CN108014658B - Preparation method for preparing porous gelatin film from Graphene Oxide (GO) stable Pickering emulsion - Google Patents
Preparation method for preparing porous gelatin film from Graphene Oxide (GO) stable Pickering emulsion Download PDFInfo
- Publication number
- CN108014658B CN108014658B CN201711362070.1A CN201711362070A CN108014658B CN 108014658 B CN108014658 B CN 108014658B CN 201711362070 A CN201711362070 A CN 201711362070A CN 108014658 B CN108014658 B CN 108014658B
- Authority
- CN
- China
- Prior art keywords
- film
- membrane
- gelatin
- porous
- pickering emulsion
- 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
-
- 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
- B01D71/74—Natural macromolecular material or derivatives thereof
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Colloid Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a preparation method of a porous gelatin film prepared from Graphene Oxide (GO) stable Pickering emulsion, which comprises the following steps: adding a proper amount of GO into deionized water to prepare GO suspension dispersion liquid, and carrying out ultrasonic treatment; adding a gelatin solution into the GO suspension for dissolving, adding benzoate as an oil phase, and performing ultrasonic treatment; placing the sample in a water bath and then casting to obtain an uncrosslinked film; and soaking the uncrosslinked membrane in a solution containing a crosslinking agent for a period of time to crosslink the membrane, cleaning the membrane by using ethanol and deionized water, and finally drying the membrane to obtain the gelatin membrane with a porous structure. The preparation process for preparing the porous gelatin film from the Pickering emulsion is simple, green and environment-friendly, has low requirements on equipment, high stability of an aqueous solution, uniform porous structure and easy scale production, and has wide application prospects in the fields of wastewater treatment, gas separation, food emulsification, catalysis, detection of heavy metal ions and the like.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the field of preparation of porous gelatin films, and particularly relates to a preparation method of a porous gelatin film prepared from a Pickering emulsion with stable Graphene Oxide (GO).
[ background of the invention ]
Polymer membranes play a crucial role in the water separation and filtration industry. However, the preparation process uses a large amount of toxic organic solvent, and the post-treatment of the organic solvent is very expensive. Bio-based polymers can be used to replace petroleum-based polymers due to their renewability. There are still many disadvantages to be overcome in preparing porous membranes from bio-based polymers: (1) most bio-based polymers are water soluble compared to petroleum-based polymers; therefore, for use under aqueous conditions, it is essential that it be capable of maintaining structural stability in water. (2) Temperature changes during the preparation process cause strong changes in their conformation (e.g. physical gelatinization, starch gelatinization and retrogradation) which in turn limit their range of use. Because of these specific properties, the use of conventional methods to directly impart a porous structure to bio-based polymers does not result in a good overall performance.
Gelatin is obtained by hydrolyzing collagen, and fibrous insoluble protein widely exists in nature and is a main component of skin, bone and connective tissue, so that it has wide source and low cost. Such structurally complex bio-based polymers are widely used in the food and pharmaceutical industries due to their gelling and deformation properties. For gas and water separation, however, a selective dense layer structure, which is important for absorption and diffusion, must be formed on the gelatin film, i.e., a controlled porous structure required for fluid permeation is introduced into the gelatin film.
Graphene Oxide (GO) is composed of two-dimensional nanosheets, and is made by graphite oxidation exfoliation. GO is amphiphilic in that ionizable carboxylate groups, hydroxyl groups render it hydrophilic, while the carbon backbone renders it hydrophobic. The high surface area of GO also helps stabilize the emulsion by lowering the interfacial energy. GO has stronger pi-pi interaction with aromatic solvents, so that GO has higher affinity for aromatic solvents than aliphatic solvents. Thus, GO is one of the best emulsifiers to stabilize aromatic solvent/gelatin emulsions. Currently, GO has been widely used to stabilize Pickering emulsions.
Currently, porous polymer films are mainly prepared by inducing the separation of a polymer solution into two phases. Phase separation of the polymer solution by adjusting thermodynamic parameters (e.g., solubility parameters, temperature) to minimize the free energy of the polymer solution; the polymer-rich phase rapidly solidifies and forms a matrix of membranes after phase separation, while the polymer-free phase gives membranes with a porous structure. However, many crystalline polymers with strong hydrogen bonding have poor solubility at room temperature and are difficult to have suitable solvents, so that the conventional solvent-induced phase separation method cannot be used for preparing the membrane; meanwhile, the method needs to use a large amount of organic solvent, and the organic solvent remained in the film influences the performance of the film and causes solvent waste, so that a more environment-friendly and effective method is needed. The emulsion method is a new method for preparing a film with a porous structure at present, but the gelatin emulsion is easy to agglomerate, so that the particle size distribution of liquid drops is wider. Meanwhile, the gelatin emulsion stabilized by the surfactant is not easy to form small drops; in addition, nonionic surfactants are inefficient in stabilizing gelatin emulsions. Therefore, controlling pore size and its distribution and maintaining porous structure are critical for the manufacture of porous gelatin films.
Therefore, in view of the above, there is still a lack of an efficient and economical method for preparing a porous gelatin film.
[ summary of the invention ]
In view of the above, the applicant has invented a preparation method of a porous gelatin film prepared from a Graphene Oxide (GO) stable Pickering emulsion, and the film prepared by dialdehyde crosslinking is stable in porous form and insoluble in water. The preparation method has the advantages of simple process, environmental protection, low requirement on equipment, high stability of aqueous solution, uniform porous structure and easy scale production, and has wide application prospect in the fields of wastewater treatment, gas separation, food emulsification, catalysis, detection of heavy metal ions and the like.
A preparation method for preparing a porous gelatin film from a Pickering emulsion with stable Graphene Oxide (GO) is characterized by comprising the following steps:
the method comprises the following steps: adding a proper amount of GO into deionized water, and carrying out ultrasonic treatment for 10-60min to prepare GO suspension dispersion liquid with the concentration of 0.5-7g.L < -1 >; adding 10-50% W/V gelatin solution into GO suspension at 25-50 ℃ for dissolving, adding benzoate as an oil phase, wherein the oil-water volume ratio (O/W) is 0.2-0.8, carrying out ultrasonic treatment for 5-20min, placing in a water bath at 35-65 ℃ for 0.5-2 h, then casting to form a film, and then placing at 35-65 ℃ for 2-4 days to obtain an uncrosslinked film; the mass ratio of GO to gelatin is 1:1000-70: 1000.
Step two: immersing the uncrosslinked membrane in 0.5-5 wt% dialdehyde solution with ethanol as solvent, and keeping the solution in the dialdehyde solution for 2-8h at 35-65 ℃ to crosslink the membrane; washing the crosslinked membrane with ethanol and deionized water until the supernatant is clear and transparent; the film was then dried again to give a gelatin film with a porous structure.
The benzoate is one or a mixture of any more of methyl benzoate, ethyl benzoate, propyl benzoate and butyl benzoate.
The dialdehyde crosslinking agent is one or a mixture of any more of glyoxal, malonaldehyde, succinaldehyde and glutaraldehyde.
The preparation of the porous gelatin film from the Pickering emulsion with stable Graphene Oxide (GO) provided by the invention is based on the preparation of the Pickering emulsion. Pickering emulsions are emulsions stabilized by solid nanoparticles adsorbed at the oil/water interface, rather than organic surfactants. The stability of the solid particles entails that the coalescence of the emulsion droplets is greatly reduced, while the use of nanoparticles allows to control the pore distribution and to add new properties to the membrane. Has wide application prospect in the fields of wastewater treatment, gas separation, food emulsification, catalysis, heavy metal ion detection and the like.
Compared with the prior art, the invention has the following advantages:
(1) the preparation method of the porous gelatin film by using the Pickering emulsion method has the advantages that the use of toxic reagents or solvents is avoided by using water as a dispersing agent, and the preparation process is green and environment-friendly.
(2) The preparation condition for preparing the porous gelatin film by the Pickering emulsion method is mild, the process is simple, the operation is convenient, the cost of the raw materials is low, the raw materials are easy to obtain, and the preparation method is suitable for large-scale production.
(3) The porous gelatin film prepared by the Pickering emulsion method has high stability in water, the obtained porous structure is uniform, and the porous structure is not influenced after the cross-linking.
(4) The porous gelatin film prepared by the Pickering emulsion method has good water separation and filtration effects, and the porous structure is adjustable.
[ detailed description ] embodiments
The present invention will be further described with reference to the following examples.
Example 1
Adding a proper amount of GO into deionized water to obtain the product with the concentration of 1g.L-1The GO is suspended in the dispersion liquid and is subjected to ultrasonic treatment for 10 min; adding 15% W/V gelatin solution into GO suspension at 30 deg.C for dissolving, adding ethyl benzoate as oil phase with oil-water volume ratio (O/W) of 0.25, ultrasonic treating for 5min, placing in 40 deg.C water bath for 0.5 hr, casting to form film, standing at 40 deg.C for 2 days to obtain non-crosslinked productAnd (3) a membrane.
Immersing the uncrosslinked membrane in a 1 wt% glyoxal solution with ethanol as a solvent, and keeping the crosslinking in the glyoxal solution for 3 hours at 40 ℃; washing the crosslinked membrane with ethanol and deionized water until the supernatant is clear and transparent; the film was then dried again to give a gelatin film with a porous structure.
Example 2
Adding a proper amount of GO into deionized water to obtain a solution with the concentration of 3g-1The GO is suspended in the dispersion liquid and is subjected to ultrasonic treatment for 30 min; adding 30% W/V gelatin solution into GO suspension at 40 ℃ to dissolve, adding propyl benzoate as oil phase, performing ultrasonic treatment for 10min, placing in 50 ℃ water bath for 1h, casting to form film, and standing at 50 ℃ for 3 days to obtain non-crosslinked film.
Immersing the uncrosslinked membrane in 2.5 wt% malonaldehyde solution with ethanol as solvent, and keeping crosslinking in the malonaldehyde solution for 5h at 50 ℃; washing the crosslinked membrane with ethanol and deionized water until the supernatant is clear and transparent; the film was then dried again to give a gelatin film with a porous structure.
Example 3
Adding a proper amount of GO into deionized water to obtain the product with the concentration of 6g.L-1The GO is suspended in the dispersion liquid and is subjected to ultrasonic treatment for 60 min; adding 45% W/V gelatin solution into GO suspension at 50 ℃ to dissolve, adding butyl benzoate as an oil phase, carrying out ultrasonic treatment for 15min, placing in a water bath at 60 ℃ for 1.5h, casting to form a film, and then placing at 60 ℃ for 4 days to obtain an uncrosslinked film.
Immersing the uncrosslinked membrane in a 4 wt% glutaraldehyde solution with ethanol as a solvent, and keeping the crosslinking in the glutaraldehyde solution for 7 hours at 60 ℃; washing the crosslinked membrane with ethanol and deionized water until the supernatant is clear and transparent; the film was then dried again to give a gelatin film with a porous structure.
Claims (3)
1. A preparation method for preparing a porous gelatin film from a Pickering emulsion with stable Graphene Oxide (GO) is characterized by comprising the following steps:
the method comprises the following steps: adding a proper amount of GO into deionized water to obtain a solution with the concentration of 0.5-7g.L-1Carrying out ultrasonic treatment on the GO suspension dispersion liquid for 10-60 min; adding 10-50% W/V gelatin solution into GO suspension at 25-50 ℃ for dissolving, adding benzoate as an oil phase, wherein the oil-water volume ratio (O/W) is 0.2-0.8, carrying out ultrasonic treatment for 5-20min, placing in a water bath at 35-65 ℃ for 0.5-2 h, then casting to form a film, and then placing at 35-65 ℃ for 2-4 days to obtain an uncrosslinked film; the mass ratio of GO to gelatin is 1:1000-70: 1000;
step two: soaking the uncrosslinked membrane in 0.5-5 wt% dialdehyde solution with ethanol as solvent, and maintaining at 35-65 deg.C in the dialdehyde solution for 2-8 hr to crosslink the membrane; washing the crosslinked membrane with ethanol and deionized water until the supernatant is clear and transparent; and then drying the film to obtain the gelatin film with a porous structure.
2. The method for preparing a porous gelatin film from Graphene Oxide (GO) stabilized Pickering emulsion according to claim 1, wherein the benzoate is one or a mixture of any of methyl benzoate, ethyl benzoate, propyl benzoate and butyl benzoate.
3. The method for preparing the porous gelatin film from the Graphene Oxide (GO) stabilized Pickering emulsion according to claim 1, wherein the dialdehyde solution is one or a mixture of any two of glyoxal, malondialdehyde, succindialdehyde and glutaraldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711362070.1A CN108014658B (en) | 2017-12-18 | 2017-12-18 | Preparation method for preparing porous gelatin film from Graphene Oxide (GO) stable Pickering emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711362070.1A CN108014658B (en) | 2017-12-18 | 2017-12-18 | Preparation method for preparing porous gelatin film from Graphene Oxide (GO) stable Pickering emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108014658A CN108014658A (en) | 2018-05-11 |
| CN108014658B true CN108014658B (en) | 2021-03-26 |
Family
ID=62074120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711362070.1A Active CN108014658B (en) | 2017-12-18 | 2017-12-18 | Preparation method for preparing porous gelatin film from Graphene Oxide (GO) stable Pickering emulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108014658B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109621490B (en) * | 2018-12-18 | 2021-01-08 | 辽宁大学 | Pickering emulsion packed column and method for separating and extracting organic matters based on Pickering emulsion packed column |
| CN111700265B (en) * | 2020-04-17 | 2023-03-21 | 天津科技大学 | Preparation method and application of collagen-based pickering emulsion |
| CN111760330A (en) * | 2020-07-07 | 2020-10-13 | 南京水沝淼净化科技有限公司 | Polyester composite PTFE oil-water separation material |
| CN114558471B (en) * | 2021-12-25 | 2023-05-09 | 福建师范大学 | Application of a kind of terpineol modified graphene oxide nanoparticles in Pickering emulsion |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130048743A (en) * | 2013-04-08 | 2013-05-10 | 이재환 | Liquid curable composition |
| CN103408786A (en) * | 2013-07-26 | 2013-11-27 | 复旦大学 | Preparation method of porous graphene-polymer composite material |
| CN104211977A (en) * | 2014-09-10 | 2014-12-17 | 浙江碳谷上希材料科技有限公司 | Preparation method of graphene-based composite membrane |
| CN106964262A (en) * | 2017-04-13 | 2017-07-21 | 东华大学 | A kind of nanofiber-based osmosis vaporizing compound membrane and preparation method thereof |
-
2017
- 2017-12-18 CN CN201711362070.1A patent/CN108014658B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130048743A (en) * | 2013-04-08 | 2013-05-10 | 이재환 | Liquid curable composition |
| CN103408786A (en) * | 2013-07-26 | 2013-11-27 | 复旦大学 | Preparation method of porous graphene-polymer composite material |
| CN104211977A (en) * | 2014-09-10 | 2014-12-17 | 浙江碳谷上希材料科技有限公司 | Preparation method of graphene-based composite membrane |
| CN106964262A (en) * | 2017-04-13 | 2017-07-21 | 东华大学 | A kind of nanofiber-based osmosis vaporizing compound membrane and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Gelatin Particle-Stabilized High Internal Phase Emulsions as Nutraceutical Containers;Huan Tan et al.;《ACS Applied Materials & Interfaces》;20140808;第6卷(第16期);第5页左栏第2段-右栏第2段，附图4-6 * |
| 基于壳聚糖的新型Pickering乳液及相应功能材料的制备和应用;刘浩;《中国博士学位论文全文数据库 工程科技I辑》;20141115(第11期);第65页倒数第1段-第66页第1段，第67页倒数第3段，第75页倒数第1段，第76页倒数第1段，第89页第2段-第90页第2段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108014658A (en) | 2018-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108014658B (en) | Preparation method for preparing porous gelatin film from Graphene Oxide (GO) stable Pickering emulsion | |
| US20160355662A1 (en) | Method for manufacturing porous cellulose particles and porous cellulose particles | |
| CN111748109B (en) | A chitosan microsphere prepared by using a chitosan solution with a pH value of 6 to 8 and a preparation method thereof | |
| Suzuki et al. | Preparation of cellulose particles using an ionic liquid | |
| CN104014259B (en) | A kind of preparation method of hydrophobic separation membrane | |
| Guo et al. | Gradient cross-linked structure: Towards superior PVA nanofiltration membrane performance | |
| CN105617882B (en) | A kind of compound forward osmosis membrane of chitosan-modified stannic oxide/graphene nano and preparation method thereof | |
| CN105642233B (en) | A kind of method that continuity method prepares CMC/GO composite hydrogel microballoons | |
| CN101254417A (en) | Cross-linked hyperbranched polymer composite nanofiltration membrane and preparation method thereof | |
| Chaudhari et al. | Poly (vinyl alcohol) and poly (vinyl amine) blend membranes for isopropanol dehydration | |
| CN106317442A (en) | Dopamine and dopamine derivative polymerization and high-molecular material surface modification technology | |
| CN111363188A (en) | Preparation method of ultra-light cellulose nanocrystal aerogel material | |
| CN110975649A (en) | Modified polyvinylidene fluoride ultrafiltration membrane and preparation method thereof | |
| CN104226191B (en) | Normal temperature preparation method of ethyl cellulose porous particles | |
| CN102068921A (en) | PH sensitive polyvinylidene fluoride gel film and preparation method thereof | |
| CN102091540A (en) | Preparation method of sulfonated polyethersulfone/TiO2 nanocomposite ultrafiltration membrane | |
| Napso et al. | Cellulose gel dispersion: From pure hydrogel suspensions to encapsulated oil-in-water emulsions | |
| CN113750813B (en) | Oil-water separation film and preparation method thereof | |
| Wang et al. | Preparation and separation characteristics of polyelectrolyte complex membranes containing sulfated carboxymethyl cellulose for water–ethanol mixtures at low pH | |
| CN106496597B (en) | A kind of method that utilizes ionic liquid to prepare polysaccharide microspheres | |
| CN111871209A (en) | Preparation method of heat-resistant condensation tetrafluoroethylene composite nanofiltration membrane | |
| CN107892757B (en) | Preparation method for preparing porous chitosan membrane from Graphene Oxide (GO) stable Pickering emulsion | |
| CN108892781A (en) | A kind of modified preparation and its application based on bionics ultrafiltration membrane | |
| CN107998907B (en) | A kind of preparation method of graphene oxide (GO)-stabilized Pickering emulsion to prepare porous polylysine membrane | |
| CN100438957C (en) | Preparation method of polymer microfiltration membrane and porogen |
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 |