CN106543309A - Catalyst support used for olefinic polymerization and catalyst for olefines polymerizing and their preparation method and application - Google Patents
Catalyst support used for olefinic polymerization and catalyst for olefines polymerizing and their preparation method and application Download PDFInfo
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- CN106543309A CN106543309A CN201510612362.0A CN201510612362A CN106543309A CN 106543309 A CN106543309 A CN 106543309A CN 201510612362 A CN201510612362 A CN 201510612362A CN 106543309 A CN106543309 A CN 106543309A
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Abstract
The present invention relates to field of olefin polymerisation, discloses a kind of catalyst support used for olefinic polymerization and catalyst for olefines polymerizing and their preparation method and application, the preparation method of the catalyst support used for olefinic polymerization of the present invention includes：1) by the magnesium halide and general formula R shown in formula M gXY1Alcohol compound and optional inert liquid medium shown in OH is contacted to form emulsion；2) by step 1) emulsion that obtains with the oxirane compound shown in logical formula (I) with ratio as 1.5-6：1 flow-rate ratio carries out haptoreaction.The method of the present invention can need not using surfactant under conditions of obtain pattern preferably, the catalyst support used for olefinic polymerization of high income and low production cost.
Description
Technical field
The present invention relates to field of olefin polymerisation, in particular it relates to a kind of catalyst support used for olefinic polymerization
Preparation method and the catalyst support used for olefinic polymerization prepared by the method, a kind of olefinic polymerization
The catalyst for olefines polymerizing prepared with the preparation method of catalyst and by the method should with which
With.
Background technology
It is well known that the Ziegler-Natta catalyst of chlorination magnesium alcoholate load is used for alkene (particularly
Propylene) polymerization when, its performance is substantially better than the catalyst loaded by other carriers.Therefore, currently used for
The catalyst of olefinic polymerization is prepared into by halogenated titanium is carried on chlorination magnesium alcoholate mostly
Arrive.In order to obtain ball type carrier, can be by spray drying, spray cooling, high pressure extrusion, high-speed stirring
Mix, prepared by the method such as mulser method and high-gravity rotating bed method, such as WO1999044009A1 with
US4399054 etc. is disclosed can be after high-speed stirred emulsified magnesium chloride alcohol adduct system under high temperature
It is quenched to form spherical alcohol adduct.
Above-mentioned chlorination magnesium alcoholate is to adopt cryogenic quenching means to solidify the alcohol adduct melt system of high temperature
Must, not only the consumption to the energy is larger, complicated process of preparation, the multiple reactors of need carry out joint system
The particle diameter distribution of standby and obtained alcohol adduct is wider.In order to solve the problem,
CN102040683A is disclosed one kind and is reacted to make by magnesium halide alcohol adduct with oxirane compound
The method of standby carrier, and after specifically disclosing magnesium halide alcohol adduct melting dispersion, add oxirane
Class compound；Or will be added directly into containing ethylene oxide after magnesium halide alcohol adduct melting dispersion
In the reactor of compound.The feature of the method is in high temperature using epoxychloropropane with the alcohol adduct for melting
Lower reaction obtains solid.However, preparing catalyst carrier using the method has preparation process shakiness
It is fixed, carrier adhesion, and the bad shortcoming of carrier molding effect are susceptible to, accordingly, it would be desirable to prepare
During add other surfactants, such as stearic acid, span, quaternary ammonium compound etc..These materials
Add, not only increase cost, and the recycling to by-product has a negative impact, separately
Outward, in the post processing of by-product is reclaimed, the recovery of ethanol and epoxy compounds is more difficult, this
Also increase operating cost.
The method of prior art is magnesium halide alcohol adduct to be melted after dispersion, by ethylene oxide chemical combination
Thing is directly added in the system, or will be added directly into containing ring after magnesium halide alcohol adduct melting dispersion
In the reactor of oxidative ethane class compound.Due to the property of high-viscous liquid, experiment condition is wayward,
The method prepares unstable result, is susceptible to carrier adhesion phenomenon, causes carrier molding effect bad
Shortcoming.
Therefore, develop a kind of new olefin polymerization catalysis of drawbacks described above that can overcome prior art
Agent carrier is significant.
The content of the invention
The purpose of the present invention is the drawbacks described above for overcoming prior art, there is provided one kind need not use table
The catalyst for olefines polymerizing of preferable pattern, high income and low production cost is obtained under conditions of the activating agent of face
The method of carrier.
To achieve these goals, in a first aspect, the present invention provides a kind of catalyst support used for olefinic polymerization
Preparation method, the method includes：
1) by the magnesium halide and general formula R shown in formula M gXY1Alcohol compound shown in OH and appoint
The inert liquid medium of choosing is contacted to form emulsion；
2) by step 1) emulsion that obtains with the oxirane compound shown in logical formula (I) with ratio
For 1.5-6：1 flow-rate ratio carries out haptoreaction；
Wherein, in formula M gXY, X is chlorine or bromine, and Y is selected from chlorine, bromine, C1-C14Alkane
Base, C1-C14Alkoxyl, C6-C14Aryl or C6-C14Aryloxy group composition group；
In general formula R1In OH, R1For C1-C12Alkyl, C3-C10Cycloalkyl or C6-C10Aryl；
The oxirane compound has structure shown in formula (I)：
In formula (I), R2And R3It is each independently hydrogen, C1-C5Alkyl or haloalkyl.
Second aspect, the present invention provide the catalyst support used for olefinic polymerization prepared by said method,
It is preferred that the particle diameter distribution of the carrier<1.2.
The third aspect, the present invention provide a kind of preparation method of catalyst for olefines polymerizing, and the method includes：
1) prepare carrier：Carrier is prepared using aforesaid method of the invention；
2) prepare catalyst：By step 1) carrier and the titanium source and internal electron donor compound that obtain carry out
Haptoreaction.
Fourth aspect, the present invention provide the catalyst for olefines polymerizing prepared by said method.
In terms of 5th, the present invention provides the catalyst for olefines polymerizing answering in olefinic polyreaction
With.
The preparation method of the above-mentioned catalyst support used for olefinic polymerization of the present invention can increase stablizing for preparation
Property, the yield of product is improved, formed product effect is good.
Specifically, the preparation method of above-mentioned catalyst support used for olefinic polymerization of the invention is to be initially formed
Magnesium halide alcohol adduct, and after emulsification by which with certain flow and the epoxy second with certain flow
Alkyl compound carries out haptoreaction.The method of the present invention reduces the collision probability of unformed particle, subtracts
Lack carrier particle adhesion phenomenon, substantially increase the stability and dispersibility of carrier preparation.Improve
Product yield, considerably increases economic benefit.The catalyst bulk density prepared using the carrier compared with
Height, polymer particle shape are good.
The method of the present invention need not use surfactant, so as to reduce production cost, and avoid
Impurity pollutes.
Other features and advantages of the present invention will give specifically in subsequent specific embodiment part
It is bright.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of description,
It is used for explaining the present invention together with detailed description below, but does not constitute the limit to the present invention
System.In the accompanying drawings：
Fig. 1 is the process unit signal that the method according to the invention prepares catalyst support used for olefinic polymerization
Figure.
Description of reference numerals
1st, emulsion 2, oxirane compound
3rd, agitator
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place
The specific embodiment of description is merely to illustrate and explains the present invention, is not limited to the present invention.
In a first aspect, the invention provides a kind of preparation method of catalyst support used for olefinic polymerization, the party
Method includes：
1) by the magnesium halide and general formula R shown in formula M gXY1Alcohol compound shown in OH and appoint
The inert liquid medium of choosing is contacted to form emulsion；
2) by step 1) emulsion that obtains with the oxirane compound shown in logical formula (I) with ratio
For 1.5-6：1 flow-rate ratio carries out haptoreaction；
Wherein, in formula M gXY, X is chlorine or bromine, and Y is selected from chlorine, bromine, C1-C14Alkane
Base, C1-C14Alkoxyl, C6-C14Aryl or C6-C14Aryloxy group composition group；
In general formula R1In OH, R1For C1-C12Alkyl, C3-C10Cycloalkyl or C6-C10Aryl；
The oxirane compound has structure shown in formula (I)：
In formula (I), R2And R3It is each independently hydrogen, C1-C5Alkyl or haloalkyl.
In the present invention, described " and optional inert liquid medium " refers to the inert liquid medium
Can participate in mixing or being not involved in mixing.That is, can need in the method for the present invention or not
Need inert liquid medium.
In the present invention, the C1-C14Alkyl refer to carbon number be 1-14 alkyl, including
Alkyl group and branched alkyl, including unsubstituted alkyl and hydrogen atom be optionally substituted by halogen element etc.
Replace alkyl.
In the present invention, the C1-C14Alkoxyl refer to carbon number be 1-14 alkoxyl, bag
Branched alkoxy and branched alkoxy, including unsubstituting alkoxy and hydrogen atom are included optionally by halogen unit
The substituted substituted alkoxy such as element.
In the present invention, the C6-C14Aryl refer to carbon number be 6-14 aryl, the virtue
Base includes phenyl, the C6-C14Aryl can include hydrogen atom by the substituted aryl such as halogen element.
In the present invention, the C6-C14Aryloxy group refer to carbon number be 6-14 aryloxy group, institute
Stating aryloxy group includes phenoxy group, the C6-C14Aryloxy group can be taken by halogen element etc. including hydrogen atom
The aryloxy group in generation.
In the present invention, the C1-C5Alkyl include methyl, ethyl, n-pro-pyl, isopropyl, just
Butyl, isobutyl group, n-pentyl, isopentyl.
In the present invention, it is preferred in the case of, in formula M gXY, X is chlorine element or bromo element, Y
Selected from chlorine element, bromo element, C1-C5Alkyl, C1-C5Alkoxyl, C6-C10Aryl or
C6-C10Aryloxy group composition group.The C1-C5Alkyl for example can for methyl, ethyl, positive third
Base, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, uncle penta
Base or neopentyl, the C1-C5Alkoxy can such as be methoxyl group, ethyoxyl, propoxyl group, different
Propoxyl group, butoxy or isobutoxy, the C6-C10Aryl can for example be phenyl, adjacent toluene
Base, a tolyl, p-methylphenyl, adjacent ethylbenzene, an ethylbenzene, to ethylbenzene or naphthyl, it is described
C6-C10Aryloxy group can for example be phenoxy group or naphthoxy.Formula can be with for the magnesium halide of MgXY
For a kind of magnesium halide, or the mixture of various magnesium halides.Tool of the formula for the magnesium halide of MgXY
Body example can be but be not limited to：Magnesium chloride, magnesium bromide, chlorination phenoxy group magnesium, chlorination isopropoxy
One or more in magnesium and chlorination n-butoxy magnesium.From the ready availability angle of raw material, preferably
Magnesium chloride.
In the present invention, it is preferred in the case of, in general formula R1In OH, R1For C1-C6Alkyl or C3-C8
Cycloalkyl.In the case of more preferably, in general formula R1In OH, R1For C1-C5Alkyl or C3-C6
Cycloalkyl.In the case of particularly preferably, in general formula R1In OH, R1For methyl, ethyl, n-pro-pyl,
Isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, cyclopropyl, cyclopenta, methyl ring third
Base, Dimethvlcvclopropvl, cyclohexyl, methylcyclopentyl.
Another kind of preferred embodiment of the invention, in the present invention, the formula
R1Alcohol compound shown in OH selected from ethanol, propanol, isopropanol, n-butyl alcohol, isobutanol, penta
The group of alcohol, isoamyl alcohol, hexanol, n-octyl alcohol and 2-Ethylhexyl Alcohol composition.
In the present invention, in formula (I), R2And R3It is each independently hydrogen, methyl, ethyl, just
Propyl group, isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, chloromethyl, bromomethyl, chlorine
Ethyl, chloropropyl, bromopropyl.
Another kind of preferred embodiment of the invention, in the present invention, the formula (I)
Shown oxirane compound is selected from oxirane, expoxy propane, epoxy butane, epoxy chlorine
The group of propane, epoxy chlorobutane, epoxy bromopropane and epoxy n-butyl bromide composition.
Under preferable case, in the present invention, in step 2) in, preferably by step 1) emulsion that obtains with
Oxirane compound shown in logical formula (I) is with ratio as 2-4：1 flow-rate ratio carries out haptoreaction.
In the present invention, it should be strongly noted that there is no spy to the method for the flow of the control raw material
Other restriction, those skilled in the art can be controlled according to ordinary skill in the art means.
In addition to being limited by operating pressure and equipment region, above-mentioned pipe range can change in a wide range.
Described pipe range refers to the length of the tubular area for conveying emulsion or conveys oxirane compound
The length of the tubular area reacted for both after tubular area length or mixing.
" tubular area " term of indication of the present invention refers to the region with tube shape, and this region is excellent
The example of choosing is pipeline or tubular reactor.
A kind of preferred embodiment of the invention, the emulsion and the epoxy of the present invention
Ethane compound can pass through pipeline transportation.The method of the present invention does not have spy to the internal diameter of the pipeline yet
Other restriction.
According to the present invention, in step 2) in, before haptoreaction occurs, the stream of the preferred emulsion
The angle of the flow direction of dynamic direction and the oxirane compound is less than 90 °.
In the case of more preferably, in step 2) in, before haptoreaction occurs, the stream of the emulsion
The angle of the flow direction of dynamic direction and the oxirane compound is less than or equal to 15 °.The present invention's
Inventor has found, by the flow direction of the flow direction of the emulsion and the oxirane compound
When angle is limited in the range of less than or equal to 15 °, the carrier granular form for preparing is enabled to
It is good, and when being reacted using the catalyst containing the carrier for preparing so that polymeric articles
Heap density is high.
In the present invention, in step 2) in, the preferably emulsion is existed with the oxirane compound
Transported by different pipelines before carrying out haptoreaction respectively, and from described in different pipelines
Emulsion merges into one to carry out the haptoreaction with the oxirane compound.In the present invention
In, it should be strongly noted that the emulsion and the oxirane compound are merging into one it
Just reacted in pipeline afterwards.In the present invention, described " being transported by different pipelines respectively "
Refer to that the emulsion and the oxirane compound are not transported in same pipeline, but fortune
The defeated emulsion and profile material of two pipelines of the oxirane compound etc. can be with identical.
A kind of preferred embodiment of the invention, the method for the present invention is by using Fig. 1 institutes
The process unit for showing is carried out, and specifically, the emulsion 1 is led to respectively with the oxirane compound 2
Cross different pipelines to be transported, and one is converged in the pipeline for preferably comprising agitator 3 to carry out
Haptoreaction, and generate product by the pipeline containing agitator 3 to follow-up collecting zone
In.
According to the present invention, formula is the magnesium halide of MgXY, formula is R1The compound of OH, epoxy second
The consumption of alkyl compound can be carried out suitably according to the composition of expected catalyst support used for olefinic polymerization
Selection.In the present invention, it is relative to the magnesium halide shown in 1mol formula Ms gXY, preferably described logical
Formula R1The consumption of the compound shown in OH is 4-30mol, and the consumption of the oxirane compound is
1-10mol。
In the case of more preferably, in the present invention, relative to the halogenation shown in 1mol formula Ms gXY
Magnesium, the general formula R1The consumption of the compound shown in OH be 10-25mol, the ethylene oxide chemical combination
The consumption of thing is 3-6mol.
According to the present invention, the minor amount of water in above-mentioned each reactant can also participate in forming olefin polymerization urges
The reaction of agent carrier.
According to the present invention, the consumption of the optional inert liquid medium can be according to formula M gXY institute
The consumption of the magnesium halide for showing is selecting.Usually, with the magnesium halide shown in 1mol formula Ms gXY as base
Standard, the consumption of the inert liquid medium can be 0.8-10L, preferably 2-8L.The inert fluid
Medium can be it is commonly used in the art it is various do not occur with reactant and product it is chemically interactive
Liquid medium.For example：The inert liquid medium can be silicone oil and/or inert fluid varsol.
Specifically, the inert liquid medium is preferably kerosene, paraffin oil, vaseline oil, white oil, methyl
At least one in silicone oil, ethyl silicon oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil
Or it is various.Inert liquid medium of the present invention is particularly preferably white oil.
According to the present invention, in step 1) in, preferably described contact is included with the condition for forming emulsion：Temperature
Spend for 0-100 DEG C, the time is 0.1-6h.
In the present invention, in step 1) in, it is described formation emulsion the step of can include：By formula
Magnesium halide and general formula R shown in MgXY1Alcohol compound and optional inert fluid shown in OH is situated between
Matter is mixed, and gained mixture is stirred, and the condition of the stirring includes：Rotating speed is
50-1000rpm, more preferably 200-600rpm.
In the present invention, in step 2) in, the emulsion is connect with the oxirane compound
The condition for touching reaction can include：Temperature is 60-120 DEG C, and the time is 0.1-2h.
The emulsion and the oxirane compound are preferably preheated by the method for the present invention in advance
With reach contacted when required temperature.
According to the present invention, the method can also be included through step 2) product that obtains carries out solid-liquid point
From washing and be dried solid product.The solid-liquid separation can be it is existing it is various can be real
The method of existing solid phase and liquid phase separation, such as sucking filtration, filter pressing or centrifugation, under preferable case, institute
The method for stating solid-liquid separation is filter press technique.The present invention is not particularly limited to the condition of filter pressing, with to the greatest extent
May fully realize that solid phase is separated with liquid phase to be defined.The washing can adopt people in the art
The solid product for obtaining is washed by method known to member, for example, can adopt inert hydrocarbon solvent (example
Such as：Pentane, hexane, heptane, petroleum ether and gasoline) solid product to obtaining washs.This
The bright condition for the drying is not particularly limited, for example：The temperature of the drying can be
20-70 DEG C, the time of the drying can be 0.5-10 hours.According to the present invention, the drying can be with
Carry out under normal pressure or reduced pressure.
Second aspect, the present invention provide the catalyst support used for olefinic polymerization prepared by said method.
Under preferable case, in the present invention, the average particulate diameter of the carrier is 10-100 microns,
Particle diameter distribution is less than 1.2.
In the case of more preferably, the average particulate diameter of carrier of the present invention is 30-70 microns, particle diameter
It is distributed as 0.7-0.9.In the preferred implementation, prepared by the catalyst support used for olefinic polymerization
Catalyst for olefines polymerizing can obtain the olefin polymer with more high-bulk-density.In the present invention
In, the average particulate diameter and particle diameter distribution of the catalyst support used for olefinic polymerization can be adopted
2000 laser particle analyzers of Master Sizer (being manufactured by Malvern Instruments Ltd) are measured.
The third aspect, the present invention provide a kind of preparation method of catalyst for olefines polymerizing, and the method includes：
1) prepare carrier：Carrier is prepared using aforesaid method of the invention；
2) prepare catalyst：By step 1) carrier and the titanium source and internal electron donor compound that obtain carry out
Haptoreaction.
In the present invention, it is preferred to the titanium source in terms of titanium elements, the carrier in terms of magnesium elements and
The weight ratio of internal electron donor compound is 1：5-15：2-15；More preferably 1：6-13：3-12.
In the present invention, the internal electron donor compound can be to prepare catalyst for olefines polymerizing
During conventional use of various internal electron donor compounds, the preferably internal electron donor compound is
At least one in carboxylate, alcohol ester, ether, ketone, nitrile, amine and silane；Give in more preferably described
Electron compound be unitary or polyhydric aliphatic race carboxylate, unitary or polynary aromatic carboxylic acid esters, two
At least one in first alcohol ester and binary ether.In the present invention, the unitary or polyhydric aliphatic race carboxylic acid
The specific kind of selection of ester, unitary or polynary aromatic carboxylic acid esters, binary alcohol esters and binary ether
Selected with reference to prior art, here of the present invention is no longer described in detail.
According to the present invention, the titanium source can be prepare catalyst for olefines polymerizing during routinely make
Various titanium-containing compounds.It is preferred that the titanium source titanium source is selected from formula Ti (OR4)4-aX’aShown chemical combination
Thing, wherein, R4For C1-C14Aliphatic group, X ' is halogen, integers of a for 0-4.More preferably
In the case of, the titanium source be titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, three butoxy titanium chlorides,
Dibutoxy titanium chloride, butoxy titanous chloride., triethoxy titanium chloride, diethoxy dichloride
At least one in titanium and ethyoxyl titanous chloride..
In the present invention, to it is described carrier and titanium source and internal electron donor compound are carried out it is catalytic
There is no particular limitation for condition, and under preferable case, the catalytic condition can include：Reaction temperature
Spend for 80-130 DEG C, the response time is 0.5-10 hours.
In the present invention, it is preferred to titanium source and the catalyst support used for olefinic polymerization are first entered at low temperature
Row contact mixing, it is then slow again to heat up to reach above-mentioned reaction temperature.Those skilled in the art exist
Can be operated according to Conventional wisdom in the art after having solved technical scheme, this
It is bright to will not be described here.
Fourth aspect, the present invention provide the catalyst for olefines polymerizing prepared by said method.
Under preferable case, the present invention also provides a kind of catalyst for olefinic polymerization, and the catalyst contains
Have：Catalyst for olefines polymerizing of the present invention, alkyl aluminum compound and optional outer electron
Body compound." the optional external donor compound " refers to that external donor compound can
It is present or not present in the catalyst for olefinic polymerization of the present invention, that is to say, that institute of the present invention
The catalyst for olefinic polymerization stated can contain or not contain external donor compound.
In the present invention, the composition of the catalyst for olefines polymerizing is had been carried out above in detail
Description, will not be described here.
In the present invention, it is poly- containing alkene of the present invention in the catalyst for olefinic polymerization
Catalysts, therefore, the catalyst for olefinic polymerization according to the present invention is as alkene
During the catalyst of polyreaction, the heap density of the polymer for obtaining that is polymerized is greatly improved.
And, the catalyst for olefinic polymerization of the invention is for alkyl aluminum compound and outward
The species and consumption of electron donor compound is not particularly limited.
Usually, the alkyl aluminum chemical combination in the catalyst for olefinic polymerization, in terms of aluminium element
The mol ratio of thing and the catalyst for olefines polymerizing counted with titanium elements can be as 1-2000：1, preferably
20-500：1；The external donor compound with the mol ratio of alkyl aluminum compound can be
0.005-0.5：1, preferably 0.01-0.4：1.
Catalyst for olefinic polymerization of the invention, the alkyl aluminum compound can be ability
The conventional various alkyl aluminum compounds in domain.For example, the alkyl aluminum compound can for triethyl aluminum,
Triisobutyl aluminium, three n-butylaluminums, tri-n-hexyl aluminum, aluminium diethyl monochloride, a chlorine diisobutyl
Aluminum, a chlorine di-n-butyl aluminum, a chlorine di-n-hexyl aluminum, one aluminium ethide of dichloro, one isobutyl group of dichloro
One or more in aluminum, one n-hexyl aluminum of one n-butylaluminum of dichloro and dichloro.
Catalyst for olefinic polymerization of the invention, the external donor compound can be
Various external donor compounds commonly used in the art, for example, the external donor compound can be with
For the one kind in carboxylic acid, anhydride, ester, ketone, ether, alcohol, organic phosphorus compound and organo-silicon compound
Or it is various；Preferably, the external electron donor is with general formula R8 aR9 bSi(OR10)cSilicon compound,
Wherein, a and b be respectively 0,1 or 2 integer, c for 1-3 integer, and a+b+c's and be 4,
R8、R9、R10It is each independently C1-C18Substituted or unsubstituted alkyl；It is highly preferred that a and b
Respectively 1, c is 2, R8、R9It is each independently C3-C10Substituted or unsubstituted alkyl, R10
For C1-C10Substituted or unsubstituted alkyl.Specifically, the example of the organo-silicon compound can be with
For but be not limited to：Cyclohexyl Methyl Dimethoxysilane, diisopropyl dimethoxy silane, two positive fourths
Base dimethoxysilane, second, isobutyl dimethoxy silane, dimethoxydiphenylsilane, methyl- tert
Butyldimethoxysilane, dicyclopentyl dimethoxyl silane, 2- ethyl piperidine base -2- tert-butyl group diformazans
TMOS and (tri- fluoro- 2- propyl group of 1,1,1-) -2- ethyl piperidine base dimethoxysilanes and (tri- fluoro- 2- of 1,1,1-
Propyl group)-methyl dimethoxysilane.
In terms of 5th, the present invention provides the catalyst for olefines polymerizing answering in olefinic polyreaction
With.
The application of the present invention includes：Under olefin polymerization conditions, by least one alkene and institute of the present invention
The catalyst for olefines polymerizing stated carries out olefinic polyreaction.
The method of olefinic polymerization according to the present invention, by using the olefinic polymerization of the present invention
With catalyst, can prepare that particle shape is good, the polymer that heap density is high.The alkene of the present invention
The method of polymerized hydrocarbon is not particularly limited for olefin polymerization conditions and the alkene for being used.The alkene
For example can for ethylene, propylene, 1-butylene, 2-butylene, 2-methyl-1-butene alkene, 3-methyl-1-butene,
One or more in 2- methyl-2-butenes, 1- amylenes, 2- amylenes, 1- hexenes and styrene, preferably
One or more in ethylene, propylene, 1-butylene, 2-butylene and styrene.
The method of olefinic polymerization of the invention, the olefinic polymerization can be according to the routines of this area
Method is carried out.For example, the olefinic polymerization can be polymerisation in bulk, gas-phase polymerization or slurry polymerization.
Olefine polymerizing process of the invention, the olefin polymerization conditions can be the conventional strip of this area
Part, for example, polymerization temperature can be 0-150 DEG C, preferably 60-90 DEG C；Polymerization pressure can be normal
Pressure is pressurizeed.
Application according to the present invention, preferably under olefin polymerization conditions, by least one alkene and the present invention
The catalyst for being previously described for olefinic polymerization carries out olefinic polyreaction.
In following preparation example, embodiment and comparative example, in case of no particular description, made
Various raw materials are all from commercially available.
1st, the average particulate diameter and particle diameter distribution of catalyst support used for olefinic polymerization adopts Masters
2000 particle size analyzers of Sizer (being manufactured by Malvern Instruments Ltd) are measured；
2nd, the heap density of polyolefine powder is measured using the method that GB/T 1636-2008 specify.
In order to verify that the catalyst that the carrier that the method for the present invention is obtained is prepared has preferably catalysis
The heap density of performance and the polymerizate for obtaining is higher, exemplarily adopts in following examples
One kind in conventional techniques is illustrating.Specific experimental technique is as shown in the following example.This
Art personnel should not be construed as the restriction to technical scheme.
Preparation example 1
In the reactor of 0.6L, 0.08mol magnesium chlorides, 1.7mol ethanol are added, is heated up under agitation
To 90 DEG C.After isothermal reaction 1 hour, high-speed stirred (1800rpm) 0.5h, pressurize input channel,
So that flow of the emulsion in the pipeline is 15mL/min, while the entrance from another pipeline is defeated
Inbound traffics be 5mL/min, the epoxychloropropane (angle between two pipelines is 12 °) that temperature is 90 DEG C,
Both are mixed in the reactor equipped with hexane in tubular area, and conveying finishes rear filter pressing, by filter pressing
Product hexane is washed 5 times, vacuum drying, obtains catalyst support used for olefinic polymerization Z1.
The average particulate diameter (D50) of the catalyst support used for olefinic polymerization Z1 is 70 microns, grain
Footpath distribution ((D90-D10)/D50) is 0.8.The particle shape of catalyst support used for olefinic polymerization Z1
Comparison is regular, and surface is smooth, is essentially all spherical, and particle size distribution compares concentration, and base
In sheet, no irregular particle is present.
Contrast preparation example 1
In the reactor of 0.6L, 0.08mol magnesium chlorides, 1.7mol ethanol are added, is heated up under agitation
To 90 DEG C.After isothermal reaction 1 hour, then high-speed stirred (1800rpm) 0.5h is added thereto to
The epoxychloropropane isothermal reaction 0.5h of 90 DEG C of 0.3mol, then carries out filter pressing, and filter pressing product is used
Hexane is washed 5 times, vacuum drying, obtains carrier D-Z1.
The average particulate diameter (D50) of the D-Z1 is 98 microns, particle diameter distribution ((D90-D10)
/ D50) for 1.7.There is substantial amounts of irregular particle in carrier D-Z1, and surface is more coarse.
Preparation example 2
In the reactor of 0.6L, 0.08mol magnesium chlorides, 1.2mol ethanol are added, is heated up under agitation
To 65 DEG C.After isothermal reaction 1 hour, 85 DEG C after high-speed stirred (1800rpm) 0.5h, are warming up to, plus
Pressure input channel so that flow of the emulsion in the pipeline is 20mL/min, while from another
The epoxychloropropane that the inlet feed stream amount of pipeline is 5mL/min, temperature is 85 DEG C is (between two pipelines
Angle is 12 °), both are mixed in the reactor equipped with hexane in tubular area, after conveying is finished
Filter pressing, filter pressing product is washed with hexane 5 times, vacuum drying, obtains catalyst support used for olefinic polymerization
Z2。
The average particulate diameter (D50) of the catalyst support used for olefinic polymerization Z2 is 72 microns, grain
Footpath distribution ((D90-D10)/D50) is 0.8.The particle shape of catalyst support used for olefinic polymerization Z2
Comparison is regular, and surface is smooth, is essentially all spherical, and particle size distribution compares concentration, and base
In sheet, no irregular particle is present.
Preparation example 3
In the reactor of 0.6L, 0.08mol magnesium chlorides, 1.0mol ethanol are added, it is high at 25 DEG C
Speed stirring (1800rpm) is warming up to 100 DEG C after 1 hour, pressurize input channel so that the emulsion exists
Flow in the pipeline is 10mL/min, while from the inlet feed stream amount of another pipeline being
5mL/min, temperature are 100 DEG C of epoxychloropropane (angle between two pipelines is 12 °), both
It is mixed in the reactor equipped with hexane in tubular area, conveying finishes rear filter pressing, by filter pressing product
Washed with hexane 5 times, be vacuum dried, obtain catalyst support used for olefinic polymerization Z3.
The average particulate diameter (D50) of the catalyst support used for olefinic polymerization Z3 is 75 microns, grain
Footpath distribution ((D90-D10)/D50) is 0.9.The particle shape of catalyst support used for olefinic polymerization Z3
Comparison is regular, and surface is smooth, is essentially all spherical, and particle size distribution compares concentration, and base
In sheet, no irregular particle is present.
Preparation example 4
In the reactor of 0.6L, 0.08mol magnesium chlorides, 1.2mol ethanol are added, it is high at 10 DEG C
Speed stirring (1800rpm) is warming up to 90 DEG C after 1 hour, pressurize input channel so that the emulsion exists
Flow in the pipeline is 8mL/min, while from the inlet feed stream amount of another pipeline being
2mL/min, temperature are 90 DEG C of epoxychloropropane (angle between two pipelines is 12 °), Liang Zhe
Tubular area is mixed in the reactor equipped with hexane, and conveying finishes rear filter pressing, and filter pressing product is used
Hexane is washed 5 times, vacuum drying, obtains catalyst support used for olefinic polymerization Z4.
The average particulate diameter (D50) of the catalyst support used for olefinic polymerization Z4 is 73 microns, grain
Footpath distribution ((D90-D10)/D50) is 0.8.The particle shape of catalyst support used for olefinic polymerization Z4
Comparison is regular, and surface is smooth, is essentially all spherical, and particle size distribution compares concentration, and base
In sheet, no irregular particle is present.
Preparation example 5
In the reactor of 0.6L, 0.08mol magnesium chlorides, 1.7mol ethanol are added, is heated up under agitation
To 90 DEG C.After isothermal reaction 1 hour, high-speed stirred (1800rpm) 0.5h, pressurize input channel,
So that flow of the emulsion in the pipeline is 30mL/min, while the entrance from another pipeline is defeated
Inbound traffics be 5mL/min, the epoxychloropropane (angle between two pipelines is 12 °) that temperature is 90 DEG C,
Both are mixed in the reactor equipped with hexane in tubular area, and conveying finishes rear filter pressing, by filter pressing
Product hexane is washed 5 times, vacuum drying, obtains catalyst support used for olefinic polymerization Z5.
The average particulate diameter (D50) of the catalyst support used for olefinic polymerization Z5 is 77 microns, grain
Footpath distribution ((D90-D10)/D50) is 1.0.The particle shape of catalyst support used for olefinic polymerization Z5
Comparison is regular, and surface is smooth, is essentially all spherical, and particle size distribution compares concentration, and base
In sheet, no irregular particle is present.
Embodiment 1
(1) preparation of catalyst for olefines polymerizing
The titanium tetrachloride of 100mL in the reaction bulb of 300mL, is added, -20 DEG C is cooled to, by 40
Gram the catalyst support used for olefinic polymerization Z1 obtained by preparation example 1 be added thereto, and at -20 DEG C
Lower stirring 30min.Afterwards, start to be to slowly warm up to 110 DEG C, add 1.5mL's in temperature-rise period
Diisobutyl phthalate, filters off liquid after maintaining 30min at 110 DEG C.Then, add tetrachloro
Change titanium to wash 2 times, finally washed 3 times with hexane, after being dried, obtain catalyst for olefines polymerizing C1.
(3) propylene polymerization
In the autoclave of a 5L, purged using stream of nitrogen gas, then in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of the triethyl aluminum of middle introducing 1mmol,
The Cyclohexylmethyldimethoxysilane of 0.05mmol, the anhydrous hexane of 10mL and 10mg by step
(1) hydrogen and the liquid of 2.5L of catalyst for olefines polymerizing C1,1.5L (normal volume) for obtaining
Propylene.70 DEG C are warming up to, and are reacted 1 hour at such a temperature, cooling bleeds off pressure, and discharges dry
To polypropylene powder.
As a result：The heap density for measuring polypropylene powder is 0.44g/cm3, additionally, the polypropylene powder
Grain form is good, is substantially not present special-shaped material.
Comparative example 1
The titanium tetrachloride of 100mL in the reaction bulb of 300mL, is added, -20 DEG C is cooled to, by 40
Gram be added thereto by the contrast catalyst support used for olefinic polymerization D-Z1 that obtains of preparation example 1, and
30min is stirred at -20 DEG C.Afterwards, start to be to slowly warm up to 110 DEG C, add in temperature-rise period
The diisobutyl phthalate of 1.5mL, filters off liquid after maintaining 30min at 110 DEG C.Then,
Add titanium tetrachloride to wash 2 times, finally washed 3 times with hexane, after being dried, obtain catalyst for olefines polymerizing
D-C1。
(3) propylene polymerization
In the autoclave of a 5L, purged using stream of nitrogen gas, then in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of the triethyl aluminum of middle introducing 1mmol,
The Cyclohexylmethyldimethoxysilane of 0.05mmol, the anhydrous hexane of 10mL and 10mg by step
(1) hydrogen and the liquid of 2.5L of catalyst for olefines polymerizing D-C1,1.5L (normal volume) for obtaining
Body propylene.70 DEG C are warming up to, and are reacted 1 hour at such a temperature, cooling bleeds off pressure, discharge drying
Obtain polypropylene powder.
As a result：The heap density for measuring polypropylene powder is 0.37g/cm3, additionally, the polypropylene powder
All it is special-shaped material in grain, mobility is bad.
Embodiment 2
(1) preparation of catalyst for olefines polymerizing
The titanium tetrachloride of 100mL in the reaction bulb of 300mL, is added, -10 DEG C is cooled to, by 40
Gram the catalyst support used for olefinic polymerization Z2 obtained by preparation example 2 be added thereto, and at -10 DEG C
Lower stirring 45min.Afterwards, start to be to slowly warm up to 100 DEG C, add 1.5mL's in temperature-rise period
Diisobutyl phthalate, filters off liquid after maintaining 30min at 100 DEG C.Then, add tetrachloro
Change titanium to wash 2 times, finally washed 3 times with hexane, after being dried, obtain catalyst for olefines polymerizing C2.
(3) propylene polymerization
In the autoclave of a 5L, purged using stream of nitrogen gas, then in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of the triethyl aluminum of middle introducing 1mmol,
The Cyclohexylmethyldimethoxysilane of 0.05mmol, the anhydrous hexane of 10mL and 10mg by step
(1) hydrogen and the liquid of 2.5L of catalyst for olefines polymerizing C2,1.5L (normal volume) for obtaining
Propylene.85 DEG C are warming up to, and are reacted 1 hour at such a temperature, cooling bleeds off pressure, and discharges dry
To polypropylene powder.
As a result：The heap density for measuring polypropylene powder is 0.43g/cm3, additionally, the polypropylene powder
Grain form is good, is substantially not present special-shaped material.
Embodiment 3
(1) preparation of catalyst for olefines polymerizing
The titanium tetrachloride of 100mL in the reaction bulb of 300mL, is added, -20 DEG C is cooled to, by 40
Gram the catalyst support used for olefinic polymerization Z3 obtained by preparation example 3 be added thereto, and at -20 DEG C
Lower stirring 30min.Afterwards, start to be to slowly warm up to 110 DEG C, add 1.5mL's in temperature-rise period
Diisobutyl phthalate, filters off liquid after maintaining 30min at 110 DEG C.Then, add tetrachloro
Change titanium to wash 2 times, finally washed 3 times with hexane, after being dried, obtain catalyst for olefines polymerizing C3.
(3) propylene polymerization
In the autoclave of a 5L, purged using stream of nitrogen gas, then in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of the triethyl aluminum of middle introducing 1mmol,
The Cyclohexylmethyldimethoxysilane of 0.05mmol, the anhydrous hexane of 10mL and 10mg by step
(1) hydrogen and the liquid of 2.5L of catalyst for olefines polymerizing C3,1.5L (normal volume) for obtaining
Propylene.85 DEG C are warming up to, and are reacted 1 hour at such a temperature, cooling bleeds off pressure, and discharges dry
To polypropylene powder.
As a result：The heap density for measuring polypropylene powder is 0.45g/cm3, additionally, the polypropylene powder
Grain form is good, is substantially not present special-shaped material.
Embodiment 4
(1) preparation of catalyst for olefines polymerizing
The titanium tetrachloride of 100mL in the reaction bulb of 300mL, is added, -10 DEG C is cooled to, by 40
Gram the catalyst support used for olefinic polymerization Z4 obtained by preparation example 4 be added thereto, and at -10 DEG C
Lower stirring 45min.Afterwards, start to be to slowly warm up to 100 DEG C, add 1.5mL's in temperature-rise period
Diisobutyl phthalate, filters off liquid after maintaining 30min at 100 DEG C.Then, add tetrachloro
Change titanium to wash 2 times, finally washed 3 times with hexane, after being dried, obtain catalyst for olefines polymerizing C4.
(3) propylene polymerization
In the autoclave of a 5L, purged using stream of nitrogen gas, then in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of the triethyl aluminum of middle introducing 1mmol,
The Cyclohexylmethyldimethoxysilane of 0.05mmol, the anhydrous hexane of 10mL and 10mg by step
(1) hydrogen and the liquid of 2.5L of catalyst for olefines polymerizing C4,1.5L (normal volume) for obtaining
Propylene.85 DEG C are warming up to, and are reacted 1 hour at such a temperature, cooling bleeds off pressure, and discharges dry
To polypropylene powder.
As a result：The heap density for measuring polypropylene powder is 0.44g/cm3, additionally, the polypropylene powder
Grain form is good, is substantially not present special-shaped material.
Embodiment 5
(1) preparation of catalyst for olefines polymerizing
The titanium tetrachloride of 100mL in the reaction bulb of 300mL, is added, -20 DEG C is cooled to, by 40
Gram the catalyst support used for olefinic polymerization Z5 obtained by preparation example 5 be added thereto, and at -20 DEG C
Lower stirring 30min.Afterwards, start to be to slowly warm up to 110 DEG C, add 1.5mL's in temperature-rise period
Diisobutyl phthalate, filters off liquid after maintaining 30min at 110 DEG C.Then, add tetrachloro
Change titanium to wash 2 times, finally washed 3 times with hexane, after being dried, obtain catalyst for olefines polymerizing C5.
(3) propylene polymerization
In the autoclave of a 5L, purged using stream of nitrogen gas, then in stream of nitrogen gas
The hexane solution (concentration of triethyl aluminum is 0.5mmol/mL) of the triethyl aluminum of middle introducing 1mmol,
The Cyclohexylmethyldimethoxysilane of 0.05mmol, the anhydrous hexane of 10mL and 10mg by step
(1) hydrogen and the liquid of 2.5L of catalyst for olefines polymerizing C5,1.5L (normal volume) for obtaining
Propylene.70 DEG C are warming up to, and are reacted 1 hour at such a temperature, cooling bleeds off pressure, and discharges dry
To polypropylene powder.
As a result：The heap density for measuring polypropylene powder is 0.40g/cm3, additionally, the polypropylene powder
Grain form is good, is substantially not present special-shaped material.
As can be seen from the above results, it is catalyzed using the olefin polymerization that the method for the present invention is prepared
The particle shape of agent carrier is good, surface is smooth, be not in irregular particle substantially, and with gained
Carrier prepare catalyst be used for alkene (particularly propylene) be polymerized when, additionally it is possible to improve polymerizate
Heap density, substantially without the opposite sex material appearance, great prospects for commercial application.
And, present method avoids and use surfactant.
In addition, the result of comparative example 1 and embodiment 5 is can also be seen that emulsion and oxirane
The carrier for enabling to obtain when the flow ratio control system of class compound is in the preferred scope of the present invention
Particle diameter distribution is more excellent, and, system is enabled to during using the catalyst polyreaction containing the carrier
The heap density of the standby polymeric articles for obtaining is higher.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned
Detail in embodiment, in the range of the technology design of the present invention, can be to the skill of the present invention
Art scheme carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid not
Necessary repetition, the present invention are no longer separately illustrated to various possible compound modes.
Additionally, combination in any between a variety of embodiments of the present invention, can also be carried out, as long as
Its thought without prejudice to the present invention, which should equally be considered as content disclosed in this invention.
Claims (14)
1. a kind of preparation method of catalyst support used for olefinic polymerization, it is characterised in that the method includes：
1) by the magnesium halide and general formula R shown in formula M gXY1Alcohol compound shown in OH and appoint
The inert liquid medium of choosing is contacted to form emulsion；
2) by step 1) emulsion that obtains with the oxirane compound shown in logical formula (I) with ratio
For 1.5-6：1 flow-rate ratio carries out haptoreaction；
Wherein, in formula M gXY, X is chlorine or bromine, and Y is selected from chlorine, bromine, C1-C14Alkane
Base, C1-C14Alkoxyl, C6-C14Aryl or C6-C14Aryloxy group composition group；
In general formula R1In OH, R1For C1-C12Alkyl, C3-C10Cycloalkyl or C6-C10Aryl；
The oxirane compound has structure shown in formula (I)：
In formula (I), R2And R3It is each independently hydrogen, C1-C5Alkyl or haloalkyl.
2. method according to claim 1, wherein, in step 2) in, by step 1) obtain
Emulsion with the oxirane compound shown in logical formula (I) with ratio as 2-4：1 flow-rate ratio is carried out
Haptoreaction.
3. method according to claim 1, wherein, in step 2) in, occur in haptoreaction
Before, the angle of the flow direction of the flow direction of the emulsion and the oxirane compound is less than
90°；It is preferred that
The angle of the flow direction of the flow direction of the emulsion and the oxirane compound is less than
Equal to 15 °.
4. the method according to any one in claim 1-3, wherein, in step 2) in, institute
State emulsion and pass through different pipelines before haptoreaction is carried out respectively from the oxirane compound
Transported, and the emulsion from different pipelines is merged into one with the oxirane compound
Stock is carrying out the haptoreaction.
5. the method according to any one in claim 1-3, wherein, relative to 1mol halogenations
Magnesium, general formula R1The consumption of the compound shown in OH is 4-30mol, preferably 10-25mol；
The consumption of oxirane compound is 1-10mol, preferably 3-6mol.
6. the method according to any one in claim 1-3, wherein, in step 1) in, institute
Stating contact is included with the condition for forming emulsion：Temperature is 0-100 DEG C, and the time is 0.1-6h.
7. the method according to any one in claim 1-3, wherein, in step 1) in, institute
Stating the step of forming emulsion includes：By magnesium halide and general formula R shown in formula M gXY1Alcohol shown in OH
Class compound and optional inert liquid medium are mixed, and gained mixture is stirred,
The condition of the stirring includes：Rotating speed is 50-1000rpm, preferably 200-600rpm.
8. the method according to any one in claim 1-3, wherein, in step 2) in, institute
Stating emulsion and carrying out catalytic condition with the oxirane compound includes：Temperature is
60-120 DEG C, the time is 0.1-2h.
9. the catalyst for olefines polymerizing that the method in claim 1-8 described in any one is prepared
The particle diameter distribution of carrier, the preferably carrier<1.2.
10. a kind of preparation method of catalyst for olefines polymerizing, it is characterised in that the method includes：
1) prepare carrier：Carrier is prepared using the method described in any one in claim 1-8；
2) prepare catalyst：By step 1) carrier and the titanium source and internal electron donor compound that obtain carry out
Haptoreaction.
11. methods according to claim 10, wherein, the titanium source is selected from formula Ti (OR4)4-aX’a
Shown compound, wherein, R4For C1-C14Aliphatic group, X ' is halogen, integers of a for 0-4；
It is preferred that
During the internal electron donor compound is ester, ether, ketone, nitrile, amine, amide and alkoxy silane
At least one.
12. methods according to claim 10, wherein, in step 2) in, the haptoreaction
Condition include：Temperature is 80-130 DEG C, and the time is 0.5-10h.
The olefin polymerization catalysis that method in 13. claim 10-12 described in any one is prepared
Agent.
Application of the catalyst for olefines polymerizing described in 14. claim 13 in olefinic polyreaction.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109400763A (en) * | 2017-08-18 | 2019-03-01 | 中国石油化工股份有限公司 | Carrier for olefin polymerization catalyst and its preparation method and application |
| CN109400772A (en) * | 2017-08-18 | 2019-03-01 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and catalyst and olefine polymerizing process for olefinic polymerization |
| CN109678989A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | The recoverying and utilizing method and solid catalyst carrier of polyolefin catalyst carrier and its application |
| CN111072802A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Olefin polymerization catalyst carrier, preparation method and application thereof |
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|---|---|---|---|---|
| CN102453127A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Spherical carrier for olefin polymerization catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102453127A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Spherical carrier for olefin polymerization catalyst and preparation method thereof |
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| CN109400763A (en) * | 2017-08-18 | 2019-03-01 | 中国石油化工股份有限公司 | Carrier for olefin polymerization catalyst and its preparation method and application |
| CN109400772A (en) * | 2017-08-18 | 2019-03-01 | 中国石油化工股份有限公司 | Catalytic component for olefinic polymerization and preparation method thereof and catalyst and olefine polymerizing process for olefinic polymerization |
| CN109400763B (en) * | 2017-08-18 | 2021-03-16 | 中国石油化工股份有限公司 | Olefin polymerization catalyst carrier, preparation method and application thereof |
| CN109400772B (en) * | 2017-08-18 | 2021-08-03 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, catalyst for olefin polymerization and olefin polymerization method |
| CN109678989A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | The recoverying and utilizing method and solid catalyst carrier of polyolefin catalyst carrier and its application |
| CN109678989B (en) * | 2017-10-19 | 2021-08-03 | 中国石油化工股份有限公司 | Method for recycling polyolefin catalyst carrier, solid catalyst carrier and application thereof |
| CN111072802A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Olefin polymerization catalyst carrier, preparation method and application thereof |
| CN111072802B (en) * | 2018-10-19 | 2022-07-12 | 中国石油化工股份有限公司 | Olefin polymerization catalyst carrier, preparation method and application thereof |
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