CN103007901A - Cyclodextrin-clay composite and preparation method thereof - Google Patents
Cyclodextrin-clay composite and preparation method thereof Download PDFInfo
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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 the composite preparing technical field.
Background technology
Cyclodextrin (CD) is the product that is acted on starch by cyclodextrin glycosyl transferases, it by a plurality of 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 consist of, lower end (smaller opening end) is by C
6Primary hydroxyl consist of, have hydrophily; And formed hydrophobic region owing to be subject to the shielding action of c h bond in the cavity, its hydrophobicity cavity can be combined with organic guest molecule of more size coupling and be formed the host-guest inclusion thing, therefore can be used for inclusion inorganic matter and aromatic series organic molecule such as medicine, essence and flavoring agent etc., its hydrophilic hydroxyl in outside has huge legendary turtle cooperation usefulness to metal ion, therefore is used 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 crystalline, each unit cell consists of by carrying one deck alumina octahedral secretly in the middle of two silicon-oxy tetrahedrons, connect by sharing oxygen atom between the two, interlamellar spacing is approximately about 1nm.The part trivalent aluminium is made a layer inner surface have negative electrical charge by divalence magnesium isomorphous substitution on the imvite alumina octahedral, and superfluous negative electrical charge compensates by the cation of interlayer absorption, such as Na
+, K
+, Ca
2+Deng, they are easy to exchange with inorganic or organic cation.Because montmorillonite layered design feature, it has larger specific area and cation exchange capacity, again preferably 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 that contains magnesium, lithium, silicon, and crystal structure is the trioctahedron type.Be generally canescence, quality is fine and smooth, and hardness is little and have a sliding sense.Hectorite is added to the water, can very fast expansion, form the gel that comprises a large amount of networks of rivers network structure, and have preferably 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, the hectorite specific area is little than imvite, thereby its reactivity is higher.
Because cyclodextrin and clay have good adsorptivity to aromatic series organic matter and metal ion respectively, if both characteristic is combined, can reach the performance that has simultaneously adsorb organic compound and metal ion.Yet the composite of only had at present one piece of patent report cyclodextrin and imvite is used 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 imvite carries out, and do not have chemical bonds between imvite and cyclodextrin.The present invention combines clay and cyclodextrin by covalent bond, the gained composite has more played consistently clay mineral to metal biosorption, combine again cyclodextrin to the efficient Binding ability of organic aromatic molecule, this processes adsorbent to the exploitation new type water will have certain theory and realistic meaning.
Summary of the invention
The purpose 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 take two kinds of inorganic claies (imvite, hectorite) and cyclodextrin as base stock, clay and cyclodextrin are carried out amidation process after the modification respectively 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 cyclodextrin in the control composite: the 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 the 12L toluene solution, and behind 80 ℃ of lower return stirring 6h, stirred overnight at room temperature; Reaction is filtered after finishing, and washs 12h with apparatus,Soxhlet's, and the at last imvite that modification is good is dried by the fire 24h in 80 ℃ vacuum drying oven;
(2) carboxy methylation of cyclodextrin: the mol ratio by cyclodextrin (CD), sodium chloroacetate and NaOH is 1: 17: 14, add the 2L deionized water, at 80 ℃ of reaction 3h, then cool off with ice bath, after solution temperature is down to room temperature, with 3mol/L hydrochloric acid the pH value is transferred to 6, also repeatedly dissolve-precipitate to remove unreacted raw material and accessory substance with a large amount of methanol extractions; Again product is changed into hydrogen ion by ion exchange resin (Z001 * 4) with sodium ion, through freeze drying, prepare carboxymethylated cyclodextrin (CMCD);
(3) amidatioon of clay mineral and cyclodextrin: with 97.2g CMCD, 19.2g inferior amine salt hydrochlorate (EDC) and 27g I-hydroxybenzotriazole (HOBT) are dissolved among the 1L DMF, under condition of ice bath, mentioned solution progressively is added drop-wise in the DMF dirty solution that contains the silane coupler modified clay mineral of 100g with constant pressure funnel, repeatedly wash with DMF and deionized water behind the reaction 48h, at last product is placed 80 ℃ vacuum drying oven to dry.
During as raw material, the gained composite is expressed as CD/MMT take imvite and cyclodextrin; During as raw material, the gained composite is expressed as CD/LAPONITE take hectorite and cyclodextrin; 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, is respectively:
(1) when 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 structure of products therefrom with fourier transform infrared spectroscopy (FTIR), proton magnetic resonance (PMR) (
1H-NMR) and X-ray diffraction (XRD) characterize; And detecting the content of cyclodextrin in organic content in the modified montmorillonoid and the compound with thermal gravimetric analyzer (TGA), the result proves that the access amount of cyclodextrin is 5～30%, as shown in Table 1 and Table 2; At last with product by phenolphthalein is carried out inclusion, with 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 to the metal biosorption performance, cyclodextrin is combined by silane coupler with clay mineral, this composite by chemical bonds is more stable, can reach the simultaneously performance of efficient adsorption organic matter and metal ion, and this will have certain theory and realistic meaning to the water treatment absorbent that exploitation contains cyclodextrin.
Description of 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).
The specific embodiment
(α-CD), 466g sodium chloroacetate and 192g NaOH are in the reactor of 25L with the alpha-cyclodextrin of 278g, measure the 2L deionized water, at 80 ℃ of reaction 3h, then cool off with ice bath, after solution temperature is down to room temperature, the hydrochloric acid that drips 3mol/l is transferred to 6 with the value of pH, with a large amount of methanol extractions also repeatedly unreacted raw material of dissolution precipitation flush away and accessory substance sodium chloride.At last product is changed into hydrogen ion by ion exchange resin (Z001 * 4) exchange with sodium ion, until post product is placed a dry week of freeze drier after finishing, obtain at last carboxymethylated cyclodextrin (α-CMCD).
(β-CD), 466g sodium chloroacetate and 192g NaOH are in the reactor of 25L with the beta-schardinger dextrin-of 324g, measure the 2L deionized water, at 80 ℃ of reaction 3h, then cool off with ice bath, after solution temperature is down to room temperature, the hydrochloric acid that drips 3mol/l is transferred to 6 with the value of pH, with a large amount of methanol extractions also repeatedly unreacted raw material of dissolution precipitation flush away and accessory substance sodium chloride.At last product is changed into hydrogen ion by ion exchange resin (Z001 * 4) exchange with sodium ion, until post product is placed a dry week of freeze drier after finishing, obtain at last carboxymethylated cyclodextrin (β-CMCD).
(γ-CD), 466g sodium chloroacetate and 192g NaOH are in the reactor of 25L with the gamma-cyclodextrin of 370g, measure the 2L deionized water, at 80 ℃ of reaction 3h, then cool off with ice bath, after solution temperature is down to room temperature, the hydrochloric acid that drips 3mol/l is transferred to 6 with the value of pH, with a large amount of methanol extractions also repeatedly unreacted raw material of dissolution precipitation flush away and accessory substance sodium chloride.At last product is changed into hydrogen ion by ion exchange resin (Z001 * 4) exchange with sodium ion, until post product is placed a dry week of freeze drier after finishing, obtain at last carboxymethylated cyclodextrin (γ-CMCD).
Embodiment 4
330g imvite (MMT), 690mL Silane coupling agent KH550 are added in the reactor that fills the 12L toluene solution successively, behind 80 ℃ of return stirring 6h, stirred overnight at room temperature.Filter after reaction finishes, wash 12h with apparatus,Soxhlet's, the at last imvite that modification is good is dried by the fire 24h in 80 ℃ vacuum drying oven, prepares the amino imvite (MMT-KH550) after the KH550 modification.
Take by weighing 100g MMT-KH550 in the single port flask of the DMF that 1L is housed in ice bath dispersed with stirring, take by weighing again simultaneously 97.2g CMCD, 19.2g being dissolved in the beaker of the DMF that 1L is housed, inferior amine salt hydrochlorate (EDC) and 27g I-hydroxybenzotriazole (HOBT) in ice bath, stir 1h, then with constant pressure funnel solution progressively is added drop-wise in the imvite dirty solution after the modification, reaction 48h, use DMF and the repeated multiple times washing of deionized water after finishing, at last product is placed 80 ℃ vacuum drying oven to dry, prepare cyclodextrin-imvite (CD-MMT-KH550).
330g MMT, 627mL silane coupler KH602 are added in the reactor that fills the 12L toluene solution successively 80 ℃ of return stirring 6h, stirred overnight at room temperature.Filter after reaction finishes, wash 12h with apparatus,Soxhlet's, the at last imvite that modification is good is dried by the fire 24h in 80 ℃ vacuum drying oven, prepares the amino imvite (MMT-KH602) after the KH602 modification.
Take by weighing in the single port flask of DMF that 100g MMT-KH602 is equipped with 1L dispersed with stirring in ice bath, take by weighing again simultaneously 97.2g CMCD, 19.2g being dissolved in the beaker of the DMF that 1L is housed, EDC and 27g HOBT in ice bath, stir 1h, then with constant pressure funnel solution progressively is added drop-wise in the imvite dirty solution after the modification, reaction 48h, use DMF and the repeated multiple times washing of deionized water after finishing, at last product is placed 80 ℃ vacuum drying oven to dry, prepare cyclodextrin-imvite (CD-MMT-KH6002).
330g MMT, 759mL silane coupler HD702 are added in the reactor that fills the 12L toluene solution successively 80 ℃ of return stirring 6h, stirred overnight at room temperature.Filter after reaction finishes, wash 12h with apparatus,Soxhlet's, the at last imvite that modification is good is dried by the fire 24h in 80 ℃ vacuum drying oven, prepares the amino imvite (MMT-HD702) after the HD702 modification.
Take by weighing 100g MMT-HD702 in the single port flask of the DMF that 1L is housed in ice bath dispersed with stirring, take by weighing again simultaneously 97.2g CMCD, 19.2g being dissolved in the beaker of the DMF that 1L is housed, EDC and 27g HOBT in ice bath, stir 1h, then with constant pressure funnel solution progressively is added drop-wise in the imvite dirty solution after the modification, reaction 48h, use DMF and the repeated multiple times washing of deionized water after finishing, at last product is placed 80 ℃ vacuum drying oven to dry, prepare cyclodextrin-imvite (CD-MMT-HD702).
330g hectorite (LAPONITE), 690mL KH550 are added in the reactor that fills the 12L toluene solution successively 80 ℃ of return stirring 6h, stirred overnight at room temperature.Filter after reaction finishes, wash 12h with apparatus,Soxhlet's, the at last imvite that modification is good is dried by the fire 24h in 80 ℃ vacuum drying oven, prepares the lithium amide saponite (LAPONITE-KH550) after the KH550 modification.
Take by weighing hectorite after the 100g KH550 modification in the single port flask of the DMF that 1L is housed in ice bath dispersed with stirring, take by weighing again simultaneously 97.2g CMCD, 19.2g being dissolved in the beaker of the DMF that 1L is housed, EDC and 27g HOBT in ice bath, stir 1h, then with constant pressure funnel solution progressively is added drop-wise in the imvite dirty solution after the modification, reaction 48h, use DMF and the repeated multiple times washing of deionized water after finishing, at last product is placed 80 ℃ vacuum drying oven to dry, prepare cyclodextrin-hectorite (CD-LAPONITE-KH550).
Embodiment 8
330g LAPONITE, 627mL KH602 are added in the reactor that fills the 12L toluene solution successively 80 ℃ of return stirring 6h, stirred overnight at room temperature.Filter after reaction finishes, wash 12h with apparatus,Soxhlet's, the at last imvite that modification is good is dried by the fire 24h in 80 ℃ vacuum drying oven, prepares the amino imvite (MMT-KH602) after the KH602 modification.
Take by weighing hectorite after the 100g KH602 modification in the single port flask of the DMF that 1L is housed in ice bath dispersed with stirring, take by weighing again simultaneously 97.2g CMCD, 19.2g being dissolved in the beaker of the DMF that 1L is housed, EDC and 27g HOBT in ice bath, stir 1h, then with constant pressure funnel solution progressively is added drop-wise in the imvite dirty solution after the modification, reaction 48h, use DMF and the repeated multiple times washing of deionized water after finishing, at last product is placed 80 ℃ vacuum drying oven to dry, prepare cyclodextrin-hectorite (CD-LAPONITE-KH602).
Embodiment 9
330g LAPONITE, 759mL HD702 are added in the reactor that fills the 12L toluene solution successively 80 ℃ of return stirring 6h, stirred overnight at room temperature.Filter after reaction finishes, wash 12h with apparatus,Soxhlet's, the at last imvite that modification is good is dried by the fire 24h in 80 ℃ vacuum drying oven, prepares the amino imvite (LAPONITE-HD702) after the HD702 modification.
Take by weighing 100g LAPONITE-HD702 in the single port flask of the DMF that 1L is housed in ice bath dispersed with stirring, take by weighing again simultaneously 97.2g CMCD, 19.2g being dissolved in the beaker of the DMF that 1L is housed, EDC and 27g HOBT in ice bath, stir 1h, then with constant pressure funnel solution progressively is added drop-wise in the imvite dirty solution after the modification, reaction 48h, use DMF and the repeated multiple times washing of deionized water after finishing, at last product is placed 80 ℃ vacuum drying oven to dry, prepare cyclodextrin-hectorite (CD-LAPONITE-HD702).
Claims (5)
1. cyclodextrin-clay composite material and preparation method thereof belongs to the composite preparing technical field.It is characterized in that respectively take two kinds of inorganic claies (imvite, hectorite) and cyclodextrin as base stock, clay and cyclodextrin are carried out amidation process after the modification respectively prepare cyclodextrin-clay composite material; By changing function radix order and the chain length of silane coupler, reach the mass fraction of cyclodextrin in the control composite: the cyclodextrin mass percent is 5.3～29.4%.
2. cyclodextrin-clay composite material according to claim 1, its preparation method is:
(1) clay is aminated: 330g clay mineral, 3mol silane coupler are added in the 12L toluene solution, and behind 80 ℃ of lower return stirring 6h, stirred overnight at room temperature; Reaction is filtered after finishing, and washs 12h with apparatus,Soxhlet's, and the at last imvite that modification is good is dried by the fire 24h in 80 ℃ vacuum drying oven;
(2) carboxy methylation of cyclodextrin: the mol ratio by cyclodextrin (CD), sodium chloroacetate and NaOH is 1: 17: 14, add the 2L deionized water, at 80 ℃ of reaction 3h, then cool off with ice bath, after solution temperature is down to room temperature, with 3mol/L hydrochloric acid the pH value is transferred to 6, also repeatedly dissolve-precipitate to remove unreacted raw material and accessory substance with a large amount of methanol extractions; Again product is changed into hydrogen ion by ion exchange resin (Z001 * 4) with sodium ion, through freeze drying, prepare carboxymethylated cyclodextrin (CMCD);
(3) amidatioon of clay mineral and cyclodextrin: with 97.2g CMCD, 19.2g inferior amine salt hydrochlorate (EDC) and 27g I-hydroxybenzotriazole (HOBT) are dissolved among the 1L DMF, under condition of ice bath, mentioned solution progressively is added drop-wise in the DMF dirty solution that contains the silane coupler modified clay mineral of 100g with constant pressure funnel, repeatedly wash with DMF and deionized water behind the reaction 48h, at last product is placed 80 ℃ vacuum drying oven to dry.
3. cyclodextrin according to claim 1-clay mineral composite is characterized in that, described cyclodextrin is alpha-cyclodextrin, beta-schardinger dextrin-or gamma-cyclodextrin.
4. cyclodextrin according to claim 1-clay mineral composite is characterized in that employed clay mineral is imvite and hectorite, and the composite that forms with cyclodextrin is expressed as respectively CD/MMT and CD/LAPONITE, and its structure is:
R：(1)
(2)
(3)
5. cyclodextrin-clay composite material according to claim 1, this material can Effective Raise metal ions in sewages and the adsorption capacity of aromatic organic compounds, can be used for the fields such as sewage disposal and purification of pharmaceuticals.
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| CN103433003A (en) * | 2013-09-11 | 2013-12-11 | 江南大学 | Cyclodextrin (CD) polymer/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 |
| CN104437414A (en) * | 2014-12-25 | 2015-03-25 | 江南大学 | Montmorillonite-reinforced polyethylene glycol/ cyclodextrin gel and preparation method thereof |
| CN104525263A (en) * | 2014-12-25 | 2015-04-22 | 江南大学 | Preparation method of cyclodextrin/montmorillonite/heteropoly acid composite catalyst |
| CN105879046A (en) * | 2016-04-18 | 2016-08-24 | 天津工业大学 | Preparation method of beta-cyclodextrin modified organic hectorite based antibacterial agent |
| CN107540750A (en) * | 2017-10-19 | 2018-01-05 | 无锡甜丰食品有限公司 | A kind of preparation method of carboxymethyl maltodextrin |
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| CN104437414A (en) * | 2014-12-25 | 2015-03-25 | 江南大学 | Montmorillonite-reinforced polyethylene glycol/ cyclodextrin gel and preparation method thereof |
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