CN114437339B - Preparation method and application of high-absorbance honeycomb polyamide membrane - Google Patents
Preparation method and application of high-absorbance honeycomb polyamide membrane Download PDFInfo
- Publication number
- CN114437339B CN114437339B CN202011207844.5A CN202011207844A CN114437339B CN 114437339 B CN114437339 B CN 114437339B CN 202011207844 A CN202011207844 A CN 202011207844A CN 114437339 B CN114437339 B CN 114437339B
- Authority
- CN
- China
- Prior art keywords
- film
- polyamide
- honeycomb
- acid
- casting
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a simple preparation method of a cellular polyamide 6 membrane, which is characterized in that the cellular polyamide 6 membrane with rapid self-stretching performance is obtained through a classical non-solvent induced phase separation process by grafting modification and mixing of a pore-forming agent. The structural morphology of the polyamide 6 film is changed due to the graphene oxide, more importantly, the graphene oxide is used as a photo-thermal conversion layer, and the heat insulation performance of the material is improved due to the fact that a large number of pore defects exist. The solar energy evaporation system greatly improves the efficiency of steam generation in a local heating mode; the cellular surface roughness provides the system with a light absorption of approximately 99.9%. The honeycomb polyamide 6 film has the characteristics of low cost, high stability and strong acid and alkali corrosion resistance when applied to solar evaporation, is suitable for various scenes such as sea water desalination, sewage treatment and the like, has excellent performance, and has huge practical application value and excavation potential.
Description
Technical Field
The invention relates to the field of new materials, in particular to preparation and application of a honeycomb polyamide membrane with high light absorbance and high water transmission.
Background
The development of human society has greatly accelerated the speed of global energy consumption, especially in natural environments and fresh water reserves. Because of the shortage of various sources of energy, people begin to look at technologies and energy exploration capable of sustainable development and regeneration, such as wind energy, nuclear energy, tidal energy, biomass energy, solar energy and the like; among them, solar energy is recognized as a green energy source having the most development value for coping with global environmental pollution and water resource shortage problems in the 21 st century due to its huge energy reserve and regeneration capability and convenience of acquisition in nature. Meanwhile, with rapid development and application of solar technology, solar collectors, solar thermal power generation, large-scale solar concentration systems, solar evaporation and other widely applied technologies based on solar energy gradually show potential practical application values and development prospects in fields related to human life such as sea water desalination, sewage treatment and the like.
At present, with the proposal of solar evaporation concept, namely, the requirement of improving the photo-thermal conversion efficiency and the water vapor generation rate through the construction of local heating sites, various photo-thermal materials such as biomass carbon, plasma absorbers, carbon materials, a plurality of layers of composite materials and the like are developed. Various modes and forms are designed to realize the improvement of light absorptivity and efficient photo-thermal conversion performance, and simultaneously, good evaporation performance is also obtained. However, due to the complexity of the practical application environment, the stability of the solar evaporation system is particularly important, and the most ideal result is to obtain the efficient and stable solar evaporation system suitable for various complex environments through the simplest preparation process.
The polyamide 6 is widely applied to various engineering plastics as a material with good mechanical stability and corrosion resistance, and is easy to process and stable in performance. However, the performance of polyamide plastics in practical application is seriously affected by the moisture absorption of the polyamide plastics, so the polyamide plastics are often regarded as a performance defect. However, there is an urgent need for such "film" materials with continuous water supply capability in solar energy evaporation systems, while the hygroscopic properties of polyamide 6 films meet this performance requirement. At the same time, the stable mechanical property of the polyamide 6 composite material also provides possibility for the successful application of the polyamide membrane in complex environments. Therefore, we propose a preparation method of a honeycomb film material with high absorbance and high water transmission based on polyamide 6 modification, and the honeycomb polyamide 6 film obtained through a classical non-solvent induced phase separation (NIPS) process has the advantages of simple and convenient procedure, low cost, strong acid and alkali resistance stability, and more importantly, the evaporation performance of the polyamide film in solar evaporation experiments is greatly improved, meanwhile, excellent performance effects are obtained in multiple scenes such as sea water desalination, sewage treatment and the like, and huge excavation potential is shown.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method of a honeycomb film material with high light absorbance and high water transmission based on polyamide 6 modification. The surface morphology and the structure of the polyamide 6 film are regulated and controlled by adding graphene oxide and pore-forming agent lithium chloride, so that the water supply capacity required by an evaporation system is improved, and a large number of local hot spots are successfully constructed on the surface of the film, so that the light absorption rate and the evaporation performance of the whole system are greatly improved.
For this purpose, the technical scheme of the invention is as follows:
synthesis of polyamide 6 (PA 6) composite: firstly, a one-pot method is adopted, polymer monomers are added into a four-neck flask, 0.1 to 2 weight percent of dried grafting modified monomers are added, after heating and melting, mechanical stirring is carried out to uniformly disperse the monomers, the temperature is programmed to 220 ℃, and the reaction is carried out for 2 hours at constant temperature; then heating to 260 ℃, reacting for 2-8 hours at constant temperature, and stopping the reaction; the polymerization product is rapidly poured out of the reaction vessel and cooled to obtain the composite material.
Preparing a casting solution: cutting the composite material into small pieces by using a diagonal pliers, putting the small pieces into pure water for steaming, and drying the product to constant weight in a vacuum oven. Slicing the raw materials into an acid solution, dissolving the raw materials into 10 to 25 weight percent of casting solution, then adding 1 to 20 weight percent of pore-forming agent, magnetically stirring the mixture for 10 hours at normal temperature until the mixture is uniformly dispersed, and carrying out vacuum defoaming for 60 to 120 minutes to obtain the casting solution.
Preparing a coagulation bath: three types of coagulation baths are included; wherein the first coagulating bath is an air bath, the second coagulating bath is a mixed solution of deionized water and 0.05-1.0wt% of ethanol, and the third coagulating bath is deionized water.
Preparation of polyamide 6 film: pouring a proper amount of casting film liquid on a film scraping machine uniformly, wherein the film scraping speed is set to be 30-60 mm/s, the temperature is set to be 25-30 ℃, then the casting film liquid is scraped out on the film scraping machine at a uniform speed, after the air bath is stabilized for 5-30 seconds, the casting film liquid is immersed in a second coagulating bath, is coagulated into a film in a phase inversion process, is taken out after 5-10 minutes, is immersed in a deionized water coagulating bath and is stored for standby, and is cut into films with proper sizes when in use.
Further, the polymer monomer in the step 1) is one or a mixture of any proportion of caprolactam and 6-aminocaproic acid, caprolactam, polyamide 6 and polyamide 66.
Further, the grafting modification monomer in the step 1) is Graphene Oxide (GO), reduced graphene oxide (rGO), carbon Black (CB), carbon Nanotubes (CNT), molybdenum disulfide (MuS) 2 ) One or a mixture of any proportion of the components.
Further, the specific gravity of the graft modification monomer in the step 1) is 0.1 to 2wt%.
Further, the acid liquor in the step 2) is one or a mixed solvent of any proportion of formic acid, acetic acid, hydrochloric acid, sulfuric acid and nitric acid.
Further, the concentration of the casting solution in the step 2) is 10 to 25wt%.
Further, the pore-forming agent in the step 2) is lithium chloride (LiCl) or calcium chloride (CaCl) 2 ) Lithium perchlorate (LiClO) 4 ) One or a combination of polyvinyl pyridine, polyoxyethylene and polyvinyl alcohol.
Further, the specific gravity of the pore-forming agent in the step 2) is 1 to 20wt%.
Further, the second coagulation bath in step 3) may also be methanol (CH) 3 OH), chloroform (CHCl) 3 ) Hydrogen peroxide (H) 2 O 2 ) Mixing one or any proportion of hydrogen chloride (HCl) into the coagulating bath.
Further, the film scraping speed in the step 4) is set to be 30-60 mm/s, and the temperature is 25-30 ℃.
Further, the polyamide membrane in step 4) undergoes a phase inversion in the second coagulation bath for a period of time ranging from 5 to 10 minutes.
Compared with the prior art, the method has the following advantages:
according to the invention, the polyamide composite material is subjected to grafting modification, so that the hydrophilicity of the polyamide membrane is greatly improved on the basis of keeping the self water absorption of the material, the porosity is obviously improved, and the moisture evaporated on the surface of the polyamide membrane is timely and continuously supplied.
The pore-forming agent improves the pore distribution and the surface morphology of the polyamide 6 film, the surface roughness is obviously increased, and the light absorptivity in the wavelength range of 200-2500nm is as high as 99.8%.
The invention has low manufacturing cost, simple and convenient process, good film forming property, strong acid and alkali resistance stability, high removal rate of various dyes and salts up to 99.9 percent, and is suitable for being used in various complex environments.
Drawings
FIG. 1 is a scanning electron microscope image of the honeycomb polyamide 6 film obtained in example 1. The surface morphology (a) of the pure polyamide 6 film, the water contact surface morphology (b) of the honeycomb polyamide 6 film, the honeycomb surface morphology (c) and the pore morphology (d) of the section;
FIG. 2 is a scanning electron microscope image of the surface morphology of the water contact surface (a) and the honeycomb (b) of the honeycomb polyamide 6 film obtained in comparative example 1;
FIG. 3 is a scanning electron microscope image of the surface morphology of the water contact surface (a) and the honeycomb (b) of the honeycomb polyamide 6 film obtained in comparative example 2;
FIG. 4 is a true color confocal photograph of the honeycomb polyamide 6 film obtained in example 1;
FIG. 5 is an infrared spectrum of a honeycomb polyamide 6 film obtained in example 1;
FIG. 6 is an infrared photograph showing the temperature distribution of the honeycomb polyamide 6 film obtained in example 1 before and after 60 minutes of irradiation with light.
Detailed Description
The technical scheme of the present invention will be described in detail with reference to examples.
Example 1
1) Synthesis of polyamide 6 composite: firstly, adopting a one-pot method, adding 3g of caprolactam and 27g of 6-aminocaproic acid as reaction monomers into a four-neck flask, adding 0.5wt% of dried graphene oxide, heating and melting, mechanically stirring to uniformly disperse the graphene oxide, heating to 220 ℃ with a program, and reacting for 2 hours at a constant temperature; then heating to 260 ℃, reacting for 8 hours at constant temperature, and stopping the reaction; the polymerization product is rapidly poured out of the reaction vessel and cooled to obtain the composite material.
2) Preparing a casting solution: cutting the composite material into small pieces by using a diagonal pliers, putting the small pieces into pure water for steaming, and drying the product to constant weight in a vacuum oven. Slicing the raw materials into a proper amount, dissolving in a formic acid solution, preparing a casting solution with the weight percent of 20%, then adding a pore-forming agent lithium chloride with the weight percent of 9%, magnetically stirring for 10 hours at normal temperature until the materials are uniformly dispersed, and carrying out vacuum defoaming for 60 minutes to obtain the casting solution.
3) Preparing a coagulation bath: three types of coagulation baths are included; wherein the first coagulation bath is an air bath, the second coagulation bath is a mixed solution of deionized water and 1.0wt% of ethanol, and the third coagulation bath is deionized water.
Scraping a polyamide 6 film: pouring a proper amount of casting film liquid on a film scraping machine uniformly, wherein the film scraping speed is set to be 50 mm/s, the temperature is 25 ℃, then scraping the casting film liquid on the film scraping machine at a uniform speed, immersing the casting film liquid in a second coagulating bath after the air bath is stabilized for 10 seconds, coagulating the casting film into a film in a phase inversion process, taking out the casting film after 10 minutes, immersing the casting film liquid in a deionized water coagulating bath for later use, and cutting the casting film into films with proper sizes when the casting film is used.
The Scanning Electron Microscope (SEM) morphology of the polyamide 6 membrane obtained in this example is shown in fig. 1, and from fig. 1b, it is evident that the pore distribution and pore size increase at the water contact surface are observed, while the surface tends to be smoother. From fig. 1c and 1d, a cellular surface morphology and a cross-sectional pore morphology can be observed. From the true color confocal photograph of fig. 4, it can be seen that the honeycomb surface roughness is significantly increased, thus increasing the number of refraction times of light, so that the light absorptivity is enhanced. Meanwhile, it can be observed from the infrared spectrogram of FIG. 5 that the polyamide film has a wavelength of 2860cm due to the stretching vibration of the C-H bond peculiar to the PA6 segment -1 And 2930cm -1 A stronger new peak appears respectively; at 1640cm -1 Characteristic absorption peaks of the C=0 group stretching vibration in the amide bond appear; at the same time at 1536cm -1 New peaks of bending vibration of N-H bond and stretching vibration of C-N bond in amide group appear, confirming successful preparation of honeycomb polyamide 6 film.
Under the conditions of the ambient temperature of about 25 ℃ and the relative humidity of 35-45%, the test calculates that the cellular polyamide 6 film respectively has the illumination power of 1kw m -2 、2kw m -2 The following results were obtained by illuminating for 60 minutes the water evaporation amount, evaporation rate, evaporation efficiency, and light absorption rate of the film:
comparative example 1
The preparation process is basically the same as in example 1, except that: in the step 2), the pore-forming agent lithium chloride is changed into polyvinyl alcohol.
The SEM morphology of the honeycomb polyamide 6 film obtained in the comparative example is shown in fig. 2a and 2b, which show the water contact surface and the honeycomb surface morphology, respectively, and the difference in pore distribution and the change in pore size of the film surface can be clearly observed.
Under the conditions of the ambient temperature of about 25 ℃ and the relative humidity of 35-45%, the test calculates that the cellular polyamide 6 film respectively has the illumination power of 1kw m -2 、2kw m -2 The infrared photograph of the temperature distribution before and after the irradiation of light is shown in fig. 6, and the following results are obtained:
as can be seen from comparison with the comparative examples, when the concentration of the pore-forming agent in the comparative examples is changed to polyvinyl alcohol, the evaporation capacity, evaporation rate and evaporation efficiency of water and the light absorptivity of the film are significantly reduced, and the above-mentioned tests show that the pore distribution and pore size of the film surface are determined by the types of the pore-forming agent, so that the stable continuity of the water supply channel and the water supply system is affected, and in addition, the light absorptivity is also affected due to the change of the surface morphology. Therefore, the choice of the appropriate pore former type is important for the solar evaporation performance.
Comparative example 2
1) Synthesis of polyamide 6 composite: firstly, adopting a one-pot method, adding 3g of caprolactam and 27g of 6-aminocaproic acid as reaction monomers into a four-neck flask, adding 0.5wt% of dried graphene oxide, heating and melting, mechanically stirring to uniformly disperse the graphene oxide, heating to 220 ℃ with a program, and reacting for 2 hours at a constant temperature; then heating to 260 ℃, reacting for 8 hours at constant temperature, and stopping the reaction; the polymerization product is rapidly poured out of the reaction vessel and cooled to obtain the composite material.
2) Preparing a casting solution: cutting the composite material into small pieces by using a diagonal pliers, putting the small pieces into pure water for steaming, and drying the product to constant weight in a vacuum oven. Slicing the raw materials into a proper amount, dissolving in a formic acid solution, preparing a casting solution with the weight percent of 20%, then adding a pore-forming agent lithium chloride with the weight percent of 9%, magnetically stirring for 10 hours at normal temperature until the materials are uniformly dispersed, and carrying out vacuum defoaming for 60 minutes to obtain the casting solution.
3) Preparing a coagulation bath: including two types of coagulation baths; wherein the first coagulation bath is an air bath, and the second coagulation bath is deionized water.
Scraping a polyamide 6 film: pouring a proper amount of casting film liquid on a film scraping machine uniformly, wherein the film scraping speed is set to be 50 mm/s, the temperature is 25 ℃, then scraping the casting film liquid on the film scraping machine at a uniform speed, immersing the casting film liquid in a second coagulating bath after the air bath is stabilized for 10 seconds, coagulating the casting film into a film in a phase inversion process, taking out the casting film after 10 minutes, immersing the casting film liquid in a deionized water coagulating bath for later use, and cutting the casting film into films with proper sizes when the casting film is used.
The Scanning Electron Microscope (SEM) morphology of the flat plate membrane obtained in this example is shown in fig. 3, and the reduction of pore size and the distribution of the surface of the water contact surface are clearly observed from fig. 3 a. From fig. 3b, the non-uniformity of the surface honeycomb distribution and the morphology of the breakage can be observed.
Under the conditions of the ambient temperature of about 25 ℃ and the relative humidity of 35-45%, the test calculates that the cellular polyamide 6 film respectively has the illumination power of 1kw m -2 、2kw m -2 Under the condition of illumination for 60min, the water evaporation capacity, the evaporation rate and the evaporation efficiency and the light absorptivity of the film are obtained
The following are provided:
examples 2 to 6
The preparation process is basically the same as in example 1, except that: changing the concentration of GO in step 2).
The following tables are specific embodiments of examples 2-5
Examples 7 to 10
The preparation process is basically the same as in example 1, except that: changing the concentration of the porogen in step 2).
The invention has been described in more detail with reference to the accompanying drawings and tables, but the invention is not limited by the above-described modes, and various modifications made by adopting the method concept and technical scheme of the invention are within the scope of the invention.
Claims (3)
1. A method for preparing a high-absorbance honeycomb polyamide 6 film, which is characterized by comprising the following steps:
1) Synthesis of polyamide 6 composite: firstly, a one-pot method is adopted, polymer monomers are added into a four-neck flask, 0.1 to 2 weight percent of dried grafting modified monomers are added, after heating and melting, mechanical stirring is carried out to uniformly disperse the monomers, the temperature is programmed to 220 ℃, and the reaction is carried out for 2 hours at constant temperature; then heating to 260 ℃, reacting for 2-8 hours at constant temperature, and stopping the reaction; rapidly pouring the polymerization product out of the reaction vessel, and cooling to obtain a composite material; the polymer monomer is one or a mixture of caprolactam and 6-aminocaproic acid in any proportion; the grafting modification monomer is graphene oxide (G0);
2) Preparing a casting solution: cutting the composite material into small blocks by using a diagonal pliers, putting the small blocks into pure water for steaming, and drying the product to constant weight in a vacuum oven; slicing a proper amount of the raw materials into acid liquor, dissolving to prepare 10-25 wt% of casting solution, then adding 1-20 wt% of pore-forming agent, magnetically stirring for 10 hours at normal temperature until the materials are uniformly dispersed, and vacuum defoaming for 60-120 minutes to obtain the casting solution;
3) Preparing a coagulation bath: three types of coagulation baths are included; wherein the first coagulating bath is an air bath, the second coagulating bath is a mixed solution of deionized water and 0.05-1.0wt% of ethanol, and the third coagulating bath is deionized water;
4) Preparation of polyamide 6 film: pouring a proper amount of casting film liquid on a film scraping machine uniformly, wherein the film scraping speed is set to be 30-60 mm/s, the temperature is set to be 25-30 ℃, then the casting film liquid is scraped out on the film scraping machine at a uniform speed, after the air bath is stabilized for 5-30 seconds, the casting film liquid is immersed in a second coagulating bath, is coagulated into a film in a phase inversion process, is taken out after 5-10 minutes, is immersed in a deionized water coagulating bath and is stored for standby, and is cut into films with proper sizes when in use.
2. The method for producing a honeycomb polyamide 6 film according to claim 1, wherein: the acid liquor in the step 2) is one or mixed solvents of any proportion of formic acid, acetic acid, hydrochloric acid, sulfuric acid and nitric acid.
3. The method for producing a honeycomb polyamide 6 film according to claim 1, wherein: the pore-forming agent in the step 2) is lithium chloride (LiCl) or calcium chloride (CaCl) 2 ) One of polyoxyethylene and polyvinyl alcohol or a compound thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011207844.5A CN114437339B (en) | 2020-11-03 | 2020-11-03 | Preparation method and application of high-absorbance honeycomb polyamide membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011207844.5A CN114437339B (en) | 2020-11-03 | 2020-11-03 | Preparation method and application of high-absorbance honeycomb polyamide membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114437339A CN114437339A (en) | 2022-05-06 |
| CN114437339B true CN114437339B (en) | 2023-07-21 |
Family
ID=81360873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011207844.5A Active CN114437339B (en) | 2020-11-03 | 2020-11-03 | Preparation method and application of high-absorbance honeycomb polyamide membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114437339B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5952429A (en) * | 1995-06-14 | 1999-09-14 | Nippon Shokubai Co., Ltd. | Carbon black graft polymer, method for production thereof, and use thereof |
| CN104383821A (en) * | 2014-09-12 | 2015-03-04 | 天津工业大学 | Preparation method for organic-inorganic composite separation membrane with hydrophilicity and function of photocatalytic degradation of pollutants |
| CN105688694A (en) * | 2016-01-22 | 2016-06-22 | 唐山海清源科技股份有限公司 | High-hydrophilic compound reverse osmosis membrane and preparation method of high-hydrophilic compound reverse osmosis membrane |
| CN106621862A (en) * | 2016-12-30 | 2017-05-10 | 北京清大国华环境股份有限公司 | Anti-dirt blockage type PVDF (polyvinylidene fluoride) modified membrane and preparation method thereof |
| CN107174950A (en) * | 2017-06-28 | 2017-09-19 | 北京师范大学 | The positive osmosis composite membrane of high-performance and preparation method that a kind of graphene oxide is modified |
| CN107537320A (en) * | 2017-08-25 | 2018-01-05 | 杭州高瓴环境科技有限公司 | A kind of composite membrane and preparation method thereof |
| CN109092087A (en) * | 2018-09-28 | 2018-12-28 | 南京科技职业学院 | A kind of graphene oxide modified polyamide composite nanometer filtering film and preparation method thereof |
| CN109224888A (en) * | 2017-07-10 | 2019-01-18 | 浙江工业大学 | A kind of graphene oxide framework modified polyamide reverse osmose membrane and its application |
-
2020
- 2020-11-03 CN CN202011207844.5A patent/CN114437339B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5952429A (en) * | 1995-06-14 | 1999-09-14 | Nippon Shokubai Co., Ltd. | Carbon black graft polymer, method for production thereof, and use thereof |
| CN104383821A (en) * | 2014-09-12 | 2015-03-04 | 天津工业大学 | Preparation method for organic-inorganic composite separation membrane with hydrophilicity and function of photocatalytic degradation of pollutants |
| CN105688694A (en) * | 2016-01-22 | 2016-06-22 | 唐山海清源科技股份有限公司 | High-hydrophilic compound reverse osmosis membrane and preparation method of high-hydrophilic compound reverse osmosis membrane |
| CN106621862A (en) * | 2016-12-30 | 2017-05-10 | 北京清大国华环境股份有限公司 | Anti-dirt blockage type PVDF (polyvinylidene fluoride) modified membrane and preparation method thereof |
| CN110538583A (en) * | 2016-12-30 | 2019-12-06 | 北京清大国华环境股份有限公司 | Anti-fouling PVDF (polyvinylidene fluoride) modified membrane and preparation method thereof |
| CN107174950A (en) * | 2017-06-28 | 2017-09-19 | 北京师范大学 | The positive osmosis composite membrane of high-performance and preparation method that a kind of graphene oxide is modified |
| CN109224888A (en) * | 2017-07-10 | 2019-01-18 | 浙江工业大学 | A kind of graphene oxide framework modified polyamide reverse osmose membrane and its application |
| CN107537320A (en) * | 2017-08-25 | 2018-01-05 | 杭州高瓴环境科技有限公司 | A kind of composite membrane and preparation method thereof |
| CN109092087A (en) * | 2018-09-28 | 2018-12-28 | 南京科技职业学院 | A kind of graphene oxide modified polyamide composite nanometer filtering film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114437339A (en) | 2022-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109509856B (en) | Aromatic polyamide microporous membrane and preparation method and application thereof | |
| CN108807786B (en) | Reinforcing film for battery isolation and preparation method thereof | |
| CN111892742A (en) | Photo-thermal conversion polymer solar energy absorption material and preparation method and application thereof | |
| CN110304624B (en) | Carbon quantum dot functionalized graphene oxide laminated membrane and preparation and application thereof | |
| KR100860552B1 (en) | Preparation method of separator with high tensile strength for lithium secondary battery and The lithium secondary battery thereby | |
| CN115928145A (en) | Organic-inorganic composite diaphragm for hydrogen production by alkaline electrolysis of water and preparation method thereof | |
| CN117138605B (en) | Ultralow-pressure reverse osmosis membrane and preparation method thereof | |
| CN114437339B (en) | Preparation method and application of high-absorbance honeycomb polyamide membrane | |
| Bei et al. | Preparation and characterization of PVDF/CaCO3 composite membranes etched by hydrochloric acid | |
| CN112467303B (en) | Degradable lithium battery diaphragm and preparation method thereof | |
| CN110752337A (en) | Composite diaphragm, preparation method and application thereof | |
| CN117276610A (en) | High-toughness COFs/PTFE composite proton exchange membrane and preparation method thereof | |
| CN110350131B (en) | Method for preparing composite polypropylene microporous membrane by phase inversion method, product and application thereof | |
| CN113233532B (en) | Low-cost photo-thermal material based on solar interface evaporation and preparation method thereof | |
| KR20110129111A (en) | Polyimide porous nanofiber web and method for manufacturing the same | |
| CN115521500A (en) | Preparation method of ultrathin high-strength composite proton exchange membrane based on biaxially stretched ultrahigh molecular weight polyethylene | |
| CN112259771B (en) | Proton exchange membrane with wide operating temperature, and preparation method and application thereof | |
| CN113097549B (en) | High-enhancement type fluorine-chlorine-containing alkaline fuel cell membrane | |
| CN112844077A (en) | Reverse osmosis membrane with PE microporous membrane as base material and preparation method thereof | |
| JP2005502157A (en) | Organic ion conductive membrane for fuel cell and manufacturing method thereof | |
| CN114464854B (en) | Preparation method of composite filling electrolyte membrane | |
| CN115337796B (en) | Hollow fiber membrane of poly perfluoroethylene propylene | |
| CN115920665B (en) | Preparation method of composite carbon film | |
| JPS5936939B2 (en) | Method for manufacturing porous film | |
| KR102018538B1 (en) | A Separator for Zn-Br Redox Flow Battery, Manufacturing method thereof and A Zn-Br Redox Flow Battery containing the same |
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 |