CN111013199A - Preparation method of intelligent pH response type melamine foam oil-water separation material - Google Patents
Preparation method of intelligent pH response type melamine foam oil-water separation material Download PDFInfo
- Publication number
- CN111013199A CN111013199A CN201911409934.XA CN201911409934A CN111013199A CN 111013199 A CN111013199 A CN 111013199A CN 201911409934 A CN201911409934 A CN 201911409934A CN 111013199 A CN111013199 A CN 111013199A
- Authority
- CN
- China
- Prior art keywords
- melamine foam
- foam
- water separation
- oil
- water
- 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.)
- Pending
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
- B01D17/047—Breaking emulsions with separation aids
Landscapes
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention belongs to the technical field of oil absorption materials and environmental protection, and particularly relates to a preparation method of an intelligent pH response type melamine foam oil-water separation material. Firstly, performing silanization modification on melamine foam by using aminopropyl trimethoxy silane; and then copper sulfate is used as a catalyst, free radicals are generated in an aqueous solution through copper amine redox reaction to initiate diethylaminoethyl methacrylate to carry out graft polymerization, so that the pH response type melamine foam oil-water separation material is prepared. According to the invention, melamine foam with high internal porosity and large absorption capacity is selected as a substrate, and free radical graft polymerization is initiated by a simple copper ammonium redox two-step method to prepare an oil-water separation foam material containing a pH response layer; the material has switchable wettability in different pH environments; the foam modification process has simple process and is easy to realize industrial production.
Description
Technical Field
The invention belongs to the technical field of oil absorption materials and environmental protection, and relates to a preparation method of an intelligent pH response type melamine foam oil-water separation material.
Background
Because of petroleum leakage caused by accidents, the discharge of industrial oily wastewater and domestic oily sewage and pollution to clean water systems, the society urgently needs a technology for effectively separating oily wastewater to solve the global environmental pollution problem. The traditional methods for removing the oil stains comprise an in-situ combustion method, a chemical dispersion method, an oil skimming method, a bioremediation method and the like, but the traditional methods have the defects of low efficiency, high operation cost, easiness in causing secondary pollution and the like. Currently, there are two types of emerging oil-water separation methods, namely, filter materials (e.g., mesh, woven/non-woven fabrics, membranes, etc.) and absorbent materials (e.g., particles, foams, aerogels, etc.), and these two types of oil-water separation materials are not only beneficial to greatly reduce environmental pollution, but also have the ability to save energy and recover resources, compared with the conventional methods.
In the field of oil-water separation, selective absorption and filtration are realized by intelligently controlling surface wettability so as to prepare oil-water separation materials, and reports are more. The pH responsive material with shorter response time is more, and the material controls the wetting and the absorptivity by changing the pH value of the medium at room temperature. Materials that can change wettability between hydrophilic and hydrophobic properties under pH stimulation are very promising for oil absorption and recovery, especially when recovering more valuable chemicals, compared to foamed oil absorbing materials that recover oils or reagents by extrusion, and in a manner that does not destroy the internal structure of the foam.
Chinese patent CN 106944016A firstly silanizes melamine foam, and then grafts 4-vinylpyridine to the foam surface by an Atom Transfer Radical Polymerization (ATRP) method to prepare the pH-responsive oil-water separation foam, the foam is super-hydrophilic/super-oleophobic in a solution with a lower pH value, and is highly hydrophobic/super-oleophilic in a solution with a higher pH value. However, the method needs silanization treatment on the foam, then ATRP (atom transfer radical polymerization) initiation functional groups are introduced through esterification under complex reaction conditions, then monomer polymerization is initiated under the conditions of no water and no oxygen and the addition of amine ligands, and a pH response coating is grafted and polymerized on the surface of the foam, so that the pH intelligent response foam absorbent is finally obtained. The whole process comprises silanization, introduction of ATRP initiating functional group by esterification and ATRP polymerization 'three-step' reaction, so that the process has higher cost.
Disclosure of Invention
The invention aims to overcome the defect of complex preparation process of pH response foam, changes the original three-step ATRP grafting method into two steps, and directly grafts the poly diethylaminoethyl methacrylate in the aqueous solution by a simple method of directly initiating free radical graft polymerization in the aqueous solution through copper amine redox reaction to construct the intelligent pH response type melamine foam oil-water separation material.
The invention adopts a technical scheme for solving the technical problem to prepare the intelligent pH response type melamine foam oil-water separation material, which comprises the following steps:
(1) and putting the melamine foam into a toluene solution of 3-aminopropyltrimethoxysilane for refluxing and soaking for a certain time for silanization modification, taking out and drying.
(2) Dissolving diethylaminoethyl methacrylate and copper sulfate in deionized water to prepare a mixed solution. And (2) adding the foam obtained in the step (1) into the mixed solution, reacting for a certain time at a certain temperature, taking out, washing with deionized water and ethanol, and drying to obtain the pH response type melamine foam oil-water separation material.
Further, in the step (1), the mass percent of the 3-aminopropyltrimethoxysilane in the toluene is 0.5-1.9%.
Further, in the step (1), the reflux temperature is 110-120 ℃, and the soaking reaction time is 1-5 hours.
Further, in the step (2), the percentage of the diethylaminoethyl methacrylate in the deionized water is 0.5-1.9%, and the percentage of the copper sulfate in the deionized water is 0.25-1%.
Further, the reaction temperature in the step (2) is 70-90 ℃, and the reaction time is 2-6 hours.
The invention has the beneficial effects that: melamine foam with high internal porosity is selected as a matrix, so that the modified oil-water separation material has good oil absorption capacity and higher separation flux; the modified melamine foam has switchable wettability under different pH environments; the copper ammonium redox initiation free radical graft polymerization method with a simpler process is used in the foam modification process, and the industrial production is easy to realize.
The invention is further described below with reference to the accompanying drawings.
Drawings
FIG. 1 is an infrared spectrum of the surface of a melamine foam and the modified melamine foam obtained in example 1;
FIG. 2 is a scanning electron micrograph of the surface of a melamine foam and the modified melamine foam obtained in example 1;
FIG. 3 shows the water contact angles of the modified melamine foam obtained in example 5 for water droplets at different pH values in air and the oil contact angles for oil droplets at different pH values under water.
Detailed Description
The following examples are intended to further illustrate the invention, but not to limit the scope of the invention.
The melamine foam adopted by the invention is a commercial product for cleaning, and the density is 8.07mg/cm3The diameter of the cells is about 92 microns, and other raw materials and reagents are also commercial products.
Example 1
(1) The volume is 1.5X 2cm3The melamine foam is put into 32 g of toluene solution dissolved with 0.16 g of 3-aminopropyltrimethoxysilane for 1 hour of reflux soaking at 110 ℃ for silanization modification, and is dried in an oven at 60 ℃ to constant weight after being taken out.
(2) 0.2g of diethylaminoethyl methacrylate and 0.1g of copper sulfate were dissolved in 40 g of deionized water to prepare a mixed solution. And (2) adding the foam obtained in the step (1) into the mixed solution, reacting for 2 hours at 80 ℃, taking out, washing with deionized water and ethanol for three times respectively, and drying in an oven at 60 ℃ to constant weight to obtain the pH response type melamine foam oil-water separation material.
And (5) characterizing the obtained oil-water separation material. FIG. 1 shows that the modified melamine foam obtained in example 1 is at 1730cm-1The stretching vibration peak of carbonyl appears, which indicates that the diethylaminoethyl methacrylate is successfulThe polymeric graft is coated on the surface of the melamine foam.
FIG. 2 is a Scanning Electron Microscope (SEM) image of a foam, a and b are unmodified melamine foam, c and d are foam surfaces after silanization in example 1, and e and f are foam surfaces grafted with diethylaminoethyl methacrylate polymer. It can be seen that all foam surfaces have a three-dimensional network of high porosity. The original foam and silanized foam had smoother surfaces and the foam grafted with diethylaminoethyl methacrylate polymer had a rougher surface.
The foam was tested for water contact angle, which is 0 degrees when water with a pH of 2 was used; when water with pH 7 was used, the contact angle was 135 degrees; when water having a pH of 9 was used, the contact angle was 138 degrees. The foam is proved to be hydrophilic under acidic conditions, hydrophobic under neutral and alkaline conditions and oleophilic.
Example 2
(1) The volume is 1.5X 2cm3The melamine foam is put into 32 g of toluene solution dissolved with 0.4g of 3-aminopropyltrimethoxysilane and is refluxed and soaked for 3 hours at 115 ℃ for silanization modification, and after being taken out, the melamine foam is dried in an oven at 60 ℃ to constant weight.
(2) 0.4g of diethylaminoethyl methacrylate and 0.2g of copper sulfate were dissolved in 40 g of deionized water to prepare a mixed solution. And (2) adding the foam obtained in the step (1) into the mixed solution, reacting for 2 hours at 70 ℃, taking out, washing with deionized water and ethanol for three times respectively, and drying in an oven at 60 ℃ to constant weight to obtain the pH response type melamine foam oil-water separation material.
The foam was tested for water contact angle, which is 0 degrees when water with a pH of 2 was used; when water with pH 7 was used, the contact angle was 132 degrees; when water having a pH of 9 was used, the contact angle was 134 degrees. The foam is proved to be hydrophilic under acidic conditions, hydrophobic under neutral and alkaline conditions and oleophilic.
Example 3
(1) The volume is 1.5X 2cm3The melamine foam is put into 32 g of toluene solution dissolved with 0.6 g of 3-aminopropyl trimethoxy silane and is refluxed and soaked for 5 hours at 115 ℃ for silanization modification, and after being taken out, the melamine foam is put into a reactor for silanization modificationDrying in an oven at 60 ℃ to constant weight.
(2) 0.6 g of diethylaminoethyl methacrylate and 0.4g of copper sulfate were dissolved in 40 g of deionized water to prepare a mixed solution. And (2) adding the foam obtained in the step (1) into the mixed solution, reacting for 6 hours at 70 ℃, taking out, washing with deionized water and ethanol for three times respectively, and drying in an oven at 60 ℃ to constant weight to obtain the pH response type melamine foam oil-water separation material.
The foam was tested for water contact angle, which is 0 degrees when water with a pH of 2 was used; when water with pH 7 was used, the contact angle was 140 degrees; when water having a pH of 9 was used, the contact angle was 142 degrees. The foam is proved to be hydrophilic under acidic conditions, hydrophobic under neutral and alkaline conditions and oleophilic.
Example 4
(1) The volume is 1.5X 2cm3The melamine foam is put into 32 g of toluene solution dissolved with 0.6 g of 3-aminopropyl trimethoxy silane and is refluxed and soaked for 5 hours at 115 ℃ for silanization modification, and after being taken out, the melamine foam is dried in an oven at 60 ℃ to constant weight.
(2) 0.2g of diethylaminoethyl methacrylate and 0.2g of copper sulfate were dissolved in 40 g of deionized water to prepare a mixed solution. And (2) adding the foam obtained in the step (1) into the mixed solution, reacting for 4 hours at 90 ℃, taking out, washing with deionized water and ethanol for three times respectively, and drying in an oven at 60 ℃ to constant weight to obtain the pH response type melamine foam oil-water separation material.
The foam was tested for water contact angle, which is 0 degrees when water with a pH of 2 was used; when water with pH 7 was used, the contact angle was 138 degrees; when water having a pH of 9 was used, the contact angle was 140 degrees. The foam is proved to be hydrophilic under acidic conditions, hydrophobic under neutral and alkaline conditions and oleophilic.
Example 5
(1) The volume is 1.5X 2cm3The melamine foam is put into 32 g of toluene solution dissolved with 0.2g of 3-aminopropyltrimethoxysilane for 3 hours at 120 ℃ for reflux soaking for silanization modification, and after being taken out, the melamine foam is dried in an oven at 60 ℃ to constant weight.
(2) 0.6 g of diethylaminoethyl methacrylate and 0.3g of copper sulfate were dissolved in 40 g of deionized water to prepare a mixed solution. And (2) adding the foam obtained in the step (1) into the mixed solution, reacting for 4 hours at 80 ℃, taking out, washing with deionized water and ethanol for three times respectively, and drying in an oven at 60 ℃ to constant weight to obtain the pH response type melamine foam oil-water separation material.
FIG. 3 shows the water contact angles of the modified melamine foam obtained in example 5 for water droplets at different pH values in air and the oil contact angles for oil droplets at different pH values under water. (a) The figure shows that the drop of a neutral water drop in air on the surface of the functionalized melamine foam can form a sphere with a water contact angle of 137 deg., and the drop remains in its original shape after standing in air for 600 seconds, indicating that the surface of the functionalized melamine foam has high hydrophobicity to neutral water. (b) When a drop of acidic water (pH 2.0) is dropped in air on the surface of the functionalized melamine foam, it completely wets the foam within 0.4 seconds, indicating that the surface of the functionalized melamine foam has super-hydrophilicity to acidic water. (c) The oil droplets form spheres with an Oil Contact Angle (OCA) of 158 ° when dropped under acidic water on the functionalized foam surface, demonstrating that the membrane is superoleophobic in acidic water. (d) The foam is fixed at pH 7 below the water surface and the elevator is moved so that once a drop of oil (chloroform) contacts the foam surface, it is absorbed by the foam within 0.3 seconds, indicating that the foam is super-oleophilic in neutral water.
Basic properties of the pH-responsive melamine foams obtained in examples 1 to 5: when pH is 3 and 3 or less, the foam is in a hydrophilic-oleophobic state. When the pH is above 7 and 7, the foam is in an oleophilic and hydrophobic state. When the pH of the medium is switched, the foam can be freely switched in two wet states.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (6)
1. A preparation method of an intelligent pH response type melamine foam oil-water separation material is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) putting the melamine foam into a toluene solution of 3-aminopropyltrimethoxysilane for reflux soaking, carrying out silanization modification, taking out and drying;
(2) dissolving diethylaminoethyl methacrylate and copper sulfate in deionized water to prepare a mixed solution; and (2) adding the foam obtained in the step (1) into the mixed solution for reaction, taking out, washing with deionized water and ethanol, and drying to obtain the pH response type melamine foam oil-water separation material.
2. The preparation method of the intelligent pH-responsive melamine foam oil-water separation material according to claim 1, wherein: in the step (1), the mass percent of the 3-aminopropyl trimethoxy silane in the toluene is 0.5-1.5%.
3. The preparation method of the intelligent pH-responsive melamine foam oil-water separation material according to claim 1, wherein: in the step (1), the reflux temperature is 110-120 ℃, and the soaking reaction time is 1-5 hours.
4. The preparation method of the intelligent pH-responsive melamine foam oil-water separation material according to claim 1, wherein: in the step (2), the diethylaminoethyl methacrylate accounts for 0.5-1.9% of the water by mass.
5. The preparation method of the intelligent pH-responsive melamine foam oil-water separation material according to claim 1, wherein: the mass percentage of the copper sulfate in the water in the step (2) is 0.25-1%.
6. The preparation method of the intelligent pH-responsive melamine foam oil-water separation material according to claim 1, wherein: in the step (2), the reaction temperature is 70-90 ℃, and the reaction time is 2-6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911409934.XA CN111013199A (en) | 2019-12-31 | 2019-12-31 | Preparation method of intelligent pH response type melamine foam oil-water separation material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911409934.XA CN111013199A (en) | 2019-12-31 | 2019-12-31 | Preparation method of intelligent pH response type melamine foam oil-water separation material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111013199A true CN111013199A (en) | 2020-04-17 |
Family
ID=70197666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911409934.XA Pending CN111013199A (en) | 2019-12-31 | 2019-12-31 | Preparation method of intelligent pH response type melamine foam oil-water separation material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111013199A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114196066A (en) * | 2021-12-06 | 2022-03-18 | 南京林业大学 | Thermal response type intelligent sponge and preparation method and application thereof |
| CN114752102A (en) * | 2022-03-11 | 2022-07-15 | 广州大学 | Oil-absorbing foam with pH/thermal response, flame retardance and sterilization functions as well as preparation method and application thereof |
| CN117903491A (en) * | 2024-03-13 | 2024-04-19 | 西南石油大学 | Benzoxazine modified super-hydrophobic melamine foam and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4734205A (en) * | 1986-09-08 | 1988-03-29 | Exxon Research And Engineering Company | Hydrophobically associating polymers for oily water clean-up |
| CN102731734A (en) * | 2012-04-23 | 2012-10-17 | 常州大学 | Method for grafting polymer on nano-grade SiO2 surface |
| CN104874295A (en) * | 2015-05-04 | 2015-09-02 | 哈尔滨工业大学 | Preparation method of super-hydrophilic self-cleaning multifunctional graded oil-water separation material |
| CN105837852A (en) * | 2016-03-09 | 2016-08-10 | 杭州师范大学 | Hydrophobic and oleophobic open-cell foam material and preparation method thereof |
| CN106893135A (en) * | 2017-03-22 | 2017-06-27 | 常州大学 | A kind of preparation method of the melamine foamed plastic oil absorption material that toughness improves |
| CN106928465A (en) * | 2017-03-02 | 2017-07-07 | 山东师范大学 | A kind of pH response types metal organic frame nanocrystal and preparation method and application |
| CN106944016A (en) * | 2017-03-18 | 2017-07-14 | 华南理工大学 | A kind of pH responses water-oil separating foam and preparation method thereof |
-
2019
- 2019-12-31 CN CN201911409934.XA patent/CN111013199A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4734205A (en) * | 1986-09-08 | 1988-03-29 | Exxon Research And Engineering Company | Hydrophobically associating polymers for oily water clean-up |
| CN102731734A (en) * | 2012-04-23 | 2012-10-17 | 常州大学 | Method for grafting polymer on nano-grade SiO2 surface |
| CN104874295A (en) * | 2015-05-04 | 2015-09-02 | 哈尔滨工业大学 | Preparation method of super-hydrophilic self-cleaning multifunctional graded oil-water separation material |
| CN105837852A (en) * | 2016-03-09 | 2016-08-10 | 杭州师范大学 | Hydrophobic and oleophobic open-cell foam material and preparation method thereof |
| CN106928465A (en) * | 2017-03-02 | 2017-07-07 | 山东师范大学 | A kind of pH response types metal organic frame nanocrystal and preparation method and application |
| CN106944016A (en) * | 2017-03-18 | 2017-07-14 | 华南理工大学 | A kind of pH responses water-oil separating foam and preparation method thereof |
| CN106893135A (en) * | 2017-03-22 | 2017-06-27 | 常州大学 | A kind of preparation method of the melamine foamed plastic oil absorption material that toughness improves |
Non-Patent Citations (1)
| Title |
|---|
| 陈肖博: "玻璃表面铜-胺氧化还原引发自由基接枝聚合", 《高分子学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114196066A (en) * | 2021-12-06 | 2022-03-18 | 南京林业大学 | Thermal response type intelligent sponge and preparation method and application thereof |
| CN114752102A (en) * | 2022-03-11 | 2022-07-15 | 广州大学 | Oil-absorbing foam with pH/thermal response, flame retardance and sterilization functions as well as preparation method and application thereof |
| CN117903491A (en) * | 2024-03-13 | 2024-04-19 | 西南石油大学 | Benzoxazine modified super-hydrophobic melamine foam and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111013199A (en) | Preparation method of intelligent pH response type melamine foam oil-water separation material | |
| Su et al. | Recent progress in electrospun nanofibrous membranes for oil/water separation | |
| You et al. | Direct coating of a DKGM hydrogel on glass fabric for multifunctional oil-water separation in harsh environments | |
| Wu et al. | Self-cleaning pH/thermo-responsive cotton fabric with smart-control and reusable functions for oil/water separation | |
| Wang et al. | Ultrafast fabrication of metal–organic framework-functionalized superwetting membrane for multichannel oil/water separation and floating oil collection | |
| Liu et al. | Surface modification of porous substrates for oil/water separation using crosslinkable polybenzoxazine as an agent | |
| CN109261127B (en) | Non-selective oleophobic hydrophilic material and preparation method and application thereof | |
| Xiang et al. | Recent advances in eco-friendly fabrics with special wettability for oil/water separation | |
| Zhiheng et al. | A bio-inspired green method to fabricate pH-responsive sponge with switchable surface wettability for multitasking and effective oil-water separation | |
| Liu et al. | High-efficiency oil/water absorbent using hydrophobic silane-modified plant fiber sponges | |
| Li et al. | Superwetting pH-responsive polyaniline coatings: toward versatile separation of complex oil–water mixtures | |
| Zhang et al. | Fabrication of robust superhydrophobic filter paper for oil/water separation based on the combined octadecanoyl chain bonding and polymer grafting via surface-initiated ATRP | |
| Mir et al. | Recent advances in oil/water separation using nanomaterial-based filtration methods for crude oil processing-a review | |
| Abu Elella et al. | Superwetting cotton textiles for separation of oil/water mixtures | |
| Satilmis et al. | Superhydrophobic hexamethylene diisocyanate modified hydrolyzed polymers of intrinsic microporosity electrospun ultrafine fibrous membrane for the adsorption of organic compounds and oil/water separation | |
| Shami et al. | Durable light-driven three-dimensional smart switchable superwetting nanotextile as a green scaled-up oil–water separation technology | |
| CN110734655A (en) | pH-responsive super-hydrophobic coating material, and preparation method and application thereof | |
| CN110280048B (en) | Underwater super-oleophobic and oil-super-hydrophobic material for oil-water emulsion separation and solvent-free preparation method thereof | |
| Chen et al. | Functionalization of biodegradable PLA nonwoven fabrics as super-wetting membranes for simultaneous efficient dye and oil/water separation | |
| Wang et al. | Beadlike porous fibrous membrane with switchable wettability for efficient oil/water separation | |
| Xin et al. | Different types of membrane materials for oil-water separation: Status and challenges | |
| CN108341990A (en) | A kind of simple, the super-hydrophobic composite material of low cost preparation method | |
| CN106944016B (en) | A kind of pH responsiveness water-oil separating foam and preparation method thereof | |
| Wang et al. | Fabrication of a superhydrophilic/underwater superoleophobic stainless steel mesh for oil/water separation with ultrahigh flux | |
| AU2021103727A4 (en) | Deoiling and purification device for emulsified wastewater |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200417 |