CN105084379A - Method for preparing kaolin intercalation compound - Google Patents
Method for preparing kaolin intercalation compound Download PDFInfo
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- CN105084379A CN105084379A CN201510464913.3A CN201510464913A CN105084379A CN 105084379 A CN105084379 A CN 105084379A CN 201510464913 A CN201510464913 A CN 201510464913A CN 105084379 A CN105084379 A CN 105084379A
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- kaolin
- carboxymethyl
- dimethyl sulfoxide
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- methylimidazole
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Abstract
The invention discloses a method for preparing a kaolin intercalation compound. Kaolin, dimethyl sulfoxide and distilled water are mixed, and are heated and stirred for 48-72 hours at the temperature of 25 DEG C to 75 DEG C; centrifugal separation, washing and drying are carried out to obtain a kaolin/dimethyl sulfoxide intercalation compound; the obtained kaolin/dimethyl sulfoxide intercalation compound and 1-carboxymethyl-3 methylimidazole chlorine salt are mixed and heated in the environment of 190 DEG C to 210 DEG C under inert gas shielding, and cooling is carried out after heat preservation is carried out for 4-12 h; 1-carboxymethyl-3 methylimidazole chlorine salt is removed through washing of dimethyl sulfoxide, then washing is carried out through absolute ethyl alcohol, centrifugal separation and drying are carried out, and the kaolin/1- carboxymethyl-3 methylimidazole chlorine salt intercalation compound is obtained. According to the method, imidazole ionic liquid can enter an interlayer of the kaolin in an intercalation mode only through a two-step method, and therefore the preparation process is short in time and high in intercalation efficiency.
Description
Technical field
The present invention relates to kaolin material field of deep, be specifically related to a kind of preparation method of kaolin intercalation mixture.
Background technology
Kaolin is a kind of common clay mineral, is widely used in the fields such as papermaking, coating, pottery, building materials, refractory materials, petrochemical complex, agricultural, national defence sophisticated technology.The kaolinic main component of nature is kaolinite, and be a kind of typical layer silicate mineral, interlamellar spacing d (001) is about 0.72nm.Kaolin, as 1:1 type laminate structure clay mineral, is applied widely in composite organic-inorganic material.Comparatively active for kaolinic intercalation research in recent years, organic intercalation kaolin can significantly improve kaolinic interlamellar spacing, and make kaolin composite material have kaolin and organic physics-chem characteristic simultaneously, be therefore widely used in the preparation of kaolin intercalation mixture.Compared with the clay mineral such as polynite, kaolin intercalation reacts and is not easy, and major cause is that kaolin interlayer connects with hydrogen bond, containing tradable positively charged ion, and has stronger reactive force between layers.That injects kaolin interlayer therefore, it is possible to direct only has the strong polar micromolecules of small portion (as dimethyl sulfoxide (DMSO), urea, hydrazine etc.), and larger molecular organics needs just can enter kaolin interlayer by a step or multistep displacement.
Patent CN201310280849 relates to the preparation method that a kind of kaolin-silane is fitted together to intercalation modifying mixture.First kaolin is mixed with intercalant solution, under liquid condition, direct intercalation is carried out to kaolin, then prepare kaolin-ol mixture, finally kaolin-ol mixture is joined magnetic agitation in solution of silane, the centrifugal kaolin-silane that obtains is fitted together to intercalation modifying mixture.
Patent 200710168746.3 relates to a kind of method preparing octadecyl amine/kaolin inserted layer composition.The method take Coaseries kaolin as raw material, first kaolin and hydrazine hydrate mix and blend are prepared hydrazine/kaolin intercalation mixture, then in ammonium acetate saturated solution, mix and blend obtains ammonium acetate/kaolin intercalation mixture, then obtains octadecyl amine/kaolin inserted layer composition with ammonium acetate/kaolin intercalation mixture for presoma joins reacting by heating in stearylamine.
Ionic liquid is a kind of material be composed entirely of ions in dissolving or molten state, and it has the special performance that many molecular solvent do not have, as low vapour pressure, higher solubility property, and good heat conductivity and electroconductibility etc.Wherein, 1-carboxymethyl-3-Methylimidazole villaumite is a kind of mono carboxylic functionalized ion liquid, and this types of ion liquid is used as the fields such as green solvent, catalyzer and electrochemistry more.
Research at present about ionic liquid intercalation kaolin mixture is also few:
Patent CN201310737981.3 relates to the preparation method of a kind of kaolin/1-butyl-3-methy limidazolium intercalation composite material, prepares kaolin/imidazoles intercalated compound mainly through three-step approach.Its preparation method is: first use dimethyl sulfoxide (DMSO) (DMSO) to insert kaolin interlayer, kaolin 001 surface layer spacing is made to expand 1.10nm to by 0.72nm, then go out DMSO by methanol replacement and prepare kaolin/methanol complex, kaolin/imidazoles intercalated compound is prepared finally by imidazole ion liquid displacement, XRD result display imidazole ion liquid inserts kaolin and makes kaolin interlamellar spacing expand about 1.41nm to, and its intercalation rate can reach 86%.
Above technique study has successfully prepared imidazole ion liquid intercalation kaolin soil mixture, but there is more shortcoming: one is that reactions steps is more more complicated, two is that reaction time is long, three is kaolin/methyl alcohol intercalated compound less stables, high temperature or humidity comparatively overall situation methyl alcohol be easy to, four is that aforesaid method runs into the higher ionic liquid of fusing point and is difficult to insert it into kaolin interlayer.For overcoming above-mentioned difficulties, the present invention, using 1-carboxymethyl-3 Methylimidazole villaumite as raw material, adopts scorification two step to prepare 1-carboxymethyl-3 Methylimidazole villaumite/kaolin intercalation mixture.
Summary of the invention
The object of the invention is to provide a kind of method preparing 1-carboxymethyl-3 Methylimidazole villaumite/kaolin intercalation mixture, the method can well overcome the higher water-soluble strong ionic liquid of fusing point and be difficult to insert kaolinic difficulty, can reduce again the impact of water on kaolin intercalation, the intercalation kaolin soil composite properties that this method is prepared is stablized simultaneously.
For achieving the above object, adopt technical scheme as follows:
A preparation method for kaolin intercalation mixture, comprises the following steps:
1) be the ratio of 1:1 in Monochloro Acetic Acid and 1-Methylimidazole mol ratio, Monochloro Acetic Acid be placed in 70 ~ 80 DEG C of environment meltings, add 1-Methylimidazole reaction 4 ~ 6 hours, obtain reddish-brown thick liquid; Be white solid upper strata with washes of absolute alcohol to lower floor be colourless transparent liquid, white solid taken out drying and obtain ionic liquid 1-carboxymethyl-3 Methylimidazole villaumite;
2) by kaolin: dimethyl sulfoxide (DMSO): distilled water three mixes according to 15g:60 ~ 80mL:5 ~ 15mL, heated and stirred 48 ~ 72 hours under 25 ~ 75 DEG C of conditions; Centrifugation, cleaning, drying, obtain kaolin/dimethyl sulfoxide intercalated compound;
3) gained kaolin/dimethyl sulfoxide intercalated compound: 1-carboxymethyl-3 Methylimidazole villaumite 1:(2 ~ 5 in mass ratio) mixing, under protection of inert gas in 190 ~ 210 DEG C of environment heat treated, insulation 4 ~ 12h after cool;
4) with dimethyl sulfoxide (DMSO) cleaning step 3) products therefrom, remove 1-carboxymethyl-3 Methylimidazole villaumite, then use washes of absolute alcohol, centrifugation, drying, obtain kaolin/1-carboxymethyl-3 Methylimidazole villaumite intercalated compound.
Beneficial effect of the present invention is as follows:
(1) larger molecule is inserted kaolin interlayer, make its (001) surface layer spacing increase to 1.34 ~ 1.36nm by 0.72nm.
(2) glyoxaline ion liquid is difficult to prepare kaolin intercalation mixture by single stage method, need to carry out multistep intercalation to realize to kaolin, all carry out three-step reaction (as first inserted dimethyl sulfoxide (DMSO) in great majority research, insert methyl alcohol again, finally just insert imidazole ion liquid), only just can realize imidazole ion liquid intercalation by two-step approach enters kaolin interlayer in the present invention, and therefore preparation technology's time is short, and intercalation rate is higher.
(3) ionic liquid much all has good solubility property, and this class ionic liquid can enter kaolin interlayer according to the method intercalation dissolved.1-carboxymethyl-3 Methylimidazole villaumite is a kind of salt very strong to water-soluble, but the solvent solubility for other is poor, the present invention carries out kaolin intercalation under complete anhydrous state, can ensure that ionic liquid injects the impact be not hydrolyzed in kaolin process.
(4) 1-carboxymethyl-3 Methylimidazole villaumite is the ionic liquid that a kind of melt temperature is higher, and the present invention's 1-carboxymethyl-3 Methylimidazole villaumite under 210 DEG C of conditions can enter in dimethyl sulfoxide (DMSO) intercalation kaolin soil mixture and dimethyl sulfoxide (DMSO) be cemented out.
Accompanying drawing explanation
Fig. 1: kaolin X-ray powder diffraction pattern used;
Fig. 2: the X-ray powder diffraction pattern of kaolin/dimethyl sulfoxide intercalated compound;
Fig. 3: the X-ray powder diffraction pattern of embodiment 1 kaolin/1-carboxymethyl-3 Methylimidazole villaumite intercalated compound;
Fig. 4: the X-ray powder diffraction pattern of embodiment 2 kaolin/1-carboxymethyl-3 Methylimidazole villaumite intercalated compound
Fig. 5: the X-ray powder diffraction pattern of embodiment 3 kaolin/1-carboxymethyl-3 Methylimidazole villaumite intercalated compound
Fig. 6: the X-ray powder diffraction pattern of embodiment 4 kaolin/1-carboxymethyl-3 Methylimidazole villaumite intercalated compound
Embodiment
Following examples explain technical scheme of the present invention further, but not as limiting the scope of the invention.
The preparation process of kaolin intercalation mixture of the present invention is as follows:
Be the ratio of 1:1 in Monochloro Acetic Acid and 1-Methylimidazole mol ratio, Monochloro Acetic Acid be placed in 70 ~ 80 DEG C of environment meltings, add 1-Methylimidazole reaction 4 ~ 6 hours, obtain reddish-brown thick liquid; Be white solid upper strata with washes of absolute alcohol to lower floor be colourless transparent liquid, white solid taken out drying and obtain ionic liquid 1-carboxymethyl-3 Methylimidazole villaumite; For subsequent use.
By kaolin: dimethyl sulfoxide (DMSO): distilled water three mixes according to 15g:60 ~ 80mL:5 ~ 15mL, heated and stirred 48 ~ 72 hours under 25 ~ 75 DEG C of conditions; Centrifugation, cleaning, drying, obtain kaolin/dimethyl sulfoxide intercalated compound; Its interlamellar spacing d (001) increases to 1.12nm by 0.72nm, and intercalation rate is about 92%, for subsequent use.
As shown in Figure 1, gained kaolin/dimethyl sulfoxide intercalated compound X-ray powder diffraction pattern as shown in Figure 2 for kaolin X-ray powder diffraction pattern used.
Embodiment 1
Take kaolin/dimethyl sulfoxide intercalated compound 0.5g for subsequent use to mix with 1g1-carboxymethyl-3 Methylimidazole villaumite, mix with mortar grinder.
Ground mixture is placed in autoclave, passes into nitrogen protection, put into 210 DEG C of loft drier heat treated 4h.
With dimethyl sulfoxide (DMSO) cleaning reaction product removing 1-carboxymethyl-3 Methylimidazole villaumite residue repeatedly, then use washes of absolute alcohol 3-4 centrifugation.
The reaction product obtained is put into 80 DEG C of vacuum drying ovens dry.
The X-ray powder diffraction pattern of kaolin in the present embodiment/1-carboxymethyl-3 Methylimidazole villaumite intercalated compound is as Fig. 3, as can be seen from the figure, kaolin interlamellar spacing increases to 1.36nm by 0.71nm, and intercalated compound diffraction peak is strong larger, illustrate that kaolin/1-carboxymethyl-3 Methylimidazole villaumite intercalation rate is higher, intercalation rate reaches 86.05%.
Embodiment 2
Take kaolin/dimethyl sulfoxide intercalated compound 0.5g for subsequent use to mix with 1.5g1-carboxymethyl-3 Methylimidazole villaumite, mix with mortar grinder.
Ground mixture is placed in autoclave, passes into nitrogen protection, put into 210 DEG C of loft drier heat treated 4h.
With dimethyl sulfoxide (DMSO) cleaning reaction product removing 1-carboxymethyl-3 Methylimidazole villaumite residue repeatedly, then use washes of absolute alcohol 3-4 centrifugation.
The reaction product obtained is put into 80 DEG C of vacuum drying ovens dry.
The X-ray powder diffraction pattern of the present embodiment kaolin/1-carboxymethyl-3 Methylimidazole villaumite intercalated compound is as Fig. 4, and its (001) surface layer spacing is 1.35nm, and intercalation rate reaches 84.00%.
Embodiment 3
Take kaolin/dimethyl sulfoxide intercalated compound 0.5g for subsequent use to mix with 2g1-carboxymethyl-3 Methylimidazole villaumite, mix with mortar grinder.
Ground mixture is placed in autoclave, passes into nitrogen protection, put into 210 DEG C of loft drier heat treated 4h.
With dimethyl sulfoxide (DMSO) cleaning reaction product removing 1-carboxymethyl-3 Methylimidazole villaumite residue repeatedly, then use washes of absolute alcohol 3-4 centrifugation.
The reaction product obtained is put into 80 DEG C of vacuum drying ovens dry.
The X-ray powder diffraction pattern of the present embodiment kaolin/1-carboxymethyl-3 Methylimidazole villaumite intercalated compound is as Fig. 5, and its (001) surface layer spacing is 1.35nm, and intercalation rate reaches 88.75%.
Embodiment 4
Take kaolin/dimethyl sulfoxide intercalated compound 0.5g for subsequent use to mix with 2.5g1-carboxymethyl-3 Methylimidazole villaumite, mix with mortar grinder.
Ground mixture is placed in autoclave, passes into nitrogen protection, put into 210 DEG C of loft drier heat treated 4h.
With dimethyl sulfoxide (DMSO) cleaning reaction product removing 1-carboxymethyl-3 Methylimidazole villaumite residue repeatedly, then use washes of absolute alcohol 3-4 centrifugation.
The reaction product obtained is put into 80 DEG C of vacuum drying ovens dry.
The X-ray powder diffraction pattern of the present embodiment kaolin/1-carboxymethyl-3 Methylimidazole villaumite intercalated compound is as Fig. 6, and its (001) surface layer spacing is 1.37nm, and intercalation rate reaches 80.72%.In 4 embodiments, kaolinic (001) surface layer spacing difference is very little, and just intercalation rate is slightly different, illustrates that kaolin 1-carboxymethyl-3 Methylimidazole villaumite intercalated compound material laminate structure is more regular.
Claims (1)
1. a preparation method for kaolin intercalation mixture, is characterized in that comprising the following steps:
1) be the ratio of 1:1 in Monochloro Acetic Acid and 1-Methylimidazole mol ratio, Monochloro Acetic Acid be placed in 70 ~ 80 DEG C of environment meltings, add 1-Methylimidazole reaction 4 ~ 6 hours, obtain reddish-brown thick liquid; Be white solid upper strata with washes of absolute alcohol to lower floor be colourless transparent liquid, white solid taken out drying and obtain ionic liquid 1-carboxymethyl-3 Methylimidazole villaumite;
2) by kaolin: dimethyl sulfoxide (DMSO): distilled water three mixes according to 15g:60 ~ 80mL:5 ~ 15mL, heated and stirred 48 ~ 72 hours under 25 ~ 75 DEG C of conditions; Centrifugation, cleaning, drying, obtain kaolin/dimethyl sulfoxide intercalated compound;
3) gained kaolin/dimethyl sulfoxide intercalated compound: 1-carboxymethyl-3 Methylimidazole villaumite 1:(2 ~ 5 in mass ratio) mixing, under protection of inert gas in 190 ~ 210 DEG C of environment heat treated, insulation 4 ~ 12h after cool;
4) with dimethyl sulfoxide (DMSO) cleaning step 3) products therefrom, remove 1-carboxymethyl-3 Methylimidazole villaumite, then use washes of absolute alcohol, centrifugation, drying, obtain kaolin/1-carboxymethyl-3 Methylimidazole villaumite intercalated compound.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793784A (en) * | 2018-07-07 | 2018-11-13 | 河源市极致知管信息科技有限公司 | One kind containing kaolin composite material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787348A (en) * | 2013-12-27 | 2014-05-14 | 中国地质大学（武汉） | Preparation method of kaolin/1-butyl-3-methyl bromide imidazole intercalated nanocomposite |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787348A (en) * | 2013-12-27 | 2014-05-14 | 中国地质大学（武汉） | Preparation method of kaolin/1-butyl-3-methyl bromide imidazole intercalated nanocomposite |
Non-Patent Citations (4)
| Title |
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| GUSTAVE KENNE DEDZO ET AL.: "Kaolinite–ionic liquid nanohybrid materials as electrochemical sensors for size-selective detection of anions", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| ZHAOFU FEI ET AL.: "Bronsted Acidic Ionic Liquids and Their Zwitterions:Synthesis,Characterization and pKa Determination", 《CHEM. EUR. J.》 * |
| 侯桂香等: "高岭土/咪唑插层复合物的制备与表征", 《中国陶瓷》 * |
| 梁蕊等: "氯化1-羧甲基-3-甲基咪唑的热稳定性、平衡蒸汽压和升华焓", 《河南师范大学学报(自然科学版)》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793784A (en) * | 2018-07-07 | 2018-11-13 | 河源市极致知管信息科技有限公司 | One kind containing kaolin composite material and preparation method thereof |
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Application publication date: 20151125 |