Controllable preparation method and application of small-particle-size amphiphilic polymer microsphere material

Abstract

The application discloses a controllable preparation method and application of small-particle-size amphiphilic polymer microsphere material, and belongs to the field of polymer microspheres. The preparation method comprises the following steps: S1, preparing a water-phase solution A containing an emulsifier and a dispersing agent; S2, preparing an oil-phase solution B containing a pore-forming agent, an initiator and a hydrophilic monomer; S3, preparing an oil-phase solution C containing a pore-forming agent, an initiator and a hydrophobic monomer; S4, mixing the oil-phase solution B and the water-phase solution A, and performing a first temperature-raising treatment; after the first temperature-raising treatment is completed, the oil-phase solution C is further added, a second temperature-raising treatment is performed, and a reaction liquid is obtained; S5, performing shearing emulsification on the reaction liquid obtained in the step S4, and obtaining an emulsion; and S6, performing a second-stage polymerization reaction on the emulsion obtained in the step S5, and obtaining the amphiphilic polymer microsphere material. The main use of the application is to prepare small-particle-size amphiphilic polymer monodisperse microspheres with good uniformity.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polymer microspheres, more particularly to a controllable preparation method and application of small-particle-size amphiphilic polymer microsphere material. BACKGROUND

[0002] Amphiphilic polymer microspheres have a balance of hydrophilic and hydrophobic surfaces, and are widely used in the enrichment, separation and analysis testing of organic compounds. The polymer microspheres are generally synthesized by a suspension-emulsion polymerization method, and the synthesis process is complex and the yield is low, and the monodispersity of the particle size of the product is difficult to control. Small-particle-size polymer microspheres are an important component of analytical chromatographic packing materials, and are also one of the technologies that need to be broken through in China. The uniformity of the microspheres can directly affect the chromatographic separation and column efficiency of the chromatographic column, and is a core index in the production process of the microspheres.

[0003] The Chinese patent application file with the publication number CN105037630A discloses a hydrophilic polymer microsphere and a simple preparation method thereof. The technical solution provided by the application polymerizes N-vinylpyrrolidone and divinylbenzene, and improves the hydrophilicity of the polymer microspheres by increasing the amount of N-vinylpyrrolidone. However, the microspheres prepared by this method have a wide particle size distribution, the amount of N-vinylpyrrolidone is too high, and the yield is unstable. The Chinese patent application file with the publication number CN109942737A discloses a particle-size-uniform amphiphilic polymer microsphere material, a preparation method and application. The hydrophilic and hydrophobic monomers are uniformly dispersed in an emulsion in water by a certain method, and then polymerization is carried out by strictly controlling the temperature and rotation speed, and finally the amphiphilic polymer material is obtained. However, the operation steps in the production process of this technology are complicated, especially when preparing two-phase polymer microspheres with a diameter of 20 μm or less, it is difficult to effectively control the particle size of the product, the comprehensive yield is low, and the monodispersity of the particle size needs to be further improved.

[0004] Therefore, how to control the uniformity and stability of the emulsion droplets of small-particle-size (20 μm or less) amphiphilic polymer microspheres in the polymerization process is a scientific problem that needs to be explored in this field; how to simplify the operation process of the small-particle-size amphiphilic polymer reaction process and improve the comprehensive yield is a technical problem that needs to be solved in this technical field. SUMMARY

[0005] 1. Technical problem to be solved by the application

[0006] In view of the shortcomings of the prior art in preparing small-particle-size amphiphilic polymer microspheres with non-ideal particle size uniformity, a controllable preparation method of small-particle-size amphiphilic polymer microsphere material is provided, which aims to obtain small-particle-size amphiphilic polymer microspheres with controllable particle size and good particle size uniformity by a new high-speed shearing-emulsification-polymerization method.

[0007] 2. Technical solution

[0008] To achieve the above object, the technical scheme provided by the present application is:

[0009] The controllable preparation method of the small-particle-size amphiphilic polymer microsphere material of the present application comprises the following steps:

[0010] S1. Preparation of an aqueous phase solution A containing an emulsifier, a dispersant and an aqueous solvent;

[0011] S2. Preparation of an oil phase solution B containing a porogen, an initiator and a hydrophilic monomer;

[0012] S3. Preparation of an oil phase solution C containing a porogen, an initiator and a hydrophobic monomer;

[0013] S4. Mixing of the oil phase solution B and the aqueous phase solution A, and first temperature raising treatment;

[0014] After the first temperature raising treatment, the oil phase solution C is mixed again, and second temperature raising treatment is performed to obtain a reaction liquid;

[0015] S5. Shear emulsification of the reaction liquid obtained in step S4 to obtain an emulsion;

[0016] S6. Second stage polymerization reaction of the emulsion obtained in step S5 to obtain an amphiphilic polymer microsphere material;

[0017] In step S5, the shear emulsification time is 10-300 s, and the rotation speed is 5000-30000 rpm.

[0018] It should be noted that the amphiphilic polymer microsphere refers to a polymer microsphere containing both hydrophilic and hydrophobic groups, and the microsphere has good adsorption and separation effect on hydrophilic and hydrophobic organic compounds.

[0019] It should be further noted that the first stage polymerization reaction comprises steps S4 and S5, and the reactants will undergo polymerization reaction in steps S4 and S5. In the first stage polymerization reaction process, the particle size of the emulsion droplets in the reaction system is controlled by high-speed shearing, and the stability of the droplets is controlled by the polymerization reaction of the monomers in steps S4 and S5 to obtain a solid-liquid suspension with constant particle size;

[0020] Then, the solid-liquid suspension with constant particle size is subjected to second stage polymerization reaction to obtain small-particle-size amphiphilic polymer microspheres with good particle size uniformity.

[0021] Specifically, in step S5, the shear emulsification time can be 10-300 s, 50-300 s, 100-300 s, 150-300 s, 200-300 s or 250-300 s.

[0022] The rotation speed of the shear emulsification can be 5000-30000 rpm, 7000-30000 rpm, 10000-20000 rpm, 10000-25000 rpm, 10000-30000 rpm, 15000-30000 rpm, 20000-30000 rpm, or 25000-30000 rpm.

[0023] Further, the shear emulsification is performed by a high-speed shear mixer.

[0024] It should be noted that the high-speed shear mixer, as a process intensification device, its core component is a shear head composed of a stator and a rotor. When the shear emulsification is performed by the high-speed shear mixer, the rotation speed is the rotation speed of the rotor in the high-speed shear mixer.

[0025] It should be further noted that, in the process of shear emulsification, the average droplet size and droplet size distribution (DSD) after shearing are key parameters for evaluating the emulsification performance, because they have a significant impact on the mass transfer area, stability and rheology of the emulsion. In suspension polymerization, the droplets will gradually be converted into polymer microspheres as the reaction proceeds.

[0026] Further, in step S4, the conditions of the first temperature rising treatment include rising the temperature to 70-75℃ for 10-30 minutes.

[0027] The conditions of the second temperature rising treatment include rising the temperature to 76-80℃ for 10-30 minutes.

[0028] Further, step S4 can specifically include: adding the oil phase solution B to the aqueous phase solution A, after stirring uniformly at room temperature, performing the first temperature rising treatment.

[0029] After the first temperature rising treatment is completed, the oil phase solution C is added again, and the second temperature rising treatment is performed to obtain the reaction liquid.

[0030] Further, in step S4, the mass ratio of the aqueous solvent in the aqueous phase solution A, the hydrophilic monomer in the oil phase solution B, and the hydrophobic monomer in the oil phase solution C is 20:1-2:1-3.

[0031] It should be noted that controlling the mass ratio of water, hydrophilic monomer and hydrophobic monomer within the above range is beneficial to improve the uniformity of the particle size distribution and the yield of the product, amphiphilic polymer microspheres.

[0032] Further, in step S6, the temperature of the second-stage polymerization reaction is 81-90℃ for 1-5 hours.

[0033] Further, in step S2, the amount of the porogen is 0.2-2 times the amount of the hydrophilic monomer, calculated by mass.

[0034] Further, in step S2, the amount of the initiator is 0.5% to 4% of the amount of the hydrophilic monomer by mass.

[0035] Further, the step S2 specifically comprises: adding the porogen and the initiator into the hydrophilic monomer to obtain an oil phase solution B.

[0036] Further, in step S2, the hydrophilic monomer comprises one, two or more of N-vinyl pyrrolidone (NVP), glycidyl methacrylate and methyl acrylate.

[0037] Further, in step S2, the porogen comprises one or both of toluene and xylene.

[0038] Further, in step S2, the initiator comprises azobisisobutyronitrile (AIBN).

[0039] Preferably, in step S2, the initiator is azobisisobutyronitrile.

[0040] Further, in step S3, the amount of the porogen is 0.2 to 2 times of the amount of the hydrophobic monomer by mass.

[0041] Further, in step S3, the amount of the initiator is 1% to 2% of the amount of the hydrophobic monomer by mass.

[0042] Further, the step S3 specifically comprises: adding the porogen and the initiator into the hydrophobic monomer to obtain an oil phase solution C.

[0043] It should be noted that controlling the amount of the initiator in the oil phase solution C and the oil phase solution B is conducive to obtaining the amphiphilic polymer microsphere material with good particle size uniformity.

[0044] Further, in step S3, the hydrophobic monomer comprises one, two or more of styrene, divinylbenzene (DVB) and 4-chloromethyl styrene.

[0045] Further, in step S3, the porogen comprises one or both of toluene and xylene.

[0046] Further, in step S3, the initiator comprises azobisisobutyronitrile.

[0047] Preferably, in step S3, the initiator is azobisisobutyronitrile.

[0048] Further, in step S1, the amount of the emulsifier is 1% to 5% of the amount of the aqueous solvent by mass.

[0049] Further, in step S1, the dispersant is used in an amount of 1% to 5% by mass of the aqueous solvent.

[0050] Further, the step S1 specifically comprises: adding an emulsifier and a dispersant into the aqueous solvent to obtain the aqueous solution A.

[0051] Further, in step S1, the aqueous solvent comprises water.

[0052] Preferably, the aqueous solvent is water.

[0053] Further, in step S1, the emulsifier comprises sodium dodecyl sulfate (SDS).

[0054] Further, in step S1, the dispersant comprises polyvinylpyrrolidone (PVP).

[0055] Preferably, the emulsifier is sodium dodecyl sulfate;

[0056] The dispersant is polyvinylpyrrolidone.

[0057] The application further provides the amphiphilic polymer microsphere material prepared by the preparation method,

[0058] The particle size of the amphiphilic polymer microsphere material is 0.2 to 20 μm.

[0059] The application further provides the amphiphilic polymer microsphere material prepared by the preparation method or the application of the amphiphilic polymer microsphere material in separation, purification and analysis test.

[0060] Further, the amphiphilic polymer microsphere material with a diameter less than 5 μm can be used as an analytical chromatographic column filler.

[0061] The amphiphilic polymer microsphere material with a diameter of 3 to 10 μm can be used for solid phase microextraction or online solid phase extraction.

[0062] The amphiphilic polymer microsphere material with a diameter of more than 10 μm can be used for separation and purification in the field of biological medicine.

[0063] 3. Beneficial effects

[0064] Compared with the prior art, the technical scheme provided by the application has the following beneficial effects:

[0065] (1) The small particle size amphiphilic polymer microsphere material controllable preparation method provided by the application can prepare small particle size amphiphilic polymer microspheres with better particle size uniformity through a high-speed shearing-emulsification-polymerization method. Specifically, in the preparation process of small particle size amphiphilic polymer microspheres, the innovative high-speed shearing emulsification method is introduced, for example, high-speed shearing emulsification can be realized through a high-speed shearing device such as a high-speed shearing mixer; in the first stage of polymerization reaction, the evolution of the emulsion droplets is strictly controlled by the shearing time and speed, which is the core element of the application, and the evolution includes the following four stages:

[0066] ① Transition stage: When high-speed shearing just starts, the breakage rate of the droplets is greater than the coagulation rate, and the size of the droplets / polymer decreases; ② Quasi-stable stage: With the shearing and monomer polymerization, the droplets gradually transition to the stage where the breakage rate and the coagulation rate are equivalent, and the droplets / polymer are in a dynamic balance stage with constant size; ③ Growth stage: The viscosity of the droplets increases, resulting in a coagulation rate greater than a breakage rate, and the size of the droplets / polymer increases and the size distribution widens; ④ Constant stage: At the end, the breakage and coagulation of the droplets stop, and the emulsion will completely change into a solid-liquid suspension with constant particle size; wherein the polymerization reaction of the monomer in the first stage of polymerization reaction controls the stability of the droplets, and the constant particle size solid-liquid suspension can obtain small particle size amphiphilic polymer microspheres through the second stage of polymerization reaction. Compared with the prior art, the preparation and control method of small particle size monodisperse amphiphilic polymer microspheres can effectively solve the problems and deficiencies of the existing preparation technology of amphiphilic polymer microspheres, such as difficulty in controlling particle size.

[0067] (2) In the small particle size amphiphilic polymer microsphere material controllable preparation method provided by the application, the forming process of the polymer microspheres can be controlled by adjusting the speed and time of high-speed shearing emulsification. The traditional amphiphilic microsphere polymerization method generally uses emulsion or suspension polymerization, which is difficult to accurately control the particle size of the product microspheres in the small particle size range and has a complicated operation process. The method of preparing small particle size monodisperse amphiphilic polymer microspheres is simple to operate, easy to implement, and has good stability, good controllability of the particle size range, and good uniformity.

[0068] (3) The preparation method of the amphiphilic polymer microsphere material provided by the application mixes the oil phase solution containing the hydrophilic monomer with the aqueous phase solution first, then adds the oil phase solution containing the hydrophobic monomer, generates block chain copolymer between the hydrophilic monomer and the hydrophobic monomer, and then performs high-speed shearing to mix the chains of the hydrophilic monomer and the hydrophobic monomer again, so as to generate the amphiphilic polymer microsphere with more uniform hydrophilic and hydrophobic monomers. In the first temperature rising treatment, the reaction temperature is 70-75 DEG C, and the reaction rate is moderate. After the hydrophobic monomer is added and the temperature is raised to 76-80 DEG C, the reaction rate is increased. Moreover, the high-speed shearing process is an exothermic process, the reaction liquid can be heated in the shearing process, the polymerization reaction speed of the monomer is faster, the synthesis efficiency of the amphiphilic polymer microsphere material can be further improved, the preparation operation process is simplified, and the yield is improved.

[0069] (4) The amphiphilic polymer microsphere material provided by the application has more uniform hydrophilic and hydrophobic functional group distribution on the surface of the small particle size monodisperse amphiphilic polymer porous microsphere, the preparation process is simple and fast, the research and development and production cost of the microsphere can be reduced, the microsphere is better applied in the chromatographic separation and analysis test field. BRIEF DESCRIPTION OF DRAWINGS

[0070] Figure 1 It is an electron microscope image of the amphiphilic polymer microsphere product prepared in Example 1 of the application.

[0071] Figure 2 It is an electron microscope image of the amphiphilic polymer microsphere product prepared in Example 2 of the application.

[0072] Figure 3 It is an electron microscope image of the amphiphilic polymer microsphere product prepared in Comparative Example 4 of the application.

[0073] Figure 4 It is an electron microscope image of the product prepared in Comparative Example 6 of the application.

[0074] Figure 5 It is an electron microscope image of the product prepared in Comparative Example 8 of the application.

[0075] Figure 6 It is a separation diagram of fructose and sucrose by using the chromatographic column made of the amphiphilic polymer microsphere prepared in Example 2 of the application. DETAILED DESCRIPTION

[0076] The present disclosure can be more easily understood by reference to the following description in conjunction with the examples included herein. All references are incorporated herein by reference in their entirety. It should be understood that the present disclosure is not limited to the particular products, methods, conditions or parameters described and / or shown herein, unless otherwise specified.

[0077] It should also be understood that, for clarity purposes, certain characteristics of the disclosure can have been described in the context of separate embodiments, but can also be provided in combination in a single embodiment. That is, unless explicitly stated otherwise, each separate embodiment is considered to be combinable with any other embodiment, and the combination is considered to represent another, different embodiment. Conversely, the various features of the disclosure described in the context of a single embodiment can also be provided separately or in any sub-combination. Finally, while a particular embodiment can be described as part of a series of steps or as part of a more general structure, each step or sub-structure can itself be considered an independent embodiment.

[0078] Unless otherwise stated, it is to be understood that each individual element in a list and each combination of individual elements in that list are to be construed as a separate embodiment. For example, a list of embodiments recited as “A, B, or C” is to be construed as including the embodiments of “A,” “B,” “C,” “A or B,” “A or C,” “B or C,” or “A, B, or C.”

[0079] In the present disclosure, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a substance” is a reference to at least one of such a substance and equivalents thereof.

[0080] When describing items by using the conjunctive term “and / or,” etc., the description is to be understood to include any one of the associated listed items, as well as all combinations of one or more of them.

[0081] Generally, use of the term“about” indicates approximations that can vary depending on the desired properties to be obtained by the disclosed subject matter and will be construed based on functionality in a context-dependent manner. Thus, a person of ordinary skill in the art will be able to interpret the degree of difference on a case-by-case basis. In some cases, the number of significant digits used in expressing a particular value can be representative of the degree of precision to which the term“about” allows for variation. In other cases, a range of values can be used to determine the degree of precision to which the term“about” allows for variation. Further, all ranges in the present disclosure are inclusive and combinable, and a reference to a value in a range includes each value in the range.

[0082] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the application belongs; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. Any and all combinations of one or more relevant items listed in the description are expressly contemplated.

[0083] The following examples are not intended to be specific conditions, but are carried out under conventional conditions or manufacturer's recommended conditions. The reagents or instruments used are not specified by the manufacturer, but are conventional products that can be obtained by commercial purchase.

[0084] The following embodiments are further described in conjunction with specific examples, but the examples do not limit the application in any form. Unless otherwise specified, the reagents, methods and equipment used in the application are conventional reagents, methods and equipment in the art. The essential features and significant effects of the application can be embodied in the examples described below, which are part of the embodiments of the application, but not all of the embodiments. Therefore, they do not limit the application in any way, and those skilled in the art can make some non-essential improvements and adjustments according to the content of the application, which are within the scope of protection of the application.

[0085] Example 1

[0086] (1) 4 g emulsifier SDS, 4 g dispersant PVP were added to 400 g water to obtain aqueous solution A;

[0087] (2) 20 g porogen toluene, 0.5 g initiator AIBN were added to 20 g hydrophilic monomer NVP to obtain oil phase solution B;

[0088] (3) 20 g porogen toluene, 0.5 g initiator AIBN were added to 30 g hydrophobic monomer DVB to obtain oil phase solution C;

[0089] (4) Oil phase solution B was added to aqueous solution A, which was stirred uniformly at room temperature and then heated to 75℃, and oil phase solution C was added after 30 minutes, and heated to 80℃ for another 30 minutes;

[0090] (5) Use a high-shear mixer to emulsify the reaction solution by high-speed shear for 300 seconds and at a speed of 15,000 rpm.

[0091] (6) The emulsion obtained in step (5) was subjected to a second-stage polymerization reaction at 85°C for 2 hours to obtain amphiphilic polymer microspheres.

[0092] Depend on Figure 1 It can be seen that the average particle size of the amphiphilic polymer microspheres prepared in this embodiment is 5 μm, and the amphiphilic polymer microspheres have good monodispersity. Elemental analysis of the amphiphilic polymer microspheres prepared in this embodiment shows that the nitrogen content is 1.7%, the contact angle is 79°, and the particle size variation coefficient is 5%.

[0093] Example 2

[0094] Under the same conditions as in Example 1, the effects of different high-speed shear emulsification conditions on material properties were investigated. The experimental results are shown in Table 1.

[0095] Table 1. Effects of different high-speed shear emulsification conditions on the synthesis of materials

[0096]

[0097] In this embodiment, the experimental product No. 1 has a particle size of approximately 2 μm and exhibits good monodispersity. Its specific morphology is as follows: Figure 2 As shown.

[0098] Referring to Table 1, it can be seen from this embodiment and the comparative example that when the shear emulsification speed is low, increasing the shear time does not improve the monodispersity of the product. Referring to Comparative Example 4, when the shear emulsification speed is low and the shear time is short, the shearing effect is poor. Although amphiphilic polymer microspheres can still be obtained, the product exhibits obvious agglomeration, and the morphology of the product is as follows... Figure 3 As shown.

[0099] Example 3

[0100] Under the same conditions as in Example 1, the effects of different first and second heating treatments on the material properties were examined, and the experimental results are shown in Table 2.

[0101] Table 2. Effects of different first and second heating treatment conditions on the synthesized materials

[0102]

[0103]

[0104] From Table 2, it can be seen from the present example and comparative examples that, in combination with Comparative Example 5, when the first temperature rise is low, the pre-polymerization degree of the hydrophilic monomer is not enough, the product has obvious strong hydrophobicity, and is not spherical. Figure 4

[0105] Example 4

[0106] Other conditions are the same as in Example 1, and the effects of different addition ratios of water in the aqueous solution A, the hydrophilic monomer in the oil phase solution B, and the hydrophobic monomer in the oil phase solution C on the material properties are tested. The experimental results are shown in Table 3.

[0107] Table 3 Effects of different addition ratios of water, hydrophilic monomer, and hydrophobic monomer on the synthesized material

[0108]

[0109] From Table 3, it can be seen from the present example and comparative examples that, in combination with Comparative Example 5, when the first temperature rise is low, the pre-polymerization degree of the hydrophilic monomer is not enough, the product has obvious strong hydrophobicity, and is not spherical. Figure 5

[0110] Comparative Example 9

[0111] Other conditions are the same as in Example 1, except that in step (4), the oil phase solution C is first added to the aqueous solution A, and after stirring uniformly at room temperature, the temperature is raised to 75°C, and after 30 minutes, the oil phase solution B is added, and the temperature is raised to 85°C, and then continued for another 30 minutes.

[0112] The final hydrophilic monomer cannot be introduced into the polymer, and the amphiphilic polymer microspheres cannot be obtained.

[0113] Comparative Example 10

[0114] Other conditions are the same as in Example 1, except that in step (4), the oil phase solution C and the oil phase solution B are simultaneously added to the aqueous solution A, and after stirring uniformly at room temperature, the temperature is raised to 75°C, and after 30 minutes, the temperature is raised to 85°C, and then continued for another 30 minutes.

[0115] The final hydrophilic monomer cannot be introduced into the polymer, and the amphiphilic polymer microspheres cannot be obtained.

[0116] Application Example 1

[0117] The microspheres synthesized in Example 1 are modified by functional groups, including the following steps:​​

[0118] 1. Friedel-Crafts reaction to introduce chloro group: 200 g of the above polymer microspheres were mixed with 100 mL of chloromethyl ether in a three-necked flask, 120 g of anhydrous FeCl3 was added after two hours, 50 mL of sulfuric acid was added dropwise into the reaction system, the temperature was raised to 47.5 °C after one hour of reaction, and the reaction was carried out at this temperature for 24 hours.

[0119] 2. Amination reaction of polymer chloro group microspheres: 5 g of chloro group microspheres, 200 mL of acetone were added in a three-necked round-bottom flask (equipped with a stirring rod and a reflux condenser), and ultrasonic dispersion was carried out for 3 min, then 200 mL of a piperazine acetone solution was added into the flask, the temperature of the reaction system was maintained at 70 °C, and the rotation speed was controlled at 100 r / min. The suspension was refluxed for 12 hours, and after cooling, the product was washed with anhydrous ethanol for 5 times until the pH of the washing liquid was about 6-7, and yellowish microspheres were obtained.

[0120] The microspheres modified by piperazine on the surface were used for adsorption experiment, and the experimental results are shown in Table 4. In the adsorption experiment, equal amounts of the piperazine-modified microspheres of the application example and commercial microspheres were added into 15 mL of a mixed standard solution containing 21 kinds of antibiotics (each 500 ng / L) for adsorption experiment. As can be seen from Table 4, the microspheres have more excellent enrichment capacity than the commercial microspheres (Oasis WAX adsorption material of Waters Company, USA), and can realize simultaneous efficient extraction of compounds with different physicochemical properties.

[0121] Table 4 Enrichment capacity of the microspheres of the application example and commercial microspheres for 21 kinds of antibiotics

[0122]

[0123] The microspheres modified by piperazine on the surface in the application example were used as the coating layer of solid phase microextraction for solid phase microextraction experiment of 21 kinds of antibiotic pollutants in water. The solid phase microextraction and liquid chromatography-tandem mass spectrometry method for 21 kinds of antibiotic pollutants established based on the piperazine-modified microspheres in the application example (wherein the liquid chromatography column was ACQUITY UPLC BEH C18 (1.7 μm, 2.1 x 100 mm) of Waters Company, the injection amount was 10 μL, the flow rate was 0.5 mL / min, the column temperature was 25 °C, and the types of mobile phase were 0.1% formic acid water and acetonitrile.) The performance is shown in Table 5.

[0124] Table 5 Performance of SPME-LC-MS / MS method for 21 kinds of antibiotic pollutants

[0125]

[0126] Note: K fe: enrichment factor / partition coefficient, the ratio of the coating to the analyte concentration in the sample at the extraction equilibrium.

[0127] Application Example 2

[0128] The microsphere product surface obtained from the experiment in No. 1 in Example 2 was modified with diethylamine functional groups and packed into a chromatographic column for chromatographic analysis experiments of sucrose and fructose. The separation degree was good, and the specific chromatographic separation conditions are shown in Table 6 and Table 7. Figure 6 and Table 6, wherein, Figure 6 The peak at the retention time of 3.703 min in Table 6 is the peak of fructose, and the peak at the retention time of 6.003 min is the peak of sucrose. It can be seen that the separation degree of sucrose and fructose is good.

[0129] Table 6 Chromatographic analysis conditions of the chromatographic column packed in this application example for sucrose and fructose

[0130]

[0131]

Claims

1. A controllable preparation method of a small particle size amphiphilic polymer microsphere material, characterized in that, The method comprises the following steps: S1. preparing an aqueous phase solution A containing an emulsifier, a dispersant, and an aqueous solvent; S2. preparing an oil phase solution B containing a porogen, an initiator, and a hydrophilic monomer; S3. preparing an oil phase solution C containing a porogen, an initiator, and a hydrophobic monomer; S4. mixing the oil phase solution B and the aqueous phase solution A, and performing a first temperature raising treatment; After the first temperature raising treatment, the oil phase solution C is mixed, and a second temperature raising treatment is performed to obtain a reaction solution; The mass ratio of the aqueous solvent in the aqueous phase solution A, the hydrophilic monomer in the oil phase solution B, and the hydrophobic monomer in the oil phase solution C is 20:1-2:1-3; The first temperature raising treatment is performed at 70-75°C for 10-30 minutes; The second temperature raising treatment is performed at 76-80°C for 10-30 minutes; S5. performing shearing emulsification on the reaction solution obtained in step S4 to obtain an emulsion; The shearing emulsification is performed for 10-300 seconds at a rotation speed of 5,000-30,000 rpm; S6. performing a second stage polymerization reaction on the emulsion obtained in step S5 to obtain an amphiphilic polymer microsphere material, wherein the particle size of the amphiphilic polymer microsphere material is 0.2-20 μm.

2. The controllable preparation method of the small particle size amphiphilic polymer microsphere material according to claim 1, wherein: In step S6, the second stage polymerization reaction is performed at a temperature of 81-90°C for 1-5 hours.

3. The controllable preparation method of the small particle size amphiphilic polymer microsphere material according to claim 2, wherein: In step S2, the amount of the porogen is 0.2-2 times the amount of the hydrophilic monomer by mass; In step S2, the amount of the initiator is 0.5%-4% of the amount of the hydrophilic monomer by mass.

4. The controllable preparation method of the small particle size amphiphilic polymer microsphere material according to claim 3, wherein: In step S3, the amount of the porogen is 0.2-2 times the amount of the hydrophobic monomer by mass; In step S3, the amount of the initiator is 1%-2% of the amount of the hydrophobic monomer by mass.

5. The controllable preparation method of the small particle size amphiphilic polymer microsphere material according to claim 4, wherein: In step S1, the amount of the emulsifier is 1%-5% of the amount of the aqueous solvent by mass; In step S1, the amount of the dispersant is 1%-5% of the amount of the aqueous solvent by mass.

6. The controllable preparation method of the small particle size amphiphilic polymer microsphere material according to claim 5, wherein: In step S1, the emulsifier comprises sodium dodecyl sulfate; In step S1, the dispersant comprises polyvinylpyrrolidone; In step S1, the aqueous solvent comprises water; In step S2, the hydrophilic monomer comprises one or both of N-vinylpyrrolidone and glycidyl methacrylate; In step S2, the porogen comprises one or both of toluene and xylene; In step S2, the initiator comprises azobisisobutyronitrile. In step S3, the hydrophobic monomer includes one, two or more of styrene, divinylbenzene, 4-chloromethylstyrene; In step S3, the porogen includes one or both of toluene and xylene; In step S3, the initiator includes azobisisobutyronitrile.

7. Use of the small-sized amphiphilic polymer microsphere material according to any one of claims 1 to 6 in separation, purification and analytical testing.

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