Porous polymer material as well as preparation method and application thereof

Abstract

The invention relates to a porous polymer material and a preparation method and application thereof.The preparation method comprises the steps that firstly, a compound containing sulfydryl and thiolactone is designed and synthesized, a mixed solution of the compound, a polar solvent and a surfactant serves as a continuous phase, a non-polar solvent serves as a dispersion phase, oil-in-oil type high-internal-phase emulsion is formed after emulsification, and the porous polymer material is obtained; and reacting with a polyamine compound to obtain the sulfydryl-containing porous polymer material. The prepared porous material can adsorb heavy metal ions in water and can be used in the field of water treatment.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of porous polymer materials, and particularly relates to a porous polymer material and a preparation method and application thereof. BACKGROUND

[0002] High internal phase emulsion (HIPE) is a viscous emulsion with a dispersed phase volume fraction greater than 74.05%. The use of high internal phase emulsion templating method to prepare porous materials not only has the characteristics of adjustable pore size and distribution, but also has the advantages of light weight, high porosity, and high specific surface area, and thus is concerned in the field of functional material preparation. The traditional high internal phase emulsion is generally composed of an aqueous phase and an oil phase, and its research is earlier and relatively mature. Oil-in-oil high internal phase emulsion is a supplement to the traditional oil-water system. Its water-free environment can allow certain water-sensitive reactants or catalysts to exist stably in the emulsion system, and the application temperature range of the oil-in-oil emulsion system is obviously expanded according to the selected emulsion two phases, which can be used as a reaction medium for various high / low temperature reactions, thereby widening the application field of high internal phase emulsion.

[0003] In recent years, with the continuous advancement of the research on high internal phase emulsion, oil-in-oil high internal phase emulsion has also gradually attracted attention, but the current related research is still very few. CN110229306A discloses a preparation method of a cellulose-based porous material, and a cellulose-based porous material is prepared in an oil-in-oil high internal phase emulsion, but the preparation period of the method is long, and it needs to be reacted at 60-80℃ for 8-24h. CN116444849A discloses a surfactant-stabilized oil-in-oil high internal phase Pickering emulsion formed by the cooperative assembly of nanoparticles and polymer ligands, and a method for preparing a porous polyurethane composite material by reacting isocyanate and polyol using the high internal phase emulsion as a template. The method also needs to be reacted at high temperature (60-100℃) for 24h, and the application field is not mentioned.

[0004] Therefore, it is of great significance to develop a simple and efficient preparation method of porous materials, and further expand the application field of oil-in-oil high internal phase emulsion and porous materials.

[0005] Adsorption method is a method for adsorbing pollutants in water by using porous solid substances, and is one of the commonly used methods for treating wastewater containing heavy metals. Heavy metal adsorbents are generally composed of solid materials with porosity or high specific surface area. Compared with traditional adsorbents such as activated carbon, polymer-based materials are widely used in wastewater treatment due to their stable chemical properties, high mechanical strength, adjustable structure, and easy functionalization. However, the current polymer-based adsorbents have problems such as complex preparation process, high synthesis condition requirement, low adsorption capacity, and low reusability.

[0006] Therefore, it is necessary to develop a polymer porous material with high adsorption capacity and reusability to solve the problems existing in the prior art. SUMMARY

[0007] In view of the above problems existing in the prior art, the present application provides a porous polymer material based on oil-in-oil high internal phase emulsion and amino ring-opening thiolactone reaction. Compared with the traditional preparation method, the preparation method has the advantages of rapid and efficient, simple operation, etc.

[0008] The porous polymer material prepared by the present application can be used in the field of water treatment, and has the advantages of high adsorption capacity and good reusability.

[0009] To achieve the above purposes, the technical solutions of the present application are as follows:

[0010] In a first aspect, the present application provides a preparation method of a porous polymer material, comprising the following steps:

[0011] 1) reacting isocyanate thiolactone with mercapto alcohol to obtain a thiolactone compound containing mercapto;

[0012] 2) mixing the surfactant, the thiolactone compound containing mercapto, and the polar solvent uniformly to obtain a continuous phase;

[0013] 3) adding a non-polar solvent as a dispersed phase into the continuous phase of step 2) to obtain an oil-in-oil high internal phase emulsion after emulsification;

[0014] 4) adding a polyamine compound to the high internal phase emulsion of step 3) for reaction, then washing, drying to obtain the porous polymer material.

[0015] In an embodiment, the isocyanate thiolactone of step 1) has the following formula (1):

[0016]

[0017] The isocyanate thiolactone is a product disclosed in the prior art, and the present application does not have specific requirements for its source. It can be prepared by itself using conventional methods known in the art. The preparation method of such products is a disclosed technology in the art. In practical applications, the synthesis method and process can refer to the method disclosed in the literature Responsive thiolactone derived N-substituted poly(urethane-amide)s[J]. Macromol Rapid Commun, 2017, 38(7): 1600783. The specific preparation method will not be described here.

[0018] In one embodiment, the thiol alcohol in step 1) is selected from one or more of dithiothreitol, dimercaprol, 3-mercaptopropanol.

[0019] In one embodiment, the molar ratio of the isocyanate thiolactone to the hydroxyl (-OH) in the thiol alcohol in step 1) is 1:0.8-1.2, for example, 1:0.8, 1:0.9, 1:1, 1:1.2, 1:2, etc.

[0020] In one embodiment, the reaction in step 1) is carried out in a solvent environment, and the solvent is selected from one or more of esters, ketones, halogenated hydrocarbons, preferably one or more of ethyl acetate, butyl acetate;

[0021] Optionally, the content of the isocyanate thiolactone in the solvent is 0.01-1 g / mL, for example, 0.01, 0.1, 0.3, 0.5, 0.8, 1 g / mL.

[0022] In one embodiment, the reaction in step 1) is carried out at a temperature of -10-60°C, for example, -10, 0, 10, 30, 50, 60°C, etc., for a time of 1-24 h, for example, 1, 5, 10, 15, 20, 24 h, etc.

[0023] After the reaction in step (1) is completed, washing, drying, etc. can also be included, which can be carried out using known conventional methods, and the present application does not have specific requirements.

[0024] In one embodiment, the surfactant in step 2) is selected from one or more of polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer, polystyrene-poly(methyl methacrylate) block copolymer, polybutadiene-polyethylene oxide block copolymer, alkylamine modified polythioether, cellulose nanoparticle, hydrophobically modified silica particle, optionally Pluronic F-127 (Arlacel), P188 (Arlacel).

[0025] In one embodiment, the polar solvent in step 2) is selected from one or more of acetonitrile, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO).

[0026] In one embodiment, the continuous phase in step 2) has a mass percentage composition of 10-45% of the thiol-containing thiolactone compound, 2-10% of the surfactant, and 45-88% of the polar solvent. Specifically, the thiol-containing thiolactone compound is 10, 15, 20, 25, 30, 40, 45%, etc., the surfactant is 2, 4, 6, 8, 10%, etc., and the polar solvent is 45, 50, 60, 70, 80, 88%, etc.

[0027] In one embodiment, the non-polar solvent in step 3) is selected from one or more of alkanes, aromatic hydrocarbons, preferably one or more of n-hexane, n-octane, dodecane, tetradecane, hexadecane.

[0028] In one embodiment, the mass ratio of the non-polar solvent in step 3) to the continuous phase is 1:0.1-0.4, for example 1:0.1, 1:0.2, 1:0.3, 1:0.4, etc.

[0029] In one embodiment, the stirring speed in the emulsification process in step 3) is 500-3000 rpm, for example 500, 1000, 2000, 3000 rpm, etc., and the stirring time is 1-30 min, for example 1, 5, 10, 20, 30 min, etc.

[0030] In one embodiment, the polyamine compound in step 4) is selected from one or more of isophorone diamine, propylene diamine, 4,4'-diaminodicyclohexyl methane, hexamethylene diamine, pentamethylene diamine, diethylene triamine, triethylene tetramine, polyether amine.

[0031] In one embodiment, the molar ratio of the thiol-containing thiolactone compound in step 2) to the amino group (-NH2) in the polyamine compound in step 4) is 1:1-2, for example 1:1, 1:1.3, 1:1.5, 1:1.8, 1:2, etc., preferably 1:1-1.5.

[0032] 1.8, 1:2, etc., preferably 1:1-1.5.

[0033] In one embodiment, the reaction temperature in step 4) is 0-60℃, for example 0, 10, 20, 30, 40, 50, 60℃, etc., and the reaction time is 1-24 h, for example 1, 3, 5, 8, 10, 13, 15, 18, 20, 24 h, etc.

[0034] After the above reaction in step (4) is completed, it further includes washing and drying operations, which are all conventional operations in the field. For example, in one specific example, the washing is performed using ethanol to remove other components, and then the product is soaked in water for 0.5-12 h to remove the ethanol, and the drying is preferably freeze-drying.

[0035] In a second aspect, the present application provides a porous polymer material prepared by the above method.

[0036] In a third aspect, the present application provides an application of the porous polymer material.

[0037] The porous polymer material prepared according to the above preparation method can be used for adsorbing copper (Cu 2+ ), mercury (Hg 2+heavy metal ions such as Cu2+, Pb2+, Cd2+, Hg2+, Cr3+, Ni2+, Co2+, Zn2+, Mn2+, Fe3+, and the like, for water treatment.

[0038] In a specific application, the porous polymer material is added to the water to be treated, stirred at 20-200 rpm for 1-24 h, and then separated.

[0039] Optionally, the amount of the porous polymer material added to the water to be treated is 100-5000 mg / L.

[0040] After the adsorption treatment of the porous polymer material, the content of heavy metal copper ions (Cu 2+ ) in the wastewater can be reduced to below 10 mg / L.

[0041] Compared with the prior art, the present application has the following beneficial effects:

[0042] The present application designs and synthesizes a compound containing a thiol group and a thiolactone group, and then further utilizes an amino group to open the thiolactone for cross-linking reaction and generate a thiol group, to prepare a porous polymer foam with high thiol content. The thiol group and the porous structure in the polymer foam can adsorb heavy metal ions in water, and can be used in the field of water treatment, and have the advantages of high adsorption capacity and good reusability. BRIEF DESCRIPTION OF DRAWINGS

[0043] Figure 1 Scanning electron microscope image of the porous polymer foam prepared in Example 1;

[0044] Figure 2 Copper ion distribution graph of the porous polymer foam after adsorbing copper ions in Example 1. DETAILED DESCRIPTION

[0045] In order to facilitate the understanding of the present application, the present application will be further described below in conjunction with examples. It should be understood that the following examples are only for better understanding of the present application, and do not mean that the present application is limited to the following examples. Those skilled in the art should understand that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific methods, etc. fall within the protection scope and disclosure scope of the present application.

[0046] It should be noted that the endpoints of the ranges and any values disclosed in this specification are not limited to the precise values stated. These ranges and values should be construed as being approximate. In the case of numerical values, the endpoints of the ranges are not included. The ranges and values are approximations that are already "rounded", and thus are not to be construed as being limited to the precise values recited. Each numerical value should be considered as being approximated, and as being only an example within the scope of the ranges or values. Each range of values should be considered as not including the endpoints, unless the context clearly indicates otherwise.

[0047] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The term "and / or" as used herein refers to and encompasses any and all combinations of one or more of the associated listed items.

[0048] Unless otherwise specified, the reagents, materials and instruments used in the following examples are conventional reagents, conventional materials and conventional instruments in the art, which can be obtained by commercial purchase, and the reagents involved can also be synthesized by conventional methods in the art.

[0049] In the examples and comparative examples of the present application, the main raw materials used are as follows:

[0050] Isocyanate thiolactone: the structure is as follows,

[0051] Prepared according to the method disclosed in the literature Responsive thiolactone derived N-substituted poly(urethane-amide)s[J]. Macromol Rapid Commun, 2017, 38(7): 1600783.

[0052] Dithiothreitol: Aldrich;

[0053] Pluronic F-127: Aldrich;

[0054] 1,3-propanediamine: Aldrich;

[0055] Diethylenetriamine: Wanhua Chemical Group Co., Ltd.;

[0056] Isophorone diamine: Wanhua Chemical Group Co., Ltd.

[0057] The main analysis methods used in the examples and comparative examples of the present application are as follows:

[0058] Metal ion content in water test: tested by inductively coupled plasma spectrometer (ICP), instrument model Agilent-5110 ICP-OES.

[0059] Energy dispersive spectrometer (EDS) scanning: the elements on the surface of the porous polymer foam are tested by a high-resolution field emission scanning electron microscope, instrument model Verios G4.

[0060] 1H NMR: the chemical structure of the thiol-containing thiolactone compound is analyzed by nuclear magnetic resonance spectrometer, instrument model Bruker 600M.

[0061] Example 1

[0062] 1) Preparation of thiol-containing thiolactone: 1.43 g (10 mmol) of isocyanate thiolactone was dissolved in 5 mL of ethyl acetate, 0.77 g (5 mmol) of dithiothreitol was added, and the reaction was stirred at 35 °C for 1 h. After washing with water and drying, thiol-containing thiolactone compound A was obtained.

[0063] Structure characterization of thiolactone compound A: 1H NMR (400 MHz, CDC13) δ ppm 1.49-1.51 (2H), 2.48-2.53 (4H), 2.78-2.82 (4H), 2.84-2.90 (4H), 4.45 (2H), 4.86 (2H), 7.99-8.01 (2H).

[0064] 2) The continuous phase was prepared by uniformly mixing 0.44 g (2 mmol of thiolactone ring) of compound A, 2 g of acetonitrile, and 0.2 g of surfactant Pluronic F-127.

[0065] 3) 8 g of dodecane was added to the continuous phase, and a white viscous emulsion was formed by emulsifying with a vortex at 2000 rpm for 3 min.

[0066] 4) 0.074 g (2 mmol-NH2) of 1,3-propanediamine was added to the emulsion, and the reaction was terminated after 3 h of reaction at 25 °C to obtain a foamy crude product. Ethanol was used to wash off other components, and then the product was soaked in water for 10 min to remove ethanol. After freeze-drying, a thiol-containing porous polymer material was obtained.

[0067] Example 2

[0068] 1) Preparation of thiol-containing thiolactone: 1.43 g (10 mmol) of isocyanate thiolactone was dissolved in 5 mL of ethyl acetate, 0.77 g (5 mmol) of dithiothreitol was added, and the reaction was stirred at 35 °C for 1 h. After washing with water and drying, thiol-containing thiolactone compound A was obtained.

[0069] 2) The continuous phase was prepared by uniformly mixing 0.44 g (2 mmol of thiolactone ring) of compound A, 2 g of acetonitrile, and 0.2 g of surfactant Pluronic F-127.

[0070] 3) 8 g of dodecane was added to the continuous phase, and a white viscous emulsion was formed by emulsifying with a vortex at 2000 rpm for 3 min.

[0071] 4) 0.074 g (2 mmol-NH2) of 1,3-propanediamine was added to the emulsion, and the reaction was terminated after 3 h of reaction at 25 °C to obtain a foamy crude product. Ethanol was used to wash off other components, and then the product was soaked in water for 10 min to remove ethanol. After freeze-drying, a thiol-containing porous polymer material was obtained.

[0072] Example 3

[0073] 1) Preparation of thiol-containing thiolactone: 0.72 g (5 mmol) of isocyanate thiolactone was weighed into 3 mL of ethyl acetate, and 0.39 g (2.5 mmol) of dithiothreitol was added. After stirring at 25 °C for 2 h, the reaction was washed with water and dried to obtain thiol-containing thiolactone compound A.

[0074] 2) Compound A (0.66 g, 3 mmol of thiolactone ring), 2 g of DMF, and 0.24 g of surfactant Pluronic F-127 were mixed to form a continuous phase.

[0075] 3) 10 g of n-hexane was added to the continuous phase, and a white viscous emulsion was formed by emulsifying with a vortex at 3000 rpm for 2 min.

[0076] 4) 0.51 g (6 mmol-NH2) of isophorone diamine was added to the emulsion, and the reaction was completed after 1 h at 60 °C to obtain a foamy crude product. The other components were removed by washing with ethanol, and then the ethanol was removed by soaking in water for 10 min. After freeze-drying, a thiol-containing porous polymer material was obtained.

[0077] Comparative Example 1

[0078] A porous polymer material was prepared according to the method of Example 1, except that in step 2) the thiol-containing thiolactone compound was replaced with 0.29 g (2 mmol) of isocyanate thiolactone, and step 1) was omitted, and the other operations and conditions were unchanged.

[0079] Comparative Example 2

[0080] A porous polymer material was prepared according to the method of Example 1, except that in step 1) the dithiothreitol was replaced with 0.75 g (5 mmol) of 1,6-hexanedithiol, and the other operations and conditions were unchanged.

[0081] Comparative Example 3

[0082] A porous polymer material was prepared according to the method of Example 1, except that in step 1) the dithiothreitol was replaced with 0.31 g (5 mmol) of ethylene glycol, and the other operations and conditions were unchanged.

[0083] Performance test of the porous polymer materials prepared in Examples 1-3 and Comparative Examples:

[0084] 50 mg of the porous polymer material prepared in the above examples and comparative examples was weighed into 100 mL of copper sulfate solution with a copper ion concentration of 100 mg / L, sealed, and placed in a constant-temperature water bath shaker at 100 rpm for 2 h of adsorption.

[0085] After the adsorption, the concentration of copper ions in the solution was tested by ICP. The porous polymer material adsorbed with metal ions was washed with 1wt% HCl solution until no metal ions were detected in the waste liquid, washed with water until neutral, dried and then used for adsorption test. The repeated use performance was tested for five times, and the results are shown in Table 1 below.

[0086] Table 1

[0087]

[0088] The porous polymer material after adsorption in Example 1 was dried and then the copper element on the surface of the foam was scanned by an energy dispersive spectrometer (EDS). The results showed that the copper element existed, as shown in Table 2 below. Figure 2 It can be seen that the porous polymer material containing thiol prepared by the present application has excellent adsorption capacity for copper ions in water and good repeated use performance, and can be used for treating heavy metal wastewater.

[0089] It is easily understood that the above examples are only examples for clearly illustrating the present application, and do not mean that the present application is limited to this. Based on the above description, other different forms of changes or variations can be made by those skilled in the art. Here, it is not necessary and impossible to exhaust all the embodiments. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A method for preparing a porous polymer material, characterized in that, Includes the following steps: 1) Thiol-containing thiolactone compounds are prepared by reacting isocyanate thiolactones with mercapto alcohols. 2) The surfactant, the thiolactone compound containing thiol groups, and the polar solvent are mixed until homogeneous to obtain a continuous phase; 3) A nonpolar solvent is added as the dispersed phase to the continuous phase in step 2), and after emulsification, an oil-in-oil type high internal phase emulsion is obtained; 4) Add a polyamine compound to the high internal phase emulsion of step 3) to react, then wash and dry to obtain the porous polymer material.

2. The preparation method according to claim 1, characterized in that, The isocyanate thiolactone described in step 1) has the structure shown in formula (1): And / or, Step 1) The mercapto alcohol is selected from one or more of dithiothreitol, dimercaprol, and 3-mercaprol; and / or, In step 1), the isocyanate thiolactone has a molar ratio of 1:0.8-1.2 to the hydroxyl group in the mercapto alcohol, based on the isocyanate group.

3. The preparation method according to claim 1 or 2, characterized in that, The reaction in step 1) is carried out in a solvent environment, wherein the solvent is selected from one or more of esters, ketones, and halogenated hydrocarbons, preferably one or more of ethyl acetate and butyl acetate; Optionally, the content of the isocyanate thiolactone in the solvent is 0.01-1 g / mL.

4. The preparation method according to any one of claims 1-3, characterized in that, The reaction described in step 1) is carried out at a temperature of -10 to 60°C for 1 to 24 hours.

5. The preparation method according to any one of claims 1-4, characterized in that, Step 2) The surfactant is selected from one or more of the following: polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer, polystyrene-polymethyl methacrylate block copolymer, polybutadiene-polyoxyethylene block copolymer, alkylamine-modified polysulfide, cellulose nanoparticles, and hydrophobically modified silica particles; and / or, Step 2) The polar solvent is selected from one or more of acetonitrile, N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO); and / or, The continuous phase described in step 2) has the following composition by mass percentage: 10-45% thiolactone compound containing thiol group, 2-10% surfactant, and 45-88% polar solvent.

6. The preparation method according to any one of claims 1-5, characterized in that, Step 3) The nonpolar solvent is selected from one or more alkanes and aromatic hydrocarbons, preferably one or more of n-hexane, n-octane, dodecane, tetradecane, and hexadecane; and / or In step 3), the mass ratio of the nonpolar solvent to the continuous phase is 1:0.1-0.

4.

7. The preparation method according to any one of claims 1-6, characterized in that, In step 3), the emulsification process is carried out at a stirring speed of 500-3000 rpm for 1-30 minutes.

8. The preparation method according to any one of claims 1-7, characterized in that, Step 4) The polyamine compound is selected from one or more of isophorone diamine, propylene diamine, 4,4′-diaminodicyclohexylmethane, hexamethylenediamine, pentanediamine, diethylenetriamine, triethylenetetramine, and polyetheramine; and / or, The molar ratio of the thiolactone compound containing a thiol group in step 2) to the amino group (-NH2) in the polyamine compound in step 4) is 1:1-2, preferably 1:1-1.5, based on the thiolactone ring therein; and / or The reaction described in step 4) is carried out at a temperature of 0-60℃ for a time of 1-24 hours.

9. A porous polymer material prepared by the preparation method according to any one of claims 1-8.

10. The application of porous polymer materials prepared by the preparation method according to any one of claims 1-8 in the field of water treatment.

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