α -diimine metal complex-loaded load and application thereof in olefin polymerization
阅读说明：本技术 一种负载α-二亚胺金属配合物的负载物及其在烯烃聚合中的应用 (α -diimine metal complex-loaded load and application thereof in olefin polymerization ) 是由 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 于 2018-08-20 设计创作，主要内容包括：本发明提供了一种负载α-二亚胺金属配合物的负载物及其在烯烃聚合中的应用。该负载α-二亚胺金属配合物的负载物是由α-二亚胺金属配合物与经过改性剂处理的载体反应而得到的,或者是由α-二亚胺化合物的负载物与后过渡金属盐反应得到的。本发明所提供的负载α-二亚胺金属配合物的负载物所采用的α-二亚胺配体上带有羟基,该羟基可以与化学改性后的载体上的活性基团进行反应形成共价键,使得该α-二亚胺化合物以化学键联的方式将其牢固地负载在载体上,避免了它们从载体上脱离。该配体具有很大位阻基团,基于该配体的配合物催化剂在烯烃聚合时的耐高温性能非常好,可以实现在工业上的应用。而且,该带有羟基的胺的制备过程比较简单,它们以及基于它们的α-二亚胺催化剂的制备成本很低,有利于实现产业化的推广。(The invention provides a α -diimine metal complex-loaded load and application thereof in olefin polymerization, wherein the α -diimine metal complex-loaded load is obtained by reacting α -diimine metal complex with a modifier-treated carrier, or α -diimine compound-loaded load with a late transition metal salt, the α -diimine ligand adopted by the α -diimine metal complex-loaded load provided by the invention has hydroxyl groups which can react with active groups on a chemically modified carrier to form covalent bonds, so that the α -diimine compound is firmly loaded on the carrier in a chemical bonding manner, and the separation of the compounds from the carrier is avoided.)
1. A α -diimine metal complex-loaded support obtained by reacting α -diimine metal complex with a modifier-treated support, or a α -diimine compound-loaded support obtained by reacting a late transition metal salt;
the α -diimine metal complex-loaded load is prepared by one of the following two methods:
the method I comprises the following steps:
adding a carrier treated by a modifier into an anhydrous organic solvent under the nitrogen atmosphere, adding 10-100mL of the anhydrous organic solvent into each gram of the carrier treated by the modifier, adding an α -diimine metal complex anhydrous organic solvent solution with the concentration of 0.001-0.1mmol/mL, adding α -diimine metal complex with the concentration of 1-10mmol into each gram of the carrier treated by the modifier, reacting for 1-48 hours at the reaction temperature of 0-200 ℃, carrying out reduced pressure concentration on the reaction liquid to obtain a concentrated solution, adding a precipitator with the volume ten to fifty times that of the concentrated solution for precipitation, carrying out suction filtration, washing a solid by the precipitator, and carrying out vacuum drying to obtain a load of the α -diimine metal complex;
the α -diimine metal complex is prepared by α -diimine compound and late transition metal salt through the following steps of adding the late transition metal salt into an anhydrous organic solvent solution of α -diimine compound with the concentration of 0.001-0.1mmol/mL in a reactor under the nitrogen atmosphere for reaction, wherein the late transition metal salt and α -diimine compound have the same molar weight, stirring for reaction for 1-48 hours at the reaction temperature of 0-200 ℃, 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 α -diimine metal complex;
the second method comprises the following steps:
mixing an anhydrous organic solvent, a load of α -diimine compound and post-transition metal salt with equal molar weight of α -diimine compound under nitrogen atmosphere, adding 10-100mL of the anhydrous organic solvent into each gram of the α -diimine compound load, wherein the concentration of the post-transition metal salt is 0.001-1mmol/mL of the anhydrous organic solvent solution, stirring and reacting for 1-48 hours at the reaction temperature of 0-200 ℃, carrying out reduced pressure concentration on the reaction solution to obtain a concentrated solution, adding a precipitator with ten to fifty times of the volume of the concentrated solution for precipitation, carrying out suction filtration, washing the solid with the precipitator, and carrying out vacuum drying to obtain the load of the α -diimine metal complex;
the α -diimine compound load is prepared by adding an anhydrous organic solvent into a modifier-treated carrier under a nitrogen atmosphere, adding 10-100mL of the anhydrous organic solvent into each gram of the modifier-treated carrier, adding an anhydrous 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 modifier-treated carrier is 1-10mmol of α -diimine compound added into each gram of the modifier-treated carrier, reacting for 1-48 hours at the reaction temperature of 0-200 ℃, concentrating the reaction liquid under reduced pressure to obtain a concentrated solution, adding a precipitant precipitate with the volume ten times to fifty times that of the concentrated solution, performing suction filtration, washing a solid with the precipitant, and performing vacuum drying to obtain the α -diimine compound load.
2. The α -diimine metal complex-supporting load of claim 1, wherein in the first and second methods, the modifier-treated support is prepared by adding the support to an anhydrous organic solvent under a nitrogen atmosphere to obtain a suspension, wherein the concentration of the support in the suspension is 0.01-0.1g/mL, adding the modifier in an amount of 0.1-50mmol of the modifier to 1g of the support, reacting for 4-16 hours at a reaction temperature of 0-50 ℃, filtering after the reaction is finished, and washing with the anhydrous organic solvent and the precipitant respectively to obtain the modified support.
3. The α -diimine metal complex-supporting support of claim 1 or 2, wherein the modifier is aluminum alkoxide, aluminum alkyl, zinc dialkyl, silicon dialkyl dichloride, silicon dialkyl dibromide, silicon monoalkyl trichloride, silicon monoalkyl tribromide, TiX4、ZrX4、SiX4And BX3Wherein X is chlorine or bromine.
4. The α -diimine metal complex-supporting load of claim 3, wherein the modifier is methylaluminoxane, ethylaluminoxane, modified methylaluminoxane, AlMe3、AlEt3、Al(i-Bu)3、AlEt2Cl、ZnEt2、TiCl4、ZrCl4、SiCl4And BCl3One or more of the above.
5. The α -diimine metal complex-loaded 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.
6. The α -diimine metal complex-supporting support of claim 5, wherein the late transition metal salt is (DME) NiBr2、(DME)NiCl2、(COD)PdClCH3、(PhCN)2PdCl2Or (COD) PdMe (NCMe).
7. The α -diimine metal complex-supporting load of claim 1, wherein the α -diimine compound has hydroxyl groups on its ligands.
8. The α -diimine metal complex-supporting load of claim 7, wherein 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.
9. The α -diimine metal complex-supporting load 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.
10. The α -diimine metal complex-loaded support of claim 9, wherein the organic solvent comprises a combination of one or more of dichloromethane, chloroform, 1, 2-dichloroethane, chlorobenzene, dichlorobenzene, toluene, tetrahydrofuran, and 1, 4-dioxane.
11. The α -diimine metal complex-supporting load of claim 1, wherein the precipitant is C5-C20Alkane and C5-C20And (c) one or more of (a) cycloalkanes.
12. The α -diimine metal complex-supporting support of claim 11, wherein the precipitant comprises a combination of one or more of n-pentane, n-hexane, n-heptane, n-octane, and cyclohexane.
13. The α -diimine metal complex-supporting 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 resins, carbon black, carbon nanotubes, and graphene.
14. The α -diimine metal complex-supporting material of claim 13, 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.
15. Use of the α -diimine metal complex-supporting support of any one of claims 1-14 as a catalyst in olefin polymerization reactions.
16. Use according to claim 15, 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.
17. The use of claim 16, wherein the α -diimine metal complex-loaded support is used as a procatalyst in olefin polymerization.
18. Use according to claim 15, 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.
Technical Field
The invention relates to the field of olefin catalysis, in particular to a load of α -diimine metal complex and application thereof in olefin polymerization.
Background
Brookhart et al (New Pd (II) -and Ni (II) -Based Catalysts for Polymerization of Ethylene and. alpha. -Olefins, J Am Chem Soc,1995,117:6414) discovered that α -nickel-palladium late transition metal Catalysts catalyze Ethylene Polymerization to High molecular weight polymers at normal pressure, however, they discovered earlier that such Catalysts have relatively poor High temperature resistance and are not commercially viable.A further study subsequently found that High temperature resistance is further enhanced as the α -Diimine ligand substituent becomes larger in volume.
α -diimine complexes generally need to be supported on a support if used in Slurry or gas phase olefin polymerization. α -diimine complexes can be supported directly by physical adsorption Another method of supporting α -diimine complexes is α -diimine complexes are chemically bonded to a support, which solves the problem of α -diimine complexes falling off3、SiCl4Or BCl3Treating silica to react with hydroxyl on the surface of the carrier to load, and synthesizing the product with-NH2Or α -diimine complexes of-OH functional groups via-NH on α -diimine2or-OH reacts with Al-Me, Si-Cl or B-Cl bonds on the surface of the carrier, and α -diimine complexes are loaded on the carrier through chemical bonds (such as the following reaction formula).
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a novel α -diimine metal complex-supported carrier, which is directly supported on a chemically modified carrier through hydrogen bonds of ligands or complexes of α -diimine via hydroxyl groups on the ligands, thereby preventing the supports from being separated from the carrier.
To achieve the above object, the present invention provides an α -diimine metal complex-loaded support obtained by reacting α -diimine metal complex with a modifier-treated support, or obtained by reacting a α -diimine compound-loaded support with a late transition metal salt;
the α -diimine metal complex-loaded load is prepared by one of the following two methods:
the method I comprises the following steps:
adding a carrier treated by a modifier into an anhydrous organic solvent under a nitrogen atmosphere, adding 10-100mL of the anhydrous organic solvent into each gram of the carrier treated by the modifier, adding an α -diimine metal complex anhydrous organic solvent solution with the concentration of 0.001-0.1mmol/mL, adding α -diimine metal complex with the concentration of 1-10mmol into each gram of the carrier treated by the modifier, reacting for 1-48 hours at the reaction temperature of 0-200 ℃, 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 a solid by the precipitator, and carrying out vacuum drying to obtain a α -diimine metal complex-loaded load;
the α -diimine metal complex is prepared by reacting α -diimine compound and post-transition metal salt, and the preparation method of α -diimine metal complex comprises the following steps of adding the post-transition metal salt into an α -diimine compound anhydrous organic solvent solution with the concentration of 0.001-0.1mmol/mL in a reactor under the nitrogen atmosphere for reaction, wherein the post-transition metal salt and α -diimine compound have equal molar weight, stirring for reaction for 1-48 hours at the reaction temperature of 0-200 ℃, 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 α -diimine metal complex;
the second method comprises the following steps:
mixing an anhydrous organic solvent, a load of α -diimine compound and post-transition metal salt with equal molar weight of α -diimine compound under nitrogen atmosphere, adding 10-100mL of the anhydrous organic solvent into each gram of the α -diimine compound load, wherein the concentration of the post-transition metal salt is 0.001-1mmol/mL of the anhydrous organic solvent solution, stirring and reacting for 1-48 hours at the reaction temperature of 0-200 ℃, carrying out reduced pressure concentration on the reaction solution to obtain a concentrated solution, adding a precipitator with ten to fifty times of the volume of the concentrated solution for precipitation, carrying out suction filtration, washing the solid with the precipitator, and carrying out vacuum drying to obtain the load of the α -diimine metal complex;
the α -diimine compound load is prepared by adding an anhydrous organic solvent into a modifier-treated carrier under a nitrogen atmosphere, adding 10-100mL of the anhydrous organic solvent into each gram of the modifier-treated carrier, adding an anhydrous 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 modifier-treated carrier is 1-10mmol of α -diimine compound added into each gram of the modifier-treated carrier, reacting for 1-48 hours at the reaction temperature of 0-200 ℃, concentrating the reaction liquid under reduced pressure to obtain a concentrated solution, adding a precipitant precipitate with the volume ten times to fifty times that of the concentrated solution, performing suction filtration, washing a solid with the precipitant, and performing vacuum drying to obtain the α -diimine compound load.
According to a specific embodiment of the present invention, preferably, in the first and second methods, the modifier-treated support is prepared by: adding a carrier into an anhydrous organic solvent under the nitrogen atmosphere to obtain a suspension, wherein the concentration of the carrier in the suspension is 0.01-0.1g/mL, adding a modifier according to the amount of 0.1-50mmol of the modifier added into 1g of the carrier, reacting for 4-16 hours at the reaction temperature of 0-50 ℃, filtering after the reaction is finished, and washing with the anhydrous organic solvent and a precipitator respectively to obtain the modified carrier.
According to a specific embodiment of the present invention, preferably, the modifier is aluminum alkoxide, aluminum alkyl, zinc dialkyl, silicon dialkyl dichloride, silicon dialkyl dibromide, silicon monoalkyl trichloride, silicon monoalkyl tribromide, TiX4、ZrX4、SiX4And BX3And the like, wherein X is chlorine or bromine. More preferably, the modifier is Methylaluminoxane (MAO), Ethylaluminoxane (EAO), Modified Methylaluminoxane (MMAO), AlMe3、AlEt3、Al(i-Bu)3、AlEt2Cl、ZnEt2、TiCl4、ZrCl4、SiCl4And BCl3And the like.
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), etc.
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 dichloromethane, trichloromethane, 1, 2-dichloroethyleneAlkane, chlorobenzene, dichlorobenzene, toluene, tetrahydrofuran, 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 a specific embodiment of the present invention, preferably, the support is a composite support of one or more of inorganic oxide, metal salt, clay, diatomaceous earth, montmorillonite, polystyrene resin, carbon black, carbon nanotube, graphene, and the like. 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-loaded load as a catalyst in olefin polymerization reaction.
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 application, preferably, the α -diimine metal complex-supported carrier is used as a main catalyst in olefin polymerization.
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 ligand adopted by the α -diimine metal complex-loaded load provided by the invention is provided with hydroxyl, and the hydroxyl can react with an active group on a chemically modified carrier to form a covalent bond, so that α -diimine compounds are firmly loaded on the carrier in a chemical bonding mode, and the separation of the hydroxyl from the carrier is avoided.
The α -diimine metal complex-supporting material can be applied to a gas-phase polymerization unit or a slurry polymerization unit for catalyzing olefin by the existing catalyst.
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