CN110845359A - α -diimine metal complex hydrogen bond load and application thereof in olefin polymerization - Google Patents

α -diimine metal complex hydrogen bond load and application thereof in olefin polymerization Download PDF

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CN110845359A
CN110845359A CN201810946574.6A CN201810946574A CN110845359A CN 110845359 A CN110845359 A CN 110845359A CN 201810946574 A CN201810946574 A CN 201810946574A CN 110845359 A CN110845359 A CN 110845359A
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diimine
metal complex
hydrogen bond
carrier
load
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韦德帅
侯彦辉
任合刚
王登飞
宋磊
高宇新
付义
杨国兴
赵增辉
闫义彬
姜进宪
王玉如
何书艳
胡博文
郭海洋
路小敏
王东青
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Petrochina Co Ltd
Tianjin Polytechnic University
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Petrochina Co Ltd
Tianjin Polytechnic University
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Abstract

The invention provides a α -diimine metal complex hydrogen bond load and application thereof in olefin polymerization, wherein the α -diimine metal complex hydrogen bond load is obtained by compounding a α -diimine metal complex and a carrier, or compounding a load of α -diimine compound and a late transition metal salt.

Description

α -diimine metal complex hydrogen bond load and application thereof in olefin polymerization
Technical Field
The invention relates to the field of olefin catalysis, in particular to an α -diimine metal complex hydrogen bond load and application thereof in olefin polymerization.
Background
Brookhart et al (J Am Chem Soc,1995,117:6414) in 1995 discovered that post-transition metal catalysts of α -nickel diimine and palladium catalyzed ethylene polymerization to high molecular weight polymers at normal pressure, however, they discovered earlier that the high temperature resistance of such catalysts was poor and could not be industrialized, and further studies subsequently revealed that the high temperature resistance of α -diimine ligand substituents increased with volume, and now satisfied the temperature requirements for industrial olefin polymerization.
α -diimine complex is generally supported on a carrier if it is used in slurry olefin polymerization or gas phase olefin polymerization. α -diimine complex can be directly supported by physical adsorption. although the direct physical adsorption supporting method is simple, the catalyst and the carrier have weak force and the active center of the catalyst is easily dropped off during the catalytic polymerization. α -diimine complex is supported by α -diimine complex which is chemically bonded to the carrier (Appl Catal A: Gen,2004,262: 13; J Mol Catal A: Chem,2008,287: 57; Macromolecules,2006, 6339: 41) so that the dropping off of α -diimine complex can be solved.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a novel α -diimine metal complex hydrogen bond supporter, wherein a ligand or a complex of α -diimine is directly supported on a carrier in a hydrogen bond manner through a hydroxyl group on the ligand.
In order to achieve the purpose, the invention provides an α -diimine metal complex hydrogen bond load, which is obtained by compounding α -diimine metal complex and a carrier, or compounding a load of α -diimine compound and a late transition metal salt;
the α -diimine metal complex hydrogen bond load is prepared by one of the following two methods:
the method I comprises the following steps:
mixing an organic solvent and a carrier, adding 10-100mL of the organic solvent into each gram of the carrier, adding α -diimine metal complex organic solvent solution with the concentration of 0.001-0.1mmol/mL, wherein the proportion of α -diimine metal complex to the carrier is that 1-10mmol of α -diimine metal complex is added into each gram of the carrier, stirring for 1-48 hours at the temperature of 0-200 ℃, then carrying out reduced pressure concentration on reaction liquid to obtain concentrated solution, adding precipitator with the volume ten times to fifty times that of the concentrated solution for precipitation, carrying out suction filtration, washing solids with the precipitator, and carrying out vacuum drying to obtain α -diimine metal complex hydrogen bond load;
adding the post-transition metal salt into a α -diimine compound solution with the concentration of 0.001-0.1mmol/mL for reaction, wherein the post-transition metal salt and the α -diimine compound have equal molar weight, stirring and reacting for 1-48 hours at room temperature, carrying out reduced pressure concentration on the reaction liquid to obtain a concentrated solution, adding a precipitator with the volume ten times to fifty times that of the concentrated solution for precipitation, carrying out suction filtration, washing the solid with the precipitator, and carrying out vacuum drying to obtain the α -diimine metal complex;
the second method comprises the following steps:
mixing an organic solvent, α -diimine compound load and α -diimine compound equimolar late transition metal salt, wherein 10-100mL of organic solvent is added into each gram of α -diimine compound load, stirring for 1-48 hours at the temperature of 0-200 ℃, then carrying out reduced pressure concentration on reaction liquid, adding a precipitator with volume ten times to fifty times that of the concentrated liquid for precipitation, carrying out suction filtration, washing the solid with the precipitator, and carrying out vacuum drying to obtain α -diimine metal complex hydrogen bond load;
adding an organic solvent and a carrier into a reaction bottle, adding 10-100mL of the organic solvent into every 1g of the carrier, adding an organic solvent solution of α -diimine compound with the concentration of 0.001-0.1mmol/mL, wherein the ratio of α -diimine compound to the carrier is that 1-10mmol of α -diimine compound is added into every gram of the carrier, stirring for 1-48 hours at the temperature of 0-200 ℃, then carrying out reduced pressure concentration on the reaction solution, adding a precipitating agent with the volume ten times to fifty times that of the concentrated solution for precipitation, carrying out suction filtration, washing the solid with the precipitating agent, and carrying out vacuum drying to obtain the α -diimine compound load.
The α -diimine ligand adopted by the α -diimine metal complex hydrogen bond load provided by the invention is provided with hydroxyl, the hydroxyl can directly load the ligand or the complex on a carrier in a hydrogen bond mode, meanwhile, the aromatic group on the imino group in the α -diimine compound can be randomly changed according to the requirement, and the α -diimine ligand is simple to prepare and is beneficial to the application of the α -diimine metal complex hydrogen bond load in olefin polymerization.
According to a specific embodiment of the present invention, preferably, the late transition metal salt is one of a nickel salt, a palladium salt, a platinum salt, an iron salt, a cobalt salt, and the like. More preferably, the late transition metal salt is (DME) NiBr2、(DME)NiCl2、(COD)PdClCH3、(PhCN)2PdCl2Or (COD) PdMe (NCMe).
According to a specific embodiment of the present invention, it is preferred that the α -diimine compound has hydroxyl groups on its ligands.
According to a particular embodiment of the present invention, preferably, the α -diimine compound has the formula:
wherein X is CH2Or OCH2CH2(ii) a R, Ar are each independently substituted or unsubstituted C6-C60Aryl radical, C3-C60One of the heterocyclic aromatic hydrocarbon groups of (1); n is any integer of 0 to 30;
A. b is hydrogen, alkyl of C1-C15, aryl of C6-C30, or A, B and adjacent carbon atoms form acenaphthyl, phenanthryl or C1-C30 naphthenic base.
According to a particular embodiment of the present invention, preferably, the organic solvent is C1-C20Chlorinated alkane of (C)6-C20Chlorinated aromatic hydrocarbons of (2), C6-C20And C is an aromatic hydrocarbon2-C20And the like. More preferably, the organic solvent comprises one or a combination of more of dichloromethane, trichloromethane, 1, 2-dichloroethane, chlorobenzene, dichlorobenzene, toluene, tetrahydrofuran, and 1, 4-dioxane, and the like.
According to a particular embodiment of the invention, preferably, the precipitating agent is C5-C20Alkane and C5-C20And the like. More preferably, the precipitation agent comprises a combination of one or more of n-pentane, n-hexane, n-heptane, n-octane, cyclohexane, and the like.
According to the specific embodiment of the present invention, preferably, the support is a complex of one or more of inorganic oxides, metal salts, clay, diatomaceous earth, montmorillonite, polystyrene resin, carbon black, carbon nanotubes, graphene, and the likeAnd (4) synthesizing a carrier. More preferably, the carrier is SiO2、MgCl2Diatomite, montmorillonite and Al2O3、Fe3O4、SiO2/MgCl2Composite Carrier, SiO2/diatomite composite carrier, montmorillonite/MgCl2Composite support, diatomaceous earth/MgCl2Composite Carrier, Al2O3/MgCl2Composite carrier or Fe3O4/MgCl2A composite carrier, and the like.
According to the specific embodiment of the invention, in the process of preparing α -diimine metal complex hydrogen bond load, when concentration under reduced pressure is carried out, most of the solvent is evaporated and removed, and the reaction solution can be concentrated to 1/5 volume or less, preferably 1/10 volume or less, and generally 1/40 volume or less.
The invention also provides application of the α -diimine metal complex hydrogen bond load as a catalyst in olefin polymerization reaction, and the α -diimine metal complex hydrogen bond load provided by the invention can solve the defects of kettle adhesion, difficult control of polymer form, large using amount of cocatalyst, poor thermal stability and the like in the practical application of a homogeneous α -diimine late transition metal catalyst in the prior art.
In the above application, preferably, the olefin polymerization reaction includes gas phase polymerization of ethylene or propylene, or liquid phase bulk polymerization or slurry polymerization of an olefin monomer.
In the above applications, it is preferred that the α -diimine metal complex hydrogen bond support be used as a procatalyst in olefin polymerization reactions.
In the above application, preferably, the olefin polymerization conditions are: the polymerization temperature is-20 ℃ to 120 ℃; the pressure is 0.1-10MPa when the olefin monomer is gas;
the olefin monomer is one or more of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene, norbornene, vinyl norbornene, ethylidene norbornene, dicyclopentadiene, 1, 4-butadiene, styrene, α -methyl styrene and divinylbenzene.
The α -diimine metal complex hydrogen bond load is prepared by directly loading α -diimine compound metal complex on a carrier which is not chemically modified through hydrogen bond action, and the loading method is simple, convenient and effective, and meanwhile, aromatic groups on imino groups in the α -diimine complex can be randomly changed according to needs, so that the controllability of the structure and the high-temperature resistant catalytic activity are improved.
Compared with the α -diimine catalyst of the classical Brookhart with poor thermal stability, the α -diimine metal complex hydrogen bond load as a load type catalyst has good thermal stability during olefin polymerization, and the polymerization activity can still reach 10 at the reaction temperature of 80 DEG C6The length of an alkyl chain on α -diimine ligand is changed, so that the distance between a carrier and a catalytic active center can be changed, and the influence of the carrier on the catalytic active center is adjusted.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Synthesis of mono- α -diimine metal complex
Example 1
2, 3-bis {2, 6-bis [ bis (4-fluorophenyl) methyl group]-4-hydroxyethylbenzimine } butane nickel bromide (Nil)1) Synthesis of (2)
Under nitrogen atmosphere, ligand l is added into a reaction bottle1(1.133g,1mmol), 1, 2-Dimethoxyethanenickel Bromide (DME) NiBr2(0.309g,1mmol) and 30mL of methylene chloride, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was then concentrated under reduced pressure to 5mL, and 50mL of n-hexane was added to precipitate a reddish brown solid. Suction filtration, washing the solid with n-hexane, and vacuum drying to obtain the complex Nil11.321g, yield: 97％。
Complex Nil1Elemental analysis of (2): c72H56Br2F8N2NiO2Theoretical value: c, 63.98%, H, 4.18%, N, 2.07%. Experimental values: c63.95%, H4.19%, N2.06%. ICP assay, Ni 4.33%.
Ligand 2, 3-bis {2, 6-bis [ bis (4-fluorophenyl) methyl]-4-hydroxyethylbenzimide } butane (l)1) The chemical structure of (A) is as follows:
example 2
1, 2-bis [2, 6-bis (benzhydryl) -4- (6-hydroxyhexyloxy) phenylimine]Acenaphthene nickel bromide (Nil)2) Synthesis of (2)
Complex Nil2With the Complex Nil of example 11The preparation process is the same, wherein ligand l is adopted2Instead of l in example 11. Complex Nil2The yield of (3) was 97%.
Complex Nil2Elemental analysis of (2): c88H80Br2N2NiO4Theoretical value: 72.99% of C, 5.57% of H and 1.93% of N; experimental values: 72.95% of C, 5.56% of H and 1.98% of N. ICP assay, Ni 4.02%.
Ligand 1, 2-bis [2, 6-bis (benzhydryl) -4- (6-hydroxyhexyloxy) phenylimine]Acenaphthene (l)2) The chemical structure of (A) is as follows:
Figure BDA0001770374580000052
example 3
1- {2, 6-bis [ bis (2-benzothienyl) methyl]-4-hydroxyethylbenzimide } -2- (2, 4-dimethyl-6-benzhydrylbenzeneimine) acenaphthylene nickel bromide (Nil)3) Synthesis of (2)
Complex Nil3With the Complex Nil of example 11The preparation process is the same, wherein ligand l is adopted3Instead of l in example 11. Complex Nil3The yield of (3) was 95%.
Complex Nil3Elemental analysis of (2): c75H54Br2N2NiOS4Theoretical value: c66.92%, H4.04%, N2.08%; experimental values: c66.88%, H4.07%, N2.05%. ICP determination, Ni, 4.35%.
Ligand 1- {2, 6-bis [ bis (2-benzothienyl) methyl]-4-hydroxyethylbenzimide } -2- (2, 4-dimethyl-6-benzhydrylbenzeneimine) acenaphthene (l)3) The chemical structure of (A) is as follows:
Figure BDA0001770374580000061
example 4
2, 3-bis {2, 6-bis [ bis (4-fluorophenyl) methyl group]-4-hydroxyethylbenzimine } butane palladium (Pdl) chloride1) The synthesis of (2):
under nitrogen atmosphere, ligand l is added into a reaction bottle1(1.133g,1mmol)、(PhCN)2PdCl2(0.384g,1mmol) and 30mL of methylene chloride, and the mixture was stirred at room temperature for 24 hours. The reaction mixture was then concentrated under reduced pressure to 5mL, and 50mL of n-hexane was added to precipitate a reddish brown solid. Filtering, washing the solid with n-hexane, and drying in vacuum to obtain the complex Pdl10.801g, yield: 90 percent.
Complex Pdl1Elemental analysis of (2): c72H56Cl2F8N2O2Theoretical value of Pd: c65.99%, H4.31%, N2.14%; experimental values: c65.96%, H4.34%, N, 2.16%. ICP assay, Pd 8.11%.
Synthesis of bis, α -diimine Supports
The method comprises the following steps:
example 5
2, 3-bis {2, 6-bis [ bis (4-fluorophenyl) methyl group]-4-hydroxyethylbenzimine } butane silica SiO2-l1Synthesis of (2)
50mL of methylene chloride and SiO were added to the reaction flask in this order21g, then slowly dropping ligand l under mechanical stirring1Dichloromethane solution (0.8 mm)ol Compound l120mL of methylene chloride). Stirring at room temperature for 20 hours, adding 100mL of n-hexane for precipitation, performing suction filtration, washing with n-hexane for 3 times, and drying to obtain an orange solid product SiO2-l11.92 g. Load SiO2-l1Elemental analysis of (2): c36.63% and N1.18%.
Example 6
1, 2-bis [2, 6-bis (benzhydryl) -4- (6-hydroxyhexyloxy) phenylimine]Acenaphthene aluminium oxide load Al2O3-l2Synthesis of (2)
Supported Al2O3-l2The preparation process of (1) and the SiO loading substance in example 52-l1The preparation process is the same, wherein Al is adopted2O3Instead of SiO in example 52Ligand l2Instead of l in example 51. Supported Al2O3-l2Elemental analysis of (2): c43.84%, N1.17%.
Example 7
1- {2, 6-bis [ bis (2-benzothienyl) methyl]-4-hydroxyethylbenzimide } -2- (2, 4-dimethyl-6-benzhydrylbenzeneimine) acenaphthylene montmorillonite and magnesium chloride composite carrier load montmorillonite/MgCl2-l3Synthesis of (2)
Adding 50mL of n-heptane solvent and 1g of anhydrous MgCl into a five-mouth bottle with mechanical stirring in turn under the protection of argon2Adding a certain amount of n-butanol (the molar ratio of the n-butanol to the magnesium chloride is 4:1) at 35 ℃, and then raising the temperature to 90 ℃ by a program for 3 hours to obtain a colorless transparent solution. Then cooling the solution to 60 ℃, and then adding a certain amount of montmorillonite (MgCl)2The mass ratio of montmorillonite to montmorillonite is equal to 1:1), stirring for 2 hours at the temperature, stopping, and obtaining montmorillonite/MgCl through suction filtration and drying2And (3) a composite carrier.
Supported montmorillonite/MgCl2-l3The preparation process of (1) and the SiO loading substance in example 52-l1The preparation process is the same, wherein montmorillonite/MgCl is adopted2Instead of SiO in example 52Ligand l3Instead of l in example 221. Supported montmorillonite/MgCl2-l3Elemental analysis of (2): c35.09% and N1.09%.
Synthesis of supported metal complex
The method comprises the following steps:
example 8
2, 3-bis {2, 6-bis [ bis (4-fluorophenyl) methyl group]-4-hydroxyethylbenzimine } butane nickel bromide silica loading SiO2-Nil1Synthesis of (2)
The supported material SiO obtained in example 5 was charged into a reaction flask under a nitrogen atmosphere2-l11.92g, 0.247g (0.8mmol) of 1, 2-dimethoxyethane nickel bromide and 30mL of methylene chloride were stirred at room temperature for 24 hours. Then, the reaction mixture was concentrated under reduced pressure to 5mL, and 50mL of n-hexane was added. Suction filtration, washing the solid with normal hexane, and vacuum drying to obtain the load SiO2-Nil12.09 g. Load SiO2-Nil1The content of Ni: 2.2 percent.
Example 9
1, 2-bis [2, 6-bis (benzhydryl) -4- (6-hydroxyhexyloxy) phenylimine]Naphthene nickel bromide aluminum oxide load Al2O3-Nil2Synthesis of (2)
Supported Al2O3-Nil2The preparation process of (1) and the SiO loading substance in example 82-Nil1The same procedure was used, using Al from example 62O3-l2Instead of SiO in example 82-Nil1. Supported Al2O3-Nil2The content of Ni: 2.8 percent.
Example 10
1- {2, 6-bis [ bis (2-benzothienyl) methyl]-4-hydroxyethylbenzimide } -2- (2, 4-dimethyl-6-benzhydrylbenzeneimine) acenaphthene nickel bromide montmorillonite and magnesium chloride composite carrier loaded montmorillonite/MgCl2-Nil3Synthesis of (2)
Supported montmorillonite/MgCl2-Nil3The preparation process of (1) and the SiO loading substance in example 82-Nil1The procedure was the same, using the montmorillonite/MgCl prepared in example 72-l3Instead of SiO in example 82-Nil1. Supported montmorillonite/MgCl2-Nil3The content of Ni: 2.6 percent.
Example 11
2, 3-bis {2, 6-bis [ bis (4-fluorophenyl) methyl group]-4-hydroxyethylbenzimine } butane palladium chloride silica Supported SiO2-Pdl1Synthesis of (2)
Load SiO2-Pdl1The preparation process of (1) and the SiO loading substance in example 82-Nil1The procedure was the same, except that palladium chloride dibenzonitrile was used instead of nickel 1, 2-dimethoxyethane bromide in example 8. Load SiO2-Pdl1The content of Pd in the solution: 3.7 percent.
The second method comprises the following steps:
example 12
2, 3-bis {2, 6-bis [ bis (4-fluorophenyl) methyl group]-4-hydroxyethylbenzimine } butane nickel bromide silica loading SiO2-Nil1Synthesis of (2)
Load SiO2-Nil1The preparation process of (1) and the SiO loading substance in example 52-l1The same procedure was used, wherein the Nil obtained in example 1 was used1Instead of l in example 51. Load SiO2-Nil1The content of Ni: 2.3 percent.
Example 13
2, 3-bis {2, 6-bis [ bis (4-fluorophenyl) methyl group]-4-hydroxyethylbenzimine } butane palladium chloride silica Supported SiO2-Pdl1Synthesis of (2)
Load SiO2-Pdl1The preparation process of (1) and the SiO loading substance in example 52-l1The same procedure was used, wherein the Pdl obtained in example 4 was used1Instead of l in example 51. Load SiO2-Pdl1The content of Pd in the solution: 3.8 percent.
Tetra, olefin polymerization
Example 14
Load SiO2-Nil1As main catalyst for catalyzing ethylene polymerization
50mL of anhydrous toluene was added to a 250mL reaction vessel which had been purged with nitrogen and charged with ethylene three times, the reaction vessel was heated to 30 ℃ and was kept at a constant temperature, ethylene was introduced while stirring to maintain the pressure in the reaction vessel at 0.5MPa, and 20mg of the SiO supported material obtained in example 8 was added to each of the reaction vessels2-Nil11.4mol/L of cocatalyst MAO (5.4mL, the molar ratio of the cocatalyst to the main catalyst is 1000:1), the polymerization time is 1 hour, then 10mL of acidified ethanol with the volume percentage concentration of 10% (namely, concentrated hydrochloric acid with the volume ratio of 37%: absolute ethanol: 1:9) is added until the reaction is terminated, the polymer is washed by water and ethanol, filtered, and dried in a vacuum drying oven at 60 ℃ for 8 hours, and 2.2g of the product polyethylene is obtained. Load SiO2-Nil1Has a catalytic activity of 3X 105g/mol. h (activity calculated from the mass of the polymerization product/(amount of metal species in the catalyst. times. per hour)). The Mw (weight average molecular weight) of the polymer was 5.6X 105g/mol, MWD (molecular weight distribution) 2.2 (determined by GPC).13The degree of branching of the polymer was determined by C NMR to be 45/1000 carbon atoms.
Example 15
Load SiO2-Nil1As main catalyst for catalyzing ethylene polymerization
The ethylene polymerization conditions and the specific operation were the same as in example 14. Wherein the main catalyst uses the load SiO prepared in example 122-Nil1SiO as a substitute for the support in example 142-Nil1. Supported SiO prepared from example 122-Nil1Has a catalytic activity of 2.7X 105g/mol. h (activity calculated from the mass of the polymerization product/(amount of metal species in the catalyst. times. per hour)). The Mw (weight average molecular weight) of the polymer was 6.2X 105g/mol, MWD 2.3 (measured by GPC).13The degree of branching of the polymer was determined by C NMR to be 41/1000 carbon atoms.
Example 16
Supported Al2O3-Nil2Catalyzing propylene polymerization as a procatalyst
The solvent is anhydrous toluene, the propylene pressure is 2.0MPa, the reaction temperature is 60 ℃, and the main catalyst is the load Al prepared in the embodiment 92O3-Nil2The procedure of example 14 was repeated except that the cocatalyst MAO was used in a molar ratio of 500:1, and the polymerization time was 2 hours. Supported Al2O3-Nil2Has a catalytic activity of 6.3X 104g/mol. h, a polymer Mw of 2.1X 105g/mol, MWD 3.1.
Example 17
Supported montmorillonite/MgCl2-Nil3As the main catalyst to catalyze the copolymerization of 1-butene and ethylene
The solvent was anhydrous toluene, the pressure ratio of 1-butene to ethylene was 0.5, the pressure in the reactor was maintained at 0.5MPa, the reaction temperature was 80 ℃ and the procatalyst was supported on montmorillonite/MgCl prepared in example 102-Nil3Cocatalyst B (C)6F5)4(molar ratio of cocatalyst to procatalyst 800:1), the procedure of example 14 was followed, and the polymerization time was 1.5 hours. Supported montmorillonite/MgCl2-Nil3Has a catalytic activity of 4.4X 105g/mol. h, a polymer Mw of 5.7X 105g/mol, MWD 2.8.
Example 18
Load SiO2-Pdl1Catalyzing polymerization of 1-hexene as main catalyst
50mL of anhydrous toluene was added to a 250mL reaction vessel purged with nitrogen three times, and 5mL of 1-hexene and the SiO supported material obtained in example 11 were added2-Pdl1And a cocatalyst Al2Et3Cl3(the molar ratio of the cocatalyst to the main catalyst is 800:1), stirring and heating to 40 ℃, polymerizing for 2 hours, then adding 10mL of 10% acidified ethanol until the reaction is finished, washing with water and ethanol, filtering the polymer, and drying in a vacuum drying oven at 60 ℃ for 8 hours to obtain the product polyhexene. Load SiO2-Pdl1Has a catalytic activity of 7.6X 104g/mol. h, a polymer Mw of 2.3X 105g/mol, MWD 3.6.
Example 19
Load SiO2-Pdl1As the main catalyst to catalyze the copolymerization of styrene and 1-decene
Using the Supported SiO obtained in example 132-Pdl1SiO as a substitute for the support in example 182-Pdl11.6g of styrene and 1.1g of 1-decene, co-catalyst MAO (molar ratio of co-catalyst to main catalyst 800:1), reaction temperature 70 ℃ and operation were carried out as in example 18. Load SiO2-Pdl1Has a catalytic activity of 1.6X 105g/mol. h, a polymer Mw of 3.5X 105g/mol, MWD 2.6.
Example 20
Load SiO2-Nil1Catalytic ethylene gas phase polymerization as main catalyst
The gas phase polymerization of ethylene was carried out in a 2L simulated gas phase reactor, 100g of heat-treated sodium chloride was added as a seedbed, ethylene was added, 5mmol of co-catalyst MAO was added, the temperature was raised to 50 ℃ and the SiO supported material prepared in example 8 was added2-Nil120mg, the polymerization time is 3 hours, the reaction pressure is 1.2MPa, ethylene gas is added into the reaction kettle through an electromagnetic valve, the reaction is finished and discharged, and sodium chloride is dissolved by water to obtain 1.6g of polyethylene. Supported SiO from example 82-Nil1Has a catalytic activity of 4.1X 105g/mol. h. The Mw of the polymer was 4.6X 105g/mol, MWD 2.5. The polymer branching degree was 49/1000 carbon atoms.
Example 21
Load SiO2-Nil1As main catalyst for catalyzing ethylene polymerization
The ethylene polymerization conditions and the specific operation were the same as in example 20. Wherein the main catalyst uses the load SiO prepared in example 122-Nil1SiO as a substitute for the support in example 202-Nil1. Supported SiO prepared from example 122-Nil1Has a catalytic activity of 3.9X 105g/mol. h (activity calculated from the mass of the polymerization product/(amount of metal species in the catalyst. times. per hour)). The Mw (weight average molecular weight) of the polymer was 5.1X 105g/mol, MWD (molecular weight distribution) 2.6 (measured by GPC).13The degree of branching of the polymer was determined by C NMR to be 46/1000 carbon atoms.

Claims (15)

1. An α -diimine metal complex hydrogen bond load, which is obtained by compounding α -diimine metal complex and a carrier, or compounding a load of α -diimine compound and a late transition metal salt;
the α -diimine metal complex hydrogen bond load is prepared by one of the following two methods:
the method I comprises the following steps:
mixing an organic solvent and a carrier, adding 10-100mL of the organic solvent into each gram of the carrier, adding α -diimine metal complex organic solvent solution with the concentration of 0.001-0.1mmol/mL, wherein the proportion of α -diimine metal complex to the carrier is that 1-10mmol of α -diimine metal complex is added into each gram of the carrier, stirring for 1-48 hours at the temperature of 0-200 ℃, then carrying out reduced pressure concentration on reaction liquid to obtain concentrated solution, adding precipitator with the volume ten times to fifty times that of the concentrated solution for precipitation, carrying out suction filtration, washing solids with the precipitator, and carrying out vacuum drying to obtain α -diimine metal complex hydrogen bond load;
the α -diimine metal complex is prepared by adding a α -diimine compound and a post-transition metal salt into a α -diimine compound solution with the concentration of 0.001-0.1mmol/mL for reaction, wherein the post-transition metal salt and the α -diimine compound have equal molar weight, stirring and reacting for 1-48 hours at room temperature, carrying out reduced pressure concentration on reaction liquid to obtain concentrated solution, adding a precipitator with the volume ten times to fifty times that of the concentrated solution for precipitation, carrying out suction filtration, washing a solid with the precipitator, and carrying out vacuum drying to obtain a α -diimine metal complex;
the second method comprises the following steps:
mixing an organic solvent, α -diimine compound load and α -diimine compound equimolar late transition metal salt, wherein 10-100mL of organic solvent is added into each gram of α -diimine compound load, stirring for 1-48 hours at the temperature of 0-200 ℃, then carrying out reduced pressure concentration on reaction liquid, adding a precipitator with volume ten times to fifty times that of the concentrated liquid for precipitation, carrying out suction filtration, washing the solid with the precipitator, and carrying out vacuum drying to obtain α -diimine metal complex hydrogen bond load;
adding an organic solvent and a carrier into a reaction bottle, adding 10-100mL of the organic solvent into every 1g of the carrier, adding an organic solvent solution of α -diimine compound with the concentration of 0.001-0.1mmol/mL, wherein the ratio of α -diimine compound to the carrier is that 1-10mmol of α -diimine compound is added into every gram of the carrier, stirring for 1-48 hours at the temperature of 0-200 ℃, then carrying out reduced pressure concentration on the reaction solution, adding a precipitating agent with the volume ten times to fifty times that of the concentrated solution for precipitation, carrying out suction filtration, washing the solid with the precipitating agent, and carrying out vacuum drying to obtain the α -diimine compound load.
2. The α -diimine metal complex hydrogen bond support of claim 1, wherein the late transition metal salt is one of a nickel salt, a palladium salt, a platinum salt, an iron salt, and a cobalt salt.
3. The α -diimine metal complex hydrogen bond support of claim 2, wherein the late transition metal salt is (DME) NiBr2、(DME)NiCl2、(COD)PdClCH3、(PhCN)2PdCl2Or (COD) PdMe (NCMe).
4. The α -diimine metal complex hydrogen bond support of claim 1, wherein the α -diimine compound has hydroxyl groups on its ligands.
5. The α -diimine metal complex hydrogen bond support of claim 4, wherein the α -diimine compound has the formula:
Figure FDA0001770374570000021
wherein X is CH2Or OCH2CH2(ii) a R, Ar are each independently substituted or unsubstitutedSubstituted C6-C60Aryl radical, C3-C60One of the heterocyclic aromatic hydrocarbon groups of (1); n is any integer of 0 to 30;
A. b is hydrogen, alkyl of C1-C15, aryl of C6-C30, or A, B and adjacent carbon atoms form acenaphthyl, phenanthryl or C1-C30 naphthenic base.
6. The α -diimine metal complex hydrogen bond support of claim 1, wherein the organic solvent is C1-C20Chlorinated alkane of (C)6-C20Chlorinated aromatic hydrocarbons of (2), C6-C20And C is an aromatic hydrocarbon2-C20And combinations of one or more of (a) an oxygen-containing alkane.
7. The α -diimine metal complex hydrogen bond support of claim 6, wherein the organic solvent comprises a combination of one or more of dichloromethane, trichloromethane, 1, 2-dichloroethane, chlorobenzene, dichlorobenzene, toluene, tetrahydrofuran, and 1, 4-dioxane.
8. The α -diimine metal complex hydrogen bond support of claim 1, wherein the precipitant is C5-C20Alkane and C5-C20And (c) one or more of (a) cycloalkanes.
9. The α -diimine metal complex hydrogen bond support of claim 8, wherein the precipitant comprises a combination of one or more of n-pentane, n-hexane, n-heptane, n-octane, and cyclohexane.
10. The α -diimine metal complex hydrogen bond support of claim 1, wherein the support is a composite support of one or more of inorganic oxides, metal salts, clays, diatomaceous earth, montmorillonite, polystyrene resin, carbon black, carbon nanotubes, and graphene.
11. The α -diimine metal complex hydrogen bond support of claim 10, wherein the support is SiO2、MgCl2Diatomite, montmorillonite and Al2O3、Fe3O4、SiO2/MgCl2Composite Carrier, SiO2/diatomite composite carrier, montmorillonite/MgCl2Composite support, diatomaceous earth/MgCl2Composite Carrier, Al2O3/MgCl2Composite carrier or Fe3O4/MgCl2One kind of composite carrier.
12. Use of the α -diimine metal complex hydrogen bond support of any one of claims 1-11 as a catalyst in olefin polymerization reactions.
13. Use according to claim 12, wherein the olefin polymerisation reaction comprises a gas phase polymerisation of ethylene or propylene, or a liquid phase bulk or slurry polymerisation of olefin monomers.
14. The use of claim 13, wherein the α -diimine metal complex hydrogen bond support is used as a procatalyst in an olefin polymerization reaction.
15. Use according to claim 12, wherein the olefin polymerization conditions are: the polymerization temperature is-20 ℃ to 120 ℃; the pressure is 0.1-10MPa when the olefin monomer is gas;
the olefin monomer is one or more of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene, norbornene, vinyl norbornene, ethylidene norbornene, dicyclopentadiene, 1, 4-butadiene, styrene, α -methyl styrene and divinylbenzene.
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