CN109503741B - Alkoxy magnesium composite microsphere particle and solid polyethylene catalyst prepared from same - Google Patents

Alkoxy magnesium composite microsphere particle and solid polyethylene catalyst prepared from same Download PDF

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CN109503741B
CN109503741B CN201811330321.2A CN201811330321A CN109503741B CN 109503741 B CN109503741 B CN 109503741B CN 201811330321 A CN201811330321 A CN 201811330321A CN 109503741 B CN109503741 B CN 109503741B
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刘宏祥
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Shanghai Gelan Chemical Technology Co ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene

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Abstract

The invention discloses an alkoxy magnesium composite microsphere particle and a solid polyethylene catalyst prepared from the same. The alkoxy magnesium composite microsphere particles are obtained by spray drying a suspension mixed with an alkoxy magnesium compound in a gel dispersion form and magnesium chloride, wherein the chemical structural formula of the alkoxy magnesium compound is Mg (OR)1)(OR2) Wherein R is1、R2Is an alkyl group having 2 to 10 carbon atoms. Contacting alkoxy magnesium composite microsphere particles with titanium tetrachloride in an inert medium at the temperature of not more than 50 ℃, then gradually heating to 100-130 ℃, and carrying out contact reaction at the temperature; and separating the obtained product to obtain solid microsphere particles, and washing the solid microsphere particles with an inert medium. The solid polyethylene catalyst component has good particle shape, and when the solid polyethylene catalyst component is used for ethylene polymerization, resin powder has good particle shape, higher bulk density and obviously reduced fine powder content.

Description

Alkoxy magnesium composite microsphere particle and solid polyethylene catalyst prepared from same
Technical Field
The invention belongs to the technical field of polyolefin catalysts, and relates to alkoxy magnesium composite microsphere particles, a solid polyethylene catalyst component prepared from the alkoxy magnesium composite microsphere particles, a preparation method and application of the solid polyethylene catalyst component.
Background
In recent 40 years, the preparation technology of polyolefin catalysts has been greatly developed, a batch of high-efficiency polyethylene catalysts are developed, the development work of high-performance polyethylene products is powerfully supported, and the consumption cost of the catalysts in the polyethylene products is reduced. The polymerization catalyst used in the slurry process polyethylene process is mainly divided into magnesium chloride-based and magnesium alkoxide-based catalysts according to the source of precursor magnesium. The preparation route of the magnesium chloride-based catalyst is generally that magnesium chloride is dissolved by adopting Lewis base solution, and precipitated under the action of titanium-containing compound to form catalyst precursor, and the technical scheme of the catalyst is disclosed in patent documents such as CN201510716358.9, CN201510717138.8, CN201510684825.4, CN201410273530.3, CN201210397456.7, CN201110270295.0, CN201110197236.5, CN98118334.4 and the like. The catalyst generally has the advantages of higher polymerization activity, concentrated particle size distribution, wider particle size adjusting range and the like, but generally has poorer hydrogen regulation sensitivity and lower polymerization activity under high hydrogen condition. The preparation technical route of the magnesium alkoxy group catalyst is mainly divided into two types, one type is that alkyl magnesium is prepared into particles, and then the alkyl magnesium particles react with a titanium compound in an inert solvent to form a catalyst precursor; the other is to dissolve the magnesium alkoxide and the titanium alkoxide to form a solution containing the magnesium alkoxide and the titanium alkoxide, and precipitate out under the action of a chlorinating agent/alkyl aluminum to form a catalyst precursor. Technical schemes of the catalyst are disclosed in patent documents such as US4859749A, US5292837A, US5648309, US7649061, US7759445, WO2011060954, WO0138405, CN200580025162, CN03819076, CN200580025162, CN200680004879, CN200980122271, CN201080035834, CN201180029854, US6335411, US6545106, CN96110046, CN201410725832, CN201410743733 and the like. The catalyst generally has the advantages of high activity, high hydrogen regulation sensitivity, tool performance and the like, and is particularly suitable for developing and producing bimodal resin products, but generally, the particle form is poor, the fluidity of resin powder is poor, the bulk density of the resin powder still needs to be further improved, the content of fine powder is high, the production load is improved due to the defects, and the blockage of a discharge pipeline is easily caused.
In view of the importance of catalyst particle morphology control, there is a need to develop an alkoxymagnesium-based slurry polyethylene catalyst having improved particle morphology while meeting production requirements in terms of catalyst activity and other properties.
Disclosure of Invention
The invention aims to solve the problems that: in the prior art, the alkoxy magnesium-based polyethylene catalyst has the defects of poor particle shape, high fine powder content and low powder bulk density.
In order to solve the above problems, the present invention provides an alkoxymagnesium composite microsphere particle characterized by being obtained by spray-drying a suspension in which an alkoxymagnesium compound having the chemical formula of Mg (OR) and magnesium chloride are mixed in the form of a gel dispersion1)(OR2) Wherein R is1、R2Is an alkyl group having 2 to 10 carbon atoms.
Preferably, said R is1、R2Are all-C2H5。
Preferably, the solvent used for the suspension is a polar liquid medium which does not react chemically with the magnesium alkoxide compound and is capable of dissolving magnesium chloride.
More preferably, the solvent employed for the suspension is an ether, a ketone or an alcohol.
Further, the solvent is ethanol. Because the alkoxy magnesium compound is slightly soluble in alcohol and insoluble in ether, the alkyl magnesium compound mainly exists in a solid state in liquid alcohol, small liquid drops which are formed by atomization and contain alkoxy magnesium fine particles are dried to form alkoxy magnesium microsphere particles in the spray drying process, but the force used among secondary particles in the alkoxy magnesium microsphere particles is weaker, the structural strength of the alkoxy magnesium microsphere particles is lower, the fine powder content of the alkoxy magnesium particles is higher, and further the catalyst particles prepared from the alkoxy magnesium particles and the fine powder content of polymer powder obtained by polymerization are higher. A proper amount of magnesium chloride solution is mixed into a gel dispersion of an alkoxy magnesium compound, a small liquid drop formed by atomizing the suspension separates out a magnesium chloride complex in the drying process, and the magnesium chloride complex plays a role in bonding alkoxy magnesium fine particles, so that the structural strength of alkyl magnesium microsphere particles obtained by spray drying is improved, the risk of particle breakage is reduced, and the fine powder content of the particles is reduced.
Preferably, the molar ratio of the magnesium chloride to the alkoxy magnesium compound is (0.01-1): 1.
More preferably, the molar ratio of the magnesium chloride to the magnesium alkoxide compound is (0.05-0.3): 1.
The polyethylene catalyst prepared by using magnesium chloride as a magnesium source has lower hydrogen regulation performance than the polyethylene catalyst prepared by using alkoxy magnesium as a magnesium source, so the addition amount of the magnesium chloride is not suitable to be too high.
The preparation process of the suspension in which the magnesium alkoxide compound in the form of a gel dispersion and the magnesium chloride in the form of a solution are mixed is not particularly limited, and a suspension formed by physically mixing a suspension of the magnesium alkyl compound, which has been dispersed in the form of a gel dispersion, with a magnesium chloride solution in a ratio of the magnesium alkyl compound to the magnesium chloride; it is also possible to add the desired amount of magnesium chloride to the suspension of the alkylmagnesium compound which has been dispersed in the form of a gel dispersion, and dissolve the magnesium chloride to form a suspension in which the alkoxymagnesium compound in the form of a gel dispersion and the magnesium chloride solution are mixed. The method for preparing the gel dispersion of the magnesium alkoxide compound in suspension is not particularly limited, and a method of preparing the gel dispersion of the magnesium alkoxide compound in suspension is not particularly limited, andusing any dispersion technique known in the art. By way of example, commercially available large-particle magnesium alkoxide can be initially comminuted by grinding in an inert atmosphere to a particle size of 5 to 50 μm, then suspended and dispersed in a dispersion medium, and the magnesium alkoxide suspension can subsequently be dispersed in a high-speed disperser (e.g., Ultra-Turrax or Dispax, IKA-Maschinenbau Janke)&Kunkel GmbH) into a gel-like dispersion under high shear stress. So-called magnesium alkoxide gel-like dispersions are dispersions of magnesium alkoxide having an average particle size of less than 1 micron dispersed in a liquid medium, which dispersions are relatively stable, settle very slowly and are capable of producing the tyndall phenomenon. Said commercially available magnesium alkoxide is in particular Mg (OC)2H5)2Having an average particle size of 200-1200 μm, preferably about 500-700 μm. The magnesium alkoxide gel dispersion may be prepared by reacting magnesium powder with alcohol to prepare magnesium alkoxide particles autonomously, dispersing the particles in alcohol without drying, and passing the particles through a high-speed dispersing machine (e.g., Ultra-Turrax or Dispax, IKA-Maschinenbau Janke)&Kunkel GmbH) into a gel-like dispersion under high shear stress. Therefore, the step of grinding and crushing large-particle alkoxy magnesium is not needed, and the alkoxy magnesium with smaller particle size (such as less than 20 microns) can be prepared by optimizing the reaction conditions of magnesium powder and alcohol, so that the process is shortened, and the energy and the cost are saved.
The invention has no special limitation on the related spray drying process and the equipment and conditions used in the spray drying process, and the equipment and the method which can be used for spray forming and drying of organic phase materials in the prior art can be introduced into the invention for preparing the magnesium alkoxide microsphere particles. As examples, the spray drying apparatus may employ a pressure type spray dryer, a rotary type spray dryer or a two-fluid type spray dryer; the material drying process can be completed by a spray dryer at one time, or can be continuously dried after the spray dryer is connected with one or more drying devices in other forms (such as fluidized bed drying) in series, so that the drying is complete.
In order to ensure the smooth forming and drying process of the small fog drops formed by the atomization of the suspension in the spray drying process, the solid content in the suspension, namely the total weight content of the alkoxy magnesium compound and the magnesium chloride in the suspension, is 5-80%, and preferably 10-40%.
The invention also provides a solid polyethylene catalyst which is characterized by being prepared by the following steps:
step 1): contacting the alkoxy magnesium composite microsphere particles with titanium tetrachloride in an inert medium at the temperature of not more than 50 ℃, then gradually heating to 100-130 ℃, and carrying out contact reaction at the temperature;
step 2): separating the product obtained in the step 1) to obtain solid microsphere particles, and washing the solid microsphere particles with an inert medium.
Preferably, the Ti/Mg molar ratio in said step 1) is greater than 1, preferably in the range of 1.5 to 4, more preferably in the range of 1.75 to 2.75; the contact time at lower temperature is more than 15 minutes, the contact reaction time at higher temperature is more than or equal to 15 minutes, and the contact time is preferably 0.5-5 hours.
After completion of step 1), inert alkane washing at a temperature of 60-80 ℃ can be carried out until the Cl and Ti concentration of the suspension mother liquor is less than 10 mmol/l. The solid obtained at the end of the washing step has a Cl/Ti molar ratio of at least 2.5, preferably at least 3, more preferably between 3 and 5. The resulting solid had the following typical composition: mg, Ti and Cl are 1 to (0.8-1.5) to (3.2-4.2).
Preferably, the inert medium in step 1) is an aliphatic hydrocarbon, a cycloaliphatic hydrocarbon, an aromatic hydrocarbon or a white spirit, hydrogenated diesel fraction from which oxides, sulphur compounds, nitrides and moisture have been removed. The hydrocarbon may be butane, pentane, hexane, heptane, cyclohexane, isooctane, benzene, toluene xylene, etc.
Preferably, further comprising step 3): further contacting the solid microspherical particles obtained in step 2) with an alkyl aluminum halide; the particle size of the obtained solid polyethylene catalyst is 5-20 μm, preferably 7-15 μm. The reaction can be carried out in a stirred vessel at a temperature of 0 to 150 ℃, preferably 30 to 100 ℃ for 0.5 to 5 hours. The alkylaluminum chloride compound is used in an amount such that the Al/Ti molar ratio (calculated with respect to the Ti content of the solid catalyst component as obtained by the previous step) is comprised between 0.05 and 1, preferably between 0.1 and 0.5. WhereinThe Cl/Ti molar ratio is increased with respect to the Cl/Ti molar ratio of the solid before step 3), and is generally at least 3, more preferably higher than 3.5. This step may bring some degree of titanium atoms from the oxidized state Ti+4Reduced to Ti in oxidized state+3。
More preferably, the alkylaluminum halide has the formula R3 2Dialkylaluminum monochloride of AlCl or with the chemical formula R3 3Al2Cl3Wherein R is3Are identical or different alkyl radicals having from 1 to 16 carbon atoms.
More preferably, the alkylaluminum halide is diethylaluminum monochloride or ethylaluminum sesquichloride.
The present invention also provides a catalyst system for slurry polymerization of ethylene, characterized in that it is obtained by reacting the above solid polyethylene catalyst with an organoaluminum compound, which is a trialkylaluminum compound, or a mixture of trialkylaluminum and an alkylaluminum halide. Such as Trimethylaluminum (TMA), Triethylaluminum (TEAL), Triisobutylaluminum (TIBA), tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, triisopentadienylaluminum. Alkylaluminum halides and especially alkylaluminum chlorides such as diethylaluminum chloride (DEAC), diisobutylaluminum chloride, Al-sesquichloride and dimethylaluminum chloride (DMAC) can also be used in a mixture with the trialkylaluminum (trialkyl), preferably TEAL and TIBA are used.
Preferably, the preactivated catalyst system is first reacted with an alpha-olefin, preferably linear C2-C10-olefin and especially ethylene or propylene prepolymerisation, followed by using the resulting prepolymerised catalyst system in a main polymerisation. The mass ratio of the catalyst solid used in the prepolymerization to the monomer polymerized thereon is usually 1: 0.1 to 20.
The catalyst system of the present invention is particularly suitable for slurry polymerization processes. In practice, average particle sizes such as less than 20 μm, preferably from 7 to 15 μm, are particularly suitable for slurry polymerizations in an inert medium, which can be carried out continuously in stirred reactors or loop reactors. In a preferred embodiment, the ethylene polymerization process is carried out in two or more serially connected loop reactors or stirred reactors, producing polymers with different molecular weights and/or different compositions in each reactor, thereby showing a broad molecular weight distribution and/or monomer composition as a whole.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below.
Example 1
a) Preparation of composite magnesium ethoxide microsphere particles
57g (0.5mol) Mg (OC)2H5)2The solid powder and 200mL of ethanol dried by molecular sieve were put into a 500mL milling jar and milled for 5 hours by a PM-400 ball mill from Leishi, Germany to obtain Mg (OC) having an average particle size of 5.5 μm2H5)2A suspension of (a).
Collecting the ground Mg (OC)2H5)2100mL of the suspension of (2) is transferred to N250mL of ethanol dried with a molecular sieve was added to the replaced four-neck reaction flask, and a high-speed disperser (Krupp super) was usedTMForm S200) was treated at 60 ℃ for 20 hours, thereby forming a gel-like dispersion.
To warp N250mL of ethanol dried with a molecular sieve and 2.38g of magnesium chloride (0.025mol) were put into the replaced four-necked reaction flask, stirred to dissolve the ethanol and transferred to the above gel dispersion to obtain a magnesium ethoxide gel-like dispersion suspension containing a magnesium chloride solution.
And (3) carrying out spray drying (Buchi B290) on the obtained gel dispersion suspension to obtain solid microsphere particles, wherein the spraying conditions are that the inlet temperature is 210 ℃, the outlet temperature is 168 ℃, the opening degree of a feed pump is 30 percent, and the flow rate of atomized gas is 742L/h. The solid microspheroidal particle D50 was 10.1 μm.
b) Preparation of solid catalyst component a:
weighing 10g of the magnesium ethoxide microspheroidal particles prepared in step a), adding into the solution2200mL of toluene is added into the replaced four-mouth reaction bottle, stirring is started, the stirring speed is adjusted to be 200r/min, and the oil bath temperature is reduced to 5 ℃. Slowly dropping19.6mL of TiCl were added4(molar ratio Ti/Mg ═ 2), after completion of the dropwise addition, maintained at 5 ℃ for 30min, then slowly warmed to 110 ℃ and maintained at 110 ℃ for reaction for 2hr, then left to stand, filtered and washed twice with toluene, 200mL of toluene per time, 200mL of toluene was added, 0.18mmol of ethyl aluminum sesquichloride was slowly added dropwise with stirring, and reacted at 80 ℃ for 30min, then left to stand, and washed three times with hexane, 200mL of hexane per time, and then dried by purging with high-purity nitrogen gas to obtain a solid catalyst component. The solid catalyst component D50 was 10.4 μm.
c) Polymerization of ethylene in suspension:
1L of hexane, 5mmol of triethylaluminum and a certain amount of catalyst are added into a 2L stainless steel stirring kettle, then the temperature is increased to 80 ℃, 0.28MPa of hydrogen is added at a time, then the total pressure of the system is maintained at 0.73MPa by using ethylene for polymerization reaction, after 2 hours of reaction, the addition of ethylene is stopped, the temperature is reduced, the pressure is relieved, polyethylene powder is weighed, the activity of the catalyst is calculated, and the bulk density and the melt index under the load of 2.16Kg of the polyethylene powder are tested, and the results are shown in Table 1.
Example 2
a) Preparation of magnesium ethoxide microspheroidal particles
57g (0.5mol) Mg (OC)2H5)2The solid powder and 200mL of ethanol were placed in a 500mL milling jar and milled for 5 hours using a PM-400 ball mill from Lechly, Germany to obtain Mg (OC) having an average particle size of 5.5 μm2H5)2A suspension of (a).
Collecting the ground Mg (OC)2H5)2100mL of the suspension of (2) is transferred to N2To the replaced four-necked reaction flask, 50mL of ethanol was added and a high-speed disperser (Krupp Superaton) was usedTMForm S200) was treated at 60 ℃ for 20 hours, thereby forming a gel-like dispersion.
To warp N250mL of ethanol dried with a molecular sieve and 3.57g of magnesium chloride (0.0375mol) were put into the replaced four-necked reaction flask, stirred and dissolved, and then transferred to the above gel dispersion to obtain a magnesium ethoxide gel-like dispersion suspension containing a magnesium chloride solution.
And (3) spray drying the obtained gel dispersion suspension (Buchi B290) to obtain solid microsphere particles, wherein the spraying conditions are that the inlet temperature is 200 ℃, the outlet temperature is 1650 ℃, the opening degree of a feed pump is 25 percent, and the flow rate of atomized gas is 742L/h. The solid microspheroidal particle D50 was 11.5 μm.
b) Preparation of solid catalyst component a:
as in example 1, the solid catalyst component D50 was 11.3 μm.
c) Polymerization of ethylene in suspension:
the same as in example 1.
Example 3
a) Preparation of magnesium ethoxide microspheroidal particles
Same as example 1
b) Preparation of solid catalyst component a:
weighing 10g of the magnesium ethoxide microspheroidal particles prepared in step a), adding into the solution2200mL of toluene is added into the replaced four-mouth reaction bottle, stirring is started, the stirring speed is adjusted to be 200r/min, and the oil bath temperature is reduced to 0 ℃. 24.5mL of TiCl were slowly added dropwise4(molar ratio Ti/Mg ═ 2.5), after completion of the dropwise addition, maintained at 0 ℃ for 30min, then slowly warmed to 115 ℃ and maintained at 115 ℃ for reaction for 2hr, then left to stand, filtered and washed twice with toluene, 200mL of toluene per time, 200mL of toluene was added, 0.18mmol of ethyl aluminum sesquichloride was slowly added dropwise with stirring, and reacted at 80 ℃ for 30min, then left to stand, and washed three times with hexane, 200mL of hexane per time, and then dried by purging with high-purity nitrogen gas to obtain a solid catalyst component. The solid catalyst component D50 was 10.2 μm
c) Polymerization of ethylene in suspension:
the same as in example 1.
Comparative example 1
a) Preparation of composite magnesium ethoxide microsphere particles
57g (0.5mol) Mg (OC)2H5)2The solid powder and 200mL of ethanol dried by molecular sieve were put into a 500mL milling jar and milled for 5 hours by a PM-400 ball mill from Leili, Germany to obtain Mg with an average particle size of 5.5 μm(OC2H5)2A suspension of (a).
Collecting the ground Mg (OC)2H5)2100mL of the suspension of (2) is transferred to N250mL of ethanol dried with a molecular sieve was added to the replaced four-neck reaction flask, and a high-speed disperser (Krupp super) was usedTMForm S200) was treated at 60 ℃ for 20 hours, thereby forming a gel-like dispersion.
And (3) spray drying (Buchi B290) the obtained gel dispersion to obtain solid microsphere particles, wherein the spraying conditions are that the inlet temperature is 190 ℃, the outlet temperature is 171 ℃, the opening degree of a feed pump is 30 percent, and the atomizing gas flow is 742L/h. The solid microspheroidal particle D50 was 10.5 μm.
b) Preparation of solid catalyst component a:
weighing 10g of the magnesium ethoxide microspheroidal particles prepared in step a), adding into the solution2200mL of toluene is added into the replaced four-mouth reaction bottle, stirring is started, the stirring speed is adjusted to be 200r/min, and the oil bath temperature is reduced to 5 ℃. 19.6mL of TiCl were slowly added dropwise4(molar ratio Ti/Mg ═ 2), after completion of the dropwise addition, maintained at 5 ℃ for 30min, then slowly warmed to 110 ℃ and maintained at 110 ℃ for reaction for 2hr, then left to stand, filtered and washed twice with toluene, 200mL of toluene per time, 200mL of toluene was added, 0.18mmol of ethyl aluminum sesquichloride was slowly added dropwise with stirring, and reacted at 80 ℃ for 30min, then left to stand, and washed three times with hexane, 200mL of hexane per time, and then dried by purging with high-purity nitrogen gas to obtain a solid catalyst component. The solid catalyst component D50 was 10.7 μm.
c) Polymerization of ethylene in suspension:
1L of hexane, 5mmol of triethylaluminum and a certain amount of catalyst are added into a 2L stainless steel stirring kettle, then the temperature is increased to 80 ℃, 0.28MPa of hydrogen is added at a time, then the total pressure of the system is maintained at 0.73MPa by using ethylene for polymerization reaction, after 2 hours of reaction, the addition of ethylene is stopped, the temperature is reduced, the pressure is relieved, polyethylene powder is weighed, the activity of the catalyst is calculated, and the bulk density and the melt index under the load of 2.16kg of the polyethylene powder are tested, and the results are shown in Table 1.
Comparative example 2
a) Preparation of magnesium ethoxy granules
40g (0.5mol) of Mg (OC)2H5)2The solid powder and 200mL of toluene were charged into a 500mL milling jar and milled for 5 hours using a PM-400 ball mill from Lechly, Germany to obtain Mg (OC) having an average particle size of 5.5 μm2H5)2A suspension of (a).
Collecting the ground Mg (OC)2H5)250mL of the suspension of (2) is transferred to N2To the replaced four-necked reaction flask, 150mL of toluene was added and a high-speed disperser (Krupp Superaton) was usedTMForm S200) was treated at 40 ℃ for 30 hours, thereby forming a gel-like dispersion.
b) Preparation of solid catalyst component a:
transferring the gel-like dispersion obtained in a) to a column via N2In the replaced four-mouth reaction bottle, stirring is started, the stirring speed is adjusted to 200r/min, and the oil bath temperature is reduced to 5 ℃. 24.5mL of TiCl were slowly added dropwise4(molar ratio Ti/Mg ═ 2.5), after completion of the dropwise addition, it was maintained at 5 ℃ for 30min, then slowly warmed to 110 ℃ and maintained at 110 ℃ for 2hr of reaction, then left to stand, filtered and washed twice with toluene, 200mL each time, 200mL of toluene was added, 0.18mmol of ethyl aluminum sesquichloride was slowly added dropwise with stirring, and reacted at 80 ℃ for 30min, then left to stand and washed three times with hexane, 200mL each time, and then dried by purging with high-purity nitrogen gas to obtain a solid catalyst component. The solid catalyst component D50 was 10.5 μm.
c) Polymerization of ethylene in suspension:
the same as in example 1.
TABLE 1
Figure BDA0001859790370000091
As can be seen from Table 1, the solid polyethylene catalyst component obtained by the present invention has good particle morphology, resin powder used in ethylene polymerization has good particle morphology, higher bulk density, and significantly reduced fine powder content.

Claims (9)

1. An alkoxy magnesium composite microsphere particle, which is obtained by spray-drying a suspension mixed with an alkoxy magnesium compound in the form of a gel dispersion having a chemical formula of Mg (OR) and magnesium chloride1)(OR2) Wherein R is1、R2Are all-C2H5(ii) a The molar ratio of the magnesium chloride to the alkoxy magnesium compound is (0.05-0.075): 1.
2. The magnesium alkoxide composite microsphere particle of claim 1, wherein the solvent used for the suspension is a polar liquid medium that does not chemically react with the magnesium alkoxide compound and is capable of dissolving magnesium chloride; the solid content in the suspension is 5-80%.
3. A solid polyethylene catalyst, characterized in that it is prepared by the following steps:
step 1): contacting the magnesium alkoxide composite microspheroidal particles of any one of claims 1 to 2 with titanium tetrachloride in an inert medium at a temperature of not more than 50 ℃ followed by a gradual increase in temperature to 100 ℃ to 130 ℃ and a contact reaction at this temperature;
step 2): separating the product obtained in the step 1) to obtain solid microsphere particles, and washing the solid microsphere particles with an inert medium.
4. The solid polyethylene catalyst according to claim 3, wherein step 1) the Ti/Mg molar ratio is greater than 1; the contact time is 0.5-5 hours.
5. The solid polyethylene catalyst according to claim 3, wherein the inert medium in step 1) is an aliphatic hydrocarbon, a cycloaliphatic hydrocarbon, an aromatic hydrocarbon or a white spirit, hydrogenated diesel fraction from which oxides, sulfur compounds, nitrides and moisture have been removed.
6. The solid polyethylene catalyst according to claim 3, further comprising step 3): further contacting the solid microspherical particles obtained in step 2) with an alkyl aluminum halide; the particle size of the obtained solid polyethylene catalyst is 5-20 mu m.
7. The solid polyethylene catalyst according to claim 6, wherein the alkylaluminum halide has the formula R3 2Dialkylaluminum monochloride of AlCl or with the chemical formula R3 3Al2Cl3Wherein R is3Are identical or different alkyl radicals having from 1 to 16 carbon atoms.
8. The solid polyethylene catalyst according to claim 6 or 7, wherein the alkylaluminum halide is diethylaluminum monochloride or ethylaluminum sesquichloride.
9. A catalyst system for slurry polymerization of ethylene obtained by reacting the solid polyethylene catalyst according to any one of claims 3 to 8 with an organoaluminum compound which is a trialkylaluminum compound or a mixture of trialkylaluminum and alkylaluminum halide.
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CN108690152A (en) * 2018-06-06 2018-10-23 朴蓝聚烯烃科技发展（上海）有限公司 A kind of alkoxyl magnesium microsphere particle and its solid polyethylene catalytic component of preparation

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* Cited by examiner, † Cited by third party
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CN108690152A (en) * 2018-06-06 2018-10-23 朴蓝聚烯烃科技发展（上海）有限公司 A kind of alkoxyl magnesium microsphere particle and its solid polyethylene catalytic component of preparation

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