CN114425269B - High-efficiency oil-water separation composite foam based on surface engineering and preparation method thereof - Google Patents
High-efficiency oil-water separation composite foam based on surface engineering and preparation method thereof Download PDFInfo
- Publication number
- CN114425269B CN114425269B CN202210093966.9A CN202210093966A CN114425269B CN 114425269 B CN114425269 B CN 114425269B CN 202210093966 A CN202210093966 A CN 202210093966A CN 114425269 B CN114425269 B CN 114425269B
- Authority
- CN
- China
- Prior art keywords
- water separation
- composite foam
- oil
- silicon dioxide
- separation composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000006260 foam Substances 0.000 title claims abstract description 99
- 239000002131 composite material Substances 0.000 title claims abstract description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000000926 separation method Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000012407 engineering method Methods 0.000 title description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 121
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 48
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 47
- 238000005187 foaming Methods 0.000 claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 239000012530 fluid Substances 0.000 claims abstract description 13
- 238000013012 foaming technology Methods 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 239000006261 foam material Substances 0.000 claims description 25
- 239000011148 porous material Substances 0.000 claims description 19
- 238000000465 moulding Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 8
- 229920000098 polyolefin Polymers 0.000 claims description 8
- 125000001165 hydrophobic group Chemical group 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 4
- 239000004626 polylactic acid Substances 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 4
- 230000008961 swelling Effects 0.000 claims description 4
- 229920000307 polymer substrate Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 abstract description 9
- 238000010276 construction Methods 0.000 abstract description 5
- 125000003636 chemical group Chemical group 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000009736 wetting Methods 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 42
- 235000019198 oils Nutrition 0.000 description 40
- 238000001179 sorption measurement Methods 0.000 description 23
- 238000010521 absorption reaction Methods 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 10
- 239000011358 absorbing material Substances 0.000 description 9
- 230000002209 hydrophobic effect Effects 0.000 description 9
- 230000006872 improvement Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000019486 Sunflower oil Nutrition 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002600 sunflower oil Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000004533 oil dispersion Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/04—Pressure vessels, e.g. autoclaves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/002—Component parts of these vessels not mentioned in B01J3/004, B01J3/006, B01J3/02 - B01J3/08; Measures taken in conjunction with the process to be carried out, e.g. safety measures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/34—Feeding the material to the mould or the compression means
-
- 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
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/08—Supercritical fluid
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/204—Keeping clear the surface of open water from oil spills
Abstract
The invention provides a high-efficiency oil-water separation composite foam based on surface engineering and a preparation method thereof. The preparation method of the efficient oil-water separation composite foam comprises the following steps: adding nano silicon dioxide into the mixed solution of the silane coupling agent according to a preset proportion, and reacting for 40-60min at 35-55 ℃ to obtain modified nano silicon dioxide; processing the polymer by a supercritical fluid foaming technology to obtain an open-cell foaming material; adding the obtained modified nano silicon dioxide into ethanol according to a preset proportion to prepare a solution; and immersing the obtained open-cell foaming material into the obtained solution, and carrying out ultrasonic load treatment to obtain the high-efficiency oil-water separation composite foam. The invention is based on the construction of polymer-based foaming material surface engineering for the first time, and the wetting behavior of liquid drops is changed cooperatively by the regulation and control of the surface morphology structure of the foaming material and the introduction of chemical groups, so that the purposes of superhydrophobicity and lipophilicity are achieved; the method has the advantages of flexibility, low cost, green environmental protection and the like.
Description
Technical Field
The invention relates to the technical field of composite material oil-water separation, in particular to a high-efficiency oil-water separation composite foam based on surface engineering and a preparation method thereof.
Background
The oil leakage and sewage discharge of various transportation causes great damage to the human living environment, seriously affects the quality of our living environment, and mainly comprises industrial oil leakage accidents and industrial oil-containing wastewater. Conventional oil adsorption and treatment methods mainly include the use of adsorbents, plant and microbial degradation, combustion and oil dispersion.
At present, oil-absorbing materials are mainly divided into inorganic oil-absorbing materials, organic natural oil-absorbing materials and organic synthetic oil-absorbing materials. The inorganic oil absorption material has wide sources and high oil absorption multiplying power, but has the problems of low cyclic utilization rate and poor oil-water selectivity. The organic natural oil-absorbing material absorbs oil and absorbs water at the same time, so that the operation is difficult in the actual oil-absorbing process. Compared with inorganic oil absorbing materials and organic natural oil absorbing materials, the organic synthetic oil absorbing materials have the characteristics of oleophilic and hydrophobic and are widely applied.
The ideal oil absorbing material needs to have outstanding lipophilic and hydrophobic properties, high oil absorption and recyclability. Some of the adsorption materials capable of rapidly absorbing oil, such as carbon aerogel, fiber gel, graphene support materials and the like, which are developed at present, show good oil absorption performance, but in consideration of the economic problem of the oil absorption materials, the high adsorption materials are difficult to realize mass production.
Polymeric microporous foams are considered to be very effective, inexpensive and recyclable adsorbent materials, but due to the limitations of the production conditions, the pore size of the microporous foam is less than 70nm or difficult to control, which limits its application in oil-water separation.
The patent with the application number of CN202010783319.1 discloses a preparation method of an oil-absorbing hydrophobic sponge, which comprises the steps of firstly mixing silica sol with a silane coupling agent to obtain modified silica sol; adding melamine sponge into the diluent of the modified silica sol to obtain a silica modified sponge; then mixing the silicon dioxide modified sponge with polytetrafluoroethylene emulsion and dimethylformamide to obtain a silicon dioxide/polytetrafluoroethylene modified sponge; finally, vacuum drying the silica/polytetrafluoroethylene modified sponge at 240-300 ℃ to obtain the oil-absorbing and hydrophobic sponge finished product. The method has the following defects: the polytetrafluoroethylene particles are free in a cross-linked network structure, are not bonded with silicon dioxide and sponge through chemical bonds, and are subjected to high-temperature drying in the later period, so that part of polytetrafluoroethylene particles can be lost, and the hydrophobic oil absorption performance is reduced.
In view of the above, there is a need to design an improved high-efficiency oil-water separation composite foam based on surface engineering and a preparation method thereof, so as to solve the above problems.
Disclosure of Invention
The invention aims to provide an improved high-efficiency oil-water separation composite foam based on surface engineering and a preparation method thereof.
In order to achieve the aim of the invention, the invention provides a preparation method of a high-efficiency oil-water separation composite foam based on surface engineering, which comprises the following steps:
s1, modifying nano silicon dioxide: adding nano silicon dioxide into the mixed solution of the silane coupling agent according to a preset proportion, and reacting for 40-60min at 35-55 ℃ to obtain modified nano silicon dioxide;
s2, preparing an open-cell foam material: processing the polymer substrate by a supercritical fluid foaming technology to obtain an open-cell foaming material;
s3, preparing high-efficiency oil-water separation composite foam: adding the modified nano silicon dioxide prepared in the step S1 into ethanol according to a preset proportion to prepare a solution; and immersing the open-cell foaming material prepared in the step S2 into the obtained solution, and carrying out ultrasonic load treatment to obtain the high-efficiency oil-water separation composite foam.
As a further improvement of the present invention, a heat-conducting medium is added to the polymer substrate in step S2 to enhance the foaming effect of the supercritical fluid.
As a further improvement of the present invention, the method for preparing the open-cell foam material comprises the steps of:
s21, mixing and granulating: putting the polymer and the heat conducting medium into a double-screw extrusion granulator for blending granulation to obtain mixed master batch;
s22, hot press molding: placing the mixed master batch prepared in the step S21 into a molding press for hot press molding to obtain a composite board;
s23, supercritical foaming: placing the composite board prepared in the step S22 into a high-pressure reaction kettle, introducing supercritical fluid into the high-pressure reaction kettle, and swelling for 0.5-10h at the temperature of 100-230 ℃ and the pressure of 5-30 Mpa; and then rapidly decompressing to obtain the open-cell foam material.
As a further improvement of the present invention, the polymer comprises one or more of polyolefin, polylactic acid, polyurethane.
As a further improvement of the present invention, the pore size of the open-cell foam material in step S2 is 1 μm to 200. Mu.m.
As a further improvement of the invention, the ratio of the modified nano-silica to the ethanol in the step S3 is 1 (5-40).
As a further improvement of the present invention, the nano silica in step S1 is prepared by a sol-gel method; the ratio of the nano silicon dioxide to the silane coupling agent is (5-20): 1, and the group connected to one end of the silane coupling agent which does not react with the nano silicon dioxide is a hydrophobic group.
As a further improvement of the present invention, the frequency of the ultrasonic load treatment in step S3 is greater than 250Hz for a period of time greater than 15min.
The invention also provides the high-efficiency oil-water separation composite foam based on surface engineering, which is prepared by adopting the preparation method.
As a further improvement of the invention, the water contact angle of the high-efficiency oil-water separation composite foam can reach 152.5 degrees, and the foam can be recycled.
The beneficial effects of the invention are as follows:
(1) The invention provides a preparation method of high-efficiency oil-water separation composite foam based on surface engineering, which comprises the steps of firstly modifying nano silicon dioxide by using a silane coupling agent to enable the surface of the nano silicon dioxide to be grafted with a hydrophobic group through chemical bonds; then preparing an open-cell foam material with proper pore diameter and aperture ratio by a supercritical technology; finally immersing the open-cell foaming material in an ethanol solution containing modified nano silicon dioxide for ultrasonic load treatment to obtain the high-efficiency oil-water separation composite foam. The modified nano silicon dioxide is uniformly distributed on the surface and inside of the open-cell foam material by controlling the aperture and the aperture ratio of the open-cell foam material, and the existence of the surface silane coupling agent increases the surface roughness of the open-cell foam material on one hand, changes the surface structure morphology of the foam material, and is favorable for absorbing oil liquid; on the other hand, the hydrophobic and oleophylic groups with exposed surfaces can increase the hydrophobicity, namely, the droplet wetting behavior of the foaming material is changed through the synergistic effect of the regulation and control of the surface morphology structure of the foaming material and the introduction of chemical groups, so that the purposes of superhydrophobicity and oleophylic are achieved. In addition, the open-cell foaming material is adopted, so that oil can more easily pass through the pores of the foaming material to enter the foaming material, and the adsorption of the oil is facilitated; on the other hand, the open pore structure enables the inside of the foaming material to be mutually communicated, ultrasonic loading treatment is convenient for the deposition of nano silicon dioxide particles on the surface and inside of the foaming material, and a cross-linked network structure is formed, so that the modified nano silicon dioxide is firmly and uniformly wrapped by the foaming material.
(2) The invention provides a preparation method of a high-efficiency oil-water separation composite foam based on surface engineering, which is based on the construction of polymer-based foaming material surface engineering for the first time, changes the appearance of the foam surface structure, introduces hydrophobic lipophilic groups, ensures that the water contact angle of the composite foam reaches the super-hydrophobic level of 152.5 degrees, improves the oil absorption rate, and solves the problem of poor oil-water separation effect of the polymer-based foaming material.
(3) The invention provides a preparation method of a high-efficiency oil-water separation composite foam based on surface engineering, which combines physical and chemical surface engineering construction of a polymer-based foaming material with a green environment-friendly physical foaming process means for the first time, realizes the preparation of the high-efficiency oil-water separation adsorption material, and solves the bottleneck problem of the adsorption material field applied to oil-water separation. The method has the advantages of flexibility, low cost, green environmental protection and the like.
Drawings
FIG. 1 is a flow chart of a method for preparing the efficient oil-water separation composite foam based on surface engineering.
FIG. 2 is a scanning electron microscope image of the high-efficiency oil-water separation composite foam and the open-cell foam material prepared in example 1 of the present invention, wherein the scale a is 100 μm, the scale b is 50 μm, the scale c is 50 μm, and the scale d is 5 μm.
Fig. 3 is a graph showing water contact angles of the high-efficiency oil-water separation composite foam and the open-cell foaming material prepared in example 1 of the present invention.
FIG. 4 is a drawing showing the absorption of oil by the high-efficiency oil-water separation composite foam prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Referring to fig. 1, the invention provides a preparation method of a high-efficiency oil-water separation composite foam based on surface engineering, which comprises the following steps:
s1, modifying nano silicon dioxide:
dissolving a silane coupling agent in absolute ethyl alcohol to form a solution, adding nano silicon dioxide into the obtained solution, ensuring that the ratio of the nano silicon dioxide to the silane coupling agent is (5-20): 1, and reacting for 40-60min at 35-55 ℃ to obtain the modified nano silicon dioxide.
Wherein the nano silicon dioxide is prepared by a sol-gel method. The method comprises the following specific steps: TEOS (tetraethyl silicate) is dissolved in ethanol, and an active monomer is generated through hydrolysis reaction, and the active monomer is polymerized to obtain silica sol; over time, the colloidal particles are connected with each other to form a network, so as to obtain silica gel with a certain space structure; and drying and heat-treating the silica gel to obtain the nano silica particles.
The general formula of the silane coupling agent is expressed as Y-SiX 3 . Wherein X is a group which can undergo hydrolysis reaction and generate a silicon hydroxyl group (Si-OH), such as an alkoxy group, an acetoxy group, a halogen, etc.; y is a hydrophobic organic functional group such as a hydrocarbon group, an ester group, a nitro group, etc., and the hydrocarbon group is specifically a hydrocarbon group of C10 to C20 or a hydrocarbon group containing an aryl group, an ester, an ether, an amine, an amide, etc., or a hydrocarbon group containing a double bond.
In the process, the silane coupling agent is hydrolyzed to generate a silanol structure, and the silane coupling agent is rapidly spread on the surface of the nano silicon dioxide; the silicon hydroxyl generated by the hydrolysis of the silane coupling agent and the hydroxyl rich on the surface of the nano silicon dioxide form hydrogen bond, so that hydrolysis condensation reaction occurs, and at the moment, the nano silicon dioxide and the silane coupling agent form firm chemical bonds, so that the nano silicon dioxide presents hydrophobicity.
S2, preparing an open-cell foam material:
one or more polymers in polyolefin, polylactic acid and polyurethane are treated by supercritical fluid foaming technology to obtain the open-cell foam material with the aperture of 1-200 mu m and the aperture ratio of 96%.
Wherein the supercritical fluid foaming technique comprises the following steps:
s21, mixing and granulating: placing a polymer and a heat-conducting medium (one or more of graphene, carbon black, silver particles and other heat-conducting nano particles) into a double-screw extrusion granulator for blending granulation to obtain mixed master batch; the proportion of the heat conducting medium is not more than 30% of the total mass of the mixture of polyolefin and the heat conducting medium;
s22, hot press molding: placing the mixed master batch prepared in the step S21 into a molding press for hot press molding to obtain a composite board;
s23, supercritical foaming: placing the composite board prepared in the step S22 into a high-pressure reaction kettle, introducing supercritical fluid into the high-pressure reaction kettle, and swelling for 0.5-10h at the temperature of 100-230 ℃ and the pressure of 5-30 Mpa; and then rapidly decompressing to obtain the open-cell foam material.
The open-cell material prepared by the method has high aperture ratio, is favorable for the transmission of oil, and ensures that the oil can be adsorbed on the surface of the foaming material and can be adsorbed in the foaming material.
The pore diameter of the open pore material prepared by the method is proper, and the pores are uniform, so that the adsorption of oil liquid is facilitated, and the deposition of nano silicon dioxide particles is facilitated.
S3, preparing high-efficiency oil-water separation composite foam:
adding the modified nano silicon dioxide prepared in the step S1 into ethanol according to a preset proportion 1 (5-40) to prepare a solution; and immersing the open-cell foaming material prepared in the step S2 into the obtained solution, and carrying out ultrasonic loading treatment to uniformly load the modified nano silicon dioxide into the open-cell foam to obtain the high-efficiency oil-water separation composite foam.
Wherein the frequency of ultrasonic load treatment is more than 250Hz, and the time is more than 15min.
The invention also provides the high-efficiency oil-water separation composite foam based on surface engineering, which is prepared by adopting the preparation method. The water contact angle of the high-efficiency oil-water separation composite foam can reach 152.5 degrees, and the high-efficiency oil-water separation composite foam can be recycled.
The invention is described in detail below by means of several examples:
example 1
A preparation method of a high-efficiency oil-water separation composite foam based on surface engineering comprises the following steps:
s1, modifying nano silicon dioxide:
dissolving a silane coupling agent vinyl trimethoxy silane in an absolute ethyl alcohol solution, adding nano silicon dioxide into the obtained solution, ensuring that the ratio of the nano silicon dioxide to the silane coupling agent is 5:1, and reacting at 45 ℃ for 50min to obtain the modified nano silicon dioxide.
Wherein the nano silicon dioxide is prepared by a sol-gel method. The method comprises the following specific steps: dissolving TEOS in ethanol, generating an active monomer through hydrolysis reaction, and polymerizing the active monomer to obtain silica sol; over time, the colloidal particles are connected with each other to form a network, so as to obtain silica gel with a certain space structure; and drying and heat-treating the silica gel to obtain the nano silica particles.
S2, preparing an open-cell foam material:
the polypropylene is treated by supercritical fluid foaming technology to obtain the open-cell foam material with the aperture of 45 μm and the aperture ratio of 96%.
Wherein the supercritical fluid foaming technique comprises the following steps:
s21, mixing and granulating: placing polylactic acid and nano carbon black into a double-screw extrusion granulator for blending granulation to obtain mixed master batch; the proportion of the heat conducting medium is not more than 20% of the total mass of the mixture of polyolefin and the heat conducting medium;
s22, hot press molding: placing the mixed master batch prepared in the step S21 into a molding press for hot press molding to obtain a composite board;
s23, supercritical foaming: placing the composite board prepared in the step S22 into a high-pressure reaction kettle, introducing supercritical fluid into the high-pressure reaction kettle, and swelling for 1h at the temperature of 100 ℃ and the pressure of 15 Mpa; and then rapidly decompressing for 100s to obtain the open-cell foam material.
S3, preparing high-efficiency oil-water separation composite foam:
adding the modified nano silicon dioxide prepared in the step S1 into ethanol according to a preset ratio of 1:5 to prepare a solution; and immersing the open-cell foaming material prepared in the step S2 into the obtained solution, and carrying out ultrasonic loading treatment to uniformly load the modified nano silicon dioxide into the open-cell foam to obtain the high-efficiency oil-water separation composite foam.
Wherein the frequency of ultrasonic load treatment is 260Hz and the time is 20min.
As shown in the scanning electron microscope image of the composite foam (i.e. the high-efficiency oil-water separation composite foam) and the original foam (i.e. the open-cell foam material prepared in the step S2) shown in fig. 2, the walls of the original foam are smoother, the open-cell effect is better, conditions are provided for the adhesion of silicon dioxide and the absorption of oil liquid, and a large amount of modified silicon dioxide is uniformly adhered to the walls of the composite foam holes as shown in fig. 2 b and d, which means that the modified silicon dioxide is uniformly adhered to the surface and the inside of the composite foam by ultrasonic treatment, and the hydrophobicity and the lipophilicity of the modified silicon dioxide are improved.
As shown in the water contact angle diagram of the high-efficiency oil-water separation composite foam and the open-cell foaming material shown in fig. 3, the original foam shows certain hydrophilicity; the prepared composite foam cannot be wetted by water, presents strong hydrophobicity, and the water contact angle can reach 152.5 degrees. This is mainly because the original foam is in an open cell structure and exhibits uniform pores, with larger pores, allowing part of the water to enter the original foam; the surface of the composite foam has a layer of hydrophobic groups, and the pores of the composite foam are uniformly occupied by modified silicon dioxide, so that the pore diameter of the composite foam is reduced, the composite foam is more compact, the entry of moisture is prevented, and the composite foam presents strong hydrophobicity.
As shown in the adsorption rate diagram of the high-efficiency oil-water separation composite foam to oil (comprising oil and organic solvent) in the figure 4 a, the adsorption rate of the composite foam to sunflower oil, carbon tetrachloride and dimethyl silane is up to more than 96%. Wherein, the adsorption rate of the composite foam to carbon tetrachloride is highest, the adsorption rate of the composite foam to the dimethyl silane is slightly lower. Through multiple cycles (after oil absorption each time, mechanical extrusion is carried out, then oil absorption is carried out, the next oil absorption is carried out, and each time oil absorption is taken as one cycle), the adsorption rate of the composite foam to oil liquid is gradually decreased, but the adsorption rate is still higher, and the composite foam is suitable for recycling the oil liquid.
As shown in the adsorption capacity diagram of the oil-water separation composite foam shown in fig. 4 b on the oil (comprising oil and organic solvent), the adsorption effect of the composite foam on diesel oil, toluene, ethanol, carbon tetrachloride and sunflower oil is better, wherein the adsorption capacity of the composite foam on toluene is up to about 42g/g, and the adsorption effect on normal hexane and petroleum ether is slightly poorer.
Examples 2 to 3
Compared with the embodiment 1, the preparation method of the high-efficiency oil-water separation composite foam based on surface engineering is different in that in the step S1, the mass ratio m of the nano silicon dioxide and the silane coupling agent is as follows 1 :m 2 Other differences are substantially the same as those of embodiment 1, and will not be described here again.
The open-cell polyolefin foam materials prepared in examples 1 to 3 were subjected to performance test, and the results are shown in Table 1:
TABLE 1 Water contact Angle test of high efficiency oil-Water separation composite foam prepared in examples 1-3
| Examples | m 1 :m 2 | Contact angle of water |
| Example 1 | 5:1 | 152.5° |
| Example 2 | 10:1 | 150.6° |
| Example 3 | 20:1 | 143.8° |
As can be seen from table 1, the water contact angle of the syntactic foam showed a tendency to increase with increasing content of the silane coupling agent. This is mainly because, as the content of the silane coupling agent increases, the higher the reaction concentration of the silane coupling agent, the greater the number of silane coupling agents grafted to the surface of the nanosilica, i.e., the greater the number of hydrophobic groups; in addition, the surface of the composite foam presents a special morphology structure, which is more beneficial to the absorption of oil liquid, so that the hydrophobicity and lipophilicity of the composite foam are enhanced.
Examples 4 to 6
The preparation method of the high-efficiency oil-water separation composite foam based on surface engineering is different from that of the embodiment 1 in that in the step S2, the pore diameters of the open-cell foaming materials are different, and the other materials are substantially the same as those of the embodiment 1, and are not described herein.
The open-cell polyolefin foam materials prepared in examples 4 to 6 were subjected to performance test, and the results are shown in Table 2:
table 2 water contact angle test of high efficiency oil-water separation composite foam prepared in examples 4-6
| Examples | Aperture (mum) | Contact angle of water |
| Example 1 | 45 | 152.5° |
| Example 4 | 10 | 153.7° |
| Example 5 | 168 | 146.2° |
| Example 6 | 200 | 140.8° |
As can be seen from table 2, the water contact angle of the composite foam gradually decreased as the pore size of the open-cell foam increased. On one hand, the number of hydrophobic groups on the surface of the composite foam is small and the distribution is loose, so that a continuous gas layer is not easy to form between water drops and interfaces, and the surface morphology is unfavorable for the adsorption of oil liquid; on the other hand, the larger pore diameter is not easy to wrap the oil in the foam, so that the oil is easy to run off, and therefore, the hydrophobicity and the lipophilicity are relatively poor. Although the hydrophobicity and lipophilicity are gradually reduced, the water contact angle is still larger, and the hydrophobicity and lipophilicity still reach higher levels.
When the pore diameter of the open-cell foam is less than 45 μm, the tendency of the water contact angle of the composite foam to increase is gentle.
Examples 7 to 8
The preparation method of the high-efficiency oil-water separation composite foam based on surface engineering is different from that of the embodiment 1 in that in the step S3, the ratio of the modified nano silicon dioxide to the ethanol is different, and the other parts are approximately the same as the embodiment 1, and are not repeated here.
The open-cell polyolefin foam materials prepared in examples 7 to 8 were subjected to performance test, and the results are shown in Table 3:
TABLE 3 Water contact Angle test of high efficiency oil-Water separation composite foam prepared in examples 7-8
| Examples | Ratio of modified nanosilicon dioxide to ethanol | Contact angle of water |
| Example 1 | 1:5 | 152.5° |
| Example 7 | 1:10 | 151.7° |
| Example 8 | 1:20 | 148.8° |
As shown in table 3, as the content of the modified silica increases, the water contact angle of the composite foam gradually increases, and when the ratio of the modified nano silica to the ethanol is 1:5, the water contact angle of the composite foam is as high as 152.5 degrees, which indicates that the higher the loading amount of the modified nano silica in the composite foam is, the more hydrophobic groups are exposed on the surface of the composite foam, and the better the hydrophobicity of the composite foam is. Meanwhile, the higher the load of the modified nano silicon dioxide in the composite foam is, the larger the surface appearance change of the composite foam is, the larger the surface roughness is, and the special surface appearance is more beneficial to the adsorption of oil.
Comparative example 1
Compared with the embodiment 1, the preparation method of the high-efficiency oil-water separation composite foam based on surface engineering is different in that in the step S2, the preparation method of the foaming material is different, no heat conducting medium is added in the preparation process of the foaming material, and the obtained foaming material has low aperture ratio and more closed pores; otherwise, the water contact angle of the obtained oil-water separation composite foam is 128.7 degrees, the adsorption capacity of the oil is 9.3g/g, and the water contact angle and the adsorption capacity of the oil are obviously reduced, so that the open-cell foam material provides necessary hydrophobic and oleophylic conditions for the composite foam.
In summary, the invention provides the high-efficiency oil-water separation composite foam based on the surface engineering and the preparation method thereof, and the construction of the surface engineering of the polymer-based foaming material is based for the first time, and the pore diameter and the aperture ratio of the open-cell foaming material are controlled, so that the modified nano silicon dioxide is uniformly distributed on the surface and the inside of the open-cell foaming material, the regulation and control of the surface morphology structure of the foaming material and the introduction of chemical groups are cooperated, the wetting behavior of liquid drops is changed, and the purposes of superhydrophobicity and oleophylic are achieved; the physical and chemical surface engineering construction of the polymer-based foaming material is combined with the green physical foaming process means for the first time, so that the preparation of the efficient oil-water separation adsorption material is realized, and the bottleneck problem of the adsorption material field applied to oil-water separation is solved. The method has the advantages of flexibility, low cost, green environmental protection and the like.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. A preparation method of a high-efficiency oil-water separation composite foam based on surface engineering is characterized by comprising the following steps: the method comprises the following steps:
s1, modifying nano silicon dioxide: adding nano silicon dioxide into the mixed solution of the silane coupling agent according to a preset proportion, and reacting for 40-60min at 35-55 ℃ to obtain modified nano silicon dioxide;
s2, preparing an open-cell foam material: processing the polymer substrate by a supercritical fluid foaming technology to obtain an open-cell foaming material; a heat conducting medium is added into the polymer base material to improve the foaming effect of the supercritical fluid;
s3, preparing high-efficiency oil-water separation composite foam: adding the modified nano silicon dioxide prepared in the step S1 into ethanol according to a preset proportion to prepare a solution; immersing the open-cell foaming material prepared in the step S2 into the obtained solution, and carrying out ultrasonic load treatment to obtain the high-efficiency oil-water separation composite foam;
in step S2, the preparation method of the open-cell foam material includes the following steps:
s21, mixing and granulating: putting the polymer and the heat conducting medium into a double-screw extrusion granulator for blending granulation to obtain mixed master batch;
s22, hot press molding: placing the mixed master batch prepared in the step S21 into a molding press for hot press molding to obtain a composite board;
s23, supercritical foaming: placing the composite board prepared in the step S22 into a high-pressure reaction kettle, introducing supercritical fluid into the high-pressure reaction kettle, and swelling for 0.5-10h at the temperature of 100-230 ℃ and the pressure of 5-30 Mpa; then rapidly decompressing to obtain an open-cell foam material; the pore diameter of the open-cell foam material is 10-45 μm.
2. The preparation method of the surface engineering-based efficient oil-water separation composite foam is characterized by comprising the following steps of: the polymer comprises one or more of polyolefin, polylactic acid and polyurethane.
3. The preparation method of the surface engineering-based efficient oil-water separation composite foam is characterized by comprising the following steps of: the ratio of the modified nano silicon dioxide to the ethanol in the step S3 is 1 (5-40).
4. The preparation method of the surface engineering-based efficient oil-water separation composite foam is characterized by comprising the following steps of: the nano silicon dioxide in the step S1 is prepared by a sol-gel method; the ratio of the nano silicon dioxide to the silane coupling agent is (5-20): 1, and the group connected to one end of the silane coupling agent which does not react with the nano silicon dioxide is a hydrophobic group.
5. The preparation method of the surface engineering-based efficient oil-water separation composite foam is characterized by comprising the following steps of: the frequency of the ultrasonic load treatment in the step S3 is more than 250Hz, and the time is more than 15min.
6. A high-efficiency oil-water separation composite foam based on surface engineering is characterized in that: is prepared by the preparation method according to any one of claims 1 to 5.
7. The surface engineering-based high efficiency oil-water separation composite foam according to claim 6, wherein: the water contact angle of the high-efficiency oil-water separation composite foam can reach 152.5 degrees, and the high-efficiency oil-water separation composite foam can be recycled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210093966.9A CN114425269B (en) | 2022-01-26 | 2022-01-26 | High-efficiency oil-water separation composite foam based on surface engineering and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210093966.9A CN114425269B (en) | 2022-01-26 | 2022-01-26 | High-efficiency oil-water separation composite foam based on surface engineering and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114425269A CN114425269A (en) | 2022-05-03 |
| CN114425269B true CN114425269B (en) | 2023-12-22 |
Family
ID=81313959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210093966.9A Active CN114425269B (en) | 2022-01-26 | 2022-01-26 | High-efficiency oil-water separation composite foam based on surface engineering and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114425269B (en) |
Citations (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531770A (en) * | 2008-05-15 | 2009-09-16 | 上海高分子功能材料研究所 | Preparation and application of open-cell foamed polyolefin |
| CN102250305A (en) * | 2011-06-01 | 2011-11-23 | 中蓝晨光化工研究院有限公司 | Hydrophobic swelling polyurethane foam and preparation method and use thereof |
| CN103205013A (en) * | 2013-03-22 | 2013-07-17 | 浙江工业大学 | Polymer supercritical carbon dioxide foaming nucleating agent and preparation method and application thereof |
| CN103804714A (en) * | 2014-01-23 | 2014-05-21 | 华南理工大学 | Superhydrophobic and superlipophilic sponge as well as preparation method and application of superhydrophobic and superlipophilic sponge |
| CN105254915A (en) * | 2015-10-27 | 2016-01-20 | 南京理工大学 | Preparation method for super-hydrophobic super-oleophilic magnetic polystyrene function foam |
| 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 |
| KR20160107090A (en) * | 2015-03-03 | 2016-09-13 | 주식회사 로빈첨단소재 | Polymer graft Nanosilica and Process for preparing the same |
| CN105949498A (en) * | 2016-05-19 | 2016-09-21 | 北京林业大学 | Melamine-based sponge for absorbing oil slick and preparation method |
| CN106750148A (en) * | 2016-11-11 | 2017-05-31 | 江苏大学 | A kind of preparation method and application of the micro-nano aluminum oxide polyurethane foam that is modified |
| CN106902767A (en) * | 2017-02-27 | 2017-06-30 | 江苏大学 | Hollow MnO2@SiO2The preparation method and application of nano material modified polyurethane foam |
| CN107022106A (en) * | 2017-03-23 | 2017-08-08 | 华南理工大学 | A kind of super-hydrophobic oil suction foamed material of various dimensions Nanoparticle Modified and preparation method thereof |
| CN107583470A (en) * | 2017-09-18 | 2018-01-16 | 上海大学 | Super hydrophilic and underwater superoleophobic water-oil separationg film and preparation method thereof |
| CN107930600A (en) * | 2017-09-10 | 2018-04-20 | 梅玉杰 | A kind of preparation method of nano combined water-purifying material |
| CN108816055A (en) * | 2018-07-04 | 2018-11-16 | 青岛科技大学 | A kind of preparation method of biodegradable water-oil separating perforated membrane |
| CN109370128A (en) * | 2018-10-01 | 2019-02-22 | 浙江纺织服装职业技术学院 | A kind of preparation method of polyvinyl alcohol/silicon dioxide microcellular foam material |
| CN109467734A (en) * | 2018-10-01 | 2019-03-15 | 宁波大学 | A kind of polyvinyl alcohol/silicon dioxide composition microcellular foam material |
| CN109535475A (en) * | 2018-11-27 | 2019-03-29 | 同济大学 | Melamine sponge of area load nanoparticle and its preparation method and application |
| CN109824866A (en) * | 2019-02-26 | 2019-05-31 | 嘉兴烯成新材料有限公司 | A kind of graphene in-situ polymerization reinforced epoxy and preparation method thereof |
| CN111057267A (en) * | 2019-11-29 | 2020-04-24 | 南京理工大学 | Preparation method of magnetic melamine hydrophobic oleophylic sponge |
| CN111234492A (en) * | 2020-04-02 | 2020-06-05 | 福建安达福新材料科技有限公司 | PLA/TPU supercritical foaming composite material and preparation method thereof |
| CN111589186A (en) * | 2020-06-02 | 2020-08-28 | 林多炉 | Magnetic super-hydrophobic polyurethane sponge oil-water separation material and preparation method thereof |
| CN112029142A (en) * | 2020-08-06 | 2020-12-04 | 武汉工程大学 | Preparation method of oil-absorbing hydrophobic sponge and oil-absorbing hydrophobic sponge prepared by same |
| CN112175600A (en) * | 2020-08-31 | 2021-01-05 | 西南石油大学 | Novel foam stabilizer and preparation method thereof |
| CN112403292A (en) * | 2020-09-27 | 2021-02-26 | 武汉纺织大学 | Oil-water separation composite membrane and preparation method thereof |
| CN112961395A (en) * | 2021-04-22 | 2021-06-15 | 郑州大学 | High-foaming-ratio PLA/PBAT/Talc composite foaming oil absorption material and preparation method thereof |
| CN113462009A (en) * | 2021-07-29 | 2021-10-01 | 南京旭智材料科技有限公司 | Magnetic oil-absorbing polyolefin foam material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7053131B2 (en) * | 2002-12-03 | 2006-05-30 | Kimberly-Clark Worldwide, Inc. | Absorbent articles comprising supercritical fluid treated HIPE, I-HIPE foams and other foams |
| IN2014DN03394A (en) * | 2011-09-28 | 2015-06-05 | Univ King Abdullah Sci & Tech |
-
2022
- 2022-01-26 CN CN202210093966.9A patent/CN114425269B/en active Active
Patent Citations (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531770A (en) * | 2008-05-15 | 2009-09-16 | 上海高分子功能材料研究所 | Preparation and application of open-cell foamed polyolefin |
| CN102250305A (en) * | 2011-06-01 | 2011-11-23 | 中蓝晨光化工研究院有限公司 | Hydrophobic swelling polyurethane foam and preparation method and use thereof |
| CN103205013A (en) * | 2013-03-22 | 2013-07-17 | 浙江工业大学 | Polymer supercritical carbon dioxide foaming nucleating agent and preparation method and application thereof |
| CN103804714A (en) * | 2014-01-23 | 2014-05-21 | 华南理工大学 | Superhydrophobic and superlipophilic sponge as well as preparation method and application of superhydrophobic and superlipophilic sponge |
| KR20160107090A (en) * | 2015-03-03 | 2016-09-13 | 주식회사 로빈첨단소재 | Polymer graft Nanosilica and Process for preparing the same |
| CN105254915A (en) * | 2015-10-27 | 2016-01-20 | 南京理工大学 | Preparation method for super-hydrophobic super-oleophilic magnetic polystyrene function foam |
| 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 |
| CN105949498A (en) * | 2016-05-19 | 2016-09-21 | 北京林业大学 | Melamine-based sponge for absorbing oil slick and preparation method |
| CN106750148A (en) * | 2016-11-11 | 2017-05-31 | 江苏大学 | A kind of preparation method and application of the micro-nano aluminum oxide polyurethane foam that is modified |
| CN106902767A (en) * | 2017-02-27 | 2017-06-30 | 江苏大学 | Hollow MnO2@SiO2The preparation method and application of nano material modified polyurethane foam |
| CN107022106A (en) * | 2017-03-23 | 2017-08-08 | 华南理工大学 | A kind of super-hydrophobic oil suction foamed material of various dimensions Nanoparticle Modified and preparation method thereof |
| CN107930600A (en) * | 2017-09-10 | 2018-04-20 | 梅玉杰 | A kind of preparation method of nano combined water-purifying material |
| CN107583470A (en) * | 2017-09-18 | 2018-01-16 | 上海大学 | Super hydrophilic and underwater superoleophobic water-oil separationg film and preparation method thereof |
| CN108816055A (en) * | 2018-07-04 | 2018-11-16 | 青岛科技大学 | A kind of preparation method of biodegradable water-oil separating perforated membrane |
| CN109370128A (en) * | 2018-10-01 | 2019-02-22 | 浙江纺织服装职业技术学院 | A kind of preparation method of polyvinyl alcohol/silicon dioxide microcellular foam material |
| CN109467734A (en) * | 2018-10-01 | 2019-03-15 | 宁波大学 | A kind of polyvinyl alcohol/silicon dioxide composition microcellular foam material |
| CN109535475A (en) * | 2018-11-27 | 2019-03-29 | 同济大学 | Melamine sponge of area load nanoparticle and its preparation method and application |
| CN109824866A (en) * | 2019-02-26 | 2019-05-31 | 嘉兴烯成新材料有限公司 | A kind of graphene in-situ polymerization reinforced epoxy and preparation method thereof |
| CN111057267A (en) * | 2019-11-29 | 2020-04-24 | 南京理工大学 | Preparation method of magnetic melamine hydrophobic oleophylic sponge |
| CN111234492A (en) * | 2020-04-02 | 2020-06-05 | 福建安达福新材料科技有限公司 | PLA/TPU supercritical foaming composite material and preparation method thereof |
| CN111589186A (en) * | 2020-06-02 | 2020-08-28 | 林多炉 | Magnetic super-hydrophobic polyurethane sponge oil-water separation material and preparation method thereof |
| CN112029142A (en) * | 2020-08-06 | 2020-12-04 | 武汉工程大学 | Preparation method of oil-absorbing hydrophobic sponge and oil-absorbing hydrophobic sponge prepared by same |
| CN112175600A (en) * | 2020-08-31 | 2021-01-05 | 西南石油大学 | Novel foam stabilizer and preparation method thereof |
| CN112403292A (en) * | 2020-09-27 | 2021-02-26 | 武汉纺织大学 | Oil-water separation composite membrane and preparation method thereof |
| CN112961395A (en) * | 2021-04-22 | 2021-06-15 | 郑州大学 | High-foaming-ratio PLA/PBAT/Talc composite foaming oil absorption material and preparation method thereof |
| CN113462009A (en) * | 2021-07-29 | 2021-10-01 | 南京旭智材料科技有限公司 | Magnetic oil-absorbing polyolefin foam material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114425269A (en) | 2022-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | Nanocellulose-based lightweight porous materials: A review | |
| Nguyen et al. | Green aerogels from rice straw for thermal, acoustic insulation and oil spill cleaning applications | |
| RU2729992C2 (en) | Aerogel composite and method for production thereof | |
| Yu et al. | High porosity supermacroporous polystyrene materials with excellent oil–water separation and gas permeability properties | |
| Kumar et al. | Utilization and regeneration of waste sugarcane bagasse as a novel robust aerogel as an effective thermal, acoustic insulator, and oil adsorbent | |
| CN105837852B (en) | A kind of both hydrophobic and oleophobic open-cell foam materials and preparation method thereof | |
| CN105924686A (en) | Biology base polymer aerogel oil absorption material and preparation method thereof | |
| Cai et al. | Wood sponge reinforced with polyvinyl alcohol for sustainable oil–water separation | |
| Yu et al. | Superhydrophobic and superoleophilic “sponge-like” aerogels for oil/water separation | |
| He et al. | Preparation and hydrophobic modification of carboxymethyl chitosan aerogels and their application as an oil adsorption material | |
| CN107674406A (en) | A kind of supercritical CO2Expanded material bio-based porous carbon materials | |
| Riyajan et al. | Fabrication and properties of macrocellular modified natural rubber-poly (vinyl alcohol) foam for organic solvent/oil absorption | |
| CN114425269B (en) | High-efficiency oil-water separation composite foam based on surface engineering and preparation method thereof | |
| CN1653119A (en) | Hydrocarbon copolymer or polymer based aerogel and method for the preparation thereof | |
| CN105618006A (en) | Preparation method for straw hydrogel composite material special for sewage treatment | |
| CN109096534A (en) | The melamine foamed plastic oil absorption material and preparation method thereof of graphene/chlorinated polypropylene modified | |
| CN112029142A (en) | Preparation method of oil-absorbing hydrophobic sponge and oil-absorbing hydrophobic sponge prepared by same | |
| Ma et al. | Melamine foam with pH‐responsive wettability for fast oil absorption and desorption | |
| CN113024885B (en) | Emulsion separation material and preparation method thereof | |
| CN109092260B (en) | Petroleum adsorption degradation material and preparation method thereof | |
| CN114106396A (en) | Preparation method of thermoplastic polyurethane foam material | |
| CN112609465B (en) | High-thermal-conductivity infiltration material for photo-thermal conversion and preparation method thereof | |
| CN113122190A (en) | Aerogel composite material and preparation method thereof | |
| CN112709005A (en) | Preparation method of high-oil-absorption melt-blown non-woven fabric | |
| CN108841207B (en) | Novel low-temperature plasma preparation process of super-hydrophobic white carbon black |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |