Preparation method of metal organic ligand polymer

Abstract

The invention relates to the technical field of metal organic ligand polymers, and particularly discloses a preparation method of a metal organic ligand polymer. Comprising the following operation steps: 1, adding imidazole and sodium hydroxide into dimethyl sulfoxide, heating to 60-65 DEG C, reacting for 1-2 hours, adding p-dichlorobenzene, reacting for 2-3 hours, carrying out reduced pressure distillation, cooling to room temperature, and purifying to obtain a rigid polymer ligand; (2) adding a semi-rigid polymer ligand and a rigid polymer ligand into deionized water, and uniformly mixing to obtain an organic ligand mixed solution; and 2, adding metal salt into deionized water to obtain a metal salt solution, stirring the metal salt solution at a low speed at room temperature, dropwise adding the organic ligand mixed solution, uniformly mixing, adjusting the pH value, carrying out solvothermal reaction, cooling to room temperature, washing, filtering and drying to obtain the metal organic ligand polymer.

Description

Technical Field

[0001] The invention relates to the technical field of metal organic ligand polymers, in particular to a preparation method of a metal organic ligand polymer. Background Art

[0002] Coordination polymers intersect and penetrate with inorganic chemistry, organic chemistry, crystal engineering, materials chemistry and solid-state chemistry, and have become one of the research hotspots in the fields of chemistry and materials. Coordination polymers are compounds formed by inorganic or organic ligands coordinating with metal ions. They are the general term for infinite arrays of metal ions bridged by certain ligands. Among them, porous coordination polymers are also called metal organic frameworks. Metal organic framework materials are formed by metal ions or metal clusters connected to organic ligands through coordination bonds. These metal ions or metal clusters usually have strong coordination ability and can form stable coordination bonds with multiple ligands, while organic ligands are usually molecules containing functional groups, such as carboxylic acids, nitrogen heterocycles, phosphates, etc. Metal centers usually include transition metal ions (such as copper, zinc, iron, cobalt, etc.) and certain rare earth metals. Ligands play a vital role in molecular design. They not only determine the topological structure of the framework, but also affect the stability, porosity, adsorption properties, etc. of MOF.

[0003] In the prior art, coordination polymers are divided into coordination polymers containing carboxylic acid, nitrogen and mixed ligands according to different organic ligands; they can be divided into coordination polymers of transition metals, rare earth metals and alkaline earth metals according to different metal types; they can be divided into one-dimensional chain coordination polymers, two-dimensional network coordination polymers and three-dimensional network coordination polymers according to the topological structure of the coordination polymer; and according to the different spatial flexibility of the organic ligands, coordination polymers can be divided into flexible ligands, rigid ligands and coordination polymers with both rigid and flexible ligands.

[0004] At present, the preparation methods of MOF mainly include solvothermal synthesis, hydrothermal synthesis, microwave synthesis, supercritical fluid method, etc. Different preparation methods have a significant impact on the structure, morphology, porosity, crystallinity and other properties of MOF.

[0005] Among them, hydrothermal synthesis is a special form of solvothermal synthesis; its characteristic is that the reaction is carried out in water or aqueous solution. Water is a cheap and environmentally friendly solvent; secondly, under hydrothermal reaction conditions, many metal salts and ligands can react efficiently to synthesize MOF materials with high crystallinity and stability. Hydrothermal synthesis is usually used to synthesize metal-organic framework materials with water as a solvent. Since water has high polarity and strong coordination ability at room temperature, water molecules play a dual role of solvent and ligand in the coordination process of metal ions and organic ligands. Compared with traditional solvothermal synthesis, hydrothermal synthesis usually requires 80°C to 200°C and longer reaction time.

[0006] The present invention relates to a method for preparing a metal organic ligand polymer through a self-assembly reaction of metal ions and organic ligands; the polymer has excellent gas adsorption capacity, selective catalytic performance and separation characteristics, and can be widely used in the fields of gas storage, molecular screening, catalysis and drug delivery. Summary of the invention

[0007] The purpose of the present invention is to provide a method for preparing a metal organic ligand polymer to solve the problems raised in the above background technology.

[0008] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0009] A method for preparing a metal organic ligand polymer comprises the following steps:

[0010] Step 1: (1) adding imidazole and sodium hydroxide to dimethyl sulfoxide, heating to 60° C. to 65° C. to react for 1 to 2 hours, adding p-dichlorobenzene to react for 2 to 3 hours, distilling under reduced pressure, cooling to room temperature, and purifying to obtain a rigid polymer ligand; (2) adding a semi-rigid polymer ligand and a rigid polymer ligand to deionized water, uniformly mixing, and obtaining an organic ligand mixed solution;

[0011] Step 2: Add metal salt to deionized water to obtain metal salt solution, stir it at low speed at room temperature, add organic ligand mixed solution dropwise and mix evenly, adjust pH, perform solvent thermal reaction, cool to room temperature, wash, filter and dry to obtain metal organic ligand polymer.

[0012] More optimally, the raw materials of the organic ligand mixed solution include the following components: 0.4-0.5 parts of semi-rigid polymer ligand, 2-3 parts of rigid polymer ligand, and 5-10 parts of deionized water, calculated by mass.

[0013] More optimally, the raw materials of the metal organic ligand polymer include the following components: by mass, 0.8 to 1 parts of metal salt, 2 to 4 parts of organic ligand mixed solution, and 5 to 8 parts of deionized water.

[0014] More optimally, the raw materials of the rigid polymer ligand include the following components: by mass, 7 to 8 parts of imidazole, 4 to 5 parts of sodium hydroxide, 7 to 7.5 parts of p-dichlorobenzene, and 25 to 30 parts of dimethyl sulfoxide.

[0015] Preferably, the metal salt solution includes one or more of copper salt, zinc salt and cobalt salt.

[0016] More optimally, the pH is 7 to 9; in the solvothermal reaction, the temperature is 150° C. to 200° C., and the time is 12 to 72 hours.

[0017] A more optimized method for preparing the semi-rigid polymer ligand is as follows: (1) adding 4,7-dibromo-1H-benzimidazole and tripotassium phosphate to 1,4-dioxane and mixing uniformly, adding 3-ethyl propionate phenylboronic acid, introducing nitrogen, adding tetrakis(triphenylphosphine)palladium, reacting at 90°C to 100°C for 20 to 24 hours, purifying, and obtaining an intermediate; (2) adding the intermediate to a mixed solution of ethanol and tetrahydrofuran, mixing uniformly, adding a 2 mol / L sodium hydroxide solution dropwise, heating to 70 to 80°C and reacting for 8 to 10 hours, cooling to room temperature, rotary evaporating to remove the organic solvent, adding deionized water to dilute, adjusting the pH to 4 to 5, filtering, washing, and drying to obtain a semi-rigid polymer ligand.

[0018] More optimally, the raw materials of the intermediate include the following components: by mass, 1.58 to 1.6 parts of 4,7-dibromo-1H-benzimidazole, 3.5 to 4.2 parts of tripotassium phosphate, 2 to 3 parts of 3-ethyl propionate phenylboronic acid, 0.02 to 0.04 parts of tetrakis(triphenylphosphine)palladium, and 15 to 20 parts of 1,4-dioxane; the mass ratio of the ethanol, tetrahydrofuran, and 2 mol / L sodium hydroxide solution is 1:1:1.

[0019] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0020] The invention uses a rigid polymer ligand as a main ligand and a semi-rigid polymer ligand as an auxiliary ligand, and reacts the two with a metal salt through solvent thermal reaction to prepare a metal organic ligand polymer.

[0021] In the scheme, imidazole replaces the two chlorine groups on p-dichlorobenzene to obtain a rigid polymer ligand; the imidazole group contains nitrogen atoms and can coordinate with metal ions through nitrogen atoms, so after the introduction of the imidazole group, the coordination ability of the ligand is enhanced. Among them, the combination of the benzene ring and the imidazole group allows the ligand to maintain a certain planarity and rigidity in space, which helps to maintain the stability of the metal organic ligand polymer, and can also adjust the structure and pore properties of the metal organic ligand polymer, which is beneficial for application in gas adsorption, catalysis and other fields; rigid polymer ligands usually have good mechanical strength and thermal stability, so the introduction of p-dichlorobenzene can improve the physical and chemical properties of the final material, so that it can maintain good structural stability under high temperature or long-term reaction conditions.

[0022] In the scheme, the two bromine groups on 4,7-dibromo-1H-benzimidazole reacted with the boronic acid groups on 3-ethylpropionatephenylboronic acid respectively, introducing ethyl propionate to obtain an intermediate, which was then hydrolyzed to obtain a semi-rigid polymer ligand containing a carboxyl group.

[0023] Among them, the benzimidazole ring is rigid, which can effectively constrain the spatial configuration of the ligand and prevent the ligand from being excessively bent or irregularly conformed; the ethyl propionate part in 3-ethyl propionate phenylboronic acid is a flexible structure, which introduces moderate flexibility into the ligand and increases the adaptability of the polymer chain, so that the polymer can more flexibly adjust its geometric configuration during the coordination reaction; semi-rigid polymer ligands can adapt to the size and shape changes of metal ions to a certain extent when coordinating metal ions, so that they can form complexes with a wider range of metal centers.

[0024] In summary, rigid ligands provide a stable coordination environment, while semi-rigid polymer ligands can adjust their own configuration to a certain extent, so that the ligand polymer can adapt to the needs of different metal ions. Mixing these two types of ligands can improve the flexibility of the coordination system, while ensuring the stability of metal organic ligand polymers, and is beneficial to improving their gas adsorption, etc. DETAILED DESCRIPTION

[0025] The following is a preferred implementation of the embodiment of the present invention. Obviously, the described embodiment is only a part of the embodiment of the present invention, not all of the embodiments. For ordinary technicians in this technical field, all other embodiments obtained by ordinary technicians in this field without creative work without departing from the principle of the embodiment of the present invention are within the scope of protection of the present invention.

[0026] In the following specific embodiments, the parts are by mass. In this embodiment, it should be noted that the purchase manufacturers of all raw materials involved in the present invention are not subject to any special restrictions. Examples include: CAS No. 148185-66-4 of 4,7-dibromo-1H-benzimidazole, purchased from Hubei Chengfeng Chemical Co., Ltd.; CAS No. S31111 of tripotassium phosphate, purchased from Shanghai Yuanye Biotechnology Co., Ltd.; CAS No. 913835-82-2 of ethyl propionate phenylboronic acid, purchased from Hubei Hengjingrui Chemical Co., Ltd.; CAS No. 4334-88-7 of 4-ethoxycarbonylphenylboronic acid, purchased from Shanghai Yuanye Biotechnology Co., Ltd.; ... 148185-66-4 of 4,7-dibromo-1H-benzimidazole, purchased from Hubei Chengfeng Chemical Co., Ltd.; CAS No. 148185-66-4 of tripotassium phosphate, purchased from Shanghai Yuanye Biotechnology Co., Ltd. The CAS number of 1,4-dioxane is 123-91-1, which was purchased from Shandong Yihong Chemical Co., Ltd.; the CAS number of imidazole is 288-32-4, which was purchased from Shanghai Yuanye Biotechnology Co., Ltd.; the CAS number of sodium hydroxide is 1310-73-2, which was purchased from Langfang Qianyao Technology Co., Ltd.; the CAS number of dimethyl sulfoxide is 67-68-5, which was purchased from Shanghai Yuanye Biotechnology Co., Ltd.; the CAS number of p-dichlorobenzene is 106-46-7, which was purchased from Jinan Huifengda Chemical Co., Ltd.; the CAS number of zinc acetate is 557-34-6, which was purchased from Shanghai Yuanye Biotechnology Co., Ltd.

[0027] Example 1: A method for preparing a metal organic ligand polymer;

[0028] Step 1: (1) Add 1.58 parts of 4,7-dibromo-1H-benzimidazole and 3.5 parts of tripotassium phosphate to 15 parts of 1,4-dioxane and mix evenly, add 2.4 parts of 3-ethyl propionate phenylboronic acid, introduce nitrogen, add 0.03 parts of tetrakis(triphenylphosphine)palladium, react at 100°C for 22 hours, purify, and obtain an intermediate; (2) Prepare ethanol, tetrahydrofuran, and 2 mol / L sodium hydroxide solution in a mass ratio of 1:1:1; add the intermediate to a mixed solution of ethanol and tetrahydrofuran, mix evenly, add 2 mol / L sodium hydroxide solution dropwise, heat to 80°C, react for 9 hours, cool to room temperature, remove the organic solvent by rotary evaporation, add deionized water to dilute, adjust the pH to 4.5, filter, wash, and dry to obtain a semi-rigid polymer ligand;

[0029] (3) adding 7 parts of imidazole and 4.2 parts of sodium hydroxide to 25 parts of dimethyl sulfoxide, heating to 65° C. for reaction for 2 hours, adding 7.5 parts of p-dichlorobenzene for reaction for 3 hours, distilling under reduced pressure, cooling to room temperature, and purifying to obtain a rigid polymer ligand;

[0030] (4) adding 0.4 parts of semi-rigid polymer ligand and 3 parts of rigid polymer ligand to 6 parts of deionized water, and mixing them evenly to obtain an organic ligand mixed solution;

[0031] Step 2: Add 0.8 parts of zinc acetate to 5 parts of deionized water to obtain a zinc acetate solution, stir it at low speed at room temperature, add 3 parts of the organic ligand mixed solution dropwise and mix evenly, adjust the pH to 8, perform a solvothermal reaction at 160° C. for 36 hours, cool to room temperature, wash, filter, and dry to obtain a metal organic ligand polymer.

[0032] Example 2: A method for preparing a metal organic ligand polymer;

[0033] Step 1: (1) Add 1.58 parts of 4,7-dibromo-1H-benzimidazole and 3.5 parts of tripotassium phosphate to 15 parts of 1,4-dioxane and mix evenly, add 2.4 parts of 3-ethyl propionate phenylboronic acid, introduce nitrogen, add 0.03 parts of tetrakis(triphenylphosphine)palladium, react at 100°C for 22 hours, purify, and obtain an intermediate; (2) Prepare ethanol, tetrahydrofuran, and 2 mol / L sodium hydroxide solution in a mass ratio of 1:1:1; add the intermediate to a mixed solution of ethanol and tetrahydrofuran, mix evenly, add 2 mol / L sodium hydroxide solution dropwise, heat to 80°C, react for 9 hours, cool to room temperature, remove the organic solvent by rotary evaporation, add deionized water to dilute, adjust the pH to 4.5, filter, wash, and dry to obtain a semi-rigid polymer ligand;

[0034] (3) adding 7 parts of imidazole and 4.2 parts of sodium hydroxide to 25 parts of dimethyl sulfoxide, heating to 65° C. for reaction for 2 hours, adding 7.5 parts of p-dichlorobenzene for reaction for 3 hours, distilling under reduced pressure, cooling to room temperature, and purifying to obtain a rigid polymer ligand;

[0035] (4) adding 0.4 parts of semi-rigid polymer ligand and 2.5 parts of rigid polymer ligand to 6 parts of deionized water, and mixing them evenly to obtain an organic ligand mixed solution;

[0036] Step 2: Add 1 part of zinc acetate to 5 parts of deionized water to obtain a zinc acetate solution, stir it at low speed at room temperature, add 3 parts of the organic ligand mixed solution dropwise and mix evenly, adjust the pH to 8, perform solvothermal reaction at 160°C for 36 hours, cool to room temperature, wash, filter and dry to obtain a metal organic ligand polymer.

[0037] Example 3: A method for preparing a metal organic ligand polymer;

[0038] Step 1: (1) Add 1.58 parts of 4,7-dibromo-1H-benzimidazole and 3.5 parts of tripotassium phosphate to 15 parts of 1,4-dioxane and mix evenly, add 2.4 parts of 3-ethyl propionate phenylboronic acid, introduce nitrogen, add 0.03 parts of tetrakis(triphenylphosphine)palladium, react at 100°C for 22 hours, purify, and obtain an intermediate; (2) Prepare ethanol, tetrahydrofuran, and 2 mol / L sodium hydroxide solution in a mass ratio of 1:1:1; add the intermediate to a mixed solution of ethanol and tetrahydrofuran, mix evenly, add 2 mol / L sodium hydroxide solution dropwise, heat to 80°C, react for 9 hours, cool to room temperature, remove the organic solvent by rotary evaporation, add deionized water to dilute, adjust the pH to 4.5, filter, wash, and dry to obtain a semi-rigid polymer ligand;

[0039] (3) adding 7 parts of imidazole and 4.2 parts of sodium hydroxide to 25 parts of dimethyl sulfoxide, heating to 65° C. for reaction for 2 hours, adding 7.5 parts of p-dichlorobenzene for reaction for 2 to 3 hours, distilling under reduced pressure, cooling to room temperature, and purifying to obtain a rigid polymer ligand;

[0040] (4) adding 0.5 parts of semi-rigid polymer ligand and 3 parts of rigid polymer ligand to 6 parts of deionized water and mixing them evenly to obtain an organic ligand mixed solution;

[0041] Step 2: Add 1 part of zinc acetate to 5 parts of deionized water to obtain a zinc acetate solution, stir it at low speed at room temperature, add 4 parts of the organic ligand mixed solution dropwise and mix evenly, adjust the pH to 8, carry out solvothermal reaction at 160°C for 36 hours, cool to room temperature, wash, filter and dry to obtain a metal organic ligand polymer.

[0042] Comparative Example 1 is based on Example 2, and a rigid polymer ligand is introduced alone;

[0043] Step 1: add 7 parts of imidazole and 4.2 parts of sodium hydroxide to 25 parts of dimethyl sulfoxide, heat to 65°C for reaction for 2 hours, add 7.5 parts of p-dichlorobenzene for reaction for 3 hours, distill under reduced pressure, cool to room temperature, purify to obtain a rigid polymer ligand; add 2.2 parts of the rigid polymer ligand to 5 parts of deionized water, mix evenly to obtain an organic ligand solution;

[0044] Step 2: Add 1 part of zinc acetate to 5 parts of deionized water to obtain a zinc acetate solution, stir it at low speed at room temperature, add 3 parts of organic ligand solution dropwise and mix evenly, adjust the pH to 8, carry out solvothermal reaction at 160°C for 36 hours, cool to room temperature, wash, filter and dry to obtain a metal organic ligand polymer.

[0045] Comparative Example 2 Based on Example 2, imidazole was mixed with the semi-rigid polymer ligand alone;

[0046] Step 1: (1) 1.58 parts of 4,7-dibromo-1H-benzimidazole and 3.5 parts of tripotassium phosphate were added to 15 parts of 1,4-dioxane and mixed evenly, 2.4 parts of 3-ethyl propionate phenylboronic acid were added, nitrogen was introduced, 0.03 parts of tetrakis(triphenylphosphine)palladium were added, the mixture was reacted at 100° C. for 22 hours, and purified to obtain a semi-rigid polymer ligand;

[0047] (2) adding 0.4 parts of semi-rigid polymer ligand and 2.5 parts of rigid polymer ligand to 6 parts of deionized water, and mixing them evenly to obtain an organic ligand mixed solution;

[0048] Step 2: Add 1 part of zinc acetate to 5 parts of deionized water to obtain a zinc acetate solution, stir it at low speed at room temperature, add 3 parts of the organic ligand mixed solution dropwise and mix evenly, adjust the pH to 8, perform solvothermal reaction at 160°C for 36 hours, cool to room temperature, wash, filter and dry to obtain a metal organic ligand polymer.

[0049] Comparative Example 3 is based on Example 2; the semi-rigid polymer ligand is made into a rigid polymer ligand;

[0050] Step 1: (1) Add 1.58 parts of 4,7-dibromo-1H-benzimidazole and 3.5 parts of tripotassium phosphate to 15 parts of 1,4-dioxane and mix evenly, add 2.4 parts of 4-ethoxycarbonylphenylboronic acid, introduce nitrogen, add 0.03 parts of tetrakis(triphenylphosphine)palladium, react at 100°C for 22 hours, purify, and obtain an intermediate; (2) Prepare ethanol, tetrahydrofuran, and 2 mol / L sodium hydroxide solution in a mass ratio of 1:1:1; add the intermediate to a mixed solution of ethanol and tetrahydrofuran, mix evenly, add 2 mol / L sodium hydroxide solution dropwise, heat to 80°C, react for 9 hours, cool to room temperature, remove the organic solvent by rotary evaporation, add deionized water to dilute, adjust the pH to 4.5, filter, wash, and dry to obtain a rigid polymer ligand A;

[0051] (3) adding 7 parts of imidazole and 4.2 parts of sodium hydroxide to 25 parts of dimethyl sulfoxide, heating to 65° C. for reaction for 2 hours, adding 7.5 parts of p-dichlorobenzene for reaction for 3 hours, distilling under reduced pressure, cooling to room temperature, and purifying to obtain a rigid polymer ligand;

[0052] (4) adding 0.4 parts of rigid polymer ligand A and 2.5 parts of rigid polymer ligand to 6 parts of deionized water, and mixing them evenly to obtain an organic ligand mixed solution;

[0053] Step 2: Add 1 part of zinc acetate to 5 parts of deionized water to obtain a zinc acetate solution, stir it at low speed at room temperature, add 3 parts of the organic ligand mixed solution dropwise and mix evenly, adjust the pH to 8, perform solvothermal reaction at 160°C for 36 hours, cool to room temperature, wash, filter and dry to obtain a metal organic ligand polymer.

[0054] Comparative Example 4 is based on Example 2, but the content of the metal salt is increased;

[0055] Step 1: (1) Add 1.58 parts of 4,7-dibromo-1H-benzimidazole and 3.5 parts of tripotassium phosphate to 15 parts of 1,4-dioxane and mix evenly, add 2.4 parts of 3-ethyl propionate phenylboronic acid, introduce nitrogen, add 0.03 parts of tetrakis(triphenylphosphine)palladium, react at 100°C for 22 hours, purify, and obtain an intermediate; (2) Prepare ethanol, tetrahydrofuran, and 2 mol / L sodium hydroxide solution in a mass ratio of 1:1:1; add the intermediate to a mixed solution of ethanol and tetrahydrofuran, mix evenly, add 2 mol / L sodium hydroxide solution dropwise, heat to 80°C, react for 9 hours, cool to room temperature, remove the organic solvent by rotary evaporation, add deionized water to dilute, adjust the pH to 4.5, filter, wash, and dry to obtain a semi-rigid polymer ligand;

[0056] (3) adding 7 parts of imidazole and 4.2 parts of sodium hydroxide to 25 parts of dimethyl sulfoxide, heating to 65° C. for reaction for 2 hours, adding 7.5 parts of p-dichlorobenzene for reaction for 3 hours, distilling under reduced pressure, cooling to room temperature, and purifying to obtain a rigid polymer ligand;

[0057] (4) adding 0.4 parts of semi-rigid polymer ligand and 2.5 parts of rigid polymer ligand to 6 parts of deionized water, and mixing them evenly to obtain an organic ligand mixed solution;

[0058] Step 2: Add 2.7 parts of zinc acetate to 5 parts of deionized water to obtain a zinc acetate solution, stir it at low speed at room temperature, add 3 parts of the organic ligand mixed solution dropwise and mix evenly, adjust the pH to 8, perform a solvothermal reaction at 160° C. for 36 hours, cool to room temperature, wash, filter, and dry to obtain a metal organic ligand polymer.

[0059] Test experiment 1: Gas adsorption test: First, the test samples were activated: the metal organic ligand polymers of Examples 1 to 3 and Comparative Examples 1 to 4 were immersed in methanol for 3 days, and fresh methanol was replaced every 8 hours to remove the solvent in the pores of the metal organic ligand polymer, and then dried at 80°C for 10 hours to remove the residual methanol; 0.1 g of each of the activated Examples 1 to 3 and Comparative Examples 1 to 4 was placed in a flow rate of 82 cm 3 / min, an adsorption temperature of 40°C, and a desorption temperature of 120°C in a mixed gas adsorption test; wherein the mixed gas includes: by volume percentage, 16% CO2(SO2), 4% O2, 5% H2O, and 75% N2.

[0060] <![CDATA[CO2 adsorption capacity (mmol / g)]]> <![CDATA[SO2 adsorption capacity (mmol / g)]]> Example 1 5.19 3.40 Example 2 5.23 3.42 Example 3 5.16 3.37 Comparative Example 1 4.43 2.92 Comparative Example 2 4.54 3.14 Comparative Example 3 4.72 3.23 Comparative Example 4 4.37 2.78

[0061] Table 1

[0062] Conclusion: Comparative Example 1 is based on Example 2, and a rigid polymer ligand is introduced alone; resulting in a decrease in gas adsorption capacity, because the semi-rigid polymer ligand contains functional groups, which can form hydrogen bonds, electrostatic forces or coordination effects with gas molecules, which is beneficial to increase the amount of gas adsorption. Comparative Example 2 is based on Example 2, and imidazole is mixed with a semi-rigid polymer ligand alone; thereby reducing the gas adsorption of the metal organic ligand polymer; because the combination of the benzene ring and the imidazole group can adjust the structure and pore properties of the metal organic ligand polymer, which is beneficial to improve the gas adsorption. Comparative Example 3 is based on Example 2; the semi-rigid polymer ligand is made into a rigid polymer ligand; thereby the gas adsorption performance of the metal organic ligand polymer ligand is reduced. Comparative Example 4 is based on Example 2, and the content of metal salt is increased; resulting in some metal ions not being fully coordinated, affecting the porosity and specific surface area, forming an irregular coordination environment, and thus resulting in a decrease in the gas adsorption performance of the metal organic ligand polymer.

[0063] Finally, it should be noted that the above is only a preferred embodiment of the present invention, but the protection scope of this application is not limited thereto. Any changes or substitutions that can be easily thought of by any technician familiar with the technical field within the spirit and principle of the present invention and within the technical scope disclosed in this application should be included in the protection scope of this application; in the absence of conflict, the embodiments of this application and the features in the embodiments can be combined with each other. Therefore, the protection scope of this application shall be based on the protection scope of the claims.

Claims

1. A method for preparing a metal organic ligand polymer, characterized in that: The steps include: Step 1: (1) adding imidazole and sodium hydroxide to dimethyl sulfoxide, heating to 60° C. to 65° C. to react for 1 to 2 hours, adding p-dichlorobenzene to react for 2 to 3 hours, distilling under reduced pressure, cooling to room temperature, and purifying to obtain a rigid polymer ligand; (2) adding a semi-rigid polymer ligand and a rigid polymer ligand to deionized water, uniformly mixing, and obtaining an organic ligand mixed solution; Step 2: Add metal salt to deionized water to obtain metal salt solution, stir it at low speed at room temperature, add organic ligand mixed solution dropwise and mix evenly, adjust pH, perform solvent thermal reaction, cool to room temperature, wash, filter and dry to obtain metal organic ligand polymer.

2. The method for preparing a metal organic ligand polymer according to claim 1, characterized in that: The raw materials of the organic ligand mixed solution include the following components: 0.4-0.5 parts of semi-rigid polymer ligand, 2-3 parts of rigid polymer ligand, and 5-10 parts of deionized water, calculated by mass.

3. The method for preparing a metal organic ligand polymer according to claim 1, characterized in that: The raw materials of the metal organic ligand polymer include the following components: by weight, 0.8 to 1 parts of metal salt, 2 to 4 parts of organic ligand mixed solution, and 5 to 8 parts of deionized water.

4. The method for preparing a metal organic ligand polymer according to claim 1, characterized in that: The raw materials of the rigid polymer ligand include the following components: by weight, 7 to 8 parts of imidazole, 4 to 5 parts of sodium hydroxide, 7 to 7.5 parts of p-dichlorobenzene, and 25 to 30 parts of dimethyl sulfoxide.

5. The method for preparing a metal organic ligand polymer according to claim 2, characterized in that: The metal salt solution includes one or more of copper salt, zinc salt and cobalt salt.

6. The method for preparing a metal organic ligand polymer according to claim 1, characterized in that: The pH is 7 to 9; in the solvent thermal reaction, the temperature is 150° C. to 200° C., and the time is 12 to 72 hours.

7. The method for preparing a metal organic ligand polymer according to claim 1, characterized in that: The preparation method of the semi-rigid polymer ligand is as follows: (1) adding 4,7-dibromo-1H-benzimidazole and tripotassium phosphate to 1,4-dioxane and mixing uniformly, adding 3-ethyl propionate phenylboronic acid, introducing nitrogen, adding tetrakis(triphenylphosphine)palladium, reacting at 90°C to 100°C for 20 to 24 hours, purifying, and obtaining an intermediate; (2) adding the intermediate to a mixed solution of ethanol and tetrahydrofuran, mixing uniformly, dropping a 2 mol / L sodium hydroxide solution, heating to 70 to 80°C and reacting for 8 to 10 hours, cooling to room temperature, rotary evaporating to remove the organic solvent, adding deionized water to dilute, adjusting the pH to 4 to 5, filtering, washing, and drying, and obtaining a semi-rigid polymer ligand.

8. The method for preparing a metal organic ligand polymer according to claim 7, characterized in that: The raw materials of the intermediate include the following components: 1.58 to 1.6 parts of 4,7-dibromo-1H-benzimidazole, 3.5 to 4.2 parts of tripotassium phosphate, 2 to 3 parts of 3-ethyl propionate phenylboronic acid, 0.02 to 0.04 parts of tetrakis(triphenylphosphine)palladium, and 15 to 20 parts of 1,4-dioxane, in terms of mass fractions; the mass ratio of the ethanol, tetrahydrofuran, and 2 mol / L sodium hydroxide solution is 1:1:

1. 9 . A metal-organic ligand polymer prepared according to the method for preparing a metal-organic ligand polymer according to any one of claims 1 to 8 .