CN104162293A - Sponge material with polyurethane sponge surface modified by constructing zinc oxide fine structure, and preparation method thereof - Google Patents
Sponge material with polyurethane sponge surface modified by constructing zinc oxide fine structure, and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a sponge material with a polyurethane sponge surface modified by constructing a zinc oxide fine structure, and a preparation method thereof. According to the preparation method, a sol-gel method and a hydrothermal method are combined to use, wherein prepared zinc oxide nanometer crystal seeds are uniformly paved on the polyurethane sponge surface through the sol-gel method; then zinc oxide nano-rods grow on the surface in a directional manner through the hydrothermal synthesis method; a long-chain fatty acid-palmitic acid is adopted to modify so as to achieve super-hydrophobicity; and finally the hydrophobic effect and the oil absorption capacity of the modified sponge are determined. According to the present invention, the special morphology structure of zinc oxide is adopted to construct the super-hydrophobic sponge surface, and the super oil absorption capacity of the sponge surface is not affected, such that the sponge material has potential application value for petroleum-contaminated water body repair.
Description
Technical field
The present invention relates to a kind of sponge material and preparation method thereof, particularly a kind of sponge material of constructing zinc oxide fine structure modified polyurethane sponge surface and preparation method thereof.
Background technology
Be poured into every year according to statistics the oil total amount of ocean between 600 ~ 1,000 ten thousand tons, development along with China Petroleum, petroleum-polluted ocean area constantly expands, pollution level is also day by day serious, the whole nation directly enters every year approximately more than 10 ten thousand tons, the oil in coastal waters, and only fishery loss just reaches several hundred million units every year.According to national marine environmental monitoring net monitoring, the oceanic area that China coastal seas oils content surpasses one or two class sea water quality standards has reached 5.6 ten thousand km
2.Petroleum pollution in ocean is pressed oil input type, can be divided into sudden input and chronic long input.Sudden input comprises leakage and the gas blowout accident of oil tanker accident and offshore oil exploitation, and chronic long input has that the discharge of operation oil-polluted water, the oil-containing sedimentary rock of industrial civil waste water discharge, harbour and boats and ships ooze out after being corroded, natural sea bottom percolation, the sedimentation of oil-containing waste gas etc.The reason polluting is mainly reflected in: the marine transportation of oil frequently makes marine oil overflow accident occurrence probability increase; The operation of harbour handling oil is frequent, has the hidden danger of spill and leakage oil; The maximization of oil tanker has increased the possibility that great marine oil overflow accident occurs, and has improved the difficulty that oil spilling is processed; Leakage in offshore oilfield petroleum exploration and development and oil extraction waste water discharge.
For oil pollution incident, current representational processing method has three kinds: the first is natural purification method, adopts microorganism to degrade to oil, and shortcoming is that time-consuming is long, can use oil dispersant and precipitating reagent accelerated degradation process; Second method is to reduce oil surface tension with oily coagulating agent, is easy to process after oils is condensed, and after these two kinds of methods are processed, oils can not be recycled and can cause secondary pollution; The third method is with oil absorption material, oils to be processed.Therefore, the surface of solids with super-hydrophobic and super oil absorption has caused numerous researchers' interest, and because they have the ability of optionally adsorbing oils and not absorbing water completely, while making it adsorb oil product under oil mixing with water condition, can show stem-winding ability.Wherein, relation between surface of solids fine structure and wetability has more caused scientific worker's broad interest, because fine structure has increased the roughness of the surface of solids, by modification, its hydrophobicity is strengthened, along with the research that deepens continuously to occurring in nature super hydrophobic surface phenomenon and microstructure, the mankind have grasped principle and the method on bionic super-hydrophobic surface gradually.
Summary of the invention
One of object of the present invention is to provide a kind of sponge material of constructing zinc oxide fine structure modified polyurethane sponge surface.
Two of object of the present invention is to provide the preparation method of this material.
Provided by the present invention is a kind of method that makes polyurethane sponge surface reach super-hydrophobic super oleophylic, the concrete technical scheme adopting is: at the fine structure of sponge surface structure zinc oxide, by hydrophobically modified, make it have super-hydrophobicity, and due to itself super-oleophilic matter, it is carried out to lyophobic oil-absorption and can test.
For achieving the above object, the present invention adopts following technical scheme:
Construct the sponge material on zinc oxide fine structure modified polyurethane sponge surface, it is characterized in that there is zinc oxide nanocrystalline layer at the area load of this polyurethane sponge, this zinc oxide nanocrystalline vertical-growth, on sponge hole wall and surface, and becomes bar-shaped; This bar-shaped zinc oxide nanocrystalline particle size range is at 54.51 ~ 73.40nm, and the distance between nanometer rods is 11.32 ~ 13.11nm, and nanocrystalline length is at 30.20 ~ 42.41nm.
A method of preparing the sponge material on above-mentioned structure zinc oxide fine structure modified polyurethane sponge surface, is characterized in that the concrete steps of the method are:
A. at 60 ~ 65 ℃ of temperature, prepare the alcoholic solution of 0.05mol/L zinc acetate, under stirring, dropwise add 0.10mol/L ammoniacal liquor alcoholic solution, until generate transparent zinc oxide crystal seed solution, then continue to stir 2h, obtain the colloidal solution of zinc oxide, there is Tyndall phenomenon;
B. the sponge cleaning up is flooded to 2 ~ 3min in the colloidal solution of the zinc oxide of step a gained, then push sponge, put into the dry 5min of 80 ~ 85 ℃ of baking ovens, then put into the curing 3 ~ 5min of 170 ℃ of baking ovens;
C. repeating step b no longer increases to the sponge weight after solidifying, thereby forms zinc-oxide nano crystal seed film closely on sponge surface;
D. the aqueous solution of the aqueous solution of 0.03mol/L zinc nitrate and 0.03mol/L hexa being pressed to the volume ratio of 1:1 mixes, be mixed with mixed solution, step c gained sponge is immersed in described mixed solution, react 3h at 90 ~ 95 ℃ after, sponge is taken out, with drying at 70 ℃ after deionized water rinsing;
E. prepare the ethanolic solution of 1mmol/L palmitic acid; Steps d gained sponge is irradiated to 10min under uviol lamp, kept flat afterwards standing reaction 48h in the ethanolic solution that is immersed in the palmitic acid preparing; Finally take out with alcohol flushing repeatedly, dry, obtain constructing the sponge material on zinc oxide fine structure modified polyurethane sponge surface.
The present invention utilizes the special appearance of zinc oxide to construct super-hydrophobic sponge surface, and owing to not affecting itself super oil absorption, this has potential using value in the reparation of oil pollution water body.
Accompanying drawing explanation
Fig. 1 is hydrophobic effect figure before polyurethane sponge modification.
Fig. 2 is hydrophobic effect figure after polyurethane sponge modification.
Fig. 3 is hydrophobic oleophylic effect contrast figure.
Fig. 4 is design sketch before and after nano oxidized spelter coating polyurethane sponge oil suction.
The specific embodiment
1. material is prepared
(1) preparation of reagent
Main reagent has: palmitic acid (hexadecylic acid), absolute ethyl alcohol (CH
3cH
2oH), ammoniacal liquor (NH
4oH), glacial acetic acid (CH
3cOOH), hexa (C
6h
12n
4), zinc nitrate (Zn (NO
3)
26H
2o), zinc acetate (Zn (CH
3cOO)
22H
2o)
(2) for examination sponge
Polyurethane sponge, local producer buys.
(3) experimental instruments
Heat-collecting magnetic stirring device, FA1004B-assay balance, baking oven, supersonic wave cleaning machine, uviol lamp
2. the processing of sponge and the mensuration of hydrophobic oil-wet behavior thereof
(1) processing of sponge
Sponge is carried out to ultrasonic cleaning with deionized water and ethanol, stand-by.
(2) for examination oil
No. zero diesel oil (Ming He of China Petrochemical Industry gas station).
Embodiment mono-: the described concrete processing method at sponge surface structure zinc oxide fine structure is as follows:
1) preparation of zinc-oxide nano crystal seed.Main method is the alcoholic solution at 60 ~ 65 ℃ of preparation 25ml 0.05mol/L zinc acetates, under the condition constantly stirring, dropwise add appropriate 0.10mol/L ammoniacal liquor alcoholic solution, until generate transparent zinc oxide crystal seed solution, continue again to stir 2h, obtain the colloidal solution of zinc oxide, have faint Tyndall phenomenon.
2) coating procedure.The sponge that is about to clean up (through deionized water and ethanol ultrasonic cleaning) is flooded 2 ~ 3min in the zinc oxide nano-crystal solution of above-mentioned preparation, then with clean glass bar, push gently sponge, put into the dry 5min of 80 ~ 85 ℃ of baking ovens, put into again 170 ℃ of baking ovens and solidify 3 ~ 5min, same process repeats 3 times, thereby forms zinc-oxide nano crystal seed film closely at surface of cotton fabric.
3) growth of zinc oxide nano rod.Prepare respectively the aqueous solution of 25ml 0.03mol/L zinc nitrate and the aqueous solution of 25ml 0.03mol/L hexa, after mixing, proceed in reactor, the sponge that is paved with zinc oxide crystal seed is put in the reactor of mixed liquor, react 3h at 90 ~ 95 ℃ after, sponge is taken out, with drying at 70 ℃ 0.5 hour after deionized water rinsing.
4) hydrophobically modified of zinc oxide nano rod.Method is the ethanolic solution of preparation 1mmol/L fatty acids (palmitic acid); The sponge of the good zinc oxide fine structure of superficial growth is irradiated to 10min under uviol lamp, kept flat afterwards above-mentioned prepare containing standing reaction 48h in the organic solvent of hydrophobic substance; Finally take out with alcohol flushing repeatedly, and dry at low temperatures, measure its hydrophobic oleophylic effect.
The mensuration of hydrophobic oleophylic effect after Zinc oxide coating polyurethane sponge
1) (shape is identical with thickness growth to be had to zinc oxide nano rod hydrophobically modified even eight equal portions of sponge, about 1g), get any three parts and be put in water surface 5min after weighing respectively, after its absorption is saturated, be moved in time on rack, standing 1min, weighs and calculates the water absorption rate of this modification sponge; Wherein, as a control group, the 4th sponge is directly put in to water surface 5min, is moved in time on rack, standing 1min, weighs and calculates the water absorption rate of non-modified sponge.
2) separately get three parts of sponges of having weighed and be put in pasta 5min, until its absorption, move in time on rack after saturated, standing 1min, weighs and calculates the oil absorbency of this modification sponge; Meanwhile, as a control group, last piece sponge is directly put in to pasta 5min, until its absorption, is moved in time on rack after saturated, standing 1min, weighs and calculates the oil absorbency of unmodified sponge.
3. the measurement result of the hydrophobic oil suction effect of Zinc oxide coating sponge:
The water absorption rate of modification sponge=(W
2-W
1)/W
1, the water absorption rate of unmodified sponge=(m
2-m
1)/m
1;
The oil absorbency of modification sponge=(W
3-W
1)/W
1, the oil absorbency of unmodified sponge=(m
3-m
1)/m
1;
Rate of water absorption=water absorption rate/t of modification sponge, swelling rate=oil absorbency/t of modification sponge;
Wherein, W
1=modification sponge weight/g, W
2=modification sponge+water absorption/g, m
1=unmodified sponge weight/g, m
2=unmodified sponge+water absorption/g, W
3=modification sponge+oil absorption/g, m
3=unmodified sponge+oil absorption/g, t is adsorption time/s.
By experiment, recorded, water absorption rate and the oil absorbency of sponge are as shown in table 1 below.
Water absorption rate and the oil absorbency of the Novel sponge material of table 1 preparation
?
| Sample | Water absorption rate (g/g) | Rate of water absorption (g/s) | Oil absorbency (g/g) | Swelling rate (g/s) |
| Unmodified sponge | 49.24 0.15 | 1.61 0.02 | 47.31 0.12 | 1.59 0.02 |
| Modification sponge | 1.07 0.18 | 0.04 0.02 | 51.12 0.15 | 1.70 0.02 |
studies have shown that, the sponge of preparing through zinc oxide nanocrystalline modification is to the rate of adsorption of diesel oil much larger than the rate of adsorption to water, and its water absorption rate obviously declines, and oil absorbency increases to some extent; Modification sponge is 156o to the contact angle of water, has super-hydrophobicity.Therefore,, at polyurethane sponge surface structure zinc oxide fine structure, after modification, there is good hydrophobicity and oil absorption; From SEM (SEM) the pattern test comparison figure (Fig. 3) of the reflected sponge structure feature before and after nano-ZnO load, also can find out, sponge structure feature after loaded with nano ZnO demonstrates, and at the microcosmic of the epontic nano-ZnO crystal grain of sponge, arranges and is more conducive to improve its adsorption capacity to pollutant.Above feature has all proved that the sponge material that zinc oxide nanocrystalline modification prepares has larger potentiality in the application of adsorbed water body petroleum class pollutant.
Claims (2)
1. construct the sponge material on zinc oxide fine structure modified polyurethane sponge surface, it is characterized in that there is zinc oxide nanocrystalline layer at the area load of this polyurethane sponge, this zinc oxide nanocrystalline vertical-growth, on sponge hole wall and surface, and becomes bar-shaped; This bar-shaped zinc oxide nanocrystalline particle size range is at 54.51 ~ 73.40nm, and the distance between nanometer rods is 11.32 ~ 13.11nm, and nanocrystalline length is at 30.20 ~ 42.41nm.
2. a method of preparing the sponge material on structure zinc oxide fine structure modified polyurethane sponge according to claim 1 surface, is characterized in that the concrete steps of the method are:
A. at 60 ~ 65 ℃ of temperature, prepare the alcoholic solution of 0.05mol/L zinc acetate, under stirring, dropwise add 0.10mol/L ammoniacal liquor alcoholic solution, until generate transparent zinc oxide crystal seed solution, then continue to stir 2h, obtain the colloidal solution of zinc oxide, there is Tyndall phenomenon;
B. the sponge cleaning up is flooded to 2 ~ 3min in the colloidal solution of the zinc oxide of step a gained, then push sponge, put into the dry 5min of 80 ~ 85 ℃ of baking ovens, then put into the curing 3 ~ 5min of 170 ℃ of baking ovens;
C. repeating step b no longer increases to the sponge weight after solidifying, thereby forms zinc-oxide nano crystal seed film closely on sponge surface;
D. the aqueous solution of the aqueous solution of 0.03mol/L zinc nitrate and 0.03mol/L hexa being pressed to the volume ratio of 1:1 mixes, be mixed with mixed solution, step c gained sponge is immersed in described mixed solution, react 3h at 90 ~ 95 ℃ after, sponge is taken out, with drying at 70 ℃ after deionized water rinsing;
E. prepare the ethanolic solution of 1mmol/L palmitic acid; Steps d gained sponge is irradiated to 10min under uviol lamp, kept flat afterwards standing reaction 48h in the ethanolic solution that is immersed in the palmitic acid preparing; Finally take out with alcohol flushing repeatedly, dry, obtain constructing the sponge material on zinc oxide fine structure modified polyurethane sponge surface.
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Cited By (7)
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| CN105001443A (en) * | 2015-08-04 | 2015-10-28 | 北京化工大学 | Polyurethane sponge compositely modified through expanded graphite and zinc oxide and preparing method thereof |
| CN106824110A (en) * | 2017-02-17 | 2017-06-13 | 中国科学院宁波材料技术与工程研究所 | Super-hydrophobic super-oleophylic cellulose sponge, its preparation method and application |
| CN109603780A (en) * | 2019-01-10 | 2019-04-12 | 福州大学 | A kind of compound organic solvent absorbent of sponge and preparation method thereof |
| KR20190049382A (en) * | 2017-11-01 | 2019-05-09 | 울산대학교 산학협력단 | Composite based melamine resin, and oil-water separating materials |
| CN113019345A (en) * | 2021-04-20 | 2021-06-25 | 福州大学 | Sponge-based composite absorbent for low-concentration organic solvent wastewater treatment and preparation method and application thereof |
| CN114805921A (en) * | 2022-05-09 | 2022-07-29 | 西南交通大学 | Preparation method of hydrophobic oleophylic polyurethane sponge and oil-water separation device |
| CN115739055A (en) * | 2022-11-14 | 2023-03-07 | 哈尔滨师范大学 | Super-hydrophobic oleophylic nano sponge based on melamine foam and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001443A (en) * | 2015-08-04 | 2015-10-28 | 北京化工大学 | Polyurethane sponge compositely modified through expanded graphite and zinc oxide and preparing method thereof |
| CN106824110A (en) * | 2017-02-17 | 2017-06-13 | 中国科学院宁波材料技术与工程研究所 | Super-hydrophobic super-oleophylic cellulose sponge, its preparation method and application |
| CN106824110B (en) * | 2017-02-17 | 2019-08-23 | 中国科学院宁波材料技术与工程研究所 | Super-hydrophobic-super oleophylic cellulose sponge, preparation method and application |
| KR20190049382A (en) * | 2017-11-01 | 2019-05-09 | 울산대학교 산학협력단 | Composite based melamine resin, and oil-water separating materials |
| KR102038386B1 (en) * | 2017-11-01 | 2019-10-31 | 울산대학교 산학협력단 | Composite based melamine resin, and oil-water separating materials |
| CN109603780A (en) * | 2019-01-10 | 2019-04-12 | 福州大学 | A kind of compound organic solvent absorbent of sponge and preparation method thereof |
| CN113019345A (en) * | 2021-04-20 | 2021-06-25 | 福州大学 | Sponge-based composite absorbent for low-concentration organic solvent wastewater treatment and preparation method and application thereof |
| CN114805921A (en) * | 2022-05-09 | 2022-07-29 | 西南交通大学 | Preparation method of hydrophobic oleophylic polyurethane sponge and oil-water separation device |
| CN115739055A (en) * | 2022-11-14 | 2023-03-07 | 哈尔滨师范大学 | Super-hydrophobic oleophylic nano sponge based on melamine foam and preparation method and application thereof |
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