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

Abstract

The application belongs to the technical field of olefin polymerization, and discloses a catalyst component for olefin polymerization and a preparation method, a catalyst and application thereof. 1 R 2 , R 1 and R 2 may be the same or different, R 1 and R 2 are each independently selected from substituted or unsubstituted C1-C 10 hydrocarbon groups, and the substituent is selected from at least one of a hydroxyl group, a carboxyl group, an alkoxy group, a halogen atom and a heteroatom; the carbonate compound comprises at least one of the compounds of formula I; wherein R1-R6 are each independently a C1-C8 hydrocarbon group, a C1-C8 halogenated hydrocarbon group, H or halogen; the catalyst has higher activity and higher polymer powder bulk density, and has better hydrogen regulation sensitivity.

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] 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.

[0003] Titanium-magnesium catalysts generally include basic components such as magnesium, titanium, halogens, and electron donors. Patent application CN200410078280.4 discloses a catalyst for ethylene polymerization or copolymerization, which is formed by dissolving magnesium halide in organic epoxy compounds, organic phosphorus compounds, organic alcohol compounds, and inert solvents to form a homogeneous solution, precipitating it with titanium halides in the presence of a precipitation aid, and then adding silicon compounds for modification.

[0004] Patent application CN200810104957.5 discloses a catalyst for slurry-based ethylene polymerization or copolymerization, which involves dissolving magnesium halide in an organic epoxy compound, an organic phosphorus compound, an electron donor compound, and an inert solvent to form a homogeneous solution, precipitating it with titanium halides in the presence of a co-precipitant, and then adding ether compounds for modification.

[0005] Patent application CN201510531912.6 states that when organic acid anhydrides / acetic acid esters / aromatic esters are introduced as complex electron donors into the N-type polyolefin catalyst preparation system, spherical / ellipsoidal magnesium / titanium-containing solid particles can be prepared.

[0006] The catalysts mentioned above all use phosphorus-containing compounds that are known to be harmful to the environment during their preparation. Currently, with the increasing demands for product safety in the consumer market, developing environmentally friendly technologies has become a new direction for development. 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 carbonate compounds used in this invention are relatively environmentally friendly, and the catalyst prepared using them has good overall performance. While having high activity and high polymer powder bulk density, the catalyst also has better hydrogen regulation sensitivity.

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

[0009] The general formula of the magnesium-containing compound is MgR. 1 R 2 R 1 and R 2 They can be the same or different, 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, alkoxy, halogen atom and heteroatom;

[0010] 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;

[0011]

[0012] A second aspect of the present invention provides a method for preparing the above-mentioned catalyst component, the method comprising: in the presence of a diluent, reacting the magnesium-containing compound, optionally an alcohol compound, a carbonate compound, a titanium compound, and optionally other electron donor compounds in a contact reaction to obtain the catalyst component.

[0013] A third aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising the following components:

[0014] Component A: The catalyst component as described above;

[0015] 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;

[0016] 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;

[0017] 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.

[0018] A fourth aspect of the present invention provides the application of the above-described catalyst component or catalyst in olefin polymerization reactions.

[0019] Compared with existing technologies, the present invention has the following obvious advantages:

[0020] (1) First, the carbonate compounds used in this invention are relatively environmentally friendly and easy to operate; 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 better hydrogen regulation sensitivity while having higher activity and higher polymer powder packing density.

[0021] (2) The raw materials used in the catalyst of the present invention are relatively environmentally friendly, and the catalyst preparation process is simple.

[0022] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0023] 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.

[0024] A first aspect of the present invention provides a catalyst composition for olefin polymerization, the catalyst composition comprising a reaction product of a magnesium-containing compound, optionally an alcohol compound, a carbonate compound, a titanium compound, and optionally other electron-donating compounds.

[0025] The general formula of the magnesium-containing compound is MgR. 1 R 2 R 1 and R 2 They can be the same or different, 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, alkoxy, halogen atom and heteroatom;

[0026] 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;

[0027]

[0028] In this invention, the inventors, through extensive experimental research during the development of polyethylene catalysts, surprisingly discovered that specific carbonate compounds, as shown in Formula I, can significantly improve the overall performance of specific titanium-magnesium polyolefin catalysts when used as components, especially by significantly enhancing the catalyst's high hydrogen sensitivity. Based on this discovery, this invention provides a catalyst component for olefin homopolymerization or copolymerization.

[0029] In this invention, the C1-C10 The hydrocarbon group can be alkyl, cycloalkyl, alkenyl, alkynyl, aryl, or aralkyl, etc. Specifically:

[0030] The C1-C 10 The alkyl group is preferably 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.

[0031] 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. (C6-C) 10 Examples of aryl groups may include, but are not limited to, phenyl, 4-methylphenyl, and 4-ethylphenyl.

[0032] C2-C 10 Examples of alkenyl groups may include, but are not limited to, vinyl and allyl groups.

[0033] 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.

[0034] In this invention, "substituted C1-C" 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.

[0035] In the preferred case, R 1 and R 2 Selected from substituted or unsubstituted C1-C 10 Alkyl groups.

[0036] According to the present invention, preferably, the magnesium-containing compound is at least one selected from dimethyl magnesium, diethyl magnesium, diisopropyl magnesium, isopropylmethyl magnesium, n-butylethyl magnesium, di-n-butyl magnesium, butyloctyl magnesium, dihexyl magnesium, and dioctyl magnesium.

[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, and more preferably di(trichloromethyl) carbonate.

[0038] 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;

[0039] 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.

[0040] According to the present invention, preferably, the alcohol compound has the general formula ROH, and is preferably C1-C2. 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;

[0041] Preferably, the alcohol compound is 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; more preferably, at least one of ethanol, isopropanol, butanol, 2-ethylhexanol, benzyl alcohol, and phenethyl alcohol.

[0042] In this invention, methanol, ethanol, propanol, butanol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, n-decanol, and dodecanol belong to aliphatic alcohols; cyclohexanol and methylcyclohexanol belong to alicyclic alcohols; and benzyl alcohol and phenylethanol belong to aromatic alcohols.

[0043] 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.

[0044] According to the present invention, preferably, the other electron-donating compound is selected from at least one of organic acids, organic acid esters, silicon-containing compounds, organic acyl halides, ethers, ketones, amines, phosphate esters, amides, phenols, and pyridine; 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;

[0045] The other electron-donating compounds are preferably at least one selected from 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.

[0046] According to the present invention, preferably, per mole of magnesium-containing compound, the carbonate compound is 0.001 to 10 moles, more preferably 0.002 to 1 mole; the titanium compound is 0.2 to 100 moles, more preferably 1.0 to 30 moles; the alcohol compound is 0 to 10 moles, more preferably 0 to 4 moles; and the other electron-donating compound is 0 to 5 moles, more preferably 0 to 1 mole.

[0047] A second aspect of the present invention provides a method for preparing the above-mentioned catalyst component, the method comprising: in the presence of a diluent, reacting the magnesium-containing compound, optionally an alcohol compound, a carbonate compound, a titanium compound, and optionally other electron donor compounds in a contact reaction to obtain the catalyst component.

[0048] In this invention, the diluent is a liquid hydrocarbon, preferably a halogenated or non-halogenated aromatic hydrocarbon and / or aliphatic hydrocarbon, and more preferably at least one of benzene and its homologues, chlorobenzene, dichlorobenzene, hexane, heptane, decane, kerosene, dichloromethane, dichloroethane, chloroform and cyclohexane.

[0049] In this invention, preferably, the catalyst component can be prepared by, but is not limited to, the following methods:

[0050] Method 1: (When no alcohol compounds need to be added)

[0051] 1) In the presence of a diluent, magnesium-containing compounds, carbonate compounds, and titanium compounds are brought into contact and reacted; optionally, other electron-donating compounds are added to continue the reaction; finally, the reaction system is raised to a high temperature (e.g., 50–150°C) and held at that temperature for 1 minute to 10 hours to produce a precipitate.

[0052] 2) Remove unreacted substances and solvents, wash the precipitate, and obtain the catalyst component.

[0053] Preferably, the contact reaction of the magnesium-containing compound, the titanium compound, and the carbonate compound includes: first reacting the magnesium-containing compound with the titanium compound, and then adding the carbonate compound to continue the reaction; or first reacting the magnesium-containing compound with the carbonate compound, and then adding the titanium compound to continue the reaction.

[0054] Method 2: (When alcohol compounds need to be added)

[0055] 1) In the presence of a diluent, the magnesium-containing compound is reacted with an alcohol compound to obtain a reaction mixture; wherein, the reaction temperature of the magnesium-containing compound and the alcohol compound is preferably 0 to 150°C, and the reaction time is 0.1 to 10 hours;

[0056] 2) The reaction mixture obtained in step 1), carbonate compounds, and titanium compounds are brought into contact for reaction; other electron-donating compounds are optionally added to continue the reaction; finally, the reaction system is raised to a high temperature (e.g., 50-150°C) and held at that temperature for 1 minute to 10 hours to produce a precipitate.

[0057] 3) Remove unreacted substances and solvent, wash the precipitate, and obtain the catalyst component.

[0058] Preferably, the contact reaction of the reaction mixture obtained in step 1), the carbonate compound, and the titanium compound includes: first reacting the reaction mixture with the titanium compound, and then adding the carbonate compound to continue the reaction; or first reacting the reaction mixture with the carbonate compound, and then adding the titanium compound to continue the reaction.

[0059] In either method 1 or method 2 above, preferably, when the magnesium compound, carbonate compound and optional alcohol compound are reacted, the reaction temperature is 0 to 150°C, more preferably 10 to 130°C; when the titanium compound and optional electron donor compound are added and reacted, the reaction temperature is -35 to 60°C, more preferably -30 to 30°C.

[0060] The above preparation methods are merely illustrative descriptions of the catalyst components of this invention. Carbonate compounds are the basic components of this invention. In actual synthesis, other conventional internal electron donors and auxiliaries may also be optionally added, but these will not be listed here.

[0061] More specifically, a method for preparing the catalyst component of the present invention is as follows: A magnesium-containing compound is added to a mixture at a temperature of 0–150°C, preferably 10–130°C, under stirring and in the presence of liquid hydrocarbons. The mixture is then reacted for a period of time with the added carbonate compound. At a temperature of -35–60°C, preferably -30–30°C, a titanium halide or its derivative is added dropwise to the mixture, or the mixture is added dropwise to a titanium compound. After the addition is complete, the mixture can be maintained for a period of time. Optionally, other conventional electron donors, such as organosilicon compounds, can also be added. The temperature is then increased, preferably 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.

[0062] 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.

[0063] A third aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising the following components:

[0064] Component A: The catalyst component as described above;

[0065] 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;

[0066] 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;

[0067] 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.

[0068] In this invention, R is a hydrocarbon group having 1 to 20 carbon atoms, wherein the hydrocarbon group can be alkyl, aralkyl, aryl, etc.

[0069] 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.

[0070] 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.

[0071] A fourth aspect of the present invention provides the application of the above-described catalyst component or catalyst in olefin polymerization reactions.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] The following embodiments are examples of the present invention in more detail, but the present invention is not limited to these embodiments.

[0076] In the following examples and comparative examples:

[0077] 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.

[0078] Polymer bulk density was determined using the test method for apparent density, volume factor and pourability of plastics (ASTM D1895).

[0079] (I) Preparation of catalyst components

[0080] Example 1

[0081] Preparation of solid catalyst component a

[0082] In a reactor repeatedly purged with high-purity nitrogen, 3.0 mL of dimethyl carbonate was added dropwise to 40 mL of a heptane solution (1 M) of di-n-butylmagnesium at 30 °C with stirring for 0.5 hours. This solution was then slowly added dropwise to 40 mL of titanium tetrachloride at -10 °C, and the temperature was maintained for 1 hour after the addition was complete. The system was then gradually heated to 80 °C and maintained 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 toluene and hexane before drying to obtain solid catalyst component a.

[0083] Comparative Example 1

[0084] Preparation of solid catalyst component a*

[0085] In a reactor repeatedly purged with high-purity nitrogen, 40 mL of a heptane solution (1 M) of di-n-butylmagnesium was slowly added dropwise to 40 mL of titanium tetrachloride at -10°C at room temperature. After the addition was complete, the temperature was maintained for 1 hour. The system was then gradually heated 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 a*.

[0086] Example 2

[0087] Preparation of solid catalyst component b

[0088] In a reactor repeatedly purged with high-purity nitrogen, 1 mL of diethyl carbonate was added dropwise to 40 mL of a heptane solution (1 M) of di-n-butylmagnesium at 30 °C with stirring for 0.5 hours. This solution was then slowly added dropwise to 60 mL of titanium tetrachloride at -20 °C, and the temperature was maintained for 1 hour after the addition was complete. The system was then gradually heated to 80 °C and maintained 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 toluene and hexane before drying to obtain solid catalyst component b.

[0089] Comparative Example 2

[0090] Preparation of solid catalyst component b*

[0091] In a reactor repeatedly purged with high-purity nitrogen, 40 mL of a heptane solution (1 M) of di-n-butylmagnesium was slowly added dropwise to 60 mL of titanium tetrachloride at -20°C at room temperature. After the addition was complete, the temperature was maintained for 1 hour. The system was then gradually heated 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 b*.

[0092] Example 3

[0093] Preparation of solid catalyst component c

[0094] In a reactor repeatedly purged with high-purity nitrogen, 40 mL of a heptane solution (1 M) of di-n-butylmagnesium was mixed with 1.0 mL of ethanol at 30 °C and kept at this temperature for 15 minutes. Then, 0.5 g of bis(trichloromethyl) carbonate was added and maintained for 0.5 hours. This carbonate was then slowly added dropwise to 50 mL of titanium tetrachloride at -10 °C, and the mixture was kept at this temperature for 1 hour after the addition was complete. The system was then gradually heated to 80 °C and kept at this temperature 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 c.

[0095] Comparative Example 3

[0096] Preparation of solid catalyst component c*

[0097] In a reactor repeatedly purged with high-purity nitrogen, 40 mL of a heptane solution (1 M) of di-n-butylmagnesium was mixed with 1.0 mL of ethanol at 30°C and kept at this temperature for 15 minutes. This mixture was then slowly added dropwise to 50 mL of titanium tetrachloride at -10°C, and the mixture was kept at this temperature for 1 hour after the addition was complete. The system was then gradually heated to 80°C and kept at this temperature 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 c*.

[0098] Example 4

[0099] Preparation of solid catalyst component d

[0100] In a reactor repeatedly purged with high-purity nitrogen, 40 mL of a heptane solution (1 M) of di-n-butylmagnesium was mixed with 2.0 mL of phenylethanol at 30 °C and kept at this temperature for 15 minutes. Then, 0.2 g of bis(trichloromethyl) carbonate was added and maintained for 0.5 hours. This carbonate was then slowly added dropwise to 50 mL of titanium tetrachloride at -15 °C, and the mixture was kept at this temperature for 1 hour after the addition was complete. The system was then gradually heated to 95 °C and kept at this temperature 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.

[0101] Comparative Example 4

[0102] Preparation of solid catalyst component d*

[0103] In a reactor repeatedly purged with high-purity nitrogen, 40 mL of a heptane solution (1 M) of di-n-butylmagnesium was mixed with 2.0 mL of phenylethanol at 30 °C and kept at this temperature for 15 minutes. Then, the mixture was slowly added dropwise to 50 mL of titanium tetrachloride at -15 °C, and kept at this temperature for 1 hour after the addition was complete. The system was then gradually heated to 95 °C and kept at this temperature 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*.

[0104] Example 5

[0105] Preparation of solid catalyst component e

[0106] In a reactor repeatedly purged with high-purity nitrogen, 40 mL of a heptane solution (1 M) of di-n-butylmagnesium was mixed with 3.0 mL of 2-ethylhexanol at 30 °C and kept at this temperature for 15 minutes. Then, 2.0 g of di(trichloromethyl) carbonate was added and maintained for 0.5 hours. This solution was then slowly added dropwise to 90 mL of titanium tetrachloride at -10 °C, and the mixture was kept at this temperature for 0.5 hours after the addition was complete. Next, 5 mL of tetraethoxysilane was added dropwise and the mixture was kept at this temperature for 1 hour. The system was then gradually heated to 80 °C and kept at this temperature 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 e.

[0107] Comparative Example 5

[0108] Preparation of solid catalyst component e*

[0109] In a reactor repeatedly purged with high-purity nitrogen, 40 mL of a heptane solution (1 M) of di-n-butylmagnesium was mixed with 3.0 mL of 2-ethylhexanol at 30 °C and kept at this temperature for 15 minutes. Then, the mixture was slowly added dropwise to 90 mL of titanium tetrachloride at -10 °C. After the addition was complete, the mixture was kept at this temperature for 0.5 hours. Next, 5 mL of tetraethoxysilane was added dropwise, and the mixture was kept at this temperature for 1 hour. The system was then gradually heated to 80 °C and kept at this temperature 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 e*.

[0110] Example 6

[0111] Preparation of solid catalyst component f

[0112] In a reactor repeatedly purged with high-purity nitrogen, 40 mL of a heptane solution (1 M) of di-n-butylmagnesium was mixed with 2.0 mL of 2-ethylhexanol and 1.0 mL of ethanol at 30 °C and kept at this temperature for 15 minutes. Then, 3.0 g of di(trichloromethyl) carbonate was added and maintained for 0.5 hours. This carbonate was then slowly added dropwise to 70 mL of titanium tetrachloride at -15 °C, and the mixture was kept at this temperature for 0.5 hours after the addition was complete. Next, 5 mL of tetraethoxysilane was added dropwise and the mixture was kept at this temperature for 1 hour. The system was then gradually heated to 80 °C and kept at this temperature 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 f.

[0113] Comparative Example 6

[0114] Preparation of solid catalyst component f*

[0115] In a reactor repeatedly purged with high-purity nitrogen, 40 mL of a heptane solution (1 M) of di-n-butylmagnesium was mixed with 2.0 mL of 2-ethylhexanol and 1.0 mL of ethanol at 30°C and kept at this temperature for 15 minutes. Then, the mixture was slowly added dropwise to 70 mL of titanium tetrachloride at -15°C. After the addition was complete, the mixture was kept at this temperature for 0.5 hours. Next, 5 mL of tetraethoxysilane was added dropwise, and the mixture was kept at this temperature for 1 hour. The system was then gradually heated to 80°C and kept at this temperature 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 f*.

[0116] Example 7

[0117] Preparation of solid catalyst component g

[0118] In a reactor repeatedly purged with high-purity nitrogen, 40 mL of a heptane solution (1 M) of di-n-butylmagnesium was mixed with 2.0 mL of 2-ethylhexanol and 1.0 mL of ethanol at 30 °C and kept at this temperature for 15 minutes. Then, 1.0 g of di(trichloromethyl) carbonate was added and maintained for 0.5 hours. This carbonate was then slowly added dropwise to 70 mL of titanium tetrachloride at -15 °C, and the mixture was kept at this temperature for 0.5 hours after the addition was complete. Next, 5 mL of tetraethoxysilane was added dropwise and the mixture was kept at this temperature for 1 hour. The system was then gradually heated to 80 °C and kept at this temperature 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 g of solid catalyst component.

[0119] Comparative Example 7

[0120] Preparation of solid catalyst component g*

[0121] In a reactor that has undergone repeated purging with high-purity nitrogen, 4.0 g of anhydrous magnesium chloride, 50 ml of toluene, 2.0 ml of epichlorohydrin, and 3.0 ml of tributyl phosphate were added sequentially. The mixture was heated to 50 °C with stirring and maintained for 15 minutes. Then, 6.0 ml of ethanol was added and the mixture was maintained for 15 minutes. The temperature was then lowered to -5 °C, and a mixture of 30 ml of titanium tetrachloride and 30 ml of heptane was added dropwise. Finally, 2 ml of diethyl ether was added, and the system was gradually heated to 80 °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, the mixture was dried to obtain g* of solid catalyst component.

[0122] Comparative Example 8

[0123] Preparation of solid catalyst component a**

[0124] The specific method is the same as in Example 1, except that 3.0 mL of dimethyl carbonate is replaced with 3.0 mL of tetraethoxysilane.

[0125] Comparative Example 9

[0126] Preparation of solid catalyst component c**

[0127] The specific method is the same as in Example 3, except that 0.5g of bis(trichloromethyl) carbonate is replaced with 0.5mL of tetraethoxysilane.

[0128] Comparative Example 10

[0129] Preparation of solid catalyst component e**

[0130] The specific method is the same as in Example 5, except that 2.0 g of bis(trichloromethyl) carbonate is replaced with 2.1 mL of tetraethoxysilane.

[0131] (II) Ethylene Polymerization

[0132] 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 0.26 MPa (gauge pressure). Ethylene was then introduced to bring the pressure inside the reactor to 0.72 MPa (gauge pressure), and polymerization was carried out at 80°C for 2 hours. The experimental results are shown in the table below:

[0133] Table 1: Experimental Results

[0134]

[0135] As can be seen from the data in the table above, the present invention can significantly improve the overall performance of existing polyethylene catalysts by using specific carbonate compounds to prepare catalyst components. While having high activity and high polymer powder packing density, the catalyst also has better hydrogen regulation sensitivity.

[0136] 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 component comprises reaction products of magnesium-containing compounds, optional alcohols, carbonates, titanium compounds, and optional other electron-donating compounds; The general formula of the magnesium-containing compound is MgR. 1 R 2 R 1 and R 2 They can be the same or different, 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, alkoxy, halogen atom and heteroatom; The carbonate compound is bis(trichloromethyl) carbonate.

2. The catalyst component according to claim 1, wherein the magnesium-containing compound is at least one selected from dimethyl magnesium, diethyl magnesium, diisopropyl magnesium, isopropylmethyl magnesium, n-butylethyl magnesium, di-n-butyl magnesium, butyloctyl magnesium, dihexyl magnesium, and dioctyl magnesium.

3. 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.

4. The catalyst component according to claim 3, 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.

5. The catalyst component according to claim 4, wherein, The titanium compound is at least one of titanium tetrachloride, titanium tetraethoxy, and titanium tetrabutoxy.

6. The catalyst component according to claim 1, 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.

7. The catalyst component according to claim 6, 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.

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

9. The catalyst component according to claim 1, wherein, The other electron-donating compound may be selected from at least one of organic acids, organic acid esters, silicon-containing compounds, organic acyl halides, ethers, ketones, amines, phosphate esters, amides, phenols, and pyridine; 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, 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.

10. The catalyst component according to claim 9, wherein, The other electron-donating compounds are at least one of 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.

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

12. The catalyst component according to claim 11, wherein, Based on the amount of magnesium-containing compounds, the carbonate compounds are 0.002 to 1 mole; the titanium compounds are 1.0 to 30 moles; the alcohol compounds are 0 to 4 moles; and the other electron-donating compounds are 0 to 1 mole.

13. The method for preparing the catalyst component according to any one of claims 1-12, characterized in that, The preparation method includes: in the presence of a diluent, reacting the magnesium-containing compound, optionally an alcohol compound, a carbonate compound, a titanium compound, and optionally other electron donor compounds to obtain the catalyst component.

14. 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 7; 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.

15. The catalyst according to claim 14, wherein, X is chlorine or bromine.

16. The catalyst according to claim 14, wherein, The molar ratio of aluminum in component B to titanium in component A is 1 to 1000:

1.

17. The catalyst according to claim 16, wherein, The molar ratio of aluminum in component B to titanium in component A is 5 to 500:

1.

18. The catalyst according to claim 14, 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.

19. The catalyst according to claim 18, wherein, The organoaluminum compound is triethylaluminum and / or triisobutylaluminum.

20. The use of a catalyst component according to any one of claims 1-12 or a catalyst according to any one of claims 14-19 in an olefin polymerization reaction.

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