CN104059174A - Supported single metallocene catalyst used for ethylene polymerization - Google Patents
Supported single metallocene catalyst used for ethylene polymerization Download PDFInfo
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Abstract
The invention relates to a supported single metallocene catalyst used for ethylene polymerization and a preparation method thereof. The catalyst comprises a single metallocene compound, a chlorinated alkyl silicon modifier, a halogenated alkyl magnesium modifier, alkyl aluminoxane and a silica gel carrier reaction product; the preparation method comprises the following steps: 1) preparation of a chlorinated hydroxyl silicon modified silica gel carrier, 2) preparation of a halogenated alkyl magnesium modified silica gel carrier, 3)preparation of an alkyl aluminoxane modified silica gel carrier, and 4)preparation of the silica gel supported single metallocene catalyst; and the obtained single metallocene catalyst has high polymerization activity for catalyzing vinyl polymerization or copolymerization. The preparation method of the silica gel carrier is simple, the obtained supported catalyst particles have good morphology and have adjustable size.
Description
Technical field
The present invention relates to a kind of preparation method of modified silica-gel load single metallocene catalyst, and the application of gained catalyzer aspect olefinic polymerization.
Technical background
The Application and Development of single metallocene catalyst is after traditional Ziegler-Natta catalyst, the another important breakthrough, the particularly eighties in olefin polymerization catalysis field, the people such as Kaminsky and Sinn (Angew.Chem., 1980,19,390; Adv.Organoment.Chem., 1980,18,99) develop efficient promotor methylaluminoxane (MAO), make the research of single metallocene catalyst enter into a fast-developing stage.Due to homogeneous phase single metallocene catalyst, will to reach the required MAO consumption of high reactivity large, production cost is high, and the polymkeric substance obtaining is amorphous, cannot in widely used slurry process or gas phase polymerization technique, use, the effective way that overcomes the problems referred to above is exactly that solubility single metallocene catalyst loadization is processed.
At present, relevant mono-metallocene loadization research report is very many, wherein adopts the catalyzer of spherical magnesium chloride (containing alcohol) load mono-metallocene to have good particle form, as PCT Int.Appl.99/21898; US6,455,647; J.Mol.Catal.A2002,188,123; PCT Int.APP1.2004/078804, but in carrier, contain the components such as alcohol, water, alkoxyl group, carrier preparation is complicated; And with Si0
2for the report research of carrier also a lot, as CN1174848; CN1174849; CN1356343; US4,808,561; US5,026,797; US5,763,543; US5,661,098; But in carrier preparation, need to use a large amount of aluminum alkylss, and the load efficiency of catalyzer is lower, in polymerization process, still will introduce a large amount of methylaluminoxane, above drawbacks limit the industrial application of silica gel load single metallocene catalyst.Also there is bibliographical information to use and contain carrier loaded mono-metallocene (Polymer International, 51:417-423,2002 such as magnesium chloride, silica gel; US5962360; CN102336855A), but activity is very low, and need to add a large amount of MAO when polymerization.Above drawbacks limit the industrial application of silica gel load single metallocene catalyst.
Summary of the invention
One of the object of the invention is to provide a kind of preparation method of alkylaluminoxane/halogenation alkyl magnesium/chlorination silicon alkyl/silica gel load single metallocene catalyst.
Two of the object of the invention is by above-mentioned load single metallocene catalyst, for vinyl polymerization or copolymerization, to have high polymerization activity.
A kind of load single metallocene catalyst for vinyl polymerization of the present invention, this catalyzer comprises the reaction product of following component:
(1) mono-metallocene compound;
(2) chlorination silicon alkyl;
(3) halogenation alkyl magnesium;
(4) alkylaluminoxane;
(5) silica-gel carrier;
The described mono-metallocene compound of component (1), refers to the mono-metallocene title complex shown in general formula 1,
general formula 1
In general formula 1: M is the transition metal of periodic table of elements Zhong 4 families; X
1and X
2be selected from halogen or unsubstituted aliphatics, aromatics or cyclic group, or its combination.
X3 is selected from and replaces or unsubstituted cyclopentadienyl, indenyl or fluorenyl, at X
3on substituting group be selected from hydrogen atom or replacement or unsubstituted aliphatics, aromatics or cyclic group, or its combination; X
3preferably replace or unsubstituted cyclopentadienyl X
3on the preferred hydrogen atom of each substituting group, methyl, ethyl, propyl group, normal-butyl, the tertiary butyl or hexyl.
X
4for-O-R
a,-NH-R
a,-PH-R
a,-N=R
a,-S-R
a,-O-Si-R
b 3or-O-C-R
b, wherein:
R
ato replace or unsubstituted aliphatics, aromatics or cyclic group or its combination, preferable methyl, ethyl, propyl group, normal-butyl, the tertiary butyl, methoxyl group, oxyethyl group, propoxy-or butoxy; R
bbe selected from hydrogen atom or replacement or unsubstituted aliphatics, aromatics or cyclic group or its combination;
The described chlorination alkyl of component (2) silica modifier refers to compound: Cl described in following general formula
nsi (R
1)
4-n
R wherein
1represent C
1-C
20alkyl, n represents the integer of 1-4,
The described alkyl magnesium halide of component (3) refers to compound: X described in following general formula
1mgR
2
R in formula
2represent C
1-C
20alkyl, X
1for halogen;
The described alkylaluminoxane general formula of component (4) is:
or
Wherein R represents C
1-C
12alkyl, a represents the integer of 4-30.
In general formula 1, X
1and X
2be selected from methyl, phenyl, benzyl or halogen.
X
3be selected from and replace or unsubstituted cyclopentadienyl, X
3on the preferred hydrogen atom of each substituting group, methyl, ethyl, propyl group, normal-butyl, the tertiary butyl or hexyl.
X
4preferably-O-R
aor-N=R
a; And X
4be-O-R
atime, R
athe dibasic aryl of 2,6-, R
athe above substituting group is methyl, ethyl, propyl group, normal-butyl, the tertiary butyl, cyclopentyl, cyclohexyl, methoxyl group, oxyethyl group, propoxy-or butoxy; X
4be-N=R
atime, R
ait is alkyl.
The preferred titanium of central metal M or zirconium.
The described chlorination silicon alkyl of component (2) R
1preferable methyl, ethyl, propyl group or phenyl, concrete as trimethylchlorosilane, chlorotriethyl silane, tri isopropyl chlorosilane, dimethyl ethyl chlorosilane, diethyl propyl chloride silane, dipropyl methyl chlorosilane, dichloro-dimethyl silicon, Dichlorodiethyl silicon, dichloro phenylbenzene silicon, dichloromethyl n-propyl silane, dichloromethyl phenyl silane, trichloromethyl silane, trichloroethyl silane, phenyl-trichloro-silicane or silicon tetrachloride etc., preferred trimethylchlorosilane, chlorotriethyl silane, dichloro-dimethyl silicon, Dichlorodiethyl silicon, dichloro phenylbenzene silicon, trichloromethyl silane, trichloroethyl silane and silicon tetrachloride.
The preferred chlorine of the described alkyl magnesium halide X1 of component (3), bromine or iodine, R
2preferable methyl, ethyl, propyl group, butyl, amyl group, hexyl, phenyl, octyl group, decyl or dodecyl, specifically be selected from methylmagnesium-chloride, ethylmagnesium chloride, n-propyl chlorination magnesium, isopropylmagnesium chloride, normal-butyl chlorination magnesium, tertiary butyl chlorination magnesium, isobutyl-chlorination magnesium, hexyl magnesium chloride, phenyl-magnesium-chloride, benzylmagnesium chloride, 1-octyl group magnesium chloride, 2-aminomethyl phenyl magnesium chloride, 4-aminomethyl phenyl magnesium chloride, methyl-magnesium-bromide, ethylmagnesium bromide, isopropyl magnesium bromide, tertiary butyl bromination magnesium, amyl group magnesium bromide, cyclopentyl bromination magnesium, hexyl magnesium bromide, phenyl-magnesium-bromide, heptyl magnesium bromide, 4-aminomethyl phenyl magnesium bromide, octyl group magnesium bromide, 2, 6-3,5-dimethylphenyl magnesium bromide, 2, 3-3,5-dimethylphenyl magnesium bromide, 4-n-propyl phenyl magnesium bromide, 4-tert-butyl-phenyl magnesium bromide, decyl magnesium bromide, dodecyl bromination magnesium, methyl magnesium iodide.Preferable methyl magnesium chloride, ethylmagnesium chloride, n-propyl chlorination magnesium or isopropylmagnesium chloride etc.
R preferable methyl in the described alkylaluminoxane of component (4), a represents the integer of 10-30.Preferable methyl aikyiaiurnirsoxan beta (MAO) and improved methylaluminoxane (MMAO).
Load single metallocene catalyst for ethylene polymerization, ratio between each reactant is in every gram of silica-gel carrier, chloric ether SiClx add-on is that the add-on of 0.01-3mmol alkylaluminoxane is 0.01-30mmol, the add-on of alkyl magnesium halide is 0.01-30mmol, and the add-on of mono-metallocene compound is 1-1000 μ mol.
In load single metallocene catalyst, the weight content of magnesium is 1-50%, preferred 1-20%, and aluminium weight content is 1-50%, preferred 1-15%, the weight content of central metal M is 0.01-5%, preferably 0.05-2%.
The preparation method of a kind of load single metallocene catalyst for vinyl polymerization of the present invention, comprises the steps:
(1) preparation of the silica-gel carrier of chlorination silicon alkyl modification:, as under nitrogen protection silica-gel carrier is added in reactor at rare gas element, add solvent, be dispersed into suspension, add chlorination alkyl silicon, be warming up to 0-90 ℃, stirring reaction 3-24 hour; Preferred 20-80 ℃, stirring reaction 3-6 hour, with 30-60 ℃ of the best.Then with solvent wash for several times, vacuum-drying, obtains the silica supports that contains the modification of chlorination alkyl silicon of good fluidity, and described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexanaphthene; Preferred toluene or saturated alkane.
(2) preparation of the magnesium-modified silica-gel carrier of halogenated alkyl:, as under nitrogen protection the modified silica gel carrier obtaining in (1) step is added in reactor at rare gas element, add solvent, be dispersed into suspension, add alkyl magnesium halide, be warming up to 0-90 ℃, stirring reaction 3-24 hour; Preferred 20-80 ℃, then with solvent wash for several times, vacuum-drying, obtains the magnesium-modified silica supports of halogenated alkyl of good fluidity, and described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexanaphthene; Preferred toluene, hexane or both mixtures.
(3) preparation of the silica-gel carrier of alkylaluminoxane: at rare gas element as under nitrogen protection, the silica-gel carrier obtaining in (2) step is added in reactor, add solvent, be dispersed into suspension, add alkylaluminoxane, be warming up to 30-90 ℃, preferred 40-90 ℃, stirring reaction 3-24 hour, preferred 3-8 hour, then with solvent wash for several times, vacuum-drying, obtain the silica-gel carrier that contains alkylaluminoxane of good fluidity, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexanaphthene; The preferred toluene of solvent.
(4) preparation of modified silica-gel load single metallocene catalyst: at rare gas element as under nitrogen protection, the silica-gel carrier that contains alkylaluminoxane that will prepare in (3) step, join and in solvent, make slurries, the solution of mono-metallocene compound is slowly added drop-wise in these slurries, at 0-80 ℃, reaction 1-120 minute, obtain load single metallocene catalyst, slurries can be directly used in to polyreaction, or gained reactant is removed to desolventizing, after washing is dry, obtain the solid supported single metallocene catalyst of good fluidity, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexanaphthene, the preferred toluene of solvent, hexane or both mixtures.
Load single metallocene catalyst for ethylene polymerization of the present invention can be used in different polymerization processs, as vapour phase polymerization and slurry polymerization etc.The equal polymerization or the copolymerization that can be used for alkene, be specially adapted to that ethylene homo closes or the copolymerization of ethene and other alpha-olefin, and wherein alpha-olefin adopts propylene, butylene, amylene, hexene, octene, 4-methylpentene-1 etc.
The catalyzer of preparing in load single metallocene catalyst method of the present invention can be directly used in olefinic polymerization, as in gas-phase polymerization process; Also can be used for olefinic polymerization by additional aluminum alkyl catalyst, particularly in slurry process, add aluminum alkyls can remove the impurity in system, improve to a certain extent polymerization activity, and need not add expensive MAO to make promotor.
The solvent that wherein polymerization is used is selected from alkane, aromatic hydrocarbon or halohydrocarbon.Preferably a kind of in hexane, pentane, heptane, benzene, toluene, methylene dichloride, chloroform, ethylene dichloride or their mixture, most preferably be a kind of in hexane, toluene, heptane or their mixture.
The concentration of load single metallocene catalyst 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 ℃-100 ℃, preferably 20 ℃-90 ℃.
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 granules of catalyst form obtaining is good, and catalyst particle size is adjustable.
2, the catalyzer of preparing in load single metallocene catalyst method of the present invention has very high vinyl polymerization catalytic activity.
3, the catalyzer of preparing in load single metallocene catalyst method of the present invention has good catalyzed ethylene and the copolymerization of high alpha-olefin, and Copolymerization activity is high.
4, load single metallocene catalyst of the present invention obtains resin powder and has good particle form for olefinic polymerization, and tap density is high, goes for slurry process and vapor phase process polymerization technique.
The analysis and characterization instrument using in the present invention is as follows:
1, ICP (plasma emission spectrum) characterizes: the weight percent of metal in quantitative assay carried catalyst.The P1000 type ICP-AES plasma emission spectrometer that instrument selection U.S. PE company produces.
2, the sign of polymericular weight and molecular weight distribution: molecular weight and distribution thereof are measured by gel permeation chromatography (GPC), instrument adopts Waters Alliance GPCV2000, and solvent is 1; 2; 4-trichlorobenzene, sample concentration is lmg/ml, solvent flow rate is 1.0ml/min; Measuring temperature is 150 ℃.Each sample measurement secondary.
3, in polymkeric substance, co-monomer content characterizes: in polymkeric substance, hexene monomer content is by nuclear-magnetism
13c-NMR measures, and instrument adopts Bruker AVANCE400, sweep rate l00.6MHz, and temperature is 398K.Sampling time is 5sec, and be 10sec time of lag, 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, get 10.0 grams of dry silica-gel carriers and add in glass reactor, add 100 milliliters of dried hexanes, be dispersed into suspension, add 1 milliliter of SiCl
2(n-Bu)
2, start stirring, be warming up to 30 ℃, to react 4 hours, vacuum-drying, obtains the pressed powder of good fluidity.
(2) preparation of alkyl magnesium halide/chlorination silicon alkyl/magnesium chloride support
Under nitrogen protection; getting 10.0 grams of above-mentioned modified silica gel carriers adds in glass reactor; add 100 milliliters of dried toluene; be dispersed into suspension, adding concentration is 2M ethylmagnesium chloride 5ml, starts stirring; be warming up to 30 ℃; react 4 hours, vacuum-drying, obtains the pressed powder of good fluidity.
(3) preparation of alkylaluminoxane/halogenation alkyl magnesium/chlorination silicon alkyl/magnesium chloride support
Under nitrogen protection; get 5.0 grams of modified silica gel carriers obtained above and add in glass reactor, add 60 milliliters of dried toluene, be dispersed into suspension; MAO (methylaluminoxane) toluene solution that adds 18 milliliters of 10wt%; be warming up to 50 ℃, stirring reaction 4 hours, then uses 50 milliliters * 3 toluene wash three times; then with hexane, wash; vacuum-drying, obtains the pressed powder of good fluidity, contains the silica-gel carrier of methylaluminoxane.
(4) preparation of load single metallocene catalyst A
Under nitrogen protection, by 2.50 grams of the silica-gel carriers that contains methylaluminoxane obtaining above, join in glass reactor, add 35 milliliters of dried toluene to make slurries, will be dissolved in 0.108 gram of Cp*TiCl in 20 milliliters of toluene
2(O-2,6-
ipr
2c
6h
3) solution be added drop-wise in reactor, 30 ℃ reaction 30 minutes, then use 35 milliliters of toluene wash, vacuum-drying, obtains load post-transition metal catalyst A.Through ICP, characterize, in catalyst A, Ti weight content is that 0.33%, Al weight content is 10.20%.
Comparing embodiment 1
(1) preparation of magnesium chloride/silica-gel carrier
Under nitrogen protection; in 2g Magnesium Chloride Anhydrous, add 1500 milliliters of dry tetrahydrofuran (THF)s; after starting stirring, add 13.2g silica gel (GRACE955; under nitrogen; 150 ℃ of roastings 2.5 hours, are warming up to 300 ℃ of roastings 2 hours, then 600 ℃ of roastings 5 hours) 65oC reaction 2 hours; evaporation, except desolventizing, obtains white solid powder.By the vacuum-drying 2 hours under 100oC of white solid powder, then vacuum-drying 10 hours under 300oC, obtain the pressed powder of good fluidity, through gas chromatographic analysis, fail to detect tetrahydrofuran (THF).
(2) preparation of alkylaluminoxane/magnesium chloride/silica-gel carrier
Under nitrogen protection; get 7.01 grams of magnesium chloride/silica-gel carriers obtained above and add in glass reactor, add 90 milliliters of dried toluene, be dispersed into suspension; the MAO(methylaluminoxane that adds 40 milliliters of 10wt%) toluene solution; be warming up to 50 ℃, stirring reaction 4 hours, then uses 50 milliliters * 3 toluene wash three times; then with hexane, wash; vacuum-drying, obtains the pressed powder of good fluidity, i.e. alkylaluminoxane/magnesium chloride/silica-gel carrier.
(3) preparation of load single metallocene catalyst A*
Under nitrogen protection, 2.50 grams of the above-mentioned alkylaluminoxane/silica-gel carriers preparing are joined in glass reactor, add 25 milliliters of dried toluene to make slurries, will be dissolved in 0.108 gram of Cp*TiCl in 20 milliliters of toluene
2(O-2,6-
ipr
2c
6h
3) solution droplets be added in reactor, 30 ℃ reaction 30 minutes, then use 30 milliliters of toluene wash, vacuum-drying, obtains supported non-metallocene single site catalysts A*.Through ICP, characterize, in catalyst A *, Ti weight content is that 0.33%, 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 1
2(n-Bu)
2be changed to SiCl
4.
(2), (3), (4) are with (2), (3), (4) preparation method in embodiment 1.
Obtain load metallocene catalyst B.Through ICP, characterize, in catalyst B, Ti weight content is that 0.31%, 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.Through ICP, characterize, in catalyzer C, Ti weight content is that 0.29%, 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 steps (1), only by SiCl in embodiment 3
4be changed to C
6h
5siCl
3.
(2), (3), (4) are with embodiment 3 steps (2), (3), (4) preparation method
Obtain load metallocene catalyst D.Through ICP, characterize, in catalyzer D, Ti weight content is that 0.30%, 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 1
2(O-2,6-
ipr
2c
6h
3) replace with 0..081 gram of CpTiCl
2(N=C
tbu
2), obtain load metallocene catalyst E.Through ICP, characterize, in catalyzer E, Ti weight content is that 0.29%, Al weight content is 9.92%, and magnesium weight content is 2.48%.
High-pressure ethylene polymerization experiment
High-pressure ethylene polymerization experiment process is as follows:
In the stainless steel polymermaking autoclave of 2 liters, with nitrogen and ethene, respectively replace three times, then add 1000 milliliters of hexane solvents, along with adding of hexane, the 1-hexene of the triethyl aluminum of 2 milliliter of 1 mol/L (TEA) hexane solution and requirement is added, and the load single metallocene catalyst 50-100 milligram that then adds above-described embodiment to make, is warming up to 80 ℃, pressure is risen to and maintained 1.0MPa, react 1 hour.After polyreaction finishes, cooling, collects polyethylene particle powder, weighs.
Concrete polymerization result is listed in table 1.
Table 1, load single metallocene catalyst polymerization result
Claims (10)
1. for a load single metallocene catalyst for vinyl polymerization, it is characterized in that, this catalyzer comprises the reaction product of following component:
(1) mono-metallocene compound;
(2) chlorination silicon alkyl;
(3) halogenation alkyl magnesium;
(4) alkylaluminoxane;
(5) silica-gel carrier;
The described mono-metallocene compound of component (1), refers to the mono-metallocene title complex shown in general formula 1,
general formula 1
In general formula 1: M is the transition metal of periodic table of elements Zhong 4 families; X
1and X
2be selected from halogen or unsubstituted aliphatics, aromatics or cyclic group, or its combination; X
3to replace or unsubstituted cyclopentadienyl, indenyl or fluorenyl, at X
3on substituting group be selected from hydrogen atom or replacement or unsubstituted aliphatics, aromatics or cyclic group, or its combination;
X
4for-O-R
a,-NH-R
a,-PH-R
a,-N=R
a,-S-R
a,-O-Si-R
b 3or-O-C-R
b 3, wherein:
R
ato replace or unsubstituted aliphatics, aromatics or cyclic group or its combination; R
bbe selected from hydrogen atom or replacement or unsubstituted aliphatics, aromatics or cyclic group or its combination;
The described chlorination alkyl of component (2) silica modifier refers to compound: Cl described in following general formula
nsi (R
1)
4-n
R wherein
1represent C
1-C
20alkyl, n represents the integer of 1-4,
The described halogenation alkyl of component (3) magnesium refers to compound: X described in following general formula
1mgR
2
R in formula
2represent C
1-C
20alkyl, X
1for halogen;
The described alkylaluminoxane general formula of component (4) is:
or
Wherein R represents C
1-C
12alkyl, a represents the integer of 4-30.
2. the load single metallocene catalyst for vinyl polymerization according to claim 1, is characterized in that, described mono-metallocene title complex, and central metal M is titanium or zirconium, X
1and X
2be selected from methyl, phenyl, benzyl or halogen; X
3that replace or unsubstituted cyclopentadienyl, X
3on each substituting group be selected from hydrogen atom, methyl, ethyl, propyl group, normal-butyl, the tertiary butyl or hexyl.
3. the load single metallocene catalyst for vinyl polymerization according to claim 1, is characterized in that, described mono-metallocene title complex, X
4be-O-R
aor-N=R
a; And X
4be-O-R
atime, R
ait is the dibasic aryl of 2,6-; X
4be-N=R
atime, R
ait is alkyl.
4. the load single metallocene catalyst for vinyl polymerization according to claim 1, R
athe above substituting group is methyl, ethyl, propyl group, normal-butyl, the tertiary butyl, methoxyl group, oxyethyl group, propoxy-or butoxy.
5. the load single metallocene catalyst for vinyl polymerization according to claim 1, is characterized in that, described chlorination silicon alkyl, wherein R
1for methyl, ethyl, propyl group or phenyl; Described alkylaluminoxane is methylaluminoxane (MAO) or improved methylaluminoxane (MMAO).
6. the load single metallocene catalyst for vinyl polymerization according to claim 1, it is characterized in that, ratio between each reactant is in every gram of silica-gel carrier, chloric ether SiClx add-on is 0.01-3mmol, the add-on of halogenation alkyl magnesium is 0.01-30mmol, the add-on 0.01-30mmol of alkylaluminoxane, the add-on of mono-metallocene compound is 1-1000 μ mol.
7. the load single metallocene catalyst for vinyl polymerization according to claim 1, is characterized in that, in load single metallocene catalyst, and the preferred 1-20% of the weight content of magnesium, aluminium weight content is 1-15%; The weight content of central metal M is 0.05-2%.
8. the preparation method of the load single metallocene catalyst for vinyl polymerization described in one of claim 1-7, is characterized in that, comprises the following steps:
The first step: under protection of inert gas, silica-gel carrier reacts 3-24 hour with chlorination silicon alkyl at 0-90 ℃;
Second step: under protection of inert gas, the first step gained modified silica-gel is reacted to 3-24 hour with halogenation alkyl magnesium at 0-90 ℃;
The 3rd step: under protection of inert gas, the magnesium-modified silica gel of second step gained halogenation alkyl is reacted to 3-24 hour with alkylaluminoxane at 0-90 ℃;
The 4th step: under protection of inert gas, the 3rd step gained alkylaluminoxane modified silica-gel is reacted to 0.5-24 hour with mono-metallocene compound at 0-90 ℃;
The dispersion agent of above-mentioned reaction is toluene, benzene, dimethylbenzene, hexane, heptane or hexanaphthene.
9. the preparation method of the load single metallocene catalyst for vinyl polymerization according to claim 8, is characterized in that, in the first step reaction, temperature of reaction is 20-60 ℃, and solvent for use is toluene or saturated alkane; In second step reaction, temperature of reaction is 20-80 ℃, and dispersion agent used is toluene, hexane or both mixtures; In three-step reaction, temperature of reaction is 20-90 ℃, and dispersion agent used is toluene; In four-step reaction, reaction dispersion agent is toluene, hexane or both mixtures.
In claim 1-7 the load single metallocene catalyst for vinyl polymerization described in any one in the application of olefinic polymerization.
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| Title |
|---|
| 王亚明、李传峰: "以硅胶为载体的茂金属催化剂研究进展", 《现代塑料加工应用》, vol. 16, no. 1, 28 February 2004 (2004-02-28), pages 43 - 46 * |
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