CN103232572B - Molecular imprinting polymer for roxarsone detection, and preparation method thereof - Google Patents

Abstract

The invention belongs to the technical field of material chemistry, and discloses a molecular imprinting polymer for roxarsone detection, and a preparation method thereof. The molecular imprinting polymer preparation method comprises the following steps: carrying out polymerization of a template, a pore forming agent, a functional monomer, a cross-linking agent and an initiator for 8-48 h at a temperature of 50-80 DEG C, and removing the template to obtain the molecular imprinting polymer for roxarsone detection. According to the present invention, a roxarsone recovery rate of the prepared molecular imprinting polymer is more than 90%, and the prepared molecular imprinting polymer shows a high roxarsone cross reaction, has high selectivity and high specificity, and provides broad application prospects in the field of application of the prepared molecular imprinting polymer as a sample purification pretreatment material for roxarsone analysis in feeds, animal tissues, environment water and other matrixes.

Description

Molecularly imprinted polymer for detecting roxarsone and preparation method thereof

technical field

The invention belongs to the technical field of material chemistry, and in particular relates to a molecularly imprinted polymer for detecting roxarsone and a preparation method thereof.

Background technique

Roxarsone (Roxarsone), chemical name: 3-nitro-4-hydroxy-phenylarsine acid, and arsanilic acid (P-Arsanilic acid) are two arsenic-containing feed additives that have been widely used in countries around the world for many years , and roxarsone is more widely used than arsanic acid. Roxarsone is the most economical multifunctional organic arsine preparation, which can promote the growth of livestock and poultry, improve the feed conversion rate, promote the deposition of livestock pigment, and increase the effect of other anticoccidial drugs on poultry; it can treat dysentery and enteritis of pigs, Increase the laying rate of laying hens. The Ministry of Agriculture of my country approved the use of the drug in 1996, and then domestic production gradually began, and it was widely used in chicken and pig farming. However, later studies found that it was easy to cause environmental pollution. In 1999, the European Union banned the use of roxarsone as a medicine for chicken feed. Considering the safety of animal food, my country's Ministry of Agriculture Announcement No. 235 also formulated the maximum residue limit of roxar arsenic. The drug has certain residual toxicity and potential carcinogenicity to humans, so its detection has rapidly become a research hotspot at home and abroad. However, all current pretreatment methods for roxarsone detection are purified by traditional solid-phase extraction cartridges (such as MAX), which lack selectivity and specificity, thus affecting the sensitivity and accurate quantification of the entire detection method.

Molecularly imprinted solid-phase extraction technology based on the similar antigen-antibody interaction has high selectivity and specificity, and is a kind of solid-phase extraction material with broad application prospects. If some antibody-like polymer adsorption materials with high selectivity to roxarsone can be synthesized like antibodies, the sensitivity and accuracy of roxarsone detection can be greatly improved.

Molecular imprinting (molecular imprinting) is a new research field that has developed rapidly based on molecular recognition theory in recent years. Molecular imprinting technology is also known as the technology for manufacturing "plastic antibodies". Molecular imprinting polymers (molecular imprinting polymers, MIP) are a class of cross-linked polymers with holes of fixed size and shape inside and functional groups with definite arrangement. Because MIP is customized according to imprinted molecules, it has a special molecular structure and functional groups, which can selectively recognize imprinted molecules.

The preparation of molecularly imprinted polymers generally goes through the following three steps:

(1) Functional monomers gather around template molecules to form reversible complexes by interacting with template molecules (covalent or non-covalent bonds);

(2) Copolymerization of functional monomers and excess cross-linking agent in the presence of porogens to form high polymers;

(3) The template molecule is dissociated from the polymer, and a binding site capable of recognizing the template molecule is formed in the polymer.

This imprinted polymer can be used as a stationary phase of liquid chromatography, a selective catalyst, a sensing element of a chemical sensor, and a solid-phase extraction material, and is also widely used in clinical drug analysis.

Contents of the invention

In order to overcome the deficiencies of the prior art, the primary purpose of the present invention is to provide a method for preparing molecularly imprinted polymers for detecting roxarsone. The preparation method has low cost and simple operation.

Another object of the present invention is to provide a molecularly imprinted polymer for detecting roxarsone prepared by the above preparation method. The molecularly imprinted polymer has high selectivity and affinity for roxarsone, and the recovery rate for roxarsone is over 90%.

The purpose of the present invention is achieved through the following technical solutions:

A method for preparing a molecularly imprinted polymer for detecting roxarsone, comprising the following steps: polymerizing a template, a porogen, a functional monomer, a cross-linking agent and an initiator at 50-80°C for 8-48 hours, removing After the template, the molecularly imprinted polymer used to detect roxarsone is obtained;

The template is arsanic acid or ethyl p-hydroxybenzoate.

The ratio of the template, functional monomer, crosslinking agent, porogen and initiator is 1:2～16:10～40:1～200:10～60, and the ratio is mmol:mmol:mmol :mL:mg.

The functional monomer is 2-vinylpyridine, methacrylic acid, acrylic acid, 4-vinylpyridine, p-vinylbenzoic acid or acrylamide.

The cross-linking agent is ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or divinylbenzene;

The porogen is more than one of methanol, acetonitrile, chloroform, and acetone; the preferred porogen is pure acetonitrile or a mixture of methanol and acetonitrile with a volume ratio of 1:1. On the one hand, the porogen must ensure the full dissolution of the template. On the other hand, the amount of the porogen has an important impact on the strength and surface properties of the prepared molecularly imprinted polymer. The recognition of roxarsone is also very critical. When methanol-acetonitrile (1:1, V/V) is selected as the porogen, molecularly imprinted polymers with highly specific recognition for roxarsone can be prepared.

The initiator is a water-soluble initiator or an oil-soluble initiator; the oil-soluble initiator is azobisisobutyronitrile; and the water-soluble initiator is ammonium persulfate.

A method for preparing a molecularly imprinted polymer for detecting roxarsine, the preferred specific steps are:

(1) Preparation of prepolymer: add porogen to the template, vortex until the template dissolves, add functional monomer, sonicate, stand still to obtain prepolymer;

(2) Polymerization and solidification: add crosslinking agent and initiator to the prepolymer, ultrasonicate, nitrogen gas under ice bath, seal, and polymerize in a vacuum drying oven to obtain block polymer;

(3) Preparation of molecularly imprinted polymers for detection of roxarsone: the bulk polymer is processed into fine particles, washed with solvent A to remove the template, washed with solvent B, and dried in vacuum to obtain the molecularly imprinted polymer for the detection of roxarsone Molecularly imprinted polymers.

The ultrasonic time described in step (1) is 5 minutes; the standing time is 1 hour;

The ultrasonic time in the step (2) is 5 minutes; the nitrogen gas flow time in the ice bath is 5 minutes; the polymerization temperature in the vacuum drying oven is 50-80° C., and the time is 8-48 hours.

The solvent A described in step (3) is a mixed solution of acetic acid and methanol, the volume ratio of acetic acid and methanol in the mixed solution is 1:9; the flow rate of the solvent A washing is below 1mL/min; the solvent A B is methanol with a volume of 40 mL; the vacuum drying temperature is 60° C. and the time is 12 hours.

The molecularly imprinted polymer for detecting roxarsone prepared according to the above-mentioned preparation method, the recovery rate of the molecularly imprinted polymer for roxarsine is over 90%.

The molecularly imprinted polymer of the present invention has been tested and found that: the polymer is used for solid phase extraction purification (50 mg/column), and the adsorption capacity of the polymer bound to roxarsone is about 930 μg/g polymer; in aqueous solution (tap water) , underground and surface water), the recovery rate test of roxarsone added showed that the recovery rate of roxarsone was greater than 90% within the concentration range of 1.0 to 50 μg/mL; the solid-phase extraction cartridge packed with molecularly imprinted polymer , after repeated use 10 times, the recovery rate of roxarsone is still greater than 80%.

Compared with the prior art, the present invention has the following advantages and effects:

(1) When the molecularly imprinted polymer is prepared in the present invention, the porogen used is methanol-acetonitrile (1:1, V/V), which is beneficial to the dissolution of the template and makes the prepared imprinted polymer have a strong specific recognition ability.

(2) The preparation method of the present invention can directly add a crosslinking agent and an initiator to the prepolymer and then carry out thermal polymerization curing at 50-80°C, or perform low-temperature photopolymerization first and then carry out thermal polymerization curing at 50-80°C. This can further improve the specificity of molecularly imprinted polymers.

(3) The molecularly imprinted polymer of the present invention exhibits high affinity and selectivity for roxarsone in methanol and acetonitrile, and the recovery rate is greater than 90%.

(4) The MIP prepared by using ethyl p-hydroxybenzoate or arsanic acid as a template in the present invention shows high cross-reactivity to roxarsone, and has high selectivity and specificity. Compared with MIP, it can prevent the incomplete elution of roxarsone from affecting the detection results of roxarsone due to "template leakage" (residual roxarsone template) in MIP during use. Roxarsone sample purification pretreatment materials in environmental water and other matrices have broad application prospects.

Description of drawings

Figure 1: Chromatograms (10 μg/mL) of Roxarsone acetonitrile solution passing through MIP1 and NIP1 solid-phase extraction columns;

Among them, a: chromatogram of roxarsone acetonitrile solution passed through MIP1 solid phase extraction; b: chromatogram of roxarsone acetonitrile solution passed through NIP1 solid phase extraction.

Figure 2: Chromatograms (10 μg/mL) of Roxarsone acetonitrile solution passing through MIP2 and NIP2 solid phase extraction columns;

Wherein, c: roxarsone acetonitrile solution crosses the chromatogram of MIP2 solid-phase extraction; d: roxarsone acetonitrile solution crosses the chromatogram of NIP2 solid-phase extraction.

Figure 3: Chromatogram (5 μg/mL) of roxarsone tap water solution passing through MIP1 and NIP1 solid-phase extraction columns;

Wherein, e: the chromatogram of the roxarsone tap water solution passing through the MIP1 solid phase extraction column; f: the chromatogram of the roxarsone tap water solution passing through the NIP1 solid phase extraction column.

Figure 4: Chromatograms of Roxarsone surface water solution passing through MIP2 and NIP2 solid-phase extraction columns; (0.5 μg/mL);

Among them, g: the chromatogram of the surface water solution of roxarsone passing through the MIP1 solid phase extraction column; h: the chromatogram of the surface water solution of roxarsone passing through the NIP1 solid phase extraction column.

Figure 5: Chromatograms of roxarsone groundwater solution passing through MIP2 and NIP2 solid-phase extraction columns; (50 μg/mL);

Among them, i: the chromatogram of the roxarsone underground water solution passing through the MIP2 solid phase extraction column; j: the chromatogram of the roxarsone underground water solution passing through the NIP2 solid phase extraction column.

Figure 6: Standard curve of the chromatogram of Roxarsone.

Figure 7: Adsorption isotherms of Roxarsone at 25°C.

Detailed ways

The present invention will be further described in detail below in conjunction with the embodiments and the accompanying drawings, but the embodiments of the present invention are not limited thereto.

Example 1

(1) Weigh 0.166g (1mmoL) of ethyl p-hydroxybenzoate into a test tube, add 1mL of acetonitrile, vortex to dissolve, then add 0.434mL (4mmoL) of 2-vinylpyridine functional monomer, sonicate for 5min, and let stand for 1h , forming a prepolymer.

(2) Add 4mL (20mmoL) of ethylene glycol dimethacrylate and 60mg (0.365mmol) of azobisisobutyronitrile to the above prepolymer, sonicate for 5min, pass nitrogen gas for 5min under ice bath, seal, and vacuum at 60°C Polymerized in a dry box for 24 hours to obtain block polymer.

(3) Grind the above-mentioned massive polymer, pass through a 200-mesh sieve, and repeatedly settle with methanol to remove fine particles, put it into a 15mL solid-phase extraction column, and first use a mixed solution of acetic acid and methanol (the volume ratio of acetic acid and methanol is 1 : 9) Wash with 200mL to remove the template ethyl p-hydroxybenzoate, control the flow rate below 1mL/min, wash with 40mL of methanol to remove acetic acid, and dry in a vacuum oven at 60°C for 12 hours to obtain the molecule for detection of roxarsone Imprint the polymer and store in a desiccator for future use. The prepared molecularly imprinted polymer (MIP1) for the detection of roxarsone has an average yield of 64.5% compared with the synthesized bulk polymer.

Preparation of non-imprinted polymer (NIP1) was prepared and processed as above except that template molecules were not added.

Example 2

(1) Weigh 0.217g (1mmoL) of arsanic acid into a test tube, add 6mL of methanol-acetonitrile solution (the volume ratio of methanol to acetonitrile is 1:1), vortex to dissolve, then add 0.434mL (4mmoL) of 2-ethylene Pyridine functional monomer, ultrasonic 5min, stand for 1h to form a pre-polymer.

(2) Add 4mL (20mmoL) of ethylene glycol dimethacrylate and 60mg (0.365mmol) of azobisisobutyronitrile to the above prepolymer, sonicate for 5min, pass nitrogen gas for 5min under ice bath, seal, and vacuum at 60°C Polymerized in a dry box for 24 hours to obtain block polymer.

(3) Grind the above-mentioned massive polymer, pass through a 200-mesh sieve, and repeatedly settle with methanol to remove fine particles, put it into a 15mL solid-phase extraction column, and first use a mixed solution of acetic acid and methanol (the volume ratio of acetic acid and methanol is 1 : 9) Wash with 200mL to remove the template arsanic acid, control the flow rate below 1mL/min, wash with 40mL of methanol to remove acetic acid, and dry in a vacuum oven at 60°C for 12 hours to obtain a molecularly imprinted polymer for the detection of roxarsone , stored in a desiccator for later use. Compared with the synthesized bulk polymer, the molecularly imprinted polymer (MIP2) prepared for the detection of roxarsone had an average yield of 58.2%.

The preparation of the non-imprinted polymer (NIP2) was prepared and processed as described above except that template molecules were not added.

Example 3

(1) Weigh 0.217g (1mmoL) of arsanic acid into a test tube, add 6mL of methanol-acetonitrile (1:1, V/V) solution, vortex to dissolve, then add 0.171mL (2mmoL) of methacrylic acid functional monomer , sonicated for 5 minutes, and allowed to stand for 1 hour to form a prepolymer.

(2) Add 3.19mL (10mmoL) of trimethylolpropane trimethacrylate and 10mg (0.06mmoL) of azobisisobutyronitrile to the above prepolymer, sonicate for 5min, blow nitrogen gas for 5min under ice bath, seal, Polymerize in a vacuum oven at 50°C for 48 hours to obtain block polymer.

(3) Grind the blocky polymer above, pass through a 200-mesh sieve, and repeatedly settle with methanol to remove fine particles, put it into a 15 mL solid-phase extraction column, and first use a mixed solution of acetic acid and methanol (1:9, V/V ) 200mL to remove the template arsanic acid, the flow rate was controlled below 1mL/min, then washed with 40mL methanol to remove acetic acid, and dried in a vacuum oven at 60°C for 12h to obtain a molecularly imprinted polymer for the detection of roxarsone, which was then dried Save it in the storage device for later use. Compared with the synthesized bulk polymer, the molecularly imprinted polymer prepared for detection of roxarsone had an average yield of 52.6%.

Example 4

(1) Weigh 0.166g (1mmoL) of ethyl p-hydroxybenzoate into a test tube, add 10.5mL of acetonitrile, vortex to dissolve, then add 1.82mL (16mmoL) of p-vinylbenzoic acid functional monomer, sonicate for 5min, and let stand 1h, a prepolymer is formed.

(2) Add 5.60mL (40mmoL) of divinylbenzene and 60mg (0.365mmoL) of azobisisobutyronitrile to the above-mentioned prepolymer, sonicate for 5min, flow nitrogen gas under ice bath for 5min, seal, and polymerize in a vacuum oven at 50°C After 48h, blocky polymer was obtained.

(3) Grind the above-mentioned massive polymer, pass through a 200-mesh sieve, and repeatedly settle with methanol to remove fine particles, put it into a 15mL solid-phase extraction column, and first use a mixed solution of acetic acid and methanol (the volume ratio of acetic acid and methanol is 1 : 9) Wash with 200mL to remove the template ethyl p-hydroxybenzoate, control the flow rate below 1mL/min, wash with 40mL of methanol to remove acetic acid, and dry in a vacuum oven at 80°C for 8h to obtain the molecular imprint for detection of roxarsone Polymers are stored in a desiccator for later use. Compared with the synthesized bulk polymer, the molecularly imprinted polymer prepared for detection of roxarsone had an average yield of 48.3%.

Example 5

(1) Weigh 0.217 g (1 mmoL) of arsanic acid into a test tube, add 9.3 mL of methanol-acetonitrile (1:1, V/V) solution, vortex to dissolve, then add 1.42 mL (16 mmoL) of methacrylic acid Functional monomer, ultrasonic 5 min, stand still for 1 h to form a pre-polymer.

(2) Add 12.8 mL (40 mmoL) of trimethylolpropane trimethacrylate and 60 mg (0.365 mmoL) of azobisisobutyronitrile to the above prepolymer, ultrasonicate for 5 min, and pass nitrogen gas for 5 min under ice bath, Sealed and polymerized in a vacuum oven at 50°C for 48 h to obtain block polymer.

(3) Grind the above-mentioned massive polymer, pass through a 200-mesh sieve, and repeatedly settle with methanol to remove fine particles, put it into a 15 mL solid-phase extraction column, and first use a mixed solution of acetic acid and methanol (1:9, V/V ) was washed with 200 mL to remove the template arsanic acid, the flow rate was controlled below 1 mL/min, and then washed with 40 mL of methanol to remove acetic acid, and dried in a vacuum oven at 60 °C for 12 h to obtain the molecularly imprinted polymer for the detection of roxarsone stored in a desiccator for later use. The prepared molecularly imprinted polymer for the detection of roxarsone has an average yield of 46.7% compared with the synthesized bulk polymer

Example 6

(1) Weigh 0.166g (1 mmoL) of ethyl p-hydroxybenzoate into a test tube, add 3mL of acetonitrile, vortex to dissolve, then add 0.23 mL (2mmoL) of p-vinylbenzoic acid functional monomer, sonicate for 5 min, statically Set for 1 h to form a prepolymer.

(2) Add 1.4 mL (10 mmoL) of divinylbenzene and 10 mg (0.06 mmoL) of azobisisobutyronitrile to the above prepolymer, sonicate for 5 min, and pass nitrogen gas for 5 min under ice bath, seal it, and put it in a vacuum oven at 50 °C Polymerized in medium for 48 h to obtain block polymer.

(3) Grind the above-mentioned massive polymer, pass through a 200-mesh sieve, and repeatedly settle with methanol to remove fine particles, put it into a 15 mL solid-phase extraction column, and first use a mixed solution of acetic acid and methanol (the volume ratio of acetic acid and methanol is 1:9) Wash with 200 mL to remove the template ethyl p-hydroxybenzoate, control the flow rate below 1 mL/min, wash with 40 mL of methanol to remove acetic acid, and dry in a vacuum oven at 80°C for 8 h to obtain The molecularly imprinted polymer of sarsine is stored in a desiccator for future use. Compared with the synthesized bulk polymer, the molecularly imprinted polymer prepared for detection of roxarsone had an average yield of 54.2%.

Example 7

The molecularly imprinted polymers MIP1 and MIP2 (particle size: 54-75 μm) prepared in Examples 1 and 2 for the detection of roxarsone were loaded into a 1 mL solid-phase extraction empty cartridge (50 mg/column), and sequentially washed with 2 mL of methanol, Equilibrium activation with 2 mL of deionized water.

Take 1 mL of roxarsone acetonitrile solution with serial concentrations of 0.5, 5, 20 and 50 μg/mL to pass through the column, wash with 2 mL of water and 2 mL of methanol successively, press dry, and then use a mixture of ammonia water and methanol (the volume ratio of ammonia water to methanol 5:95) 2mL elution. Dry the eluate with nitrogen gas, dissolve it with 50mmoL/L potassium dihydrogen phosphate solution, centrifuge, and detect it with high performance liquid chromatography (UV).

The operation steps of passing the roxarsone acetonitrile solution through the NIP1 and NIP2 solid-phase extraction columns are the same as above.

The specific calculation process of recovery rate:

Qualitative according to retention time, quantitative by external standard method, measure the response value of standard solution of roxarsone with serial concentrations (0.5, 5, 20, 50 μg/mL), and obtain the area A _s of the chromatographic peak integration, according to the obtained peak area and concentration C _s , make a standard curve as shown in Figure 6, then measure the peak area A _i of the samples respectively, bring it into the standard curve to calculate, the recovery rate R(%)=100×C _i /C _s .

Example 8

The molecularly imprinted polymer (with a particle size of 54-75 μm) prepared in Example 1 for the detection of roxarsone was loaded into a 1 mL solid-phase extraction empty cartridge (50 mg/column), and activated with 2 mL of methanol and 2 mL of water in sequence.

Take 1 mL of roxarsone tap water solution with serial concentrations of 0.5, 5, 20 and 50 μg/mL to pass through the column, wash with 2 mL of water and 2 mL of methanol successively, press dry, and then use 5% ammonia water and methanol mixture (the volume of ammonia water and methanol The ratio is 5:95) 2mL elution. Dry the eluate with nitrogen gas, dissolve it with 50mmoL/L potassium dihydrogen phosphate solution, centrifuge, and detect it with high performance liquid chromatography (UV).

The operation steps for passing the roxarsone tap water solution through the NIP1 solid-phase extraction column are the same as above.

Groundwater and surface water implementation plan except that the roxarsone tap water solution is replaced by surface water and groundwater, the rest of the steps are exactly the same.

Fig. 3 is the chromatogram (5μg/mL) that roxarsone tap water passes through MIP1 and NIP1 solid-phase extraction column; Fig. 4 is the chromatogram of roxarsone surface aqueous solution passing through MIP2 and NIP2 solid-phase extraction column; Fig. 5 is roxarsone The chromatograms of arsine groundwater solution passing through MIP2 and NIP2 solid phase extraction columns. Table 1 shows the recoveries of MIP and NIP to different concentrations of roxarsone in three water matrices. The assay method of recovery is the same as in Example 7.

Table 1 Recovery rate of different concentrations of roxarsone in three kinds of water matrix (n=3)

The results in Table 1 show that the recoveries of Roxarsone water, tap water, surface water and underground aqueous solution of series concentrations are all greater than 90% on the prepared MIP1 and MIP2 solid-phase extraction columns, and the recovery rates on the NIP solid-phase extraction columns are all less than 40%. %.

Example 9

In this study, the static adsorption method was used to investigate the adsorption isotherms of ROX-MIPs. Accurately weigh 18 portions of 20.0 mg MIP, add them to a 25 mL Erlenmeyer flask, and then add 2 mL series concentrations of roxarsone in acetonitrile (1, 2, 5, 10, 20, 50, 100, 200, 300.0 μg/mL). Place in the dark at room temperature for 24 hours, centrifuge at 15000 rpm, pass through a needle filter, and determine the unadsorbed free roxarsone in the supernatant by HPLC. According to the change of roxarsone concentration in the solution before and after adsorption, use the formula Q=(C ₀ -C)V ₀ /m to calculate the adsorption amount of MIPs to roxarsone, measure 3 times in parallel, take the arithmetic mean value, and use roxarsone Concentration (C) is the abscissa, polymer equilibrium adsorption capacity (Q) is the ordinate, and the adsorption isotherm is drawn. where C is the original concentration (μg/mL), C is the equilibrium concentration (μg/mL), m is the mass of the imprinted polymer ( _g ), _V is the volume of the adsorption solution (mL), and Q is the adsorbent per gram Micrograms of roxarsone adsorbed (μg/g). The adsorption test of NIP1 is the same as above except that the polymers weighed are different. The adsorption isotherm diagram of roxarsine is shown in Figure 7. The results showed that the maximum adsorption capacity of MIP1 combined with roxarsine was 930 μg/g polymer, and that of NIP1 was below 470 μg/g polymer.

The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.

Claims (9)

1. one kind for detecting the preparation method of the molecularly imprinted polymer of roxarsone, it is characterized in that: comprise the following steps: by template, pore-creating agent, function monomer, linking agent and initiator at 50 ~ 80 DEG C of polymerization 8 ~ 48 h, after removing template, obtain the molecularly imprinted polymer for detecting roxarsone;

Described template is Pro-gen 90 or ethyl p-hydroxybenzoate;

The ratio of described template, function monomer, linking agent, pore-creating agent and initiator is 1: 2 ~ 16: 10 ~ 40: 1 ~ 200: 10 ~ 60, and described ratio is mmol: mmol: mmol: mL: mg.

2. preparation method according to claim 1, is characterized in that: described function monomer be 2-vinyl pyridine, methacrylic acid, vinylformic acid, 4-vinylpridine, to vinylbenzoic acid or acrylamide.

3. preparation method according to claim 1, is characterized in that: described linking agent is ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or divinylbenzene.

4. preparation method according to claim 1, is characterized in that: described pore-creating agent is more than one in methyl alcohol, acetonitrile, chloroform, acetone; Described initiator is water soluble starter or oil-soluble initiator.

5. preparation method according to claim 4, is characterized in that: described pore-creating agent is acetonitrile; Described oil-soluble initiator is Diisopropyl azodicarboxylate; Described water soluble starter is ammonium persulphate.

6. preparation method according to claim 4, is characterized in that: described pore-creating agent is volume ratio is the methyl alcohol of 1:1 and the mixed solution of acetonitrile.

7. preparation method according to claim 1, is characterized in that: comprise the following steps:

(1) preparation of prepolymer: add pore-creating agent in template, vortex dissolves to template, adds function monomer, ultrasonic, leaves standstill, obtains prepolymer;

(2) polymerizing curable: add linking agent and initiator in prepolymer, ultrasonic, logical nitrogen under ice bath, sealing, is polymerized in vacuum drying oven, obtains bulk polymer;

(3) for detecting the preparation of the molecularly imprinted polymer of roxarsone: bulk polymer is treated to fine particle, template is gone in solvent orange 2 A washing, and after solvent B washs, vacuum-drying, obtains the molecularly imprinted polymer for detecting roxarsone.

8. preparation method according to claim 7, is characterized in that: the ultrasonic time described in step (1) is 5min; Time of repose is 1h;

Ultrasonic time described in step (2) is 5min; It is 5min that described ice bath leads to the nitrogen time; The temperature of being polymerized in described vacuum drying oven is 50 ~ 80 DEG C, and the time is 8 ~ 48h;

Solvent orange 2 A described in step (3) is the mixing solutions of acetic acid and methyl alcohol, and in mixing solutions, the volume ratio of acetic acid and methyl alcohol is 1:9; The flow velocity of described solvent orange 2 A washing is 1 below mL/min; Described solvent B is methyl alcohol, and volume is 40mL; Described vacuum drying temperature is 60 DEG C, and the time is 12h.

9. the molecularly imprinted polymer for detecting roxarsone that the preparation method according to any one of claim 1 ~ 8 prepares, is characterized in that: this molecularly imprinted polymer is more than 90% to the rate of recovery of roxarsone.