CN104338519A - Modified graphene-loaded polyurethane sponge and preparation method thereof - Google Patents
Modified graphene-loaded polyurethane sponge and preparation method thereof Download PDFInfo
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- CN104338519A CN104338519A CN201410474339.5A CN201410474339A CN104338519A CN 104338519 A CN104338519 A CN 104338519A CN 201410474339 A CN201410474339 A CN 201410474339A CN 104338519 A CN104338519 A CN 104338519A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
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Abstract
The invention relates to modified graphene-loaded polyurethane sponge which is characterized in that a modified graphene coating is loaded on the surface of the polyurethane sponge, and is 0.5mm-1.0mm thick, a silane coupling agent is coated on the surface of the modified graphene, wherein the mass ratio of the silane coupling agent to the graphene is 1 to 100. Experiments prove that by measuring the dewatering effect and the oil absorption capability of the loaded sponge, the sponge is super-hydrophobic from hydrophilic (a contact angle is 161 degrees), the oil absorption capability is remarkably enhanced, and the saturation adsorption amount for diesel reaches 37.89g. According to the modified graphene-loaded polyurethane sponge, the modified graphene is loaded on the sponge by using the silane coupling agent, so that the sponge has super-hydrophobic and super-oleophylic performances, and has a potential application value in a process of remediating a petroleum pollution water body.
Description
Technical field
The present invention relates to a kind of modified graphene load polyurethane sponge and preparation method thereof.
Background technology
Along with the fast development of the modern industry, the increasingly deficient and mankind's increasing rapidly energy demand of land resources, shallow sea petroleum resources is continually developed.But along with the exploitation of submarine oil and crude oil etc., its product also constantly at sea transports, this just inevitably creates a lot of marine oil pollution event, the leakage accident etc. of gas blowout accident and Transport Oiler Ship during as developed.Deepwater oil leaks and not only brings huge economic loss to us, the more important thing is and causes great pollution to the marine eco-environment and periphery seashore.First, the hydrobiological existence of oil meeting serious harm, after ocean mammal takes in oil spilling, viscera function is damaged, some petroleum component can make lactation animal and free mushroom lack of proper care to the consciousness of chemical stimulation, and hinders the chemical information transmission between aqueous bio; Greasy dirt can make the feather of aquatic bird lose thermal insulating and water-proof effect, and wing is stained with greasy dirt and is also difficult to flight.There are some researches show: as long as the water surface has very thin oil film, sunlight, air will be changed significantly to " input " of water body, thus the death of the marine alga of causing birds to eat and other lower hydrobiont.In addition the toxicity of oil product, causes ecological environment sharply to worsen, and even can bring out marine red tide.It is reported, immediate and mid-term is because of existing more than the 1000 kind of sea hydrobiont extinction of oil pollution, and marine organisms decrease 40%; In addition, oil spilling also produces important impact to health.Comet to be accumulated by the poisonous substance in the shellfish body of oil spill by analysis of experiments, find certain density polycyclic aromatic hydrocarbon (PAH), if people have eaten the fish and shellfish absorbing oil, long-acting poisonous substance such as the carcinogenic substance in oil will be brought in body.Moreover the organic steam that oil volatilization is formed is diffused in air also can pollutant atmosphere, causes photochemical fog, equally can the vision of stimulating human, the organic matter in damage to the environment, causes plant necrosis etc.
In order to administer petroleum pollution in ocean, reduce its harm to greatest extent, lot of domestic and foreign scholar has carried out many-sided research.And administering method common at present has Mechanical Method, combustion method, biological restoration, material absorption process etc.Mechanical absorption method physically, not only solves oil slick problem on ocean, also energy recovery is utilized not waste, but the oil fence can not be guaranteed rapidly, fully control the trend of oil diffusion, therefore it still has certain limitation.It is the simplest method that combustion method seems, but the product after burning can cause secondary pollution to environment, and therefore up to the present all high sea leakage of oil events did not all adopt this kind of method.What biological prosthetic fado adopted is that surfactant realizes, especially biosurfactant combines the hydrophobicity of surfactant and the degradation function of microorganism, can reach efficient, nontoxic, antibacterial, economical, the easy advantage such as degraded and non-secondary pollution, but consider the problems such as industrial cost, the ecological balance and time is longer, be not also commonly used for oil spill process.Current material absorption process, because it efficiently, fast, not produces secondary pollution, and can carry out the advantage such as recycling, become the prefered method of oil spill process.The kind of absorbent has polymeric type absorbent, natural material absorbent and fibrous material absorbent etc. now, wherein Graphene is due to the two-dimensional structure of its uniqueness, and special hydrophobic oleophilic oil characteristic, it has become the focus of oil absorption material research as a kind of coating material, but the method utilizing γ-methacryloxypropyl trimethoxy silane (KH-570) modified graphene to load on polyurethane sponge is not yet studied.
Summary of the invention
An object of the present invention is to provide a kind of modified graphene load polyurethane sponge.
Two of object of the present invention is the preparation method providing this polyurethane sponge.
Provided by the present invention is a kind of method making polyurethane sponge surface reach super-hydrophobic super-oleophylic, the technical scheme of concrete employing is: restore modified for graphene oxide the Graphene generating modification with the hydrolysate of KH-570, and loaded to sponge surface, form the material with super-hydrophobicity and super-oleophilic matter, carrying out lyophobic oil-absorption to it can test.
For achieving the above object, the present invention adopts following technical scheme:
A kind of modified graphene load polyurethane sponge, it is characterized in that this polyurethane sponge has modified graphite ene coatings at the area load of polyurethane sponge, this coating layer thickness is 0.5 ~ 1.0mm; Described modified graphene is at the coated silane coupler of graphenic surface, and wherein the mass ratio of silane coupler and Graphene is 1:100.
The preparation method of above-mentioned modified graphene load polyurethane sponge, it is characterized in that described silane coupler has: gamma-aminopropyl-triethoxy-silane (KH-550), γ-glycidyl ether oxygen propyl trimethoxy silicane (KH-560), γ-methacryloxypropyl trimethoxy silane (KH-570) etc.
Prepare a method for above-mentioned modified graphene load polyurethane sponge, it is characterized in that the concrete steps of the method are:
A. graphite oxide is dissolved in absolute ethyl alcohol and is mixed with the suspension that concentration is 2mg/ml;
B. silane coupler, distilled water and absolute ethyl alcohol are pressed the volume ratio mixing of 1:1:18, regulate the pH value of this solution to be 4.0 ~ 4.5, then add in suspension that step a obtains, make the mass ratio of graphite oxide and silane coupler be 100:1; Back flow reaction 4h; Then suction filtration, filter cake distilled water washs, then with ethanol washing, is scraped by gained modified graphene oxide from filter paper, weighs after fully drying; Be distributed in ethanolic solution, be made into 2mg/ml graphene oxide alcohol suspension, wait until use;
C. the polyurethane sponge cleaned up is immersed in 1h in the suspension of step b gained, then regulates pH to be 9, graphene oxide is reduced 1.5h at 95 DEG C with hydrazine hydrate afterwards; Sponge is taken out, by washed with de-ionized water, dries, namely obtain modified graphene load polyurethane sponge
Through silane coupler modified graphene-supported sponge to the rate of adsorption of diesel oil much larger than the rate of adsorption to water, and its water absorption rate decline more obvious than Protospongia, and oil absorbency increases to some extent, can reach 37.89g to the saturated extent of adsorption of diesel oil; The contact angle (CA) of modified sponge to water is 161o, has super-hydrophobicity.Therefore, at polyurethane sponge area load through silane coupler modified Graphene, make originally not only to absorb water but also the sponge of oil suction has good hydrophobicity and stronger oil absorption, the sponge material that these features all demonstrate prepared by the hydrolyzed modified graphene-supported sponge of silane coupler has larger potentiality in the application of adsorbed water body petroleum class pollutant.
Accompanying drawing explanation
Fig. 1: Protospongia (a) comparison diagram directly perceived with modified sponge (b).
Fig. 2: Protospongia (a) and modified sponge (b) hydrophobic contact angle (CA) comparison diagram.
Fig. 3: Protospongia (a) and modified sponge (b) ESEM (SEM) comparison diagram.
Detailed description of the invention
1. material prepares
(1) preparation of reagent
Main reagent has: the concentrated sulfuric acid (H
2sO
4, 98%), sodium nitrate (NaNO
3), ammoniacal liquor (NH
4oH), glacial acetic acid (CH
3cOOH), potassium permanganate (KMnO
4), hydrogen peroxide (H
2o
2, 30%), hydrochloric acid (HCl, 5%), barium chloride (BaCl
2), absolute ethyl alcohol (CH
3cH
2oH), γ-methacryloxypropyl trimethicone (KH-570), hydrazine hydrate (N
2h
4h
2o).
The preparation method of graphite oxide please refer to document: Singh, E., Chen, Z., Houshmand, F., Ren, W., Peles, Y., Cheng, H. M. and Koratkar, N., Superhydrophobic graphene foams, Small, 2013,9 (1): 75-80.
(2) for examination sponge
(density is 0.025g/cm to polyurethane sponge
3), local producer buys.
(3) experimental instruments
Heat-collecting magnetic stirring device, FA1004B-assay balance, vacuum drying chamber, baking oven, supersonic wave cleaning machine, supercentrifuge, water-bath, vacuum filtration pump, magnetic agitation oil bath pan
2. the process of sponge and the mensuration of hydrophobic oleophilic oil characteristic thereof
(1) process of sponge
Sponge deionized water and ethanol are carried out ultrasonic cleaning, stand-by.
(2) for examination oil
No. zero diesel oil (China Petrochemical Industry bright and gas station).
Embodiment one:
1) preparation of graphene oxide (GO).Main method is in ice-water bath, adds 2g natural flake graphite in the beaker of 500mL, then adds the dense H of 46mL
2sO
4(98%) 1g NaNO, is added
3, temperature is controlled below 20 DEG C, adds 6g KMnO while stirring
4, temperature is raised to 35 ~ 36 DEG C, solution keeps 1.5h at this temperature, now has gas and releases; 92mL deionized water slowly added in mixed liquor, bath temperature rises to 98 DEG C subsequently, and keeps 15min, to increase the degree of oxidation of GO at this; With 280mL deionized water dilution mixture liquid, and by the H of 6mL 30%
2o
2solution slowly adds in above-mentioned solution, if there is not glassy yellow to generate, then continue to drip until generate glassy yellow, mixture, through suction filtration or centrifugation, repeatedly rinses until use BaCl with 5% HCl solution
2do not detect SO
4 2-, more repeatedly rinse by deionized water and remove acid, by block after the filter that obtains 60 DEG C of dryings, wait until for subsequent use after weighing.
2) preparation of KH-570 modified graphene oxide.Added in 250ml beaker by 100mg GO, adding 100ml absolute ethyl alcohol becomes suspension, ultrasonic 2h.Separately get a clean small beaker, add 10ml Silane coupling reagent KH-570, add 10ml distilled water and 180ml ethanol solution (three's volume ratio is 1:1:18) more wherein, stir, add the acetic acid solution of 36% until the pH value of solution is 4.0 ~ 4.5, join after mixing in the alcohol suspension of graphene oxide, continue to carry out the ultrasonic process of 30min to system.System is proceeded in 80 DEG C of constant temperature oil baths, carry out condensing reflux 4h.Then by reaction system vacuum filtration, filter cake 100ml distilled water washs 2 times, then washs 3 times with 100ml ethanol.Gained modified graphene oxide is scraped from filter paper, weighs after fully drying; Be distributed in ethanolic solution, be made into 2mg/ml graphene oxide alcohol suspension, wait until use.
3) preparation of KH-570 modified graphene load sponge.Sponge is cut into the bulk of length, width and height equalization, and ultrasonic cleaning in ethanolic solution, then use deionized water rinsing sponge, dry in 60 DEG C of baking ovens; Sponge is immersed 1h in the GO suspension of 2mg/ml, then slow ammonia spirit to be dropped to GO suspension to pH be 9, GO reduced 1.5h at 95 DEG C afterwards with hydrazine hydrate; Sponge is taken out, by washed with de-ionized water, and dries 24h in the vacuum drying oven of 30 DEG C, the PU sponge of the GO after reducing and modified graphite ene coatings can be obtained.
Embodiment two:
1) preparation of graphene oxide (GO).Main method is in ice-water bath, adds 2g natural flake graphite in the beaker of 500mL, then adds the dense H of 46mL
2sO
4(98%) 1g NaNO, is added
3, temperature is controlled below 20 DEG C, adds 6g KMnO while stirring
4, temperature is raised to 35 ~ 36 DEG C, solution keeps 1.5h at this temperature, now has gas and releases; 92mL deionized water slowly added in mixed liquor, bath temperature rises to 98 DEG C subsequently, and keeps 15min, to increase the degree of oxidation of GO at this; With 280mL deionized water dilution mixture liquid, and by the H of 6mL 30%
2o
2solution slowly adds in above-mentioned solution, if there is not glassy yellow to generate, then continue to drip until generate glassy yellow, mixture, through suction filtration or centrifugation, repeatedly rinses until use BaCl with 5% HCl solution
2do not detect SO
4 2-, more repeatedly rinse by deionized water and remove acid, by block after the filter that obtains 60 DEG C of dryings, wait until for subsequent use after weighing.
2) preparation (Lv Xiang, 2011) of KH-560 modified graphene oxide.By 100mg graphene dispersion in 100ml absolute ethyl alcohol, add 2ml water, the ratio of 5ml acetic acid and 10mgKH-560(silane coupler and Graphene is 7:100), ultrasonic evenly after at 80 DEG C, react 4h, reduce in ethanol system after the abundant drying of gained modified product, end product is KH-560 modified graphene.The lipophile of the more unmodified Graphene of modified graphene strengthens, but compared to KH-570, its consumption increases, and reduction effect is relatively low, and carries out oil absorption mensuration without load sponge, so its oil absorbing effect is unknown due to KH-560 modified graphene.
The mensuration of hydrophobic oleophilic oil effect after embodiment three: KH-570 modified graphene load polyurethane sponge
1) (shape is identical with thickness load even eight equal portions of the sponge of KH-570 modified graphene, about 1g), get any three parts weigh respectively after be put in water surface 5min, until its absorption saturated after be moved in time on rack, leave standstill 1min, weigh and calculate the water absorption rate of this modified sponge; Wherein, as a control group, be put in water surface 5min after being weighed by one block of Protospongia, be moved on rack in time, leave standstill 1min, weigh and calculate the water absorption rate of Protospongia.
2) separately get three parts of sponges of having weighed and be put in pasta 5min, move in time on rack after its absorption is saturated, leave standstill 1min, weigh and calculate the oil absorbency of this modified sponge; Meanwhile, as a control group, one block of Protospongia is directly put in pasta 5min, is moved in time on rack after its absorption is saturated, leaves standstill 1min, weigh and calculate the oil absorbency of Protospongia.
3. the measurement result of hydrophobic oleophilic oil effect after KH-570 modified graphene load polyurethane sponge:
Water absorption rate=(the W of modified sponge
2-W
1)/W
1, the water absorption rate=(m of Protospongia
2-m
1)/m
1;
Oil absorbency=(the W of modified sponge
3-W
1)/W
1, the oil absorbency=(m of Protospongia
3-m
1)/m
1;
Rate of water absorption=water absorption rate/the t of modified sponge, the swelling rate=oil absorbency/t of modified sponge;
Rate of water absorption=water absorption rate/the t of Protospongia, the swelling rate=oil absorbency/t of Protospongia;
Wherein, W
1=modified sponge weight (g), W
2=modified sponge+water absorption (g), m
1=unmodified sponge weight (g), m
2=unmodified sponge+water absorption (g), W
3=modified sponge+oil absorption (g), m
3=unmodified sponge+oil absorption (g), t is adsorption time (g).
Recorded by experiment, water absorption rate and the oil absorbency of sponge are as shown in table 1.
The water absorption rate of Novel sponge material prepared by table 1 and oil absorbency
| Sample | Water absorption rate (g/g) | Rate of water absorption (g/s) | Oil absorbency (g/g) | Swelling rate (g/s) |
| Protospongia | 34.78 0.10 | 1.72 0.02 | 34.69 0.12 | 1.59 0.02 |
| Modified sponge | 1.06 0.09 | 0.04 0.01 | 37.89 0.15 | 1.50 0.02 |
Visible this modified graphene load polyurethane sponge of the present invention is the material with super-hydrophobicity and super-oleophilic matter really, and effective, using value is high.
Claims (3)
1. a modified graphene load polyurethane sponge, it is characterized in that this polyurethane sponge has modified graphite ene coatings at the area load of polyurethane sponge, this coating layer thickness is 0.5 ~ 1.0mm; Described modified graphene is at the coated silane coupler of graphenic surface, and wherein the mass ratio of silane coupler and Graphene is 1:100.
2. the preparation method of modified graphene load polyurethane sponge according to claim 1, it is characterized in that described silane coupler has: gamma-aminopropyl-triethoxy-silane (KH-550), γ-glycidyl ether oxygen propyl trimethoxy silicane (KH-560) or γ-methacryloxypropyl trimethoxy silane (KH-570).
3. prepare a method for modified graphene load polyurethane sponge according to claim 1 and 2, it is characterized in that the concrete steps of the method are:
A. graphite oxide is dissolved in absolute ethyl alcohol and is mixed with the suspension that concentration is 2mg/ml;
B. silane coupler, distilled water and absolute ethyl alcohol are pressed the volume ratio mixing of 1:1:18, regulate the pH value of this solution to be 4.0 ~ 4.5, then add in suspension that step a obtains, make the mass ratio of graphite oxide and silane coupler be 100:1; Back flow reaction 4h; Then suction filtration, filter cake distilled water washs, then with ethanol washing, is scraped by gained modified graphene oxide from filter paper, weighs after fully drying; Be distributed in ethanolic solution, be made into 2mg/ml graphene oxide alcohol suspension, wait until use;
C. the polyurethane sponge cleaned up is immersed in 1h in the suspension of step b gained, then regulates pH to be 9, graphene oxide is reduced 1.5h at 95 DEG C with hydrazine hydrate afterwards; Sponge is taken out, by washed with de-ionized water, dries, namely obtain modified graphene load polyurethane sponge.
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Cited By (21)
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| CN104841294A (en) * | 2015-05-22 | 2015-08-19 | 福州大学 | Silane coupling agent-modified hydrophilic PES/GO (polyether sulfone/graphene oxide) composite film and preparation method for same |
| CN105056879A (en) * | 2015-07-13 | 2015-11-18 | 安徽成方新材料科技有限公司 | Composite spherical activated carbon added with polyester fibers and capable of improving mechanical strength as well as preparation method of composite spherical activated carbon |
| CN105413656A (en) * | 2015-12-03 | 2016-03-23 | 梅庆波 | Preparation method of super-hydrophobic polyurethane sponge/iron oxide composite material used for oil-water separation |
| CN105647159A (en) * | 2016-01-04 | 2016-06-08 | 杭州师范大学 | Graphene ribbon modified polymer-based foam material and preparation method and application thereof |
| 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 |
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