CN111574652B - Monodisperse carboxyl functional polymer microsphere based on redox reaction initiation, and preparation method and application thereof - Google Patents
Monodisperse carboxyl functional polymer microsphere based on redox reaction initiation, and preparation method and application thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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Abstract
The invention belongs to the field of polymer microspheres, and particularly relates to a monodisperse carboxyl functional polymer microsphere based on redox reaction initiation, and a preparation method and application thereof. The preparation method comprises the following steps: and carrying out polymerization reaction on a system consisting of a carboxyl functional monomer, a second monomer, a solvent and an initiator to obtain the monodisperse carboxyl functional polymer microsphere, wherein the initiator comprises an oxidant and a reducing agent. The preparation method provided by the invention uses a redox initiation system with lower activation energy, and has the advantages of high reaction rate, lower energy consumption and mild conditions in the polymerization process; the process is simple to operate, avoids the influence of a surfactant in the post-treatment process of the microsphere emulsion, and accords with the concepts of green environmental protection and sustainable development; the material is easy to obtain, the cost is low, the microsphere yield is high, and the method is suitable for large-scale popularization; meanwhile, the particle size of the polymer microsphere can be regulated, and the obtained monodisperse carboxyl functional polymer microsphere can meet the requirements of the fields of biomedicine, cytology and the like.
Description
Technical Field
The invention belongs to the field of polymer microspheres, and particularly relates to a monodisperse carboxyl functional polymer microsphere based on redox reaction initiation, and a preparation method and application thereof.
Background
The functional polymer microsphere particles with reactive groups on the surface have wide application value in the fields of printing ink, coating, chromatography, protein synthesis, biological analysis and the like. Carboxyl functionalized polymer microspheres are an important group, and the combination of carboxyl groups into polymer microspheres has several advantages: (1) the carboxyl can be combined with various metal ions or groups through electrostatic interaction, which is very important for preparing polymer micro-nano particle composite materials with unusual catalytic, optical and mechanical properties; (2) the derivatization of carboxyl can be easily realized by using a water-soluble coupling agent, and then functionalized microsphere particles for biomedical and diagnostic applications can be produced; (3) when the microsphere particles contain a large number of carboxyl groups, the solubility and the swelling property of the microsphere particles can be changed along with the change of pH in an aqueous environment, and the microsphere particles show pH responsiveness, so the microsphere particles also have high research and application values in the fields of early disease diagnosis, drug delivery, biotechnology, biosensing and the like.
In order to prepare carboxyl-functional Polymer microspheres with uniform particle size, several polymerization methods have been developed, mainly (two-step) dispersion polymerization (Song J S, et al macromolecules,2006,39(17): 5729. times. 5737; Yang W L, et al journal of Polymer Science Part A: Polymer Chemistry,2001,39(4): 555. times. 561; Nippon flame, Liyang, peri Art Peak. paint industry, 2008,38(11): 4-7; Lee S G, et al macromolecules Research,2016,24(8): 675. times. 683), traditional emulsion polymerization (Okubo M, et al., Colloid & Polymer Science,1987,265(3): 246. times. 249; Wang P H, Colloid & Polymer Science,2001, 1: 98-103; Wang P H, Wang P88. times. et al., 279, journal of emulsion polymerization, 2003, Australin et al, 1757, Australin et al, Australin emulsion polymerization (7), 2007,23(10): 5367-5376; plum, Gongxing, plastics industry, 2016,44(1): 129-; coen E M, et al macromolecules,1996,29(15): 5128-; vorwerg L, et al, macromolecules,2000,33(18): 6693-6703; slawinski M, et al, journal of Applied Polymer Science,2000,76(7): 1186-1196; reynhout X E E, et al, journal of Polymer Science Part A, Polymer Chemistry,2003,41(19): 2985-; kang K, et al, European Polymer Journal,2005,41(3): 439-; duangpolarn Polpanich, et al, colloid & Polymer Science,2005,284(2):183-191), and the like. However, the above polymerization methods all involve the use of additives such as dispersing agents, emulsion agents or emulsion aids, which reduce the properties of the final product and increase the cost of the purification process of the polymer microspheres, thus easily polluting the environment.
The soap-free emulsion polymerization method can overcome the problems, can prepare the polymer microspheres with clean surfaces and uniform particle sizes, and broadens the application of the polymer microspheres in the fields of clinical medicine, cytology, chromatographic separation and the like with higher requirements on surface cleanliness and particle size uniformity. However, in the soap-free emulsion polymerization for preparing functional polymer microspheres, a thermal initiator is usually used to initiate the polymerization of olefin, and the polymerization needs to be carried out at a higher temperature, which results in higher energy consumption.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of monodisperse carboxyl functional polymer microspheres based on redox reaction initiation, wherein a system consisting of a carboxyl functional monomer, a second monomer, a solvent and an initiator is subjected to polymerization reaction to obtain the monodisperse carboxyl functional polymer microspheres, and the initiator comprises an oxidant and a reducing agent.
According to an embodiment of the invention, the preparation method comprises the steps of:
(1) dissolving a carboxyl functional monomer in a solvent, adding a second monomer into the solvent, and uniformly dispersing to form a monomer system;
(2) respectively adding an oxidant and a reducing agent into the monomer system obtained in the step (1) at a specified temperature to carry out polymerization reaction;
(3) and (3) carrying out post-treatment on the reaction emulsion obtained in the step (2) to obtain the monodisperse carboxyl functional polymer microsphere.
According to an embodiment of the present invention, the sum of the amounts of the carboxyl functional monomer and the second monomer is the total amount of monomers, and the mass fraction of the total amount of monomers relative to the solvent in the monomer system may be 1 to 20 wt%, for example 2 to 10 wt%, such as 4.3 wt%, 4.4 wt%, 7.2 wt%;
the carboxyl functional monomer may be 1 to 50 mol%, for example 3 to 30 mol%, such as 3.9 mol%, 10 mol%, 16.6 mol%, 20 mol% of the total amount of the monomers;
the amount of the oxidant may be 1 to 20 wt%, for example 1 to 5 wt%, such as 1.5 wt%, 2 wt%, 3 wt% of the total amount of the monomers;
the molar ratio of the oxidizing agent to the reducing agent may be (0.5 to 10):1, for example (0.5 to 5): 1.
According to an embodiment of the present invention, the carboxyl functional monomer may be one or more of itaconic acid, crotonic acid, acrylic acid, methacrylic acid, maleic acid, and aconitic acid, preferably one or more of itaconic acid, acrylic acid, and methacrylic acid.
According to an embodiment of the present invention, the second monomer may be a styrenic monomer and/or an acrylate monomer.
According to an embodiment of the present invention, the styrenic monomer may be one or more of styrene, 3-bromostyrene, 4-bromostyrene, 3-chlorostyrene, 4-methylstyrene, 4-chloromethylstyrene, 2, 4-dimethylstyrene, α -methylstyrene, β -methylstyrene, α -ethylstyrene, preferably one or more of styrene, α -methylstyrene, 4-chloromethylstyrene.
According to an embodiment of the present invention, the acrylate monomer may be any one or more of methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl acrylate, glycidyl methacrylate, preferably one or more of methyl methacrylate, n-butyl acrylate, glycidyl methacrylate.
According to an embodiment of the present invention, when the second monomer includes a styrene-based monomer and an acrylate-based monomer, the molar ratio of the styrene-based monomer to the acrylate-based monomer may be (0.1 to 20):1, for example (0.1 to 10): 1.
According to an embodiment of the present invention, the solvent may be deionized water.
According to an embodiment of the present invention, the oxidizing agent may be any one or more of sodium persulfate, ammonium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, preferably one or more of hydrogen peroxide, sodium persulfate.
According to an embodiment of the present invention, the reducing agent may be one or more of ferrous chloride, cuprous chloride, ferrous sulfate heptahydrate, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium sulfite, sodium sulfite, potassium thiosulfate, ammonium thiosulfate, sodium thiosulfate, ethylenediamine, ascorbic acid, sodium D-isoascorbate, sodium oxalate, potassium oxalate, preferably one or more of ascorbic acid, potassium bisulfite, sodium sulfite.
According to the embodiment of the invention, after the uniform dispersion in the step (1) is completed, the obtained monomer system can be continuously stirred for 10-60 min, such as 30min, under an inert atmosphere, and the stirring can be performed at room temperature; the inert atmosphere may be any one or more of nitrogen, argon, helium.
According to an embodiment of the invention, the specified temperature in step (2) may be from 20 ℃ to 50 ℃, for example from 25 ℃ to 45 ℃, such as 40 ℃;
the polymerization reaction is carried out under stirring, and the stirring speed can be 250-1000 r/min, such as 300-800 r/min, for example 500r/min, 700 r/min.
According to an embodiment of the invention, the time interval between the addition of the oxidizing agent and the addition of the reducing agent in step (2) is less than or equal to 10min, preferably less than or equal to 5 min.
According to an embodiment of the present invention, the polymerization time in step (2) may be 4 to 12 hours, for example 4 to 10 hours, such as 6 hours, 8 hours.
According to an embodiment of the present invention, the polymerization reaction in step (2) may be carried out under an inert atmosphere, which has the above-mentioned definition.
According to an embodiment of the invention, the post-treatment in step (3) comprises one or more of centrifugation, washing, drying;
the detergent used for the washing may be an ethanol/water mixture;
the drying can be vacuum drying, the drying temperature can be 30-50 ℃, for example 40 ℃, and the drying time can be 24-72 hours, for example 48 hours.
According to an embodiment of the invention, the preparation method has a spheronization rate of 60% to 90%, such as 63.3%, 71.1%, 73.1%, 78.9%, 84.0%, 86.3%, 88.3%.
The invention also provides the monodisperse carboxyl functional polymer microsphere obtained by the preparation method, wherein the particle size of the monodisperse carboxyl functional polymer microsphere is 100-800 nm, and the dispersion coefficient is 0.01-0.04.
Furthermore, the invention also provides application of the monodisperse carboxyl functional polymer microsphere in the fields of biomedicine, cytology and the like.
The invention has the beneficial effects that:
the preparation method provided by the invention has the advantages of mild conditions, simple process operation, easily obtained materials, low cost and higher microsphere yield, and is suitable for large-scale popularization. In addition, the initiator used in the invention is a redox initiation system with lower activation energy, the reaction rate is high in the polymerization process, the energy consumption is lower, meanwhile, the influence of a surfactant in the post-treatment process of the microsphere emulsion is avoided, and the green environmental protection and sustainable development concept is met. In addition, the particle size and the particle size distribution of the carboxyl functional polymer microspheres can be controlled by reasonably optimizing different polymerization reaction conditions, and the obtained monodisperse carboxyl functional polymer microspheres can meet the requirements of the fields of biomedicine, cytology and the like.
Drawings
FIG. 1 is a scanning electron microscope image of monodisperse carboxyl-functionalized polystyrene microspheres prepared in example 1.
FIG. 2 is a scanning electron microscope image of the monodisperse carboxyl-functionalized polystyrene microsphere prepared in example 2.
FIG. 3 is a scanning electron microscope image of the monodisperse carboxyl functionalized polystyrene microsphere prepared in example 3.
FIG. 4 is a scanning electron microscope image of the monodisperse carboxyl-functionalized polystyrene microsphere prepared in example 4.
FIG. 5 is a scanning electron microscope image of monodisperse carboxyl functionalized polystyrene microspheres prepared in example 5.
FIG. 6 is a scanning electron microscope image of monodisperse carboxyl-functionalized polymethyl methacrylate microspheres prepared in example 6.
FIG. 7 is a scanning electron microscope image of monodisperse carboxyl-functionalized poly (styrene-methyl methacrylate) microspheres prepared in example 7.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Firstly, injecting 46mL of deionized water into a 100mL single-mouth reaction bottle, then adding 244mg of itaconic acid for full dissolution, further adding 1756mg of styrene, performing ultrasonic treatment at room temperature for 20min until the mixture is uniformly dispersed, then stirring the mixture for 30min at the speed of 700r/min under the protection of nitrogen, rapidly heating the mixture to 40 ℃, after the temperature is constant, adding 2mL of initiator aqueous solution containing 60mg of hydrogen peroxide and 311mg of ascorbic acid into the mixture at one time by using an injector, and reacting the mixture at constant temperature for 6h, wherein the whole reaction process is under the protection of nitrogen. And naturally cooling to room temperature after the reaction is finished, repeatedly cleaning the microspheres by using an ethanol/water mixture, centrifuging by using a high-speed centrifuge, removing supernatant, and drying the precipitate in a vacuum oven at 40 ℃ for 48 hours to obtain the monodisperse carboxyl functionalized polystyrene microspheres. The prepared monodisperse carboxyl functionalized polystyrene microsphere has the balling rate of 84.0 percent, the particle size (measured by a JSM-6700F type scanning electron microscope) of 415nm and the dispersion coefficient of 0.028. FIG. 1 is a scanning electron microscope image of monodisperse carboxyl-functionalized polystyrene microspheres prepared in this example.
Example 2
Firstly, injecting 46mL of deionized water into a 100mL single-mouth reaction bottle, then adding 476mg of itaconic acid for full dissolution, then further adding 1524mg of styrene, performing ultrasonic treatment at room temperature for 20min until the mixture is uniformly dispersed, then stirring the mixture for 30min at the speed of 700r/min under the protection of nitrogen, rapidly heating the mixture to 40 ℃, after the temperature is constant, adding 2mL of initiator aqueous solution containing 40mg of hydrogen peroxide and 207mg of ascorbic acid into the mixture at one time by using an injector, and reacting the mixture at constant temperature for 6h, wherein the whole reaction process is under the protection of nitrogen. And naturally cooling to room temperature after the reaction is finished, repeatedly cleaning the microspheres by using an ethanol/water mixture, centrifuging by using a high-speed centrifuge, removing supernatant, and drying the precipitate in a vacuum oven at 40 ℃ for 48 hours to obtain the monodisperse carboxyl functionalized polystyrene microspheres. The prepared monodisperse carboxyl functionalized polystyrene microsphere has the balling rate of 71.1 percent, the particle size (measured by a JSM-6700F type scanning electron microscope) of 372nm and the dispersion coefficient of 0.019. FIG. 2 is a scanning electron microscope image of the monodisperse carboxyl-functionalized polystyrene microsphere prepared in this example.
Example 3
Firstly, injecting 46mL of deionized water into a 100mL single-mouth reaction bottle, then adding 476mg of itaconic acid for full dissolution, then further adding 1524mg of styrene, performing ultrasonic treatment at room temperature for 20min until the mixture is uniformly dispersed, then stirring the mixture for 30min at the speed of 700r/min under the protection of nitrogen, rapidly heating the mixture to 25 ℃, after the temperature is constant, adding 2mL of initiator aqueous solution containing 60mg of hydrogen peroxide and 311mg of ascorbic acid into the mixture at one time by using an injector, and reacting the mixture at constant temperature for 6h, wherein the whole reaction process is under the protection of nitrogen. And naturally cooling to room temperature after the reaction is finished, repeatedly cleaning the microspheres by using an ethanol/water mixture, centrifuging by using a high-speed centrifuge, removing supernatant, and drying the precipitate in a vacuum oven at 40 ℃ for 48 hours to obtain the monodisperse carboxyl functionalized polystyrene microspheres. The prepared monodisperse carboxyl functionalized polystyrene microsphere has the balling rate of 63.3 percent, the particle size (measured by a JSM-6700F type scanning electron microscope) of 210nm and the dispersion coefficient of 0.033. FIG. 3 is a scanning electron microscope image of the monodisperse carboxyl-functionalized polystyrene microsphere prepared in this example.
Example 4
Firstly, injecting 46mL of deionized water into a 100mL single-mouth reaction bottle, then adding 143mg of acrylic acid for full dissolution, then further adding 1867mg of styrene, performing ultrasonic treatment at room temperature for 20min until uniform dispersion is achieved, then stirring at the speed of 500r/min for 30min under the protection of nitrogen, rapidly heating to 40 ℃, after the temperature is constant, adding 2mL of initiator aqueous solutions containing 60mg of hydrogen peroxide and 311mg of ascorbic acid into the reaction bottle at one time by using an injector, and reacting at constant temperature for 6h, wherein the whole reaction process is under the protection of nitrogen. And naturally cooling to room temperature after the reaction is finished, repeatedly cleaning the microspheres by using an ethanol/water mixture, centrifuging by using a high-speed centrifuge, removing supernatant, and drying the precipitate in a vacuum oven at 40 ℃ for 48 hours to obtain the monodisperse carboxyl functionalized polystyrene microspheres. The prepared monodisperse carboxyl functionalized polystyrene microsphere has the balling rate of 78.9 percent, the particle diameter (measured by a JSM-6700F type scanning electron microscope) of 671nm and the dispersion coefficient of 0.014. FIG. 4 is a scanning electron microscope image of the monodisperse carboxyl-functionalized polystyrene microsphere prepared in this example.
Example 5
Firstly, injecting 46mL of deionized water into a 100mL single-mouth reaction bottle, then adding 343mg of methacrylic acid for full dissolution, further adding 1657mg of styrene, performing ultrasonic treatment at room temperature for 20min until the styrene is uniformly dispersed, then stirring at the speed of 500r/min for 30min under the protection of nitrogen, rapidly heating to 40 ℃, after the temperature is constant, adding 2mL of initiator aqueous solution containing 60mg of hydrogen peroxide and 311mg of ascorbic acid into the reaction bottle at one time by using an injector, and reacting at constant temperature for 6h, wherein the whole reaction process is under the protection of nitrogen. And naturally cooling to room temperature after the reaction is finished, repeatedly cleaning the microspheres by using an ethanol/water mixture, centrifuging by using a high-speed centrifuge, removing supernatant, and drying the precipitate in a vacuum oven at 40 ℃ for 48 hours to obtain the monodisperse carboxyl functionalized polystyrene microspheres. The prepared monodisperse carboxyl functionalized polystyrene microsphere has the balling rate of 88.3 percent, the particle size (measured by a JSM-6700F type scanning electron microscope) of 687nm and the dispersion coefficient of 0.038. FIG. 5 is a scanning electron microscope image of the monodisperse carboxyl-functionalized polystyrene microsphere prepared in this example.
Example 6
Firstly, injecting 46mL of deionized water into a 100mL single-mouth reaction bottle, then adding 100mg of itaconic acid for full dissolution, further adding 1900mg of methyl methacrylate, performing ultrasonic treatment at room temperature for 20min until the methyl methacrylate is uniformly dispersed, then stirring at the speed of 500r/min for 30min under the protection of nitrogen, rapidly heating to 40 ℃, after the temperature is constant, adding 2mL of initiator aqueous solutions containing 30mg of sodium persulfate and 21mg of sodium bisulfite by using an injector at one time, and reacting at constant temperature for 10h, wherein the whole reaction process is under the protection of nitrogen. And naturally cooling to room temperature after the reaction is finished, repeatedly cleaning the microspheres by using an ethanol/water mixture, centrifuging by using a high-speed centrifuge, removing supernatant, and drying the precipitate in a vacuum oven at 40 ℃ for 48 hours to obtain the monodisperse carboxyl functionalized polystyrene microspheres. The prepared monodisperse carboxyl functionalized polystyrene microsphere has the balling rate of 73.1 percent, the particle size (measured by a JSM-6700F type scanning electron microscope) of 244nm and the dispersion coefficient of 0.038. FIG. 6 is a scanning electron microscope image of monodisperse carboxyl-functionalized polymethyl methacrylate microspheres prepared in this example.
Example 7
Firstly, injecting 46mL of deionized water into a 100mL single-mouth reaction bottle, then adding 667mg of itaconic acid for full dissolution, further adding 2333mg of styrene and 333mg of methyl methacrylate, performing ultrasonic treatment at room temperature for 20min until uniform dispersion is achieved, then stirring at the speed of 700r/min for 30min under the protection of nitrogen, rapidly heating to 45 ℃, after the temperature is constant, adding 2mL of initiator aqueous solutions containing 67mg of sodium persulfate and 47mg of sodium bisulfite once by using an injector, and reacting at constant temperature for 8h, wherein the whole reaction process is under the protection of nitrogen. And naturally cooling to room temperature after the reaction is finished, repeatedly cleaning the microspheres by using an ethanol/water mixture, centrifuging by using a high-speed centrifuge, removing supernatant, and drying the precipitate in a vacuum oven at 40 ℃ for 48 hours to obtain the monodisperse carboxyl functionalized polystyrene microspheres. The prepared monodisperse carboxyl functionalized polystyrene microsphere has the balling rate of 86.3 percent, the particle diameter (measured by a JSM-6700F type scanning electron microscope) of 197nm and the dispersion coefficient of 0.014. FIG. 7 is a scanning electron microscope image of monodisperse carboxyl-functionalized poly (styrene-methyl methacrylate) microspheres prepared in this example.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of monodisperse carboxyl functional polymer microspheres based on redox reaction initiation is characterized by comprising the following steps:
(1) dissolving a carboxyl functional monomer in a solvent, adding a second monomer into the solvent, and uniformly dispersing to form a monomer system;
(2) respectively adding an oxidant and a reducing agent into the monomer system obtained in the step (1) at a specified temperature to carry out polymerization reaction;
(3) carrying out post-treatment on the reaction emulsion obtained in the step (2) to obtain the monodisperse carboxyl functional polymer microspheres;
the sum of the using amounts of the carboxyl functional monomer and the second monomer is the total amount of the monomers, in the monomer system, the mass fraction of the total amount of the monomers relative to the solvent is 1-20 wt%, the using amount of the carboxyl functional monomer is 1-50 mol% of the total amount of the monomers, the using amount of the oxidant is 1-20 wt% of the total amount of the monomers, and the molar ratio of the oxidant to the reducing agent is (0.5-10): 1;
the carboxyl functional monomer is one or more of itaconic acid, crotonic acid, acrylic acid, methacrylic acid, maleic acid and aconitic acid; the oxidant is any one or more of sodium persulfate, ammonium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl hydroperoxide and cumene hydroperoxide;
the second monomer is a styrene monomer and/or an acrylate monomer;
the reducing agent is one or more of ferrous chloride, cuprous chloride, ferrous sulfate heptahydrate, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium sulfite, sodium sulfite, potassium thiosulfate, ammonium thiosulfate, sodium thiosulfate, ethylenediamine, ascorbic acid, D-sodium erythorbate, sodium oxalate and potassium oxalate.
2. The method according to claim 1, wherein the styrene monomer is one or more selected from styrene, 3-bromostyrene, 4-bromostyrene, 3-chlorostyrene, 4-methylstyrene, 4-chloromethylstyrene, 2, 4-dimethylstyrene, α -methylstyrene, β -methylstyrene, and α -ethylstyrene.
3. The method according to claim 1, wherein the acrylic monomer is any one or more of methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl acrylate, and glycidyl methacrylate.
4. The preparation method according to claim 2, wherein when the second monomer comprises a styrene monomer and an acrylate monomer, the molar ratio of the styrene monomer to the acrylate monomer is (0.1-20): 1.
5. The method of any one of claims 1-4, wherein the polymerization temperature is 20 ℃ to 50 ℃.
6. The method according to any one of claims 1 to 4, wherein the polymerization is carried out under stirring at a speed of 250 to 1000 r/min; the polymerization reaction time is 4-12 h.
7. The method of any one of claims 1-4, wherein the method has a balling rate of 60% to 90%.
8. The monodisperse carboxyl functional polymer microsphere obtained by the preparation method of any one of claims 1 to 4, which has a particle size of 100 to 800nm and a dispersion coefficient of 0.01 to 0.04.
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