CN116675896B - Phenolic resin sponge material with asymmetric structure and preparation method thereof - Google Patents
Phenolic resin sponge material with asymmetric structure and preparation method thereof Download PDFInfo
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- CN116675896B CN116675896B CN202310468784.XA CN202310468784A CN116675896B CN 116675896 B CN116675896 B CN 116675896B CN 202310468784 A CN202310468784 A CN 202310468784A CN 116675896 B CN116675896 B CN 116675896B
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- 239000005011 phenolic resin Substances 0.000 title claims abstract description 82
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 title description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 68
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 20
- 229920000570 polyether Polymers 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 14
- 239000011592 zinc chloride Substances 0.000 claims description 13
- 235000005074 zinc chloride Nutrition 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000502 dialysis Methods 0.000 claims description 12
- 238000010306 acid treatment Methods 0.000 claims description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000008098 formaldehyde solution Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 33
- 230000005540 biological transmission Effects 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000010612 desalination reaction Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000013535 sea water Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- 235000019441 ethanol Nutrition 0.000 description 21
- 239000011148 porous material Substances 0.000 description 19
- 239000011240 wet gel Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- 230000008020 evaporation Effects 0.000 description 8
- 238000007710 freezing Methods 0.000 description 7
- 230000008014 freezing Effects 0.000 description 7
- 238000001000 micrograph Methods 0.000 description 7
- 229920000128 polypyrrole Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 229920003987 resole Polymers 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S70/00—Details of absorbing elements
- F24S70/10—Details of absorbing elements characterised by the absorbing material
- F24S70/14—Details of absorbing elements characterised by the absorbing material made of plastics
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
- C08J2201/0422—Elimination of an organic solid phase containing oxygen atoms, e.g. saccharose
-
- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/044—Elimination of an inorganic solid phase
- C08J2201/0444—Salts
-
- 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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with monohydric phenols
- C08J2361/10—Phenol-formaldehyde condensates
Abstract
The invention discloses a phenolic resin sponge with an asymmetric structure and a preparation method thereof. The method is simple to operate, and the prepared phenolic resin sponge with the asymmetric structure has the advantages of high porosity, controllable microstructure, good hydrophilicity and chemical corrosion resistance, can realize rapid water transmission and reduce heat loss, and has potential application value in the fields of sea water desalination, waste water purification and the like.
Description
Technical Field
The invention relates to a phenolic resin sponge material with an asymmetric structure and a preparation method thereof, belonging to the technical field of material science.
Background
Phenolic resin sponge has been used in the fields of adsorption/filtration materials, sea water desalination or waste water purification, etc. because of the advantages of low density, large specific surface area, controllable porosity, low raw material price, simple preparation method, strong chemical corrosion resistance and heat resistance, etc.
The phenolic resin sponge synthesized at present is a solid material with a reticular framework structure formed by crosslinking polymer molecules. The traditional synthesis method is to dissolve two monomers in deionized water, add acid or alkali catalyst to make them produce sol-gel reaction, then make ageing, solvent replacement and drying treatment to obtain phenolic resin sponge. However, the obtained phenolic resin sponge is generally in a symmetrical structure, has higher water storage property, and is extremely easy to cause heat loss in modes of conduction, convection, radiation and the like, so that the photo-thermal conversion efficiency of an interface is reduced, and the application of the phenolic resin sponge in the photo-thermal conversion field such as the interface solar evaporation field is limited. Therefore, in order to further improve the water transmission characteristic and the heat insulation performance of the phenolic resin sponge, development of a convenient and efficient method for preparing the phenolic resin sponge is needed, and rapid water transmission, efficient heat insulation and interface photo-thermal conversion efficiency are achieved.
Disclosure of Invention
Aiming at the problems, the invention aims to provide the phenolic resin sponge with an asymmetric structure so as to improve the water transmission performance of the phenolic resin sponge.
The invention discloses a preparation method of a phenolic resin sponge with an asymmetric structure, which comprises the following steps: mixing phenol, formaldehyde solution and sodium hydroxide solution, heating to react, regulating the pH of the solution to 5-9, drying, adding the dried solution into ethanol solution containing pore-forming agent, stirring, pouring the solution into an open container to volatilize ethanol, performing heat treatment after vacuum bubble removal, and obtaining the phenolic resin sponge with an asymmetric structure through acid treatment, ethanol water solution dialysis and freeze drying.
In one embodiment of the invention, phenol: formaldehyde: the molar ratio of the sodium hydroxide is 20:40 (0.1-2).
In one embodiment of the present invention, the temperature at the time of the heating reaction is 65 to 80℃and the reaction time is 0.5 to 2 hours.
In one embodiment of the present invention, the drying is preferably vacuum drying, and the vacuum drying time is 12 to 72 hours.
In one embodiment of the invention, the pore-forming agent is a mixture of polyether and zinc chloride, the polyether is polyether P123 or polyether F127, and the mass ratio of the polyether to the zinc chloride is 0.16-0.48.
In one embodiment of the present invention, the mass ratio of the pore-forming agent to phenol is 0.03 to 0.26.
In one embodiment of the present invention, the temperature at the time of the heat treatment is 100 to 145 ℃ and the heat treatment time is 12 to 72 hours.
In one embodiment of the present invention, the temperature at the time of the acid treatment is 90 to 100℃and the time is 6 to 24 hours.
In one embodiment of the present invention, the acid used in the acid treatment includes at least one of sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid, wherein the concentration of sulfuric acid is 20 to 98wt%, the concentration of hydrochloric acid is 20 to 37%, the concentration of phosphoric acid is 20 to 47%, and the concentration of nitric acid is 20 to 67%.
In one embodiment of the present invention, the concentration of the aqueous ethanol solution used in the dialysis is 5 to 30wt% and the dialysis time is 1 to 7 days.
In one embodiment of the present invention, the freeze-drying temperature is-150 to-50 ℃, the freeze time is 2 to 10 hours, and the drying time is 48 to 96 hours.
The invention discloses a phenolic resin sponge with an asymmetric structure, which is prepared by using the preparation method.
The invention also discloses application of the phenolic resin sponge in the field of photo-thermal conversion.
[ Advantageous effects ]
(1) The method is simple to operate, green and environment-friendly, and is a novel method for preparing the phenolic resin sponge conveniently and efficiently.
(2) The phenolic resin sponge with an asymmetric structure is prepared by regulating and controlling the microstructure of the material. Firstly preparing resol, then stirring the resol, a pore-forming agent and absolute ethyl alcohol to form a homogeneous solution through mechanical stirring, and obtaining the resol sponge with an asymmetric structure through heat treatment, acid treatment and freeze drying process treatment. On one hand, a three-dimensional porous structure is constructed, the pore-forming agent is easy to remove, and the material has better strength; on the other hand, an asymmetric pore structure has faster water transport properties than a symmetric pore structure.
(3) The phenolic resin sponge prepared by the method has the advantages of high porosity, fast water transmission, small heat loss and the like, can absorb water rapidly within 62ms, has good water transmission performance, and can absorb solar light with the absorption rate of 96.8% by the sponge evaporator after being prepared into the sponge evaporator.
(4) The evaporation efficiency of the solar evaporator prepared from the phenolic resin sponge with the asymmetric structure is higher than that of the solar evaporator prepared from the phenolic resin sponge with the symmetric structure in the prior art.
Drawings
FIG. 1 is a physical diagram of a phenolic resin sponge with an asymmetric structure prepared in example 1 of the present invention;
FIG. 2 is a diagram showing the structure of the bottom of a phenolic resin sponge with an asymmetric structure prepared in example 1 of the present invention, wherein (a) and (b) are a scanning electron microscope image and a sponge aperture statistical image, respectively;
FIG. 3 is a diagram showing the top structure of a phenolic resin sponge with an asymmetric structure prepared in example 1 of the present invention, wherein (a) and (b) are a scanning electron microscope image and a sponge aperture statistical image, respectively;
Fig. 4 is a water contact angle test chart of the pore diameter surface of the phenolic resin sponge with asymmetric structure prepared in example 1 of the present invention.
Fig. 5 is a water contact angle test chart of the large pore diameter surface of the phenolic resin sponge with asymmetric structure prepared in example 1 of the present invention.
Fig. 6 is absorbance of sunlight by the phenolic resin sponge evaporator prepared in example 1.
Fig. 7 is a bottom structural view of the phenolic resin sponge with asymmetric structure prepared in example 2.
Fig. 8 is a top structural view of the phenolic resin sponge with asymmetric structure prepared in example 2.
Fig. 9 is a bottom structural view of the phenolic resin sponge with asymmetric structure prepared in example 3.
Fig. 10 is a top structural view of the phenolic resin sponge with asymmetric structure prepared in example 3.
Fig. 11 is a bottom structural view of the phenolic resin sponge with asymmetric structure prepared in example 4.
Fig. 12 is a top structural view of the phenolic resin sponge with asymmetric structure prepared in example 4.
Fig. 13 is a physical view of the phenolic resin sponge having an asymmetric structure prepared in example 5.
FIG. 14 is a Fourier transform infrared spectrum of the sponge prepared in comparative example 2.
FIG. 15 is a bottom structural view and a physical view of the sponge prepared in comparative example 3; wherein (a) is a bottom structure diagram and (b) is a physical diagram.
Fig. 16 is a water contact angle test chart of the symmetrical phenol resin sponge of comparative example 4.
Fig. 17 is a graph comparing evaporation rates of the phenolic resin sponge evaporators of asymmetric and symmetric structures.
Detailed Description
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Example 1
Mixing 0.61g of phenol, 0.13g of 20wt% sodium hydroxide solution and 1.05g of 37wt% formaldehyde solution, stirring the mixture in a water bath at 75 ℃ for reaction for 1h, adjusting the pH of the mixed solution to 7 by using 0.6mol/L hydrochloric acid, vacuum drying at 45 ℃ for 12h, adding 3mL of ethanol solution containing 0.96g of polyether F127 and 6g of zinc chloride, stirring for volatilizing ethanol, then placing the ethanol solution in a vacuum oven for bubble discharge, then performing heat treatment at 100 ℃ for 60h to obtain a phenolic resin wet gel, placing the wet gel in 55wt% sulfuric acid, performing treatment at 100 ℃ for 7h, then placing the wet gel in 20wt% ethanol aqueous solution for dialysis for 6h, freezing at-70 ℃ for 6h, and further freeze-drying for 48h to obtain the phenolic resin sponge material with an asymmetric structure.
Phenolic resin sponge material with asymmetric structure and characterization of preparation method thereof
Fig. 1 is a physical view of a phenolic resin sponge with an asymmetric structure prepared in example 1, and a lightweight cylinder shape.
Fig. 2 (a) and 2 (b) are a bottom scanning electron microscope image and a pore size distribution diagram, respectively, of the phenolic resin sponge having an asymmetric structure prepared in example 1. The obtained phenolic resin sponge has a porous structure, the skeleton consists of nano particles, and the average pore diameter is about 0.47 mu m.
Fig. 3 (a) and 3 (b) are a top scanning electron microscope image and a pore size distribution diagram, respectively, of the phenolic resin sponge having an asymmetric structure prepared in example 1. The top pore size of the resulting phenolic resin sponge was about 3.16 μm and 6.7 times the bottom pore size.
Fig. 4 is a graph showing water contact angle test of the phenolic resin sponge with asymmetric structure prepared in example 1, and the small pore diameter side rapidly absorbs water within 62ms, and has good water transmission performance.
Fig. 5 is a graph showing the water contact angle test of the phenolic resin sponge with asymmetric structure prepared in example 1, wherein the water transmission performance is reduced on the surface with large pore diameter, and the absorption is completed within 0.936 s.
Spraying a thin layer of pyrrole on one surface of the macropores of the sponge, and then spraying a layer of ammonium persulfate solution (2 g/mL), wherein the photo-thermal layer polypyrrole is successfully prepared. The phenolic resin sponge evaporator with an asymmetric structure is obtained. The absorbance of sunlight by the evaporator in the wavelength range of 500-2500nm was tested using an ultraviolet-visible-near infrared diffuse reflectance spectrophotometer (Shimadzu UV-3600i Plus). The test results are shown in fig. 6. The result shows that the macroporous polymeric polypyrrole is beneficial to increasing the multiple reflection of the evaporator to sunlight, and the absorption rate of the sunlight is as high as 96.8%.
EXAMPLE 2 modification of sodium hydroxide usage
Mixing 0.61g of phenol, 0.065g of 20wt% of sodium hydroxide and 1.05g of 37wt% of formaldehyde, stirring and reacting for 1h in a water bath at 75 ℃, adjusting the pH of the solution to 5 by using 0.6mol/L of hydrochloric acid, vacuum drying at 45 ℃ for 12h, adding 3mL of ethanol solution containing 0.96g of polyether F127 and 6g of zinc chloride, stirring and volatilizing ethanol, then placing the mixture in a vacuum oven for bubble discharge, then carrying out heat treatment at 145 ℃ for 60h to obtain a phenolic resin wet gel, placing the wet gel in 65wt% of sulfuric acid, carrying out treatment at 100 ℃ for 24h, then dialyzing the wet gel in deionized water for 6h, freezing at-70 ℃ for 6h, and further freeze-drying for 48h to obtain the phenolic resin sponge material with an asymmetric structure.
Fig. 7 and 8 are respectively a bottom and a top scanning electron microscope images of the phenolic resin sponge with an asymmetric structure prepared in example 2, the obtained phenolic resin sponge has a porous structure, a skeleton is composed of nano particles, and compared with fig. 7 and 2, it can be seen that in the skeleton structure at the bottom of the sponge, the size of the nano particles is reduced, and the smaller particles are in tight connection, so that the pore diameter at the bottom of the prepared sponge is reduced, which is beneficial to water transmission. As can be seen by comparing fig. 8 and fig. 3, the pore size of the nanoparticle and the sponge varies little in the skeleton structure of the sponge top.
EXAMPLE 3 modification of sodium hydroxide usage
Mixing 0.61g of phenol, 0.2g of 20wt% of sodium hydroxide and 1.05g of 37wt% of formaldehyde, stirring and reacting for 1h in a water bath at 75 ℃, adjusting the pH of the solution to 7 by using 0.6mol/L of hydrochloric acid, vacuum drying at 45 ℃ for 12h, adding 3mL of ethanol solution containing 0.96g of polyether F127 and 6g of zinc chloride, stirring and volatilizing ethanol, then placing the mixture in a vacuum oven for bubble discharge, then performing heat treatment at 100 ℃ for 60h to obtain a phenolic resin wet gel, placing the wet gel in 75wt% of sulfuric acid, performing treatment at 100 ℃ for 7h, then placing the wet gel in a 30wt% ethanol aqueous solution for dialysis for 7 days, freezing at-50 ℃ for 6h, and further performing freeze drying for 48h to obtain the phenolic resin sponge material with an asymmetric structure.
Fig. 9 and 10 are bottom and top scanning electron microscope images of the phenolic resin sponge with an asymmetric structure prepared in example 3, respectively, the obtained phenolic resin sponge has a porous structure, a skeleton is composed of nano particles, and as can be seen by comparing fig. 9 and 2, in the skeleton structure of the bottom of the sponge, the size of the nano particles is increased, so that the pore diameter of the prepared sponge is increased, and the water transmission performance is deteriorated. As can be seen by comparing fig. 10 and fig. 3, the pore size of the nanoparticle and the sponge varies little in the skeleton structure of the sponge top.
EXAMPLE 4 modification of sodium hydroxide usage
Mixing 0.61g of phenol, 0.26g of 20wt% of sodium hydroxide and 1.05g of 37wt% of formaldehyde, stirring and reacting for 1h in a water bath at 75 ℃, adjusting the pH of the solution to 9 by using 0.6mol/L of hydrochloric acid, vacuum drying at 45 ℃ for 12h, adding 3mL of ethanol solution containing 0.96g of polyether F127 and 6g of zinc chloride, stirring and volatilizing ethanol, then placing the ethanol solution in a vacuum oven for bubble discharge, then performing heat treatment at 100 ℃ for 60h to obtain a phenolic resin wet gel, placing the wet gel in 20wt% of hydrochloric acid, performing treatment at 100 ℃ for 7h, then placing the wet gel in a 20wt% of ethanol aqueous solution for dialysis for 7 days, freezing at-50 ℃ for 6h, and further performing freeze drying for 48h to obtain the phenolic resin sponge material with an asymmetric structure.
Fig. 11 and 12 are bottom and top scanning electron microscope images of the phenolic resin sponge with an asymmetric structure prepared in example 4, respectively, the obtained phenolic resin sponge has a porous structure, a skeleton is composed of nano particles, and compared with fig. 11 and 2, the size of the nano particles is increased in the skeleton structure at the bottom of the sponge. As can be seen by comparing fig. 12 and fig. 3, the pore size of the nanoparticles and the sponge varies little in the sponge top skeleton structure. According to analysis, as the alkali content is further increased, the condensation reaction of the phenolic resin is blocked, so that the strength of a gel skeleton is reduced, the compression strength of the prepared gel is reduced, and finally, the compact material without a pore structure is obtained.
EXAMPLE 5 modification of Zinc oxide usage
Mixing 0.61g of phenol, 0.065g of 20wt% of sodium hydroxide and 1.05g of 37wt% of formaldehyde, stirring and reacting for 1h in a water bath at 75 ℃, adjusting the pH of the solution to 8 by using 0.6mol/L of hydrochloric acid, vacuum drying at 45 ℃ for 12h, adding 3mL of ethanol solution containing 0.96g of polyether P123 and 3g of zinc chloride, stirring and volatilizing ethanol, then placing the mixture in a vacuum oven for bubble discharge, then performing heat treatment at 100 ℃ for 60h to obtain a phenolic resin wet gel, placing the wet gel in 85wt% of sulfuric acid, performing treatment at 100 ℃ for 7h, then placing the wet gel in a 20wt% of ethanol aqueous solution for dialysis for 7 days, freezing at-70 ℃ for 6h, and further performing freeze drying for 48h to obtain the phenolic resin sponge material with an asymmetric structure.
Fig. 13 is a physical diagram of the phenolic resin sponge with asymmetric structure prepared in example 5, and it can be seen from the experimental result that after the zinc chloride dosage is reduced, a certain air bubble is generated on the surface of the prepared sponge.
Comparative example 1
Comparative example 1 differs from example 1 in that sodium hydroxide was not added in comparative example 1. The prepared phenolic resin sponge material with an asymmetric structure has loose structure, the three-dimensional structure is easy to collapse, and a complete block-shaped sponge cannot be formed.
Comparative example 2
Comparative example 2 is different from example 1 in that the high-temperature acid treatment was not performed, and the impurities were removed by direct dialysis with deionized water.
As shown in FIG. 14, the water treated sample had a distinct peak at 1100cm -1, which demonstrated that polyether F127 was not completely removed, and the ether bond in polyether F127 disappeared after the acid treatment, and the corresponding peak disappeared, which demonstrated that polyether F127 was completely removed. It can be seen from the results of example 2 that the acid treatment has a great influence on the removal rate of the pore-forming agent, and zinc chloride can be removed but polyether cannot be completely removed without high-temperature acid treatment.
Comparative example 3
Comparative example 3 differs from example 1 in that no zinc oxide was added in comparative example 3.
As can be seen from fig. 15, when zinc chloride was not added, a hard resin was formed, a porous sponge was not formed, and the resin did not have water transport properties.
Comparative example 4
Mixing 0.61g of phenol, 0.13g of 20wt% sodium hydroxide solution and 1.05g of 37wt% formaldehyde solution, stirring the mixture solution in a water bath at 75 ℃ for reaction for 1h, adjusting the pH of the mixed solution to 7 by using 0.6mol/L hydrochloric acid, vacuum drying at 45 ℃ for 12h, adding 3mL of ethanol solution containing 0.96g of polyether F127 and 6g of zinc chloride, placing the obtained mixed solution in a closed container, then placing the mixed solution in a vacuum oven for bubble discharge, then performing heat treatment at 100 ℃ for 60h to obtain a phenolic resin wet gel, placing the wet gel in 55wt% sulfuric acid, performing treatment at 100 ℃ for 7h, then placing the wet gel in a 20wt% ethanol aqueous solution for dialysis for 6h, and then freezing at-70 ℃ for 6h, and further freezing and drying for 48h to obtain the phenolic resin sponge material with a symmetrical structure.
Fig. 16 is a graph showing water contact angle test of the prepared phenolic resin sponge with symmetrical structure, and it can be seen from the graph that the sponge can absorb water within 1.358s, which shows that the sponge with symmetrical structure has poor water transmission performance.
In FIG. 17, AP-PPy-PFDS-B, AP-PPy-PFDS-U and AP-PPy-PFDS are the evaporation rates of the small pore diameter side of the asymmetric phenolic resin sponge after PPy is polymerized, the evaporation rate of the closed environment prepared phenolic resin sponge after PPy is polymerized, and the evaporation rate of the large pore diameter side of the asymmetric phenolic resin sponge after PPy is polymerized, respectively. The preparation method of the phenolic resin sponge with the asymmetric structure involved in the experiment is the same as that of the embodiment 1, and the method for polymerizing PPy on the phenolic resin sponge is the same as that of the phenolic resin sponge evaporator of the embodiment 1.
From the results, the asymmetric phenolic resin sponge of the macroporous surface polymerized PPy has the best solar evaporation rate, and the asymmetric phenolic resin sponge has better solar evaporation rate than the symmetric phenolic resin sponge.
While the invention has been described with reference to the preferred embodiments, it is not limited thereto, and various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention, which is defined by the appended claims.
Claims (10)
1. A method for preparing a phenolic resin sponge with an asymmetric structure, which is characterized by comprising the following steps:
Mixing phenol, formaldehyde solution and sodium hydroxide solution, heating to react, regulating the pH of the solution to 5-9, drying, adding the dried solution into ethanol solution containing pore-forming agent, stirring, pouring the solution into an open container, performing heat treatment after vacuum bubble removal, and obtaining the phenolic resin sponge with an asymmetric structure through acid treatment, ethanol water solution dialysis and freeze drying;
Wherein, phenol: formaldehyde: the molar ratio of the sodium hydroxide is 20:40 (1-2), and the pore-forming agent is a mixture of polyether and zinc chloride.
2. The preparation method according to claim 1, wherein the heating reaction is carried out at a temperature of 65 to 80 ℃ for a reaction time of 0.5 to 2 hours.
3. The method according to claim 1, wherein the drying is vacuum drying for 12 to 72 hours.
4. The preparation method according to claim 1, wherein the polyether is polyether P123 or polyether F127, and the mass ratio of the polyether to the zinc chloride is 0.16-0.48.
5. The preparation method according to claim 1, wherein the mass ratio of the pore-forming agent to phenol is 0.03 to 0.26.
6. The method according to claim 1, wherein the temperature during the heat treatment is 100 to 145 ℃ and the heat treatment time is 12 to 72 hours.
7. The method according to claim 1, wherein the acid treatment is carried out at a temperature of 90 to 100 ℃ for a time of 6 to 24 hours, wherein the acid used in the acid treatment comprises at least one of sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid, the concentration of the sulfuric acid is 20 to 98wt%, the concentration of the hydrochloric acid is 20 to 37%, the concentration of the phosphoric acid is 20 to 47%, and the concentration of the nitric acid is 20 to 67%.
8. The method according to claim 1, wherein the concentration of the aqueous ethanol solution used in the dialysis is 5 to 30wt% and the dialysis time is 1 to 7 days.
9. The phenolic resin sponge with an asymmetric structure prepared by the preparation method according to any one of claims 1 to 8.
10. The use of the phenolic resin sponge of claim 9 in the field of photothermal conversion.
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| US4997804A (en) * | 1988-05-26 | 1991-03-05 | The United States Of America As Represented By The United States Department Of Energy | Low density, resorcinol-formaldehyde aerogels |
| CN103709346A (en) * | 2013-11-27 | 2014-04-09 | 中国科学技术大学 | Preparation method of phenolic resin aerogel |
| CN114506892A (en) * | 2022-02-18 | 2022-05-17 | 天津海特热管理科技有限公司 | Photo-thermal interface evaporator and preparation method and application thereof |
| CN114715878A (en) * | 2022-04-29 | 2022-07-08 | 上海活性炭厂有限公司 | Phenolic resin-based carbon aerogel and preparation method thereof |
| CN115010882A (en) * | 2022-06-22 | 2022-09-06 | 南京林业大学 | Phenolic resin ionic liquid gel for photo-thermal water evaporation and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4997804A (en) * | 1988-05-26 | 1991-03-05 | The United States Of America As Represented By The United States Department Of Energy | Low density, resorcinol-formaldehyde aerogels |
| CN103709346A (en) * | 2013-11-27 | 2014-04-09 | 中国科学技术大学 | Preparation method of phenolic resin aerogel |
| CN114506892A (en) * | 2022-02-18 | 2022-05-17 | 天津海特热管理科技有限公司 | Photo-thermal interface evaporator and preparation method and application thereof |
| CN114715878A (en) * | 2022-04-29 | 2022-07-08 | 上海活性炭厂有限公司 | Phenolic resin-based carbon aerogel and preparation method thereof |
| CN115010882A (en) * | 2022-06-22 | 2022-09-06 | 南京林业大学 | Phenolic resin ionic liquid gel for photo-thermal water evaporation and preparation method thereof |
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