CN103787348A - Preparation method of kaolin/1-butyl-3-methyl bromide imidazole intercalated nanocomposite - Google Patents
Preparation method of kaolin/1-butyl-3-methyl bromide imidazole intercalated nanocomposite Download PDFInfo
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Abstract
The invention discloses a preparation method of a kaolin/1-butyl-3-methyl bromide imidazole intercalated nanocomposite. The method comprises the following steps: firstly, directly intercalating the kaolin by using dimethyl sulfoxide to obtain a kaolin/dimethyl sulfoxide intercalated composite; then intercalating the kaolin intercalated composite by using methyl alcohol to obtain a kaolin/methyl alcohol intercalated composite; and finally, enabling synthesized 1-butyl-3-methyl bromide imidazole and the kaolin/methyl alcohol intercalated composite to carry out intercalating reaction in room-temperature and atmospheric environment so as to obtain a kaolin/1-butyl-3-methyl bromide imidazole intercalated nanocomposite. Through the preparation method of the kaolin/1-butyl-3-methyl bromide imidazole intercalated nanocomposite, imidazole ionic liquid carries out intercalating reaction with the kaolin/methyl alcohol intercalated composite under the room-temperature and atmospheric environment for the first time so as to obtain the kaolin/1-butyl-3-methyl bromide imidazole intercalated nanocomposite; and the kaolin/1-butyl-3-methyl bromide imidazole intercalated nanocomposite is integral in structure, stable in property, good in heat resistance, fluorescence property and ultraviolet absorbency.
Description
Technical field
The preparation method who the present invention relates to a kind of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite, belongs to Organic/Inorganic Composite Nanomaterials synthesis technical field.
Background technology
Kaolin is a kind of typical layer silicate mineral, and its desirable chemical formula is Al
2[(OH)
4/ Si
2o
5], be by [SiO
4] tetrahedral six side's stratum reticulares and [AlO
2(OH)
4] octahedral layer press 1:1 in conjunction with the laminate structure forming c-axis direction periodically repeated arrangement form.At [SiO
4] tetrahedron and [AlO
2(OH)
4] in the unit layer of octahedra composition, all [SiO
4] tetrahedral top all towards same direction, point to [AlO
2(OH)
4] octahedron, tetrahedral edge is Sauerstoffatom, and octahedral edge is hydrogen-oxygen group.Between crystal layer because hydrogen bond and Van der Waals force acting in conjunction form overlapping stacked in layers, interlamellar spacing (d
001) be about 0.72nm.
Because kaolin crystalline structure is more complete, defect is few, its interlayer is connected by hydrogen bond, electric charge is saturated, exchangeable cation capacity is little, directly intercalation is very difficult, and what can direct reaction enter its interlayer only limits to several strong polar micromolecules (as dimethyl sulfoxide (DMSO), urea etc.), and larger molecular organics need to enter kaolin interlayer by a step or multistep displacement.Organic intercalation kaolin can significantly expand kaolin interlayer space, and the nano composite material of preparation often has the chemically reactive of kaolinic physical property and organic molecule concurrently, and its potential applicability in fields such as ion-exchange, ionogen, heat-stable material, catalyzer and sorbing materials is proved.
Ionic liquid (Ionic Liquids) is to be made up of ion completely, and at room temperature presents liquid material.Wherein, 1,3-dialkyl group substituted imidazole ionic liquid can reach molten state at a lower temperature compared with other ionic liquids, conventionally presents liquid state under room temperature; Compared with ordinary organic solvents, there is the ability of stronger dissolved organic matter, inorganics and superpolymer; Glyoxaline ion liquid also has extremely low vapour pressure, good electroconductibility, high thermal stability and chemical stability, higher ion migration and velocity of diffusion.The fields such as electrochemistry, chemical separation and catalysis organic synthesis are widely used at present.
The correlative study of preparing at present kaolin/glyoxaline ion liquid intercalated nano-composite is both at home and abroad as follows:
The Letaief of University of Ottawa and team thereof have studied by two step substitution methods and have prepared several glyoxaline ion liquid intercalation kaolin soil nano composite materials.Its two steps substitution method is: first with the abundant intercalation of dimethyl sulfoxide (DMSO) heat treated kaolin in advance; then under the melt temperature (190 ℃) of dimethyl sulfoxide (DMSO) and nitrogen protection, carry out the replacement(metathesis)reaction of glyoxaline ion liquid; after XRD result shows ionic liquid intercalation, kaolin (001) surface layer spacing reaches 1.32～2.2nm, and intercalation rate can reach 90%.（Tonle?I?K,Letaief?S,Ngameni?E.Journal?of?Materials?Chemistry,2009,19:5996-6003.Letaief?S,Diaco?T,Pell?W,et?al.Chemistry?of?Materials,2008,20:7136-7142.）
Although more than kaolin/glyoxaline ion liquid intercalated nano-composite has successfully been prepared in research, but still comes with some shortcomings: (1) kaolin needs thermal treatment in advance; (2) preparation temperature is high, and temperature will reach more than 190 ℃; (3) reaction time long, at least take more than 15 days; (4) reaction conditions is harsher, need under nitrogen protection, carry out; (5) primary first-order equation amount is few, is unfavorable for scale operation.
Summary of the invention
The problem existing in order to overcome prior art, the present invention proposes the preparation method of a kind of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite, kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite structural integrity that the method obtains, good heat resistance has good uv absorption property and fluorescence property simultaneously.And in the method, all intercalation conditions are simple, can carry out, and the reaction times are short under room temperature and atmospheric environment, be applicable to producing in enormous quantities.
Realizing the technical scheme that the object of the invention adopts is:
The preparation method of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite comprises the steps:
A preparation method for kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite, comprises the steps:
1) preparation of kaolin/dimethyl sulfoxide intercalated compound: according to the mass volume ratio of Gao Ling Tu ﹕ bis-Jia base Ya Feng ﹕ deionized water=1g ﹕ 7.5～15ml ﹕ 0.75～1.5mL, kaolin is joined in the mixing solutions being formed by dimethyl sulfoxide (DMSO) and deionized water, under 20～35 ℃ and agitation condition, react 48～120 hours, to react after gains suction filtration, washing, carry out again drying treatment, obtain kaolin/dimethyl sulfoxide intercalated compound;
2) preparation of kaolin/methyl alcohol intercalated compound: according to the mass volume ratio of kaolin/dimethyl sulfoxide intercalation Fu He Wu ﹕ methyl alcohol=1g ﹕ 12～20mL, kaolin/dimethyl sulfoxide intercalated compound is added in methyl alcohol, under 5～35 ℃ and agitation condition, react 96～168 hours, be 1000～4000 rev/min conditions under centrifugal layering by the suspension liquid of reaction gained at rotating speed every 12～48 hours, after centrifugal, outwell supernatant liquid, the methyl alcohol more renewing continues reaction, after for the last time centrifugal, outwell supernatant liquid, obtain kaolin/methyl alcohol intercalated compound;
3) preparation of glyoxaline ion liquid: the mass volume ratio of pressing N-Jia base Mi Zuo ﹕ bromination of n-butane=1g ﹕ 1.06～1.85mL, N-Methylimidazole is joined in bromination of n-butane, under 35～80 ℃ of water-baths and agitation condition, react 24～60 hours, to react again gains washing, separatory, remove after supernatant liquid, carry out drying treatment, obtain 1-butyl-3-methyl bromination imidazoles;
4) preparation of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite: the mass volume ratio that closes again thing ﹕ 1-butyl-3-methyl bromination imidazoles=1g ﹕ 8～12mL by kaolin/methyl alcohol intercalation, kaolin/methyl alcohol intercalated compound is joined in 1-butyl-3-methyl bromination imidazoles, under 5～35 ℃ and agitation condition, react 48～60 hours, to react again gains washing, centrifugal, finally be dried, obtain kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite.
Above-mentioned the rotating speed while stirring in is in steps 300～600 revs/min.
Kaolin/1-butyl-3-methyl bromination imidazoles intercalated compound laminate structure rule of gained, its interlamellar spacing d001:1.41nm≤d001≤1.42nm of 001, the intercalation rate of step 5) is high, and intercalation rate is: 86.54%≤intercalation rate≤89.92%.
As shown from the above technical solution: first the method obtains kaolin/dimethyl sulfoxide intercalated compound with the direct intercalation kaolin soil of dimethyl sulfoxide (DMSO), then obtain kaolin/methyl alcohol intercalated compound with methyl alcohol intercalation kaolin soil/dimethyl sulfoxide (DMSO) intercalated compound, finally synthetic 1-butyl-3-methyl bromination imidazoles and kaolin/methyl alcohol intercalated compound are carried out to intercalation under room temperature and atmospheric environment, obtain kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite.The present invention carries out intercalation with kaolin/methyl alcohol intercalated compound by glyoxaline ion liquid first under room temperature and Atmospheric Condition, obtain structural integrity, stable in properties, good heat resistance, there is kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite of fluorescence property and good uv absorption property simultaneously.
Compared with prior art, its beneficial effect and advantage are in the present invention:
1) in the method, all intercalation temperature is all lower, all intercalation processes all can be carried out at ambient temperature, the particularly intercalation of 1-butyl-3-methyl bromination imidazoles and kaolin/methyl alcohol intercalated compound, this reaction is carried out at ambient temperature, does not need heating.
2) the required ambient conditions of in the method, 1-butyl-3-methyl bromination imidazoles and kaolin/methyl alcohol intercalated compound carry out intercalation is simple, and reaction is carried out under atmospheric environment, need under the protection of specific gas, not react.
3) the method has greatly shortened and has prepared kaolin/1-butyl-3-methyl bromination imidazoles required time of intercalated nano-composite, and the reaction times is omnidistance only needs about ten days.
4) in the method, 1-butyl-3-methyl bromination imidazoles and kaolin/methyl alcohol intercalated compound carry out intercalation under normal temperature and atmospheric environment, the required condition of this reaction is simple, the time of reacting required is short, thereby the required cost of the method will reduce widely, is applicable to large scale investment and produces.
5) kaolin (001) the surface layer spacing of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite that the present invention obtains is large, and between 1.41nm nanometer and 1.42nm nanometer, and this reaction intercalation rate is high, up to 89.9%.
6) kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite that adopts the method to prepare, because all intercalations are all at normal temperature, under atmospheric environment, carry out, do not destroy the structure of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite, and two step substitution methods of University of Ottawa all need heating, temperature is up to more than 190 ℃, heating easily destroys the structure of kaolin/glyoxaline ion liquid intercalated nano-composite, poor heat stability, make it at 400 ℃ of just easy dehydroxylations, just easily take off glyoxaline ion liquid 270 ℃ of left and right.Kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite structural integrity prepared by the present invention, Heat stability is good, the temperature of dehydroxylation can improve 40～50 ℃, and the temperature of taking off 1-butyl-3-methyl bromination imidazole ion liquid can improve 50 ℃ of left and right.
7) find that after deliberation the present invention prepares Gao ridge soil/1-butyl-3-methyl bromination imidazoles intercalated nano-composite and possesses fluorescence property and be superior to kaolinic uv absorption property, uv absorption property excellence, can be used as carrier of photocatalyst, improve photocatalysis efficiency.Fluorescence property is mainly from the fluorescence property of interlayer glyoxaline ion liquid, the fluorescence property of general ionic liquid just can show in solvent, but has also produced in the such solid phase material of the kaolin that the fluorescence property of ionic liquid is prepared in the present invention/1-butyl-3-methyl bromination imidazoles intercalated nano-composite.
Accompanying drawing explanation
Fig. 1 is kaolinic X ray powder crystal diffraction (XRD) figure.
Fig. 2 is kaolinic scanning electron microscope (SEM) figure.
Fig. 3 is X ray powder crystal diffraction (XRD) figure of the kaolin/dimethyl sulfoxide intercalated compound prepared of embodiment 1.
Fig. 4 is X ray powder crystal diffraction (XRD) figure of kaolin/methyl alcohol intercalated compound of preparing of embodiment 1.
Fig. 5 is that the UV, visible light of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite of preparing of embodiment 1 absorbs spectrogram.
Fig. 6 is the fluorescence spectrum figure of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite of preparing of embodiment 1.
Fig. 7 is X ray powder crystal diffraction (XRD) figure of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite of preparing of embodiment 1.
Fig. 8 is scanning electron microscope (SEM) figure of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite of preparing of embodiment 1.
Fig. 9 is X ray powder crystal diffraction (XRD) figure of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite of preparing of embodiment 2.
Figure 10 is scanning electron microscope (SEM) figure of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite of preparing of embodiment 2.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
1) preparation of kaolin/dimethyl sulfoxide intercalated compound: take 3g kaolin, join in the mixing solutions being formed by 45ml dimethyl sulfoxide (DMSO) and 4.5ml deionized water, at 20 ℃ with react 48 hours under 300 revs/min of agitation conditions take rotating speed with magnetic stirrer, to react again after gains suction filtration, washing, 60 ℃ dry, obtains kaolin/dimethyl sulfoxide intercalated compound;
2) preparation of kaolin/methyl alcohol intercalated compound: take 2g kaolin/dimethyl sulfoxide intercalated compound, join in 24ml methyl alcohol, at 20 ℃ with react 96 hours under 400 revs/min of agitation conditions take rotating speed with magnetic stirrer, be 1000 rev/min conditions under centrifugal 15 minute by reacted suspension liquid at rotating speed every 12 hours, after centrifugal, outwell supernatant liquid, the methyl alcohol that more renews continues reaction, outwells supernatant liquid after centrifugal for the last time, obtains kaolin/methyl alcohol intercalated compound;
3) preparation of 1-butyl-3-methyl bromination imidazoles: take 8.2gN-Methylimidazole and join in 8.67ml bromination of n-butane, under 500 revs/min of agitation conditions, react 60 hours take rotating speed 65 ℃ of water-baths with magnetic stirrer, to react again gains washing, separatory, remove after supernatant liquid, 85 ℃ dry, obtains 1-butyl-3-methyl bromination imidazoles;
4) preparation of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite: take 1g kaolin/methyl alcohol intercalated compound, joined in 10ml1-butyl-3-methyl bromination imidazole ion liquid, at 20 ℃ with react 48 hours under 600 revs/min of agitation conditions take rotating speed with magnetic stirrer, to react again gains washing, centrifugal, 50 ℃ dry, obtain kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite, the interlamellar spacing d001 of 001 of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite of gained is 1.41nm, the intercalation rate of this reaction is 88.87%.
As shown in Figure 1, as can be seen from the figure kaolinic interlamellar spacing is up to 0.714nm to kaolinic X ray powder crystal diffractogram in the present embodiment, and interlamellar spacing is less and diffraction peak is very sharp-pointed, illustrates that kaolin crystallization degree is better.As shown in Figure 2, as can be seen from Figure 2, original kaolin is the sheet accumulation body that particle is larger to kaolinic scanning electron microscope (SEM) photograph, and plate is straight, and lamella interconnects, and has formed lamella aggregation, and the flaggy thickness presenting is larger.
As shown in Figure 3, kaolin/dimethyl sulfoxide intercalated compound interlamellar spacing is for being 1.09nm, although the higher intercalation rate of interlamellar spacing little as can be seen from Fig. for the X ray powder crystal diffractogram of the kaolin/dimethyl sulfoxide intercalated compound in the present embodiment.
The X ray powder crystal diffractogram of the kaolin/methyl alcohol intercalated compound in the present embodiment as shown in Figure 4, as can be seen from the figure the interlamellar spacing of kaolin/methyl alcohol intercalated compound is 1.088nm, the intensity of this diffraction peak is larger, illustrates that its intercalation rate increases compared with the intercalation rate of dimethyl sulfoxide (DMSO) intercalation kaolin soil.
The UV, visible light of the kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite in the present embodiment absorbs spectrogram as shown in Figure 5, the uv absorption property of kaolin as can be seen from Figure 5 ,/1-butyl-3-methyl bromination imidazoles intercalated compound is obviously better than original kaolin.Because kaolin/1-butyl-3-methyl bromination imidazoles intercalated compound possesses good uv absorption property, can be used as carrier of photocatalyst, improve the efficiency that carrier of photocatalyst absorbs UV-light, make photocatalyst generate more efficiently electron hole equity to have the material of catalytic activity, improve photocatalysis efficiency.
As shown in Figure 6, the fluorescence property of kaolin/glyoxaline ion liquid intercalated nano-composite mainly comes from the fluorescence property of interlayer glyoxaline ion liquid to the fluorescence spectrum figure of the kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite in the present embodiment.The fluorescence property of general ionic liquid just can show in solvent, and the emission peak of glyoxaline ion liquid generally appears at 467nm left and right.As can be seen from Figure 6, the fluorescence property of ionic liquid has also produced in this solid phase material of kaolin/1-butyl-3-methyl bromination imidazoles intercalated compound, and its emission peak appears at 420nm, 467nm and 627nm left and right.
The X ray powder crystal diffraction (XRD) of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite prepared by the present embodiment is schemed as shown in Figure 7, the interlamellar spacing of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite is 1.41nm, the intensity of this diffraction peak is larger, illustrates that the intercalation rate of 1-butyl-3-methyl bromination imidazoles intercalation kaolin soil/methyl alcohol intercalated compound is higher.
The scanning electron microscope (SEM) of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite prepared by the present embodiment is schemed as shown in Figure 8, as can be seen from Figure 8, the nano composite material that kaolin obtains after 1-butyl-3-methyl bromination imidazoles intercalation is still plate accumulation body, plate is straight, pattern is high-visible, the laminate structure that kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite prepared by the present invention is described is similar with kaolinic laminate structure, very regular.
Embodiment 2
1) preparation of kaolin/dimethyl sulfoxide intercalated compound: take 2g Lincang soft kaolin, join in the mixing solutions being formed by 15ml dimethyl sulfoxide (DMSO) and 1.5ml deionized water, at 35 ℃ with react 72 hours under 400 revs/min of agitation conditions take rotating speed with magnetic stirrer, to react again gains suction filtration, washing, 50 ℃ dry, obtain kaolin/dimethyl sulfoxide intercalated compound, Al in this Lincang soft kaolin
2o
3quality percentage composition be 37.7%, Fe
2o
3quality percentage composition be 0.19%, TiO
2quality percentage composition be 0.13%, whiteness is 86, median size is 10 μ m;
2) preparation of kaolin/methyl alcohol intercalated compound: take 2g kaolin/dimethyl sulfoxide intercalated compound, joined in 30ml methyl alcohol and obtained mixing solutions, at 35 ℃ with react 120 hours under 500 revs/min of agitation conditions take rotating speed with magnetic stirrer, be 4000 rev/min conditions under centrifugal 20 minute by reacted suspension liquid at rotating speed every 24 hours, after centrifugal, outwell supernatant liquid, the methyl alcohol more renewing continues reaction, after for the last time centrifugal, outwell supernatant liquid, obtain kaolin/methyl alcohol intercalated compound;
3) preparation of 1-butyl-3-methyl bromination imidazoles: take 8.2gN-Methylimidazole and join in 10.83ml bromination of n-butane, under 600 revs/min of agitation conditions, react 36 hours take rotating speed 65 ℃ of water-baths with magnetic stirrer, to react again gains washing, separatory, remove after supernatant liquid, 55 ℃ dry, obtains 1-butyl-3-methyl bromination imidazole ion liquid;
4) preparation of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite: take 0.5g kaolin/methyl alcohol intercalated compound, join in 6ml1-butyl-3-methyl bromination imidazole ion liquid, at 35 ℃ with react 55 hours under with 400 revs/min of agitation conditions with magnetic stirrer, to react again gains washing, centrifugal, 25 ℃ dry, obtain kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite, the interlamellar spacing d001 of 001 of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite of gained is 1.41nm, the intercalation rate of this reaction is 88.92%.
The X ray powder crystal diffractogram of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite prepared by embodiment 2 as shown in Figure 9, the interlamellar spacing of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite is 1.41nm, interlamellar spacing and embodiment 1(1.41nm) in consistent, the laminate structure comparison rule of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite is described; Under different condition, its interlamellar spacing is basic identical, and difference is the variation of its intercalation rate.
The scanning electron microscope (SEM) photograph of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite prepared by embodiment 2 as shown in figure 10, crystalline structure, pattern and the composition of kaolin as can be seen from Figure 10/1-butyl-3-methyl bromination imidazoles intercalated nano-composite inside.The nano composite material that kaolin obtains after 1-butyl-3-methyl bromination imidazoles intercalation is still plate accumulation body, plate is straight, pattern is high-visible, the laminate structure that kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite prepared by the present invention is described is similar with kaolinic laminate structure, very regular.In kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite, kaolin lamella is softened, and lamellar spacing obviously reduces, and becomes the very large two-dirnentional structure of radius-thickness ratio, and bedding void is filled by 1-butyl-3-methyl bromination imidazoles.1-butyl-3-methyl bromination imidazole molecule of these sheet surfaces couples together lamella take lamellar kaolin lamella after intercalation as skeleton, and whole skeleton structure has formed the different many holes that differ in size.In addition, can find out that by the SEM photo of lower multiple kaolin surface is coated by 1-butyl-3-methyl bromination imidazole molecule more or less, inter-adhesively between these particles become larger particle.
Embodiment 3
1) preparation of kaolin/dimethyl sulfoxide intercalated compound: take 4g Lincang soft kaolin, join in the mixing solutions being formed by 30ml dimethyl sulfoxide (DMSO) and 3ml deionized water, at 35 ℃ with react 96 hours under with 500 revs/min of agitation conditions with magnetic stirrer, to react again gains suction filtration, washing, 55 ℃ dry, obtains kaolin/dimethyl sulfoxide intercalated compound;
2) preparation of kaolin/methyl alcohol intercalated compound: take 3g kaolin/dimethyl sulfoxide intercalated compound, join in 60ml methyl alcohol, at 10 ℃ with react 144 hours under with 400 revs/min of agitation conditions with magnetic stirrer, be 4000 rev/min conditions under centrifugal 5 minute by reacted suspension liquid at rotating speed every 24 hours, after centrifugal, outwell supernatant liquid, the methyl alcohol that more renews continues reaction, outwells supernatant liquid after centrifugal for the last time, obtains kaolin/methyl alcohol intercalated compound;
3) preparation of 1-butyl-3-methyl bromination imidazoles: take 8.2gN-Methylimidazole and join in 13ml bromination of n-butane, react 48 hours under with 300 revs/min of agitation conditions 35 ℃ of water-baths with magnetic stirrer, to react again gains washing, separatory, remove after supernatant liquid, 70 ℃ dry, obtains 1-butyl-3-methyl bromination imidazole ion liquid;
4) preparation of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite: take 2g kaolin/methyl alcohol intercalated compound, joined in 16ml1-butyl-3-methyl bromination imidazole ion liquid, at 10 ℃ with react 60 hours under with 300 revs/min of agitation conditions with magnetic stirrer, to react again gains washing, centrifugal, 75 ℃ dry, obtain kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite, the interlamellar spacing d001 of 001 of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite of gained is 1.42nm, the intercalation rate of this reaction is 87.88%.
1) preparation of kaolin/dimethyl sulfoxide intercalated compound: take 3g kaolin, joined in the mixing solutions being formed by 45ml dimethyl sulfoxide (DMSO) and 2.25ml deionized water, at 20 ℃ with react 120 hours under with 600 revs/min of agitation conditions with magnetic stirrer, to react again gains suction filtration, washing, 60 ℃ dry, obtains kaolin/dimethyl sulfoxide intercalated compound;
2) preparation of kaolin/methyl alcohol intercalated compound: take 2g kaolin/dimethyl sulfoxide intercalated compound, joined in 34ml methyl alcohol, at 5 ℃ with react 168 hours under with 600 revs/min of agitation conditions with magnetic stirrer, be 4000 rev/min conditions under centrifugal 10 minute by reacted suspension liquid at rotating speed every 48 hours, after centrifugal, outwell supernatant liquid, the methyl alcohol that more renews continues reaction, outwells supernatant liquid after centrifugal for the last time, obtains kaolin/methyl alcohol intercalated compound;
3) preparation of 1-butyl-3-methyl bromination imidazoles: take 8.2gN-Methylimidazole and join in 15.17ml bromination of n-butane, react 24 hours under with 400 revs/min of agitation conditions 80 ℃ of water-baths with magnetic stirrer, to react again gains washing, separatory, remove after supernatant liquid, 40 ℃ dry, obtains 1-butyl-3-methyl bromination imidazole ion liquid;
4) preparation of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite: take 0.5g kaolin/methyl alcohol intercalated compound, joined in 6ml1-butyl-3-methyl bromination imidazole ion liquid, at 5 ℃ with react 55 hours under with 400 revs/min of agitation conditions with magnetic stirrer, to react again gains washing, centrifugal, 50 ℃ dry, obtain kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite, the interlamellar spacing d001 of 001 of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite of gained is 1.41nm, the intercalation rate of this reaction is 86.54%.
Claims (3)
1. a preparation method for kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite, is characterized in that comprising the steps:
1) preparation of kaolin/dimethyl sulfoxide intercalated compound: according to the mass volume ratio of Gao Ling Tu ﹕ bis-Jia base Ya Feng ﹕ deionized water=1g ﹕ 7.5～15ml ﹕ 0.75～1.5mL, kaolin is joined in the mixing solutions being formed by dimethyl sulfoxide (DMSO) and deionized water, under 20～35 ℃ and agitation condition, react 48～120 hours, to react after gains suction filtration, washing, carry out again drying treatment, obtain kaolin/dimethyl sulfoxide intercalated compound;
2) preparation of kaolin/methyl alcohol intercalated compound: according to the mass volume ratio of kaolin/dimethyl sulfoxide intercalation Fu He Wu ﹕ methyl alcohol=1g ﹕ 12～20mL, kaolin/dimethyl sulfoxide intercalated compound is added in methyl alcohol, under 5～35 ℃ and agitation condition, react 96～168 hours, be 1000～4000 rev/min conditions under centrifugal layering by the suspension liquid of reaction gained at rotating speed every 12～48 hours, after centrifugal, outwell supernatant liquid, the methyl alcohol more renewing continues reaction, after for the last time centrifugal, outwell supernatant liquid, obtain kaolin/methyl alcohol intercalated compound;
3) preparation of glyoxaline ion liquid: the mass volume ratio of pressing N-Jia base Mi Zuo ﹕ bromination of n-butane=1g ﹕ 1.06～1.85mL, N-Methylimidazole is joined in bromination of n-butane, under 35～80 ℃ of water-baths and agitation condition, react 24～60 hours, to react again gains washing, separatory, remove after supernatant liquid, carry out drying treatment, obtain 1-butyl-3-methyl bromination imidazoles;
4) preparation of kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite: the mass volume ratio that closes again thing ﹕ 1-butyl-3-methyl bromination imidazoles=1g ﹕ 8～12mL by kaolin/methyl alcohol intercalation, kaolin/methyl alcohol intercalated compound is joined in 1-butyl-3-methyl bromination imidazoles, under 5～35 ℃ and agitation condition, react 48～60 hours, to react again gains washing, centrifugal, finally be dried, obtain kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite.
2. the preparation method of kaolin according to claim 1/1-butyl-3-methyl bromination imidazoles intercalated nano-composite, is characterized in that: above-mentioned the rotating speed while stirring in is in steps 300～600 revs/min.
3. the preparation method of kaolin according to claim 1/1-butyl-3-methyl bromination imidazoles intercalated nano-composite, it is characterized in that: gained kaolin/1-butyl-3-methyl bromination imidazoles intercalated nano-composite laminate structure rule, its interlamellar spacing d001:1.41nm≤d001≤1.42nm of 001, the intercalation rate of step 5) is high, and intercalation rate is: 86.54%≤intercalation rate≤89.92%.
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