CN107233871B - Immobilized 1- amine ethyl-3-methylimidazole bromide solid extracting agent of chloromethyl polystyrene resin and its preparation method and application - Google Patents
Immobilized 1- amine ethyl-3-methylimidazole bromide solid extracting agent of chloromethyl polystyrene resin and its preparation method and application Download PDFInfo
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Abstract
Disclosure of the invention a kind of chloromethyl polystyrene resin immobilized 1- amine ethyl-3-methylimidazole bromide solid extracting agent and its preparation method and application, belongs to Solid Phase Extraction and Sample Pretreatment Technique field.Technical solution of the present invention main points are as follows: the immobilized 1- amine ethyl-3-methylimidazole bromide solid extracting agent of chloromethyl polystyrene resin, the solid extracting agent is the structural formula by the way that 1- amine ethyl-3-methylimidazole bromide ionic liquid to be grafted on made from chloromethyl polystyrene resin surface as chemical bonding are as follows:
Description
Technical field
The invention belongs to Solid Phase Extraction and Sample Pretreatment Technique fields, and in particular to a kind of chloromethyl polystyrene resin
Immobilized 1- amine ethyl-3-methylimidazole bromide solid extracting agent and its preparation method and application.
Background technique
With the fast development of industrialization and urbanization, various organic pollutants are discharged into environment, are caused serious
Environmental problem.P-nitrophenol is in medicine, pesticide, dyestuff, artificial resin, explosive and other fine chemicals production processes
Essential industry raw material and intermediate, it is easy to enter in these production processes and polluted-water.Paranitrophenol is as water environment
In common phenolic comp ' ds pollution, there is carcinogenic, teratogenesis, mutagenic genotoxic potential and be difficult to degrade, even if very low concentration
Very big murder by poisoning can be caused to aquatile and water body, and priority pollutant is classified as by the environmental protection institution of US and European,
It is one of the six kinds of phenols for being classified as recent control object in China's water in priority pollutant blacklist.Therefore, in water to nitro
The detection and removal of phenol are especially urgent and important.
The content of paranitrophenol is lower in actual environment sample, and complicated component, Matrix effects are big, general analysis method due to
Sensitivity is low to be difficult to detect content therein, is the sensitivity of improvement method, and carrying out pre-treatment to the sample containing paranitrophenol is
It is necessary.Sample pre-treatments can be enriched with determinand, and exclusive PCR substance is indispensable link in environmental analysis.To nitre
The common Sample Pretreatment Technique of base phenol such as the methods of solvent extraction, Soxhlet extraction, ultrasonic extraction is cumbersome, each step it
Between transfer be readily incorporated error, poor reproducibility；And often require to use a large amount of volatile organic solvent.Solid Phase Extraction skill
Art (SPE) is the sample pre-treatments new technology for being widely used and being becoming increasingly popular in recent years, is had efficient, fast and convenient, molten
The advantages that agent dosage is few and reproducible, and commercialization pillar appropriate can be selected as needed or voluntarily fill sorption extraction material
Material, is very suitable to the advanced treating of the separation and concentration of phenols or phenol wastewater in water sample.
The property of solid extracting agent directly determine solid-phase extraction column to the superiority and inferiority of target analytes adsorption selectivity with
And the height of analysis detection sensitivity, therefore, the key of solid phase extraction techniques is the selection of solid extracting agent.Ionic liquid by
In many unique physicochemical properties such as vapour pressures are extremely low, non-volatile, extracting power is strong, stability is good and referred to as environment is friendly
Good type solvent.But ionic liquid is expensive, separately as solvent using when dosage it is big and generally require cumbersome mutually to separate
Journey is not easy to be separated from the water completely when in use, it is easy to pollute to water body, be restricted so as to cause its use.It will
Not only the good adsorbent performance of ionic liquid can be kept on ionic liquid supported to solid phase carrier, but also can substantially reduce ionic liquid
Dosage, prevents the loss of ionic liquid, and is easily isolated, easy to use, is a kind of environment material more friendly to atmosphere, water body
Material.
The present invention uses chemical bonding technology, and the cation of ionic liquid is bonded in chloromethyl polyphenyl by chemical reaction
Vinyl surface prepares resin surface solid-loaded ionic-liquid new material.The material is used for water as sample pre-treatments adsorbent
The separation and concentration of middle trace paranitrophenol has many advantages, such as to adsorb high sensitivity, selectivity well and equilibration time is short.New material was both
Ionic liquid is maintained to the good absorption property of phenolic comp ' ds pollution, and reduces the dosage of ionic liquid, it is therefore prevented that ionic liquid
Pollution of the loss of body to environment, and be easy to be separated by solid-liquid separation and recycle, it is handled before environmental sample for it and waste water advanced
Application in processing provides scientific basis.
The reported solid extracting agent for phenols separation and concentration includes graphene, carbon nanotube, key in document at present
Close silica gel, molecularly imprinted polymer and novel nano-material etc..Select the immobilized 1- amine second of chloromethyl polystyrene resin carrier
Base -3- methylimidazole bromide ionic liquid, which is prepared into pertinent literature of the adsorbent for solvent free extract paranitrophenol, yet there are no report
Road.The related phenols solid extracting agent retrieved and the immobilized amino ionic liquid prior art related to the present invention are such as
Under:
The patent of Publication No. CN104402729A discloses a kind of using silica gel bonded dimethyl propylene aminooimidazole solid phase
The method that extractant adsorbs 2,4- dinitrophenol dinitrophenolate in water.The technical solution is to be bonded aminooimidazole on silica gel, surface texture
It is not ionic liquid structure, the not no extraction advantage of ionic liquid, and also silica gel itself has certain adsorption capacity, and it can be to material
The selectivity of material affects, and without investigating selective absorption of the solid-phase extraction column for 2,4- dinitrophenol dinitrophenolate in text
Performance.
The patent of Publication No. CN104927063A discloses a kind of side of adsorption recovery Phenols In Industrial Liquid Waste class compound
The preparation method of method and adsorbent material.It is adsorbent choosing using the polymer that the immobilized beta-cyclodextrin of chloromethylated polystyrene is formed
Adsorb to selecting property the phenolic substances in industrial wastewater.The synthesis of adsorbent need to be through multistep reaction, synthesis process in the technical solution
In various crosslinking agents, initiator, dispersing agent etc. need to be added, it is complicated for operation.And the product of synthesis is not ionic liquid structure, is not had
The advantage of standby solid-loaded ionic-liquid, the maximum adsorption that Pyrogentisinic Acid, salicylic acid etc. have the Phenol Industrial Wastewater of phenolic hydroxyl group to be adsorbed
24mg/g, 532mg/g are measured, well below this material to the adsorbance of paranitrophenol 1752.7mg/g.Also without research water in text
The disturbed condition of middle common ion and neutral molecule.The also patent of Publication No. CN105295059A of similar situation, utilizes
The phenolic substances in Polymer adsorption industrial wastewater that the immobilized cationized cyclodextrins of chloromethylated polystyrene are formed.
The patent of Publication No. CN104549495A discloses a kind of activated carbon immobilized ionic liquid catalyst, active carbon
Successively oxidation-treated, chlorination processing, is added bromination 1- (2- amine ethyl hydrobromic acid) -3- methylimidazole ionic liquid, has
Machine amine flows back in tetrahydrofuran, filter after add low temperature stirring in potassium hydroxide solution be made the active carbon solid-carrying type from
Sub- liquid catalyst, for being catalyzed Knoevenagel condensation reaction.The synthesis of immobilized amino ionic liquid in the technical solution
Need to be through multistep reaction, synthesis cycle is long, and material complicated for operation and synthesized is used for catalytic synthesis rather than absorbing phenolic
Substance.There are also the patents of Publication No. CN105504121A to disclose one kind using Bio-sil as the immobilized 1- second of carrier for similar situation
The double trifluoromethanesulfonimide salt ion solutions of base -3- ethylamino- imidazoles and azodiisobutyronitrile are used for CO absorption2.Publication No.
The patent of CN105149002B is using metal-organic framework materials ZIF-8 as the immobilized 1- of carrier (3- aminopropyl) -3- methylimidazole chlorine
Compound is used for CO2Absorption-catalyst.
From the above, it can be seen that existing support type phenols extractant or be not ionic liquid structure, does not have ion
The advantage of liquid；Selected carrier does not have selectivity, and mode of loading is also different, cannot be optionally sequestered richness to phenols
Collection；It is that ionic liquid type on immobilized is different from the present invention, the adsorbent being prepared has different structures, thus
The mechanism and effect of absorption are also different.And active carbon, silica gel are mainly immobilized in relation to the technology of amino ionic liquid supported
On equal porous carriers, mode and the mechanism difference not only loaded can also reduce selective absorption of the material to pollutant, and
Using mainly make catalyst or absorb CO2, there is no examine or check the separation and concentration effect of phenolic compound.
Summary of the invention
The technical problem to be solved by the present invention is to provide it is a kind of can efficient rapid sensitive absorption paranitrophenol chloromethyl
Immobilized 1- amine ethyl-3-methylimidazole bromide solid extracting agent of polystyrene resin and preparation method thereof, which can
Paranitrophenol in the presence of common ion and organic matter in selective absorption sample, even if salinity is up to 1mol/ in sample
L, still can remove in sample that for concentration down to the paranitrophenol of 0.0025 μ g/mL, maximal absorptive capacity may be up to 1752.7mg/g, and
The rate of adsorption is fast, easy to operate, and use condition is mild, and the solid extracting agent regenerating easily after use can be recycled for multiple times, be
A kind of solid extracting agent of ideal fast separating concentration and paranitrophenol in removal sample.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, the immobilized 1- amine second of chloromethyl polystyrene resin
Base -3- methylimidazole bromide solid extracting agent, it is characterised in that the solid extracting agent is by by 1- amine ethyl-3-methylimidazole
Bromide ionic liquid is grafted on made from chloromethyl polystyrene resin surface as chemical bonding, and structural formula is
The immobilized 1- amine ethyl-3-methylimidazole bromide solid extracting agent of chloromethyl polystyrene resin of the present invention
Preparation method, it is characterised in that specific steps are as follows: take chloromethyl styrene resin that N-Methyl pyrrolidone swelling 12-24h is added,
1- amine ethyl-3-methylimidazole bromide and alkali compounds are added, medium alkaline compound is Anhydrous potassium carbonate, Carbon Dioxide
Sodium or triethylamine are cooled to room temperature after reaction then in 60-100 DEG C of reaction 8-24h, successively use deionized water, anhydrous second
Alcohol washed product removes unreacted 1- amine ethyl-3-methylimidazole bromide and N-Methyl pyrrolidone, and place the product in 45 DEG C
Under the conditions of be dried in vacuo for 24 hours, the final obtained immobilized 1- amine ethyl-3-methylimidazole bromine of yellow solid chloromethyl polystyrene resin
Salt solid extracting agent.
Further preferably, the chloromethyl polystyrene resin and 1- amine ethyl-3-methylimidazole bromide feed intake mole
Than for 1:3-1:10.
The immobilized 1- amine ethyl-3-methylimidazole bromide solid extracting agent of chloromethyl polystyrene resin of the present invention
Preparation method, it is characterised in that the reaction equation in preparation process are as follows:
The immobilized 1- amine ethyl-3-methylimidazole bromide solid extracting agent of chloromethyl polystyrene resin of the present invention is used
The separation and concentration and sample pre-treatments of trace paranitrophenol in environmental water sample, it is characterised in that detailed process are as follows: extracted with solid phase
Agent is taken to prepare solid-phase extraction column, the sodium hydroxide that with molar concentration be 0.1mol/L hydrochloric acid solution or molar concentration is 0.1mol/L
Solution adjusts the pH to 6 of the water sample containing paranitrophenol, and water sample containing paranitrophenol is passed through Solid Phase Extraction with the flow velocity of 0.5-2mL/min
Column, the paranitrophenol that eluant, eluent is used after the completion of extraction to adsorb on the flow velocity elution solid-phase extraction column of 0.2mL/min is to realize
The regeneration cycle of solid-phase extraction column uses, and wherein eluant, eluent is the mixed liquor or nothing of dehydrated alcohol, methanol, dehydrated alcohol and hydrochloric acid
The mixed liquor of water-ethanol and acetic acid, solid-phase extraction column to the enrichment multiplying power of the water sample containing paranitrophenol up to 629.33 times, minimum inspection
Concentration is 0.0025 μ g/mL out.
Solid extracting agent of the present invention has simple synthetic method, large amount of adsorption, the good, anti-interference ability of selectivity
By force, high sensitivity and the advantages that can be recycled, can paranitrophenol in high-salt wastewater in selective separation enrichment sample,
Be very suitable to the separation and concentration of paranitrophenol and removal in the high-salt wastewaters such as waste water from dyestuff, pharmacy waste water, wastewater from chemical industry, have compared with
Good industrial application value.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment 1
After weighing the addition 40mLN- methyl pyrrolidone swelling for 24 hours of 5g chloromethyl polystyrene resin, 13.5g 1- is added
Amine ethyl-3-methylimidazole bromide (the molar ratio 1:3 of chloromethyl polystyrene resin and 1- amine ethyl-3-methylimidazole bromide)
With 2.5g anhydrous K2CO3, add 60mLN- methyl pyrrolidone, mixture sealing is placed in 80 DEG C of oil bath pans and reacts
12h is cooled to room temperature after reaction, successively with deionized water, dehydrated alcohol washed product to can't detect 1- amine ethyl -3-
The absorbance of methylimidazole bromide and N-Methyl pyrrolidone, place the product in be dried to can't see obvious water sample in air dry oven
It is dried in vacuo under the conditions of being placed in 45 DEG C again afterwards for 24 hours, finally the obtained immobilized 1- amine second of faint yellow solid chloromethyl polystyrene resin
Base -3- methylimidazole bromide ionic liquid solid extracting agent, product is sealed in bottle, is stored in spare in drier.
Selectivity of the solid extracting agent to common ion in water and other neutral molecules
The solid extracting agent of the above-mentioned preparation of 0.05g is filled into solid phase extraction column, solid-phase extraction column is made, taken containing one
The sample solution of quantitative paranitrophenol adjusts sample solution with the hydrochloric acid solution or 0.1mol/L sodium hydroxide solution of 0.1mol/L
PH to 6 or so, with the flow velocity of 1mL/min by the solid-phase extraction column of preparation, the paranitrophenol in sample solution can be in solid phase
100% enrichment on extraction column.When the substance in table 1 coexists with paranitrophenol, the absorption of paranitrophenol is not interfered.Allow to exist
Interference multiplying power be shown in Table 1:
The interference of 1 coexisting ion of table allows multiplying power
As it can be seen from table 1 common ion such as K in water+、Na+、Ca2+、NO3 -、Cl-The presence of plasma and neutral molecule
Solid-phase extraction column selective extraction paranitrophenol is not interfered.Above the experimental results showed that prepared solid extracting agent is for nitre
Base phenol has good slective extraction performance, especially in NaCl, KCl, Ca of high concentration2Cl、Mg2In the presence of Cl and nitrate,
The absorption for not influencing paranitrophenol is very suitable to the separation and concentration of paranitrophenol and removal in high-salt wastewater, has good work
Industry application value.
Absorption sensitivity to trace paranitrophenol
It takes the paranitrophenol of 5 μ g to be dissolved in the aqueous solution of different volumes, Solid Phase Extraction is passed through with the flow velocity of 1mL/min
Then column selects the ethanol solution of 3mL to elute with the flow velocity of 0.2mL/min, measure paranitrophenol concentration in eluent.It is real
Test the result shows that, when loading volume is 2000mL, when paranitrophenol concentration is 0.0025 μ g/mL in water, the recycling of paranitrophenol
Rate still reaches 94.37%, and being enriched with multiplying power at this time is 629.33 times, and the concentration is well below domestic water standard requirements to nitro
The standard limited value (0.02 μ g/mL) of phenol shows that synthesized solid extracting agent for high sensitivity when adsorbing paranitrophenol, can be used
The separation and concentration of trace paranitrophenol and removal in environmental water sample.
Paranitrophenol with dehydrated alcohol to be adsorbed on the flow velocity of 0.2mL/min elution solid-phase extraction column, then spend from
Sub- water rinses out remaining dehydrated alcohol in column.This method can be used for the regeneration of solid-phase extraction column, achieve the purpose that recycle.It is real
Verify bright, the solid-phase extraction column of preparation is recycled 20 times, for paranitrophenol accumulation rate still close to 100%, illustrate made
Standby solid-phase extraction column can be recycled and high recycling rate.
Solid extracting agent applies the removal and detection of paranitrophenol in actual sample
Solid-phase extraction column is made in the solid extracting agent of synthesis with above-mentioned experimental method to be used for right in actual environment water sample
The removal and analysis detection of nitrophenols, experimental result are shown in Table 2:
The analysis of 2 actual sample of table
As can be seen from the table, prepared solid-phase extraction column exists to the rate of recovery of paranitrophenol in actual environment sample
Between 98.4%-109.6%, illustrate that this method can exclude complicated Matrix effects, the choosing for paranitrophenol in actual sample
When selecting property separation and concentration, good, the high sensitivity of selectivity has certain practical application meaning.
Embodiment 2
After weighing 0.5g chloromethyl polystyrene resin addition 10mL N-Methyl pyrrolidone swelling 12h, 4.6g is added
1- amine ethyl-3-methylimidazole bromide (molar ratio 1 of chloromethyl polystyrene resin and 1- amine ethyl-3-methylimidazole bromide:
10) with 0.2mL triethylamine, 20mL N-Methyl pyrrolidone is added, mixture sealing is placed in 100 DEG C of oil bath pans anti-
8h is answered, is cooled to room temperature after reaction, successively with deionized water, dehydrated alcohol washed product to can't detect 1- amine ethyl-
The absorbance of 3- methylimidazole bromide and N-Methyl pyrrolidone, place the product in be dried to can't see obvious water in air dry oven
It is dried in vacuo under the conditions of being placed in 45 DEG C again after sample for 24 hours, finally the obtained immobilized 1- amine of faint yellow solid chloromethyl polystyrene resin
Ethyl-3-methylimidazole bromide ionic liquid solid extracting agent, product is sealed in bottle, is stored in spare in drier.
The solid extracting agent of the above-mentioned preparation of 0.03g is filled into solid phase extraction column, solid-phase extraction column is made, taken containing one
The sample solution of quantitative paranitrophenol, with the flow velocity of 0.5mL/min by the solid-phase extraction column of preparation, in sample solution to nitre
Base phenol can 100% enrichment on solid-phase extraction column.Common ion such as K in water+、Na+、Ca2+、NO3 -、Cl-Plasma and solubility
Starch, glucose neutral molecule etc. do not interfere the extraction of paranitrophenol by Solid Phase Extraction post separation.
The mixed liquor of the dehydrated alcohol and hydrochloric acid solution (1mo/L) that are 9:1 with volume ratio is eluted with the flow velocity of 0.2mL/min
The paranitrophenol adsorbed on solid-phase extraction column, then with deionized water rinse solid-phase extraction column until efflux be in neutrality, this method
The regeneration that can be used for solid-phase extraction column achievees the purpose that recycle.It is demonstrated experimentally that the solid-phase extraction column of preparation is recycled 20
Secondary, performance is basically unchanged, and illustrates that prepared solid-phase extraction column can be recycled and high recycling rate.
Embodiment 3
After weighing the addition 10mLN- methyl pyrrolidone swelling for 24 hours of 1g chloromethyl polystyrene resin, 5.6g 1- amine is added
Ethyl-3-methylimidazole bromide (the molar ratio 1:6 of chloromethyl polystyrene resin and 1- amine ethyl-3-methylimidazole bromide) and
0.5g anhydrous Na2CO3, 20mLN- methyl pyrrolidone is added, mixture sealing is placed in 70 DEG C of oil bath pans and reacts 14h,
It is cooled to room temperature after reaction, successively with deionized water, dehydrated alcohol washed product to can't detect 1- amine ethyl -3- methyl
The absorbance of imidazoles bromide and N-methyl pyrrolidones, place the product in be dried in air dry oven can't see obvious water sample after again
It is dried in vacuo under the conditions of being placed in 45 DEG C for 24 hours, finally the obtained immobilized 1- amine ethyl -3- of faint yellow solid chloromethyl polystyrene resin
Methylimidazole bromide ionic liquid solid extracting agent, product is sealed in bottle, is stored in spare in drier.
The solid extracting agent of the above-mentioned preparation of 0.1g is filled into solid phase extraction column, solid-phase extraction column is made, taken containing certain
The sample solution of paranitrophenol is measured, passes through the solid-phase extraction column of preparation, the paranitrophenol in sample solution with the flow velocity of 2mL/min
It can 100% enrichment on solid-phase extraction column.Common ion such as K in water+、Na+、Ca2+、NO3 -、Cl-Plasma and soluble starch,
Glucose neutral molecule etc. does not interfere the extraction of paranitrophenol by Solid Phase Extraction post separation.
The mixed liquor of the dehydrated alcohol and acetic acid (1mol/L) that are 9:1 with volume ratio is solid with the flow velocity elution of 0.2mL/min
Then the paranitrophenol adsorbed on phase extraction column rinses solid-phase extraction column until efflux is in neutrality with deionized water, this method can
For the regeneration of solid-phase extraction column, achieve the purpose that recycle.It is demonstrated experimentally that the solid-phase extraction column of preparation is recycled 20
Secondary, performance is basically unchanged, and illustrates that prepared solid-phase extraction column can be recycled and high recycling rate.
Embodiment 4
After weighing the addition 10mL N-Methyl pyrrolidone swelling for 24 hours of 0.5g chloromethyl polystyrene resin, 2.3g is added
1- amine ethyl-3-methylimidazole bromide (molar ratio 1 of chloromethyl polystyrene resin and 1- amine ethyl-3-methylimidazole bromide:
And 0.2g anhydrous K 5)2CO3, 20mLN- methyl pyrrolidone is added, mixture sealing is placed on 60 DEG C of reactions for 24 hours, reaction
After be cooled to room temperature, successively with deionized water, dehydrated alcohol washed product to can't detect 1- amine ethyl-3-methylimidazole
The absorbance of bromide and N-Methyl pyrrolidone, place the product in be dried in air dry oven can't see obvious water sample after be placed in again
It is dried in vacuo under the conditions of 45 DEG C for 24 hours, finally the obtained immobilized 1- amine ethyl -3- methyl miaow of yellow solid chloromethyl polystyrene resin
Azoles bromide ionic liquid solid extracting agent, product is sealed in bottle, is stored in spare in drier.
The solid extracting agent of the above-mentioned preparation of 0.03g is filled into solid phase extraction column, solid-phase extraction column is made, taken containing one
The sample solution of quantitative paranitrophenol with the flow velocity of 0.5mL/min by the solid-phase extraction column of preparation, in sample solution to nitre
Base phenol can 100% enrichment on solid-phase extraction column.Common ion such as K in water+、Na+、Ca2+、NO3 -、Cl-Plasma and solubility
Starch, glucose neutral molecule etc. do not interfere the extraction of paranitrophenol by Solid Phase Extraction post separation.
Paranitrophenol with methanol solution to be adsorbed on the flow velocity of 0.2mL/min elution solid-phase extraction column, then spend from
Sub- water rinses solid-phase extraction column, this method can be used for the regeneration of solid-phase extraction column, achieve the purpose that recycle.It is demonstrated experimentally that system
Standby solid-phase extraction column is recycled 20 times, and performance is basically unchanged, and illustrates that prepared solid-phase extraction column can be recycled, repeats
Utilization rate is high.
Embodiment 5
After weighing 0.5g chloromethyl polystyrene resin addition 10mL N-Methyl pyrrolidone swelling 12h, 2.3g is added
1- amine ethyl-3-methylimidazole bromide (molar ratio 1 of chloromethyl polystyrene resin and 1- amine ethyl-3-methylimidazole bromide:
And 0.2g anhydrous Na 5)2CO3, 20mLN- methyl pyrrolidone is added, mixture sealing is placed on 90 DEG C of reaction 10h, instead
It is cooled to room temperature after answering, successively with deionized water, dehydrated alcohol washed product to can't detect 1- amine ethyl -3- methyl miaow
The absorbance of azoles bromide and N-Methyl pyrrolidone, place the product in be dried in air dry oven can't see obvious water sample after set again
It is dried in vacuo under the conditions of 45 DEG C for 24 hours, finally the obtained immobilized 1- amine ethyl -3- methyl of yellow solid chloromethyl polystyrene resin
Imidazoles bromide ionic liquid solid extracting agent, product is sealed in bottle, is stored in spare in drier.
The solid extracting agent of the above-mentioned preparation of 0.05g is filled into solid phase extraction column, solid-phase extraction column is made, taken containing one
The sample solution of quantitative paranitrophenol, with the flow velocity of 1.5mL/min by the solid-phase extraction column of preparation, in sample solution to nitre
Base phenol can 100% enrichment on solid-phase extraction column.Common ion such as K in water+、Na+、Ca2+、NO3 -、Cl-Plasma and solubility
Starch, glucose neutral molecule etc. do not interfere the extraction of paranitrophenol by Solid Phase Extraction post separation.
With ethanol solution with the paranitrophenol adsorbed on the flow velocity elution solid-phase extraction column of 0.2mL/min, then use
Deionized water rinses solid-phase extraction column, this method can be used for the regeneration of solid-phase extraction column, achieve the purpose that recycle.Experiment card
Bright, the solid-phase extraction column of preparation is recycled 20 times, and performance is basically unchanged, and illustrating that prepared solid-phase extraction column is recyclable makes
With high recycling rate.
Embodiment 6
After weighing 0.5g chloromethyl polystyrene resin addition 10mL N-Methyl pyrrolidone swelling 12h, 2.3g is added
1- amine ethyl-3-methylimidazole bromide (molar ratio 1 of chloromethyl polystyrene resin and 1- amine ethyl-3-methylimidazole bromide:
And 0.2g anhydrous Na 5)2CO3, add 10mLN- methyl pyrrolidone.Mixture sealing is placed on 70 DEG C of reaction 14h, is reacted
After be cooled to room temperature, successively with deionized water, dehydrated alcohol washed product to can't detect 1- amine ethyl-3-methylimidazole
The absorbance of bromide and N-Methyl pyrrolidone, place the product in be dried in air dry oven can't see obvious water sample after be placed in again
It is dried in vacuo under the conditions of 45 DEG C for 24 hours, finally the obtained immobilized 1- amine ethyl -3- methyl miaow of yellow solid chloromethyl polystyrene resin
Azoles bromide ionic liquid solid extracting agent, product is sealed in bottle, is stored in spare in drier.
The solid extracting agent of the above-mentioned preparation of 0.05g is filled into solid phase extraction column, solid-phase extraction column is made, taken containing one
The sample solution of quantitative paranitrophenol, with the flow velocity of 1mL/min by the solid-phase extraction column of preparation, in sample solution to nitro
Phenol can 100% enrichment on solid-phase extraction column.Common ion such as K in water+、Na+、Ca2+、NO3 -、Cl-Plasma and soluble shallow lake
Powder, glucose neutral molecule etc. do not interfere the extraction of paranitrophenol by Solid Phase Extraction post separation.
With ethanol solution with the paranitrophenol adsorbed on the flow velocity elution solid-phase extraction column of 0.25mL/min, then use
Deionized water rinses solid-phase extraction column, this method can be used for the regeneration of solid-phase extraction column, achieve the purpose that recycle.Experiment card
Bright, the solid-phase extraction column of preparation is recycled 20 times, and performance is basically unchanged, and illustrating that prepared solid-phase extraction column is recyclable makes
With high recycling rate.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (6)
1. the immobilized 1- amine ethyl-3-methylimidazole bromide solid extracting agent of chloromethyl polystyrene resin, it is characterised in that this is solid
Phase extractant is by the way that 1- amine ethyl-3-methylimidazole bromide ionic liquid is grafted on chloromethyl polyphenyl second by chemical bonding
Made from olefine resin surface, structural formula is
2. a kind of immobilized 1- amine ethyl-3-methylimidazole bromide solid phase extraction of chloromethyl polystyrene resin described in claim 1
Take the preparation method of agent, it is characterised in that specific steps are as follows: take chloromethyl styrene resin that N-Methyl pyrrolidone swelling is added
12-24h, adds 1- amine ethyl-3-methylimidazole bromide and alkali compounds, medium alkaline compound be Anhydrous potassium carbonate,
Natrium carbonicum calcinatum or triethylamine are cooled to room temperature after reaction then in 60-100 DEG C of reaction 8-24h, successively use deionization
Water, dehydrated alcohol washed product remove unreacted 1- amine ethyl-3-methylimidazole bromide and N-Methyl pyrrolidone, will produce
Object is dried in vacuo for 24 hours under the conditions of being placed in 45 DEG C, finally the obtained immobilized 1- amine ethyl -3- of yellow solid chloromethyl polystyrene resin
Methylimidazole bromide solid extracting agent.
3. the immobilized 1- amine ethyl-3-methylimidazole bromide solid phase extraction of chloromethyl polystyrene resin according to claim 2
Take the preparation method of agent, it is characterised in that: the throwing of the chloromethyl polystyrene resin and 1- amine ethyl-3-methylimidazole bromide
Material molar ratio is 1:3-1:10.
4. the immobilized 1- amine ethyl-3-methylimidazole bromide solid phase extraction of chloromethyl polystyrene resin according to claim 2
Take the preparation method of agent, it is characterised in that the reaction equation in preparation process are as follows:
5. the immobilized 1- amine ethyl-3-methylimidazole bromide solid extracting agent of chloromethyl polystyrene resin described in claim 1
For the separation and concentration of trace paranitrophenol in environmental water sample, the solid-phase extraction column repetitive cycling after elution is used, and is stripped
Eluant, eluent in journey is the mixed liquor or dehydrated alcohol of dehydrated alcohol, methanol, dehydrated alcohol and hydrochloric acid and the mixed liquor of acetic acid.
6. the immobilized 1- amine ethyl-3-methylimidazole bromide solid phase extraction of chloromethyl polystyrene resin according to claim 5
Take agent for the separation and concentration of trace paranitrophenol in environmental water sample, it is characterised in that detailed process are as follows: with solid extracting agent system
Standby solid-phase extraction column, the sodium hydroxide solution tune that with molar concentration be 0.1mol/L hydrochloric acid solution or molar concentration is 0.1mol/L
Water sample containing paranitrophenol is passed through solid-phase extraction column, extraction with the flow velocity of 0.5-2mL/min by the pH to 6 for saving the water sample containing paranitrophenol
The paranitrophenol that eluant, eluent is used after the completion of taking to adsorb on the flow velocity elution solid-phase extraction column of 0.2mL/min is to realize that solid phase extracts
The regeneration cycle of column is taken to use, wherein eluant, eluent is the mixed liquor or dehydrated alcohol of dehydrated alcohol, methanol, dehydrated alcohol and hydrochloric acid
With the mixed liquor of acetic acid, solid-phase extraction column to the enrichment multiplying power of the water sample containing paranitrophenol up to 629.33 times, concentration limit
For 0.0025 μ g/mL.
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| CN101225176A (en) * | 2007-12-18 | 2008-07-23 | 南京大学 | Imidazolyl modified complex functional high-crosslinked adsorption resin and preparation method thereof |
| CN104209102A (en) * | 2014-09-29 | 2014-12-17 | 河南师范大学 | Heavy metal ion adsorbent for grafting glycine to chloromethylated polystyrene, preparation method and application thereof |
| CN104327080A (en) * | 2014-11-04 | 2015-02-04 | 崇州合瑞科技有限公司 | Method for extracting theophylline from tea leaves by using chloromethyl polystyrene resin |
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| CN101225176A (en) * | 2007-12-18 | 2008-07-23 | 南京大学 | Imidazolyl modified complex functional high-crosslinked adsorption resin and preparation method thereof |
| CN104209102A (en) * | 2014-09-29 | 2014-12-17 | 河南师范大学 | Heavy metal ion adsorbent for grafting glycine to chloromethylated polystyrene, preparation method and application thereof |
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