CN110935489B - Supported transition metal catalyst system through hydrogen bond action and preparation method thereof - Google Patents
Supported transition metal catalyst system through hydrogen bond action and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a supported transition metal catalyst system through hydrogen bond action and a preparation method thereof, wherein the preparation method comprises the following steps: mixing a catalyst containing transition metal and having a functional group as a hydrogen bond acceptor with a carrier having a functional group as a hydrogen bond donor in an organic solvent to prepare a supported transition metal catalyst system under the action of hydrogen bonds, wherein the organic solvent is a good solvent of the catalyst and is a poor solvent of the carrier; the prepared supported transition metal catalyst system through hydrogen bond action mainly comprises a catalyst containing transition metal and a carrier, wherein a functional group serving as a hydrogen bond acceptor on the catalyst and a functional group serving as a hydrogen bond donor on the carrier interact to form a hydrogen bond. The supported transition metal catalyst system through hydrogen bond effectively solves the problem that a homogeneous polymerization system is not suitable for a gas phase polymerization or slurry polymerization device produced by the existing olefin polymerization industry, and has the advantages of simple preparation method and low preparation cost.
Description
Technical Field
The invention belongs to the technical field of supported transition metal catalyst systems, and relates to a supported transition metal catalyst system under the action of hydrogen bonds and a preparation method thereof.
Background
Since the advent of Ziegler-Natta catalysts, polyolefin materials, such as polyethylene and polypropylene, have found widespread use in commercial processes. Based on metallocene catalyst and transition metal homogeneous catalyst represented by nickel and palladium metal complex, more choices are provided for high performance of polyolefin material, but in the process of preparing polyolefin material, the homogeneous polymerization system is easy to agglomerate, the phenomenon of sticking kettle occurs, the product form is not controllable, and the industrial application of large-scale gas phase polymerization and slurry polymerization is seriously hindered.
The preparation of heterogeneous supported catalysts (heterogeneous catalysts) by incorporating a solid support in a homogeneous catalyst system is an effective way to solve the above problems. The homogeneous transition metal catalyst using nickel and palladium as the center has great advantages in the direct synthesis of functional polyolefin and has been widely studied, while the research based on the supported transition metal catalyst is few, and the research content is mainly limited to the homopolymerization of ethylene and the copolymerization of ethylene and non-polar monomers such as alpha-olefin, and the research on the supported transition metal catalyst for catalyzing the direct copolymerization of ethylene and polar monomers is more rarely reported. The currently reported supported catalyst systems are divided into a direct supported system and an indirect supported system, as shown in fig. 1 and fig. 2, respectively, the direct supported system achieves a supporting effect by allowing a carrier and a catalyst to interact to form a covalent bond, and the indirect supported system is formed by firstly supporting a cocatalyst on the carrier and then forming an indirect supported catalyst system by the ion pair interaction of the cocatalyst and a main catalyst. However, the traditional direct loading system needs to generate covalent bond between the carrier and the catalyst, and the preparation process is relatively complex; in the case of the indirect loading system, a large amount of expensive cocatalyst is consumed in the loading process, so that the cost of industrial application is greatly increased, and the large-scale application is limited.
Therefore, it is necessary to research a simple and low-cost method for preparing a supported transition metal catalyst system to solve the problems of easy agglomeration and kettle sticking in the gas phase polymerization and slurry polymerization processes of olefin polymerization industrial production.
Disclosure of Invention
The invention aims to solve the problem that a homogeneous catalyst system in the prior art is not suitable for a gas-phase polymerization or slurry polymerization device produced in the prior olefin polymerization industry, and provides a supported transition metal catalyst system under the action of hydrogen bonds and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following scheme:
the supported transition metal catalyst system through hydrogen bond action mainly comprises a catalyst containing transition metal (which can be front transition metal or back transition metal and is within the protection range of the invention) and a carrier for heterogeneous supported catalyst, wherein the catalyst is provided with a functional group as a hydrogen bond acceptor, the carrier is provided with a functional group as a hydrogen bond donor, and the functional group as the hydrogen bond acceptor on the catalyst and the functional group as the hydrogen bond donor on the carrier interact to form hydrogen bond.
The load mode of the catalyst system of the invention is to utilize the hydrogen bond acceptor on the catalyst to interact with the hydrogen bond donor on the carrier to form the hydrogen bond, thus make the catalyst load on the carrier directly and form the load type catalyst system, the improvement of the catalytic effect of the direct load type catalyst system through the hydrogen bond to its homogeneous phase catalyst system is similar to the improvement of the catalytic effect of the traditional direct load type system through covalent bond to its homogeneous phase catalyst system, but the synthetic method is simpler and more convenient, it can not only give play to the characteristic of the original heterogeneous transition metal catalyst system, solve the homogeneous phase catalyst system and is not suitable for the gas phase polymerization or slurry polymerization apparatus that the existing olefin polymerization industry produces, and can avoid the complicated synthetic process, avoid using the expensive cocatalyst at the same time, greatly save the cost.
As a preferable scheme:
in the above supported transition metal catalyst system through hydrogen bonding, the transition metal is Ni or Pd, only two common late transition metals are listed here, and other late transition metals and early transition metals are also suitable for the present invention, and the catalyst is a quinone complex, a phosphosulfonic acid complex, a phosphobenzoic acid complex, or a phosphophenol fluoro substituent complex; the catalyst of the present invention includes but is not limited to these complexes, and other transition metal-containing complexes with proton accepting ability are also within the scope of the present invention; the catalyst not only is effective for homopolymerization catalysis of olefin, but also can catalyze olefin copolymerization, including copolymerization with polar monomers;
the quinone complex is anilino naphthoquinone metalloid complex and cationic derivatives thereof, and the structural formula of the quinone complex is as follows:
wherein Mt is Ni or Pd; r1Is isopropyl i-Pr, benzyl CH (Ph)2Or methoxy OMe; r2Is hydrogen H or methyl Me; r' is methyl Me, ethyl Et, phenyl Ph or benzyl CH2Ph; l is triphenylphosphine PPh3Trimethyl phosphine PMe3Dimethyl sulfoxide DMSO, pyridine py, 2,4-Lutidine or 2,6-Lutidine 2, 4-Lutidine; r' and L are 1, 5-cyclooctadiene COD and allyl eta when coordinated together3-CH2CHCH2Or benzyl eta3-CH2Ph and X are chlorine atoms Cl or bromine atoms Br;
the phospho-sulfonic acid complex is diphenyl phospho-sulfonic acid metal complex, and the structural formula is as follows:
in the formula, R3And R4Respectively is one of alkyl or aryl and substituent derivatives thereof;
the phosphorus benzoic acid complex is diphenyl phosphorus benzoic acid metal complex, and the structural formula is as follows:
the phosphophenol fluorine substituent group metal complex is diphenyl phosphophenol fluorine substituent group metal complex, and the structural formula is as follows:
wherein R' is F, CF3Or C6F5；
Some of the catalysts with different substituent groups in the catalyst category are reported, the catalysts containing other substituent groups which are not reported are also in the protection scope of the patent, the catalysts can be directly loaded by the loading method of the invention, the loading combination of the catalyst and the carrier is not fixed and matched, and the catalysts of different categories can be loaded by matching with a plurality of carriers related in the patent.
In the supported transition metal catalyst system based on hydrogen bonding, the catalyst has a monomolecular structure, and the size of the carrier is nano-scale.
The supported transition metal catalyst system through hydrogen bond interaction has SiO as carrier2Pretreated carbon nanofiber, pretreated graphene, cellulose nanocrystal and Fe3O4Or surface treated carbon nanotube, and may also be MgCl2Other nanoscale inorganic compound particles and other inorganic substances containing hydroxyl, carboxyl, amino, sulfydryl, fluorine-containing substituent groups and other groups; SiO as a support2Cellulose nanocrystals or Fe3O4The carbon fiber, the carbon nanotube and the graphene are not provided with functional groups, and need to be pretreated before loading, such as acid etching and the like, so that the surface of the carbon fiber, the carbon nanotube and the graphene is connected with groups such as hydroxyl, carboxyl or amino, and the like, thereby having loading capacity. The carrier of the present invention includes but is not limited to these several types of materials, and other carriers having hydrogen bond donor ability are also within the scope of the present invention.
According to the supported transition metal catalyst system based on the hydrogen bond effect, the molar ratio of the catalyst to the carrier is 1: 1-10000: 1, the minimum requirement for meeting the loading condition is that the catalyst and the carrier group can form the hydrogen bond under the action of 1:1, for different carriers, the molar ratio of the catalyst to the carrier is in a certain range, the catalyst cannot be successfully loaded if the number of the functional groups contained on the surface is different, and no special requirement exists if the number of the functional groups contained on the surface is lower than 1:1, so that the catalyst is suitable for a moderate ratio.
The invention also provides a method for preparing the supported transition metal catalyst system through the hydrogen bond effect, which comprises the steps of mixing a catalyst containing transition metal and having a functional group as a hydrogen bond acceptor with a carrier having a functional group as a hydrogen bond donor in an organic solvent to prepare the supported transition metal catalyst system through the hydrogen bond effect, wherein the organic solvent is a good solvent of the catalyst and a poor solvent of the carrier; the mixing in the present invention refers to the state of the whole system before the reaction is started, and the order of adding the catalyst and the carrier to the organic solvent is not limited and is within the protection scope of the present invention.
As a preferable scheme:
the method comprises the following specific steps:
(1) under the protection of nitrogen or inert gas (argon or helium), dissolving a catalyst with a functional group as a hydrogen bond acceptor in an organic solvent at the temperature of 10-30 ℃ and under the pressure of normal pressure (one standard atmospheric pressure is 101.325kPa) to obtain a catalyst solution, wherein the ratio of the catalyst to the organic solvent has no specific requirement, and the catalyst solution is different according to the dissolving capacities of different solvents as long as the amount of the added organic solvent is ensured to dissolve the catalyst;
(2) stirring and mixing the catalyst solution and a carrier with a functional group as a hydrogen bond donor for 1-10 minutes under the conditions that the temperature is 10-30 ℃ and the pressure is normal pressure to obtain a supported transition metal catalyst system under the action of the hydrogen bond, wherein the stirring time can be changed within a proper range, the stirring time is too short, the supporting process is insufficient, the stirring time is too long, and the complex is active and is easy to decompose and deteriorate; the organic solvent is more than one of n-heptane, toluene, chlorobenzene, acetonitrile, dichloromethane, chloroform and tetrahydrofuran, and the types of the organic solvents include but are not limited to the above solvents, so long as the catalyst can be dissolved and the carrier is not dissolved, the protection scope of the invention is provided.
Has the advantages that:
(1) the load type transition metal catalyst system through the hydrogen bond action can well solve the problem that a homogeneous polymerization system is not suitable for a gas phase polymerization or slurry polymerization device produced by the existing olefin polymerization industry;
(2) compared with the preparation method of the supported catalyst system in the prior art, the preparation method of the supported transition metal catalyst system through hydrogen bond action is simpler and more convenient;
(3) the preparation method of the supported transition metal catalyst system through the hydrogen bond action can avoid using expensive cocatalyst and greatly save the economic cost.
Drawings
FIG. 1 is a prior art direct supported catalyst system (Mt is the catalyst);
FIG. 2 is a prior art indirect supported catalyst system (Mt is catalyst);
FIG. 3 is a supported transition metal catalyst system (Mt is catalyst) by hydrogen bonding according to the present invention.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of a supported transition metal catalyst system through hydrogen bond action comprises the following specific steps:
(1) under the protection of nitrogen, dissolving a catalyst with a structural formula (I) in toluene at the temperature of 10 ℃ and under the pressure of normal pressure to obtain a catalyst solution;
(2) the catalyst solution is mixed with nano SiO under the conditions of 10 ℃ and normal pressure2Stirring and mixing for 1 minute to obtain a supported transition metal catalyst system through hydrogen bond action, wherein the catalyst with the structural formula (I) and the nano SiO2Is 1: 1.
The final supported transition metal catalyst system through hydrogen bond action has the structural formula shown as (II), and mainly comprises catalyst with the structural formula shown as (I) and nano-scale SiO2And (3) the functional groups of the two interact to form hydrogen bonds.
The finally prepared supported transition metal catalyst system through hydrogen bond action and the catalyst with the structural formula (I) are respectively used for ethylene homopolymerization, and under the same reaction condition (the reaction temperature is 40 ℃, the ethylene pressure is 1MPa, the methylbenzene is 30mL, no cocatalyst is added), the polymerization activities obtained by testing the two polymerization systems are in the same order of magnitude and can reach 430kg mol-1h-1The direct supported catalyst system through hydrogen bond action can achieve heterogeneous effect without influencing catalytic activity, and the direct supported catalyst system through hydrogen bond action (shown in figure 3) and a corresponding homogeneous system without catalyst loading have similar polymerization activity, and the loading can not generate great influence on the polymerization activity of the catalyst;
the solution homogeneity of the finally prepared supported transition metal catalyst system through the hydrogen bond effect is compared with the solution homogeneity of the directly supported catalyst system (namely, the catalyst is connected with the carrier through covalent bonds) in the prior art, so that the two system solutions can form a heterogeneous effect, and the phenomena of kettle adhesion and agglomeration which easily occur in the homogeneous system can not be generated.
Example 2
The preparation method of the supported transition metal catalyst system through hydrogen bond action comprises the following specific steps:
(1) under the protection of helium, dissolving a catalyst with a structural formula (III) in toluene at the temperature of 20 ℃ and under the pressure of normal pressure to obtain a catalyst solution;
(2) and (2) stirring and mixing the catalyst solution and the cellulose nano-microcrystal with the hydroxyl on the surface for 3 minutes under the conditions that the temperature is 20 ℃ and the pressure is normal pressure to obtain a supported transition metal catalyst system under the action of a hydrogen bond, wherein the molar ratio of the catalyst with the structural formula (III) to the cellulose nano-microcrystal with the hydroxyl on the surface is 10: 1.
The structural formula of the finally prepared supported transition metal catalyst system through the hydrogen bond action is shown as (IV), the supported transition metal catalyst system mainly comprises a catalyst with the structural formula of (III) and cellulose nano-microcrystal with hydroxyl on the surface, and the catalyst and the cellulose nano-microcrystal interact to form the hydrogen bond.
Example 3
The preparation method of the supported transition metal catalyst system through hydrogen bond action comprises the following specific steps:
(1) under the protection of helium, dissolving a catalyst with a structural formula (V) in toluene at the temperature of 30 ℃ and under the pressure of normal pressure to obtain a catalyst solution;
(2) the catalyst solution is reacted with nano-grade Fe with hydroxyl on the surface under the conditions that the temperature is 30 ℃ and the pressure is normal pressure3O4Stirring and mixing for 5 minutes to obtain a supported transition metal catalyst system through hydrogen bond action, wherein the catalyst with the structural formula of (V) and the nanoscale Fe with hydroxyl on the surface3O4Is 100: 1.
The supported transition metal catalyst system through hydrogen bond action, which is finally prepared, has a structural formula shown as (VI), and mainly comprises a catalyst with a structural formula shown as (V) and nano-scale Fe with hydroxyl on the surface3O4Composition, the two interact to form hydrogen bond.
Example 4
The preparation method of the supported transition metal catalyst system through hydrogen bond action comprises the following specific steps:
(1) under the protection of argon, dissolving a catalyst with a structural formula (VII) in toluene at the temperature of 30 ℃ and under the pressure of normal pressure to obtain a catalyst solution;
(2) stirring and mixing the catalyst solution with the surface carboxylated carbon nano tube for 8 minutes under the conditions that the temperature is 30 ℃ and the pressure is normal pressure to obtain a supported transition metal catalyst system through hydrogen bond action, wherein the molar ratio of the catalyst with the structural formula (VII) to the surface carboxylated carbon nano tube is 1000:1, and the surface carboxylation treatment process of the carbon nano tube is as follows: first, carbon nanotubes were added to HNO3And carrying out ultrasonic treatment on the solution for 60 minutes, then violently stirring and refluxing the solution for 24 hours at the temperature of 130 ℃, then washing the black suspension for a plurality of times by using deionized water and ethanol until the black suspension reaches neutral pH, and finally drying the black suspension in a vacuum drying oven to obtain the surface carboxylated carbon nanotube.
The finally prepared supported transition metal catalyst system through hydrogen bond action has a structural formula shown as (VIII), and mainly comprises a catalyst with a structural formula shown as (VII) and a surface carboxylated carbon nanotube, wherein the catalyst and the surface carboxylated carbon nanotube interact to form a hydrogen bond.
Example 5
The preparation method of the supported transition metal catalyst system through hydrogen bond action has the steps basically the same as the steps in the embodiment 4, except that the surface hydroxylated carbon nanotube is used for replacing the surface carboxylated carbon nanotube, and the surface hydroxylation treatment process of the carbon nanotube is as follows: mixing the multi-walled carbon nano-tube with potassium hydroxide in a ball milling tank, adding a proper amount of ethanol, carrying out ball milling for 15 hours, washing reactants to be neutral by deionized water, and then putting the treated carbon nano-tube into a vacuum drying oven at 100 ℃ for drying for 12 hours for later use.
The finally prepared supported transition metal catalyst system through hydrogen bond action mainly comprises a catalyst with a structural formula (VII) and a surface hydroxylated carbon nanotube, wherein the catalyst and the surface hydroxylated carbon nanotube interact to form a hydrogen bond.
Example 6
The preparation method of the supported transition metal catalyst system through hydrogen bond action comprises the following specific steps:
(1) under the protection of argon, dissolving a catalyst with a structural formula (IX) in toluene at the temperature of 30 ℃ and under the pressure of normal pressure to obtain a catalyst solution;
(2) stirring and mixing the catalyst solution with the hydroxylated carbon nano-fiber for 10 minutes under the conditions that the temperature is 30 ℃ and the pressure is normal pressure to obtain a supported transition metal catalyst system through hydrogen bond action, wherein the molar ratio of the catalyst with the structural formula of (IX) to the hydroxylated carbon nano-fiber is 10000:1, and the hydroxylation treatment process of the carbon nano-fiber is as follows: firstly, mixing carbon nanofibers with concentrated sulfuric acid, magnetically stirring for 24 hours at room temperature, then adding the concentrated nitric acid into a flask, magnetically stirring at the temperature of 140 ℃, condensing and refluxing for 30 minutes, then washing and filtering with distilled water for multiple times, and drying to prepare the hydroxylated carbon nanofibers.
The finally prepared supported transition metal catalyst system through hydrogen bond action mainly comprises a catalyst with a structural formula of (IX) and hydroxylated carbon nano-fibers, and the catalyst and the hydroxylated carbon nano-fibers interact to form hydrogen bonds.
Example 7
The preparation method of the supported transition metal catalyst system by hydrogen bond action has the steps basically the same as those of the example 6, except that the carboxylated carbon nanofiber is used for replacing the hydroxylated carbon nanofiber, and the carboxylation treatment process of the carbon nanofiber is as follows: firstly, vacuumizing a single-neck flask, removing water vapor, filling nitrogen, then placing the hydroxylated carbon nano fiber in the single-neck flask, vacuumizing again, filling nitrogen, injecting N, N-Dimethylformamide (DMF) into the single-neck flask in a convection mode, and carrying out ultrasonic treatment for 30 min; injecting acrylic acid into the single-neck flask, and carrying out ultrasonic treatment for 30 min; dissolving azodiisobutyronitrile in DMF, injecting into a single-neck flask, and performing ultrasonic treatment for 30 min; heating in a constant-temperature oil bath at 60 ℃, magnetically stirring for 5 hours, taking out, washing with distilled water for multiple times, carrying out vacuum filtration, washing with acetone for multiple times, and carrying out vacuum filtration to remove water molecules; finally drying in a vacuum drying oven at 60 ℃ until the quality is constant.
The structural formula of the finally prepared supported transition metal catalyst system through hydrogen bond action is shown as (X), and the supported transition metal catalyst system mainly comprises a catalyst with the structural formula of (IX) and carboxylated carbon nanofibers, wherein the catalyst and the carboxylated carbon nanofibers interact to form hydrogen bonds.
Example 8
The preparation method of the supported transition metal catalyst system through hydrogen bond action has the steps basically the same as those of the example 7, except that the carbon nanofiber is used for replacing the carboxylated carbon nanofiber, and the amination treatment process of the carbon nanofiber comprises the following steps: firstly, vacuumizing a single-neck flask, removing water vapor, filling nitrogen, then placing the carboxylated carbon nanofibers in the single-neck flask, vacuumizing again, filling nitrogen, injecting DMF (dimethyl formamide) into the single-neck flask in a convection mode, and carrying out ultrasonic treatment for 30 min; dissolving amino-terminated polyether D400 in DMF, injecting into a single-neck flask, and performing ultrasonic treatment for 30min again; then putting the mixture into a constant-temperature oil bath at 70 ℃ for heating and magnetically stirring for 24 hours, cooling the liquid, washing the liquid with distilled water for many times, and carrying out vacuum filtration; and finally, drying in a vacuum drying oven at 60 ℃ until the mass is constant, thus obtaining the aminated carbon nanofiber.
The finally prepared supported transition metal catalyst system through hydrogen bond action mainly comprises a catalyst with a structural formula of (IX) and aminated carbon nano-fibers, and the catalyst and the aminated carbon nano-fibers interact to form hydrogen bonds.
Example 9
The preparation method of the supported transition metal catalyst system through hydrogen bond action has the same steps as the example 6, and the difference is that hydroxylated graphene is used for replacing hydroxylated carbon nano-fiber, and the finally prepared supported transition metal catalyst system through hydrogen bond action mainly comprises a catalyst with a structural formula (IX) and the hydroxylated graphene, and the catalyst and the hydroxylated graphene interact to form hydrogen bond.
Claims (3)
1. The application of the supported transition metal catalyst system through hydrogen bond action in olefin polymerization reaction is characterized in that: the method is applied to olefin homopolymerization and copolymerization of olefin and polar monomer; the supported transition metal catalyst system through hydrogen bond action mainly comprises a catalyst containing transition metal and a carrier, wherein the catalyst is provided with a functional group as a hydrogen bond acceptor, the carrier is provided with a functional group as a hydrogen bond donor, and the functional group as the hydrogen bond acceptor on the catalyst and the functional group as the hydrogen bond donor on the carrier interact to form a hydrogen bond;
the catalyst containing transition metal is
The carrier is SiO2Pretreated carbon nanofiber, pretreated graphene, cellulose nanocrystal and Fe3O4Or surface-treated carbon nanotubes;
the preparation method of the supported transition metal catalyst system through hydrogen bond action comprises the following steps: mixing a catalyst containing transition metal and having a functional group as a hydrogen bond acceptor with a carrier having a functional group as a hydrogen bond donor in an organic solvent to prepare a supported transition metal catalyst system under the action of hydrogen bonds, wherein the organic solvent is a good solvent of the catalyst and is a poor solvent of the carrier;
the preparation method comprises the following specific steps:
(1) under the protection of nitrogen or inert gas, dissolving a catalyst with a functional group as a hydrogen bond acceptor in an organic solvent at the temperature of 10-30 ℃ and under the normal pressure to obtain a catalyst solution;
(2) and stirring and mixing the catalyst solution and the carrier with the functional group as the hydrogen bond donor for 1-10 minutes under the conditions that the temperature is 10-30 ℃ and the pressure is normal pressure to obtain the supported transition metal catalyst system under the action of the hydrogen bond.
2. Use of a supported transition metal catalyst system via hydrogen bonding in olefin polymerization reactions according to claim 1, characterized in that the support has a size in the nanometer range.
3. The use of a supported transition metal catalyst system via hydrogen bonding in olefin polymerization according to claim 1, wherein the molar ratio of catalyst to support is 1:1 to 10000: 1.
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