted and reacted to produce precipitates;

[0016] (3) Remove unreacted substances and solvents, wash the precipitate, and obtain the catalyst component.

[0017] A third aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising the following components:

[0018] Component A: The catalyst components mentioned above;

[0019] Component B: Organoaluminum compound; its general formula is AlR n X 3-n In the formula, R is a hydrocarbon group with 1 to 20 carbon atoms; X is a halogen, preferably chlorine or bromine; n is an integer 0 < n ≤ 3;

[0020] Preferably, the molar ratio of aluminum in component B to titanium in component A is 1 to 1000:1, more preferably 5 to 500:1;

[0021] The organoaluminum compound is preferably at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydrogen, diisobutylaluminum hydrogen, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, and diethylaluminum chloride; more preferably triethylaluminum and / or triisobutylaluminum.

[0022] A fourth aspect of the present invention provides the application of the above-described catalyst component or catalyst in olefin polymerization reactions.

[0023] Compared with existing technologies, the present invention has the following obvious advantages:

[0024] First, the carbonate compounds used in this invention are relatively environmentally friendly and easy to handle. Second, the carbonate compounds used in this invention can significantly improve the overall performance of existing polyethylene catalysts when used to prepare catalyst components, so that the catalyst of this invention has high activity, high polymer powder packing density and better hydrogen regulation sensitivity, while the resulting polymer has less fine powder.

[0025] The raw materials used in the catalyst of this invention are relatively environmentally friendly, and the catalyst preparation process is simple.

[0026] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0027] Preferred embodiments of the invention will now be described in more detail. While preferred embodiments of the invention are described below, it should be understood that the invention can be implemented in various forms and should not be limited to the embodiments set forth herein.

[0028] A first aspect of the present invention provides a catalyst composition for olefin polymerization, the catalyst composition comprising a magnesium-containing liquid component, a carbonate compound, a titanium compound, and optionally other electron-donating compounds as reaction products.

[0029] The magnesium-containing liquid component is prepared by reacting a magnesium-containing compound, an alcohol compound, an optional organic epoxy compound, and an optional organic phosphorus compound in the presence of an inert solvent to obtain the magnesium-containing liquid component.

[0030] The magnesium-containing compound is magnesium dihalide or MgR. 1 Cl and Mg(OR) 2 At least one of Cl; R 1 and R 2 Each is independently selected from substituted or unsubstituted C1-C 10 The hydrocarbon group, wherein the substituent is selected from at least one of hydroxyl, carboxyl, halogen atom and alkoxy group;

[0031] The carbonate compounds comprise at least one of the compounds shown in Formula I; wherein R1-R6 are each independently a C1-C8 hydrocarbon group, a C1-C8 halohydrocarbon group, H, or a halogen;

[0032]

[0033] During the research and development of polyethylene catalysts, the inventors of this invention made a surprising discovery through extensive experimental studies: specific carbonate compounds, as shown in Formula I, when used as components of specific titanium-magnesium polyolefin catalysts, can significantly improve the overall performance of the catalysts. This results in catalysts with excellent overall performance, particularly exhibiting high activity, high polymer powder packing density, and better hydrogen sensitivity, while producing polymers with less fine powder. Based on this discovery, this invention provides a catalyst component for the homopolymerization or copolymerization of olefins.

[0034] According to the present invention, preferably, the magnesium dihalide is at least one of magnesium dichloride, magnesium dibromide and magnesium diiodide, and more preferably magnesium dichloride;

[0035] The MgR 1 Cl is CH3MgCl and / or CH3CH2MgCl;

[0036] The Mg(OR) 2 Cl is MgCl(OCH2CH3) and / or MgCl(OBu).

[0037] According to the present invention, preferably, the carbonate compound includes at least one of the following: iodomethyl isopropyl carbonate, methyl carbonate, dimethyl carbonate, di(trichloromethyl) carbonate, dimethyl chlorocarbonate, ethyl methyl carbonate, diethyl carbonate, diisopropyl carbonate, 1-chloroethylethyl carbonate, isopropyl chloromethyl carbonate, and 1-chloroethyl isopropyl carbonate, preferably at least one of the following halogenated carbonates, more preferably di(trichloromethyl) carbonate.

[0038] According to the present invention, preferably, the general formula of the alcohol compound is R. 3 OH, where R 3 Selected from substituted or unsubstituted C1-C 10 The hydrocarbon group, wherein the substituent is selected from at least one of hydroxyl, carboxyl, halogen atom and alkoxy group;

[0039] The alcohol compound is preferably C1-C6. 12 fatty alcohols, C7-C 12 At least one of aromatic alcohols and substituted alcohols, wherein the substituted alcohol is C1 to C2. 12 fatty alcohols and / or C7-C6 12 Substituted alcohols derived from aromatic alcohols;

[0040] The alcohol compound is further preferably at least one of methanol, ethanol, propanol, butanol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, n-decanol, dodecanol, cyclohexanol, methylcyclohexanol, benzyl alcohol, phenethyl alcohol, and haloalcohols derived from the above alcohols; even more preferably at least one of ethanol, isopropanol, butanol, 2-ethylhexanol, benzyl alcohol, and phenethyl alcohol.

[0041] In this invention, methanol, ethanol, propanol, butanol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, n-decanol, and dodecanol are aliphatic alcohols; cyclohexanol and methylcyclohexanol are alicyclic alcohols; and benzyl alcohol and phenylethanol are aromatic alcohols.

[0042] In this invention, the haloalcohols derived from the above-mentioned alcohols refer to haloalcohols derived from methanol, ethanol, propanol, butanol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, n-decanol, dodecanol, cyclohexanol, methylcyclohexanol, benzyl alcohol, and phenylethanol.

[0043] In this invention, the C1-C... in the general formula of the aforementioned magnesium-containing compounds and alcohol compounds... 10 The hydrocarbon group can be alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or aralkyl, etc. Specifically:

[0044] C1-C 10 Alkyl refers to C1-C 10 Straight-chain alkyl or C3-C 10 Branched alkyl groups, non-limiting examples of which include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, and n-decyl.

[0045] C3-C 10 Examples of cycloalkyl groups may include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, and 4-n-butylcyclohexyl.

[0046] C6-C 10 Examples of aryl groups may include, but are not limited to, phenyl, 4-methylphenyl, and 4-ethylphenyl.

[0047] C2-C 10 Examples of alkenyl groups may include, but are not limited to, vinyl and allyl groups.

[0048] C7-C 10 Examples of aralkyl groups may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-tert-butyl, and phenylisopropyl.

[0049] In this invention, the "substituted C1-C" in the general formula of the aforementioned magnesium-containing compounds and alcohol compounds refers to... 10 "hydrocarbon group" refers to "C1-C 10 The hydrogen atom (preferably one hydrogen atom) and / or carbon atom on the hydrocarbon group are replaced by the substituents.

[0050] In the preferred case, R 1 and R 2 Selected from substituted or unsubstituted C1-C 10 Alkyl groups.

[0051] According to the present invention, preferably, the organic epoxy compound is selected from at least one of oxides of C2-C8 aliphatic olefins, glycidyl ethers of C2-C8 aliphatic olefins, internal ethers of C2-C8 aliphatic olefins, oxides of C2-C8 halogenated aliphatic olefins, glycidyl ethers of C2-C8 halogenated aliphatic olefins, and internal ethers of C2-C8 halogenated aliphatic olefins; preferably at least one of ethylene oxide, propylene oxide, butane oxide, butane dioxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, and tetrahydrofuran; more preferably at least one of ethylene oxide, propylene oxide, epichlorohydrin, and tetrahydrofuran;

[0052] The organophosphorus compounds are trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, triisopropyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate, tri-tert-butyl phosphate, tri-n-pentyl phosphate, triisopentyl phosphate, tri-n-hexyl phosphate, triisohexyl phosphate, tri-n-heptyl phosphate, triisoheptyl phosphate, tri-n-octyl phosphate, triisooctyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, tri-tert-butyl phosphite, tri-n-pentyl phosphite, and triisopentyl phosphite. The ester, at least one of tri-n-hexyl phosphite, triisohexyl phosphite, tri-n-heptyl phosphite, triisoheptyl phosphite, tri-n-octyl phosphite, triisooctyl phosphite, triphenyl phosphite, and di-n-butyl phosphite; preferably at least one of triethyl phosphate, tributyl phosphate, triisooctyl phosphate, triphenyl phosphate, triethyl phosphite, tributyl phosphite, and di-n-butyl phosphite; more preferably at least one of triethyl phosphate, tributyl phosphate, triisooctyl phosphate, triphenyl phosphate, triethyl phosphite, tributyl phosphite, and di-n-butyl phosphite.

[0053] According to the present invention, preferably, the titanium compound has the general formula TiX. n (OR) 4-n Where: X is a halogen, and R is a C1 to C2 halogen. 14 aliphatic hydrocarbon groups or C6~C 14 Aromatic hydrocarbon groups, where n is an integer from 0 to 4;

[0054] The titanium compound is preferably at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetraethoxy, titanium tetrabutoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloroethoxy, and more preferably at least one of titanium tetrachloride, titanium tetraethoxy, and titanium tetrabutoxy.

[0055] According to the present invention, the other electron-donating compound can be a conventional electron-donating compound used in the art. Preferably, the other electron-donating compound is selected from at least one of organic acid anhydrides, organic acids, organic acid esters, silicon-containing compounds, organic acyl halides, ethers, ketones, amines, phosphate esters, amides, phenols, pyridines, and organic alcohols; the silicon-containing compound is of general formula R. 1 x R 2 y Si(OR 3 ) z The silicon compound shown has no active hydrogen atoms, where R 1 and R 2 Each is an independent hydrocarbon group or halogen with 1 to 10 carbon atoms, R 3 It is a hydrocarbon group with 1 to 10 carbon atoms, where x, y, and z are positive integers, 0≤x≤2, 0≤y≤2 and 0≤z≤4, and x+y+z=4;

[0056] The other electron-donating compounds are further preferably at least one selected from acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl benzoate, ethyl benzoate, butyl benzoate, ethyl p-methylbenzoate, di-n-butyl phthalate, diisobutyl phthalate, diethyl succinate, dipropyl succinate, diisopropyl succinate, methyl naphthol, ethyl naphthol, methyl methyl benzoate, acyl chloride, diethyl ether, butyl ether, tetrahydrofuran, acetone, butanone, cyclohexanone, phenol, silicon tetrachloride, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and tetra(2-ethylhexyloxy)silane.

[0057] According to the present invention, preferably, the inert solvent is a liquid hydrocarbon, which preferably includes at least one of halogenated aromatic hydrocarbons, non-halogenated aromatic hydrocarbons, halogenated aliphatic hydrocarbons, and non-halogenated aliphatic hydrocarbons; more preferably, at least one of benzene and its homologues, chlorobenzene, dichlorobenzene, hexane, heptane, decane, kerosene, dichloromethane, dichloroethane, chloroform, and cyclohexane.

[0058] According to the present invention, preferably, per mole of magnesium-containing compound, the alcohol compound is 0.01 to 10 moles, more preferably 0.1 to 4 moles; the organic epoxy compound is 0 to 10 moles, more preferably 0 to 4 moles; the organophosphorus compound is 0 to 10 moles, more preferably 0 to 4 moles; the carbonate compound is 0.001 to 10 moles, more preferably 0.002 to 1 mole; the other electron-donating compound is 0 to 5 moles, more preferably 0 to 1 mole; and the titanium compound is 0.2 to 100 moles, more preferably 1.0 to 20 moles.

[0059] A second aspect of the present invention provides a method for preparing the above-mentioned catalyst component, the method comprising:

[0060] (1) In the presence of an inert solvent, the magnesium-containing compound, alcohol, optional organophosphorus compound and optional organic epoxy compound are reacted to obtain the magnesium-containing liquid component;

[0061] (2) The magnesium-containing liquid component obtained in step (1), carbonate compounds, titanium compounds and optional other electron-donating compounds are contacted and reacted to produce precipitates;

[0062] (3) Remove unreacted substances and solvents, wash the precipitate, and obtain the catalyst component.

[0063] In this invention, the magnesium-containing liquid component is a homogeneous solution.

[0064] In this invention, preferably, in step (1), the reaction temperature is 40-150°C and the reaction time is 0.1-10 hours;

[0065] In this invention, preferably, in step (2), the contact reaction of the magnesium-containing liquid component, carbonate compound, titanium compound and optional other electron-donating compound obtained in step (1) is as follows: the magnesium-containing liquid component obtained in step (1) is reacted with the carbonate compound, optional other electron-donating compounds are added for reaction, and then reacted with the titanium compound.

[0066] The above preparation method is merely an example description of the catalyst components of the present invention. The carbonate compounds mentioned therein are the basic components of the present invention. In actual synthesis, it is not limited to these basic components. If necessary, other electron donor compounds and auxiliaries may be optionally added. The present invention will not point them out one by one here.

[0067] More specifically, a method for preparing the catalyst component of the present invention is as follows: The magnesium dihalide and MgR are stirred and reacted in the presence of an inert solvent. 1 Cl and Mg(OR) 2At least one of Cl, an alcohol, an optional organic epoxy compound, and an optional organophosphorus compound are reacted at a temperature of 50–150 °C to form a magnesium-containing liquid component. The carbonate compound is added and reacted for a period of time. At a temperature of -35–60 °C, preferably -30–30 °C, a titanium compound is added dropwise to the mixture, or the mixture is added dropwise to the titanium compound. Optionally, other conventional electron donors, such as organosilicon compounds, may be added before or after the dropwise addition. The temperature is then increased at a rate of 4–200 °C per hour. The reaction mixture is then stirred at a temperature of 30–150 °C, preferably 50–130 °C, for 1 minute to 10 hours. Stirring is stopped, the mixture is allowed to settle, filtered, and the mother liquor is removed. The solid is washed with hydrocarbon solvents such as toluene and hexane (the washed solid can also be treated again with a titanium-containing compound and washed during the process) to obtain a titanium-containing solid catalyst component.

[0068] After the above steps, component A of the catalyst of the present invention is obtained, which can be used in the form of a solid or a suspension.

[0069] A third aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising the following components:

[0070] Component A: The catalyst components mentioned above;

[0071] Component B: Organoaluminum compound; its general formula is AlR n X 3-n In the formula, R is a hydrocarbon group with 1 to 20 carbon atoms; X is a halogen, preferably chlorine or bromine; n is an integer 0 < n ≤ 3;

[0072] Preferably, the molar ratio of aluminum in component B to titanium in component A is 1 to 1000:1, more preferably 5 to 500:1;

[0073] The organoaluminum compound is preferably at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydrogen, diisobutylaluminum hydrogen, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, and diethylaluminum chloride; more preferably triethylaluminum and / or triisobutylaluminum.

[0074] In this invention, R is a hydrocarbon group having 1 to 20 carbon atoms, wherein the hydrocarbon group can be alkyl, aralkyl, aryl, etc.

[0075] In this invention, trimethylaluminum, triethylaluminum, triisobutylaluminum, and trioctylaluminum belong to trialkylaluminum; diethylaluminum monohydrogen and diisobutylaluminum monohydrogen belong to alkylaluminum hydrogenates; and diethylaluminum monochloro, diisobutylaluminum monochloro, sesquiethylaluminum chloride, and diethylaluminum dichlorochloride belong to alkylaluminum chlorides.

[0076] The A and B components (organoaluminum compounds) of the catalyst of this invention can be directly applied to the polymerization system, or they can be pre-complexed and then applied to the polymerization system.

[0077] A fourth aspect of the present invention provides the use of the above-described catalyst component or the above-described catalyst in olefin polymerization reactions.

[0078] The catalyst component or catalyst of the present invention can be used for homopolymerization of ethylene, and can also be used for copolymerization of ethylene and α-olefins. The comonomer can be propylene, butene, pentene, hexene, octene, or 4-methyl-1-pentene.

[0079] Polymerization can be performed in either the liquid phase or the gas phase. In liquid phase polymerization, inert solvents such as propane, hexane, heptane, cyclohexane, isobutane, isopentane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, and xylene, or saturated aliphatic or aromatic hydrocarbons, can be used as the reaction medium. Prepolymerization can be performed before polymerization. Polymerization can be carried out in batch, semi-continuous, or continuous processes.

[0080] The polymerization temperature is room temperature to 150°C, preferably 50°C to 100°C. Hydrogen is used as a molecular weight regulator to adjust the polymer's molecular weight.

[0081] The following embodiments are examples of the present invention in more detail, but the present invention is not limited to these embodiments.

[0082] In the following examples and comparative examples:

[0083] Determination of polymer melt index (MI): According to ASTM D1238-99, the test was conducted at 190°C with a load of 2.16 kg.

[0084] Polymer bulk density was determined using the test method for apparent density, volume factor and pourability of plastics (ASTM D1895).

[0085] (I) Preparation of catalyst components

[0086] Example 1

[0087] Preparation of solid catalyst component a

[0088] In a reactor that has undergone repeated purging with high-purity nitrogen, 4.0 g of anhydrous magnesium chloride and 60 mL of n-decane were added sequentially. 22 mL of 2-ethylhexanol was then added with stirring. The temperature was raised to 130 °C and maintained for 1 hour. The system was then cooled to 30 °C, and 3.0 mL of dimethyl carbonate was slowly added dropwise. After the addition was complete, the temperature was maintained for 0.5 hours. Then, 3 mL of tetraethoxysilane was added dropwise. After the addition was complete, the temperature was maintained for 0.5 hours. This mixture was then added dropwise to 90 mL of titanium tetrachloride at -15 °C. After the addition was complete, the temperature was maintained for 1 hour. The temperature was then gradually raised to 110 °C and maintained for 2 hours. Stirring was stopped, the mixture was allowed to stand, the supernatant was removed, and the solution was washed repeatedly with hexane and dried to obtain solid catalyst component a.

[0089] Comparative Example 1

[0090] Preparation of solid catalyst component a*

[0091] In a reactor that has undergone repeated purging with high-purity nitrogen, 4.0 g of anhydrous magnesium chloride and 60 mL of n-decane were added sequentially. 22 mL of 2-ethylhexanol was then added with stirring. The mixture was heated to 130 °C and maintained for 1 hour. The temperature was then lowered to 30 °C, and 3 mL of tetraethoxysilane was added dropwise. After the addition was complete, the temperature was maintained for 0.5 hours. Subsequently, 90 mL of titanium tetrachloride at -15 °C was added dropwise. After the addition was complete, the temperature was maintained for 1 hour. The temperature was then gradually increased to 110 °C and held for 2 hours. Stirring was stopped, the mixture was allowed to stand, and the supernatant was removed. After washing with hexane multiple times and drying, solid catalyst component a* was obtained.

[0092] Example 2

[0093] Preparation of solid catalyst component b

[0094] In a reactor that has undergone repeated purging with high-purity nitrogen, 4.0 g of anhydrous magnesium chloride and 60 mL of n-decane were added sequentially. 22 mL of 2-ethylhexanol was then added with stirring. The temperature was raised to 130 °C and maintained for 1 hour. The system was then cooled to 60 °C, and 2 mL of epichlorohydrin was added dropwise. After the addition was complete, the temperature was maintained for 0.5 hours. Then, 3.0 mL of diethyl carbonate was slowly added dropwise. After the addition was complete, the temperature was maintained for 0.5 hours. This mixture was then added dropwise to 90 mL of titanium tetrachloride at -5 °C. After the addition was complete, the temperature was maintained for 1 hour. The temperature was then gradually raised to 110 °C and held for 2 hours. Stirring was stopped, the mixture was allowed to stand, and the supernatant was removed. After washing with hexane multiple times and drying, solid catalyst component b was obtained.

[0095] Comparative Example 2

[0096] Preparation of solid catalyst component b*

[0097] In a reactor that has undergone repeated purging with high-purity nitrogen, 4.0 g of anhydrous magnesium chloride and 60 mL of n-decane were added sequentially. 22 mL of 2-ethylhexanol was then added with stirring. The temperature was raised to 130 °C and maintained for 1 hour. The system was then cooled to 60 °C, and 2 mL of epichlorohydrin was added dropwise. After the addition was complete, the temperature was maintained for 1 hour. The mixture was then added dropwise to 90 mL of titanium tetrachloride at -5 °C. After the addition was complete, the temperature was maintained for 1 hour, and then gradually raised to 110 °C and held at that temperature for 2 hours. Stirring was stopped, the mixture was allowed to stand, the supernatant was removed, and the solution was washed repeatedly with hexane and dried to obtain solid catalyst component b*.

[0098] Example 3

[0099] Preparation of solid catalyst component c

[0100] In a reactor that has undergone repeated purging with high-purity nitrogen, 4.0 g of anhydrous magnesium chloride and 60 mL of n-decane were added sequentially. While stirring, 22 mL of 2-ethylhexanol and 2 mL of tri-n-butyl phosphate were added. The mixture was heated to 130 °C and maintained for 1 hour. The temperature was then lowered to 40 °C, and 3.0 g of di(trichloromethyl) carbonate was added. The mixture was maintained for 0.5 hours. This mixture was then added dropwise to 90 mL of titanium tetrachloride at -15 °C. After the addition was complete, the temperature was maintained for 1 hour, then gradually increased to 110 °C and held at that temperature for 2 hours. Stirring was stopped, the mixture was allowed to stand, and the supernatant was removed. After washing with hexane multiple times and drying, solid catalyst component c was obtained.

[0101] Comparative Example 3

[0102] Preparation of solid catalyst component c*

[0103] In a reactor that has undergone repeated purging with high-purity nitrogen, 4.0 g of anhydrous magnesium chloride and 60 mL of n-decane were added sequentially. While stirring, 22 mL of 2-ethylhexanol and 2 mL of tri-n-butyl phosphate were added. The mixture was heated to 130 °C and maintained for 1 hour. The temperature was then lowered to 40 °C and maintained for 0.5 hours. This mixture was then added dropwise to 90 mL of titanium tetrachloride at -15 °C. After the addition was complete, the temperature was maintained for 1 hour, then gradually increased to 110 °C and held at that temperature for 2 hours. Stirring was stopped, the mixture was allowed to stand, and the supernatant was removed. After washing with hexane multiple times and drying, solid catalyst component c* was obtained.

[0104] Example 4

[0105] Preparation of solid catalyst component d

[0106] 4.0 g of anhydrous magnesium chloride, 50 mL of toluene, 3.0 mL of epichlorohydrin, 8.0 mL of tri-n-butyl phosphate, and 5.0 mL of ethanol were sequentially added to a reactor that had undergone repeated purging with high-purity nitrogen. The reaction was carried out at 70 °C for 2 hours. The system was then cooled to 50 °C, and 0.2 g of bis(trichloromethyl) carbonate was added. The temperature was maintained for 0.5 hours, and the system was then cooled to -15 °C. 30 mL of titanium tetrachloride was added, and the temperature was gradually increased to 80 °C and maintained for 2 hours. Stirring was stopped, the mixture was allowed to stand, the supernatant was removed, and the solution was washed repeatedly with toluene and hexane before drying to obtain solid catalyst component d.

[0107] Comparative Example 4

[0108] Preparation of solid catalyst component d*

[0109] 4.0 g of anhydrous magnesium chloride, 50 mL of toluene, 3.0 mL of epichlorohydrin, 8.0 mL of tri-n-butyl phosphate, and 5.0 mL of ethanol were sequentially added to a reactor that had undergone repeated purging with high-purity nitrogen. The reaction was carried out at 70 °C for 2 hours. The system was then cooled to 50 °C and maintained for 0.5 hours. The system was then cooled to -15 °C, and 30 mL of titanium tetrachloride was added. The temperature was gradually increased to 80 °C and maintained for 2 hours. Stirring was stopped, the mixture was allowed to stand, the supernatant was removed, and the solution was washed repeatedly with toluene and hexane before drying to obtain the solid catalyst component d*.

[0110] Example 5

[0111] Preparation of solid catalyst component e

[0112] 4.0 g of anhydrous magnesium chloride, 50 mL of toluene, 3.0 mL of epichlorohydrin, 8.0 mL of tri-n-butyl phosphate, and 5.0 mL of ethanol were sequentially added to a reactor that had undergone repeated purging with high-purity nitrogen. The reaction was carried out at 70 °C for 2 hours. The system was then cooled to 50 °C, and 0.5 g of bis(trichloromethyl) carbonate was added. The temperature was maintained for 0.5 hours, and the system was then cooled to -15 °C. Subsequently, 60 mL of titanium tetrachloride was added, and the temperature was gradually increased to 90 °C and maintained for 2 hours. Stirring was stopped, the mixture was allowed to stand, the supernatant was removed, and the solution was washed repeatedly with toluene and hexane and then dried to obtain solid catalyst component e.

[0113] Comparative Example 5

[0114] Preparation of solid catalyst component e*

[0115] 4.0 g of anhydrous magnesium chloride, 50 mL of toluene, 3.0 mL of epichlorohydrin, 8.0 mL of tri-n-butyl phosphate, and 5.0 mL of ethanol were sequentially added to a reactor that had undergone repeated purging with high-purity nitrogen. The reaction was carried out at 70 °C for 2 hours. The system was then cooled to 50 °C and maintained for 0.5 hours. The system was then cooled to -15 °C, and 60 mL of titanium tetrachloride was added. The temperature was gradually increased to 90 °C and maintained for 2 hours. Stirring was stopped, the mixture was allowed to stand, and the supernatant was removed. After washing repeatedly with toluene and hexane, the mixture was dried to obtain a solid catalyst component e* with good flowability.

[0116] Example 6

[0117] Preparation of solid catalyst component f

[0118] 4.0 g of anhydrous magnesium chloride, 50 mL of toluene, 3.0 mL of epichlorohydrin, 8.0 mL of tri-n-butyl phosphate, and 5.0 mL of ethanol were sequentially added to a reactor that had undergone repeated purging with high-purity nitrogen. The reaction was carried out at 70 °C for 2 hours. The system was then cooled to 50 °C, and 2.0 g of bis(trichloromethyl) carbonate was added. The temperature was maintained for 0.5 hours, and the system was then cooled to -15 °C. Subsequently, 90 mL of titanium tetrachloride was added, and the temperature was gradually increased to 110 °C and maintained for 2 hours. Stirring was stopped, the mixture was allowed to stand, the supernatant was removed, and the solution was washed repeatedly with toluene and hexane and then dried to obtain a solid catalyst component f with good flowability.

[0119] Comparative Example 6

[0120] Preparation of solid catalyst component f*

[0121] 4.0 g of anhydrous magnesium chloride, 50 mL of toluene, 3.0 mL of epichlorohydrin, 8.0 mL of tri-n-butyl phosphate, and 5.0 mL of ethanol were sequentially added to a reactor that had undergone repeated purging with high-purity nitrogen. The reaction was carried out at 70 °C for 2 hours. The system was then cooled to 50 °C and maintained for 0.5 hours. The system was then cooled to -15 °C, and 90 mL of titanium tetrachloride was added. The temperature was gradually increased to 110 °C and maintained for 2 hours. Stirring was stopped, the mixture was allowed to stand, and the supernatant was removed. After washing repeatedly with toluene and hexane, the mixture was dried to obtain a solid catalyst component f* with good flowability.

[0122] Example 7

[0123] Preparation of solid catalyst component g

[0124] 4.0 g of anhydrous magnesium chloride, 50 mL of toluene, 3.0 mL of epichlorohydrin, 8.0 mL of tri-n-butyl phosphate, and 5.0 mL of ethanol were sequentially added to a reactor that had undergone repeated purging with high-purity nitrogen. The reaction was carried out at 60 °C for 2 hours. Subsequently, 1.0 g of bis(trichloromethyl) carbonate was added, and the mixture was maintained for 0.5 hours. The system was then cooled to -15 °C, followed by the addition of 90 mL of titanium tetrachloride. The temperature was gradually increased to 110 °C and held at this temperature for 2 hours. Stirring was stopped, the mixture was allowed to stand, and the supernatant was removed. After washing with toluene and hexane multiple times, the mixture was dried to obtain g of a solid catalyst component with good flowability.

[0125] Comparative Example 8

[0126] Preparation of solid catalyst component c**

[0127] The specific method is the same as in Example 3, except that 3.0g of bis(trichloromethyl) carbonate is replaced with 2.2mL of tetraethoxysilane.

[0128] (II) Ethylene Polymerization

[0129] A 2-liter stainless steel reactor was fully purged with H2, then 1000 mL of hexane, 1.0 mL of a 1 mol / L triethylaluminum hexane solution, and a measured amount (containing approximately 0.01 mmol of titanium) of the prepared solid catalyst were added. The reactor was heated to 70°C and hydrogen was added at 0.28 MPa (gauge pressure). Ethylene was then introduced to bring the pressure inside the reactor to 0.73 MPa (gauge pressure), and polymerization was carried out at 80°C for 2 hours. The experimental results are shown in the table below:

[0130] Table 1: Experimental Results

[0131]

[0132] As can be seen from the data in the table above, the catalyst has good overall performance, especially in terms of high activity, high polymer powder packing density and better hydrogen regulation sensitivity, while the resulting polymer has less fine powder.

[0133] 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 catalyst component for olefin polymerization, characterized in that, The catalyst composition comprises a magnesium-containing liquid component, carbonate compounds, titanium compounds, and optional other electron-donating compounds as reaction products. The magnesium-containing liquid component is prepared by reacting a magnesium-containing compound, an alcohol compound, an optional organic epoxy compound, and an optional organic phosphorus compound in the presence of an inert solvent to obtain the magnesium-containing liquid component. The magnesium-containing compound is magnesium dihalide or MgR. 1 Cl and Mg (OR) 2 At least one of Cl; R 1 and R 2 Each is independently selected from substituted or unsubstituted C1-C 10 The hydrocarbon group, wherein the substituent is selected from at least one of hydroxyl, carboxyl, halogen atom and alkoxy group; The carbonate compound is bis(trichloromethyl) carbonate.

2. The catalyst component according to claim 1, wherein, The magnesium dihalide is at least one of magnesium dichloride, magnesium dibromide, and magnesium diiodide; The MgR 1 Cl is CH3MgCl and / or CH3CH2MgCl; The Mg(OR) 2 Cl is MgCl(OCH2CH3) and / or MgCl(OBu).

3. The catalyst component according to claim 2, wherein, The magnesium dihalide mentioned is magnesium dichloride.

4. The catalyst component according to claim 1, wherein, The general formula of the alcohol compounds is R 3 OH, where R 3 Selected from substituted or unsubstituted C1-C 10 The hydrocarbon group, wherein the substituent is selected from at least one of hydroxyl, carboxyl, halogen atom and alkoxy group.

5. The catalyst component according to claim 4, wherein, The alcohol compound is C1-C6. 12 fatty alcohols, C7-C 12 At least one of aromatic alcohols and substituted alcohols, wherein the substituted alcohol is C1 to C2. 12 fatty alcohols and / or C7-C6 12 Substituted alcohols derived from aromatic alcohols.

6. The catalyst component according to claim 5, wherein, The alcohols are at least one of methanol, ethanol, propanol, butanol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, n-decanol, dodecanol, cyclohexanol, methylcyclohexanol, benzyl alcohol, phenethyl alcohol, and haloalcohols derived from the above alcohols.

7. The catalyst component according to claim 6, wherein, The alcohol compound is at least one of ethanol, isopropanol, butanol, 2-ethylhexanol, benzyl alcohol, and phenylethanol.

8. The catalyst component according to claim 1, wherein, The organic epoxy compound is selected from at least one of the following: oxides of C2-C8 aliphatic olefins, glycidyl ethers of C2-C8 aliphatic olefins, internal ethers of C2-C8 aliphatic olefins, oxides of C2-C8 halogenated aliphatic olefins, glycidyl ethers of C2-C8 halogenated aliphatic olefins, and internal ethers of C2-C8 halogenated aliphatic olefins. The organophosphorus compound is at least one selected from the following: trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, triisopropyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate, tri-tert-butyl phosphate, tri-n-pentyl phosphate, triisopentyl phosphate, tri-n-hexyl phosphate, triisohexyl phosphate, tri-n-heptyl phosphate, triisoheptyl phosphate, tri-n-octyl phosphate, triisooctyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, tri-tert-butyl phosphite, tri-n-pentyl phosphite, triisopentyl phosphite, tri-n-hexyl phosphite, triisoheptyl phosphite, tri-n-octyl phosphite, triisooctyl phosphite, triphenyl phosphite, and di-n-butyl phosphite.

9. The catalyst component according to claim 8, wherein, The organic epoxy compound is at least one selected from ethylene oxide, propylene oxide, butane oxide, butadiene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, and tetrahydrofuran.

10. The catalyst component according to claim 9, wherein, The organic epoxy compound is at least one of ethylene oxide, propylene oxide, epichlorohydrin, and tetrahydrofuran.

11. The catalyst component according to claim 8, wherein, The organophosphorus compound is at least one selected from triethyl phosphate, tributyl phosphate, triisooctyl phosphate, triphenyl phosphate, triethyl phosphite, tributyl phosphite, and di-n-butyl phosphite.

12. The catalyst component according to claim 1, wherein, The general formula of the titanium compound is TiX. n (OR) 4-n Where: X is a halogen, and R is a C1 to C2 halogen. 14 aliphatic hydrocarbon groups or C6~C 14 Aromatic hydrocarbon group, where n is an integer from 0 to 4.

13. The catalyst component according to claim 12, wherein, The titanium compound is at least one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetraethoxy, titanium tetrabutoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloromonoethoxy.

14. The catalyst component according to claim 13, wherein, The titanium compound is at least one of titanium tetrachloride, titanium tetraethoxy, and titanium tetrabutoxy.

15. The catalyst component according to claim 1, wherein, The other electron-donating compound may be selected from at least one of organic acid anhydrides, organic acids, organic acid esters, silicon-containing compounds, organic acyl halides, ethers, ketones, amines, phosphate esters, amides, phenols, pyridines, and organic alcohols; the silicon-containing compound is of the formula R. 1 x R 2 y Si(OR 3 ) z The silicon compound shown has no active hydrogen atoms, wherein R 1 and R 2 Each is an independent hydrocarbon group or halogen with 1 to 10 carbon atoms, R 3 It is a hydrocarbon group with 1 to 10 carbon atoms, where x, y, and z are positive integers, 0≤x≤2, 0≤y≤2 and 0≤z≤4, and x+y+z=4.

16. The catalyst component according to claim 15, wherein, The other electron-donating compounds are at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl benzoate, ethyl benzoate, butyl benzoate, ethyl p-methylbenzoate, di-n-butyl phthalate, diisobutyl phthalate, diethyl succinate, dipropyl succinate, diisopropyl succinate, methyl naphthol, ethyl naphthol, methyl methyl benzoate, acyl chloride, diethyl ether, butyl ether, tetrahydrofuran, acetone, butanone, cyclohexanone, phenol, silicon tetrachloride, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and tetra(2-ethylhexyloxy)silane.

17. The catalyst component according to claim 1, wherein, The inert solvent is a liquid hydrocarbon.

18. The catalyst component according to claim 17, wherein, The liquid hydrocarbon includes at least one of halogenated aromatic hydrocarbons, non-halogenated aromatic hydrocarbons, halogenated aliphatic hydrocarbons, and non-halogenated aliphatic hydrocarbons.

19. The catalyst component according to claim 18, wherein, The liquid hydrocarbon is at least one of benzene and its homologues, chlorobenzene, dichlorobenzene, hexane, heptane, decane, kerosene, dichloromethane, dichloroethane, chloroform, and cyclohexane.

20. The catalyst component according to claim 1, wherein, Based on the amount of magnesium-containing compounds, the alcohol compounds are 0.01 to 10 moles; the organic epoxy compounds are 0 to 10 moles; the organic phosphorus compounds are 0 to 10 moles; the carbonate compounds are 0.001 to 10 moles; the other electron-donating compounds are 0 to 5 moles; and the titanium compounds are 0.2 to 100 moles.

21. The catalyst component according to claim 20, wherein, Based on the amount of magnesium-containing compounds, the alcohol compounds are 0.1 to 4 moles; the organic epoxy compounds are 0 to 4 moles; the organic phosphorus compounds are 0 to 4 moles; the carbonate compounds are 0.002 to 1 mole; the other electron-donating compounds are 0 to 1 mole; and the titanium compounds are 1.0 to 20 moles.

22. The method for preparing the catalyst component according to any one of claims 1-21, characterized in that, The preparation method includes: (1) In the presence of an inert solvent, the magnesium-containing compound, alcohol, optional organophosphorus compound and optional organic epoxy compound are reacted to obtain the magnesium-containing liquid component; (2) The magnesium-containing liquid component obtained in step (1), carbonate compounds, titanium compounds and optional other electron-donating compounds are subjected to a contact reaction to produce a precipitate; (3) Remove unreacted substances and solvents, wash the precipitate, and obtain the catalyst component.

23. A catalyst for olefin polymerization, characterized in that, The catalyst comprises the following components: Component A: The catalyst component as described in any one of claims 1 to 21; Component B: Organoaluminum compound; its general formula is AlR n X 3-n In the formula, R is a hydrocarbon group with 1 to 20 carbon atoms; X is a halogen; and n is an integer 0 < n ≤ 3.

24. The catalyst according to claim 23, wherein, X is chlorine or bromine.

25. The catalyst according to claim 23, wherein the molar ratio of aluminum in component B to titanium in component A is 1 to 1000:

1.

26. The catalyst according to claim 25, wherein the molar ratio of aluminum in component B to titanium in component A is 5 to 500:

1.

27. The catalyst according to claim 23, wherein, The organoaluminum compound is at least one selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydrogen, diisobutylaluminum hydrogen, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, and diethylaluminum chloride.

28. The catalyst according to claim 27, wherein, The organoaluminum compound is triethylaluminum and / or triisobutylaluminum.

29. The use of a catalyst component according to any one of claims 1-21 or a catalyst according to any one of claims 23-28 in an olefin polymerization reaction.

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