CN114752102A - Oil-absorbing foam with pH/thermal response, flame retardance and sterilization functions as well as preparation method and application thereof - Google Patents

Oil-absorbing foam with pH/thermal response, flame retardance and sterilization functions as well as preparation method and application thereof Download PDF

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CN114752102A
CN114752102A CN202210242320.2A CN202210242320A CN114752102A CN 114752102 A CN114752102 A CN 114752102A CN 202210242320 A CN202210242320 A CN 202210242320A CN 114752102 A CN114752102 A CN 114752102A
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foam
pda
thermal response
flame retardant
oil
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CN114752102B (en
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林璟
陈雅
刘自力
左建良
王琪莹
叶婉仪
刘健伟
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Guangzhou University
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Abstract

The invention relates to a multifunctional material and a preparation method and application thereof. The multifunctional material has a three-dimensional porous melamine formaldehyde resin substrate with high porosity; fe with photo-thermal effect is deposited on the melamine formaldehyde resin substrate3O4PDA composite nanoparticles to form Fe3O4-PDA @ MF; said Fe3O4In situ polymerization on-PDA @ MF of pH/temperature-responsive copolymer NIPAAm-co-DMAEMA consisting of n-isopropylacrylamide and 2- (dimethylamino) ethyl methacrylateA layer. The surface layer of the foam material is modified with hexadecyl trimethoxy silane to form P-Fe with switchable surface wettability3O4-PDA @ MF functional pH/thermal response, flame retardant, bactericidal functional oil-absorbing foam. The multifunctional oil absorption foam with pH/thermal response, flame retardance and sterilization functions is used for absorption and desorption recycling of high-viscosity crude oil, and can be connected with a power supply and a lamp bead to serve as an alarm in the early stage of fire.

Description

Oil-absorbing foam with pH/thermal response, flame retardance and sterilization functions as well as preparation method and application thereof
Technical Field
The invention relates to the field of multifunctional materials, in particular to a multifunctional material for oil-water separation, and a preparation method and application thereof.
Background
With the development of industry and the progress of technology, the problems of frequent oil spill accidents, chemical leakage, discharge of industrial oily wastewater and domestic sewage and the like are increasingly prominent, which poses great threats to the ecological environment and human health and wastes energy. Although many methods can treat the oily wastewater at present, such as flocculation, in-situ combustion, microbial decomposition and remediation, oil skimmers, gravity separation and the like, the methods have the disadvantages of complicated separation process, high operation cost, low separation efficiency, even secondary pollution and the like, and cannot fully meet the complex oily wastewater treatment requirements. The oil absorption material with special wettability is gradually one of the hot spots and directions of the oil-water separation research at home and abroad at present due to high adsorption capacity, good mechanical durability, low cost and simple design.
At present, more oil-absorbing materials are disclosed in Chinese patent CN111054317A, which is published by 2020.04.24, and discloses a preparation method of a porous polyacrylate oil-absorbing material with ultrahigh porosity. The invention takes acrylic ester as monomer, and the solution obtained by dissolving emulsifier in the monomer is oil phase; taking an aqueous solution containing an electrolyte and an initiator as a water phase; and adding the water phase into the stirred oil phase to obtain a high internal phase emulsion, transferring the obtained emulsion into a mould, putting the mould into a constant-temperature water tank for polymerization, and drying the obtained material to obtain the polyacrylate porous material with an open pore structure, high water oil separation efficiency and porosity of 97.5%. The material has adjustable porous structure and higher oil absorption multiplying power and speed than the material obtained by the prior art. Although the oil absorption material has high porosity, most of the oil absorption materials only meet simple oil absorption requirements and cannot meet the harsh operating conditions in complex oil-containing wastewater or oil-water separation, for example, high-viscosity crude oil (the viscosity is more than 103mPa & s) at normal temperature is not easily adsorbed by the oil absorption material, and the existing oil absorption material can only adsorb but cannot desorb, so that the treatment problem of secondary pollutants is caused; in addition, aiming at the problem that the oil absorption material is easily interfered by severe weather conditions such as sea wind and the like in the spilled oil recovery operation, the operability is seriously influenced; in addition, the oil product has flammability, and has great fire safety hidden trouble in the process of storage and transportation; a large amount of bacterial communities and microorganisms usually exist in the oily wastewater, and if biological pollution still exists in the treated water, diseases can be transmitted through a water medium, so that the human health is threatened. Therefore, in view of the above-mentioned troublesome problems, it is still a great challenge to develop a multi-response type oil-water separation material capable of meeting the requirements of complex oily wastewater treatment.
Disclosure of Invention
Aiming at the problem of single function of the existing oil absorption material, the invention provides a multifunctional oil absorption foam with acid-base and thermal response and combustion supporting and/or photo-thermal sterilization, so as to solve the technical problems that the conventional or high-viscosity crude oil cannot be efficiently adsorbed, the oil absorption material cannot be recycled and the like, and realize green treatment of complex oily wastewater.
The first purpose of the present invention is to provide a flame-retardant and bactericidal oil-absorbing foam with acid-base and thermal response functions, which has a three-dimensional porous melamine-formaldehyde resin (polymer obtained by the reaction of melamine and formaldehyde, also known as melamine-formaldehyde resin and melamine resin, abbreviated as MF in english) substrate with high porosity; fe with a photo-thermal effect is deposited on the melamine formaldehyde resin substrate3O4PDA composite sodiumRice grains forming Fe3O4-PDA @ MF; said Fe3O4-PDA @ MF on-site polymerisation of a pH/temperature responsive copolymer NIPAAm-co-DMAEMA consisting of n-isopropylacrylamide (NIPAAm) and 2- (dimethylamino) ethyl methacrylate (DMAEMA) to form a foam skin.
The surface layer of the foam material is modified with hexadecyl trimethoxy silane (HDTMS) to form P-Fe with switchable surface wettability 3O4-PDA @ MF functional pH/thermal response, flame retardant, bactericidal functional oil absorbing foam.
The second purpose of the invention is to provide a preparation method of the oil absorption foam with acid-base and thermal response functions, flame retardance and sterilization functions, which comprises the following steps:
s1 deposition of Fe with photo-thermal effect on three-dimensional porous MF substrate with high porosity3O4PDA composite nanoparticles to obtain Fe3O4-PDA@MF；
S2 at said Fe3O4-in situ polymerization on PDA @ MF of a pH/temperature responsive copolymer NIPAAm-co-DMAEMA consisting of n-isopropylacrylamide and 2- (dimethylamino) ethyl methacrylate, forming a foam surface layer;
s3 hexadecyl trimethoxy silane is modified on the surface layer of the foam material to form P-Fe with switchable surface wettability3O4-PDA @ MF functional pH/thermal response, flame retardant, bactericidal functional oil-absorbing foam.
Preferably, the S1 specifically includes:
s1.1 adding a certain amount of FeCl3·6H2O and CH3COONa·3H2Preparation of Fe by O by hydrothermal method3O4NPs powder;
s1.2 adding dopamine hydrochloride and CuSO with certain concentration4And H2O2Dissolving the melamine formaldehyde resin in a tris (hydroxymethyl) aminomethane buffer solution to form a mixed solution, and soaking a melamine formaldehyde resin substrate in the mixed solution to obtain PDA @ MF;
s1.3 soaking the PDA @ MFF in Fe with a certain concentration 3O4In NPs dispersion, Fe is obtained3O4-PDA@MF。
Preferably, the S2 specifically includes:
s2.1 in said Fe3O4Grafting Vinyltrimethoxysilane (VTMS) on PDA @ MF to obtain VTMS-Fe3O4-PDA@MF；
S2.2 combining the VTMS-Fe3O4-PDA @ MF is added into deionized water containing N-isopropylacrylamide, 2- (dimethylamino) ethyl methacrylate (ETA) and N, N' -Methylenebisacryloyl (MBA), and the mixture is uniformly stirred to form a mixed reaction solution;
s2.3, dropwise adding an Ammonium Persulfate (APS) initiator solution into the mixed reaction solution, and carrying out in-situ free radical polymerization reaction to form a foam material surface layer with a pH/temperature response type copolymer NIPAAm-co-DMAEMA;
preferably, the S3 specifically includes:
s3.1, dissolving a predetermined amount of hexadecyl trimethoxy silane (HDTMS) in an ethanol solution containing deionized water, and dropwise adding ammonia water to adjust the pH value to about 10 to form an HDTMS solution;
s3.2, immersing the foam material into the HDTMS solution for silanization reaction, washing with deionized water, and drying in a baking oven to obtain P-Fe3O4-PDA @ MF functional pH/thermal response, flame retardant, bactericidal functional oil-absorbing foam.
The third purpose of the invention is to provide an application method of the flame-retardant and bactericidal oil-absorbing foam with acid-base and thermal response functions, wherein the pH/thermal response, flame-retardant and bactericidal oil-absorbing foam is used for absorption and reuse of high-viscosity crude oil.
Preferably, the pH/thermal response, flame retardant and sterilization oil absorption foam is used under the irradiation of sunlight, the temperature can be raised to 50-70 ℃, and the oil absorption capacity on water and under water is enhanced.
Preferably, the pH/thermal response, flame retardant and bactericidal oil absorption foam full of crude oil is soaked in a solution with the pH value of 1 for crude oil desorption, so that the crude oil and the pH/thermal response, flame retardant and bactericidal oil absorption foam are recycled.
The fourth purpose of the invention is to provide another application method aiming at the oil absorption foam with acid-base and thermal response functions and flame retardant and sterilization functions, and the oil absorption foam with pH/thermal response, flame retardant and sterilization functions is connected with a power supply and a lamp bead to serve as an alarm device in the early stage of fire.
Compared with the prior art, the functional oil-absorbing foam and the preparation method and application thereof provided by the invention have the following beneficial effects:
(1) the invention is characterized in that Fe is deposited on the melamine porous foam3O4The PDA composite nano particles trigger the temperature-sensitive response of a PNIPAAm polymer chain on the foam by utilizing the synergistic photothermal effect of the nano particles under illumination, so that the wettability of the foam from hydrophilic/oleophilic to hydrophobic/oleophilic is changed, the foam shows excellent oil absorption performance on water and under water, and the oil absorption capacity is 18.67-43.83 g.g.g.g -1。
(2)Fe3O4The PDA composite nano-particle has excellent photo-thermal effect, can quickly heat high-viscosity crude oil to 35 ℃, and the viscosity is 1.39 multiplied by 105The viscosity is reduced to 71.77 mPas, the viscosity is obviously reduced by 4 orders of magnitude, the fluidity of the crude oil is improved, and the oil spill capacity (12.8 g) of the crude oil recovered by the oil absorption foam is greatly improved-1)。
(3) By introducing PDMAEMA into the foam, the absorbed oil can be automatically desorbed from the foam under the condition of pH response (pH is 1) without additional energy input, the maximum desorption rate is 98.4%, and the oil contact angles (UOCA) of underwater light oil (cyclohexane) and heavy oil (1, 2-dichloroethane) can reach 154.5 +/-0.2 degrees and 153.8 +/-0.3 degrees respectively, so that the oil absorption foam has good recycling performance.
(4) The functional oil absorption foam can separate oil and bacteria from complex bacteria-containing oily wastewater, shows excellent antibacterial performance and remarkable antifouling effect, benefits from excellent photo-thermal antibacterial performance of the foam, has low oil adhesive force, and forms a hydration layer on the surface.
(5) The oil absorption foam has the advantages that the overflowing oil can be remotely adsorbed due to the fire resistance and the magnetism, and can be rapidly recovered even in a fire disaster caused by large-range oil overflowing, so that the further diffusion and spread of the fire can be prevented.
(6) Fire early warning and response can also be realized to this function oil absorption foam, can regard as the alarm of conflagration emergence prophase behind external 60V power and 1.5W's the LED lamp, when contacting the burning things which may cause a fire disaster after, can light the LED lamp in 37s, provide abundant response time for each side's reply major fire risk.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, without inventive effort, further drawings may be derived from the following figures.
FIG. 1 is P-Fe in example 23O4-water contact angle test plot after PDA @ MF illumination;
FIG. 2 is P-Fe in example 23O4Photographs of the adsorption of PDA @ MF on light oil (cyclohexane) and heavy oil (1, 2-dichloroethane);
FIG. 3 is P-Fe in example 23O4-graph of the adsorption capacity of PDA @ MF on different oily substances;
FIG. 4 is P-Fe in example 23O4-graph of adsorption and desorption rates of PDA @ MF on different oily substances;
FIG. 5 is P-Fe in example 33O4-graph of the absorption of PDA @ MF on crude oil without and after illumination;
FIG. 6 is a photograph and a distribution chart of particle size of a mixed emulsion of Staphylococcus aureus and Escherichia coli in example 4 after being spread on an agar plate before and after filtration;
FIG. 7 shows P-Fe before and after irradiation in example 43O4-temperature variation of PDA @ MF and graph of bactericidal effect on staphylococcus aureus and escherichia coli;
FIG. 8 is P-Fe in example 53O4-PDA @ MF oil absorbing flame retardant picture;
FIG. 9 is P-Fe in example 53O4-oil absorption fire extinguishing pictures of PDA @ MF under magnetically controlled and non-magnetically controlled conditions;
FIG. 10 is P-Fe in example 53O4-PDA@MF fire sensing alarm pictures;
FIG. 11 is an electron microscope image of a functional pH/thermal response, flame retardant, germicidal functional oil absorbing foam provided by the present invention.
Detailed Description
The pH/thermal response, flame retardation and sterilization oil-absorbing foam provided by the present invention, the preparation method and application thereof are further described below with reference to the accompanying drawings, and it should be noted that the technical solution and design principle of the present invention are described in detail below with only one optimized technical solution.
Preferably, the flame-retardant and bactericidal oil-absorbing foam with acid-base and thermal response functions has a three-dimensional porous melamine formaldehyde resin (MF) substrate foam with high porosity; fe with photo-thermal effect is deposited on the MF substrate3O4PDA composite nanoparticles to form Fe3O4-PDA @ MF, which has the function of absorbing the solar energy converted into thermal energy; said Fe 3O4In situ polymerization on-PDA @ MF of a pH/temperature responsive copolymer poly (NIPAAm-co-DMAEMA) consisting of n-isopropylacrylamide (NIPAAm) and 2- (dimethylamino) ethyl methacrylate (DMAEMA) to form a foam skin. The surface layer of the foam material is modified with hexadecyl trimethoxy silane (HDTMS) to form P-Fe with switchable surface wettability3O4-PDA @ MFpH/thermal response, flame retardant, germicidal functional oil absorbent foam, wherein the pH/thermal response, flame retardant, germicidal functional oil absorbent foam is shown in figure 11.
The preparation method of the oil absorption foam with acid-base, thermal response function, flame retardance and sterilization functions comprises the following steps:
s1 depositing Fe3O4/PDA composite nano particles with photo-thermal effect on the three-dimensional porous MF substrate with high porosity to obtain Fe3O4-PDA@MF；
S2 at said Fe3O4-in situ polymerization on PDA @ MF of a pH/temperature responsive copolymer NIPAAm-co-DMAEMA consisting of n-isopropylacrylamide and 2- (dimethylamino) ethyl methacrylate, forming a foam surface layer;
s3 the surface layer of the foam material is modified with hexadecyl trimethoxy silane to form P-Fe with switchable surface wettability3O4-PDA @ MF functional pH/thermal response, flame retardant, bactericidal functional oil-absorbing foam.
Wherein, the S1 specifically includes:
s1.1 applying a defined amount of FeCl3·6H2O and CH3COONa·3H2Preparation of Fe from O by hydrothermal method3O4NPs powder;
s1.2 adding dopamine hydrochloride and CuSO with certain concentration4And H2O2Dissolving the melamine formaldehyde resin in a tris (hydroxymethyl) aminomethane buffer solution to form a mixed solution, and soaking a melamine formaldehyde resin substrate in the mixed solution to obtain PDA @ MF;
s1.3 soaking the PDA @ MFF in Fe with a certain concentration3O4In the NPs dispersion, Fe is obtained3O4-PDA@MF。
The S2 specifically includes:
s2.1 in said Fe3O4Grafting Vinyltrimethoxysilane (VTMS) on PDA @ MF to obtain VTMS-Fe3O4-PDA@MF；
S2.2 combining the VTMS-Fe3O4-PDA @ MF is added into deionized water containing N-isopropylacrylamide, 2- (dimethylamino) ethyl methacrylate and N, N' -methylenebisacryloyl, and the mixture is uniformly stirred to form a mixed reaction solution;
s2.3, dropwise adding an ammonium persulfate initiator solution into the mixed reaction liquid, and carrying out in-situ free radical polymerization reaction to form a foam material surface layer with a pH/temperature response type copolymer NIPAAm-co-DMAEMA;
the S3 specifically includes:
s3.1, dissolving a predetermined amount of hexadecyl trimethoxy silane in an ethanol solution containing deionized water, and dropwise adding ammonia water to adjust the pH value to about 10 to form an HDTMS solution;
S3.2, immersing the foam material into the HDTMS solution for silanization reaction, washing with deionized water, and drying in a baking oven to obtain P-Fe3O4-PDA @ MF functional pH/thermal response, flame retardance and sterilization functional oil absorption foam.
The pH/thermal response, flame retardant, germicidal functional oil absorbing foam and the specific preparation and application are detailed below by specific examples:
example 1
A preparation method of a functional oil absorption foam with pH/thermal response, flame retardance and photo-thermal sterilization comprises the following steps:
(1) 1.35g FeCl3·6H2O and 3.6g CH3COONa·3H2Dissolving O in 40mL of ethylene glycol, stirring for 10 minutes at room temperature, transferring into a high-pressure autoclave with a polytetrafluoroethylene lining, placing the high-pressure autoclave into a drying oven with the temperature of 200 ℃, heating and reacting for 8 hours, performing solid-liquid separation by using a magnet, respectively washing with absolute ethyl alcohol and deionized water for three times, and finally drying by using a freeze dryer to obtain Fe3O4NPs powder.
(2) Dopamine hydrochloride (2 mg. mL)-1),CuSO4(5mmol·L-1) And H2O2(19.6mmol·L-1) Dissolving in Tris buffer (pH 8.5,0.2 mol. L)-1) A mixed solution was formed, and then the foam was immersed in the mixed solution for 1 hour, rinsed three times with deionized water, and placed in an oven at 80 ℃ for drying to give PDA @ MF. Soaking PDA @ MF in 3 mg.mL-1Fe (b) of 3O4In the NPs dispersion, repeating the steps for three times to obtain Fe3O4-PDA@MF。
(3) Dissolving 300 μ L of VTMS in 15mL of ethanol solution containing 20% deionized water, dropwise adding a certain amount of ammonia water (25%) to adjust the pH value to 10, and adding Fe3O4-PDA @ MF is immersed in the solution for a silanization reaction for 30 minutes, washed by deionized water and then dried in an oven at 100 ℃ for 1 hour to obtain VTMS-Fe3O4-PDA@MF。
(4) The prepared VTMS-Fe3O4Adding the-PDA @ MF into a deionized water (solid content is 4 wt%) mixed reaction solution containing NIPAAm, DMAEMA and 8:2 (molar ratio) and N, N' -Methylene Bisacryloyl (MBA) (accounting for 2.5 wt% of the total monomer content), uniformly stirring, and adding an Ammonium Persulfate (APS) initiator solution (2 mg. mL)-1) Dropwise adding the mixture into the mixed reaction solution, and carrying out in-situ radical polymerization at 80 ℃ for 6 hours to modify a layer of pH/temperature response type copolymer poly (NIPAAm-co-DMAEMA) on the foam.
(5) Dissolving 50 mu L of HDTMS in 15mL of ethanol solution containing 20% of deionized water, dropwise adding ammonia water (25%) to adjust the pH value to 10, immersing the foam in the solution (4) in the HDTMS solution for silanization reaction for 30 minutes, washing with deionized water, and drying in an oven at 100 ℃ for 1 hour to obtain P-Fe3O4-PDA@MF。
Example 2
The embodiment relates to application of the pH/thermal response, flame retardance and photo-thermal sterilization functional oil absorption foam in separation of oil-water mixtures.
(1) The P-Fe obtained above is added3O4PDA @ MF simulated solar illumination for 5 minutes on a xenon lamp changed the wettability of the foam surface from hydrophilic/lipophilic to hydrophobic/lipophilic, as shown in FIG. 1, the water contact angle in air was 145.3. + -. 0.1 ℃ and the lasting hydrophobicity could be maintained for 10 min.
(2) Subjecting the hydrophobic/lipophilic P-Fe of (1) above to3O4PDA @ MF is used for the adsorption of light oil on water (cyclohexane) and heavy oil under water (1, 2-dichloroethane), as shown in fig. 2, air is trapped around the froth to form an air/water/solid interface, reducing the contact area of the solid surface with water, and then oil is rapidly sucked by the froth, achieving separation of oil-water mixture and recovery of oil.
(3) Separately reacting the hydrophobic/lipophilic P-Fe of (1) above3O4-PDA @ MF was immersed in different oily substances (tetrachloromethane, 1, 2-dichloroethane, toluene, petroleum ether, acetone, cyclohexane) and oils (silicone oil, pump oil, crude oil) until adsorption was saturated, and tested for their oil absorption capacity on different oils. The saturated oil absorption capacity of the foam was calculated according to the formula eq 1.
Figure BDA0003542913830000091
Wherein m is1Is P-Fe after oil absorption3O4-the quality of PDA @ MF,m0is P-Fe before oil absorption3O4Quality of PDA @ MF, kaIs the saturated oil absorption capacity.
P-Fe as shown in FIG. 33O4The adsorption capacity of the PDA @ MF foam to various oily substances is 18.67-43.83 g g of the self mass -1The foam is shown to have good adsorption and separation performance on oil/water mixture.
(4) P-Fe after absorbing light oil (cyclohexane) and heavy oil (1, 2-dichloroethane)3O4-PDA @ MF is transferred to a separation device containing an aqueous solution with pH 1 and soaked to convert the foam surface wettability to hydrophilic/underwater superoleophobic. The adsorbed oil is desorbed and the oil and water are separated by a valve of the separator according to the difference in density and weighed. The desorption rate of the foam oil was calculated according to the formula eq 2.
Figure BDA0003542913830000092
Wherein m is2Mass of desorbed oil, m1Is P-Fe after oil absorption3O4Quality of PDA @ MF, m0Is P-Fe before oil absorption3O4Quality of PDA @ MF, kdThe oil desorption rate.
P-Fe as shown in FIG. 43O4The desorption rate of the-PDA @ MF foam to various oily substances (CYH: cyclohexane, DCE:1, 2-dichloroethane, TL: toluene, NHD: n-hexane and PE: petroleum ether) is 92.7-98.4%, which indicates that the foam can realize the recovery of oil and the recycling of oil-absorbing foam materials, and the 10 th desorption recovery rate can still reach 91.9% through the test of the circulating absorption-desorption oil (1, 2-dichloroethane), so that the foam has better recycling performance.
Example 3
The embodiment relates to application of the pH/thermal response, flame retardance and photo-thermal sterilization functional oil absorption foam in photo-thermal adsorption of high-viscosity spilled oil.
As shown in FIG. 5, under the condition of 25 ℃ ambient temperature without light, the liquid drops of the high-viscosity crude oil are in P-Fe3O4-PDA @ MF surface supportAfter 45 minutes, no obvious morphological change exists, and the foam can not absorb the foam. Under the illumination condition (the illumination intensity is 1.0 kW.m)-2)，P-Fe3O4PDA @ MF can rapidly raise the temperature due to the light-to-heat characteristic, and the temperature of the crude oil is raised to 30.4 ℃ within 10s, so that the viscosity of the crude oil is greatly reduced, and the flow permeability of the crude oil is enhanced, and when the temperature reaches 27s, the temperature of the crude oil is raised to 35.8 ℃ and the crude oil can completely permeate into the oil absorption foam. The rapid temperature rise of the foam can improve the temperature of the crude oil through heat conduction, thereby reducing the viscosity of the crude oil, accelerating the absorption rate of the foam on the heavy oil, and leading the crude oil absorption capacity to reach 12.8 g.g-1。
Example 4
The embodiment relates to application of the intelligent multi-response functional oil absorption foam in separation of bacteria-containing oil-in-water emulsion and photothermal antibiosis
(1) P-Fe3O4PDA @ MF foam is squeezed into a separating funnel and the oil-in-water emulsion containing staphylococcus aureus or escherichia coli is filtered, bacteria and oil droplets are trapped in the pores of the compressed foam, clean water is collected in the filter flask. As shown in FIG. 6, the average particle size of the emulsion before filtration was 2360nm (gold dextran) and 2365nm (large intestine), and the average particle size of the pure water after filtration was 100.4nm (gold dextran) and 102.4nm (large intestine). Coating the bacteria-containing emulsion before and after filtration on agar plate, and culturing at 37 deg.C for 24 hr to find that the emulsion before filtration contains a large amount of bacterial colony, and no Escherichia coli or Staphylococcus aureus is found in the filtrate, indicating that most bacteria are trapped in P-Fe 3O4-PDA @ MF.
(2) After the filtration, the filter was moved to a place under a xenon lamp, and the illumination intensity was set to 3.0 kW.m-2And continuously irradiating for 1 hour and 30 minutes, and observing P-Fe in an experimental group of staphylococcus aureus and escherichia coli by using a thermal infrared imager3O4-PDA @ MF foam was heated to 74.6 ℃ and 70.3 ℃ respectively, and bacteria were detached from the foam surface by shaking in PBS solution for 30 minutes, as shown in FIG. 7, a large amount of bacteria were visible on the culture medium after the non-light-treated foam was cultured by coating, and no bacteria appeared on the light-treated foam culture mediumFalling off, indicating P-Fe3O4The excellent photo-thermal sterilization capability of PDA @ MF shows excellent potential in the field of bacteria-containing wastewater treatment, and the problem of drug resistance of the traditional antibacterial agent can be solved.
Example 5
The embodiment relates to application of the functional oil absorption foam with pH/thermal response, flame retardance and photo-thermal sterilization in magnetic fire extinguishment and fire sensing alarm.
(1) As shown in FIG. 8, we put P-Fe into a Petri dish containing oil (cyclohexane) immediately after ignition combustion3O4PDA @ MF foam to petri dish, it was observed that the foam rapidly absorbed oil into the foam, the fire rapidly decreased, and finally extinguished. Fe3O4The introduction of the foam can endow the foam with certain magnetic response characteristics, and the foam can be applied to remote control oil absorption. Further controlling the foam with the magnet, as shown in fig. 9, it was found that the magnet controlled foam oil absorption operation more rapidly absorbed a wide range of oils (12s) than the non-magnetically controlled oil absorption time (33s), and rapidly decreased the temperature around the fire source, reducing the possibility of fire spreading.
(2) In P-Fe3O4The PDA @ MF foam is connected with a 60V power supply on both sides and a small bulb to form a series circuit, so as to move the fire source to the vicinity of the foam, as shown in fig. 10, and the foam can light the small bulb within 37s after contacting with flame to perform response early warning, which provides enough and timely response time for people to deal with serious fire risks.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that several modifications, substitutions, improvements and embellishments of the steps can be made without departing from the spirit and scope of the invention, and these modifications, substitutions, improvements and embellishments should also be construed as the scope of the invention.

Claims (9)

1. A pH/thermal response, flame retardant, germicidal oil absorbing foam having a high porosity three dimensional porous melamine formaldehyde resin substrate;
fe with a photo-thermal effect is deposited on the melamine formaldehyde resin substrate3O4PDA composite nanoparticles to form Fe3O4-PDA@MF；
Said Fe3O4-in situ polymerization on PDA @ MF of a pH/temperature responsive copolymer NIPAAm-co-DMAEMA consisting of n-isopropylacrylamide and 2- (dimethylamino) ethyl methacrylate, forming a foam surface layer;
The surface layer of the foam material is modified with hexadecyl trimethoxy silane to form P-Fe with switchable surface wettability3O4-PDA @ MF functional pH/thermal response, flame retardant, bactericidal functional oil absorbing foam.
2. A method for preparing the pH/thermal response, flame retardant, bactericidal functional oil absorbing foam of claim 1, which comprises the following steps:
s1 deposition of Fe with photo-thermal effect on three-dimensional porous melamine formaldehyde resin substrate with high porosity3O4PDA composite nanoparticles to obtain Fe3O4-PDA@MF；
S2 at said Fe3O4-in situ polymerization on PDA @ MF of a pH/temperature responsive copolymer NIPAAm-co-DMAEMA consisting of n-isopropylacrylamide and 2- (dimethylamino) ethyl methacrylate, forming a foam surface layer;
s3 hexadecyl trimethoxy silane is modified on the surface layer of the foam material to form P-Fe with switchable surface wettability3O4-PDA @ MF functional pH/thermal response, flame retardant, bactericidal functional oil-absorbing foam.
3. The method for preparing the pH/thermal response, flame retardant and bactericidal functional oil absorption foam as claimed in claim 2, wherein the pH/thermal response, flame retardant and bactericidal functional oil absorption foam comprises the following steps: the S1 specifically includes:
s1.1 adding a certain amount of FeCl3·6H2O and CH3COONa·3H2Preparation of Fe by O by hydrothermal method3O4NPs powder;
s1.2 adding dopamine hydrochloride and CuSO with certain concentration 4And H2O2Dissolving the melamine formaldehyde resin in a tris (hydroxymethyl) aminomethane buffer solution to form a mixed solution, and soaking a melamine formaldehyde resin substrate in the mixed solution to obtain PDA @ MF;
s1.3 soaking the PDA @ MFF in Fe with a certain concentration3O4In NPs dispersion, Fe is obtained3O4-PDA@MF。
4. The method for preparing the pH/thermal response, flame retardant and bactericidal functional oil absorption foam as claimed in claim 2, wherein the pH/thermal response, flame retardant and bactericidal functional oil absorption foam comprises the following steps: the S2 specifically includes:
s2.1 in said Fe3O4Grafting vinyl trimethoxy silane on-PDA @ MF to obtain VTMS-Fe3O4-PDA@MF；
S2.2 combining the VTMS-Fe3O4-PDA @ MF is added into deionized water containing N-isopropylacrylamide, 2- (dimethylamino) ethyl methacrylate and N, N' -methylenebisacryloyl, and the mixture is uniformly stirred to form a mixed reaction solution;
s2.3, dropwise adding an ammonium persulfate initiator solution into the mixed reaction liquid, and carrying out in-situ free radical polymerization reaction to form a foam material surface layer with a pH/temperature response type copolymer NIPAAm-co-DMAEMA.
5. The method for preparing the pH/thermal response, flame retardant and bactericidal functional oil absorption foam as claimed in claim 2, wherein the pH/thermal response, flame retardant and bactericidal functional oil absorption foam comprises the following steps: the S3 specifically includes:
s3.1, dissolving a predetermined amount of hexadecyl trimethoxy silane in an ethanol solution containing deionized water, and dropwise adding ammonia water to adjust the pH value to be more than 10 to form an HDTMS solution;
S3.2, soaking the foam material into the HDTMS solution for silanization reaction, washing with deionized water, and drying in a drying oven to obtain P-Fe3O4-PDA @ MF functional pH/thermal response, flame retardant, bactericidal functional oil absorbing foam.
6. Use of the pH/thermal responsive, flame retardant, germicidal functional oil absorbent foam of claim 1 for absorption and re-use of high viscosity crude oil.
7. The application of the pH/thermal response, flame retardant and bactericidal oil absorption foam as claimed in claim 6, wherein the pH/thermal response, flame retardant and bactericidal oil absorption foam is used under the irradiation of sunlight, the temperature of the pH/thermal response, flame retardant and bactericidal oil absorption foam is raised to 50-70 ℃, and the oil absorption capacity on water and under water is enhanced.
8. The application of the pH/thermal response, flame retardant and bactericidal function oil absorption foam as claimed in claim 7, wherein the pH/thermal response, flame retardant and bactericidal function oil absorption foam full of crude oil is soaked in a solution with a pH value of 1 for crude oil desorption, so that the crude oil and the pH/thermal response, flame retardant and bactericidal function oil absorption foam are recycled.
9. The application of the pH/thermal response, flame retardant and bactericidal functional oil absorption foam as claimed in claim 1, and the application of the pH/thermal response, flame retardant and bactericidal functional oil absorption foam connected with a power supply and a lamp bead as an alarm for the early stage of fire.
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