α -diimine metal complex hydrogen bond load and application thereof in olefin polymerization
阅读说明：本技术 一种α-二亚胺金属配合物氢键负载物及其在烯烃聚合中的应用 (α -diimine metal complex hydrogen bond 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α-二亚胺金属配合物氢键负载物及其在烯烃聚合中的应用。该α-二亚胺金属配合物氢键负载物是由α-二亚胺金属配合物与载体复合而得,或者是由α-二亚胺化合物的负载物与后过渡金属盐复合得到。本发明提供的α-二亚胺金属配合物氢键负载物是通过氢键作用将α-二亚胺化合物的金属配合物直接负载在不经过化学改性的载体上,这样的负载方法简便且有效。同时,α-二亚胺配体中亚胺基上的芳香基团可根据需要而任意改变,从而增加了结构的可调控性以及耐高温催化活性。(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.)
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:
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.
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