CN101817893B - Method for preparing magnesium chloride loaded late transition metal catalyst - Google Patents
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- CN101817893B CN101817893B CN2009100785951A CN200910078595A CN101817893B CN 101817893 B CN101817893 B CN 101817893B CN 2009100785951 A CN2009100785951 A CN 2009100785951A CN 200910078595 A CN200910078595 A CN 200910078595A CN 101817893 B CN101817893 B CN 101817893B
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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 ultra cladodification of narrow molecular weight distributions through ethylene homo, and iron, cobalt series catalyst generate the linear polyethylene of wide molecular weight distribution.But olefinic polymerization is in homogeneous phase, to carry out, and the polymkeric substance that obtains is metamict, can't on the slurry process of widespread use or gas phase polymerization technology, use.
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 like 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 of preparing carriers and catalyst cupport is high, 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, preparing carriers is complicated, 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 drum, add a certain amount of Magnesium Chloride Anhydrous, add an amount of THF then, stir and heat up its dissolving; Use airtight spray-dryer to prepare spherical magnesium chloride/THF particle, the D of grain diameter then
50It is 10～100 microns.With spherical magnesium chloride/THF particle vacuum-drying number hour under heating condition, remove THF, through gas chromatographic analysis, do not detect 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 drum, add solvent; Be dispersed into suspension-s, 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 obtains the magnesium chloride support that contains alkylaluminoxane of good fluidity, and wherein solvent can adopt aromatic hydrocarbons or aliphatic hydrocarbon; Like toluene, benzene, YLENE, hexane, heptane, hexanaphthene etc., 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 process 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, can slurries directly be used for polyreaction, or the gained reactant removed desolvate, wash the solid supported post-transition metal catalyst that obtains good fluidity after the drying; Described solvent is toluene, benzene, YLENE, hexane, heptane, hexanaphthene etc., selects toluene, hexane or both mixtures best.
Above-mentioned alkylaluminoxane general structure is:
Wherein R representes C
1～C
12Alkyl is preferably methyl, a representes 4～30 integer, is preferably 10～30 integer.Alkylaluminoxane preferable methyl aikyiaiurnirsoxan beta (MAO), improved MAO (MMAO).In the load non-metallocene single site catalysts, the aluminium weight content is 1～50%, is preferably 1～15%.
Late transition metal catalyst precursor above-mentioned is meant the metal complexes shown in general formula 1 and 2,
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, 2-tolyl, 3-tolyl, 4-tolyl, 2,6-xylyl, 2; 4,6-trimethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,6-diethylammonium phenyl, 2,4; 6-trimethylphenyl, 2-isopropyl phenyl, 3-isopropyl phenyl, 4-isopropyl phenyl, 2,6-diisopropyl phenyl, 2,4,6-triisopropyl phenyl, 2-tert-butyl-phenyl, 3-tert-butyl-phenyl, 4-tert-butyl-phenyl, 2; 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, 1-naphthyl, 2-naphthyl, 2-phenyl, 3-phenyl, 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 Wasserstoffatoms, 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 Wasserstoffatoms, 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 substituted phenyl of nitro, halogenophenyl, alkyl-substituted phenyl, naphthyl, xenyl, trityl, diphenyl-methyl, tristane base, 2-phenyl-sec.-propyl, pyridyl, pyrryl, Azacyclyl, oxa-cyclic group, methyl-silicane base, dimetylsilyl, trimethyl silyl, ethyl silicane base, diethylsilane base, triethylsilyl, diphenylmethylsilane base, trityl group silyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, uncle's propoxy-, methylthio group, ethylmercapto group, phenoxy, thiophenyl etc., wherein preferred Wasserstoffatoms, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, isohexyl, uncle's hexyl, phenyl, 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 Wasserstoffatoms, halogen, alkyl, allyl group, cyclopentadienyl moiety, alkoxyl group, the fragrant-oxyl.Most preferably be chlorine, bromine, iodine, methoxyl group, oxyethyl group, isopropoxy, isobutoxy, butoxy, phenoxy, 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, 2-tolyl, 3-tolyl, 4-tolyl, 2,6-xylyl, 2; 4,6-trimethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,6-diethylammonium phenyl, 2,4; 6-trimethylphenyl, 2-isopropyl phenyl, 3-isopropyl phenyl, 4-isopropyl phenyl, 2,6-diisopropyl phenyl, 2,4,6-triisopropyl phenyl, 2-tert-butyl-phenyl, 3-tert-butyl-phenyl, 4-tert-butyl-phenyl, 2; 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, 1-naphthyl, 2-naphthyl, 2-phenyl, 3-phenyl, 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 Wasserstoffatoms, 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 Wasserstoffatoms, 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 substituted phenyl of nitro, halogenophenyl, alkyl-substituted phenyl, naphthyl, xenyl, trityl, diphenyl-methyl, tristane base, 2-phenyl-sec.-propyl, pyridyl, pyrryl, Azacyclyl, oxa-cyclic group, methyl-silicane base, dimetylsilyl, trimethyl silyl, ethyl silicane base, diethylsilane base, triethylsilyl, diphenylmethylsilane base, trityl group silyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, uncle's propoxy-, methylthio group, ethylmercapto group, phenoxy, thiophenyl etc., wherein preferred Wasserstoffatoms, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, isohexyl, uncle's hexyl, phenyl, 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 Wasserstoffatoms, halogen, alkyl, allyl group, cyclopentadienyl moiety, alkoxyl group, the fragrant-oxyl.Most preferably be chlorine, bromine, iodine, methoxyl group, oxyethyl group, isopropoxy, isobutoxy, butoxy, phenoxy, 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 methods, like 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 terminal olefin, and wherein terminal 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 directly be used for 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 the 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 tap density is high, goes for slurry process and vapor phase process polymerization technique.
Employed analysis and characterization instrument is following among the present invention:
1, GC (gc) characterizes: measure the content of THF in the carrier, its THF minimum detectable activity is 0.1%-wt;
2, ICP (plasma emission spectrum) characterizes: the weight percent of metal in the quantitatively determined 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 MWD: 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 THFs then, start stirring, be warming up to 65 ℃; Stirring and dissolving 5 hours guarantees that magnesium chloride dissolves fully, prepares spherical magnesium chloride/THF particle through Buchi B-290 spraying drying appearance then; Content of tetrahydrofuran 23wt%, particle diameter are D
50It is 16 microns.
Spherical magnesium chloride/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 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-s, add MAO (MAO) toluene solution of 28 milliliters of 10wt%, be warming up to 50 ℃; Stirring reaction 4 hours is used 50 milliliters * 3 toluene wash three times then, uses hexane wash then; Vacuum-drying obtains the pressed powder of good fluidity, promptly contains the magnesium chloride support of MAO.
Under nitrogen protection, the magnesium chloride support that contains MAO 2.57 grams with the front obtains join in the glass reactor; Add 35 milliliters of dried toluene and process slurries, (2,6-is two, and [1-(2 will to be dissolved in 20 milliliters of toluene 0.048 gram Fe catalyst precursor; 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 drum; 30 ℃ of reactions 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/THF particle on pilot plant.
Under the nitrogen protection, in reactor drum, add 7.2 kilograms of Magnesium Chloride Anhydrouss under the room temperature; Add 200 liters of dried THFs then, start stirring, be warming up to 65 ℃; Stirring and dissolving 7 hours guarantees that magnesium chloride dissolves fully, prepares spherical magnesium chloride/THF particle through 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/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 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-s, add MAO (MAO) toluene solution of 28 milliliters of 10wt%, be warming up to 50 ℃; Stirring reaction 4 hours is used 50 milliliters * 3 toluene wash three times then, uses hexane wash then; Vacuum-drying obtains the pressed powder of good fluidity, promptly contains the magnesium chloride support of MAO.
Under nitrogen protection, the magnesium chloride support that contains MAO 2.54 grams with the front obtains join in the glass reactor; Add 35 milliliters of dried toluene and process slurries, (2,6-is two, and [1-(2 will to be dissolved in 20 milliliters of toluene 0.053 gram Fe catalyst precursor; 4,6-Three methyl Benzene imines) ethyl] the pyridine ferrous chloride) drips of solution be added in the reactor drum, 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-s, add MAO (MAO) toluene solution of 21 milliliters of 10wt%, be warming up to 50 ℃; Stirring reaction 4 hours is used 50 milliliters * 3 toluene wash three times then, uses hexane wash then; Vacuum-drying obtains the pressed powder of good fluidity, promptly contains the magnesium chloride support of MAO.
Under nitrogen protection, the magnesium chloride support that contains MAO 2.25 grams with the front obtains join in the glass reactor; Add 35 milliliters of dried toluene and process slurries, (2,3-two (2 will to be dissolved in 20 milliliters of toluene 0.175 gram Ni catalyst precursor; 6-diisopropyl benzene imines) butane Nickel Bromide, structure is as follows) drips of solution be added in the reactor drum, 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 following:
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 keep 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 drum, add a certain amount of Magnesium Chloride Anhydrous, add an amount of THF then, stir and heat up its dissolving; Use airtight spray-dryer to prepare spherical magnesium chloride/THF particle, the D of grain diameter then
50It is 10～100 microns; With spherical magnesium chloride/THF particle vacuum-drying number hour under heating condition, remove THF, through gas chromatographic analysis, do not detect THF, the spheroidal particle of the good fluidity that obtains is magnesium chloride support;
(2) preparation of the magnesium chloride support of alkylaluminoxane: under protection of inert gas, the magnesium chloride support that obtains in (1) step is added in the reactor drum, add solvent; Be dispersed into suspension-s, 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, YLENE, 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 process 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, or the gained reactant removed desolvate, wash the solid supported post-transition metal catalyst that obtains good fluidity after the drying, described solvent is toluene, benzene, YLENE, 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 representes C
1～C
12Alkyl, a are represented 4～30 integer, and in loaded late transition metal catalyst, the aluminium weight content is 1～15%.
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 representes 10～30 integer.
4. the method for magnesium chloride loaded late transition metal catalyst according to claim 3 is characterized in that, described alkylaluminoxane is MAO (MAO), improved MAO (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 or 2,
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 Wasserstoffatoms, 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;
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 Wasserstoffatoms, 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 the magnesium chloride loaded late transition metal catalyst for preparing in the method for any described magnesium chloride loaded late transition metal catalyst in the claim 1～7 in olefinic polymerization.
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| CN104059173B (en) * | 2013-03-21 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of supported late transition metal catalyst for vinyl polymerization |
| US11123726B2 (en) * | 2016-10-27 | 2021-09-21 | Univation Technologies, Lle | Method of preparing a molecular catalyst |
| CN114478867B (en) * | 2020-10-27 | 2023-03-14 | 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 |
| CN114478866B (en) * | 2020-10-27 | 2023-04-11 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization, preparation method and application thereof |
| CN114478865B (en) * | 2020-10-27 | 2023-04-11 | 中国石油化工股份有限公司 | Late transition metal catalyst for olefin polymerization, preparation method and application thereof |
| CN114478869B (en) * | 2020-10-27 | 2023-04-11 | 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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