CN114367202B - Preparation method of sulfonated polyether ether ketone/sulfonated mesoporous silica composite membrane material for alkali diffusion dialysis - Google Patents
Preparation method of sulfonated polyether ether ketone/sulfonated mesoporous silica composite membrane material for alkali diffusion dialysis Download PDFInfo
- Publication number
- CN114367202B CN114367202B CN202210030854.9A CN202210030854A CN114367202B CN 114367202 B CN114367202 B CN 114367202B CN 202210030854 A CN202210030854 A CN 202210030854A CN 114367202 B CN114367202 B CN 114367202B
- Authority
- CN
- China
- Prior art keywords
- speek
- sms
- sulfonated
- mesoporous silica
- composite membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/52—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a preparation method of a sulfonated polyetheretherketone/sulfonated mesoporous silica composite membrane material for basic diffusion dialysis, which comprises the steps of firstly preparing sulfonated mesoporous silica microspheres SMS by controlling the proportion of solvents in the synthesis process; then, carrying out sulfonation modification treatment on the polyether-ether-ketone by using concentrated sulfuric acid to obtain SPEEK; and then ultrasonically dispersing the SMS in DMF, adding SPEEK with a certain mass ratio, uniformly mixing, and forming a film to prepare the SPEEK/SMS composite film for basic diffusion dialysis with high ion flux and selectivity. The method can obtain the SPEEK/SMS composite membrane with obviously improved separation performance under the condition of lower addition of inorganic particles: hydroxyl dialysis coefficient (U) of composite membrane OH ) 0.007-0.018m/h, separation coefficient (S) 11.4-38.6, and Ion Exchange Capacity (IEC) 2.28-2.38mmol/g.
Description
Technical Field
The invention relates to a preparation method of a composite separation membrane, in particular to a preparation method of a sulfonated polyether-ether-ketone/sulfonated mesoporous silica composite membrane material for basic diffusion dialysis.
Background
Alkaline waste liquor is produced in many industrial processes, such as paper making, leather, printing and dyeing, and the direct discharge of waste can cause great harm to the environment. In the traditional process, the treatment method of the alkaline waste materials comprises an acid neutralization method, a concentration method and the like, but the further development of the methods is hindered by the defects of headache, high energy consumption, complex operation and the like of the treatment of byproduct salts of the methods. In recent years, the technology of alkali separation by membrane process has been gradually developed, including nanofiltration, electrodialysis, diffusion dialysis, etc., wherein the diffusion dialysis membrane separation technology is a process of achieving ion separation effect by using the driving of concentration gradient, does not need any external power supply, and has the characteristics of low energy consumption, environmental protection, simple operation, low installation economic cost, etc.
In the alkali recovery ion exchange membrane, by combining the characteristics of the organic polymer and the inorganic material, the inorganic material can be dispersed in the organic polymer to obtain a composite membrane of desired mechanical strength and separation performance. Mondal et al prepared silica functionalized aminoisophthalic crosslinked PVA membranes by a sol-gel process and used them for diffusion dialysis base recovery. Liu and the like adopt a free radical polymerization method to synthesize sodium poly (styrene sulfonate), are crosslinked with PVA, TEOS and APTS, and are used for an alkali diffusion dialysis process, and the separation factor is up to 25.7.Ashraf et al adopt a sol-gel method to crosslink two silicon-based functionalized sodium glutamate (GMSG and VMSG)/polyvinyl alcohol (PVA) to prepare novel hybrid Cation Exchange Membranes (CEMs), and when diffusion dialysis alkali recovery is carried out, the separation factor is 18.2-34.8.
The Sulfonated Mesoporous Silica (SMS) material has narrow pore size distribution, high specific surface area and stable performance, and the activity of the Sulfonated Mesoporous Silica (SMS) material is increased by introducing surface sulfonic acid groups, so the Sulfonated Mesoporous Silica (SMS) material has potential application prospects in the aspects of catalysis, biomedicine, adsorption and the like. Sulfonated Polyetheretherketone (SPEEK) has good thermal stability, chemical stability and excellent mechanical properties. Based on the method, the SMS is synthesized firstly, then the SMS is dispersed in the DMF, the SPEEK is dissolved in the dispersion liquid, and the membrane is formed after uniform mixing, so that the special basic composite membrane for diffusion dialysis with high ion flux and selectivity is prepared. The sulfonic acid group on the surface of the SMS and the sulfonic acid group carried by the SPEEK interact with each other at the interface of the two phases through hydrogen bonds, so that the interface compatibility between the two phases is improved, and a transfer channel for improving the ion transfer rate and selectivity is jointly constructed.
Disclosure of Invention
The invention provides a preparation method of a sulfonated polyether ether ketone/sulfonated mesoporous silicon oxide composite membrane material for alkali diffusion dialysis, so that a special composite membrane for alkali diffusion dialysis with good selectivity and separation performance is obtained, sulfonic acid groups carried by sulfonated polyether ether ketone and sulfonated mesoporous silicon oxide interact at the interface of two phases through hydrogen bonds, the interface compatibility between the two phases is improved, a transfer channel for improving the ion transfer rate and selectivity is jointly constructed, and the tradeoff effect between the ion flux and the selectivity in the diffusion dialysis process can be broken.
The invention relates to a preparation method of a sulfonated polyether ether ketone/sulfonated mesoporous silica composite membrane material for alkali diffusion dialysis, which comprises the steps of firstly preparing sulfonated mesoporous Silica Microspheres (SMS) by controlling the proportion of solvents in the synthesis process; then, carrying out sulfonation modification treatment on PEEK of 450G model by concentrated sulfuric acid to obtain SPEEK; and then ultrasonically dispersing SMS in DMF, adding SPEEK in a certain mass ratio, uniformly mixing and forming a film to prepare the special alkali diffusion dialysis composite film with high ion flux and selectivity. The method specifically comprises the following steps:
step 1: preparation of sulfonated mesoporous silica microspheres
Dissolving a template and CTAB in a mixed solvent of water, ethanol and ammonia water at normal temperature, preparing sulfonated mesoporous silica microspheres by using TEOS as a silicon source and gamma-mercaptopropyltriethoxysilane and hydrogen peroxide as surface modifiers, and removing the template in the mixed solvent of ethanol and hydrochloric acid by using a Soxhlet extraction method; and oxidizing the obtained sample by using a hydrogen peroxide solution, and oxidizing sulfydryl into sulfonic acid groups to obtain the sulfonated mesoporous silica microspheres.
And 2, step: sulfonation of PEEK
Using concentrated sulfuric acid as a solvent and a sulfonating agent at the same time, slowly dissolving PEEK in the concentrated sulfuric acid, controlling the sulfonation degree by controlling the sulfonation time and temperature, gradually pouring the solution into an ice water bath while stirring after the reaction is finished to terminate the reaction and precipitate SPEEK solids, then washing the SPEEK solids with deionized water until the water is neutral, and drying the SPEEK solids to obtain the SPEEK.
And step 3: preparation of SPEEK/SMS composite membrane
Ultrasonically dispersing SMS microspheres with a certain mass in DMF, adding SPEEK, and magnetically stirring at 70 ℃ for 12-24h to obtain a membrane casting solution; and then pouring the casting membrane liquid on a glass plate, scraping the thickness of the membrane control membrane by using a scraper, heating at 60 ℃, curing and forming, and drying in vacuum at 100 ℃ for 12 hours to obtain the SPEEK/SMS composite membrane.
In step 1, ethanol: water: ammonia water: molar ratio CTAB 19.9:80-124:10.4:0.3; the TEOS is added drop by drop during the addition, and the dropping rate is controlled to be 0.4-0.5mL/min; the reaction is carried out for 24 hours at 40 ℃ when the modified product is modified by gamma-mercaptopropyltriethoxysilane, and the ratio of a solvent to a sample during soxhlet extraction is 200mL of ethanol: 1.5g of HCl:1g of sample.
In order to control the shape of the mesoporous silica by adjusting the proportion of the solvent during the synthesis of the mesoporous silica, the invention preferably selects ethanol: water: ammonia water: CTAB molar ratio 19.9:80:10.4:0.3, obtaining the spherical mesoporous silica at the ratio.
In the step 2, at normal temperature, concentrated sulfuric acid is used for completely dissolving PEEK, and then temperature is raised for sulfonation, wherein the adding proportion of the PEEK and the concentrated sulfuric acid is 1g/10mL, the temperature used during sulfonation is 55 ℃, and the sulfonation time is controlled within 3-5h.
In step 3, the added mass of SMS is 2% -10% of the mass of SPEEK.
The method can obtain the SPEEK/SMS composite membrane with obviously improved separation performance under the condition of lower addition of inorganic particles: hydroxyl dialysis coefficient (U) of composite membrane OH ) 0.007-0.018m/h, separation coefficient (S) 11.4-38.6, and Ion Exchange Capacity (IEC) 2.28-2.38mmol/g.
Drawings
FIG. 1 is an SEM photograph of a sulfonated mesoporous silica synthesized in example 1 of the present invention;
FIG. 2 is ion exchange capacity performance test data for composite membranes prepared in examples 1-4 of the present invention;
FIG. 3 is separation performance test data for composite membranes prepared in examples 1-4 of the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1:
1. preparation of sulfonated mesoporous silica: at normal temperature, 18g of deionized water, 10.94g of ethanol and 4.45g of ammonia water are weighed and added into a 100mL three-neck flask for mixing and stirring uniformly, 1.37g of CTAB is added and stirred until the CTAB is completely dissolved, then 2.64g of TEOS is added dropwise for about 5min, and the mixture is magnetically stirred for 2h at 25 ℃; then adding 2mL of gamma-mercaptopropyltriethoxysilane, and magnetically stirring for 24h at 40 ℃; suction filtration, drying, then removing the template by using a Soxhlet (wherein 200mL of ethanol is 1.5g of HCl.
2. Sulfonation of PEEK: drying polyetheretherketone in an oven at 80 ℃ for 12h in advance to remove water, weighing 50mL concentrated sulfuric acid, adding into a 100mL three-neck flask, weighing 5g polyetheretherketone, gradually adding polyetheretherketone under mechanical stirring, stirring at normal temperature until completely dissolving, heating an oil bath to 55 ℃, heating and stirring for 3.5h. After the reaction is finished, pouring the reaction solution into an ice-water bath under mechanical stirring to terminate the reaction and simultaneously precipitate solids, then washing the reaction solution by deionized water until the solution soaking the solids is neutral, and then drying the obtained solids in vacuum at 100 ℃ for 12h to obtain SPEEK with the sulfonation degree of 82%.
3. Preparing a composite membrane: adding 0.03g of spherical mesoporous silica with the mass fraction of 2% of SPEEK into 10ml DMF for ultrasonic dispersion for 1h, pouring into a three-neck flask, then adding 1.5g of SPEEK, magnetically stirring for 24h at 70 ℃ to obtain a membrane casting solution, then pouring the membrane casting solution on a glass plate, scraping the thickness of a membrane control membrane by using a scraper, placing the glass plate on a heating plate, heating at 60 ℃ to solidify and mold the membrane, and then drying the membrane in vacuum for 12h at 100 ℃.
4. And (3) performance testing:
(1) Ion Exchange Capacity (IEC) test: the film was dried in an oven overnight at 60 ℃, weighed to record mass, and soaked in 1 mh 2 SO 4 Washing with deionized water for 12 hr until the water for soaking the membrane is neutral, soaking the membrane in 1M NaCl solution for 24 hr, and replacing with H + Finally, the membrane-soaked NaCl solution was titrated with a 0.02M NaOH solution.
(2) And (3) diffusion dialysis process: before testing, the membranes were soaked in 1M NaOH/Na 2 WO 4 Taking out from the mixed alkali for 1h, washing the membrane to clean, and testing, wherein the effective area of the membrane is 6.0cm 2 Adding 100mL deionized water and 100mL mixed alkali solution into the cell chambers at two sides of the membrane, respectively, mechanically stirring to avoid concentration polarization, pouring out the solutions at two sides after 1h, and measuring OH-ion concentration at the alkali side and water side by 0.1M HCl solution titration method to obtain dialysis coefficient of hydroxyl (U) OH ) Determination of WO by UV spectrophotometry 4 2- Concentration to obtain the dialysis coefficient (U) of tungstate radical W ) Thereby obtaining the separation coefficient (S) of the membrane.
Wherein M is the amount of permeating ions, A is the effective mass transfer area, t is the time,
and
respectively representing the ion concentration of the diffusion liquid at time 0 and t,
representing the ion concentration of the dialysate at time t.
Through tests, the performance parameters of the composite film obtained in the embodiment are as follows: ion exchange capacity of 2.38mmol/g, dialysis coefficient of hydroxide (U) OH ) 0.0118m/h, separation coefficient 23.9.
Example 2:
the preparation method and performance test of the composite membrane in this example are the same as those in example 1, except that the mass of the spherical mesoporous silica added in this example is 0.06g.
Through tests, the performance parameters of the composite membrane obtained in the embodiment are as follows: ion exchange capacity of 2.36mmol/g, dialysis coefficient of hydroxyl group (U) OH ) 0.0178m/h and a separation coefficient of 38.6.
Example 3:
the preparation method and performance test of the composite membrane in this example are the same as those in example 1, except that the mass of the spherical mesoporous silica added in this example is 0.09g.
Through tests, the performance parameters of the composite film obtained in the embodiment are as follows: ion exchange capacity of 2.35mmol/g, dialysis coefficient of hydroxyl (U) OH ) 0.0137m/h and a separation coefficient of 25.7.
Example 4:
the preparation method and performance test of the composite membrane in this example are the same as those in example 1, except that the mass of the spherical mesoporous silica added in this example is 0.12g.
Through tests, the performance parameters of the composite film obtained in the embodiment are as follows: ion exchange capacity of 2.28mmol/g, dialysis coefficient of hydroxyl group (U) OH ) 0.0070m/h, separation coefficient 11.4.
Fig. 1 is an SEM image of the mesoporous silica prepared in example 1 of the present invention, and it can be seen that it has a spherical shape with a spherical diameter of about 200nm.
Fig. 2 is an IEC test of the composite membranes prepared in examples 1 to 4, and it can be seen that when the mesoporous silica is added in an amount of 2%, the IEC is up to 2.38, and decreases as the addition amount increases.
Fig. 3 is a separation performance test of the composite membranes prepared in examples 1 to 4, and it can be seen that the separation performance of the composite membranes shows a tendency of increasing first and then decreasing as the content of mesoporous silica increases.
The above-mentioned embodiments of the present invention are not intended to limit the scope of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (5)
1. A preparation method of a sulfonated polyether ether ketone/sulfonated mesoporous silica composite membrane material for basic diffusion dialysis is characterized by comprising the following steps:
firstly, preparing sulfonated mesoporous silica microspheres SMS by controlling the proportion of solvents in the synthesis process; then, carrying out sulfonation modification treatment on the polyether-ether-ketone by using concentrated sulfuric acid to obtain SPEEK; then ultrasonically dispersing SMS in DMF, adding SPEEK in a certain mass ratio, uniformly mixing, and forming a film to prepare the special alkali diffusion dialysis composite film with high ion flux and selectivity; the method comprises the following steps:
step 1: preparation of sulfonated mesoporous silica microspheres
Dissolving a template agent CTAB in a mixed solvent of water, ethanol and ammonia water at normal temperature, preparing sulfonated mesoporous silica microspheres by using TEOS as a silicon source and gamma-mercaptopropyltriethoxysilane and hydrogen peroxide as surface modifiers, and removing the template in the mixed solvent of ethanol and hydrochloric acid by using a Soxhlet extraction method; oxidizing the obtained sample by using a hydrogen peroxide solution, and oxidizing sulfydryl into sulfonic acid groups to obtain sulfonated mesoporous silica microspheres SMS;
and 2, step: sulfonation of PEEK
Using concentrated sulfuric acid as a solvent and a sulfonating agent at the same time, slowly dissolving polyether-ether-ketone in the concentrated sulfuric acid, controlling the sulfonation degree by controlling the sulfonation time and temperature, gradually pouring the solution into an ice-water bath while stirring after the reaction is finished to terminate the reaction and precipitate SPEEK solids, then washing the SPEEK solids with deionized water until the water is neutral, and drying the SPEEK solids to obtain SPEEK;
and step 3: preparation of SPEEK/SMS composite membrane
Ultrasonically dispersing SMS microspheres with a certain mass in DMF, adding SPEEK, and magnetically stirring at 70 ℃ for 12-24h to obtain a membrane casting solution; then pouring the casting membrane liquid on a glass plate, scraping the thickness of the membrane control membrane by using a scraper, heating at 60 ℃, curing, forming and vacuum drying to obtain an SPEEK/SMS composite membrane;
in step 1, ethanol: water: ammonia water: molar ratio CTAB 19.9:80-124:10.4:0.3;
in step 3, the added mass of SMS is 2% -6% of the mass of SPEEK.
2. The method of claim 1, wherein:
in the step 1, TEOS is added dropwise while the TEOS is added, and the dropping rate is controlled to be 0.4-0.5mL/min.
3. The method of claim 1, wherein:
in the step 1, the reaction temperature is 40 ℃ and the reaction time is 24h when the gamma-mercaptopropyltriethoxysilane is added for modification.
4. The method of claim 1, wherein:
in step 1, the ratio of solvent to sample used in the extraction is 200mL ethanol: 1.5g of HCl:1g of sample.
5. The method of claim 1, wherein:
in the step 2, completely dissolving PEEK by concentrated sulfuric acid at normal temperature, and then heating for sulfonation, wherein the adding proportion of the PEEK to the concentrated sulfuric acid is 1g/10mL, the temperature used during sulfonation is 55 ℃, and the sulfonation time is controlled to be 3-5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210030854.9A CN114367202B (en) | 2022-01-12 | 2022-01-12 | Preparation method of sulfonated polyether ether ketone/sulfonated mesoporous silica composite membrane material for alkali diffusion dialysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210030854.9A CN114367202B (en) | 2022-01-12 | 2022-01-12 | Preparation method of sulfonated polyether ether ketone/sulfonated mesoporous silica composite membrane material for alkali diffusion dialysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114367202A CN114367202A (en) | 2022-04-19 |
| CN114367202B true CN114367202B (en) | 2023-01-31 |
Family
ID=81143852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210030854.9A Active CN114367202B (en) | 2022-01-12 | 2022-01-12 | Preparation method of sulfonated polyether ether ketone/sulfonated mesoporous silica composite membrane material for alkali diffusion dialysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114367202B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115178103B (en) * | 2022-07-12 | 2024-04-19 | 安徽大学 | Method for preparing SPVDF porous cation exchange membrane by adopting thermally induced phase separation process and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10207411A1 (en) * | 2002-02-21 | 2003-09-04 | Daimler Chrysler Ag | Preparation of composite membranes from branched polyalkoxysilane, useful in production of polymer electrolyte membrane fuel cells, comprises mixing branched polyalkoxysilane and organic proton conductor |
| CN103897336A (en) * | 2014-03-13 | 2014-07-02 | 天津大学 | Sulfonated polyether-ether-ketone/phosphorylated mesoporous silica hybrid membrane preparation and application |
| CN104209023B (en) * | 2014-08-27 | 2016-08-17 | 天津大学 | Sulfonated polyether-ether-ketone-sulfonation silicon dioxide microsphere hybridized film and preparation and application |
| CN105837842B (en) * | 2016-03-21 | 2018-12-21 | 安徽大学 | A method of diffusion dialysis cationic membrane is prepared using mesopore silicon oxide |
| CN109590025B (en) * | 2018-11-30 | 2021-11-19 | 安徽大学 | Preparation method of polyvinyl alcohol/phosphotungstic acid loaded mesoporous silica hybrid membrane special for basic diffusion dialysis |
| CN113041849B (en) * | 2021-04-07 | 2023-02-03 | 合肥星邦新材料科技有限公司 | Method for preparing hydrogenated nitrile rubber/mesoporous silica composite cation exchange membrane by utilizing semi-interpenetrating network polymerization method and application thereof |
-
2022
- 2022-01-12 CN CN202210030854.9A patent/CN114367202B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114367202A (en) | 2022-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109174023B (en) | Nano-cellulose crosslinked graphene/chitosan aerogel and preparation method and application thereof | |
| Wu et al. | QPPO/PVA anion exchange hybrid membranes from double crosslinking agents for acid recovery | |
| CN106492646B (en) | A kind of preparation method for the preferential mesoporous silicon oxide hybridized film of alcohol infiltration evaporation thoroughly | |
| CN102974238B (en) | Film surface hydrophilicity modifying method through PVA grafting by utilizing biological preparation | |
| Wu et al. | Cation exchange PVA/SPPO/SiO2 membranes with double organic phases for alkali recovery | |
| Gu et al. | PVA-based hybrid membranes from cation exchange multisilicon copolymer for alkali recovery | |
| CN106750051B (en) | The modified Nano material and preparation method thereof of heteropoly acid stability in a kind of raising proton exchange membrane | |
| CN114367202B (en) | Preparation method of sulfonated polyether ether ketone/sulfonated mesoporous silica composite membrane material for alkali diffusion dialysis | |
| CN103304979B (en) | Phosphorylation titanium dioxide hollow sphere-filled sulfonated polyether ether ketone film as well as preparation and application | |
| Miao et al. | Sulfonated poly (2, 6-dimethyl-1, 4-phenyleneoxide)/nano silica hybrid membranes for alkali recovery via diffusion dialysis | |
| CN106188591B (en) | The preparation method of photo-crosslinking sulfonated polysulfone amberplex | |
| CN113209841B (en) | Mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol, and preparation method and application thereof | |
| CN109289531A (en) | A kind of preparation method of the dimethyl silicone polymer for organic solvent nanofiltration/meso-porous nano silicon composite membrane | |
| CN113262648B (en) | Lithium ion selective permeation membrane and application thereof | |
| CN105837842B (en) | A method of diffusion dialysis cationic membrane is prepared using mesopore silicon oxide | |
| CN110433673A (en) | A kind of quaternary ammonium salt functionalization polysulfones-nano-attapulgite stone hybrid anion exchange membrane and preparation method thereof | |
| Li et al. | Preparation and properties of sulfonated poly (2, 6-dimethyl-1, 4-phenyleneoxide)/mesoporous silica hybrid membranes for alkali recovery | |
| CN107140644A (en) | A kind of room temperature has the SiO of fluid behavior2Porous liquid and preparation method | |
| EP3611218A1 (en) | Method for hydrophilizing porous membrane and method for manufacturing ion-exchange membrane using same | |
| Dai et al. | Crosslinked PVA-based hybrid membranes containing di-sulfonic acid groups for alkali recovery | |
| CN112717731A (en) | Ion conductive film and preparation method thereof | |
| Miao et al. | Hybrid membranes from sulphonated poly (2, 6-dimethyl-1, 4-phenylene oxide) and sulphonated nano silica for alkali recovery | |
| CN112742222A (en) | Preparation method of PVC aliphatic zwitterionic ion exchange membrane | |
| CN113041849B (en) | Method for preparing hydrogenated nitrile rubber/mesoporous silica composite cation exchange membrane by utilizing semi-interpenetrating network polymerization method and application thereof | |
| JP2009185250A (en) | Manufacturing method of isolated polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |