CN109092265A - A kind of Studies On Preparation And Properties of Cellulose-based Adsorbents and its preparation method and application that polyimidazole is ion liquid modified - Google Patents
A kind of Studies On Preparation And Properties of Cellulose-based Adsorbents and its preparation method and application that polyimidazole is ion liquid modified Download PDFInfo
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- CN109092265A CN109092265A CN201811050817.4A CN201811050817A CN109092265A CN 109092265 A CN109092265 A CN 109092265A CN 201811050817 A CN201811050817 A CN 201811050817A CN 109092265 A CN109092265 A CN 109092265A
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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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
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- 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
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- 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
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- 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
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- 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 present invention provides a kind of Studies On Preparation And Properties of Cellulose-based Adsorbents and its preparation method and application that polyimidazole is ion liquid modified comprising following steps: step 1, preparing dialdehyde cellulose and polyimidazole ionic liquid respectively；Step 2, dialdehyde cellulose is immersed in water, by polyimidazole ion liquid dissolving in HCl solution, the HCl solution of dialdehyde cellulose aqueous solution and polyimidazole ionic liquid is mixed, pH is controlled in the range of 2.5~3.5, is stirred at 20~45 DEG C and obtains within 4~8 hours the ion liquid modified cellulose crude product of polyimidazole；Step 3, the ion liquid modified cellulose crude product of polyimidazole is rinsed through ethyl alcohol, water, drying obtains the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole.The adsorbent can effectively solve that cellulose adsorption capacity in water phase is low and existing modification technology in single grafting glyoxaline ion liquid functional group adsorption site it is few, the weak problem of suction-operated can be used for the processing of waste water from dyestuff.
Description
Technical field
The invention belongs to the preparations of high-efficiency adsorbent and development technique field, and it is ion liquid modified to be related to a kind of polyimidazole
Studies On Preparation And Properties of Cellulose-based Adsorbents and its preparation method and application.
Background technique
In recent years, due to printing and dyeing, weaving, the fast development of paper industry, environmental pollution is got worse, especially containing dye
The wastewater discharge cumulative year after year of material, heavy metal.Since dyeing waste water toxicity is high, easy carcinogenic, teratogenesis, processing has become urgent
Problem to be solved.There are many methods to be applied to processing dyeing waste water, such as electrolysis, ultrafiltration, chemical flocculation, chemical oxygen at present
Change, absorption, dialysis and anaerobic-aerobic etc..Based on it is high-efficient, at low cost and easily operated the advantages that, absorption is that processing printing and dyeing are useless
The more practical method of water.
Cellulose is the most abundant biopolymer resource in the world, due to its unique intrinsic characteristic, such as biology drop
Xie Xing, environment friendly etc. are expected to the adsorbent for replacing active carbon to become wastewater treatment.However, the hydroxyl of cellulose is to moisture
It is sub sensitive, and the interaction between contaminant molecule is weak, causes its adsorption capacity lower.Therefore, it is necessary to fiber material
Material is modified, and is introduced into the functional group that can generate electrostatic, π-πconjugation in water phase with pollutant, can be to a certain degree
The upper absorption property for improving cellulose adsorbent.
Ionic liquid refers to that the liquid being composed entirely of ions, imidazole ring are the 5-member heterocyclic ring containing nitrogen with armaticity, nitrogen
Alkyl chain is introduced imidazole ring after alkylated reaction by atom, and imidazole ring is made to become positively charged cation, constitutes imidazoles
Ionic liquid.The structural property is stablized, and positive charge is evenly distributed, and glyoxaline ion liquid functional group can generate more with pollutant
Therefore heavy phase interaction can be obtained by introducing glyoxaline ion liquid functional group in cellulose with good adsorption effect
The sorbent material of fruit.
But be to be modified by single functional group to cellulosic-based material at present, adsorption effect is still difficult to full
Sufficient actual demand.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of cellulose base that polyimidazole is ion liquid modified suction
Attached dose and its preparation method and application, it is low and existing change which can effectively solve cellulose adsorption capacity in water phase
Single grafting glyoxaline ion liquid functional group adsorption site is few in property technology, the weak problem of suction-operated.
The present invention is to be achieved through the following technical solutions:
A kind of Studies On Preparation And Properties of Cellulose-based Adsorbents that polyimidazole is ion liquid modified, shown in structural formula such as formula (1):
Wherein, it is 25~100 that n, which is 400~10000, m,.
A kind of preparation method for the Studies On Preparation And Properties of Cellulose-based Adsorbents that the polyimidazole is ion liquid modified, comprising the following steps:
Step 1, dialdehyde cellulose and polyimidazole ionic liquid are prepared respectively；
Step 2, dialdehyde cellulose is immersed in water, by polyimidazole ion liquid dissolving in HCl solution, by dialdehyde
The mixing of the HCl solution of base cellulose aqueous solution and polyimidazole ionic liquid controls pH in the range of 2.5~3.5, and 20~45 DEG C
Lower stirring obtains the ion liquid modified cellulose crude product of polyimidazole in 4~8 hours；
Step 3, by the ion liquid modified cellulose crude product of polyimidazole through ethyl alcohol, water rinse, drying, obtain polyimidazole from
Sub- liquid modifying Studies On Preparation And Properties of Cellulose-based Adsorbents.
Preferably, in step 1, the preparation method of dialdehyde cellulose specifically: cellulose is immersed in sodium metaperiodate water
In solution, it is protected from light at 30~80 DEG C 3~7 hours, adds ethylene glycol and reacted, dialdehyde cellulose is prepared
Crude product；Dialdehyde cellulose crude product with water and ethyl alcohol are washed repeatedly, until washing to supernatant is neutral, obtain dialdehyde
Base cellulose.
Preferably, the concentration of sodium metaperiodate aqueous solution is 8~32gL-1。
Preferably, cellulose origin is dissolution regeneration gossypin, bacteria cellulose, microcrystalline cellulose or nanofiber
Element；Cellulosed molded article is film, hydrogel, aeroge, paper or powder.
Preferably, which is characterized in that in step 1, the preparation method of polyimidazole ionic liquid specifically:
(1) 1- vinyl imidazole and 3- propantheline bromide hydrobromide are dissolved in dehydrated alcohol, and stirring is mixed in a nitrogen atmosphere
Close, 60~80 DEG C back flow reaction 10~30 hours, obtain ionic liquid 1- vinyl -3- aminopropylimidazol hydrobromate and slightly produce
Object；
(2) ethyl acetate is added in ionic liquid 1- vinyl -3- aminopropylimidazol crude hydrobromide product, precipitates
Separating ionic liquid is eventually adding ethyl alcohol, is dried to obtain ionic liquid 1- vinyl -3- aminopropylimidazol hydrobromate；
(3) ionic liquid 1- vinyl -3- aminopropylimidazol hydrobromate and azodiisobutyronitrile are dissolved in N, N- bis-
Methylformamide is stirred under atmosphere under a nitrogen, 60~75 DEG C back flow reaction 5~8 hours, obtain polyimidazole ionic liquid
Crude product；
(4) ether precipitating is added in poly ion liquid crude product, sediment is added n,N-Dimethylformamide and is configured to
Saturated solution, after being dialysed with water, freeze-drying obtains polyimidazole ionic liquid.
Further, the mass ratio of 1- vinyl imidazole and 3- propantheline bromide hydrobromide is (1~2.5): 1.
Further, 1- vinyl -3- aminopropylimidazol hydrobromate and azodiisobutyronitrile mass ratio are 2:(0.02
~0.2).
Further, in step 2, the mass ratio of dialdehyde cellulose and polyimidazole ionic liquid is 1:(1~7).
A kind of application of the Studies On Preparation And Properties of Cellulose-based Adsorbents that the polyimidazole is ion liquid modified in processing waste water, waste water are
Anionic dye waste water or effluent containing heavy metal ions.
Compared with prior art, the invention has the following beneficial technical effects:
The present invention has been grafted polyimidazole ionic liquid on cellulose, poly ion liquid be have on repetitive unit yin,
The polymer of cationic polyelectrolyte group, it combines the properties of ionic liquid and polymer, poly ion liquid is used for
The modification of adsorbent material increases suction-operated site, can improve single grafting glyoxaline ion liquid functional group adsorption potential
It puts less, the disadvantage that suction-operated is weak, the adsorption capacity of cellulose will be greatlyd improve.Meanwhile by glyoxaline ion liquid
Imidazole functionalities' a variety of interactions that organic matter adsorbate is provided, such as hydrophobic effect, Van der Waals force, electrostatic interaction, hydrogen
Key and π-are pi-conjugated etc., improve cellulose to the absorption property of water pollutant, can effectively solve cellulose and adsorb in water phase
Ability is low and the functional group of existing modification technology modified cellulose acts on single, adsorbance to dyestuff and is unsatisfactory for demand etc. and asks
Topic.Meanwhile prepared adsorbent has good degradability and biocompatibility, is conducive to the sustainable development of environment, it can
It is widely used in the processing of waste water from dyestuff.Therefore, polyimidazole ionic liquid is used for the graft modification of cellulosic material, can get
A kind of biomass adsorbent cheap, degradable, adsorption capacity is strong.
The preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole of the present invention is simple, and reaction condition is mild, instead
Object small toxicity is answered, and reaction process is safer, process has both economy and simplicity, and the adsorbent is degradable, is conducive to
Environment sustainable development；And reaction raw materials source is wide, is conducive to the popularization and application of the material.
The ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole of the present invention is to anionic dye and heavy metal ion
Adsorption capacity with higher can be used for the processing of waste water from dyestuff.
Detailed description of the invention
The infrared spectrum comparison diagram of Fig. 1 rear cellulose for dialdehyde cellulose in the embodiment of the present invention 1 and before modified, A are to change
Property before cellulose, B be dialdehyde cellulose, C be the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
The invention discloses a kind of Studies On Preparation And Properties of Cellulose-based Adsorbents that polyimidazole is ion liquid modified, shown in structural formula such as formula (1):
Wherein, it is 25~100 that n, which is 400~10000, m,.
The invention also discloses the preparation methods of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of above-mentioned polyimidazole, including with
Lower step:
S1,2g cellulose is immersed in the certain density sodium metaperiodate aqueous solution of 25mL, is placed in 30~80 DEG C of water-bath
In, it is protected from light 3~7 hours, adds 3mL glycol reaction 1 hour, prepare dialdehyde cellulose crude product；
S2, by S1 dialdehyde cellulose crude product deionized water and ethyl alcohol wash repeatedly, wash away dialdehyde-based fiber
The unreacted sodium metaperiodate in plain surface and ethylene glycol solution obtain dialdehyde cellulose until washing to supernatant is neutrality；
S3,1- vinyl imidazole and 3- propantheline bromide hydrobromide are dissolved in 20mL dehydrated alcohol, and stirred in a nitrogen atmosphere
Mixture is mixed, 60~80 DEG C are flowed back 1 hour, and ionic liquid 1- vinyl -3- aminopropylimidazol crude hydrobromide product is obtained；
Acetic acid second is added in S4, the ionic liquid 1- vinyl -3- aminopropylimidazol crude hydrobromide product in S3
Ester, precipitation and separation ionic liquid.It is eventually adding 5mL ethyl alcohol, 60 DEG C of vacuum drying obtain ionic liquid 1- vinyl -3- in 24 hours
Aminopropylimidazol hydrobromate；
S5, by the ionic liquid 1- vinyl -3- aminopropylimidazol hydrobromate and 0.02~0.2g azo in 2g S4
Bis-isobutyronitrile is dissolved in 45mL N,N-dimethylformamide.Mixture is stirred under atmosphere under a nitrogen, 60~75 DEG C of reflux 5~8 are small
When, obtain poly ion liquid crude product；
Ether precipitating is added in S6, the poly ion liquid crude product in S5,10~20mL N, N- diformazan is added in sediment
Base formamide is configured to saturated solution, after being dialysed 48 hours with pure water, is freeze-dried 48 hours, obtains poly ion liquid；
S7, the dialdehyde cellulose in 2g S2 is immersed in 1L deionized water, the poly ion liquid in S6 is dissolved in
Concentration is to mix the HCl solution of dialdehyde cellulose aqueous solution and polyimidazole ionic liquid in the HCl solution of 19.2g/L, control
PH control processed stirs 4~8 hours at 20~45 DEG C in the range of 2.5~3.5 and obtains the ion liquid modified cellulose of polyimidazole
Crude product；
S8, the ion liquid modified cellulose crude product of polyimidazole in S7 is dried, is obtained through ethyl alcohol, deionized water flushing
To the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole.
Cellulose origin in S1 is dissolution regeneration gossypin, bacteria cellulose, microcrystalline cellulose or nano-cellulose；
Cellulosed molded article is film, hydrogel, aeroge, paper or powder.
The concentration of sodium metaperiodate aqueous solution in S1 is 8~32gL-1。
1- vinyl imidazole and 3- propantheline bromide hydrobromide mass ratio in S3 are (2.5~1): the dialdehyde-based in 1, S7 is fine
Dimension element is 1:(1~7 with poly ion liquid mass ratio).
The invention also discloses application of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of above-mentioned polyimidazole in processing waste water.
The waste water is anionic dye waste water or effluent containing heavy metal ions.
Specific embodiment is as follows.
Embodiment 1
The process of the preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of one of the present embodiment polyimidazole includes
The following steps:
1) 2g nano-cellulose film (shown in structure such as formula (2)) is immersed in 25mL 32gL-1Sodium metaperiodate aqueous solution
In, it is placed in 50 DEG C of water-bath, is protected from light 4 hours, adds 3mL glycol reaction 1 hour, it is thick to prepare dialdehyde cellulose
Product.
2) reaction terminates, and is washed repeatedly with deionized water and ethyl alcohol, washes away the unreacted high iodine in dialdehyde cellulose surface
Sour sodium and ethylene glycol solution until washing to supernatant is neutral, obtain dialdehyde cellulose, shown in structure such as formula (3).
3) the 1- vinyl imidazole and 3- bromine propylamine hydrogen bromine that mass ratio is 2:1 are added in container (such as 25mL round-bottomed flask)
The two is dissolved in 20mL dehydrated alcohol, and stirs mixture in a nitrogen atmosphere by hydrochlorate, and 60 DEG C are flowed back 24 hours, obtains ion
Liquid 1- vinyl -3- aminopropylimidazol crude hydrobromide product.
4) ethyl acetate, precipitation and separation ionic liquid are added after reaction.It is eventually adding 5mL ethyl alcohol, 60 DEG C of vacuum are dry
Ionic liquid 1- vinyl -3- aminopropylimidazol hydrobromate is obtained within dry 24 hours, shown in structure such as formula (4).
5) 2g ionic liquid and 0.04g azodiisobutyronitrile are dissolved in 45mL N,N-dimethylformamide.In nitrogen atmosphere
Lower stirring mixture, 75 DEG C are flowed back 6 hours, obtain poly ion liquid crude product.
6) ether precipitating is added after reaction, sediment addition 10mL n,N-Dimethylformamide is configured to be saturated molten
Liquid after being dialysed 48 hours with pure water, is freeze-dried 48 hours, obtains poly ion liquid.
7) 2g dialdehyde cellulose is immersed in 1L deionized water, it is 19.2g/ that 2g poly ion liquid, which is dissolved in concentration,
In the HCl solution of L, the HCl solution of dialdehyde cellulose aqueous solution and polyimidazole ionic liquid is mixed, control pH is adjusted to 3,25
It is stirred at DEG C and obtains within 6 hours the ion liquid modified cellulose crude product of polyimidazole.
8) it after reaction, is rinsed through ethyl alcohol, deionized water, drying obtains the ion liquid modified cellulose of polyimidazole
Base adsorbent, shown in structure such as formula (1).
Embodiment 2
The process of the preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of one of the present embodiment polyimidazole includes
The following steps:
1) 2g bacteria cellulose film (shown in structure such as formula (2)) is immersed in 25mL 16gL-1Sodium metaperiodate aqueous solution
In, it is placed in 50 DEG C of water-bath, is protected from light 5 hours, adds 3mL glycol reaction 1 hour, it is thick to prepare dialdehyde cellulose
Product.
2) reaction terminates, and is washed repeatedly with deionized water and ethyl alcohol, washes away the unreacted high iodine in dialdehyde cellulose surface
Sour sodium and ethylene glycol solution until washing to supernatant is neutral, obtain dialdehyde cellulose, shown in structure such as formula (3).
3) the 1- vinyl imidazole and 3- bromine propylamine hydrogen that mass ratio is 2.1:1 are added in container (such as 25mL round-bottomed flask)
The two is dissolved in 20mL dehydrated alcohol, and stirs mixture in a nitrogen atmosphere by bromate, 80 DEG C flow back 24 hours, obtain from
Sub- liquid 1- vinyl -3- aminopropylimidazol crude hydrobromide product.
4) ethyl acetate, precipitation and separation ionic liquid are added after reaction.It is eventually adding 5mL ethyl alcohol, 60 DEG C of vacuum are dry
Ionic liquid 1- vinyl -3- aminopropylimidazol hydrobromate is obtained within dry 24 hours, shown in structure such as formula (4).
5) 2g ionic liquid and 0.04g azodiisobutyronitrile are dissolved in 45mL N,N-dimethylformamide.In nitrogen atmosphere
Lower stirring mixture, 65 DEG C are flowed back 6 hours, obtain poly ion liquid crude product.
6) ether precipitating is added after reaction, sediment addition 10mL n,N-Dimethylformamide is configured to be saturated molten
Liquid after being dialysed 48 hours with pure water, is freeze-dried 48 hours, obtains poly ion liquid.
7) 2g dialdehyde cellulose is immersed in 1L deionized water, it is 19.2g/ that 4g poly ion liquid, which is dissolved in concentration,
In the HCl solution of L, the HCl solution of dialdehyde cellulose aqueous solution and polyimidazole ionic liquid is mixed, control pH is adjusted to 3.3,
It is stirred at 25 DEG C and obtains within 5 hours the ion liquid modified cellulose crude product of polyimidazole.
8) it after reaction, is rinsed through ethyl alcohol, deionized water, drying obtains the ion liquid modified cellulose base of polyimidazole
Adsorbent, shown in structure such as formula (1).
Embodiment 3
The process of the preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of one of the present embodiment polyimidazole includes
The following steps:
1) 2g microcrystalline cellulose film (shown in structure such as formula (2)) is immersed in 25mL 32gL-1Sodium metaperiodate aqueous solution
In, it is placed in 60 DEG C of water-bath, is protected from light 5 hours, adds 3mL glycol reaction 1 hour, it is thick to prepare dialdehyde cellulose
Product.
2) reaction terminates, and is washed repeatedly with deionized water and ethyl alcohol, washes away the unreacted high iodine in dialdehyde cellulose surface
Sour sodium and ethylene glycol solution until washing to supernatant is neutral, obtain dialdehyde cellulose, shown in structure such as formula (3).
3) the 1- vinyl imidazole and 3- bromine propylamine hydrogen bromine that mass ratio is 2:1 are added in container (such as 25mL round-bottomed flask)
The two is dissolved in 20mL dehydrated alcohol, and stirs mixture in a nitrogen atmosphere by hydrochlorate, and 60 DEG C are flowed back 24 hours, obtains ion
Liquid 1- vinyl -3- aminopropylimidazol crude hydrobromide product.
4) ethyl acetate, precipitation and separation ionic liquid are added after reaction.It is eventually adding 5mL ethyl alcohol, 60 DEG C of vacuum are dry
Ionic liquid 1- vinyl -3- aminopropylimidazol hydrobromate is obtained within dry 24 hours, shown in structure such as formula (4).
5) 2g ionic liquid and 0.04g azodiisobutyronitrile are dissolved in 45mL N,N-dimethylformamide.In nitrogen atmosphere
Lower stirring mixture, 75 DEG C are flowed back 6 hours, obtain poly ion liquid crude product.
6) ether precipitating is added after reaction, sediment addition 10mL n,N-Dimethylformamide is configured to be saturated molten
Liquid after being dialysed 48 hours with pure water, is freeze-dried 48 hours, obtains poly ion liquid.
7) 2g dialdehyde cellulose is immersed in 1L deionized water, it is 19.2g/ that 6g poly ion liquid, which is dissolved in concentration,
In the HCl solution of L, the HCl solution of dialdehyde cellulose aqueous solution and polyimidazole ionic liquid is mixed, control pH is adjusted to 2.5,
It is stirred 6 hours at 25 DEG C and obtains the ion liquid modified cellulose of polyimidazole.
8) it after reaction, is rinsed through ethyl alcohol, deionized water, drying obtains the ion liquid modified cellulose base of polyimidazole
Adsorbent, shown in structure such as formula (1).
Embodiment 4
The process of the preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of one of the present embodiment polyimidazole includes
The following steps:
1) 2g is dissolved into regeneration cotton cellulose aerogels (shown in structure such as formula (2)) and is immersed in 25mL 16gL-1High iodine
It in acid sodium aqueous solution, is placed in 50 DEG C of water-bath, is protected from light 5 hours, adds 3mL glycol reaction 1 hour, prepare dialdehyde
Base cellulose crude product.
2) reaction terminates, and is washed repeatedly with deionized water and ethyl alcohol, washes away the unreacted high iodine in dialdehyde cellulose surface
Sour sodium and ethylene glycol solution until washing to supernatant is neutral, obtain dialdehyde cellulose, shown in structure such as formula (3).
3) the 1- vinyl imidazole and 3- bromine propylamine hydrogen that mass ratio is 2.2:1 are added in container (such as 25mL round-bottomed flask)
The two is dissolved in 20mL dehydrated alcohol, and stirs mixture in a nitrogen atmosphere by bromate, 80 DEG C flow back 24 hours, obtain from
Sub- liquid 1- vinyl -3- aminopropylimidazol crude hydrobromide product.
4) ethyl acetate, precipitation and separation ionic liquid are added after reaction.It is eventually adding 5mL ethyl alcohol, 60 DEG C of vacuum are dry
Ionic liquid 1- vinyl -3- aminopropylimidazol hydrobromate is obtained within dry 24 hours, shown in structure such as formula (4).
5) 2g ionic liquid and 0.04g azodiisobutyronitrile are dissolved in 45mL N,N-dimethylformamide.In nitrogen atmosphere
Lower stirring mixture, 65 DEG C are flowed back 7 hours, obtain poly ion liquid crude product.
6) ether precipitating is added after reaction, sediment addition 10mL n,N-Dimethylformamide is configured to be saturated molten
Liquid after being dialysed 48 hours with pure water, is freeze-dried 48 hours, obtains poly ion liquid.
7) 2g dialdehyde cellulose is immersed in 1L deionized water, it is 19.2g/ that 6g poly ion liquid, which is dissolved in concentration,
In the HCl solution of L, the HCl solution of dialdehyde cellulose aqueous solution and polyimidazole ionic liquid is mixed, control pH is adjusted to 3,25
It is stirred 6 hours at DEG C and obtains the ion liquid modified cellulose of polyimidazole.
8) it after reaction, is rinsed through ethyl alcohol, deionized water, drying obtains the ion liquid modified cellulose base of polyimidazole
Adsorbent, shown in structure such as formula (1).
Embodiment 5
The process of the preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of one of the present embodiment polyimidazole includes
The following steps:
1) 2g is dissolved into regeneration cotton cellulose aerogels (shown in structure such as formula (2)) and is immersed in 25mL 32gL-1High iodine
It in acid sodium aqueous solution, is placed in 80 DEG C of water-bath, is protected from light 7 hours, adds 3mL glycol reaction 1 hour, prepare dialdehyde
Base cellulose crude product.
2) reaction terminates, and is washed repeatedly with deionized water and ethyl alcohol, washes away the unreacted high iodine in dialdehyde cellulose surface
Sour sodium and ethylene glycol solution until washing to supernatant is neutral, obtain dialdehyde cellulose, shown in structure such as formula (3).
3) the 1- vinyl imidazole and 3- bromine propylamine hydrogen bromine that mass ratio is 2:1 are added in container (such as 25mL round-bottomed flask)
The two is dissolved in 20mL dehydrated alcohol, and stirs mixture in a nitrogen atmosphere by hydrochlorate, and 60 DEG C are flowed back 24 hours, obtains ion
Liquid 1- vinyl -3- aminopropylimidazol crude hydrobromide product.
4) ethyl acetate, precipitation and separation ionic liquid are added after reaction.It is eventually adding 5mL ethyl alcohol, 60 DEG C of vacuum are dry
Ionic liquid 1- vinyl -3- aminopropylimidazol hydrobromate is obtained within dry 24 hours, shown in structure such as formula (4).
5) 2g ionic liquid and 0.04g azodiisobutyronitrile are dissolved in 45mL N,N-dimethylformamide.In nitrogen atmosphere
Lower stirring mixture, 65 DEG C are flowed back 7 hours, obtain poly ion liquid crude product.
6) ether precipitating is added after reaction, sediment addition 10mL n,N-Dimethylformamide is configured to be saturated molten
Liquid after being dialysed 48 hours with pure water, is freeze-dried 48 hours, obtains poly ion liquid.
7) 2g dialdehyde cellulose is immersed in 1L deionized water, it is 19.2g/ that 6g poly ion liquid, which is dissolved in concentration,
In the HCl solution of L, the HCl solution of dialdehyde cellulose aqueous solution and polyimidazole ionic liquid is mixed, control pH is adjusted to 3,25
It is stirred 6 hours at DEG C and obtains the ion liquid modified cellulose of polyimidazole.
8) it after reaction, is rinsed through ethyl alcohol, deionized water, drying obtains the ion liquid modified cellulose base of polyimidazole
Adsorbent, shown in structure such as formula (1).
Embodiment 6
The process of the preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of one of the present embodiment polyimidazole includes
The following steps:
1) 2g dissolution of bacteria cellulose powder (shown in structure such as formula (2)) is immersed in 25mL 8gL-1Sodium metaperiodate
It in aqueous solution, is placed in 30 DEG C of water-bath, is protected from light 7 hours, adds 3mL glycol reaction 1 hour, preparation dialdehyde-based is fine
Tie up plain crude product.
2) reaction terminates, and is washed repeatedly with deionized water and ethyl alcohol, washes away the unreacted high iodine in dialdehyde cellulose surface
Sour sodium and ethylene glycol solution until washing to supernatant is neutral, obtain dialdehyde cellulose, shown in structure such as formula (3).
3) the 1- vinyl imidazole and 3- bromine propylamine hydrogen bromine that mass ratio is 1:1 are added in container (such as 25mL round-bottomed flask)
The two is dissolved in 20mL dehydrated alcohol, and stirs mixture in a nitrogen atmosphere by hydrochlorate, and 65 DEG C are flowed back 24 hours, obtains ion
Liquid 1- vinyl -3- aminopropylimidazol crude hydrobromide product.
4) ethyl acetate, precipitation and separation ionic liquid are added after reaction.It is eventually adding 5mL ethyl alcohol, 60 DEG C of vacuum are dry
Ionic liquid 1- vinyl -3- aminopropylimidazol hydrobromate is obtained within dry 24 hours, shown in structure such as formula (4).
5) 2g ionic liquid and 0.04g azodiisobutyronitrile are dissolved in 45mL N,N-dimethylformamide.In nitrogen atmosphere
Lower stirring mixture, 60 DEG C are flowed back 8 hours, obtain poly ion liquid crude product.
6) ether precipitating is added after reaction, sediment addition 10mL n,N-Dimethylformamide is configured to be saturated molten
Liquid after being dialysed 48 hours with pure water, is freeze-dried 48 hours, obtains poly ion liquid.
7) 2g dialdehyde cellulose is immersed in 1L deionized water, it is 19.2g/ that 8g poly ion liquid, which is dissolved in concentration,
In the HCl solution of L, the HCl solution of dialdehyde cellulose aqueous solution and polyimidazole ionic liquid is mixed, control pH is adjusted to 3.5,
It is stirred 6 hours at 30 DEG C and obtains the ion liquid modified cellulose of polyimidazole.
8) it after reaction, is rinsed through ethyl alcohol, deionized water, drying obtains the ion liquid modified cellulose base of polyimidazole
Adsorbent, shown in structure such as formula (1).
Embodiment 7
The process of the preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of one of the present embodiment polyimidazole includes
The following steps:
1) 2g is dissolved into microcrystalline cellulose hydrogel (shown in structure such as formula (2)) and is immersed in 25mL20gL-1Periodic acid
It in sodium water solution, is placed in 70 DEG C of water-bath, is protected from light 3 hours, adds 3mL glycol reaction 1 hour, prepare dialdehyde-based
Cellulose crude product.
2) reaction terminates, and is washed repeatedly with deionized water and ethyl alcohol, washes away the unreacted high iodine in dialdehyde cellulose surface
Sour sodium and ethylene glycol solution until washing to supernatant is neutral, obtain dialdehyde cellulose, shown in structure such as formula (3).
3) the 1- vinyl imidazole and 3- bromine propylamine hydrogen that mass ratio is 1.5:1 are added in container (such as 25mL round-bottomed flask)
The two is dissolved in 20mL dehydrated alcohol, and stirs mixture in a nitrogen atmosphere by bromate, 70 DEG C flow back 24 hours, obtain from
Sub- liquid 1- vinyl -3- aminopropylimidazol crude hydrobromide product.
4) ethyl acetate, precipitation and separation ionic liquid are added after reaction.It is eventually adding 5mL ethyl alcohol, 60 DEG C of vacuum are dry
Ionic liquid 1- vinyl -3- aminopropylimidazol hydrobromate is obtained within dry 24 hours, shown in structure such as formula (4).
5) 2g ionic liquid and 0.04g azodiisobutyronitrile are dissolved in 45mL N,N-dimethylformamide.In nitrogen atmosphere
Lower stirring mixture, 70 DEG C are flowed back 5 hours, obtain poly ion liquid crude product.
6) ether precipitating is added after reaction, sediment addition 10mL n,N-Dimethylformamide is configured to be saturated molten
Liquid after being dialysed 48 hours with pure water, is freeze-dried 48 hours, obtains poly ion liquid.
7) 2g dialdehyde cellulose is immersed in 1L deionized water, 10g poly ion liquid, which is dissolved in concentration, is
In the HCl solution of 19.2g/L, the HCl solution of dialdehyde cellulose aqueous solution and polyimidazole ionic liquid is mixed, controls pH tune
It is to stir 6 hours to obtain the ion liquid modified cellulose of polyimidazole at 3.5,35 DEG C.
8) it after reaction, is rinsed through ethyl alcohol, deionized water, drying obtains the ion liquid modified cellulose base of polyimidazole
Adsorbent, shown in structure such as formula (1).
Embodiment 8
The process of the preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of one of the present embodiment polyimidazole includes
The following steps:
1) 2g is dissolved into microcrystalline cellulose hydrogel (shown in structure such as formula (2)) and is immersed in the periodic acid of 25mL20gL-1
It in sodium water solution, is placed in 70 DEG C of water-bath, is protected from light 3 hours, adds 3mL glycol reaction 1 hour, prepare dialdehyde-based
Cellulose crude product.
2) reaction terminates, and is washed repeatedly with deionized water and ethyl alcohol, washes away the unreacted high iodine in dialdehyde cellulose surface
Sour sodium and ethylene glycol solution until washing to supernatant is neutral, obtain dialdehyde cellulose, shown in structure such as formula (3).
3) the 1- vinyl imidazole and 3- bromine propylamine hydrogen that mass ratio is 2.5:1 are added in container (such as 25mL round-bottomed flask)
The two is dissolved in 20mL dehydrated alcohol, and stirs mixture in a nitrogen atmosphere by bromate, 70 DEG C flow back 28 hours, obtain from
Sub- liquid 1- vinyl -3- aminopropylimidazol crude hydrobromide product.
4) ethyl acetate, precipitation and separation ionic liquid are added after reaction.It is eventually adding 5mL ethyl alcohol, 60 DEG C of vacuum are dry
Ionic liquid 1- vinyl -3- aminopropylimidazol hydrobromate is obtained within dry 24 hours, shown in structure such as formula (4).
5) 2g ionic liquid and 0.02g azodiisobutyronitrile are dissolved in 45mL N,N-dimethylformamide.In nitrogen atmosphere
Lower stirring mixture, 70 DEG C are flowed back 5 hours, obtain poly ion liquid crude product.
6) ether precipitating is added after reaction, sediment addition 10mL n,N-Dimethylformamide is configured to be saturated molten
Liquid after being dialysed 48 hours with pure water, is freeze-dried 48 hours, obtains poly ion liquid.
7) 2g dialdehyde cellulose is immersed in 1L deionized water, 14g poly ion liquid, which is dissolved in concentration, is
In the HCl solution of 19.2g/L, the HCl solution of dialdehyde cellulose aqueous solution and polyimidazole ionic liquid is mixed, controls pH tune
It is to stir 6 hours to obtain the ion liquid modified cellulose of polyimidazole at 3.5,25 DEG C.
8) it after reaction, is rinsed through ethyl alcohol, deionized water, drying obtains the ion liquid modified cellulose base of polyimidazole
Adsorbent, shown in structure such as formula (1).
Embodiment 9
The process of the preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of one of the present embodiment polyimidazole includes
The following steps:
1) 2g bacteria cellulose film (shown in structure such as formula (2)) is immersed in 25mL 16gL-1Sodium metaperiodate aqueous solution
In, it is placed in 50 DEG C of water-bath, is protected from light 5 hours, adds 3mL glycol reaction 1 hour, it is thick to prepare dialdehyde cellulose
Product.
2) reaction terminates, and is washed repeatedly with deionized water and ethyl alcohol, washes away the unreacted high iodine in dialdehyde cellulose surface
Sour sodium and ethylene glycol solution until washing to supernatant is neutral, obtain dialdehyde cellulose, shown in structure such as formula (3).
3) the 1- vinyl imidazole and 3- bromine propylamine hydrogen that mass ratio is 2.1:1 are added in container (such as 25mL round-bottomed flask)
The two is dissolved in 20mL dehydrated alcohol, and stirs mixture in a nitrogen atmosphere by bromate, 80 DEG C flow back 10 hours, obtain from
Sub- liquid 1- vinyl -3- aminopropylimidazol crude hydrobromide product.
4) ethyl acetate, precipitation and separation ionic liquid are added after reaction.It is eventually adding 5mL ethyl alcohol, 60 DEG C of vacuum are dry
Ionic liquid 1- vinyl -3- aminopropylimidazol hydrobromate is obtained within dry 24 hours, shown in structure such as formula (4).
5) 2g ionic liquid and 0.08g azodiisobutyronitrile are dissolved in 45mL N,N-dimethylformamide.In nitrogen atmosphere
Lower stirring mixture, 65 DEG C are flowed back 6 hours, obtain poly ion liquid crude product.
6) ether precipitating is added after reaction, sediment addition 10mL n,N-Dimethylformamide is configured to be saturated molten
Liquid after being dialysed 48 hours with pure water, is freeze-dried 48 hours, obtains poly ion liquid.
7) 2g dialdehyde cellulose is immersed in 1L deionized water, it is 19.2g/ that 4g poly ion liquid, which is dissolved in concentration,
In the HCl solution of L, the HCl solution of dialdehyde cellulose aqueous solution and polyimidazole ionic liquid is mixed, control pH is adjusted to 3.3,
It is stirred at 25 DEG C and obtains within 5 hours the ion liquid modified cellulose crude product of polyimidazole.
8) it after reaction, is rinsed through ethyl alcohol, deionized water, drying obtains the ion liquid modified cellulose base of polyimidazole
Adsorbent, shown in structure such as formula (1).
Embodiment 10
The process of the preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of one of the present embodiment polyimidazole includes
The following steps:
1) 2g bacteria cellulose film (shown in structure such as formula (2)) is immersed in 25mL 16gL-1Sodium metaperiodate aqueous solution
In, it is placed in 50 DEG C of water-bath, is protected from light 5 hours, adds 3mL glycol reaction 1 hour, it is thick to prepare dialdehyde cellulose
Product.
2) reaction terminates, and is washed repeatedly with deionized water and ethyl alcohol, washes away the unreacted high iodine in dialdehyde cellulose surface
Sour sodium and ethylene glycol solution until washing to supernatant is neutral, obtain dialdehyde cellulose, shown in structure such as formula (3).
3) the 1- vinyl imidazole and 3- bromine propylamine hydrogen that mass ratio is 2.1:1 are added in container (such as 25mL round-bottomed flask)
The two is dissolved in 20mL dehydrated alcohol, and stirs mixture in a nitrogen atmosphere by bromate, 80 DEG C flow back 30 hours, obtain from
Sub- liquid 1- vinyl -3- aminopropylimidazol crude hydrobromide product.
4) ethyl acetate, precipitation and separation ionic liquid are added after reaction.It is eventually adding 5mL ethyl alcohol, 60 DEG C of vacuum are dry
Ionic liquid 1- vinyl -3- aminopropylimidazol hydrobromate is obtained within dry 24 hours, shown in structure such as formula (4).
5) 2g ionic liquid and 0.10g azodiisobutyronitrile are dissolved in 45mL N,N-dimethylformamide.In nitrogen atmosphere
Lower stirring mixture, 65 DEG C are flowed back 6 hours, obtain poly ion liquid crude product.
6) ether precipitating is added after reaction, sediment addition 10mL n,N-Dimethylformamide is configured to be saturated molten
Liquid after being dialysed 48 hours with pure water, is freeze-dried 48 hours, obtains poly ion liquid.
7) 2g dialdehyde cellulose is immersed in 1L deionized water, it is 19.2g/ that 4g poly ion liquid, which is dissolved in concentration,
In the HCl solution of L, the HCl solution of dialdehyde cellulose aqueous solution and polyimidazole ionic liquid is mixed, control pH is adjusted to 3.3,
It is stirred at 20 DEG C and obtains within 4 hours the ion liquid modified cellulose crude product of polyimidazole.
8) it after reaction, is rinsed through ethyl alcohol, deionized water, drying obtains the ion liquid modified cellulose base of polyimidazole
Adsorbent, shown in structure such as formula (1).
Embodiment 11
The process of the preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of one of the present embodiment polyimidazole includes
The following steps:
1) 2g bacteria cellulose film (shown in structure such as formula (2)) is immersed in 25mL 16gL-1Sodium metaperiodate aqueous solution
In, it is placed in 50 DEG C of water-bath, is protected from light 5 hours, adds 3mL glycol reaction 1 hour, it is thick to prepare dialdehyde cellulose
Product.
2) reaction terminates, and is washed repeatedly with deionized water and ethyl alcohol, washes away the unreacted high iodine in dialdehyde cellulose surface
Sour sodium and ethylene glycol solution until washing to supernatant is neutral, obtain dialdehyde cellulose, shown in structure such as formula (3).
3) the 1- vinyl imidazole and 3- bromine propylamine hydrogen that mass ratio is 2.1:1 are added in container (such as 25mL round-bottomed flask)
The two is dissolved in 20mL dehydrated alcohol, and stirs mixture in a nitrogen atmosphere by bromate, 80 DEG C flow back 15 hours, obtain from
Sub- liquid 1- vinyl -3- aminopropylimidazol crude hydrobromide product.
4) ethyl acetate, precipitation and separation ionic liquid are added after reaction.It is eventually adding 5mL ethyl alcohol, 60 DEG C of vacuum are dry
Ionic liquid 1- vinyl -3- aminopropylimidazol hydrobromate is obtained within dry 24 hours, shown in structure such as formula (4).
5) 2g ionic liquid and 0.15g azodiisobutyronitrile are dissolved in 45mL N,N-dimethylformamide.In nitrogen atmosphere
Lower stirring mixture, 65 DEG C are flowed back 6 hours, obtain poly ion liquid crude product.
6) ether precipitating is added after reaction, sediment addition 10mL n,N-Dimethylformamide is configured to be saturated molten
Liquid after being dialysed 48 hours with pure water, is freeze-dried 48 hours, obtains poly ion liquid.
7) 2g dialdehyde cellulose is immersed in 1L deionized water, it is 19.2g/ that 4g poly ion liquid, which is dissolved in concentration,
In the HCl solution of L, the HCl solution of dialdehyde cellulose aqueous solution and polyimidazole ionic liquid is mixed, control pH is adjusted to 3.3,
It is stirred at 45 DEG C and obtains within 6 hours the ion liquid modified cellulose crude product of polyimidazole.
8) it after reaction, is rinsed through ethyl alcohol, deionized water, drying obtains the ion liquid modified cellulose base of polyimidazole
Adsorbent, shown in structure such as formula (1).
Embodiment 12
The process of the preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of one of the present embodiment polyimidazole includes
The following steps:
1) 2g bacteria cellulose film (shown in structure such as formula (2)) is immersed in 25mL 16gL-1Sodium metaperiodate aqueous solution
In, it is placed in 50 DEG C of water-bath, is protected from light 5 hours, adds 3mL glycol reaction 1 hour, it is thick to prepare dialdehyde cellulose
Product.
2) reaction terminates, and is washed repeatedly with deionized water and ethyl alcohol, washes away the unreacted high iodine in dialdehyde cellulose surface
Sour sodium and ethylene glycol solution until washing to supernatant is neutral, obtain dialdehyde cellulose, shown in structure such as formula (3).
3) the 1- vinyl imidazole and 3- bromine propylamine hydrogen that mass ratio is 2.1:1 are added in container (such as 25mL round-bottomed flask)
The two is dissolved in 20mL dehydrated alcohol, and stirs mixture in a nitrogen atmosphere by bromate, 80 DEG C flow back 20 hours, obtain from
Sub- liquid 1- vinyl -3- aminopropylimidazol crude hydrobromide product.
4) ethyl acetate, precipitation and separation ionic liquid are added after reaction.It is eventually adding 5mL ethyl alcohol, 60 DEG C of vacuum are dry
Ionic liquid 1- vinyl -3- aminopropylimidazol hydrobromate is obtained within dry 24 hours, shown in structure such as formula (4).
5) 2g ionic liquid and 0.2g azodiisobutyronitrile are dissolved in 45mL N,N-dimethylformamide.In nitrogen atmosphere
Lower stirring mixture, 65 DEG C are flowed back 6 hours, obtain poly ion liquid crude product.
6) ether precipitating is added after reaction, sediment addition 10mL n,N-Dimethylformamide is configured to be saturated molten
Liquid after being dialysed 48 hours with pure water, is freeze-dried 48 hours, obtains poly ion liquid.
7) 2g dialdehyde cellulose is immersed in 1L deionized water, it is 19.2g/ that 4g poly ion liquid, which is dissolved in concentration,
In the HCl solution of L, the HCl solution of dialdehyde cellulose aqueous solution and polyimidazole ionic liquid is mixed, control pH is adjusted to 3.3,
It is stirred at 20 DEG C and obtains within 8 hours the ion liquid modified cellulose crude product of polyimidazole.
8) it after reaction, is rinsed through ethyl alcohol, deionized water, drying obtains the ion liquid modified cellulose base of polyimidazole
Adsorbent, shown in structure such as formula (1).
Following characterization has been carried out to the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole prepared by the present invention:
1) infrared spectrum analysis
To the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole obtained in the embodiment of the present invention 1 and dialdehyde cellulose into
Row infrared spectrum analysis, referring to Fig. 1, wherein A is that cellulose, B are dialdehyde cellulose before modified in Fig. 1, and C is polyimidazole ion
Liquid modifying Studies On Preparation And Properties of Cellulose-based Adsorbents.By infrared spectrum analysis, cellulose only shows the typical absorption band of cellulose skeleton,
3340cm-1It is attributed to O-H key；Dialdehyde cellulose has more 1740cm compared with cellulose-1Locate peak, is C=O aldehyde radical stretching vibration
Peak；The ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole is in 1240cm-1And 1454cm-1Place has absorption peak, is imidazoles function
The framework characteristic peak of group, it was demonstrated that the present invention successfully connects imidazole ion liquid structure in cellulose skeleton.
2) hydrogen nuclear magnetic resonance spectrum analysis
Hydrogen nuclear magnetic resonance is carried out to the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole obtained in the embodiment of the present invention 1
Spectrum analysis further confirms to have synthesized target product.1HNMR(D2O, 298K) δ: 2.15 (m, 2H ,-C-CH2- C-), 2.97 (m,
2H ,-NCH2), 4.12 (m, 2H ,-Im-CH2), 5.33 (dd, 1H ,-CHH), 5.70 (m, 1H ,-CHH), 7.06 (m ,=CH-
Im), 7.48 (dd, 1H, C-CH-N, Im), 7.71 (m, 1H, N-CH-C, Im), 9.02 (s, 1H, N-CH-N, Im), Im refers to imidazoles
Ring.
3) Absorbency Test
The ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole obtained in 0.05g Examples 1 to 3 and 5 is separately added into
In the Congo red solution of 10mL for being 3g/L to concentration, the ion liquid modified cellulose base of polyimidazole obtained in embodiment 4 is inhaled
Attached dose is added in the solution for the 10mL heavy metal ion chromium ion that concentration is 3g/L, and (absorption) 24 is then reacted at 25 DEG C
It after hour, measures that remaining anionic dye in solution is Congo red, concentration of heavy metal ion chromium ion, calculates separately adsorbent pair
Anionic dye is Congo red, heavy metal ion chromium ion adsorbance.
The ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole is Congo red to anionic dye, heavy metal ion chromium ion
Adsorbance, calculation formula are as follows:
Wherein, Q indicates that adsorbent is Congo red to anionic dye or the adsorbance of heavy metal ion chromium ion, mgL-1；
C0Indicate that anionic dye is Congo red or the initial concentration of heavy metal ion chromium ion, mgL-1；CtIndicate anion after adsorbing
Dyestuff is Congo red or heavy metal ion chromium ion concentration, mgL-1；V indicate that anionic dye is Congo red or heavy metal ion chromium from
The volume of sub- solution, L；M indicates the quality of adsorbent, g；The results are shown in Table 1 for Absorbency Test.
1 Absorbency Test result of table
Test result shows that the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole prepared by the present invention is to anionic dye
With heavy metal ion adsorption capacity with higher, the processing of dyeing waste water can be widely applied to.
The ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of a kind of polyimidazole of the invention is to prepare synthesis by two-step reaction to inhale
Attached dose, first is that the preparation of dialdehyde cellulose, second is that the ion liquid modified cellulose of polyimidazole；It is related to dissolving 2g into regeneration cotton fiber
Element, bacteria cellulose, microcrystalline cellulose or nano-cellulose film, hydrogel, aeroge, paper or powder be immersed in 25mL 8~
In the sodium metaperiodate aqueous solution of 32gL-1,30~80 DEG C are protected from light 3~7 hours, add 3mL glycol reaction 1 hour,
Deionized water and ethyl alcohol wash repeatedly, until supernatant is neutral；By mass ratio be 2.5~1:1 1- vinyl imidazole and
3- propantheline bromide hydrobromide is dissolved in 20mL dehydrated alcohol, and stirs mixture in a nitrogen atmosphere, and 60~80 DEG C are flowed back 24 hours,
Ethyl acetate is added, 5mL ethyl alcohol is added in precipitation and separation ionic liquid, and 60 DEG C are dried in vacuo 24 hours；By 2g ionic liquid 1- second
Alkenyl -3- aminopropylimidazol hydrobromate and 0.04g azodiisobutyronitrile are dissolved in 45mL n,N-Dimethylformamide, in nitrogen
Mixture is stirred under gas atmosphere, 60~75 DEG C are flowed back 5~8 hours, and ether precipitating is added, and 10~20mL N, N- is added in sediment
Dimethylformamide is configured to saturated solution, after being dialysed 48 hours with pure water, is freeze-dried 48 hours；By 2g dialdehyde cellulose
It is immersed in 1L deionized water, it is 19.2g/L's that the poly ion liquid of 1~7 times of dialdehyde cellulose quality, which is dissolved in concentration,
In HCl solution, and by the pH of solution control in the range of 2.5~3.5, after being stirred 6 hours at 25 DEG C, through ethyl alcohol, deionization
Water rinses, and drying obtains the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole.
This adsorbent efficiently, economic is by a variety of interactions, such as hydrophobic effect, electrostatic interaction, hydrogen bond and π-π
Conjugation etc., to pollutant adsorption capacity with higher, it is low and existing can effectively to solve cellulose adsorption capacity in water phase
The problems such as functional group of modification technology modified cellulose is single to dyestuff effect, and adsorbance is unsatisfactory for demand.With graft modification list
One imidazole ion liquid functional group compares, and the present invention is increased by utilizing modification of the polyimidazole ionic liquid to cellulose
Suction-operated site can effectively adsorb water pollutant.The adsorbent can be widely applied to the processing of dyeing waste water, preparation side
Method is simple, and reaction condition is mild, reactant small toxicity, and reaction process is safer, and reaction raw materials source is wide, process have both through
Ji property and simplicity, and the adsorbent is degradable, is conducive to environment sustainable development.
Claims (10)
1. a kind of Studies On Preparation And Properties of Cellulose-based Adsorbents that polyimidazole is ion liquid modified, which is characterized in that shown in structural formula such as formula (1):
Wherein, it is 25~100 that n, which is 400~10000, m,.
2. a kind of preparation method for the Studies On Preparation And Properties of Cellulose-based Adsorbents that polyimidazole described in claim 1 is ion liquid modified, feature
It is, comprising the following steps:
Step 1, dialdehyde cellulose and polyimidazole ionic liquid are prepared respectively；
Step 2, dialdehyde cellulose is immersed in water, by polyimidazole ion liquid dissolving in HCl solution, by dialdehyde-based fibre
The HCl solution mixing for tieing up plain aqueous solution and polyimidazole ionic liquid, controls pH in the range of 2.5~3.5, stirs at 20~45 DEG C
It mixes and obtains within 4~8 hours the ion liquid modified cellulose crude product of polyimidazole；
Step 3, the ion liquid modified cellulose crude product of polyimidazole is rinsed through ethyl alcohol, water, drying obtains polyimidazole ionic liquid
Modifies Studies On Preparation And Properties of Cellulose-based Adsorbents.
3. the preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole according to claim 2, feature
It is, in step 1, the preparation method of dialdehyde cellulose specifically: cellulose is immersed in sodium metaperiodate aqueous solution, in 30
It is protected from light at~80 DEG C 3~7 hours, adds ethylene glycol and reacted, dialdehyde cellulose crude product is prepared；By two
Aldocellulose crude product with water and ethyl alcohol wash repeatedly, until washing to supernatant is neutral, obtain dialdehyde cellulose.
4. the preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole according to claim 3, feature
It is, the concentration of sodium metaperiodate aqueous solution is 8~32gL-1。
5. the preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole according to claim 3, feature
It is, cellulose origin is dissolution regeneration gossypin, bacteria cellulose, microcrystalline cellulose or nano-cellulose；Cellulose shape
Formula is film, hydrogel, aeroge, paper or powder.
6. the preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole according to claim 2, feature
It is, in step 1, the preparation method of polyimidazole ionic liquid specifically:
(1) 1- vinyl imidazole and 3- propantheline bromide hydrobromide are dissolved in dehydrated alcohol, and are stirred in a nitrogen atmosphere, 60
~80 DEG C back flow reaction 10~30 hours, obtain ionic liquid 1- vinyl -3- aminopropylimidazol crude hydrobromide product；
(2) ethyl acetate, precipitation and separation is added in ionic liquid 1- vinyl -3- aminopropylimidazol crude hydrobromide product
Ionic liquid is eventually adding ethyl alcohol, is dried to obtain ionic liquid 1- vinyl -3- aminopropylimidazol hydrobromate；
(3) ionic liquid 1- vinyl -3- aminopropylimidazol hydrobromate and azodiisobutyronitrile are dissolved in N, N- dimethyl
Formamide is stirred under atmosphere under a nitrogen, 60~75 DEG C back flow reaction 5~8 hours, obtain polyimidazole ionic liquid and slightly produce
Object；
(4) ether precipitating is added in poly ion liquid crude product, sediment is added n,N-Dimethylformamide and is configured to be saturated
Solution, after being dialysed with water, freeze-drying obtains polyimidazole ionic liquid.
7. the preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole according to claim 6, feature
It is, the mass ratio of 1- vinyl imidazole and 3- propantheline bromide hydrobromide is (1~2.5): 1.
8. the preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole according to claim 6, feature
It is, 1- vinyl -3- aminopropylimidazol hydrobromate and azodiisobutyronitrile mass ratio are 2:(0.02~0.2).
9. the preparation method of the ion liquid modified Studies On Preparation And Properties of Cellulose-based Adsorbents of polyimidazole according to claim 2, feature
It is, in step 2, the mass ratio of dialdehyde cellulose and polyimidazole ionic liquid is 1:(1~7).
10. a kind of Studies On Preparation And Properties of Cellulose-based Adsorbents that polyimidazole described in claim 1 is ion liquid modified answering in processing waste water
With, which is characterized in that waste water is anionic dye waste water or effluent containing heavy metal ions.
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