CN113861390B - Porous organic polymer with hierarchical pore distribution and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a preparation method of a porous organic polymer with hierarchical pore distribution, which is characterized in that connectors with different lengths are added at intervals in the polymerization process of the porous organic polymer, and the adding proportion and the adding time of each connector are regulated and controlled at intervals, so that the pore distribution and the structure of the porous organic polymer are regulated and controlled, and the porous organic polymer with the hierarchical pore distribution is obtained. The invention has the advantages of simple operation, mild condition, obvious effect, environmental protection and the like, can realize the regulation and control of the porous organic polymer pore structure without using any additional template agent or carrying out complex operation, can effectively improve the adsorption capacity of the porous polymer on metal ions, and enhances the diffusion mass transfer capacity of the metal ions in the porous polymer pore, thereby having wide application prospect.
Description
Technical Field
The invention belongs to the field of synthesis of chemical functional materials, and particularly relates to a porous organic polymer with hierarchical pore distribution, a preparation method thereof and application thereof in metal ion adsorption.
Background
Porous Organic Polymers (POPs) refer to organic polymers with rich pore channels, wherein microporous conjugated polymers (Conjugated Microporous Polymer, CMP) are porous organic polymers with conjugated structures, are an important subclass of porous materials, and are formed into a network structure with pi-conjugated units and rich micropores by coupling and connecting rigid aromatic groups through covalent bonds, so that the porous organic polymers have the important characteristics of considerable specific surface area, micropore adjustability, high thermal stability, chemical stability and the like. Meanwhile, the microporous conjugated polymer also has a modularized polymeric coupling characteristic, and various building units can be introduced into a network structure according to requirements so as to regulate and control functions and the network structure. CMPs are currently widely used in a variety of fields such as gas adsorption and separation, and chemisorption. It is worth mentioning that CMPs have the advantages of large specific surface area, abundant conjugated groups, high porosity and the like, so that the CMPs have wide application prospects in the aspect of water treatment.
However, there is still a problem in the water treatment applications of CMPs that is greater when using shorter linkers than CMPs using longer linkersThe surface area has larger storage space in thermodynamic aspect, but the pore canal size is usually smaller, so that the CMPs use M (H 2 O) X n+ The metal ions existing in the hydrated form of the catalyst are difficult to effectively diffuse in the micropore canals, so that the problems that the internal canals are not fully utilized and the like exist, and finally, the adsorption quantity is low and the diffusion rate is slow are caused.
On the basis of the CMPs molecular structural formula, the invention gradually introduces the short-to-long connectors in the preparation process to construct a pore structure with hierarchical distribution from inside to outside, and the porous organic polymer can utilize the pore with larger outer layer size as a diffusion pore, and simultaneously can utilize the pore with smaller inner layer size as a storage pore, thereby finally realizing the effective diffusion of hydrated metal ions from outside to inside in the pore and the improvement of the utilization rate of the inner pore, further improving the adsorption rate and adsorption capacity of the porous organic polymer on pollutants such as heavy metal mercury ions and overcoming the defects of the prior material.
Disclosure of Invention
Aiming at the challenges and the shortcomings, the invention aims to provide a porous organic polymer with hierarchical pore distribution, a preparation method and application thereof, and the porous organic polymer has the advantages that the pore structure of a porous organic polymer material is constructed and optimized to improve the adsorption capacity of the porous organic polymer material to pollutants such as mercury ions, and the like, so that the problems that the internal pore of the porous organic polymer is not fully utilized, the adsorption mass transfer is poor and the like are solved.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the first object of the invention is to protect a preparation method of a porous organic polymer with hierarchical pore distribution, which is to sequentially introduce different connectors from short to long in the polymerization process, and regulate the adding proportion and the adding interval time of each connector so as to effectively regulate the pore distribution of a polymer network and construct the porous organic polymer with hierarchical pore distribution.
The method specifically comprises the following steps:
1) Uniformly mixing the solvent with the center, the catalyst, the ligand, the alkali and the salt;
2) Sequentially adding different linkers with the length from short to long into the mixed solution obtained in the step 1), and reacting for a period of time at intervals after each addition;
3) After adding the connector with the longest length, continuing to react for a period of time, and carrying out suction filtration, washing and drying on the product to obtain the porous organic polymer with hierarchical pore distribution.
Further, the solvent in the step 1) is an organic solvent which can dissolve or dissolve a small amount of the above chemical substances, such as tetrahydrofuran, 1, 4-dioxane or toluene.
Further, the center is an arylamine compound containing three or more coupling groups such as-Br, -Cl, -I and the like, and the arylamine compound can be selected from tri (4-bromophenyl) amine and the like.
Further, the catalyst is a palladium catalyst, which can be selected from bis (benzalacetone) palladium and the like.
Further, the ligand is 2-dicyclohexylphosphorus-2 ',4',6' -triisopropylbiphenyl.
Further, the base is an inorganic base, which may be selected as sodium t-butoxide.
Further, the salt is an inorganic salt, which may be selected as NaF.
Further, the linker has two or more-NH 2 A chemical substance of an linking group; the different linkers differ by one benzene ring or two benzene rings in length; the matching modes of different connectors which can be adopted are as follows: para-phenylenediamine of shorter length and 4,4' -diaminodiphenylamine of longer length; tri (4-aminophenyl) amine, p-phenylenediamine, 4' -diaminodiphenylamine of successively increasing length.
Further, the molar ratio of linker to center used is 0.1:1 to 1:1.
Further, the temperature of the reaction at intervals in the step 2) is 60-67 ℃ and the time is 0-500min.
Further, the temperature of the reaction in the step 3) is 60-67 ℃ and the time is 100-3000min.
A second object of the present invention is to protect the porous organic polymer with hierarchical cell distribution prepared by the above method.
The third purpose of the invention is to protect the application of the porous organic polymer with hierarchical pore distribution in the aspect of adsorbing metal ions in water or organic solvent, wherein the metal ions are mercury ions, lead ions and copper ions with the equal density of more than 4.5 g/cm 3 At least one of the alkaline earth metal ions such as sodium ion and calcium ion is preferably mercury ion.
The invention adopts a space addition method, namely, connectors from short to long are gradually introduced in a certain interval time to construct the porous organic polymer with a hierarchical pore distribution structure from inside to outside, and the porous organic polymer can utilize pore channels with larger outer layers to promote more hydrated metal ions to enter the pore channels and uses pore channels with smaller inner layers as storage spaces to store more metal ions so as to improve the adsorption mass transfer and diffusion capacity of the porous organic polymer and realize the efficient adsorption of pollutants such as metal ions.
The invention has the remarkable advantages that: the method has the advantages of simple operation, mild condition, obvious effect and environment protection, can realize the regulation and control of the structure distribution of the polymer pore canal without any additional template agent or complex operation condition, and can increase the Hg ion adsorption amount by more than 100% in the treatment of mercury-containing wastewater, thereby having wide application prospect.
Drawings
FIG. 1 is an infrared spectrum of CMPA-M-1 (1:X: Y) obtained by polymerizing CMPA-2, CMPA-3 and the linker of example 1 in different proportions;
FIG. 2 is a graph showing the desorption of nitrogen and pore size distribution of CMPA-2 and CMPA-3 polymerized with different proportions of linkers in example 1 to obtain CMPA-M-1 (1: X: Y);
FIG. 3 is an infrared spectrum of CMPA-M-2 and reverse CMPA-M-3 polymerized by adding three linkers at intervals;
FIG. 4 is a graph showing the adsorption and desorption of nitrogen and a graph showing the pore size distribution of CMPA-M-2 obtained by polymerization by adding three linkers at intervals;
FIG. 5 is a graph of adsorption kinetics of a hierarchical microporous conjugated polymer material to mercury ions;
fig. 6 is a graph of an intra-particle diffusion model obtained by fitting adsorption kinetics data of mercury ions to hierarchical microporous conjugated polymer materials.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
For comparison, CMPA-1, CMPA-2 and CMPA-3 were synthesized as follows: 1.0 mmol of tris (4-bromophenyl) amine was used as a center, and 1.0 mmol of tris (4-aminophenyl) amine, 1.5 mmol of p-phenylenediamine and 1.5 mmol of 4,4' -diaminodiphenylamine were mixed with 5 mol% Pd (dba), respectively 2 9 mol percent of xPhos,7 eq. NaOtBu and 1 mmol of NaF are added into 50 mL tetrahydrofuran (solvent) together, after 48 h reaction is carried out at 66 ℃, the obtained products are respectively soaked and washed by solution such as chloroform, ethanol and the like after suction filtration, and then the polymers CMPA-1, CMPA-2 and CMPA-3 are respectively obtained after vacuum drying.
Adsorption experiment of mercury: 10 mg adsorbing material is added into 1000mg/L solution containing metallic mercury, and 24 h is adsorbed under the conditions of oscillation speed of 200 rpm and temperature of 25 ℃. Separating the adsorbent after adsorption, and detecting the concentration of metallic mercury in the clarified liquid by ICP-9000.
Example 1:
p-phenylenediamine with shorter length and 4,4 '-diaminodiphenylamine with longer length are used as connectors, and polymerization is carried out by adopting a BH coupling method by regulating and controlling the adding proportion of the p-phenylenediamine and the 4,4' -diaminodiphenylamine, so that the influence condition of the adding proportion on the pore canal structure is examined:
0.3 mmol, 0.4 mmol, 0.5 mmol and 0.6 mmol of p-phenylenediamine are added as the first linker to a solution containing 1.0 mmol of tris (4-bromophenyl) amine (centrosome) and 5 mol% Pd (dba) 2 In 9 mol% xPhos, 7. 7 eq. NaOtBu, 1 mmol NaF and 20. 20 mL tetrahydrofuran (solvent) at 66℃for 0.5h, 0.7 mmol, 0.6 are added accordinglymmol, 0.5 mmol and 0.4 mmol of 4,4' -diaminodiphenylamine are used as a second connector, the reaction is continued at 66 ℃ for 48 h, the obtained product is soaked and washed by chloroform, ethanol and other solutions respectively after suction filtration, and vacuum drying is carried out, so that a series of hierarchical microporous conjugated polyaniline materials CMPA-M-1 (1:X: Y) (wherein 1 is the molar ratio of a central component, X is the molar ratio of a shorter-length connector to the central component, Y is the molar ratio of a longer-length connector to the central component, namely CMPA-M-1 (1:0.3:0.7), CMPA-M-1 (1:0.4:0.6), CMPA-M-1 (1:0.5:0.5) and CMPA-M-1 (1:0.6:0.4)) are obtained.
FIG. 1 is an infrared spectrum of CMPA-M-1 (1:X: Y) obtained by polymerizing CMPA-2, CMPA-3 with different proportions of linkers. As can be seen from the figure, the spectrum of CMPA-M-1 shows the central tris (4-bromophenyl) amine at 710, 1004 and 1070 cm -1 The C-Br bond characteristic vibration peak at the position and the spectrum of the connector p-phenylenediamine and 4,4' -diaminodiphenylamine are 3400-3300 and 3300 cm -1 NH at 2 The characteristic vibrational peaks of the bond are not observed, but are found at 1500 cm -1 A new peak of C-N bond appears nearby, indicating efficient coupling of tri (4-bromophenyl) amine to two linkers and successful preparation of CMPA-M-1.
FIG. 2 is a graph showing the nitrogen adsorption and desorption curves and pore size distribution of CMPA-M-1 (1:X: Y) obtained by polymerizing CMPA-2 and CMPA-3 with different proportions of linkers. As can be seen from the graph, the prepared CMPA-M-1 shows a nitrogen adsorption and desorption curve of type I, which shows that the CMPA-M-1 has a large number of micropores and a large specific surface area. The pore structure data are shown in Table 1. The result shows that the specific surface area, the pore size distribution and the pore channel structure of the porous polymer can be regulated and controlled by changing the proportion of the two connectors. And the micropore amount also shows an ascending trend along with the increase of the proportion of the short linker of the inner layer, from 0.1003 cm 3 Increase/g to 0.1741 cm 3 And/g. Through the adsorption experiment on mercury, the adsorption capacity of the material on mercury ions can be effectively regulated and controlled by regulating the proportion of the connector, and the invention can effectively increase the diffusion pore canal and the storage space of the material.
TABLE 1 pore structure data for CMPA-M-1 obtained by polymerization of different proportions of linkers
Example 2:
taking a molar ratio of 1:0.5:0.5 as an addition amount, regulating and controlling the interval addition time (0.5 h, 1.0 h and 2.0 h respectively) of two connectors with different configurations and lengths in the embodiment 1, and polymerizing by adopting a BH coupling method to examine the influence condition of the interval addition time on the pore channel structure:
0.5 mmol of p-phenylenediamine as the first linker was added to 1.0 mmol of tris (4-bromophenyl) amine (center) and it was reacted with 5 mol% Pd (dba) 2 9 mol% of xPhos, 7. 7 eq. NaOtBu and 1 mmol of NaF are added into 20 mL tetrahydrofuran (solvent) together, 0.5h, 1.0 h and 2.0 h are respectively reacted at 66 ℃, 0.5 mmol of 4,4' -diaminodiphenylamine serving as a second connector is added, the reaction is continued at 66 ℃ for 48 h, the obtained product is respectively soaked and washed by solution such as chloroform and ethanol after suction filtration, and the obtained product is vacuum-dried to obtain the hierarchical microporous conjugated polyaniline material.
Table 2 shows the pore structure data of the polymer materials obtained by adding at different intervals. The result shows that the specific surface area, the pore size distribution and the pore canal structure of the material can be further regulated and controlled by regulating and controlling the interval adding time. And increases from 0.5h to 1.0 h over time, the micropore size exhibiting a value of from 0.1448 cm 3 Increase/g to 0.1560 cm 3 And/g, demonstrating that extending the interval favors the growth of the first linker and reduces competing polymerization of the two linkers. The adsorption experiment on mercury shows that the interval time is increased from 0.5 to h to 1.0 to h, and the adsorption capacity can be improved to 495 mg/g, so that the effectiveness of the invention on improving the adsorption capacity of the material on mercury ions is further demonstrated.
TABLE 2 pore structure data for BH coupled polymerization before and after controlled addition time at different intervals
Example 3:
1. to further increase the adsorption capacity for mercury ions, a shorter linker was further introduced into the innermost layer to form a polymer with a larger specific surface area and more internal storage space, i.e., three linkers (tris (4-aminophenyl) amine, p-phenylenediamine, 4' -diaminodiphenylamine, respectively) with a short to long interval introduced length were polymerized by BH coupling method to examine the universality of the method:
0.3 mmol of tris (4-aminophenyl) amine was added as the first linker to 1.0 mmol of tris (4-bromophenyl) amine (centrosome) and this was reacted with 5 mol% Pd (dba) 2 Adding 9 mol% of xPhos, 7. 7 eq. NaOtBu and 1 mmol of NaF into 20 mL tetrahydrofuran (solvent), reacting at 66 ℃ for 1.0 h, adding 0.3 mmol of p-phenylenediamine as a second connector, continuing to react for 1.0 h, adding 0.3 mmol of 4,4' -diaminodiphenylamine as a third connector, continuing to react at 66 ℃ for 48 h, filtering, separating the obtained product, soaking and washing with chloroform, ethanol and other solutions, and vacuum drying to obtain the hierarchical microporous conjugated polyaniline material CMPA-M-2.
FIG. 3 is an infrared spectrum of CMPA-M-2 formed after the introduction of three linkers. As can be seen from the spectra of CMPA-M-2, the centrosome tris (4-bromophenyl) amine was found in 710, 1004 and 1070 cm -1 The C-Br bond characteristic vibration peak at the site and the linker at 3400-3300 cm -1 NH at 2 The key feature vibration peak is not observed in the polymer spectrum, but it is found in 1500 cm -1 A new peak of C-N bond appears nearby, indicating efficient coupling of tri (4-bromophenyl) amine to three linkers and successful preparation of CMPA-M-2.
FIG. 4 is a graph showing the adsorption and desorption of nitrogen gas and a graph showing the pore size distribution of CMPA-M-2 obtained by adding three linkers at intervals. The results show that the prepared CMPA-M-2 shows a nitrogen adsorption and desorption curve of I type, which shows that the CMPA-M-2 has a large number of micropores and a large specific surface area. And from the pore size distribution diagram, after the linker from short to long is introduced layer by layer, the obvious pore size distribution areas appear at three positions of 0.7 nm, 0.8 nm and 1.4 nm, which proves that the method can successfully construct and regulate the molecular pore canal of the microporous conjugated polymer material. The adsorption capacity of the porous organic polymer is further improved to 746 mg/g through the adsorption experiment of mercury, which shows that the porous organic polymer is effective in improving the adsorption capacity of mercury ions.
2. In order to prove that the adsorption diffusion has good effect by gradually introducing the short-to-long connectors and constructing a hierarchical pore channel distribution structure from inside to outside, a group of control experiments are carried out, wherein the shortest connectors are constructed on the outermost layer to form reverse construction, and polymerization is carried out by a BH coupling method, and the specific steps are as follows:
0.3 mmol of p-phenylenediamine was added as a first linker to 1.0 mmol of tris (4-bromophenyl) amine (centrosome) and it was reacted with 5 mol% Pd (dba) 2 Adding 9 mol% of xPhos,7 eq. NaOtBu and 1 mmol of NaF into 20 mL tetrahydrofuran (solvent), reacting at 66 ℃ for 1.0 h, adding 0.3 mmol of second linker 4,4' -diaminodiphenylamine, continuing to react for 1.0 h, introducing 0.3 mmol of third shortest linker tris (4-aminophenyl) amine, continuing to react at 66 ℃ for 48 h, filtering the obtained product, soaking and washing with chloroform, ethanol and other solutions respectively, and vacuum drying to obtain the reverse-level microporous conjugated polyaniline material (CMPA-M-3).
As can be seen from FIG. 3, CMPA-M-3 has the same FTIR spectrum as CMPA-M-2 due to the fact that the molecular structure is the same, confirming successful polymerization of CMPA-M-3.
Table 3 shows the pore structure data of the resulting hierarchical pore conjugated microporous polymer materials CMPA-M-2 and CMPA-M-3. The result shows that the mesoporous quantity of the microporous conjugated polymer CMPA-M-2 obtained by introducing three linkers layer by layer according to the length is improved to 0.2039 cm 3 And/g, it has been shown that the incorporation of the longest linker in the outermost layer is advantageous for the establishment of diffusion channels.
TABLE 3 different order of linker introduction to obtain pore structure data for hierarchical microporous conjugated polymer materials
Fig. 5 and 6 are graphs of intra-particle diffusion models obtained by fitting adsorption kinetics of mercury ions by hierarchical microporous conjugated polymer materials CMPA-M-2 and CMPA-M-3 and obtained kinetic data, respectively. As can be seen from FIG. 5, in the mercury ion solution with the initial concentration of 50mg/L, the CMPA-M-2 constructed by the invention can reach adsorption equilibrium within about 20 min. The reverse CMPA-M-3 constructed in the opposite step can reach adsorption equilibrium after 1.0 h, which proves that the method provided by the invention has important influence on improving the diffusion of metal ions in the pore canal. FIG. 6 further reveals the effect of the diffusion channel constructed in accordance with the present invention (fitting data are shown in Table 4), which shows that heavy metal ions only diffuse in the peripheral liquid film and not in the in-channel diffusion during adsorption of CMPA-1 and reverse CMPA-M-3 having smaller-sized channels; and in the adsorption process of CMPA-3 and CMPA-M-2 with larger pore channels on the outer layer, heavy metal ions have an intra-particle diffusion stage besides liquid film diffusion.
Table 4 intra-particle diffusion kinetics model fitting data
In conclusion, the preparation method provided by the invention can effectively construct a diffusion channel, can obviously improve the diffusion and storage of heavy metal ions in the pore canal, and has important significance for practical applications such as wastewater adsorption treatment and the like.
Application examples:
in order to further examine the adsorption effect of the hierarchical microporous conjugated polymer material on metal ions, adsorption experiments of various metal ions are carried out, and the specific steps are as follows:
10 mg of CMPA-1, CMPA-2, CMPA-3 and CMPA-M-1 prepared in example 1 (1:0.5:0.5), CMPA-M-1 prepared in example 2 (1.0 h) and CMPA-M-2 and CMPA-3 prepared in example 3 are respectively added into 10 mL metal mercury ion 1000mg/L water body to be treated, and are adsorbed 24 h under the conditions of oscillation speed of 200 rpm and temperature of 25 ℃. And (3) separating the adsorbent by using a filter head after adsorption, and detecting the concentration of metal in the treated water body by using ICP-9000 to obtain a clarified liquid.
Test results show that after 24 h adsorption, the adsorption capacities of CMPA-1, CMPA-2, CMPA-3, CMPA-M-1 (1:0.5:0.5), CMPA-M-1 (1.0 h) and CMPA-M-3 for Hg (II) are 438 mg/g, 430 mg/g, 375 mg/g, 441 mg/g, 495 mg/g and 547 mg/g respectively; compared with CMPA-3, the adsorption capacity of the hierarchical microporous conjugated polymer material CMPA-M-2 on mercury ions can reach 746 mg/g, and the adsorption capacity is improved by nearly 100%, which shows that the prepared hierarchical microporous conjugated polymer material CMPA-M-2 has remarkable superiority in mercury ion adsorption.
Meanwhile, in order to show the advancement of the invention in actual adsorption, a mixed ion competitive adsorption experiment is carried out, and the specific experimental steps are as follows:
the CMPA-M-2 material prepared in example 3 of 10 mg was added to a mixed metal solution of 10 mL containing Hg (II), ni (II), la (III) and Pb (II) at a concentration of 100mg/L, and adsorbed at a shaking speed of 200 rpm and a temperature of 25℃for 24 h. And (3) separating the adsorbent by using a filter head after adsorption, and detecting the metal concentration in the treated water body by using ICP-9000.
The test results show that after 24 h adsorption, the hierarchical microporous conjugated polymer material only shows adsorption capacity to Hg (II), and the removal rate is as high as 93%. The method shows that the hierarchical microporous conjugated polymer material prepared by the method has excellent adsorption selectivity in mixed ion competitive adsorption, and has important significance for the adsorption treatment of Hg (II) in complex water.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (5)
1. A preparation method of a porous organic polymer with hierarchical pore distribution is characterized by comprising the following steps: the method comprises the following steps:
1) Uniformly mixing the solvent with the center, the catalyst, the ligand, the alkali and the salt;
2) Sequentially adding different linkers with the length from short to long into the mixed solution obtained in the step 1), and reacting for a period of time at intervals after each addition;
3) Adding the connector with the longest length, continuing to react for a period of time, and carrying out suction filtration, washing and drying on the product to obtain the porous organic polymer with hierarchical pore distribution;
the center is tri (4-bromophenyl) amine, the linker is p-phenylenediamine with shorter length and 4,4 '-diaminodiphenylamine with longer length, and the molar ratio of the tri (4-bromophenyl) amine to the p-phenylenediamine to the 4,4' -diaminodiphenylamine is 1:0.5:0.5.
2. The method for preparing a porous organic polymer with hierarchical cell distribution according to claim 1, wherein: the solvent is tetrahydrofuran, 1, 4-dioxane or toluene;
the catalyst is a palladium catalyst;
the ligand is 2-dicyclohexylphosphorus-2 ',4',6' -triisopropyl biphenyl;
the alkali is inorganic alkali;
the salt is an inorganic salt.
3. The method for preparing a porous organic polymer with hierarchical cell distribution according to claim 1, wherein: the temperature of the interval reaction in the step 2) is 60-67 ℃ and the time is 0-500min.
4. The method for preparing a porous organic polymer with hierarchical cell distribution according to claim 1, wherein: the temperature of the reaction in the step 3) is 60-67 ℃ and the time is 100-3000min.
5. Use of a porous organic polymer having a hierarchical pore distribution prepared by the method of claim 1 for adsorption of mercury ions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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