CN109046280A - A kind of beta cyclo dextrin polymer adsorbent and its preparation method and application - Google Patents
A kind of beta cyclo dextrin polymer adsorbent and its preparation method and application Download PDFInfo
- Publication number
- CN109046280A CN109046280A CN201810968743.6A CN201810968743A CN109046280A CN 109046280 A CN109046280 A CN 109046280A CN 201810968743 A CN201810968743 A CN 201810968743A CN 109046280 A CN109046280 A CN 109046280A
- Authority
- CN
- China
- Prior art keywords
- beta
- parts
- cyclodextrin
- metal ion
- volume
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
Abstract
The invention discloses one kind can be used for dyestuff and heavy metal ion adsorbed beta cyclo dextrin polymer adsorbent and its preparation method and application simultaneously; this method is that the modification beta-cyclodextrin that the beta-cyclodextrin derivative of protected silane is obtained with alkenyl anhydride reaction is carried out radical crosslinking copolyreaction with heterocycle vinyl monomer to be made, and general structure is as follows:The modification beta-cyclodextrin and heterocycle vinyl monomer used due to the present invention can form porous, large specific surface area copolymer in copolymerization, and different adsorption sites is provided for organic dyestuff and heavy metal ion, thus the adsorbent is not only greatly improved the adsorption capacity of adsorbent, can also be effectively improved organic dyestuff and heavy metal ion and mutually inhibit and the status of poor removal effect simultaneously.
Description
Technical field
The invention belongs to polymer absorbant and its preparation and applied technical fields, and in particular to a kind of beta-cyclodextrin polymerization
Object adsorbent and its preparation method and application.
Background technique
With the sharply development of China's economy and urbanization, in the waste water of the industries such as metallurgy, mineral products, battery, weaving, leather
Contain a large amount of dyestuff and heavy metal ion.It, can since most organic dyestuff and heavy metal ion have very strong toxicity
It carcinogenic, teratogenesis, mutagenesis and is easily enriched in vivo, therefore even if the organic dyestuff of low concentration and heavy metal ion
Human health and the entire ecosystem can be caused to seriously threaten.For this purpose, the dyestuff and heavy metal ion in removal water body have been compeled
In the eyebrows and eyelashes.
The conventional treatment method of dyestuff and effluent containing heavy metal ions has at present: coagulant sedimentation, evaporation absorption method, UF membrane
Method, advanced oxidation processes, absorption method etc., wherein absorption method has the characteristics that high-efficient, easy to operate, low in cost, at sewage
Using relatively broad in reason.However, most of conventional adsorbent such as active carbon, zeolite, clay etc. is only to organic dyestuff or again
Metal ion Single Pollution species type has suction-operated, this disadvantage limits it as absorption organic dyestuff and heavy metal ion
The practical application of material.Therefore, the status coexisted extensively in waste water for organic dyestuff and heavy metal ion, exploitation design can
Efficient absorption organic dyestuff and the adsorbent of heavy metal ion are most important simultaneously.
However, going the research of removal organic polluter and heavy metal ion at home and abroad simultaneously using a kind of adsorbent at this stage
It is still rare and generally existing because organic pollutant and heavy metal ion compete same adsorption site and cause adsorbent to the two
Adsorption capacity the problem of being suppressed.Such as V.Hern á ndez-Montoya et al. (Journal of Environmental
Management, 2013,116,213-221) it is prepared for a kind of using hydroxyl as the zeolite adsorbents of adsorption site, which exists
To dye of positive ion Basic violet 3 and Pb in Single Pollution object component solution2+Removal rate be respectively 75% and 100%,
And in mixed solution, the removal rate of the two drops to 2% and 85% respectively.Salim Bekkouche et al.
(Desalination and Water Treatment, 2012,37,364) is prepared for a kind of titania nanoparticles absorption
Agent, in the mixed solution of metal ion and phenol, Cd2+、Zn2+、Cu2+Presence make under the adsorbance of adsorbent Pyrogentisinic Acid
Drop 30~60%, and the presence of phenol is but also the adsorbance of each metal ion species has dropped 30~50% differs.To avoid
The competitive Adsorption of organic dyestuff and heavy metal ion, people start the characteristics of combining organic dyestuff and heavy metal ion, using tax
The different functional group of adsorbent is given, realizes its absorption synchronized by different reaction types in different adsorption sites.
A kind of unique functionality is shown if beta-cyclodextrin molecule, i.e. a beta-cyclodextrin derivative molecule can be organic dyestuff
Different adsorption sites is provided with heavy metal ion, to achieve the purpose that organic dyestuff and heavy metal ion while adsorb.
Beta-cyclodextrin is a kind of substance generated under the action of cyclodextrin transferase through bioconversion by starch, is had
The advantages that low in cost, environment-protecting and non-poisonous, receives great attention in field of environment protection.On the one hand, since beta-cyclodextrin is by 7 D-
Glucopyranose forms by α-(Isosorbide-5-Nitrae) glucosides key connection and is formed a hollow truncated cone shape special construction, which can be with
Inclusion compound is formed by Host-guest interaction and many hydrophobic organics, therefore organic pollutant can be adsorbed and removed from water.Such as
CN107376875A discloses the preparation and application of a kind of beta-cyclodextrin porous material with quick adsorption ability, the adsorption material
Expect that for the adsorbance of bisphenol-A in water be 37.9mg/g, the adsorbance in water 4,4 '-dihydroxydiphenylsulisomers is 38.3mg/
g.For another example CN1352199A discloses a kind of preparation method of water purifying adsorbent polycyclodextrin, the poly- β-that this method is prepared
The adsorption capacity of cyclodextrin adsorbent Pyrogentisinic Acid is 12mg/g, and the adsorption capacity of p-nitrophenol is 18mg/g.On the other hand, people
Find that a large amount of easily modified hydroxyls are contained in the section of beta-cyclodextrin, if will there is Electrostatic Absorption or coordination to make to metal ion
These hydroxyls are modified by functional group, so that it may obtain the adsorbent for having larger adsorbance to heavy metal ion.Such as
A.Z.M.Badruddoza et al. (Journal of Hazardous Materials.2011,185,1177-1186) is just prepared
A kind of Fe of carboxymethyl-β-cyclodextrin modification3O4Nano particle, the particle using beta-cyclodextrin hydroxyl and modification to its first
The carboxyl in section, to Cu2+Adsorbance up to 47.2mg/g.However beta-cyclodextrin adsorbent is to organic dyestuff and heavy metal ion
While absorption but rarely have reported in literature.As Feiping Zhao et al. (Environ.Sci.Technol.2015,49,
Beta-cyclodextrin and ethylenediamine tetra-acetic acid 10570-10580) are synthesized into a kind of adsorbent by polycondensation reaction, on the one hand, the suction
The attached dose of cavity using cyclodextrin and organic matter form inclusion compound to adsorb dyestuff methylene blue and safranin O, and adsorbance respectively can
Reach 98mg/g and 59mg/g；On the other hand, which can provide chelating site of the ethylenediamine tetra-acetic acid as metal ion
With Adsorption of Cu2+, adsorbance 79mg/g.However, making crosslinking agent since ethylenediamine tetra-acetic acid had not only made chelating agent, and it is easy to block
Cyclodextrin cavity, therefore cause the adsorbent not ideal enough to the adsorbance of organic dyestuff and heavy metal ion.
Summary of the invention
The object of the present invention is to provide a kind of not only strong to single organic dyestuff or heavy metal ion adsorbed ability, and by
The novel beta cyclo dextrin polymer of good adsorption ability is still maintained in the mixed system of organic dyestuff and heavy metal ion composition
Adsorbent.
It is a further object of the present invention to provide a kind of preparation methods of simple and easy beta cyclo dextrin polymer adsorbent.
Another object of the present invention is to provide a kind of application of above-mentioned beta cyclo dextrin polymer adsorbent.
The purpose of the present invention is achieved through the following technical solutions.
It can be used for dyestuff and heavy metal ion adsorbed β-ring simultaneously in order to reach one kind provided by the purpose of the present invention
Dextrin polymer absorbant, it is characterised in that the adsorbent be using radical crosslinking copolymerization method, by modified beta-cyclodextrin with
Heterocycle vinyl monomer copolymerzation with cross-linking forms, and general structure is as follows:
Wherein, RIFor-Si (RI-1)2C(RI-2)3, RI-1=-H ,-CH3Or-Ph, RI-2=-H or-CH3；RII~RⅦFor-H
Or-CH3, RII~RⅦCan be identical, it can not also be identical；
In formula, work as RⅧ-1R1, R2, R4, R5Any of for-(CH2)n, and when n=0~3, then remaining for-H or-
CH3Or-CH2CH3, it can be identical, it can not also be identical；Work as RⅧ-2R2, R3, R4, R5, R6Any of for-(CH2)n, and n
When=0~3, then remaining is-H or-CH3Or-CH2CH3, it can be identical, it can not also be identical；Work as RⅧ-3R2, R4, R5In appoint
One is-(CH2)n, and when n=0~3, then remaining is-H or-CH3Or-CH2CH3, it can be identical, it can not also be identical.
A kind of preparation method of above-mentioned beta cyclo dextrin polymer adsorbent provided by the invention, this method includes following step
It is rapid:
(1) by 2~10 the first section of parts by weight protected silane beta-cyclodextrin derivatives, 0.6~20 parts by volume alkenyl acid anhydrides
It is dissolved in the pyridine of 25-150 parts by volume with 0.1~1.5 parts by weight 4-dimethylaminopyridine, under nitrogen protection in 40~80
Through cold water precipitating, washing, dry after DEG C reaction 14-24h, modified beta-cyclodextrin (β-CDs) is obtained.
(2) by 2~5 part by weight modified beta-cyclodextrins, 0.4~18 parts by volume heterocycle vinyl monomer and 0.1~1.2 parts by weight
Initiator is dissolved in 20~100 parts by volume organic solvents, under nitrogen protection in 55~80 DEG C of 10~30h of reaction, product warp
It is dried after precipitating reagent precipitating, water washing, beta cyclo dextrin polymer adsorbent can be obtained.
In the step of method made above (1), the first section protected silane beta-cyclodextrin derivative is bibliography
Method disclosed in (Biomacromolecules.2010,11,934-943) is prepared.The specific method is as follows: by 2~10 weights
Part beta-cyclodextrin stirring and dissolving is measured in the dry pyridine of 40~180 parts by volume, be cooled to 0 DEG C hereinafter, then will dissolved with 1~
20~100 parts by volume dry pyridine solution of 18 parts by weight silane protectants are slowly dropped in the solution, react 10 at room temperature
~remove pyridine afterwards for 24 hours, obtained solid product is re-dissolved in organic solvent and successively uses KHSO4Aqueous solution and deionized water
The remaining pyridine in organic solvent is washed, organic phase is collected and simultaneously removes solvent, obtain white solid product, be dried in vacuo, obtain the
One section protected silane beta-cyclodextrin derivative.Wherein, the silane protectant is ClSi (R1)2C(R2)3, wherein R1=-H ,-
CH3Or-Ph, R2=-H or-CH3。
In the step of method made above (1), the alkenyl acid anhydrides is (R1R2C=CR3CO)2O, wherein R1, R2, R3=-H
Or-CH3, R1, R2, R3Can be identical, it can not also be identical.
In the step of method made above (2), the heterocycle vinyl monomer is any in following general structure [A-C]
Kind:
R in A formula1, R2, R4, R5Any of be RxRyC=CRz-(CH2)n, Rx, Ry, Rz=-H or-CH3, Rx,
Ry, RzCan be identical, can not also be identical, and when n=0~3, then remaining is-H or-CH3Or-CH2CH3, it can be identical, it can also
With not identical.
R in B formula2, R3, R4, R5, R6Any of be RxRyC=CRz-(CH2)n, Rx, Ry, Rz=-H or-CH3,
Rx, Ry, RzCan be identical, can not also be identical, and when n=0~3, then remaining is-H or-CH3Or-CH2CH3, it can be identical,
It can not be identical.
R in C formula2, R4, R5Any of be RxRyC=CRz-(CH2)n, Rx, Ry, Rz=-H or-CH3, Rx, Ry,
RzCan be identical, can not also be identical, and when n=0~3, then remaining is-H or-CH3Or-CH2CH3, it can be identical, it can also be with
It is not identical.
In the step of method made above (2), the initiator is azodiisobutyronitrile, azobisisoheptonitrile or peroxidating
Any one of dibenzoyl.
In the step of method made above (2), the organic solvent is n,N-Dimethylformamide or toluene.
In the step of method made above (2), the precipitating reagent is any one of acetone, ethyl acetate or n-hexane.
It is worth noting that the corresponding relationship of parts by weight used in above method, parts by volume is: if solid weight part
Concrete unit be g, the concrete unit of corresponding volume part just should be mL；If the concrete unit of solid weight part is kg, corresponding
The concrete unit of parts by volume just should be L.
A kind of typical preparation route of beta cyclo dextrin polymer adsorbent is given below:
Above-mentioned beta cyclo dextrin polymer adsorbent provided by the invention application for absorption organic dyestuff and/or heavy metal from
Son.
Compared with the prior art, the advantages of the present invention are as follows:
(1) since the present invention is the β-ring for carrying out copolymerzation with cross-linking using heterocycle vinyl monomer and modified beta-cyclodextrin to prepare
Dextrin polymer absorbant, thus on the one hand, the cavity and organic matter that can use adsorbent cyclodextrin itself, which are formed, to be included
Object is to adsorb organic dyestuff, on the other hand, the heterocycle in adsorbent can provide again coordination atom with heavy metal ion coordination with
Adsorbing metal ions can thus allow organic dyestuff and heavy metal ion be adsorbed to the different loci of adsorbent, from
And effectively avoid the competitive Adsorption between them.
(2) imidazoles, pyridine or thiazole as contained in heterocycle vinyl monomer of the present invention are rigid base
Group, on the one hand, this rigid radical with cyclodextrine derivatives when being copolymerized because that can form porous, large specific surface area copolymerization
Object, thus the contact area of adsorbate and adsorbent can be increased, and then greatly improve the adsorption capacity of adsorbent；Another party
Face, rigid radical can change the polarity, size and shape etc. of cavity microenvironment to the modification in the second section of cyclodextrin, to increase
Clathration of the strong beta-cyclodextrin to organic matter.Therefore, obtained adsorbent has excellent adsorption effect to organic dyestuff, such as
The adsorbance Congo red to anionic dye is up to 1139mg/g, to the adsorbance of dye of positive ion rhodamine B up to 371mg/
G, while to heavy metal ion Cu2+Adsorbance up to 140mg/g, to Cd2+Adsorbance up to 165mg/g, it is seen that the absorption
Agent is more prominent than existing adsorbent adsorption effect, and application range is also more extensive.
(3) the beta cyclo dextrin polymer adsorbent provided by the invention not only absorption to single organic dyestuff or metal ion
Capacity is high, and by organic dyestuff (rhodamine B and/or Congo red etc.) and heavy metal ion (Cu2+And/or Cd2+Deng) common group
At mixed solution in, which can be equal to even higher than single adsorption system to the adsorption capacity of two pollutants,
Existing adsorbent is thus effectively improved for being gone simultaneously in mixed system due to organic dyestuff and heavy metal ion mutually inhibit
Except when effect difference status.
(4) preparation method provided by the invention is not only simple and easy, and is also heterocycle vinyl monomer and modified beta-cyclodextrin
It carries out copolymerzation with cross-linking and explores a new, effective approach the beta cyclo dextrin polymer adsorbent for preparing.
Detailed description of the invention
Fig. 1 is beta cyclo dextrin polymer adsorbent P β-CDs obtained by the embodiment of the present invention 33The infrared spectroscopy of -4-VP
Figure.In figure, 1737cm-1Place is the stretching vibration peak of C=O, 1621cm-1Place is the C=C stretching vibration peak of pyridine ring, 1490cm-1Place is the C=N stretching vibration peak of pyridine ring, thus illustrates P β-CDs3The preparation of -4-VP is successful.
Fig. 2 is beta cyclo dextrin polymer adsorbent P β-CDs obtained by the embodiment of the present invention 33The scanning electron microscope of -4-VP
Figure.The adsorbent contains loose porous structure as can be observed from Figure.
Specific embodiment
The present invention is specifically described below by embodiment.It is important to point out that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, and the person skilled in the art in the field can be with
Some nonessential modifications and adaptations are made to the present invention according to foregoing invention content.
It is worth noting that in order to investigate the absorption of above-mentioned beta cyclo dextrin polymer adsorbent prepared by present invention effect
Fruit, the present invention in application examples use following methods to organic dyestuff in simulated wastewater and heavy metal ion carried out absorption,
Detection and calculating:
Dyestuff or heavy metal ion or dyestuff and heavy metal ion are first configured to solution, adsorbent, room temperature is then added
Under in water bath chader with the speed oscillation of 100rpm for 24 hours, filtering, take supernatant detection dyestuff or heavy metal ion adsorbing
Residual concentration afterwards, and (1), (2) calculate adsorbent to the adsorbance and removal rate of dyestuff or heavy metal ion as follows:
In formula: qtIt is t moment adsorbent to the adsorbance of dyestuff or heavy metal ion, mg/g；C0For dyestuff or heavy metal from
The initial concentration of son, mg/L；CtFor the dyestuff of t moment (after absorption) or the concentration of heavy metal ion, mg/L；M is adsorbent
Quality, g；V is the volume of adsorbate, L；P is the removal rate of dyestuff or heavy metal ion, %.
Embodiment 1
(1) preparation of modified beta-cyclodextrin: by the pyridine that 2 parts by weight beta-cyclodextrin stirring and dissolvings are dry in 40 parts by volume
In, and 0 DEG C is down to hereinafter, the dry pyrrole of 30 parts by volume that 1.5 parts by weight trim,ethylchlorosilanes will have been dissolved to above-mentioned solution temperature
Pyridine solution is slowly dropped in the solution, reacts 12h at room temperature.Pyridine is removed after reaction, obtained solid product is molten
In 40 parts by volume chloroforms and successively with the KHSO of the 1mol/L of 50 parts by volume4The deionized water of aqueous solution and 50 parts by volume
The remaining pyridine in organic solvent is washed, organic phase is collected and simultaneously removes solvent, obtain white solid product, be dried in vacuo, obtain the
One section protected silane beta-cyclodextrin derivative.By 2 the first section of parts by weight protected silane beta-cyclodextrin derivatives, 0.6 volume
Part crotonic anhydride and 0.1 parts by weight 4-dimethylaminopyridine are completely dissolved in the pyridine of 25 parts by volume, under nitrogen protection in
Through cold water precipitating, washing, drying after 40 DEG C of reaction 14h, modified beta-cyclodextrin (β-CDs is obtained1)。
(2) preparation of beta cyclo dextrin polymer adsorbent: by 2.0 part by weight modified beta-cyclodextrin (β-CDs1), 0.4 volume
Part vinyl imidazole (VIm) and 0.1 parts by weight azobisisoheptonitrile are dissolved in 20 parts by volume n,N-Dimethylformamide, in nitrogen
In 55 DEG C of reaction 10h under gas shielded, product is dried after acetone precipitation, water washing, obtains beta cyclo dextrin polymer adsorbent P β-
CDs1-VIm。Pβ-CDs1The structural formula of-VIm is as follows:
Embodiment 2
(1) preparation of modified beta-cyclodextrin: by the pyridine that 7 parts by weight beta-cyclodextrin stirring and dissolvings are dry in 120 parts by volume
In, and 0 DEG C is down to hereinafter, the dry pyrrole of 40 parts by volume that 4.9 parts by weight trim,ethylchlorosilanes will have been dissolved to above-mentioned solution temperature
Pyridine solution is slowly dropped in the solution, reacts 19h at room temperature.Solvent is removed after reaction, obtained solid product is molten
In 60 parts by volume methylene chloride and successively with the KHSO of the 1mol/L of 100 parts by volume4The deionization of aqueous solution and 80 parts by volume
Remaining pyridine in water washing organic solvent collects organic phase and removes solvent, obtain white solid product, is dried in vacuo, obtains
First section protected silane beta-cyclodextrin derivative.By 7.7 the first section of parts by weight protected silane beta-cyclodextrin derivatives, 12 bodies
Product part methacrylic anhydride and 0.6 parts by weight 4-dimethylaminopyridine are completely dissolved in the pyridine of 120 parts by volume, are protected in nitrogen
Modified beta-cyclodextrin (β-CDs is obtained through cold water precipitating, washing, drying after 50 DEG C of reaction 16h under shield2)。
(2) preparation of beta cyclo dextrin polymer adsorbent: by 2.7 part by weight modified beta-cyclodextrin (β-CDs2), 5.4 volumes
Part 4- methyl -5- vinylthiazole (MVT) and 0.4 parts by weight azobisisoheptonitrile are dissolved in 40 parts by volume toluene, in nitrogen
In 70 DEG C of reaction 17h under protection, product is dried after acetone precipitation, water washing, obtains beta cyclo dextrin polymer adsorbent P β-
CDs2-MVT。Pβ-CDs2The structural formula of-MVT is as follows:
Embodiment 3
(1) preparation of modified beta-cyclodextrin: by the pyridine that 10 parts by weight beta-cyclodextrin stirring and dissolvings are dry in 180 parts by volume
In, and 0 DEG C is down to hereinafter, 100 parts by volume that 11 parts by weight tert-butyl chloro-silicanes will have been dissolved to above-mentioned solution temperature
Dry pyridine solution is slowly dropped in the solution, reacts 21h at room temperature.Solvent is removed after reaction, the solid that will be obtained
Product is dissolved in 150 parts by volume chloroforms and successively with the KHSO of the 1mol/L of 100 parts by volume4Aqueous solution and 100 parts by volume
Deionized water washing organic solvent in remaining pyridine, collect organic phase and simultaneously remove solvent, obtain white solid product, vacuum is dry
It is dry, obtain the first section protected silane beta-cyclodextrin derivative.6.1 the first section of parts by weight protected silane beta-cyclodextrins are derivative
Object, 4 parts by volume acrylic anhydrides and 0.5 parts by weight 4-dimethylaminopyridine are completely dissolved in the pyridine of 100 parts by volume, in nitrogen
Modified beta-cyclodextrin (β-CDs is obtained for 24 hours afterwards through cold water precipitating, washing, drying in 70 DEG C of reactions under protection3)。
(2) preparation of beta cyclo dextrin polymer adsorbent: by 3.9 part by weight modified beta-cyclodextrin (β-CDs3), 13 volumes
Part 4-vinylpridine (4-VP) and 1 parts by weight azodiisobutyronitrile are dissolved in 65 parts by volume n,N-Dimethylformamide,
In 60 DEG C of reaction 30h under nitrogen protection, product is precipitated through n-hexane, is dried after water washing, obtains beta cyclo dextrin polymer absorption
Agent P β-CDs3-4-VP。Pβ-CDs3The structural formula of -4-VP is as follows:
Embodiment 4
(1) preparation of modified beta-cyclodextrin: by the pyridine that 5 parts by weight beta-cyclodextrin stirring and dissolvings are dry in 120 parts by volume
In, and 0 DEG C is down to hereinafter, 55 parts by volume for having dissolved 5 parts by weight tert-butyl chloro-silicanes are done to above-mentioned solution temperature
Dry pyridine solution is slowly dropped in the solution, reacts 20h at room temperature.Solvent is removed after reaction, and obtained solid is produced
Object is dissolved in 60 parts by volume methylene chloride and successively with the KHSO of the 2mol/L of 80 parts by volume4Aqueous solution and 80 parts by volume go from
Remaining pyridine in sub- water washing organic solvent collects organic phase and removes solvent, obtain white solid product, is dried in vacuo, obtains
To the first section protected silane beta-cyclodextrin derivative.By 4.7 the first section of parts by weight protected silane beta-cyclodextrin derivatives, 10
Parts by volume methacrylic anhydride and 0.7 parts by weight 4-dimethylaminopyridine are completely dissolved in the pyridine of 70 parts by volume, in nitrogen
Modified beta-cyclodextrin (β-CDs is obtained through cold water precipitating, washing, drying after 80 DEG C of reaction 17h under protection4)。
(2) preparation of beta cyclo dextrin polymer adsorbent: by 3.5 part by weight modified beta-cyclodextrin (β-CDs4), 8 parts by volume
N- allyl imidazole (AIm) and 0.6 parts by weight dibenzoyl peroxide are dissolved in 50 parts by volume toluene, under nitrogen protection in
For 24 hours, product is precipitated through ethyl acetate, is dried after water washing for 80 DEG C of reactions, obtains beta cyclo dextrin polymer adsorbent P β-CDs4-
AIm。Pβ-CDs4The structural formula of-AIm is as follows:
Embodiment 5
(1) preparation of modified beta-cyclodextrin: 3.6 parts by weight beta-cyclodextrins are dissolved in the dry pyridine of 70 parts by volume,
And 0 DEG C is down to hereinafter, 35 parts by volume for having dissolved 4.0 parts by weight tert-butyl chloro-silicanes are dry to above-mentioned solution temperature
Pyridine solution is slowly dropped in the solution, reacts 12h at room temperature.Solvent is removed after reaction, the solid product that will be obtained
It is dissolved in 80 parts by volume methylene chloride and successively with the KHSO of the 1mol/L of 50 parts by volume4The deionization of aqueous solution and 60 parts by volume
Remaining pyridine in water washing organic solvent collects organic phase and removes solvent, obtain white solid product, is dried in vacuo, obtains
First section protected silane beta-cyclodextrin derivative.By 10.0 the first section of parts by weight protected silane beta-cyclodextrin derivatives, 20
Parts by volume crotonic anhydride and 1.5 parts by weight 4-dimethylaminopyridine are completely dissolved in the pyridine of 150 parts by volume, in nitrogen protection
Under after 70 DEG C of reaction 20h through cold water precipitating, washing, dry, obtain modified beta-cyclodextrin (β-CDs5)。
(2) preparation of beta cyclo dextrin polymer adsorbent: by 5.0 part by weight modified beta-cyclodextrin (β-CDs5), 18 volumes
Part 4- methyl -5- vinylthiazole (MVT) and 1.2 parts by weight azodiisobutyronitriles are dissolved in 100 parts by volume N, N- dimethyl methyls
In amide, under nitrogen protection in 75 DEG C of reaction 28h, product is precipitated through n-hexane, is dried after water washing, and it is poly- to obtain beta-cyclodextrin
Close object adsorbent P β-CDs5-MVT。Pβ-CDs5The structural formula of-MVT is as follows:
Application examples 1-18
Dyestuff or heavy metal ion or dyestuff and heavy metal ion are first configured to solution by table 1 or 2 by each application examples, then
Adsorbent is added by table 1 or 2, is adsorbed for 24 hours in water bath chader with the speed oscillation of 100rpm at room temperature, filtering takes supernatant
Liquid detects the residual concentration of dyestuff or heavy metal ion after absorption, is computed absorption of the adsorbent to dyestuff or heavy metal ion
Amount and removal rate are shown in Table 1 or 2:
Absorption of the different adsorbents of table 1 to organic dyestuff or heavy metal ion unitary system
Absorption of the different adsorbents of table 2 to organic dyestuff and heavy metal ion mixed system
Claims (7)
1. one kind can be used for dyestuff and heavy metal ion adsorbed beta cyclo dextrin polymer adsorbent simultaneously, it is characterised in that the suction
Attached dose is formed by modified beta-cyclodextrin and heterocycle vinyl monomer copolymerzation with cross-linking, structure using radical crosslinking copolymerization method
General formula is as follows:
Wherein, RIFor-Si (RI-1)2C(RI-2)3, RI-1=-H ,-CH3Or-Ph, RI-2=-H or-CH3；RII~RⅦFor-H or-CH3,
RII~RⅦCan be identical, it can not also be identical；
In formula, work as RⅧ-1R1, R2, R4, R5Any of for-(CH2)n, and when n=0~3, then remaining is-H or-CH3Or-
CH2CH3, it can be identical, it can not also be identical；Work as RⅧ-2R2, R3, R4, R5, R6Any of for-(CH2)n, and n=0~3
When, then remaining is-H or-CH3Or-CH2CH3, it can be identical, it can not also be identical；Work as RⅧ-3R2, R4, R5Any of for-
(CH2)n, and when n=0~3, then remaining is-H or-CH3Or-CH2CH3, it can be identical, it can not also be identical.
2. the preparation method of beta cyclo dextrin polymer adsorbent described in a kind of claim 1, method includes the following steps:
(1) by 2~10 the first section of parts by weight protected silane beta-cyclodextrin derivatives, 0.6~20 parts by volume alkenyl acid anhydrides and 0.1
~1.5 parts by weight 4-dimethylaminopyridine are dissolved in the pyridine of 25-150 parts by volume, anti-in 40~80 DEG C under nitrogen protection
It answers after 14-24h through cold water precipitating, washing, dry, obtains modified beta-cyclodextrin；
(2) 2~5 part by weight modified beta-cyclodextrins, 0.4~18 parts by volume heterocycle vinyl monomer and 0.1~1.2 parts by weight are caused
Agent is dissolved in 20~100 parts by volume organic solvents, and under nitrogen protection in 55~80 DEG C of 10~30h of reaction, product is through precipitating
It is dried after agent precipitating, water washing, beta cyclo dextrin polymer adsorbent can be obtained.
3. in the step of preparation method of beta cyclo dextrin polymer adsorbent according to claim 2, this method (1), institute
Stating alkenyl acid anhydrides is (R1R2C=CR3CO)2O, wherein R1, R2, R3=-H or-CH3, R1, R2, R3Can be identical, it can not also phase
Together.
4. in the step of preparation method of beta cyclo dextrin polymer adsorbent according to claim 2 or 3, this method (2),
The heterocycle vinyl monomer is any one of following general structure [A-C]:
R in A formula1, R2, R4, R5Any of be RxRyC=CRz-(CH2)n, Rx, Ry, Rz=-H or-CH3, Rx, Ry, Rz
Can be identical, can not also be identical, and when n=0~3, then remaining is-H or-CH3Or-CH2CH3, it can be identical, it can also not
It is identical.
R in B formula2, R3, R4, R5, R6Any of be RxRyC=CRz-(CH2)n, Rx, Ry, Rz=-H or-CH3, Rx, Ry,
RzCan be identical, can not also be identical, and when n=0~3, then remaining is-H or-CH3Or-CH2CH3, it can be identical, it can also be with
It is not identical.
R in C formula2, R4, R5Any of be RxRyC=CRz-(CH2)n, Rx, Ry, Rz=-H or-CH3, Rx, Ry, RzIt can
, can not also be identical with identical, and when n=0~3, then remaining is-H or-CH3Or-CH2CH3, it can be identical, it can not also phase
Together.
5. in the step of preparation method of beta cyclo dextrin polymer adsorbent according to claim 2 or 3, this method (2),
The initiator is any one of azodiisobutyronitrile, azobisisoheptonitrile or dibenzoyl peroxide.
6. in the step of preparation method of beta cyclo dextrin polymer adsorbent according to claim 4, this method (2), institute
Stating initiator is any one of azodiisobutyronitrile, azobisisoheptonitrile or dibenzoyl peroxide.
7. a kind of application of beta cyclo dextrin polymer adsorbent is absorption organic dyestuff and/or heavy metal ion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810968743.6A CN109046280B (en) | 2018-08-23 | 2018-08-23 | Beta-cyclodextrin polymer adsorbent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810968743.6A CN109046280B (en) | 2018-08-23 | 2018-08-23 | Beta-cyclodextrin polymer adsorbent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109046280A true CN109046280A (en) | 2018-12-21 |
| CN109046280B CN109046280B (en) | 2021-04-02 |
Family
ID=64756834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810968743.6A Active CN109046280B (en) | 2018-08-23 | 2018-08-23 | Beta-cyclodextrin polymer adsorbent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109046280B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110129922A (en) * | 2019-05-10 | 2019-08-16 | 哈尔滨工业大学 | A kind of temperature sensitive type beta-cyclodextrin/p (NIPAM-co-MAA) electrospinning fibre adsorbent and preparation method thereof |
| WO2020168104A1 (en) * | 2019-02-14 | 2020-08-20 | Cyclopure, Inc. | Charge-bearing cyclodextrin polymeric materials and methods of making and using same |
| US11001645B2 (en) | 2019-02-14 | 2021-05-11 | Cyclopure, Inc. | Charge-bearing cyclodextrin polymeric materials and methods of making and using same |
| CN113457646A (en) * | 2021-07-13 | 2021-10-01 | 长沙经济技术开发区水质净化工程有限公司 | Preparation method of modified fiber ball and application of modified fiber ball in absorbing Congo red |
| CN113845606A (en) * | 2021-09-28 | 2021-12-28 | 称意科技研发园(江苏)有限公司 | Modified cyclodextrin dye adsorbent and preparation method thereof |
| CN114573733A (en) * | 2022-03-22 | 2022-06-03 | 安徽徽科生物工程技术有限公司 | Organic silicon modified cyclodextrin organic matter, preparation method, drug delivery device and application |
| CN116059983A (en) * | 2023-03-07 | 2023-05-05 | 济宁市圣奥精细化工有限公司 | Medicament for treating textile printing and dyeing wastewater |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872836A (en) * | 2012-09-11 | 2013-01-16 | 安徽理工大学 | Cyclodextrin immobilized macromolecular polymer and preparation method and application thereof |
| CN103483594A (en) * | 2013-09-12 | 2014-01-01 | 安徽理工大学 | Cyclodextrin immobilized micro-cross-linked high-molecular polymer, method for preparing same and application thereof |
| CN104140431A (en) * | 2014-06-27 | 2014-11-12 | 江南大学 | Rhodamine fluorescent probe capable of detecting and separating heavy metal ions, and preparation method of rhodamine fluorescent probe |
| US20170173560A1 (en) * | 2015-04-20 | 2017-06-22 | Cornell University | Porous cyclodextrin polymeric materials and methods of making and using same |
| CN107096510A (en) * | 2017-04-14 | 2017-08-29 | 江南大学 | A kind of preparation method and applications of supermolecule adsorbent |
-
2018
- 2018-08-23 CN CN201810968743.6A patent/CN109046280B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872836A (en) * | 2012-09-11 | 2013-01-16 | 安徽理工大学 | Cyclodextrin immobilized macromolecular polymer and preparation method and application thereof |
| CN103483594A (en) * | 2013-09-12 | 2014-01-01 | 安徽理工大学 | Cyclodextrin immobilized micro-cross-linked high-molecular polymer, method for preparing same and application thereof |
| CN104140431A (en) * | 2014-06-27 | 2014-11-12 | 江南大学 | Rhodamine fluorescent probe capable of detecting and separating heavy metal ions, and preparation method of rhodamine fluorescent probe |
| US20170173560A1 (en) * | 2015-04-20 | 2017-06-22 | Cornell University | Porous cyclodextrin polymeric materials and methods of making and using same |
| CN107096510A (en) * | 2017-04-14 | 2017-08-29 | 江南大学 | A kind of preparation method and applications of supermolecule adsorbent |
Non-Patent Citations (5)
| Title |
|---|
| FEIPING ZHAO ET AL: "EDTA-Cross-Linked β‑Cyclodextrin: An Environmentally Friendly Bifunctional Adsorbent for Simultaneous Adsorption of Metals and Cationic Dyes", 《ENVIRON. SCI. TECHNOL.》 * |
| GOU, PENG-FEI ET AL: "Synthesis, Self-Assembly, and Drug-Loading Capacity of Well-Defined Cyclodextrin-Centered Drug-Conjugated Amphiphilic A(14)B(7) Miktoarm Star Copolymers Based on Poly(epsilon-caprolactone) and Poly(ethylene glycol)", 《BIOMACROMOLECULES》 * |
| SHAO, SHIQUN ET AL: "Jellyfish-Shaped Amphiphilic Dendrimers: Synthesis and Formation of Extremely Uniform Aggregates", 《MACROMOLECULES》 * |
| 江子滔: "以β-环糊精、2-羟丙基-β-环糊精和4-乙烯吡啶为功能单体制备氟比洛芬分子印迹聚合物及其吸附特征", 《过程工程学报》 * |
| 许悦: "β－环糊精聚合物对亚甲基蓝染料分子的吸附对比研究", 《广州化工》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114891133A (en) * | 2019-02-14 | 2022-08-12 | 赛克洛珀股份有限公司 | Charged cyclodextrin polymer materials and methods of making and using the same |
| WO2020168104A1 (en) * | 2019-02-14 | 2020-08-20 | Cyclopure, Inc. | Charge-bearing cyclodextrin polymeric materials and methods of making and using same |
| US11001645B2 (en) | 2019-02-14 | 2021-05-11 | Cyclopure, Inc. | Charge-bearing cyclodextrin polymeric materials and methods of making and using same |
| CN113056516A (en) * | 2019-02-14 | 2021-06-29 | 赛克洛珀股份有限公司 | Charged cyclodextrin polymer materials and methods of making and using the same |
| US11155646B2 (en) | 2019-02-14 | 2021-10-26 | Cyclopure, Inc. | Charge-bearing cyclodextrin polymeric materials and methods of making and using same |
| CN113056516B (en) * | 2019-02-14 | 2022-05-13 | 赛克洛珀股份有限公司 | Charged cyclodextrin polymer materials and methods of making and using the same |
| CN114891133B (en) * | 2019-02-14 | 2023-11-21 | 赛克洛珀股份有限公司 | Charged cyclodextrin polymer materials and methods of making and using the 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 |
| CN110129922A (en) * | 2019-05-10 | 2019-08-16 | 哈尔滨工业大学 | A kind of temperature sensitive type beta-cyclodextrin/p (NIPAM-co-MAA) electrospinning fibre adsorbent and preparation method thereof |
| CN113457646A (en) * | 2021-07-13 | 2021-10-01 | 长沙经济技术开发区水质净化工程有限公司 | Preparation method of modified fiber ball and application of modified fiber ball in absorbing Congo red |
| CN113845606A (en) * | 2021-09-28 | 2021-12-28 | 称意科技研发园(江苏)有限公司 | Modified cyclodextrin dye adsorbent and preparation method thereof |
| CN113845606B (en) * | 2021-09-28 | 2022-12-16 | 称意科技研发园(江苏)有限公司 | Modified cyclodextrin dye adsorbent and preparation method thereof |
| CN114573733A (en) * | 2022-03-22 | 2022-06-03 | 安徽徽科生物工程技术有限公司 | Organic silicon modified cyclodextrin organic matter, preparation method, drug delivery device and application |
| CN114573733B (en) * | 2022-03-22 | 2023-05-23 | 安徽徽科生物工程技术有限公司 | Organosilicon modified cyclodextrin organic matter, preparation method, drug administration device and application |
| CN116059983B (en) * | 2023-03-07 | 2023-08-22 | 济宁市圣奥精细化工有限公司 | Medicament for treating textile printing and dyeing wastewater |
| CN116059983A (en) * | 2023-03-07 | 2023-05-05 | 济宁市圣奥精细化工有限公司 | Medicament for treating textile printing and dyeing wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109046280B (en) | 2021-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109046280A (en) | A kind of beta cyclo dextrin polymer adsorbent and its preparation method and application | |
| Qin et al. | β-Cyclodextrin-crosslinked polymeric adsorbent for simultaneous removal and stepwise recovery of organic dyes and heavy metal ions: fabrication, performance and mechanisms | |
| Usman et al. | Simultaneous adsorption of heavy metals and organic dyes by β-Cyclodextrin-Chitosan based cross-linked adsorbent | |
| Liu et al. | Rapid and efficient removal of heavy metal and cationic dye by carboxylate-rich magnetic chitosan flocculants: role of ionic groups | |
| Zhou et al. | Cellulose/chitin beads for adsorption of heavy metals in aqueous solution | |
| Lee et al. | Equilibrium and kinetic studies of copper (II) ion uptake by chitosan-tripolyphosphate chelating resin | |
| CN106861631B (en) | Functionalized hollow mesoporous silica nano microsphere, preparation method thereof and application thereof in adsorption of heavy metal ions | |
| Song et al. | Magnetic thiolated/quaternized-chitosan composites design and application for various heavy metal ions removal, including cation and anion | |
| Yang et al. | Improved antifouling and antimicrobial efficiency of ultrafiltration membranes with functional carbon nanotubes | |
| CN107892733B (en) | Heavy metal wastewater ion adsorption resin and preparation method thereof | |
| Zhai et al. | Metal ion-small molecule complex imprinted polymer membranes: Preparation and separation characteristics | |
| Ray et al. | Peptide-based surface modified silica particles: adsorption materials for dye-loaded wastewater treatment | |
| CN113750972B (en) | Chromium ion adsorbent and preparation method thereof | |
| CN102974326A (en) | Preparation of silicon dioxide-cyclodextrin nanometer adsorbing agent and application of adsorbing agent in adsorption of heavy metal ion Cu<2+> in sewage | |
| Chao et al. | Using NaCl particles as porogen to prepare a highly adsorbent chitosan membranes | |
| Wu et al. | Organosilane-functionalized Fe3O4 composite particles as effective magnetic assisted adsorbents | |
| Su et al. | Adsorption of Ni 2+ on the surface of molecularly imprinted adsorbent from Penicillium chysogenum mycelium | |
| CN106632922B (en) | The method of the preparation method and its modified polyvinilidene fluoride microfiltration membranes of block polymer containing hydrophilic segment | |
| Elgamal et al. | Synthesis and characterization of hydrogel-based magnetite nanocomposite adsorbents for the potential removal of Acid Orange 10 dye and Cr (VI) ions from aqueous solution | |
| Filipkowska | Adsorption and desorption of reactive dyes onto chitin and chitosan flakes and beads | |
| Cao et al. | Preparation of β-cyclodextrin multi-decorated halloysite nanotubes as a catalyst and nanoadsorbent for dye removal | |
| CN106238010B (en) | A kind of chelating type metal ion floating agent, preparation method and its application method | |
| He et al. | Organic-soluble chitosan-g-PHMA (PEMA/PBMA)-bodipy fluorescent probes and film by RAFT method for selective detection of Hg2+/Hg+ ions | |
| Kimura et al. | The interaction between reactive dye containing vinylsulfone group and chitosan microspheres | |
| Wang et al. | Functionalization of loofah fibers via surface-initiated AGET ATRP for synergic adsorption of multiple pollutants from water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |