CN103359754A - Preparation method of kaolin-amine grafted complex - Google Patents
Preparation method of kaolin-amine grafted complex Download PDFInfo
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- CN103359754A CN103359754A CN2013102893374A CN201310289337A CN103359754A CN 103359754 A CN103359754 A CN 103359754A CN 2013102893374 A CN2013102893374 A CN 2013102893374A CN 201310289337 A CN201310289337 A CN 201310289337A CN 103359754 A CN103359754 A CN 103359754A
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- kaolin
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- amine compound
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- intercalator
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 69
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 69
- 238000009830 intercalation Methods 0.000 claims abstract description 35
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000138 intercalating agent Substances 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001412 amines Chemical class 0.000 claims abstract description 19
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000011229 interlayer Substances 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 239000012535 impurity Substances 0.000 claims abstract 2
- 238000003786 synthesis reaction Methods 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 36
- 230000002687 intercalation Effects 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 229910052622 kaolinite Inorganic materials 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 8
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- -1 methane amide Chemical class 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 206010013786 Dry skin Diseases 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 4
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 claims description 4
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims 2
- 229910000077 silane Inorganic materials 0.000 claims 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims 1
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical compound NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 claims 1
- XJCVRTZCHMZPBD-UHFFFAOYSA-N 3-nitroaniline Chemical compound NC1=CC=CC([N+]([O-])=O)=C1 XJCVRTZCHMZPBD-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims 1
- 239000002244 precipitate Substances 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 abstract 2
- 238000002386 leaching Methods 0.000 abstract 2
- 239000002131 composite material Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 235000011056 potassium acetate Nutrition 0.000 abstract 1
- 239000001103 potassium chloride Substances 0.000 abstract 1
- 235000011164 potassium chloride Nutrition 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 15
- 238000001228 spectrum Methods 0.000 description 15
- 239000010410 layer Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical class N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000005695 Ammonium acetate Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229960004418 trolamine Drugs 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000021321 essential mineral Nutrition 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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Abstract
The invention discloses a preparation method of kaolin-amine grafted complex. The preparation method comprises the following synthesis steps of: selecting 200-325 meshes of kaolin, and purifying to remove impurities; mixing the kaolin and an intercalator with a prepared intercalator solution in a mass ratio of 1:2, and directly intercalating the kaolin under a liquid condition, wherein the intercalator is selected from one or more of hydrazine hydrate, formamide, acetamide, methyl formamide, acrylamide, potassium acetate, dimethyl sulfoxide, urea and potassium chloride; repeatedly leaching the directly intercalated kaolin for ten times by liquid alcohol to prepare a kaolin-alcohol composite, wherein each leaching lasts for 10-48 hours; adding the kaolin-alcohol grated body into an amine solution under a wet condition and magnetically stirring for 40 times; and centrifuging to obtain precipitates, drying the precipitates to separate out excessive amine to obtain the kaolin-amine grafted body, wherein the interlayer distance of the kaolin-amine grafted body can be changed with the difference of intercalated amine molecule size to reach nearly 6.0nm. And the complex is of significance to nanometer research of the kaolin.
Description
Technical field
The invention belongs to nonmetallic mineral material deep processing field.Be specifically related to a kind of method for preparing than large interlamellar spacing kaolin organic intercalation composition.
Background technology
Kaolinite is the mineral of the first take Chinese country of origin as common name in the world, kaolin is take kaolinite as the essential mineral composition, and it is the indispensable raw mineral materialss of multiple industry such as plastics, rubber, cable, refractory materials, coating, papermaking, cement, paint, printing ink, pottery, catalyzer, environmental protection, agricultural.At present, global kaolin ultimate production is about 4,000 ten thousand tons, and after nano-kaoline uses as a kind of high-quality functional filler, can significantly improve every application parameter of product, will greatly improve the utilising efficiency of kaolin raw ore under the present condition.
Kaolinic deep process technology mainly comprises ore dressing purification, superfine grinding and surface modification etc.Intercalation--delaminating belongs to a kind of technology of superfine grinding category.At present, the kaolinite stripping method can be divided into high pressure extrusion molding, chemical immersion method, mill strip, chemical immersion-mill strip, intercalation-ultrasonic method etc.From the realization of prior art, obtaining the most general feasible method of nano-kaoline is intercalation-stripping process.Kaolinic intercalation can be divided into liquid phase intercalation and mechanical force and chemical intercalation according to the intercalation mode; Can be divided into direct intercalation and indirect intercalation according to intercalation step.Existence-OH key and Si-O key between the kaolin unit layer, easily form hydrogen bond, add interlamellar spacing very little, but only have between segment polarity organic molecule interposed layer and make pitch enlargement, this micromolecular comprises methane amide, methylformamide, acrylamide, urea, Potassium ethanoate, dimethyl sulfoxide (DMSO), hydrazine hydrate etc.In recent years, the investigator begins to pay close attention to kaolinic indirect intercalation effect, to such an extent as to thereby because indirectly intercalation can make kaolinic interlamellar spacing reach larger the generations effect acquisition prospect of utilizing more likely of delaminating.Indirectly intercalator it is reported amino acid, pyridine, p-Nitroaniline, acrylamide etc.Delaminating is by machinery or chemical method, makes the kaolinite of laminated or book shape peel off into monolithic, makes its particle size reduction to nano level.In order to obtain the kaolinite sheet layer material of higher radius-thickness ratio, require in the process of delaminating kaolinic lamella not to be damaged.Therefore, if pass through the intercalation process so that kaolinite produces than large interlamellar spacing, reactive force between layers just reduces greatly, at this moment, kaolinic delaminating just more easily carried out, if intercalation rate is higher, then it delaminated then relatively simple, more easily obtain the kaolinite that granularity is superfine and its crystal formation is not destroyed, thereby reach the nanometer of kaolin raw ore.
Application number is 03115823.4 patent, has introduced a kind of preparation method of ultrafine kaolin sheet layer material.It adopts polishing and kaolin mixed grinding intercalation with Potassium ethanoate as intercalator, and by washing, centrifugal, the Potassium ethanoate of going out is delaminated kaolin, and oven dry gets product.The method raw material is easy to get, and production cost is low, can be worth the ultrafine kaolin sheet layer material.
Application number is 200710168746.3 patent, has introduced a kind of method for preparing stearylamine/Coaseries kaolin intercalated compound.Its step is to prepare first coal series kaolinite/hydrazine intercalated compound; Second step adds this mixture in the saturated ammonium acetate solution, and reaction makes ammonium acetate/kaolin intercalation mixture; The 3rd step added ammonium acetate/kaolin intercalation mixture the stearylamine that accounts for its quality 5-40%, 60-80 ℃ of lower the stirring 1-2 hour, again in 50-75 ℃ of constant temperature 12-24 hour, after the cooling, with solution washing, the suction filtration of product with ethanol, namely obtain octadecyl amine/kaolin inserted layer composition.
Application number be CN200910022364.9 patent Introduction intercal type organic nano kaolin and preparation thereof and the application in preparation polyurethane nano composite foam material.Its method is that hydrochloric acid activation, dried kaolin are mixed, disperse intercalation namely to get kaolin-dimethyl sulfoxide (DMSO) Colloidal fluid through ball mill grinding with the mass ratio of dimethyl sulfoxide (DMSO) with 1: 2～1: 6, gets the kaolin intercalation presoma in 3～6 hours in 150～170 ℃ of lower reactions; 160～190 ℃ of replacement(metathesis)reactions 1～4 hour, drying obtained having the intercal type organic nano kaolin of fabulous organic phase capacitive and good dispersiveness with the trolamine of kaolin intercalation presoma and its 3～9 times of total mass numbers.This intercal type organic nano kaolin Ball milling in polyethers, is obtained the compound polyethers of organic nano kaolin; Again take the compound polyethers of organic nano kaolin as component, make intercal type kaolin/polyurethane nano composite foam material by known flexible PU foam method, its flame retardant resistance is obviously improved, all charings and without drippage after the burning, limiting oxygen index(LOI) is higher than general polyurethane foams material accordingly.
Application number is the patent of CN201110032215.8, has introduced a kind of kaolinite nanotube and preparation method thereof.The kaolin powder with after intercalator mixes, is added dry grinding in the ball mill, then with carry out quaternizedly with methyl iodide after the trolamine generation replacement(metathesis)reaction, last and anionic surfactant solution hydro-thermal reaction are calcined and are namely got the kaolinite nanotube.
Because kaolin is in the advantage of the aspects such as whiteness, interlayer charge, mineral deposit purity, so develop the active demand that kaolinic nano composite material is modern industry.Above-mentioned listed method has all had better realization at present, but the comparatively single problem of ubiquity intercalator, and use the kaolin kind also comparatively to limit to, be unfavorable for the development of follow-up study.
Summary of the invention
The present invention has been intended to propose a kind of method that greatly enlarges kaolin intercalation agent scope, use first alcohol that the direct intercalated compound presoma of kaolin (polarity organic molecule intercalated compound) is carried out drip washing, so that alkoxyl group is passed through substitute mode grafting such as kaolin interlayer, after so processing, kaolinic interlayer structure hydroxyl is partly removed, greatly reduce kaolinic interlaminar action power, therefore the kaolin interlayer just has than high reaction activity, in this way, this type organic of amine can be inserted the kaolin interlayer at a lower temperature, and intercalation rate is high, can reach more than 80%, and can draw according to the Structure Calculation of use amine the kaolin of a series of designated layer spacings.After the reaction, its interlamellar spacing can reach 1.6nm-6.0nm.
The invention provides a kind of kaolin intercalation novel method, can greatly enlarge kaolinic intercalator source, make kaolinic interlamellar spacing be extended to original 2-8 doubly, greatly reduce the reactive force of interlayer, be conducive to the carrying out of delaminating, thereby make the kaolin nanoscale twins material of the large radius-thickness ratio of preparation become possibility.It may further comprise the steps:
The first step: the used kaolin of present method is soft kaolin or coal-measure hard kaolin, the sharp crystallinity index 0.8-1.4 of Hank, and original ore powder is broken to the 200-325 order before using.
Second step: selected kaolin is carried out liquid phase intercalation, kaolin and intercalator mass ratio be 1:0.2 to 1:2, the ratio of intercalator and solvent (being generally water) is that 1:1 is to 9:1; Kaolin and intercalator solution reaction time are 10-72 hour, and temperature of reaction is 25 ℃-60 ℃.
The 3rd step, kaolin and intercalator are mixed with the intercalator solution for preparing according to mass ratio 1:2, under liquid condition, kaolin is carried out direct intercalation; Intercalator be selected from following one or more: hydrazine hydrate, methane amide, ethanamide, methylformamide, Potassium ethanoate, dimethyl sulfoxide (DMSO), urea, Repone K;
The 4th step to the repeatedly drip washing three to ten times of direct intercalation kaolin soil, was 10-48 hour with liquid alcohol at every turn, made kaolin-pure mixture;
The 5th step, kaolin-pure mixture is dried in room temperature, add excess amine, stir with the room temperature condition lower magnetic force.React after 24 hours, centrifugally go out drying precipitate, make it separate out excess amine, namely get kaolin-amine graft.
Alcohol used in the present invention is methyl alcohol, ethanol, Virahol, ethylene glycol, butyleneglycol, hydroxyacetone, propylene glycol, glycerine, Pentyl alcohol, and the temperature of kaolin being replaced grafting when reaction drip washing is between room temperature to 140 ℃.And the alcoholic solution amount that adds is about 10-15 times of kaolin mixture quality.Use listed alcohols lessivation, can adopt and repeat supersound process or long-time magnetic agitation dual mode for three times: wherein ultrasonic time is 30 minutes, interval 30 minutes; The magnetic agitation time is 3-24 hour.Add amine amount be about 1 times to 3 times of kaolinite-pure mixture quality.If amine is solid, then first with its according to mass ratio 5:1 to 2:1 and methyl alcohol obtain solution, mix with kaolinite-pure mixture with mass ratio 3:1 afterwards.When carrying out the intercalation of amine, temperature of reaction is between the room temperature to 100 ℃.
If it is pointed out that kaolin can't be separated out naturally in the throw out, then need adopt washing soln that throw out is washed suction filtration.Wash being precipitated thing, can eliminate the amine that adsorb on the kaolinite surface, but the amine that should avoid grafting being entered the kaolin interlayer washes out.Selected washing soln is one or more in methyl alcohol, ethanol, Virahol, acetone, ether, the toluene.
Description of drawings
Fig. 1 is kaolin raw material XRD figure spectrum.
Fig. 2 is kaolin-dimethyl sulfoxide (DMSO) mixture XRD figure spectrum.
Fig. 3 is the methyl alcohol displacement kaolin that kaolin-the dimethyl sulfoxide (DMSO) mixture obtains-methyl alcohol mixture XRD figure spectrum.Fig. 4 is kaolin-normal hexyl Amine intercalated compound XRD figure spectrum.
Fig. 5 is the methyl alcohol displacement kaolin that kaolin-the urea mixture obtains-methyl alcohol mixture XRD figure spectrum.
Fig. 6 is kaolin-normal hexyl Amine intercalated compound XRD figure spectrum.
Fig. 7 is kaolin-amino dodecane intercalated compound XRD figure spectrum.
Embodiment
Embodiment 1:
Get 325 orders white soft kaolin 50g, its XRD figure spectrum sees that accompanying drawing 1. adds intercalator solution 100ml according to mass ratio 1:2, and this solution is that proportionally 9:1 is formulated for dimethyl sulfoxide (DMSO) and water.Slurry reacted 24 hours under 60 ℃ of environment, and centrifuging and taking gets throw out in 60 ℃ of dryings 1 day, obtained intercalation rate and be 96% kaolin-dimethyl sulfoxide (DMSO) intercalated compound.Its XRD figure spectrum is seen accompanying drawing 2.5g kaolin-dimethyl sulfoxide (DMSO) mixture is added 100ml methyl alcohol, stirred 24 hours in the normal temperature lower magnetic force, centrifugation adds new methyl alcohol after going out throw out, and 8 times so repeatedly, can get kaolin-methyl alcohol mixture, its XRD figure spectrum is seen accompanying drawing 3.Treat that kaolin-methyl alcohol mixture is at room temperature dry, add normal hexyl Amine, in room temperature condition reaction one day.Centrifugation obtains throw out and is kaolin-normal hexyl Amine grafting intercalated compound, its d(001) value is 2.67nm, is nearly 4 times of original 0.71nm.Its XRD figure spectrum is seen accompanying drawing 4.
Get 325 orders white soft kaolin 50g, its XRD figure spectrum sees that accompanying drawing 1. adds urea saturated solution 150ml, and reaction is 24 hours under 60 ℃ of environment, and centrifuging and taking gets throw out in 60 ℃ of dryings 2 days, obtains intercalation rate and be 80% kaolin-urea intercalated compound.Its XRD figure spectrum is seen accompanying drawing 5.4g kaolin-urea intercalated compound is added 100ml methyl alcohol, normal temperature magnetic agitation 24 hours, centrifugation adds new methyl alcohol after going out throw out, and 8 times so repeatedly, can get kaolin-methyl alcohol mixture, its XRD figure spectrum is seen accompanying drawing 6.Treat that kaolin-methyl alcohol mixture is at room temperature dry, add normal hexyl Amine 40ml, in room temperature condition reaction one day.Centrifugation obtains throw out and continues to add the 50ml amino dodecane, in 40 ℃ of reactions 30 hours, centrifugally go out throw out 40 ℃ of dryings, the spontaneous excess amine of separating out of throw out namely obtains kaolin-amino dodecane grafting mixture, the kaolin interlamellar spacing reaches 4.3nm at this moment, is 6 times of kaolin raw ore.Its XRD figure spectrum is seen accompanying drawing 7.
Get 325 orders white soft kaolin 20g, add methylformamide solution (methylformamide and water ratio be 8:1 approximately) 150ml, reaction is 30 hours under normal temperature environment, and centrifuging and taking gets throw out in 60 ℃ of dryings 2 days, obtains intercalation rate and be 75% kaolin-methylformamide intercalated compound.5g kaolin-methylformamide intercalated compound is added 100ml methyl alcohol, normal temperature magnetic agitation 24 hours, centrifugation adds new methyl alcohol after going out throw out, 6 times so repeatedly, can get kaolin-methyl alcohol mixture.To add amino dodecane in kaolin-methyl alcohol mixture, in 40 ℃ of magnetic agitation 24 hours.Centrifugation obtains throw out and is kaolin-amino dodecane grafting mixture.
Claims (15)
1. the synthetic method of a kaolin-amine compound is characterized in that, comprises following synthesis step:
1. select 200-325 order kaolin, purify and remove impurity;
2. kaolin is mixed with the intercalator solution for preparing, under liquid condition, kaolin is carried out direct intercalation;
3. with liquid alcohol to repeatedly drip washing 3-10 time of direct intercalation kaolin soil, be 3-48 hour at every turn, make kaolin-pure mixture;
4. kaolin-pure mixture is added amine aqueous solution, magnetic agitation 24 hours centrifugally goes out throw out, and throw out in 60 ℃ of dryings, is separated out excess amine, namely gets kaolin-amine compound.
2. the synthetic method of kaolin-amine compound according to claim 1 is characterized in that, used kaolin is white soft kaolin or coal series hard kaolinite, and the sharp degree of crystallinity of Hank is 0.8-1.4.
3. the synthetic method of kaolin-amine compound according to claim 1, it is characterized in that, intercalator is selected from one or more in hydrazine hydrate, methane amide, ethanamide, methylformamide, acrylamide, Potassium ethanoate, dimethyl sulfoxide (DMSO), urea, the Repone K.
4. the synthetic method of the kaolin-amine compound described in according to claim 1, it is characterized in that, kaolin and intercalator solution mix according to mass ratio 1:10, wherein kaolin and intercalator mass ratio be 1:0.2 to 1:2, the ratio of intercalator and solvent is that 1:1 is to 9:1.
5. the preparation method of the chimeric intercalation modifying mixture of kaolinite-silane according to claim 1 is characterized in that, kaolin and intercalator solution reaction time are 10-72 hour, and temperature of reaction is 25 ℃-60 ℃.
6. the synthetic method of the kaolin-amine compound described in according to claim 1 is characterized in that, carries out in the lessivation with liquid alcohol, and the temperature of liquid alcohol drip washing is between room temperature to 140 ℃.
7. the synthetic method of the kaolin-amine compound described in according to claim 1 is characterized in that, selected liquid alcohol is one or more in methyl alcohol, ethanol, Virahol, ethylene glycol, hydroxyacetone, propylene glycol, butyleneglycol, glycerine, the Pentyl alcohol.
8. the preparation method of the chimeric intercalation modifying mixture of kaolin-silane according to claim 1, it is characterized in that, the 3. in the step, use the liquid alcohol lessivation, can adopt and repeat supersound process or long-time magnetic agitation dual mode for three times: wherein ultrasonic time is 30 minutes, interval 30 minutes; The magnetic agitation time is 3-24 hour.
9. the synthetic method of the kaolin-amine compound described in according to claim 1, it is characterized in that, amine is one or more in n-Butyl Amine 99, Isopropylamine, normal hexyl Amine, positive heptyl amice, octylame, aniline, para-totuidine, o-bromoaniline, m-nitraniline, amino dodecane, cetylamine, the stearylamine.
10. the synthetic method of the kaolin-amine compound described in according to claim 1 is characterized in that, add amine amount be about 1 times to 3 times of kaolin-pure mixture quality.
11. the synthetic method of the kaolin-amine compound according to claim 1 is characterized in that, first with amine according to mass ratio 5:1 to 2:1 and methyl alcohol obtain solution, mix with kaolin-pure mixture with mass ratio 3:1 afterwards.
12. the synthetic method of the kaolin-amine compound according to claim 1 is characterized in that, when carrying out the amine intercalation, temperature of reaction is between the room temperature to 100 ℃.
13. the synthetic method of the kaolin-amine compound according to claim 1 is characterized in that, kaolin-amine compound basal spacing d(001) at 1.6nm between the 6.0nm.
14. the synthetic method of kaolin-amine compound according to claim 1 is characterized in that, selected washing soln is one or more in methyl alcohol, ethanol, Virahol, acetone, ether, the toluene.
15. the synthetic method according to the kaolin-amine compound described in the right 1 is characterized in that, alcohol carries out drip washing to direct intercalation kaolin soil mixture, and alkoxyl group is passed through the substitute mode grafting at the internal surface of kaolin interlayer.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104479791A (en) * | 2014-12-12 | 2015-04-01 | 广东电网有限责任公司电力科学研究院 | Method for reducing emission of ultrafine particles in fire coal based on organic intercalation modified kaolin |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186305A (en) * | 2007-12-11 | 2008-05-28 | 中国地质大学（武汉） | Method for preparing octadecyl amine/kaolin inserted layer composition |
-
2013
- 2013-07-10 CN CN2013102893374A patent/CN103359754A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186305A (en) * | 2007-12-11 | 2008-05-28 | 中国地质大学（武汉） | Method for preparing octadecyl amine/kaolin inserted layer composition |
Non-Patent Citations (2)
| Title |
|---|
| YOSHIHIKO KOMORI ET AL.: "Intercalation of alkylamines and water into kaolinite with methanol kaolinite as an intermediate", 《APPLIED CLAY SCIENCE》 * |
| 潘晓兵等: "高岭土插层复合材料研究进展", 《高岭土插层复合材料研究进展》 * |
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Application publication date: 20131023 |