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

Abstract

The invention discloses a controllable preparation method and application of a 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 dispersant; s2, preparing an oil phase solution B containing a pore-foaming agent, an initiator and a hydrophilic monomer; s3, preparing an oil phase solution C containing a pore-foaming agent, an initiator and a hydrophobic monomer; s4, mixing the oil phase solution B and the water phase solution A, and carrying out first heating treatment; after the first heating treatment is completed, adding the oil phase solution C, and carrying out second heating treatment to obtain a reaction solution; s5, shearing and emulsifying the reaction liquid obtained in the step S4 to obtain an emulsion; and S6, carrying out second-stage polymerization reaction on the emulsion obtained in the step S5 to obtain the amphiphilic polymer microsphere material. The preparation method is mainly used for preparing small-particle-size amphiphilic polymer monodisperse microspheres with good uniformity.

Description

Technical Field

[0001] The invention relates to the technical field of polymer microspheres, and more particularly to a controllable preparation method and application of small-diameter amphiphilic polymer microsphere materials. Background Art

[0002] Amphiphilic polymer microspheres are widely used in the enrichment, separation and analytical testing of organic compounds due to the hydrophilic-hydrophobic balance on their surfaces. The polymer microspheres are generally prepared by suspension-emulsion polymerization, which has a complex synthesis process and low yield, and the monodispersity of the product particle size is difficult to control. Small-particle polymer microspheres are an important component of analytical chromatographic fillers and one of the technologies that my country urgently needs to break through. The uniformity of the microspheres can directly affect chromatographic separation and chromatographic column efficiency, and is a core indicator in the microsphere production process.

[0003] The Chinese patent application document with publication number CN105037630A discloses a hydrophilic polymer microsphere and a simple preparation method thereof, and the technical solution provided by the invention polymerizes N-vinyl pyrrolidone and divinylbenzene, and improves the hydrophilicity of the polymer microsphere by increasing the amount of N-vinyl pyrrolidone, but the microsphere particle size distribution prepared by this method is wide, the amount of N-vinyl pyrrolidone is too high, and the yield is unstable. The Chinese patent application document with publication number CN109942737A discloses a uniform particle size amphiphilic polymer microsphere material, preparation method and application, and forms an emulsion uniformly dispersed in the aqueous phase by a certain method for hydrophilic and hydrophobic monomers; and then polymerizes by strict temperature and rotation speed and other conditions, and finally obtains an amphiphilic polymer material. However, the operation steps of the technology are cumbersome in the production process, especially when preparing amphiphilic polymer microspheres with a diameter of less than 20 μm, it is difficult to effectively control the product particle size, 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 (less than 20 μm) amphiphilic polymer microspheres during the polymerization process is a scientific problem that urgently needs to be explored in this field; how to simplify the operating procedures of the small-particle amphiphilic polymer reaction process and improve the overall yield is a technical problem that needs to be solved in this technical field. Summary of the invention

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

[0006] In view of the shortcoming of the existing technology in preparing small-particle amphiphilic polymer microspheres with unsatisfactory particle size uniformity, a controllable preparation method of small-particle amphiphilic polymer microsphere materials is provided, which aims to obtain small-particle amphiphilic polymer microspheres with controllable particle size and good particle size uniformity through a new high-speed shear-emulsification-polymerization method.

[0007] 2. Technical solution

[0008] In order to achieve the above object, the technical solution provided by the present invention is:

[0009] A controllable preparation method of a small-size amphiphilic polymer microsphere material of the present invention comprises the following steps:

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

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

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

[0013] S4. The oil phase solution B and the aqueous phase solution A are mixed and subjected to a first heating treatment;

[0014] After the first heating treatment is completed, the mixture is mixed with the oil phase solution C and subjected to a second heating treatment to obtain a reaction solution;

[0015] S5. The reaction solution obtained in step S4 is sheared and emulsified to obtain an emulsion;

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

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

[0018] It should be noted that the amphiphilic polymer microspheres refer to polymer microspheres containing both hydrophilic and hydrophobic groups, and the microspheres have good adsorption and separation effects on both hydrophilic and hydrophobic organic compounds.

[0019] It should also be noted that the first stage polymerization reaction includes steps S4 and S5, in which the reactants undergo polymerization reactions. During the first stage polymerization reaction, the particle size of the emulsion droplets in the reaction system is regulated by high-speed shearing, and the stability of the droplets is controlled by the polymerization reaction of the monomers in steps S4 and S5, so as to obtain a solid-liquid suspension with a constant particle size;

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

[0021] Specifically, in step S5, the shear emulsification time may be 10 to 300 s, 50 to 300 s, 100 to 300 s, 150 to 300 s, 200 to 300 s or 250 to 300 s;

[0022] The rotation speed of the shear emulsification may 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] Furthermore, the shear emulsification is performed by a high-speed shear mixer.

[0024] It should be noted that, as a process intensification device, the core component of the high-speed shear mixer is a shear head composed of a stator and a rotor. When 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 also be noted that in the shear emulsification process, 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, as the reaction proceeds, the droplets will gradually transform into polymer microspheres.

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

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

[0028] Furthermore, step S4 may specifically include: adding the oil phase solution B to the water phase solution A, stirring evenly at room temperature, and then performing a first heating treatment;

[0029] After the first heating treatment is completed, the oil phase solution C is added and the second heating treatment is performed to obtain a reaction solution.

[0030] Furthermore, 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 improving the uniformity of particle size distribution and yield of the product amphiphilic polymer microspheres.

[0032] Furthermore, in step S6, the temperature of the second stage polymerization reaction is 81-90° C. and lasts for 1-5 hours.

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

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

[0035] Furthermore, the step S2 specifically includes: adding the porogen and initiator to the hydrophilic monomer to obtain the oil phase solution B.

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

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

[0038] Furthermore, in step S2, the initiator includes azobisisobutyronitrile (AIBN).

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

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

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

[0042] Furthermore, the step S3 specifically includes: adding the porogen and the initiator to the hydrophobic monomer to obtain the oil phase solution C.

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

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

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

[0046] Furthermore, in step S3, the initiator includes azobisisobutyronitrile.

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

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

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

[0050] Furthermore, the step S1 specifically includes: adding an emulsifier and a dispersant to an aqueous solvent to obtain an aqueous phase solution A.

[0051] Furthermore, in step S1, the aqueous solvent includes water.

[0052] Preferably, the aqueous solvent is water.

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

[0054] Furthermore, in step S1, the dispersant includes polyvinyl pyrrolidone (PVP).

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

[0056] The dispersant is polyvinyl pyrrolidone.

[0057] The present invention also provides an amphiphilic polymer microsphere material prepared by the above preparation method,

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

[0059] The present invention also provides an amphiphilic polymer microsphere material prepared by the preparation method or the use of the amphiphilic polymer microsphere material in separation, purification and analytical testing.

[0060] Furthermore, the amphiphilic polymer microsphere material with a diameter less than 5 μm can be used as a filler in an analytical chromatography column;

[0061] Amphiphilic polymer microsphere materials with a diameter of 3 to 10 μm can be used for solid phase microextraction or on-line solid phase extraction;

[0062] Amphiphilic polymer microsphere materials with a diameter of more than 10 μm can be used for separation and purification in the biomedical field.

[0063] 3. Beneficial effects

[0064] Compared with the prior art, the technical solution provided by the present invention has the following beneficial effects:

[0065] (1) The invention provides a controllable preparation method for small-particle amphiphilic polymer microsphere materials. In the first stage of the polymerization reaction, the particle size of the emulsion droplets in the reaction system is regulated by high-speed shearing, and the stability of the droplets is controlled by the first stage polymerization. Then, the second stage of the polymerization reaction is performed to prepare a small-particle amphiphilic polymer microsphere material with better particle size uniformity. Specifically, in the preparation process of small-particle amphiphilic polymer microspheres, an innovative method of introducing high-speed shear emulsification is used. For example, high-speed shear emulsification can be achieved by a high-speed shearing device such as a high-speed shearing mixer. In the first stage of the polymerization reaction, the evolution of the emulsion droplets is strictly controlled by shearing time and rotation speed, which is the core element of the invention. The evolution includes the following four stages:

[0066] ① Transition stage: At the beginning of high-speed shearing, the droplet breakage rate is greater than the coagulation rate, and the droplet / polymer size decreases; ② Quasi-steady-state stage: As shearing and monomer polymerization proceed, the droplet breakage rate gradually transitions to the equivalent coagulation rate, and the droplet / polymer is in a dynamic equilibrium stage with unchanged size; ③ Growth stage: The droplet viscosity increases, resulting in a coagulation rate greater than the breakage rate, the droplet / polymer size increases, and the size distribution becomes wider; ④ Constant stage: At the end, the droplet breakage and coagulation stop, and the emulsion will be completely transformed into a solid-liquid suspension with a constant particle size; wherein, the polymerization reaction of the monomer during the first stage polymerization reaction controls the stability of the droplets, and finally the solid-liquid suspension with a constant particle size can obtain small-particle-size amphiphilic polymer microspheres through the second stage polymerization reaction. Compared with the prior art, the method of preparing and regulating small-particle-size monodisperse amphiphilic polymer microspheres of the present invention can effectively solve the problems and deficiencies of the existing preparation technology of amphiphilic polymer microspheres, such as the difficulty in particle size control.

[0067] (2) In the controllable preparation method of small-particle amphiphilic polymer microspheres provided by the present invention, when preparing small-particle amphiphilic polymer microspheres, the molding process of the polymer microspheres can be controlled by regulating the speed and time of high-speed shear 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 within a small particle size range and the operation process is cumbersome. The method of preparing small-particle monodisperse amphiphilic polymer microspheres of the present invention is simple to operate, easier to implement, and the particle size range of the microspheres is controllable, the uniformity is good, and it also has good stability.

[0068] (3) In the preparation method of the amphiphilic polymer microsphere material provided by the present invention, the oil phase solution containing the hydrophilic monomer and the aqueous phase solution are first mixed, and then the oil phase solution containing the hydrophobic monomer is added, and the block chain copolymer is generated between the hydrophilic monomer and the hydrophobic monomer, and then high-speed shearing is performed, and the chains of the hydrophilic monomer and the hydrophobic monomer are mixed again, thereby generating amphiphilic polymer microspheres with more uniform hydrophilic and hydrophobic monomers; moreover, in the first heating treatment, the reaction temperature is 70-75°C, and the reaction rate is moderate; after the hydrophobic monomer is added and the temperature is raised to 76-80°C, the reaction rate is increased; moreover, the high-speed shearing process is an exothermic process, and the reaction solution can be heated during the shearing process, and the polymerization reaction rate of the monomer is faster, which can further improve the synthesis efficiency of the amphiphilic polymer microsphere material, simplify the preparation operation process, and improve the yield.

[0069] (4) Compared with existing amphiphilic polymer microspheres, the amphiphilic polymer microsphere material provided by the present invention has a more uniform distribution of hydrophilic and hydrophobic functional groups on its surface. The preparation process is simple and fast, which can reduce the R&D and production costs of the microspheres, making them better applicable in the fields of chromatographic separation and analytical testing. BRIEF DESCRIPTION OF THE DRAWINGS

[0070] Figure 1 This is an electron micrograph of the amphiphilic polymer microsphere product prepared in Example 1 of the present invention.

[0071] Figure 2 This is an electron micrograph of the amphiphilic polymer microsphere product prepared in the experiment No. 1 in Example 2 of the present invention.

[0072] Figure 3 This is an electron micrograph of the amphiphilic polymer microsphere product prepared in Comparative Example 4 of the present invention.

[0073] Figure 4 This is an electron microscope image of the product prepared in Comparative Example 6 of the present invention.

[0074] Figure 5 This is an electron microscope image of the product prepared in Comparative Example 8 of the present invention.

[0075] Figure 6 This is a diagram of the separation of fructose and sucrose by a chromatographic column made of amphiphilic polymer microspheres prepared by the experiment No. 1 in Example 2 in Application Example 2 of the present invention. DETAILED DESCRIPTION

[0076] The present disclosure may be more easily understood by reference to the following description in conjunction with examples, all of which constitute a part of the present disclosure. It should be understood that the present disclosure is not limited to the specific products, methods, conditions or parameters described and / or illustrated herein. Further, the terms used herein are only used for the purpose of describing specific embodiments by way of example and are not intended to be limiting unless otherwise indicated.

[0077] It should also be understood that, for the sake of clarity, certain features of the present disclosure may be described herein in the context of separate embodiments, but may also be provided in combination with each other in a single embodiment. That is, unless clearly incompatible or specifically not included, each separate embodiment is considered to be combinable with any other embodiment, and the combination is considered to represent another different embodiment. Conversely, for the sake of simplicity, the various features of the present disclosure described in the context of a single embodiment may also be provided individually or in any sub-combination. Finally, although a particular embodiment may be described as part of a series of steps or part of a more general structure, each step or substructure itself may also be considered to be an independent embodiment.

[0078] Unless otherwise indicated, it should be understood that each individual element in a list and each combination of individual elements in the list will be interpreted as a different embodiment. For example, a list of embodiments represented as "A, B, or C" should be interpreted to include embodiments "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 of the articles "a," "an," and "the" also include the corresponding plural references, and a reference to a specific value includes at least that specific value unless the context clearly indicates otherwise. Thus, for example, a reference to "a substance" is a reference to at least one of that substance and equivalents thereof.

[0080] When items are described by using the conjunction terms "... and / or...," etc., the description should be understood to include any one of the associated listed items and all combinations of one or more thereof.

[0081] In general, the use of the term "about" indicates an approximate value that can vary depending on the desired properties obtained by the disclosed subject matter, and will be interpreted in a context-dependent manner based on function. Therefore, one of ordinary skill in the art will be able to interpret a certain degree of difference on a case-by-case basis. In some cases, the number of significant figures used when expressing a particular value can be a representative technique for determining the difference allowed by the term "about". In other cases, a gradient in a range of values ​​can be used to determine the range of differences allowed by the term "about". Further, all ranges in this disclosure are inclusive and combinable, and reference to a value in a range includes each value within that 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 invention belongs; the terms used herein and / or include any and all combinations of one or more of the associated listed items.

[0083] In the following examples, if no specific conditions are specified, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used, if no manufacturer is specified, are all conventional products that can be purchased commercially.

[0084] The present invention is further described below in conjunction with specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art. The essential characteristics and remarkable effects of the present invention can be reflected from the following examples, and the described embodiments are part of the embodiments of the present invention, rather than all the embodiments, and therefore, they do not limit the present invention in any way, and those skilled in the art make some non-essential improvements and adjustments based on the content of the present invention, which all belong to the protection scope of the present invention.

[0085] Example 1

[0086] (1) Add 4 g of emulsifier SDS and 4 g of dispersant PVP to 400 g of water to obtain aqueous solution A;

[0087] (2) adding 20 g of porogen toluene and 0.5 g of initiator AIBN to 20 g of hydrophilic monomer NVP to obtain oil phase solution B;

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

[0089] (4) Add the oil phase solution B to the water phase solution A, stir evenly at room temperature, then heat to 75°C, continue for 30 minutes, then add the oil phase solution C, heat to 80°C, and continue for another 30 minutes;

[0090] (5) using a high shear mixer to perform high-speed shear emulsification on the reaction solution, the high-speed shear emulsification time is 300 s, and the rotation speed is 15000 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 monodispersity of the amphiphilic polymer microspheres is good. The amphiphilic polymer microspheres prepared in this embodiment have an N content of 1.7% through elemental analysis, a contact angle of 79° through static contact angle analysis, and a particle size variation coefficient of 5%.

[0093] Example 2

[0094] Other conditions were the same 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 Effect of different high-speed shear emulsification conditions on synthetic materials

[0096]

[0097] The particle size of the experimental product No. 1 in this embodiment is about 2 μm, and the monodispersity performance is good. The specific morphology is as follows Figure 2 shown.

[0098] Combined with 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 cannot improve the monodispersity of the product. Combined with Comparative Example 4, when the shear emulsification speed is low and the shear time is short, the shear effect is poor. Although amphiphilic polymer microspheres can be obtained, the product has obvious agglomeration phenomenon, and the morphology of the product is as follows: Figure 3 shown.

[0099] Example 3

[0100] The other conditions were the same as those in Example 1. The effects of different first and second heating treatment conditions on the material properties were tested. The experimental results are shown in Table 2.

[0101] Table 2 Effect of different first and second heating treatment conditions on the synthetic materials

[0102]

[0103]

[0104] Combined with Table 2, it can be seen from this embodiment and the comparative example that, combined with comparative example 5, when the first temperature rise is low, the prepolymerization degree of the hydrophilic monomer is insufficient, the product is obviously hydrophobic and not spherical. Combined with comparative example 6, when the first and second temperature rises are both high, the polymerization reaction implodes, the product is obviously hydrophobic, and the morphology of the product is as follows: Figure 4 shown.

[0105] Example 4

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

[0107] Table 3 Effect of different addition ratios of water, hydrophilic monomer and hydrophobic monomer on the synthesis of materials

[0108]

[0109] Combined with Table 3, it can be seen from this embodiment and the comparative example that in the addition ratio of the water phase and the hydrophilic and hydrophobic monomers, when the amount of the hydrophobic monomer increases, the hydrophobicity of the microsphere surface is enhanced, and the microsphere particle size will increase; when the proportion of water is reduced, the concentration of organic matter in the system increases, and after prepolymerization and high-speed shearing, the microsphere particle size will decrease; combined with comparative example 8, further reducing the proportion of water will cause the system to be disordered, and the microspheres cannot be obtained. The product is fragmented, and the morphology of the product is as follows Figure 5 shown.

[0110] Comparative Example 9

[0111] The other conditions were the same as those in Example 1, except that in step (4), the oil phase solution C was first added to the water phase solution A, stirred evenly at room temperature, and then heated to 75° C. for 30 minutes, after which the oil phase solution B was added, and the temperature was raised to 85° C. for another 30 minutes.

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

[0113] Comparative Example 10

[0114] The other conditions are the same as those in Example 1, except that in step (4), the oil phase solution C and the oil phase solution B are added to the water phase solution A simultaneously, stirred evenly at room temperature, and then heated to 75° C. for 30 minutes, and then heated to 85° C. for another 30 minutes.

[0115] Finally, the 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 functionalized, comprising the following steps:

[0118] 1. Introduction of chlorine groups by Friedel-Crafts reaction: 200 g of the above polymer microsphere material was uniformly mixed with 100 mL of chloromethyl ether in a three-necked flask. After two hours, 120 g of anhydrous FeCl3 was added. Then, 50 mL of sulfuric acid was added dropwise to the reaction system. After one hour of reaction, the temperature was raised to 47.5°C and the reaction was continued at this temperature for 24 hours.

[0119] 2. Amination reaction of polymer chlorine-based microspheres: Add 5g of chlorine-based microspheres and 200mL of acetone to a three-necked round-bottom flask (equipped with a stirring rod and a reflux condenser), ultrasonically disperse for 3 minutes, then add 200ml of piperazine acetone solution to the flask, maintain the temperature of the reaction system at 70°C, and control the speed at 100r / min. Reflux the suspension for 12 hours, and after cooling, rinse the product with anhydrous ethanol 5 times until the pH of the washing solution is about 6-7 to obtain slightly yellow microspheres.

[0120] The adsorption experiment was conducted using the microspheres with piperazine modified on the surface. The experimental results are shown in Table 4, where the adsorption experiment conditions are as follows: 15 mL of a mixed standard solution containing 21 antibiotics (500 ng / L each) was added with equal amounts of the microspheres modified with piperazine in this application example and commercial microspheres for adsorption experiments. Combined with Table 4, it can be seen that the microspheres have a better enrichment capacity than commercial microspheres (Oasis WAX adsorption material from Waters, USA), and can achieve simultaneous and efficient extraction of compounds with different physical and chemical properties.

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

[0122]

[0123] In this application example, the microspheres with piperazine modified on the surface were used as coatings for solid phase microextraction to conduct solid phase microextraction experiments on 21 antibiotic pollutant solutions in water. The solid phase microextraction and liquid chromatography-tandem mass spectrometry method for 21 antibiotic pollutants established based on the microspheres modified with piperazine in this application example (wherein the liquid chromatography column used was Waters' ACQUITY UPLC BEH C18 (1.7μm, 2.1×100mm), the injection volume was 10μL, the flow rate was 0.5mL / min, the column temperature was 25°C, and the mobile phase was 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 antibiotic pollutants

[0125]

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

[0127] Application Example 2

[0128] The surface of the microsphere product obtained in the experiment No. 1 in Example 2 was modified with diethylamine functional groups and then filled into a chromatographic column to perform chromatographic analysis experiments on sucrose and fructose. The separation degree was good. The specific chromatographic separation conditions are as follows: Figure 6 As shown in Table 6, Figure 6 The peak at the retention time of 3.703 min 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 of sucrose and fructose using the chromatographic column filled in this application example

[0130]

[0131]

Claims

1. A controllable preparation method of small-size amphiphilic polymer microsphere material, characterized in that: The following steps are involved: S1. Prepare an aqueous 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. The oil phase solution B and the aqueous phase solution A are mixed and subjected to a first heating treatment; After the first heating treatment is completed, the mixture is mixed with the oil phase solution C and subjected to a second heating treatment to obtain a reaction solution; S5. The reaction solution obtained in step S4 is sheared and emulsified to obtain an emulsion; S6. subjecting the emulsion obtained in step S5 to a second stage polymerization reaction to obtain an amphiphilic polymer microsphere material; Wherein, in step S5, the shear emulsification time is 10 to 300 s, and the rotation speed is 5000 to 30000 rpm.

2. The controllable preparation method of small-size amphiphilic polymer microsphere material according to claim 1, characterized in that: In step S4, the conditions of the first temperature treatment include heating to 70-75° C. for 10-30 minutes; The conditions of the second temperature treatment include heating to 76-80° C. for 10-30 minutes.

3. The controllable preparation method of small-size amphiphilic polymer microsphere material according to any one of claims 1 to 2, characterized in that: 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.

4. The controllable preparation method of small-size amphiphilic polymer microsphere material according to claim 3, characterized in that: In step S6, the temperature of the second stage polymerization reaction is 81-90°C and the time is 1-5 hours.

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

6. The controllable preparation method of small-size amphiphilic polymer microsphere material according to claim 5, characterized in that: In step S3, the amount of the porogen used is 0.2 to 2 times the amount of the hydrophobic monomer used, calculated by mass; In step S3, the amount of the initiator used is 1% to 2% of the amount of the hydrophobic monomer used, calculated by mass.

7. The controllable preparation method of small-size amphiphilic polymer microsphere material according to claim 6, characterized in that: In step S1, the amount of the emulsifier used is 1% to 5% of the amount of the aqueous solvent used, calculated by mass; In step S1, the amount of the dispersant used is 1% to 5% of the amount of the aqueous solvent used, calculated by mass.

8. The controllable preparation method of small-size amphiphilic polymer microsphere material according to claim 7, characterized in that: In step S1, the emulsifier includes sodium lauryl sulfate; In step S1, the dispersant includes polyvinyl pyrrolidone; In step S1, the aqueous solvent includes water; In step S2, the hydrophilic monomer includes one, two or more of N-vinyl pyrrolidone, glycidyl methacrylate, and methyl acrylate; In step S2, the porogen includes one or both of toluene and xylene; In step S2, the initiator includes azobisisobutyronitrile; In step S3, the hydrophobic monomer includes one, two or more of styrene, divinylbenzene and 4-chloromethylstyrene; In step S3, the porogen includes one or both of toluene and xylene; In step S3, the initiator includes azobisisobutyronitrile.

9. A small-size amphiphilic polymer microsphere material prepared by the controllable preparation method of small-size amphiphilic polymer microsphere material according to any one of claims 1 to 8, characterized in that: The particle size of the amphiphilic polymer microsphere material is 0.2-20 μm.

10. Use of the amphiphilic polymer microsphere material as claimed in claim 9 in separation, purification and analytical testing.

Images