CN108864438B - Preparation method and application of polymer microsphere with core-shell and hierarchical pore structure - Google Patents
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Abstract
The invention relates to a preparation method and application of polymer microspheres with core-shell and hierarchical pore structures, wherein 3-hydroxy-4-aminobenzoic acid and terephthalaldehyde are subjected to reflux reaction in an ethanol solvent to obtain a ligand with Schiff base functional groups, the ligand is purified by using the solvent and is dried in vacuum to obtain yellow powder, the powder and zinc nitrate hexahydrate are added into a reactor, N-dimethylformamide and ethanol are added into the reactor as solvents, the mixture is stirred uniformly and then is placed into an oven to be heated, the mixture is washed for a plurality of times by the N, N-dimethylformamide and the ethanol, and the mixture is dried in vacuum overnight to obtain the metal polymer microspheres with the core-shell structures and the mesoporous-microporous-macroporous hierarchical pore structures. Compared with the prior art, the catalyst is used as a heterogeneous catalyst for performing 2-pyridinemethanol acetate deacetylation reaction, the reaction yield can be stably up to 90% after the catalyst can be circulated for up to 7 times, and the catalytic activity of the catalyst is not remarkably lost.
Description
Technical Field
The invention relates to a metal polymer microsphere, in particular to a preparation method and application of a metal polymer microsphere with a core-shell structure and a mesoporous-microporous-macroporous hierarchical pore structure.
Background
As an important functional polymer material, the polymer microsphere is more and more concerned in various fields such as catalytic carriers, drug delivery, enzyme immobilization, controlled release, adsorption separation and the like due to the unique porous property of the polymer microsphere.
The core-shell structure material is a composite material of a self-assembly structure formed by coating through chemical bonds or other interactions, and generally consists of a core at the center and a shell coated outside. The polymer having a core-shell structure can not only prevent agglomeration but also enhance selectivity and activity of the reaction, and its synthesis is considered to be one of the most convenient and effective methods for obtaining nanoparticles and synergistic effects. Generally, the method for obtaining the core-shell structure model is mainly a template method. The template method is classified into a hard template such as a polymer and a metal core, and a soft template such as a surfactant micelle or an ionic solvent. Template-assisted synthesis is an effective method, however, its ability to build complex structures is often limited by the template. Moreover, this method typically requires the use of surfactants or some polymers to remove the template, and the process is generally cumbersome. In addition, the material with the hierarchical pore or core-shell structure has the internal gaps which provide effective transportation channels and has potential application in the aspects of catalysis, drug delivery and the like. Few materials with both hierarchical porous and core-shell structures have been reported, and synthesis by such a simple method is itself a challenge.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method and application of a metal polymer microsphere with a core-shell structure and a meso-microporous-macroporous hierarchical pore structure.
The purpose of the invention can be realized by the following technical scheme:
the preparation method of the polymer microsphere with the core-shell structure and the hierarchical pore structure comprises the following steps:
(1) carrying out reflux reaction on 3-hydroxy-4-aminobenzoic acid and terephthalaldehyde in an ethanol solvent to obtain a ligand 4,4'- ((1E, 1' E) -1, 4-phenyl-bis (methylene)) bis (azophenyl) bis (3-hydroxybenzoic acid) with a Schiff base functional group, purifying by using the solvent, and carrying out vacuum drying to obtain yellow powder;
(2) adding the powder and zinc nitrate hexahydrate into a reactor, adding N, N-dimethylformamide and ethanol as solvents, uniformly stirring, then placing into an oven for heating to obtain a dark red solid, washing with the N, N-dimethylformamide and the ethanol for a plurality of times, and carrying out vacuum drying overnight to obtain the metal polymer microsphere with the core-shell structure and the mesoporous-microporous-macroporous hierarchical pore structure.
In the step (1), the molar ratio of the 3-hydroxy-4-aminobenzoic acid to the terephthalaldehyde is 2:1, the reflux reaction temperature is 50-80 ℃, the reaction time is 5-8h, the solvent for purification is methanol, the drying temperature for vacuum drying is 40-80 ℃, and the drying time is 2-8h, preferably 4-7 h.
The mol ratio of the powder to the zinc nitrate hexahydrate in the step (2) is 1:3-1:4, and the volume ratio of the N, N-dimethylformamide to the ethanol is 1: 1. The powder is stirred with zinc nitrate hexahydrate for 5-60min, preferably 10-20 min. The heating time in the oven is 2-144h, preferably 12-48h, and the heating temperature is 120-160 ℃, preferably 140 ℃. The temperature for vacuum drying overnight was 60 ℃.
The application of the polymer microsphere with the core-shell and hierarchical pore structures as a heterogeneous catalyst for performing 2-pyridinemethanol acetate deacetylation reaction can ensure that the catalyst can be circulated for up to 7 times, the reaction yield can still stably reach 90 percent, and the catalytic activity of the catalyst is not remarkably lost, which indicates that the catalyst has recoverability and good catalytic performance.
Compared with the prior art, the invention has the following characteristics:
(1) the invention synthesizes the metal microsphere with a core-shell structure in one step under the hydrothermal condition, and the metal microsphere has a hierarchical structure of micropore-mesopore-macropore.
(2) The invention synthesizes the metal microsphere with the core-shell structure in one step, and the metal microsphere has a micropore-mesopore-macropore hierarchical structure because the invention adopts the reaction of 3-hydroxy-4-aminobenzoic acid and terephthalaldehyde to synthesize the ligand containing Schiff base. The ligand and zinc nitrate hexahydrate quickly react under the hydrothermal condition to form metal solid microsphere precipitate Zn-L-CP. Due to continuous rotation of the Schiff base ligand in space and non-unique spatial configuration, the ligand and zinc nitrate hexahydrate can have various coordination forms, which is also the reason for micropores and mesopores in the microsphere. Furthermore, the presence of trace amounts of water in the system can lead to hydrolysis of the C = N bond in the ligand. And meanwhile, DMF in the solvent can react with terephthalaldehyde generated after the ligand is hydrolyzed, so that the hydrolysis of the Schiff base is further promoted. Therefore, the solid microspheres formed at the beginning of the reaction generate a macroporous structure along with the hydrolysis of the Schiff base, then the solvent is continuously etched along the macropores, and then loose and porous shells are etched on the periphery of the solid microspheres, so that the appearance of the core-shell structure is generated.
(3) The reaction time is the same, the higher the reaction temperature is, the faster the process of etching the solid microspheres into the core-shell structure is, which shows that the hydrolysis of Schiff base is promoted by the high temperature, and the etching process is accelerated. Therefore, the present invention can control the above conditions affecting the formation of the core-shell structure, and synthesize a material having a porous hierarchical structure and a core-shell structure by a simple method.
(4) The metal polymer catalyst has a core-shell structure and a micropore-mesopore-macropore hierarchical structure, so that the metal polymer catalyst is beneficial to the mass transfer process in the catalysis process, and has good catalysis performance. And because the metal polymer belongs to a heterogeneous catalyst and is easy to separate and recycle, the metal polymer has stable catalytic performance and no obvious loss of catalytic activity.
Drawings
FIG. 1 shows the ligand L and the metal polymer Zn-L-CP of the present invention13C CP/MAS NMR spectra.
FIG. 2 is a TEM image of a metal polymer of the present invention.
FIG. 3 is an SEM image of a metal polymer of the present invention.
FIG. 4 is a Zn-L-CP nitrogen adsorption and desorption isotherm of the metal polymer of the present invention; the inset is the pore size distribution curve (140 ℃/48h)
FIG. 5 is a cycle experiment of catalytic deacetylation of Zn-L-CP of the present invention under optimal conditions.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
Synthesis of Schiff base ligand L
0.2683g of 4-amino-3-hydroxybenzoic acid and 0.6126g of terephthalaldehyde were weighed into a flask containing 30mL of EtOH and slowly refluxed at 55 ℃ for 6 hours. The colorless mixture was clearly seen to gradually turn yellow. Then, it was filtered to give a yellow powdery solid, which was washed several times with cold ethanol and then vacuum-dried at 40 ℃.
Example 2
Preparing the metal polymer microsphere with a core-shell structure and a meso-porous-macroporous hierarchical pore structure.
0.0809g of ligand L were weighed into a Teflon lined autoclave followed by DMF and EtOH (V)DMF: VEtOH=1:1,15 mL) to form a homogeneous solution. 0.2677g of Zn (NO 3) 2.6H 2O were added to the resulting solution, followed by stirring for 10-20 minutes, and finally the autoclave was placed in an oven and heated at 140 ℃ for 48 hours. Cooling to room temperature, suction filtration to obtain dark red powder solid, washing with DMF and EtOH three times respectively, and finally vacuum drying at 60 ℃ overnight.
Example 3
The Schiff base ligand L and the metal polymer Zn-L-CP of the invention13The C CP/MAS NMR spectrum is shown in FIG. 1.13The strong signal at 175.7ppm for ligand L in the C CP/MAS NMR spectrum was assigned to the carbon on the carboxyl group of ligand L attached to the benzene ring. The strong signal at 161.6ppm is attributed to the formation of carbon on the Schiff base and the strong signal at 156.6ppmThe symbol is the carbon on the phenyl ring to which the hydroxyl group is attached. The peaks marked with asterisks are due to the spinning sidebands (denoted by).13Signals of the metal polymer Zn-L-CP in a C CP/MAS NMR spectrogram at 178.9ppm, 167.6ppm and 161.6ppm are caused by low-field movement and increased chemical shift after the carboxyl, Schiff base and hydroxyl in the ligand L are coordinated with Zn2 +. Thus further demonstrating Zn2+The coordination with the ligand L was successful.
Example 4
TEM images of the metal polymer of the present invention at different time points at 140 ℃ are shown in FIG. 2. The TEM image shows the effect of fixing the reaction temperature and changing the reaction time on the product morphology. After reacting for 2 hours, solid microspheres (a) which are uniform, smooth and have an average particle size of 3-5 μm are obtained. It is clear that the edges of the solid microspheres etched a thin shell (b) after 12 hours of reaction. Interestingly, as the reaction time increased, the solid microspheres were further etched and the proportion of the shell layer gradually increased. From the figure (c-d), we can see Zn-L-CP forming a well-defined core-shell structure. With further extension of the reaction time, the solid microspheres are further etched, the core gradually shrinks, and the proportion of the shell increases (e). Finally, after 6 days the core was completely etched, leaving microspheres that were all loose porous shells, but the morphology was somewhat damaged (f).
Example 5
SEM images of the metal polymer of the present invention at different time points at 140 ℃ are shown in FIG. 3. From the SEM image, it can be seen that after 2 hours of reaction, smooth solid microspheres having an average particle size of 4 μm were obtained, as shown in (a) of the figure. After 12 hours of reaction, it was observed that the edges of the solid microspheres began to etch out a thin shell (b). From fig. 2 (c) - (e), it can be observed that the Zn-L-CP microspheres have a well-defined core-shell structure, and that the core of the microspheres gradually shrinks under the etching action, and the proportion of the shell is continuously increased. Finally, the microspheres were completely etched after 144 hours, leaving a loose porous shell (f) that was all easily broken.
Example 6
The Zn-L-CP nitrogen adsorption and desorption isotherm of the metal polymer of the invention is shown in figure 4Shown; the inset is the pore size distribution curve (140 ℃/48 h). From the nitrogen adsorption-desorption isotherm of Zn-L-CP and the interpolated pore size distribution curve, the material has H4The typical IV-type isotherm of the hysteresis loop also shows that the material has micropores with a size of about 1.7-1.9nm, while the mesopores have a wider size distribution, which can be seen in the figure to be about 2-50 nm.
Example 7
The cycle experiment of catalytic deacetylation of Zn-L-CP under the optimal conditions is shown in FIG. 5. Zn-L-CP is a heterogeneous catalyst, and has the advantages of easy recovery and stability. Therefore, we studied the cycle experiment of the catalyst deacetylation reaction under the optimum conditions. The Zn-L-CP catalyst (140 ℃ C./48 hours) was reacted with methanol as a solvent for 27 hours and then recovered from the reaction mixture by filtration conveniently and efficiently. The Zn-L-CP catalyst can be directly subjected to the second, third and fourth series of circulation experiments without further treatment, and the yield can still stably reach 90 percent by circulating for up to 7 times, which indicates that the catalyst has recoverability and good catalytic performance.
TABLE 1 catalytic Effect of Zn-L-CP catalyst in deacetylation reaction
| No. | Solvent | Catalyst | Yield(%)[b] |
| 1 | MeOH | × | 16 |
| 2 | MeOH | √ | 96 |
| 3 | EtOH | × | 2 |
| 4 | EtOH | √ | 60 |
The present inventors conducted a catalytic performance study using 2-pyridinemethanol acetate as a representative substrate and methanol or ethanol as a solvent (as shown in table 1). Methanol is used as a solvent, the reaction is carried out for 27h at 60 ℃, when no catalyst is added, the yield of 2-pyridinol is only 16%, and when Zn-L-CP polymer microspheres (synthesized at 140 ℃/48h) with a core-shell structure are used as the catalyst, the yield of 2-pyridinol is up to 96%. When ethanol is used as a solvent, the reaction is carried out for 27h at 60 ℃, the yield of the 2-pyridinol is 2% without adding a catalyst, and the yield of the 2-pyridinol is 60% after adding the catalyst. Thus, it could be confirmed that the catalyst had good catalytic performance.
Example 8
The preparation method of the polymer microsphere with the core-shell structure and the hierarchical pore structure comprises the following steps:
(1) mixing 3-hydroxy-4-aminobenzoic acid and terephthalaldehyde according to a molar ratio of 2:1, carrying out reflux reaction in an ethanol solvent at the reflux reaction temperature of 50 ℃ for 8 hours to obtain ligand 4,4'- ((1E, 1' E) -1, 4-phenyl-bis (methylene)) bis (azophenyl) bis (3-hydroxybenzoic acid) with Schiff base functional groups, purifying by using a methanol solvent, and carrying out vacuum drying at the drying temperature of 40 ℃ for 8 hours to obtain yellow powder;
(2) adding the powder and zinc nitrate hexahydrate into a reactor according to a molar ratio of 1:3, adding N, N-dimethylformamide and ethanol serving as solvents according to a volume ratio of 1:1, stirring for 5min to enable the mixture to be uniform, then placing the mixture into an oven to be heated for 2h at 160 ℃ to obtain dark red solids, washing the dark red solids for a plurality of times by using the N, N-dimethylformamide and the ethanol, and carrying out vacuum drying at 60 ℃ overnight to obtain the metal polymer microspheres with the core-shell structure and the mesoporous-microporous-macroporous hierarchical pore structure.
Example 9
The preparation method of the polymer microsphere with the core-shell structure and the hierarchical pore structure comprises the following steps:
(1) mixing 3-hydroxy-4-aminobenzoic acid and terephthalaldehyde according to a molar ratio of 2:1, carrying out reflux reaction in an ethanol solvent at a reflux reaction temperature of 60 ℃ for 6 hours to obtain a ligand 4,4'- ((1E, 1' E) -1, 4-phenyl-bis (methylene)) bis (azophenyl) bis (3-hydroxybenzoic acid) with a Schiff base functional group, purifying by using a methanol solvent, and carrying out vacuum drying at a drying temperature of 50 ℃ for 7 hours to obtain yellow powder;
(2) adding the powder and zinc nitrate hexahydrate into a reactor according to a molar ratio of 1:3, adding N, N-dimethylformamide and ethanol serving as solvents according to a volume ratio of 1:1, stirring for 10min to enable the mixture to be uniform, then placing the mixture into an oven to be heated for 12h at the temperature of 140 ℃ to obtain dark red solids, washing the dark red solids for a plurality of times by using the N, N-dimethylformamide and the ethanol, and carrying out vacuum drying overnight at the temperature of 60 ℃ to obtain the metal polymer microspheres with the core-shell structure and the mesoporous-microporous-macroporous hierarchical pore structure.
Example 10
The preparation method of the polymer microsphere with the core-shell structure and the hierarchical pore structure comprises the following steps:
(1) mixing 3-hydroxy-4-aminobenzoic acid and terephthalaldehyde according to a molar ratio of 2:1, carrying out reflux reaction in an ethanol solvent at a reflux reaction temperature of 60 ℃ for 6 hours to obtain a ligand 4,4'- ((1E, 1' E) -1, 4-phenyl-bis (methylene)) bis (azophenyl) bis (3-hydroxybenzoic acid) with a Schiff base functional group, purifying by using a methanol solvent, and carrying out vacuum drying at a drying temperature of 70 ℃ for 4 hours to obtain yellow powder;
(2) adding the powder and zinc nitrate hexahydrate into a reactor according to a molar ratio of 1:4, adding N, N-dimethylformamide and ethanol serving as solvents according to a volume ratio of 1:1, stirring for 20min to enable the mixture to be uniform, then placing the mixture into an oven to be heated for 48h at 120 ℃ to obtain dark red solids, washing the dark red solids for a plurality of times by using the N, N-dimethylformamide and the ethanol, and carrying out vacuum drying at 60 ℃ overnight to obtain the metal polymer microspheres with the core-shell structure and the mesoporous-microporous-macroporous hierarchical pore structure.
Example 11
The preparation method of the polymer microsphere with the core-shell structure and the hierarchical pore structure comprises the following steps:
(1) mixing 3-hydroxy-4-aminobenzoic acid and terephthalaldehyde according to a molar ratio of 2:1, carrying out reflux reaction in an ethanol solvent at the reflux reaction temperature of 80 ℃ for 5 hours to obtain ligand 4,4'- ((1E, 1' E) -1, 4-phenyl-bis (methylene)) bis (azophenyl) bis (3-hydroxybenzoic acid) with Schiff base functional groups, purifying by using a methanol solvent, and carrying out vacuum drying at the drying temperature of 80 ℃ for 2 hours to obtain yellow powder;
(2) adding the powder and zinc nitrate hexahydrate into a reactor according to a molar ratio of 1:4, adding N, N-dimethylformamide and ethanol serving as solvents according to a volume ratio of 1:1, stirring for 60min to enable the mixture to be uniform, then placing the mixture into an oven to be heated for 144h at 120 ℃ to obtain dark red solids, washing the dark red solids for a plurality of times by using the N, N-dimethylformamide and the ethanol, and carrying out vacuum drying at 60 ℃ overnight to obtain the metal polymer microspheres with the core-shell structure and the mesoporous-microporous-macroporous hierarchical pore structure.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. The preparation method of the polymer microsphere with the core-shell structure and the hierarchical pore structure is characterized by comprising the following steps:
(1) carrying out reflux reaction on 3-hydroxy-4-aminobenzoic acid and terephthalaldehyde in an ethanol solvent to obtain a ligand 4,4'- ((1E, 1' E) -1, 4-phenyl-bis (methylene)) bis (azophenyl) bis (3-hydroxybenzoic acid) with a Schiff base functional group, purifying by using the solvent, and carrying out vacuum drying to obtain yellow powder;
(2) adding the powder and zinc nitrate hexahydrate into a reactor, adding N, N-dimethylformamide and ethanol as solvents, uniformly stirring, then placing into an oven for heating to obtain a dark red solid, washing with the N, N-dimethylformamide and the ethanol for a plurality of times, and carrying out vacuum drying overnight to obtain the metal polymer microsphere with the core-shell structure and the mesoporous-microporous-macroporous hierarchical pore structure.
2. The method for preparing polymer microspheres with core-shell and hierarchical pore structures according to claim 1, wherein the molar ratio of 3-hydroxy-4-aminobenzoic acid to terephthalaldehyde in step (1) is 2:1, the reflux reaction temperature is 50-80 ℃, and the reaction time is 5-8 h.
3. The method for preparing polymer microspheres with core-shell and hierarchical pore structures according to claim 1, wherein the solvent used for purification in step (1) is methanol.
4. The preparation method of the polymer microsphere with the core-shell and hierarchical pore structure according to claim 1, wherein the drying temperature of the vacuum drying in the step (1) is 40-80 ℃, and the drying time is 2-8 h.
5. The preparation method of the polymer microsphere with the core-shell structure and the hierarchical pore structure according to claim 1, wherein the molar ratio of the powder to the zinc nitrate hexahydrate in the step (2) is 1:3-1: 4.
6. The method for preparing polymer microspheres with core-shell and hierarchical pore structures according to claim 1, wherein the volume ratio of N, N-dimethylformamide to ethanol in step (2) is 1: 1.
7. The method for preparing polymer microspheres with core-shell and hierarchical pore structures according to claim 1, wherein the stirring time in step (2) is 5-60 min.
8. The method for preparing polymer microspheres with core-shell and hierarchical pore structures as claimed in claim 1, wherein the heating time in the oven in step (2) is 2-144h, and the heating temperature is 120-160 ℃.
9. The method for preparing polymer microspheres with core-shell and hierarchical pore structures according to claim 1, wherein the temperature for vacuum drying overnight in step (2) is 60 ℃.
10. The use of the polymer microsphere having both core-shell and hierarchical pore structure prepared by the method of claim 1 as a heterogeneous catalyst for deacetylation of 2-pyridinemethanol acetate.
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