CN112126013B - Bis (p-nitrophenol) phosphate imprinted polymer and preparation method thereof - Google Patents
Bis (p-nitrophenol) phosphate imprinted polymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a bis (p-nitrophenol) phosphate imprinted polymer and a preparation method thereof, wherein the raw materials comprise: bis (p-nitrophenol) phosphate, a functional monomer, a cross-linking agent and an initiator; the preparation method comprises the steps of self-assembling a functional monomer and bis (p-nitrophenol) phosphate, synthesizing an imprinted polymer by a precipitation polymerization method under an anaerobic condition, performing Soxhlet extraction and elution, and drying a blank imprinted polymer to obtain the product; the imprinted polymer synthesized by the preparation method has remarkable selective recognition performance on the bis (p-nitrophenol) phosphate molecules, the recovery rate is higher than 95%, adsorption balance can be achieved within 10min, the recovery rate is still higher than 90% after five times of repeated cyclic utilization, detection cost is effectively reduced, operation and use are simple, and the imprinted polymer has good practical application value; the imprinted polymer is simple in preparation method and has good market application and popularization prospects.
Description
Technical Field
The invention relates to the technical field of detection material preparation, and particularly relates to a bis (p-nitrophenol) phosphate imprinted polymer and a preparation method thereof.
Background
Nerve agents and blister agents are two main types of virulent chemical warfare agents, nerve agents including G-type nerve agents (sarin, soman and tabun) and V-type nerve agents (such as VX), are virulent organophosphate compounds, are mainly used for causing ground and object toxicities through liquid, and once oxygen is contacted, the toxic toxicants are changed into gas which can be transmitted through air or water sources and can be hardly detected, and the poisoning can be caused by the contact or inhalation of human skin, so that central nervous system disorder and respiratory arrest are caused, and finally death is caused. Since nerve agents irreversibly inhibit acetylcholinesterase in nerve synapses to interfere with nerve pulse transmission, which in severe cases leads to paralysis of respiratory muscles and death, the development of effective adsorption and detection materials for nerve agents is imminent.
The research and the use process of neurotoxicity chemical agents are limited due to the defects of virulent nature, easy leakage, strong accumulated toxicity and the like, so that the selection of the simulants of the chemical warfare agents is very important. The chemical structural formula of the VX toxin agent nerve agent is shown in figure 1(a), and the chemical structural formula of the bis (p-nitrophenol) phosphate is shown in figure 1 (b); the bis (p-nitrophenol) phosphate molecule is an excellent chemical warfare agent simulant because the bis (p-nitrophenol) phosphate molecule has an acetylcholinesterase inhibiting group, is the same as a chemical warfare agent in recognition site and toxicity mechanism, and has stable chemical properties.
Currently, there are many methods available for detecting and adsorbing compounds, such as liquid extraction, high performance liquid chromatography, solid phase extraction, gas chromatography, and mass spectrometry. These methods, while highly accurate and relatively efficient, suffer from the disadvantages of being expensive, time consuming, and complex instrumentation and operation. The molecular imprinting technology can realize high-efficiency adsorption by designing specific recognition sites, and the elution and reabsorption processes are easy to realize, so that the method has the advantages of high sensitivity, good specificity, convenience in operation, easiness in signal detection, good reusability and the like, and is very suitable for being used as an analysis and detection method for the bis (p-nitrophenol) phosphate.
Specifically, the molecular imprinting technique is a method for preparing a polymer having a specific recognition ability for a specific molecule, and the polymer having a specific recognition ability is called a molecularly imprinted polymer (hereinafter abbreviated as MIPs). MIPs have attracted extensive attention and applications in various fields such as chiral separation, antibody simulation, chemical sensors, targeted drug delivery, wastewater treatment and the like, due to their advantages of high recognition performance, low cost, high physical and chemical stability, customizable application recognition sites and the like.
Disclosure of Invention
The invention aims to provide a bis (p-nitrophenol) phosphate imprinted polymer which has stable adsorption performance, high recovery rate and good reusability.
The invention also aims to provide a preparation method of the bis (p-nitrophenol) phosphate imprinted polymer.
Therefore, the technical scheme of the invention is as follows:
a bis (p-nitrophenol) phosphate imprinted polymer is prepared from the following raw materials: bis (p-nitrophenol) phosphate, a functional monomer, a cross-linking agent and an initiator; wherein the functional monomer is at least one of acidic functional monomer, alkaline functional monomer and neutral functional monomer; the acidic functional monomer is at least one of acrylic acid and methacrylic acid; the basic functional monomer is at least one of 2-vinylpyridine and 4-vinylpyridine; the neutral functional monomer is at least one of zinc methacrylate, methyl methacrylate and 4-methacrylamidoantipyrine; the molar ratio of the bis (p-nitrophenol) phosphate to the functional monomer is 1: 3-5; the molar ratio of the bis (p-nitrophenol) phosphate to the cross-linking agent is 1: 15-25; the molar ratio of the bis (p-nitrophenol) phosphate to the initiator is 1: 3-6.
Preferably, the crosslinking agent is ethylene glycol dimethacrylate (EDMA), trimethylolpropane Trimethacrylate (TRIM), or N, N-Methylenebisacrylamide (MBA).
Preferably, the initiator is azobisisobutyronitrile, azobisisoheptonitrile, or dibenzoyl peroxide.
The preparation method of the bis (p-nitrophenol) phosphate imprinted polymer comprises the following steps:
s1, dissolving the bis (p-nitrophenol) phosphate and the functional monomer in an anhydrous organic solvent, and stirring under a closed condition to carry out self-assembly between the functional monomer and the bis (p-nitrophenol) phosphate;
s2, adding a cross-linking agent and an initiator into the S1, stirring until the cross-linking agent and the initiator are dissolved, introducing nitrogen for 10-40 min, heating to 50-70 ℃, thermally initiating polymerization for 18-30 h, and synthesizing a bis (p-nitrophenol) phosphate imprinted polymer solid by a precipitation polymerization method;
s3, performing Soxhlet extraction and elution on the bis (p-nitrophenol) phosphate imprinted polymer, and removing the mixed bis (p-nitrophenol) phosphate to obtain a blank imprinted polymer;
s4, drying the obtained blank imprinted polymer for later use.
Preferably, in step S1, the organic solvent is dimethyl sulfoxide, N-dimethylformamide or acetonitrile; the amount of the organic solvent added is 200 times the weight of the bis (p-nitrophenol) phosphate.
Preferably, in step S3, the specific steps of soxhlet elution are: firstly, washing the imprinted polymer for at least 3 times by using clear water, and then eluting the bis (p-nitrophenol) phosphate in the imprinted polymer by using an eluent at 80 ℃ by using a Soxhlet extractor for 48 hours; wherein the eluent is prepared by mixing acetic acid and methanol in a volume ratio of 1: 4-9.
More preferably, the eluent is prepared by mixing acetic acid and methanol in a weight ratio of 1: 9.
Preferably, in step S4, the drying treatment may specifically be air drying, vacuum drying or freeze drying.
The bis (p-nitrophenol) phosphate ester imprinted polymer takes a bis (p-nitrophenol) phosphate ester with special phosphate ester groups, low toxicity and high stability as a template, and a cross-linked network molecule with a porous structure, namely the bis (p-nitrophenol) phosphate ester imprinted polymer, is prepared through cross-linking polymerization. The imprinted polymer can be applied to adsorption and detection of nerve toxicants.
Compared with the prior art, the bis (p-nitrophenol) phosphate imprinted polymer has remarkable selective recognition performance on bis (p-nitrophenol) phosphate molecules, the recovery rate is higher than 95%, adsorption balance can be achieved within 10 minutes, the recovery rate is still higher than 90% after five times of repeated cyclic utilization, detection cost is effectively reduced, operation and use are simple, and the bis (p-nitrophenol) phosphate imprinted polymer has good practical application value; in addition, the preparation method of the bis (p-nitrophenol) phosphate imprinted polymer is simple, and has good market application and popularization prospects.
Drawings
Fig. 1(a) is a schematic chemical structure of a VX toxin agent nerve agent;
FIG. 1(b) is a schematic diagram of the chemical structure of bis (p-nitrophenol) phosphate;
FIG. 2(a) is a scanning electron micrograph of a bis (p-nitrophenol) phosphate imprinted polymer prepared in example 10 of the present invention;
FIG. 2(b) is a scanning electron micrograph of a bis (p-nitrophenol) phosphate imprinted polymer prepared in example 12 of the present invention;
FIG. 3 is a line graph showing the absorbance of bis (p-nitrophenol) phosphate in the supernatant of the dynamic adsorption process of the bis (p-nitrophenol) phosphate imprinted polymer prepared in example 10 according to the present invention as a function of time;
FIG. 4 is a bar graph of the recovery of 5 recycles of the bis (p-nitrophenol) phosphate imprinted polymer prepared in example 10 of the present invention.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, which are not intended to limit the invention in any way.
Example 1
A bis (p-nitrophenol) phosphate imprinted polymer is prepared by the following steps:
s1, adding 0.17g of bis (p-nitrophenol) phosphate, 0.142g of acrylamide and 35mL of dimethyl sulfoxide into a 100mL three-neck flask, magnetically stirring until the materials are dissolved, and stirring for 2 hours under a closed condition to carry out self-assembly between the functional monomer and the bis (p-nitrophenol) phosphate;
s2, adding 1.98g of cross-linking agent ethylene glycol dimethacrylate and 0.4g of initiator azodiisobutyronitrile into a three-neck flask, stirring to dissolve, introducing nitrogen for 20min to exhaust air, stopping magnetic stirring, heating a reaction system in an oil bath constant temperature reactor to 60 ℃ to thermally initiate polymerization for 24h, and synthesizing the bis (p-nitrophenol) phosphate imprinted polymer solid through a precipitation polymerization method;
s3, mechanically crushing the molecularly imprinted polymer solid, washing the obtained granular molecularly imprinted polymer with deionized water for three times, and then eluting the bis (p-nitrophenol) phosphate in the molecularly imprinted polymer by using a Soxhlet extractor at 80 ℃ for 48 hours by using a mixed solution prepared from acetic acid and methanol in a volume ratio of 1:9 as an eluent to obtain a blank molecularly imprinted polymer;
s4, the obtained blank imprinted polymer is subjected to freeze drying treatment for 12h for standby.
Example 2
A bis (p-nitrophenol) phosphate imprinted polymer is prepared by the following steps:
s1, adding 0.17g of bis (p-nitrophenol) phosphate, 0.107g of acrylamide and 35mL of dimethyl sulfoxide into a 100mL three-neck flask, magnetically stirring until the mixture is dissolved, and stirring for 2 hours under a sealed condition to carry out self-assembly between the functional monomer and the bis (p-nitrophenol) phosphate;
s2, adding 1.485g of cross-linking agent ethylene glycol dimethacrylate and 0.3g of initiator azodiisobutyronitrile into a three-neck flask, stirring and dissolving, introducing nitrogen for 20min to exhaust air, stopping magnetic stirring, heating a reaction system in an oil bath constant-temperature reactor to 60 ℃ to thermally initiate polymerization for 24h, and synthesizing a bis (p-nitrophenol) phosphate imprinted polymer solid through a precipitation polymerization method;
s3, mechanically crushing the molecularly imprinted polymer solid, washing the obtained granular molecularly imprinted polymer with deionized water for three times, and then eluting the bis (p-nitrophenol) phosphate in the molecularly imprinted polymer by using a Soxhlet extractor at 80 ℃ for 48 hours by using a mixed solution prepared from acetic acid and methanol in a volume ratio of 1:9 as an eluent to obtain a blank molecularly imprinted polymer;
s4, the obtained blank imprinted polymer is subjected to freeze drying treatment for 12h for standby.
Example 3
A bis (p-nitrophenol) phosphate imprinted polymer is prepared by the following steps:
s1, adding 0.17g of bis (p-nitrophenol) phosphate, 0.178g of acrylamide and 35mL of dimethyl sulfoxide into a 100mL three-neck flask, magnetically stirring until the mixture is dissolved, and stirring for 2 hours under a closed condition to carry out self-assembly between the functional monomer and the bis (p-nitrophenol) phosphate;
s2, adding 2.475g of cross-linking agent ethylene glycol dimethacrylate and 0.5g of initiator azodiisobutyronitrile into a three-neck flask, stirring and dissolving, introducing nitrogen for 20min, stopping magnetic stirring, heating a reaction system in an oil bath constant temperature reactor to 60 ℃ to thermally initiate polymerization for 24h, and synthesizing bis (p-nitrophenol) phosphate imprinted polymer solid through a precipitation polymerization method;
s3, mechanically crushing the molecularly imprinted polymer solid, washing the obtained granular molecularly imprinted polymer with deionized water for three times, and then eluting the bis (p-nitrophenol) phosphate in the molecularly imprinted polymer by using a Soxhlet extractor at 80 ℃ for 48 hours by using a mixed solution prepared from acetic acid and methanol in a volume ratio of 1:9 as an eluent to obtain a blank molecularly imprinted polymer;
s4, the obtained blank imprinted polymer is subjected to freeze drying treatment for 12h for standby.
Example 4
A bis (p-nitrophenol) phosphate imprinted polymer is prepared by the following steps:
s1, adding 0.17g of bis (p-nitrophenol) phosphate, 0.172g of acrylamide and 35mL of acetonitrile into a 100mL three-neck flask, magnetically stirring until the mixture is dissolved, and stirring for 2 hours under a closed condition to carry out self-assembly between the functional monomer and the bis (p-nitrophenol) phosphate;
s2, adding 3.384g of cross-linking agent trimethylolpropane trimethyl methyl acrylate and 0.4g of initiator azodiisobutyronitrile into a three-neck flask, stirring and dissolving, introducing nitrogen for 20min, stopping magnetic stirring, heating a reaction system in an oil bath constant-temperature reactor to 50 ℃ to thermally initiate polymerization for 18h, and synthesizing a bis (p-nitrophenol) phosphate imprinted polymer solid through a precipitation polymerization method;
s3, mechanically crushing the molecularly imprinted polymer solid, washing the obtained granular molecularly imprinted polymer with deionized water for three times, and then eluting the bis (p-nitrophenol) phosphate in the molecularly imprinted polymer by using a Soxhlet extractor at 80 ℃ for 48 hours by using a mixed solution prepared from acetic acid and methanol in a volume ratio of 1:9 as an eluent to obtain a blank molecularly imprinted polymer;
s4, the obtained blank imprinted polymer is subjected to freeze drying treatment for 12h for standby.
Example 5
A bis (p-nitrophenol) phosphate imprinted polymer is prepared by the following steps:
s1, adding 0.17g of bis (p-nitrophenol) phosphate, 0.144g of acrylamide and 35mL of acetonitrile into a 100mL three-neck flask, magnetically stirring until the mixture is dissolved, and stirring for 2 hours under a closed condition to carry out self-assembly between the functional monomer and the bis (p-nitrophenol) phosphate;
s2, adding 3.384g of cross-linking agent trimethylolpropane trimethyl methyl acrylate and 0.4g of initiator azobisisobutyronitrile into the three-neck flask, stirring and dissolving, introducing nitrogen for 20min, stopping magnetic stirring, heating the reaction system in an oil bath constant temperature reactor to 50 ℃ to thermally initiate polymerization for 18 h;
s3, mechanically crushing the molecularly imprinted polymer solid, washing the obtained granular molecularly imprinted polymer with deionized water for three times, and then eluting the bis (p-nitrophenol) phosphate in the molecularly imprinted polymer by using a Soxhlet extractor at 80 ℃ for 48 hours by using a mixed solution prepared from acetic acid and methanol in a volume ratio of 1:9 as an eluent to obtain a blank molecularly imprinted polymer;
s4, the obtained blank imprinted polymer is subjected to freeze drying treatment for 12h for standby.
Example 6
A bis (p-nitrophenol) phosphate imprinted polymer is prepared by the following steps:
s1, adding 0.17g of bis (p-nitrophenol) phosphate, 0.471g of zinc methacrylate and 35mL of acetonitrile into a 100mL three-neck flask, magnetically stirring until the materials are dissolved, and stirring for 2 hours under a closed condition to carry out self-assembly between the functional monomer and the bis (p-nitrophenol) phosphate;
s2, adding 3.384g of cross-linking agent trimethylolpropane trimethyl methyl acrylate and 0.4g of initiator azobisisobutyronitrile into the three-neck flask, stirring and dissolving, introducing nitrogen for 30min, stopping magnetic stirring, heating the reaction system in an oil bath constant temperature reactor to 50 ℃ to thermally initiate polymerization for 18 h;
s3, mechanically crushing the molecularly imprinted polymer solid, washing the obtained granular molecularly imprinted polymer with deionized water for three times, and then eluting the bis (p-nitrophenol) phosphate in the molecularly imprinted polymer by using a Soxhlet extractor at 80 ℃ for 48 hours by using a mixed solution prepared from acetic acid and methanol in a volume ratio of 1:9 as an eluent to obtain a blank molecularly imprinted polymer;
s4, the obtained blank imprinted polymer is subjected to freeze drying treatment for 12h for standby.
Example 7
A bis (p-nitrophenol) phosphate imprinted polymer is prepared by the following steps:
s1, adding 0.17g of bis (p-nitrophenol) phosphate, 0.2g of methyl methacrylate and 35mL of N, N-dimethylformamide into a 100mL three-neck flask, magnetically stirring until the methyl methacrylate, the methyl methacrylate and the N, N-dimethylformamide are dissolved, and stirring for 2 hours under a closed condition to carry out self-assembly between the functional monomer and the bis (p-nitrophenol) phosphate;
s2, adding 1.54g of cross-linking agent N, N-methylene bisacrylamide and 0.4g of initiator azobisisobutyronitrile into the three-neck flask, stirring and dissolving, introducing nitrogen for 20min, heating to 70 ℃ to thermally initiate polymerization for 30h, and synthesizing a bis (p-nitrophenol) phosphate imprinted polymer solid by a precipitation polymerization method;
s3, mechanically crushing the molecularly imprinted polymer solid, washing the obtained granular molecularly imprinted polymer with deionized water for three times, and then eluting the bis (p-nitrophenol) phosphate in the molecularly imprinted polymer by using a Soxhlet extractor at 80 ℃ for 48 hours by using a mixed solution prepared from acetic acid and methanol in a volume ratio of 1:9 as an eluent to obtain a blank molecularly imprinted polymer;
s4, the obtained blank imprinted polymer is subjected to freeze drying treatment for 12h for standby.
Example 8
A bis (p-nitrophenol) phosphate imprinted polymer is prepared by the following steps:
s1, adding 0.17g of bis (p-nitrophenol) phosphate, 0.542g of 4-methacrylamide antipyrine and 35mLN, N-dimethylformamide into a 100mL three-neck flask, magnetically stirring until the mixture is dissolved, and stirring for 2 hours under a closed condition to carry out self-assembly between the functional monomer and the bis (p-nitrophenol) phosphate;
s2, adding 1.54g of cross-linking agent N, N-methylene bisacrylamide and 0.4g of initiator azobisisobutyronitrile into a three-neck flask, stirring to dissolve, introducing nitrogen for 20min, heating to 70 ℃ to thermally initiate polymerization for 30h, and synthesizing bis (p-nitrophenol) phosphate imprinted polymer solid by a precipitation polymerization method;
s3, mechanically crushing the molecularly imprinted polymer solid, washing the obtained granular molecularly imprinted polymer with deionized water for three times, and then eluting the bis (p-nitrophenol) phosphate in the molecularly imprinted polymer by using a Soxhlet extractor at 80 ℃ for 48 hours by using a mixed solution prepared from acetic acid and methanol in a volume ratio of 1:9 as an eluent to obtain a blank molecularly imprinted polymer;
s4, the obtained blank imprinted polymer is subjected to freeze drying treatment for 12h for standby.
Example 9
A bis (p-nitrophenol) phosphate imprinted polymer is prepared by the following steps:
s1, adding 0.17g of bis (p-nitrophenol) phosphate, 0.1355g of 4-methylacrylamidoantipyrine, 0.142g of acrylamide and 35mL of dimethyl sulfoxide into a 100mL three-neck flask, magnetically stirring until the materials are completely dissolved, and stirring for 2 hours under a closed condition to carry out self-assembly between the functional monomer and the bis (p-nitrophenol) phosphate;
s2, adding 1.98g of cross-linking agent ethylene glycol dimethacrylate and 0.4g of initiator azodiisobutyronitrile into a three-neck flask, stirring and dissolving, introducing nitrogen for 20min, heating to 60 ℃ to thermally initiate polymerization for 24h, and synthesizing a bis (p-nitrophenol) phosphate ester imprinted polymer solid by a precipitation polymerization method;
s3, mechanically crushing the molecularly imprinted polymer solid, washing the obtained granular molecularly imprinted polymer with deionized water for three times, and then eluting the bis (p-nitrophenol) phosphate in the molecularly imprinted polymer by using a Soxhlet extractor at 80 ℃ for 48 hours by using a mixed solution prepared from acetic acid and methanol in a volume ratio of 1:9 as an eluent to obtain a blank molecularly imprinted polymer;
s4, the obtained blank imprinted polymer is subjected to freeze drying treatment for 12h for standby.
Example 10
A bis (p-nitrophenol) phosphate imprinted polymer is prepared by the following steps:
s1, adding 0.17g of bis (p-nitrophenol) phosphate, 0.1355g of 4-methacrylamidoantipyrine, 0.172g of methacrylic acid and 35mL of dimethyl sulfoxide into a 100mL three-neck flask, magnetically stirring until the mixture is dissolved, and stirring for 2 hours under a closed condition to carry out self-assembly between the functional monomer and the bis (p-nitrophenol) phosphate;
s2, adding 1.98g of cross-linking agent ethylene glycol dimethacrylate and 0.4g of initiator azodiisobutyronitrile into a three-neck flask, stirring and dissolving, introducing nitrogen for 20min, heating to 60 ℃ to thermally initiate polymerization for 24h, and synthesizing a bis (p-nitrophenol) phosphate ester imprinted polymer solid by a precipitation polymerization method;
s3, mechanically crushing the molecularly imprinted polymer solid, washing the obtained granular molecularly imprinted polymer with deionized water for three times, and then eluting the bis (p-nitrophenol) phosphate in the molecularly imprinted polymer by using a Soxhlet extractor at 80 ℃ for 48 hours by using a mixed solution prepared from acetic acid and methanol in a volume ratio of 1:9 as an eluent to obtain a blank molecularly imprinted polymer;
s4, the obtained blank imprinted polymer is subjected to freeze drying treatment for 12h for standby.
Example 11
A bis (p-nitrophenol) phosphate imprinted polymer is prepared by the following steps:
s1, adding 0.17g of bis (p-nitrophenol) phosphate, 0.1355g of 4-methylacrylamidoantipyrine, 0.471g of zinc methacrylate and 35mL of dimethyl sulfoxide into a 100mL three-neck flask, magnetically stirring until the mixture is dissolved, and stirring for 2 hours under a closed condition to carry out self-assembly between the functional monomer and the bis (p-nitrophenol) phosphate;
s2, adding 1.98g of cross-linking agent ethylene glycol dimethacrylate and 0.4g of initiator azodiisoheptanonitrile into a three-neck flask, stirring and dissolving, introducing nitrogen for 20min, heating to 60 ℃ to thermally initiate polymerization for 24h, and synthesizing a bis (p-nitrophenol) phosphate imprinted polymer solid by a precipitation polymerization method;
s3, mechanically crushing the molecularly imprinted polymer solid, washing the obtained granular molecularly imprinted polymer with deionized water for three times, and then eluting the bis (p-nitrophenol) phosphate in the molecularly imprinted polymer by using a Soxhlet extractor at 80 ℃ for 48 hours by using a mixed solution prepared from acetic acid and methanol in a volume ratio of 1:9 as an eluent to obtain a blank molecularly imprinted polymer;
s4, the obtained blank imprinted polymer is subjected to freeze drying treatment for 12h for standby.
Example 12
A bis (p-nitrophenol) phosphate imprinted polymer is prepared by the following steps:
s1, adding 0.17g of bis (p-nitrophenol) phosphate, 0.1355g of 4-methylacrylamidoantipyrine, 0.2g of methyl methacrylate and 35mL of dimethyl sulfoxide into a 100mL three-neck flask, magnetically stirring until the mixture is dissolved, and stirring for 2 hours under a closed condition to perform self-assembly between the functional monomer and the bis (p-nitrophenol) phosphate;
s2, adding 1.98g of cross-linking agent ethylene glycol dimethacrylate and 0.4g of initiator dibenzoyl peroxide into a three-neck flask, stirring and dissolving, introducing nitrogen for 20min, heating to 60 ℃ to thermally initiate polymerization for 24h, and synthesizing a bis (p-nitrophenol) phosphate imprinted polymer solid by a precipitation polymerization method;
s3, mechanically crushing the molecularly imprinted polymer solid, washing the obtained granular molecularly imprinted polymer with deionized water for three times, and then eluting the bis (p-nitrophenol) phosphate in the molecularly imprinted polymer by using a Soxhlet extractor at 80 ℃ for 48 hours by using a mixed solution prepared from acetic acid and methanol in a volume ratio of 1:9 as an eluent to obtain a blank molecularly imprinted polymer;
s4, the obtained blank imprinted polymer is subjected to freeze drying treatment for 12h for standby.
And (3) performance testing:
the adsorption capacity detection of the blank bis (p-nitrophenol) phosphate imprinted polymer prepared in the example 1-12 is carried out, and the recovery rate of the imprinted polymer to the bis (p-nitrophenol) phosphate is calculated according to the adsorption amount of the imprinted polymer obtained by detection.
The specific detection method comprises the following steps: weighing 0.04g of the bis (p-nitrophenol) phosphate imprinted polymer prepared in each example, adding the bis (p-nitrophenol) phosphate-acetonitrile standard solution to 8mL0.2mmol/L, placing the solution on a shaking bed to shake and adsorb for 12 hours, centrifuging and taking out the supernatant after adsorption, measuring the absorbance of the standard solution after adsorption by an ultraviolet spectrophotometer, and calculating the residual concentration to obtain the recovery rate of the bis (p-nitrophenol) phosphate imprinted polymer to the bis (p-nitrophenol) phosphate. The calculation results are shown in table 1 below.
Table 1:
the calculation results in table 1 show that the bis (p-nitrophenol) phosphate imprinted polymer prepared by the method has high-efficiency adsorption capacity, and the recovery rate of the bis (p-nitrophenol) phosphate can reach 73.1-96.3%; among them, the recovery rate of the bis (p-nitrophenol) phosphate imprinted polymer prepared in example 10 was the best.
FIG. 2(a) is a scanning electron micrograph of a bis (p-nitrophenol) phosphate imprinted polymer prepared in example 10; FIG. 2(b) shows the SEM image of the imprinted polymer of bis (p-nitrophenol) phosphate prepared in example 12. As can be seen from the detection results shown in fig. 2(a) and 2 (b): the prepared bis (p-nitrophenol) phosphate imprinted polymer has specific holes, so that the bis (p-nitrophenol) phosphate is preferentially selectively adsorbed in a water body containing the bis (p-nitrophenol) phosphate, and the bis (p-nitrophenol) phosphate in a polluted water body is effectively removed.
The imprinted polymer prepared in example 10 was further subjected to dynamic equilibrium time detection by the following specific detection method: 0.4g of imprinted polymer was added to 80mL of 0.2mmol/L bis (p-nitrophenol) phosphate-acetonitrile standard solution, and the supernatant was collected once every minute, and the absorbance of the standard solution after adsorption was measured by an ultraviolet spectrophotometer.
The test results are shown in the following tables 2-1, 2-2 and FIG. 3.
Table 2-1:
tables 2 to 2:
| adsorption time | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 |
| Absorbance value | 0.53 | 0.33 | 0.13 | 0.12 | 0.12 | 0.12 | 0.12 | 0.12 |
As can be seen from the test results of the above tables 2-1 and 2-2, and FIG. 3, the adsorption efficiency of the bis (p-nitrophenol) phosphate ester imprinted polymer is high, and the adsorption equilibrium can be reached within about 10 minutes.
FIG. 3 is a line graph plotting absorbance of bis (p-nitrophenol) phosphate in supernatant of a dynamic adsorption process versus time for the imprinted polymer of bis (p-nitrophenol) phosphate prepared in example 10 based on the test results of Table 2-1 and Table 2-2;
further carrying out repeated adsorption detection on the imprinted polymer prepared in the example 10, wherein the specific detection method comprises the steps of adding 0.04g of the imprinted polymer into 8mL of 0.2mmol/L of bis (p-nitrophenol) phosphate-acetonitrile standard solution, and measuring the absorbance of the adsorbed standard solution by an ultraviolet spectrophotometer after adsorption is achieved; after the adsorbed imprinted polymer was eluted as described above, the adsorption detection was repeated five times.
The calculation results are shown in table 3 below and fig. 4.
Table 3:
| number of times of |
1 | 2 | 3 | 4 | 5 |
| Percent recovery% | 96.3 | 94.1 | 91.4 | 93.5 | 92.7 |
From the test results in table 3, it can be seen that the recovery rate of the bis (p-nitrophenol) phosphate imprinted polymer can still reach more than 90% after the bis (p-nitrophenol) phosphate imprinted polymer is recycled for 5 times, and the bis (p-nitrophenol) phosphate imprinted polymer has good stability and recycling value. As shown in fig. 4, a bar graph of the recovery rate of 5 reuses of the bis (p-nitrophenol) phosphate imprinted polymer prepared in example 10, which is plotted based on the test results of table 3.
In conclusion, the bis (p-nitrophenol) phosphate imprinted polymer has the advantages of high recovery rate, quick absorption capacity and good reusability.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. 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 (6)
1. The bis (p-nitrophenol) phosphate imprinted polymer is characterized by being prepared from the following raw materials: bis (p-nitrophenol) phosphate, a functional monomer, a cross-linking agent and an initiator; wherein, the first and the second end of the pipe are connected with each other,
the functional monomers are 4-methacrylamidoantipyrine and methacrylic acid;
the molar ratio of the bis (p-nitrophenol) phosphate to the functional monomer is 1: 3-5;
the molar ratio of the bis (p-nitrophenol) phosphate to the cross-linking agent is 1: 15-25;
the molar ratio of the bis (p-nitrophenol) phosphate to the initiator is 1: 3-6.
2. The bis (p-nitrophenol) phosphate imprinted polymer of claim 1, wherein the cross-linking agent is ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, or N, N-methylenebisacrylamide.
3. The bis (p-nitrophenol) phosphate imprinted polymer of claim 1, wherein the initiator is azobisisobutyronitrile, azobisisoheptonitrile, or dibenzoyl peroxide.
4. A method for preparing a bis (p-nitrophenol) phosphate imprinted polymer according to any of claims 1 to 3, characterized in that the steps are as follows:
s1, dissolving the bis (p-nitrophenol) phosphate and the functional monomer in an anhydrous organic solvent, and stirring under a closed condition to carry out self-assembly between the functional monomer and the bis (p-nitrophenol) phosphate;
s2, adding a cross-linking agent and an initiator into the step S1, stirring until the cross-linking agent and the initiator are dissolved, introducing nitrogen for 10-40 min, heating to 50-70 ℃, carrying out thermal initiation polymerization for 18-30 h, and synthesizing a bis (p-nitrophenol) phosphate imprinted polymer solid by a precipitation polymerization method;
s3, performing Soxhlet extraction and elution on the bis (p-nitrophenol) phosphate imprinted polymer, and removing the bis (p-nitrophenol) phosphate to obtain a blank imprinted polymer;
s4, drying the obtained blank imprinted polymer for later use.
5. The method for preparing a bis (p-nitrophenol) phosphate imprinted polymer according to claim 4, wherein in the step S1, the organic solvent is dimethyl sulfoxide, N-dimethylformamide or acetonitrile; the addition amount of the organic solvent is 160-230 times of the weight of the bis (p-nitrophenol) phosphate.
6. The method for preparing a bis (p-nitrophenol) phosphate imprinted polymer according to claim 4, wherein in step S3, the specific steps of Soxhlet extraction elution are as follows: firstly, washing the imprinted polymer for at least 3 times by using clear water, and then eluting the bis (p-nitrophenol) phosphate in the imprinted polymer by using an eluent at 80 ℃ by using a Soxhlet extractor for 48 hours; wherein the eluent is prepared by mixing acetic acid and methanol in a volume ratio of 1: 4-9.
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