CN103787348B - The preparation method of a kind of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite - Google Patents
The preparation method of a kind of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite, first the method obtains kaolin/dimethyl sulfoxide intercalated compound with the direct intercalation kaolin soil of dimethyl sulfoxide (DMSO), then kaolin/methyl alcohol intercalated compound is obtained with methyl alcohol intercalation kaolin soil/dimethyl sulfoxide (DMSO) intercalated compound, finally the 1-butyl-3-methy limidazolium of synthesis and kaolin/methyl alcohol intercalated compound are carried out intercalation under room temperature and atmospheric environment, obtain kaolin/1-butyl-3-methy limidazolium intercalated nano-composite.Glyoxaline ion liquid is carried out intercalation with kaolin/methyl alcohol intercalated compound by the present invention first under room temperature and Atmospheric Condition, obtain structural integrity, stable in properties, good heat resistance, there is the kaolin/1-butyl-3-methy limidazolium intercalated nano-composite of fluorescence property and good uv absorption property simultaneously.
Description
Technical field
The present invention relates to the preparation method of a kind of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite, belong 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 combine the laminate structure that formed in c-axis direction periodically repeated arrangement form.At [SiO
4] tetrahedron and [AlO
2(OH)
4] octahedra composition unit layer in, all [SiO
4] tetrahedral top all towards same direction, point to [AlO
2(OH)
4] octahedra, tetrahedral edge is Sauerstoffatom, and octahedral edge is hydrogen-oxygen group.Overlapping stacked in layers is formed due to hydrogen bond and Van der Waals force acting in conjunction, interlamellar spacing (d between crystal layer
001) be about 0.72nm.
Because kaolin crystal structure is more complete, defect is few, its interlayer is connected by hydrogen bond, electric charge is saturated, exchangeable cation capacity is little, direct intercalation is very difficult, can direct reaction enter its interlayer be only limitted to several strong polar micromolecules (as dimethyl sulfoxide (DMSO), urea etc.), larger molecular organics needs 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 it is proved in the potential applicability in the fields such as ion-exchange, ionogen, heat-stable material, catalyzer and sorbing material.
Ionic liquid (Ionic Liquids) is made up of ion completely, and at room temperature present liquid material.Wherein, 1,3-dialkyl group substituted imidazole ionic liquid comparatively other ionic liquids can reach molten state at a lower temperature, usually 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 preparing kaolin/glyoxaline ion liquid intercalated nano-composite at present is both at home and abroad as follows:
The Letaief of University of Ottawa and team thereof have studied prepares several glyoxaline ion liquid intercalation kaolin soil nano composite material by two step substitution methods.Its two steps substitution method is: first with the kaolin that the abundant intercalation heat treatment in advance of dimethyl sulfoxide (DMSO) is crossed; then under the melt temperature (190 DEG C) and nitrogen protection of dimethyl sulfoxide (DMSO), carry out the replacement(metathesis)reaction of glyoxaline ion liquid; after XRD result display 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 heat treatment in advance; (2) preparation temperature is high, and temperature will reach more than 190 DEG C; (3) reaction time is long, at least takes more than 15 days; (4) reaction conditions is harsher, needs to carry out under nitrogen protection; (5) primary first-order equation amount is few, is unfavorable for scale operation.
Summary of the invention
In order to overcome prior art Problems existing, the present invention proposes the preparation method of a kind of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite, the kaolin that the method obtains/1-butyl-3-methy limidazolium intercalated nano-composite structural integrity, 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-methy limidazolium intercalated nano-composite comprises the steps:
A preparation method for kaolin/1-butyl-3-methy limidazolium 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 be made up of dimethyl sulfoxide (DMSO) and deionized water, reaction 48 ~ 120 hours under 20 ~ 35 DEG C and agitation condition, after gains suction filtration, washing will be reacted, carry out drying treatment again, 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, reaction 96 ~ 168 hours under 5 ~ 35 DEG C and agitation condition, suspension liquid centrifugal layering under rotating speed is 1000 ~ 4000 revs/min of conditions of gained will be reacted every 12 ~ 48 hours, supernatant liquid is outwelled after centrifugal, the methyl alcohol more renewed continues reaction, outwell supernatant liquid after centrifugal for the last time, obtain kaolin/methyl alcohol intercalated compound;
3) preparation of glyoxaline ion liquid: by the mass volume ratio of N-Jia base Mi Zuo ﹕ bromination of n-butane=1g ﹕ 1.06 ~ 1.85mL, N-Methylimidazole is joined in bromination of n-butane, react 24 ~ 60 hours under 35 ~ 80 DEG C of water-baths and agitation condition, gains washing, separatory will be reacted again, after removing supernatant liquid, carry out drying treatment, obtain 1-butyl-3-methy limidazolium;
4) preparation of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite: by the mass volume ratio of kaolin/methyl alcohol intercalation Fu He Wu ﹕ 1-butyl-3-methy limidazolium=1g ﹕ 8 ~ 12mL, kaolin/methyl alcohol intercalated compound is joined in 1-butyl-3-methy limidazolium, reaction 48 ~ 60 hours under 5 ~ 35 DEG C and agitation condition, to react again gains washing, centrifugal, finally carry out drying, obtain kaolin/1-butyl-3-methy limidazolium intercalated nano-composite.
Above-mentioned in steps in rotating speed when stirring be 300 ~ 600 revs/min.
Kaolin/1-butyl-3-methy limidazolium intercalated compound laminate structure the rule of gained, its interlamellar spacing d001:1.41nm of 001≤d001≤1.42nm, 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 kaolin/methyl alcohol intercalated compound is obtained with methyl alcohol intercalation kaolin soil/dimethyl sulfoxide (DMSO) intercalated compound, finally the 1-butyl-3-methy limidazolium of synthesis and kaolin/methyl alcohol intercalated compound are carried out intercalation under room temperature and atmospheric environment, obtain kaolin/1-butyl-3-methy limidazolium intercalated nano-composite.Glyoxaline ion liquid is carried out intercalation with kaolin/methyl alcohol intercalated compound by the present invention first under room temperature and Atmospheric Condition, obtain structural integrity, stable in properties, good heat resistance, there is the kaolin/1-butyl-3-methy limidazolium 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) all in the method intercalation temperature are all lower, all intercalation processes all can be carried out at ambient temperature, the particularly intercalation of 1-butyl-3-methy limidazolium and kaolin/methyl alcohol intercalated compound, this reaction is carried out at ambient temperature, does not need heating.
2) ambient conditions needed for intercalation that in the method, 1-butyl-3-methy limidazolium and kaolin/methyl alcohol intercalated compound carry out is simple, reacts and carries out under atmospheric environment, do not need to react under the protection of specific gas.
3) the method substantially reduces the time of preparing needed for kaolin/1-butyl-3-methy limidazolium intercalated nano-composite, reaction times omnidistance only needs about ten days.
4) in the method, 1-butyl-3-methy limidazolium and kaolin/methyl alcohol intercalated compound carry out intercalation under normal temperature and atmospheric environment, condition needed for this reaction is simple, time needed for reaction is short, and the cost thus needed for 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-methy limidazolium intercalated nano-composite that obtains of the present invention 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-methy limidazolium intercalated nano-composite adopting the method to prepare, because all intercalations are all at normal temperature, carry out under atmospheric environment, do not destroy the structure of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite, and two step substitution methods of University of Ottawa all need heating, temperatures as high more than 190 DEG C, heating easily destroys the structure of kaolin/glyoxaline ion liquid intercalated nano-composite, poor heat stability, make it at 400 DEG C with regard to easy dehydroxylation, just easily glyoxaline ion liquid is taken off at about 270 DEG C.Kaolin prepared by the present invention/1-butyl-3-methy limidazolium intercalated nano-composite structural integrity, Heat stability is good, the temperature of dehydroxylation can improve 40 ~ 50 DEG C, and the temperature of taking off 1-butyl-3-methy limidazolium ionic liquid can improve about 50 DEG C.
7) find that the present invention prepares high ridge soil/1-butyl-3-methy limidazolium intercalated nano-composite and possesses fluorescence property and be superior to kaolinic uv absorption property after deliberation, uv absorption property is excellent, 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 a solvent, but also creates in the such solid phase material of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite of preparing in the present invention of the fluorescence property of ionic liquid.
Accompanying drawing explanation
Fig. 1 is kaolinic X-ray powder diffraction (XRD) figure.
Fig. 2 is kaolinic scanning electron microscope (SEM) figure.
Fig. 3 is X-ray powder diffraction (XRD) figure of kaolin/dimethyl sulfoxide intercalated compound prepared by embodiment 1.
Fig. 4 is X-ray powder diffraction (XRD) figure of kaolin/methyl alcohol intercalated compound prepared by embodiment 1.
Fig. 5 is the ultraviolet-visible absorption spectra figure of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite prepared by embodiment 1.
Fig. 6 is the fluorescence spectrum figure of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite prepared by embodiment 1.
Fig. 7 is X-ray powder diffraction (XRD) figure of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite prepared by embodiment 1.
Fig. 8 is scanning electron microscope (SEM) figure of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite prepared by embodiment 1.
Fig. 9 is X-ray powder diffraction (XRD) figure of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite prepared by embodiment 2.
Figure 10 is scanning electron microscope (SEM) figure of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite prepared by 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 be made up of 45ml dimethyl sulfoxide (DMSO) and 4.5ml deionized water, 20 DEG C and reaction 48 hours under being 300 revs/min of agitation conditions with magnetic stirrer with rotating speed, after gains suction filtration, washing will be reacted again, 60 DEG C of dryings, obtain 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, 20 DEG C and reaction 96 hours under being 400 revs/min of agitation conditions with magnetic stirrer with rotating speed, every 12 hours by reacted suspension liquid under rotating speed is 1000 revs/min of conditions centrifugal 15 minutes, supernatant liquid is outwelled after centrifugal, the methyl alcohol that more renews continues reaction, outwells supernatant liquid, obtain kaolin/methyl alcohol intercalated compound after centrifugal for the last time;
3) preparation of 1-butyl-3-methy limidazolium: take 8.2gN-Methylimidazole and join in 8.67ml bromination of n-butane, in 65 DEG C of water-baths and reaction 60 hours under being 500 revs/min of agitation conditions with magnetic stirrer with rotating speed, gains washing, separatory will be reacted again, after removing supernatant liquid, 85 DEG C of dryings, obtain 1-butyl-3-methy limidazolium;
4) preparation of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite: take 1g kaolin/methyl alcohol intercalated compound, joined in 10ml1-butyl-3-methy limidazolium ionic liquid, 20 DEG C and reaction 48 hours under being 600 revs/min of agitation conditions with magnetic stirrer with rotating speed, gains washing will be reacted again, centrifugal, 50 DEG C of dryings, obtain kaolin/1-butyl-3-methy limidazolium intercalated nano-composite, the interlamellar spacing d001 of the kaolin/1-butyl-3-methy limidazolium intercalated nano-composite 001 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 diffraction pattern 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 defines lamella aggregation, and the flaggy thickness presented is larger.
As shown in Figure 3, kaolin/dimethyl sulfoxide intercalated compound interlamellar spacing is for being 1.09nm as can be seen from Fig., although the higher intercalation rate of interlamellar spacing is also little for the X-ray powder diffraction pattern of the kaolin/dimethyl sulfoxide intercalated compound in the present embodiment.
The X-ray powder diffraction pattern of the kaolin in the present embodiment/methyl alcohol intercalated compound as shown in Figure 4, the interlamellar spacing of as can be seen from the figure kaolin/methyl alcohol intercalated compound is 1.088nm, the intensity of this diffraction peak is comparatively large, illustrates that its intercalation rate increases compared with the intercalation rate of dimethyl sulfoxide (DMSO) intercalation kaolin soil.
The ultraviolet-visible absorption spectra figure of the kaolin in the present embodiment/1-butyl-3-methy limidazolium intercalated nano-composite as shown in Figure 5, as can be seen from Figure 5, the uv absorption property of kaolin/1-butyl-3-methy limidazolium intercalated compound is obviously better than original kaolin.Because kaolin/1-butyl-3-methy limidazolium 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 the reciprocity material with catalytic activity in electron hole more efficiently, 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 in the present embodiment/1-butyl-3-methy limidazolium intercalated nano-composite.The fluorescence property of general ionic liquid just can show in a solvent, and the emission peak of glyoxaline ion liquid generally appears at about 467nm.As can be seen from Figure 6, the fluorescence property of ionic liquid also creates in kaolin/this solid phase material of 1-butyl-3-methy limidazolium intercalated compound, and its emission peak appears at about 420nm, 467nm and 627nm.
X-ray powder diffraction (XRD) figure of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite prepared by the present embodiment as shown in Figure 7, the interlamellar spacing of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite is 1.41nm, the intensity of this diffraction peak is comparatively large, illustrates that the intercalation rate of 1-butyl-3-methy limidazolium intercalation kaolin soil/methyl alcohol intercalated compound is higher.
Scanning electron microscope (SEM) figure of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite prepared by the present embodiment as shown in Figure 8, as can be seen from Figure 8, the nano composite material that kaolin obtains after 1-butyl-3-methy limidazolium intercalation is still plate accumulation body, plate is straight, pattern is high-visible, illustrate that the laminate structure of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite prepared by the present invention 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 be made up of 15ml dimethyl sulfoxide (DMSO) and 1.5ml deionized water, 35 DEG C and reaction 72 hours under being 400 revs/min of agitation conditions with magnetic stirrer with rotating speed, gains suction filtration, washing will be reacted again, 50 DEG C of dryings, obtain kaolin/dimethyl sulfoxide intercalated compound, Al in this Lincang soft kaolin
2o
3mass percentage be 37.7%, Fe
2o
3mass percentage be 0.19%, TiO
2mass percentage be 0.13%, whiteness is 86, and median size is 10 μm;
2) preparation of kaolin/methyl alcohol intercalated compound: take 2g kaolin/dimethyl sulfoxide intercalated compound, joined in 30ml methyl alcohol and obtained mixing solutions, 35 DEG C and reaction 120 hours under being 500 revs/min of agitation conditions with magnetic stirrer with rotating speed, every 24 hours by reacted suspension liquid under rotating speed is 4000 revs/min of conditions centrifugal 20 minutes, supernatant liquid is outwelled after centrifugal, the methyl alcohol more renewed continues reaction, outwell supernatant liquid after centrifugal for the last time, obtain kaolin/methyl alcohol intercalated compound;
3) preparation of 1-butyl-3-methy limidazolium: take 8.2gN-Methylimidazole and join in 10.83ml bromination of n-butane, in 65 DEG C of water-baths and reaction 36 hours under being 600 revs/min of agitation conditions with magnetic stirrer with rotating speed, gains washing, separatory will be reacted again, after removing supernatant liquid, 55 DEG C of dryings, obtain 1-butyl-3-methy limidazolium ionic liquid;
4) preparation of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite: take 0.5g kaolin/methyl alcohol intercalated compound, join in 6ml1-butyl-3-methy limidazolium ionic liquid, 35 DEG C and with magnetic stirrer with 400 revs/min of agitation conditions under reaction 55 hours, gains washing will be reacted again, centrifugal, 25 DEG C of dryings, obtain kaolin/1-butyl-3-methy limidazolium intercalated nano-composite, the interlamellar spacing d001 of the kaolin/1-butyl-3-methy limidazolium intercalated nano-composite 001 of gained is 1.41nm, the intercalation rate of this reaction is 88.92%.
The X-ray powder diffraction pattern of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite prepared by embodiment 2 as shown in Figure 9, the interlamellar spacing of kaolin/1-butyl-3-methy limidazolium 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-methy limidazolium intercalated nano-composite is described; Under different condition, its interlamellar spacing is substantially identical, and difference is the change of its intercalation rate.
The scanning electron microscope (SEM) photograph of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite prepared by embodiment 2 as shown in Figure 10, the crystalline structure of kaolin as can be seen from Figure 10/1-butyl-3-methy limidazolium intercalated nano-composite inside, pattern and composition.The nano composite material that kaolin obtains after 1-butyl-3-methy limidazolium intercalation is still plate accumulation body, plate is straight, pattern is high-visible, illustrate that the laminate structure of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite prepared by the present invention is similar with kaolinic laminate structure, very regular.In kaolin/1-butyl-3-methy limidazolium intercalated nano-composite, kaolin lamella is softened, and lamellar spacing obviously reduces, and become the very large two-dirnentional structure of radius-thickness ratio, bedding void is filled by 1-butyl-3-methy limidazolium.1-butyl-3-methy limidazolium the molecule of these sheet surfaces is with kaolin lamella lamellar after intercalation for lamella couples together by skeleton, and whole skeleton structure defines the different many holes that differ in size.In addition, can find out that kaolin surface is coated by 1-butyl-3-methy limidazolium molecule more or less by the SEM photo of lower multiple, 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 be made up of 30ml dimethyl sulfoxide (DMSO) and 3ml deionized water, 35 DEG C and with magnetic stirrer with 500 revs/min of agitation conditions under reaction 96 hours, gains suction filtration, washing will be reacted again, 55 DEG C of dryings, obtain 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, 10 DEG C and with magnetic stirrer with 400 revs/min of agitation conditions under reaction 144 hours, every 24 hours by reacted suspension liquid under rotating speed is 4000 revs/min of conditions centrifugal 5 minutes, supernatant liquid is outwelled after centrifugal, the methyl alcohol that more renews continues reaction, outwells supernatant liquid, obtain kaolin/methyl alcohol intercalated compound after centrifugal for the last time;
3) preparation of 1-butyl-3-methy limidazolium: take 8.2gN-Methylimidazole and join in 13ml bromination of n-butane, 35 DEG C of water-baths and with magnetic stirrer with 300 revs/min of agitation conditions under reaction 48 hours, gains washing, separatory will be reacted again, after removing supernatant liquid, 70 DEG C of dryings, obtain 1-butyl-3-methy limidazolium ionic liquid;
4) preparation of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite: take 2g kaolin/methyl alcohol intercalated compound, joined in 16ml1-butyl-3-methy limidazolium ionic liquid, 10 DEG C and with magnetic stirrer with 300 revs/min of agitation conditions under reaction 60 hours, gains washing will be reacted again, centrifugal, 75 DEG C of dryings, obtain kaolin/1-butyl-3-methy limidazolium intercalated nano-composite, the interlamellar spacing d001 of the kaolin/1-butyl-3-methy limidazolium intercalated nano-composite 001 of gained is 1.42nm, the intercalation rate of this reaction is 87.88%.
Embodiment 4
1) preparation of kaolin/dimethyl sulfoxide intercalated compound: take 3g kaolin, joined in the mixing solutions be made up of 45ml dimethyl sulfoxide (DMSO) and 2.25ml deionized water, 20 DEG C and with magnetic stirrer with 600 revs/min of agitation conditions under carry out reaction 120 hours, gains suction filtration, washing will be reacted again, 60 DEG C of dryings, obtain 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, 5 DEG C and with magnetic stirrer with 600 revs/min of agitation conditions under reaction 168 hours, every 48 hours by reacted suspension liquid under rotating speed is 4000 revs/min of conditions centrifugal 10 minutes, supernatant liquid is outwelled after centrifugal, the methyl alcohol that more renews continues reaction, outwells supernatant liquid, obtain kaolin/methyl alcohol intercalated compound after centrifugal for the last time;
3) preparation of 1-butyl-3-methy limidazolium: take 8.2gN-Methylimidazole and join in 15.17ml bromination of n-butane, 80 DEG C of water-baths and with magnetic stirrer with 400 revs/min of agitation conditions under reaction 24 hours, gains washing, separatory will be reacted again, after removing supernatant liquid, 40 DEG C of dryings, obtain 1-butyl-3-methy limidazolium ionic liquid;
4) preparation of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite: take 0.5g kaolin/methyl alcohol intercalated compound, joined in 6ml1-butyl-3-methy limidazolium ionic liquid, 5 DEG C and with magnetic stirrer with 400 revs/min of agitation conditions under reaction 55 hours, gains washing will be reacted again, centrifugal, 50 DEG C of dryings, obtain kaolin/1-butyl-3-methy limidazolium intercalated nano-composite, the interlamellar spacing d001 of the kaolin/1-butyl-3-methy limidazolium intercalated nano-composite 001 of gained is 1.41nm, the intercalation rate of this reaction is 86.54%.
Claims (2)
1. a preparation method for kaolin/1-butyl-3-methy limidazolium 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 be made up of dimethyl sulfoxide (DMSO) and deionized water, reaction 48 ~ 120 hours under 20 ~ 35 DEG C and agitation condition, after gains suction filtration, washing will be reacted, carry out drying treatment again, 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, reaction 96 ~ 168 hours under 5 ~ 35 DEG C and agitation condition, suspension liquid centrifugal layering under rotating speed is 1000 ~ 4000 revs/min of conditions of gained will be reacted every 12 ~ 48 hours, supernatant liquid is outwelled after centrifugal, the methyl alcohol more renewed continues reaction, outwell supernatant liquid after centrifugal for the last time, obtain kaolin/methyl alcohol intercalated compound;
3) preparation of glyoxaline ion liquid: by the mass volume ratio of N-Jia base Mi Zuo ﹕ bromination of n-butane=1g ﹕ 1.06 ~ 1.85mL, N-Methylimidazole is joined in bromination of n-butane, react 24 ~ 60 hours under 35 ~ 80 DEG C of water-baths and agitation condition, gains washing, separatory will be reacted again, after removing supernatant liquid, carry out drying treatment, obtain 1-butyl-3-methy limidazolium;
4) preparation of kaolin/1-butyl-3-methy limidazolium intercalated nano-composite: by the mass volume ratio of kaolin/methyl alcohol intercalation Fu He Wu ﹕ 1-butyl-3-methy limidazolium=1g ﹕ 8 ~ 12mL, kaolin/methyl alcohol intercalated compound is joined in 1-butyl-3-methy limidazolium, reaction 48 ~ 60 hours under 5 ~ 35 DEG C and agitation condition, gains washing will be reacted again, centrifugal, finally carry out drying, obtain kaolin/1-butyl-3-methy limidazolium intercalated nano-composite, gained kaolin/1-butyl-3-methy limidazolium intercalated nano-composite laminate structure rule, its interlamellar spacing d001:1.41nm of 001≤d001≤1.42nm, intercalation rate is: 86.54%≤intercalation rate≤89.92%.
2. the preparation method of kaolin according to claim 1/1-butyl-3-methy limidazolium intercalated nano-composite, is characterized in that: above-mentioned in steps in rotating speed when stirring be 300 ~ 600 revs/min.
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| CN105084379A (en) * | 2015-07-31 | 2015-11-25 | 中国地质大学（武汉） | Method for preparing kaolin intercalation compound |
| CN105461983A (en) * | 2015-12-17 | 2016-04-06 | 合肥杰明新材料科技有限公司 | Natural rubber material containing gibbsite and preparation method thereof |
| CN105461985A (en) * | 2015-12-17 | 2016-04-06 | 合肥杰明新材料科技有限公司 | Composite silane natural rubber material and preparation method thereof |
| CN105504374A (en) * | 2015-12-17 | 2016-04-20 | 合肥杰明新材料科技有限公司 | Flame-retardant natural rubber material and preparation method thereof |
| CN105524306A (en) * | 2015-12-17 | 2016-04-27 | 合肥杰明新材料科技有限公司 | Composite rubber material and preparation method thereof |
| CN105461980A (en) * | 2015-12-17 | 2016-04-06 | 合肥杰明新材料科技有限公司 | Flexible and elastic natural rubber material and preparation method thereof |
| CN105985539A (en) * | 2015-12-17 | 2016-10-05 | 合肥杰明新材料科技有限公司 | Anti-ultraviolet natural rubber material and method for preparing same |
| CN105461979A (en) * | 2015-12-17 | 2016-04-06 | 合肥杰明新材料科技有限公司 | Hydrophobic and anti-seepage natural rubber material and preparation method thereof |
| CN105461981A (en) * | 2015-12-17 | 2016-04-06 | 合肥杰明新材料科技有限公司 | Oxidization-resistant natural rubber material and preparation method thereof |
| CN105461986A (en) * | 2015-12-17 | 2016-04-06 | 合肥杰明新材料科技有限公司 | Long-lasting heat-resistant natural rubber material and preparation method thereof |
| CN105504375A (en) * | 2015-12-17 | 2016-04-20 | 合肥杰明新材料科技有限公司 | High-weather-resistance natural rubber material and preparation method thereof |
| CN105461982A (en) * | 2015-12-17 | 2016-04-06 | 合肥杰明新材料科技有限公司 | Environment-friendly natural rubber material and preparation method thereof |
| CN110368985B (en) * | 2019-07-04 | 2022-05-31 | 浙江工业大学 | Catalyst for 5-HMF synthesis and preparation method of 5-HMF |
| CN111204728B (en) * | 2020-03-10 | 2021-09-24 | 辽宁盛泽精细化工科技有限公司 | Preparation method of ultrathin two-dimensional vanadium phosphorus oxygen composite metal oxide nanosheet |
| CN114192187A (en) * | 2021-12-06 | 2022-03-18 | 内蒙古工业大学 | Coal series kaolinite-based catalyst, preparation method thereof and application thereof in toluene catalytic degradation |
| CN114849654B (en) * | 2022-05-13 | 2023-03-17 | 成都理工大学 | Preparation method and adsorption application of oxalic acid intercalation expanded kaolin |
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