CN109280100A - It is a kind of to load the catalyst for having alpha-diimine metal complex and its application in olefin polymerization - Google Patents

It is a kind of to load the catalyst for having alpha-diimine metal complex and its application in olefin polymerization Download PDF

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CN109280100A
CN109280100A CN201811155509.8A CN201811155509A CN109280100A CN 109280100 A CN109280100 A CN 109280100A CN 201811155509 A CN201811155509 A CN 201811155509A CN 109280100 A CN109280100 A CN 109280100A
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alpha
diimine
carrier
metal complex
compound
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杨敏
赵丁丁
侯彦辉
张锐芳
崔咪咪
宋小雪
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Hebei University of Technology
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Hebei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/70—Iron group metals, platinum group metals or compounds thereof
    • C08F4/7001—Iron group metals, platinum group metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
    • C08F4/7003—Bidentate ligand
    • C08F4/7004—Neutral ligand
    • C08F4/7006—NN
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • C08F4/025—Metal oxides

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Abstract

The present invention is that a kind of load has the application of alpha-diimine metal complex catalysts in olefin polymerization.They react forming covalent bond with the active group on the carrier after chemical modification, so that it is supported on carrier by the alpha-diimine compound securely in a manner of chamical binding, avoids and be detached from from carrier.The alpha-diimine can but show catalytic activity resistant to high temperature when having smaller steric group.Meanwhile the aromatic group in alpha-diimine compound on imido grpup can change as needed and arbitrarily.Moreover, the ligand preparation of alpha-diimine is simple, the loaded article conducive to the alpha-diimine metal complex is applied in olefin polymerization.The loaded article of the alpha-diimine metal complex, which can improve, glues the problems such as kettle, polymer morphology are uncontrollable, co-catalyst dosage is more, thermal stability is poor present in homogeneous alpha-diimine late transition metal catalyst practical application in current techniques.

Description

It is a kind of to load the catalyst and its in olefin polymerization for having alpha-diimine metal complex Application
Technical field
The present invention relates to olefin catalytic field, specially it is a kind of load the catalyst for having alpha-diimine metal complex and its Application in olefin polymerization.
Background technique
Although nineteen ninety-five Brookhart et al. (J Am Chem Soc, 1995,117:6414) discovery, alpha-diimine nickel, The late transition metal catalyst of palladium under normal pressure catalyzed ethylene polymerization at heavy polymer.But they it has also been found that such The high temperature resistance of catalyst is poor, not can be carried out industrialization.Subsequent people further study show that, if alpha-diimine is matched The volume of body substituent group becomes larger, and high temperature resistance can also be further enhanced.Long etc., which is reported, to be had the following structure Alpha-diimine nickel (ACS Catal.2014,4,2501-2504), which still has vinyl polymerization at 90 DEG C well Catalytic activity can satisfy the requirement of industrialization.
If alpha-diimine complex is used for slurry olefin polymerization or gas-phase olefin polymerization, generally require by itself and carrier into Row load.The carrying method of alpha-diimine complex can directly be loaded by physical absorption.Though direct physical adsorption load method It is so easy, but the active force of catalyst and carrier is weaker, and catalyst active center is easy to fall off in catalyzed polymerization process.In addition A kind of method is that the functional group that will contain on catalyst is chemically reacted with carrier, passes through the covalent bond formed between the two Catalyst is supported on carrier, this mode of loading can make catalyst very securely in conjunction with carrier, avoid catalyst From falling off on carrier, influence of the functional group to catalyst activity of carrier surface is reduced, and catalytic activity does not reduce, Even also increase.Such as patent CN201110189126.4 reports alpha-diimine palladium catalyst and is supported on acryloyl rate and changes On the magnesium chloride support of property；Document (Macromolecules, 2002,35:6074；J Mol Catal A:Chem,2008, 287:57；Appl Catal A:Gen,2004,262:13；Polymer, 2010,51:2271) pass through alpha-diimine ligand structure In aniline reacted with active group, active group, will in the way of covalently bonded again with silica or magnesium chloride Catalyst is supported on carrier surface.Brookhart et al. (Macromolecules, 2006,39:6341) uses AlMe3、SiCl4Or BCl3Silica is handled, its hydroxyl reaction load with carrier surface is made, has then been synthesized again with-NH2Or-OH is functional The alpha-diimine complex of group, passes through-the NH on alpha-diimine2Or Al-Me, Si-Cl or B-Cl key of-OH and carrier surface Reaction, loads on carrier (such as following reaction equation) by chemical bond for alpha-diimine complex.Although the catalysis of the load Agent has good catalytic activity, but the high temperature resistance of the catalyst of their reports is general, and the synthesis step of ligand More complicated, cost is relatively high.
Summary of the invention
The purpose of the present invention is to provide a kind of catalyst of the alpha-diimine metal complex of load.The alpha-diimine is matched Hydroxyl is had on body, they react forming covalent bond with the active group on the carrier after chemical modification, so that should It is supported on carrier by alpha-diimine compound securely in a manner of chamical binding, is avoided them and is detached from from carrier. The alpha-diimine can but show good heat resistance and high-temperature catalytic activity when having smaller steric group.Together When, the aromatic group in alpha-diimine compound on imido grpup can change as needed and arbitrarily.Also, the ligand of alpha-diimine Preparation is simple, and the loaded article for being conducive to the alpha-diimine metal complex is applied in olefin polymerization.
The technical scheme adopted by the invention is that:
A kind of alpha-diimine metal complex of load, it is characterized in that by alpha-diimine metal complex and passing through modifying agent The carrier of processing is reacted and is obtained, or is obtained by the loaded article of alpha-diimine compound with late transition metal reactant salt；
The preparation method of the loaded article of the alpha-diimine metal complex is one of following two method,
Method one, comprising the following steps: in reaction flask in a nitrogen atmosphere, under stiring, modifier treatment will be passed through Carrier be added in anhydrous organic solvent, 10-100mL anhydrous organic solvent is added in every gram of carrier；Adding concentration is The anhydrous organic solvent solution of the alpha-diimine metal complex of 0.001-0.1mmol/mL, every gram of load by modifier treatment The alpha-diimine metal complex of 1-10mmol is added in body, reacts 1-48 hours, 0-100 DEG C of reaction temperature, reaction is concentrated under reduced pressure It is heavy to add ten times of the volume of the concentrated liquid extremely fiftyfold precipitating reagent to 1st/1/10th to 50 of original solution volume for liquid It forms sediment, filters, after solid is washed with precipitating reagent, vacuum drying obtains the loaded article of alpha-diimine metal complex；
Wherein the alpha-diimine metal complex is made by alpha-diimine compound and late transition metal reactant salt；
The preparation method of the alpha-diimine metal complex, comprising the following steps: reactor in a nitrogen atmosphere In, the anhydrous organic solvent that late transition metal salt is added to the alpha-diimine compound that concentration is 0.001-0.1mmol/mL is molten It is reacted in liquid, wherein late transition metal salt and alpha-diimine compound equimolar amounts；1-48 hours are stirred to react, reaction temperature 0-100 DEG C, reaction solution is concentrated under reduced pressure to 1st/1/10th to 50 of original solution volume, adds ten times of the volume of the concentrated liquid It precipitates, filters to fiftyfold precipitating reagent, after solid is washed with precipitating reagent, vacuum drying obtains alpha-diimine metal complex；
Alternatively, method two, comprising the following steps:
In reaction flask in a nitrogen atmosphere, it is sub- that anhydrous organic solvent, the compound loaded object of alpha-diimine and α-two is added The late transition metal salt of amine compounds equimolar amounts, it is anhydrous organic molten that 10-100mL is added in the compound loaded object of every gram of alpha-diimine Agent, late transition metal salinity are 0.001-1mmol/mL anhydrous organic solvent solution, are stirred to react 1-48 hours, reaction temperature 0-100 DEG C, reaction solution is concentrated under reduced pressure to 1st/1/10th to 50 of original solution volume, adds ten times of the volume of the concentrated liquid It precipitates, filters to fiftyfold precipitating reagent, after solid is washed with precipitating reagent, vacuum drying obtains alpha-diimine metal complex Loaded article；
Wherein the loaded article of the alpha-diimine compound is by alpha-diimine compound and by the load of modifier treatment Precursor reactant is made, and preparation method is the following steps are included: in reaction flask in a nitrogen atmosphere, under stiring, toward passing through modifying agent Anhydrous organic solvent is added in the carrier of processing, 10-100mL anhydrous organic solvent is added in every 1g carrier；Adding concentration is The anhydrous organic solvent solution of the alpha-diimine compound of 0.001-0.1mmol/mL, wherein alpha-diimine compound and process Alpha-diimine compound of the ratio of the carrier of modifier treatment for every gram of carrier addition 1-10mmol, reaction 1-48 hours, instead 0-100 DEG C of temperature is answered, reaction solution is concentrated under reduced pressure to 1st/1/10th to 50 of original solution volume, adds concentrated liquid Ten times of product precipitate to fiftyfold precipitating reagent, filter, after solid is washed with precipitating reagent, vacuum drying obtains alpha-diimine compound Loaded article；
The wherein preparation method of the carrier by modifier treatment, comprising the following steps: in a nitrogen atmosphere In reaction flask, under mechanical stirring, carrier is added in anhydrous organic solvent and obtains suspension, makes the concentration of carrier in suspension For 0.01-0.1g/mL, then by the amount that 0.1-50mmol modifying agent is added in 1g carrier modifying agent is added, reacts 4-16 hour, react Temperature is 0-50 DEG C, filters after reaction, washs to obtain modified support with anhydrous organic solvent, precipitating reagent respectively；
The late transition metal salt is one of nickel salt, palladium salt, platinum salt, molysite or cobalt salt；
The organic solvent is C1-C20Chloralkane, C6-C20Chlorination aromatic hydrocarbon, C6-C20Aromatic hydrocarbon or C2- C20One of oxygen-containing alkane or a variety of mixtures；
The precipitating reagent is C5-C20Alkane or C5-C20One of cycloalkane or a variety of mixtures；
The carrier is inorganic oxide, metal salt, clay, diatomite, montmorillonite, polystyrene resin, carbon black, carbon One of nanotube and graphene or a variety of complex carriers；
The modifying agent be aluminum alkoxide, alkyl aluminum, dialkyl group zinc, dialkyl group silicon dichloride, dialkyl group dibromo SiClx, One alkyl trichlorosilicane, an alkyl tribromo SiClx, TiX4、ZrX4、SiX4Or BX3One of or a variety of mixtures, wherein X be Chlorine or bromine；
The alpha-diimine compound, it is characterized in that the structural formula of alpha-diimine compound are as follows:
Wherein, R is substituted base or unsubstituted C6-C60Aryl, C6-C60One of heterocyclic arene base；Ar To have the following structure one of group:
Wherein, n=1,2,3,4,5,6 or 7；R' is C1-C20Alkyl.
The alpha-diimine metal complex of a kind of load, it is characterized in that the preferred dichloromethane of the organic solvent One of alkane, chloroform, 1,2- dichloroethanes, chlorobenzene, dichloro-benzenes, toluene, tetrahydrofuran or 1,4- dioxane are more Kind mixture.
The alpha-diimine metal complex of a kind of load, it is characterized in that the preferred pentane of the precipitating reagent, just One of hexane, normal heptane, normal octane or hexamethylene or a variety of mixtures.
The alpha-diimine metal complex of a kind of load, it is characterized in that the late transition metal salt is preferred (DME)NiBr2、(DME)NiCl2、(COD)PdClCH3、(PhCN)2PdCl2Or (COD) PdMe (NCMe).
The alpha-diimine metal complex of a kind of load, it is characterized in that the carrier is preferably SiO2、MgCl2、 Diatomite, montmorillonite, Al2O3、Fe3O4、SiO2/MgCl2Complex carrier, SiO2/ composite diatomite carrier, montmorillonite/MgCl2It is multiple Close carrier, diatomite/MgCl2Complex carrier, Al2O3/MgCl2Complex carrier or Fe3O4/MgCl2One of complex carrier.
The alpha-diimine metal complex of a kind of load, it is characterized in that the modifying agent is preferably methyl alumina Alkane (MAO), ethylaluminoxane (EAO), modified methylaluminoxane (MMAO), AlMe3、AlEt3、Al(i-Bu)3、AlEt2Cl、 ZnEt2、TiCl4、ZrCl4、SiCl4Or BCl3One of or a variety of mixtures；
The application of the alpha-diimine metal complex of a kind of load, it is characterized in that being applied to second as major catalyst In the liquid-phase bulk polymerization or slurry polymerization of the gas-phase polymerization or olefinic monomer of alkene or propylene.
The application of the alpha-diimine metal complex of a kind of load, it is characterized in that the complex is as major catalyst Using in olefin polymerization, including following reaction condition: polymeric reaction temperature is -20-120 DEG C；Olefinic monomer is pressed when being gas Power is 0.1-10MPa；Olefinic monomer is specially ethylene, propylene, 1- butylene, 1- amylene, 4-methyl-1-pentene, 1- hexene, 1- heptan Alkene, 1- decene, norbornene, vinyl norbornene, ethylidene norbornene, bicyclopentadiene, 1,4- butadiene, benzene second One of alkene, α-methylstyrene and divinylbenzene or a variety of mixing.
Beneficial effects of the present invention: the present invention provides a kind of alpha-diimine metal complexs of load.The alpha-diimine Hydroxyl is had on ligand, they react forming covalent bond with the active group on the carrier after chemical modification, so that It is supported on carrier by the alpha-diimine compound securely in a manner of chamical binding, is avoided them and is taken off from carrier From.The alpha-diimine can but show good heat resistance and high-temperature catalytic activity when having smaller steric group, Application industrially may be implemented.Meanwhile the aromatic group in alpha-diimine compound on imido grpup can appoint as needed Meaning changes.Moreover, the ligand preparation cost of alpha-diimine is relatively low, conducive to the alpha-diimine metal complex loaded article in alkene It is applied in polymerized hydrocarbon.It present invention can be suitably applied to the gas phase polymerization apparatus or slurry polymerization device of existing catalyst alkene.
Specific embodiment
The present invention is described further with reference to embodiments.It should be noted that following embodiments cannot function as pair The limitation of the scope of the present invention, any improvement made on the basis of the present invention is all without prejudice to spirit of the invention.
One, the synthesis of alpha-diimine metal complex
Embodiment 1
The synthesis of bis- (2,6- diisopropyl) the benzene imines nickelous bromides (NiI1) of 5- (4- hydroxymethyl phenyl) acenaphthenequinone
Bis- (2,6- diisopropyl) the benzene imines (I1) of ligand 5- (4- hydroxymethyl phenyl) acenaphthenequinone (i.e. such as structure of Compound I, Wherein Ar=p-methylphenyl, R=(2,6- diisopropyl) phenyl) preparation route it is as follows:
The synthesis of bis- (2,6- diisopropyl) the benzene imines a1 of bis- bromo acenaphthenequinone of 5-:
5- bromo acenaphthenequinone (2.09g, 8mmol) is added into the reaction flask of 250mL, 2,6-DIPA (3.36g, 19mmol) and the anhydrous methanol of 150mL, and 10 drop anhydrous formic acids, the mixture back flow reaction 48 hours are instilled.Thin layer chromatography chases after Track reaction, until raw material fully reacting filters to obtain brown-red solid, which mentions after reaction mixture is cooling It is pure, obtain 4.27g yellow solid a1, yield 92%.1H NMR(400MHz,CDCl3): δ 8.10 (d, J=8.4Hz, 1H), 7.61 (d, J=7.7Hz, 1H), 7.47 (t, J=7.9Hz, 1H), 7.30-7.27 (m, 6H), 6.67 (d, J=7.2Hz, 1H), 6.45 (d, J=7.7Hz, 1H), 3.07-2.91 (m, 4H), 1.23 (d, J=6.8Hz, 12H), 0.98-0.95 (m, 12H) .MS (ESI):m/z 579(M+H).
The synthesis of bis- (2,6- diisopropyl) the benzene imines I1 of 5- (4- hydroxymethyl phenyl) acenaphthenequinone:
By compound a 1 (2.32g, 4mmol), 4- methylol phenyl boric acid (0.76g, 5mmol), tetrakis triphenylphosphine palladium (0.46g, 0.4mmol), Anhydrous potassium carbonate (1.66g, 12mmol), 100mL toluene and 50mL water are added in two-mouth bottle, and argon gas is protected Shield, is heated to reflux 10h.It after being cooled to room temperature, is extracted with dichloromethane, after organic phase anhydrous sodium sulfate drying, filters to hang and do, 2.31g yellow solid I1, yield 95% are obtained finally by column column layer chromatography separating-purifying.1H NMR(400MHz,CDCl3):δ 7.98 (d, J=8.4Hz, 1H), 7.49 (s, 4H), 7.35-7.27 (m, 5H), 6.70-6.65 (m, 2H), 4.79 (s, 2H), 3.08-3,05 (m, 4H), 1.25 (d, J=6.6Hz, 12H), 1.02-0.98 (m, 12H) .MS (ESI): m/z 607 (M+H)
The synthesis of bis- (2,6- diisopropyl) the benzene imines nickelous bromides (NiI1) of 5- (4- hydroxymethyl phenyl) acenaphthenequinone:
In a nitrogen atmosphere, ligand i 1 (0.61g, 1mmol) is added into reaction flask, 1,2- dimethoxy-ethane nickelous bromide (DME)NiBr2(0.309g, 1mmol), methylene chloride 50mL are stirred at room temperature 24 hours.Then reaction solution is concentrated under reduced pressure to 5mL, 50mL n-hexane is added and is settled out red brown solid.It filters, after solid is washed with n-hexane, vacuum drying obtains complex NiI1 0.788g, yield: 96%.The elemental analysis of complex NiI1, C43H46Br2N2NiO theoretical value: C, 62.58%, H, 5.62%, N, 3.39%.Experiment value: C 62.61%, H 5.59%, N 3.37%.ICP measurement, Ni 7.09%.
Embodiment 2
Bis- [2,4- dimethyl -6- two (4- fluorobenzene) methyl] the benzene imines nickelous bromides (NiI2) of 5- (4- hydroxy phenyl) acenaphthenequinone Synthesis
Benzene imines (I2) is (i.e. for ligand 5- (4- hydroxy phenyl) acenaphthenequinone bis- [2,4- dimethyl -6- two (4- fluorobenzene) methyl] Such as the structure of Compound I, wherein Ar=is to phenyl, R=[2,4- dimethyl -6- two (4- fluorobenzene) methyl] phenyl) preparation Route is as follows:
The preparation of compound I2 is identical as compound I1 preparation process in embodiment 1, wherein using 2,4- dimethyl -6- two (4- fluorobenzene) methylaniline replaces the 2,6-DIPA in embodiment 1, and toluene replaces the dichloromethane in embodiment 1 Alkane, p-methyl benzenesulfonic acid replace the formic acid in embodiment 1, and 4- hydroxyl benzpinacol borate replaces the 4- hydroxyl first in embodiment 1 Base phenyl boric acid, bis- (dibenzalacetone) palladiums replace the tetrakis triphenylphosphine palladium in embodiment 1, and natrium carbonicum calcinatum replaces embodiment Anhydrous potassium carbonate in 1.The yield of compound I2 is 86%.1H NMR(400MHz,CDCl3): δ 7.76 (d, J=8.5Hz, 1H), 7.30 (d, J=8.2Hz, 2H), 7.13-6.90 (m, 14H), 6.81-6.78 (m, 4H), 6.62 (d, J=5.6Hz, 2H), 6.37-6.32 (m, 2H), 6.06-6.01 (m, 4H), 5.67 (s, 2H), 2.33 (s, 6H), 2.29 (d, J=6.0Hz, 6H) .MS (ESI):m/z 885(M+H).
Complex NiI2 is identical as complex NiI1 preparation process in embodiment 1, wherein replacing embodiment 1 using ligand i 2 In I1.The yield of complex NiI2 is 97%.The elemental analysis of complex NiI2, C60H44Br2F4N2NiO theoretical value: C 65.31%, H 4.02%, N 2.54%；Experiment value: C 65.29%, H 4.03%, N 2.56%.ICP measurement, Ni 5.33%.
Embodiment 3
Bis- [(the benzhydryl) -4- of 2,6- bis- methoxyl group] the benzene imines nickelous bromides (NiI3) of 5- (4- hydroxymethyl phenyl) acenaphthenequinone Synthesis
Bis- [(the benzhydryl) -4- of 2,6- bis- methoxyl group] the benzene imines (I3) of ligand 5- (4- hydroxymethyl phenyl) acenaphthenequinone are (i.e. such as I The structure of compound, wherein Ar=p-methylphenyl, R=[2,6- bis- (benzhydryl) -4- methoxyl group] phenyl) preparation route It is as follows:
The preparation of compound I3 is identical as compound I1 preparation process in embodiment 1, wherein using 2,6- benzhydryl -6- Aminoanisole replaces the 2,6-DIPA in embodiment 1, and toluene replaces the methylene chloride in embodiment 1, to methyl Benzene sulfonic acid replaces the formic acid in embodiment 1, and Carbon Dioxide caesium replaces the Anhydrous potassium carbonate in embodiment 1.The yield of compound I3 It is 79%.1H NMR(400MHz,CDCl3): δ 7.66 (d, J=8.4Hz, 1H), 7.57 (d, J=7.9Hz, 2H), 7.41 (d, J =7.9Hz, 2H), 7.21-7.12 (m, 20H), 6.96-6.91 (m, 9H), 6.76-6.61 (m, 17H), 6.34 (d, J= 7.1Hz, 1H), 6.08 (d, J=7.3Hz, 1H), 5.80 (s, 2H), 5.74 (s, 2H), 4.86 (s, 2H), 3.69 (s, 3H), 3.68(s,3H).MS(ESI):m/z 1164(M+H).
Complex NiI3 is identical as complex NiI1 preparation process in embodiment 1, wherein replacing embodiment 1 using ligand i 3 In I1.The yield of complex NiI3 is 95%.The elemental analysis of complex NiI3, C85H66Br2N2NiO3Theoretical value: C 73.88%, H 4.81%, N 2.03%；Experiment value: C 73.89%, H 4.79%, N 2.05%.ICP measurement, Ni, 4.26%.
Embodiment 4
The synthesis of bis- (2,6- diisopropyl) the benzene imines palladium chlorides (PdI1) of 5- (4- hydroxymethyl phenyl) acenaphthenequinone
Embodiment 1 is shown in the preparation of compound I1.In a nitrogen atmosphere, into reaction flask be added ligand i 1 (0.61g, 1mmol)、(PhCN)2PdCl2(0.384g, 1mmol), methylene chloride 30mL is stirred at room temperature 24 hours.Then reaction is concentrated under reduced pressure Liquid is added 50mL n-hexane and is settled out red brown solid to 5mL.It filters, after solid is washed with n-hexane, vacuum drying is matched Close object PdI1 0.765g, yield: 96%.The elemental analysis of complex PdI1, C43H46Cl2N2OPd theoretical value: C 65.86%, H 5.91%, N 3.57%；Experiment value: C 65.87%, H 5.90%, N, 3.56%.ICP measurement, Pd 13.56%.Two, α-two The synthesis of imines loaded article
Embodiment 5
Trimethyl aluminium key connects the silicon dioxide carried object of bis- (2,6- diisopropyl) the benzene imines of 5- (4- hydroxymethyl phenyl) acenaphthenequinone SiO2The synthesis of-AlMe-I1
In a nitrogen atmosphere, 50mL toluene is added into reaction flask, by 600 DEG C of burnt SiO2(1g), then exists Under mechanical stirring, it is warmed to room temperature after trimethyl aluminium (15mmol) is added under zero degree.After stirring 2 hours, filter in a nitrogen atmosphere Remove solvent, products obtained therefrom successively with 20mL toluene wash three times, after 20mL n-hexane washed once, addition 20mL dichloromethane Then alkane slowly instills dichloromethane solution (2mmol alpha-diimine compound I1, the 20mL dichloro of alpha-diimine compound I1 Methane).After being stirred at room temperature 2 hours, filters remove methylene chloride in a nitrogen atmosphere, and after washing 3 times with methylene chloride It is dry, obtain orange solid product SiO2-AlMe-I1.Loaded article SiO2The elemental analysis of-AlMe-I1: C 29.79%, N 1.62%.
Embodiment 6
Titanium tetrachloride key connects bis- [2,4- dimethyl -6- two (4- fluorobenzene) methyl] the benzene imines of 5- (4- hydroxy phenyl) acenaphthenequinone Loaded article SiO2/MgCl2-TiCl2The synthesis of-I2
It is anhydrous sequentially adding solvent n-heptane 50mL and 1g under protection of argon gas with churned mechanically five mouthfuls of bottles MgCl2, and a certain amount of n-butanol (molar ratio of n-butanol and magnesium chloride is 4:1) is added at 35 DEG C, then temperature programming is arrived 90 DEG C are kept for 3 hours, obtain colourless transparent solution.Then solution is cooled to 60 DEG C, adds a certain amount of SiO2(MgCl2With SiO2Mass ratio is equal to 1:1), and stop after this temperature stirs 2 hours, SiO is dried to obtain through filtering2/MgCl2Complex carrier.
Loaded article SiO2/MgCl2-TiCl2Loaded article SiO in the preparation process and embodiment 5 of-I22The preparation of-AlMe-I1 Process is identical, wherein the trimethyl aluminium in embodiment 5 is replaced using titanium tetrachloride, using SiO2/MgCl2Complex carrier replaces real Apply the SiO in example 52, the I1 in embodiment 5 is replaced using compound I2.Loaded article SiO2/MgCl2-TiCl2The element of-I2 point Analysis: C 24.43%, N 0.95%.
Embodiment 7
Methylaluminoxane key connects bis- [(the benzhydryl) -4- of 2,6- bis- methoxyl group] the benzene imines of 5- (4- hydroxymethyl phenyl) acenaphthenequinone Aluminum oxide loaded article Al2O3The synthesis of-AlOMe-I3
Loaded article Al2O3Loaded article SiO in the preparation process and embodiment 5 of-AlOMe-I32The preparation process of-AlMe-I1 It is identical, the trimethyl aluminium in embodiment 5 is replaced using methylaluminoxane, the SiO in embodiment 5 is replaced using aluminum oxide2, I1 in embodiment 5 is replaced using compound I3.Loaded article Al2O3The elemental analysis of-AlOMe-I3: C 22.82%, N 0.63%.Three, the synthesis of the loaded article of alpha-diimine metal complex
Method one:
Embodiment 8
Trimethyl aluminium key connects bis- (2,6- diisopropyl) the benzene imines nickelous bromide silica of 5- (4- hydroxymethyl phenyl) acenaphthenequinone Loaded article SiO2The synthesis of-AlMe-NiI1
In a nitrogen atmosphere, 50mL toluene is added into reaction flask, by 600 DEG C of burnt SiO21g, then in machine Under tool stirring, it is warmed to room temperature after trimethyl aluminium (15mmol) is added under zero degree.After stirring 2 hours, filters remove in a nitrogen atmosphere Removing solvent, products obtained therefrom is successively washed three times, after 20mL n-hexane washed once, 50mL methylene chloride is added with 20mL toluene, Then the dichloromethane solution (2mmol NiI1,20mL methylene chloride) of the NiI1 as obtained in embodiment 1 is slowly instilled.In room It after the lower stirring of temperature 5 hours, filters remove methylene chloride in a nitrogen atmosphere, and drying after wash 3 times with methylene chloride, obtain solid Product SiO2-AlMe-NiI1.ICP measures loaded article SiO2The Ni content of-AlMe-NiI1: 1.9% (Wt).
Embodiment 9
Boron chloride key connects bis- [2,4- dimethyl -6- two (4- fluorobenzene) methyl] the benzene imines of 5- (4- hydroxy phenyl) acenaphthenequinone Nickelous bromide ferroso-ferric oxide loaded article Fe3O4The synthesis of-BCl-NiI2
Loaded article Fe3O4Loaded article SiO in the preparation process and embodiment 8 of-BCl-NiI22The preparation of-AlMe-NiI1 Cheng Xiangtong is replaced in embodiment 8 wherein replacing the trimethyl aluminium in embodiment 8 using boron chloride using ferroso-ferric oxide SiO2, the NiI1 in embodiment 8 is replaced using the complex NiI2 as made from embodiment 2.Loaded article Fe3O4The Ni of-BCl-NiI2 Content: 1.6%.
Embodiment 10
Diethyl zinc key connects bis- [(the benzhydryl) -4- of 2,6- bis- methoxyl group] the benzene imines bromines of 5- (4- hydroxymethyl phenyl) acenaphthenequinone Change the synthesis of nisiloy diatomaceous earth loaded article diatomite-Zn-NiI3
Loaded article SiO in the preparation process and embodiment 8 of loaded article diatomite-Zn-NiI32The preparation of-AlMe-NiI1 Cheng Xiangtong replaces the SiO in embodiment 8 using diatomite wherein replacing the trimethyl aluminium in embodiment 8 using diethyl zinc2, NiI1 in embodiment 8 is replaced using the complex NiI3 as made from embodiment 3.The Ni's of loaded article diatomite-Zn-NiI3 contains Amount: 1.2%.
Embodiment 11
Silicon tetrachloride key connects bis- (2,6- diisopropyl) the benzene imines palladium chloride silica of 5- (4- hydroxymethyl phenyl) acenaphthenequinone Loaded article SiO2-SiCl2The synthesis of-PdI1
Loaded article SiO2-SiCl2Loaded article SiO in the preparation process and embodiment 8 of-PdI12The preparation of-AlMe-NiI1 Cheng Xiangtong replaces the trimethyl aluminium in embodiment 8 using silicon tetrachloride, wherein using the complex PdI1 as made from embodiment 4 Instead of the NiI1 in embodiment 8.Loaded article SiO2-SiCl2The content of the Pd of-PdI1: 3.9%.
Method two:
Embodiment 12
Trimethyl aluminium key connects bis- (2,6- diisopropyl) the benzene imines nickelous bromide silica of 5- (4- hydroxymethyl phenyl) acenaphthenequinone Loaded article SiO2The synthesis of-AlMe-NiI1
In a nitrogen atmosphere, loaded article SiO obtained in methylene chloride 50mL, embodiment 5 is added into reaction flask2- AlMe-I1 is added and loaded article SiO2Considerable amount of (DME) NiBr of ligand on-AlMe-I12, mechanical stirring 24 at room temperature Hour.Then reaction solution is concentrated under reduced pressure to 5mL, 50mL n-hexane is added.It filters, after solid is washed with n-hexane, vacuum drying Obtain loaded article SiO2-AlMe-NiI1.Loaded article SiO2The content of the Ni of-AlMe-NiI1: 2.5%.
Embodiment 13
Titanium tetrachloride key connects bis- [2,4- dimethyl -6- two (4- fluorobenzene) methyl] the benzene imines of 5- (4- hydroxy phenyl) acenaphthenequinone Nickelous bromide loaded article SiO2/MgCl2-TiCl2The synthesis of-NiI2
Loaded article SiO2/MgCl2-TiCl2Loaded article SiO in the preparation process and embodiment 12 of-NiI22-AlMe-NiI1 Preparation process it is identical, wherein using by loaded article SiO obtained in embodiment 62/MgCl2-TiCl2- I2 replaces embodiment 12 In SiO2-AlMe-I1.Loaded article SiO2/MgCl2-TiCl2The content of the Ni of-NiI2: 1.6%.
Embodiment 14
Methylaluminoxane key connects bis- [(the benzhydryl) -4- of 2,6- bis- methoxyl group] the benzene imines of 5- (4- hydroxymethyl phenyl) acenaphthenequinone Aluminum oxide loaded article Al2O3The synthesis of-AlOMe-PdI3
Loaded article Al2O3Loaded article SiO in the preparation process and embodiment 12 of-AlOMe-PdI32The preparation of-AlMe-NiI1 Process is identical, wherein using by loaded article Al obtained in embodiment 72O3- AlOMe-I3 replaces the SiO in embodiment 122- AlMe-I1 replaces (DME) NiBr in embodiment 12 using two benzonitrile palladium chlorides2.Loaded article Al2O3- AlOMe-PdI3's The content of Pd: 4.3%.
Four, olefin polymerization
Embodiment 15
Loaded article SiO2- AlMe-NiI1 is used as major catalyst catalyzed ethylene polymerization
It is re-filled with addition 50mL dry toluene in the 250mL reaction kettle of ethylene three times to through nitrogen displacement, heats simultaneously constant temperature To 80 DEG C, stirring, which is passed through ethylene, to be made to keep pressure 0.5MPa in reactor, is separately added into 10mg by the resulting loaded article of embodiment 8 SiO2The co-catalyst MAO (2.3mL, co-catalyst and major catalyst molar ratio are 1000:1) of-AlMe-NiI1,1.4mol/L, Polymerization time is 1 hour, and the acidic ethanol that 10mL concentration expressed in percentage by volume is 10% is then added, and (i.e. volume ratio is 37% dense salt Acid: dehydrated alcohol=1:9) to reaction terminating, with water, ethanol washing, filtered polymeric, then the drying in 60 DEG C of vacuum ovens 8 hours, obtain product polyethylene 2.8g.SiO2The catalytic activity of-AlMe-NiI1 is 8.6 × 105(activity is by polymerizeing by g/molh Product quality/(in catalyst the amount of metallics × per hour) is calculated).Polymer Mw (weight average molecular weight) be 5.6 × 105G/mol, MWD (molecular weight distribution) are 2.6 (GPC is measured).13The polymer branching degree of C NMR measurement is 65/1000 carbon original Son.
Embodiment 16
Loaded article SiO2- AlMe-NiI1 is used as major catalyst catalyzed ethylene polymerization
Vinyl polymerization condition and concrete operations are the same as embodiment 15.Wherein, major catalyst is negative with being prepared by embodiment 12 Loading SiO2- AlMe-NiI1 replaces the loaded article SiO in embodiment 152- AlMe-NiI1, co-catalyst AlEt2Cl replaces implementing MAO in example 15.The loaded article SiO prepared by embodiment 122The catalytic activity of-AlMe-NiI1 is 5.1 × 105g/mol·h。 Polymer Mw is 6.2 × 105G/mol, MWD 2.5.Polymer branching degree is 66/1000 carbon atom.
Embodiment 17
Loaded article Fe3O4- BCl-NiI2 is used as major catalyst catalyzed ethylene polymerization
Solvent is anhydrous n-hexane, and ethylene pressure 5.0MPa, reaction temperature is 60 DEG C, and major catalyst is prepared with embodiment 9 Loaded article Fe3O4- BCl-NiI2, co-catalyst AlEt2Cl (co-catalyst is 1000:1 with major catalyst molar ratio), specifically With embodiment 15, polymerization time is 1 hour for operation.Loaded article Fe3O4The catalytic activity of-BCl-NiI2 is 6.9 × 105g/mol· H, polymer Mw are 7.6 × 105G/mol, MWD 1.9, polymer branching degree are 46/1000 carbon atom.
Embodiment 18
Loaded article diatomite-Zn-NiI3 is catalyzed propylene polymerization as major catalyst
Solvent is dry toluene, and propylene pressure 2.0MPa, reaction temperature is 40 DEG C, and major catalyst is prepared with embodiment 10 Loaded article diatomite-Zn-NiI3, co-catalyst MAO (co-catalyst is 2000:1 with major catalyst molar ratio), concrete operations are same
Embodiment 15, polymerization time are 2 hours.The catalytic activity of loaded article diatomite-Zn-NiI3 is 7.9 × 104g/ Molh, polymer Mw are 2.6 × 105G/mol, MWD 4.3.
Embodiment 19
Loaded article SiO2-SiCl2- PdI1 is as major catalyst catalysis 1- butylene and ethylene copolymer
Solvent is dry toluene, and 1- butylene and ethylene pressure ratio are 0.5, makes to keep pressure 0.5MPa in reactor, reaction Temperature is 60 DEG C, the loaded article SiO that major catalyst is prepared with embodiment 112-SiCl2- PdI1, cocatalyst B (C6F5)4It (helps and urges Agent and the molar ratio of major catalyst are 800:1), with embodiment 15, polymerization time is 1.5 hours for concrete operations.Loaded article SiO2-SiCl2The catalytic activity of-PdI1 is 5.8 × 105G/molh, polymer Mw are 4.7 × 105G/mol, MWD 3.8.
Embodiment 20
Loaded article SiO2/MgCl2-TiCl2- NiI2 is catalyzed 1- hexene oligomerization as major catalyst
50mL dry toluene is added in through nitrogen displacement 250mL reaction kettle three times, be separately added into 5mL 1- hexene, The resulting loaded article SiO of embodiment 132/MgCl2-TiCl2- NiI2, co-catalyst Al2Et3Cl3(co-catalyst and major catalyst Molar ratio be 800:1), stirring is warming up to 20 DEG C, and polymerization time is 2 hours, and the acidic ethanol of 10mL 10% then is added extremely Reaction terminating is obtained product and is gathered oneself with water, ethanol washing, filtered polymeric, then drying 8 hours in 60 DEG C of vacuum ovens Alkene.Loaded article SiO2/MgCl2-TiCl2The catalytic activity of-NiI2 is 1.1 × 105G/molh, polymer Mw are 2.8 × 105g/ Mol, MWD 3.9.
Embodiment 21
Loaded article Al2O3- AlOMe-PdI3 is copolymerized as major catalyst catalysis norbornene and 1- decene
With the resulting complex loaded article Al of embodiment 142O3- AlOMe-PdI3 replaces the loaded article in embodiment 20 SiO2/MgCl2-TiCl2- NiI2,1.6g norbornene and 1.1g 1- decene, co-catalyst MAO (co-catalyst and major catalyst Molar ratio be 1200:1), 70 DEG C of reaction temperature, operate with embodiment 20.Loaded article Al2O3The catalytic activity of-AlOMe-PdI3 It is 3.5 × 105G/molh, polymer Mw are 3.6 × 105G/mol, MWD 3.3.
Embodiment 22
Loaded article SiO2- AlMe-NiI1 is catalyzed ethene gas-phase polymerization as major catalyst
The gas-phase polymerization of ethylene carries out in the simulation gas phase reaction kettle of 2L, and 100g is added and makees through the sodium chloride of Overheating Treatment For seed bed, ethylene is added, adds co-catalyst AlEt2Cl 5mmol is warming up to 90 DEG C, and the negative of the preparation of embodiment 8 is added Loading SiO2- AlMe-NiI1 20mg, polymerization time are 3 hours, reaction pressure 1.5MPa, are mended by solenoid valve to reaction kettle Add ethylene gas, reaction terminates blowing, is dried to obtain polyethylene 18g after sodium chloride is washed with water.Loaded article SiO2-AlMe- The catalytic activity of NiI1 is 3.0 × 106g/mol·h.Polymer Mw is 5.1 × 105G/mol, MWD 3.6.Polymer branching degree For 58/1000 carbon atom.
By embodiment 15 and embodiment 22 as can be seen that only the catalyst after the NiI1 load with isopropyl just has Good high temperature resistant catalytic activity not only it is poly- can also to be catalyzed ethylene by vapor phase method by slurry catalytic vinyl polymerization It closes, illustrates that they are applicable in the commercial plant of vinyl polymerization.
Unaccomplished matter of the present invention is well-known technique.

Claims (8)

1. the alpha-diimine metal complex of a kind of load, it is characterized in that by alpha-diimine metal complex and passing through modifying agent The carrier of reason is reacted and is obtained, or is obtained by the loaded article of alpha-diimine compound with late transition metal reactant salt；
The preparation method of the loaded article of the alpha-diimine metal complex is one of following two method,
Method one, comprising the following steps:, under stiring, will be by the load of modifier treatment in reaction flask in a nitrogen atmosphere Body is added in anhydrous organic solvent, and 10-100mL anhydrous organic solvent is added in every gram of carrier；Adding concentration is 0.001- The anhydrous organic solvent solution of the alpha-diimine metal complex of 0.1mmol/mL, every gram of carrier by modifier treatment are added The alpha-diimine metal complex of 1-10mmol reacts 1-48 hours, 0-100 DEG C of reaction temperature, reaction solution is concentrated under reduced pressure to original Reaction solution is concentrated under reduced pressure to 1st/1/10th to 50 of original solution volume in 1/10th of liquor capacity, adds concentration Ten times of liquid product precipitate to fiftyfold precipitating reagent, filter, and after solid is washed with precipitating reagent, vacuum drying obtains alpha-diimine gold The loaded article of metal complex；
Wherein the alpha-diimine metal complex is made by alpha-diimine compound and late transition metal reactant salt；
The preparation method of the alpha-diimine metal complex, comprising the following steps:, will in reactor in a nitrogen atmosphere Late transition metal salt is added in the anhydrous organic solvent solution for the alpha-diimine compound that concentration is 0.001-0.1mmol/mL Reaction, wherein late transition metal salt and alpha-diimine compound equimolar amounts；It is stirred to react 1-48 hours, reaction temperature 0-100 DEG C, reaction solution is concentrated under reduced pressure to 1st/1/10th to 50 of original solution volume, adds the volume of the concentrated liquid ten again to five Ten times of precipitating reagent precipitating, filters, and after solid is washed with precipitating reagent, vacuum drying obtains alpha-diimine metal complex；
Alternatively, method two, comprising the following steps:
In reaction flask in a nitrogen atmosphere, anhydrous organic solvent, the compound loaded object of alpha-diimine and alpha-diimine is added The late transition metal salt of object equimolar amounts is closed, 10-100mL anhydrous organic solvent is added in the compound loaded object of every gram of alpha-diimine, Late transition metal salinity is 0.001-1mmol/mL anhydrous organic solvent solution, is stirred to react 1-48 hours, reaction temperature 0- 100 DEG C, reaction solution is concentrated under reduced pressure to 1st/1/10th to 50 of original solution volume, adds ten times of the volume of the concentrated liquid extremely Fiftyfold precipitating reagent precipitating, filters, and after solid is washed with precipitating reagent, vacuum drying obtains the negative of alpha-diimine metal complex Loading；
Wherein the compound loaded object of alpha-diimine is reacted by alpha-diimine compound with by the carrier of modifier treatment It is made, preparation method is the following steps are included: in reaction flask in a nitrogen atmosphere, under stiring, toward by modifier treatment Anhydrous organic solvent is added in carrier, 10-100mL anhydrous organic solvent is added in every 1g carrier；Adding concentration is 0.001- The anhydrous organic solvent solution of the alpha-diimine compound of 0.1mmol/mL, wherein alpha-diimine compound with pass through modifying agent The ratio of the carrier of processing is the alpha-diimine compound that 1-10mmol is added in every gram of carrier, is reacted 1-48 hours, reaction temperature 0-100 DEG C, reaction solution is concentrated under reduced pressure to 1st/1/10th to 50 of original solution volume, adds ten times of the volume of the concentrated liquid It precipitates, filters to fiftyfold precipitating reagent, after solid is washed with precipitating reagent, it is compound loaded that vacuum drying obtains alpha-diimine Object；
The wherein preparation method of the carrier by modifier treatment, comprising the following steps: reaction in a nitrogen atmosphere In bottle, under mechanical stirring, carrier is added in anhydrous organic solvent and obtains suspension, make the concentration of carrier in suspension 0.01-0.1g/mL, then modifying agent is added by the amount that 0.1-50mmol modifying agent is added in 1g carrier, it reacts 4-16 hours, reaction temperature Degree is 0-50 DEG C, filters after reaction, washs to obtain modified support with anhydrous organic solvent, precipitating reagent respectively；
The late transition metal salt is one of nickel salt, palladium salt, platinum salt, molysite or cobalt salt；
The organic solvent is C1-C20Chloralkane, C6-C20Chlorination aromatic hydrocarbon, C6-C20Aromatic hydrocarbon or C2-C20's One of oxygen-containing alkane or a variety of mixtures；
The precipitating reagent is C5-C20Alkane or C5-C20One of cycloalkane or a variety of mixtures；
The carrier is inorganic oxide, metal salt, clay, diatomite, montmorillonite, polystyrene resin, carbon black, carbon nanometer One of pipe and graphene or a variety of complex carriers；
The modifying agent is aluminum alkoxide, alkyl aluminum, dialkyl group zinc, dialkyl group silicon dichloride, dialkyl group dibromo SiClx, an alkane Base trichlorosilicane, an alkyl tribromo SiClx, TiX4、ZrX4、SiX4Or BX3One of or a variety of mixtures, wherein X be chlorine or Bromine；
The alpha-diimine compound, it is characterized in that the structural formula of alpha-diimine compound are as follows:
Wherein, R is substituted base or unsubstituted C6-C60Aryl, C6-C60One of heterocyclic arene base；Ar is tool Just like one of flowering structure group:
Wherein, n=1,2,3,4,5,6 or 7；R' is C1-C20Alkyl.
2. a kind of alpha-diimine metal complex of load as described in claim 1, it is characterized in that the organic solvent is excellent It selects in methylene chloride, chloroform, 1,2- dichloroethanes, chlorobenzene, dichloro-benzenes, toluene, tetrahydrofuran or 1,4- dioxane One or more mixtures.
3. a kind of alpha-diimine metal complex of load as described in claim 1, it is characterized in that the precipitating reagent is preferred One of pentane, n-hexane, normal heptane, normal octane or hexamethylene or a variety of mixtures.
4. a kind of alpha-diimine metal complex of load as described in claim 1, it is characterized in that the late transition metal Salt preferably (DME) NiBr2、(DME)NiCl2、(COD)PdClCH3、(PhCN)2PdCl2Or (COD) PdMe (NCMe).
5. a kind of alpha-diimine metal complex of load as described in claim 1, it is characterized in that the carrier is preferably SiO2、MgCl2, diatomite, montmorillonite, Al2O3、Fe3O4、SiO2/MgCl2Complex carrier, SiO2/ composite diatomite carrier, illiteracy are de- Soil/MgCl2Complex carrier, diatomite/MgCl2Complex carrier, Al2O3/MgCl2Complex carrier or Fe3O4/MgCl2In complex carrier One kind.
6. a kind of alpha-diimine metal complex of load as described in claim 1, it is characterized in that the modifying agent is preferred For methylaluminoxane (MAO), ethylaluminoxane (EAO), modified methylaluminoxane (MMAO), AlMe3、AlEt3、Al(i-Bu)3、 AlEt2Cl、ZnEt2、TiCl4、ZrCl4、SiCl4Or BCl3One of or a variety of mixtures.
7. a kind of application of the alpha-diimine metal complex of load as described in claim 1, it is characterized in that as main catalytic Agent is applied in the gas-phase polymerization of ethylene or propylene or the liquid-phase bulk polymerization or slurry polymerization of olefinic monomer.
8. a kind of application of the alpha-diimine metal complex of load as described in claim 1, it is characterized in that the complex is made Apply in olefin polymerization for major catalyst, including following reaction condition: polymeric reaction temperature is -20-120 DEG C；Olefinic monomer Pressure is 0.1-10MPa when for gas；Olefinic monomer be specially ethylene, propylene, 1- butylene, 1- amylene, 4-methyl-1-pentene, 1- hexene, 1- heptene, 1- decene, norbornene, vinyl norbornene, ethylidene norbornene, bicyclopentadiene, 1,4- fourth One of diene, styrene, α-methylstyrene and divinylbenzene or a variety of mixtures.
CN201811155509.8A 2018-09-30 2018-09-30 It is a kind of to load the catalyst for having alpha-diimine metal complex and its application in olefin polymerization Pending CN109280100A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113185415A (en) * 2021-04-30 2021-07-30 河北工业大学 Aromatic amine with multiple hydroxyl groups and pyridine diimine compound, complex and load thereof
CN113233994A (en) * 2021-04-30 2021-08-10 河北工业大学 Alpha-diimine compound with multiple hydroxyl groups, complex, load and application thereof
CN115260345A (en) * 2021-04-29 2022-11-01 中国石油化工股份有限公司 Supported diimine catalyst, preparation method thereof, composite catalyst containing supported diimine catalyst and application of composite catalyst
RU2790674C1 (en) * 2022-07-03 2023-02-28 Федеральное государственное бюджетное учреждение науки Иркутский институт химии им. А.Е. Фаворского Сибирского отделения Российской академии наук Complex nickel hydrogenation catalyst

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104829488A (en) * 2015-04-30 2015-08-12 天津工业大学 Supported alpha-diimine metal complex, and its application in olefin polymerization
CN108530563A (en) * 2017-03-03 2018-09-14 天津工业大学 A kind of application of the loaded article of alpha-diimine and its metal complex in olefin polymerization

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104829488A (en) * 2015-04-30 2015-08-12 天津工业大学 Supported alpha-diimine metal complex, and its application in olefin polymerization
CN108530563A (en) * 2017-03-03 2018-09-14 天津工业大学 A kind of application of the loaded article of alpha-diimine and its metal complex in olefin polymerization

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115260345A (en) * 2021-04-29 2022-11-01 中国石油化工股份有限公司 Supported diimine catalyst, preparation method thereof, composite catalyst containing supported diimine catalyst and application of composite catalyst
CN115260345B (en) * 2021-04-29 2023-07-21 中国石油化工股份有限公司 Supported diimine catalyst, preparation method thereof, composite catalyst containing supported diimine catalyst and application of supported diimine catalyst
CN113185415A (en) * 2021-04-30 2021-07-30 河北工业大学 Aromatic amine with multiple hydroxyl groups and pyridine diimine compound, complex and load thereof
CN113233994A (en) * 2021-04-30 2021-08-10 河北工业大学 Alpha-diimine compound with multiple hydroxyl groups, complex, load and application thereof
CN113233994B (en) * 2021-04-30 2023-01-06 河北工业大学 Alpha-diimine compound with multiple hydroxyl groups, complex, load and application thereof
RU2790674C1 (en) * 2022-07-03 2023-02-28 Федеральное государственное бюджетное учреждение науки Иркутский институт химии им. А.Е. Фаворского Сибирского отделения Российской академии наук Complex nickel hydrogenation catalyst

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Application publication date: 20190129