阅读说明：本技术 一种多孔有机聚合物及其制备方法和应用 (Porous organic polymer and preparation method and application thereof ) 是由 陈杰 邱挺 叶长燊 熊卓 王红星 黄智贤 杨臣 李玲 王晓达 葛雪惠 王清莲 于 2021-09-23 设计创作，主要内容包括：本发明公开了一种多孔有机聚合物及其制备方法和应用,通过提高反应温度至溶剂沸点温度之上,一步实现对多种聚合单体在多种偶联反应中的高效聚合。本发明设备操作简单、合成周期短、产率高、产物性状优良、反应规模易扩大,在无需外加任何催化剂、助催化剂、增溶剂等复杂药剂,无需进行任何除水除氧的脱气操作的情况下,即可实现聚合物的比表面积提高20倍、CO-(2)吸附量增加150%以上、H-(2)吸附量提高到4 wt%以上、对水相中汞离子吸附量提高到1111 mg/g。本发明所得产品在吸附催化、化学传感、气体储存、电化学等方面还具有广泛的应用前景。(The invention discloses a porous organic polymer and a preparation method and application thereof, which can realize the high-efficiency polymerization of various polymerization monomers in various coupling reactions in one step by increasing the reaction temperature to be higher than the boiling point temperature of a solvent. The method has the advantages of simple equipment operation, short synthesis period, high yield, excellent product properties, easily-enlarged reaction scale, no need of adding any complex medicament such as catalyst, cocatalyst, solubilizer and the like, and no need of performing any degassing operation for removing water and oxygenNamely, the specific surface area of the polymer can be improved by 20 times, and CO can be realized 2 The adsorption capacity is increased by more than 150 percent, and H 2 The adsorption capacity is improved to more than 4 wt%, and the adsorption capacity to mercury ions in a water phase is improved to 1111 mg/g. The product obtained by the invention also has wide application prospects in the aspects of adsorption catalysis, chemical sensing, gas storage, electrochemistry and the like.)

1. A method for preparing a porous organic polymer, characterized in that: the reaction temperature is increased to be higher than the boiling point temperature of the solvent, and the porous organic polymer is prepared by carrying out polymerization reaction on the connecting monomer with two or more active sites in one step.

2. The method of claim 1, wherein: the reaction vessel can bear 0-10 MPa pressure.

3. The method of claim 1, wherein: the active site comprises aromatic halogenated groups, aromatic trifluoromethanesulfonic acid, aromatic olefin, aromatic alkyne, aromatic aldehyde groups and aryl ammonia.

4. A porous organic polymer obtainable by the process of any one of claims 1 to 3.

5. A porous organic polymer as claimed in claim 4 in CO₂Adsorption, H₂Storage and heavy metal ion adsorption.

Technical Field

The invention belongs to the field of synthesis of porous organic materials, and particularly relates to a porous organic polymer and a preparation method and application thereof.

Background

Porous Organic Polymers (POPs) are an emerging class of Porous materials, formed by strong covalent bonding of Organic building blocks of different geometries and topologies. Common Porous organic Polymers include Microporous Conjugated Polymers (CMPs), hypercrosslinked Polymers (HCPs), intrinsically Microporous Polymers (PIMs), Porous Aromatic Frameworks (PAFs). Generally, porous organic polymers have the advantages of strong physical and chemical stability, high inherent porosity, light weight, designable structural function and the like, and are widely applied to the fields of metal adsorption, anisotropic catalysis, energy storage and conversion, gas separation and storage.

The current method for synthesizing the above porous polymer mainly comprises: Sonagashira-Hagihara reaction (palladium catalyzed C-C coupling reaction between aryl halide or and aryl alkyne), Suzuki-Miyaura reaction (palladium catalyzed C-C coupling between aryl halide and aryl boronic acid), Yamamoto reaction (nickel catalyzed coupling or self-polymerization of aryl halide), Buchwald-Hartwig reaction (palladium catalyzed C-N coupling of aryl halide to aryl amine), and the like. It is obvious that the coupling reaction often requires noble metal transition elements such as palladium and nickel as catalysts. The palladium and the nickel have rich empty orbitals, are easy to be oxidized and added with unsaturated carbon to form Pd-C and Ni-C bonds and form a coupling intermediate, but simultaneously, in storage and use, the catalyst is also easy to react with oxygen in the air to cause catalyst inactivation, finally the reaction failure is caused, and the reproducibility of the synthetic effect is poor. More importantly, in order to avoid the influence of oxygen, the catalytic reaction process needs to be carried out in an anhydrous and oxygen-free double-row pipe, so that the operation is complicated, the problem of severely limited yield is also faced, and the large-scale batch preparation is difficult. Another big problem in the current synthesis is that the economy and reactivity of the reaction monomers are difficult to combine. For example, many of the above-mentioned reactions use aromatic halides as building monomers, the aromatic halides often participate in the oxidative addition step as the first step reactant, and the activity of the halides increases in turn as the atomic radius increases (-Cl < -Br < -I), so many reactions difficult to perform oxidative addition can only select aryl iodides with high activity as reactants, which not only limits the extension of reaction substrates, but also greatly increases the reaction cost.

Therefore, in the process of synthesizing the porous organic polymer, the use and storage conditions of the polymerization catalyst are severe due to the low reactivity of the noble metal catalyst and the reactant, and the experiment must be performed in a glove box or by repeated degassing operations through a double-row pipe or other devices, and the actual experiment operation is often complicated. The yield of the product is low and the synthesis time is long in the process of preparing the material by adopting a conventional method; for some groups with low reactivity (such as p-dichlorobenzene and the like), palladium-catalyzed coupling cannot be carried out by adopting the conventional method; the polymers obtained by some polymerization reactions, such as Buchwald-Hartwig (B-H), also have the problems of low specific surface area, insignificant porosity characteristics, etc.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a simple synthesis method for solving the problems of low reaction activity, incapability of batch production, complicated operation conditions and the like in the current porous organic polymer polymerization process, which has the advantages of simple operation, high reaction efficiency, capability of greatly shortening the reaction time, realization of large-scale production of porous organic polymers and capability of obtaining a plurality of porous organic polymers with large specific surface area and rich pore canals. By adjusting the reaction temperature, the specific surface area of the material can be enlarged, more adsorption catalytic sites are exposed, the adsorption capacity of carbon dioxide is improved, the adsorption capacity of mercury ions in wastewater is also greatly improved, and abundant micropores are also H₂The storage creates favorable conditions.

The technical scheme adopted by the invention is as follows:

putting a monomer into a high-pressure reaction kettle, adding a reaction catalyst, a ligand, an organic base or an inorganic base (and a solvent of the base) and a solvent, increasing the reaction temperature to be higher than the boiling point temperature of the solvent under the reaction pressure of 0-10 MPa, reacting for 1-48 h, filtering after the reaction is finished, and washing a filter cake by respectively using tetrahydrofuran, trichloromethane, ethanol and hot water. The solid product is dried under vacuum at 50-100 deg.C for 24-48 hours.

The invention relates to a preparation process of an organic porous polymer with good universality, wherein a building module of the polymer is generally composed of an aromatic monomer with a plurality of reaction sites. The combination mode is generally An + Bn, (A, B, etc. represent connecting monomers, n represents the number of active sites on the monomers, n is more than or equal to 2), and it is particularly noted that the building module is not limited to two monomers, but can also be self-coupling reaction of the monomers A and B which are completely the same, or statistical polymerization of three or more monomers. Building blocks need to possess active sites including, but not limited to, aryl halo groups, aromatic triflate groups, aromatic alkenes, aromatic alkynes, aromatic aldehydic groups, arylamines.

The polymerization catalyst of the present invention is a palladium catalyst, including but not limited to tetrakis (triphenylphosphine) palladium (Pd (PPh)₃)₄) Bis (dibenzylideneacetone) -palladium (Pd (dba)₂) Bis (triphenylphosphine palladium chloride) (Pd (PPh)₃)₂Cl₂) Palladium acetate (Pd (OAc)₂) Palladium chloride (PdCl)₂) Palladium acetylacetonate (Pd (acca)₂)。

The polymerization catalyst ligands contemplated by the present invention include, but are not limited to, triphenylphosphine (PPh)₃) 2-dicyclohexylphosphonium-2 ',4',6' -triisopropylbiphenyl (XPhos), dicyclohexyl [3, 6-dimethoxy-2 ',4',6' -triisopropyl [1,1' -biphenyl]-2-yl]Phos-type ligands such as phosphine (Brettphos) and pyridine-type ligands.

The polymerization solvent provided by the invention comprises but is not limited to tetrahydrofuran, toluene, 1, 4-dioxane, p-xylene, N-heptane, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidinone and other solvents or compound solvents thereof.

The reaction base involved in the invention can be organic base or inorganic base, including but not limited to potassium carbonate, potassium phosphate, sodium tert-butoxide, triethylamine, diethylamine and the like.

The invention has the beneficial effects that: the invention can realize the high-efficiency polymerization of various polymerization monomers in various coupling reactions in one step without complicated steps such as water removal, oxygen removal and the like by increasing the reaction temperature to be higher than the boiling temperature of the solvent, reducing the oxygen partial pressure in the reaction container by utilizing steam and reducing the toxic action of oxygen on the catalyst. Meanwhile, based on the principle that the reaction temperature influences the reactivity of the monomers, the reaction efficiency and the reaction rate can be greatly improved by changing the temperature. The method can realize the successful and efficient synthesis of various porous organic polymers (generally requiring 48 hours in the traditional method) within extremely short time (one hour), and can also realize the efficient coupling of groups which are difficult to couple and polymerize (such as p-dichlorobenzene and the like) and realize the expansion of reaction monomers. The increase of the reaction efficiency can also improve the specific surface area of the obtained polymer and optimize the pore canal of the product. Furthermore, the present invention can also be applied toRealizes the scale production of the porous organic polymer and breaks through the problem of limited yield in the prior process of preparing the polymer in the double-row pipe. The improvement of the pore canal porosity can also promote the exposure of active sites in the porous organic polymer and improve the performance of the porous organic polymer in adsorption application. Therefore, the method has the advantages of simple equipment operation, short synthesis period, high yield, excellent product properties and easily enlarged reaction scale, can improve the specific surface area of the polymer by 20 times without adding any complex medicament such as catalyst, cocatalyst, solubilizer and the like and without any degassing operation for removing water and oxygen, and can realize CO₂The adsorption capacity is increased by more than 150 percent, and H₂The adsorption capacity is improved to more than 4 wt%, and the adsorption capacity to mercury ions in a water phase is improved to 1111 mg/g. The product obtained by the invention also has wide application prospects in the aspects of adsorption catalysis, chemical sensing, gas storage, electrochemistry and the like.

Drawings

FIG. 1 is an infrared spectrum of a B-H coupled polymerized PTPA and its building block under different reaction temperatures;

FIG. 2 is a graph of the nitrogen desorption profile and the pore size and pore volume profiles of B-H coupled polymerized PTPA of the present invention at different reaction temperatures;

FIG. 3 is an infrared spectrum of a B-H coupled polymerized PTPA and its building block under different reaction times;

FIG. 4 is a graph of the nitrogen desorption profile and the pore size and pore volume profiles of B-H coupled polymerized PTPA of the present invention at various reaction times;

FIG. 5 is an infrared spectrum of a B-H coupled polymerized PTPA and its building block under different reaction pressures;

FIG. 6 is a graph of nitrogen desorption and pore size distribution and pore volume distribution of B-H coupled polymerized PTPA of the present invention at various reaction pressures;

FIG. 7 is an isothermal adsorption model fit of preferred PTPA-120 samples to mercury;

FIG. 8 is a preferred PTPA-120 sample at 273K and 298K for CO₂An adsorption isotherm diagram;

FIG. 9 is the H at 77K for the preferred PTPA-120 sample₂An adsorption isotherm diagram;

FIG. 10 is an infrared spectrum of a Sonogashira-Hagihara coupled polymerization precursor and a polymer CMP-1 under temperature control;

FIG. 11 is a graph showing a nitrogen desorption profile, a pore diameter distribution and a pore volume distribution of a Sonogashira-Hagihara coupled polymerized polymer CMP-1 under temperature control;

FIG. 12 shows Suzuki coupled polymerization precursors and polymers under temperature controlp-ir spectrum of PPF.

Detailed Description

The technical solutions of the present invention will be further described with reference to the following detailed description, but the applicable examples of the present invention are not limited thereto.

Example 1:

the different reaction temperatures regulate the pore channels of the B-H coupled polymer PTPA: 1mmol of tris (4-bromophenyl) amine (centre), 1mmol of p-phenylenediamine (linker), 5mol% Pd (dba)₂Adding 9 mol% of xPhos and 7 eq. NaOtBu into a miniature high-pressure autoclave, injecting 70 ml of tetrahydrofuran, reacting at 100 ℃, 120 ℃, 140 ℃ and 160 ℃ under the reaction pressure of 2 MPa for 5 hours, sequentially filtering and washing the obtained product by tetrahydrofuran, trichloromethane, ethanol and hot water, and drying the solid product PTPA at 70 ℃ for 24 hours in vacuum to remove the solvent. The product is bright blue, shows obvious redox polyaniline characteristics, is insoluble in various organic solvents and acid-base solvents, and has good experimental reproducibility. Calculating the product yield after drying, obtaining the average yield of more than 95 percent and the specific surface area of the rich micropores as high as 1145 m²(ii) in terms of/g. This is generally less than 50% lower than the yield exhibited by the previous synthesis; the product still has more oligomers even after long-time synthesis, and the atom utilization rate is low; the pore passage of the product cannot be expressed, and the specific surface area is only 58 m²The phenomenon of/g and the like is greatly improved.

FIG. 1 shows the IR spectrum of a linker and the IR spectrum of PTPA obtained by B-H coupling reaction at different reaction temperatures. As can be seen from the infrared spectrum, the characteristic peaks of the products at different temperatures are basically consistent and all contain the center of tris (4-aminophenyl) amine andcharacteristic vibration peak of the linker p-phenylenediamine and is positioned 3500-3250 cm in a linker spectrogram^-1The N-H stretching vibration peak obviously disappears and weakens, which indicates that primary amine is converted into secondary amine, C-Br indicating a coupling site is greatly weakened after reaction, indicates that C-N bond is successfully coupled, and further confirms the successful polymerization of PTPA. It was confirmed that the polymerization can be carried out with high efficiency within 5 hours by using the present invention.

FIG. 2 is a nitrogen adsorption and desorption curve and a pore size distribution diagram of B-H coupled polymer PTPA under different temperature control. From the results shown in the figure, it is obvious that the PTPA before temperature change presents a II-type nitrogen adsorption and desorption isotherm, and the PTPA is easy to reach an adsorption platform, small in specific surface area, low in porosity and not expressed in micropore characteristics. After temperature regulation and control, the PTPA shows a type I nitrogen adsorption and desorption isotherm, which shows that a large number of micropores are formed in the material, and the specific surface area is from 58 cm³The volume/g is respectively increased to 688cm³/g、1003 cm³/g、804 cm³/g、334 cm³The maximum increase of the/g is nearly 20 times. According to the density functional theory, the total pore volume is also from 0.06cm³Increase in/g to 0.39cm³/g、0.67 cm³/g、0.43 cm³/g、0.38 cm³The material also has concentrated ultramicropores (the pore diameter is less than 0.7 nm) with the volume of the ultramicropores reaching 0.16 cm³(ii) in terms of/g. The superiority and obvious improvement of the invention compared with the conventional synthetic method are proved.

Example 2:

the different reaction times regulate the pore channels of the B-H coupled polymer PTPA: 1mmol of tris (4-bromophenyl) amine (centre), 1mmol of p-phenylenediamine (linker), 5mol% Pd (dba)₂Adding 9 mol% of xPhos and 7 eq. NaOtBu into a miniature high-pressure autoclave, injecting 70 ml of tetrahydrofuran, reacting at 120 ℃ and 2 MPa for 1, 5 and 16 hours respectively, sequentially filtering and washing the obtained product by tetrahydrofuran, trichloromethane, ethanol and hot water, and drying the solid product PTPA at 70 ℃ in vacuum for 24 hours to remove the solvent. It was found that, even if the reaction time is shortened to 1 hour, a product having an excellent shape can be obtained at an elevated temperatureThe product realizes rapid reaction, and solves the problems that the prior reaction is limited by low reaction activity, and the reaction time is usually required to be 2 to 3 days or even weeks.

FIG. 3 is an IR spectrum of a linker and an IR spectrum of PTPA obtained by B-H coupling reaction at different reaction times. It was found that all samples had infrared characteristic peaks substantially identical to those of example 1, and that corresponding amino characteristic peaks and a decrease in C-Br peak were observed. The PTPA product can be successfully synthesized in a very short time.

FIG. 4 shows the nitrogen adsorption and desorption curves and the pore size distribution diagram of B-H coupled polymer PTPA under different time control. Also exhibited abundant microporous character, demonstrating the effectiveness of this synthetic approach.

Example 3:

the different reaction pressures regulate the pore channels of the B-H coupled polymer PTPA: 1mmol of tris (4-bromophenyl) amine (centre), 1mmol of p-phenylenediamine (linker), 5mol% Pd (dba)₂Adding 9 mol% of xPhos and 7 eq. NaOtBu into a miniature high-pressure autoclave, injecting 70 ml of tetrahydrofuran, reacting for 5 hours at 120 ℃, setting the reaction pressure to be 0 MPa, 1 MPa and 2 MPa respectively, sequentially filtering and washing the obtained product by tetrahydrofuran, trichloromethane, ethanol and hot water, and drying the solid product PTPA for 24 hours at 70 ℃ in vacuum to remove the solvent.

FIG. 5 is an IR spectrum of a linker and an IR spectrum of PTPA obtained by B-H coupling reaction at different reaction times. It was found that all samples had infrared characteristic peaks substantially identical to those of example 1, and that the corresponding amino characteristic peaks and a reduction in the C-Br peak were observed, indicating the successful synthesis of the product PTPA.

FIG. 6 shows the nitrogen adsorption and desorption curves and the pore size distribution diagram of B-H coupled polymer PTPA under different time control. The obtained material presents a nitrogen adsorption and desorption isotherm of the type I, which indicates that the material has a large number of micropores, and the material also has considerable specific surface area as can be observed from the figure.

Example 4:

the PTPA-120 preferred in examples 1, 2 and 3 was subjected to heavy metal ion Hg²⁺Adsorption experiment ofThe results are shown in FIG. 7. The adsorption kinetics and adsorption isotherms of the materials were studied. The adsorption kinetics selects 3 concentrations of 50 mg/L, 200 mg/L and 400 mg/L to explore the mercury adsorption rate of the material in the water body, the fitting degree of the material to two models is found to be higher through quasi-first-level and quasi-second-level kinetic fitting, the coupling of physical adsorption and chemical adsorption is presumed to exist in the adsorption process, and even under the condition of higher metal concentration, the material still shows very fast adsorption rate after temperature regulation and control, and can reach adsorption balance within 20 minutes. The adsorption isotherms were carried out at 25 deg.C, 35 deg.C and 45 deg.C, respectively, and from the results, adsorption proceeded in a more favorable direction as the temperature increased. At room temperature of 25 ℃, the maximum adsorption capacity of the material can reach 1111mg/g, compared with the maximum adsorption capacity of 285.8 mg/g under the same condition of synthesizing the product in a conventional mode, the mercury adsorption capacity is improved by 3.8 times. The material has the advantages that more micropores are generated by regulating and controlling the temperature, more adsorption sites are exposed and fully utilized, and the adsorption and removal of heavy metal ions are facilitated, so that the superiority and the advancement of the performance of the material prepared by the invention are proved.

Example 5:

preferred PTPA-120 of examples 1, 2, 3 was subjected to CO at 1 atm, 273K, 298K₂And (4) performing adsorption experiments. The results are shown in fig. 8, and it is proved that the exposure of more N sites is promoted by the increase of the specific surface area, whereas the PTPA of the example material is rich in N element, has lone pair electrons, and is an advantageous carbon dioxide adsorption site. The carbon dioxide adsorption capacity under 273K is improved from 0.91 mmol/g to 3.51mmol/g, and is improved by more than 8 times, and the carbon dioxide adsorption capacity is 28.41 kJ/mol respectively to show strong carbon dioxide adsorption capacity.

Example 6:

the preferred PTPA-120 of examples 1, 2, 3 was subjected to an H2 adsorption experiment at 77K, relative pressure of 1, to test the potential hydrogen storage performance of the material. As shown in FIG. 9, the hydrogen adsorption capacity under 77K reaches 20.95 mmol/g, and compared with 6.4 mmol/g exhibited by an intramolecular ordered covalent organic skeleton COF-1, the hydrogen storage capacity is greatly improved, compared with the H2 adsorption capacity of a synthetic material in a conventional mode, the H2 adsorption capacity is only 9.1 mmol/g, and the optimized material is also improved by more than 1 time.

Example 7:

to demonstrate the general applicability of the present invention, this example examined the control of CMP-1 specific surface area and porosity of Sonogashira-Hagihara coupled polymerization, as well as the development of low reactive monomer coupling, according to the present invention. Putting 1.0 mmol of 1,3, 5-triacetylbenzene as a reaction precursor and 1.0 mmol of 1, 4-diiodophenylbenzene (or 1, 4-dichlorobenzene with low reaction activity) in a high-pressure parallel reaction kettle, adding 50 mg of tetrakis (triphenylphosphine) palladium, 15 mg of CuI catalyst and 3 mL of toluene solvent, adding 3 mL of triethylamine as alkali, reacting at 120 ℃ for 5 hours, filtering the obtained product, soaking and washing the product with chloroform, boiling water and other solutions respectively, and drying the product in vacuum to obtain the catalyst. The product yields were calculated after drying and it was found that, also for the Sonogashira-Hagihara coupling, the product could be successfully synthesized after temperature optimization even at short reaction times, fig. 10 for the Sonogashira-Hagihara reaction pair precursors and products. The yield of the product is also as high as more than 90 percent on average, and the specific surface area is up to 1234 m²(in the case of pore channels, see FIG. 11) the specific surface area of the material is 834 m, in comparison with a reaction time of 24 hours reported in the literature²And/g, the reaction efficiency and the porous characteristic of the material are obviously improved.

Example 8:

to demonstrate the general applicability of the present invention, this example examines the polymers of the present invention for Suzuki coupled polymerizationpControl of the specific surface area of the PPF and of the porosity. Reacting a reaction precursor of 0.50 mmol of 1,3, 5-tri (4-bromophenyl) benzene, 0.50 mmol of 1, 4-phenyl diboronic acid, 2 mmol of potassium carbonate (dissolved in 4mL of water), 50 mg of catalyst of tetrakis (triphenylphosphine) palladium and 12 mL of N, N-dimethylformamide at 120 ℃ for 5 hours, filtering the obtained product, soaking and washing the product by using chloroform, boiling water and other solutions respectively, and drying the product in vacuum to obtain the catalyst. The method has the advantages that the method has very good applicability to Suzuki reaction, the yield is improved, and the infrared spectrogram shown in figure 12 can also prove that the product has improved performancepThe PPF was successfully synthesized.

The embodiment of the present invention is not limited to the above examples, and any other methods for changing the reactivity, improving the degree of crosslinking, controlling the porosity of the material, and applying the modified material, such as metal ion removal, gas storage, gas selective separation, etc., based on the temperature control method provided by the present invention are included in the scope of the present invention.