CN108690152A - A kind of alkoxyl magnesium microsphere particle and its solid polyethylene catalytic component of preparation - Google Patents
A kind of alkoxyl magnesium microsphere particle and its solid polyethylene catalytic component of preparation Download PDFInfo
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- CN108690152A CN108690152A CN201810574852.XA CN201810574852A CN108690152A CN 108690152 A CN108690152 A CN 108690152A CN 201810574852 A CN201810574852 A CN 201810574852A CN 108690152 A CN108690152 A CN 108690152A
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- magnesium
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- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- 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
Abstract
The present invention relates to a kind of alkoxyl magnesium microsphere particles, it is that Mg (OR1) (OR2) compound suspension for will being dispersed in the form of gel dispersion in inert media is spray-dried to obtain, wherein R1 and R2 are identical or different and be respectively the alkyl with 1 to 10 carbon atoms.The invention further relates to a kind of ingredient of solid catalyst, prepared by the method included the following steps:(a) alkoxyl magnesium microsphere particle as claimed in claim 1 or 2 and titanium tetrachloride are contacted in inert media at a temperature of≤50 DEG C, (b) so that the reaction mixture obtained in (a) is subjected to high temperature contact at a temperature of 100 DEG C -130 DEG C, (c) detach and wash the microspheres with solid particle by being obtained in (b) with inert media.
Description
Technical field
The invention belongs to catalyst technical field, it is related to a kind of alkoxyl magnesium microsphere particle and with the poly- second of solid of its preparation
Alkene catalytic component and its and preparation method and application.
Technical background
Over nearly more than 40 years, polyolefin catalyst technology of preparing obtains huge progress, and a collection of high-efficiency polyethylene catalyst is opened
It issues, strong supports high performance polyethylene products development, and reduces the consumption of catalyst in polyethylene product
Cost.The polymerization catalyst of slurry process polyethylene process is wherein used for by the source point of presoma magnesium, is broadly divided into magnesium dichloride-based
With alkoxy magnesium-base catalyst.Magnesium dichloride-based catalyst preparation route generally first uses Louis's bases solution that magnesium chloride is molten
Solution, the Precipitation under titanium-containing compound effect form catalyst precarsor, the technical solution of this kind of catalyst be disclosed in as
CN201510716358.9,CN201510717138.8,CN201510684825.4,CN201410273530.3,
In the patent documents such as CN201210397456.7, CN201110270295.0, CN201110197236.5, CN98118334.4.
This kind of catalyst generally has many advantages, such as that polymerization activity is higher, centralized particle diameter and particle size adjustment wider range, but usual hydrogen
Adjust sensibility poor, polymerization activity is relatively low under high hydrogen condition.Alkoxy magnesium-based catalyst preparation technology route is broadly divided into two classes,
Alkyl magnesium is prepared into expected graininess by one kind to be existing, then alkyl magnesium granules are reacted shape in atent solvent with titanium compound
At catalyst precursor;It is another kind of for alkoxyl magnesium and alkoxytitanium are dissolved to be formed it is molten containing alkoxyl magnesium and alkoxytitanium
Liquid, Precipitation forms catalyst precarsor under chlorination reagent/alkyl aluminum effect.The technical solution of this kind of catalyst is disclosed in
US4859749A,US5292837A,US5648309,US7649061,US7759445,WO2011060954,WO0138405,
CN200580025162,CN03819076,CN200580025162,CN200680004879,CN200980122271,
CN201080035834,CN201180029854,US6335411,US6545106,CN96110046,CN201410725832,
In the patent documents such as CN201410743733.This kind of catalyst generally has high activity, high hydrogen response and tool performance etc.
Advantage, particularly suitable for development and production bimodal resin product, but usually particle shape it is poor, resin-oatmeal material mobility compared with
Difference, the bulk density of resin powder still needs to be further increased, and fine powder content is higher, the produce load of these defective effects
It is promoted, and is easy to cause discharging pipeline and blocks.
In view of the importance of catalyst granules form control, it is necessary to develop a kind of slurry polyethylene of alkoxy magnesium-based and urge
Agent has improved particle shape under the premise of the performances such as catalyst activity meet production requirement.
Invention content
In order to overcome in the prior art alkoxy magnesium-based polyethylene catalysts particle shape it is poor, fine powder content is higher, powder
The relatively low defect of bulk density, the present invention provide a kind of alkoxyl magnesium microsphere particle prepared by spray drying process, further carry
For a kind of solid polyethylene catalytic component prepared by alkoxyl magnesium microsphere particle load, the solid polyethylene catalyst group
The polyethylene powder for dividing and being prepared with the catalytic component, it may have good particle shape, good mobility are relatively low
Fine powder content.
Alkoxyl magnesium microsphere particle of the present invention is the alkane that will be dispersed in the form of gel dispersion in inert media
Oxygroup magnesium suspension is spray-dried to be obtained.
It is Mg (OR that above-mentioned alkoxyl magnesium, which refers to chemical structural formula,1)(OR2) a kind of magnesium compound, R1And R2Preferably
Alkyl with 2-10 carbon atom.It is preferred that R1And R2For C1-C2- alkyl.As an example, but dimethoxy magnesium, diethyl are not limited to
Oxygroup magnesium, diisopropoxy magnesium, two positive propoxy magnesium, two n-butoxy magnesium, methoxy ethoxy magnesium, ethyoxyl positive propoxy
Magnesium, two (2- methyl-1-pentenes oxygroup) magnesium, two (2- methyl-1s-hexyloxy) magnesium, two (2- methyl-1s-heptan oxygroup) magnesium, two (2- second
Base -1- amoxys) magnesium, two (2- ethyl -1- hexyloxies) magnesium, two (2- ethyl -1- oxygroups in heptan) magnesium, two (2- propyl -1- oxygen in heptan
Base) magnesium, two (2- methoxyl group -1- ethyoxyls) magnesium, two (3- methoxyl group -1- propoxyl group) magnesium, two (4- methoxyl group -1- butoxy)
Magnesium, two (6- methoxyl group -1- hexyloxies) magnesium, two (2- ethyoxyl -1- ethyoxyls) magnesium, two (3- ethyoxyl -1- propoxyl group) magnesium, two
(4- ethyoxyl -1- butoxy) magnesium, two (6- ethyoxyl -1- hexyloxies) magnesium, two amoxy magnesium, two hexyloxy magnesium.Preferred alkane
Oxygroup magnesium is monoalkoxy magnesium, such as diethoxy magnesium, two positive propoxy magnesium and two isobutoxy magnesium.Particularly preferred magnesium ethylate.
The decentralized medium of alkoxyl magnesium gel dispersion is the liquid inert medium not chemically reacted with alkoxyl magnesium,
Such as can be liquid inert alkane, cycloalkane and aromatic hydrocarbon, liquid ether, liquid ketone, liquid alcohol etc., preferably liquid alcohol, especially
Preferably ethyl alcohol.The preparation method of alkoxyl magnesium gel dispersion is not particularly limited, and may be used any in the prior art
Dispersion technology.As an example, it can show and commercially available bulky grain alkoxyl magnesium is first ground crushing, grain size under an inert atmosphere
Reach 5-50 microns, then in a dispersion medium by its suspended dispersed, then by the alkoxyl magnesium suspension in high speed point
Dissipate machine (such as Ultra-Turrax or Dispax, IKA-Maschinenbau Janke&Kunkel GmbH) shearing force
Under effect, disperse gelled dispersion.So-called alkoxyl magnesium gel dispersion is the alkane that average grain diameter is less than 1 micron
The dispersion of oxygroup magnesium dispersion in liquid medium, this dispersion are stablized relatively, and sedimentation is very slow, and it is existing to generate dindar
As.The commercially available alkoxyl magnesium especially Mg (OC2H5)2, with 200-1200 μm, preferably from about 500-700 μm of average grain
Diameter.Prepared by alkoxyl magnesium gel dispersion can also be by independently preparing alkoxyl magnesium particle, Wu Xugan with magnesium powder and alcohol reaction
It is dry to be directly dispersing in alcohol, then through high speed dispersor (such as Ultra-Turrax or Dispax, IKA-Maschinenbau
Janke&Kunkel GmbH) shearing force effect under, disperse gelled dispersion.It in this way can be without oversized particles
Alkoxyl magnesium grinds step, and can prepare the smaller alkoxyl magnesium of grain size by optimizing the reaction condition of magnesium powder and alcohol
(such as 20 microns or less) save energy and cost so as to shorten flow.
Equipment and condition used in spray-drying process and spray-drying process according to the present invention is not special
Restriction, can be used for the molding of organic phase material spray and dry device and method in the prior art can introduce use of the present invention
In preparing alkoxyl magnesium microsphere particle.As an example, press spray drier may be used in spray drying device, can also adopt
With rotary spray dryer or two fluid-type spray dryers;Dry materials process can once be completed with spray-dried device,
The drying equipment (such as fluidized bed drying) for one or more other forms that can also connect after spray dryer continues drying, makes
It dries complete.
The invention further relates to a kind of slurry polyethylene catalytic component A, are the alkoxyl magnesiums by will be obtained by spray drying
Microsphere particle contacts to obtain the ingredient of solid catalyst for including the ingredients such as magnesium, titanium, chlorine with titanium tetrachloride.
Alkoxyl magnesium microsphere particle of the present invention does not require particularly with the titanium tetrachloride way of contact, can be according to
Techniques well known carries out, and as an example, slurry polyethylene catalytic component of the present invention is by comprising the following steps
It is prepared by method:(a) the magnesium ethylate microsphere particle and titanium tetrachloride obtained spraying is in inert media in≤50 DEG C of temperature
Lower contact (b) makes the reaction mixture obtained in (a) be subjected to high temperature contact at a temperature of 100 DEG C -130 DEG C, (c) detaches
It is used in combination inert media washing by the microspheres with solid particle obtained in (b), the ingredient of solid catalyst is with the Cl/ higher than 2.5
Ti molar ratios.
As explained, in the first step, make magnesium alkoxide and TiCl4It is reacted in inert media.
Alkoxyl magnesium and TiCl4Reaction to be higher than 1 and preferably within the scope of 1.5-4, more preferably in 1.75-2.75 ranges
It is carried out under interior Ti/Mg molar ratios.The reaction time of first stage is 0.5-8 hours, preferably 2-6 hours;Second stage is higher
At a temperature of reaction time answer >=15 minutes, preferably 0.5-5 hours, more preferably 1-3 hours.
The hydrocarbon of inertia suspension media as above-mentioned reaction include aliphatic series and cycloaliphatic hydrocarbon, such as butane, pentane, hexane,
Heptane, hexamethylene, isooctane and aromatic hydrocarbons, such as benzene, toluene and dimethylbenzene.It also can be used and have been removed oxygen, sulphur compound
With the white spirit and hydrogenated diesel fraction of moisture.
At the end of preparation method, the grain size of catalytic component (A) is preferably 5-20 μm, more preferably 7-15 μm.
Step (b) completion after, can carry out at a temperature of 60-80 DEG C hydrocarbon washing, until suspension mother liquor Cl and
Ti concentration is less than 10mmol/l.As explained above, the Cl/Ti molar ratios of the solid obtained at the end of washing step (c) are at least
2.5, more preferably at least 3, more preferably 3-5.Obtained solid has following typical composition:Mg: Ti: Cl=1: (0.8-
1.5):(3.2-4.2)。
It is the preparation method by further including step (d) the invention further relates to a kind of solid polyethylene catalytic component A
It obtains, (d) further contacts the obtained solid component of step (c) to obtain final solid catalyst with aluminum alkyl halide
Component, wherein Cl/Ti molar ratios are increased relative to the Cl/Ti molar ratios of the solid before step (d).
Wherein the aluminum alkyl halide preferably is selected from chlorination alkyl aluminum and is preferably selected from formula R3 2The monochlor(in)ate dialkyl group of AlCl
Aluminium or formula R3 3Al2Cl3Alkylaluminium sesquichloride, wherein R3It can be the identical or different alkyl with 1-16 carbon atom.
Such alkyl aluminum chloride compound can be selected from following compound as an example:(C2H5)2AlCl, (isobutyl group)2AlCl and
(C2H5)3Al2Cl3(ethyl aluminium sesquichloride).The reaction can be in stirring container at 0 DEG C -150 DEG C, preferably 30 DEG C -100 DEG C
At a temperature of carry out 0.5-5 hours.
Alkyl aluminum chloride compound so that Al/Ti molar ratios (about the solid catalyst such as obtained by previous steps
The Ti content calculations of component) it is used for the amount of 0.05-1, preferably 0.1-0.5.
As explained above, the ingredient of solid catalyst obtained by step (d), wherein Cl/Ti molar ratios increase and usually extremely
It is 3, more preferably higher than 3.5 less.By carrying out the later step (d), a degree of titanium atom can be made from oxidation state Ti+4Reduction
To oxidation state Ti+3。
The obtained catalytic component (A) is used in vinyl polymerization together with organo-aluminum compound (B).
Organo-aluminum compound (B) is preferably selected from trialkyl aluminium compound, such as trimethyl aluminium (TMA), triethyl aluminum
(TEAL), triisobutyl aluminium (TIBA), three n-butylaluminums, tri-n-hexyl aluminum, tri-n-octylaluminium, three prenyl aluminium.Alkyl
Aluminium halogenide and especially chlorination alkyl aluminum, such as diethylaluminum chloride (DEAC), di-isobutyl aluminum chloride, Al- sesquialter chlorinations
Object and chlorodimethylalumiu (DMAC) can also be used with mixture together with the trialkylaluminium (trialuminium alkyl).
It is preferable to use TEAL and TIBA.
Further preferably make preactivated catalyst system and alpha-olefin, preferably linear C2-C10-1- alkene and especially first
Ethylene or Propylene Pre-polymerization, then the pre-polymerized catalyst solid obtained by use in main polymerization.The catalysis used in prepolymerization
Agent solid and the mass ratio of monomer thereon is aggregated to usually in 1: 0.1 to 1: 20 ranges.
The catalyst system of the present invention is particularly suitable for slurry phase polymerisation process.In fact, all such as less than 20 μm, preferably 7-15 μm
Average particle size be particularly suitable for the slurry polymerization in inert media, can in stirred reactor or annular-pipe reactor continuously into
Row.In a preferred embodiment, ethene polymerization method is in two or more series connection annular-pipe reactors or stirred reactor
Middle progress generates the polymer with different molecular weight and/or different compositions in each reactor, thus shows wide point on the whole
The distribution of son amount and/or monomer composition.
Following embodiment is provided to further describe the present invention in a non-limiting manner.
Description of the drawings
Fig. 1 is that embodiment 1 obtains the electromicroscopic photograph of ingredient of solid catalyst.
Fig. 2 is that comparative example 1 obtains the electromicroscopic photograph of ingredient of solid catalyst.
Embodiment
Embodiment 1 (present invention)
A) magnesium ethylate microsphere particle is prepared
By 57g (0.5mol) Mg (OC2H5)2Solid powder and 200ml ethyl alcohol are put into the grinding pot of 500ml, are speeded with German Lay
The PM-400 ball milling instrument of company is ground 5 hours, obtains the Mg (OC that average grain diameter is 5.5 μm2H5)2Suspension.
Take the Mg (OC that above-mentioned grinding obtains2H5)2Suspension 100ml be transferred to through N2In four mouthfuls of reaction bulbs of displacement, add
Enter 100ml ethyl alcohol, high speed disperser (Krupp Supraton are used in combinationTMType S200) it is handled 20 hours at 60 DEG C, to be formed
Gel dispersion.
By Mg (OC obtained above2H5)2Gel dispersion spray-dried (Buchi B290) spray drying is consolidated
Body microsphere particle, spray condition are 210 DEG C of inlet temperature, and 158 DEG C of outlet temperature, feed pump aperture 25%, atomization gas flow is
742L/h.Microspheres with solid particle D50 is 8.4 μm.
B) ingredient of solid catalyst A is prepared:
The magnesium ethylate microsphere particle that 10g is prepared by step a) is weighed, is added to through N2In four mouthfuls of reaction bulbs of displacement, add
Enter toluene 200ml, open stirring, adjustment speed of agitator is 200r/min, and oil bath temperature is down to 5 DEG C.19.6ml is slowly added dropwise
TiCl4(Ti/Mg=2), 30min is maintained after being added dropwise to complete at 5 DEG C, is then to slowly warm up to 110 DEG C, and tieed up at 110 DEG C
Reaction 2hr is held, is then allowed to stand and is washed twice with toluene, each toluene dosage is 200ml, and 200ml toluene is added, and opens stirring
0.18mmol ethyl aluminium sesquichlorides are slowly added dropwise, and 30min is reacted at 80 DEG C, are then allowed to stand, hexane washing is used in combination three times,
The dosage of each hexane is 200ml, then purges drying with high pure nitrogen, obtains ingredient of solid catalyst.Its Electronic Speculum pattern shines
Piece such as Fig. 1.
C) vinyl polymerization in suspension:
1L hexanes, 5mmol triethyl aluminums and a certain amount of catalyst are added in 2L stainless steel stirred tanks, it then will be warm
Degree be increased to 80 DEG C, be added at one time the hydrogen of 0.28MPa, then with ethylene by the gross pressure of system maintain 0.73MPa into
Row polymerisation after reacting 2 hours, stops that ethylene, cooling is added, pressure release, polyethylene powder is weighed, and the work of catalyst is calculated
Property, the bulk density and the melt index under 2.16Kg loads for testing polyethylene powder, the results are shown in Table 1.
Embodiment 2 (present invention)
A) magnesium ethylate microsphere particle is prepared
By 57g (0.5mol) Mg (OC2H5)2Solid powder and 200ml ethyl alcohol are put into the grinding pot of 500ml, are speeded with German Lay
The PM-400 ball milling instrument of company is ground 5 hours, obtains the Mg (OC that average grain diameter is 5.5 μm2H5)2Suspension.
Take the Mg (OC that above-mentioned grinding obtains2H5)2Suspension 100ml be transferred to through N2In four mouthfuls of reaction bulbs of displacement, add
Enter 100ml ethyl alcohol, high speed disperser (Krupp Supraton are used in combinationTMType S200) it is handled 20 hours at 60 DEG C, to be formed
Gel dispersion.
By Mg (OC obtained above2H5)2Gel dispersion spray-dried (Buchi B290) spray drying is consolidated
Body microsphere particle, spray condition are 200 DEG C of inlet temperature, and 152 DEG C of outlet temperature, feed pump aperture 35%, atomization gas flow is
742L/h.Microspheres with solid particle D50 is 9.2 μm.
B) ingredient of solid catalyst A is prepared:
The magnesium ethylate microsphere particle that 10g is prepared by step a) is weighed, is added to through N2In four mouthfuls of reaction bulbs of displacement, add
Enter toluene 200ml, open stirring, adjustment speed of agitator is 200r/min, and oil bath temperature is down to 5 DEG C.19.6ml is slowly added dropwise
TiCl4(Ti/Mg=2), 30min is maintained after being added dropwise to complete at 5 DEG C, is then to slowly warm up to 110 DEG C, and tieed up at 110 DEG C
Reaction 2hr is held, is then allowed to stand and is washed twice with toluene, each toluene dosage is 200ml, and 200ml toluene is added, and opens stirring
0.18mmol ethyl aluminium sesquichlorides are slowly added dropwise, and 30min is reacted at 80 DEG C, are then allowed to stand, hexane washing is used in combination three times,
The dosage of each hexane is 200ml, then purges drying with high pure nitrogen, obtains ingredient of solid catalyst.
C) vinyl polymerization in suspension:
With embodiment 1.
Embodiment 3 (present invention)
A) magnesium ethylate microsphere particle is prepared
By 57g (0.5mol) Mg (OC2H5)2Solid powder and 200ml ethyl alcohol are put into the grinding pot of 500ml, are speeded with German Lay
The PM-400 ball milling instrument of company is ground 5 hours, obtains the Mg (OC that average grain diameter is 5.5 μm2H5)2Suspension.
Take the Mg (OC that above-mentioned grinding obtains2H5)2Suspension 100ml be transferred to through N2In four mouthfuls of reaction bulbs of displacement, add
Enter 100ml ethyl alcohol, high speed disperser (Krupp Supraton are used in combinationTMType S200) it is handled 30 hours at 60 DEG C, to be formed
Gel dispersion.
By Mg (OC obtained above2H5)2Gel dispersion spray-dried (Buchi B290) spray drying is consolidated
Body microsphere particle, spray condition are 230 DEG C of inlet temperature, and 172 DEG C of outlet temperature, feed pump aperture 25%, atomization gas flow is
670L/h.Microspheres with solid particle D50 is 10.5 μm.
B) ingredient of solid catalyst A is prepared:
The magnesium ethylate microsphere particle that 10g is prepared by step a) is weighed, is added to through N2In four mouthfuls of reaction bulbs of displacement, add
Enter toluene 200ml, open stirring, adjustment speed of agitator is 200r/min, and oil bath temperature is down to 5 DEG C.24.5ml is slowly added dropwise
TiCl4(Ti/Mg=2.5), 30min is maintained after being added dropwise to complete at 5 DEG C, is then to slowly warm up to 110 DEG C, and at 110 DEG C
Reaction 2hr is maintained, is then allowed to stand and is washed twice with toluene, each toluene dosage is 200ml, and 200ml toluene is added, and unlatching is stirred
It mixes and 0.18mmol ethyl aluminium sesquichlorides is slowly added dropwise, and 30min is reacted at 80 DEG C, be then allowed to stand, hexane is used in combination to wash three
Secondary, the dosage of each hexane is 200ml, then purges drying with high pure nitrogen, obtains ingredient of solid catalyst.
C) vinyl polymerization in suspension:
With embodiment 1.
Comparative example 1
A) magnesium ethylate particle is prepared
By 40g (0.5mol) Mg (OC2H5)2Solid powder and 200ml toluene are put into the grinding pot of 500ml, are speeded with German Lay
The PM-400 ball milling instrument of company is ground 5 hours, obtains the Mg (OC that average grain diameter is 5.5 μm2H5)2Suspension.
Take the Mg (OC that above-mentioned grinding obtains2H5)2Suspension 50ml be transferred to through N2In four mouthfuls of reaction bulbs of displacement, add
Enter 150ml toluene, high speed disperser (Krupp Supraton are used in combinationTMType S200) it is handled 20 hours at 60 DEG C, to be formed
Gel dispersion.
B) ingredient of solid catalyst A is prepared:
Gel dispersion a) obtained is transferred to through N2In four mouthfuls of reaction bulbs of displacement, stirring, adjustment stirring are opened
Rotating speed is 200r/min, and oil bath temperature is down to 5 DEG C.24.5ml TiCl are slowly added dropwise4(Ti/Mg=2.5), after being added dropwise to complete
30min is maintained at 5 DEG C, is then to slowly warm up to 110 DEG C, and maintains reaction 2hr at 110 DEG C, is then allowed to stand and is used toluene
It washes twice, each toluene dosage is 200ml, and 200ml toluene is added, and opens stirring and 0.18mmol ethyl sesquialter chlorine is slowly added dropwise
Change aluminium, and 30min is reacted at 80 DEG C, be then allowed to stand, hexane washing is used in combination three times, the dosage of each hexane is 200ml, then
Drying is purged with high pure nitrogen, obtains ingredient of solid catalyst.Its Electronic Speculum pattern photo such as Fig. 2.
C) vinyl polymerization in suspension:
With embodiment 1.
Table 1
Claims (7)
1. a kind of alkoxyl magnesium microsphere particle is the Mg (OR that will be dispersed in the form of gel dispersion in inert media1)(OR2)
Compound suspension is spray-dried to be obtained, wherein R1And R2Alkane identical or different and that respectively there is 1 to 10 carbon atoms
Base.
2. the alkoxyl magnesium microsphere particle of claim 1, wherein the alkoxyl magnesium is magnesium ethylate.
3. a kind of solid polyethylene catalytic component, is obtained by method comprising the following steps:
(a) by alkoxyl magnesium microsphere particle as claimed in claim 1 or 2 and titanium tetrachloride in inert media in≤50 DEG C of temperature
The lower contact of degree,
(b) reaction mixture obtained in (a) is made to be subjected to high temperature contact at a temperature of 100 DEG C -130 DEG C,
(c) it detaches and washs the microspheres with solid particle by being obtained in (b) with inert media.
4. the solid polyethylene catalytic component described in claim 3 is by further including step (d) by step (c) institute
Obtained solid component is further contacted with aluminum alkyl halide and is obtained in the method for obtaining final ingredient of solid catalyst.
5. the solid polyethylene catalytic component described in claim 4, the aluminum alkyl halide is selected from formula R3 2The one of AlCl
Chlorination aluminum dialkyl or formula R3 3Al2Cl3Alkylaluminium sesquichloride, wherein R3Can be identical with 1-16 carbon atom or
Different alkyl.
6. the solid polyethylene catalytic component described in claim 4, the aluminum alkyl halide is selected from aluminium diethyl monochloride
Or ethyl aluminium sesquichloride.
7. for the catalyst system of ethylene slurry polymerization, by the ingredient of solid catalyst (A) and three for making claim 3-6
Alkyl aluminum (component B) is obtained by the reaction.
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Cited By (1)
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CN109503741B (en) * | 2018-11-09 | 2021-07-30 | 上海葛蓝化工科技有限公司 | Alkoxy magnesium composite microsphere particle and solid polyethylene catalyst prepared from same |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4311817A (en) * | 1977-09-09 | 1982-01-19 | Mitsui Petrochemical Industries Ltd. | Process for polymerizing olefins and catalyst therefor |
CN86105015A (en) * | 1985-08-28 | 1987-02-25 | 国际壳牌研究有限公司 | The preparation method of spherical magnesium alkoxide particles |
CN102482371A (en) * | 2009-08-06 | 2012-05-30 | 巴塞尔聚烯烃股份有限公司 | Catalyst component for the polymerization of olefins |
CN106928381A (en) * | 2017-04-27 | 2017-07-07 | 谢炳 | A kind of preparation method of polyethylene catalysts |
-
2018
- 2018-06-06 CN CN201810574852.XA patent/CN108690152A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4311817A (en) * | 1977-09-09 | 1982-01-19 | Mitsui Petrochemical Industries Ltd. | Process for polymerizing olefins and catalyst therefor |
CN86105015A (en) * | 1985-08-28 | 1987-02-25 | 国际壳牌研究有限公司 | The preparation method of spherical magnesium alkoxide particles |
CN102482371A (en) * | 2009-08-06 | 2012-05-30 | 巴塞尔聚烯烃股份有限公司 | Catalyst component for the polymerization of olefins |
CN106928381A (en) * | 2017-04-27 | 2017-07-07 | 谢炳 | A kind of preparation method of polyethylene catalysts |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109503741B (en) * | 2018-11-09 | 2021-07-30 | 上海葛蓝化工科技有限公司 | Alkoxy magnesium composite microsphere particle and solid polyethylene catalyst prepared from same |
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