CN115106067B - Functional macroporous organic silica gel material and preparation method and application thereof - Google Patents
Functional macroporous organic silica gel material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a functional macroporous organic silica gel material, a preparation method and application thereof, and specifically comprises the following steps: (1) The method comprises the steps of (1) carrying out free radical polymerization on a siloxane monomer and an organic monomer containing functional groups in the presence of a free radical initiator and a solvent to obtain a copolymer containing siloxane and the functional groups; (2) And (3) carrying out hydrolysis polycondensation reaction on the copolymer prepared in the step (1) in the presence of water and a catalyst to obtain the functional macroporous organosilicon adsorption material. According to the invention, functional groups are introduced into the main chain of the polymerized silicon-based precursor in advance, and then the siloxane is used for hydrolysis and polycondensation to form a crosslinking structure, so that the macroporous organic silicon adsorption material is prepared, has high porosity and rich functional groups on the surface, can be used for static adsorption and dynamic separation of heavy metal ions, has a static adsorption capacity of up to 568.18mg/g for uranyl ions, has good recycling performance, and has good application prospect in high-efficiency adsorption and separation of heavy metal ions.
Description
Technical Field
The invention relates to the technical field of adsorption materials, in particular to a functional macroporous organic silica gel material and a preparation method and application thereof.
Background
Heavy metal pollution causes serious harm to water and natural environment and human production and life. 90% of the waste liquid from nuclear power plants is low-radioactive, including radionuclides with radioactive hazards 235 U、 90 Sr、 137 Cs、 99 Tc, etc. Cr, pb, hg, cd and other heavy metal ions are toxic pollutants in industrial wastewater, enter organisms through food chains to cause bioaccumulation, and can cause kidney diseases, pain diseases, water diseases and even cancers. In order to realize effective purification of heavy metal ions and ensure sustainable development of ecological environment, various methods for removing heavy metal ions from wastewater have been developed at present, such as flocculation, precipitation, evaporation, solvent extraction, membrane separation, column separation and the like. The column separation method has the advantages of economy, simplicity, easiness in operation, less sludge generation and the like, and is favored in the field of heavy metal ion separation and removal. However, the concentration of heavy metal ions in various waste liquids is uneven, the types are complex,especially, the adsorption capacity and selectivity of the adsorption material are seriously affected by coexistence of a large amount of non-toxic ions such as alkali metal or alkaline earth metal. Therefore, development of a high-performance adsorption material for column separation, such as a functional porous material having an adjustable pore size and a high specific surface area, introducing functional groups into a framework, has been widely studied for efficient adsorption separation of heavy metal ions.
At present, very good static adsorption capacities of heavy metal ions are obtained in micro-pore and mesoporous materials such as covalent organic metal frameworks (MOFs), covalent organic framework materials (COFs), porous Organic Polymers (POPs), porous aromatic framework materials (PAFs), mesoporous silicon and the like. However, the small pore size can restrict the transmission of the adsorbate in the adsorption material, which results in unreachable or even blocking of the action sites in the pores of the material, affecting the adsorption capacity and the pressure of the separation column, and being unfavorable for practical application. The macroporous material is favorable for the transmission of adsorbate and can fully act on adsorption sites in the pore channels, but the low specific surface area leads to the reduction of modifiable sites so as to influence the adsorption efficiency.
Silicon-based materials are commonly used for column separation as a class of classical adsorptive separation materials. The surface of the material contains abundant hydroxyl groups, and the internal pore canal is also beneficial to the physical adsorption of adsorbates, but is directly used for the limited adsorption separation capacity. The current improvement on silicon-based materials mainly comprises surface modification, namely modification of functional groups on the surface of silica gel and ionization. However, surface grafting may cause blocking of pores inside the material, non-uniform distribution of organic functional groups and uncertain grafting efficiency, so that the adsorption capacity is still not high. Co-condensing siloxane and a small molecular silicon precursor containing organic functional groups is an effective method for directly preparing a functional silicon-based material, but the hydrolysis-polycondensation rates of the organic silicon precursor and the siloxane are obviously different, and the organic silicon precursor and the siloxane respectively tend to be homogeneously condensed, so that a considerable number of functional groups cannot be introduced into the silicon-based material as expected, and the adsorption capacity is improved to a limited extent; in addition, a template agent is needed to be added in the preparation process, so that organic functional groups on the surface of the material can be subjected to Soxhlet extraction and elution only under the heating condition of organic solvents such as ethanol and the like, and the problems of waste liquid, energy consumption, complex preparation process and the like exist.
Therefore, there is a need for a macroporous material with high adsorption capacity that can be effectively used for selective and efficient adsorption column separation of heavy metal ions.
Disclosure of Invention
The invention aims to solve the technical problem of providing a functional macroporous organic silica gel material, a preparation method and application thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
the first aspect of the invention provides a preparation method of a functional organic silica gel material, which comprises the following steps:
(1) The method comprises the steps of (1) carrying out free radical polymerization reaction on a siloxane monomer and an organic monomer containing functional groups in the presence of a free radical initiator and a solvent to obtain a copolymer containing siloxane and the functional groups;
(2) And (3) carrying out hydrolytic polycondensation reaction on the copolymer prepared in the step (1) in the presence of water and a catalyst to obtain the functional organic silica gel material.
Further, in the step (1), the siloxane monomer is selected from one or more of a compound shown in a formula (1) and a compound shown in a formula (2), and the structures of the formula (1) and the formula (2) are as follows:
wherein n is any integer from 0 to 10, R 1 Selected from one of hydrogen, C1-C3 alkyl, C1-C3 alkoxy, R 2 One selected from hydrogen and C1-C3 alkyl;
m is any integer from 0 to 10, R 3 Selected from one of hydrogen, C1-C3 alkyl, C1-C3 alkoxy, R 4 One selected from hydrogen and C1-C3 alkyl, R 5 One selected from hydrogen, methyl, ethyl, phenyl and benzyl.
Further, in the step (1), the organic monomer containing a functional group is selected from one or more of acrylonitrile, vinyl phosphoric acid, acrylamide, acrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, and a compound shown in a formula (3), and the structure of the formula (3) is as follows:
wherein x is any integer from 0 to 10, R 6 Selected from one of hydrogen, methyl and ethyl.
Further, in the step (1), the molar ratio of the siloxane monomer in the total monomer content is 10-95 mol%; the total monomer content is the total amount of siloxane monomers and organic monomers containing functional groups.
Further, in the step (1), the temperature of the free radical polymerization reaction is 60-150 ℃ and the reaction time is 1-48 hours.
Further, in the step (1), the free radical initiator is one or more of benzoyl peroxide, di-tert-butyl peroxide, azobisisobutyronitrile, azobisisovaleronitrile and ammonium persulfate.
Further, in the step (1), the molar ratio of the free radical initiator to the total monomer is 0.001-0.05%: 1; the total monomer amount is the total amount of the siloxane monomer and the organic monomer containing the functional group.
Further, in the step (1), the solvent is one or more of methanol, ethanol, isopropanol, dichloromethane, chloroform, acetone, butanone, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, acetonitrile and water.
In the step (2), the catalyst is one of hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide, potassium hydroxide and hydrazine hydrate, and the molar ratio of the catalyst to the total monomer is 0.001-0.02:1.
Further, in the step (2), the addition amount of water and the molar ratio of the siloxane structural units in the copolymer are 150-300:1.
Further, in the step (2), the temperature of the hydrolytic polycondensation reaction is 35-100 ℃ and the reaction time is 24-72 hours
In a second aspect, the invention provides a functional silicone material prepared by the preparation method in the first aspect.
Further, the average pore diameter of the functional organic silica gel material is 50 nm-100 μm.
The third aspect of the invention provides an application of the functional organic silica gel material in the second aspect as an adsorption material in adsorption separation of heavy metal ions.
Further, the adsorption separation includes static adsorption and dynamic adsorption.
Further, the static adsorption specifically comprises: and placing the functional organic silica gel material serving as a solid adsorbent into the waste liquid containing the heavy metal ions at the temperature of 25-50 ℃, and oscillating for 2-48 hours to adsorb the heavy metal ions in the waste liquid.
Further, the dynamic adsorption specifically comprises: placing functional organic silica gel material as filler into adsorption column at 25-50deg.C, injecting into simulated radioactive waste liquid containing heavy metal ions at 0.5-100 mL/min via peristaltic pump, and adsorbing heavy metal ions therein.
The invention has the beneficial effects that:
1. according to the preparation method, functional groups are introduced into the main chain of the polymerized silicon-based precursor in advance, and siloxane is hydrolyzed and polycondensed to form a crosslinking structure, so that the prepared functional macroporous organic silica gel material is simple in preparation method, mild in reaction condition and capable of realizing batch production; in addition, the functional organic silica gel material prepared by the invention has high porosity and large pore diameter, the surface is rich in functional groups, and the content of the functional groups and the pore diameter can be regulated and controlled by regulating the proportion of two monomers; the functional organic silica gel material with high functional group density has large adsorption capacity, the functional groups and the matrix material are tightly combined through covalent bonds, and the high-efficiency adsorption separation of heavy metal ions in the waste liquid is realized through the synergistic effect of physical and chemical adsorption.
2. The functional organic silica gel material prepared by the invention can be used as an adsorption material for static adsorption or dynamic adsorption of heavy metal ions in waste liquid, and the static adsorption capacity of the functional organic silica gel material reaches 568.18mg U/g, and is at an extremely high level in the adsorption capacity of the currently reported silicon-based adsorption material; in addition, the functional organic silica gel material prepared by the invention is used as an adsorption material to fill an adsorption column, is used for adsorbing waste liquid containing uranyl ions, shows excellent adsorption performance, basically has no change in adsorption performance of the eluted adsorption material, shows good recycling performance, and has good application prospect in the aspect of high-efficiency adsorption and separation of heavy metal ions.
Drawings
FIG. 1 is a flow chart of the preparation of a functional silicone material according to examples 1-3;
fig. 2 is an EDX diagram of the functional silicone gel material prepared in examples 1 to 3, (a): POsi-1, (B): POsi-2, (C): POsi-3;
fig. 3 is a graph of pore-performance mercury intrusion test run of the organic silica gel materials prepared in examples 1 to 3 and comparative example 1, and (a): mercury intrusion/mercury withdrawal curve, (B): a pore size distribution map;
fig. 4 is an adsorption isotherm of uranyl ions by the organic silica gel materials prepared in examples 1 to 3 and comparative example 1, a: OSi, b: POsi-1, c: POsi-2, d: POsi-3;
fig. 5 is a linear fitting diagram of langmuir adsorption of uranyl ions by the silicone gel materials prepared in examples 1 to 3 and comparative example 1, a: OSi, b: POsi-1, c: POsi-2, d: POsi-3;
fig. 6 is a frank-rich linear fitting chart of adsorption of uranyl ions by the organic silica gel materials prepared in examples 1 to 3 and comparative example 1, a: OSi, b: POsi-1, c: POsi-2, d: POsi-3;
FIG. 7 is a schematic diagram of a dynamic column separation experimental device of a functional organic silica gel material, wherein 1 is a feed liquid storage device, 2 is a peristaltic pump, 3 is a chromatographic column, and 4 is an eluent collecting device;
FIG. 8 is a graph of the penetration of a dynamic column separation experiment of a functional silicone material;
FIG. 9 is an elution profile after dynamic column uranyl ion adsorption of a functional silicone material;
fig. 10 is a graph showing the comparison of the functional silicone material before and after uranyl ion adsorption and after elution, i: before adsorption, ii: after adsorption is complete, iii: after the elution is complete.
Description of the embodiments
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Unless defined otherwise, 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 invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Example 1
The embodiment relates to a preparation method of a functional macroporous organic silica gel material, wherein the preparation process is shown in fig. 1, and specifically comprises the following steps:
(1) 13.3217 g (70 mmol) vinyltriethoxysilane (TEVS) and 4.9242 g (30 mmol) of diethyl vinylphosphate (DEVP) were added to 20 mL THF, and 0.1462 g (1 mmol) of di-tert-butanol peroxide was added and then deoxygenated sufficiently, and the reaction was continued with stirring at 120℃for 48 h.
(2) The polymer solution obtained by the above reaction was dispersed in 105.30 mL ultra pure water, 5.42: 5.42 mL concentrated HCl was added thereto, and the mixture was stirred at 35℃for 24: 24 h, and then placed in a muffle furnace for 2 days at 100 ℃. The obtained white powdery solid is alternately washed with water and ethanol for 3 times, and dried overnight in vacuum, so that the organic silica gel material POSi-1 is prepared with the yield of about 50%.
Example 2
The embodiment relates to a preparation method of a functional macroporous organic silica gel material, which is the same as that of the embodiment 1, and the organic silica gel material POSi-2 is prepared by only changing the feeding ratio of TEVS to DEVP to be 1:1.
Example 3
The embodiment relates to a preparation method of a functional macroporous organic silica gel material, which is the same as that of the embodiment 1, and the organic silica gel material POsi-3 is prepared by only changing the feeding ratio of TEVS to DEVP to be 3:7.
Comparative example
The comparative example was used as a control to directly prepare the silicone material OSi without the addition of the DEVP functional monomer, and the preparation process was as follows:
(1) 19.031 g (100 mmol) vinyltriethoxysilane was added to 20 mL THF, and after 0.1462 g (1 mmol) di-tert-butanol peroxide was added, sufficient oxygen was removed and the reaction was continued with stirring at 120℃48 h.
(2) The polymer solution obtained by the above reaction was dispersed in 105.30 mL ultra pure water, 5.42: 5.42 mL concentrated HCl was added thereto, and the mixture was stirred at 35℃for 24: 24 h, and then placed in a muffle furnace for 2 days at 100 ℃. The obtained white powdery solid was alternately washed 3 times with water and ethanol, and dried overnight in vacuo to obtain the organic silica gel material OSi.
(1) Influence of different monomer feed ratios on the content of functional groups in the organic silica gel material
The phosphorus content of the functional macroporous silicone materials prepared in examples 1 to 3 was tested by X-ray photoelectron spectroscopy (EDX), as shown in fig. 2, and the test results are summarized in table 1.
Table 1 phosphorus content of the organic silica gel materials prepared in examples 1 to 3
As can be seen from fig. 2 and the table above, as the proportion of functional monomer DEVP increases, the P content increases from 7.2% to 16.1%, with a corresponding increase in phosphate functionality, but the trend of increase is slowed down.
(2) Pore structure study of materials
The pore structures of the functional macroporous organic silica gel materials prepared in examples 1-3 and comparative examples were analyzed and characterized by mercury intrusion, the characterization results are shown in fig. 3, and the test results are summarized in table 2.
TABLE 2 pore Structure parameters of the organic silica gel materials prepared in examples 1 to 3 and comparative examples
As can be seen from fig. 3 and table 2, the porosity of the functional macroporous silicone materials was very high, about 70%. The pore diameter of the material reaches the micron level by introducing the phosphate, the higher the content of the phosphate, the larger the pore diameter, the pore diameter of POsi-3 even reaches 31.411 mu m, which indicates that as the hydrophilic functional group of the phosphate increases, more solvent is used as a pore-forming agent to be mixed in an organic silica gel crosslinked network structure in the hydrolysis-polycondensation forming process, and the larger the pore diameter of the prepared organic silica gel material; the large pore diameter and the ultrahigh porosity enable the feed liquid to fully soak into the adsorbent in the adsorption process, so that the excellent adsorption performance is realized.
(3) Static adsorption applications
The functional macroporous organic silica gel materials prepared in the examples 1-3 and the comparative example are used as adsorbents for static adsorption of uranyl ions in wastewater, and the specific operation is as follows:
to UO 2 (NO 3 ) 2 . 6H 2 O is dissolved in ultrapure water and diluted to the required concentration, and 1 wt percent nitric acid and 1 wt percent sodium hydroxide are used for adjusting the solution to a preset value pH of 6, so as to prepare the uranyl solution. 2.0. 2.0 mg adsorbent was added to the plastic tube and dispersed in 10 mL uranyl solution and the shaker was shaken overnight at room temperature and 120 rpm until adsorption equilibrated. And diluting the sample to the range of the instrument range, and measuring the concentration of uranyl solution before and after adsorption by using ICP-OES.
Balance adsorption capacity%q e ) Calculated by the formula (1):
(1)
in the formula (1)C 0 、C e (mg/L)、V(L) andM(g) Respectively representThe initial concentration of uranyl ions, the equilibrium concentration, the volume of uranyl solution and the mass of the adsorbent.
The langmuir model describes a monolayer adsorption process based on all adsorption sites having the same affinity for the target ion and each site being independent of the other, as shown in equation (2):
（2）
in the formula (2)q max (mg/g) represents the maximum adsorption capacity of the adsorbent, and b (L/mg) is the Langmuir constant, which is related to the affinity of the binding site. To be used forC e /q e For a pair ofC e Mapping and linear fitting, from slope and intercept, can be calculatedq max And b.
The frank model describes a multi-layer adsorption process, as shown in equation (3):
（3）
in (3)K F (mol 1-n L n Per g) and n are frank constants and mean coefficients, respectively, by logq e Log of pairC e The slope and intercept of the plot and linear fit are calculated.
The maximum adsorption capacity of the material was determined by adsorption isotherm test at pH 6 room temperature conditions. The concentration range is selected to be 5 x 10 -5 ~2.5ⅹ10 -3 Adsorption test is carried out on the uranyl solution with mol/L.q e Along with itC e The variation of (a) is shown in fig. 4, and the data of fitting adsorption isotherms with a langmuir model and a frank-rich model are shown in fig. 5 and 6, respectively, wherein the langmuir and frank-rich adsorption isotherms fitting parameters of different silicone materials are shown in table 3.
TABLE 3 Langmuir and Francisells adsorption isotherm fitting parameters for different organosilicon materials
From the correlation data of the two model fits, the correlation coefficient (R 2 ) The adsorption process of the material is described more conveniently, and adsorption sites are uniformly distributed on the surface of the material, because the adsorbent is worth hydrolyzing and polycondensing by polymerizing with TEVS and DEVP monomers, and functional groups are uniformly distributed in the whole material. The maximum static adsorption capacity of the functional macroporous organic silica gel material POsi-3 is 568.18mg/g, which is at an extremely high level in the adsorption capacity of the silicon-based adsorption materials reported at present. This is because POsi-3 material surface has abundant ligand and big aperture, can realize superior adsorbate transmission and adsorption performance.
(4) Dynamic adsorption applications
The POSI-3 prepared in example 3 was subjected to dynamic adsorption test by using a dynamic adsorption apparatus as shown in FIG. 7, and the specific operation is as follows:
loading 1 g adsorbent POSI-3 into an empty chromatographic column (model 4 g) containing 5×10 -5 Feed liquid of mol/L uranyl ion and pH=6+ -0.1 was injected into the column from the upper end by a peristaltic pump, and the flow rate was adjusted to 1.0 mL/min and kept constant. The effluent is collected by an automatic fraction collector, the content of uranyl ions is tested by ICP-OES, and a penetration curve is drawn.
After the effluent liquid and the feed liquid have the same concentration, the upper limit of the use of the adsorption column is reached, then 1M NaHCO is used 3 The aqueous solution was used as eluent, and the eluent was pumped from the upper end of the column by a peristaltic pump, and the flow rate was adjusted to 0.1 mL/min and kept constant. The effluent is collected by an automatic fraction collector, and the content of uranyl ions is tested by ICP-OES, and the elution is carried out until the concentration of the effluent is less than 0.1 ppm.
As shown in FIG. 8, the feed solution was continuously fed into the column by peristaltic pump, and after 2315/BV (column volume) treatment, the effluent had an initial concentration of 5% (C/C 0 Uranyl ion exudation, i.e. reaching the breakthrough point of the column, dynamic adsorption capacity 68.87, =5%mg/g. Because of the difference between the adsorption rate and the adsorption mass transfer efficiency, the chromatographic column does not reach adsorption equilibrium, has adsorption performance, and breaks down completely (C/C) after being processed to 4980 and BV (column volume) 0 =95%). Using 1M NaHCO 3 The eluent is repeatedly used for three times after elution, and the dynamic adsorption performance is basically unchanged.
As shown in FIG. 9, the organic silica gel material after uranium acyl ions are adsorbed is eluted by using 1M NaHCO 3 Eluting, and the highest effluent concentration reaches 22000 ppm. The eluent of six PE pipes (each of which is 1 column volume) which flows out first is collected, the eluent is obviously yellow-green, the color is gradually decreased along with the collection time sequence of the effluent, and the color is the characteristic color of uranyl ions, and the concentration efficiency is approximately 220 times. FIG. 10 shows the visual changes of the column before (i), after (ii) and after (iii) elution, the adsorption material in the column before adsorption is white, the adsorption material after uranyl ion adsorption is yellowish green, and NaHCO is used for the column after adsorption 3 The adsorption material recovers white after elution, and the phenomenon proves that the organic silica gel material prepared by the invention has good adsorption and elution performance on uranyl ions.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (7)
1. The preparation method of the functional organic silica gel material is characterized by comprising the following steps of:
(1) The method comprises the steps of (1) carrying out free radical polymerization reaction on a siloxane monomer and an organic monomer containing functional groups in the presence of a free radical initiator and a solvent to obtain a copolymer containing siloxane and the functional groups; the mol ratio of the siloxane monomer in the total monomer content is 10-95%;
(2) Carrying out hydrolytic polycondensation reaction on the copolymer prepared in the step (1) in the presence of water and a catalyst to obtain a functional organic silica gel material;
the siloxane monomer is a compound shown in a formula (1), and the structure of the formula (1) is as follows:
，
wherein n is any integer from 0 to 10, R 1 Selected from one of hydrogen, C1-C3 alkyl, C1-C3 alkoxy, R 2 One selected from hydrogen and C1-C3 alkyl;
the organic monomer containing the functional group is a compound shown in a formula (3), and the structure of the formula (3) is as follows:
，
wherein x is any integer from 0 to 10, R 6 Selected from one of hydrogen, methyl and ethyl.
2. The method according to claim 1, wherein in the step (1), the temperature of the radical polymerization reaction is 60 to 150 ℃ and the reaction time is 1 to 48 hours.
3. The preparation method of claim 1, wherein in the step (1), the free radical initiator is one or more of benzoyl peroxide, di-tert-butyl peroxide, azobisisobutyronitrile, azobisisovaleronitrile and ammonium persulfate, and the molar ratio of the free radical initiator to the total amount of monomers is 0.001-0.05:1;
the solvent is one or more of methanol, ethanol, isopropanol, dichloromethane, chloroform, acetone, butanone, tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, acetonitrile and water.
4. The preparation method of claim 1, wherein in the step (2), the catalyst is one of hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide, potassium hydroxide and hydrazine hydrate, and the molar ratio of the catalyst to the total monomer is 0.001-0.02:1.
5. The preparation method according to claim 1, wherein in the step (2), the addition amount of water and the molar ratio of the siloxane structural units in the copolymer are 150 to 300:1; the temperature of the hydrolytic polycondensation reaction is 35-100 ℃, and the reaction time is 24-72 hours.
6. A functional silicone material prepared by the preparation method according to any one of claims 1 to 5.
7. Use of the functional organic silica gel material as claimed in claim 6 as an adsorption material for adsorption separation of heavy metal ions.
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| CN105688844A (en) * | 2016-02-22 | 2016-06-22 | 东华理工大学 | Mesoporous chelate resin containing phosphorus-oxygen functional groups and method for separating and enriching uranium |
| US20170326530A1 (en) * | 2016-05-13 | 2017-11-16 | Ut-Battelle, Llc | Surface-functionalized polyolefin fibers and their use in methods for extracting metal ions from liquid solutions |
| CN106345324A (en) * | 2016-08-31 | 2017-01-25 | 山东天维膜技术有限公司 | Method for preparing hybridized ion exchange membrane |
| CN108786759A (en) * | 2018-06-15 | 2018-11-13 | 山东交通学院 | A kind of water-oil separating material and preparation method thereof with antifouling sterilization and Dye Adsorption function |
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| 尹晓康.微交联两亲聚丙烯酰胺的合成及性能应用研究.中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑.2020,(第11期),第20-21页. * |
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