CN103007901B - Cyclodextrin-clay composite and preparation method thereof - Google Patents
Cyclodextrin-clay composite and preparation method thereof Download PDFInfo
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- CN103007901B CN103007901B CN201210513818.4A CN201210513818A CN103007901B CN 103007901 B CN103007901 B CN 103007901B CN 201210513818 A CN201210513818 A CN 201210513818A CN 103007901 B CN103007901 B CN 103007901B
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Abstract
The invention relates to a cyclodextrin-clay composite and a preparation method thereof, belonging to the technical field of composite preparation. The cyclodextrin-clay composite is prepared by reacting montmorillonite and hectorite as basic materials with carboxymethylation cyclodextrin, wherein the mass fraction of cyclodextrin in the composite can be controlled by changing the function base number and chain length of the silane coupling agent. The method has the advantages of being easily available in raw materials, low in cost and simple. The cyclodextrin-clay composite can achieve the purpose of simultaneously removing metal ions and organic aromatic compounds by exchange adsorbility of clay to metal ions and clathration of cyclodextrin to organic matters (especially aromatic organic matters).
Description
Technical field
The present invention relates to a kind of cyclodextrin-clay mineral composite and preparation method thereof, belong to composite preparing technical field.
Background technology
Cyclodextrin (CD) is the product that is acted on starch by cyclodextrin glycosyl transferases, it by multiple glucose molecules with 1, the cyclic oligosaccharide that is formed by connecting of 4-glycosidic bond.It has slightly tapered hollow cylinder three-dimensional ring structure, and in its empty structure, outer upper end (larger openend) is by C
2and C
3secondary hydroxyl form, lower end (smaller opening end) is by C
6primary hydroxyl form, there is hydrophily; And formed hydrophobic region owing to being subject to the shielding action of c h bond in cavity, its hydrophobicity cavity can be combined and form host-guest inclusion thing with organic guest molecule of more size coupling, therefore can be used for inclusion inorganic matter and aromatic series organic molecule as medicine, essence and flavoring agent etc., its hydrophilic hydroxyl in outside has huge legendary turtle cooperation use to metal ion, therefore for sewage disposal, cosmetics, medicine and other fields.
Clay mineral comprises kaolin, talcum, imvite, mica etc., wherein imvite (MMT) is a kind of silicates clay, belong to typical 2: 1 type laminated crystallines, each unit cell forms by carrying one deck alumina octahedral secretly in the middle of two silicon-oxy tetrahedrons, between the two, connect by sharing oxygen atom, interlamellar spacing is approximately 1nm left and right.On imvite alumina octahedral, part trivalent aluminium, by divalence magnesium isomorphous substitution, makes a layer inner surface have negative electrical charge, and the cation that superfluous negative electrical charge adsorbs by interlayer compensates, as Na
+, K
+, Ca
2+deng, they are easy to exchange with inorganic or organic cation.Due to montmorillonite layered design feature, it has larger specific area and cation exchange capacity, again good absorption property and other unique mineral attribute and physicochemical property.Imvite wide material sources, the cheap attention that has caused Mineral Processing Subject and environmental protection subject; the research of imvite mineral environment-friendly materials also becomes a research field with bright prospects, and control and the processing of in environmental protection, water being polluted have extremely important effect.
Hectorite (LAPONITE) is a kind of clay mineral containing magnesium, lithium, silicon, and crystal structure is trioctahedron type.Be generally canescence, quality exquisiteness, hardness is little and have a sliding sense.Hectorite is added to the water, and can expand very soon, forms the gel that comprises a large amount of water network structures, has good thixotropy, dispersiveness, suspension and thickening property.Therefore, hectorite can be used as thickener, dispersant, suspending agent, smoke agent, latex stabilizing agent, rubber latex agent etc. for multiple coating, cosmetics, medicine and other fields.Compare hectorite and imvite, hectorite specific area is little compared with imvite, thereby its reactivity is higher.
Because cyclodextrin and clay have good adsorptivity to aromatic series organic matter and metal ion respectively, if both characteristics are combined, can reach the performance simultaneously with adsorb organic compound and metal ion.But the composite of only had at present one section of patent report cyclodextrin and imvite is for organic dyestuff water treatment agent (patent publication No.: CN101177310A).And in their research, it is compound that the interlayer that directly cyclodextrin is simply inserted to imvite carries out, between imvite and cyclodextrin, there is no chemical bonds.The present invention combines clay and cyclodextrin by covalent bond, gained composite has more played consistently the adsorptivity of clay mineral to metal ion, combine again the efficient Binding ability of cyclodextrin to organic aromatic molecule, this processes adsorbent to exploitation new type water and will have certain theory and realistic meaning.
Summary of the invention
The object of this invention is to provide a kind of cyclodextrin-clay composite material and preparation method thereof, by chemical bond, clay mineral and cyclodextrin are combined, obtain having the water treatment agent of efficient adsorption metal ion and aromatic series organic matter performance.
Technical scheme of the present invention: respectively taking two kinds of inorganic claies (imvite, hectorite) and cyclodextrin as base stock, clay and cyclodextrin are carried out to amidation process after modification respectively and prepare cyclodextrin-clay composite material; By changing function radix order and the chain length of silane coupler (KH550, KH602, HD702), reach the mass fraction of controlling cyclodextrin in composite: cyclodextrin mass percent is 5.3～29.4%.
Preparation method of the present invention is:
(1) clay mineral is aminated: 330g clay mineral, 3mol silane coupler are added in 12L toluene solution, and at 80 DEG C after return stirring 6h, stirred overnight at room temperature; Reaction finishes rear filtration, washs 12h with apparatus,Soxhlet's, finally imvite good modification is dried to 24h in the vacuum drying oven of 80 DEG C;
(2) carboxy methylation of cyclodextrin: be 1: 17: 14 by the mol ratio of cyclodextrin (CD), sodium chloroacetate and NaOH, add 2L deionized water, at 80 DEG C of reaction 3h, then use ice bath cooling, after solution temperature is down to room temperature, pH value is adjusted to 6 with 3mol/L hydrochloric acid, with a large amount of methanol extractions and repeatedly dissolve-precipitation to remove unreacted raw material and accessory substance; Again product is changed into hydrogen ion by ion exchange resin (Z001 × 4) by sodium ion, through freeze drying, prepare carboxymethylated cyclodextrin (CMCD);
(3) amidatioon of clay mineral and cyclodextrin: by 97.2g CMCD, 19.2g inferior amine salt hydrochlorate (EDC) and 27g1-hydroxybenzotriazole (HOBT) are dissolved in 1L DMF, under condition of ice bath, above-mentioned solution is progressively added drop-wise in the DMF dirty solution that contains the silane coupler modified clay mineral of 100g with constant pressure funnel, after reaction 48h, repeatedly wash by DMF and deionized water, the vacuum drying oven that finally product is placed in to 80 DEG C is dried.
Taking imvite and cyclodextrin, during as raw material, gained composite is expressed as CD/MMT; Taking hectorite and cyclodextrin, during as raw material, gained composite is expressed as CD/LAPONITE; Their structure is:
Wherein, R is silane coupled group, it is characterized in that, containing the silane coupler of different chain length and function base, being respectively:
(1) in the time being aminopropyl triethoxysilane (KH550), R is:
(2) when be 3-(2-aminoethyl)-(aminopropyl methyl dimethoxysilane) (KH602), R is:
(3) 3-[2-(2-aminoethylamino) ethylamino] propyl group-trimethoxy silane (HD702), R is:
The fourier transform infrared spectroscopy for structure (FTIR) of products therefrom, proton magnetic resonance (PMR) (
1h-NMR) and X-ray diffraction (XRD) characterize; And detecting the content of cyclodextrin in organic content in modified montmorillonoid and compound with thermal gravimetric analyzer (TGA), result proves that the access amount of cyclodextrin is 5～30%, as shown in Table 1 and Table 2; Finally by product by phenolphthalein is carried out to inclusion, by the inclusion performance of visible ultraviolet spectrometer test compound material.
Table 1CD and the mass fraction of silane coupler in CD-MMT.
Table 2CD and the mass fraction of silane coupler in CD-LAPONITE.
Beneficial effect of the present invention: the present invention utilize cyclodextrin to aromatic series organic matter and clay mineral the absorption property to metal ion, cyclodextrin is combined by silane coupler with clay mineral, this composite by chemical bonds is more stable, can reach the performance of efficient adsorption organic matter and metal ion simultaneously, and this water treatment absorbent that exploitation is contained to cyclodextrin will have certain theory and realistic meaning.
Brief description of the drawings
Fig. 1 imvite and compound MMT (a) thereof, MMT-KH550 (b), the XRD collection of illustrative plates of CD-MMT-KH550 (c).
Fig. 2 imvite and compound MMT (a) thereof, MMT-KH550 (b), the TGA curve of CD-MMT-KH550 (c).
Fig. 3 hectorite and compound LAPONITE (a) thereof, LAPONITE-KH550 (b), the TGA curve of CD-LAPONITE-KH550 (c).
Detailed description of the invention
Embodiment 1
By the alpha-cyclodextrin of 278g (α-CD), 466g sodium chloroacetate and 192g NaOH in the reactor of 25L, measure 2L deionized water, at 80 DEG C of reaction 3h, then use ice bath cooling, after solution temperature is down to room temperature, drip the hydrochloric acid of 3mol/1 the value of pH be transferred to 6, with a large amount of methanol extractions also repeatedly dissolution precipitation wash away unreacted raw material and accessory substance sodium chloride.Finally product is changed into hydrogen ion by ion exchange resin (Z001 × 4) exchange by sodium ion, until post product is placed in to freeze drier dry one week after finishing, finally obtain carboxymethylated cyclodextrin (α-CMCD).
Embodiment 2
By the beta-schardinger dextrin-of 324g (β-CD), 466g sodium chloroacetate and 192g NaOH in the reactor of 25L, measure 2L deionized water, at 80 DEG C of reaction 3h, then use ice bath cooling, after solution temperature is down to room temperature, drip the hydrochloric acid of 3mol/1 the value of pH be transferred to 6, with a large amount of methanol extractions also repeatedly dissolution precipitation wash away unreacted raw material and accessory substance sodium chloride.Finally product is changed into hydrogen ion by ion exchange resin (Z001 × 4) exchange by sodium ion, until post product is placed in to freeze drier dry one week after finishing, finally obtain carboxymethylated cyclodextrin (β-CMCD).
Embodiment 3
By the gamma-cyclodextrin of 370g (γ-CD), 466g sodium chloroacetate and 192g NaOH in the reactor of 25L, measure 2L deionized water, at 80 DEG C of reaction 3h, then use ice bath cooling, after solution temperature is down to room temperature, drip the hydrochloric acid of 3mol/1 the value of pH be transferred to 6, with a large amount of methanol extractions also repeatedly dissolution precipitation wash away unreacted raw material and accessory substance sodium chloride.Finally product is changed into hydrogen ion by ion exchange resin (Z001 × 4) exchange by sodium ion, until post product is placed in to freeze drier dry one week after finishing, finally obtain carboxymethylated cyclodextrin (γ-CMCD).
Embodiment 4
330g imvite (MMT), 690mL Silane coupling agent KH550 are added in the reactor that fills 12L toluene solution successively, after 80 DEG C of return stirring 6h, stirred overnight at room temperature.Reaction finishes rear filtration, washs 12h with apparatus,Soxhlet's, finally imvite good modification is dried to 24h in the vacuum drying oven of 80 DEG C, prepares the amino imvite (MMT-KH550) after KH550 modification.
Take 100g MMT-KH550 in the single port flask of DMF that 1L is housed in ice bath dispersed with stirring, take again 97.2g CMCD simultaneously, 19.2g inferior amine salt hydrochlorate (EDC) and 27g1-hydroxybenzotriazole (HOBT) are dissolved in the beaker of the DMF that 1L is housed and in ice bath, stir 1h, then with constant pressure funnel, solution is progressively added drop-wise in the imvite dirty solution after modification, reaction 48h, after finishing, use DMF and the repeated multiple times washing of deionized water, the vacuum drying oven that finally product is placed in to 80 DEG C is dried, prepare cyclodextrin-imvite (CD-MMT-KH550).
Embodiment 5
330g MMT, 627mL silane coupler KH602 are added in the reactor that fills 12L toluene solution successively to 80 DEG C of return stirring 6h, stirred overnight at room temperature.Reaction finishes rear filtration, washs 12h with apparatus,Soxhlet's, finally imvite good modification is dried to 24h in the vacuum drying oven of 80 DEG C, prepares the amino imvite (MMT-KH602) after KH602 modification.
Take in the single port flask of DMF that 100g MMT-KH602 is equipped with 1L dispersed with stirring in ice bath, take again 97.2g CMCD simultaneously, 19.2g EDC and 27g HOBT are dissolved in the beaker of the DMF that 1L is housed and in ice bath, stir 1h, then with constant pressure funnel, solution is progressively added drop-wise in the imvite dirty solution after modification, reaction 48h, after finishing, use DMF and the repeated multiple times washing of deionized water, the vacuum drying oven that finally product is placed in to 80 DEG C is dried, and prepares cyclodextrin-imvite (CD-MMT-KH6002).
Embodiment 6
330g MMT, 759mL silane coupler HD702 are added in the reactor that fills 12L toluene solution successively to 80 DEG C of return stirring 6h, stirred overnight at room temperature.Reaction finishes rear filtration, washs 12h with apparatus,Soxhlet's, finally imvite good modification is dried to 24h in the vacuum drying oven of 80 DEG C, prepares the amino imvite (MMT-HD702) after HD702 modification.
Take 100g MMT-HD702 in the single port flask of DMF that 1L is housed in ice bath dispersed with stirring, take again 97.2g CMCD simultaneously, 19.2g EDC and 27g HOBT are dissolved in the beaker of the DMF that 1L is housed and in ice bath, stir 1h, then with constant pressure funnel, solution is progressively added drop-wise in the imvite dirty solution after modification, reaction 48h, after finishing, use DMF and the repeated multiple times washing of deionized water, the vacuum drying oven that finally product is placed in to 80 DEG C is dried, and prepares cyclodextrin-imvite (CD-MMT-HD702).
Embodiment 7
330g hectorite (LAPONITE), 690mL KH550 are added in the reactor that fills 12L toluene solution successively to 80 DEG C of return stirring 6h, stirred overnight at room temperature.Reaction finishes rear filtration, washs 12h with apparatus,Soxhlet's, finally imvite good modification is dried to 24h in the vacuum drying oven of 80 DEG C, prepares the lithium amide saponite (LAPONITE-KH550) after KH550 modification.
Take hectorite after 100g KH550 modification in the single port flask of DMF that 1L is housed in ice bath dispersed with stirring, take again 97.2g CMCD simultaneously, 19.2g EDC and 27g HOBT are dissolved in the beaker of the DMF that 1L is housed and in ice bath, stir 1h, then with constant pressure funnel, solution is progressively added drop-wise in the imvite dirty solution after modification, reaction 48h, after finishing, use DMF and the repeated multiple times washing of deionized water, the vacuum drying oven that finally product is placed in to 80 DEG C is dried, and prepares cyclodextrin-hectorite (CD-LAPONITE-KH550).
Embodiment 8
330g LAPONITE, 627mL KH602 are added in the reactor that fills 12L toluene solution successively to 80 DEG C of return stirring 6h, stirred overnight at room temperature.Reaction finishes rear filtration, washs 12h with apparatus,Soxhlet's, finally imvite good modification is dried to 24h in the vacuum drying oven of 80 DEG C, prepares the amino imvite (MMT-KH602) after KH602 modification.
Take hectorite after 100g KH602 modification in the single port flask of DMF that 1L is housed in ice bath dispersed with stirring, take again 97.2g CMCD simultaneously, 19.2g EDC and 27g HOBT are dissolved in the beaker of the DMF that 1L is housed and in ice bath, stir 1h, then with constant pressure funnel, solution is progressively added drop-wise in the imvite dirty solution after modification, reaction 48h, after finishing, use DMF and the repeated multiple times washing of deionized water, the vacuum drying oven that finally product is placed in to 80 DEG C is dried, and prepares cyclodextrin-hectorite (CD-LAPONITE-KH602).
Embodiment 9
330g LAPONITE, 759mL HD702 are added in the reactor that fills 12L toluene solution successively to 80 DEG C of return stirring 6h, stirred overnight at room temperature.Reaction finishes rear filtration, washs 12h with apparatus,Soxhlet's, finally imvite good modification is dried to 24h in the vacuum drying oven of 80 DEG C, prepares the amino imvite (LAPONITE-HD702) after HD702 modification.
Take 100g LAPONITE-HD702 in the single port flask of DMF that 1L is housed in ice bath dispersed with stirring, take again 97.2g CMCD simultaneously, 19.2g EDC and 27g HOBT are dissolved in the beaker of the DMF that 1L is housed and in ice bath, stir 1h, then with constant pressure funnel, solution is progressively added drop-wise in the imvite dirty solution after modification, reaction 48h, after finishing, use DMF and the repeated multiple times washing of deionized water, the vacuum drying oven that finally product is placed in to 80 DEG C is dried, and prepares cyclodextrin-hectorite (CD-LAPONITE-HD702).
Claims (6)
1. the preparation method of a cyclodextrin-clay composite material, it is characterized in that, respectively taking inorganic clay and cyclodextrin as base stock, first adopt silane coupler to carry out aminated modification to clay, again the clay after silane coupler modified and carboxymethylated cyclodextrin are carried out to amidation process, thereby prepare cyclodextrin-clay composite material; By changing function radix order and the chain length of silane coupler, reach the mass fraction of controlling cyclodextrin in composite: cyclodextrin mass percent is 5.3～29.4%.
2. the preparation method of cyclodextrin-clay composite material according to claim 1, is being characterised in that, preparation method is:
(1) clay is aminated: 330g clay, 3mol silane coupler are added in 12L toluene solution, and at 80 DEG C after return stirring 6h, stirred overnight at room temperature; Reaction finishes rear filtration, washs 12h with apparatus,Soxhlet's, finally clay good modification is dried to 24h in the vacuum drying oven of 80 DEG C;
(2) carboxy methylation of cyclodextrin: be 1: 17: 14 by the mol ratio of cyclodextrin, sodium chloroacetate and NaOH, add 2L deionized water, at 80 DEG C of reaction 3h, then use ice bath cooling, after solution temperature is down to room temperature, pH value is adjusted to 6 with 3mol/L hydrochloric acid, with a large amount of methanol extractions and repeatedly dissolve-precipitation to remove unreacted raw material and accessory substance; Again product is changed into hydrogen ion by ion exchange resin by sodium ion, through freeze drying, prepare carboxymethylated cyclodextrin;
(3) amidatioon of clay and cyclodextrin: by carboxymethylated 97.2g cyclodextrin, 19.2g inferior amine salt hydrochlorate and 27g1-hydroxybenzotriazole are dissolved in 1L dimethyl formamide, under condition of ice bath, above-mentioned solution is progressively added drop-wise in the dimethyl formamide dirty solution that contains the silane coupler modified clay of 100g with constant pressure funnel, after reaction 48h, repeatedly wash by dimethyl formamide and deionized water, the vacuum drying oven that finally product is placed in to 80 DEG C is dried.
3. the preparation method of cyclodextrin-clay composite material according to claim 1, is characterized in that, described cyclodextrin is alpha-cyclodextrin, beta-schardinger dextrin-or gamma-cyclodextrin.
4. the preparation method of cyclodextrin-clay composite material according to claim 1, is characterized in that, described inorganic clay is imvite and hectorite, and the composite forming with cyclodextrin is expressed as CD/MMT and CD/LAPONITE, and its structure is:
5. cyclodextrin-clay composite material, is characterized in that, the cyclodextrin-clay composite material of telling prepare according to the preparation method of the cyclodextrin-clay composite material described in any one in claim 1-4.
6. a purposes for cyclodextrin-clay composite material according to claim 5, is characterized in that, described cyclodextrin-clay composite material is for sewage disposal and purification of pharmaceuticals field.
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| CN103433003B (en) * | 2013-09-11 | 2015-10-14 | 江南大学 | A kind of cyclodextrin/montmorillonite composite material and preparation method thereof |
| CN104307483A (en) * | 2014-11-05 | 2015-01-28 | 华文蔚 | Preparation method of composite adsorbent for domestic sewage treatment |
| CN104525263A (en) * | 2014-12-25 | 2015-04-22 | 江南大学 | Preparation method of cyclodextrin/montmorillonite/heteropoly acid composite catalyst |
| CN104437414B (en) * | 2014-12-25 | 2017-05-17 | 江南大学 | Montmorillonite-reinforced polyethylene glycol/ cyclodextrin gel and preparation method thereof |
| CN105879046B (en) * | 2016-04-18 | 2019-09-20 | 天津工业大学 | The preparation method of the organic lithium soapstone based antimicrobials of beta-cyclodextrin modified |
| CN107540750B (en) * | 2017-10-19 | 2019-10-15 | 无锡甜丰食品有限公司 | A kind of preparation method of carboxymethyl maltodextrin |
| CN108035148B (en) * | 2017-11-28 | 2020-07-28 | 江苏宏远药业有限公司 | Amino modified TiO2Preparation method of leather fiber |
| CN107938164A (en) * | 2017-12-25 | 2018-04-20 | 合肥洁诺无纺布制品有限公司 | A kind of preparation method of the antibacterial plant fiber non-woven fabric of fragrance |
| CN110124625A (en) * | 2019-05-29 | 2019-08-16 | 西南石油大学 | A kind of environment-friendly type bentonite and its preparation method and application |
| CN110801815B (en) * | 2019-11-05 | 2021-01-29 | 江南大学 | Modified cyclodextrin/mesoporous silicon for adsorbing Pb and Cd and application thereof |
| CN113813929B (en) * | 2021-06-30 | 2023-10-24 | 盘锦富瑞达环保科技有限公司 | Preparation method of oil sludge treatment agent |
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| JPS62191416A (en) * | 1986-02-14 | 1987-08-21 | Natl Inst For Res In Inorg Mater | Montmorillonite-methylated cyclodextrin-type crystalline composite and production thereof |
| CN100410314C (en) * | 2004-11-05 | 2008-08-13 | 中国科学院化学研究所 | Polyethylene /montmorillonite nanometer composite material and preparation method |
| CN101177310B (en) * | 2007-11-02 | 2010-05-19 | 西南石油大学 | Method for preparing waste-water treating agent containing organic dye |
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