Hydrophilic-hydrophobic heterogeneous folded polymer microsphere as well as preparation method and application thereof

Abstract

The invention discloses a hydrophilic-hydrophobic heterogeneous folded polymer microsphere as well as a preparation method and application thereof. The polymer microspheres are prepared from an oil-phase solution and a water-phase solution based on a suspension-interfacial polymerization method, the oil-phase solution is prepared from a hydrophobic monomer, a swelling solvent and an initiator, and the mass-volume ratio of the hydrophobic monomer to the swelling solvent to the initiator is (3-5) mL: (1-4) mL: (0.05-0.2) g; the water-phase solution is prepared from the following raw materials: a water-soluble monomer, a stabilizer and a solvent in a mass-volume ratio of (0.5-2) mL: (1-2) g: (75-100) mL. The polymer microspheres prepared by the method have good particle size uniformity, the surfaces of the microspheres are in a wrinkle shape, and the polymer microspheres have large specific surface area and can be applied to the fields of drug carriers, catalytic carriers or biosensors and the like.

Description

Technical Field

[0001] The invention relates to the technical field of biomaterials, and in particular to a hydrophilic-hydrophobic heterogeneous wrinkled polymer microsphere and a preparation method and application thereof. Background Art

[0002] As a typical soft matter material, polymer microspheres are widely used in catalysis, drug delivery, biosensors, microreactors, chemical separation, and coating materials due to their unique microscale, diffusivity, permeability, and modifiability. Heterogeneous polymer microspheres have attracted more and more attention in recent years due to their different compositions and morphological characteristics. The surface morphology of heterogeneous polymer microspheres significantly affects their physical and chemical properties. Usually, the properties such as catalytic performance and efficiency, self-assembly structure, platelet adhesion characteristics, and biochemical reaction degree can be adjusted by regulating the structure, size, and composition, thereby achieving wide application in the fields of biomaterials, pharmacology, and chemical engineering.

[0003] In the related art, the preparation methods of polymer microspheres include polymerization methods (such as emulsion polymerization, suspension polymerization, precipitation polymerization), emulsion-solvent evaporation methods (such as phase separation, interface instability), micro-machining methods (such as soft printing, microfluidics), etc. Usually, in the polymerization system, since the free energy of the droplet interface tends to be minimized, the polymer microspheres prepared by polymerization tend to have a smoother surface. Regarding the problem of how to break through the limitations of the spherical interface to produce polymer microspheres with rough surfaces, although relevant records indicate that the interface can be disturbed by adjusting the droplet interface properties to obtain a rough surface, the uniformity of the polymer microspheres obtained and the texture morphology of the microsphere surface are not ideal, and it is difficult to prepare hydrophilic-hydrophobic heterogeneous wrinkled microspheres.

[0004] Based on this, the present invention proposes a method for preparing polymer microspheres with a hydrophilic-hydrophobic heterogeneous wrinkled structure, and the prepared polymer microspheres have good particle size uniformity. Summary of the invention

[0005] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes a hydrophilic-hydrophobic heterogeneous wrinkled polymer microsphere and its preparation method and application. The present invention uses a suspension-interfacial polymerization method to assemble the hydrophilic monomer in the aqueous solution and the hydrophobic monomer in the oil phase solution into suspended droplets under stirring conditions, and copolymerizes at the interface by temperature control to obtain microspheres with hydrophilic-hydrophobic heterogeneous structures and surface wrinkles. The microsphere preparation method of the present invention is simple, the experimental conditions are easy to control, the post-treatment method is simple and easy, and the obtained polymer microspheres have good particle size uniformity, which can be used for industrial production.

[0006] In a first aspect of the present invention, a hydrophilic-hydrophobic heterogeneous wrinkled polymer microsphere is provided, wherein the raw materials for preparing the microsphere include:

[0007] a) an oil phase solution, wherein the raw materials for preparing the oil phase solution include a hydrophobic monomer, a swelling solvent and an initiator, and the mass volume ratio of the hydrophobic monomer, the swelling solvent and the initiator is 3-5 mL: 1-4 mL: 0.05-0.2 g; and,

[0008] b) an aqueous phase solution, wherein the raw materials for preparing the aqueous phase solution include a water-soluble monomer, a stabilizer and a solvent, and the mass volume ratio of the water-soluble monomer, the stabilizer and the solvent is 0.5-2 mL: 1-2 g: 75-100 mL.

[0009] The hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres according to the embodiments of the present invention have at least the following beneficial effects: the polymer microspheres prepared by using the optimized raw material ratio of the present invention not only have good uniformity, but also can form a wrinkled structure on the surface of the microspheres, which helps to increase the specific surface area of ​​the polymer microspheres.

[0010] In some embodiments of the present invention, the hydrophobic monomer is selected from at least one of styrene, divinylbenzene, vinylimidazole, vinylpyridine, ethyl methacrylate, vinyl chloride, methyl methacrylate, vinylthiazole, cyclohexyl vinyl ether, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, vinyl n-butyl ether, octadecenoic acid, methacrylic anhydride, and glyceryl methacrylate.

[0011] In some preferred embodiments of the present invention, the hydrophobic monomers are styrene and divinylbenzene.

[0012] Styrene and divinylbenzene as polymer monomers have advantages including good thermal stability, high mechanical strength, high chemical stability, degradability, high exchange capacity, enhanced stability, improved mechanical properties and efficient ion exchange, and are widely applicable. At the same time, styrene and divinylbenzene copolymer microspheres are easy to swell and insoluble in swelling solvents, so it is easy to form wrinkles on the surface of the microspheres.

[0013] In some preferred embodiments of the present invention, the mass ratio of styrene to divinylbenzene is 1 to 4:1;

[0014] More preferably, the mass ratio of styrene to divinylbenzene is 1 to 3:1.

[0015] In some embodiments of the present invention, the swelling solvent is selected from at least one of alkylbenzene, n-hexane, n-heptane, petroleum ether, ethyl acetate, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, imidazole, pyridine and tetrahydrofuran.

[0016] In some embodiments of the present invention, the alkylbenzene includes at least one of toluene, xylene, ethylbenzene and propylbenzene.

[0017] In some preferred embodiments of the present invention, the swelling solvent is selected from at least one of toluene, petroleum ether, cyclohexane, and chloroform. Toluene, petroleum ether, cyclohexane, and chloroform have different swelling capacities, thereby achieving the regulation of the wrinkle degree on the surface of the wrinkled microspheres.

[0018] In some embodiments of the present invention, the initiator is selected from at least one of azobisisobutyronitrile, benzoyl peroxide, and dimethyl azobisisobutyrate.

[0019] In some embodiments of the present invention, the water-soluble monomer is selected from at least one of acrylic acid, vinyl pyrrolidone, methacrylic acid, methyl methacrylate, pentaerythritol triacrylate, acrylamide, itaconic acid, sodium styrene sulfonate, ethylene urea, N-styryl urea, fumaric acid, maleic acid, and maleic anhydride.

[0020] In some preferred embodiments of the present invention, the water-soluble monomer is acrylic acid and / or acrylamide. These two monomers are more likely to form hydrophilic-hydrophobic heterogeneous wrinkles on the surface of the wrinkled microspheres than other water-soluble monomers.

[0021] In some embodiments of the present invention, the stabilizer is selected from at least one of sodium octadecyl sulfonate, sodium octadecyl sulfate, hexadecyl trimethyl ammonium bromide, polyvinyl alcohol, polyacrylic acid, polyethylene glycol, polydimethylsiloxane, polyethylene glycol ether, polypropylene ether, polyoxyethylene ethyl ether, polyethylene glycol sulfate, polyoxyethylene monostearate, isobutyl hydroxyphenyl ether, isoprene dihydroxyphenyl ether, polyethylene glycol distearate, polyacrylamide, and polyvinyl pyrrolidone.

[0022] In some preferred embodiments of the present invention, the stabilizer is selected from at least two of sodium octadecyl sulfonate, sodium octadecyl sulfate, hexadecyl trimethyl ammonium bromide, polyvinyl alcohol, and polyacrylic acid. The stabilizer of the present invention is more conducive to the oil phase to form droplets through stirring, thereby polymerizing to prepare wrinkled microspheres.

[0023] In some embodiments of the invention, the solvent comprises water.

[0024] In some embodiments of the present invention, the volume ratio of the aqueous phase solution to the oil phase solution is 2 to 100:1.

[0025] In some preferred embodiments of the present invention, the volume ratio of the aqueous phase solution to the oil phase solution is 2 to 10:1.

[0026] In some embodiments of the present invention, the average particle size of the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres is 1 to 1500 μm.

[0027] The second aspect of the present invention provides a method for preparing the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres as described in any one of the first aspects, comprising the following steps:

[0028] S1, mixing the hydrophobic monomer, swelling solvent and initiator to obtain the oil phase solution;

[0029] S2, mixing the water-soluble monomer, stabilizer and solvent to obtain the aqueous phase solution;

[0030] S3, mixing the oil phase solution with the water phase solution to prepare suspended droplets under stirring conditions, then introducing an inert gas and reacting at 50-100° C. to obtain.

[0031] Among them, the mass volume ratio of the preparation raw materials in the oil phase solution and the water phase solution in the preparation method is the same as described in the first aspect.

[0032] The preparation method according to the embodiment of the present invention has at least the following beneficial effects:

[0033] The invention is based on a suspension-interfacial polymerization method, wherein under stirring conditions, hydrophilic monomers in an aqueous solution and hydrophobic monomers in an oily solution are assembled into suspended droplets, and copolymerization occurs at the interface by temperature control under inert atmosphere conditions to obtain microspheres having a hydrophilic-hydrophobic heterogeneous structure and surface wrinkles. The microsphere preparation method of the invention is simple, the experimental conditions are easy to control, the post-treatment method is simple and easy to perform, and the obtained polymer microspheres have good particle size uniformity, and can be used for industrial production.

[0034] In some embodiments of the present invention, in step S3, the mixing temperature is 10-40°C.

[0035] In some embodiments of the present invention, in step S3, the stirring speed is 50 to 1500 rpm.

[0036] In some embodiments of the present invention, in step S3, the stirring time is 5 to 60 minutes.

[0037] In some embodiments of the present invention, in step S3, the inert gas includes at least one of helium, argon, and nitrogen.

[0038] In some embodiments of the present invention, in step S3, the reaction time is 1 to 72 hours.

[0039] In some embodiments of the present invention, in step S3, the reaction time is 6 to 24 hours.

[0040] In some embodiments of the present invention, in step S3, washing with alcohol and / or aqueous solution is further included after the reaction.

[0041] The third aspect of the present invention provides the use of the preparation method of the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres as described in any one of the first aspect or the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres as described in any one of the second aspect in any of the following:

[0042] c) preparing catalytic materials;

[0043] d) preparing chemical separation materials;

[0044] e) preparing a drug delivery vehicle;

[0045] f) Preparation of biosensor.

[0046] Other features and advantages of the present invention will be set forth in the description which follows. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] The present invention will be further described below with reference to the accompanying drawings and embodiments, wherein:

[0048] Figure 1 The particle size distribution diagram of the hydrophilic-hydrophobic heterogeneous wrinkled microspheres prepared in Example 1 of the present invention;

[0049] Figure 2 This is an optical microscope photo of the hydrophilic-hydrophobic heterogeneous wrinkled microspheres prepared in Example 1 of the present invention;

[0050] Figure 3 The scanning microscope photographs of the hydrophilic-hydrophobic heterogeneous wrinkled microspheres and the wrinkles on the surface of the microspheres prepared in Example 1 of the present invention;

[0051] Figure 4 Transmission electron microscope photograph of the wrinkles on the surface of the ultrathin slice of the hydrophilic-hydrophobic heterogeneous wrinkled microspheres prepared in Example 1 of the present invention and the hydrophilic-hydrophobic heterogeneous structure;

[0052] Figure 5 This is an optical microscope photo of the hydrophilic-hydrophobic heterogeneous wrinkled microspheres prepared in Example 2 of the present invention;

[0053] Figure 6 The scanning microscope photographs of the hydrophilic-hydrophobic heterogeneous wrinkled microspheres and the wrinkles on the surface of the microspheres prepared in Example 2 of the present invention;

[0054] Figure 7 This is an optical microscope photo of the hydrophilic-hydrophobic heterogeneous wrinkled microspheres prepared in Example 3 of the present invention;

[0055] Figure 8 The scanning microscope photographs of hydrophilic-hydrophobic heterogeneous wrinkled microspheres and wrinkles on the surface of the microspheres prepared in Example 3 of the present invention;

[0056] Fig. 9This is an optical microscope photo of the hydrophilic-hydrophobic heterogeneous wrinkled microspheres prepared in Example 4 of the present invention;

[0057] Fig.10 The scanning microscope photographs of hydrophilic-hydrophobic heterogeneous wrinkled microspheres and wrinkles on the surface of the microspheres prepared in Example 4 of the present invention;

[0058] Fig.11 This is a scanning microscope photograph of the smooth hydrophilic-hydrophobic heterogeneous microspheres prepared in Comparative Example 1 of the present invention. DETAILED DESCRIPTION

[0059] The following will be combined with the embodiments to clearly and completely describe the concept of the present invention and the technical effects produced, so as to fully understand the purpose, characteristics and effects of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative work are all within the scope of protection of the present invention.

[0060] The words "preferably", "more preferably", etc. in the present invention refer to embodiments of the present invention that may provide certain beneficial effects in certain circumstances. However, other embodiments may also be preferred under the same circumstances or other circumstances. In addition, the description of one or more preferred embodiments does not imply that other embodiments are not applicable, nor is it intended to exclude other embodiments from the scope of the present invention.

[0061] When a numerical range is disclosed herein, the above range is considered to be continuous and includes the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0062] In the description of the present invention, the reference term "and / or" includes all and any combinations of one or more of the associated listed items.

[0063] In the description of the present invention, the description with reference to the terms "one embodiment", "some embodiments", "illustrative embodiments", "examples", "specific examples", or "some examples" means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner.

[0064] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. If the manufacturers of the reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0065] Example 1

[0066] This embodiment provides a hydrophilic-hydrophobic heterogeneous wrinkled polymer microsphere and a preparation method thereof, wherein the hydrophilic-hydrophobic heterogeneous wrinkled polymer microsphere is prepared by mixing an aqueous phase and an oil phase, and the specific preparation raw materials are shown in Table 1.

[0067] Table 1: Raw materials for the preparation of hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres

[0068]

[0069]

[0070] The preparation method of the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres specifically comprises the following steps:

[0071] S1. Weigh 1.0 g of polyvinyl alcohol, 0.01 g of sodium octadecyl sulfate, and 1.5 mL of acrylic acid and dissolve them in 100 mL of water to prepare an aqueous phase;

[0072] S2, weigh 2.5 mL of styrene, 1.5 mL of divinylbenzene, 3.5 mL of chloroform and 0.06 g of azobisisobutyronitrile, mix well, and prepare an oil phase;

[0073] S3. The water phase and oil phase prepared above are mixed in a volume ratio of 7.5 mL:101.5 mL, and stirred at 300 rpm for 30 min at 30°C to obtain suspended droplets, and then nitrogen gas (which can also be replaced by other inert gases according to actual conditions) is introduced, and the temperature is raised to 70°C for polymerization for 12 h, and then washed with ethanol and water in turn.

[0074] The average particle size of the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres prepared by the embodiment of the present invention is 120±5 μm, and the particle size distribution diagram is as follows: Figure 1 As shown. Further, an optical microscope was used to observe it, and the results are as follows Figure 2 As shown, the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres are spherical and have good uniformity.

[0075] The hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres prepared in the present invention were observed by scanning electron microscope. Figure 3 As shown in the figure, the microsphere surface has a uniform wrinkle morphology, and the wrinkle degree is at the micro-nano level. Furthermore, the hydrophilic-hydrophobic heterogeneous wrinkled microspheres were sliced ​​ultrathinly and observed using a transmission electron microscope. The results are shown in the figure. Figure 4 As shown, wrinkles are formed on the surface of the microspheres, and hydrophilic-hydrophobic regions exist in the wrinkle regions. The polymer microspheres prepared by the embodiment of the present invention are hydrophilic-hydrophobic heterogeneous wrinkled microspheres.

[0076] Example 2

[0077] This embodiment provides a hydrophilic-hydrophobic heterogeneous wrinkled polymer microsphere and a preparation method thereof, wherein the hydrophilic-hydrophobic heterogeneous wrinkled polymer microsphere is prepared by mixing an aqueous phase and an oil phase, and the specific preparation raw materials are shown in Table 2.

[0078] Table 2: Raw materials for the preparation of hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres

[0079]

[0080]

[0081] The preparation method of the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres specifically comprises the following steps:

[0082] S1. Weigh 1.0 g polyvinyl pyrrolidone, 0.05 g sodium octadecyl sulfate, and 0.75 mL vinyl pyrrolidone and dissolve them in 80 mL water to prepare the aqueous phase;

[0083] S2, weigh 2 mL of styrene, 2 mL of divinylbenzene, 3.5 mL of petroleum ether and 0.08 g of azobisisobutyronitrile, mix and prepare an oil phase;

[0084] S3. The water phase and oil phase prepared above were mixed in a volume ratio of 7.5 mL:80.75 mL, and stirred at 200 rpm for 10 min at 40 ° C to obtain suspended droplets, and then nitrogen was introduced and the temperature was raised to 80 ° C for polymerization for 12 h, and then washed with ethanol and water in turn.

[0085] The average particle size of the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres prepared by the embodiment of the present invention is 170±8 μm. Further, an optical microscope is used to observe the microspheres, and the results are as follows: Figure 5 As shown in the figure, the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres are spherical and uniform. The results are shown in the figure. Figure 6 As shown, uniform wrinkle morphology can be seen on the surface of the microspheres, and the degree of wrinkles has reached the micron level.

[0086] Example 3

[0087] This embodiment provides a hydrophilic-hydrophobic heterogeneous wrinkled polymer microsphere and a preparation method thereof, wherein the hydrophilic-hydrophobic heterogeneous wrinkled polymer microsphere is prepared by mixing an aqueous phase and an oil phase, and the specific preparation raw materials are shown in Table 3.

[0088] Table 3: Raw materials for the preparation of hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres

[0089]

[0090]

[0091] The preparation method of the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres specifically comprises the following steps:

[0092] S1. Weigh 1.0 g of polyethylene glycol, 0.01 g of hexadecyltrimethylammonium bromide, and 1.5 mL of acrylic acid and dissolve them in 100 mL of water to prepare an aqueous phase;

[0093] S2, weigh 2.5 mL of styrene, 1.5 mL of divinylbenzene, 2.5 mL of cyclohexane and 0.06 g of azobisisobutyronitrile, mix well, and prepare an oil phase;

[0094] S3. The aqueous phase and oil phase prepared above were mixed in a volume ratio of 6.5 mL:101.5 mL, and stirred at 200 rpm at 35 ° C for 1 hour to obtain suspended droplets, and then nitrogen was introduced, and the temperature was raised to 70 ° C for polymerization for 16 hours, and then washed with ethanol and water in turn.

[0095] The average particle size of the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres prepared by the embodiment of the present invention is 500±25 μm. Further, an optical microscope is used to observe the microspheres, and the results are as follows: Figure 7 As shown in the figure, the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres present a spherical structure with good uniformity. The results are shown in the figure. Figure 8 As shown, uniform wrinkled morphology can be seen on the surface of the microspheres, and the degree of wrinkling exceeds that of the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres prepared in Example 2 above.

[0096] Example 4

[0097] This embodiment provides a hydrophilic-hydrophobic heterogeneous wrinkled polymer microsphere and a preparation method thereof, wherein the hydrophilic-hydrophobic heterogeneous wrinkled polymer microsphere is prepared by mixing an aqueous phase and an oil phase, and the specific preparation raw materials are shown in Table 4.

[0098] Table 4: Raw materials for preparation of hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres

[0099]

[0100] The preparation method of the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres specifically comprises the following steps:

[0101] S1. Weigh 1.0 g of polyvinyl alcohol, 0.01 g of sodium octadecyl sulfate, and 1.5 mL of acrylic acid and dissolve them in 100 mL of water to prepare an aqueous phase;

[0102] S2, weigh 3 mL of styrene, 1 mL of divinylbenzene, 1.5 mL of toluene and 0.12 g of azobisisobutyronitrile, mix well, and prepare an oil phase;

[0103] S3. The water phase and oil phase prepared above were mixed in a volume ratio of 5.5 mL:101.5 mL, and stirred at 600 rpm for 30 min at 40 ° C to obtain suspended droplets, and then nitrogen was introduced and the temperature was raised to 70 ° C for polymerization for 12 h, and then washed with ethanol and water in turn.

[0104] The average particle size of the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres prepared by the embodiment of the present invention is 20±2 μm. Further, an optical microscope is used to observe the microspheres, and the results are as follows: Fig. 9 As shown in the figure, the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres present a spherical structure with good uniformity. The results are shown in the figure. Fig.10 As shown, uniform wrinkle morphology can be seen on the surface of the microspheres, and the degree of wrinkles is between that of the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres prepared in Example 1 and Example 2.

[0105] Comparative Example 1

[0106] This comparative example provides a hydrophilic-hydrophobic heterogeneous polymer microsphere and a preparation method thereof, wherein the hydrophilic-hydrophobic heterogeneous polymer microsphere is prepared by mixing an aqueous phase and an oil phase, and the specific preparation raw materials are shown in Table 5.

[0107] Table 5: Raw materials for preparation of hydrophilic-hydrophobic heterogeneous polymer microspheres

[0108]

[0109] The preparation method of the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres specifically comprises the following steps:

[0110] S1. Weigh 0.2 g polyvinyl alcohol, 0.1 g polyethylene glycol, and 1.5 mL acrylic acid and dissolve them in 100 mL water to prepare the aqueous phase;

[0111] S2, weigh 1 mL of styrene, 6 mL of divinylbenzene, 0.2 mL of toluene and 0.06 g of azobisisobutyronitrile, mix well, and prepare an oil phase;

[0112] S3. The water phase and oil phase prepared above were mixed in a volume ratio of 7.2 mL:101.5 mL, and stirred at 400 rpm for 30 min at 40°C to obtain suspended droplets. Nitrogen was then introduced and the temperature was raised to 70°C for polymerization for 12 h. The mixture was washed with ethanol and water in turn to obtain a suspension.

[0113] The average particle size of the hydrophilic-hydrophobic heterogeneous polymer microspheres prepared in this comparative example is similar to that in Example 1. Further, a scanning electron microscope was used to observe the microspheres, and the results are as follows: Fig.11 As shown, the surface of the hydrophilic-hydrophobic heterogeneous polymer microspheres is smooth, and it is difficult to see that they have a wrinkled structure. It is speculated that this is related to the swelling solvent. Since the relative proportion of the swelling solvent is too low, the microspheres cannot swell, and thus wrinkles cannot be formed on the surface of the microspheres.

[0114] Comparative Example 2

[0115] This comparative example provides a hydrophilic-hydrophobic heterogeneous polymer microsphere and a preparation method thereof, which differs from Example 1 in that the polymerization conditions are different. The raw materials for preparation are described in Table 1. The preparation method comprises the following steps:

[0116] S1. Weigh 1.0 g of polyvinyl alcohol, 0.01 g of sodium octadecyl sulfate, and 1.5 mL of acrylic acid and dissolve them in 100 mL of water to prepare an aqueous phase;

[0117] S2, weigh 2.5 mL of styrene, 1.5 mL of divinylbenzene, 3.5 mL of chloroform and 0.06 g of azobisisobutyronitrile, mix well, and prepare an oil phase;

[0118] S3. The water phase and oil phase prepared above were mixed in a volume ratio of 7.5 mL:101.5 mL, and stirred at 300 rpm for 30 min at 30°C to obtain suspended droplets, which were then heated to 45°C for polymerization for 12 h, and washed with ethanol and water in turn.

[0119] The microspheres prepared in Comparative Example 2 were observed, and the results showed that it was difficult to prepare hydrophilic-hydrophobic heterogeneous polymer microspheres using this comparative example. It is speculated that the initiator is easily consumed by oxygen in the air without the introduction of inert gas, making it difficult to initiate polymerization of the polymer monomers, and thus polymer microspheres cannot be prepared. In addition, lower temperatures are not conducive to the preparation of polymer microspheres.

[0120] In summary, the present invention provides a hydrophilic-hydrophobic heterogeneous wrinkled polymer microsphere and its preparation method and application. The present invention uses a suspension-interfacial polymerization method to assemble hydrophilic monomers and hydrophobic monomers into suspended droplets under stirring conditions, and copolymerizes at the interface by temperature control to obtain microspheres with hydrophilic-hydrophobic heterogeneous structures and surface wrinkles. It can be found from the above embodiments that the width and thickness of the wrinkles on the surface of the microspheres can be controlled by changing the type of swelling solvent, and the control from nanometer to micrometer level can be achieved. The microsphere preparation method of the present invention is simple, the experimental conditions are easy to control, the post-processing method is simple and easy, and the obtained polymer microspheres have good particle size uniformity, and have excellent large-scale production and application value.

[0121] The above is a detailed description of the embodiments of the present invention, but the present invention is not limited to the above embodiments. Various changes can be made within the knowledge of ordinary technicians in the relevant technical field without departing from the purpose of the present invention. In addition, the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.

Claims

1. A hydrophilic-hydrophobic heterogeneous wrinkled polymer microsphere, characterized in that: The raw materials for preparation include: a) an oil phase solution, wherein the raw materials for preparing the oil phase solution include a hydrophobic monomer, a swelling solvent and an initiator, and the mass volume ratio of the hydrophobic monomer, the swelling solvent and the initiator is 3-5 mL: 1-4 mL: 0.05-0.2 g; and, b) an aqueous phase solution, wherein the raw materials for preparing the aqueous phase solution include a water-soluble monomer, a stabilizer and a solvent, and the mass volume ratio of the water-soluble monomer, the stabilizer and the solvent is 0.5-2 mL: 1-2 g: 75-100 mL.

2. The hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres according to claim 1, characterized in that: The hydrophobic monomer is selected from at least one of styrene, divinylbenzene, vinylimidazole, vinylpyridine, ethyl methacrylate, vinyl chloride, methyl methacrylate, vinylthiazole, cyclohexyl vinyl ether, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, vinyl n-butyl ether, octadecenoic acid, methacrylic anhydride, and glyceryl methacrylate; and / or, the swelling solvent is selected from at least one of alkylbenzene, n-hexane, n-heptane, petroleum ether, ethyl acetate, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, imidazole, pyridine and tetrahydrofuran; And / or, the initiator is selected from at least one of azobisisobutyronitrile, benzoyl peroxide, and dimethyl azobisisobutyrate.

3. The hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres according to claim 1, characterized in that: The water-soluble monomer is selected from at least one of acrylic acid, vinyl pyrrolidone, methacrylic acid, methyl methacrylate, pentaerythritol triacrylate, acrylamide, itaconic acid, sodium styrene sulfonate, ethylene urea, N-styryl urea, fumaric acid, maleic acid, and maleic anhydride; And / or, the stabilizer is selected from at least one of sodium octadecyl sulfonate, sodium octadecyl sulfate, cetyltrimethylammonium bromide, polyvinyl alcohol, polyacrylic acid, polyethylene glycol, polydimethylsiloxane, polyethylene glycol ether, polypropylene ether, polyoxyethylene ethyl ether, polyethylene glycol sulfate, polyoxyethylene monostearate, isobutyl hydroxyphenyl ether, isopentyl dihydroxyphenyl ether, polyethylene glycol distearate, polyacrylamide, and polyvinyl pyrrolidone; And / or, the solvent comprises water.

4. The hydrophilic-hydrophobic heterogeneous wrinkled polymer microsphere according to any one of claims 1 to 3, characterized in that: The volume ratio of the aqueous phase solution to the oil phase solution is 2 to 100:

1.

5. A method for preparing hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1, mixing the hydrophobic monomer, swelling solvent and initiator to obtain the oil phase solution; S2, mixing the water-soluble monomer, stabilizer and solvent to obtain the aqueous phase solution; S3, mixing the oil phase solution with the water phase solution to prepare suspended droplets under stirring conditions, then introducing an inert gas and reacting at 50-100° C. to obtain.

6. The preparation method according to claim 5, characterized in that: In step S3, the mixing temperature is 10 to 40°C; And / or, the stirring speed is 50 to 1500 rpm; And / or, the stirring time is 5 to 60 minutes.

7. The preparation method according to claim 5, characterized in that: In step S3, the inert gas includes at least one of helium, argon and nitrogen.

8. The preparation method according to claim 5, characterized in that: In step S3, the reaction time is 1 to 72 hours.

9. The preparation method according to claim 8, characterized in that: In step S3, washing with alcohol and / or aqueous solution is further included after the reaction.

10. Use of the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres according to any one of claims 1 to 4 or the preparation method of the hydrophilic-hydrophobic heterogeneous wrinkled polymer microspheres according to any one of claims 5 to 9 in any of the following: c) preparing catalytic materials; d) preparing chemical separation materials; e) preparing a drug delivery vehicle; f) Preparation of biosensor.

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