CN105622790B - Carrier and its catalyst used in a kind of ethylene homo conjunction or copolymerization catalyst - Google Patents
Carrier and its catalyst used in a kind of ethylene homo conjunction or copolymerization catalyst Download PDFInfo
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Abstract
The present invention relates to a kind of polymer-doped type carrier used for ethylene rolymerization catalyst, and prepared by polymer-doped type carrier ethene polymerization catalyst component, the preparation method and its catalyst of catalytic component.Magnesium chloride/organic phosphorus compound/epoxide/alcohol compound with carbon-carbon double bond can form the solution of clear in inert hydrocarbon solvent, the solution is in temperature-rise period, epoxide or its reaction product in system with carbon-carbon double bond can be copolymerized conjunction reaction with the free yl polymerizating monomer then added, so as to separate out the carrier of doped polymer.The polyethylene catalysts particle diameter distribution prepared by the carrier is narrow, and hydrogen adjusts susceptibility high, non-breakable in the course of the polymerization process, so fine powder is less, its gained polyethylene powder can also be made to have wide molecular weight distribution.
Description
Technical field
It is used for vinyl polymerization or polymer-doped type carrier, the ingredient of solid catalyst of combined polymerization the present invention relates to a kind of,
And catalyst containing the ingredient of solid catalyst and preparation method thereof.
Background technology
A kind of common preparation method of Ziegler-Natta type polyolefin catalysts is：First prepare with certain particle shape
With the magnesium compound of size distribution (or magnesium compound and electron donor are formed solid complex) carrier, such as patent
Alkoxyl magnesium carrier described in CN102020534A, or magnesium chloride/ethanolic vehicle described in patent CN1091748A.Again by de-
The methods of alcohol, chlorination, carrier is converted into the skeleton structure of magnesium chloride, polyolefin catalyst is completed finally by load titanium chloride
Preparation process.
In this area, most common magnesium compound (or magnesium compound/electron donor) carrier is magnesium chloride/ethanolic vehicle, such as
Described in patent CN1091748A.By introducing polymer into magnesium chloride/ethanolic vehicle, such as polyethers (CN101544710A) and poly-
Ester (CN101550205A) etc., it can assign support/catalyst higher resistant to breakage ability.In addition, other sides for preparing carrier
Method includes：1st, such as CN102020534A and CN101663332A disclose the method for preparing alkoxyl magnesium carrier；2nd, such as
WO2011/044761A1 discloses chlorination magnesium alcoholate solution and reacted with epoxide, prepares novel ball magnesium compound load
The method of body；3rd, such as CN101554595A is disclosed comprising magnesium chloride/styrol copolymer/silica gel/tetrahydrofuran/butanediol group
The preparation method of the polymer-doped type carrier divided.
Catalyst in polymerization whether the easily broken mechanical strength for being primarily limited to carrier, if the mechanical strength of carrier
Relatively low, then the catalyst for being processed obtaining also is easily broken, and a certain amount of polyethylene fine powder can be produced in polymerization, this for
The stable operation of fluid bed is unfavorable.The mechanical strength for strengthening carrier is to avoid catalyst breakage, and then reduces polymerization technique
The optimization approach of middle fine powder content, and it is effective ways that polymer is introduced into carrier.Therefore mixed, it is necessary to prepare a kind of polymer
Miscellaneous type carrier and catalyst.
In addition, in order to obtain the polyolefin products of wide molecular weight distribution, a variety of electron donors are generally introduced into catalyst,
As described in patent CN101554595A.Copolymer is introduced into catalytic component, then the different structure unit of copolymer is similar to
Different electron donors, different activated centres can be produced, and then the polyolefin products of wide molecular weight distribution can be obtained.
The present inventor it has been investigated that, magnesium chloride/organic phosphorus compound/carry carbon-carbon double bond epoxide/alcohols
Compound can form the solution of clear in inert hydrocarbon solvent, and the solution carries carbon in temperature-rise period in system
The epoxide of carbon double bond or its reaction product can be copolymerized conjunction reaction with the free yl polymerizating monomer then added, from
And the carrier of doped polymer can be separated out.The polyethylene catalysts particle diameter distribution prepared by the carrier is narrow, and hydrogen adjusts susceptibility
Height, it is non-breakable in the course of the polymerization process, so fine powder is less, it can also make its gained polyethylene powder that there is wide molecular weight point
Cloth.
The content of the invention
The technical problem to be solved in the present invention is to provide the polymer-doped type carrier that a kind of ethylene rolymerization catalyst uses
Preparation method, this method is simple to operate, without being adjusted to conventional equipment.One kind is additionally provided to be carried by polymer-doped type
Ethene polymerization catalyst component prepared by body, its catalytic component can be with polymerising ethylenes with co-catalyst.Prepared by the carrier
Polyethylene catalysts not only there is the characteristics of particle diameter distribution is narrow, and non-breakable, hydrogen response is high, gained polymerization powder
Particle diameter distribution is especially concentrated, fine powder is less and molecular weight distribution is wider.
Polymer-doped type carrier used in a kind of ethylene rolymerization catalyst of the present invention, the carrier include following group
The reaction product divided：(1) magnesium compound；(2) organic phosphorus compound；(3) epoxide of carbon-carbon double bond is carried；(4) alcohols
Compound；(5) free yl polymerizating monomer；
Described magnesium compound is selected from magnesium dihalide, the hydrate of magnesium dihalide or alcohol adduct and magnesium dihalide molecular formula
In one kind in the derivative replaced by oxyl or halo oxyl of one of halogen atom, or their mixture；
Described organic phosphorus compound is the hydrocarbyl carbonate or halogenated hydrocarbons base ester of orthophosphoric acid or phosphorous acid；
The described epoxide with carbon-carbon double bond includes aliphatic olefin, alkadienes or halogen with carbon-carbon double bond
At least one of the oxide of fat subsitutes race alkene or alkadienes, glycidol ether and inner ether；
Described alcohol compound includes carbon number at least one of 1~18 fatty alcohol or aromatic alcohol；
Described free yl polymerizating monomer be acrylate and its derivative, Styrene and its derivatives and acrylonitrile and its
Derivative.
Specifically, the magnesium compound described in component (1) includes MgCl2、MgBr2、MgI2、MgCl(OEt)、MgCl(OBu)
And MgCl2- mROH etc..
Organic phosphorus compound described in component (2) is triethyl phosphate, tributyl phosphate, triisooctyl phosphate, tricresyl phosphate
Phenyl ester, triethyl phosphite, at least one of tributyl phosphite, di-n-butyl phosphite.
The epoxide with carbon-carbon double bond described in component (3) includes GMA and acrylic acid
Ethylene oxidic ester etc..
Alcohol compound described in component (4) include methanol, ethanol, propyl alcohol, isopropanol, butanol, isobutanol, the tert-butyl alcohol,
At least one of hexanol, cyclohexanol, octanol, isooctanol, phenmethylol, benzyl carbinol.
Free yl polymerizating monomer described in component (5) is methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid
Butyl ester, hydroxy-ethyl acrylate, methyl methacrylate, EMA, propyl methacrylate, methacrylic acid fourth
At least one of ester, hydroxyethyl methacrylate, styrene, chlorostyrene, acrylonitrile etc..
For ratio between each reactant in terms of every mole of magnesium, organic phosphorus compound is 0.1~5.0 mole, double with carbon carbon
The epoxide of key be 0.1~5.0 mole, alcohol compound be 0.1~5.0 mole, free yl polymerizating monomer be 0.1~
5.0 mole.
A kind of preparation method of polymer-doped type carrier for used in ethylene rolymerization catalyst of the present invention, bag
Include following step：
(1) magnesium compound described in component (1) is dispersed in hydro carbons atent solvent, obtains suspension；
(2) organic phosphorus compound described in component (2) is added into suspension, carries carbon-carbon double bond described in component (3)
Epoxide and component (4) described in alcohol compound, 20-50 DEG C react certain time after formed homogeneous transparent it is molten
Liquid；
(3) at 20~50 DEG C, the radical polymerization list described in component (5) is added into the homogeneous transparent solution of step (2)
Body, solids is separated out in slow temperature-rise period, after reacting the regular hour, remove unreacted reactant, and use inert diluent
Washing, obtain the polymer-doped type carrier of the present invention.
The invention further relates to a kind of catalytic component for vinyl polymerization, and it includes the reaction product of following components：
(1) above-mentioned polymer-doped type carrier；
(2) one or more are by formula Ti (OR)nX4-nShown titanium compound, R is C in formula1~C8Alkyl, X is halogen
Atom, 0≤n≤4；
(3) one or more are by formula Al R 'aXbHcShown organo-aluminum compound, R ' is C in formula1~C14Alkyl, X
For halogen, a, b, c are 0~3 integer, and a+b+c=3；
(4) one or more electron donor compounds, selected from carboxylate, aromatic ester, aliphatic ether and cycloaliphatic ether etc.；
Ratio between wherein each reactant in terms of every mole of magnesium in the polymer-doped type carrier described in component (1),
Component (2) titanium compound is 0.1~15.0 mole；Component (3) organo-aluminum compound is 0.1~5.0 mole；Component (4) is to electricity
Donor compound is 0.1~5.0 mole.
Titanium compound formula described in component (2) is Ti (OR)nX4-n, R is C in formula1~C8Alkyl, X is halogen atom, 0
≤ n≤3, including：TiCl4、TiBr4、TiI4、Ti(OC2H5)Cl3、Ti(OCH3)Cl3、Ti(OC4H9)Cl3、Ti(OC2H5)Br3、Ti
(OC2H5)2Cl2、Ti(OCH3)2Cl2、Ti(OCH3)2I2、Ti(OC2H5)3Cl、Ti(OCH3)3Cl、Ti(OC2H5)3I etc..
The formula of organo-aluminum compound described in component (3) is Al R 'aXbHcShown, R ' is C in formula1~C14Hydrocarbon
Base, X are halogen, and a, b, c are 0~3 integer, and a+b+c=3.Particular compound is such as：Al(CH3)3、Al(CH2CH3)3、Al
(i-Bu)3、Al(n-C6H13)3、AlH(CH2CH3)2、AlH(i-Bu)2、AlCl(CH2CH3)2、Al2Cl3(CH2CH3)3、AlCl
(CH2CH3)2、AlCl2(CH2CH3) etc. alkyl aluminum compound, wherein preferably Al (CH2CH3)3、Al(n-C6H13)3、Al(i-Bu
)3.Most preferably Al (CH2CH3)3.These organo-metallic compounds both may be used alone, two or more kinds can also be used in combination.
Electron donor compound described in component (4) is selected from carboxylate, aliphatic ether, cyclic aliphatic ether or aliphatic ketone, preferably
For C1~C4Arrcostab, the C of aliphatic saturated monocarboxylic acid1~C8Arrcostab, the C of aromatic carboxylic acids2~C12Aliphatic ether, C3~C4Cyclic ethers, C3
~C6Saturated fat ketone.Particular compound is such as：Methyl formate, ethyl acetate, butyl acetate, acetic acid n-octyl, ethyl benzoate,
Butyl benzoate, ether, hexyl ether, tetrahydrofuran, acetone and methyl iso-butyl ketone (MIBK) etc., these electron donor compounds both can be with
Be used alone, can also two or more be applied in combination.
The preparation method of catalytic component of the present invention for ethylene polymerization, it comprises the following steps：
(1) the polymer-doped type support dispersion described in component (1) is obtained into suspension in hydro carbons atent solvent；
(2) by suspension in -40~50 DEG C and component (3) organo-aluminum compound and component (4) one or more electrons
Body compound carries out haptoreaction；
(3) mixture of step (2) is to slowly warm up to 20~60 DEG C, after reacting the regular hour, removes unreacted reactant,
And washed using inert diluent；
(4) add component (2) titanium compound to be reacted, then washed using inert diluent, obtain urging for the present invention
Agent component.
It is used for vinyl polymerization or the catalyst of combined polymerization present invention also offers a kind of, it includes reaction of following components and produced
Thing：
(1) catalytic component of the invention described above；
(2) formula is AlRdX3-dOrgano-aluminum compound, the alkyl that R is hydrogen or carbon number is l~20 in formula, X is halogen
Plain atom, 0<d≤3.
Component (2) formula of is AlRdX3-dOrgano-aluminum compound, R can be hydrogen in formula or carbon number is l~20
Alkyl, particularly alkyl, aralkyl, aryl；X is halogen atom, particularly chlorine and bromine；0<d≤3.Particular compound is such as：Al
(CH3)3、Al(CH2CH3)3、Al(i-Bu)3、AlH(CH2CH3)2、AlH(i-Bu)2、AlCl(CH2CH3)2、Al2Cl3(CH2CH3)3、
AlCl(CH2CH3)2、AlCl2(CH2CH3) etc. alkyl aluminum compound.Preferably Al (CH2CH3)3、Al(i-Bu)3.Wherein component
(2) mol ratio of aluminium and titanium in component (1) is 5~500, preferably 20~200 in.
Liquid polymerization medium includes：Iso-butane, hexane, heptane, hexamethylene, naphtha, raffinate oil, hydrogasoline, kerosene,
The atent solvent such as the aliphatic saturated hydrocarbons such as benzene,toluene,xylene or aromatic hydrocarbon.
In order to adjust the molecular weight of final polymer, molecular weight regulator is made using hydrogen.
The present inventor it has been investigated that, magnesium chloride/organic phosphorus compound/carry carbon-carbon double bond epoxide/alcohols
Compound can form the solution of clear in inert hydrocarbon solvent, and the solution carries carbon in temperature-rise period in system
The epoxide of carbon double bond or its reaction product can be copolymerized conjunction reaction with the free yl polymerizating monomer then added, from
And the carrier of doped polymer can be separated out.The polyethylene catalysts particle diameter distribution prepared by the carrier is narrow, and hydrogen adjusts susceptibility
Height, it is non-breakable in the course of the polymerization process, so fine powder is less, it can also make its gained polyethylene powder that there is wide molecular weight point
Cloth.
Embodiment
Method of testing：
1. the relative weight percents of titanium elements in catalyst system：Using AAS；
2. the relative weight percents of polymer in catalyst system：Using core magnetic survey；
3rd, in catalyst system polymer molecular weight, measured by gel chromatography PL220；
4th, the measure (MI/2.16Kg) of melt index：According to ASTM D1238-99；
The present invention is described with embodiment below, but the not limitation scope of the invention.
Embodiment 1
The preparation of polymer-doped type carrier
By 4.0 grams of magnesium chlorides, 90ml toluene, 20ml TRI N BUTYL PHOSPHATEs, 8.0ml GMAs, 1ml
Ethanol is added in reactor, under conditions of speed of agitator 450rpm, temperature are 40 DEG C, constant temperature 2 hours.Added to system
3ml methyl methacrylates, 90 degree are to slowly warm up to, carrier particle gradually separates out.Constant temperature 1 hour, mother liquor is filtered off, it is dilute through inertia
Release agent washing for several times.Transferred them to by hexane in chromatography funnel, dried up with high pure nitrogen, obtain the narrow polymerization of particle diameter distribution
Thing doping type carrier.
Embodiment 2
The preparation of polymer-doped type carrier
By 4.0 grams of magnesium chlorides, 80ml toluene, 18ml triethyl phosphates, 6.0ml glycidyl acrylates, 2ml ethanol add
Enter into reactor, under conditions of speed of agitator 450rpm, temperature are 40 DEG C, constant temperature 2 hours.3ml propylene is added to system
Nitrile, 90 degree are to slowly warm up to, carrier particle gradually separates out.Constant temperature 1 hour, mother liquor is filtered off, through inert diluent washing for several times.It is logical
Cross hexane to transfer them in chromatography funnel, dried up with high pure nitrogen, obtain the narrow polymer-doped type carrier of particle diameter distribution.
Embodiment 3
The preparation of polymer-doped type carrier
By 3.0 grams of magnesium chlorides, 80ml toluene, 18ml tricresyl phosphate propyl ester, 10.0ml glycidyl acrylates, 2ml ethanol
It is added in reactor, under conditions of speed of agitator 450rpm, temperature are 40 DEG C, constant temperature 2 hours.6ml first is added to system
Base hydroxy-ethyl acrylate, 90 degree are to slowly warm up to, carrier particle gradually separates out.Constant temperature 1 hour, mother liquor is filtered off, through inert diluents
Agent is washed for several times.Transferred them to by hexane in chromatography funnel, dried up with high pure nitrogen, obtain the narrow polymer of particle diameter distribution
Doping type carrier.
Embodiment 4
(1) preparation of catalytic component
In the reactor being sufficiently displaced from by high pure nitrogen, the polymer-doped type carriers of 4.0g are sequentially added (by reality
Example 1 is applied to prepare), hexane 100ml, -10 DEG C are cooled under stirring, the hexane solution (triethyl aluminum of 40ml triethyl aluminums is added dropwise：
1.2M) and 0.5ml ethyl benzoates, 50 DEG C are then heated to, and maintenance reaction 2 hours.Stop stirring, stand, suspension
Be layered quickly, extract supernatant liquor, sediment hexane in room temperature washing twice.100ml hexanes are added, the system is cooled to
0 DEG C, titanium tetrachloride 6ml is slowly added dropwise, is warming up to 60 DEG C afterwards, reacts 2 hours.Stop stirring, stand, suspension divides quickly
Layer, extracts supernatant liquor, after sediment washs twice with hexane, is transferred them to by hexane in chromatography funnel, uses High Purity Nitrogen
Air-blowing is done, and obtains the ingredient of solid catalyst of good fluidity, narrow particle size distribution.Catalyst composition is shown in Table 1.
(2) polymerisation：
Volume is 2L stainless steel cauldron, and after high pure nitrogen is sufficiently displaced from, it is 1M to add 1L hexanes and 1.0ml concentration
Triethyl aluminum, add the ingredient of solid catalyst (contain 0.6 milligram of titanium) prepared by the above method, be warming up to 70 DEG C, it is logical
Entering hydrogen makes pressure in kettle reach 0.28Mpa, then being passed through ethene makes stagnation pressure in kettle reach 0.73Mpa (gauge pressure), in 80 DEG C of conditions
Lower polymerization 2 hours, polymerization result is shown in Table 2.
(3) polymerisation：
Volume is 2L stainless steel cauldron, and after high pure nitrogen is sufficiently displaced from, it is 1M to add 1L hexanes and 1.0ml concentration
Triethyl aluminum, add the ingredient of solid catalyst (contain 1.8 milligrams of titaniums) prepared by the above method, be warming up to 70 DEG C, it is logical
Entering hydrogen makes pressure in kettle reach 0.58Mpa, then being passed through ethene makes stagnation pressure in kettle reach 0.73Mpa (gauge pressure), in 80 DEG C of conditions
Lower polymerization 2 hours, polymerization result is shown in Table 3.
Embodiment 5
(1) preparation of catalytic component
In the reactor being sufficiently displaced from by high pure nitrogen, the polymer-doped type carriers of 5.0g are sequentially added (by reality
Example 2 is applied to prepare), hexane 100ml, -10 DEG C are cooled under stirring, the hexane solution (triethyl aluminum of 50ml triethyl aluminums is added dropwise：
1.2M) and 0.5ml acetic acid n-octyls, 50 DEG C are then heated to, and maintenance reaction 2 hours.Stop stirring, stand, suspension
Be layered quickly, extract supernatant liquor, sediment hexane in room temperature washing twice.100ml hexanes are added, the system is cooled to
0 DEG C, titanium tetrachloride 8ml is slowly added dropwise, is warming up to 60 DEG C afterwards, reacts 2 hours.Stop stirring, stand, suspension divides quickly
Layer, extracts supernatant liquor, after sediment washs twice with hexane, is transferred them to by hexane in chromatography funnel, uses High Purity Nitrogen
Air-blowing is done, and obtains the ingredient of solid catalyst of good fluidity, narrow particle size distribution.Catalyst composition is shown in Table 1.
(2) polymerisation：With embodiment 4, polymerization result is shown in Table 2.
Embodiment 6
(1) preparation of catalytic component
In the reactor being sufficiently displaced from by high pure nitrogen, the polymer-doped type carriers of 3.0g are sequentially added (by reality
Example 3 is applied to prepare), hexane 100ml, -10 DEG C are cooled under stirring, hexane solution (three n-hexyls of 40ml tri-n-hexyl aluminums are added dropwise
Aluminium：1.0M) and 0.5ml butyl benzoates, 50 DEG C are then heated to, and maintenance reaction 2 hours.Stop stirring, stand, suspend
Liquid is layered quickly, extracts supernatant liquor, sediment hexane in room temperature washing twice.100ml hexanes are added, the system is cooled down
To 0 DEG C, titanium tetrachloride 6ml is slowly added dropwise, is warming up to 60 DEG C afterwards, reacts 2 hours.Stop stirring, stand, suspension divides quickly
Layer, extracts supernatant liquor, after sediment washs twice with hexane, is transferred them to by hexane in chromatography funnel, uses High Purity Nitrogen
Air-blowing is done, and obtains the ingredient of solid catalyst of good fluidity, narrow particle size distribution.Catalyst composition is shown in Table 1.
(2) polymerisation：With embodiment 4, polymerization result is shown in Table 2 and table 3.
Comparative example 1
(1) preparation of catalytic component
In the reactor being sufficiently displaced from by high pure nitrogen, 4.0g ball type carriers MgCl is sequentially added2·
2.6C2H5OH, hexane 100ml, -10 DEG C are cooled under stirring, the hexane solution (triethyl aluminum of 40ml triethyl aluminums is added dropwise：
1.2M), 50 DEG C are then heated to, and maintenance reaction 2 hours.Stop stirring, stand, suspension is layered quickly, extracts upper strata
Clear liquid, sediment hexane in room temperature washing twice.100ml hexanes are added, the system is cooled to 0 DEG C, tetrachloro is slowly added dropwise
Change titanium 6ml, be warming up to 60 DEG C afterwards, react 2 hours.Stop stirring, stand, suspension is layered quickly, extracts supernatant liquor, is sunk
After starch washs twice with hexane, transferred them to by hexane in chromatography funnel, dried up with high pure nitrogen, obtain mobility
Good, the solid spherical catalytic component of narrow particle size distribution.Catalyst composition is shown in Table 1.
(2) polymerisation：With embodiment 4, polymerization result is shown in Table 2 and table 3.
Comparative example 2
(1) preparation of catalytic component
In the reactor being sufficiently displaced from by high pure nitrogen, 5.0g ball type carriers MgCl is sequentially added2·
2.6C2H5OH, hexane 100ml, -10 DEG C are cooled under stirring, the hexane solution (tri-n-hexyl aluminum of 50ml tri-n-hexyl aluminums is added dropwise：
1.0M), ethyl benzoate 2ml, then heats to 50 DEG C, and maintenance reaction 2 hours.Stop stirring, stand, suspension is quickly
Layering, extracts supernatant liquor, sediment hexane in room temperature washing twice.100ml hexanes are added, the system is cooled to 0 DEG C,
Titanium tetrachloride 6ml is slowly added dropwise, is warming up to 60 DEG C afterwards, reacts 2 hours.Stop stirring, stand, suspension is layered, taken out quickly
Except supernatant liquor, after sediment washs twice with hexane, transferred them to by hexane in chromatography funnel, with High Purity Nitrogen air-blowing
It is dry, obtain the solid spherical catalytic component of good fluidity, narrow particle size distribution.Catalyst composition is shown in Table 1.
(2) polymerisation：With embodiment 4, polymerization result is shown in Table 2.
The composition of the catalytic component of table 1
It was found from the data of table 1, the catalytic component Unusually narrow particle size distribution obtained by the present invention, span values are not higher than 0.7.It is poly-
The narrower span values of compound doping type carrier come from its slow precipitation mode.And the span values of comparative example catalyst be limited to it is spherical
The particle diameter distribution of magnesium chloride/ethanolic vehicle.Wherein Span is defined as follows：[(particle diameters of 90% cumulative particle sizes)-(10% is accumulative
The particle diameter of granularity)]/(particle diameters of 50% cumulative particle sizes), the cumulative particle sizes of term 90%/10%/50% expression granularity limit value, limiting
The particle of 90%/10%/50% cumulative amount is both less than the granularity limit value at value.
The catalyst of table 2 and properties of powder
It was found from the data of table 2, the polyethylene powder that is gone out by catalyst preparation obtained by the present invention, melt index is higher, and 190
Fine powder content below mesh is less than 0.5% (wt), and molecular weight distribution is wider.As can be seen here, present invention gained catalyst particle
It is non-breakable in the course of the polymerization process.
The hydrogen of the catalyst of table 3 adjusts susceptibility
The catalyst hydrogen response that the present invention is can be seen that from the data of table 3 is good.
Claims (17)
1. the polymer-doped type carrier used in a kind of ethylene rolymerization catalyst, the carrier include the reaction product of following component：
(1) magnesium compound；
(2) organic phosphorus compound；
(3) epoxide of carbon-carbon double bond is carried；
(4) alcohol compound；
(5) free yl polymerizating monomer；
Described magnesium compound in magnesium dihalide, the hydrate of magnesium dihalide or alcohol adduct and magnesium dihalide molecular formula its
In one kind in the derivative replaced by oxyl or halo oxyl of a halogen atom, or their mixture；
Described organic phosphorus compound is the hydrocarbyl carbonate or halogenated hydrocarbons base ester of orthophosphoric acid or phosphorous acid；
The described epoxide with carbon-carbon double bond is the aliphatic olefin with carbon-carbon double bond, alkadienes or halogenated aliphatic
At least one of the oxide of race's alkene or alkadienes, glycidol ether and inner ether；
Described alcohol compound is carbon number at least one of 1~18 fatty alcohol or aromatic alcohol；
Described free yl polymerizating monomer is acrylate and its derivative, Styrene and its derivatives and acrylonitrile and its derivative
Thing.
2. the polymer-doped type carrier used in a kind of ethylene rolymerization catalyst according to claim 1, it is characterised in that
Ratio between each reactant is in terms of every mole of magnesium, and organic phosphorus compound is 0.1~5.0 mole, the epoxy with carbon-carbon double bond
Compound is 0.1~5.0 mole, and alcohol compound is 0.1~5.0 mole, and free yl polymerizating monomer is 0.1~5.0 mole.
3. the polymer-doped type carrier used in a kind of ethylene rolymerization catalyst according to claim 1, it is characterised in that
Described free yl polymerizating monomer is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid hydroxyl second
Ester, methyl methacrylate, EMA, propyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate second
At least one of ester, styrene, chlorostyrene, acrylonitrile.
4. the polymer-doped type carrier used in a kind of ethylene rolymerization catalyst according to claim 1, it is characterised in that
The described epoxide with carbon-carbon double bond is selected from GMA and glycidyl acrylate.
5. the polymer-doped type carrier used in a kind of ethylene rolymerization catalyst according to claim 1, it is characterised in that
Described organic phosphorus compound is triethyl phosphate, tributyl phosphate, triisooctyl phosphate, triphenyl phosphate, phosphorous triethylenetetraminehexaacetic acid
Ester, at least one of tributyl phosphite, di-n-butyl phosphite.
6. the polymer-doped type carrier used in a kind of ethylene rolymerization catalyst according to claim 1, it is characterised in that
Described alcohol compound is selected from methanol, ethanol, propyl alcohol, isopropanol, butanol, isobutanol, the tert-butyl alcohol, hexanol, cyclohexanol, pungent
At least one of alcohol, isooctanol, phenmethylol, benzyl carbinol.
7. the polymer-doped type carrier used in a kind of ethylene rolymerization catalyst according to claim 1, it is characterised in that
Described magnesium compound is selected from MgCl2、MgBr2、MgI2, MgCl (OEt), MgCl (OBu) and MgCl2-mROH。
8. the preparation of the polymer-doped type carrier used in a kind of ethylene rolymerization catalyst according to one of claim 1-7
Method, comprise the steps：
(1) described magnesium compound is dispersed in hydro carbons atent solvent, obtains suspension；
(2) described organic phosphorus compound, epoxide and alcohol compound with carbon-carbon double bond are added into suspension,
Homogeneous transparent solution is formed after reacting certain time at 20~50 DEG C；
(3) at 20~50 DEG C, described free yl polymerizating monomer is added into the homogeneous transparent solution of step (2), is slowly being risen
Solids is separated out during temperature, after reacting the regular hour, removes unreacted reactant, and is washed using inert diluent, obtains institute
State polymer-doped type carrier.
9. a kind of catalytic component for ethylene polymerization, it is characterised in that include the reaction product of following components：
(1) the polymer-doped type carrier used in the ethylene rolymerization catalyst described in one of claim 1-7；
(2) at least one formula is Ti (OR3)nX4-nTitanium compound, R in formula3For C1~C8Alkyl, X is halogen atom, 0≤n
≤4；
(3) at least one is by formula AlRa’XbHcShown organo-aluminum compound, R ' is C in formula1~C14Alkyl, X is halogen,
A, b, c are 0~3 integer, and a+b+c=3；
(4) at least one electron donor compound, selected from carboxylate, aromatic ester, aliphatic ether and cycloaliphatic ether；
In terms of every mole of magnesium in described polymer-doped type carrier, titanium compound is ratio between wherein each reactant
0.1~15.0 mole；Organo-aluminum compound is 0.1~5.0 mole；Electron donor compound is 0.1~5.0 mole.
A kind of 10. catalytic component for ethylene polymerization according to claim 9, it is characterised in that catalyst group
The particle diameter distribution Span divided is less than or equal to 0.7.
A kind of 11. catalytic component for ethylene polymerization according to claim 9, it is characterised in that described titanium
Compound is selected from TiCl4、TiBr4、TiI4、Ti(OC2H5)Cl3、Ti(OCH3)Cl3、Ti(OC4H9)Cl3、Ti(OC2H5)Br3、Ti
(OC2H5)2Cl2、Ti(OCH3)2Cl2、Ti(OCH3)2I2、Ti(OC2H5)3Cl、Ti(OCH3)3Cl、Ti(OC2H5)3I。
12. a kind of catalytic component for ethylene polymerization according to claim 9, it is characterised in that described has
Machine aluminium compound is selected from Al (CH3)3、Al(CH2CH3)3、Al(i-Bu)3、Al(n-C6H13)3、AlH(CH2CH3)2、AlH(i-Bu)2、
AlCl(CH2CH3)2、Al2Cl3(CH2CH3)3、AlCl(CH2CH3)2、AlCl2(CH2CH3)。
13. a kind of catalytic component for ethylene polymerization according to claim 9, it is characterised in that described gives
Electron compound be selected from methyl formate, ethyl acetate, butyl acetate, acetic acid n-octyl, ethyl benzoate, butyl benzoate,
Ether, hexyl ether, tetrahydrofuran, acetone and methyl iso-butyl ketone (MIBK).
14. a kind of preparation method of catalytic component for ethylene polymerization described in claim 9, including following step
Suddenly：
(1) described polymer-doped type support dispersion is obtained into suspension in hydro carbons atent solvent；
(2) suspension is subjected to haptoreaction in -40~50 DEG C and organo-aluminum compound and at least one electron donor compound；
(3) mixture of step (2) is to slowly warm up to 20~60 DEG C, after reacting the regular hour, removes unreacted reactant, and adopt
Washed with inert diluent；
(4) add titanium compound to be reacted, then washed using inert diluent, obtain the catalytic component.
15. a kind of catalyst for ethylene polymerization, it includes the reaction product of following components：
(1) catalytic component described in claim 9；
(2) formula is AlR "dX3-dOrgano-aluminum compound, the alkyl that R " is hydrogen or carbon number is l~20 in formula, X is that halogen is former
Son, 0<d≤3.
16. the catalyst according to claim 15 for ethylene polymerization, it is characterised in that aluminium and group in component (2)
The mol ratio for dividing titanium in (1) is 20~200.
17. the catalyst for ethylene polymerization described in claim 15 is in ethylene homo closes reaction or copolymerization
Application.
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