CN113248778B - Preparation method and application of surface modified cellulose-based porous membrane - Google Patents
Preparation method and application of surface modified cellulose-based porous membrane Download PDFInfo
- Publication number
- CN113248778B CN113248778B CN202110406001.6A CN202110406001A CN113248778B CN 113248778 B CN113248778 B CN 113248778B CN 202110406001 A CN202110406001 A CN 202110406001A CN 113248778 B CN113248778 B CN 113248778B
- Authority
- CN
- China
- Prior art keywords
- porous membrane
- based porous
- cellulose
- modified cellulose
- preparing
- 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
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K17/00—Carrier-bound or immobilised peptides; Preparation thereof
- C07K17/02—Peptides being immobilised on, or in, an organic carrier
- C07K17/10—Peptides being immobilised on, or in, an organic carrier the carrier being a carbohydrate
- C07K17/12—Cellulose or derivatives thereof
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
- C12N11/12—Cellulose or derivatives thereof
-
- 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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention provides a preparation method and application of a surface modified cellulose-based porous membrane, belonging to the field of preparation of membrane materials; in the present invention, N-methylmorpholine-N-oxide/dimethyl sulfoxide/deionized water (NMMO/DMSO/H) is used 2 O) is used as a solvent system of cellulose, after dissolution and organic solvent coagulation bath regeneration, a cellulose-based porous membrane with a uniform pore structure is obtained, and then surface modification is carried out to obtain the surface modified cellulose-based porous membrane, wherein the surface modified cellulose-based porous membrane has good application in biomacromolecule adsorption and fixation.
Description
Technical Field
The invention belongs to the field of preparation of membrane materials, and relates to a preparation method and application of a surface modified cellulose-based porous membrane.
Background
At present, the surface modified porous membrane taking cellulose as a matrix material is widely applied to the fields of biological medicine, environment, chemical industry, food and the like. Cellulose-based porous membranes are mostly prepared by a dissolution and regeneration method, cellulose is dissolved into a uniform solution and then regenerated, but a large amount of intramolecular and intermolecular hydrogen bonds exist in the molecular structure of cellulose, the crystallinity is high, and the cellulose-based porous membranes are difficult to dissolve in a general organic solvent system.
Traditional surface modified cellulose-based porous membranesIn the preparation method, the cellulose solvent mainly comprises cuprammonium solution and CS 2 The NaOH system, but the process route for preparing cellulose films using these two solvent systems is complicated, the raw material and energy costs are large, and the environmental pollution is severe. In the existing preparation method of the novel cellulose-based porous membrane, a cellulose solvent system comprises NaOH/urea, lithium chloride/dimethylacetamide (LiCl/DMAc), N-methylmorpholine-N-oxide (NMMO), ionic liquid, zinc chloride and the like, and the novel solvent system has the characteristics of green and pollution-free, but a cellulose membrane obtained by using the solvent system has a compact structure and a small pore structure, so that the specific surface area of the cellulose membrane is small, and further application of the cellulose membrane material is limited.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method and application of a surface modified cellulose-based porous membrane. In the present invention, N-methylmorpholine-N-oxide/dimethyl sulfoxide/deionized water (NMMO/DMSO/H) is used 2 O) is used as a solvent system of cellulose, a cellulose base porous membrane with a uniform pore structure is obtained after dissolution and regeneration of an organic solvent coagulating bath, and then the surface modified cellulose base porous membrane is obtained through chemical modification, wherein the surface modified cellulose base porous membrane has good application in biological macromolecule adsorption and fixation.
The invention firstly provides a surface modified cellulose-based porous membrane, which is formed by modifying the cellulose-based porous membrane; the cellulose-based porous membrane is prepared from N-methylmorpholine-N-oxide/dimethyl sulfoxide/deionized water NMMO/DMSO/H 2 O is a solvent system, and is obtained by regenerating and replacing an organic solvent coagulation bath, and the interior of the organic solvent coagulation bath has a uniform micron-sized macroporous structure.
The invention also provides a preparation method of the surface modified cellulose-based porous membrane, which comprises the following steps:
(1) preparation of cellulose-based porous membrane:
adding dimethyl sulfoxide DMSO to dried cellulose, and adding N-methylmorpholine-N-oxideSubstance/deionized water NMMO/H 2 O to obtain a mixed system, then adding a propyl gallate stabilizer, uniformly mixing, stirring, defoaming in vacuum, scraping to form a film, immersing in an organic solvent coagulation bath for regeneration and replacement, and drying to obtain a cellulose-based porous membrane;
(2) preparing a surface modified cellulose base porous membrane:
and dissolving sodium periodate in an acetic acid buffer solution, then immersing the cellulose-based porous membrane, carrying out oscillation reaction under the condition of keeping out of the sun, and washing to obtain the surface modified cellulose-based porous membrane.
Further, in the step (1), the final concentration of the cellulose in the mixed system is 2-15 wt%; the NMMO accounts for 40-50 wt% of the mixed system; 4-6 wt% of deionized water in the mixed system; the DMSO concentration in the mixture system is 35-48 wt%.
Further, in the step (1), the propyl gallate stabilizer accounts for 0.2-1.0 wt% of the cellulose.
Further, in the step (1), the stirring conditions are as follows: stirring for 10 min-5 h at 80-150 ℃.
Further, in the step (1), the coagulation bath used after film formation comprises one or more of methanol, ethanol, acetone and the like, and the coagulation bath is immersed for 20 min-1 h.
Further, in the step (1), the displacement bath comprises one or more of methanol, ethanol, acetone, isopropanol, n-butanol and the like, and the displacement time in the displacement bath is 12-36 h.
Further, in the step (2), the final concentration of the sodium periodate is 1-10 mg/mL.
Further, in the step (2), the concentration of the acetic acid buffer solution is 0.1mol/L, and the pH value is 4.
Further, in the step (2), the shaking reaction is carried out for 15 min-10 h at 4-40 ℃ under stirring reaction conditions.
The invention also provides application of the surface modified cellulose-based porous membrane as a biomacromolecule fixing carrier material.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses cellulose as raw material, has rich storage in nature, low price, high stability and good biocompatibility, and the surface contains a large amount of hydroxyl groups for later modification, thus being an ideal raw material for preparing the porous membrane.
The present invention uses a green solvent system N-methylmorpholine-N-oxide/dimethyl sulfoxide/deionized water (NMMO/DMSO/H) 2 O) dissolving cellulose, then using an organic solvent as a coagulating bath to obtain a cellulose-based porous membrane material, and carrying out chemical modification on the cellulose-based porous membrane material to obtain the surface-modified cellulose-based porous membrane.
The method has the advantages of mild dissolution conditions, environmental friendliness, no toxicity, simple operation process, suitability for large-scale production and the like, the prepared cellulose-based porous membrane material has a uniform porous internal structure, and then the obtained cellulose-based porous membrane is subjected to surface modification, so that the surface-modified cellulose-based porous membrane can be used as a solid carrier material for biomacromolecules such as enzymes, proteins and the like.
Drawings
Fig. 1 is a scanning electron micrograph of a cellulose-based porous film.
FIG. 2 is a graph showing the recyclability of lipase immobilized on a surface-modified cellulose-based porous membrane.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
Example 1:
adding dimethyl sulfoxide DMSO to dried cellulose, and adding N-methylmorpholine-N-oxide/deionized water NMMO/H 2 Adding a propyl gallate stabilizer into the mixed solvent of O, and uniformly mixing to obtain a mixed system, wherein in the system, the concentration of cellulose is 5wt%, the proportion of DMSO is 45wt%, the proportion of NMMO is 45wt%, the proportion of deionized water is 5wt%, and the content of propyl gallate is 0.5wt% of cellulose; stirring at 100 deg.C for 2hAnd then, carrying out vacuum defoaming, uniformly scraping the prepared cellulose solution on a glass plate to form a film, immersing the film in an acetone coagulating bath for replacing for 40min, then fully replacing for 15h in an isopropanol solution, and finally, heating and drying in vacuum to obtain the cellulose-based porous film.
The surface modification method comprises the specific steps of weighing 40 mg of sodium periodate to be completely dissolved in 40 mL of 0.1M acetic acid buffer solution (pH 4.0), then immersing the cellulose-based porous membrane into the sodium periodate solution, stirring the reaction system at room temperature under the condition of keeping out of the sun for reaction for 10 hours, and fully washing the reaction system with ice water for at least three times after the reaction is finished to obtain the surface modified cellulose-based porous membrane with aldehyde groups.
FIG. 1 is a scanning electron microscope image of a cellulose-based porous membrane, and it can be seen that the material has a uniform micro-scale macroporous internal pore structure.
Example 2:
to the dried cellulose was added dimethyl sulfoxide DMSO followed by N-methylmorpholine-N-oxide/deionized water NMMO/H 2 O, and adding a propyl gallate stabilizer, and uniformly mixing to obtain a mixed system, wherein in the system, the concentration of cellulose is 6wt%, the proportion of DMSO is 44wt%, the proportion of NMMO is 46wt%, the proportion of deionized water is 4wt%, and propyl gallate is 0.6wt% of cellulose; stirring for 1h at 120 ℃, then carrying out vacuum defoaming, uniformly scraping the prepared cellulose solution on a glass plate to form a film, immersing the film in an acetone coagulating bath for 50min for replacement, then fully replacing the film in an isopropanol solution for 20h, and finally carrying out vacuum heating and drying to obtain the cellulose-based porous film.
The surface modification method comprises the specific steps of weighing 200 mg of sodium periodate and completely dissolving the sodium periodate into 40 mL of 0.1M acetic acid buffer solution (pH 4.0), then immersing the cellulose-based porous membrane into the sodium periodate solution, stirring the reaction system under the condition of keeping out of the sun and reacting for 5 hours at room temperature, and fully washing the cellulose-based porous membrane with ice water for at least three times after the reaction is finished to obtain the surface modified cellulose-based porous membrane with aldehyde groups.
Example 3:
to the dried cellulose was added dimethyl sulfoxide DMSO followed by N-methylmorpholine-N-oxide/deionized water NMMO/H 2 Adding a propyl gallate stabilizer into the mixed solvent of O, and uniformly mixing to obtain a mixed system, wherein in the system, the concentration of cellulose is 4wt%, the proportion of DMSO is 50wt%, the proportion of NMMO is 40wt%, the proportion of deionized water is 6wt%, and propyl gallate is 0.6wt% of cellulose; stirring for 5h at 80 ℃, then carrying out vacuum deaeration, uniformly scraping the prepared cellulose solution on a glass plate to form a film, immersing the film in an acetone coagulating bath for replacing for 40min, then fully replacing for 12h in an isopropanol solution, and finally carrying out vacuum heating and drying to obtain the cellulose-based porous film.
The surface modification method comprises the specific steps of weighing 200 mg of sodium periodate and completely dissolving the sodium periodate into 40 mL of 0.1M acetic acid buffer solution (pH 4.0), then immersing the cellulose-based porous membrane into the sodium periodate solution, stirring the reaction system at 30 ℃ under the condition of keeping out of the sun for reaction for 2 hours, and fully washing the reaction system with ice water for at least three times after the reaction is finished to obtain the surface modified cellulose-based porous membrane with aldehyde groups.
Example 4:
the surface modified cellulose-based porous membrane with aldehyde groups prepared in example 1 was used to perform adsorption immobilization on lipase, and the specific steps were:
the lipase was sufficiently dissolved in a phosphate buffer (pH 7.0, 10 mM) to prepare a solution having a concentration of 1.0 mg/mL, and then the surface-modified cellulose-based porous membrane having aldehyde groups was immersed in the solution, and the adsorption and immobilization of the lipase was carried out by shaking the reaction at room temperature. After the reaction is carried out for 10h, the lipase content in the solution before and after adsorption is measured by using a Coomassie brilliant blue method, and the enzyme adsorption and immobilization capacity of the surface modified cellulose-based porous membrane with aldehyde groups is 5.5 mg/g. The results of the recycling assay of the lipase adsorbed and immobilized on the surface-modified cellulose-based porous membrane having aldehyde groups are shown in fig. 2, and the activity of the enzyme is not significantly reduced after 5 times of repeated use, indicating that the lipase adsorbed and immobilized on the surface-modified cellulose-based porous membrane having aldehyde groups has excellent recycling performance.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. A method of preparing a surface-modified cellulose-based porous membrane, comprising:
(1) preparation of cellulose-based porous membrane:
to the dried cellulose was added dimethyl sulfoxide DMSO followed by N-methylmorpholine-N-oxide/deionized water NMMO/H 2 O to obtain a mixed system, then adding a propyl gallate stabilizer, uniformly mixing, stirring, defoaming in vacuum, scraping to form a film, immersing in an organic solvent coagulation bath for regeneration, replacing in a replacement bath, and drying to obtain a cellulose-based porous membrane;
(2) preparing a surface modified cellulose base porous membrane:
and dissolving sodium periodate in an acetic acid buffer solution, then immersing the cellulose-based porous membrane, carrying out oscillation reaction under the condition of keeping out of the sun, and washing to obtain the surface modified cellulose-based porous membrane.
2. The method of preparing a surface-modified cellulose-based porous membrane according to claim 1, wherein in the step (1), the final concentration of the cellulose in the mixed system is 2 to 15wt%, the final concentration of NMMO in the mixed system is 40 to 50wt%, the final concentration of deionized water in the mixed system is 4 to 6wt%, the final concentration of DMSO in the mixed system is 35 to 48wt%, and the final concentration of the propyl gallate stabilizer is 0.2 to 1.0wt% of the cellulose.
3. The method for preparing the surface-modified cellulose-based porous membrane according to claim 1, wherein the stirring conditions in step (1) are: stirring for 10 min-5 h at 80-150 ℃.
4. The method for preparing the surface-modified cellulose-based porous membrane according to claim 1, wherein in the step (1), the coagulation bath used after the membrane formation comprises one or more of methanol, ethanol and acetone, and the membrane is immersed in the coagulation bath for 20min to 1 h.
5. The method for preparing the surface-modified cellulose-based porous membrane according to claim 1, wherein in the step (1), the displacement bath comprises one or more of methanol, ethanol, acetone, isopropanol and n-butanol, and the displacement time in the displacement bath is 12-36 h.
6. The method for preparing a surface-modified cellulose-based porous membrane according to claim 1, wherein the final concentration of sodium periodate in the step (2) is 1 to 10 mg/mL.
7. The method for preparing a surface-modified cellulose-based porous membrane according to claim 1, wherein the acetic acid buffer solution has a concentration of 0.1mol/L and a pH of 4 in the step (2).
8. The method for preparing the surface-modified cellulose-based porous membrane according to claim 1, wherein the shaking reaction is performed at 4 to 40 ℃ for 15min to 10h under stirring conditions in the step (2).
9. The surface-modified cellulose-based porous membrane prepared by the method according to any one of claims 1 to 8, wherein the surface-modified cellulose-based porous membrane is modified based on a cellulose-based porous membrane; the cellulose-based porous membrane is prepared from N-methylmorpholine-N-oxide/dimethyl sulfoxide/deionized water NMMO/DMSO/H 2 O is a solvent system, is obtained by regeneration of an organic solvent coagulation bath and replacement in a replacement bath, and has a uniform micron-sized macroporous structure inside.
10. Use of the surface modified cellulose-based porous membrane according to claim 9 as a biomacromolecule immobilization support material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110406001.6A CN113248778B (en) | 2021-04-15 | 2021-04-15 | Preparation method and application of surface modified cellulose-based porous membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110406001.6A CN113248778B (en) | 2021-04-15 | 2021-04-15 | Preparation method and application of surface modified cellulose-based porous membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113248778A CN113248778A (en) | 2021-08-13 |
| CN113248778B true CN113248778B (en) | 2022-09-13 |
Family
ID=77220892
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110406001.6A Active CN113248778B (en) | 2021-04-15 | 2021-04-15 | Preparation method and application of surface modified cellulose-based porous membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113248778B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023180181A1 (en) * | 2022-03-21 | 2023-09-28 | Phoenxt Pty. Ltd | Regenerating cellulose from waste textile |
| CN115041148A (en) * | 2022-06-15 | 2022-09-13 | 江苏大学 | Functionalized cellulose monolithic column porous material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219921A (en) * | 2011-05-17 | 2011-10-19 | 东华大学 | Method for preparing cellulose membrane by utilizing discarded cotton-polyester blended fabric |
| CN103774479A (en) * | 2013-12-31 | 2014-05-07 | 广州甘蔗糖业研究所 | Method for extracting biomass cellulose by adopting NMMO/DMSO mixed solvent |
| CN104419994A (en) * | 2013-08-29 | 2015-03-18 | 财团法人纺织产业综合研究所 | Preparation method of high-concentration cellulose spinning solution |
| CN109232953A (en) * | 2018-08-08 | 2019-01-18 | 西南交通大学 | A kind of polyethyleneimine amido chloramines type antibacterial cellulose film, preparation method and application |
| CN110237722A (en) * | 2019-07-15 | 2019-09-17 | 陕西科技大学 | A kind of fibrination pore membrane and preparation method thereof |
-
2021
- 2021-04-15 CN CN202110406001.6A patent/CN113248778B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219921A (en) * | 2011-05-17 | 2011-10-19 | 东华大学 | Method for preparing cellulose membrane by utilizing discarded cotton-polyester blended fabric |
| CN104419994A (en) * | 2013-08-29 | 2015-03-18 | 财团法人纺织产业综合研究所 | Preparation method of high-concentration cellulose spinning solution |
| CN103774479A (en) * | 2013-12-31 | 2014-05-07 | 广州甘蔗糖业研究所 | Method for extracting biomass cellulose by adopting NMMO/DMSO mixed solvent |
| CN109232953A (en) * | 2018-08-08 | 2019-01-18 | 西南交通大学 | A kind of polyethyleneimine amido chloramines type antibacterial cellulose film, preparation method and application |
| CN110237722A (en) * | 2019-07-15 | 2019-09-17 | 陕西科技大学 | A kind of fibrination pore membrane and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Model films of cellulose II – improved preparation method and characterization of the cellulose film;S.Falt等;《Cellulose》;20041231;第151-162页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113248778A (en) | 2021-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113248778B (en) | Preparation method and application of surface modified cellulose-based porous membrane | |
| CN103446897B (en) | Chemical and ionic cross-linked alginate hydrogel flat membrane for filtration and preparation method thereof | |
| US5066401A (en) | Flat or capillary membrane based on a homogeneous mixture of polyvinylidene fluoride and a second polymer which can be rendered hydrophilic by chemical reaction | |
| CN103225126B (en) | Fibroin/sodium alginate composite nanofiber scaffold preparation method | |
| CN106731883B (en) | Polydopamine nano lignocellulose polyvinylidene fluoride composite ultrafiltration membrane and preparation method thereof | |
| CN113750968A (en) | Water-insoluble cyclodextrin-based metal organic framework material and preparation method thereof | |
| Liu et al. | Effect of eggshell membrane as porogen on the physicochemical structure and protease immobilization of chitosan-based macroparticles | |
| Liu et al. | Reinforced chitosan beads by chitin nanofibers for the immobilization of β-glucosidase | |
| CN111253597A (en) | Chitin nanofiber/polyaniline composite gel film and preparation method thereof | |
| CN114316375B (en) | Hierarchical pore structure composite aerogel and preparation method thereof | |
| WO2023024055A1 (en) | Preparation method of polyvinyl alcohol-acrylamide -agarose hydrogelwith high mechanical strength | |
| CN112934000B (en) | Modification method of PVDF (polyvinylidene fluoride) microfiltration membrane | |
| CN101507904B (en) | Composite ultrafiltration membrane and preparation method thereof | |
| RU2471824C1 (en) | Biocompatible, biodegradable porous composite material and method of producing said material | |
| CN108118023B (en) | Fiber scaffold and preparation method and application thereof | |
| CN113150270A (en) | Phospholipid polymer and preparation method and application thereof | |
| CN113045678A (en) | Catechol amine modified cellulose material, preparation method thereof and application thereof in filter membrane | |
| CN109402106B (en) | Method for fixing Klebsiella through polyvinyl alcohol-cellulose and application of method | |
| CN114213700B (en) | Cellulose porous material and preparation method thereof | |
| CN114907620A (en) | Preparation method of regenerated cellulose membrane with drug slow-release capability | |
| CN112724450A (en) | Collagen-graphene oxide cross-linked scaffold material with uniform porous structure and preparation method thereof | |
| CN108579693B (en) | Preparation method of sodium tripolyphosphate cross-linked chitosan/sodium bentonite aerogel | |
| US5360636A (en) | Method for coating cellulosic membranes | |
| CN110237722A (en) | A kind of fibrination pore membrane and preparation method thereof | |
| CN112442196B (en) | Preparation and application of degradable, biocompatible and high-strength chitin hydrogel |
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 |