WO2020073674A1 - MAGNETIC CROSS-LINKED β-CYCLODEXTRIN POLYMER ADSORBENT AND PREPARATION METHOD THEREFOR - Google Patents

MAGNETIC CROSS-LINKED β-CYCLODEXTRIN POLYMER ADSORBENT AND PREPARATION METHOD THEREFOR Download PDF

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WO2020073674A1
WO2020073674A1 PCT/CN2019/091612 CN2019091612W WO2020073674A1 WO 2020073674 A1 WO2020073674 A1 WO 2020073674A1 CN 2019091612 W CN2019091612 W CN 2019091612W WO 2020073674 A1 WO2020073674 A1 WO 2020073674A1
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cross
cyclodextrin polymer
linked
magnetic
cyclodextrin
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PCT/CN2019/091612
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French (fr)
Chinese (zh)
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何富安
林杰赐
江洪流
谭宏伟
骆宇玮
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广东石油化工学院
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Publication of WO2020073674A1 publication Critical patent/WO2020073674A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry

Definitions

  • the invention relates to the technical field of functional materials, in particular to a magnetic cross-linked ⁇ -cyclodextrin polymer adsorbent and a preparation method thereof.
  • organic printing and dyeing wastewater accounts for about 35% of the discharged wastewater, and due to its complicated chemical structure, high stability, difficult to biodegrade, large color and high turbidity,
  • COD's advanced features have become one of the most difficult wastewaters to treat.
  • Many physical and chemical methods such as coagulation / flocculation treatment, chlorination, electrochemistry, photocatalytic degradation, adsorption, etc.
  • the adsorption method is one of the most effective methods because of its low cost, high efficiency, and easy regeneration.
  • various new types of dye adsorbents are being continuously developed, such as activated carbon, carbon aerogel, Fe 3 O 4 porous nanospheres, ZnCl 2 and activated coconut shell activated carbon, etc.
  • these adsorbents have better performance in the treatment of dye-containing wastewater, but they all have more or less certain limitations, such as: slower adsorption speed, less effective for removing relatively hydrophilic organic pollutants It requires a lot of energy for regeneration, the cost is higher, the adsorption effect after regeneration is significantly reduced, and recovery is difficult. Therefore, the development of high-efficiency dye adsorbents with good comprehensive performance is an important issue in academia and industry.
  • ⁇ -Cyclodextrin is a cyclic cavity oligomeric compound formed by seven glucopyranose units through ⁇ -1,4 glycosidic bonds.
  • the cavity of the cyclodextrin molecule is hydrophilic outside, and the inner wall of the cavity is hydrophobic due to the coverage of the hydrogen atoms by the oxygen atoms, so it can selectively accommodate various organic, inorganic, biological macromolecules and other guest molecules into the cavity. Form a stable host / guest supramolecular system.
  • various types of new cross-linked porous ⁇ -cyclodextrin polymers can be prepared as dye adsorbents.
  • the currently reported cross-linked ⁇ -CD polymers usually use epichlorohydrin, diisocyanate, di (poly) carboxylic acid, acid anhydride and acid chloride as cross-linking agents.
  • William R. Dichtel et al. Rotary removal of organic micropollutants from water by a porous ⁇ -cyclodextrin polymer, Nature, 2016, 529, 190–194
  • Aromatic groups were used to cross-link and couple ⁇ -cyclodextrin to obtain a novel ⁇ -cyclodextrin polymer containing nitrile groups.
  • the polymer has a high adsorption rate for various organic pollutants such as bisphenol A, antibiotics, organochlorine pesticides, etc., but its adsorption for cationic dyes is not good.
  • the purpose of the present invention is to provide a magnetic cross-linked ⁇ -cyclodextrin polymer adsorbent and preparation method thereof.
  • the magnetic cross-linked ⁇ -cyclodextrin polymer prepared by the present invention can effectively adsorb cationic dyes, And it can be magnetically recovered after adsorption.
  • the invention provides a method for preparing a magnetic cross-linked ⁇ -cyclodextrin polymer adsorbent, which includes the following steps:
  • step 3 Mix the hydrolysate obtained in step 2) with hydrochloric acid for neutralization reaction to obtain a cross-linked ⁇ -cyclodextrin polymer containing carboxyl groups;
  • step 3 Mix the carboxyl group-containing cross-linked ⁇ -cyclodextrin polymer, soluble ferric iron salt, soluble ferric iron salt, water and sodium hydroxide obtained in step 3), and load magnetic particles to obtain magnetic cross Bi-cyclodextrin polymer adsorbent.
  • the quantity ratio of the substances of tetrafluoroterephthalocyanine, ⁇ -cyclodextrin and potassium carbonate in the step 1) is 2: 0.7 ⁇ 1.1: 7 ⁇ 11.
  • the temperature of the cross-linking polymerization reaction in the step 1) is 82-90 ° C.
  • the time of the cross-linking polymerization reaction is 40-60 hours.
  • the dosage ratio of the cross-linked ⁇ -cyclodextrin polymer, sodium hydroxide, water and ethanol in step 2) is 0.2g: 8-10g: 30-40g: 40-50mL.
  • the temperature of the hydrolysis reaction in the step 2) is 100-120 ° C, and the time of the hydrolysis reaction is 20-30h.
  • the pH value of hydrochloric acid in step 3) is 4-5; the ratio of the amount of hydrochloric acid to the ⁇ -cyclodextrin polymer crosslinked with tetrafluoroterephthalonitrile in step 2) is 40- 50mL: 0.2g.
  • the temperature of the neutralization reaction in the step 3) is 100-120 ° C, and the time of the neutralization reaction is 2-5 hours.
  • the mass ratio of the cross-linked ⁇ -cyclodextrin polymer containing carboxyl group, soluble ferric iron salt, soluble ferric iron salt, water and sodium hydroxide in the step 4) is 0.1: 0.05-0.07: 0.13 ⁇ 0.19: 34 ⁇ 36: 4 ⁇ 6.
  • the temperature for loading the magnetic particles is 85 to 95 ° C., and the time for loading the magnetic particles is 20 to 30 h.
  • the invention also provides the magnetic cross-linked ⁇ -cyclodextrin polymer adsorbent prepared by the preparation method.
  • the invention provides a magnetic cross-linked ⁇ -cyclodextrin polymer adsorbent and a preparation method thereof.
  • the preparation method includes the following steps: mixing tetrafluoroterephthalocyanine, ⁇ -cyclodextrin, potassium carbonate and a solvent to perform Cross-linking polymerization reaction to obtain ⁇ -cyclodextrin polymer cross-linked with tetrafluoroterephthalonitrile; the solvent is a mixture of tetrahydrofuran and N, N-dimethylformamide; the obtained cross-linked ⁇ -cyclodextrin
  • the refined polymer, water, sodium hydroxide and ethanol are mixed to perform a hydrolysis reaction to obtain a hydrolysate; the hydrolysate is mixed with hydrochloric acid to perform a neutralization reaction to obtain a cross-linked ⁇ -cyclodextrin polymer containing a carboxyl group;
  • ⁇ -cyclodextrin poly and tetrafluoroterephthalonitrile are used as the polymerization monomers, and cross-linked ⁇ -cyclodextrin poly and tetrafluoroterephthalonitrile crosslinked ⁇ -cyclodextrin polymers are obtained by crosslinking polymerization, and then The carboxyl group is introduced into the skeleton of the polymer through hydrolysis.
  • the carboxylate anion after the carboxyl group is ionized in water is used as the site to adsorb the divalent iron cation and the trivalent iron cation and react with sodium hydroxide to realize the loading of the magnetic particles.
  • Magnetic cross-linked ⁇ -cyclodextrin polymer adsorbent.
  • the carboxyl group of the magnetic cross-linked ⁇ -cyclodextrin polymer adsorbent can be ionized in water and become a negatively charged carboxylate anion, it can effectively adsorb cationic dyes and can be magnetically recovered after adsorption.
  • FIG. 1 is a synthetic route diagram of CT- ⁇ -CD in Example 1;
  • 2 is an infrared spectrum diagram of magnetic CT- ⁇ -CD obtained by ⁇ -CD, TFPN, T- ⁇ -CD, CT- ⁇ -CD, and examples 1, 2, and 3;
  • Example 3 is a scanning electron microscope picture of the magnetic CT- ⁇ -CD obtained in Example 3;
  • FIG. 5 is a Zeta potential diagram of the magnetic CT- ⁇ -CD obtained in Examples 1 to 5.
  • FIG. 5 is a Zeta potential diagram of the magnetic CT- ⁇ -CD obtained in Examples 1 to 5.
  • the invention provides a method for preparing a magnetic cross-linked ⁇ -cyclodextrin polymer adsorbent, which includes the following steps:
  • step 3 Mix the hydrolysate obtained in step 2) with hydrochloric acid for neutralization reaction to obtain a cross-linked ⁇ -cyclodextrin polymer containing carboxyl groups;
  • tetrafluoroterephthalocyanine, ⁇ -cyclodextrin, potassium carbonate and a solvent are mixed for crosslinking polymerization to obtain a tetrafluoroterephthalonitrile crosslinked ⁇ -cyclodextrin polymer; the solvent is tetrahydrofuran With N, N-dimethylformamide.
  • the amount ratio of the substances of tetrafluoroterephthalocyanine, ⁇ -cyclodextrin and potassium carbonate is preferably 2: 0.7 to 1.1: 7 to 11, more preferably 2: 0.8 to 0.9: 8 to 9.
  • the volume ratio of the tetrahydrofuran to N, N-dimethylformamide is preferably 20 to 30: 5, and more preferably 25 to 27: 5.
  • the amount of the solvent is not particularly limited, and the amount well-known to those skilled in the art may be used.
  • the temperature of the crosslinking polymerization reaction is preferably 82 to 90 ° C, more preferably 85 ° C; the time of the crosslinking reaction is preferably 40 to 60h, more preferably 45 to 55h; the crosslinking The polymerization reaction was carried out under the protection of nitrogen.
  • the resulting reaction solid-liquid mixture after the cross-linking polymerization reaction, it is further preferred to sequentially cool the resulting reaction solid-liquid mixture to room temperature, first centrifugation, hydrochloric acid washing, second centrifugation, water washing, third centrifugation, tetrahydrofuran washing, and fourth centrifugation , Ethanol washing, fifth centrifugation and vacuum drying to obtain ⁇ -cyclodextrin polymer cross-linked with tetrafluoroterephthalonitrile.
  • the cooling method is not particularly limited, and a cooling method well known to those skilled in the art may be used.
  • the hydrochloric acid washing is to wash the solid obtained after the first centrifugation with hydrochloric acid.
  • the specific method of the hydrochloric acid washing is not particularly limited, and a method well known to those skilled in the art may be used.
  • the water washing is to wash the solid obtained by the second centrifugation.
  • the specific method of the water washing is not particularly limited, and a water washing method well known to those skilled in the art may be used.
  • the tetrahydrofuran washing is to wash the solid obtained by the third centrifugation with tetrahydrofuran.
  • the specific method for washing the tetrahydrofuran is not particularly limited, and a method well known to those skilled in the art may be used.
  • the ethanol washing is to wash the solid obtained by the fourth centrifugation with ethanol.
  • the specific method of the ethanol washing is not particularly limited, and a method well known to those skilled in the art may be used.
  • the rotation speeds of the first centrifugation, the second centrifugation, the third centrifugation, the fourth centrifugation, and the fifth centrifugation are independently 8000 to 10000 rpm, and the time is independently preferably 4 to 6 min.
  • the vacuum drying is preferably vacuum drying the solid obtained by the fifth centrifugation.
  • the temperature of the vacuum drying is preferably 60 to 70 ° C, more preferably 65 ° C; the time of the vacuum drying is preferably 10 to 20h, more preferably 12 to 15h.
  • the present invention mixes the obtained ⁇ -cyclodextrin polymer crosslinked with tetrafluoroterephthalonitrile, sodium hydroxide, water and ethanol Hydrolysis reaction to obtain hydrolysate.
  • the water is preferably deionized water.
  • the dosage ratio of the tetrafluoroterephthalonitrile cross-linked ⁇ -cyclodextrin polymer, sodium hydroxide, water and ethanol is preferably 0.2g: 8-10g: 30-40g: 40-50mL It is more preferably 0.2 g: 9 g: 35 to 37 g: 45 to 47 mL.
  • the temperature of the hydrolysis reaction is preferably 100 to 120 ° C, more preferably 110 to 115 ° C, and the time of the hydrolysis reaction is preferably 20 to 30h, more preferably 24h.
  • reaction solid-liquid product After the hydrolysis reaction, it is further preferred to sequentially cool the obtained reaction solid-liquid product to room temperature and centrifuge to obtain a hydrolysis product.
  • cooling rate and method are not particularly limited, and the rate and method well known to those skilled in the art may be used.
  • the solid obtained after the centrifugation is a hydrolysate.
  • the nitrile group of the ⁇ -cyclodextrin polymer crosslinked with tetrafluoroterephthalonitrile is converted into carboxylate ion through hydrolysis reaction, and then hydrochloric acid is added to mix to carry out the neutralization reaction to obtain a crosslinked ⁇ -ring containing a carboxyl group Dextrin polymer
  • the pH value of the hydrochloric acid is preferably 4 to 5; the ratio of the ⁇ -cyclodextrin polymer cross-linked between the hydrochloric acid and tetrafluoroterephthalonitrile is preferably 40 to 50 mL: 0.2 g, more preferably 45 mL: 0.2 g.
  • the temperature of the neutralization reaction is preferably 100 to 120 ° C, more preferably 110 to 115 ° C; and the time of the neutralization reaction is preferably 2 to 5 hours.
  • the neutralization reaction preferably further includes sequentially cooling the obtained reaction solid-liquid mixture to room temperature, first centrifugation, water washing, second centrifugation, ethanol washing, third centrifugation, and vacuum drying to obtain a carboxyl-containing cross ⁇ -cyclodextrin polymer.
  • cooling rate and method are not particularly limited, and the rate and method well known to those skilled in the art may be used.
  • the water washing is to wash the solid obtained after the first centrifugation.
  • the specific method of the water washing is not particularly limited, and a method well known to those skilled in the art may be used.
  • the ethanol washing is ethanol washing of the solid obtained by the second centrifugation.
  • the specific method of the ethanol washing is not particularly limited, and a method well known to those skilled in the art may be used.
  • the rotation speeds of the first centrifugation, the second centrifugation, and the third centrifugation are independently preferably 8000 to 10000 rpm, and the time is independently preferably 4 to 6 min.
  • the present invention will obtain the carboxyl group-containing cross-linked ⁇ -cyclodextrin polymer, soluble ferric salt, soluble ferric salt, water and sodium hydroxide After mixing, magnetic particles are loaded to obtain a magnetic cross-linked ⁇ -cyclodextrin polymer adsorbent.
  • the water is preferably deionized water.
  • the mass ratio of the carboxyl group-containing cross-linked ⁇ -cyclodextrin polymer, soluble divalent iron salt, soluble ferric iron salt, water and sodium hydroxide is preferably 0.1: 0.05 to 0.07: 0.13 to 0.19: 34 to 36: 4 to 6, more preferably 0.1: 0.06: 0.15 to 0.18: 35: 5.
  • the temperature at which the magnetic particles are loaded is preferably 80 to 100 ° C, more preferably 90 to 95 ° C; the time at which the magnetic particles are loaded is preferably 20 to 30 hours, and more preferably 24 to 26 hours.
  • the present invention after obtaining the carboxyl group-containing cross-linked ⁇ -cyclodextrin polymer, the present invention will obtain the carboxyl group-containing cross-linked ⁇ -cyclodextrin polymer, soluble divalent iron salt, soluble ferric iron salt,
  • the specific method of mixing a part of water and sodium hydroxide is to first mix the carboxyl group-containing cross-linked ⁇ -cyclodextrin polymer, soluble ferric iron salt, soluble ferric iron salt and water under stirring under nitrogen, and then mix The liquid and sodium hydroxide are mixed for co-precipitation to prepare magnetic particles, and at the same time, the magnetic particles are loaded.
  • the sodium hydroxide is preferably added in the form of an aqueous sodium hydroxide solution; in the present invention, the sodium hydroxide is mixed with the remaining part of water to obtain an aqueous sodium hydroxide solution.
  • the amount of the first part of water and the remaining part of the water is not particularly limited, and the amount well-known to those skilled in the art may be used.
  • the stirring method is not particularly limited, and the stirring method well known to those skilled in the art may be selected.
  • the stirring time is preferably 25 to 40 minutes, and more preferably 30 to 35 minutes.
  • the co-precipitation is preferably carried out under stirring conditions.
  • the stirring method is not particularly limited, and the stirring method well known to those skilled in the art may be selected.
  • the loading of the magnetic particles preferably further includes sequentially cooling the solid-liquid mixture obtained after loading the magnetic particles to room temperature, magnetic separation, water washing, ethanol washing, and drying to obtain magnetic cross-linked ⁇ -cyclodextrin polymer Sorbent.
  • cooling rate and method are not particularly limited, and the rate and method well known to those skilled in the art may be used.
  • the magnetic separation is preferably close to the outer wall of the beaker with a magnet, the magnetic cross-linked ⁇ -cyclodextrin polymer adsorbent is deposited on the wall of the beaker, and after 2 to 5 minutes of attraction, the clear solution is poured off.
  • the water washing is to wash the product obtained after magnetic separation.
  • the method for water washing is not particularly limited in the present invention, and a water washing method well known to those skilled in the art may be used.
  • the method for ethanol washing is not particularly limited in the present invention, and the ethanol washing method well known to those skilled in the art may be used.
  • the invention also provides the magnetic cross-linked ⁇ -cyclodextrin polymer adsorbent prepared by the preparation method.
  • TFPN tetrafluoroterephthalocyanine
  • ⁇ -CD ⁇ -cyclodextrin
  • K 2 CO 3 1.23g, 0.0089mol
  • T- ⁇ - CD tetrafluoroterephthalocyanine-crosslinked ⁇ -cyclodextrin polymer
  • the adsorption capacity of the obtained T- ⁇ -CD was only 140.0mg / g (adsorption experiment conditions: methylene blue solution 25mL, methylene blue solution concentration 80mg / L, T- ⁇ -CD dosage 10mg, adsorption time 3h), the removal of methylene blue in water The rate is only 70.0 wt.%.
  • T- ⁇ -CD (0.2g) was added to a 250mL glass flask, followed by deionized aqueous solution (40g) containing 20wt.% Sodium hydroxide and ethanol (40mL), and refluxed at 120 ° C for 24h.
  • CT- ⁇ -CD carboxyl-containing cross-linked ⁇ -cyclodextrin polymer
  • magnetic CT- ⁇ -CD magnetic cross-linked ⁇ -cyclodextrin polymer
  • the adsorption capacity of the obtained magnetic CT- ⁇ -CD to methylene blue in water was 198.2mg / g, and the removal rate was 99.1wt.% (Adsorption experiment conditions: methylene blue solution 25mL, methylene blue solution concentration 80mg / L, magnetic CT- ⁇ -CD dosage 10mg, adsorption time 30min).
  • Step 1) and step 2) are the same as Example 1, and step 3) is as follows:
  • the mass ratio of generated Fe 3 O 4 to the fed CT- ⁇ -CD is 0.7: 1, add FeCl 2 ⁇ 4H 2 O (0.0600g), FeCl to a 100mL glass flask 3 ⁇ 6H 2 O (0.1631g), CT- ⁇ -CD (0.1g), deionized water (20mL), evacuated and flushed with nitrogen for protection, stirred for 30min to prepare a mixed solution, and then injected with 20wt% sodium hydroxide The deionized aqueous solution (20g) was filled with nitrogen at 90 ° C to protect and stir the reaction for 24h.
  • the adsorption capacity of the obtained magnetic CT- ⁇ -CD was 198.4mg / g (adsorption experiment conditions: methylene blue solution 25mL, methylene blue solution concentration 80mg / L, magnetic CT- ⁇ -CD dosage 10mg, adsorption time 30min), the migration of methylene blue in water The removal rate is 99.2 wt.%.
  • Step 1) and step 2) are the same as Example 1, and step 3) is as follows:
  • the mass ratio of generated Fe 3 O 4 to the fed CT- ⁇ -CD is 0.6: 1, add FeCl 2 ⁇ 4H 2 O (0.0514g), FeCl to a 100mL glass flask 3 ⁇ 6H 2 O (0.1398g), CT- ⁇ -CD (0.1g), deionized water (20mL), evacuated and purged with nitrogen protection, stirred for 30min to prepare a mixed solution, and then injected with 20wt% sodium hydroxide The deionized aqueous solution (20g) was filled with nitrogen at 90 ° C to protect and stir the reaction for 24h.
  • T- ⁇ -CD has both infrared characteristic peaks of ⁇ -CD and TFPN, which proves that ⁇ -CD and TFPN successfully prepared T- ⁇ -CD through cross-linking reaction; while CT- ⁇ -CD and T- Compared with ⁇ -CD, its infrared peak intensity at 2248 cm-1 is significantly weakened and its infrared peak intensity at 1685 cm-1 is significantly enhanced, which proves that the nitrile group of T- ⁇ -CD is treated with sodium hydroxide and hydrochloric acid in sequence.
  • CT- ⁇ -CD It has been converted to a carboxyl group to obtain CT- ⁇ -CD; in addition to the infrared characteristic peak of CT- ⁇ -CD, magnetic CT- ⁇ -CD also has an infrared characteristic peak of Fe 3 O 4 at 580 cm-1, which proves The loading of magnetic particles was successful.
  • the scanning electron micrograph of the obtained magnetic CT- ⁇ -CD is shown in FIG. 3, and it can be seen from FIG. 3 that a large number of magnetic particles are loaded on the CT- ⁇ -CD.
  • the adsorption capacity of the obtained magnetic CT- ⁇ -CD was 198.8mg / g (adsorption experiment conditions: methylene blue solution 25mL, methylene blue solution concentration 80mg / L magnetic CT- ⁇ -CD dosage 10mg, adsorption time 30min), the removal of methylene blue in water The rate is 99.4 wt.%.
  • T- ⁇ -CD (0.2g) was added to a 250mL glass flask, followed by deionized aqueous solution (40g) containing 20wt.% Sodium hydroxide and ethanol (40mL), and refluxed at 120 ° C for 24h.
  • the adsorption capacity of the obtained magnetic CT- ⁇ -CD was 187.2mg / g (adsorption experiment conditions: methylene blue solution 25mL, methylene blue solution concentration 80mg / L, magnetic CT- ⁇ -CD dosage 10mg, adsorption time 30min), the migration of methylene blue in water The removal rate is 93.6 wt.%.
  • the adsorption capacity of the obtained magnetic CT- ⁇ -CD was 197.5mg / g (adsorption experiment conditions: methylene blue solution 25mL, methylene blue solution concentration 80mg / L, magnetic CT- ⁇ -CD dosage 10mg, adsorption time 30min), the migration of methylene blue in water The removal rate is 98.75wt.%.
  • the magnetic saturation intensity of the magnetic CT- ⁇ -CD obtained in Examples 1 to 5 was measured using a vibrating sample magnetometer. The results are shown in FIG. 4. From FIG. 4, the magnetic saturation intensity of Examples 1 to 5 is respectively It is 24.0emu / g, 19.1emu / g, 16.6emu / g, 23.4emu / g, 24.3emu / g, indicating that they all have magnetic function and can be recovered after adsorption treatment.
  • the potentials of the magnetic CT- ⁇ -CD obtained in Examples 1 to 5 were measured. The results are shown in FIG. 5, and from FIG. 5, the Zeta potentials of the magnetic CT- ⁇ -CD in Examples 1 to 5 were: -17.7mV, -23.6mV, -27.6mV, -13.4mV, -29.8mV, indicating that the surface of the magnetic CT- ⁇ -CD is negatively charged because it contains ionizable carboxyl groups, which can better absorb methylene blue cations in water Type dye, so the adsorption capacity is better than T- ⁇ -CD.

Abstract

Provided are a magnetic cross-linked β-cyclodextrin polymer adsorbent and a preparation method therefor. The method comprises: using β-cyclodextrin and tetrafluoroterephthalonitrile as polymerization monomers; cross-linking and polymerizing to obtain a tetrafluoroterephthalonitrile-crosslinked β-cyclodextrin polymer; then introducing carboxyl groups onto a backbone of the cross-linked β-cyclodextrin polymer by means of hydrolysis; using carboxylate anions of the carboxyl groups ionized in water as sites to adsorb divalent iron cations and trivalent iron cations and react with sodium hydroxide to achieve the loading of magnetic particles; and finally obtaining a magnetic cross-linked β-cyclodextrin polymer adsorbent. Since the carboxyl group of the magnetic cross-linked β-cyclodextrin polymer adsorbent may generate negatively charged carboxylate anions after ionization in water, the present adsorbent may effectively adsorb cationic dyes, and magnetic recovery may be performed after adsorption.

Description

[根据细则37.2由ISA制定的发明名称]　磁性交联β-环糊精聚合物吸附剂及其制备方法 [Name of invention formulated by ISA according to Rule 37.2] Magnetic cross-linked β-cyclodextrin polymer adsorbent and its preparation method 技术领域Technical field
本发明涉及功能材料技术领域，特别涉及一种磁性交联β-环糊精聚合物吸附剂及其制备方法。The invention relates to the technical field of functional materials, in particular to a magnetic cross-linked β-cyclodextrin polymer adsorbent and a preparation method thereof.
背景技术Background technique
水体污染已成为全球关注的重大环境问题，其中有机染料污染物废水处理是治理难点之一。据统计，在排放的废水中有机印染废水占到35％左右，且因其化学结构复杂，稳定性高，难以生化降解，色度大，浊度高，Water pollution has become a major environmental issue of global concern, and the treatment of organic dye pollutant wastewater is one of the difficulties in governance. According to statistics, organic printing and dyeing wastewater accounts for about 35% of the discharged wastewater, and due to its complicated chemical structure, high stability, difficult to biodegrade, large color and high turbidity,
COD高等特点，已经成为当前最难处理的废水之一。众多物理和化学方法(如混凝/絮凝处理法、氯化、电化学、光催化降解、吸附等)已被应用于去除废水中的染料。其中吸附法因成本低、效率高、易于再生等特点成为最有效的方法之一。目前，各类新型的染料吸附剂正被不断地开发，如活性炭、碳气凝胶、Fe 3 O 4 多孔纳米球、ZnCl 2 及活化的椰壳活性炭等。总体而言，这些吸附剂在处理含染料废水方面具有较好的性能，但都或多或少存在一定的局限性，如：吸附速度较慢，对于相对亲水的有机污染物去除效果不明显，再生需要消耗大量能量，成本较高，再生后的吸附效果明显下降，回收困难等。因此，开发综合性能良好的高效染料吸附剂是学术界和工业界的一个重要课题。COD's advanced features have become one of the most difficult wastewaters to treat. Many physical and chemical methods (such as coagulation / flocculation treatment, chlorination, electrochemistry, photocatalytic degradation, adsorption, etc.) have been applied to remove dyes from wastewater. Among them, the adsorption method is one of the most effective methods because of its low cost, high efficiency, and easy regeneration. At present, various new types of dye adsorbents are being continuously developed, such as activated carbon, carbon aerogel, Fe 3 O 4 porous nanospheres, ZnCl 2 and activated coconut shell activated carbon, etc. In general, these adsorbents have better performance in the treatment of dye-containing wastewater, but they all have more or less certain limitations, such as: slower adsorption speed, less effective for removing relatively hydrophilic organic pollutants It requires a lot of energy for regeneration, the cost is higher, the adsorption effect after regeneration is significantly reduced, and recovery is difficult. Therefore, the development of high-efficiency dye adsorbents with good comprehensive performance is an important issue in academia and industry.
β-环糊精(β-CD)是由七个吡喃葡萄糖单元通过α-l,4糖苷键形成的环状腔型低聚化合物。环糊精分子的空腔外部具有亲水性，空腔内壁则由于氢原子对氧原子的覆盖而疏水，因此可以选择性地容纳各种有机、无机、生物大分子等客体分子进入空腔，形成一种稳定的主/客体超分子体系。更为重要的是：通过不同交联剂的使用，可以制备各类新型的交联型多孔β-环糊精高聚物作为染料吸附剂。目前已报道的交联型β-CD聚合物通常采用环氧氯丙烷、二异氰酸酯、二(多)元羧酸、酸酐和酰氯等作为交联剂。William R.Dichtel等(Rapid removal of organic micropollutants from water by a porousβ-cyclodextrinpolymer,Nature,2016,529,190–194)利用芳香基团使β-环糊精交联耦合，得到了一种新型的含有腈基的β-环糊精聚合物。该聚合物对多种有机污染物如双酚A，抗生素，有机氯农药等具有很高的吸附率，但是其对阳离子染料的吸附性不好。β-Cyclodextrin (β-CD) is a cyclic cavity oligomeric compound formed by seven glucopyranose units through α-1,4 glycosidic bonds. The cavity of the cyclodextrin molecule is hydrophilic outside, and the inner wall of the cavity is hydrophobic due to the coverage of the hydrogen atoms by the oxygen atoms, so it can selectively accommodate various organic, inorganic, biological macromolecules and other guest molecules into the cavity. Form a stable host / guest supramolecular system. More importantly: through the use of different cross-linking agents, various types of new cross-linked porous β-cyclodextrin polymers can be prepared as dye adsorbents. The currently reported cross-linked β-CD polymers usually use epichlorohydrin, diisocyanate, di (poly) carboxylic acid, acid anhydride and acid chloride as cross-linking agents. William R. Dichtel et al. (Rapid removal of organic micropollutants from water by a porous β-cyclodextrin polymer, Nature, 2016, 529, 190–194) Aromatic groups were used to cross-link and couple β-cyclodextrin to obtain a novel β-cyclodextrin polymer containing nitrile groups. The polymer has a high adsorption rate for various organic pollutants such as bisphenol A, antibiotics, organochlorine pesticides, etc., but its adsorption for cationic dyes is not good.
技术问题technical problem
有鉴于此，本发明目的在于提供一种磁性交联β-环糊精聚合物吸附剂及其制备方法，本发明制备得到的磁性交联β-环糊精聚合物可有效吸附阳离子型染料，且吸附后可进行磁回收。In view of this, the purpose of the present invention is to provide a magnetic cross-linked β-cyclodextrin polymer adsorbent and preparation method thereof. The magnetic cross-linked β-cyclodextrin polymer prepared by the present invention can effectively adsorb cationic dyes, And it can be magnetically recovered after adsorption.
技术解决方案Technical solution
本发明提供了一种磁性交联β-环糊精聚合物吸附剂的制备方法，包括以下步骤：The invention provides a method for preparing a magnetic cross-linked β-cyclodextrin polymer adsorbent, which includes the following steps:
1)将四氟对苯二氰、β-环糊精、碳酸钾和溶剂混合进行交联聚合反应，得到四氟对苯二腈交联的β-环糊精聚合物；所述溶剂为四氢呋喃和N，N-二甲基甲酰胺的混合物；1) Mixing tetrafluoroterephthalocyanine, β-cyclodextrin, potassium carbonate and a solvent for crosslinking polymerization to obtain a β-cyclodextrin polymer crosslinked with tetrafluoroterephthalonitrile; the solvent is tetrahydrofuran With N, N-dimethylformamide;
2)将所述步骤1)得到的四氟对苯二腈交联的β-环糊精聚合物、氢氧化钠、水和乙醇混合进行水解反应，得到水解产物；2) The tetrafluoroterephthalonitrile cross-linked β-cyclodextrin polymer obtained in the above step 1), sodium hydroxide, water and ethanol are mixed for hydrolysis reaction to obtain a hydrolysate;
3)将所述步骤2)得到的水解产物与盐酸混合进行中和反应，得到含有羧基的交联β-环糊精聚合物；3) Mix the hydrolysate obtained in step 2) with hydrochloric acid for neutralization reaction to obtain a cross-linked β-cyclodextrin polymer containing carboxyl groups;
4)将所述步骤3)得到的含有羧基的交联β-环糊精聚合物、可溶性二价铁盐、可溶性三价铁盐、水和氢氧化钠混合后进行磁性粒子负载，得到磁性交联β-环糊精聚合物吸附剂。4) Mix the carboxyl group-containing cross-linked β-cyclodextrin polymer, soluble ferric iron salt, soluble ferric iron salt, water and sodium hydroxide obtained in step 3), and load magnetic particles to obtain magnetic cross Bi-cyclodextrin polymer adsorbent.
优选地，所述步骤1)中四氟对苯二氰、β-环糊精和碳酸钾的物质的量比为2：0.7～1.1：7～11。Preferably, the quantity ratio of the substances of tetrafluoroterephthalocyanine, β-cyclodextrin and potassium carbonate in the step 1) is 2: 0.7 ～ 1.1: 7 ～ 11.
优选地，所述步骤1)中交联聚合反应的温度为82～90℃，交联聚合反应的时间为40～60h。Preferably, the temperature of the cross-linking polymerization reaction in the step 1) is 82-90 ° C., and the time of the cross-linking polymerization reaction is 40-60 hours.
优选地，所述步骤2)中交联β-环糊精聚合物、氢氧化钠、水和乙醇的用量比为0.2g：8～10g：30～40g：40～50mL。Preferably, the dosage ratio of the cross-linked β-cyclodextrin polymer, sodium hydroxide, water and ethanol in step 2) is 0.2g: 8-10g: 30-40g: 40-50mL.
优选地，所述步骤2)中水解反应的温度为100～120℃，水解反应的时间为20～30h。Preferably, the temperature of the hydrolysis reaction in the step 2) is 100-120 ° C, and the time of the hydrolysis reaction is 20-30h.
优选地，所述步骤3)中盐酸的pH值为4～5；所述盐酸与所述步骤2)中四氟对苯二腈交联的β-环糊精聚合物的用量比为40～50mL：0.2g。Preferably, the pH value of hydrochloric acid in step 3) is 4-5; the ratio of the amount of hydrochloric acid to the β-cyclodextrin polymer crosslinked with tetrafluoroterephthalonitrile in step 2) is 40- 50mL: 0.2g.
优选地，所述步骤3)中中和反应的温度为100～120℃，中和反应的时间为2～5h。Preferably, the temperature of the neutralization reaction in the step 3) is 100-120 ° C, and the time of the neutralization reaction is 2-5 hours.
优选地，所述步骤4)中含有羧基的交联β-环糊精聚合物、可溶性二价铁盐、可溶性三价铁盐、水和氢氧化钠的质量比为0.1：0.05～0.07：0.13～0.19：34～36：4～6。Preferably, the mass ratio of the cross-linked β-cyclodextrin polymer containing carboxyl group, soluble ferric iron salt, soluble ferric iron salt, water and sodium hydroxide in the step 4) is 0.1: 0.05-0.07: 0.13 ~ 0.19: 34 ~ 36: 4 ~ 6.
优选地，所述步骤4)中磁性粒子负载的温度为85～95℃，磁性粒子负载的时间为20～30h。Preferably, in step 4), the temperature for loading the magnetic particles is 85 to 95 ° C., and the time for loading the magnetic particles is 20 to 30 h.
本发明还提供了上述制备方法制备得到的磁性交联β-环糊精聚合物吸附剂。The invention also provides the magnetic cross-linked β-cyclodextrin polymer adsorbent prepared by the preparation method.
 A
有益效果Beneficial effect
本发明提供了一种磁性交联β-环糊精聚合物吸附剂及其制备方法，其制备方法包括以下步骤：将四氟对苯二氰、β-环糊精、碳酸钾和溶剂混合进行交联聚合反应，得到四氟对苯二腈交联的β-环糊精聚合物；所述溶剂为四氢呋喃和N，N-二甲基甲酰胺的混合物；将得到的交联β-环糊精聚合物、水、氢氧化钠和乙醇混合进行水解反应，得到水解产物；将水解产物与盐酸混合进行中和反应，得到含有羧基的交联β-环糊精聚合物；将得到的含有羧基的交联β-环糊精聚合物、可溶性二价铁盐、可溶性三价铁盐、水和氢氧化钠混合后进行磁性粒子负载，得到磁性交联β-环糊精聚合物吸附剂。本发明以β-环糊精聚和四氟对苯二腈为聚合单体，交联聚合得到β-环糊精聚和四氟对苯二腈的交联β-环糊精聚合物，再通过水解将羧基引入到聚合物的骨架上，以羧基在水中电离后的羧酸根阴离子为位点吸附二价铁阳离子与三价铁阳离子并与氢氧化钠反应实现磁性粒子的负载，最终得到新型磁性交联β-环糊精聚合物吸附剂。由于磁性交联β-环糊精聚合物吸附剂的羧基能在水中电离后成为带负电荷的羧酸根阴离子，可有效吸附阳离子型染料，且吸附后可进行磁回收。The invention provides a magnetic cross-linked β-cyclodextrin polymer adsorbent and a preparation method thereof. The preparation method includes the following steps: mixing tetrafluoroterephthalocyanine, β-cyclodextrin, potassium carbonate and a solvent to perform Cross-linking polymerization reaction to obtain β-cyclodextrin polymer cross-linked with tetrafluoroterephthalonitrile; the solvent is a mixture of tetrahydrofuran and N, N-dimethylformamide; the obtained cross-linked β-cyclodextrin The refined polymer, water, sodium hydroxide and ethanol are mixed to perform a hydrolysis reaction to obtain a hydrolysate; the hydrolysate is mixed with hydrochloric acid to perform a neutralization reaction to obtain a cross-linked β-cyclodextrin polymer containing a carboxyl group; The cross-linked β-cyclodextrin polymer, soluble ferric iron salt, soluble ferric iron salt, water and sodium hydroxide are mixed and then magnetic particles are loaded to obtain a magnetic cross-linked β-cyclodextrin polymer adsorbent. In the invention, β-cyclodextrin poly and tetrafluoroterephthalonitrile are used as the polymerization monomers, and cross-linked β-cyclodextrin poly and tetrafluoroterephthalonitrile crosslinked β-cyclodextrin polymers are obtained by crosslinking polymerization, and then The carboxyl group is introduced into the skeleton of the polymer through hydrolysis. The carboxylate anion after the carboxyl group is ionized in water is used as the site to adsorb the divalent iron cation and the trivalent iron cation and react with sodium hydroxide to realize the loading of the magnetic particles. Magnetic cross-linked β-cyclodextrin polymer adsorbent. Since the carboxyl group of the magnetic cross-linked β-cyclodextrin polymer adsorbent can be ionized in water and become a negatively charged carboxylate anion, it can effectively adsorb cationic dyes and can be magnetically recovered after adsorption.
附图说明BRIEF DESCRIPTION
图1为实施例1中CT-β-CD的合成路线图；FIG. 1 is a synthetic route diagram of CT-β-CD in Example 1;
图2为β-CD，TFPN，T-β-CD，CT-β-CD，实施例1，2，3得到的磁性CT-β-CD的红外光谱图；2 is an infrared spectrum diagram of magnetic CT-β-CD obtained by β-CD, TFPN, T-β-CD, CT-β-CD, and examples 1, 2, and 3;
图3为实施例3中得到的磁性CT-β-CD的扫描电镜图片；3 is a scanning electron microscope picture of the magnetic CT-β-CD obtained in Example 3;
图4为实施例1～5得到的磁性CT-β-CD的磁饱和强度图；4 is a graph of magnetic saturation intensity of the magnetic CT-β-CD obtained in Examples 1 to 5;
图5为实施例1～5中得到的磁性CT-β-CD的Zeta电位图。5 is a Zeta potential diagram of the magnetic CT-β-CD obtained in Examples 1 to 5. FIG.
本发明的实施方式Embodiments of the invention
本发明提供了一种磁性交联β-环糊精聚合物吸附剂的制备方法，包括以下步骤：The invention provides a method for preparing a magnetic cross-linked β-cyclodextrin polymer adsorbent, which includes the following steps:
1)将四氟对苯二氰、β-环糊精、碳酸钾和溶剂混合进行交联聚合反应，得到四氟对苯二腈交联的β-环糊精聚合物；所述溶剂为四氢呋喃和N，N-二甲基甲酰胺的混合物；1) Mixing tetrafluoroterephthalocyanine, β-cyclodextrin, potassium carbonate and a solvent for crosslinking polymerization to obtain a β-cyclodextrin polymer crosslinked with tetrafluoroterephthalonitrile; the solvent is tetrahydrofuran With N, N-dimethylformamide;
2)将所述步骤1)得到的四氟对苯二腈交联的β-环糊精聚合物、氢氧化钠、水和乙醇混合进行水解反应，得到水解产物；2) The tetrafluoroterephthalonitrile cross-linked β-cyclodextrin polymer obtained in the above step 1), sodium hydroxide, water and ethanol are mixed for hydrolysis reaction to obtain a hydrolysate;
3)将所述步骤2)得到的水解产物与盐酸混合进行中和反应，得到含有羧基的交联β-环糊精聚合物；3) Mix the hydrolysate obtained in step 2) with hydrochloric acid for neutralization reaction to obtain a cross-linked β-cyclodextrin polymer containing carboxyl groups;
4)将所述步骤3)中得到的含有羧基的交联β-环糊精聚合物、可溶性二价铁盐、可溶性三价铁盐、水和氢氧化钠混合后进行磁性粒子负载，得到磁性交联β-环糊精聚合物吸附剂。4) Mix the carboxyl-containing cross-linked β-cyclodextrin polymer obtained in the above step 3), soluble ferric iron salt, soluble ferric iron salt, water and sodium hydroxide, and load magnetic particles to obtain magnetic properties Cross-linked β-cyclodextrin polymer adsorbent.
本发明将四氟对苯二氰、β-环糊精、碳酸钾和溶剂混合进行交联聚合反应，得到四氟对苯二腈交联的β-环糊精聚合物；所述溶剂为四氢呋喃和N，N-二甲基甲酰胺的混合物。In the present invention, tetrafluoroterephthalocyanine, β-cyclodextrin, potassium carbonate and a solvent are mixed for crosslinking polymerization to obtain a tetrafluoroterephthalonitrile crosslinked β-cyclodextrin polymer; the solvent is tetrahydrofuran With N, N-dimethylformamide.
在本发明中，所述四氟对苯二氰、β-环糊精和碳酸钾的物质的量比优选为2：0.7～1.1：7～11，更优选为2：0.8～0.9：8～9。In the present invention, the amount ratio of the substances of tetrafluoroterephthalocyanine, β-cyclodextrin and potassium carbonate is preferably 2: 0.7 to 1.1: 7 to 11, more preferably 2: 0.8 to 0.9: 8 to 9.
在本发明中，所述四氢呋喃和N，N-二甲基甲酰胺的体积比优选为20～30：5，更优选为25～27：5。本发明对所述溶剂的用量没有特殊限定，选用本领域技术人员熟知的用量即可。In the present invention, the volume ratio of the tetrahydrofuran to N, N-dimethylformamide is preferably 20 to 30: 5, and more preferably 25 to 27: 5. In the present invention, the amount of the solvent is not particularly limited, and the amount well-known to those skilled in the art may be used.
在本发明中，所述交联聚合反应的温度优选为82～90℃，更优选为85℃；所述交联反应的时间优选为40～60h，更优选为45～55h；所述交联聚合反应在氮气保护下进行。In the present invention, the temperature of the crosslinking polymerization reaction is preferably 82 to 90 ° C, more preferably 85 ° C; the time of the crosslinking reaction is preferably 40 to 60h, more preferably 45 to 55h; the crosslinking The polymerization reaction was carried out under the protection of nitrogen.
在本发明中，所述交联聚合反应后还优选包括对所得反应固液混合物依次进行冷却至室温、第一离心、盐酸洗涤、第二离心、水洗、第三离心、四氢呋喃洗涤、第四离心、乙醇洗涤、第五离心和真空干燥，得到交四氟对苯二腈交联的β-环糊精聚合物。In the present invention, after the cross-linking polymerization reaction, it is further preferred to sequentially cool the resulting reaction solid-liquid mixture to room temperature, first centrifugation, hydrochloric acid washing, second centrifugation, water washing, third centrifugation, tetrahydrofuran washing, and fourth centrifugation , Ethanol washing, fifth centrifugation and vacuum drying to obtain β-cyclodextrin polymer cross-linked with tetrafluoroterephthalonitrile.
本发明对冷却的方法没有特殊限定，选用本领域技术人员熟知的冷却方法即可。In the present invention, the cooling method is not particularly limited, and a cooling method well known to those skilled in the art may be used.
在本发明中，所述盐酸洗涤为将第一离心后所得固体进行盐酸洗涤。本发明对所述盐酸洗涤的具体方法没有特殊限定，选用本领域技术人员熟知的方法即可。In the present invention, the hydrochloric acid washing is to wash the solid obtained after the first centrifugation with hydrochloric acid. In the present invention, the specific method of the hydrochloric acid washing is not particularly limited, and a method well known to those skilled in the art may be used.
在本发明中，所述水洗为将第二离心所得固体进行水洗。本发明对所述水洗的具体方法没有特殊限定，选用本领域技术人员熟知的水洗方法即可。In the present invention, the water washing is to wash the solid obtained by the second centrifugation. In the present invention, the specific method of the water washing is not particularly limited, and a water washing method well known to those skilled in the art may be used.
在本发明中，所述四氢呋喃洗涤为将第三离心所得固体进行四氢呋喃洗涤。本发明对所述四氢呋喃洗涤的具体方法没有特殊限定，选用本领域技术人员熟知的方法即可。In the present invention, the tetrahydrofuran washing is to wash the solid obtained by the third centrifugation with tetrahydrofuran. In the present invention, the specific method for washing the tetrahydrofuran is not particularly limited, and a method well known to those skilled in the art may be used.
在本发明中，所述乙醇洗涤为将第四离心所得固体进行乙醇洗涤。本发明对所述乙醇洗涤的具体方法没有特殊限定，选用本领域技术人员熟知的方法即可。In the present invention, the ethanol washing is to wash the solid obtained by the fourth centrifugation with ethanol. In the present invention, the specific method of the ethanol washing is not particularly limited, and a method well known to those skilled in the art may be used.
在本发明中，所述第一离心、第二离心、第三离心、第四离心和第五离心的转速独立地优选为8000～10000rpm，时间独立地优选为4～6min。In the present invention, the rotation speeds of the first centrifugation, the second centrifugation, the third centrifugation, the fourth centrifugation, and the fifth centrifugation are independently 8000 to 10000 rpm, and the time is independently preferably 4 to 6 min.
在本发明中，所述真空干燥优选为对第五离心所得固体进行真空干燥。所述真空干燥的温度优选为60～70℃，更优选为65℃；所述真空干燥的时间优选为10～20h，更优选为12～15h。In the present invention, the vacuum drying is preferably vacuum drying the solid obtained by the fifth centrifugation. The temperature of the vacuum drying is preferably 60 to 70 ° C, more preferably 65 ° C; the time of the vacuum drying is preferably 10 to 20h, more preferably 12 to 15h.
得到四氟对苯二腈交联的β-环糊精聚合物后，本发明将得到的四氟对苯二腈交联的β-环糊精聚合物、氢氧化钠、水和乙醇混合进行水解反应，得到水解产物。After obtaining the β-cyclodextrin polymer crosslinked with tetrafluoroterephthalonitrile, the present invention mixes the obtained β-cyclodextrin polymer crosslinked with tetrafluoroterephthalonitrile, sodium hydroxide, water and ethanol Hydrolysis reaction to obtain hydrolysate.
在本发明中，所述水优选为去离子水。In the present invention, the water is preferably deionized water.
在本发明中，所述四氟对苯二腈交联的β-环糊精聚合物、氢氧化钠、水和乙醇的用量比优选为0.2g：8～10g：30～40g：40～50mL，更优选为0.2g：9g：35～37g：45～47mL。In the present invention, the dosage ratio of the tetrafluoroterephthalonitrile cross-linked β-cyclodextrin polymer, sodium hydroxide, water and ethanol is preferably 0.2g: 8-10g: 30-40g: 40-50mL It is more preferably 0.2 g: 9 g: 35 to 37 g: 45 to 47 mL.
在本发明中，所述水解反应的温度优选为100～120℃，更优选为110～115℃，所述水解反应的时间优选为20～30h，更优选为24h。In the present invention, the temperature of the hydrolysis reaction is preferably 100 to 120 ° C, more preferably 110 to 115 ° C, and the time of the hydrolysis reaction is preferably 20 to 30h, more preferably 24h.
在本发明中，所述水解反应后还优选包括对所得反应固液产物依次冷却至室温和离心，得到水解产物。In the present invention, after the hydrolysis reaction, it is further preferred to sequentially cool the obtained reaction solid-liquid product to room temperature and centrifuge to obtain a hydrolysis product.
本发明对冷却的速率和方法没有特殊限定，选用本领域技术人员熟知的速率和方法即可。In the present invention, the cooling rate and method are not particularly limited, and the rate and method well known to those skilled in the art may be used.
在本发明中，所述离心后所得固体为水解产物。In the present invention, the solid obtained after the centrifugation is a hydrolysate.
本发明通过水解反应将四氟对苯二腈交联的β-环糊精聚合物的腈基转变为羧酸根离子，然后再加入盐酸混合进行中和反应，得到含有羧基的交联β-环糊精聚合物；In the present invention, the nitrile group of the β-cyclodextrin polymer crosslinked with tetrafluoroterephthalonitrile is converted into carboxylate ion through hydrolysis reaction, and then hydrochloric acid is added to mix to carry out the neutralization reaction to obtain a crosslinked β-ring containing a carboxyl group Dextrin polymer
在本发明中，所述盐酸的pH值优选为4～5；所述盐酸与四氟对苯二腈交联的β-环糊精聚合物的用来那个比为优选为40～50mL：0.2g，更优选为45mL：0.2g。In the present invention, the pH value of the hydrochloric acid is preferably 4 to 5; the ratio of the β-cyclodextrin polymer cross-linked between the hydrochloric acid and tetrafluoroterephthalonitrile is preferably 40 to 50 mL: 0.2 g, more preferably 45 mL: 0.2 g.
在本发明中，所述中和反应的温度优选为100～120℃，更优选为110～115℃；所述中和反应的时间优选为2～5h。In the present invention, the temperature of the neutralization reaction is preferably 100 to 120 ° C, more preferably 110 to 115 ° C; and the time of the neutralization reaction is preferably 2 to 5 hours.
在本发明中，所述中和反应后还优选包括对所得反应固液混合物依次冷却至室温、第一离心、水洗、第二离心、乙醇洗涤、第三离心和真空干燥，得到含有羧基的交联β-环糊精聚合物。In the present invention, the neutralization reaction preferably further includes sequentially cooling the obtained reaction solid-liquid mixture to room temperature, first centrifugation, water washing, second centrifugation, ethanol washing, third centrifugation, and vacuum drying to obtain a carboxyl-containing cross Β-cyclodextrin polymer.
本发明对冷却的速率和方法没有特殊限定，选用本领域技术人员熟知的速率和方法即可In the present invention, the cooling rate and method are not particularly limited, and the rate and method well known to those skilled in the art may be used.
在本发明中，所述水洗为对第一离心后所得固体进行水涤。本发明对所述水洗的具体方法没有特殊限定，选用本领域技术人员熟知的方法即可。In the present invention, the water washing is to wash the solid obtained after the first centrifugation. In the present invention, the specific method of the water washing is not particularly limited, and a method well known to those skilled in the art may be used.
在本发明中，所述乙醇洗涤为对第二离心所得固体进行乙醇洗涤。本发明对所述乙醇洗涤的具体方法没有特殊限定，选用本领域技术人员熟知的方法即可。In the present invention, the ethanol washing is ethanol washing of the solid obtained by the second centrifugation. In the present invention, the specific method of the ethanol washing is not particularly limited, and a method well known to those skilled in the art may be used.
在本发明中，所述第一离心、第二离心和第三离心的转速独立地优选为8000～10000rpm，时间独立地优选为4～6min。In the present invention, the rotation speeds of the first centrifugation, the second centrifugation, and the third centrifugation are independently preferably 8000 to 10000 rpm, and the time is independently preferably 4 to 6 min.
得到含有羧基的交联β-环糊精聚合物后，本发明将得到的含有羧基的交联β-环糊精聚合物、可溶性二价铁盐、可溶性三价铁盐、水和氢氧化钠混合后进行磁性粒子负载，得到磁性交联β-环糊精聚合物吸附剂。After obtaining the carboxyl group-containing cross-linked β-cyclodextrin polymer, the present invention will obtain the carboxyl group-containing cross-linked β-cyclodextrin polymer, soluble ferric salt, soluble ferric salt, water and sodium hydroxide After mixing, magnetic particles are loaded to obtain a magnetic cross-linked β-cyclodextrin polymer adsorbent.
在本发明中，所述水优选为去离子水。In the present invention, the water is preferably deionized water.
在本发明中，所述含有羧基的交联β-环糊精聚合物、可溶性二价铁盐、可溶性三价铁盐、水和氢氧化钠的质量比优选为0.1：0.05～0.07：0.13～0.19：34～36：4～6，更优选为0.1：0.06：0.15～0.18:35:5。In the present invention, the mass ratio of the carboxyl group-containing cross-linked β-cyclodextrin polymer, soluble divalent iron salt, soluble ferric iron salt, water and sodium hydroxide is preferably 0.1: 0.05 to 0.07: 0.13 to 0.19: 34 to 36: 4 to 6, more preferably 0.1: 0.06: 0.15 to 0.18: 35: 5.
在本发明中，所述磁性粒子负载的温度优选为80～100℃，更优选为90～95℃；所述磁性粒子负载的时间优选为20～30h，更优选为24～26h。In the present invention, the temperature at which the magnetic particles are loaded is preferably 80 to 100 ° C, more preferably 90 to 95 ° C; the time at which the magnetic particles are loaded is preferably 20 to 30 hours, and more preferably 24 to 26 hours.
在本发明中，得到含有羧基的交联β-环糊精聚合物后，本发明将得到的含有羧基的交联β-环糊精聚合物、可溶性二价铁盐、可溶性三价铁盐、一部分水和氢氧化钠混合的具体方法为先将含有羧基的交联β-环糊精聚合物、可溶性二价铁盐、可溶性三价铁盐和水混合在氮气保护下搅拌，再将所得混合液与氢氧化钠混合进行共沉淀制备磁性粒子，并同时实现磁性粒子的负载。在本发明中，所述氢氧化钠优选以氢氧化钠水溶液的形式加入；在本发明中，所述氢氧化钠与剩余部分的水混合后得到氢氧化钠水溶液。本发明对第一部分水和剩余部分水的用量没有特殊限定，选用本领域技术人员熟知的用量即可。In the present invention, after obtaining the carboxyl group-containing cross-linked β-cyclodextrin polymer, the present invention will obtain the carboxyl group-containing cross-linked β-cyclodextrin polymer, soluble divalent iron salt, soluble ferric iron salt, The specific method of mixing a part of water and sodium hydroxide is to first mix the carboxyl group-containing cross-linked β-cyclodextrin polymer, soluble ferric iron salt, soluble ferric iron salt and water under stirring under nitrogen, and then mix The liquid and sodium hydroxide are mixed for co-precipitation to prepare magnetic particles, and at the same time, the magnetic particles are loaded. In the present invention, the sodium hydroxide is preferably added in the form of an aqueous sodium hydroxide solution; in the present invention, the sodium hydroxide is mixed with the remaining part of water to obtain an aqueous sodium hydroxide solution. In the present invention, the amount of the first part of water and the remaining part of the water is not particularly limited, and the amount well-known to those skilled in the art may be used.
本发明对搅拌的方法没有特殊限定，选用本领域技术人员熟知的搅拌方法即可。在本发明中，所述搅拌的时间优选为25～40min，更优选为30～35min。In the present invention, the stirring method is not particularly limited, and the stirring method well known to those skilled in the art may be selected. In the present invention, the stirring time is preferably 25 to 40 minutes, and more preferably 30 to 35 minutes.
在本发明中，所述共沉淀优选在搅拌条件下进行。本发明对搅拌的方法没有特殊限定，选用本领域技术人员熟知的搅拌方法即可。In the present invention, the co-precipitation is preferably carried out under stirring conditions. In the present invention, the stirring method is not particularly limited, and the stirring method well known to those skilled in the art may be selected.
在本发明中，所述磁性粒子负载后还优选包括对磁性粒子负载后所得的固液混合物依次冷却至室温、磁分离、水洗、乙醇洗涤和干燥，得到磁性交联β-环糊精聚合物吸附剂。In the present invention, the loading of the magnetic particles preferably further includes sequentially cooling the solid-liquid mixture obtained after loading the magnetic particles to room temperature, magnetic separation, water washing, ethanol washing, and drying to obtain magnetic cross-linked β-cyclodextrin polymer Sorbent.
本发明对冷却的速率和方法没有特殊限定，选用本领域技术人员熟知的速率和方法即可In the present invention, the cooling rate and method are not particularly limited, and the rate and method well known to those skilled in the art may be used.
在本发明中，所述磁选优选为用磁铁贴近烧杯外壁，使磁性交联β-环糊精聚合物吸附剂堆积在烧杯壁上，吸引2～5min后，倒去清液。In the present invention, the magnetic separation is preferably close to the outer wall of the beaker with a magnet, the magnetic cross-linked β-cyclodextrin polymer adsorbent is deposited on the wall of the beaker, and after 2 to 5 minutes of attraction, the clear solution is poured off.
在本发明中，所述水洗为对磁选后所得产物进行水洗。本发明对水洗的方法没有特殊限定，选用本领域技术人员熟知的水洗方法即可。In the present invention, the water washing is to wash the product obtained after magnetic separation. The method for water washing is not particularly limited in the present invention, and a water washing method well known to those skilled in the art may be used.
本发明对乙醇洗涤的方法没有特殊限定，选用本领域技术人员熟知的乙醇洗涤方法即可。The method for ethanol washing is not particularly limited in the present invention, and the ethanol washing method well known to those skilled in the art may be used.
本发明还提供了上述制备方法制备得到的磁性交联β-环糊精聚合物吸附剂。The invention also provides the magnetic cross-linked β-cyclodextrin polymer adsorbent prepared by the preparation method.
为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。In order to better understand the present invention, the content of the present invention will be further clarified in conjunction with the following examples, but the content of the present invention is not limited to the following examples.
实施例1Example 1
1)向100mL玻璃烧瓶中依次加入四氟对苯二氰(TFPN,0.5g,0.002mol)、β-环糊精(β-CD,0.962g，0.00084mol)、K 2 CO 3 (1.23g，0.0089mol)，立即抽真空后通入氮气进行保护，再依次向玻璃烧瓶中依次注入27mL无水四氢呋喃与5mL无水N，N-二甲基甲酰胺，然后在85℃下搅拌反应48h。冷却至室温，离心后倒去上层清液后用1M盐酸溶液洗涤至无气泡产生，然后离心去除上层清液，再用去离子水洗涤、离心两次，用四氢呋喃洗涤、离心两次，最后用无水乙醇洗涤、离心一次(上述离心条件皆为10000rpm下离心5min)，最后在真空60℃下干燥12h得到四氟对苯二氰交联的β-环糊精聚合物，简称T-β-CD。1) Into a 100mL glass flask, add tetrafluoroterephthalocyanine (TFPN, 0.5g, 0.002mol), β-cyclodextrin (β-CD, 0.962g, 0.00084mol), and K 2 CO 3 (1.23g, 0.0089mol), immediately after evacuating and passing nitrogen gas for protection, then sequentially inject 27mL of anhydrous tetrahydrofuran and 5mL of anhydrous N, N-dimethylformamide into the glass flask, and then stir the reaction at 85 ° C for 48h. Cool to room temperature, pour off the supernatant after centrifugation, wash with 1M hydrochloric acid solution until no bubbles are generated, then centrifuge to remove the supernatant, then wash with deionized water, centrifuge twice, wash with tetrahydrofuran, centrifuge twice, and finally use Wash with anhydrous ethanol and centrifuge once (the above centrifugation conditions are all centrifuged at 10000rpm for 5min), and finally dry at 60 ℃ for 12h to obtain tetrafluoroterephthalocyanine-crosslinked β-cyclodextrin polymer, referred to as T-β- CD.
所得T-β-CD的吸附能力仅为140.0mg/g(吸附实验条件：亚甲基蓝溶液25mL，亚甲基蓝溶液浓度80mg/L，T-β-CD用量10mg，吸附时间3h)，对水中亚甲基蓝的移除率仅为70.0wt.％。The adsorption capacity of the obtained T-β-CD was only 140.0mg / g (adsorption experiment conditions: methylene blue solution 25mL, methylene blue solution concentration 80mg / L, T-β-CD dosage 10mg, adsorption time 3h), the removal of methylene blue in water The rate is only 70.0 wt.%.
2)向250mL玻璃烧瓶中加入T-β-CD(0.2g)，再依次加入含20wt.％氢氧化钠的去离子水溶液(40g)以及乙醇(40mL)，在120℃下回流24h。冷却至室温，在离心后倒去上层清液，所得固体为水解产物，再向离心产物中加入pH为5的盐酸溶液(40mL)继续在120℃下回流2h，冷却、离心，再用去离子水洗涤、离心三次至中性，再用无水乙醇洗涤、离心一次，最后在真空60℃下干燥12h得到含有羧基的交联β-环糊精聚合物，简称CT-β-CD(上述离心条件皆为10000rpm下离心5min)。图1为CT-β--CD的合成路线图。2) T-β-CD (0.2g) was added to a 250mL glass flask, followed by deionized aqueous solution (40g) containing 20wt.% Sodium hydroxide and ethanol (40mL), and refluxed at 120 ° C for 24h. Cool to room temperature, pour off the supernatant after centrifugation, the resulting solid is a hydrolysate, and then add a hydrochloric acid solution (40mL) at pH 5 to the centrifuge product and continue to reflux at 120 ° C for 2h, cool, centrifuge, and use deionization Wash with water, centrifuge three times to neutral, then wash with anhydrous ethanol, centrifuge once, and finally dry under vacuum at 60 ℃ for 12h to obtain carboxyl-containing cross-linked β-cyclodextrin polymer, referred to as CT-β-CD The conditions are all centrifuged at 10000 rpm for 5 min). Figure 1 is a synthetic route of CT-β-CD.
3)根据生成的Fe 3 O 4 与投料的CT-β-CD的质量比为0.8:1，向100mL玻璃烧瓶中加入FeCl 2 ·4H 2 O(0.0686g)、FeCl 3 ·6H 2 O(0.1864g)、CT-β-CD(0.1g)、去离子水(20mL)，抽真空后充氮气保护，搅拌30min分钟配成混合溶液，再注入含20wt％氢氧化钠的去离子水溶液(20g)，在90℃下充氮保护搅拌反应24h。冷却后倒入烧杯中，再用磁铁贴近烧杯外壁，使磁性交联β-环糊精聚合物(简称磁性CT-β-CD)因磁力吸引堆积在烧杯壁上，吸引2min后，倒去清液。所得固体反复用去离子水(每次100mL)洗涤并磁分离共4次至中性，然后用无水乙醇洗涤1次并磁分离，最后在真空60℃下干燥12h，得到磁性CT-β-CD。3) According to the mass ratio of generated Fe 3 O 4 to the fed CT-β-CD is 0.8: 1, add FeCl 2 · 4H 2 O (0.0686g), FeCl to a 100mL glass flask 3. 6H 2 O (0.1864g), CT-β-CD (0.1g), deionized water (20mL), after vacuuming, filled with nitrogen protection, stirred for 30min to prepare a mixed solution, and then injected with 20wt% sodium hydroxide The deionized aqueous solution (20g) was filled with nitrogen at 90 ° C to protect and stir the reaction for 24h. After cooling, pour into the beaker, and then close the outer wall of the beaker with a magnet, so that the magnetic cross-linked β-cyclodextrin polymer (referred to as magnetic CT-β-CD) accumulates on the wall of the beaker due to magnetic attraction. liquid. The obtained solid was repeatedly washed with deionized water (100 mL each time) and magnetically separated 4 times to neutral, then washed with anhydrous ethanol once and magnetically separated, and finally dried under vacuum at 60 ° C for 12 h to obtain magnetic CT-β- CD.
所得磁性CT-β-CD的对水中亚甲基蓝吸附能力为198.2mg/g，移除率为99.1wt.％(吸附实验条件：亚甲基蓝溶液25mL，亚甲基蓝溶液浓度80mg/L，磁性CT-β-CD用量10mg，吸附时间30min)。The adsorption capacity of the obtained magnetic CT-β-CD to methylene blue in water was 198.2mg / g, and the removal rate was 99.1wt.% (Adsorption experiment conditions: methylene blue solution 25mL, methylene blue solution concentration 80mg / L, magnetic CT-β-CD dosage 10mg, adsorption time 30min).
实施例2Example 2
步骤1)和步骤2)与实施例1相同，步骤3)如下：Step 1) and step 2) are the same as Example 1, and step 3) is as follows:
根据生成的Fe 3 O 4 与投料的CT-β-CD的质量比为0.7:1，向100mL玻璃烧瓶中加入FeCl 2 ·4H 2 O(0.0600g)、FeCl 3 ·6H 2 O(0.1631g)、CT-β-CD(0.1g)、去离子水(20mL)，抽真空后冲氮气保护，搅拌30min分钟配成混合溶液，再注入含20wt％氢氧化钠的去离子水溶液(20g)，在90℃下充氮保护搅拌反应24h。冷却后倒入烧杯中，再用磁铁贴近烧杯外壁，使磁性CT-β-CD因磁力吸引堆积在烧杯壁上，吸引2min后，倒去清液。所得固体反复用去离子水(每次100mL)洗涤并磁分离共4次至中性，然后用无水乙醇洗涤1次并磁分离，最后在真空60℃下干燥12h，得到磁性CT-β-CD。According to the mass ratio of generated Fe 3 O 4 to the fed CT-β-CD is 0.7: 1, add FeCl 2 · 4H 2 O (0.0600g), FeCl to a 100mL glass flask 3 · 6H 2 O (0.1631g), CT-β-CD (0.1g), deionized water (20mL), evacuated and flushed with nitrogen for protection, stirred for 30min to prepare a mixed solution, and then injected with 20wt% sodium hydroxide The deionized aqueous solution (20g) was filled with nitrogen at 90 ° C to protect and stir the reaction for 24h. After cooling, pour into the beaker, and then close the outer wall of the beaker with a magnet, so that the magnetic CT-β-CD is accumulated on the wall of the beaker due to magnetic attraction. After 2 minutes of attraction, the clear solution is poured. The obtained solid was repeatedly washed with deionized water (100 mL each time) and magnetically separated 4 times to neutral, then washed with anhydrous ethanol once and magnetically separated, and finally dried under vacuum at 60 ° C for 12 h to obtain magnetic CT-β- CD.
所得磁性CT-β-CD的吸附能力为198.4mg/g(吸附实验条件：亚甲基蓝溶液25mL，亚甲基蓝溶液浓度80mg/L，磁性CT-β-CD用量10mg，吸附时间30min)，对水中亚甲基蓝的移除率为99.2wt.％。The adsorption capacity of the obtained magnetic CT-β-CD was 198.4mg / g (adsorption experiment conditions: methylene blue solution 25mL, methylene blue solution concentration 80mg / L, magnetic CT-β-CD dosage 10mg, adsorption time 30min), the migration of methylene blue in water The removal rate is 99.2 wt.%.
实施例3Example 3
步骤1)和步骤2)与实施例1相同，步骤3)如下：Step 1) and step 2) are the same as Example 1, and step 3) is as follows:
根据生成的Fe 3 O 4 与投料的CT-β-CD的质量比为0.6:1，向100mL玻璃烧瓶中加入FeCl 2 ·4H 2 O(0.0514g)、FeCl 3 ·6H 2 O(0.1398g)、CT-β-CD(0.1g)、去离子水(20mL)，抽真空后冲氮气保护，搅拌30min分钟配成混合溶液，再注入含20wt％氢氧化钠的去离子水溶液(20g)，在90℃下充氮保护搅拌反应24h。冷却后倒入烧杯中，再用磁铁贴近烧杯外壁，使磁性CT-β-CD因磁力吸引堆积在烧杯壁上，吸引2min后，倒去清液。所得固体反复用去离子水(每次100mL)洗涤并磁分离共4次至中性，然后用无水乙醇洗涤1次并磁分离，最后在真空60℃下干燥12h，得到磁性CT-β-CD。According to the mass ratio of generated Fe 3 O 4 to the fed CT-β-CD is 0.6: 1, add FeCl 2 · 4H 2 O (0.0514g), FeCl to a 100mL glass flask 3 · 6H 2 O (0.1398g), CT-β-CD (0.1g), deionized water (20mL), evacuated and purged with nitrogen protection, stirred for 30min to prepare a mixed solution, and then injected with 20wt% sodium hydroxide The deionized aqueous solution (20g) was filled with nitrogen at 90 ° C to protect and stir the reaction for 24h. After cooling, pour into the beaker, and then close the outer wall of the beaker with a magnet, so that the magnetic CT-β-CD is accumulated on the wall of the beaker due to magnetic attraction. After 2 minutes of attraction, the clear solution is poured. The obtained solid was repeatedly washed with deionized water (100 mL each time) and magnetically separated 4 times to neutral, then washed with anhydrous ethanol once and magnetically separated, and finally dried under vacuum at 60 ° C for 12 h to obtain magnetic CT-β- CD.
β-CD，TFPN，T-β-CD，CT-β-CD，实施例1～3中得到的磁性CT-β-CD的红外光谱结果如图2所示。从图2可知：T-β-CD同时具有β-CD与TFPN的红外特征峰，证明β-CD与TFPN通过交联反应成功制备了T-β-CD；而CT-β-CD与T-β-CD相比，其2248厘米-1处的红外峰强度明显减弱且1685厘米-1处的红外峰强度明显增强，证明了T-β-CD的腈基依次经氢氧化钠与盐酸处理后已经转变为羧基，得到CT-β-CD；磁性CT-β-CD除了具有CT-β-CD的红外特征峰外，在580厘米 - 1处还有Fe 3 O 4 的红外特征峰，证明了磁性粒子的负载成功。The infrared spectrum results of β-CD, TFPN, T-β-CD, CT-β-CD, and the magnetic CT-β-CD obtained in Examples 1 to 3 are shown in FIG. 2. It can be seen from Figure 2: T-β-CD has both infrared characteristic peaks of β-CD and TFPN, which proves that β-CD and TFPN successfully prepared T-β-CD through cross-linking reaction; while CT-β-CD and T- Compared with β-CD, its infrared peak intensity at 2248 cm-1 is significantly weakened and its infrared peak intensity at 1685 cm-1 is significantly enhanced, which proves that the nitrile group of T-β-CD is treated with sodium hydroxide and hydrochloric acid in sequence. It has been converted to a carboxyl group to obtain CT-β-CD; in addition to the infrared characteristic peak of CT-β-CD, magnetic CT-β-CD also has an infrared characteristic peak of Fe 3 O 4 at 580 cm-1, which proves The loading of magnetic particles was successful.
所得磁性CT-β-CD的扫描电镜图如图3所示，由图3可知有大量的磁性粒子负载于CT-β-CD上。The scanning electron micrograph of the obtained magnetic CT-β-CD is shown in FIG. 3, and it can be seen from FIG. 3 that a large number of magnetic particles are loaded on the CT-β-CD.
所得磁性CT-β-CD的吸附能力为198.8mg/g(吸附实验条件：亚甲基蓝溶液25mL，亚甲基蓝溶液浓度80mg/L磁性CT-β-CD用量10mg，吸附时间30min)，对水中亚甲基蓝的移除率为99.4wt.％。The adsorption capacity of the obtained magnetic CT-β-CD was 198.8mg / g (adsorption experiment conditions: methylene blue solution 25mL, methylene blue solution concentration 80mg / L magnetic CT-β-CD dosage 10mg, adsorption time 30min), the removal of methylene blue in water The rate is 99.4 wt.%.
实施例4Example 4
1)向100mL玻璃烧瓶中依次加入四氟对苯二氰(0.5g，0.002mol)、β-环糊精(1.100g，0.00097mol)、K 2 CO 3 (1.41g，0.0102mol)，立即抽真空后通入氮气进行保护，再依次向玻璃烧瓶中依次注入27mL无水四氢呋喃与5mL无水N，N-二甲基甲酰胺，然后在85℃下搅拌反应48h。冷却至室温，离心后倒去上层清液后用1M盐酸溶液洗涤至无气泡产生，然后离心去除上层清液，再用去离子水洗涤、离心两次，用四氢呋喃洗涤、离心两次，最后用无水乙醇洗涤、离心一次(上述离心条件皆为10000rpm下离心5min)，最后在真空60℃下干燥12h得到T-β-CD。1) Into a 100mL glass flask, add tetrafluoroterephthalocyanine (0.5g, 0.002mol), β-cyclodextrin (1.100g, 0.00097mol), K 2 CO 3 (1.41g, 0.0102mol), and immediately draw After vacuuming, nitrogen gas was introduced for protection, and 27 mL of anhydrous tetrahydrofuran and 5 mL of anhydrous N, N-dimethylformamide were sequentially poured into the glass flask, and then the reaction was stirred at 85 ° C. for 48 h. Cool to room temperature, pour off the supernatant after centrifugation, wash with 1M hydrochloric acid solution until no bubbles are generated, then centrifuge to remove the supernatant, then wash with deionized water, centrifuge twice, wash with tetrahydrofuran, centrifuge twice, and finally use Wash with anhydrous ethanol and centrifuge once (the above centrifugation conditions are all at 10000rpm for 5min), and finally dry under vacuum at 60 ℃ for 12h to obtain T-β-CD.
2)向250mL玻璃烧瓶中加入T-β-CD(0.2g)，再依次加入含20wt.％氢氧化钠的去离子水溶液(40g)以及乙醇(40mL)，在120℃下回流24h。冷却至室温，在离心后倒去上层清液，再向离心后所得固体加入pH为5的盐酸溶液(40mL)继续在120℃下回流2h，冷却、离心，再用去离子水洗涤、离心三次至中性，再用无水乙醇洗涤、离心一次(上述离心条件皆为10000rpm下离心5min)，最后在真空60℃下干燥12h得到CT-β-CD2) T-β-CD (0.2g) was added to a 250mL glass flask, followed by deionized aqueous solution (40g) containing 20wt.% Sodium hydroxide and ethanol (40mL), and refluxed at 120 ° C for 24h. Cool to room temperature, pour off the supernatant after centrifugation, then add hydrochloric acid solution (40mL) at pH 5 to the solid after centrifugation and continue to reflux at 120 ° C for 2h, cool and centrifuge, then wash with deionized water and centrifuge three times To neutral, wash with absolute ethanol and centrifuge again (all of the above centrifugation conditions are at 10000rpm for 5min), and finally dry under vacuum at 60 ℃ for 12h to obtain CT-β-CD
3)根据生成的Fe 3 O 4 与投料的CT-β-CD的质量比为0.8:1，向100mL玻璃烧瓶中加入FeCl 2 ·4H 2 O(0.0686g)、FeCl 3 ·6H 2 O(0.1864g)、CT-β-CD(0.1g)、去离子水(20mL)，抽真空后冲氮气保护，搅拌30min分钟配成混合溶液，再注入含20wt％氢氧化钠的去离子水溶液(20g)，在90℃下充氮保护搅拌反应24h。冷却后倒入烧杯中，再用磁铁贴近烧杯外壁，使磁性CT-β-CD因磁力吸引堆积在烧杯壁上，吸引2min后，倒去清液。所得固体反复用去离子水(每次100mL)洗涤并磁分离共4次至中性，然后用无水乙醇洗涤1次并磁分离，最后在真空60℃下干燥12h，得到磁性CT-β-CD。3) According to the mass ratio of generated Fe 3 O 4 to the fed CT-β-CD is 0.8: 1, add FeCl 2 · 4H 2 O (0.0686g), FeCl to a 100mL glass flask 3. 6H 2 O (0.1864g), CT-β-CD (0.1g), deionized water (20mL), evacuated and flushed with nitrogen for protection, stirred for 30min to prepare a mixed solution, and then injected with 20wt% sodium hydroxide The deionized aqueous solution (20g) was filled with nitrogen at 90 ° C to protect and stir the reaction for 24h. After cooling, pour into the beaker, and then close the outer wall of the beaker with a magnet, so that the magnetic CT-β-CD is accumulated on the wall of the beaker due to magnetic attraction. After 2 minutes of attraction, the clear solution is poured. The obtained solid was repeatedly washed with deionized water (100 mL each time) and magnetically separated 4 times to neutral, then washed with anhydrous ethanol once and magnetically separated, and finally dried under vacuum at 60 ° C for 12 h to obtain magnetic CT-β- CD.
所得磁性CT-β-CD的吸附能力为187.2mg/g(吸附实验条件：亚甲基蓝溶液25mL，亚甲基蓝溶液浓度80mg/L，磁性CT-β-CD用量10mg，吸附时间30min)，对水中亚甲基蓝的移除率为93.6wt.％。The adsorption capacity of the obtained magnetic CT-β-CD was 187.2mg / g (adsorption experiment conditions: methylene blue solution 25mL, methylene blue solution concentration 80mg / L, magnetic CT-β-CD dosage 10mg, adsorption time 30min), the migration of methylene blue in water The removal rate is 93.6 wt.%.
实施例5Example 5
1)向100mL玻璃烧瓶中依次加入四氟对苯二氰(0.5g,0.002mol)、β-环糊精(0.900g,0.00079mol)、K 2 CO 3 (1.15g,0.0083mol)，立即抽真空后通入氮气进行保护，再依次向玻璃烧瓶中依次注入27mL无水四氢呋喃与5mL无水N，N-二甲基甲酰胺，然后在85℃下搅拌反应48h。冷却至室温，离心后倒去上层清液后用1M盐酸溶液洗涤至无气泡产生，然后离心去除上层清液，再用去离子水洗涤、离心两次，用四氢呋喃洗涤、离心两次，最后用无水乙醇洗涤、离心一次(上述离心条件皆为10000rpm下离心5min)，最后在真空60℃下干燥12h得到T-β-CD。1) Into a 100mL glass flask, add tetrafluoroterephthalocyanine (0.5g, 0.002mol), β-cyclodextrin (0.900g, 0.00079mol), K 2 CO 3 (1.15g, 0.0083mol) in sequence, immediately draw After vacuuming, nitrogen gas was introduced for protection, and 27 mL of anhydrous tetrahydrofuran and 5 mL of anhydrous N, N-dimethylformamide were sequentially poured into the glass flask, and then the reaction was stirred at 85 ° C. for 48 h. Cool to room temperature, pour off the supernatant after centrifugation, wash with 1M hydrochloric acid solution until no bubbles occur, then centrifuge to remove the supernatant, then wash with deionized water, centrifuge twice, wash with tetrahydrofuran, centrifuge twice, and finally Wash with anhydrous ethanol and centrifuge once (the above centrifugation conditions are all at 10000rpm for 5min), and finally dry under vacuum at 60 ℃ for 12h to obtain T-β-CD.
2)向250mL玻璃烧瓶中加入T-β-CD(0.2g)，再依次加入，再依次加入含20wt.％氢氧化钠的去离子水溶液(40g)以及乙醇(40mL)，在120℃下回流24h。冷却至室温，在离心后倒去上层清液，再向离心后所得固体加入pH为5的盐酸溶液(40mL)继续在120℃下回流2h，冷却、离心，再用去离子水洗涤、离心三次至中性，再用无水乙醇洗涤、离心一次(上述离心条件皆为10000rpm下离心5min)，最后在真空60℃下干燥12h得到CT-β-CD。2) Add T-β-CD (0.2g) to a 250mL glass flask, add it in sequence, and then add a deionized aqueous solution (40g) containing 20wt.% Sodium hydroxide and ethanol (40mL), and reflux at 120 ° C 24h. Cool to room temperature, pour off the supernatant after centrifugation, then add hydrochloric acid solution (40mL) at pH 5 to the solid after centrifugation and continue to reflux at 120 ° C for 2h, cool and centrifuge, then wash with deionized water and centrifuge three times To neutrality, wash again with absolute ethanol and centrifuge once (all of the above centrifugation conditions are at 10,000 rpm for 5 min), and finally dry under vacuum at 60 ° C for 12 h to obtain CT-β-CD.
3)根据生成的Fe 3 O 4 与投料的CT-β-CD的质量比为0.8:1，向100mL玻璃烧瓶中加入FeCl 2 ·4H 2 O(0.0686g)、FeCl 3 ·6H 2 O(0.1864g)、CT-β-CD(0.1g)、去离子水(20mL)，抽真空后冲氮气保护，搅拌30min分钟配成混合溶液，再注入含20wt％氢氧化钠的去离子水溶液(20g)，在90℃下充氮保护搅拌反应24h。冷却后倒入烧杯中，再用磁铁贴近烧杯外壁，使磁性CT-β-CD因磁力吸引堆积在烧杯壁上，吸引2min后，倒去清液。所得固体反复用去离子水(每次100mL)洗涤并磁分离共4次至中性，然后用无水乙醇洗涤1次并磁分离，最后在真空60℃下干燥12h，得到磁性CT-β-CD。3) According to the mass ratio of generated Fe 3 O 4 to the fed CT-β-CD is 0.8: 1, add FeCl 2 · 4H 2 O (0.0686g), FeCl to a 100mL glass flask 3. 6H 2 O (0.1864g), CT-β-CD (0.1g), deionized water (20mL), evacuated and flushed with nitrogen for protection, stirred for 30min to prepare a mixed solution, and then injected with 20wt% sodium hydroxide The deionized aqueous solution (20g) was filled with nitrogen at 90 ° C to protect and stir the reaction for 24h. After cooling, pour into the beaker, and then close the outer wall of the beaker with a magnet, so that the magnetic CT-β-CD is accumulated on the wall of the beaker due to magnetic attraction. After 2 minutes of attraction, the clear solution is poured. The obtained solid was repeatedly washed with deionized water (100 mL each time) and magnetically separated 4 times to neutral, then washed with anhydrous ethanol once and magnetically separated, and finally dried under vacuum at 60 ° C for 12 h to obtain magnetic CT-β- CD.
所得磁性CT-β-CD的吸附能力为197.5mg/g(吸附实验条件：亚甲基蓝溶液25mL，亚甲基蓝溶液浓度80mg/L，磁性CT-β-CD用量10mg，吸附时间30min)，对水中亚甲基蓝的移除率为98.75wt.％。The adsorption capacity of the obtained magnetic CT-β-CD was 197.5mg / g (adsorption experiment conditions: methylene blue solution 25mL, methylene blue solution concentration 80mg / L, magnetic CT-β-CD dosage 10mg, adsorption time 30min), the migration of methylene blue in water The removal rate is 98.75wt.%.
用振动样品磁强计对实施例1～5得到的磁性CT-β-CD的磁饱和强度进行测定，其结果如图4所示，由图4可知，实施例1～5的磁饱和强度分别为24.0emu/g、19.1emu/g、16.6emu/g、23.4emu/g、24.3emu/g，说明它们都具有磁功能，可以在进行吸附处理后再回收。The magnetic saturation intensity of the magnetic CT-β-CD obtained in Examples 1 to 5 was measured using a vibrating sample magnetometer. The results are shown in FIG. 4. From FIG. 4, the magnetic saturation intensity of Examples 1 to 5 is respectively It is 24.0emu / g, 19.1emu / g, 16.6emu / g, 23.4emu / g, 24.3emu / g, indicating that they all have magnetic function and can be recovered after adsorption treatment.
对实施例1～5中得到的磁性CT-β-CD的电位进行测定，其结果如图5所示，由图5可知，实施例1～5中磁性CT-β-CD的Zeta电位分别为-17.7mV、-23.6mV、-27.6mV、-13.4mV、-29.8mV，说明磁性CT-β-CD的表面由于含有可电离的羧基而带负电荷，从而能够较好地吸附水中的亚甲基蓝阳离子型染料，因此吸附能力优于T-β-CD。The potentials of the magnetic CT-β-CD obtained in Examples 1 to 5 were measured. The results are shown in FIG. 5, and from FIG. 5, the Zeta potentials of the magnetic CT-β-CD in Examples 1 to 5 were: -17.7mV, -23.6mV, -27.6mV, -13.4mV, -29.8mV, indicating that the surface of the magnetic CT-β-CD is negatively charged because it contains ionizable carboxyl groups, which can better absorb methylene blue cations in water Type dye, so the adsorption capacity is better than T-β-CD.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the principles of the present invention, several improvements and retouches can be made. These improvements and retouches also It should be regarded as the protection scope of the present invention.

Claims (10)

  1. 一种磁性交联β-环糊精聚合物吸附剂的制备方法，包括以下步骤： 1)将四氟对苯二氰、β-环糊精、碳酸钾和溶剂混合进行交联聚合反应，得到四氟对苯二腈交联的β-环糊精聚合物；所述溶剂为四氢呋喃和N，N-二甲基甲酰胺的混合物； 2)将所述步骤1)得到的四氟对苯二腈交联的β-环糊精聚合物、氢氧化钠、水和乙醇混合进行水解反应，得到水解产物； 3)将所述步骤2)得到的水解产物与盐酸混合进行中和反应，得到含有羧基的交联β-环糊精聚合物； 4)将所述步骤3)得到的含有羧基的交联β-环糊精聚合物、可溶性二价铁盐、可溶性三价铁盐、水和氢氧化钠混合后进行磁性粒子负载，得到磁性交联β-环糊精聚合物吸附剂。A method for preparing magnetic cross-linked β-cyclodextrin polymer adsorbent includes the following steps: 1) Mixing tetrafluoroterephthalocyanine, β-cyclodextrin, potassium carbonate and a solvent for cross-linking polymerization to obtain Β-cyclodextrin polymer crosslinked with tetrafluoroterephthalonitrile; the solvent is a mixture of tetrahydrofuran and N, N-dimethylformamide; 2) the tetrafluoroterephthalene obtained in step 1) The nitrile-crosslinked β-cyclodextrin polymer, sodium hydroxide, water and ethanol are mixed to perform a hydrolysis reaction to obtain a hydrolysate; 3) The hydrolysate obtained in step 2) is mixed with hydrochloric acid to perform a neutralization reaction to obtain a product containing Carboxyl-crosslinked β-cyclodextrin polymer; 4) the carboxyl-containing crosslinked β-cyclodextrin polymer obtained in step 3), soluble ferric iron salt, soluble ferric iron salt, water and hydrogen After mixing sodium oxide, magnetic particles are loaded to obtain a magnetic cross-linked β-cyclodextrin polymer adsorbent.
  2. 根据权利要求1所述的制备方法，其特征在于，所述步骤1)中四氟对苯二氰、β-环糊精和碳酸钾的物质的量比为2：0.7～1.1：7～11。The preparation method according to claim 1, characterized in that, in the step 1), the amount ratio of the substances of tetrafluoroterephthalocyanine, β-cyclodextrin and potassium carbonate is 2: 0.7 ～ 1.1: 7 ～ 11 .
  3. 根据权利要求1所述的制备方法，其特征在于，所述步骤1)中交联聚合反应的温度为82～90℃，交联聚合反应的时间为40～60h。The preparation method according to claim 1, wherein the temperature of the cross-linking polymerization reaction in step 1) is 82 to 90 ° C, and the time of the cross-linking polymerization reaction is 40 to 60 hours.
  4. 根据权利要求1所述的制备方法，其特征在于，所述步骤2)中四氟对苯二腈交联的β-环糊精聚合物、氢氧化钠、水和乙醇的用量比为0.2g：8～10g：30～40g：40～50mL。The preparation method according to claim 1, characterized in that, in step 2), the dosage ratio of β-cyclodextrin polymer cross-linked with tetrafluoroterephthalonitrile, sodium hydroxide, water and ethanol is 0.2 g : 8-10g: 30-40g: 40-50mL.
  5. 根据权利要求1所述的制备方法，其特征在于，所述步骤2)中水解反应的温度为100～120℃，水解反应的时间为20～30h。The preparation method according to claim 1, wherein the temperature of the hydrolysis reaction in the step 2) is 100-120 ° C, and the time of the hydrolysis reaction is 20-30h.
  6. 根据权利要求1所述的制备方法，其特征在于，所述步骤3)中盐酸的pH值为4～5；所述盐酸与所述步骤2)中四氟对苯二腈交联的β-环糊精聚合物的用量比为40～50mL：0.2g。The preparation method according to claim 1, wherein the pH value of hydrochloric acid in step 3) is 4-5; the hydrochloric acid is β-crosslinked with tetrafluoroterephthalonitrile in step 2) The dosage ratio of cyclodextrin polymer is 40-50 mL: 0.2 g.
  7. 根据权利要求1所述的制备方法，其特征在于，所述步骤3)中中和反应的温度为100～120℃，中和反应的时间为2～5h。The preparation method according to claim 1, wherein the temperature of the neutralization reaction in step 3) is 100-120 ° C, and the time of the neutralization reaction is 2-5 hours.
  8. 根据权利要求1所述的制备方法，其特征在于，所述步骤4)中含有羧基的交联β-环糊精聚合物、可溶性二价铁盐、可溶性三价铁盐、水和氢氧化钠的质量比为0.1：0.05～0.07：0.13～0.19：34～36：4～6。The preparation method according to claim 1, wherein the step 4) contains a carboxyl group-containing cross-linked β-cyclodextrin polymer, soluble ferric iron salt, soluble ferric iron salt, water and sodium hydroxide The mass ratio is 0.1: 0.05 ～ 0.07: 0.13 ～ 0.19: 34 ～ 36: 4 ～ 6.
  9. 根据权利要求1所述的制备方法，其特征在于，所述步骤4)中磁性粒子负载的温度为85～95℃，磁性粒子负载的时间为20～30h。The preparation method according to claim 1, wherein in step 4), the temperature of the magnetic particles is 85 to 95 ° C, and the time of the magnetic particles is 20 to 30 hours.
  10. 权利要求1～9任意一项所述的制备方法制备得到的磁性交联β-环糊精聚合物吸附剂。The magnetic cross-linked β-cyclodextrin polymer adsorbent prepared by the preparation method according to any one of claims 1 to 9.
PCT/CN2019/091612 2018-10-12 2019-06-18 MAGNETIC CROSS-LINKED β-CYCLODEXTRIN POLYMER ADSORBENT AND PREPARATION METHOD THEREFOR WO2020073674A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11155646B2 (en) * 2019-02-14 2021-10-26 Cyclopure, Inc. Charge-bearing cyclodextrin polymeric materials and methods of making and using same
US11512146B2 (en) 2019-02-14 2022-11-29 Cyclopure, Inc. Charge-bearing cyclodextrin polymeric materials and methods of making and using same

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109331793A (en) * 2018-10-12 2019-02-15 广东石油化工学院 A kind of magnetic crosslinking beta cyclo dextrin polymer adsorbent and preparation method thereof
CN110327985B (en) * 2019-07-15 2022-04-12 湖南工学院 Hyperbranched cyclodextrin-nano ferroferric oxide heterogeneous catalyst and preparation method and application thereof
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016172118A1 (en) * 2015-04-20 2016-10-27 Cornell University Porous cyclodextrin polymeric materials and methods of making and using same
CN107159162A (en) * 2017-06-08 2017-09-15 中国石油大学(华东) A kind of polymeric cyclodextrins desulfurizing agent for Light Oil Desulfurization
CN108404878A (en) * 2018-04-17 2018-08-17 江苏国创环保科技有限公司 A kind of preparation method and application of magnetic porous supermolecule cyclodextrin sorbing material
CN108554387A (en) * 2018-04-19 2018-09-21 南昌航空大学 A kind of beta cyclo dextrin polymer and preparation and the method for handling cationic dye wastewater using it
CN109331793A (en) * 2018-10-12 2019-02-15 广东石油化工学院 A kind of magnetic crosslinking beta cyclo dextrin polymer adsorbent and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108551387A (en) * 2018-06-27 2018-09-18 珠海市微半导体有限公司 A kind of BMC code self-adaptings decoding system and coding/decoding method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016172118A1 (en) * 2015-04-20 2016-10-27 Cornell University Porous cyclodextrin polymeric materials and methods of making and using same
CN107159162A (en) * 2017-06-08 2017-09-15 中国石油大学(华东) A kind of polymeric cyclodextrins desulfurizing agent for Light Oil Desulfurization
CN108404878A (en) * 2018-04-17 2018-08-17 江苏国创环保科技有限公司 A kind of preparation method and application of magnetic porous supermolecule cyclodextrin sorbing material
CN108554387A (en) * 2018-04-19 2018-09-21 南昌航空大学 A kind of beta cyclo dextrin polymer and preparation and the method for handling cationic dye wastewater using it
CN109331793A (en) * 2018-10-12 2019-02-15 广东石油化工学院 A kind of magnetic crosslinking beta cyclo dextrin polymer adsorbent and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11155646B2 (en) * 2019-02-14 2021-10-26 Cyclopure, Inc. Charge-bearing cyclodextrin polymeric materials and methods of making and using same
US11512146B2 (en) 2019-02-14 2022-11-29 Cyclopure, Inc. Charge-bearing cyclodextrin polymeric materials and methods of making and using same
US11965042B2 (en) 2019-02-14 2024-04-23 Cyclopure, Inc. Charge-bearing cyclodextrin polymeric materials and methods of making and using same

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