CN108912253A - A kind of solid polypropylene catalytic component - Google Patents
A kind of solid polypropylene catalytic component Download PDFInfo
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- CN108912253A CN108912253A CN201810602357.5A CN201810602357A CN108912253A CN 108912253 A CN108912253 A CN 108912253A CN 201810602357 A CN201810602357 A CN 201810602357A CN 108912253 A CN108912253 A CN 108912253A
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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
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
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Abstract
The present invention relates to a kind of ingredient of solid catalyst, a kind of ingredient of solid catalyst for olefinic polymerization, it is characterised in that it is prepared by following methods：It using spherical alkoxyl magnesium as carrier, is contacted at a certain temperature with halogenated titanium and electron donor compound, reaction obtains ingredient of solid catalyst；The spherical alkoxyl magnesium carrier is the Mg (OR that will be dispersed in inert media in the form of gel dispersion1)(OR2) compound suspension is spray-dried obtains, wherein R1And R2Alkyl identical or different and that respectively there is 1 to 10 carbon atoms.The solid polypropylene catalytic component and the polypropylene powder being polymerize with the catalytic component have good particle shape, good mobility, higher bulk density, lower fine powder content.
Description
Technical field
The present invention relates to a kind of solid catalyst component for olefine polymerization prepared by spherical dialkoxy-magnesium support, and with
This ingredient of solid catalyst is the olefin polymerization catalysis of major catalyst.
Technical background
Catalyst for olefinic polymerization especially propylene polymerization is still with ziegler-nata (Ziegler-Natta) catalysis
Based on agent.Such as the patents such as CN 85100997A, CN 1453298A, polypropylene catalyst is generally by including titanium, magnesium, chloride ion
The ingredient of solid catalyst constituted with electronq donor compound, it is poly- as the organo-aluminum compound of cocatalyst component and regulation
The external electron donor of propylene stereoregular regularity forms.Currently, the research of catalyst is concentrated mainly on following several respects：Improve catalysis
The polymerization activity of agent improves the stereoregularity of polyolefin, improves the hydrogen response of catalyst, improves olefin polymer powder
Particle shape and the bulk density etc. for promoting polymer powders.
When being used for propylene polymerization as the Ziegler-Natta catalyst of carrier using dialkoxy magnesium, have stereoregularity high
The features such as copolymer polypropylene for being used to prepare high rubber content can especially be prepared, the shared share in polypropylene catalyst
It is increasing.Currently, the Gaseous Polymerization of PP of the mainstream such as Unipol of U.S. DOW company, Ineos company of Britain in the market
The gas phases PP techniques such as the Horizone technique polymarization method for prodcing polyacrylates of Innovene technique and JPP company of Japan are mainly used with dioxane
Oxygroup magnesium is that the polymerization catalyst of carrier is produced, for developing high-performance polypropylene especially copolymer polypropylene product.
The production method of spherical/spherical dialkoxy magnesium granules is mainly the following in the prior art：First is that first passing through
Cross pure and mild magnesium metal reaction production dialkoxy magnesium, the method for then adjusting particle size with being mechanically pulverized；Second is that in metal
In the reaction of magnesium and ethyl alcohol, by the final adding proportion control of magnesium/ethyl alcohol in 9/1~1/15 range, ethyl alcohol and magnesium are in ethyl alcohol
When reflux, using the manufacturing method (Japanese Laid-Open Patent Publication 3-74341) be interrupted or continuously reacted；Third is that by the carboxylic after carboxylation
The alcoholic solution for changing magnesium is spray-dried, and decarboxylation is continued, (special come the manufacturing method for obtaining round minuteness particle with this
Open flat 6-87773).
In first and second kinds of methods, the shape of particle is easy pulverized destroy, if it is desired to obtain configuration of surface
All complete particle, relatively difficult with particle size distribution, sometimes has to output capacity lowly for cost.In method three, by
Drop is on glassy state temperature dry in spray-drying process, and particle surface is not bery smooth, surface be uniform-distribution with compared with
Big pit, similar " pea of contraction ".
The research that solid polyolefin catalytic component is prepared with dialkoxy magnesium also has very much.Patent EP0459009 is public
A kind of catalytic component for olefinic polymerization is opened, preparation method is：Pass through suspension diethoxy magnesium shape in alkylbenzene
This suspension is contacted with the dichloride of titanium tetrachloride and phthalyl at suspension, and between 80~125 DEG C, uses alkane
The washing of base benzene, finally obtained titanium-containing catalyst component, although activity when being polymerize by the catalyst that this catalytic component obtains
It is high, active lasting, but the bulk density of acrylic polymers is lower.
Patent EP 0811639 mainly discloses a kind of ingredient of solid catalyst for olefinic polymerization, it is by one kind
Made of halogenated titanium, a kind of aryl dicarboxylic acid's diester and a kind of dialkoxy magnesium react to each other.Pass through control dialkoxy magnesium
Bulk density, the indexs such as average particle size, and control the temperature contacted since halogenated titanium with dialkoxy magnesium and rise to hair
The rate (heating rate controls between 0.5~20/min) of the temperature of raw reaction, so that a kind of ingredient of solid catalyst is obtained,
It is hereby achieved that the polyolefin of a kind of high isotactic, high-bulk-density, but its fine powder content is higher.
In view of the importance of catalyst granules form control, it is necessary to develop a kind of polypropylene catalysis of alkoxy magnesium-based
Agent, under the premise of the performances such as catalyst activity meet production requirement, the particle shape of catalyst and resin powder is improved,
The fine powder content of resin powder is reduced, and bulk density gets a promotion, and the produce load potentiality of device are further promoted.
Summary of the invention
In order to overcome in the prior art alkoxy magnesium-based polypropylene catalyst particle shape it is poor, resin-oatmeal material bulk density is inclined
Low defect, the present invention provide a kind of solid polypropylene catalytic component, which is the alkane by obtaining by spraying
Oxygroup magnesium carrier contacts to obtain with halogenated titanium and electron donor compound, the solid polypropylene catalytic component and with the catalyst
The polypropylene powder that component polymerize, it may have good particle shape, good mobility, higher bulk density, compared with
Low fine powder content.
It is the alkoxyl magnesium microsphere particle by will be obtained by spray drying the present invention relates to a kind of polypropylene catalyst component
It is contacted to obtain with halogenated titanium and electron donor compound.
Alkoxyl magnesium microsphere particle of the present invention is the alkane that will be dispersed in inert media in the form of gel dispersion
Oxygroup magnesium suspension is spray-dried to be obtained.
Above-mentioned alkoxyl magnesium refers to that chemical structural formula is Mg (OR1)(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-pentene oxygroup) magnesium, two (2- methyl-1-hexyloxy) magnesium, two (2- methyl-1-heptan oxygroup) magnesium, two (2- second
Base -1- amoxy) magnesium, two (2- ethyl -1- hexyloxy) magnesium, two (2- ethyl -1- oxygroup in heptan) magnesium, two (2- propyl -1- oxygen in heptan
Base) magnesium, two (2- methoxyl group -1- ethyoxyl) magnesium, two (3- methoxyl group -1- propoxyl group) magnesium, two (4- methoxyl group -1- butoxy)
Magnesium, two (6- methoxyl group -1- hexyloxy) magnesium, two (2- ethyoxyl -1- ethyoxyl) magnesium, two (3- ethyoxyl -1- propoxyl group) magnesium, two
(4- ethyoxyl -1- butoxy) magnesium, two (6- ethyoxyl -1- hexyloxy) 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 can be used any in the prior art
Dispersion technology.As an example, it can show and first grind commercially available bulky grain alkoxyl magnesium under an inert atmosphere, partial size
Reach 5-50 microns, then in a dispersion medium by its suspended dispersed, then by the alkoxyl magnesium suspension in high speed point
Dissipate the shearing force of machine (such as Ultra-Turrax or Dispax, IKA-Maschinenbau Janke&Kunkel GmbH)
Under effect, disperse gelled dispersion.So-called alkoxyl magnesium gel dispersion is alkane of the average grain diameter less than 1 micron
The dispersion of oxygroup magnesium dispersion in liquid medium, this dispersion is relatively stable, 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.The preparation of 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 disperser (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 lesser alkoxyl magnesium of partial size by the reaction condition of optimization magnesium powder and alcohol
(such as 20 microns or less) save energy and cost so as to shorten process.
The present invention is to equipment used in related spray-drying process and spray-drying process and condition without spy
Other restriction, can be used for the molding of organic phase material spray and dry device and method in the prior art can introduce the present invention
It is used to prepare alkoxyl magnesium microsphere particle.As an example, spray drying device can use press spray drier, can also be with
Using rotary spray dryer or two fluid-type spray dryers；Dry materials process can be once complete with spray-dried device
At the drying equipment (such as fluidized bed drying) for one or more other forms that can also connect after spray dryer continues to do
It is dry, it makes it dry completely.
Donor compound of the present invention various can be used to prepare polypropylene catalyst solid component to be existing
Internal electron donor, such as can be one of carboxylate, alcohol ester, ether, ketone, amine and silane or a variety of, preferably adjacent benzene two
One of formic ether compounds, diol-lipid compound, 1,3- diether compound and succinate compound compound are more
Kind.The dosage of the electronq donor compound relative to the magnesium in magnesium diaikoxide compound molar ratio (0.005~
10):1；It is preferred that (0.01~1): 1.
The way of contact of alkoxyl magnesium microsphere particle of the present invention and halogenated titanium and electronq donor compound does not have
It is special to require, it can be carried out according to techniques well known, it as an example, can be by alkoxyl magnesium microsphere particle and halogenated titanium
Start to contact in the presence of inert liquid medium with electron donor compound, then filtration washing, then be situated between in inert fluid
It is contacted again in the presence of matter with halogenated titanium, filtration washing obtains ingredient of solid catalyst.More specifically, by alkane at≤10 DEG C
Oxygroup magnesium microsphere particle starts to contact in the presence of inert liquid medium with titanium tetrachloride, then slowly heating, and is heating up
Electron donor compound is added in the process, is warming up to 90-130 DEG C, and react 0.5-5 hours in 90-130 DEG C of maintenance, crosses diafiltration
Titanium tetrachloride is added after washing, and in the presence of inert liquid medium 100-130 DEG C contact 0.5-5 hours, filtration washing obtains
To ingredient of solid catalyst.Alkoxyl magnesium and TiCl4Reaction to be higher than 1 and preferably within the scope of 1.5-4, more preferably exist
1.75-2.75 being carried out under the Ti/Mg molar ratio in range.
The present invention in reacting be used for suspended dispersed inert media there is no special requirement, can select aliphatic series and
Cycloaliphatic hydrocarbon, such as butane, pentane, hexane, heptane, hexamethylene, isooctane and aromatic hydrocarbons, such as benzene, toluene and dimethylbenzene.
The white spirit and hydrogenated diesel fraction for having been removed oxygen, sulphur compound and moisture also can be used.Choosing of the embodiment of the present invention
It is toluene.
The present invention does not have special requirement to for the inert liquid medium in reacting for washing, can select isoamyl
The common atent solvent such as alkane, hexane, heptane, octane, decane, benzene,toluene,xylene can also be selected from two of them or more
The mixture of kind.For the method for washing, also there is no particular limitation, the modes such as is preferably decanted, filters.The use of atent solvent
Amount, wash time, washing times are not particularly limited, and the compound relative to 1 mole of magnesium is excellent usually using 1~1000 mole
It is selected as 10~500 moles of solvent, is usually washed 1~24 hour, preferably 10~6 hours.In addition from the homogeneity of washing and washing
It sets out in terms of washing efficiency, is preferably stirred in washing operation.
The olefinic polymerization that solid catalyst component for olefine polymerization is major catalyst is stated the present invention also provides more than one to urge
Agent.
The catalyst includes following components：Major catalyst A, cocatalyst B, vertical structure directing agent C.
Wherein, the major catalyst A is ingredient of solid catalyst, as described above.
The cocatalyst B is organo-aluminum compound, is AlR selected from general formulanX3-nAt least one of compound,
At least one of the alkyl that R is selected from hydrogen in formula, carbon atom number is 1~20；X is halogen, preferably is selected from chlorine and bromine；n
For the integer of 0 n≤3 <；
The cocatalyst B, more specifically example include：Trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three
Octyl aluminium, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, dichloro one
The aluminum alkyl halides such as aluminium ethide, ethyl aluminum dichloride；Wherein preferred triethyl aluminum, triisobutyl aluminium.The B and A
Between ratio, with aluminium and titanium molar ratio computing for (5~5000): 1；, preferably 20~500；
The vertical structure directing agent C is organo-silicon compound, is a kind of external electron donor, is R selected from general formula3R4Si
(OR′)2Compound, R in formula3、R4It is identical or different, is alkyl, naphthenic base or the aryl of C1~C20, R ' is containing 1~4
The alkyl of carbon atom.Ratio between component B and component C is calculated as (2~100) with aluminium and silicon mol ratio: 1, preferably (5~50):
1。
The vertical structure directing agent C, more specifically example include：Trimethylmethoxysilane, front three base oxethyl
Silane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyl diethoxysilane, cyclohexyl methyl diethoxy
Base silane, Cyclohexylmethyldimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, three second of phenyl
Oxysilane, phenyltrimethoxysila,e, the organo-silicon compound such as vinyltrimethoxysilane can preferred cyclohexyl methyl
Dimethoxysilane, diisopropyl dimethoxy silane.
The alkoxyl magnesium that the present invention uses form excellent is carrier, and the polypropylene catalyst activity prepared is high, packing ratio
Weight is higher, and particle shape is good, and is evenly distributed, and is suitable for the Gaseous Polymerization of PP, is particularly suitable for the production of copolymerized product.
Following embodiment is provided to further describe the present invention in a non-limiting manner.
Embodiment
The present invention is specifically described by embodiment, the present invention is not limited to following embodiments.
Polyolefin evaluation method is as follows：
(1) sphericity S=(L1/L2)
L1 expression is photographed with scanning electron microscope in formula, carries out the longest diameter for the particulate matter that image procossing obtains, L2 table
Show the diameter of a circle of the projected area equal to above-mentioned particulate matter；
(2) isotactic index (II) of boiling n-heptane extraction process measurement polymer；
(3) by the melt index (MI) of testing standard GB/T3682-2000 measurement polymer；
(4) 2000 n-hexane dispersing agent laser diffractometry of Malvern MastersizerTM measures dialkoxy magnesium and urges
Particle size, the size distribution of agent；
(5) bulk density is measured with the method for bulk solids weight in unit volume.
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.
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 60ml ethyl alcohol, and with high speed disperser (Krupp SupratonTMType S200) it is handled 20 hours at 60 DEG C, to be formed solidifying
Colloidal 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 35%, atomization gas flow is
742L/h.Microspheres with solid particle D50 is 25.6 μm.
B) ingredient of solid catalyst is prepared
In the reaction kettle for repeating displaced 500ml by high pure nitrogen, toluene 70ml and titanium tetrachloride 30ml, drop is added
Temperature takes above-mentioned alkoxyl magnesium 10g and toluene 50ml to be configured to suspension to -5 DEG C, and kettle then is added in prepared suspension
In, 110 DEG C are to slowly warm up to, diisobutyl phthalate (DIBP) 2.5ml is added in temperature-rise period, in 110 DEG C of constant temperature 2
Hour, then liquid pressure is filtered dry only.Then the mixed liquor that toluene 120ml and titanium tetrachloride 30ml is added is warming up to 110 DEG C and stirs
Processing 1 hour, so processing 3 times to be mixed, liquid is filtered off, resulting solid is washed 4 times with hexane 150ml, liquid and drying are filtered off,
Up to ingredient of solid catalyst.
C) propylene polymerization
In the one 5 liters stainless steel autoclaves with blender, after being replaced with nitrogen, draw in stream of nitrogen gas at room temperature
Enter hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) 5mL, Cyclohexyl Methyl Dimethoxysilane of triethyl aluminum
(CHMMS) hexane solution (concentration of CHMMS is 0.10mmol/mL) 1mL, anhydrous hexane 10mL and ingredient of solid catalyst
10mg.Autoclave is closed, hydrogen 4.5L (under standard state) and liquid propene 2.0L are introduced；Under stiring by temperature liter in 10 minutes
To 70 DEG C.At 70 DEG C after polymerization reaction 1 hour, stop stirring, removes unpolymerized propylene monomer, collected polymer.
Embodiment 2 (present invention)
A) magnesium ethylate microsphere particle is prepared
With embodiment 1.
B) ingredient of solid catalyst is prepared
In the reaction kettle for repeating displaced 500ml by high pure nitrogen, toluene 70ml and titanium tetrachloride 30ml, drop is added
Temperature takes above-mentioned alkoxyl magnesium 10g and toluene 50ml to be configured to suspension to -5 DEG C, and kettle then is added in prepared suspension
In, 110 DEG C are to slowly warm up to, 4- ethyl -3,5- heptandiol dibenzoate 2.5ml is added in temperature-rise period, in 110 DEG C of perseverances
Liquid pressure, is then filtered dry only by temperature 2 hours.Then the mixed liquor that toluene 120ml and titanium tetrachloride 30ml is added is warming up to 110 DEG C
Stir process 1 hour, so processing 3 times, filter off liquid, and resulting solid is washed 4 times with hexane 150ml, filter off liquid and do
It is dry to get ingredient of solid catalyst.
C) propylene polymerization
With embodiment 1.
Embodiment 3 (present invention)
A) magnesium ethylate microsphere particle is prepared
With embodiment 1.
B) ingredient of solid catalyst is prepared
In the reaction kettle for repeating displaced 500ml by high pure nitrogen, toluene 70ml and titanium tetrachloride 30ml, drop is added
Temperature takes above-mentioned alkoxyl magnesium 10g and toluene 50ml to be configured to suspension to -5 DEG C, and kettle then is added in prepared suspension
In, 110 DEG C are to slowly warm up to, diisobutyl phthalate 1.5ml and 2- isopropyl -2- isoamyl are added in temperature-rise period
Base -1,3- dimethoxy propane 1.5ml, 110 DEG C constant temperature 2 hours, then liquid pressure is filtered dry only.Then toluene is added
The mixed liquor of 120ml and titanium tetrachloride 30ml are warming up to 110 DEG C stir process 1 hour, so processing 3 times, filter off liquid, gained
Solid washed 4 times with hexane 150ml, it is simultaneously dry to get ingredient of solid catalyst to filter off liquid.
C) propylene polymerization
With embodiment 1.
Comparative example 1
A) magnesium ethylate microsphere particle is prepared
After adequately replacing the 1000ml reactor with blender and reflux condenser with nitrogen, it is added into reactor
Dehydrated alcohol (water content is less than 200ppm) 80ml, is added iodine 0.6g, is warming up to reflux temperature after opening stirring, is then charged into metal
Magnesium powder 4g, later every 10 minutes 1 time loading ethyl alcohol 40ml, magnesium powder 4g, reaction add anhydrous in three times after carrying out about 1.5 hours
Ethyl alcohol 100ml, the reaction was continued, until no longer existing hydrogen discharge until the reaction is complete.Then it washed, separated and is dried.
Obtained diethoxy magnesium.
B) ingredient of solid catalyst is prepared
In addition to other than the dialkoxy magnesium in above-mentioned (1), the other the same as in Example 1.
C) propylene polymerization
With embodiment 1.
The data of 1 polymerization catalyst of table and propylene polymerization
As shown in Table 1, solid polypropylene catalytic component is obtained with good particle shape by the present invention, is used for propylene
Resin powder has good particle shape, higher bulk density, lower fine powder content when polymerization.
Claims (6)
1. a kind of ingredient of solid catalyst for olefinic polymerization, it is characterised in that it is prepared by following methods：With spherical alcoxyl
Base magnesium is carrier, is contacted at a certain temperature with halogenated titanium and electron donor compound, and reaction obtains ingredient of solid catalyst；
The spherical alkoxyl magnesium carrier is the Mg (OR that will be dispersed in inert media in the form of gel dispersion1)
(OR2) compound suspension is spray-dried obtains, wherein R1And R2It is identical or different and be respectively have 1 to 10 carbon originals
The alkyl of son.
2. the ingredient of solid catalyst of claim 1, it is characterised in that preparation method comprises the steps of：By alkoxyl magnesium microballoon
Particle starts to contact in the presence of inert liquid medium with halogenated titanium and electron donor compound, then filtration washing, then
It is contacted again in the presence of inert liquid medium with halogenated titanium, filtration washing obtains ingredient of solid catalyst.
3. the ingredient of solid catalyst of claim 1, it is characterised in that preparation method comprises the steps of：By alkane at≤10 DEG C
Oxygroup magnesium microsphere particle starts to contact in the presence of inert liquid medium with titanium tetrachloride, then slowly heating, and is heating up
Electron donor compound is added in the process, is warming up to 90-130 DEG C, and react 0.5-5 hours in 90-130 DEG C of maintenance, crosses diafiltration
Titanium tetrachloride is added after washing, and in the presence of inert liquid medium 100-130 DEG C contact 0.5-5 hours, filtration washing obtains
To ingredient of solid catalyst.
4. the ingredient of solid catalyst of claim 1, wherein the alkoxyl magnesium is magnesium ethylate.
5. a kind of solid catalyst for olefinic polymerization, which is characterized in that the reaction product including following components：
A, the ingredient of solid catalyst of olefinic polymerization described in one of claim 1~7；
B, organo-aluminum compound component；Its general formula is AlRnX3-n, R is hydrogen and carbon atom number is 1~20 in formula alkyl；X is halogen
Element, n are the integer of 0 n≤3 <；
C, a kind of organo-silicon compound component being optionally added；Its general formula is R3R4Si(OR′)2, R in formula3、R4It is identical or different,
For alkyl, naphthenic base or aryl with 1 to 20 carbon atoms, R ' is the alkyl containing 1~4 carbon atom.
6. the application described in claim 5 for the solid catalyst of olefinic polymerization in olefin polymerization.
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|---|---|---|---|---|
| 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 |
| US5227542A (en) * | 1990-01-12 | 1993-07-13 | Huels Aktiengesellschaft | Process for the preparation of spherical particles of magnesium alkoxide |
| CN102399326A (en) * | 2010-09-16 | 2012-04-04 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization and catalyst |
| CN102482371A (en) * | 2009-08-06 | 2012-05-30 | 巴塞尔聚烯烃股份有限公司 | Catalyst components for the polymerization of olefins |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US5227542A (en) * | 1990-01-12 | 1993-07-13 | Huels Aktiengesellschaft | Process for the preparation of spherical particles of magnesium alkoxide |
| CN102482371A (en) * | 2009-08-06 | 2012-05-30 | 巴塞尔聚烯烃股份有限公司 | Catalyst components for the polymerization of olefins |
| CN102399326A (en) * | 2010-09-16 | 2012-04-04 | 中国石油化工股份有限公司 | Solid catalyst component for olefin polymerization and catalyst |
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| 毛炳权: "《毛炳权文集》", 31 May 2014, 冶金工业出版社 * |
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Application publication date: 20181130 |
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