CN101817893A - Method for preparing magnesium chloride loaded late transition metal catalyst - Google Patents
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- CN101817893A CN101817893A CN 200910078595 CN200910078595A CN101817893A CN 101817893 A CN101817893 A CN 101817893A CN 200910078595 CN200910078595 CN 200910078595 CN 200910078595 A CN200910078595 A CN 200910078595A CN 101817893 A CN101817893 A CN 101817893A
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Abstract
The invention discloses a method for preparing a loaded late transition metal catalyst by taking magnesium chloride as a carrier, which comprises the following steps of: (1), preparation of a magnesium chloride carrier; (2), preparation of a magnesium chloride carrier of alkyl aluminoxane; and (3), preparation of a magnesium chloride loaded late transition metal catalyst, wherein the magnesium chloride carrier is prepared by adopting a spraying method in which tetrahydrofuran is taken as a solvent. The obtained loaded late transition metal catalyst catalyzes ethylene homopolymerization or copolymerization with high polymerization activity. In the method, the preparation of the magnesium chloride carrier is simple; and the obtained loaded catalyst granule has good shape and adjustable size.
Description
Technical field
The present invention relates to a kind of preparation method of magnesium chloride loaded late transition metal catalyst, and the application of gained catalyzer aspect olefinic polymerization.
Background technology
In the evolution of olefin polymerization catalysis, the late transition metal catalyst that middle nineteen nineties in last century is found has obtained great development and concern.Particularly Ni, Pd and Fe, Co diimine catalysts system (WO9623010, WO9827124), nickel, palladium series catalyst can generate the High molecular weight polyethylene of the cladodification or even the super cladodification of narrow molecular weight distributions by ethylene homo, and iron, cobalt series catalyst generate the linear polyethylene of wide molecular weight distribution.But olefinic polymerization is to carry out in homogeneous phase, and the polymkeric substance that obtains is metamict, can't use on the slurry process of widespread use or gas phase polymerization technology.
At present, in the load research of late transition metal catalyst, everybody adopts the silica gel with good particle form basically is carrier, in WO 01/32723, use a kind of silica gel activating Fe series catalysts that has supported aluminum alkyls as Keng-Yu Shih, can use aluminum alkyls to be promotor, have good catalytic activity.Although also more (the PCT Int.Appl.99/21898 of research report for magnesium chloride compound load single site catalysts; US6,455,647; J.Mol.Catal.A 2002,188, and 123; PCT Int.Appl.2004/078804), but the cost height of preparing carriers and catalyst cupport, and the carrier particle shape is poor, uncontrollable; Though use the catalyzer that spherical magnesium chloride can proof load to have good particle form, contain components such as alcohol, water, alkoxyl group in the carrier, the preparing carriers complexity, above drawbacks limit the industrial application of magnesium chloride load single site catalysts.
Summary of the invention
One of the object of the invention is to provide a kind of magnesium chloride support preparation method of loaded late transition metal catalyst, and the magnesium chloride support that obtains with this method has good particle form.
Two of the object of the invention is to provide a kind of preparation method of the load post-transition metal catalyst with the magnesium chloride support preparation.
Three of the object of the invention is above-mentioned load post-transition metal catalyst is used for vinyl polymerization or copolymerization, has high polymerization activity.
The method of a kind of magnesium chloride loaded late transition metal catalyst of the present invention comprises the steps:
(1) magnesium chloride support preparation: under protection of inert gas; under the room temperature; in reactor, add a certain amount of Magnesium Chloride Anhydrous; add an amount of tetrahydrofuran (THF) then; stir and heat up its dissolving; use airtight spray-dryer to prepare spherical magnesium chloride/tetrahydrofuran (THF) particle, the D of grain diameter then
50It is 10～100 microns.With spherical magnesium chloride/tetrahydrofuran (THF) particle vacuum-drying a few hours under heating condition, remove tetrahydrofuran (THF), through gas chromatographic analysis, do not detect tetrahydrofuran (THF) (＜0.1%wt), the spheroidal particle of the good fluidity that obtains is magnesium chloride support.
(2) preparation of the magnesium chloride support of alkylaluminoxane: under rare gas element such as nitrogen protection; the magnesium chloride support that obtains in (1) step is added in the reactor; add solvent; be dispersed into suspension; add alkylaluminoxane; be warming up to 30～80 ℃; preferred 40～60 ℃; stirring reaction 3～6 hours, then for several times with solvent wash, vacuum-drying; obtain the magnesium chloride support that contains alkylaluminoxane of good fluidity; wherein solvent can adopt aromatic hydrocarbons or aliphatic hydrocarbon, as toluene, benzene, dimethylbenzene, hexane, heptane, hexanaphthene etc., and preferred toluene.
(3) preparation of magnesium chloride loaded late transition metal catalyst: under rare gas element such as nitrogen protection; the magnesium chloride support that contains alkylaluminoxane that will prepare in (2) step; join and make slurries in the solvent; the solution of late transition metal catalyst precursor slowly is added drop-wise in these slurries; under 0～40 ℃; reacted 1～120 minute; can obtain the supported non-metallocene single site catalysts; slurries can be directly used in polyreaction; or the gained reactant removed desolvate; obtain the solid supported post-transition metal catalyst of good fluidity after the washing drying; described solvent is a toluene; benzene; dimethylbenzene; hexane; heptane; hexanaphthenes etc. are selected toluene; hexane or both mixture the bests.
Above-mentioned alkylaluminoxane general structure is:
Wherein R represents C
1～C
12Alkyl is preferably methyl, a represents 4～30 integer, is preferably 10～30 integer.Alkylaluminoxane preferable methyl aikyiaiurnirsoxan beta (MAO), improved methylaluminoxane (MMAO).In the load non-metallocene single site catalysts, the aluminium weight content is 1～50%, is preferably 1～15%.
Be meant the metal complexes shown in general formula 1 and 2 at above-mentioned late transition metal catalyst precursor,
General formula 1
Wherein, R
1And R
7Be selected from hydrogen, halogen, C respectively
1-C
30Alkyl, substituted hydrocarbon radical, assorted alkyl, substituted heterohydrocarbyl or heterocyclic compound group.Wherein preferred C
6-C
30Aromatic hydrocarbon and substituted aroma hydrocarbon, as, phenyl, the 2-tolyl, the 3-tolyl, the 4-tolyl, 2, the 6-xylyl, 2,4, the 6-trimethylphenyl, the 2-ethylphenyl, the 3-ethylphenyl, the 4-ethylphenyl, 2,6-diethyl phenyl, 2,4, the 6-trimethylphenyl, the 2-isopropyl phenyl, the 3-isopropyl phenyl, the 4-isopropyl phenyl, 2, the 6-diisopropyl phenyl, 2,4,6-triisopropyl phenyl, the 2-tert-butyl-phenyl, the 3-tert-butyl-phenyl, the 4-tert-butyl-phenyl, 2, the 6-di-tert-butyl-phenyl, 2,4,6-tri-tert phenyl, 2-phenmethyl phenyl, 3-phenmethyl phenyl, 4-phenmethyl phenyl, 2,4-diphenyl-methyl phenyl, 2,4,6-trityl phenyl, the 1-naphthyl, the 2-naphthyl, the 2-phenyl, the 3-phenyl, the 4-phenyl, 2,4-phenylbenzene phenyl, 2,4,6-triphenyl phenyl, 2-(diphenyl-methyl) phenyl, 3-(diphenyl-methyl) phenyl, 4-(diphenyl-methyl) phenyl, 2,4-two (diphenyl-methyl) phenyl, 2,4,6-three (diphenyl-methyl) phenyl, 2-(trityl) phenyl, 3-(trityl) phenyl, 4-(trityl) phenyl, 2,4-two (trityl) phenyl or 2,4,6-three (trityl) phenyl etc.
R
2-R
6Be respectively hydrogen atom, chlorine atom, C
1-C
20Alkyl, heterocyclic compound group, contain the organic group of oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom; And R
2-R
6In two or more groups can be in ring.Preferred hydrogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, isohexyl, uncle's hexyl, phenyl, the phenyl that nitro replaces, halogenophenyl, alkyl-substituted phenyl, naphthyl, xenyl, trityl, diphenyl-methyl, the tristane base, 2-phenyl-sec.-propyl, pyridyl, pyrryl, Azacyclyl, the oxa-cyclic group, the methyl-silicane base, dimetylsilyl, trimethyl silyl, the ethyl silicane base, the diethylsilane base, triethylsilyl, the diphenylmethylsilane base, the trityl group silyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, uncle's propoxy-, methylthio group, ethylmercapto group, phenoxy group, thiophenyl etc., wherein preferred hydrogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, isohexyl, uncle's hexyl, phenyl, the tristane base, 2-phenyl-sec.-propyl, methoxyl group, oxyethyl group or uncle's propoxy-.
M is the 8th family's metal, preferred iron or cobalt.
X is selected from a kind of in hydrogen, halogen, alkyl, substituted hydrocarbon radical,-oxyl, fragrant-oxyl, acid group, the amido, is preferably a kind of in hydrogen atom, halogen, alkyl, allyl group, cyclopentadienyl, alkoxyl group, the fragrant-oxyl.Most preferably be chlorine, bromine, iodine, methoxyl group, oxyethyl group, isopropoxy, isobutoxy, butoxy, phenoxy group, oxy-o-cresyl, a tolyloxy, to tolyloxy or naphthyloxy.When n is 2 or when bigger, a plurality of X groups can be identical or different.
N is the integer that satisfies the M valence state.
The synthetic of metal complexes shown in the general formula 1 prepares according to WO9827124, WO9830612 patent.
General formula 2
Wherein, R
1And R
4Be selected from hydrogen, halogen, C respectively
1-C
30Alkyl, substituted hydrocarbon radical, assorted alkyl, substituted heterohydrocarbyl or heterocyclic compound group.Wherein preferred C
6-C
30Aromatic hydrocarbon and substituted aroma hydrocarbon, as, phenyl, the 2-tolyl, the 3-tolyl, the 4-tolyl, 2, the 6-xylyl, 2,4, the 6-trimethylphenyl, the 2-ethylphenyl, the 3-ethylphenyl, the 4-ethylphenyl, 2,6-diethyl phenyl, 2,4, the 6-trimethylphenyl, the 2-isopropyl phenyl, the 3-isopropyl phenyl, the 4-isopropyl phenyl, 2, the 6-diisopropyl phenyl, 2,4,6-triisopropyl phenyl, the 2-tert-butyl-phenyl, the 3-tert-butyl-phenyl, the 4-tert-butyl-phenyl, 2, the 6-di-tert-butyl-phenyl, 2,4,6-tri-tert phenyl, 2-phenmethyl phenyl, 3-phenmethyl phenyl, 4-phenmethyl phenyl, 2,4-diphenyl-methyl phenyl, 2,4,6-trityl phenyl, the 1-naphthyl, the 2-naphthyl, the 2-phenyl, the 3-phenyl, the 4-phenyl, 2,4-phenylbenzene phenyl, 2,4,6-triphenyl phenyl, 2-(diphenyl-methyl) phenyl, 3-(diphenyl-methyl) phenyl, 4-(diphenyl-methyl) phenyl, 2,4-two (diphenyl-methyl) phenyl, 2,4,6-three (diphenyl-methyl) phenyl, 2-(trityl) phenyl, 3-(trityl) phenyl, 4-(trityl) phenyl, 2,4-two (trityl) phenyl or 2,4,6-three (trityl) phenyl etc.
R
2And R
3Be respectively hydrogen atom, chlorine atom, C
1-C
20Alkyl, heterocyclic compound group, contain the organic group of oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom; And R
2And R
3Can be in ring.Preferred hydrogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, isohexyl, uncle's hexyl, phenyl, the phenyl that nitro replaces, halogenophenyl, alkyl-substituted phenyl, naphthyl, xenyl, trityl, diphenyl-methyl, the tristane base, 2-phenyl-sec.-propyl, pyridyl, pyrryl, Azacyclyl, the oxa-cyclic group, the methyl-silicane base, dimetylsilyl, trimethyl silyl, the ethyl silicane base, the diethylsilane base, triethylsilyl, the diphenylmethylsilane base, the trityl group silyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, uncle's propoxy-, methylthio group, ethylmercapto group, phenoxy group, thiophenyl etc., wherein preferred hydrogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, isohexyl, uncle's hexyl, phenyl, the tristane base, 2-phenyl-sec.-propyl, methoxyl group, oxyethyl group or uncle's propoxy-.
M is the 8th family's metal, preferred nickel or palladium.
X is selected from a kind of in hydrogen, halogen, alkyl, substituted hydrocarbon radical,-oxyl, fragrant-oxyl, acid group, the amido, is preferably a kind of in hydrogen atom, halogen, alkyl, allyl group, cyclopentadienyl, alkoxyl group, the fragrant-oxyl.Most preferably be chlorine, bromine, iodine, methoxyl group, oxyethyl group, isopropoxy, isobutoxy, butoxy, phenoxy group, oxy-o-cresyl, a tolyloxy, to tolyloxy or naphthyloxy.When n is 2 or when bigger, a plurality of X groups can be identical or different.
N is the integer that satisfies the M valence state.
Synthesizing of metal complexes shown in the general formula 2 according to patent WO9623010.
In the load post-transition metal catalyst, the weight content of central metal M counts 0.01～5%, is preferably 0.05～2%.
The catalyzer for preparing in the load post-transition metal catalyst method of the present invention can be used on the different polymerization processs, as vapour phase polymerization and slurry polymerization etc.The equal polymerization or the copolymerization that can be used for alkene are 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 for preparing in the load post-transition metal catalyst method of the present invention can be directly used in olefinic polymerization, as in gas-phase polymerization process; Also can add aluminum alkyl catalyst and be used for olefinic polymerization, particularly in slurry process, add aluminum alkyls and can remove impurity in the system, improve polymerization activity to a certain extent, make promotor and need not add expensive MAO.
Wherein the employed solvent of polymerization is selected from alkane, aromatic hydrocarbon or halohydrocarbon.A kind of in preferred hexane, pentane, heptane, benzene, toluene, methylene dichloride, chloroform, the ethylene dichloride or their mixture most preferably are a kind of in hexane, toluene, the heptane or their mixture.
The concentration of catalyzer when polymerization for preparing in the load post-transition metal catalyst method is 1 * 10
-8Mol～1 * 10
-3Mol, preferred concentration range for are 1 * 10
-8Mol～1 * 10
-5Mol.
Polymerization temperature is-78 ℃-100 ℃, is preferably 0 ℃-90 ℃.
Polymerization pressure is 0.01-10.0MPa, preferred 0.01-2.0MPa.
The present invention compared with prior art has following advantage:
1, magnesium chloride support preparation method of the present invention is simple, and the granules of catalyst form that obtains is good, and catalyst particle size is adjustable.
2, the catalyzer for preparing in the load post-transition metal catalyst method of the present invention has very high vinyl polymerization catalytic activity.
3, the catalyzer for preparing in the load post-transition metal catalyst method of the present invention is used for olefinic polymerization and obtains the resin powder and have good particle form, and the tap density height goes for slurry process and vapor phase process polymerization technique.
Employed analysis and characterization instrument is as follows among the present invention:
1, GC (gas-chromatography) characterizes: measure the content of THF in the carrier, its tetrahydrofuran (THF) minimum detectable activity is 0.1%-wt;
2, ICP (plasma emission spectrum) characterizes: the weight percent of metal in the quantitative assay carried catalyst.The P1000 type ICP-AES plasma emission spectrometer that instrument selection U.S. PE company produces.
3, the sign of polymericular weight and molecular weight distribution: molecular weight and distribution thereof are measured by gel permeation chromatography (GPC), and instrument adopts Waters Alliance GPCV 2000, and solvent is 1,2,4-trichlorobenzene, sample concentration are 1mg/ml, and solvent flow rate is 1.0ml/min; Measuring temperature is 150 ℃.Each sample measurement secondary.
Embodiment
Embodiment 1
Under the nitrogen protection; in glass reactor; add 25.21 gram Magnesium Chloride Anhydrouss under the room temperature, add 700 milliliters of dried tetrahydrofuran (THF)s then, start stirring; be warming up to 65 ℃; stirring and dissolving 5 hours guarantees that magnesium chloride dissolves fully, prepares spherical magnesium chloride/tetrahydrofuran (THF) particle by Buchi B-290 spraying drying instrument then; content of tetrahydrofuran 23wt%, particle diameter are D
50It is 16 microns.
Spherical magnesium chloride/tetrahydrofuran (THF) particle 100 ℃ of following vacuum-dryings 2 hours, again 300 ℃ of following vacuum-dryings 10 hours, is obtained the spherical magnesium chloride support of good fluidity,, fail to detect tetrahydrofuran (THF) through gas chromatographic analysis.
Under nitrogen protection; get the above-mentioned magnesium chloride support that obtains 4.61 grams and add in the glass reactor, add 60 milliliters of dried toluene, be dispersed into suspension; MAO (methylaluminoxane) toluene solution that adds 28 milliliters of 10wt%; be warming up to 50 ℃, stirring reaction 4 hours is used 50 milliliters * 3 toluene wash three times then; use hexane wash then; vacuum-drying obtains the pressed powder of good fluidity, promptly contains the magnesium chloride support of methylaluminoxane.
Under nitrogen protection; with the magnesium chloride support that contains methylaluminoxane 2.57 grams that obtain previously; join in the glass reactor; add 35 milliliters of dried toluene and make slurries; to be dissolved in 0.048 gram Fe catalyst precursor (2 in 20 milliliters of toluene; 6-is two, and [1-(2; 4; 6-Three methyl Benzene imines) ethyl] the pyridine ferrous chloride; structure is as follows) the synthetic drips of solution be added in the reactor, 30 ℃ the reaction 30 minutes, use 35 milliliters of toluene wash then; vacuum-drying obtains load post-transition metal catalyst A.Characterize through ICP, in the catalyst A, the Fe weight content is 0.17%, and the Al weight content is 14.2%.
Embodiment 2
Preparation spherical magnesium chloride/tetrahydrofuran (THF) particle on pilot plant.
Under the nitrogen protection; in reactor; add 7.2 kilograms of Magnesium Chloride Anhydrouss under the room temperature, add 200 liters of dried tetrahydrofuran (THF)s then, start stirring; be warming up to 65 ℃; stirring and dissolving 7 hours guarantees that magnesium chloride dissolves fully, prepares spherical magnesium chloride/tetrahydrofuran (THF) particle by pilot scale spray-dryer (per hour 3 kilograms of bearer capabilities) then; content of tetrahydrofuran 31wt%, particle diameter are D
50It is 26 microns.
Spherical magnesium chloride/tetrahydrofuran (THF) particle 200 grams 100 ℃ of following vacuum-dryings 2 hours, again 300 ℃ of following vacuum-dryings 10 hours, are obtained the magnesium chloride support of good fluidity,, fail to detect tetrahydrofuran (THF) through gas chromatographic analysis.
Under nitrogen protection; get the above-mentioned magnesium chloride support that obtains 4.83 grams and add in the glass reactor, add 60 milliliters of dried toluene, be dispersed into suspension; MAO (methylaluminoxane) toluene solution that adds 28 milliliters of 10wt%; be warming up to 50 ℃, stirring reaction 4 hours is used 50 milliliters * 3 toluene wash three times then; use hexane wash then; vacuum-drying obtains the pressed powder of good fluidity, promptly contains the magnesium chloride support of methylaluminoxane.
Under nitrogen protection; the magnesium chloride support that contains methylaluminoxane 2.54 grams with obtaining previously join in the glass reactor, add 35 milliliters of dried toluene and make slurries; to be dissolved in 0.053 gram Fe catalyst precursor (2 in 20 milliliters of toluene; two [1-(2,4,6-Three methyl Benzene imines) ethyl] the pyridine ferrous chloride of 6-) drips of solution is added in the reactor; 30 ℃ of reactions 30 minutes; use 35 milliliters of toluene wash then, vacuum-drying obtains load post-transition metal catalyst B.Characterize through ICP, in the catalyst B, the Fe weight content is 0.18%, and the Al weight content is 14.7%.
Embodiment 3
Under nitrogen protection; get magnesium chloride support 3.74 grams that obtain among the embodiment 3 and add in the glass reactor, add 60 milliliters of dried toluene, be dispersed into suspension; MAO (methylaluminoxane) toluene solution that adds 21 milliliters of 10wt%; be warming up to 50 ℃, stirring reaction 4 hours is used 50 milliliters * 3 toluene wash three times then; use hexane wash then; vacuum-drying obtains the pressed powder of good fluidity, promptly contains the magnesium chloride support of methylaluminoxane.
Under nitrogen protection; the magnesium chloride support that contains methylaluminoxane 2.25 grams with obtaining previously join in the glass reactor, add 35 milliliters of dried toluene and make slurries; to be dissolved in 0.175 gram Ni catalyst precursor (2 in 20 milliliters of toluene; two (2,6-diisopropyl benzene imines) the butane Nickel Bromides of 3-, structure is as follows) drips of solution be added in the reactor; 30 ℃ of reactions 30 minutes; use 35 milliliters of toluene wash then, vacuum-drying obtains load post-transition metal catalyst C.Characterize through ICP, among the catalyzer C, the Ni weight content is 0.49%, and the Al weight content is 14.6%.
Embodiment 4～6 high-pressure ethylene polymerization experiment
High-pressure ethylene polymerization experiment process is as follows:
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 1000 milliliters of hexane solvents then, adding along with hexane, triethyl aluminum (TEA) hexane solution of 2 milliliter of 1 mol is added, then add 50～100 milligrams of the load post-transition metal catalysts that the foregoing description makes, be warming up to 80 ℃, pressure is risen to and keeps 1.0MPa, reacted 1 hour.After polyreaction finished, the polyethylene particle powder was collected in cooling, weighs.
Concrete polymerization result is listed in the table 1.
Table 1, load post-transition metal catalyst polymerization result
Claims (8)
1. the method for a magnesium chloride loaded late transition metal catalyst is characterized in that, comprises the steps:
(1) magnesium chloride support preparation: under protection of inert gas; under the room temperature; in reactor, add a certain amount of Magnesium Chloride Anhydrous; add an amount of tetrahydrofuran (THF) then; stir and heat up its dissolving; use airtight spray-dryer to prepare spherical magnesium chloride/tetrahydrofuran (THF) particle, the D of grain diameter then
50It is 10～100 microns; With spherical magnesium chloride/tetrahydrofuran (THF) particle vacuum-drying a few hours under heating condition, remove tetrahydrofuran (THF), through gas chromatographic analysis, do not detect tetrahydrofuran (THF) (＜0.1%wt), the spheroidal particle of the good fluidity that obtains is magnesium chloride support;
(2) preparation of the magnesium chloride support of alkylaluminoxane: under rare gas element such as nitrogen protection, the magnesium chloride support that obtains in (1) step is added in the reactor, add solvent, be dispersed into suspension, add alkylaluminoxane, be warming up to 30～80 ℃, stirring reaction 3～6 hours, then for several times with solvent wash, vacuum-drying, obtain the magnesium chloride support that contains alkylaluminoxane of good fluidity, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexanaphthene;
(3) preparation of magnesium chloride loaded late transition metal catalyst: under protection of inert gas; the magnesium chloride support that contains alkylaluminoxane that will prepare in (2) step; join and make slurries in the solvent; the solution of late transition metal catalyst precursor slowly is added drop-wise in these slurries; under 0～40 ℃; reacted 1～120 minute; can obtain the load post-transition metal catalyst; slurries can be directly used in polyreaction; or the gained reactant removed desolvate; obtain the solid supported post-transition metal catalyst of good fluidity after the washing drying, described solvent is a toluene; benzene; dimethylbenzene; hexane; heptane; hexanaphthene.
2. the method for magnesium chloride loaded late transition metal catalyst according to claim 1 is characterized in that, described alkylaluminoxane general formula is:
Wherein R represents C
1～C
12Alkyl, a are represented 4～30 integer, and in loaded late transition metal catalyst, the aluminium weight content is 1～50%.
3. the method for magnesium chloride loaded late transition metal catalyst according to claim 2 is characterized in that, described alkylaluminoxane wherein R is a methyl, and a represents 10～30 integer, and in loaded late transition metal catalyst, the aluminium weight content is 1～15%.
4. the method for magnesium chloride loaded late transition metal catalyst according to claim 3 is characterized in that, described alkylaluminoxane is methylaluminoxane (MAO), improved methylaluminoxane (MMAO).
5. the method for magnesium chloride loaded late transition metal catalyst according to claim 1 is characterized in that, in the preparation of magnesium chloride support of (2) step alkylaluminoxane, add alkylaluminoxane after, be warming up to 40～60 ℃; Solvent for use is a toluene; In the preparation of the magnesium-supported late transition metal catalyst of (3) one-step chlorination, solvent for use is toluene, hexane or both mixtures.
6. the method for magnesium chloride loaded late transition metal catalyst according to claim 1 is characterized in that, described late transition metal catalyst precursor is meant the metal complexes shown in general formula 1 and 2,
General formula 1
In general formula 1, R
1And R
7Be selected from hydrogen, halogen, C respectively
1-C
30Alkyl, substituted hydrocarbon radical, assorted alkyl, substituted heterohydrocarbyl or heterocyclic compound group;
R
2-R
6Be respectively hydrogen atom, chlorine atom, C
1-C
20Alkyl, heterocyclic compound group, contain the organic group of oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom; And R
2-R
6In two or more groups randomly be in ring;
M is the 8th family's metal;
X is selected from a kind of in hydrogen, halogen, alkyl, substituted hydrocarbon radical,-oxyl, fragrant-oxyl, acid group, the amido, when n is 2 or when bigger, a plurality of X groups are identical or different; N is the integer that satisfies the M valence state;
General formula 2
In general formula 2, R
1And R
4Be selected from hydrogen, halogen, C respectively
1-C
30Alkyl, substituted hydrocarbon radical, assorted alkyl, substituted heterohydrocarbyl or heterocyclic compound group; R
2And R
3Be respectively hydrogen atom, chlorine atom, C
1-C
20Alkyl, heterocyclic compound group, contain the organic group of oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom; And R
2And R
3Randomly be in ring; M is the 8th family's metal;
X is selected from a kind of in hydrogen, halogen, alkyl, substituted hydrocarbon radical,-oxyl, fragrant-oxyl, acid group, the amido, when n is 2 or when bigger, a plurality of X groups are identical or different; N is the integer that satisfies the M valence state;
In the load post-transition metal catalyst, the weight content of central metal M counts 0.01～5%.
7. the method for magnesium chloride loaded late transition metal catalyst according to claim 6 is characterized in that, in the described late transition metal catalyst, the weight content of central metal M is 0.05～2%.
8. the application of magnesium chloride loaded late transition metal catalyst in olefinic polymerization for preparing in the method for claim 1～7 kind of any described magnesium chloride loaded late transition metal catalyst.
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| CN104059173A (en) * | 2013-03-21 | 2014-09-24 | 中国石油化工股份有限公司 | Supported late-transition-metal catalyst used for ethylene polymerization |
| CN109843938A (en) * | 2016-10-27 | 2019-06-04 | 尤尼威蒂恩技术有限责任公司 | The method for preparing molecular catalyst |
| CN114478865A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Late transition metal catalyst for olefin polymerization, preparation method and application thereof |
| CN114478866A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization and preparation method and application thereof |
| CN114478869A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Late transition metal catalyst for olefin polymerization, preparation method and application thereof |
| CN114478867A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Late transition metal catalyst for olefin polymerization and preparation method and application thereof |
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| CN101172988B (en) * | 2006-10-31 | 2011-03-23 | 中国石油化工股份有限公司 | Magnesium chloride loaded metallocene catalyst component, prepare method and application of the same |
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