CN104874358A - Preparation method for conveniently-recyclable magnetic supramolecular gel dye adsorption material - Google Patents
Preparation method for conveniently-recyclable magnetic supramolecular gel dye adsorption material Download PDFInfo
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Abstract
The invention discloses a preparation method for a conveniently-recyclable magnetic supramolecular gel dye adsorption material. The method comprises the following steps: mixing halloysite with absolute ethyl alcohol, and adding ferric nitrate into the mixture; stirring so as to enable ethanol to volatilize naturally; then dropwise adding glycol into a solid substance, subsequently calcinating, and further treating with a silane coupling agent so as to obtain a magnetic halloysite subjected to surface hydrophobic modification; and dispersing the modified magnetic halloysite into a solvent, adding a gel factor, heating for completely dissolving gel factors, and cooling, thereby obtaining the magnetic supramolecular gel dye adsorption material. According to the preparation method, a halloysite nano tube loaded with magnetic nano particles is added into a supramolecular gel, so that the defects that the supramolecular gel is low in mechanical strength, difficult in machine shaping, high in recovery difficulty and not beneficial to practical application are overcome; the enhanced magnetic supramolecular gel has favorable dye adsorption performance; furthermore, since the magnetic responsiveness is achieved, separation and recovery after adsorption are convenient.
Description
Technical field
The invention belongs to Dye Adsorption Material Field, more specifically, relate to a kind of preparation method being convenient to the magnetic supermolecular gel Dye Adsorption material reclaimed.
Background technology
Supermolecular gel is the soft material with three-dimensional net structure that a class is formed by Supramolecular self assembly.In bio-medical material, pharmaceutical carrier, sensing, molecular switch and molecular recognition field, there is great application prospect.But an inherent defect of supermolecular gel is low mechanical strength, is difficult to processing and forming, thus strongly limit its range of application.Therefore, from the development trend of supermolecular gel, improve its mechanical strength, give its new function and be still challenging problem.
The response of the supermolecular gel of the response functions such as existing optical, electrical, pH is mainly from the intrinsic chemical structure of gel.For the supermolecular gel with magnetic responsiveness, except some contains the super-molecule metal gel of iron ion, the preparation of magnetic supermolecular gel mainly passes through additional ferrous magnetic material, as Fe
3o
4realize.Be different from traditional magnetic polymer gel, because supermolecular gel contains a large amount of solvents, the greatest problem being prepared magnetic gel by additional magnetic particle is magnetic particle (especially Fe
3o
4nanoparticle) easily occur to assemble and sedimentation, magnetic particle is caused to be difficult to be dispersed in (B.Hu et al.Supramolecular magnetorheological polymer gels.J.Appl.Polym.Sci.2006 in gel rubber system, 100,2464-2479).In addition, no matter be metal gel, or the supermolecular gel problem that still unresolved mechanical strength is low (the X.Wang et al.Jellyfish gel and its hybrid hydrogels with high mechanical strength.Soft Matter of additional magnetic particle, 2011,7,211-219).
Galapectite is a kind of alumino-silicate clays of tubular structure, and its pipe range is 500 ~ 1000nm, and caliber is 15 ~ 100nm, is a kind of typical natural nano pipe.Compared to common synthesizing carbon nanotubes, galapectite, except having advantage that is inexpensive, that be easy to get, also has the caliber larger than CNT, in addition, pipe surfaces externally and internally due to galapectite has a large amount of hydroxyls and O-Si-O base (W.O.Yah et al.Biomimetic dopamine derivative for selective polymer modification ofhalloysite nanotube lumen.J.Am.Chem.Soc.2012, 134, 12134-12137), galapectite is made to may be used for pharmaceutical carrier, hydrogen is stored, catalysis, nano-reactor and be used as (the D.Rawtani et al.Multifarious applications of halloysitenanotubes:A Review such as template of preparation nano material, Rev.Adv.Mater.Sci.2012, 30, 282-295).In addition, galapectite is as a kind of reinforcer of nano-scale, at present mainly for the preparation of enhancing polymer composites (M.Liu et al.Recent advance in research on halloysite nanotubes-polymernanocomposite.Prog.Polym.Sci.2014,39,1498-1525).In our early-stage Study, once galapectite was used for strengthening supermolecular gel as reinforcer, and achieve and strengthen effect (Central China University of Science and Technology's Master's thesis: galapectite is used for gelator self assembly and strengthens the research of supermolecular gel, Wu Yi) preferably.
Dyestuff is widely used in the industrial circles such as dyeing and weaving, papermaking, food, but also produces a large amount of industrial wastes containing dyestuff simultaneously.Because dyestuff is that a class formation is stablized, is difficult to biodegradable organic compound, the industrial wastes containing dyestuff causes day by day serious environmental pollution.The normal sorbing material that adopts removes dye molecule (V.Meshko et al.Adsorption of basic dyes on granular acivatedcarbon and natural zeolite.Water Research at present, 2001,35,3357-3366).According to the tubular structure feature of galapectite itself, existing bibliographical information can as a kind of sorbing material of effective dye wastewater treatment.But due to the fine size of galapectite, be dispersed in water after imbibition, there is the problem (L.Liu being difficult to separation and recovery, et al.The removal of dye from aqueous solutionusing alginate-halloysite nanotube beads.Chem.Eng.J.2012,18,210-216).According to another report, the supermolecular gel formed by some amphipathic gel factor also can effective adsorpting dye molecule (S.Ray et al.pH-responsive, bolaamphiphile-based smartmetallo-hydrogels as potential dye-adsorbing agents, water purifier, and vitaminB12carrier.Chem.Mater.2007, 19, 1633-1639), this report will form xerogel after supermolecular gel freeze-drying (after namely removing the solvent in supermolecular gel, only surplus gelator aggregation, form similar aerocolloidal material), then for Dye Adsorption.Although aforesaid way creates certain adsorption effect, this mode preparation process is complicated, and freeze-drying cost is higher; Further, due to the three-dimensional net structure of xerogel meeting partial destruction gel, adsorption effect is affected; In addition, which is difficult to the problem reclaimed after there is absorption equally, cause very large inconvenience to practical application.
Although existing in prior art, galapectite is used for the report strengthening supermolecular gel, but the supermolecular gel that this galapectite strengthens is directly used in adsorpting dye molecule in actual application, still there is larger deficiency, although in theory, the supermolecular gel that galapectite strengthens also can adsorpting dye molecule, but because the gel after absorption is difficult to separation and recovery from system, be equally also unfavorable for practical application and popularization.Therefore, although the Dye Adsorption material reported is more, efficiency is lower usually for way of recycling that these Dye Adsorption materials adopt (as filtered), and cost is higher and consuming time, and the application of Dye Adsorption material is extremely limited to.
Summary of the invention
For above defect or the Improvement requirement of prior art, the object of the present invention is to provide a kind of preparation method being convenient to the magnetic supermolecular gel Dye Adsorption material of separation and recovery, wherein improved by the critical process step etc. in the structure to magnetic supermolecular gel, its preparation process, compared with prior art effectively can solve the problem that Dye Adsorption material is difficult to reclaim, and this magnetic supramolecular materials is to the advantages of good adsorption effect of dyestuff, there is certain mechanical strength, be convenient to machine-shaping, flexible processing can be needed by practical application.
For achieving the above object, according to one aspect of the present invention, provide a kind of preparation method being convenient to the magnetic supermolecular gel Dye Adsorption material reclaimed, it is characterized in that, comprise the following steps:
(1) preparation of the magnetic halloysite of surface hydrophobicity modification:
By 0.8 gram ~ 1.2 grams galapectites at 70 DEG C ~ 90 DEG C dry 10 hours ~ 20 hours, then add 20mL ~ 50mL ethanol wherein, then obtain the suspension mixed in ultrasonic lower process; Then, in this suspension, 0.4 gram ~ 0.8 gram Fe (NO is added
3)
39H
2o, and stirring is no less than 10 hours; Then, at room temperature stir and the ethanol in this suspension is volatilized naturally, and standing and drying makes ethanol volatilize completely to obtain solid mixture at 80 DEG C ~ 100 DEG C; Then, in this solid mixture, under agitation slowly drip the ethylene glycol of 9.6mmol ~ 14.4mmol; Then, in the nitrogen atmosphere of 350 DEG C ~ 450 DEG C, described in roasting, solid mixture obtains magnetic halloysite in 2 hours ~ 4 hours, finally obtains the magnetic halloysite of surface hydrophobicity modification again by this magnetic halloysite of gamma-aminopropyl-triethoxy-silane process;
(2) preparation of magnetic supermolecular gel:
The magnetic halloysite of surface hydrophobicity modification step (1) obtained is dispersed obtains magnetic halloysite suspension in a solvent, and described in this magnetic halloysite suspension, the mass fraction of the magnetic halloysite of surface hydrophobicity modification is 1% ~ 8%; Then, add MDBS or DBS and obtain magnetic halloysite-gelator mixture as gelator in this magnetic halloysite suspension, the mass fraction that described gelator accounts for described magnetic halloysite-gelator mixture is 1% ~ 5%; Then, heating described magnetic halloysite-gelator mixture makes gelator wherein all dissolve, cool described magnetic halloysite-gelator mixture to room temperature subsequently and obtain magnetic supermolecular gel, the magnetic supermolecular gel Dye Adsorption material of this magnetic supermolecular gel namely for ease of reclaiming.
As present invention further optimization, described in described step (2), described in magnetic halloysite suspension, the mass fraction of the magnetic halloysite of surface hydrophobicity modification is 4%.
As present invention further optimization, it is 2% that gelator described in described step (2) accounts for the mass fraction of described magnetic halloysite-gelator mixture.
As present invention further optimization, the solvent in described step (2) is 1,2-PD, or the mass ratio of ethanol and water is the alcohol-water mixed solution of 4:1.
As present invention further optimization, magnetic halloysite suspension in described step (2) is that the magnetic halloysite of surface hydrophobicity modification step (1) obtained adds in described solvent, and then ultrasonic disperse obtains after being no less than 1 hour.
According to a further aspect in the invention, a kind of its application in absorbing dye of the magnetic supermolecular gel Dye Adsorption material being convenient to reclaim prepared according to said method is provided.
By the above technical scheme that the present invention conceives, compared with prior art, there is following beneficial effect:
1. the present invention adopts the magnetic supermolecular gel of preparation directly as Dye Adsorption material, because this magnetic supermolecular gel belongs to wet gel, not only have and significantly adsorb interface, and the solvent be retained in gel rubber system is conducive to the diffusion of adsorbate, advantages of good adsorption effect.
In actual absorbing dye process, for guaranteeing fully contacting of magnetic supermolecular gel and dye solution, commonly in prior art to leave standstill for a long time except adopting, except the mode of ultrasonic assistant, also the magnetic properties of magnetic supermolecular gel self can be utilized, the mode of external magnetic field is such as applied by discontinuous above dye solution, by magnetic force, buoyancy, with the interaction of gravity, magnetic supermolecular gel is moved back and forth in the solution, and to a certain extent dye solution is stirred, improve adsorption effect.After the process of absorbing dye terminates, the mode of externally-applied magnetic field simply can be adopted to reclaim magnetic supermolecular gel, reclaim convenient, efficient, with low cost.
The present invention is found by actual experiment, under same experimental conditions, the magnetic supermolecular gel of equal in quality is better than the blank supermolecular gel (namely not adding the supermolecular gel of magnetic halloysite) of equal in quality or the galapectite nano material of equal in quality far away to Dye Adsorption effect, has outstanding effect to the improvement of Dye Adsorption ability.
On the other hand, owing to introducing magnetic nanoparticle in preparation process in galapectite, only need simply to apply external magnetic field and this magnetic supermolecular gel recyclable, process is convenient, cost recovery is cheap.
2. the present invention is preferably in preparation magnetic supermolecular gel process, and in magnetic halloysite solution, the mass fraction of the magnetic halloysite of surface hydrophobicity modification is 4%; Gelator (such as: 1,3:2,4-bis-(4-methyl benzal)-D-glucitol, i.e. MDBS; Or, 1,3:2,4-benzyl-D-glucitol, i.e. DBS) and the mass fraction that accounts for magnetic halloysite-gelator mixture is 2%.
In magnetic halloysite solution, the concentration of the magnetic halloysite of surface hydrophobicity modification decides the mechanical strength generating supermolecular gel, also the complexity of Dye Adsorption material recovery can be affected, the mechanical strength of supermolecular gel is higher, in absorbing dye process, more can keep the original pattern of sorbing material, more easily reclaim.In the present invention, in magnetic halloysite suspension, the mass fraction of the magnetic halloysite of surface hydrophobicity modification is preferably 4%, at utmost can guarantee the mechanical strength of magnetic supermolecular gel, be convenient to absorbing dye and subsequent recovery.
The mass fraction that gelator accounts for magnetic halloysite-gelator mixture decides the pattern of the supermolecular gel of generation and the performance in absorbing dye.The mass fraction that in the present invention, gelator accounts for magnetic halloysite-gelator mixture is preferably 2%, pattern and the absorbing dye performance of magnetic supermolecular gel can be guaranteed, significant as the effect of Dye Adsorption material to improving magnetic supermolecular gel further.
In sum, the present invention passes through load Fe
3o
4the halloysite nanotubes of nanoparticle joins in supermolecular gel, give supermolecular gel magnetic and enough mechanical strengths, overcome supermolecular gel mechanical strength low, be difficult to the shortcoming that machine-shaping, recovery difficult are high, be unfavorable for practical application, the magnetic supermolecular gel strengthened has good Dye Adsorption performance, can be directly used in the absorption of dye molecule; Magnetic halloysite nanotube in this supermolecular gel is not only conducive to the processing and forming of sorbing material, and owing to giving its magnetic responsiveness, is also conducive to the separation and recovery after adsorbing.
Accompanying drawing explanation
Fig. 1 is respectively galapectite (corresponding diagram 1a), (load is Fe to magnetic halloysite
3o
4, corresponding diagram 1b) and the stereoscan photograph of magnetic halloysite (corresponding diagram 1c) of surface hydrophobicity modification, the illustration wherein in Fig. 1 a is the transmission electron microscope photo of single galapectite;
Fig. 2 a is load Fe
3o
4magnetic halloysite (homologous thread 1), surface modification magnetic halloysite (homologous thread 2), and the magnetization curve of supermolecular gel (homologous thread 3) containing magnetic halloysite; Fig. 2 b is the magnetization curve of the supermolecular gel (homologous thread 3) containing magnetic halloysite after amplifying; Axis of abscissas in figure is the magnetic field intensity (Applied magnetic field) applied, and axis of ordinates is the intensity of magnetization (Magnetization);
Fig. 3 is the compression stress strain curve of gel sample, wherein, the curve 1 ~ 5 in Fig. 3 a is respectively containing 0,2,4,6, the load-deformation curve of supermolecular gel (MDBS) sample of 8wt% magnetic halloysite; Curve 1,2 in Fig. 3 b is respectively the load-deformation curve of supermolecular gel (DBS) sample containing 1wt% and 4wt% magnetic halloysite; Axis of abscissas in figure is strain (Strain), and axis of ordinates is stress (Stress);
Fig. 4 is the Dynamic Viscoelastic spectrogram of gel sample, is respectively storage modulus (G ') and loss modulus (G ") that galapectite strengthens supermolecular gel (legend be ▲ or △) and do not strengthen supermolecular gel (legend is ■ or); Axis of abscissas in figure is angular frequency (Angular Frequency);
Fig. 5 a, 5b, 5c are respectively the uv absorption spectra of the Congo red aqueous solution, methyl orange aqueous solution, malachite green solution; In Fig. 5 a, 5b, 5c curve 1,2,3 be respectively initial aqueous dye solutions, blank supermolecular gel adsorb 48 hours after and magnetic supermolecular gel adsorb the ultra-violet absorption spectrum after 48 hours; Fig. 5 d is the color change of the Congo red aqueous solution before and after absorption, and the optical photograph of gel displacement under magnetic fields.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
Reference literature (J.Dai et al.Highly-controllable imprinted polymer nanoshell atsurface of magnetic halloysite nanotubes for selective recognition and rapidadsorption of tetracycline.RSC Adv.2014,4, the method recorded 7967-7978), by ferric nitrate (Fe (NO
3)
39H
2o) be carried in galapectite, obtain load Fe by in-situ reducing reaction (reducing agent is ethylene glycol)
3o
4magnetic halloysite; Then, silane coupler (KH550) is adopted to process the magnetic halloysite that magnetic halloysite obtains surface hydrophobicity modification.The concrete steps wherein preparing the magnetic halloysite of surperficial hydrophobically modified are as follows: by 1.0 grams of galapectites at 80 DEG C dry 15 hours, then add 30mL ethanol wherein, then obtain the suspension mixed in ultrasonic lower process; Then, in this suspension, 0.6 gram of Fe (NO is added
3)
39H
2o, and stir 10 hours, ferric nitrate is dissolved; Then, at room temperature stir and make the ethanol in this suspension naturally evaporate into substantially dry, and standing and drying makes ethanol volatilize completely to obtain solid mixture at 90 DEG C; Then, in this solid mixture, under agitation slowly drip the ethylene glycol of 12.0mmol, make the surface of described solid mixture occur liquid film; Then, in the nitrogen atmosphere of 400 DEG C, described in roasting, solid mixture obtains magnetic halloysite in 4 hours, finally uses gamma-aminopropyl-triethoxy-silane (KH550) to process the magnetic halloysite that this magnetic halloysite obtains surface hydrophobicity modification again.
Measured the microscopic appearance of products therefrom by ESEM (SEM), refer to the SEM photo of accompanying drawing 1.From accompanying drawing 1, galapectite is a kind of tube of hollow, long 500 ~ 800nm, diameter 50 ~ 80nm, and smooth surface.Load Fe
3o
4the outer surface of galapectite have a small amount of particle diameter about the Fe of 10nm
3o
4particle.The pattern of galapectite is not obviously changed after KH550 hydrophobically modified.Measured the magnetic of products therefrom by magnetometer, refer to the magnetization curve of accompanying drawing 2.Load Fe
3o
4magnetic halloysite and the saturation magnetization numerical value of magnetic halloysite of hydrophobically modified between 7 ~ 8emu/g.Show that hydrophobically modified does not affect the magnetic of magnetic halloysite.In addition, from magnetization curve, prepared magnetic material is typical paramagnetic material.
Taking a certain amount of surface hydrophobicity modified magnetic galapectite joins in 1,2-PD, ultrasonic disperse 1 hour.The weight content of hydrophobically modified magnetic halloysite is in the scope of 1% ~ 8%.After galapectite is uniformly dispersed, add a certain amount of gelator MDBS (a kind of small molecular organic compounds, CAS 54686-97-4) wherein.The weight content (observation by experiment finds, the gel effect of 2% is best) in the scope of 1 ~ 5% of MDBS.Stirring in a heated condition makes MDBS dissolve completely, at room temperature naturally cools subsequently, the magnetic supermolecular gel be enhanced.
Adopt the magnetization curve of magnetometer test sample.Adopt the compression strength of universal testing machine working sample.Adopt the dynamic viscoelasticity spectrum of rheometer measurement sample.Test result is shown in accompanying drawing 2,3,4.
The mechanical property of products therefrom is characterized by static compression test and dynamic rheological experiments.Refer to the compressive stress strain curve of accompanying drawing 3 and the dynamic viscoelasticity spectrum of accompanying drawing 4.From accompanying drawing 3, all compression strength adding the gel sample (curve 2 ~ 5) of magnetic halloysite is apparently higher than the blank sample (curve 1) not adding magnetic halloysite.Such as, the compression strength of blank sample is about 19KPa.When containing 4wt% magnetic halloysite, compression strength can reach 28KPa (curve 3), improves 44%.From withstand voltage deformation, blank sample becomes 11% shape and namely breaks, and becomes 15% (curve 4) containing the shape during sample of 6wt% magnetic halloysite when breaking.Show to add the intensity that magnetic halloysite not only increases gel, the toughness of gel can also be improved simultaneously.From accompanying drawing 4, concerning the gel do not strengthened, (G ") mean value is only 2.3 × 10 to its loss modulus
4pa, and not by the impact of acting frequency.This shows that gel does not almost have toughness.The mean value of its storage modulus (G ') is 2.6 × 10
5pa.And the G ' of the gel that galapectite strengthens and G is " all higher than the sample do not strengthened.Especially G ', its mean value is 3.8 × 10
5pa.By contrast, improve 1.5 times.After this shows to add galapectite, not only increase the ability of gel collapse resistance, also improve the ability of gel resistance to deformation.This is consistent with the result of above-mentioned compression strength.Compared to general supermolecular gel, the supermolecular gel of enhancing has plastic processability, such as, can cut into the film of any thickness, and this will be conducive to making sorbing material, is also conducive to the separation and recovery after adsorbing.
Embodiment 2
By the condition of embodiment 1, DBS (a kind of small molecular organic compounds, CAS 32647-67-9 (19046-64-1)) is substituted MDBS and prepares magnetic supermolecular gel.
The weight content (observation by experiment finds, the gel effect of 2% is best) in the scope of 1 ~ 5% of MDBS.
Embodiment 3
By the condition of embodiment 1, by ethanol: water quality substitutes 1,2-PD than the ethanol/water mixed solvent for 4:1 and prepares magnetic supermolecular gel.
Embodiment 4
By the condition of embodiment 1, preparation magnetic supermolecular gel.Wherein difference is that the concrete steps of the magnetic halloysite preparing surperficial hydrophobically modified are as follows: by 0.8 gram of galapectite at 90 DEG C dry 10 hours, then add 50mL ethanol wherein, then obtain the suspension mixed in ultrasonic lower process; Then, in this suspension, 0.8 gram of Fe (NO is added
3)
39H
2o, and stir 10 hours; Then, at room temperature stir and the ethanol in this suspension is volatilized naturally, and standing and drying makes ethanol volatilize completely to obtain solid mixture at 100 DEG C; Then, in this solid mixture, under agitation slowly drip the ethylene glycol of 9.6mmol; Then, in the nitrogen atmosphere of 350 DEG C, described in roasting, solid mixture obtains magnetic halloysite in 4 hours, finally obtains the magnetic halloysite of surface hydrophobicity modification again by this magnetic halloysite of KH550 process.
Embodiment 5
By the condition of embodiment 1, preparation magnetic supermolecular gel.Wherein difference is that the concrete steps of the magnetic halloysite preparing surperficial hydrophobically modified are as follows: by 1.2 grams of galapectites at 70 DEG C dry 20 hours, then add 20mL ethanol wherein, then obtain the suspension mixed in ultrasonic lower process; Then, in this suspension, 0.4 gram of Fe (NO is added
3)
39H
2o, and stir 10 hours; Then, at room temperature stir and the ethanol in this suspension is volatilized naturally, and standing and drying makes ethanol volatilize completely to obtain solid mixture at 80 DEG C; Then, in this solid mixture, under agitation slowly drip the ethylene glycol of 14.4mmol; Then, in the nitrogen atmosphere of 450 DEG C, described in roasting, solid mixture obtains magnetic halloysite in 2 hours, finally obtains the magnetic halloysite of surface hydrophobicity modification again by this magnetic halloysite of KH550 process.
Embodiment 6
Prepare Congo red, methyl orange, malachite green solution that weight concentration is 0.5%, 0.03%, 0.03% respectively.Respectively get 10mL, 50mL and 50mL as initial dye solution.Add the blank supermolecular gel of 0.5g (not containing galapectite) and magnetic supermolecular gel (containing magnetic halloysite) respectively.Leave standstill after 48 hours, the ultra-violet absorption spectrum of sampling and testing solution.
The ultra-violet absorption spectrum of magnetic supermolecular gel to three kinds of dye molecules from accompanying drawing 5a, b, c, therefrom known, add blank supermolecular gel and magnetic supermolecular gel after 48 hours, the absorbance of three kinds of solution all has obvious reduction, shows that two kinds of gel samples all have certain adsorption capacity to dyestuff.By contrast, magnetic supermolecular gel has better adsorption effect to dye molecule.Such as, in Congo red solution, after adding blank supermolecular gel and magnetic supermolecular gel, the absorbance of solution has dropped to 0.97 and 0.22 respectively from initial 2.05.The absorbance of all the other two kinds of dye solutions also show similar variation tendency.The adsorption rate of magnetic supermolecular gel to dyestuff can be calculated by ultra-violet absorption spectrum, such as, can 89% be reached to Congo red adsorption rate, can 41% be reached to the adsorption rate of methyl orange, can 68% be reached to the adsorption rate of peacock green.From Fig. 5 d, the color of the methyl orange solution after absorption obviously shoals.Meanwhile, the gel sample after absorption under magnetic fields can from solution separation and recovery.The example reclaiming dyestuff shows, adopts the excellent of the enhancing magnetic supermolecular gel absorbing dye for absorbing dye that preparation method prepares in the present invention, can be widely used in dyestuff and reclaim field.
In addition, in the present embodiment, also adopt independent galapectite to adsorb above-mentioned three kinds of dye solutions respectively and carry out correspondence experiment, the condition of various galapectite is suitable, namely, by galapectite (with the same place of production of galapectite raw material in magnetic supermolecular gel, same batch) at 70 DEG C ~ 90 DEG C dry 10 hours ~ 20 hours, then grind, the galapectite obtained after grinding be used for contrast experiment.When carrying out absorbing dye contrast experiment, various response parameter is identical, is about to grind the galapectite that obtains and gets 0.5g respectively and join in above-mentioned three kinds of dye solutions, leave standstill 48 hours.Find through ultra-violet absorption spectrum experiment, compared with the Dye Adsorption effect of blank supermolecular gel and magnetic supermolecular gel, the Dye Adsorption effect of independent employing galapectite is negligible (namely all very close with the curve 1 in Fig. 5 a, 5b and 5c, therefore not provide in figure).Visible, the Dye Adsorption ability of magnetic supermolecular gel is all better than independent blank supermolecular gel and galapectite, has outstanding effect to the raising of Dye Adsorption ability.
Except specified otherwise part, the present invention to prepare in magnetic halloysite process other unspecified parameters all can reference literature (J.Dai et al.Highly-controllable imprinted polymernanoshell at surface of magnetic halloysite nanotubes for selective recognitionand rapid adsorption of tetracycline.RSC Adv.2014,4,7967-7978) in record content choose.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. be convenient to a preparation method for the magnetic supermolecular gel Dye Adsorption material reclaimed, it is characterized in that, comprise the following steps:
(1) preparation of the magnetic halloysite of surface hydrophobicity modification:
By 0.8 gram ~ 1.2 grams galapectites at 70 DEG C ~ 90 DEG C dry 10 hours ~ 20 hours, then add 20mL ~ 50mL ethanol wherein, then obtain the suspension mixed in ultrasonic lower process; Then, in this suspension, 0.4 gram ~ 0.8 gram Fe (NO is added
3)
39H
2o, and stirring is no less than 10 hours; Then, at room temperature stir and the ethanol in this suspension is volatilized naturally, and standing and drying makes ethanol volatilize completely to obtain solid mixture at 80 DEG C ~ 100 DEG C; Then, in this solid mixture, under agitation slowly drip the ethylene glycol of 9.6mmol ~ 14.4mmol; Then, in the nitrogen atmosphere of 350 DEG C ~ 450 DEG C, described in roasting, solid mixture obtains magnetic halloysite in 2 hours ~ 4 hours, finally obtains the magnetic halloysite of surface hydrophobicity modification again by this magnetic halloysite of gamma-aminopropyl-triethoxy-silane process;
(2) preparation of magnetic supermolecular gel:
The magnetic halloysite of surface hydrophobicity modification step (1) obtained is dispersed obtains magnetic halloysite suspension in a solvent, and described in this magnetic halloysite suspension, the mass fraction of the magnetic halloysite of surface hydrophobicity modification is 1% ~ 8%; Then, add MDBS or DBS and obtain magnetic halloysite-gelator mixture as gelator in this magnetic halloysite suspension, the mass fraction that described gelator accounts for described magnetic halloysite-gelator mixture is 1% ~ 5%; Then, heating described magnetic halloysite-gelator mixture makes gelator wherein all dissolve, cool described magnetic halloysite-gelator mixture to room temperature subsequently and obtain magnetic supermolecular gel, the magnetic supermolecular gel Dye Adsorption material of this magnetic supermolecular gel namely for ease of reclaiming.
2. be convenient to the preparation method of the magnetic supermolecular gel Dye Adsorption material reclaimed as claimed in claim 1, it is characterized in that, described in described step (2), described in magnetic halloysite suspension, the mass fraction of the magnetic halloysite of surface hydrophobicity modification is 4%.
3. be convenient to the preparation method of the magnetic supermolecular gel Dye Adsorption material reclaimed as claimed in claim 1, it is characterized in that, it is 2% that gelator described in described step (2) accounts for the mass fraction of described magnetic halloysite-gelator mixture.
4. as described in claim 1-3 any one, be convenient to the preparation method of the magnetic supermolecular gel Dye Adsorption material reclaimed, it is characterized in that, solvent in described step (2) is 1,2-PD, or the mass ratio of ethanol and water is the alcohol-water mixed solution of 4:1.
5. as described in claim 1-4 any one, be convenient to the preparation method of the magnetic supermolecular gel Dye Adsorption material reclaimed, it is characterized in that, magnetic halloysite suspension in described step (2) is that the magnetic halloysite of surface hydrophobicity modification step (1) obtained adds in described solvent, and then ultrasonic disperse obtains after being no less than 1 hour.
6. according to the application of magnetic supermolecular gel Dye Adsorption material in absorbing dye being convenient to reclaim that claim 1-5 any one prepares.
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| CN106237979A (en) * | 2016-08-31 | 2016-12-21 | 浙江工业大学 | Magnetic ZnFe2O4/ galapectite composite adsorbing material and preparation method thereof |
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