CN113209948A - Preparation method and application of multi-template molecularly imprinted composite material - Google Patents
Preparation method and application of multi-template molecularly imprinted composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000002444 silanisation Methods 0.000 claims abstract description 17
- 238000012805 post-processing Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 239000012528 membrane Substances 0.000 claims description 48
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- 239000004677 Nylon Substances 0.000 claims description 33
- 229920001778 nylon Polymers 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 22
- 238000001179 sorption measurement Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000010828 elution Methods 0.000 claims description 16
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 15
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 claims description 14
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 14
- HOLHYSJJBXSLMV-UHFFFAOYSA-N 2,6-dichlorophenol Chemical compound OC1=C(Cl)C=CC=C1Cl HOLHYSJJBXSLMV-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000012488 sample solution Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000013557 residual solvent Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 9
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 6
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- 238000004519 manufacturing process Methods 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 1
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- 229920000344 molecularly imprinted polymer Polymers 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
Abstract
The invention provides a preparation method and application of a multi-template molecularly imprinted composite material, and the preparation method of the multi-template molecularly imprinted composite material comprises the following steps: preparing a silanization modified multi-walled carbon nanotube composite material and a multi-template molecularly imprinted composite material; the preparation of the silanization modified multi-walled carbon nanotube composite material comprises the steps of uniformly mixing materials, feeding and post-processing; the preparation of the multi-template molecularly imprinted composite material comprises the steps of preparing a prepolymerization solution, mixing materials and eluting.
Description
Technical Field
The invention belongs to the technical field of material science and engineering, and relates to a preparation method and application of a multi-template molecularly imprinted composite material.
Background
Chlorophenols (CPs) belong to environmental endocrine disruptors, and have been limited in use by light industries such as leather, textile, paper making and the like due to the harm to the environment and human health. However, the domestic and foreign research reports show that CPs are detected in different concentration levels (ng/L-mug/L) in environmental water, aquatic organisms, sediments, soil, human blood, urine and milk. Because the content of CPs in a sample is low and the matrix of the sample is complex, how to selectively identify CPs is a difficult problem to be solved urgently.
Due to its excellent selectivity for templates and structural analogs, molecularly imprinted polymer materials are often used as solid phase extraction adsorbents to selectively recognize and enrich trace or trace targets. In the preparation of chlorophenol molecularly imprinted materials, one chlorophenol is mostly used as a template, such as 4-chlorophenol, 2, 4-dichlorophenol, 2,4, 6-trichlorophenol, pentachlorophenol and the like, and free radical polymerization methods such as bulk polymerization, precipitation polymerization and the like are adopted, so that the problems of difficulty in elution of template molecules, template leakage in the using process and the like exist. In the application aspect of solid phase extraction, the chlorophenol molecularly imprinted material is prepared by a free radical polymerization method and is often used in solid phase extraction and dispersive solid phase extraction technologies. When the method is applied to solid-phase extraction, the molecularly imprinted material needs to be filled in a solid-phase extraction column, the extraction column collects eluent after the steps of activation, sample loading, leaching, elution and the like, the operation steps are complex, and a special solid-phase extraction device and a vacuum-pumping device are needed. When the method is applied to dispersed solid phase extraction, a high-speed centrifuge is needed to realize the separation of materials and solution, and two times of centrifugal operation are needed in the adsorption and elution processes.
The imprinting materials of the prior art have the following drawbacks: (1) using chlorophenol as a template, wherein the recognition site of the imprinting material is single; (2) the adsorption selectivity of the parachlorophenol is poor, and the adsorption rate is low; (3) the solid phase extraction application of the imprinting material has complex operation steps; (4) the separation of the blotting material from the solution requires the use of specialized equipment.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method and application of a multi-template molecularly imprinted composite material, which realize the following purposes:
(1) preparing a multi-template molecularly imprinted composite material with 5 chlorophenol recognition sites;
(2) the adsorption selectivity of the 5 chlorophenols is improved, and the adsorption rate is improved;
(3) the operation steps are simplified, and the operation time is reduced;
(4) the multi-template molecularly imprinted membrane is manufactured, and the separation of the imprinted material and the solution can be realized without special equipment.
In order to realize the purpose, the invention adopts the following technical scheme:
a preparation method of a multi-template molecularly imprinted composite material comprises the following steps: preparing a silanization modified multi-walled carbon nanotube composite material and a multi-template molecularly imprinted composite material;
the preparation of the silanization modified multi-walled carbon nanotube composite material comprises the steps of uniformly mixing materials, feeding and post-processing;
the preparation of the multi-template molecularly imprinted composite material comprises the steps of preparing a prepolymerization solution, mixing materials and eluting.
The following is a further improvement of the technical scheme:
the preparation method of the composite material comprises the following steps: preparing a silanization modified multi-walled carbon nanotube composite material and a multi-template molecularly imprinted composite material;
the preparation of the silanization modified multi-walled carbon nanotube composite material comprises the steps of uniformly mixing materials, feeding and post-processing;
the preparation of the multi-template molecularly imprinted composite material comprises the steps of preparing a prepolymerization solution, mixing materials and eluting.
The method comprises the following specific steps:
step 1: preparation of silanization modified multi-walled carbon nanotube composite material
(1) Ultrasonic mixing
Uniformly mixing the materials, dissolving Cetyl Trimethyl Ammonium Bromide (CTAB), ethanol and water, adding the carboxylated multi-walled carbon nanotube, and uniformly stirring after uniformly dispersing by ultrasonic;
the mass volume ratio of the Cetyl Trimethyl Ammonium Bromide (CTAB) to the ethanol is 3.6-3.9 mg: 1 ml;
the volume ratio of the ethanol to the water is as follows: 1.2-1.4: 1;
the mass ratio of the Cetyl Trimethyl Ammonium Bromide (CTAB) to the carboxylated multi-walled carbon nanotube is 3.6-3.9: 1;
the mechanical stirring is carried out, the rotating speed is 170rpm, and the stirring time is 10 min;
the carboxylated multi-walled carbon nanotube: the outer diameter is 20-30 nm, and the length is 10-30 μm.
(2) Charging of
Adding ammonia water, stirring, adding tetraethyl orthosilicate (TEOS), and stirring for reaction;
the volume ratio of the ammonia water to the ethanol is 0.1: 5.2-5.4;
the concentration of the ammonia water is 25% -28%;
the volume ratio of tetraethyl orthosilicate (TEOS) to ammonia water is 1: 1.3-1.7;
the reaction time is 6 h.
(3) Post-treatment
After the post-treatment, after the reaction is finished, centrifuging the mixed solution, cleaning the residual solvent, dispersing, heating and refluxing to remove Cetyl Trimethyl Ammonium Bromide (CTAB), centrifuging again, and drying to obtain the silanized modified multi-walled carbon nanotube composite material;
dispersing, namely dispersing the centrifuged precipitate into acetone;
the heating reflux temperature is 82 ℃;
centrifuging at 7000rpm for 8 min;
and drying at 40 ℃ for 10 h.
Step 2: preparation of multi-template molecularly imprinted composite material
(1) Preparation of a prepolymerization solution
The preparation method comprises the steps of mixing 2-chlorophenol, 4-chlorophenol, 2, 4-dichlorophenol, 2, 6-dichlorophenol and 2,4, 6-trichlorophenol, adding acetonitrile, adding methacrylic acid, and standing for reaction to obtain a prepolymerization solution.
The mass ratio of the 2-chlorophenol, the 4-chlorophenol, the 2, 4-dichlorophenol, the 2, 6-dichlorophenol and the 2,4, 6-trichlorophenol is as follows: 1:1:1:1: 1;
the ratio of the 2-chlorophenol to the acetonitrile is 0.1 mmol: 18-22 ml;
the mass ratio of the 2-chlorophenol to the methacrylic acid substance is 0.1: 3.8-4.2;
and standing for reaction at 25 ℃ for 12 h.
(2) Mixing material
And mixing the materials, namely ultrasonically dispersing the silanized modified multi-wall carbon nanotube composite material and acetonitrile uniformly, adding a prepolymerization solution, ethylene glycol dimethacrylate and azodiisobutyronitrile, introducing nitrogen into the solution, sealing, placing in a constant-temperature water bath, and stirring for reaction.
The mass volume ratio of the silanization modified multi-walled carbon nanotube composite material to acetonitrile is 1.15-1.35 mg: 1 ml;
the volume ratio of the acetonitrile to the prepolymerization solution is 3.5-4.5: 1;
the mass ratio of the silanization modified multi-walled carbon nanotube composite material to the azodiisobutyronitrile is 3-3.5: 1;
introducing nitrogen for 15 min;
the temperature of the constant-temperature water bath is 60 ℃;
the stirring reaction is a magnetic stirring reaction, and the time is 24 hours.
(3) Elution is carried out
And after the elution and reaction are finished, centrifugally collecting the material, respectively carrying out shaking elution for 2 times by using methanol, carrying out shaking elution for 4 times by using methanol/acetic acid, carrying out shaking elution for 2 times by using methanol, removing the template, and drying to obtain the multi-template molecularly imprinted composite material.
The methanol is 75-85 mL/time;
the volume ratio of methanol to acetic acid is 8-10: 1;
drying at 38-42 ℃ for 10 h;
centrifuging at 6000rpm for 7 min;
and drying at 40 ℃ for 10 h.
The invention also provides application of the multi-template molecularly imprinted composite material, which comprises preparation of a multi-template molecularly imprinted-nylon membrane package and membrane package application.
The preparation method of the multi-template molecularly imprinted-nylon membrane comprises the steps of cutting, folding and heat-sealing a porous nylon membrane to prepare a membrane with an opening at one end, filling a multi-template molecularly imprinted composite material from the opening end, and heat-sealing to prepare the multi-template molecularly imprinted-nylon membrane;
the pore diameter of the nylon membrane is 0.22-1 μm.
Adding a sample solution into the nylon membrane for application, magnetically stirring, soaking the multi-template molecularly imprinted-nylon membrane with methanol, adsorbing excess solvent with dust-free paper, putting the membrane into the sample solution, and taking out the nylon membrane after adsorption; the membrane package can be recycled, and the adsorbed sample solution is filtered by a needle filter and then subjected to HPLC analysis.
The adsorption time is 60 min;
the needle filter was 0.45 μm.
Compared with the prior art, the invention has the beneficial effects that:
(1) the multi-template molecularly imprinted composite material prepared by the invention can simultaneously and selectively identify 2-chlorophenol, 4-chlorophenol, 2, 4-dichlorophenol, 2, 6-dichlorophenol and 2,4, 6-trichlorophenol.
(2) The preparation method of the multi-template molecularly imprinted composite material of the invention can fill the molecularly imprinted composite material in the porous nylon membrane without special filling equipment and heat sealing equipment to prepare the multi-template molecularly imprinted membrane.
(3) According to the preparation method of the multi-template molecularly imprinted composite material, the membrane is taken out by using tweezers, so that the separation of the solution and the adsorption material can be realized, special separation equipment is not required, and the method is simple and rapid.
(4) The multi-template molecularly imprinted composite material prepared by the invention is filled in a nylon membrane package, and when the composite material is used for adsorbing 2-chlorophenol, 4-chlorophenol, 2, 4-dichlorophenol, 2, 6-dichlorophenol and 2,4, 6-trichlorophenol, the adsorption selectivity is strong, and the adsorption efficiency is high, namely 81.4%, 88.0%, 99.6%, 96.0% and 99.3% respectively.
(5) The invention adopts carboxylated multi-walled carbon nanotubes to obtain the silanization modified multi-walled carbon nanotube composite material, and 2-chlorophenol, 4-chlorophenol, 2, 4-dichlorophenol, 2, 6-dichlorophenol, 2,4, 6-trichlorophenol and the like are added for reaction to obtain the multi-template molecularly imprinted composite material, thereby meeting the application in the light industry fields of leather, textile, papermaking and the like.
Drawings
FIG. 1 is a schematic diagram of the preparation process of a multi-template molecularly imprinted composite material of example 1;
FIG. 2 is a diagram showing the pore size distribution of the multi-template molecularly imprinted composite material prepared in example 1;
FIG. 3 is a graph of pore size distribution for the non-imprinted composite material prepared in example 2;
FIG. 4 is a schematic diagram of the process for preparing the multi-template molecularly imprinted-nylon membrane package of example 3;
FIG. 5 is a schematic diagram of the application process of the multi-template molecularly imprinted-nylon membrane package described in example 4;
FIG. 6 is a bar graph of the adsorption efficiency of the multi-template molecularly imprinted-nylon membrane of example 5 for 2-chlorophenol, 4-chlorophenol, 2, 4-dichlorophenol, 2, 6-dichlorophenol and 2,4, 6-trichlorophenol at different packing amounts.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1: preparation method of multi-template molecularly imprinted composite material
The method comprises the following steps:
step 1: preparation of silanization modified multi-walled carbon nanotube composite material
(1) Ultrasonic mixing
Sequentially adding 0.3g of CTAB, 80mL of ethanol and 60mL of water into a three-neck flask, dissolving, adding 80mg of carboxylated multi-walled carbon nanotubes, ultrasonically dispersing uniformly, mechanically stirring at 170rpm, and stirring for 10 min;
the carboxylated multi-walled carbon nanotube: the outer diameter is 20-30 nm, and the length is 10-30 mu m;
(2) charging of
Adding 1.5mL of strong ammonia water with the mass concentration of 25-28%, continuing stirring for 30min, adding 1mL of TEOS, and stirring for reacting for 6 h;
(3) post-treatment
After the reaction is finished, the mixed solution is divided into 50mL centrifuge tubes, centrifuged at 7000rpm for 8min, the residual solvent is cleaned by ultrapure water and absolute ethyl alcohol, and the centrifuged precipitate is dispersed in 150mL acetone; heating and refluxing at 82 ℃ to remove CTAB, centrifuging at 7000rpm for 8min, and drying at 40 ℃ for 10h to obtain the silanization modified multi-wall carbon nanotube composite material.
Step 2: preparation of multi-template molecularly imprinted composite material
(1) Preparation of a prepolymerization solution
Respectively weighing 0.1mmol of 2-chlorophenol, 0.1mmol of 4-chlorophenol, 0.1mmol of 2, 4-dichlorophenol, 0.1mmol of 2, 6-dichlorophenol and 0.1mmol of 2,4, 6-trichlorophenol, placing in a sample bottle, adding 20mL of acetonitrile for dissolving, then adding 4mmol of methacrylic acid, and standing at 25 ℃ for reaction for 12h to obtain a prepolymerization solution;
(2) mixing material
Adding 100mg of silanized modified multi-walled carbon nanotube composite material and 80mL of acetonitrile into a three-neck flask, ultrasonically dispersing uniformly, adding 20mL of prepolymerization solution, 1mL of ethylene glycol dimethacrylate and 30mg of azodiisobutyronitrile, introducing nitrogen into the solution for 15min, covering a flask stopper, placing in a constant-temperature water bath at 60 ℃, and magnetically stirring for reacting for 24 h;
(3) elution is carried out
And after the reaction is finished, centrifuging at 6000rpm for 7min to collect materials, respectively performing shaking elution for 2 times by using 80 mL/methanol, performing shaking elution for 4 times by using methanol/acetic acid with the volume ratio of 9:1, performing shaking elution for 2 times by using 80 mL/methanol, removing the template, and drying at 40 ℃ for 10h to obtain the multi-template molecularly imprinted composite material.
The preparation method of the multi-template molecularly imprinted composite material is shown in the attached figure 1.
The pore size distribution of the multi-template molecularly imprinted composite material is shown in figure 2, and the calculated average pore size is 6.1820 nm.
Example 2 preparation method of non-imprinted composite material
On the basis of example 1, a non-imprinted composite material was prepared by omitting the preparation of the prepolymerization solution in step 2 without adding a template, and the rest of the operation was the same as that of example 1.
The pore size distribution of the non-imprinted composite material is shown in figure 3, and the calculated average pore size is 3.9041 nm;
the pore structure of the non-imprinted composite material is derived from poly (MAA-EGDMA) generated in the polymerization process, the pore diameter is mostly distributed below 5nm, the size is small, and the non-imprinted composite material is a non-specific pore structure. The imprinted composite material comprises a specific site which is formed on an imprinting layer after a template is removed and can identify 5 chlorophenols besides a part of poly (MAA-EGDMA) pore structure; the 5 chlorophenols have different molecular structures, so that the formed pores have different sizes; the average pore diameter obtained by calculation is larger than that of the non-imprinted composite material, so that the imprinted composite material can further contain specific recognition sites of 5 chlorophenols.
Example 3 preparation of a Multi-template molecularly imprinted-Nylon Membrane
Cutting a nylon film with a pore diameter of 0.45 mu m into strips of 4cm multiplied by 2cm (length multiplied by width), folding the strips in half, and then sealing the opening parts at the two sides by a sealing machine; weighing the multi-template molecularly imprinted composite material prepared in example 1, adding the multi-template molecularly imprinted composite material from an opening at the upper end, and then thermally sealing the opening to prepare the multi-template molecularly imprinted-nylon membrane.
The schematic diagram of the manufacturing process of the multi-template molecularly imprinted-nylon membrane package is shown in figure 4.
Example 4 application of a Multi-template molecularly imprinted-Nylon Membrane
Adding 50mL of sample solution into a beaker, magnetically stirring at 500rpm, soaking the multi-template molecular imprinting-nylon membrane prepared in the embodiment 3 with methanol, adsorbing excessive solvent by using dust-free paper, putting the membrane into the sample solution, adsorbing for 60min, taking out the nylon membrane with a pair of tweezers, and recycling the membrane; the adsorbed sample solution was filtered through a 0.45 μm syringe filter and analyzed by HPLC.
The schematic diagram of the application process of the multi-template molecularly imprinted-nylon membrane is shown in figure 5.
Example 5 adsorption experiment of a Multi-template molecularly imprinted-Nylon Membrane on a 2-chlorophenol, 4-chlorophenol, 2, 4-dichlorophenol, 2, 6-dichlorophenol and 2,4, 6-trichlorophenol mixed solution
5mg, 10mg, 20mg, 30mg and 40mg of the multi-template molecularly imprinted composite material prepared in example 1 were weighed, and a nylon membrane was prepared by the method of example 3. The membrane package was placed in 40mL of a mixed solution containing 5mg/L of 2-chlorophenol, 5mg/L of 4-chlorophenol, 5mg/L of 2, 4-dichlorophenol, 5mg/L of 2, 6-dichlorophenol and 5mg/L of 2,4, 6-trichlorophenol, respectively, magnetically stirred at 500rpm, adsorbed for 180min, and then the membrane package was taken out with tweezers. The solution after adsorption was filtered through a 0.45 μm syringe filter and analyzed by HPLC.
The adsorption efficiency (%) was calculated from the ratio of the difference in the concentration of each substance in the solution before and after adsorption to the initial concentration. The adsorption efficiency of the nylon membrane packages made of different amounts of the multi-template molecularly imprinted composite material on each substance is shown in the attached figure 6.
As can be seen from the attached FIG. 6, the nylon membrane packed with 40mg of the multi-template molecularly imprinted composite material has the highest adsorption efficiency of 81.4%, 88.0%, 99.6%, 96.0% and 99.3% for 2-chlorophenol, 4-chlorophenol, 2, 4-dichlorophenol, 2, 6-dichlorophenol and 2,4, 6-trichlorophenol.
Unless otherwise stated, the percentages used in the present invention are percentages by weight, and the proportions described in the present invention are proportions by mass.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a multi-template molecularly imprinted composite material is characterized by comprising the following steps: the preparation method comprises the following steps: preparing a silanization modified multi-walled carbon nanotube composite material and a multi-template molecularly imprinted composite material;
the preparation of the silanization modified multi-walled carbon nanotube composite material comprises the steps of uniformly mixing materials, feeding and post-processing;
the preparation of the multi-template molecularly imprinted composite material comprises the steps of preparing a prepolymerization solution, mixing materials and eluting.
2. The method for preparing the multi-template molecularly imprinted composite material according to claim 1, wherein the method comprises the following steps:
uniformly mixing the materials, dissolving cetyl trimethyl ammonium bromide, ethanol and water, adding the carboxylated multi-walled carbon nanotube, ultrasonically dispersing uniformly, and stirring uniformly;
the mass volume ratio of the hexadecyl trimethyl ammonium bromide to the ethanol is 3.6-3.9 mg: 1 ml;
the volume ratio of the ethanol to the water is as follows: 1.2-1.4: 1;
the mass ratio of the hexadecyl trimethyl ammonium bromide to the carboxylated multi-walled carbon nano-tube is as follows: 3.6-3.9: 1;
the carboxylated multi-walled carbon nanotube: the outer diameter is 20-30 nm, and the length is 10-30 μm.
3. The method for preparing the multi-template molecularly imprinted composite material according to claim 1, wherein the method comprises the following steps:
adding ammonia water, stirring, adding tetraethyl orthosilicate, and stirring for reaction;
the volume ratio of the ammonia water to the ethanol is 0.1: 5.2-5.4;
the concentration of the ammonia water is 25% -28%;
the volume ratio of tetraethyl orthosilicate to ammonia water is 1: 1.3-1.7.
4. The method for preparing the multi-template molecularly imprinted composite material according to claim 1, wherein the method comprises the following steps:
after the post-treatment, after the reaction is finished, centrifuging the mixed solution, cleaning the residual solvent, dispersing, heating and refluxing to remove hexadecyl trimethyl ammonium bromide, centrifuging again, and drying to obtain the silanized modified multi-walled carbon nanotube composite material;
and dispersing the centrifuged precipitate into acetone.
5. The method for preparing the multi-template molecularly imprinted composite material according to claim 1, wherein the method comprises the following steps:
the preparation method comprises the steps of preparing a prepolymerization solution, mixing 2-chlorophenol, 4-chlorophenol, 2, 4-dichlorophenol, 2, 6-dichlorophenol and 2,4, 6-trichlorophenol, adding acetonitrile, adding methacrylic acid, and standing for reaction to obtain a prepolymerization solution;
the molar ratio of the 2-chlorophenol to the 4-chlorophenol to the 2, 4-dichlorophenol to the 2, 6-dichlorophenol to the 2,4, 6-trichlorophenol is as follows: 1:1:1:1: 1;
the ratio of the 2-chlorophenol to the acetonitrile is 0.1 mmol: 18-22 ml;
the molar ratio of the 2-chlorophenol to the methacrylic acid is 0.1: 3.8-4.2.
6. The method for preparing the multi-template molecularly imprinted composite material according to claim 1, wherein the method comprises the following steps:
the preparation method comprises the following steps of mixing materials, namely ultrasonically dispersing a silanization modified multi-wall carbon nanotube composite material and acetonitrile uniformly, adding a prepolymerization solution, ethylene glycol dimethacrylate and azobisisobutyronitrile, introducing nitrogen into the solution, sealing, placing in a constant-temperature water bath, and stirring for reaction;
the mass volume ratio of the silanization modified multi-walled carbon nanotube composite material to acetonitrile is 1.15-1.35 mg: 1 ml;
the volume ratio of the acetonitrile to the prepolymerization solution is 3.5-4.5: 1;
the mass ratio of the silanization modified multi-walled carbon nanotube composite material to the azodiisobutyronitrile is 3-3.5: 1.
7. The method for preparing the multi-template molecularly imprinted composite material according to claim 1, wherein the method comprises the following steps:
after the elution and reaction are finished, centrifugally collecting materials, respectively carrying out shaking elution for 2 times by using methanol, carrying out shaking elution for 4 times by using methanol/acetic acid, carrying out shaking elution for 2 times by using methanol, removing a template, and drying to obtain the multi-template molecularly imprinted composite material;
the methanol is 75-85 mL/time;
the volume ratio of methanol to acetic acid is 8-10: 1;
and drying at 38-42 ℃ for 10 h.
8. The application of the multi-template molecularly imprinted composite material is characterized in that:
the application comprises the preparation of a multi-template molecularly imprinted-nylon membrane package and the application of the membrane package.
9. The use of a multi-template molecularly imprinted composite material according to claim 8, wherein:
preparing a multi-template molecularly imprinted-nylon membrane package: cutting, folding and heat-sealing the porous nylon membrane to prepare a membrane package with an opening at one end, filling a multi-template molecular imprinting composite material from the opening end, and heat-sealing to prepare the multi-template molecular imprinting-nylon membrane package;
adding a sample solution into the nylon membrane for application, magnetically stirring, soaking the multi-template molecularly imprinted-nylon membrane with methanol, adsorbing excess solvent with dust-free paper, putting the membrane into the sample solution, and taking out the nylon membrane after adsorption; the membrane package can be recycled, and the adsorbed sample solution is filtered by a needle filter and then subjected to HPLC analysis;
the pore diameter of the nylon membrane is 0.22-1 μm.
10. The use of a multi-template molecularly imprinted composite material according to claim 8, wherein:
the nylon membrane of the composite material has high adsorption efficiency on 2-chlorophenol, 4-chlorophenol, 2, 4-dichlorophenol, 2, 6-dichlorophenol and 2,4, 6-trichlorophenol, and the adsorption efficiency is 81.4%, 88.0%, 99.6%, 96.0% and 99.3% respectively.
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