Functionalized porous polyoxazolidinones with alkane chains, methods of preparation, and uses

Abstract

The application provides a kind of functionalized porous polyoxamide with alkane chain, preparation method and application.Functionalized porous polyoxamide with alkane chain is formed by polyvinyl triazine diamine (PVDAT) and cheap and easily available formic acid, oxalic acid, formamide, formylhydrazine and N, N-dimethylformamide functional monomer through oxamide polymerization reaction, the functionalized polyoxamide prepared by the application has large specific surface area and rich amino and hydroxyl functional groups, and the porous polymer skeleton also contains fatty long chain, and has good application prospect in the field of organic hydrocarbon gas adsorption separation and recovery of radioactive iodine element.

Description

Technical Field

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

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

[0003] The pore surfaces of PPA materials are rich in polar functional groups such as amines and aldehydes, resulting in strong adsorption capacity. These polar functional groups play an important role in the molecular-level adsorption of gases such as carbon dioxide (CO2) and organic hydrocarbons. Because these polar functional groups can interact with the molecules of the adsorbed substance, porous polyacetalamine materials exhibit excellent performance in gas capture, separation, and recovery.

[0004] With the increasing use of nuclear energy and radioactive materials, the disposal of radioactive waste has become a major environmental challenge. Poly(pyrrolidone-polyacrylamide) (PPA) materials have been used for the treatment and recovery of radioactive waste due to their polar functional groups' excellent adsorption of radioactive elements (such as iodine and cesium). 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] While PPA materials have demonstrated excellent performance in a variety of applications, their irregular particle shape and dense particle packing often restrict the mass transfer and diffusion of gases or liquids within the material, limiting the rate and efficiency of the adsorption process. To overcome this limitation, this patented technology introduces alkane chains into the PPA material, modifying it to create a more regular morphology and a more open pore structure, thereby improving adsorption speed and efficiency. These structural optimizations help enhance the application of PPA materials in areas such as gas capture and wastewater treatment. The introduction of aliphatic alkyl chains reduces the packing density between materials, improves the pore structure, and facilitates fluid diffusion. Compared to traditional irregular morphologies, the modified PPA materials demonstrate higher efficiency in gas adsorption and liquid transport. Furthermore, the introduction of amine functional groups, enriching the material with nitrogen and oxygen, not only enhances the adsorption performance and selectivity of the porous material but also improves its structural stability, dispersibility, and versatility. These advantages make amine-modified porous materials valuable for applications in areas such as gas capture and iodine adsorption, and provide an effective solution for achieving green and sustainable chemical processes. SUMMARY

[0006] A first object of the present application is to provide a class of functionalized porous polyoxamide amine with alkane chains.

[0007] A second object of the present application is to provide a method for preparing functionalized porous polyoxamide amine with alkane chains.

[0008] A third object of the present application is to provide the use of functionalized porous polyoxamide amine with alkane chains.

[0009] Technical solutions of the present application:

[0010] A class of functionalized porous polyoxamide amine with alkane chains, which is polymerized by polyvinyl triazine diamine (PVDAT) and different functional monomers, respectively;

[0011] The polyvinyl triazine diamine (PVDAT) has the following structure:

[0012]

[0013] Wherein, n is an integer greater than 1

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

[0015] Formic acid:

[0016] Oxalic acid:

[0017] Formamide:

[0018] Formylhydrazine:

[0019] N,N-dimethylformamide:

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

[0021]

[0022] Wherein, n is an integer greater than 1

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

[0024]

[0025] Where n is an integer greater than 1

[0026] When polyvinyltriazine 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 polyvinyl triazine diamine is polymerized with formic hydrazide, 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 comprises 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 the reaction is carried out at this temperature for 24-96 hours. After cooling to room temperature, the resulting 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 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 alcohols, fatty ketones, alkanes, halogenated hydrocarbons, 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 transform 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 present invention has the beneficial effect of obtaining a functionalized porous polyaminal product containing alkane chains through a simple reaction, offering advantages such as relatively simple preparation, low manufacturing cost, and renewable use. The presence of alkane chains results in a low bulk density and low fluid resistance, which facilitates mass transfer and diffusion within the pores of the adsorbent. Furthermore, the introduced alkane chains further facilitate the adsorption of alkanes, while the amino and hydroxyl functional groups introduced into the polymer backbone effectively enhance the adsorption capacity of iodine. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 These are the infrared spectra of polymers NOPAN-1 and NOPAN-2.

[0045] Figure 2 These are 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 kinetics 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] Figure 9 This is the n-butane physical adsorption isotherm of polymer NOPAN-1 at 298K.

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

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

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

[0056] Figure 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 with reference to specific embodiments and accompanying 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 of PVDAT, 0.1 g of FA, and 25 ml of dry dimethyl sulfoxide were added to a 50 ml reaction flask. Under nitrogen, the temperature was slowly raised to 140°C and the reaction was continued at this temperature for 24 hours. After cooling and filtration, the solid was washed with dichloromethane, tetrahydrofuran, and methanol, extracted with tetrahydrofuran using a Soxhlet extractor for 12 hours, and dried under vacuum at 80°C for 48 hours to obtain NOPAN-1 as a white solid.

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

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

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

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

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

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

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

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

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

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

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

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

[0072] Example 8: Ethane, propane and n-butane adsorption performance test of polymer NOPAN-1

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

[0074] Example 9: Adsorption performance test of ethane, propane and n-butane of polymer NNPAN-3

[0075] The adsorption capacities of ethane, propane, and n-butane for the polymer NNPAN-3 at 298 K were measured, and an adsorption curve was obtained. At 298 K, the polymer had an adsorption capacity of 1.3 mmol / g for ethane, 2.0 mmol / g for propane, and 2.3 mmol / g for n-butane.

Claims

1. A functionalized porous polyaminal having an alkane chain, characterized in that: The structural formula is: 、 、 、 or , where 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 made 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: ; Formoyl hydrazide: ; N,N-dimethylformamide: ; When polyvinyltriazine 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 polyvinyltriazine 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 polyvinyltriazine 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 polyvinyl triazine diamine is polymerized with formic hydrazide, 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 and polyvinyl triazine diamine are mixed 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 resulting 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, wherein: 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, wherein: 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 3, wherein: 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 3, characterized in that: The organic solvent B is one or a mixture of two or more of fatty alcohols, fatty ketones, alkanes, halogenated hydrocarbons, tetrahydrofuran, and dioxane.

8. Use of the functionalized porous polyaminal having an alkane chain according to claim 1, or the functionalized porous polyaminal having an alkane chain obtained by the preparation method according to any one of claims 2 to 7, characterized in that: It is used for the adsorption separation of mixed organic hydrocarbon gases and the adsorption enrichment and recovery of radioactive iodine.

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