CN111841658A - Porous plastic heterogeneous catalyst carrier and preparation method and application thereof - Google Patents

Porous plastic heterogeneous catalyst carrier and preparation method and application thereof Download PDF

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CN111841658A
CN111841658A CN202010819538.0A CN202010819538A CN111841658A CN 111841658 A CN111841658 A CN 111841658A CN 202010819538 A CN202010819538 A CN 202010819538A CN 111841658 A CN111841658 A CN 111841658A
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heterogeneous catalyst
porous plastic
carrier
porous
catalyst
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胥波
齐义舟
李婷婷
齐培州
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Shanghai Group Wave Intelligent Instrument Technology Co Ltd
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Shanghai Group Wave Intelligent Instrument Technology Co Ltd
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Abstract

The invention provides a porous plastic heterogeneous catalyst carrier, a preparation method and application thereof. The catalyst prepared by the technical scheme of the invention improves the strength and the loading capacity of the heterogeneous catalyst carrier, the preparation process is simple and convenient, no solvent which is not friendly to the environment is introduced in the preparation process, the environment-friendly effect is better, and the catalyst has good industrial production potential.

Description

Porous plastic heterogeneous catalyst carrier and preparation method and application thereof
Technical Field
The invention relates to the technical field of heterogeneous catalyst loading, in particular to a porous plastic heterogeneous catalyst carrier and a preparation method and application thereof.
Background
Heterogeneous catalysis is of crucial importance in the production of chemicals. Heterogeneous catalysts are usually prepared by depositing a nanoscale active catalyst, usually a noble metal, onto a porous inorganic support, such as TiO2，Al2O3And molecular sieves). Heterogeneous catalysts, however, suffer from several disadvantages: firstly, the activity and selectivity of heterogeneous catalysts are often inferior to those of homogeneous catalysts, mainly the dispersion degree of active sites is reduced and diffusion resistance exists, and meanwhile, the micro chemical environment of active centers is changed due to immobilization; secondly, heterogeneous catalysts, although very successful in gas phase reactions, are not ideal for solution phase reactions. Many inorganic catalyst supports (e.g., Al)2O3) Have a high hardness, but when they are porous, they tend to be brittle and have poor mechanical stability, not withstanding constant stirring and impact in solution. Thus, for solution phase chemical reactions, heterogeneous catalysts (e.g., Pd/C, Pt/Al)2O3) It is often provided in the form of a fine powder or even if it is a bulk catalyst it is broken into fine powder during agitation in solution. This causes many problems such as difficulty in recovering the catalyst by filtration, leaching of heavy metals, and operational danger in handling fine catalyst particles. In particular to the problem of metal leaching, which is an urgent problem to be solved in pharmaceutical chemistry.
In recent years, polymer-supported catalysts have made significant progress. The polymer supported catalyst has the following advantages: first, inorganic ash; the steric hindrance of the active center of the catalyst and the electronic environment can be changed to adjust the activity of the catalyst, the porous organic polymer material has an adjustable structure, the pore size of the carrier can be adjusted and controlled by modifying monomer molecules, so that a space structure which is beneficial to loading the catalyst and catalytic polymerization is obtained, active sites required by reaction can be introduced into the porous organic polymer, the electronic environment of the porous organic polymer is changed, and the purpose of directionally designing the carrier is achieved; thirdly, the solid catalyst can be easily subjected to reaction post-treatment by filtering; the residual metal content in the final crude product is low; fourthly, the solid supported catalyst can be recycled, the recycling efficiency is high, and the industrial cost is reduced. The most common polymer backbone is crosslinked Polystyrene (PS), to which the active catalyst is bonded by covalent or coordinate bonds. Many polystyrene and other polymer supported catalysts have been commercialized. Although organic polymers (such as PS) are generally not brittle, their mechanical strength still cannot withstand prolonged agitation. In addition, because the active catalyst is covalently bonded to the polymer backbone, the preparation of such supported catalysts is often complex and expensive. Thus, based on heterogeneous inorganic supports such as activated carbon and TiO2Still remains the subject of industrial production. Therefore, it is an urgent need in the art to provide an organic polymer heterogeneous catalyst carrier with high mechanical strength, simple preparation method and low cost.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides an ultrahigh molecular weight porous plastic heterogeneous catalyst carrier, a preparation method and application thereof, and the following technical scheme is specifically adopted:
the invention provides a porous plastic heterogeneous catalyst carrier in a porous solid block structure;
further, the porous plastic heterogeneous catalyst carrier is in a tablet-like cylindrical structure, a spherical structure or a cubic structure;
further preferably, the solid block structure is a tablet-like cylindrical structure, the pore volume of the solid block structure is 0.3-0.6 ml/g, and the total pore area of the solid block structure is 20-25 m2(iv)/g, having an average pore diameter of 70 to 80nm, a bulk density of 0.5 to 1.0g/ml at 0.5 to 1psi, and a porosity of 20 to 30%; preferably, the pore volume of the ultrahigh molecular weight porous polyethylene heterogeneous catalyst carrier is 0.4298 ml/g; the total pore area is 23.780m2(ii)/g; the average pore diameter is 72.3 nm; the bulk density of the composite material is 0.6069g/ml under 0.5-1 psi; its porosity is 26.0850%;
further, the specifications of the tablet-like cylindrical structure porous plastic heterogeneous catalyst carrier are as follows: the inner diameter is 5.1-9 mm and the height is 2.5-4 mm; further preferably, the specifications of the porous plastic heterogeneous catalyst carrier with the tablet-like cylindrical structure are as follows: an inner diameter of 5.1mm and a height of 2.5mm, an inner diameter of 7.4mm and a height of 2.5mm, or an inner diameter of 9mm and a height of 4 mm;
further, the porous plastic has high wear resistance and is a highly chemically inert material, including but not limited to ultra-high molecular weight porous polyethylene, ultra-high molecular weight porous polypropylene, ultra-high molecular weight polytetrafluoroethylene, and ultra-high molecular weight polyvinylidene fluoride;
the second aspect of the present invention provides a preparation method of the above porous plastic heterogeneous catalyst carrier, comprising the steps of: adding the porous plastic powder into a cylindrical stainless steel grinding tool, heating to 140-155 ℃ under normal pressure, rapidly cooling to room temperature, and demolding to obtain the porous plastic powder;
further, the diameter of the porous plastic powder is 10-100 micrometers, and the molecular weight of the porous plastic powder is more than 100 ten thousand;
further, the inner diameter of the cylindrical stainless steel grinding tool is 5.1-9 mm, and the height of the cylindrical stainless steel grinding tool is 2.5-4 mm; specifically, the size of the cylindrical stainless steel grinding tool: an inner diameter of 5.1mm and a height of 2.5mm, an inner diameter of 7.4mm and a height of 2.5mm, or an inner diameter of 9mm and a height of 4 mm.
A third aspect of the present invention provides the use of the above-mentioned porous plastic heterogeneous catalyst carrier for supporting a heterogeneous catalyst to form a porous polymer catalyst;
further, the specific operation method of the application includes:
firstly, grinding a heterogeneous catalyst into powder, suspending the heterogeneous catalyst powder in an organic solvent, adding the porous plastic heterogeneous catalyst carrier while stirring, fully stirring to fully load the heterogeneous catalyst on the carrier, taking out the loaded catalyst carrier, and continuously stirring for 10-24 hours in a clean and same organic solvent at the same speed and temperature to wash off the non-loaded heterogeneous catalyst on the surface of the carrier;
further, the particle size of the heterogeneous catalyst powder is less than or equal to 5 μm;
further, the heterogeneous catalyst in the porous polymer catalyst accounts for 0.1-10% of the mass percentage of the porous plastic heterogeneous catalyst carrier;
further, the organic solvent includes, but is not limited to, ethanol, petroleum ether, toluene, tetrahydrofuran, dichloromethane; the mass of the organic solvent is 8-20 times of that of the carrier;
further, the stirring speed is 300-600 r/min, the stirring temperature is 0-30 ℃, and the stirring time is 1-24 hours;
further, the heterogeneous catalyst is an insoluble heterogeneous catalyst; further preferably, the heterogeneous catalyst is Pd/C, Pd/Al2O3，Ru/C，Ru/TiO2，Ru/Al2O3，Pt/Al2O3，Pt/C，Rh/C，Cu，Au/TiO2，Au/Al2O3And Ag/molecular sieve.
A fourth aspect of the present invention provides a porous polymer catalyst comprising a porous plastic heterogeneous catalyst carrier of any one of the above and an insoluble heterogeneous catalyst supported on the carrier;
further, the mass percentage of the insoluble heterogeneous catalyst in the porous plastic heterogeneous catalyst carrier is 0.01-40%; further preferably, the mass percentage of the insoluble heterogeneous catalyst in the porous plastic heterogeneous catalyst carrier is 0.1-10%.
A fifth aspect of the invention provides the use of a porous polymer catalyst as described above for organic catalytic chemical reactions; further, the organic catalytic chemical reaction is a hydrogenation reaction or a deprotection reaction.
Advantageous effects
The technical scheme adopted by the invention has the following technical effects:
1. the strength and the loading capacity of the heterogeneous catalyst carrier are improved: porous plastics, in particular ultra High molecular weight Polyethylene (HDPE) are white powder or granular products. No toxicity and no smell, the crystallinity is 80-90%, the softening point is 125-l 35 ℃, and the use temperature can reach 110 ℃; the hardness, tensile strength and creep property are all superior to those of low-density polyethylene; the wear resistance, the electrical insulation, the toughness and the cold resistance are good; good chemical stability, no solubility in any organic solvent at room temperature, and low corrosion resistance to acid, alkali and various salts. Therefore, the strength of the heterogeneous catalyst can be obviously improved by using the carrier for preparing the porous polymer heterogeneous catalyst; in addition, the loading capacity is better than that of active carbon and TiO2And polystyrene, which has a greater mass of supported catalyst per unit mass and is capable of better catalyzing the reaction.
2. The preparation method of the invention is simpler and more convenient: the porous plastic carrier can be obtained by operations of heating, sintering, cooling and the like under normal pressure; the catalyst can be loaded by stirring at normal temperature and normal pressure, the preparation process is simple and convenient, no solvent which is not friendly to the environment is introduced in the preparation process, and the environment-friendly effect is better.
3. The supported catalyst is more stable and has better recoverability: experiments prove that compared with the prior art, the supported catalyst has lower leaching rate, is more stable, is easy to separate and has better recoverability, thereby greatly reducing the industrial application cost.
Drawings
FIG. 1 physical photograph and scanning SEM image of blank heterogeneous catalyst support
FIG. 2 morphology of Supports loaded with different catalysts
FIG. 3 SEM images of quantitative Cu @ Tab and Pd/C @ Tab cross sections
FIG. 4 quantitative Pd/C @ Tab and quantitative Pd/Al2O3Comparison of kinetics of @ Tab
FIG. 5 cycling experiment and dissolution experiment for quantification of Cu @ Tab
Detailed Description
The invention will be further illustrated with reference to the following specific examples. 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 preparation of ultra high molecular weight porous polyethylene heterogeneous catalyst support
The method comprises the following steps: adding 50 μm ultra-high molecular weight polyethylene powder with molecular weight greater than 100 ten thousand into cylindrical stainless steel grinding tool with inner diameter of 7.4mm or 5.1mm and height of 3mm, heating to 150 deg.C under normal pressure, rapidly cooling to room temperature, and demolding. The prepared ultrahigh molecular weight porous polyethylene heterogeneous catalyst carrier has high hardness, hardly cracks in the stirring process, but can be cut by a sharp knife to prepare various shapes, and the picture of the catalyst carrier with two diameters prepared in the embodiment 1 of the invention is shown in figure 1 a; the obtained carrier was placed under a scanning electron microscope, and an SEM image obtained is shown in FIG. 1 b.
Example 2: quantitative preparation of Pd/C Supports (abbreviated hereinafter as Pd/C @ Tab)
300.0mg of heterogeneous catalyst micro Pd/C powder (commercially available, Pd content is 10 wt/wt%) is ground into powder with the particle size being less than or equal to 5 mu m, then the powder is suspended in 50ml of ethanol, and 30 pieces (80 mg/piece weight) of the ultrahigh molecular weight porous polyethylene heterogeneous catalyst carrier are added while stirring, wherein the stirring speed is 500r/min, the stirring temperature is room temperature, and the stirring time is 24 hours; fully stirring to fully load the heterogeneous catalyst to the carrier until the suspension becomes clear, then taking out the loaded catalyst, and continuing stirring for 12 hours in clean 50mL ethanol at the same speed and temperature to wash off the redundant catalyst on the surface of the catalyst carrier, thus obtaining Pd/C @ Tab, wherein the load of the carrier on micron Pd/C is 1.9 mg/sheet; preparation the quantitative Pd/C @ Tab is shown in FIG. 2 a. Through determination, the percentage content of Pd in the catalyst prepared by the method in the carrier is 0.24%.
Example 3: quantitative preparation of Pd/Al2O3Supported sheet (hereinafter abbreviated as Pd/Al)2O3@Tab)
300.0mg of heterogeneous catalyst micro Pd/Al2O3Grinding the powder (which is commercially available and has a Pd content of 5 wt/wt%) into powder with the particle size of less than or equal to 5 microns, suspending the powder in 50ml of ethanol, and adding 30 sheets (80 mg/sheet weight) of the ultrahigh molecular weight porous polyethylene heterogeneous catalyst carrier while stirring, wherein the stirring speed is 500r/min, the stirring temperature is room temperature, and the stirring time is 24 hours; fully stirring to fully load the heterogeneous catalyst to the carrier until the suspension becomes clear, then taking out the loaded catalyst, and continuing stirring for 12h in clean 50mL ethanol at the same speed and temperature to wash off the redundant catalyst on the surface of the catalyst carrier, thus obtaining the Pd/Al catalyst2O3@ Tab, said support being on micron Pd/Al2O3The loading amount of (A) was 1.9 mg/tablet; the preparation method obtains quantitative Pd/Al2O3The @ Tab photograph is shown in FIG. 2 b; quantitative Pd/Al2O3An SEM image of the @ Tab cross-section is shown in FIG. 3 b. Through determination, the catalyst Pd prepared by the method accounts for 0.12 percent of the carrier.
Example 4: quantitative preparation of Cu Supported sheet (hereinafter abbreviated as Cu @ Tab)
Grinding heterogeneous catalyst micron copper (300.0mg) into powder with the particle size of less than or equal to 5 microns, suspending the powder in 30ml of ethanol, adding 30 pieces (80 mg/piece weight) of the ultrahigh molecular weight porous polyethylene heterogeneous catalyst carrier while stirring, wherein the stirring speed is 500 revolutions per minute, the stirring temperature is room temperature, and the stirring time is 4 hours; fully stirring to fully load the heterogeneous catalyst on the carrier until the suspension becomes clear, then taking out the loaded catalyst, and continuing stirring for 12 hours in clean 30mL ethanol at the same speed and temperature to obtain Cu @ Tab, wherein the loading capacity of the carrier on micron copper is 8 mg/sheet, and the photo of the prepared and quantitatively prepared Cu loaded sheet is shown in figure 2 c; SEM images of quantitative Cu @ Tab cross sections are shown in figure 3 a. Through determination, the Cu content of the catalyst prepared by the method is 10 percent of the carrier.
Experimental example 1: for the shape and the character of the carrier after loading different catalysts
As shown in FIG. 2, from left to right are Pd/C @ Tab and Pd/Al2O3@ Tab, Cu @ Tab, Pt/C @ Tab, RhC @ Tab (see FIG. 2a, FIG. 2b, FIG. 2C, FIG. 2d, and FIG. 2e, respectively).
Experimental example 2 Strength test experiment
Pd/C @ Tab and Pd/Al prepared in examples 2-4 are respectively added2O310 pieces of @ Tab and Cu @ Tab were put in 20ml ethanol solvent, and stirred under magnetic stirring at 500 rpm for 10 days without any break.
Experimental example 3: Pd/C @ Tab and Pd/Al2O3Comparison of applications of @ Tab
Pd/C @ Tab and Pd/Al were prepared as in examples 3 and 4, respectively2O3@ Tab. Comparing the reaction based on Pd/C @ Tab with the reaction based on Pd/C powder catalyst in the hydrogenation reaction of nitro compound, the reaction has similar kinetic curve (the reaction rate of Pd/C @ Tab is slightly slower than that of Pd/C powder catalyst, as shown in figure 4 a); but as the reaction proceeded, (Pd/C @ Tab could be recycled 6 times without significantly slowing down the reaction rate (as shown in FIG. 4 b); likewise, Pd/Al2O3@ Tab and use of Pd/Al2O3The kinetic curve is better compared with the reaction carried out by the powder catalyst, Pd/Al2O3The reactivity of @ Tab is better (as shown in FIG. 4 d).
In addition, for the catalyst leaching in the recycle experiment, when Pd/C powder catalyst is used, the reacted mixture is filtered by filter paper, 13ppm of palladium remains in the reaction mixture, while our supporting method using Pd/C @ Tab can significantly reduce the leaching of palladium, and the palladium leaching in each recycle reaction mixture is less than 0.20ppm (as shown in FIG. 4C).
Experimental example 4: Pd/C @ Tab catalytic hydrogenation reaction and Pd/C @ Tab deprotection reaction applicability
(1) Suitability of Pd/C @ Tab for various hydrogenation reactions. The experimental procedure for the hydrogenation reaction was: stirring at room temperature and monitoring by TLC or GC-MS Pd/C @ Tab (1 plate, 1.8. mu. mol Pd, 1 mol%) and H2(balloon) into a dry Schlenk reaction tube, then add EtOH (2mL) via syringe to neutralize the substrate (0.18 mmol); and after the reaction is finished, taking out the Pd/C @ Tab, washing the Pd/C @ Tab with dichloromethane for 3 times, combining the reacted solution, concentrating the solution in vacuum to obtain a crude hydrogenation product, performing column chromatography on the crude hydrogenation product to obtain a corresponding hydrogenation product, and calculating the yield. As shown in Table 1, Pd/C @ Tab works well in the hydrogenation of alkenes and alkynes (entries 1-4), nitro compounds (entry 5), imines (entry 6), organic azides (entries 7-12) and ketones (entries 13-16), all giving the corresponding reduction products, with yields also reflected in Table 1.
TABLE 1 Pd/C @ Tab suitability for use in various hydrogenation reactions
Figure BDA0002633970750000081
(2) Applicability of Pd/C @ Tab in various deprotection reactions. As shown in Table 2, the deprotected product was also obtained in high isolated yield. In the control experiment, the Pd/C @ Tab was removed from the reaction solution 2 hours after the start of the reaction and then stirring was continued, even with further stirring for 2 hours, the reaction was stopped at 38% completion, indicating that the actual catalyst for the reaction was Pd/C @ Tab, rather than palladium leaching into solution to catalyze it.
TABLE 2 Pd/C @ Tab suitability for use in various deprotection reactions
Figure BDA0002633970750000091
Experimental example 5: application of Cu @ tab
As shown in fig. 5, the chamberPhenylacetylene (20.4mg, 0.2mmol), bis (pinacol) diboron (76.2mg, 0.3mmol) and Cu @ Tab (1 piece, 0.25mg, 3.9 μmol, 2% Cu to Cu @ Tab mole%) were added to a dry Schlenk reaction tube at room temperature and ethanol (2mL) was added under argon protection, the reaction was stirred for 6 hours, after the reaction was complete the Cu @ Tab was removed and washed with EtOAc 3 times; then, water was added to the reaction system, the aqueous phase was extracted with ethyl acetate (5 mL. times.3 times), and the organic layers were combined and Na-washed2SO4Dried and concentrated in vacuo to give the crude product, which was then purified by silica gel column chromatography (eluent: petroleum ether/ethyl acetate 10: 1 by volume) to give a white solid (42.8mg, 93% purity by mass). The Cu @ Tab can be recycled 8 times (as shown in fig. 5 a), except that the first metal leach out is 4.8ppm, and then the metal leach out is below 1ppm per cycle (as shown in fig. 5 b).

Claims (10)

1. A porous plastic heterogeneous catalyst carrier is characterized in that the carrier is a porous solid block structure; preferably, the porous plastic heterogeneous catalyst carrier is in a tablet-like cylindrical structure, a spherical structure or a cubic structure; further preferably, the solid block structure is a tablet-like cylindrical structure, the pore volume of the solid block structure is 0.3-0.6 ml/g, and the total pore area of the solid block structure is 20-25 m2(iv)/g, having an average pore diameter of 70 to 80nm, a bulk density of 0.5 to 1.0g/ml at 0.5 to 1psi, and a porosity of 20 to 30%; more preferably, the specifications of the tablet-like cylindrical structure porous plastic heterogeneous catalyst carrier are as follows: the inner diameter is 5.1-9 mm and the height is 2.5-4 mm.
2. The porous plastic heterogeneous catalyst carrier according to claim 1, wherein the porous plastic is any one or more of ultra-high molecular weight porous polyethylene, ultra-high molecular weight porous polypropylene, ultra-high molecular weight polytetrafluoroethylene, and ultra-high molecular weight polyvinylidene fluoride.
3. A preparation method of the porous plastic heterogeneous catalyst carrier as claimed in any one of claims 1 to 2, which is characterized by comprising the following steps: adding the porous plastic powder into a cylindrical stainless steel grinding tool, heating to 140-155 ℃ under normal pressure, rapidly cooling to room temperature, and demolding to obtain the porous plastic powder; preferably, the diameter of the porous plastic powder is 5-100 μm, and the molecular weight of the porous plastic powder is more than 100 ten thousand; preferably, the inner diameter of the cylindrical stainless steel grinding tool is 5.1-9 mm, and the height of the cylindrical stainless steel grinding tool is 2.5-4 mm.
4. Use of a porous plastic heterogeneous catalyst support according to any of claims 1 to 2 for supporting a heterogeneous catalyst to form a porous polymer catalyst.
5. The application according to claim 4, characterized in that the specific operation method of the application comprises the following steps:
firstly, grinding the heterogeneous catalyst into powder, suspending the heterogeneous catalyst powder in an organic solvent, adding the porous plastic heterogeneous catalyst carrier while stirring, fully stirring to fully load the heterogeneous catalyst on the carrier, taking out the loaded catalyst carrier, and continuously stirring for 10-24 hours in a clean and same organic solvent at the same speed and temperature to wash off the non-loaded heterogeneous catalyst on the surface of the carrier; preferably, the heterogeneous catalyst powder has a particle size of less than or equal to 5 μm; preferably, the organic solvent includes, but is not limited to, ethanol, petroleum ether, toluene, tetrahydrofuran, dichloromethane; more preferably, the mass of the organic solvent is 8 to 20 times of the mass of the carrier.
6. The use according to claim 5, wherein the insoluble heterogeneous catalyst is present in an amount of 0.01 to 40% by mass of the porous plastic heterogeneous catalyst support; preferably, the mass percentage of the insoluble heterogeneous catalyst in the porous plastic heterogeneous catalyst carrier is 0.1-10%.
7. The use according to claim 5, wherein the stirring rate is 300 to 600r/min, the stirring temperature is 0 to 30 ℃, and the stirring time is 1 to 24 hours.
8. Use according to claim 5, wherein the heterogeneous catalyst is an insoluble heterogeneous catalyst; further preferably, the heterogeneous catalyst is Pd/C, Pd/Al2O3，Ru/C，Ru/TiO2，Ru/Al2O3，Pt/Al2O3，Pt/C，Rh/C，Cu，Au/TiO2，Au/Al2O3And Ag/molecular sieve.
9. A porous polymer catalyst, which is characterized by comprising a porous plastic heterogeneous catalyst carrier according to any one of claims 1 to 2 and an insoluble heterogeneous catalyst supported on the carrier; preferably, the mass percentage of the insoluble heterogeneous catalyst in the porous plastic heterogeneous catalyst carrier is 0.01-40%; further preferably, the mass percentage of the insoluble heterogeneous catalyst in the porous plastic heterogeneous catalyst carrier is 0.1-10%.
10. Use of the porous polymer catalyst of claim 9 in an organic catalytic chemical reaction; further, the organic catalytic reaction 1 is a hydrogenation reaction or a deprotection reaction.
CN202010819538.0A 2020-08-14 2020-08-14 Porous plastic heterogeneous catalyst carrier and preparation method and application thereof Pending CN111841658A (en)

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