阅读说明：本技术 一种三唑醇分子印迹聚合物微球的制备方法 (Preparation method of triadimenol molecularly imprinted polymer microspheres ) 是由 李国栋 顾丽莉 李增良 景联鹏 唐徐禹 于 2021-10-28 设计创作，主要内容包括：本发明提供了一种三唑醇分子印迹聚合物微球的制备方法,该方法是将三唑醇与功能单体溶于溶剂中,超声混合均匀后,在无氧条件下进行预聚合；预聚合完成后,向其中添加交联剂和引发剂进行加热诱导聚合；本发明采用沉淀聚合的聚合方式,得到分子印迹聚合物；分子印迹聚合物经过碾磨、洗脱、干燥后得到三唑醇分子印迹聚合物微球；本发明制备的三唑醇分子印迹聚合物微球分布均匀,对目标物质三唑醇的吸附效果良好。(The invention provides a preparation method of triadimenol molecularly imprinted polymer microspheres, which is characterized in that triadimenol and functional monomers are dissolved in a solvent, uniformly mixed by ultrasonic waves and then prepolymerized under an anaerobic condition; after the pre-polymerization is finished, adding a cross-linking agent and an initiator into the mixture for heating to induce polymerization; the invention adopts a precipitation polymerization mode to obtain the molecularly imprinted polymer; grinding, eluting and drying the molecularly imprinted polymer to obtain the triadimenol molecularly imprinted polymer microspheres; the prepared triadimenol molecularly imprinted polymer microspheres are uniformly distributed, and have a good adsorption effect on a target substance triadimenol.)

1. A preparation method of a triadimenol molecularly imprinted polymer microsphere is characterized by comprising the following steps:

(1) putting triadimenol and functional monomer into solvent, mixing uniformly by ultrasound, introducing N₂ Placing the mixture in a constant-temperature gas bath oscillator for prepolymerization for 10-20 min to obtain a prepolymerization solution;

(2) adding a cross-linking agent and an initiator into the prepolymerization solution in the step (1), and introducing N₂ After 10-20 min, placing the mixture in a constant-temperature air bath oscillator at 35-65 ℃ for thermal polymerization for 12-24 h, centrifuging, and drying the solid to obtain a polymer;

(3) and (3) grinding, eluting and drying the polymer obtained in the step (2) to obtain the triadimenol molecularly imprinted polymer microspheres.

2. The method for preparing the triadimenol molecularly imprinted polymer microspheres according to claim 1, characterized in that: the solvent in the step (1) is methanol, acetonitrile, dichloromethane, toluene or chloroform.

3. The method for preparing the triadimenol molecularly imprinted polymer microspheres according to claim 1, characterized in that: in the step (1), the prepolymerization temperature is 15-45 ℃, and the prepolymerization time is 5-12 h.

4. The method for preparing the triadimenol molecularly imprinted polymer microspheres according to claim 1, characterized in that: the functional monomer in the step (1) is alpha-methacrylic acid, acrylic acid, trifluoromethyl acrylic acid or acrylamide; wherein the molar ratio of the functional monomer to the triadimenol is 1-8: 1.

5. The method for preparing the triadimenol molecularly imprinted polymer microspheres according to claim 1, characterized in that: in the step (2), the cross-linking agent is epichlorohydrin, ethylene glycol dimethacrylate or divinylbenzene.

6. The method for preparing the triadimenol molecularly imprinted polymer microspheres according to claim 5, characterized in that: in the step (2), the initiator is benzoyl peroxide, azobisisobutyronitrile or azobisdimethylisovaleronitrile; the molar ratio of the cross-linking agent to the initiator is 5-30: 1, and the molar ratio of the initiator to the triadimenol is 1-5: 1.

7. The method for preparing the triadimenol molecularly imprinted polymer microspheres according to claim 1, characterized in that: the elution solvent in the step (3) is a mixed solvent prepared by mixing methanol and acetic acid according to the volume ratio of 7-9: 1.

8. The method for preparing the triadimenol molecularly imprinted polymer microspheres according to claim 1, characterized in that: in the step (2) and the step (3), the drying temperature is 30-45 ℃.

Technical Field

The invention belongs to the field of molecularly imprinted polymers, and particularly relates to a preparation process of a triadimenol molecularly imprinted polymer microsphere.

Background

Triadimenol, also known as hydroxyrust, tritylone, 1- (4-chlorophenoxy) -3, 3-dimethyl-1- (1H-1,2,4 triazol-l-yl) -2-butanol; the triazole fungicide is a systemic triazole fungicide and is widely applied to the prevention and treatment of smut, leaf spot and rust disease of rice, corn and wheat crops in recent years; the triadimenol has a triaza ring structure, has stable physicochemical properties, is not easy to automatically degrade in natural environment, can exist in the environment for a long time, and can cause adverse effects on the life safety of human beings and animals.

The molecular imprinting technology is used as a special antigen-antibody artificial synthesis technology, can selectively identify target substances, and achieves the purposes of enrichment and purification. Compared with biological recognition, the molecular imprinting technology can select prepared raw materials and preparation conditions according to actual requirements, and prepare the durable molecular imprinting material which meets the actual requirements and is used for adsorbing target substances. At present, a bulk polymerization method is mostly adopted for the triadimenol molecularly imprinted polymer, the molecularly imprinted polymer is mostly in an irregular shape, and imprinted cavities are few.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a preparation method of a triadimenol molecularly imprinted polymer microsphere.

The preparation method of the triadimenol molecularly imprinted polymer microsphere comprises the following steps:

(1) putting template molecule triadimenol and functional monomer into solvent, mixing uniformly by ultrasonic wave, introducing N into the mixture₂ 10-20 min, and then placing the mixture in a constant-temperature gas bath oscillator at 15-45 ℃ for prepolymerization for 5-12 h to obtain a prepolymerization solution;

the solvent is methanol, acetonitrile, toluene, dichloromethane or chloroform; the functional monomer is alpha-methacrylic acid, acrylic acid, trifluoromethyl acrylic acid or acrylamide; wherein the molar ratio of the functional monomer to the triadimenol is 1-8: 1;

(2) adding a cross-linking agent and an initiator into the prepolymerization solution obtained in the step (1), and introducing N₂ After 10-20 min, placing the mixture in a constant-temperature air bath oscillator at 35-65 ℃ for thermal polymerization for 12-24 h, centrifuging, and drying the solid to obtain a polymer;

the crosslinking agent is epichlorohydrin, ethylene glycol dimethacrylate or divinylbenzene; the initiator is benzoyl peroxide, azobisisobutyronitrile or azobisdimethylisovaleronitrile; the molar ratio of the cross-linking agent to the initiator is 5-30: 1, and the molar ratio of the initiator to the triadimenol is 1-5: 1; the drying temperature is 30-45 ℃;

(3) and (3) grinding, eluting and drying the polymer obtained in the step (2) to obtain the triadimenol molecularly imprinted polymer microspheres.

The elution solvent is a mixed solvent prepared by mixing methanol and acetic acid according to the volume ratio of 7-9: 1, and the drying temperature is 30-45 ℃.

The invention adopts a thermal-initiated precipitation polymerization method to obtain the triadimenol molecularly imprinted polymer microspheres through the processes of prepolymerization and thermal polymerization. The molecularly imprinted polymer microspheres prepared by the method have uniform particle size distribution and obvious appearance, and the average particle size of the polymer is 78-116 nm. The invention has simple preparation, low cost and stable effect.

Drawings

FIG. 1 is a scanning electron microscope image of a triadimenol molecularly imprinted polymer;

FIG. 2 is an infrared spectrum of a triadimenol molecularly imprinted polymer;

FIG. 3 is an infrared spectrum of a blank molecularly imprinted polymer;

FIG. 4 is a liquid chromatogram for determining the content of triadimenol in the supernatant after adsorption of the MIPs material.

Detailed Description

In order to make the advantages and objects of the invention more clear, the invention is further explained in conjunction with practical embodiments. The scope of the present invention is not limited to the examples described below.

Example 1:

(1) dissolving triadimenol and alpha-methacrylic acid in methanol according to the molar ratio of 1:2 of triadimenol to alpha-methacrylic acid, ultrasonically mixing uniformly, introducing N into the mixture₂ 15min, then placing the mixture in a constant-temperature gas bath oscillator at 30 ℃ for prepolymerization reaction for 12h to obtain a prepolymerization solution;

(2) adding a crosslinking agent ethylene glycol dimethacrylate and an initiator azodimethylisovaleronitrile into the prepolymerization solution obtained in the step (1) according to the molar ratio of the crosslinking agent to the initiator of 8:1, and introducing N₂ After 15min, placing in a constant-temperature gas bath oscillator at 55 ℃ for thermal polymerization for 24h, centrifuging, and drying the solid at 35 ℃ to obtain a polymer; wherein the molar ratio of the azodimethylisovaleronitrile to the triadimenol is 1: 1; meanwhile, setting a blank control, namely adding no triadimenol, and carrying out other preparation conditions;

(3) grinding the polymer obtained in the step (2), eluting triadimenol with a methanol-acetic acid mixed solution, and drying at 40 ℃ to obtain triadimenol molecularly imprinted polymer Microspheres (MIPs) and blank molecularly imprinted polymers (NIPs); the shape of the MIPs is shown in figure 1, and it can be seen that the polymer prepared in the embodiment is spherical and relatively uniformly distributed; the infrared spectra of MIPs and NIPs are shown in FIG. 2 and FIG. 3, and it is seen that the difference of peaks is clearly shown near 666.7nm, which indicates that the triadimenol is polymerized on the polymer.

Respectively weighing 30mg of the prepared MIPs and NIPs, placing the weighed MIPs and NIPs into a 20mL glass bottle, adding 6mL of 10mg/L triazole alcohol solution, performing an adsorption test at 25 ℃, taking supernatant in the glass bottle after adsorption is completed, filtering by using a filter membrane, detecting by using liquid chromatography-tandem mass spectrometry, wherein a chromatogram of the supernatant after MIPs material is adsorbed is shown in FIG. 4, data for calculating the adsorption effect is shown in Table 1, and the imprinting factor of the MIPs is known to be 2.21 from Table 1;

table 1: adsorption effects of MIPs and NIPs

。

Example 2

(1) Dissolving triadimenol and functional monomer alpha-methacrylic acid in acetonitrile according to the molar ratio of 1:4 of triadimenol to alpha-methacrylic acid, ultrasonically mixing uniformly, and introducing N into the mixture₂ Placing for 19min, and performing prepolymerization in a constant-temperature gas bath oscillator at 25 deg.C for 10h to obtain prepolymerization solution;

(2) adding a crosslinking agent ethylene glycol dimethacrylate and an initiator azobisisobutyronitrile into the prepolymerization solution obtained in the step (1) according to the molar ratio of the crosslinking agent to the initiator of 20:1, and introducing N₂ After 10min, placing in a constant-temperature gas bath oscillator at 60 ℃ for thermal polymerization for 15h, centrifuging, and drying the solid at 40 ℃ to obtain a polymer; wherein the molar ratio of the azodiisobutyronitrile to the triadimenol is 2: 1; meanwhile, setting a blank control, namely adding no triadimenol, and carrying out other preparation conditions;

(3) grinding the polymer obtained in the step (2), eluting triadimenol with a methanol-acetic acid mixed solution, and drying at 35 ℃ to obtain triadimenol molecularly imprinted polymer Microspheres (MIPs) and blank molecularly imprinted polymers (NIPs); wherein the methanol-acetic acid mixed solution is prepared by mixing methanol and acetic acid according to the volume ratio of 9: 1;

weighing 30mg of the prepared MIPs and NIPs, placing the weighed MIPs and NIPs into a 20mL glass bottle, adding 6mL of 12mg/L triazole alcohol solution, performing an adsorption test at 25 ℃, taking supernatant in the glass bottle after adsorption is finished, filtering with a filter membrane, detecting by liquid chromatography-tandem mass spectrometry, and calculating the adsorption effect data as shown in Table 2, wherein the imprinting factor of the MIPs is 2.51 according to the Table 2;

table 2: adsorption effects of MIPs and NIPs

。

Example 3

(1) Dissolving triadimenol and trifluoromethyl acrylic acid in acetonitrile according to the molar ratio of 1:2 of triadimenol and trifluoromethyl acrylic acid, ultrasonically mixing uniformly, introducing N into the mixture₂ 20min, then placing at 22 deg.CPre-polymerizing for 9h in a constant-temperature gas bath oscillator to obtain a pre-polymerized solution;

(2) adding a crosslinking agent divinylbenzene and an initiator azobisisobutyronitrile into the prepolymerization solution obtained in the step (1) according to the molar ratio of the crosslinking agent to the initiator of 30:1, and introducing N₂ After 20min, placing in a constant-temperature gas bath oscillator at 40 ℃ for thermal polymerization for 24h, centrifuging, and drying the solid at 45 ℃ to obtain a polymer; wherein the molar ratio of azobisisobutyronitrile to triadimenol is 4: 1; meanwhile, setting a blank control, namely adding no triadimenol, and carrying out other preparation conditions;

(3) grinding the polymer obtained in the step (2), eluting triadimenol with a methanol-acetic acid mixed solution, and drying at 45 ℃ to obtain triadimenol molecularly imprinted polymer Microspheres (MIPs) and blank molecularly imprinted polymers (NIPs); wherein the methanol-acetic acid mixed solution is prepared by mixing methanol and acetic acid according to the volume ratio of 8: 1;

weighing 30mg of the prepared MIPs and NIPs, placing the weighed MIPs and NIPs into a 20mL glass bottle, adding 6mL of 15mg/L triazole alcohol solution, performing an adsorption test at 25 ℃, taking supernate in the glass bottle after adsorption is finished, performing filter membrane filtration, detecting by adopting liquid chromatography-tandem mass spectrometry, and calculating the adsorption effect data as shown in Table 3, wherein the table 3 shows that the imprinting factor of the MIPs is 2.35;

table 3: adsorption effects of MIPs and NIPs

。

Example 4:

(1) dissolving triadimenol and acrylic acid in chloroform at a molar ratio of 1:6, ultrasonically mixing, and introducing N into the mixture₂ 18min, then placing in a constant-temperature gas bath oscillator at 30 ℃ for prepolymerization for 11h to obtain a prepolymerization solution;

(2) adding crosslinking agent epichlorohydrin and initiator azobisisobutyronitrile into the prepolymerization solution obtained in the step (1) according to the molar ratio of the crosslinking agent to the initiator of 15:1, and introducing N₂ After 18min, placing in a constant temperature gas bath oscillator at 50 deg.C for thermal polymerizationCentrifuging for 20h, and drying the solid at 35 ℃ to obtain a polymer; wherein the molar ratio of the azodiisobutyronitrile to the triadimenol is 3: 1; meanwhile, setting a blank control, namely adding no triadimenol, and carrying out other preparation conditions;

(3) grinding the polymer obtained in the step (2), eluting triadimenol with a methanol-acetic acid mixed solution, and drying at 35 ℃ to obtain triadimenol molecularly imprinted polymer Microspheres (MIPs) and blank molecularly imprinted polymers (NIPs); wherein the methanol-acetic acid mixed solution is prepared by mixing methanol and acetic acid according to the volume ratio of 9: 1;

weighing 30mg of the prepared MIPs and NIPs, placing the weighed MIPs and NIPs into a 20mL glass bottle, adding 6mL of 25mg/L triazole alcohol solution, performing an adsorption test at 25 ℃, taking supernate in the glass bottle after adsorption is finished, performing filter membrane filtration, detecting by adopting liquid chromatography-tandem mass spectrometry, and calculating the adsorption effect data as shown in Table 4, wherein the imprinting factor of the MIPs is 2.34 according to Table 4;

table 4: adsorption effects of MIPs and NIPs

。