Functionalized porous polyacetal amine with alkane chain as well as preparation method and application of functionalized porous polyacetal amine

Abstract

The invention provides functionalized porous polyacetal amine with an alkane chain as well as a preparation method and application of the functionalized porous polyacetal amine. The functional porous polyacetal amine with the alkane chain is prepared by carrying out acetal amine polymerization reaction on polyvinyl triazine diamine (PVDAT) and formic acid, oxalic acid, formamide, formylhydrazine and N, N-dimethylformamide functional monomers which are low in price and easy to obtain, and the prepared functional polyacetal amine has large specific surface area and rich amino and hydroxyl functional groups; and the porous polymer skeleton also contains fat long chains, so that the porous polymer has a good application prospect in the fields of organic hydrocarbon gas adsorption separation, radioactive iodine element recovery and the like.

Description

Technical Field

[0001] The invention relates to a preparation method and application of a functionalized porous polyaminal with an alkane chain, belonging to the field of polymer materials. Background Art

[0002] Porous polyaminal (PPA) polymer materials have a wide range of application prospects in the fields of gas adsorption separation, wastewater treatment, and radioactive waste recovery due to their porous structure, polar functional groups, adjustable pore size, and large specific surface area. With the continuous optimization of material properties and the improvement of structural design, PPA materials are expected to become an important technical support for green energy, environmental protection and other industries in the future.

[0003] The pore surface of PPA material is rich in polar functional groups such as amine and aldehyde groups, and has strong adsorption capacity. These polar functional groups play an important role in the molecular adsorption process of carbon dioxide (CO2) and organic hydrocarbon gases. Since these polar functional groups can interact with the molecules of the adsorbed substances, porous polyacetalamine materials show good performance in gas capture, separation and recovery.

[0004] With the increasing use of nuclear energy and radioactive materials, how to deal with radioactive waste has become a major challenge in environmental protection. PPA materials have been used for the treatment and recovery of radioactive waste due to the good adsorption of radioactive elements (such as iodine, cesium, etc.) by their polar functional groups. By adjusting the pore size and chemical composition of PPA materials, the selective adsorption capacity for specific radioactive elements can be improved, thereby reducing the risk of radioactive waste.

[0005] Although PPA materials perform well in a variety of applications, the irregular shape of their particles and the compactness of their particle packing often lead to limited mass transfer and diffusion of gases or liquids within the material, thereby limiting the rate and efficiency of the adsorption process. In order to overcome this defect, this patented technology introduces alkane chains into PPA materials, and through modification, the material's morphology is made more regular and the pore structure is more open, thereby improving its adsorption speed and efficiency. These structural optimizations help to improve the application effect of PPA materials in gas capture, wastewater treatment and other fields. By introducing aliphatic alkyl chains, the packing density between materials can be reduced, the pore structure can be improved, and the diffusion of fluids can be promoted. Compared with traditional irregular forms, the modified PPA materials show higher efficiency in gas adsorption and liquid transport. Moreover, the introduction of amine functional groups to make them nitrogen- and oxygen-rich can not only improve the adsorption performance and selectivity of porous materials, but also improve their structural stability, dispersibility and versatility. These advantages make amine-modified porous materials have important application value in gas capture, iodine adsorption and other fields, and provide an effective solution for achieving green and sustainable chemical processes. Summary of the invention

[0006] The first object of the present invention is to provide a class of functionalized porous polyaminals having alkane chains.

[0007] The second object of the present invention is to provide a method for preparing a functionalized porous polyaminal having an alkane chain.

[0008] The third object of the present invention is to provide the use of the functionalized porous polyaminal having alkane chains.

[0009] The technical solution of the present invention:

[0010] A class of functionalized porous polyaminals with alkane chains, which are prepared by polymerizing polyvinyl triazine diamine (PVDAT) with different functional monomers;

[0011] The structure of the polyvinyl triazine diamine (PVDAT) is as follows:

[0012]

[0013] Where n is an integer greater than 1

[0014] The functional monomers are formic acid (FA), oxalic acid (OA), formamide (FAM), formic hydrazide (FHA) and N,N-dimethylformamide (DMF), and their structures are as follows:

[0015] Formic acid:

[0016] oxalic acid:

[0017] Formamide:

[0018] Formic hydrazide:

[0019] N,N-Dimethylformamide:

[0020] When polyvinyl triazine diamine is polymerized with formic acid, the functionalized porous polyaminal NOPAN-1 with alkane chains has the following structure:

[0021]

[0022] Where n is an integer greater than 1

[0023] When polyvinyl triazine diamine is polymerized with oxalic acid, the functionalized porous polyaminal NOPAN-2 with alkane chains has the following structure:

[0024]

[0025] Where n is an integer greater than 1

[0026] When polyvinyl triazine diamine is polymerized with formamide, the functionalized porous polyaminal NNPAN-1 with alkane chains has the following structure:

[0027]

[0028] Where n is an integer greater than 1

[0029] When poly(vinyl triazine diamine) and carboxylic hydrazide are polymerized, the functionalized porous polyaminal NNPAN-2 with alkane chains has the following structure:

[0030]

[0031] Where n is an integer greater than 1

[0032] When polyvinyl triazine diamine is polymerized with N,N-dimethylformamide, the functionalized porous polyaminal NNPAN-3 with alkane chains has the following structure:

[0033]

[0034] Where n is an integer greater than 1

[0035] A method for preparing a functionalized porous polyaminal having an alkane chain, comprising the following steps:

[0036] The functional monomers are mixed with polyvinyl triazine diamine in organic solvent A at room temperature, and the temperature is slowly raised to 140-200°C under an inert atmosphere, and reacted at this temperature for 24-96 hours. After cooling to room temperature, the obtained solid is extracted with organic solvent B for 12-36 hours, and vacuum dried at 80-150°C to constant weight;

[0037] The mass volume ratio of the sum of the mass of the polyvinyl triazine diamine and the functional monomer to the mass of the organic solvent A is increased from 1 g / 100 ml to 50 g / 100 ml;

[0038] The mass ratio of the functional monomer to polyvinyl triazine diamine is 0.3:1 to 1:0.8.

[0039] The organic solvent A is one or a mixture of two or more of N-methylpyrrolidone, dimethyl sulfoxide, diphenyl sulfone, o-dichlorobenzene and mesitylene.

[0040] The organic solvent B is one or a mixture of two or more of fatty alcohol, fatty ketone, alkane, halogenated hydrocarbon, tetrahydrofuran and dioxane.

[0041] The chemical structure, pore structure parameters and morphology characteristics of the functionalized porous polyaminal with alkane chains of the present invention are confirmed by Fourier infrared spectroscopy, nitrogen physical adsorption isotherm curve and scanning electron microscopy.

[0042] The functionalized porous polyaminal with alkane chains obtained by the preparation method of the present invention can be applied to the adsorption separation of mixed organic hydrocarbon gases and the adsorption enrichment and recovery of radioactive iodine.

[0043] The beneficial effect of the present invention is that a functionalized porous polyaminal target product with an alkane chain can be obtained by a simple reaction, and has the advantages of relatively simple preparation, low manufacturing cost, and renewable use. Because of the alkane chain, it has a low bulk density and a small fluid resistance, which is conducive to the mass transfer and diffusion of the adsorbent in the pores, and the introduced alkane chain is more conducive to the adsorption of alkanes, and the amino and hydroxyl functional groups introduced on the polymer skeleton can effectively increase the adsorption capacity of iodine. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 This is the infrared spectrum of polymers NOPAN-1 and NOPAN-2.

[0045] Figure 2 It is the infrared spectra of polymers NNPAN-1, NNPAN-2 and NNPAN-3.

[0046] Figure 3 This is the nitrogen physical adsorption isotherm of polymer NOPAN-1 at 77K.

[0047] Figure 4 is the pore size distribution curve of polymer NOPAN-1.

[0048] Figure 5 This is a scanning electron micrograph of the polymer NOPAN-1.

[0049] Figure 6 This is the iodine vapor adsorption kinetic curve of polymer NOPAN-1.

[0050] Figure 7 This is the ethane physical adsorption isotherm of polymer NOPAN-1 at 298K.

[0051] Figure 8 This is the propane physical adsorption isotherm of polymer NOPAN-1 at 298K.

[0052] Fig. 9 This is the n-butane physical adsorption isotherm of polymer NOPAN-1 at 298K.

[0053] Fig.10 This is the iodine vapor adsorption kinetic curve of polymer NNPAN-3.

[0054] Fig.11 This is the ethane physical adsorption isotherm of polymer NNPAN-3 at 298K.

[0055] Fig.12 This is the propane physical adsorption isotherm of polymer NNPAN-3 at 298K.

[0056] Fig.13 This is the n-butane physical adsorption isotherm of polymer NNPAN-3 at 298K. DETAILED DESCRIPTION

[0057] The present invention is described in detail below in conjunction with specific implementations and drawings. The scope of the present invention is not limited to this embodiment, but is defined by the scope of the claims.

[0058] Example 1: Preparation of polymer NOPAN-1

[0059] 0.3 g PVDAT, 0.1 g FA and 25 ml dry dimethyl sulfoxide were added to a 50 ml reaction bottle, and the temperature was slowly raised to 140°C under nitrogen protection, and the reaction was carried out at this temperature for 24 hours. After cooling and filtration, the solid was washed with dichloromethane, tetrahydrofuran and methanol, and extracted with a tetrahydrofuran Soxhlet extractor for 12 hours, and vacuum dried at 80°C for 48 hours to obtain a white solid NOPAN-1.

[0060] Example 2: Preparation of polymer NOPAN-2

[0061] 0.4 g PVDAT, 0.23 g OA and 15 ml dry dimethyl sulfoxide were added to a 50 ml reaction bottle, and the temperature was slowly raised to 180°C under nitrogen protection, and the reaction was carried out at this temperature for 72 hours. After cooling and filtration, the solid was washed with dichloromethane, tetrahydrofuran and methanol, and extracted with a tetrahydrofuran Soxhlet extractor for 24 hours, and vacuum dried at 120°C for 48 hours to obtain a white solid NOPAN-2.

[0062] Example 3: Preparation of polymer NNPAN-1

[0063] 11 g PVDAT, 13.75 g FAM and 50 ml dry dimethyl sulfoxide were added to a 100 ml reaction bottle, and the temperature was slowly raised to 200°C under nitrogen protection, and the reaction was carried out at this temperature for 96 hours. After cooling and filtration, the solid was washed with dichloromethane, tetrahydrofuran and methanol, and extracted with a tetrahydrofuran Soxhlet extractor for 36 hours, and vacuum dried at 150°C for 48 hours to obtain a white solid NNPAN-1.

[0064] Example 4: Preparation of polymer NNPAN-2

[0065] 11 g PVDAT, 8.8 g FHA and 50 ml dry dimethyl sulfoxide were added to a 100 ml reaction bottle, and the temperature was slowly raised to 180°C under nitrogen protection, and the reaction was carried out at this temperature for 72 hours. After cooling and filtration, the solid was washed with dichloromethane, tetrahydrofuran and methanol, and extracted with a tetrahydrofuran Soxhlet extractor for 24 hours, and vacuum dried at 120°C for 48 hours to obtain a gray solid NNPAN-2.

[0066] Example 5: Preparation of polymer NNPAN-3

[0067] 8 g PVDAT, 6.4 g DMF and 50 ml dry dimethyl sulfoxide were added to a 100 ml reaction bottle, and the temperature was slowly raised to 180°C under nitrogen protection, and the reaction was carried out at this temperature for 72 hours. After cooling and filtration, the solid was washed with dichloromethane, tetrahydrofuran and methanol, and extracted with a tetrahydrofuran Soxhlet extractor for 24 hours, and vacuum dried at 120°C for 48 hours to obtain a white solid NNPAN-3.

[0068] Example 6: Determination of iodine vapor adsorption performance of polymer NOPAN-1

[0069] The open vial (1.5 ml) containing the NOPAN-1 sample (20 mg) was placed in a large bottle (100 ml) containing iodine (5 g), the large bottle was sealed and placed in an oven at 80°C. After a period of time, the vial containing the NOPAN-1 sample was weighed and put back into the large bottle, the large bottle was sealed and placed back in the oven at 80°C to continue adsorption until the mass of the vial containing the NOPAN-1 sample no longer changed. The adsorption amount of iodine vapor of NOPAN-1 was 310.45 mg / g.

[0070] Example 7: Determination of iodine vapor adsorption performance of polymer NNPAN-3

[0071] The open vial (1.5 ml) containing the NNPAN-3 sample (20 mg) was placed in a large bottle (100 ml) containing iodine (5 g), the large bottle was sealed and placed in an oven at 80°C. After a period of time, the vial containing the NNPAN-3 sample was weighed and put back into the large bottle, the large bottle was sealed and placed back in the oven at 80°C to continue adsorption until the mass of the vial containing the NNPAN-3 sample no longer changed. The adsorption amount of iodine vapor of NNPAN-3 was 452 mg / g.

[0072] Example 8: Test of the adsorption performance of polymer NOPAN-1 for ethane, propane and n-butane

[0073] The adsorption amount of ethane, propane and n-butane of the polymer NOPAN-1 at 298K was measured, and its adsorption curve was obtained. At 298K, the adsorption amount of ethane was 0.9mmol / g, the adsorption amount of propane was 1.3mmol / g, and the adsorption amount of n-butane was 2.0mmol / g.

[0074] Example 9: Test of the adsorption performance of ethane, propane and n-butane of polymer NNPAN-3

[0075] The adsorption amount of ethane, propane and n-butane of the polymer NNPAN-3 at 298K was measured to obtain its adsorption curve. At 298K, the adsorption amount of ethane was 1.3mmol / g, the adsorption amount of propane was 2.0mmol / g, and the adsorption amount of n-butane was 2.3mmol / g.

Claims

1. A functionalized porous polyaminal having an alkane chain, characterized in that: The structural formula is: Here, n is an integer greater than 1.

2. The method for preparing a functionalized porous polyaminal having an alkane chain according to claim 1, characterized in that: It is formed by polymerizing polyvinyl triazine diamine with different functional monomers; The structure of the polyvinyl triazine diamine is as follows: Wherein, n is an integer greater than 1; The functional monomers are formic acid, oxalic acid, formamide, formic hydrazide or N,N-dimethylformamide, and their structures are as follows: Formic acid: oxalic acid: Formamide: Formic hydrazide: N,N-Dimethylformamide: When polyvinyl triazine diamine is polymerized with formic acid, the functionalized porous polyaminal NOPAN-1 with alkane chains has the following structure: Wherein, n is an integer greater than 1; When polyvinyl triazine diamine is polymerized with oxalic acid, the functionalized porous polyaminal NOPAN-2 with alkane chains has the following structure: Wherein, n is an integer greater than 1; When polyvinyl triazine diamine is polymerized with formamide, the functionalized porous polyaminal NNPAN-1 with alkane chains has the following structure: Wherein, n is an integer greater than 1; When poly(vinyl triazine diamine) and carboxylic hydrazide are polymerized, the functionalized porous polyaminal NNPAN-2 with alkane chains has the following structure: Wherein, n is an integer greater than 1; When polyvinyl triazine diamine is polymerized with N,N-dimethylformamide, the functionalized porous polyaminal NNPAN-3 with alkane chains has the following structure: Here, n is an integer greater than 1.

3. The method for preparing a functionalized porous polyaminal having an alkane chain according to claim 2, characterized in that: The steps are as follows: functional monomers are mixed with polyvinyl triazine diamine in organic solvent A at room temperature, the temperature is slowly raised to 140-200° C. under an inert atmosphere, and the reaction is carried out at this temperature for 24-96 hours. After cooling to room temperature, the obtained solid is extracted with organic solvent B for 12-36 hours, and vacuum dried at 80-150° C. to constant weight.

4. The method for preparing a functionalized porous polyaminal having an alkane chain according to claim 2, characterized in that: The mass volume ratio of the sum of the mass of the polyvinyl triazine diamine and the functional monomer to the mass of the organic solvent A is increased from 1 g / 100 ml to 50 g / 100 ml.

5. The method for preparing a functionalized porous polyaminal having an alkane chain according to claim 2, characterized in that: The mass ratio of the functional monomer to polyvinyl triazine diamine is 0.3:1 to 1:0.

8.

6. The method for preparing a functionalized porous polyaminal having an alkane chain according to claim 2, characterized in that: The organic solvent A is one or a mixture of two or more of N-methylpyrrolidone, dimethyl sulfoxide, diphenyl sulfone, o-dichlorobenzene and mesitylene.

7. The method for preparing a functionalized porous polyaminal having an alkane chain according to claim 2, characterized in that: The organic solvent B is one or a mixture of two or more of fatty alcohol, fatty ketone, alkane, halogenated hydrocarbon, tetrahydrofuran and dioxane.

8. The functionalized porous polyaminal having an alkane chain as claimed in claim 1, or Application of a functionalized porous polyaminal having an alkane chain prepared by any one of the preparation methods 2-7, It is characterized in that The invention is applied to the adsorption separation of mixed organic hydrocarbon gas and the adsorption enrichment and recovery of radioactive iodine.

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