CN104059174B - A kind of supported single metallocene catalyst for vinyl polymerization - Google Patents
A kind of supported single metallocene catalyst for vinyl polymerization Download PDFInfo
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Abstract
The present invention relates to a kind of supported single metallocene catalyst for vinyl polymerization and preparation method, this catalyst includes (a) mono-metallocene compound；(b) chlorination alkyl silica modifier；Magnesium-modified dose of (c) halogenation alkyl；(d) alkylaluminoxane；The product of (e) silica-gel carrier；Its preparation method includes: the preparation of (1) chlorination alkyl Si modification silica-gel carrier, the preparation of the magnesium-modified silica-gel carrier of (2) halogenation alkyl, the preparation of modified silica gel carrier of (3) alkylaluminoxane, the preparation of (4) silica gel load single metallocene catalyst, obtained single metallocene catalyst catalyzed ethylene polymerization or combined polymerization have the highest polymerization activity.The method used silica gel support preparation method is simple, and the carried catalyst particle shape of gained is good, and size is adjustable.
Description
Technical field
The present invention relates to the preparation method of a kind of modified silica-gel load single metallocene catalyst, and the application that gained catalyst is in terms of olefinic polymerization.
Technical background
The exploitation application of single metallocene catalyst is after traditional Ziegler-Natta catalyst, the another important breakthrough in olefin polymerization catalysis field, the particularly eighties, and Kaminsky and Sinn et al. (Angew.Chem., 1980,19,390；Adv.Organoment.Chem., 1980,18,99) efficient promoter MAO (MAO) is developed so that the research of single metallocene catalyst has entered into a fast-developing stage.Owing to the MAO consumption needed for homogeneous single metallocene catalyst high activity to be reached is big, production cost is high, and the polymer obtained is amorphous, cannot use on widely used slurry process or gas phase polymerization technique, the effective way overcoming the problems referred to above is exactly supported for solubility single metallocene catalyst process.
At present, the relevant supported research report of mono-metallocene is the most, wherein uses the catalyst of spherical magnesium chloride (containing alcohol) load mono-metallocene to have good particle shape, such as PCT Int.Appl.99/21898；US6,455,647；J.Mol.Catal.A2002,188,123；PCT Int.APP1.2004/078804, but containing the components such as alcohol, water, alkoxyl, carrier preparation complexity in carrier；And with Si02Report for carrier is studied also a lot, such as CN1174848；CN1174849；CN1356343；US4,808,561；US5,026,797；US5,763,543；US5,661,098；But needing to use substantial amounts of alkyl aluminum in carrier preparation, and the load efficiency of catalyst is relatively low, is still in the course of the polymerization process introduce substantial amounts of MAO, disadvantage mentioned above limits the commercial Application of silica gel load single metallocene catalyst.Also document report is had to use containing carrier loaded mono-metallocene (the Polymer International, 51:417-423,2002 such as magnesium chloride, silica gel；US5962360；CN102336855A), but activity is the lowest, and needs to add substantial amounts of MAO when polymerization.Disadvantage mentioned above limits the commercial Application of silica gel load single metallocene catalyst.
Summary of the invention
One of the object of the invention is to provide the preparation method of a kind of alkylaluminoxane/halogenation alkyl magnesium/chlorination silicon alkyl/silica gel load single metallocene catalyst.
The two of the object of the invention are above-mentioned supported single metallocene catalyst is used for vinyl polymerization or combined polymerization, have high polymerization activity.
A kind of supported single metallocene catalyst for vinyl polymerization of the present invention, this catalyst includes the product of following component:
(1) mono-metallocene compound；
(2) chlorination silicon alkyl；
(3) halogenation alkyl magnesium；
(4) alkylaluminoxane；
(5) silica-gel carrier；
Component (1) described mono-metallocene compound, refers to the mono-metallocene coordination compound shown in formula 1,
Formula 1
In formula 1: M is the transition metal of the 4th race in the periodic table of elements；X1And X2Selected from halogen or unsubstituted aliphatic, aromatics or cyclic group, or a combination thereof.
X3 is selected from substituted or unsubstituted cyclopentadienyl group, indenyl or fluorenyl, at X3On substituent group selected from hydrogen atom or substituted or unsubstituted aliphatic, aromatics or cyclic group, or a combination thereof；X3The most substituted or unsubstituted cyclopentadienyl group, X3On the preferred hydrogen atom of each substituent group, methyl, ethyl, propyl group, normal-butyl, the tert-butyl group or hexyl.
X4For-O-RA、-NH-RA、-PH-RA、-N=RA、-S-RA、-O-Si-RB 3Or-O-C-RB, wherein:
RAIt is substituted or unsubstituted aliphatic, aromatics or cyclic group or a combination thereof, preferably methyl, ethyl, propyl group, normal-butyl, the tert-butyl group, methoxyl group, ethyoxyl, propoxyl group or butoxy；RBSelected from hydrogen atom or substituted or unsubstituted aliphatic, aromatics or cyclic group or a combination thereof；
Component (2) described chlorination alkyl silica modifier refers to compound described in below general formula: ClnSi(R1)4 - n
Wherein R1Represent C1-C20Alkyl, n represents the integer of 1-4,
Component (3) described alkyl magnesium halide refers to compound described in below general formula: X1MgR2
R in formula2Represent C1-C20Alkyl, X1For halogen；
Component (4) described alkylaluminoxane formula is:
Or
Wherein R represents C1-C12Alkyl, a represents the integer of 4-30.
In formula 1, X1And X2Selected from methyl, phenyl, benzyl or halogen.
X3Selected from substituted or unsubstituted cyclopentadienyl group, X3On the preferred hydrogen atom of each substituent group, methyl, ethyl, propyl group, normal-butyl, the tert-butyl group or hexyl.
X4Preferably-O-RAOr-N=RA；And X4It is-O-RATime, RAIt is 2, the dibasic aryl of 6-, RAUpper described substituent group is methyl, ethyl, propyl group, normal-butyl, the tert-butyl group, cyclopenta, cyclohexyl, methoxyl group, ethyoxyl, propoxyl group or butoxy；X4It is-N=RATime, RAIt it is alkyl.
The preferred titanium of central metal M or zirconium.
Component (2) described chlorination silicon alkyl R1Preferably methyl, ethyl, propyl group or phenyl；Concrete such as trim,ethylchlorosilane, chlorotriethyl silane, tri isopropyl chlorosilane, dimethyl ethyl chlorosilane, diethylpropyl chlorosilane, dipropyl methylchlorosilane, dichloro-dimethyl silicon, Dichlorodiethyl silicon, dichlorophenyl silicon, dichloromethyl n-pro-pyl silane, dichloromethyl phenyl silane, trichloromethyl silane, trichloroethyl silane, phenyl trichlorosilane or Silicon chloride. etc., preferably trim,ethylchlorosilane, chlorotriethyl silane, dichloro-dimethyl silicon, Dichlorodiethyl silicon, dichlorophenyl silicon, trichloromethyl silane, trichloroethyl silane and Silicon chloride..
Component (3) the described alkyl magnesium halide preferred chlorine of X1, bromine or iodine, R2Preferably methyl, ethyl, propyl group, butyl, amyl group, hexyl, phenyl, octyl group, decyl or dodecyl；It is chosen in particular from methyl-magnesium-chloride, ethylmagnesium chloride, n-pro-pyl magnesium chloride, isopropylmagnesium chloride, n-butylmagnesium chloride magnesium, tert-butyl group magnesium chloride, isobutyl group magnesium chloride, hexyl magnesium chloride, phenyl-magnesium-chloride, benzylmagnesium chloride, 1-octylmagnesium chloride, 2-aminomethyl phenyl magnesium chloride, 4-aminomethyl phenyl magnesium chloride, methyl-magnesium-bromide, ethylmagnesium bromide, isopropyl magnesium bromide, tert-butyl group magnesium bromide, amyl group magnesium bromide, cyclopenta magnesium bromide, hexyl magnesium bromide, phenyl-magnesium-bromide, heptyl magnesium bromide, 4-methylphenyl magnesium bromide, octyl group magnesium bromide, 2, 6-3,5-dimethylphenyl magnesium bromide, 2, 3-3,5-dimethylphenyl magnesium bromide, 4-n-pro-pyl phenyl-magnesium-bromide, 4-tert-butyl-phenyl magnesium bromide, decyl magnesium bromide, dodecyl bromination magnesium, methylpyridinium iodide magnesium.Preferably methyl-magnesium-chloride, ethylmagnesium chloride, n-pro-pyl magnesium chloride or isopropylmagnesium chloride etc..
The preferred methyl of R in component (4) described alkylaluminoxane, a represents the integer of 10-30.Preferably MAO (MAO) and the MAO (MMAO) of improvement.
Load single metallocene catalyst for ethylene polymerization, ratio between each reactant is in terms of every gram of silica-gel carrier, chloric ether SiClx addition be the addition of 0.01-3mmol alkylaluminoxane be 0.01-30mmol, the addition of alkyl magnesium halide is 0.01-30mmol, and the addition of mono-metallocene compound is 1-1000 μm ol.
In load single metallocene catalyst, the weight content of magnesium is 1-50%, preferably 1-20%, and aluminum weight content is 1-50%, preferably 1-15%, and the weight content of central metal M is 0.01-5%, preferably 0.05-2%.
The preparation method of a kind of supported single metallocene catalyst for vinyl polymerization of the present invention, comprises the steps:
(1) preparation of the silica-gel carrier of chlorination alkyl Si modification: under noble gas such as nitrogen is protected, added by silica-gel carrier in reactor, adds solvent, is dispersed into suspension, adds chlorination alkyl silicon, is warming up to 0-90 DEG C, stirring reaction 3-24 hour；Preferably 20-80 DEG C, stirring reaction 3-6 hour, optimal with 30-60 DEG C.Then washing for several times with solvent, vacuum drying, obtain the silica supports containing chlorination alkyl Si modification of good fluidity, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexamethylene；Preferably toluene or saturated alkane.
(2) preparation of the silica-gel carrier that halogenated alkyl is magnesium-modified: under noble gas such as nitrogen is protected, adds in reactor by the modified silica gel carrier obtained in (1st) step, adds solvent; it is dispersed into suspension; add alkyl magnesium halide, be warming up to 0-90 DEG C, stirring reaction 3-24 hour；Preferably 20-80 DEG C, then washing for several times with solvent, vacuum drying, obtain the silica supports that the halogenated alkyl of good fluidity is magnesium-modified, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexamethylene；Preferably toluene, hexane or both mixture.
(3) preparation of the silica-gel carrier of alkylaluminoxane: under noble gas such as nitrogen is protected; the silica-gel carrier obtained in (2nd) step is added in reactor; add solvent; it is dispersed into suspension; add alkylaluminoxane; it is warming up to 30-90 DEG C; preferably 40-90 DEG C; stirring reaction 3-24 hour; preferably 3-8 hour, then wash for several times with solvent, vacuum drying; obtaining the silica-gel carrier containing alkylaluminoxane of good fluidity, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexamethylene；The preferred toluene of solvent.
(4) preparation of modified silica-gel load single metallocene catalyst: under noble gas such as nitrogen is protected, the silica-gel carrier containing alkylaluminoxane that will prepare in (3rd) step, join and solvent is made serosity, the solution of mono-metallocene compound is slowly dropped in this serosity, at 0-80 DEG C, react 1-120 minute, obtain loading single metallocene catalyst, serosity can be directly used in polyreaction, or gained reactant is removed solvent, washing obtains the solid supported single metallocene catalyst of good fluidity after drying, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexamethylene；The preferred toluene of solvent, hexane or both mixture.
Load single metallocene catalyst for ethylene polymerization of the present invention can be used in different polymerizations, such as gas-phase polymerization and slurry polymerization etc..Can be used for all polymerizations or the copolymerization of alkene, be particularly well-suited to the copolymerization of ethylene homo conjunction or ethylene and other alpha-olefin, wherein alpha-olefin uses propylene, butylene, amylene, hexene, octene, 4-methylpentene-1 etc..
In supported single metallocene catalyst method of the present invention, the catalyst of preparation is used directly for olefinic polymerization, as in gas-phase polymerization process;Can also additional aluminum alkyl catalyst for olefinic polymerization, particularly add in slurry process alkyl aluminum can impurity in removing system, improve polymerization activity to a certain extent, and expensive MAO need not be added and make promoter.
The solvent that wherein polymerization is used is selected from alkane, aromatic hydrocarbon or halogenated hydrocarbons.Preferably a kind of in hexane, pentane, heptane, benzene, toluene, dichloromethane, chloroform, dichloroethanes or their mixture, most preferably a kind of in hexane, toluene, heptane or their mixture.
The load single metallocene catalyst concentration when polymerization is 1 × 10- 8Mol/L～1 × 10- 3Mol/L, preferred concentration range is 1 × 10- 8Mol/L～1 × 10- 5Mol/L.
Polymerization temperature is-78 DEG C-100 DEG C, preferably 20 DEG C-90 DEG C.
Polymerization pressure is 0.01-10.0MPa, preferably 0.01-2.0MPa.
The present invention compared with prior art has the following advantages:
1, modified silica gel carrier preparation method of the present invention is simple, and the catalyst granules form obtained is good, and catalyst particle size is adjustable.
2, in load single metallocene catalyst method of the present invention, the catalyst of preparation has the highest vinyl polymerization catalysis activity.
3, in load single metallocene catalyst method of the present invention, the catalyst of preparation has the copolymerization of good catalyzed ethylene and high alpha-olefin, and Copolymerization activity is high.
4, load single metallocene catalyst of the present invention obtains resin powder for olefinic polymerization and has a good particle shape, and bulk density is high, goes for slurry process and vapor phase method polymerization technique.
Analysis and characterization instrument used in the present invention is as follows:
1, ICP (plasma emission spectrum) characterizes: the percentage by weight of metal in quantitative determination carried catalyst.The P1000 type ICP-AES plasma emission spectrometer that PE company of the instrument selection U.S. produces.
2, polymer molecular weight and the sign of molecular weight distribution: molecular weight and distribution thereof are measured by gel permeation chromatography (GPC), and instrument uses Waters Alliance GPCV2000, and solvent is 1,2,4-trichloro-benzenes, sample concentration is lmg/ml, and solvent flow rate is 1.0ml/min;Measuring temperature is 150 DEG C.Secondary measured by each sample.
3, in polymer, co-monomer content characterizes: in polymer, hexene monomers content is by nuclear-magnetism13C-NMR measures, and instrument uses Bruker AVANCE400, rate of scanning l00.6MHz, and temperature is 398K.Sampling time is 5sec, and time delay is 10sec, scanning times 5000 times.Sample concentration is 10-20mg/ml.
Embodiment
Embodiment 1
(1) preparation of chlorination silicon alkyl/silica-gel carrier
Under nitrogen protection, take dry silica-gel carrier 10.0 grams and add in glass reactor, add 100 milliliters of dried hexanes, be dispersed into suspension, add 1 milliliter of SiCl2(n-Bu)2, start stirring, be warming up to 30 DEG C, react 4 hours, vacuum drying, obtain the pressed powder of good fluidity.
(2) preparation of alkyl magnesium halide/chlorination silicon alkyl/magnesium chloride support
Under nitrogen protection; take above-mentioned modified silica gel carrier 10.0 grams and add in glass reactor; add 100 milliliters of dried toluene; being dispersed into suspension, adding concentration is 2M ethylmagnesium chloride 5ml, starts stirring; it is warming up to 30 DEG C; react 4 hours, vacuum drying, obtain the pressed powder of good fluidity.
(3) preparation of alkylaluminoxane/halogenation alkyl magnesium/chlorination silicon alkyl/magnesium chloride support
Under nitrogen protection; take modified silica gel carrier obtained above 5.0 grams to add in glass reactor, add 60 milliliters of dried toluene, be dispersed into suspension; add MAO (MAO) toluene solution of 18 milliliters of 10wt%; it is warming up to 50 DEG C, stirring reaction 4 hours, then wash three times with 50 milliliters × 3 toluene; then wash with hexane; vacuum drying, obtains the pressed powder of good fluidity, i.e. contains the silica-gel carrier of MAO.
(4) preparation of supported single metallocene catalyst A
Under nitrogen protection, the silica-gel carrier 2.50 grams containing MAO that will be previously obtained, join in glass reactor, add 35 milliliters of dried toluene and make serosity, be dissolved in 0.108 gram of Cp*TiCl in 20 milliliters of toluene2(O-2,6-iPr2C6H3) solution be added drop-wise in reactor, react 30 minutes at 30 DEG C, then with the washing of 35 milliliters of toluene, be vacuum dried, obtain supported late transition metal catalyst A.Characterizing through ICP, in catalyst A, Ti weight content is 0.33%, and Al weight content is 10.20%.
Comparing embodiment 1
(1) preparation of magnesium chloride/silica-gel carrier
Under nitrogen protection; 2g anhydrous magnesium chloride adds 1500 milliliters of dry oxolanes; 13.2g silica gel (GRACE955 is added after starting stirring; under nitrogen; 150 DEG C of roastings 2.5 hours, are warming up to 300 DEG C of roastings 2 hours, then 600 DEG C of roastings 5 hours) react 2 hours at 65 DEG C; evaporation of solvent, obtains white solid powder.White solid powder is vacuum dried 2 hours at 100 DEG C, then is vacuum dried 10 hours at 300 DEG C, obtain the pressed powder of good fluidity, through gas chromatographic analysis, fail oxolane to be detected.
(2) preparation of alkylaluminoxane/magnesium chloride/silica-gel carrier
Under nitrogen protection; take 7.01 grams of magnesium chlorides obtained above/silica-gel carrier to add in glass reactor, add 90 milliliters of dried toluene, be dispersed into suspension; add the MAO(MAO of 40 milliliters of 10wt%) toluene solution; it is warming up to 50 DEG C, stirring reaction 4 hours, then wash three times with 50 milliliters × 3 toluene; then wash with hexane; vacuum drying, obtains the pressed powder of good fluidity, i.e. alkylaluminoxane/magnesium chloride/silica-gel carrier.
(3) preparation of supported single metallocene catalyst A*
Under nitrogen protection, the above-mentioned alkylaluminoxane/silica-gel carrier prepared 2.50 grams is joined in glass reactor, add 25 milliliters of dried toluene and make serosity, be dissolved in 0.108 gram of Cp*TiCl in 20 milliliters of toluene2(O-2,6-iPr2C6H3) solution droplets be added in reactor, react 30 minutes at 30 DEG C, then with the washing of 30 milliliters of toluene, be vacuum dried, obtain supported non-metallocene single site catalysts A*.Characterizing through ICP, in catalyst A*, Ti weight content is 0.33%, and Al weight content is 14.24%, and magnesium weight content is 2.56%.
Embodiment 2
(1) preparation of chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (1), only by SiCl in embodiment 12(n-Bu)2It is changed to SiCl4。
(2), (3), (4) are with (2), (3), (4) preparation method in embodiment 1.
Obtain load metallocene catalyst B.Characterizing through ICP, in catalyst B, Ti weight content is 0.31%, and Al weight content is 11.21%, and magnesium weight content is 2.67%
Embodiment 3
(1) preparation of chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (1).
(2) preparation of halogenation alkyl magnesium/chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (2), only ethylmagnesium chloride in embodiment 1 is changed to ethylmagnesium bromide.
(3), (4) are with (3), (4) preparation method in embodiment 1
Obtain load metallocene catalyst C.Characterizing through ICP, in catalyst C, Ti weight content is 0.29%, and Al weight content is 10.87%, and magnesium weight content is 2.48%
Embodiment 4
(1) preparation of chlorination silicon alkyl/silica-gel carrier
With embodiment 3 step (1), only by SiCl in embodiment 34It is changed to C6H5SiCl3。
(2), (3), (4) are with embodiment 3 step (2), (3), (4) preparation method
Obtain load metallocene catalyst D.Characterizing through ICP, in catalyst D, Ti weight content is 0.30%, and Al weight content is 12.10%, and magnesium weight content is 2.24%
Embodiment 5
(1), (2), (3) are with (1), (2), (3) preparation method in embodiment 2.
(4) preparation of supported metallocene catalyst E
With embodiment 1 step (3), only by 0.108 gram of Cp*TiCl in embodiment 12(O-2,6-iPr2C6H3) replace with 0.081 gram of CpTiCl2(N=CtBu2), obtain load metallocene catalyst E.Characterizing through ICP, in catalyst E, Ti weight content is 0.29%, and Al weight content is 9.92%, and magnesium weight content is 2.48%.
High pressure ethylene polymerization is tested
High pressure ethylene polymerization experimentation is as follows:
In the rustless steel polymerization autoclave of 2 liters, three times are respectively replaced with nitrogen and ethylene, it is subsequently adding 1000 milliliters of hexane solvents, addition along with hexane, triethyl aluminum (TEA) hexane solution of 2 milliliter of 1 mol/L and the 1-hexene of requirement are added, is subsequently added into the load single metallocene catalyst 50-100 milligram that above-described embodiment prepares, is warming up to 80 DEG C, pressure rises to and maintains 1.0MPa, reacts 1 hour.After polyreaction terminates, cooling, collect polyethylene particle powder, weigh.
Concrete polymerization result is shown in Table 1.
Table 1, supported single metallocene catalyst polymerization result
Claims (10)
1. the supported single metallocene catalyst for vinyl polymerization, it is characterised in that under this catalyst includes
The product of row component:
(1) mono-metallocene compound；
(2) chlorination silicon alkyl or Silicon chloride. modifying agent；
(3) halogenation alkyl magnesium；
(4) alkylaluminoxane；
(5) silica-gel carrier；
Component (1) described mono-metallocene compound, refers to the mono-metallocene coordination compound shown in formula 1,
In formula 1: M is the transition metal of the 4th race in the periodic table of elements；X1And X2Selected from halogen；X3It is to take
Generation or unsubstituted cyclopentadienyl group, indenyl or fluorenyl, at X3On substituent group selected from hydrogen atom or replacement or
Unsubstituted aliphatic, aromatics or cyclic group, or a combination thereof；
X4For-O-RAOr-N=RA, wherein:
RAIt is substituted or unsubstituted aliphatic, aromatics or cyclic group or a combination thereof；
Component (2) described chlorination silicon alkyl or Silicon chloride. modifying agent refer to compound described in below general formula:
ClnSi(R1)4-n
Wherein R1Represent C1-C20Alkyl, n represents the integer of 1-4,
Component (3) described halogenation alkyl magnesium refers to compound described in below general formula: X1MgR2
R in formula2Represent C1-C20Alkyl, X1For halogen；
Component (4) described alkylaluminoxane formula is:
Wherein R represents C1-C12Alkyl, a represents the integer of 4-30.
Supported single metallocene catalyst for vinyl polymerization the most according to claim 1, it is characterised in that
Described mono-metallocene coordination compound, central metal M is titanium or zirconium, X3It it is substituted or unsubstituted ring penta 2
Thiazolinyl, X3On each substituent group selected from hydrogen atom, methyl, ethyl, propyl group, normal-butyl, the tert-butyl group or oneself
Base.
Supported single metallocene catalyst for vinyl polymerization the most according to claim 1, it is characterised in that
Described mono-metallocene coordination compound, X4It is-O-RATime, RAIt is 2, the dibasic aryl of 6-；X4It is-N=RA
Time, RAIt it is alkyl.
Supported single metallocene catalyst for vinyl polymerization the most according to claim 1, RATake described on
Dai Ji is methyl, ethyl, propyl group, normal-butyl, the tert-butyl group, methoxyl group, ethyoxyl, propoxyl group or fourth oxygen
Base.
Supported single metallocene catalyst for vinyl polymerization the most according to claim 1, it is characterised in that
Described chlorination silicon alkyl, wherein R1For methyl, ethyl, propyl group or phenyl；Described alkylaluminoxane,
For MAO or the MAO of improvement.
Supported single metallocene catalyst for vinyl polymerization the most according to claim 1, it is characterised in that
Ratio between each reactant in terms of every gram of silica-gel carrier, chlorination silicon alkyl or the addition of Silicon chloride. modifying agent
Amount is 0.01-3mmol, and the addition of halogenation alkyl magnesium is 0.01-30mmol, the addition of alkylaluminoxane
Amount 0.01-30mmol, the addition of mono-metallocene compound is 1-1000 μm ol.
Supported single metallocene catalyst for vinyl polymerization the most according to claim 1, it is characterised in that
In supported single metallocene catalyst, the preferred 1-20% of weight content of magnesium, aluminum weight content is 1-15%；
The weight content of central metal M is 0.05-2%.
8. the preparation method of the supported single metallocene catalyst for vinyl polymerization that one of claim 1-7 is described,
It is characterized in that, comprise the following steps:
The first step: under inert gas shielding, silica-gel carrier exists with chlorination silicon alkyl or Silicon chloride. modifying agent
0-90 DEG C is reacted 3-24 hour；
Second step: under inert gas shielding, by first step gained modified silica-gel with halogenation alkyl magnesium at 0-90 DEG C
React 3-24 hour；
3rd step: under inert gas shielding, by the second step gained halogenation alkyl same alkyl aluminum of magnesium-modified silica gel
Oxygen alkane reacts 3-24 hour at 0-90 DEG C；
4th step: under inert gas shielding, by the 3rd step gained same Dan Maojin of alkylaluminoxane modified silica-gel
Belong to compound to react 0.5-24 hour at 0-90 DEG C；
The dispersant of above-mentioned reaction is toluene, benzene, dimethylbenzene, hexane, heptane or hexamethylene.
The preparation method of the supported single metallocene catalyst for vinyl polymerization the most according to claim 8,
It is characterized in that, the first step react in, reaction temperature is 20-60 DEG C, dispersant used be toluene, oneself
Alkane, heptane or hexamethylene；In second step reacts, reaction temperature is 20-80 DEG C, and dispersant used is toluene
Or hexane；In three-step reaction, reaction temperature is 20-90 DEG C, and dispersant used is toluene；The 4th
In step reaction, reaction dispersant is toluene or hexane.
10. in claim 1-7, the supported single metallocene catalyst for vinyl polymerization described in any one exists
Application in olefinic polymerization.
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