CN107915792A - Carrier for olefin polymerization catalyst and preparation method and catalyst component for olefin polymerization and olefin polymerization catalysis and their application - Google Patents
Carrier for olefin polymerization catalyst and preparation method and catalyst component for olefin polymerization and olefin polymerization catalysis and their application Download PDFInfo
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- CN107915792A CN107915792A CN201610880733.8A CN201610880733A CN107915792A CN 107915792 A CN107915792 A CN 107915792A CN 201610880733 A CN201610880733 A CN 201610880733A CN 107915792 A CN107915792 A CN 107915792A
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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
- C08F4/022—Magnesium halide as support anhydrous or hydrated or complexed by means of a Lewis base for Ziegler-type catalysts
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/647—Catalysts containing a specific non-metal or metal-free compound
- C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/651—Pretreating with non-metals or metal-free compounds
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
- C08F4/6543—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium
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Abstract
The present invention relates to alkene catalyst field, more particularly to a kind of carrier for olefin polymerization catalyst, a kind of preparation method of carrier for olefin polymerization catalyst, a kind of catalytic component for olefinic polymerization, the application of catalyst carrier and the catalytic component for olefinic polymerization prepared by the catalyst carrier, the method in the catalyst for olefinic polymerization is prepared, a kind of catalyst for olefinic polymerization, application and a kind of olefine polymerizing process of the catalyst in olefinic polyreaction.Technical solution using the present invention, uses the compound containing hafnium halide in the preparation process of the carrier for olefin polymerization catalyst, can obtain a kind of carrier with new composition, and obtained carrier granular form is good, is substantially not present irregular particle.And carrier prepared catalyst is applied to alhpa olefin and activity during ethylene copolymer is higher, and the heap density for polymerizeing obtained polymer can be also improved.
Description
Technical field
The present invention relates to alkene catalyst field, and in particular to a kind of carrier for olefin polymerization catalyst, a kind of olefinic polymerization
It is prepared by the preparation method of catalyst carrier, a kind of catalytic component for olefinic polymerization, the catalyst carrier, the method
Catalyst carrier and the catalytic component for olefinic polymerization prepare for olefinic polymerization catalyst in should
With, a kind of catalyst for olefinic polymerization, application and a kind of olefinic polymerization of the catalyst in olefinic polyreaction
Method.
Background technology
Gather it is well known that the Ziegler-Natta catalyst of chlorination magnesium alcoholate load is used for alkene (particularly propylene)
During conjunction, its performance is substantially better than the catalyst that other carriers are loaded.Therefore, the catalyst currently used for olefinic polymerization is mostly
By the way that halogenated titanium is carried on what is be prepared on chlorination magnesium alcoholate., can be by being spray-dried, spraying in order to obtain ball type carrier
It is prepared by the methods of fog cooling, high pressure extrusion, high-speed stirred, mulser method and high-gravity rotating bed method, as WO99/44009 with
US4399054 etc., which is disclosed, to form spherical alcohol conjunction by being quenched after high-speed stirred emulsified magnesium chloride alcohol adduct system under high temperature
Thing.
But when the catalyst prepared by above-mentioned published chlorination magnesium alcoholate is used for olefinic polymerization, it is polymerizeing
During be easy to occur polymer particle Fragmentation Phenomena, so as to cause fine polymer powder more.In order to overcome this shortcoming,
People attempt electron donor compound being incorporated into advance in the carrier preparation of chlorination magnesium alcoholate again, such as：CN1169840C
Internal electron donor phthalate compound commonly understood in the industry is incorporated into chlorination magnesium alcoholate with CN1286863C to carry
In the synthesis of body, so that " magnesium dichloride-alcohol-phthalic acid ester " ball type carrier is obtained, it is then that the carrier and titanium tetrachloride is anti-
Should be to form catalyst.But the compound ball type carrier is easily tacky in preparation process, it is difficult to forms particle size and fits
Suitable spheric granules.
It is made in addition, above-mentioned chlorination magnesium alcoholate is the alcohol adduct melt for curing high temperature using cryogenic quenching, it is not only right
The consumption of the energy is larger, preparation process is complicated, must multiple reactors joints prepare, and the particle diameter distribution of obtained alcohol adduct
It is wider.In order to solve this problem, CN102040683A discloses one kind by magnesium halide alcohol adduct and oxirane compound
Reaction prepares the method for carrier, and specifically disclose by magnesium halide alcohol adduct melting it is scattered after, add ethylene oxide chemical combination
Thing；It is added directly into after either magnesium halide alcohol adduct melting is disperseed in the reactor containing oxirane compound.However,
It is unstable there are preparation process using this method preparation catalyst carrier, substantial amounts of irregular particle is easily formed, causes carrier to be sent out
Raw carrier adhesion, and the shortcomings that carrier molding effect is bad, the catalyst activity that thus prepared by carrier is relatively low, and catalysis obtains
The bulk density of polymer is relatively low, and the content of ethylene unit unit is relatively low during for being copolymerized.
The content of the invention
Present inventors discovered unexpectedly that using halogen in the preparation process of the carrier for olefin polymerization catalyst
Change chromium compound, a kind of carrier with new composition can be obtained, and obtained carrier granular form is good, does not deposit substantially
In irregular particle.And activity is higher when being applied to olefinic polymerization or copolymerization as the catalyst prepared by the carrier, and for altogether
When poly-, additionally it is possible to improve the content of ethylene unit unit in polymer.
First purpose of the present invention is to overcome the drawbacks described above of existing carrier for olefin polymerization catalyst, and is provided
A kind of new carrier for olefin polymerization catalyst.
Second object of the present invention is to provide a kind of preparation method of carrier for olefin polymerization catalyst.
Third object of the present invention is to provide a kind of catalytic component for olefinic polymerization.
Fourth object of the present invention is that catalyst prepared by catalyst carrier as described above, method as described above carries
The application of body and the catalytic component as described above for olefinic polymerization in the catalyst for olefinic polymerization is prepared.
The 5th purpose of the present invention is to provide a kind of catalyst for olefinic polymerization.
The 6th purpose of the present invention is to provide the catalyst as described above for olefinic polymerization in olefinic polyreaction
In application.
The 7th purpose of the present invention is to provide a kind of olefine polymerizing process.
On the one hand, the present invention provides a kind of carrier for olefin polymerization catalyst, which is as shown in formula (I)
Magnesium-containing compound,
Wherein, in formula (I), R1For the alkyl of the straight or branched of C1-C14；R2, R3And R4It is identical or differ, each solely
On the spot for hydrogen, C1-C5 straight or branched alkyl or C1-C5 straight or branched haloalkyl；X is halogen；Y is halogen
Element；M is 0.1-1.9, n 0.1-1.9, m+n=2；0<i<3,0≤j<3,0<k<3, i+j+k=3,0<q≤0.5.
Second aspect, the present invention provides a kind of preparation method of carrier for olefin polymerization catalyst, this method includes following
Step：
(1) it is the compound of ROH, optional inert liquid medium by hafnium halide, magnesium halide, general formula, is mixed and heated, obtains
To liquefied mixture；
(2) liquefied mixture for obtaining step (1) emulsifies, and emulsification product is contacted instead with oxirane compound
Should；
In general formula R OH, R is the alkyl of C1-C14；Shown in the structure of the oxirane compound such as formula (II)：
Wherein, R5And R6Each stand alone as hydrogen, C1-C5 straight or branched alkyl or C1-C5 straight or branched halogen
Substituted alkyl.
The third aspect, the present invention provides a kind of catalytic component for olefinic polymerization, the catalytic component contain as
The catalyst carrier that above prepared by the catalyst carrier or method as described above is interior to electricity with titanium compound and optionally
Daughter reacts to obtain product.
Fourth aspect, the present invention provides catalyst prepared by catalyst carrier as described above, method as described above
The application of carrier and the catalytic component as described above for olefinic polymerization in the catalyst for olefinic polymerization is prepared.
5th aspect, the present invention provides a kind of catalyst for olefinic polymerization, which contains：
(1) it is used for the catalytic component of olefinic polymerization as described above；
(2) alkyl aluminum compound；And
(3) optional external donor compound.
6th aspect, the present invention provides the catalyst as described above for olefinic polymerization in olefinic polyreaction
Using.
7th aspect, the present invention provides a kind of olefine polymerizing process, this method includes：, will under olefin polymerization conditions
One or more alkene are contacted with the catalyst as described above for olefinic polymerization.
Technical solution using the present invention, uses in the preparation process of the carrier for olefin polymerization catalyst and contains hafnium halide
Compound, a kind of carrier with new composition can be obtained, and obtained carrier granular form is good, is substantially not present
Irregular particle.And carrier prepared catalyst is applied to alpha-olefin and activity during ethylene copolymer is higher, and it polymerize what is obtained
The heap density of polymer can be also improved, during for olefin-copolymerization, the content of ethylene unit unit in obtained polymer
It is higher.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is carrier for olefin polymerization catalyst pattern optical microscope photograph prepared by preparation example 1；
Fig. 2 is carrier for olefin polymerization catalyst pattern optical microscope photograph prepared by preparation example 2；
Fig. 3 is carrier for olefin polymerization catalyst pattern optical microscope photograph prepared by contrast preparation example 1.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
According to the first aspect of the invention, the present invention provides a kind of carrier for olefin polymerization catalyst, the catalyst to carry
Body is the magnesium-containing compound as shown in formula (I),
Wherein, in formula (I), R1For the alkyl of the straight or branched of C1-C14；The preferably alkane of the straight or branched of C1-C8
Base, for example, the alkyl of the straight or branched of C1, C2, C3, C4, C5, C6, C7, C8；It is more highly preferred to, R1Selected from ethyl, positive third
Base, isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, n-hexyl, n-octyl and one kind or more in 2- ethylhexyls
Kind.
R2, R3And R4It is identical or differ, be each independently hydrogen, C1-C5 straight or branched alkyl or C1-C5
The haloalkyl of straight or branched, it is preferred that R2, R3And R4It is identical or differ, be each independently hydrogen, C1-C3 straight chain or
The haloalkyl of the alkyl of side chain or the straight or branched of C1-C3, for example, R2, R3And R4It is independently each hydrogen, C1, C2, C3
Straight or branched alkyl or C1, C2, C3 straight or branched haloalkyl；Wherein, haloalkyl is preferably alkyl chloride
Base and/or bromo alkyl；Preferably, R2, R3And R4It is identical or differ, be each independently hydrogen, methyl, ethyl, chloromethyl,
One or more in chloroethyl, bromomethyl and bromoethyl.
X is halogen, is preferably chlorine or bromine；Y is halogen, is preferably chlorine or bromine；
Wherein, m 0.1-1.9, n 0.1-1.9, m+n=2；0<i<3,0≤j<3,0<k<3, i+j+k=3,0<q≤
0.5。
A preferred embodiment of the invention, the average particulate diameter of the carrier for olefin polymerization catalyst can be with
For 10-100 microns, preferably 40-60 microns, particle diameter distribution is less than 1.2, is preferably 0.6-0.8.In the preferred embodiment
In, the catalyst prepared by the carrier for olefin polymerization catalyst can obtain the olefin polymer with more high-bulk-density.
In the present invention, the average particulate diameter and particle diameter distribution of the carrier for olefin polymerization catalyst can use Master Sizer
2000 laser particle analyzers (being manufactured by Malvern Instruments Ltd) measure.
According to the present invention, micro water can also be carried in the carrier for olefin polymerization catalyst, the water comes from
The minor amount of water of synthesis material and reaction medium institute band.
According to the present invention, the synthesis material of the catalyst carrier includes hafnium halide, magnesium halide, the chemical combination that general formula is ROH
Thing, oxirane compound；
Wherein, in general formula R OH, R is the alkyl of C1-C14；The structure of the oxirane compound such as formula (II) institute
Show：
Wherein, R5And R6Each stand alone as hydrogen, C1-C5 straight or branched alkyl or C1-C5 straight or branched halogen
Substituted alkyl.
According to the present invention, the content for being used to prepare the above-mentioned each component of the carrier for olefin polymerization catalyst can be larger
In the range of make choice and change, for example, on the basis of the magnesium halide of 1mol, the content of hafnium halide is 0.0001-1mol, is led to
The content for the compound that formula is ROH can be 4-30mol, and the content of the oxirane compound shown in formula (II) can be 1-
10mol；Preferably, on the basis of the magnesium halide of 1mol, the content of hafnium halide is 0.01-0.1mol, and general formula is the compound of ROH
Content be 6-20mol, the content of the oxirane compound shown in formula (II) is 2-6mol.
According to the present invention, the hafnium halide can be anhydrous hafnium halide, or the hafnium halide containing the crystallization water, preferably
, the hafnium halide is anhydrous or the chromium chloride containing the crystallization water or chromic bromide anhydrous or containing the crystallization water, more preferably
For chromium chloride anhydrous or containing the crystallization water.
According to the present invention, the magnesium halide can be a kind of magnesium halide, or the mixture of a variety of magnesium halides.Magnesium halide
Instantiation can be but be not limited to：Magnesium chloride, magnesium bromide, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and the positive fourth of chlorination
One or more in epoxide magnesium.The angle ready availability from raw material, is preferably magnesium chloride.
According to the present invention, in general formula R OH, R is preferably the alkyl of C1-C8.The alkyl of the C1-C8 for example can be first
Base, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, new penta
Base, hexyl, isohesyl, heptyl, different heptyl, octyl group or iso-octyl.The instantiation for the compound that general formula is ROH can be but not
It is limited to：In ethanol, propyl alcohol, isopropanol, n-butanol, isobutanol, amylalcohol, isoamyl alcohol, n-hexyl alcohol, n-octyl alcohol and 2-Ethylhexyl Alcohol
It is one or more.
According to the present invention, in oxirane compound of the structure as shown in formula (II), R5And R6It is preferred that each stand alone as
Hydrogen, C1-C3 straight or branched alkyl or C1-C3 straight or branched haloalkyl.The oxirane compound
Instantiation can be but be not limited to：Ethylene oxide, propylene oxide, epoxy butane, epoxychloropropane, epoxy chlorobutane, ring
One or more in oxygen N-Propyl Bromide and epoxy bromobutane.
According to the second aspect of the invention, the present invention provides a kind of preparation method of carrier for olefin polymerization catalyst,
This method comprises the following steps：
(1) it is the compound of ROH, optional inert liquid medium by hafnium halide, magnesium halide, general formula, is mixed and heated, obtains
To liquefied mixture；
(2) liquefied mixture for obtaining step (1) emulsifies, and emulsification product is contacted instead with oxirane compound
Should；
In general formula R OH, R is the alkyl of C1-C14；Shown in the structure of the oxirane compound such as formula (II)：
Wherein, R5And R6Each stand alone as hydrogen, C1-C5 straight or branched alkyl or C1-C5 straight or branched halogen
Substituted alkyl.
Wherein, hafnium halide, magnesium halide, general formula be the compound of ROH, the species of oxirane compound hereinbefore
Description, will not be described in great detail herein.
According to the present invention, hafnium halide, magnesium halide, the ethylene oxide as shown in formula (II) of compound, structure that general formula is ROH
The dosage of class compound can make appropriate choice according to the composition of expected carrier for olefin polymerization catalyst, it is preferable that with
On the basis of 1mol magnesium halides, the dosage of hafnium halide is 0.0001-1mol, and the dosage for the compound that general formula is ROH is 4-30mol,
The dosage of oxirane compound shown in formula (II) is 1-10mol；It is highly preferred that on the basis of 1mol magnesium halides, halogenation
The dosage of chromium is 0.01-0.1mol, and the dosage of the compound that general formula is ROH is 6-20mol, the ethylene oxide shown in formula (I)
The dosage of compound is 2-6mol.
According to invention, the minor amount of water in above-mentioned each reactant can also participate in forming the anti-of carrier for olefin polymerization catalyst
Should.
According to the present invention, in step (1), for by hafnium halide, magnesium halide, general formula be ROH compound with optionally it is lazy
The blend heated condition of property liquid medium is not particularly limited, as long as the condition of the heating enables to magnesium halide to melt
And react with hafnium halide, the compound that general formula is ROH.Usually, the condition of the heating includes：Temperature can be
80-120 DEG C, when the time can be 0.5-5 small；Preferably, the temperature is 80-100 DEG C, when the time is 0.5-3 small.
According to the present invention, in the case of inert media is included in step (1), the dosage of the inert liquid medium can
Selected with dosage according to magnesium halide.Usually, on the basis of the magnesium halide of 1mol, the dosage of the inert liquid medium can
Think 0.8-10L, be preferably 2-8L.The inert liquid medium can be it is commonly used in the art it is various not with reactant and reaction
Chemically interactive liquid medium occurs for product.Such as：The inert liquid medium can be silicone oil and/or inert fluid hydrocarbon
Class solvent.Specifically, the inert liquid medium can be kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon
One or more in oil, Methylethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil.Inert liquid medium of the present invention is special
You Xuanwei not white oil.
According to the present invention, in step (2), it can use that well known to a person skilled in the art various methods by step (1)
Obtained liquefied mixture emulsification.For example, the liquefied mixture can be carried out low velocity shear or high speed shear, thus by its
Emulsification.The stir speed (S.S.) of the low velocity shear is usually 400-800 revs/min.The method of the high speed shear is this area skill
Well known to art personnel, as disclosed in CN1151183C high-speed mixing method (that is, by the solution containing liquid halogenated magnesium adduct with
2000-5000 revs/min of speed is stirred).Further, it is also possible to method mixes the liquid with reference to disclosed in following patent
Compound emulsifies：The solution containing liquid halogenated magnesium adduct is carried out rotation in hypergravity bed disclosed in CN1267508C to disperse
(rotating speed can be 100-3000 revs/min)；CN1463990A is disclosed to contain the molten of liquid halogenated magnesium adduct
Liquid is exported in mulser with 1500-8000 revs/min of speed；US6020279 is disclosed will to contain liquid by spray-on process
The emulsifying soln of adduct of magnesium halides.
According to the present invention, in step (2), can be by emulsification product and the catalytic condition of oxirane compound
The existing various conditions that can form carrier for olefin polymerization catalyst, for example, the catalytic condition can including temperature
Think 50-120 DEG C, the time can be 20-60 minutes；Preferably, the temperature is 60-100 DEG C, and the time is 20-50 minutes.
According to the present invention, separation of solid and liquid is carried out in the product that this method can also include obtaining haptoreaction, by solid phase
Product is washed and is dried.The separation of solid and liquid can be the existing various methods that can realize solid phase and liquid phase separation,
Such as filter, press filtration or centrifugation, under preferable case, the method for the separation of solid and liquid is filter press technique.The present invention is to press filtration
Condition is not particularly limited, and is subject to the separation for fully realizing solid phase and liquid phase as far as possible.The washing can use this
Method is washed obtained solid product known to field technology personnel, for example, can use inert hydrocarbon solvent (such as：
Pentane, hexane, heptane, petroleum ether and gasoline) obtained solid product is washed.Condition of the present invention for the drying
It is not particularly limited, such as：The temperature of the drying can be 20-70 DEG C, when the time of the drying can be 0.5-10 small.
According to the present invention, the drying can carry out under normal pressure or reduced pressure.
In addition, the catalyst carrier of the olefinic polymerization prepared present invention also offers method as described above.
The third aspect, present invention also offers a kind of catalytic component for olefinic polymerization, which contains
The catalyst carrier and titanium compound of the olefinic polymerization prepared by catalyst carrier as described above and/or method as described above
And the product that optional internal electron donor reacts.
Catalyst according to the invention component, the carrier for olefin polymerization catalyst, titanium compound and it is optional in electricity
There is no particular limitation for the condition of the reaction of donor compound, and under preferable case, the condition of the reaction can include：Reaction temperature
For 80-130 DEG C, when the reaction time is 0.5-10 small.
More specifically, the reaction condition includes：By (- 30 DEG C to 0 of prepared catalyst carrier and titanium compound
DEG C) under conditions of -30 DEG C to 0 DEG C 20-60min is contacted, the compound after contact is then warming up to 80-130 DEG C, and rising
Temperature process in add in electron, and react 0.5-10 it is small when, obtain the present invention catalytic component, be more highly preferred to,
The step of further including the step of being washed using titanium compound to obtained product and atent solvent washing after reaction.Its
In, the atent solvent can be atent solvent commonly used in the art, for example, toluene, hexane etc..
Catalyst according to the invention component, the internal electron donor compound can be to prepare urging for olefinic polymerization
Conventional use of various internal electron donor compounds during agent, such as can be carboxylate, alcohol ester, ether, ketone, nitrile, amine
It is preferably unitary or polyhydric aliphatic race carboxylate, unitary or polynary aromatic carboxylic acid esters, binary with the one or more in silane
One or more in alcohol ester and binary ether.
Preferably, internal electron donor of the invention is diisobutyl phthalate, n-butyl phthalate, benzene two
1,3 diamyl ester of formic acid, Ethyl formate, n-propyl formate, isopropyl formate, butyl formate, methyl acetate, ethyl acetate, acetic acid
N-propyl, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, n propyl propionate, isopropyl propionate, butyl propionate,
One or more in methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, butyl butyrate, particularly preferably adjacent benzene
Dioctyl phthalate di-n-butyl, diisobutyl phthalate, ether, propyl ether, butyl ether, amyl ether, hexyl ether, tetrahydrofuran (THF), third
One or more in ketone, butanone, 2 pentanone, methyl iso-butyl ketone (MIBK).
Catalyst according to the invention component, when the synthesis material of the catalytic component includes the situation of internal electron donor
Under, described in the catalytic component of olefinic polymerization, the weight ratio of titanium elements, magnesium elements and internal electron donor compound can
Think 1:5-15:2-15, is preferably 1:6-13:3-12.In the case of not including internal electron donor, it is used for olefinic polymerization described
Catalytic component in, titanium elements, magnesium elements weight ratio can be 1:5-15, is preferably 1:6-13.
Catalyst according to the invention component, the titanium compound can be the mistake for preparing the catalyst for olefinic polymerization
Conventional use of various titanium compounds in journey.In general, the titanium compound is general formula Ti (ORa)4-rMrCompound, wherein, Ra
For the aliphatic group of C1-C14, M F, Cl or Br, r are the integer of 1-4；The titanium compound is preferably titanium tetrachloride, tetrabormated
Titanium, titanium tetrafluoride, three butoxy titanium chlorides, dibutoxy titanium chloride, butoxy titanium chloride, triethoxy titanium chloride, diethyl
One or more in epoxide titanium chloride and ethyoxyl titanium chloride.
Catalyst according to the invention component, its can by by catalyst carrier as described above and titanium compound and
Optional internal electron donor reacts acquisition according to amount ratio as above under reaction condition as above.
Fourth aspect, present invention also offers catalysis prepared by catalyst carrier as described above, method as described above
Agent carrier and the catalytic component as described above for olefinic polymerization answering in the catalyst for olefinic polymerization is prepared
With.
5th aspect, the present invention provides a kind of catalyst for olefinic polymerization, which contains：
(1) it is used for the catalytic component of olefinic polymerization as described above；
(2) alkyl aluminum compound；And
(3) optional external donor compound.
Detailed description has been carried out in the composition of the catalytic component for olefinic polymerization above, herein not
Repeat again.
Catalyst for olefinic polymerization has used according to the present invention for olefinic polymerization according to the present invention
Catalytic component, therefore the catalyst according to the present invention for olefinic polymerization is in the catalyst as olefinic polyreaction
When, the heap density for the polymer polymerizeing also is improved.
According to the present invention, the alkyl aluminum can be the conventional selection of this area, for example, the general formula of the alkyl aluminum can be with
For AlR16R16′R16", wherein, R16、R16′、R16" alkyl of C1-C8 is each independently, and wherein one or two group can
Think halogen；The instantiation of the alkyl of the C1-C8 can include but is not limited to：Methyl, ethyl, propyl group, normal-butyl, isobutyl
Base, amyl group, hexyl, n-heptyl, n-octyl, the halogen can be fluorine, chlorine, bromine, iodine.Specifically, the alkyl aluminum for example may be used
With selected from triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three n-butylaluminums, tri-n-hexyl aluminum, tri-n-octylaluminium, a hydrogen diethyl
Base aluminium, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, a chlorine di-n-butyl aluminium, a chlorine di-n-hexyl
Aluminium, one aluminium ethide of dichloro, one aluminium isobutyl of dichloro, one n-butylaluminum of dichloro, one n-hexyl aluminium of dichloro, Al (n-C6H13)3、Al
(n-C8H17)3、AlEt2One or more in Cl, are preferably triethyl aluminum and/or triisobutyl aluminium.
According to the present invention, the external electron donor can be various external electron donors commonly used in the art, for example, described outer
Electron donor can be the one or more in carboxylic acid, acid anhydrides, ester, ketone, ether, alcohol, organic phosphorus compound and organo-silicon compound；
Preferably, it containing at least one Si-OR keys and general formula is (R that the external electron donor, which is,17)a(R18)bSi(OR19)cSilication close
Thing, wherein, R17、R18And R19Alkyl for C1-C18, optionally contain hetero atom, and a and b each stand alone as the integer of 0-2, and c is
The integer of 1-3, and a, b and c and for 4.Preferably, R17、R18Alkyl, cycloalkyl for C3-C10, optionally containing miscellaneous original
Son；R19For the alkyl of C1-C10, optionally contain hetero atom.Specifically, the external electron donor can for example be selected from cyclohexyl
Methyl dimethoxysilane, diisopropyl dimethoxy silane, di-n-butyl dimethoxysilane, diisobutyl dimethoxy silicon
Alkane, dimethoxydiphenylsilane, methyl-t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, cyclohexyl front three
Oxysilane, tert-butyl trimethoxy silane, tertiary hexyl trimethoxy silane, 2- ethyl piperidine base -2- tert-butyl group dimethoxys
Silane, (the fluoro- 2- propyl group of 1,1,1- tri-) -2- ethyl piperidine base dimethoxysilanes and (1,1,1-, three fluoro- 2- propyl group)-methyl
One or more in dimethoxysilane.
Typically also, described in the catalyst of olefinic polymerization, olefinic polymerization to be used for described in terms of titanium elements
Catalytic component and the alkyl aluminum dosage in terms of aluminium element molar ratio can be 1：(1-2000), is preferably 1：(20-
500)；The molar ratio of the external electron donor and the alkyl aluminum dosage in terms of aluminium element can be 0.005-0.5:1, preferably
For 0.01-0.4:1.
According to the present invention, in the preparation process for the catalyst of olefinic polymerization, alkyl aluminum and optional outer electron
Body compound can be reacted with after being mixed for the catalytic component of olefinic polymerization respectively, or can also by alkyl aluminum and optionally
External electron donor in advance mixing after mix and react with for the catalytic component of olefinic polymerization again.
6th aspect, present invention also offers the catalyst as described above for olefinic polymerization in olefinic polyreaction
Application.
According to the present invention, it is described for olefinic polymerization when by olefinic polymerization is used for for the catalyst of olefinic polymerization
Catalytic component, alkyl aluminum and optional external electron donor can be separately added into polymer reactor, added after can also mixing poly-
Close in reactor, can also use prepolymerization method commonly understood in the industry to be added to after alkene pre-polymerization in polymer reactor.
7th aspect, the present invention provides a kind of olefine polymerizing process, this method includes：, will under olefin polymerization conditions
One or more alkene are contacted with the catalyst as described above for olefinic polymerization.
The catalytic component for theing improvement is that the ad hoc approach for employing the present invention and preparing of the present invention, and the tool of alkene
Body species, the polymerisation process of alkene and condition can be same as the prior art.
According to the present invention, above-mentioned catalyst is CH especially suitable for general formula2(wherein, R is the alkyl of hydrogen, C1-C6 to=CHR
Or C6-C12 aryl) alkene homopolymerization and copolyreaction, specifically for example, ethene, propylene, 1- butylene, 2- butylene, 2- first
Base -1- butylene, 3-methyl-1-butene, 2- methyl-2-butenes, 1- amylenes, 2- amylenes, 1- hexenes and one kind in styrene or
It is a variety of, it is preferably the one or more in ethene, propylene, 1- butylene, 2- butylene and styrene
According to the present invention, the polymerisation of the alkene can be carried out according to existing method, specifically, in inert gas
Protection under, in liquid monomer or atent solvent containing polymerized monomer, or in the gas phase, or pass through the combination in liquid phase
Polymerization technique carries out polymerisation.The temperature of the polymerisation can be generally 0-150 DEG C, be preferably 60-90 DEG C.It is described poly-
The pressure for closing reaction can be normal pressure or higher；Such as can be 0.01-10MPa, it is preferably 0.5-5MPa.The time of polymerization is
When 0.1-5 is small, when being preferably 0.5-3 small.The pressure of the present invention refers both to gauge pressure.In the course of the polymerization process, hydrogen can be used as polymer
Molecular weight regulator is added in reaction system to adjust the molecular weight of polymer and melt index.In addition, in the polymerization of alkene
In reaction process, the inert gas, the species of solvent and dosage are known to the skilled person, and will not be described in great detail herein.
The present invention will be described in detail by way of examples below.
In embodiment and comparative example：
1st, the average particulate diameter of carrier for olefin polymerization catalyst and particle diameter distribution use Masters Sizer2000 granularities
Instrument (being manufactured by Malvern Instruments Ltd) is measured；
2nd, the apparent form of carrier for olefin polymerization catalyst passes through the model Eclipse E200 commercially available from Nikon companies
Light microscope observed；
3rd, the heap density of polyolefine powder is measured using method as defined in GB/T 1636-2008；
4th, the activity of catalyst=using the obtained polymer of catalyst weight/catalyst weight.
Preparation example 1
The preparation example is used to illustrate carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
In the reaction kettle of 0.6L, 8.0g (0.08mol) magnesium chloride, 56mL (0.96mol) ethanol, 4.3g are added
(0.016mol) six hydrated chromium trichloride, is warming up to 90 DEG C under agitation.When isothermal reaction 2 is small.Mixture stirring at low speed (is stirred
Speed is mixed as 400 revs/min) it is 30 minutes scattered, to be emulsified.And epoxychloropropane 0.48mol is added in emulsification product
(38ml), reacts press filtration after half an hour, press filtration product is washed 5 times with hexane, is dried in vacuo, and obtains olefin polymerization catalysis
Agent carrier Z1.
By nuclear magnetic resonance and elemental analysis, the structural formula of obtained catalyst carrier Z1 is as follows：
The average particulate diameter (D50) of the carrier for olefin polymerization catalyst Z1 is 48 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.7.Particle morphology using optical microphotograph sem observation is as shown in Figure 1.It can be seen from the figure that olefinic polymerization
The particle shape of catalyst carrier Z1 is more regular, and surface is smooth, is essentially all spherical, particle size distribution compares collection
In, and there is no that irregular particle exists.
Preparation example 2
The preparation example is used to illustrate carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
In the reaction kettle of 1.6L, add 300mL white oils, 8.0g (0.08mol) magnesium chloride, 28mL (0.48mol) ethanol,
Six hydrated chromium trichlorides of 2.1g (0.008mol), are warming up to 100 DEG C, when isothermal reaction 0.5 is small under agitation.By mixture low speed
Stirring (stir speed (S.S.) is 800 revs/min) is 30 minutes scattered, to be emulsified.And 12.5mL is added in emulsification product
(0.16mol) epoxychloropropane, reacts press filtration after twenty minutes, press filtration product is washed 5 times with hexane, finally does product vacuum
It is dry, obtain carrier for olefin polymerization catalyst Z2.
By nuclear magnetic resonance and elemental analysis, the structural formula of obtained catalyst carrier Z2 is as follows：
The average particulate diameter (D50) of the carrier for olefin polymerization catalyst Z2 is 49 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.8.Particle morphology using optical microphotograph sem observation is as shown in Figure 2.It can be seen from the figure that olefinic polymerization
The particle shape of catalyst carrier Z2 is more regular, and surface is smooth, is essentially all spherical, particle size distribution compares collection
In, and there is no that irregular particle exists.
Preparation example 3
The preparation example is used to illustrate carrier for olefin polymerization catalyst provided by the invention and preparation method thereof.
In the reaction kettle of 1.6L, add 500mL white oils, 8.0g (0.08mol) magnesium chloride, 95mL (1.63mol) ethanol,
Six hydrated chromium trichlorides of 1.1g (0.004mol), are warming up to 80 DEG C, when isothermal reaction 3 is small under agitation.Mixture low speed is stirred
Mix (stir speed (S.S.) is 600 revs/min) to disperse 30 minutes, to be emulsified.And 25mL (0.32mol) is added in emulsification product
Epoxychloropropane, reacts press filtration after forty minutes, press filtration product is washed 5 times with hexane, finally product vacuum is dried, obtains alkene
Polymerized hydrocarbon catalyst carrier Z3.
By nuclear magnetic resonance and elemental analysis, carrier for olefin polymerization catalyst Z3 structures are consistent with formula (I) structure.
The average particulate diameter (D50) of the carrier for olefin polymerization catalyst Z2 is 46 microns, particle diameter distribution ((D90-
D10)/D50) it is 0.75.Using optical microphotograph sem observation, the particle shape of carrier for olefin polymerization catalyst Z3 is more regular, table
Face is smooth, is essentially all spherical, and particle size distribution compares concentration, and there is no that irregular particle exists.
Contrast preparation example 1
The contrast preparation example is used to illustrate reference carrier for olefin polymerization catalyst and preparation method thereof.
Method according to embodiment 1 prepares carrier for olefin polymerization catalyst, unlike, chromium chloride is added without, obtains alkene
Polymerized hydrocarbon catalyst carrier DZ1.
The average particulate diameter (D50) of the catalyst support used for olefinic polymerization DZ1 is 100 microns, particle diameter distribution
((D90-D10)/D50) is 1.6.Particle morphology using optical microphotograph sem observation is as shown in Figure 3.It can be seen from the figure that alkene
There are substantial amounts of irregular particle in polymerized hydrocarbon catalyst carrier DZ1, and surface is more coarse.
Contrast preparation example 2
The contrast preparation example is used to illustrate reference carrier for olefin polymerization catalyst and preparation method thereof.
Method according to embodiment 1 prepares carrier for olefin polymerization catalyst, unlike, by ethanol with identical weight part
Octadecyl alcolol substitutes.Obtain carrier for olefin polymerization catalyst DZ2.
The average particulate diameter (D50) of the carrier for olefin polymerization catalyst DZ2 is 100 microns, particle diameter distribution ((D90-
D10)/D50) it is 1.5.Using optical microphotograph sem observation, there are substantial amounts of irregular particle in carrier for olefin polymerization catalyst DZ2,
And surface is more coarse.
Embodiment 1
The embodiment is used for the preparation for illustrating alkene provided by the invention.
(1) preparation of olefin polymerization catalysis
In the glass reaction bottle of 300mL, the titanium tetrachloride of 100mL is added, is cooled to -20 DEG C, by 40 grams by preparing
The carrier for olefin polymerization catalyst Z1 that example 1 obtains is added thereto, and stirs 30min at -20 DEG C.Afterwards, start slow
110 DEG C are warming up to, the diisobutyl phthalate of 1.5mL is added in temperature-rise period, is filtered after maintaining 30min at 110 DEG C
Remove liquid.Then, add titanium tetrachloride to wash 2 times, finally washed 3 times with hexane, olefin polymerization catalysis C1 is obtained after dry.
(3) propylene polymerization
In the stainless steel autoclave of a 5L, purged using stream of nitrogen gas, then drawn in stream of nitrogen gas
Enter hexane solution (concentration of triethyl aluminum is 0.5mmol/mL), the methylcyclohexyl of 0.05mmol of the triethyl aluminum of 1mmol
Olefin polymerization catalysis C1,1.5L (standard obtained by step (1) of dimethoxysilane, the anhydrous hexane of 10mL and 10mg
Volume) hydrogen and 2.5L liquid propene.It is warming up to 70 DEG C, and when reaction 1 is small at such a temperature, cooling, bleeds off pressure, and discharging is dry
It is dry to obtain polypropylene powder.
The activity of catalyst is 43.9KgPP/g Cat, and the heap density of the polypropylene powder is 0.45g/cm3, in addition, should
Polypropylene powder particle shape is good, is substantially not present special-shaped material.
Embodiment 2
The embodiment is used for the preparation for illustrating alkene provided by the invention.
Propylene polymerization is carried out according to the method for embodiment 1, unlike, when reaction 1 is small, cooling, is passed through second again after bleeding off pressure
The gaseous mixture of alkene and propylene (molar ratio C2/ (C3+C2)=0.042), the reaction was continued 0.5h, cooling, bleeds off pressure, discharging is dried to obtain
Polypropylene powder.
Catalyst activity is 57.8KgPP/gCat, and the heap density of the polypropylene powder is 0.46g/cm3, in addition, this is poly-
Propylene powder particles form is good, is substantially not present special-shaped material, and ethylene unit unit % is 5.2%.
Embodiment 3
The embodiment is used for the preparation for illustrating alkene provided by the invention.
Propylene polymerization is carried out according to the method for embodiment 1, unlike, it is prepared by the carrier for olefin polymerization catalyst Z1
The carrier for olefin polymerization catalyst Z2 that example 2 obtains is substituted, and obtains polypropylene powder.
Catalyst activity is 44.1KgPP/gCat, and the heap density of the polypropylene powder is 0.46g/cm3, in addition, this is poly-
Propylene powder particles form is good, is substantially not present special-shaped material.
Embodiment 4
The embodiment is used for the preparation for illustrating alkene provided by the invention.
Propylene polymerization is carried out according to the method for embodiment 2, unlike, it is prepared by the carrier for olefin polymerization catalyst Z1
The carrier for olefin polymerization catalyst Z2 that example 2 obtains is substituted, and obtains polypropylene powder.
Catalyst activity is 58.5KgPP/gCat, and the heap density of the polypropylene powder is 0.48g/cm3, in addition, this is poly-
Propylene powder particles form is good, is substantially not present special-shaped material, and ethylene unit unit % is 5.0%.
Embodiment 5
The embodiment is used for the preparation for illustrating alkene provided by the invention.
Propylene polymerization is carried out according to the method for embodiment 1, unlike, it is prepared by the carrier for olefin polymerization catalyst Z1
The carrier for olefin polymerization catalyst Z3 that example 3 obtains is substituted, and obtains polypropylene powder.
Catalyst activity is 42.1KgPP/gCat, and the heap density of the polypropylene powder is 0.47g/cm3, in addition, this is poly-
Propylene powder particles form is good, is substantially not present special-shaped material.
Comparative example 1
The comparative example is used to illustrate prepared by the reference of alkene.
Propylene polymerization is carried out according to the method for embodiment 1, unlike, the carrier for olefin polymerization catalyst Z1 contrasts
The carrier for olefin polymerization catalyst DZ1 that preparation example 1 obtains is substituted, and obtains polypropylene powder.
Catalyst activity is 32.2KgPP/gCat, and the heap density of the polypropylene powder is 0.38g/cm3, in addition, this is poly-
All it is special-shaped material in propylene powder particles, mobility is bad.
Comparative example 2
The comparative example is used to illustrate prepared by the reference of alkene.
Propylene polymerization is carried out according to the method for comparative example 1, unlike, when reaction 1 is small, cooling, ethene is passed through after bleeding off pressure
With the gaseous mixture (molar ratio C2/ (C3+C2)=0.042) of propylene, the reaction was continued 0.5h, cooling, bleeds off pressure, and discharging is dried to obtain poly-
Propylene powder.
Catalyst activity is 43.1kgPP/gcat, and the heap density of the polypropylene powder is 0.40g/cm3, in addition, this is poly-
All it is special-shaped material in propylene powder particles, mobility is bad, and ethene % is 2.6%.
Comparative example 3
The comparative example is used to illustrate prepared by the reference of alkene.
Propylene polymerization is carried out according to the method for embodiment 1, unlike, the carrier for olefin polymerization catalyst Z1 contrasts
The carrier for olefin polymerization catalyst DZ2 that preparation example 2 obtains is substituted, and obtains polypropylene powder.
Catalyst activity is 32.5KgPP/gCat, and the heap density of the polypropylene powder is 0.39g/cm3, in addition, this is poly-
All it is special-shaped material in propylene powder particles, mobility is bad.
Comparative example 4
The comparative example is used to illustrate prepared by the reference of alkene.
Propylene polymerization is carried out according to the method for comparative example 2, unlike, the carrier for olefin polymerization catalyst Z1 contrasts
The carrier for olefin polymerization catalyst DZ2 that preparation example 2 obtains is substituted.
Catalyst activity is 43.3kgPP/gcat, and the heap density of the polypropylene powder is 0.38g/cm3, in addition, this is poly-
All it is special-shaped material in propylene powder particles, mobility is bad, and ethene % is 2.7%.
As can be seen from the above results, the olefinic polymerization with new composition that method using the present invention is prepared is urged
The particle shape of agent carrier is good, surface is smooth, is not in irregular particle substantially, and being urged with prepared by the carrier of gained
When agent is used for alkene (particularly propylene) polymerization, the activity of catalyst is high, additionally it is possible to improve polymerizate heap density and
The content of ethylene unit unit, the appearance substantially without opposite sex material in copolymerization.In addition, the contrast from embodiment 1 and comparative example 1
As can be seen that not only pattern is preferable for the carrier for olefin polymerization catalyst of new composition, but also polymer stacks density is higher, catalyst
Higher, the great prospects for commercial application applied to alpha-olefin and activity during ethylene copolymer.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (20)
1. a kind of carrier for olefin polymerization catalyst, which is the magnesium-containing compound as shown in formula (I),
Wherein, in formula (I), R1For the alkyl of the straight or branched of C1-C14；R2, R3And R4It is identical or differ, independently of one another
For the haloalkyl of the straight or branched of hydrogen, the alkyl of the straight or branched of C1-C5 or C1-C5；X is halogen；Y is halogen；M is
0.1-1.9, n 0.1-1.9, m+n=2；0<i<3,0≤j<3,0<k<3, i+j+k=3,0<q≤0.5.
2. catalyst carrier according to claim 1, wherein, R1For the alkyl of the straight or branched of C1-C8；Preferably, R1
Selected from ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, n-hexyl, n-octyl and 2- ethylhexyls
In one or more；
R2, R3And R4It is identical or differ, it is each independently the alkyl of straight or branched or the straight chain of C1-C3 of hydrogen, C1-C3
Or the haloalkyl of side chain；Preferably, R2, R3And R4It is identical or differ, be each independently hydrogen, methyl, ethyl, chloromethyl,
One or more in chloroethyl, bromomethyl and bromoethyl；
X is chlorine or bromine, and Y is chlorine or bromine.
3. catalyst carrier according to claim 1 or 2, wherein, the average particulate diameter of the catalyst carrier is 10-
100 microns, particle diameter distribution is less than 1.2；Preferably, the average particulate diameter of the catalyst carrier is 40-60 microns, particle diameter point
Cloth is 0.6-0.8.
4. catalyst carrier according to claim 1, wherein, the synthesis material of the catalyst carrier include hafnium halide,
Magnesium halide, general formula are the compound of ROH, oxirane compound；
Wherein, in general formula R OH, R is the alkyl of the straight or branched of C1-C14；The structure of the oxirane compound is such as
Shown in formula (II)：
Wherein, R5And R6Each stand alone as hydrogen, C1-C5 straight or branched alkyl or C1-C5 straight or branched alkyl halide
Base.
5. catalyst carrier according to claim 4, wherein, on the basis of the magnesium halide of 1mol, the content of hafnium halide is
0.0001-1mol, the content for the compound that general formula is ROH is 4-30mol, and the oxirane compound shown in formula (II) contains
Measure as 1-10mol；
Preferably, on the basis of 1mol magnesium halides, the content of hafnium halide is 0.01-0.1mol, and general formula is containing for the compound of ROH
Measure as 6-20mol, the content of the oxirane compound shown in formula (II) is 2-6mol.
6. catalyst carrier according to claim 4 or 5, wherein, the hafnium halide is anhydrous or containing the crystallization water chlorine
Change chromium or chromic bromide, be preferably anhydrous or containing the crystallization water chromium chloride.
7. according to the catalyst carrier described in any one in claim 4-6, wherein, the magnesium halide is selected from magnesium chloride, bromine
Change the one or more in magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and chlorination n-butoxy magnesium.
8. according to the catalyst carrier described in any one in claim 4-6, wherein, in general formula R OH, R is the straight of C1-C8
The alkyl of chain or side chain；Preferably, general formula be ROH compound be selected from ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol,
One or more in n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, n-octyl alcohol and 2-Ethylhexyl Alcohol.
9. according to the catalyst carrier described in any one in claim 4-6, wherein, in epoxy of the structure as shown in formula (II)
In ethane compound, R5And R6It is each independently the straight or branched of hydrogen, the alkyl of C1-C3 straight or brancheds or C1-C3
Haloalkyl；Preferably, the oxirane compound is selected from ethylene oxide, propylene oxide, epoxy butane, epoxy chloropropionate
One or more in alkane, epoxy chlorobutane, epoxy bromopropane and epoxy bromobutane.
10. a kind of preparation method of carrier for olefin polymerization catalyst, this method comprise the following steps：
(1) it is the compound of ROH, optional inert liquid medium by hafnium halide, magnesium halide, general formula, is mixed and heated, obtains liquid
State mixture；
(2) liquefied mixture obtained step (1) emulsifies, and by emulsification product and oxirane compound haptoreaction；
In general formula R OH, R is the alkyl of C1-C14；Shown in the structure of the oxirane compound such as formula (II)：
Wherein, R5And R6Each stand alone as hydrogen, C1-C5 straight or branched alkyl or C1-C5 straight or branched alkyl halide
Base.
11. according to the method described in claim 10, wherein, on the basis of the magnesium halide of 1mol, the dosage of hafnium halide is
0.0001-1mol, the dosage of the compound that general formula is ROH are 4-30mol, the use of the oxirane compound shown in formula (II)
Measure as 1-10mol；
Preferably, on the basis of the magnesium halide of 1mol, the dosage of hafnium halide is 0.01-0.2mol, and general formula is the compound of ROH
Dosage is 6-20mol, and the dosage of the oxirane compound shown in formula (I) is 2-6mol.
12. the method according to claim 10 or 11, wherein, in step (1), the temperature of the heating is 80-120 DEG C,
When time is 0.5-5 small；Preferably, the temperature of the heating is 80-100 DEG C, when the time is 0.5-3 small.
13. the method according to claim 10 or 11, wherein, in step (2), the catalytic condition includes temperature
For 50-120 DEG C, the time is 20-60 minutes；Preferably, it is 60-100 DEG C that the catalytic condition, which includes temperature, and the time is
20-50 minutes.
14. the method according to claim 10 or 11, wherein, on the basis of the magnesium halide of 1mol, the inert fluid is situated between
The dosage of matter is 0.8-10L；The inert liquid medium is silicone oil and/or inert fluid varsol；
Preferably, the inert liquid medium is kerosene, paraffin oil, vaseline oil, white oil, methyl-silicone oil, ethyl silicon oil, methyl
One or more in ethyl silicon oil, phenyl silicone oil and methyl phenyl silicone oil.
15. a kind of catalytic component for olefinic polymerization, which contains by any one institute in claim 1-9
Catalyst carrier prepared by the method in the catalyst carrier and/or claim 10-14 stated described in any one is closed with titanizing
The product that thing and optional internal electron donor react.
16. catalytic component according to claim 15, wherein, which contains by appointing in claim 1-9
Catalyst carrier and titanium prepared by the method in the catalyst carrier or claim 10-14 described in meaning one described in any one
The product that compound and internal electron donor react, wherein, the weight of titanium elements, magnesium elements and internal electron donor compound
Than for 1:5-15:2-15, is preferably 1:6-13:3-12.
17. the side in the catalyst carrier, claim 10-14 in claim 1-9 described in any one described in any one
The catalytic component for olefinic polymerization described in catalyst carrier and claim 15 or 16 prepared by method is used in preparation
Application in the catalyst of olefinic polymerization.
18. a kind of catalyst for olefinic polymerization, which contains：
(1) catalytic component for olefinic polymerization described in claim 15 or 16；
(2) alkyl aluminum compound；And
(3) optional external donor compound.
19. the application for the catalyst of olefinic polymerization in olefinic polyreaction described in claim 18.
20. a kind of olefine polymerizing process, this method include：, will by one or more alkene and right under olefin polymerization conditions
The catalyst for olefinic polymerization described in 18 is asked to contact.
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