CN104987528A - Modification method of oleophylic and hydrophobic nano-sponge - Google Patents
Modification method of oleophylic and hydrophobic nano-sponge Download PDFInfo
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- CN104987528A CN104987528A CN201510366736.5A CN201510366736A CN104987528A CN 104987528 A CN104987528 A CN 104987528A CN 201510366736 A CN201510366736 A CN 201510366736A CN 104987528 A CN104987528 A CN 104987528A
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Abstract
The invention relates to a preparation method of a modified nano-sponge oil absorption material capable of absorbing oil continuously and selectively. The preparation method comprises the following steps: (1) selecting proper solvents to prepare a silane coupling agent solution of a certain concentration, and adding a nano-sponge material; (2) after the nano-sponge material absorbs the solution sufficiently, soaking for a certain time, and sufficiently drying the soaked nano-sponge material in a high-temperature drying oven; (3) taking out the dried nano-sponge, washing with a solvent for 2 to 4 times, and placing the washed nano-sponge in a vacuum drying oven for drying till the weight is not changed any more. The preparation method has the advantages that as the nano-sponge material of which the internal porosity is high is taken as a reaction base body, the oil retaining capacity of the modified oil absorption material is high; the nano-sponge material is not required to be pretreated before modification; after modification, the oil absorption sponge is still as elastic as common sponge, and can be directly connected onto a pump to recover leaked oil while no water is absorbed, so that the use is convenient; the prepared sponge is higher in continuous oil absorption capability, and can be used in a circulatory manner repeatedly, so that the reusability of the prepared sponge is improved; the preparation process for modified sponge is simple to operate and mild in reaction conditions.
Description
Technical field
The invention belongs to oil absorption material and environmental protection technical field, relate to a kind of preparation method that can continue the cotton oil absorption material of modified Nano of selectivity oil suction.
Background technology
In recent years, along with the fast development of oil production and transport, the oil spill events of all size scale constantly increases, and Oil spills and chemical leakage have become affects coastal marine environment and the most important factor of the ecosystem, brings great threat to ocean environment.In order to avoid the disadvantageous effect of crude oil leakage to the ecosystem and the long-term hazards of greasy dirt, be necessary to develop the material effectively clearing up greasy dirt.
The development experience of an oil absorption material process developed to high-performance type by tradition.Initial people utilize the materials such as sponge, clay, hay, feather, straw, peat moss to carry out oil suction, but these natural oil absorption material oil absorbing effect are unsatisfactory, there is many defects.Such as, oil absorption is poor, oil suction poor selectivity in oil-water mixing system, and the saturated rear pressurized of oil suction easily analyses oil.So just limit their application.Therefore, investigators have invested synthesis oil absorption material sight.
In recent years, sponge oil suction modification becomes the new focus of oil absorption material research field.Because sponge has abundant three-dimensional pore space, a large amount of oil can be stored.By certain oil suction modification, sponge can be allowed to have oil-water selectivity, also have higher oil suction multiplying power simultaneously.But great majority all concentrate on polyurethane sponge.
The people such as Wang Yong are using polyurethane sponge as matrix, on sponge skeleton, the excessive layer of metal oxide is obtained by ald, again silane coupling agent is connected on sponge by the hydroxyl of oxide surface, obtain coupling layer, reach hydrophobically modified object (Wang Yong. a kind of oily water separation preparation method of sponge. Chinese invention patent .201310482138.5.2013-10-15).The people such as Zhou are by 1H, 1H, 2H, 2H-perfluoro capryl triethoxyl silane (PTES) and polypyrrole modifying are on polyurethane sponge surface, obtain hydrophobic oleophilic oil sponge (Zhou.Facile fabrication of superhydrophobic sponge with selective absorption and collectionof oil from water.Ind.Eng.Chem.Res.2013,52,9411-9416.).People's dodecamethylene diamine such as Liu and graphite oxide alkene reaction, then graphene oxide modified for dodecamethylene diamine is attached on polyurethane sponge, the hydrophobic sponge water contact angle obtained is up to 159 °.(Liu.Superhydrophobic polyurethane foam modified by graphene oxide.WileyPeriodicals,Inc.J.Appl.polym.SCI.130:3530-3536,2013.)。Generally speaking, the current research to oil suction sponge or oil suction foam mainly concentrates on polyurethane material, and the report preparing oil absorption material as matrix with nanometer cotton (melmac sponge) is less.Nanometer cotton is the sponge material that a kind of adsorptive power is very strong, but does not possess oil-water selectivity, therefore can consider to carry out modification to improve lipophilic-hydrophobic property to it, in addition, the oil absorption material preparation method reported generally needs polystep reaction, and operate more complicated, cost is higher.
Summary of the invention
The object of the present invention is to provide the method for modifying of a kind of oleophilic drainage type nanometer cotton, in order to promote its oil-water selectivity.
It is as follows that the present invention solves the problems of the technologies described above adopted technical scheme: the method for modifying of a kind of oleophilic drainage type nanometer cotton, comprises the following steps:
(1) select suitable solvent to prepare certain density silane coupler solution, add nanometer cotton material;
(2) it is made fully to absorb this solution, after soaking for some time, fully dry in high temperature drying case;
(3) take out dried sponge, by solvent cleaning 2-4 time, be placed in vacuum drying oven and be dried to constant weight.
By such scheme, the solvent described in step (1) is the solvent dissolving silane coupling agent, is one or more in methyl alcohol, ethanol, ether, sherwood oil, toluene, normal hexane, methylene dichloride, trichloromethane and tetracol phenixin.
By such scheme, silane coupling agent described in step (1) contains chlorine and hydro carbons group, is one or more in METHYL TRICHLORO SILANE, trimethylchlorosilane, dimethyldichlorosilane(DMCS), propyltrichlorosilan, chlorotriethyl silane, n-octyl trichlorosilane, TERT-BUTYL DIMETHYL CHLORO SILANE, tri-phenyl chloride, phenyl-trichloro-silicane and chlorine (dimethyl) phenyl silane.
By such scheme, the mass percent concentration of the silane coupler solution described in step (1) is 0.1% ~ 5.0%.
By such scheme, the described sponge soak time of step (2) is 5min ~ 30min.
Reaction mechanism of the present invention: nanometer cotton is matrix, by the silicone layer formed between nanometer cotton and silylating reagent, makes modified material have stronger hydrophobicity, thus realizes excellent oil-water selectivity, does not absorb water in water-oil interface meeting oil suction; Utilize the cotton loose porous structure of nanometer simultaneously, the continuous oil suction on water-oil interface can be realized after connecting vacuum pump.
The present invention has the following advantages:
(1) nanometer selecting wood interior porosity high is cotton as reactive matrix, makes modified oil absorption material have good oil-retaining;
(2) before modified without the need to carrying out pre-treatment to nanometer cotton;
(3) modified obtained oil suction sponge still has the elasticity of sponge, directly can be connected on pump and reclaim leakage of oil, and not absorb water, easy to use;
(4) the continuous oil absorbency of obtained sponge improves, and can repeatedly recycle, and what improve sponge can reusing;
(5) sponge modification preparation process is simple to operate, and reaction conditions is gentle.
Figure of description
Fig. 1 is modified Nano cotton (a) that obtains of embodiment 1 and the optical microscope photograph of unmodified nanometer cotton (b);
Fig. 2 is that the modified Nano cotton that embodiment 2 obtains is schemed with the cotton state vs be immersed in water after 10s of unmodified nanometer;
Fig. 3 is that the modified Nano cotton that embodiment 3 obtains is schemed with the cotton state vs after water 10min is dripped on surface of unmodified nanometer;
Fig. 4 is the cotton procedure chart that oil suction does not absorb water on water-oil interface of modified Nano that embodiment 4 obtains;
Fig. 5 is that the modified Nano cotton that embodiment 4 obtains connects the lasting oil-absorbing process figure after vacuum pump.
Embodiment
Below by embodiment, the present invention will be further described in detail, and material used in the present invention, reagent etc. if no special instructions, all can obtain from commercial channels.
Embodiment 1
Compound concentration is the toluene solution of the propyltrichlorosilan of 5.0%, is dipped in above-mentioned solution by nanometer cotton, makes it fully absorb and soak 5min, take out sponge to extract, fully dry in high temperature drying case, take out, clean 3 times with trichloromethane, extract, be placed in vacuum drying oven and be dried to constant weight.
Can see that from Fig. 1 (a) the reticulated structure skeleton of sponge has rough silicone layer.Silicone layer is very thin, porously improves its oil-water selectivity reservation nanometer is cotton simultaneously; B () figure is that unmodified nanometer is cotton, present the reticulated structure of porous.
Embodiment 2
Compound concentration is the diethyl ether solution of the trimethylchlorosilane of 0.5%, is dipped in above-mentioned solution by nanometer cotton, makes it fully absorb and soak 20min, take out sponge to extract, fully dry in high temperature drying case, take out, with ethanol purge 3 times, extract, be placed in vacuum drying oven and be dried to constant weight.
Two white cubic blocks in Fig. 2 in beaker, the left side is that modified Nano is cotton, and the right is that unmodified nanometer is cotton.It is immersed in respectively after in same volume ponding, unmodified nanometer cotton is quick and complete is sunken to the bottom, and modified nanometer cotton can be bubbled through the water column for a long time completely, shows that its hydrophobicity is significantly improved.
Embodiment 3
Compound concentration is the hexane solution of the dimethyldichlorosilane(DMCS) of 0.1%, is dipped in above-mentioned solution by nanometer cotton, makes it fully absorb and soak 10min, take out sponge to extract, fully dry in high temperature drying case, take out, clean 4 times with sherwood oil, extract, be placed in vacuum drying oven and be dried to constant weight.
Two white cubic blocks in Fig. 3, the left side is that modified Nano is cotton, and the right is that unmodified nanometer is cotton.Dripping by ink dye on the cotton surface of nanometer is blue water droplet, and can keep spherical at the cotton surperficial water droplet of modified Nano, and after 10min, also change is little, the water droplet on unmodified nanometer cotton is then inhaled in nanometer cotton and rapidly disappears.Modified nanometer is cotton cotton compared to unmodified nanometer, and its hydrophobicity obtains remarkable lifting.
Embodiment 4
Compound concentration is the hexane solution of the METHYL TRICHLORO SILANE of 1.0%, is dipped in above-mentioned solution by nanometer cotton, makes it fully absorb and soak 30min, take out sponge to extract, fully dry in high temperature drying case, take out, clean 2 times with methylene dichloride, extract, be placed in vacuum drying oven and be dried to constant weight.
As Fig. 4, in beaker, add the diesel oil (upper strata, aobvious red) of certain water gaging and Sudan red III mark, modified Nano cotton is immersed in this mixed system, can be observed diesel oil layer height to reduce until completely dissolve, nanometer cotton reddens, and water layer height does not change substantially.Modified Nano is cotton in the oil suction of oil mixing with water interfacial energy selectivity as can be seen here.
As Fig. 5, modified Nano cotton is connected vacuum absorption device by Glass tubing, and modified Nano cotton is placed on water and the labeled diesel oil interface of Sudan red III, after vacuum pump is opened, can be observed diesel oil be modified nanometer cotton absorb and be pumped in Glass tubing, after for some time, diesel oil is exhausted, and in beaker, water layer height keeps substantially constant.This illustrates this material except having certain oil storage capacity, also has the ability of lasting oil suction.
Embodiment 5
Compound concentration is the ethanolic soln of the tri-phenyl chloride of 0.5%, is dipped in above-mentioned solution by nanometer cotton, makes it fully absorb and soak 5min, take out sponge to extract, fully dry in high temperature drying case, take out, clean 4 times with normal hexane, extract, be placed in vacuum drying oven and be dried to constant weight.
Embodiment 6
Compound concentration is the chloroform soln of the n-octyl trichlorosilane of 2.0%, is dipped in above-mentioned solution by nanometer cotton, makes it fully absorb and soak 20min, take out sponge to extract, fully dry in high temperature drying case, take out, clean 2 times with toluene, extract, be placed in vacuum drying oven and be dried to constant weight.
Embodiment 7
Compound concentration is the methanol solution of the chlorotriethyl silane of 3.0%, is dipped in above-mentioned solution by nanometer cotton, makes it fully absorb and soak 5min, take out sponge to extract, fully dry in high temperature drying case, take out, by washed with methanol 4 times, extract, be placed in vacuum drying oven and be dried to constant weight.
Embodiment 8
Compound concentration is the carbon tetrachloride solution of the phenyl-trichloro-silicane of 4.0%, nanometer cotton is dipped in above-mentioned solution, it is made fully to absorb and soak 20min, take out sponge to extract, fully dry in high temperature drying case, take out, clean 3 times with tetracol phenixin, extract, be placed in vacuum drying oven and be dried to constant weight.
Claims (5)
1. a method of modifying for oleophilic drainage type nanometer cotton, comprises the following steps:
(1) select suitable solvent to prepare certain density silane coupler solution, add nanometer cotton material;
(2) it is made fully to absorb this solution, after soaking for some time, fully dry in high temperature drying case;
(3) take out dried sponge, by solvent cleaning 2-4 time, be placed in vacuum drying oven and be dried to constant weight.
2. the method for modifying of oleophilic drainage type nanometer cotton according to claim 1, it is characterized in that, solvent described in step (1) is the solvent dissolving silane coupling agent, is one or more in methyl alcohol, ethanol, ether, sherwood oil, toluene, normal hexane, methylene dichloride, trichloromethane and tetracol phenixin.
3. the method for modifying of oleophilic drainage type nanometer cotton according to claim 1, it is characterized in that, silane coupling agent described in step (1) contains chlorine and hydro carbons group, is one or more in METHYL TRICHLORO SILANE, trimethylchlorosilane, dimethyldichlorosilane(DMCS), propyltrichlorosilan, chlorotriethyl silane, n-octyl trichlorosilane, TERT-BUTYL DIMETHYL CHLORO SILANE, tri-phenyl chloride, phenyl-trichloro-silicane and chlorine (dimethyl) phenyl silane.
4. the method for modifying of oleophilic drainage type nanometer cotton according to claim 1, is characterized in that, the mass percent concentration of the silane coupler solution described in step (1) is 0.1% ~ 5.0%.
5. the method for modifying of oleophilic drainage type nanometer cotton according to claim 1, is characterized in that, the described sponge soak time of step (2) is 5min ~ 30min.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399977A (en) * | 2015-12-04 | 2016-03-16 | 武汉工程大学 | Method for preparing reusable oil-absorbing sponge |
| CN105801903A (en) * | 2016-03-17 | 2016-07-27 | 中国船舶重工集团公司第七二五研究所 | Preparation method and corrosion-preventing implementation method of super-hydrophobic sponge material |
| CN107570127A (en) * | 2017-09-08 | 2018-01-12 | 浙江工业大学 | A kind of graphene-based water-oil separating foamed material and its preparation method and application |
| CN107778515A (en) * | 2017-09-30 | 2018-03-09 | 河南大学 | A kind of short-cut method for preparing the super-hydrophobic polycarbonate plate of novel self-cleaning yellow |
| CN109212786A (en) * | 2018-11-18 | 2019-01-15 | 大连高马文化产业发展有限公司 | Anti-fog glasses cloth |
| CN110393949A (en) * | 2019-06-24 | 2019-11-01 | 舟山市质量技术监督检测研究院 | A kind of super-hydrophobic super-oleophylic polyurethane sponge material and preparation method thereof |
| CN112870766A (en) * | 2021-01-11 | 2021-06-01 | 领智科技技术(广州)有限责任公司 | Safe and pollution-free efficient organic absorbent and preparation method thereof |
| CN113150369A (en) * | 2021-03-05 | 2021-07-23 | 福建省蓝深环保技术股份有限公司 | Preparation method of graphene oxide modification-based oil absorption sponge |
| CN115228231A (en) * | 2021-04-23 | 2022-10-25 | 中国石油化工股份有限公司 | Composite material, organic gas enrichment coalescence device and method, organic gas recovery system and method and application of organic gas enrichment coalescence device and method |
| CN115364811A (en) * | 2022-08-24 | 2022-11-22 | 榆林学院 | Petroleum asphalt nano sponge base macroporous carbon and preparation method and application thereof |
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| CN104163934A (en) * | 2014-07-29 | 2014-11-26 | 江苏大学 | Preparation method of porous hydrophobic oleophylic sponge |
| CN104497346A (en) * | 2014-11-20 | 2015-04-08 | 江西先材纳米纤维科技有限公司 | Super-hydrophobic high-oil-absorbing melamine-resin sponge and preparation method thereof |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105399977A (en) * | 2015-12-04 | 2016-03-16 | 武汉工程大学 | Method for preparing reusable oil-absorbing sponge |
| CN105801903B (en) * | 2016-03-17 | 2019-01-15 | 中国船舶重工集团公司第七二五研究所 | A kind of preparation and its anticorrosion implementation method of super-hydrophobic sponge material |
| CN105801903A (en) * | 2016-03-17 | 2016-07-27 | 中国船舶重工集团公司第七二五研究所 | Preparation method and corrosion-preventing implementation method of super-hydrophobic sponge material |
| CN107570127A (en) * | 2017-09-08 | 2018-01-12 | 浙江工业大学 | A kind of graphene-based water-oil separating foamed material and its preparation method and application |
| CN107570127B (en) * | 2017-09-08 | 2020-11-06 | 浙江工业大学 | Graphene-based oil-water separation foam material and preparation method and application thereof |
| CN107778515B (en) * | 2017-09-30 | 2019-06-28 | 河南大学 | A kind of short-cut method preparing the super-hydrophobic polycarbonate plate of automatically cleaning yellow |
| CN107778515A (en) * | 2017-09-30 | 2018-03-09 | 河南大学 | A kind of short-cut method for preparing the super-hydrophobic polycarbonate plate of novel self-cleaning yellow |
| CN109212786A (en) * | 2018-11-18 | 2019-01-15 | 大连高马文化产业发展有限公司 | Anti-fog glasses cloth |
| CN110393949A (en) * | 2019-06-24 | 2019-11-01 | 舟山市质量技术监督检测研究院 | A kind of super-hydrophobic super-oleophylic polyurethane sponge material and preparation method thereof |
| CN112870766A (en) * | 2021-01-11 | 2021-06-01 | 领智科技技术(广州)有限责任公司 | Safe and pollution-free efficient organic absorbent and preparation method thereof |
| CN113150369A (en) * | 2021-03-05 | 2021-07-23 | 福建省蓝深环保技术股份有限公司 | Preparation method of graphene oxide modification-based oil absorption sponge |
| CN115228231A (en) * | 2021-04-23 | 2022-10-25 | 中国石油化工股份有限公司 | Composite material, organic gas enrichment coalescence device and method, organic gas recovery system and method and application of organic gas enrichment coalescence device and method |
| CN115364811A (en) * | 2022-08-24 | 2022-11-22 | 榆林学院 | Petroleum asphalt nano sponge base macroporous carbon and preparation method and application thereof |
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