CN109320639A - A kind of alkoxyl magnesium carrier and its polyethylene catalyst of preparation - Google Patents
A kind of alkoxyl magnesium carrier and its polyethylene catalyst of preparation Download PDFInfo
- Publication number
- CN109320639A CN109320639A CN201811066711.3A CN201811066711A CN109320639A CN 109320639 A CN109320639 A CN 109320639A CN 201811066711 A CN201811066711 A CN 201811066711A CN 109320639 A CN109320639 A CN 109320639A
- Authority
- CN
- China
- Prior art keywords
- alkoxyl magnesium
- polyethylene
- catalyst
- compound
- aluminum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a kind of alkoxyl magnesium carrier and its polyethylene catalysts of preparation.The alkoxyl magnesium carrier is obtained by the spray dried of the carboxylation alkoxyl magnesium compound of the alkoxyl magnesium compound and solution state in gel dispersion volume morphing.By alkoxyl magnesium carrier and titanium tetrachloride in inert media in≤50 DEG C at a temperature of contact；It is gradually warming up to 100-130 DEG C, and haptoreaction at this temperature；Inert media washed product is separated and uses, obtained microspheres with solid particle is polyethylene catalyst.It is reacted to obtain a kind of catalyst system for ethylene slurry polymerization with organo-aluminum compound by polyethylene catalysts.The polyethylene catalysts that the present invention obtains have good particle shape, and being used for resin powder when vinyl polymerization has good particle shape, higher bulk density, and fine powder content significantly reduces.
Description
Technical field
The present invention relates to the preparation method and application of a kind of alkoxyl magnesium carrier and its polyethylene catalyst of preparation,
Belong to polyolefin catalyst technical field.
Background technique
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.Wherein it is broadly divided into magnesium dichloride-based for the polymerization catalyst of slurry process polyethylene process by the source point of presoma magnesium
With alkoxy magnesium-base catalyst.Magnesium dichloride-based catalyst preparation route is generally first molten by magnesium chloride using Louis's bases solution
Solution, titanium-containing compound effect under Precipitation, formed 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 lower under high hydrogen condition.Alkoxy magnesium-based catalyst preparation technology route is broadly divided into two classes,
Alkyl magnesium is prepared into graininess to be existing by one kind, then alkyl magnesium granules are reacted to form catalysis with titanium compound in atent solvent
Agent presoma；Another kind of is to dissolve alkoxyl magnesium and alkoxytitanium to form the solution containing alkoxyl magnesium and alkoxytitanium,
Chlorination reagent/alkyl aluminum acts on lower Precipitation and forms catalyst precarsor.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 blocking.
In view of the importance of catalyst granules form control, it is necessary to which the slurry polyethylene for developing a kind of alkoxy magnesium-based is urged
Agent has improved particle shape under the premise of the performances such as catalyst activity meet production requirement.
Summary of the invention
The technical problems to be solved by the present invention are: existing alkoxy magnesium-based polyethylene catalysts particle shape is poor, fine powder
Content is higher, the relatively low defect of powder bulk density.
In order to solve the above-mentioned technical problems, the present invention provides a kind of alkoxyl magnesium carriers, which is characterized in that by comprising being in
The spray dried of the carboxylation alkoxyl magnesium compound of the alkoxyl magnesium compound and solution state of gel dispersion volume morphing obtains
It arrives.
It is mixed with the alkoxyl magnesium compound of the carboxylation of the alkoxyl magnesium compound and solution state in gel dispersion volume morphing
The preparation process of suspension is not particularly limited, can be according to the ratio of alkyl magnesium compound and the alkyl magnesium compound of carboxylation
The alkyl magnesium compound solution of the alkyl magnesium compound suspension for being dispersed into gel dispersion volume morphing and carboxylation is subjected to object
Manage the suspension being mixed to form；It can also be added into the alkyl magnesium compound suspension for being dispersed into gel dispersion volume morphing
The desired amount of CO2, make part alkoxyl magnesium compound carboxylation and dissolve the alkoxyl magnesium to be formed and be mixed in gel dispersion volume morphing
The suspension of the alkoxyl magnesium compound of the carboxylation of compound and solution state.Alkoxyl magnesium compound gel dispersion in suspension
Preparation method be not particularly limited, can be using any dispersion technology in the prior art.As an example, can show will be commercially available
Bulky grain alkoxyl magnesium first ground under an inert atmosphere, partial size reaches 5-50 microns, then by its suspended dispersed
In a dispersion medium, then by the alkoxyl magnesium suspension high speed disperser (such as Ultra-Turrax or Dispax,
IKA-Maschinenbau Janke&Kunkel GmbH) shearing force effect under, disperse gelled dispersion.It is so-called
Alkoxyl magnesium gel dispersion, be alkoxyl magnesium dispersion dispersion in liquid medium of the average grain diameter less than 1 micron,
This dispersion is relatively stable, and sedimentation is very slow, and can generate Tyndall phenomenon.The preparation of alkoxyl magnesium gel dispersion can also be with
By independently preparing alkoxyl magnesium particle with magnesium powder and alcohol reaction, it is directly dispersing in alcohol without drying, then through high speed disperser
The shearing force of (such as Ultra-Turrax or Dispax, IKA-Maschinenbau Janke&Kunkel GmbH) acts on
Under, disperse gelled dispersion.In this way can be without the step that grinds of oversized particles alkoxyl magnesium, and it can be by excellent
The reaction condition for changing magnesium powder and alcohol prepares the lesser alkoxyl magnesium of partial size (such as 20 microns or less), so as to shorten process, saves energy
Amount and cost.
The present invention is not special to equipment used in the spray-drying process and spray-drying process being related to and condition
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, spray drying device can use press spray drier, 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 chemical structural formula of the alkoxyl magnesium compound is Mg (OR1)(OR2)。
The chemical structural formula of the carboxylation alkoxyl magnesium compound is Mg (OR3)(OR4)·XCO2；Wherein, R1、R2、R3、R4
It is the alkyl containing 2-10 carbon atom, X 1-2.
The molar ratio of the alkoxyl magnesium compound and carboxylation alkoxyl magnesium compound is 1:(0.01-1), more preferably 1:
(0.05-0.3)。
Preferably, described R1, R2, R3, R4 are-C2H5。
Preferably, the average grain diameter of the alkoxyl magnesium compound is 200-1200 μm, preferably 500-700 μm；In order to
The small droplet shaping and drying process for ensureing that suspension atomization is formed in spray-drying process is smooth, and the solid content of the suspension is
5-80%, preferably 10-30%.The liquid medium that above-mentioned suspension is related to is the alkoxy with alkoxyl magnesium compound and carboxylation
The polar liquid medium that magnesium compound does not chemically react, such as can be liquid ether, liquid ketone, liquid alcohol, preferably liquid
Body alcohol, particularly preferably ethyl alcohol.
The present invention also provides a kind of polyethylene catalysts, which is characterized in that is obtained by method comprising the following steps
It arrives:
Step a): by above-mentioned alkoxyl magnesium carrier and titanium tetrachloride in inert media in≤50 DEG C at a temperature of connect
Touching；
Step b): the mixture of step a) is gradually warming up to 100-130 DEG C, and haptoreaction at this temperature；Compared with
Time of contact under low temperature is greater than 15 minutes, and time of contact should be no less than 15 minutes at relatively high temperatures, and preferably 0.5-5 is small
When.
Step c): the product that step b) is obtained separate and washed with inert media, obtained microspheres with solid particle
As polyethylene catalyst.
Preferably, before the step a), alkoxyl magnesium carrier is further handled in the inert atmosphere higher than 100 DEG C,
So that the alkoxyl magnesium compound decomposition of the carboxylation in microspheres with solid particle releases CO2。
Preferably, inert media includes aliphatic hydrocarbon, cycloaliphatic hydrocarbon and aromatic hydrocarbons in the step a), such as butane, pentane, oneself
The stone for having been removed oxygen, sulphur compound and moisture also can be used in alkane, heptane, hexamethylene, isooctane, benzene, toluene and dimethylbenzene
Oil solvent oil and hydrogenated diesel fraction.
Preferably, the molar ratio of Cl/Ti is higher than 2.5 in the polyethylene catalytic materials that the step c) is obtained, preferably at least
It is 3, more preferably 3-5；Ti/Mg molar ratio is higher than 1, preferably within the scope of 1.5-4, more preferably within the scope of 1.75-2.75；
The partial size of polyethylene catalytic materials is 5-20 μm, preferably 7-15 μm.
Preferably, above-mentioned steps further include step d): the microspheres with solid particle that the step c) is obtained further with alkane
Base aluminium halogenide contacts 0.5-5 hours under the conditions of 0-150 DEG C, preferably 30-100 DEG C, makes a degree of titanium atom from oxidation
State Ti4+Revert to oxidation state Ti3+；The aluminum alkyl halide is that chemical structural formula is R3 2The monochlor(in)ate aluminum dialkyl of AlCl or
Chemical structural formula is R3 3Al2Cl3Alkylaluminium sesquichloride, wherein R3It is identical or different containing 1-16 carbon atom
Alkyl；In the polyethylene catalytic materials that step d) is obtained the molar ratio of Al/Ti be 0.05-1, preferably 0.1-0.5, Cl/Ti's
Molar ratio is not less than 3 preferably more than 3.5.Cl/Ti of the Cl/Ti molar ratio relative to the solid before step d)
Molar ratio is increased.
It is highly preferred that the aluminum alkyl halide is aluminium diethyl monochloride or ethyl aluminium sesquichloride.
The present invention also provides a kind of catalyst systems for ethylene slurry polymerization, which is characterized in that by above-mentioned poly- second
Alkene catalytic component is with organo-aluminum compound with 1: the mass ratio of (0.1-20) reacts to obtain；The organo-aluminum compound is three alkane
The mixture of base aluminium compound or itself and aluminum alkyl halide.
Preferably, the trialkyl aluminium compound is trimethyl aluminium (TMA), triethyl aluminum (TEAL), triisobutyl aluminium
(TIBA), three n-butylaluminums, tri-n-hexyl aluminum, tri-n-octylaluminium or three prenyl aluminium.
Preferably, the aluminum alkyl halide is chlorination alkyl aluminum.
It is highly preferred that the chlorination alkyl aluminum is diethylaluminum chloride (DEAC), di-isobutyl aluminum chloride, Al- sesquialter chlorine
Compound and chlorodimethylalumiu (DMAC).
Above-mentioned catalyst system then uses prepolymerization in use, first by itself and alpha-olefin prepolymerization in main polymerization
Catalyst system.
Preferably, the alpha-olefin is linear C2-C10Alkene.
It is highly preferred that the alpha-olefin is ethylene or propylene.
Polyethylene catalysts produced by the present invention and its polyethylene powder being prepared have good particle shape,
Good mobility, lower fine powder content.
Catalyst system of the 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.
Specific embodiment
In order to make the present invention more obvious and understandable, it is hereby described in detail below with preferred embodiment.
Embodiment 1
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.
Mg (the OC for taking above-mentioned grinding to obtain2H5)2Suspension 100mL be transferred to through N2In four mouthfuls of reaction flasks of displacement, add
Enter 50mL ethyl alcohol, and handled 20 hours at 60 DEG C with high speed disperser (Krupp SupratonTM type S200), to be formed
Gel dispersion.
0.22g dry ice (0.005mol) is added into gel dispersion obtained above, is stirred to react 1 hour, is contained
There is the magnesium ethylate gel dispersion suspension of the magnesium ethylate solution of carboxylation.
Gel obtained above dispersion liquid suspension spray-dried (Buchi B290) spray drying is obtained into solid
Microsphere particle, spray condition are 200 DEG C of inlet temperature, and 163 DEG C of outlet temperature, feed pump aperture 25%, atomization gas flow is
742L/h.Microspheres with solid particle D50 is 9.8 μm.
Microspheres with solid particle obtained above is fitted into the quartz ampoule under nitrogen atmosphere, 130 are warming up in nitrogen stream
DEG C, and heating 10 hours is maintained, so that CO2It is effectively removed.Obtained microspheres with solid particle D50 is 9.6 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 flasks 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 tie up at 110 DEG C
Reaction 2hr is held, is then allowed to stand and is filtered and washed twice with toluene, each toluene dosage is 200mL, and 200mL toluene is added, and is opened
0.18mmol ethyl aluminium sesquichloride is slowly added dropwise in stirring, and reacts 30min at 80 DEG C, is then allowed to stand, and washed with hexane
Three times, the dosage of each hexane is 200mL, then purges drying with high pure nitrogen, obtains ingredient of solid catalyst.Solid catalysis
Agent component D50 is 10.2 μm.
C) vinyl polymerization in suspension:
1L hexane, 5mmol triethyl aluminum and a certain amount of catalyst are added in 2L stainless steel stirred tank, 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 polymerization reaction after reaction 2 hours, stops that ethylene is added, cools down, and pressure release, polyethylene powder weighing calculates the work of catalyst
Property, the bulk density and the melt index under 2.16kg load for testing polyethylene powder, the results are shown in Table 1.
Embodiment 2
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.
Mg (the OC for taking above-mentioned grinding to obtain2H5)2Suspension 100mL be transferred to through N2In four mouthfuls of reaction flasks of displacement, add
Enter 50mL ethyl alcohol, and handled 20 hours at 60 DEG C with high speed disperser (Krupp SupratonTM type S200), to be formed
Gel dispersion.
0.33g dry ice (0.0075mol) is added into gel dispersion obtained above, is stirred to react 1 hour, is contained
There is the magnesium ethylate gel dispersion suspension of the magnesium ethylate solution of carboxylation.
Gel obtained above dispersion liquid suspension spray-dried (Buchi B290) spray drying is obtained into solid
Microsphere particle, spray condition are 210 DEG C of inlet temperature, and 170 DEG C of outlet temperature, feed pump aperture 25%, atomization gas flow is
742L/h.Microspheres with solid particle D50 is 8.9 μm.
Microspheres with solid particle obtained above is fitted into the quartz ampoule under nitrogen atmosphere, 130 are warming up in nitrogen stream
DEG C, and heating 10 hours is maintained, so that CO2It is effectively removed.Obtained microspheres with solid particle D50 is 8.8 μm.
B) ingredient of solid catalyst A is prepared:
With embodiment 1, ingredient of solid catalyst D50 is 9.1 μm.
C) vinyl polymerization in suspension:
With embodiment 1.
Embodiment 3
A) magnesium ethylate microsphere particle is prepared
With embodiment 1
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 flasks of displacement, add
Enter toluene 200mL, open stirring, adjustment speed of agitator is 200r/min, and oil bath temperature is down to 0 DEG C.24.5mL is slowly added dropwise
TiCl4(Ti/Mg=2.5), 30min is maintained after being added dropwise to complete at 0 DEG C, is then to slowly warm up to 115 DEG C, and at 115 DEG C
Reaction 2hr is maintained, is then allowed to stand and is filtered and washed twice with toluene, each toluene dosage is 200mL, and 200mL toluene is added, opens
It opens stirring and 0.18mmol ethyl aluminium sesquichloride is slowly added dropwise, and react 30min at 80 DEG C, be then allowed to stand, and washed with hexane
It washs three times, the dosage of each hexane is 200mL, then purges drying with high pure nitrogen, obtains ingredient of solid catalyst.Solid is urged
Agent component D50 is 10.3 μm
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.
Mg (the OC for taking above-mentioned grinding to obtain2H5)2Suspension 50mL be transferred to through N2In four mouthfuls of reaction flasks of displacement, add
Enter 150mL toluene, and handled 30 hours at 40 DEG C with high speed disperser (Krupp SupratonTM type S200), 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 flasks of displacement, stirring, adjustment stirring are opened
Revolving speed is 200r/min, and oil bath temperature is down to 5 DEG C.24.5mL TiCl4 (Ti/Mg=2.5) is slowly added dropwise, 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 filtering and is used in combination
Toluene washes twice, and each toluene dosage is 200mL, and 200mL toluene is added, and opens stirring and 0.18mmol ethyl times is slowly added dropwise
Half aluminium chloride, and 30min is reacted at 80 DEG C, it being then allowed to stand, and washed three times with hexane, the dosage of each hexane is 200mL,
Then drying is purged with high pure nitrogen, obtains ingredient of solid catalyst.
C) vinyl polymerization in suspension:
With embodiment 1.
Table 1
As shown in Table 1, solid polyethylene catalytic component is obtained with good particle shape by the present invention, is used for ethylene
Resin powder has good particle shape, higher bulk density when polymerization, and fine powder content significantly reduces.
Claims (10)
1. a kind of alkoxyl magnesium carrier, which is characterized in that by the alkoxyl magnesium compound and solution state that are in gel dispersion volume morphing
The spray dried of carboxylation alkoxyl magnesium compound obtain；
The chemical structural formula of the alkoxyl magnesium compound is Mg (OR1)(OR2)；
The chemical structural formula of the carboxylation alkoxyl magnesium compound is Mg (OR3)(OR4)·XCO2；Wherein, R1、R2、R3、R4It is
Alkyl containing 2-10 carbon atom, X 1-2；
The molar ratio of the alkoxyl magnesium compound and carboxylation alkoxyl magnesium compound is 1:(0.01-1).
2. alkoxyl magnesium carrier as described in claim 1, which is characterized in that described R1, R2, R3, R4 are-C2H5。
3. alkoxyl magnesium carrier as described in claim 1, which is characterized in that the average grain diameter of the alkoxyl magnesium compound is
200-1200μm；The solid content of the suspension is 5-80%.
4. a kind of polyethylene catalyst, which is characterized in that obtained by method comprising the following steps:
Step a): by alkoxyl magnesium carrier of any of claims 1 or 2 and titanium tetrachloride in≤50 DEG C of temperature in inert media
It is contacted under degree；
Step b): the mixture of step a) is gradually warming up to 100-130 DEG C, and haptoreaction at this temperature；
Step c): the product that step b) is obtained separate and washed with inert media, obtained microspheres with solid particle is
Polyethylene catalyst.
5. polyethylene catalyst as claimed in claim 4, which is characterized in that before the step a), alkoxyl magnesium is carried
Body is further handled in the inert atmosphere higher than 100 DEG C.
6. polyethylene catalyst as claimed in claim 4, which is characterized in that inert media includes rouge in the step a)
Race's hydrocarbon, cycloaliphatic hydrocarbon and aromatic hydrocarbons.
7. polyethylene catalyst as claimed in claim 4, which is characterized in that the polyethylene catalysis that the step c) is obtained
The molar ratio of Cl/Ti is higher than 2.5 in object；Ti/Mg molar ratio is higher than 1；The partial size of polyethylene catalytic materials is 5-20 μm.
8. polyethylene catalyst as claimed in claim 3, which is characterized in that further include step d): by the step c)
Obtained microspheres with solid particle further contacts 0.5-5 hours under the conditions of 0-150 DEG C with aluminum alkyl halide；The alkyl aluminum
Halide is that chemical structural formula is R3 2The monochlor(in)ate aluminum dialkyl or chemical structural formula of AlCl is R3 3Al2Cl3Alkyl aluminum sesquialter
Chloride, wherein R3For the identical or different alkyl containing 1-16 carbon atom；In the polyethylene catalytic materials that step d) is obtained
The molar ratio of Al/Ti is 0.05-1, and the molar ratio of Cl/Ti is not less than 3.
9. polyethylene catalyst as claimed in claim 8, which is characterized in that the aluminum alkyl halide is a chlorine two
Aluminium ethide or ethyl aluminium sesquichloride.
10. a kind of catalyst system for ethylene slurry polymerization, which is characterized in that as described in claim 3-7 any one
Polyethylene catalyst with organo-aluminum compound with 1: the mass ratio of (0.1-20) reacts to obtain；The organo-aluminum compound
For trialkyl aluminium compound or the mixture of itself and aluminum alkyl halide；The catalyst system is in use, first by itself and α-alkene
Hydrocarbon prepolymerization then uses pre-polymerized catalyst system in main polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811066711.3A CN109320639B (en) | 2018-09-13 | 2018-09-13 | Alkoxy magnesium carrier and polyethylene catalyst component prepared from same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811066711.3A CN109320639B (en) | 2018-09-13 | 2018-09-13 | Alkoxy magnesium carrier and polyethylene catalyst component prepared from same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109320639A true CN109320639A (en) | 2019-02-12 |
| CN109320639B CN109320639B (en) | 2021-06-29 |
Family
ID=65265942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811066711.3A Active CN109320639B (en) | 2018-09-13 | 2018-09-13 | Alkoxy magnesium carrier and polyethylene catalyst component prepared from same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109320639B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4540679A (en) * | 1984-03-23 | 1985-09-10 | Amoco Corporation | Magnesium hydrocarbyl carbonate supports |
| 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 |
| CN101831015A (en) * | 2009-03-10 | 2010-09-15 | 中国石油天然气股份有限公司 | Catalyst for preparing ultra-high molecular weight polyethylene |
| 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 |
| CN105482004A (en) * | 2015-12-04 | 2016-04-13 | 淄博新塑化工有限公司 | Composite catalyst for preparation of broad peak / bimodal distribution high density polyethylene |
-
2018
- 2018-09-13 CN CN201811066711.3A patent/CN109320639B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4540679A (en) * | 1984-03-23 | 1985-09-10 | Amoco Corporation | Magnesium hydrocarbyl carbonate supports |
| 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 |
| CN101831015A (en) * | 2009-03-10 | 2010-09-15 | 中国石油天然气股份有限公司 | Catalyst for preparing ultra-high molecular weight polyethylene |
| 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 |
| CN105482004A (en) * | 2015-12-04 | 2016-04-13 | 淄博新塑化工有限公司 | Composite catalyst for preparation of broad peak / bimodal distribution high density polyethylene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109320639B (en) | 2021-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4560671A (en) | Olefin polymerization catalysts adapted for gas phase processes | |
| FI91768C (en) | The catalyst component for polymerization of ethylene or copolymerization of ethylene with an alpha-olefin | |
| CN109438593A (en) | A kind of production extrahigh-molecular weight polyolefins catalyst and its preparation method and application | |
| CN102453169A (en) | Catalyst ingredient for olefin polymerization and preparation method thereof | |
| SK279445B6 (en) | Supported ziegler-natta catalyst for ethylene polymerisation and the copolymerisation of ethylene with alpha-olefins, its preparation and use | |
| KR20130099954A (en) | Method for feeding an antistatic compound to a polymerization reactor | |
| FI79125C (en) | FOERFARANDE FOER ATT POLYMERISERA ETEN OCH SAMPOLYMERISERA ETEN MED ALFA-OLEFINER, OCH KATALYSATORER, SOM ANVAENDS I FOERFARANDET. | |
| KR100737388B1 (en) | Pro-catalyst component for polymerization of ethylene, method for preparing thereof and catalyst containing the same | |
| CN102272172A (en) | Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst | |
| CN101880339A (en) | Ziegler-Natta polyethylene catalyst with wide molecular weight distribution, and preparation method thereof | |
| CN100422223C (en) | Ball shape catalyst for ethylene polymerization and preparation process thereof | |
| CN109320639A (en) | A kind of alkoxyl magnesium carrier and its polyethylene catalyst of preparation | |
| US7402637B2 (en) | Method for producing a poly-1-olefin in the presence of a Ziegler catalyst | |
| CN108690152A (en) | A kind of alkoxyl magnesium microsphere particle and its solid polyethylene catalytic component of preparation | |
| CA1195972A (en) | Preparation of a catalyst for and a method of producing linear low density polyethylene | |
| CN102399325B (en) | Spherical catalyst component with narrow particle size distribution for olefin polymerization, catalyst thereof and application thereof | |
| CN109503741A (en) | A kind of alkoxyl magnesium complex microsphere particle and its solid polyethylene catalyst of preparation | |
| CN100549042C (en) | Ethylene polymerization catalysts component, its preparation method and application | |
| FI78485B (en) | OLEFINPOLYMERISATIONSKATALYSATORER ANPASSADE FOER GASFAS PROCESSER, DERAS PREKURSOR, FRAMSTAELLNING OCH ANVAENDNING. | |
| CN106554436A (en) | A kind of non-luxuriant transition-metal catalyst of spherical supported type | |
| US4585840A (en) | Olefin polymerization catalysts adapted for gas phase processes | |
| KR20040002782A (en) | Magnesium-diketonate complex derived polyolefin catalysts, method of making same, method of polymerizing with same | |
| CN108440692A (en) | Catalyzed ethylene polymerization Ziegler-Natta catalyst internal electron donor, catalytic component and preparation method | |
| CN109337000A (en) | A kind of ingredient of solid catalyst and its catalyst system for olefinic polymerization | |
| CN112279950B (en) | Catalyst for ethylene gas phase polymerization process, catalyst component and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |