CN103433003A - Cyclodextrin (CD) polymer/montmorillonite composite material and preparation method thereof - Google Patents
Cyclodextrin (CD) polymer/montmorillonite composite material and preparation method thereof Download PDFInfo
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- CN103433003A CN103433003A CN2013104098663A CN201310409866A CN103433003A CN 103433003 A CN103433003 A CN 103433003A CN 2013104098663 A CN2013104098663 A CN 2013104098663A CN 201310409866 A CN201310409866 A CN 201310409866A CN 103433003 A CN103433003 A CN 103433003A
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Abstract
The invention relates to a cyclodextrin (CD) polymer/montmorillonite composite material and a preparation method thereof and belongs to the technical field of composite material preparation. According to the preparation method, a pre-synthesized polymer (P(CD-MA)) of maleic anhydride (MA) and CD is introduced into dopamine (DA) through amidation reaction, and then, the montmorillonite/cyclodextrin composite material is prepared through condensation between DA and hydroxyl groups of montmorillonite. The amount of introduced CD of the composite material can be controlled through changing the molecular weight of P(CD-MA), the content of DA and the content of montmorillonite. The method has the advantages that raw materials are easily obtained, the cost is low, the method is simple, and the amount of the introduced CD is large and is easy to control. According to the cyclodextrin polymer/montmorillonite composite material, metal ions and aromatic organic compounds in sewage can be simultaneously removed by using the metal ion exchange adsorbability of montmorillonite and the organic matter (especially aromatic organic matters) inclusion effect of cyclodextrin.
Description
Technical field
The present invention relates to a kind of cyclodextrin/montmorillonite mineral composite and preparation method thereof, belong to the composite preparing technical field.
Background technology
Cyclodextrin (CD) is to be acted on the product of 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 form, lower end (smaller opening end) is by C
6primary hydroxyl form, there is hydrophily; And cavity is interior because the shielding action that is subject to c h bond has formed hydrophobic region, its hydrophobicity cavity can be combined and form the 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.
Montmorillonite mineral matter comprises kaolin, talcum, imvite, mica etc., wherein imvite (MMT) is a kind of silicates montmorillonite, belong to typical 2:1 type laminated crystalline, each unit cell forms by the middle of two silicon-oxy tetrahedrons, carrying one deck alumina octahedral secretly, between the two, by sharing oxygen atom, connect, interlamellar spacing is approximately the 1nm left and right.On the imvite alumina octahedral, the 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 be exchanged with inorganic or organic cation.Due to montmorillonite layered design feature, it has larger specific area and cation exchange capacity, again absorption property and other unique mineral attribute and physicochemical property preferably.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.
Because cyclodextrin and montmorillonite have good adsorptivity to aromatic series organic matter and metal ion respectively, if both characteristics are combined, can reach the performance that simultaneously there is adsorb organic compound and metal ion.Yet the composite of only had at present one piece 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.In the work in earlier stage of this seminar, cyclodextrin and clay are linked and prepare cyclodextrin and clay composite material by covalent bond, by changing the access amount of kind control loop dextrin in clay of clay and silane coupler.But its access amount is not also very desirable, thereby the present invention is based on previous work, with dopamine modification cyclodextrin polymer, adhesiveness and the hydroxyl condensation of the catechol excellence of recycling dopamine access cyclodextrin in montmorillonite, to improve the access amount of cyclodextrin, and improve metal ion and organic adsorption effect.
Summary of the invention
The purpose of this invention is to provide a kind of cyclodextrin/montmorillonite composite material and preparation method thereof, by chemical bond, montmorillonite mineral and cyclodextrin are combined, make in montmorillonite to contain a large amount of cyclodextrin unit, obtain having the water treatment agent of efficient adsorption metal ion and aromatic series organic matter performance.
Technical scheme of the present invention: pre-synthesis maleic anhydride (MA) and cyclodextrin (CD) polymer (P (CD-MA)) are accessed to dopamine by amidation process, and prepare montmorillonite/cyclodextrin composite by the hydroxyl condensation on dopamine and montmorillonite.
Preparation method of the present invention is:
(1) cyclodextrin (P (CD-MA)) is synthetic: take 6.81g β-CD in the there-necked flask of 250ml, use 150ml N, after dinethylformamide (DMF) dissolves, add the 1.68g sodium hydride, 25 ℃ of reaction 24h, then be warming up to 130 ℃, slowly adds 4.12g maleic anhydride (MA), reaction 4h, finally filter product and use a large amount of acetone washings;
(2) dopamine modification cyclodextrin polymer (P (CD-MA)-DA) is synthetic: take 2g P (CD-MA) in 100ml single port flask, after dissolving with the 20ml ultra-pure water, add 0.958g1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC) and 0.575g N-hydroxy-succinamide (NHS), with the hydrochloric acid of 1mol/1, pH is transferred to 5.5, add again 0.765g dopamine (DA) reaction 24h after logical nitrogen 1h, out by product with methanol extraction, through dialysis, freeze drying finally;
(3) cyclodextrin and montmorillonite composite material is synthetic: take 1g montmorillonite standing 24h after mechanical agitation 48h in 100ml single port flask, by upper strata, scattered suspension is poured in the Tris-Hcl buffer solution that 250ml pH is 8.3, add vigorous stirring 24h after 2g P (CD-MA)-DA, finally product is out centrifugal and repeatedly washing.
Take imvite and cyclodextrin as raw material, and the gained composite is expressed as PCD/MMT; Structure is:
Wherein, the matter average molecular weight of P (CD-MA) is 1 * 10
4～1 * 10
5, DA and the content of CD polymer in MMT are respectively 2% and 10.6%.
The fourier transform infrared spectroscopy for structure (FTIR) of products therefrom, proton magnetic resonance (PMR) (
1h-NMR) and X-ray diffraction (XRD) characterized; And detect the content 10.6% of cyclodextrin in the modified montmorillonoid compound with thermal gravimetric analyzer (TGA); Finally product is carried out to absorption property with visible ultraviolet spectrometer and Atomic Absorption Spectrometer test compound material to naphthylamines and lead ion.
Beneficial effect of the present invention: the present invention utilize cyclodextrin to aromatic series organic matter and montmorillonite mineral the absorption property to metal ion, cyclodextrin is combined by dopamine with montmorillonite, and this composite by chemical bonds is more stable, can reach the performance of efficient adsorption organic matter and metal ion simultaneously; In composite, the access amount of cyclodextrin can be controlled by the molecular weight that changes P (CD-MA), the content of DA and the content of montmorillonite; The advantage of this method is that raw material is easy to get, and with low cost, method is simple, and the CD of access measures many and easily control; The water treatment absorbent that the present invention contains cyclodextrin to exploitation will have certain theory and realistic meaning.
The accompanying drawing explanation
The XRD collection of illustrative plates of Fig. 1 MMT, PCD/MMT.
The TGA curve of Fig. 2 MMT, PCD/MMT.
The SEM of Fig. 3 MMT, PCD/MMT.
The specific embodiment
Embodiment 1
Take 5.84g α-CD in the there-necked flask of 250ml, use 150ml N, after dinethylformamide (DMF) dissolves, add the 1.68g sodium hydride, 25 ℃ of reaction 24h, then be warming up to 130 ℃, slowly adds the 4.12g maleic anhydride, reaction 4h, finally filter product and use a large amount of acetone washings; Finally obtain the copolymer p (α-CD-MA) of cyclodextrin and maleic anhydride.
Embodiment 2
Take 6.81g β-CD in the there-necked flask of 250ml, use 150ml N, after dinethylformamide (DMF) dissolves, add the 1.68g sodium hydride, 25 ℃ of reaction 24h, then be warming up to 130 ℃, slowly adds the 4.12g maleic anhydride, reaction 4h, finally filter product and use a large amount of acetone washings; Finally obtain the copolymer p (β-CD-MA) of cyclodextrin and maleic anhydride.
Embodiment 3
Taking 7.78g γ--CD is in the there-necked flask of 250ml, use 150ml N, after dinethylformamide (DMF) dissolves, add the 1.68g sodium hydride, 25 ℃ of reaction 24h, then be warming up to 130 ℃, slowly adds the 4.12g maleic anhydride, reaction 4h, finally filter product and use a large amount of acetone washings; Finally obtain the copolymer (P (γ-CD-MA)) of cyclodextrin and maleic anhydride.
Embodiment 4
Take 2g P (β-CD-MA) in 100ml single port flask, after dissolving with the 20ml ultra-pure water, add 0.958g1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC) and 0.575g N-hydroxy-succinamide (NHS), with the hydrochloric acid of 1mol/1, pH is transferred to 5.5, add again 0.765g dopamine reaction 24h after logical nitrogen 1h, out by product with methanol extraction finally, through dialysis, freeze drying, prepare dopamine graft (P (CD-MA)-DA).
Take 1g montmorillonite standing 24h after mechanical agitation 48h in 100ml single port flask, by upper strata, scattered suspension is poured in the Tris-Hcl buffer solution that 250ml pH is 8.3, add vigorous stirring 24h after 2gP (CD-MA)-DA, finally product is out centrifugal and repeatedly washing, prepare cyclodextrin-imvite (PCD-MMT).
Embodiment 5
Configuration pH is 2, 3, 4, 5, the plumbi nitras aqueous solution of 6 100mg/l, take successively 0.01g cyclodextrin-imvite in different pH solution, after stirring 12h, filter, filtrate is carried out the Atomic absorption test and calculated adsorbance, draw optimal adsorption pH, again under this pH condition, configuration concentration is 25mg/l, 50mg/l, 75mg/l, 100mg/l, 200mg/l, 400mg/l, 600mg/l, 800mg/l, the lead nitrate solution of 1000mg/l, take successively 0.01g cyclodextrin-imvite in the solution of variable concentrations, after stirring 12h, filter, then filtrate is carried out the Atomic absorption test and calculated adsorbance, obtain optimal adsorption concentration, be preferably under the best pH condition of optium concentration, respectively at 25 ℃, 50 ℃, 75 ℃, under 90 ℃, test draws the optimal adsorption temperature.
Embodiment 6
Configuration pH is 2, 3, 4, 5, 6, 7, 8, 9, the naphthylamines aqueous solution of 10 100mg/l, take successively 0.01g cyclodextrin-imvite in different pH solution, after stirring 12h, filter, filtrate is carried out the UV absorption test and calculated adsorbance, draw optimal adsorption pH, again under this pH condition, configuration concentration is 25mg/l, 50mg/l, 75mg/l, 100mg/l, 200mg/l, 400mg/l, 600mg/l, 800mg/l, the naphthylamines solution of 1000mg/l, take successively 0.01g cyclodextrin-imvite in the solution of variable concentrations, after stirring 12h, filter, then filtrate is carried out the UV absorption test and calculated adsorbance, obtain optimal adsorption concentration, be preferably under the best pH condition of optium concentration, respectively at 25 ℃, 50 ℃, 75 ℃, under 90 ℃, test draws the optimal adsorption temperature.
Claims (6)
1. cyclodextrin/montmorillonite composite material and preparation method thereof, belong to the composite preparing technical field.The present invention accesses dopamine by pre-synthesis maleic anhydride (MA) and cyclodextrin (CD) polymer (P (CD-MA)) by amidation process, and prepares montmorillonite/cyclodextrin composite by the hydroxyl condensation on dopamine and montmorillonite;
Its preparation method is:
(1) cyclodextrin (P (CD-MA)) is synthetic: take 6.81g β-CD in the there-necked flask of 250ml, use 150ml N, after dinethylformamide (DMF) dissolves, add the 1.68g sodium hydride, 25 ℃ of reaction 24h, then be warming up to 130 ℃, slowly adds 4.12g maleic anhydride (MA), reaction 4h, finally filter product and use a large amount of acetone washings;
(2) dopamine modification cyclodextrin polymer (P (CD-MA)-DA) is synthetic: take 2g P (CD-MA) in 100ml single port flask, after dissolving with the 20ml ultra-pure water, add 0.958g1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC) and 0.575g N-hydroxy-succinamide (NHS), with the hydrochloric acid of 1mol/1, pH is transferred to 5.5, add again 0.765g dopamine (DA) reaction 24h after logical nitrogen 1h, out by product with methanol extraction, through dialysis, freeze drying finally;
(3) cyclodextrin and montmorillonite composite material is synthetic: take 1g montmorillonite standing 24h after mechanical agitation 48h in 100ml single port flask, by upper strata, scattered suspension is poured in the Tris-Hcl buffer solution that 250ml pH is 8.3, add vigorous stirring 24h after 2g P (CD-MA)-DA, finally product is out centrifugal and repeatedly washing.
2. cyclodextrin according to claim 1-montmorillonite mineral composite, is characterized in that cyclodextrin is alpha-cyclodextrin, beta-schardinger dextrin-or gamma-cyclodextrin.
3. cyclodextrin according to claim 1-montmorillonite mineral composite, the matter average molecular weight that it is characterized in that cyclodextrin P (CD-MA) is 1 * 10
4～1 * 10
5.
4. cyclodextrin according to claim 1-montmorillonite mineral composite, the content that it is characterized in that DA is 2%.
5. cyclodextrin according to claim 1-montmorillonite mineral composite, the content that it is characterized in that cyclodextrin is 10.6%, its structure is:
Be expressed as: PCD-MMT.
6. cyclodextrin/montmorillonite composite material according to claim 1, is characterized in that the access amount of cyclodextrin in composite can be controlled by the molecular weight that changes P (CD-MA), the content of DA and the content of montmorillonite; The advantage of this method is that raw material is easy to get, and with low cost, method is simple, and the CD of access measures many and easily control; This material energy adsorbing heavy metal ions in sewage and aromatic organic compounds, the maximal absorptive capacity that in the aqueous solution that is 6 left and right at pH, plumbous maximal absorptive capacity is the 207.14mg/g naphthylamines is 196.75mg/g; Can be used for the fields such as sewage disposal and purification of pharmaceuticals.
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Cited By (6)
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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 |
| CN107893337A (en) * | 2017-12-27 | 2018-04-10 | 安徽金润发制品有限公司 | A kind of wig coloring agent |
| CN109529790A (en) * | 2018-12-11 | 2019-03-29 | 北京理工大学 | A kind of styroflex adsorbent material, preparation and its application of surface grafting beta-cyclodextrin |
| CN113209710A (en) * | 2021-05-17 | 2021-08-06 | 绍兴文理学院 | Equipment for oil-water separation |
| CN113244898A (en) * | 2021-05-27 | 2021-08-13 | 江西理工大学 | Polydopamine-kaolin-Fe3O4Composite material and preparation method and application thereof |
| CN115463109A (en) * | 2022-09-24 | 2022-12-13 | 重庆医科大学 | Bionic fusion membrane coated uricase and catalase nanoparticles and preparation method thereof |
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Cited By (9)
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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 |
| CN104437414B (en) * | 2014-12-25 | 2017-05-17 | 江南大学 | Montmorillonite-reinforced polyethylene glycol/ cyclodextrin gel and preparation method thereof |
| CN107893337A (en) * | 2017-12-27 | 2018-04-10 | 安徽金润发制品有限公司 | A kind of wig coloring agent |
| CN107893337B (en) * | 2017-12-27 | 2020-07-28 | 安徽金润发制品有限公司 | Wig coloring agent |
| CN109529790A (en) * | 2018-12-11 | 2019-03-29 | 北京理工大学 | A kind of styroflex adsorbent material, preparation and its application of surface grafting beta-cyclodextrin |
| CN113209710A (en) * | 2021-05-17 | 2021-08-06 | 绍兴文理学院 | Equipment for oil-water separation |
| CN113244898A (en) * | 2021-05-27 | 2021-08-13 | 江西理工大学 | Polydopamine-kaolin-Fe3O4Composite material and preparation method and application thereof |
| CN115463109A (en) * | 2022-09-24 | 2022-12-13 | 重庆医科大学 | Bionic fusion membrane coated uricase and catalase nanoparticles and preparation method thereof |
| CN115463109B (en) * | 2022-09-24 | 2023-07-14 | 重庆医科大学 | Bionic fusion membrane coated uricase and catalase nanoparticle and preparation method thereof |
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