CN109806853A - It is a kind of for adsorbing the support ionic liquid material preparation method of the anionic of basic dye - Google Patents
It is a kind of for adsorbing the support ionic liquid material preparation method of the anionic of basic dye Download PDFInfo
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- CN109806853A CN109806853A CN201910150013.XA CN201910150013A CN109806853A CN 109806853 A CN109806853 A CN 109806853A CN 201910150013 A CN201910150013 A CN 201910150013A CN 109806853 A CN109806853 A CN 109806853A
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Abstract
The present invention provides a kind of for adsorbing the preparation method of the support ionic liquid material of the anionic of basic dye, obtains supporting ionic liquid (ImI@TpBd- (SO with the anionic to basic dye high adsorption capacity3)2) material.The invention has the advantages that: by the present invention in that one step of sulfonic acid group is introduced into covalent organic polymer with the construction unit containing sulfonic acid group, assign the hole wall negative electrical charge of material, and glyoxaline cation is introduced into polymer, change absorption microenvironment, the adsorbance to dyestuff is further increased to the interaction of dyestuff using imidazoles, improves the rate of adsorption to dyestuff.Using the method synthesis uniform particle sizes of normal temperature and pressure solvent heat, to the covalent organic polymer material ImI@TpBd- (SO of basic dye selectivity with higher, high adsorption capacity3)2.The invention is expected to the adsorbent as basic dye for handling water pollution.
Description
Technical field
The present invention relates to a kind of ImI@TpBd- (SO3)2Preparation method and application, belong to technical field of polymer materials.
Background technique
Synthetic dyestuffs are widely used in many fields, such as various textiles, paper, leather, product purchasing, food processing, modeling
Material, cosmetics, rubber, printing, dyestuff manufacturing industry etc..The total flow of dyestuff is more than 10,000 public affairs in whole world textile industry
Ton/year and about 100 public tons/year.
Dyestuff itself has high toxicity, and dyestuff is discharged into water or even minimal amount of dyestuff causes shadow to aquatile
It rings, and dye stability is good, difficulty or ease degradation, the mankind and animals and plants is influenced maximum.Therefore development has high adsorption capacity to dyestuff,
The high material of the rate of adsorption has become a top priority.
Covalent organic polymer material (TpBd- (SO3)2) it is to be formed and being covalently keyed by organic structure ele
One kind has the novel high polymer porous material of micropore or meso-hole structure, swift and violent as a kind of development of novel absorption material.
Compared with conventional dyes adsorbent material (such as activated carbon), TpBd- (SO3)2Small with density, large specific surface area is easy to functionalization,
The advantages that aperture is adjustable, various structures, thermal stability is good is widely used in gas separation and storage, is catalyzed, inhale
It is attached, photodynamic therapy, chromatographic isolation etc..As the place to interact with guest molecule, TpBd- (SO3)2The work in hole
Journey includes the engineering of hole and the engineering of hole wall functional group absorption has been served it is extremely important.Mesoporous material is even
Be it is big it is mesoporous be conducive to mass transfer, improve the rate of adsorption, be usually used in synthesising mesoporous TpBd- (SO at present3)2Method be to pass through increase
With body length, but this method increases ligand limited length, therefore hinders TpBd- (SO3)2Further apply.TpBd-
(SO3)2The engineering of hole wall functional group assigns its interaction force different from guest molecule.In most cases,
TpBd-(SO3)2It is usually constructed by neutral construction unit, with guest molecule by weak non-covalent interaction, therefore
Make it using limited.Large-sized functional group means there are more interaction forces with guest molecule, implies enhancing point
From function, but large-sized functional group is difficult to successfully modify TpBd- (SO3)2Hole in.Ionic liquid is by organic sun
Ion and organic or inorganic anion are constituted.TpBd- (SO at present3)2It is also less in the application of dye wastewater treatment, and adsorbance
It is low, poor selectivity.Therefore, it is badly in need of synthesising mesoporous TpBd- (SO3)2Material, then using modifying TpBd- after mature ILs
(SO3)2Method, by large-sized functional group modification to TpBd- (SO3)2Hole wall in so that material and dyestuff have it is more, more
Strong interaction, to increase adsorbance, the rate of adsorption and selectivity.Therefore, mesoporous TpBd- (SO is arrived into modification after ILs3)2
In, a kind of high mass transfer rate and selective adsorbent material can be prepared.
Summary of the invention
In view of this, the invention is directed to anion of a kind of pair of basic dye with high adsorption capacity and selectivity
Type supports ionic liquid material.
In order to achieve the above objectives, the technical solution of the invention is achieved in that
By Ionic Liquid Modified to mesoporous TpBd- (SO3)2In, synthesize a kind of anionic support ionic liquid material.
Adsorbent material of the invention has very high adsorbance, the high rate of adsorption to basic dye methylene blue, and has
Good selectivity.
The invention also discloses the preparation methods of this adsorbent material:
(1) three aldehyde radical phloroglucin (Tp) of monomer will be constructed and benzidine-disulfonic acid (Bd) is separately added into ethanol solution,
Ultrasound dissolves it sufficiently, mixes in 100mL three neck round bottom flask, and the three neck round bottom flask is separately connected thermometer, nitrogen
Balloon and vacuum pump after being vacuumized three-necked flask with vacuum pump, discharge the nitrogen in nitrogen ball, under the conditions of nitrogen protection,
80 DEG C of reaction 8h；11000 turns of centrifugation 10min, obtain thick TpBd- (SO3)2；
(2) it washs, the thick TpBd- (SO that will be prepared in step (1)3)2It is placed in there-necked flask, about obtains 30mg, be added
50mL n,N-Dimethylformamide, under nitrogen protection, 150 DEG C of reaction 2h, then 11000 turns of centrifugation 10min, obtain TpBd-
(SO3)2, repeated washing is primary, washes away unreacted reactant；
(3) solvent is replaced, by the about 30-40mg TpBd- (SO after step (2) are washed3)2It is placed in there-necked flask, adds
Enter 50-60mL ethyl alcohol, 2h, 11000 turns of centrifugation 10min, 60 DEG C of vacuum drying are reacted under nitrogen protection；
(4) it is modified after ILs, the TpBd- (SO that step (3) is obtained3)2It is placed in ethyl alcohol, imidazoles is added, in room temperature normal pressure
Under the conditions of react 36h, 11000 turns, be centrifuged 10min, 60 DEG C of vacuum drying, obtain with the yin to basic dye high adsorption capacity from
Subtype supports ionic liquid material ImI@TpBd- (SO3)2。
Further, the molar ratio of Tp and Bd is 0.075:0.1125 in step (1).
Further, TpBd- (SO in step (2)3)2: imidazoles: the ratio of ethyl alcohol is 10mg:34mg:10mL.
In the above method, unmodified imidazole ion liquid, the corresponding covalent organic polymer (TpBd- of the preparation present invention
(SO3)2)。
Compared with the existing technology, the anionic that basic dye is adsorbed described in the invention supports ionic liquid material
Preparation method and application had the advantage that in dye wastewater treatment
Present invention introduces SO3The mesoporous covalent organic polymer material of H functionalization makes it provide larger surface as carrier
Long-pending and highdensity negative electrical charge.Using acid-base neutralization method synthesize support ionic liquid material, to alkaline methylene base indigo plant have it is higher
Selectivity, the fast rate of adsorption and good selectivity.The material is by the specific surface area of covalent organic polymer and large aperture
Combine with the effect identification of the multiple functions group of ionic liquid, has broad application prospects.And dyestuff is adsorbed with current
Existing material (such as: active carbon, mesoporous silicon) compare, this method has that material preparation is convenient, selectivity is high, pre-treatment letter
The advantages that single, convenient for popularizing.
Detailed description of the invention
The attached drawing for constituting a part of the invention is used to provide to further understand the invention, present invention wound
The illustrative embodiments and their description made are used to explain the present invention creation, do not constitute the improper restriction to the invention.?
In attached drawing:
Fig. 1 prepares schematic diagram for adsorbent material described in the invention embodiment.
Fig. 2 is TpBd- (SO described in the invention embodiment3)2With ImI@TpBd- (SO3)2's13C cross polarization evil spirit
Angle spinning NMR spectrum.
Fig. 3 is (b) TpBd- (SO described in the invention embodiment3)2(a) ImI@TpBd- (SO3)2Fourier
Infrared spectrogram.
Fig. 4, Fig. 5 are respectively TpBd- (SO described in the invention embodiment3)2With ImI@TpBd- (SO3)2Scanning
Electron microscope.
Fig. 6 is ImI@TpBd- (SO described in the invention embodiment3)2Nitrogen adsorption desorption isotherm.
Fig. 7 is ImI@TpBd- (SO described in the invention embodiment3)2Graph of pore diameter distribution.
Fig. 8 is TpBd- (SO described in the invention embodiment3)2With ImI@TpBd- (SO3)2To various concentration
The response curve of methylene blue.
Fig. 9 is TpBd- (SO described in the invention embodiment3)2With ImI@TpBd- (SO3)2Adsorption dynamics adsorption kinetics it is bent
Line.
Figure 10 is ImI@TpBd- (SO described in the invention embodiment3)2Acid basic dye specificity experiments.
Figure 11 is ImI@TpBd- (SO described in the invention embodiment3)2Basic dye specificity experiments.
Specific embodiment
In order to keep features described above and advantage of the present invention more clear and be readily appreciated that, below in conjunction with attached drawing to of the invention
Embodiment is described in further detail.
Covalent organic polymer material described in following embodiments is oneself synthesis, other (three aldehyde radical phloroglucins (Tp)
With benzidine-disulfonic acid (Bd), imidazoles, ethyl alcohol and n,N-Dimethylformamide) be it is commercially available, using preceding without any processing.
Embodiment 1
The present invention provides a kind of preparation method of anionic support ionic liquid material for adsorbing basic dye, specific to make
Standby route is as shown in Figure 1:
(1) 0.075mmol Tp and 0.1125mmol Bd being separately added into ethanol solution, ultrasound dissolves it sufficiently,
It is mixed in 100mL three neck round bottom flask, which is separately connected thermometer, nitrogen ball and vacuum pump, uses vacuum
Pump three-necked flask is vacuumized after, discharge nitrogen ball in nitrogen, under nitrogen protection, 80 DEG C, react 8h, then 11000 turns,
It is centrifuged 10min, obtains thick TpBd- (SO3)2；Washing, by the thick TpBd- (SO of obtained 30mg3)2It is placed in 50mL N, N- dimethyl
In formamide, under nitrogen protection, 150 DEG C, 2h is reacted, 11000 turns, 10min is centrifuged, is repeated once, washes away unreacted reactant.It will about
30mg TpBd-(SO3)2It is placed in 50mL ethyl alcohol, 2h is reacted under nitrogen protection, 11000 turns, is centrifuged 10min, 60 DEG C of vacuum are dry
It is dry.
(2) the covalent organic polymer material TpBd- (SO of 10mg is taken3)2It is scattered in 10mL ethyl alcohol, is then quickly added thereto
Enter 34.0mg imidazoles, 600 turns of stirrings 36h, 11000rpm are centrifuged 10min, and ethanol washing is obtained having and be adsorbed to basic dye height
The anionic of amount supports ionic liquid material ImI@TpBd- (SO3)2。
According to the method described above, the material of step (2), the corresponding TpBd- (SO of the preparation present invention are not carried out3)2。
The performance of the adsorbent material provided for a better understanding of the present invention, the basic material used to synthesis --- covalently
Organic material carries out13C cross polarization magic-angle-spinning nuclear magnetic resonance spectrum, FTIR spectrum, scanning electron microscope (SEM), hole
Diameter analysis is characterized.
Fig. 2 is TpBd- (SO3)2With ImI@TpBd- (SO3)2's13C cross polarization magic-angle-spinning nuclear magnetic resonance spectrum.In figure
The peak occurred at 180ppm is the peak C=O that imines is condensed and is converted into after ketone form structure, and the peak occurred at 140ppm in figure is Asia
The peak of C-N that amine is condensed and is converted into after ketone form structure, the peak that the place 165ppm occurs are the C in imidazole molecule after modifying imidazoles
The peak of=N.Illustrate that imidazoles has successfully been modified in TpBd- (SO3)2In.
Fig. 3 is TpBd- (SO3)2With ImI@TpBd- (SO3)2FTIR spectrum figure, 1240cm-1The absorption of appearance
Peak is that the stretching vibration for the C-N that imines is condensed and is converted into after ketone form structure causes, 1615cm-1It is that the stretching vibration of C=O causes
, 1589cm-1Caused by being the stretching vibration of C=C, 1448cm-1Absorption peak be in phenyl ring caused by C=C skeletal vibration.
1196cm-1It is SO2Stretching vibration caused by.750cm-1Absorption peak be that the stretching vibration of imidazole molecule C=N causes.
Fig. 4, Fig. 5 are TpBd- (SO respectively3)2With ImI@TpBd- (SO3)2Scanning electron microscope (SEM) photograph.As can be seen from the figure altogether
Valence organic polymer is more uniform at irregular bulk.
Fig. 6 is ImI@TpBd- (SO3)2Nitrogen adsorption desorption isotherm.As can be seen from the figure ImI@TpBd- (SO3)2
It shows IV thermoisopleth, shows mesoporous presence.Adsorption curve and desorption curve form a close ring, and the platform area of hysteresis loop goes out
Present P/P0 0.1-0.45。
ImI TpBd- (the SO that Fig. 7 is3)2Graph of pore diameter distribution.As shown, ImI@TpBd- (SO3)2With big Jie
Hole, aperture are 14.5nm and 23.8nm.
Embodiment 2
Study the absorption property (as shown in Figure 8) of the adsorbent material.By the TpBd- (SO of 1mg3)2With the ImI@TpBd- of 1mg
(SO3)2Being separately added into equipped with 35mL concentration is respectively 20-100ug mL-1MB standard liquid 50mL centrifuge tube in.By the mixture
Concussion a period of time at room temperature, then its absorbance value is surveyed with ultraviolet-uisible spectrophotometer.As can be seen from Figure 8, with
The raising of methylene blue concentration, adsorbance increases, under same concentrations, ImI@TpBd- (SO3)2Large amount of adsorption in TpBd-
(SO3)2Adsorbance.
Embodiment 3
Study the dynamic performance of the adsorbent material.Weigh ImI@TpBd- (SO prepared by the embodiment 1 of 1mg3)2And implementation
Example 1 prepares TpBd- (SO3)2It is respectively placed in 50mL centrifuge tube, adds 35mL 100ug mL-1Methylene blue solution,
0-18h is shaken at room temperature, then surveys its absorbance value with ultraviolet-uisible spectrophotometer.As shown in figure 9, ImI@TpBd- (SO3)2It is right
The 12h that is adsorbed on of methylene blue reaches balance.ImI@TpBd-(SO3)2Than TpBd- (SO3)2With the higher rate of adsorption, especially
It is in 0-0.5h.
Embodiment 4
It selects reactive brilliant red (RBR) for the negative dyestuff competitor of methylene blue (MB), studies the selection of the adsorbent material
Performance.Compound concentration is 100ug L respectively-1RBR and MB singly mark solution and both mixed solution.Take 35mL prepared
Solution is added in centrifuge tube, is separately added into the ImI@TpBd- (SO of 1mg3)2, 18h is shaken at room temperature, then is divided with UV, visible light
Luminosity measures its absorbance value.As shown in Figure 10 in single mark competitive Adsorption experiment of RBR and MB, ImI@TpBd- (SO3)2To MB
With good adsorption effect, to RBR almost without adsorption effect.In mixed mark competitive Adsorption experiment, although ImI@TpBd-
(SO3)2Preferable adsorption effect is maintained to MB, it is small to the adsorbance of RBR, illustrate ImI@TpBd- (SO3)2There is selection to know MB
Other property.
Embodiment 5
It selects reddish black A (AZA), reddish black B (AZB), azure C (AZC), bismarck brown (BBR), auramine (AO), crystal violet (CV),
Basic Orange (BO), dimethyl diaminophenazine chloride (BR) are the positive dyestuff competitor of methylene blue (MB), study the selection performance of the adsorbent material.
As shown in figure 11 in single mark competitive Adsorption experiment of basic dye and MB, ImI@TpBd- (SO3)2There is best absorption to MB
Effect, while also having preferable adsorption effect to other basic dyes.In mixed mark competitive Adsorption experiment, although ImI@TpBd-
(SO3)2The adsorption effect of basic dye is reduced, but preferable adsorption effect is maintained to the absorption total amount of basic dye.
The foregoing is merely the preferred embodiments of the invention, are not intended to limit the invention creation, all at this
Within the spirit and principle of innovation and creation, any modification, equivalent replacement, improvement and so on should be included in the invention
Protection scope within.
Claims (3)
1. a kind of for adsorbing the preparation method of the support ionic liquid material of the anionic of basic dye, which is characterized in that
Include the following steps:
(1) monomer Tp and Bd will be constructed to be separately added into ethanol solution, ultrasound dissolves it sufficiently, burns in tri- mouthfuls of round bottoms of 100mL
It is mixed in bottle, the three neck round bottom flask is separately connected thermometer, nitrogen ball and vacuum pump, is taken out three-necked flask very with vacuum pump
After sky, the nitrogen in nitrogen ball, under the conditions of nitrogen protection, 80 DEG C of reaction 8h are discharged；11000 turns of centrifugation 10min are obtained thick
TpBd-(SO3)2；
(2) it washs, the thick TpBd- (SO that will be prepared in step (1)3)2It is placed in there-necked flask, 50mL N, N- dimethyl formyl is added
Amine, under nitrogen protection, 150 DEG C of reaction 2h, then 11000 turns of centrifugation 10min, obtain TpBd- (SO3)2, repeated washing is primary, washes
Remove unreacted reactant；
(3) solvent is replaced, by the about 30-40mg TpBd- (SO after step (2) are washed3)2It is placed in there-necked flask, 50- is added
60mL ethyl alcohol reacts 2h, 11000 turns of centrifugation 10min, 60 DEG C of vacuum drying under nitrogen protection；
(4) it is modified after ILs, the TpBd- (SO that step (3) is obtained3)2It is placed in ethyl alcohol, imidazoles is added, in room temperature condition of normal pressure
Lower reaction 36h, is centrifuged 10min by 11000 turns, and 60 DEG C of vacuum drying are obtained with the anionic to basic dye high adsorption capacity
Support ionic liquid material ImI@TpBd- (SO3)2。
2. according to claim 1 a kind of for adsorbing the system of the support ionic liquid material of the anionic of basic dye
Preparation Method, it is characterised in that: the molar ratio of Tp and Bd is 0.075:0.1125 in step (1).
3. according to claim 1 a kind of for adsorbing the system of the support ionic liquid material of the anionic of basic dye
Preparation Method, it is characterised in that: the covalent organic polymer material TpBd- (SO of 10mg is weighed in step (4)3)2It is scattered in 10mL second
Alcohol, then rapidly joins 34.0mg imidazoles thereto, and 600 turns of stirrings 36h, 11000rpm are centrifuged 10min, ethanol washing.
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Patent Citations (4)
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| US20150266885A1 (en) * | 2012-10-12 | 2015-09-24 | Council Of Scientific & Industrial Research | Porous crystalline frameworks, process for the preparation therof and their mechanical delamination to covalent organic nanosheets (cons) |
| CN105854838A (en) * | 2016-04-13 | 2016-08-17 | 安徽大学 | Preparation method and application of selective adsorbent sulfonate poly(styrene-co-maleic anhydride) nanoparticles |
| CN108114698A (en) * | 2016-11-30 | 2018-06-05 | 中国科学院大连化学物理研究所 | Composite material by porous material loading ionic liquid and its preparation method and application |
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