CN118236995A - Porous polymer used as chromatographic packing, and preparation method and application thereof - Google Patents

Abstract

The invention provides a porous polymer used as a chromatographic packing, a preparation method and application thereof. The preparation method comprises the following steps: providing a solution A, a solution B and a solution C; in-situ polymerization and first crosslinking of the solution A under the protection of inert gas; and then alternately adding the solution B and the solution C to perform in-situ deposition and secondary crosslinking to obtain the porous polymer. The technical scheme of the invention has the advantages of simple operation, simple and convenient flow, environmental protection and low cost, and the obtained porous polymer has uniform particle size and high dynamic load and can meet the subsequent application requirements in chromatographic separation.

Description

A porous polymer as chromatographic filler and its preparation method and use

Technical Field

The invention belongs to the technical field of chromatographic fillers, and particularly relates to a porous polymer used as a chromatographic filler, a preparation method and application thereof.

Background technique

Chromatographic fillers are the core materials for liquid chromatography to achieve group separation, which directly affects the separation efficiency of chromatography and the accuracy of detection data. Porous polymer matrix fillers have the advantages of chemical stability and easy derivatization, as well as strong sample loading capacity and high chromatographic capacity, making porous polymer chromatographic fillers widely used in reverse phase, molecular exclusion, affinity chromatography, ion exchange and hydrophobic chromatography.

At present, the main methods for synthesizing porous polymers as chromatographic fillers include suspension polymerization, seed swelling polymerization, microporous membrane emulsification method, etc. In the prior art, when porous microspheres are prepared by suspension polymerization, a certain amount of inert solvent (porogen) is added to the comonomer, and after the polymerization is completed, the porogen is extracted with an appropriate solvent to obtain a porous structure. This method has high requirements on the type and polarity of the solvent, and the reaction must be carried out in alcohols or solvents dominated by alcohols, otherwise the sample will be abnormal.

In the early 1980s, Ugelstad et al. proposed seed swelling polymerization, which uses other polymerization methods, such as dispersion polymerization, to obtain microspheres with uniform particle size as the polymerization center, and then undergoes one or more steps of swelling of the monomer and porogen to obtain microspheres with larger particle size after polymerization. Li Lu et al. prepared monodisperse seed microspheres by styrene dispersion polymerization, and then prepared polystyrene-divinylbenzene porous microspheres by two-step seed swelling polymerization improved by ultrasonic dispersion. This method has a complex production process, strict reaction conditions, and a long preparation cycle, resulting in high costs. In addition, the multi-step polymerization, swelling, and cleaning lead to excessive reagent usage, serious waste and pollution, and high product costs.

Membrane emulsification is an efficient emulsification method, which is to press the dispersed phase into the continuous phase under the action of external pressure through the micropores of the inorganic membrane to form an emulsion, and then obtain porous microspheres with uniform particle size through suspension polymerization. Patent CN101229509A uses membrane emulsification to disperse the oil phase into the water phase to prepare a monodisperse emulsion, and finally uses suspension polymerization at a temperature of 65 to 100°C to prepare highly cross-linked polystyrene-divinylbenzene porous microspheres. However, in the process of preparing the microspheres, more organic raw materials are used, which pollutes the environment. At the same time, the preparation process is cumbersome, the process is complicated, the cycle is long, and the cost is high.

Summary of the invention

In view of the above-mentioned shortcomings of the prior art, the purpose of the present invention is to provide a porous polymer as a chromatographic filler and a preparation method and use thereof. The technical solution of the present invention is simple to operate, has a simple process, can reduce the amount of reagents used, thereby reducing waste and reducing costs.

To achieve the above objectives and other related objectives, the present invention is achieved through the following technical solutions.

The first aspect of the present invention provides a method for preparing a porous polymer as a chromatographic filler, comprising the following steps: providing a solution A, a solution B and a solution C; in-situ polymerizing and first crosslinking the solution A under the protection of an inert gas; then alternately adding the solution B and the solution C to perform in-situ deposition and second crosslinking to obtain the porous polymer;

Solution A includes 2wt% to 40wt% of a first monomer, 0.5wt% to 35wt% of a second monomer, 0.2wt% to 5wt% of an initiator, 0.2wt% to 15wt% of a stabilizer, and the remainder is a solvent;

Solution B includes 5wt% to 45wt% of the third monomer, 1wt% to 30wt% of the fourth monomer, 0.2wt% to 5wt% of the initiator, 8wt% to 20wt% of the porogen, and the balance is a solvent;

Solution C includes 0.2 wt% to 15 wt% of a stabilizer, and the remainder is a solvent.

After solution A is in situ polymerized and cross-linked for the first time, solution B is added dropwise for in situ deposition and second cross-linking, thereby adjusting the particle size of the porous polymer. At the same time, the addition of solution B can also increase the mechanical properties of the porous polymer and enhance its hardness. Solution C is added dropwise to make the polymer particles in the system more stable, so as to avoid agglomeration of the polymer particles in the system during the reaction, thereby failing to effectively synthesize a porous polymer with good monodispersity and failing to meet the use requirements in subsequent applications.

The porogen is added to solution B specifically. If it is added to solution A, it will lead to uneven internal pore distribution, and will only be distributed in the polymer after in-situ polymerization of solution A; if it is added to solution C, it will lose the porogen effect and cannot obtain a porous polymer.

The content of porogen of 8wt% to 20wt% is not set arbitrarily. If the content of porogen is too low, the pore size of the porous polymer will be too small, which cannot meet the subsequent use requirements as a chromatographic filler in separation and purification. If the content of porogen is too high, the pore size of the porous polymer will be too large, affecting the mechanical strength of the microspheres. In severe cases, it may even cause the porous polymer to break, resulting in the product not meeting the requirements and being unusable.

Preferably, the first monomer is selected from one or more of styrene, glycidyl methacrylate, methyl methacrylate, butyl methacrylate and hydroxyethyl methacrylate.

Preferably, the second monomer is selected from one or both of divinylbenzene and ethylene glycol dimethacrylate. These second monomers not only act as monomers to react during the reaction, but also act as crosslinking agents to achieve crosslinking polymerization during the reaction.

Preferably, the third monomer is selected from one or more of styrene, glycidyl methacrylate, methyl methacrylate, butyl methacrylate and hydroxyethyl methacrylate.

Preferably, the fourth monomer is selected from one or both of divinylbenzene and ethylene glycol dimethacrylate. These fourth monomers not only act as monomers to react during the reaction, but also act as crosslinking agents to achieve crosslinking polymerization during the reaction.

Preferably, the initiator is selected from one or more of benzoyl peroxide, diisobutyronitrile peroxide, azobisisobutyronitrile, dimethyl azobisisobutyrate, tert-butyl benzoyl peroxide, potassium persulfate, sodium persulfate and ammonium persulfate. The function of the initiator is to initiate the polymerization reaction. The addition of the initiator is conducive to promoting the smooth progress of the polymer polymerization reaction and improving the reaction efficiency.

Preferably, the stabilizer is selected from one or more of polyvinyl alcohol, polyethylene glycol, sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, polyvinyl pyrrolidone, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, β-cyclodextrin, gelatin, lignin, tween and span. After adding the stabilizer, the stability of the porous polymer can be maintained, and the collision between the porous polymers can be reduced, thereby avoiding the occurrence of agglomeration and adhesion between the porous polymers, which is conducive to obtaining well-dispersed porous polymer particles with uniform particle size.

Preferably, the porogen is selected from one or more of alkanes, alcohols, esters without carbon-carbon double bonds, and alkyl ketones.

Preferably, the porogen includes one or more of toluene, isooctane, n-heptane, n-octanol, cyclohexanol, dibutyl phthalate and 2-octanone.

In the present technical solution, the selection of the above-mentioned porogen type is also specific, which can not only better adapt to the reaction system of the preparation method, but also prepare polymer particles with suitable pore size, thereby achieving the effect of accurately controlling the polymer pore structure.

Preferably, the solvent is selected from deionized water.

Preferably, the mass ratio of solution A to solution B is (1-3): (1-55). The size of the porous polymer particles can be controlled by adjusting the amount of solution B added. For example, the mass ratio of solution A to solution B can be 1: (1-55), 1: (1-40), 1: (1-20), 1: (1-10), 1: (1-5).

Preferably, the mass ratio of solution B to solution C is (1-6):(1-20). For example, the mass ratio of solution B to solution C can be (1-3):(1-20), (1-3):(1-15), (1-3):(1-10), 1:(1-5).

Preferably, solution B and solution C are added dropwise to solution A.

The dropwise addition method used in the present technical solution adds solution B and solution C to solution A. The dropwise addition method can well control the reaction rate and the particle size of the porous polymer. If solution B, solution C and solution A are directly mixed, it is easy to cause problems such as large particles, agglomeration and adhesion between particles.

Preferably, the in-situ polymerization method includes one of photoin-situ polymerization and thermal in-situ polymerization.

Preferably, the in-situ polymerization temperature and the first cross-linking temperature are 65 to 95°C, such as 70 to 95°C, 80 to 95°C, or 75 to 85°C.

Preferably, the temperature of the in-situ deposition and the second cross-linking is 65-95°C, such as 70-95°C, 80-95°C, or 75-85°C.

Preferably, solution A is polymerized in situ for 1 to 4 hours before solution B is added. For example, the in situ polymerization time may be 1 hour, 2 hours, 3 hours, or 4 hours.

Preferably, solution C is added at least 30 minutes after the addition of solution B. The certain interval time is to allow the reaction components in solution B to deposit as much as possible and react on the surface of the porous polymer, and to avoid the formation of new particles by adding C too early, which affects the uniformity of particle size.

Preferably, the second cross-linking further includes a post-treatment step, and the post-treatment step includes washing and drying.

Preferably, ethanol and water are used for the washing.

Preferably, the drying is vacuum drying.

Preferably, the drying temperature is 60-80°C.

The second aspect of the present invention provides a porous polymer prepared by the preparation method as described above.

Preferably, the particle size of the porous polymer is 3 μm to 80 μm, such as 3 μm to 60 μm, 3 μm to 40 μm, 3 μm to 25 μm, 5 μm to 20 μm, 8 μm to 20 μm, 8 μm to 12 μm, more preferably 8 μm to 12 μm.

Preferably, the pore size of the porous polymer is 5 nm to 200 nm, such as 5 nm to 180 nm, 5 nm to 150 nm, 5 nm to 100 nm, 5 nm to 80 nm, 5 nm to 60 nm, 5 nm to 40 nm, 8 nm to 35 nm, and 12 nm to 30 nm.

The third aspect of the present invention provides a use of the porous polymer as described above as a chromatographic filler for separating macromolecular substances.

Preferably, the porous polymer is also used as a stationary phase to separate and purify macromolecular substances in the field of biological detection and analysis.

The technical solution of the present invention abandons the existing preparation method of porous chromatographic fillers in the prior art, and creatively provides a porous polymer and its preparation method and use. The preparation method adopts in-situ polymerization and cross-linking of monomers, and simultaneously continuously drips functional monomers for in-situ deposition and cross-linking, and finally realizes the one-step preparation of porous polymers with different particle sizes, different pore sizes and different cross-linking degrees.

The beneficial effects of the above technical solution of the present invention are:

The technical solution of the present application has no special requirements on the type and proportion of solvents, which can be all water or alcohol, or a mixture of water and various alcohols; the solution is simple to operate and has a simple process, which not only reduces the pollution of organic reagents to the environment, but also reduces the amount of reagents used, thereby reducing waste and reducing costs. In addition, the porous polymer prepared by this method has good performance as a chromatographic filler, uniform particle size, high dynamic loading capacity, and can meet the subsequent application requirements in the separation and purification of macromolecular substances.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an electron microscope image of the porous polymer prepared in Example 1 of the present invention.

FIG. 2 is an electron microscope image of the porous polymer prepared in Example 2 of the present invention.

FIG3 is an electron microscope image of the polymer matrix chromatographic filler prepared in Comparative Example 1 of the present invention.

FIG. 4 is an electron microscope image of the porous polymer prepared in Comparative Example 2 of the present invention.

FIG. 5 is an electron microscope image of the porous polymer prepared in Comparative Example 3 of the present invention.

FIG6 is a graph showing the dynamic loading capacity test results of the porous polymer prepared in Example 1 of the present invention as a chromatographic filler.

FIG. 7 is a graph showing the dynamic loading capacity test result of the solid polymer prepared in Comparative Example 1 of the present invention as a chromatographic filler.

Detailed ways

The following is an explanation of the embodiments of the present invention by specific examples to verify the practical feasibility of the method of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention.

It should be noted that the process equipment or devices not specifically specified in the following examples are all conventional equipment or devices in the art. In addition, it should be understood that the scope of protection of the present invention is not limited to the specific embodiments described below, and one or more method steps mentioned in the present invention do not exclude the presence of other method steps before and after the combination step or the insertion of other method steps between these explicitly mentioned steps, unless otherwise specified. It should also be understood that the terms used in the examples of the present invention are intended to describe specific embodiments, not to limit the scope of protection of the present invention. The test methods for which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under the conditions recommended by the manufacturers.

Example 1

In this embodiment, a specific porous polymer and a preparation method thereof are provided, comprising the following steps:

1) Preparation of Solution A

19.07 wt % styrene, 2.10 wt % divinylbenzene, 78.20 wt % deionized water, 0.39 wt % potassium persulfate, and 0.24 wt % hydroxypropyl cellulose were measured and dissolved at 300 rpm with stirring to obtain solution A, which was then transferred to a 500 ml three-necked flask.

2) Prepare solution B and prepare solution C

41.65 wt % of styrene, 20.70 wt % of divinylbenzene, 18.90 wt % of deionized water, 0.80 wt % of benzoyl peroxide, 6.20 wt % of toluene, and 11.75 wt % of dibutyl phthalate were measured and stirred at 300 rpm to obtain solution B.

Solution C was prepared by dissolving 0.50 wt % sodium dodecyl sulfate solution in 99.50 wt % deionized water.

3) Preparation of porous polymers

Place a three-necked flask containing 18g of solution A in an oil bath, start stirring and heat to 85°C. After 2 hours of reaction, slowly add 90g of solution B to the flask, and after 30 minutes, add 450g of solution C. Repeat this cycle until all solutions B and C have been added. Continue the reaction for 4 hours.

Then the reaction was closed, and the reactants were washed three times with ethanol and deionized water respectively, and then dried under vacuum at 70° C. The porous polymer (8 μm cross-linked porous polystyrene-divinylbenzene microspheres) prepared in this example is shown in FIG1 , and its average pore size is 30 nm.

Example 2

In this embodiment, a specific porous polymer and a preparation method thereof are provided, comprising the following steps:

1) Preparation of Solution A

11.44 wt % of glycidyl methacrylate, 32.88 wt % of ethylene glycol dimethacrylate, 55.088 wt % of deionized water, 0.254 wt % of azobisisobutyronitrile, and 0.338 wt % of polyvinyl pyrrolidone were measured and dissolved under stirring at 300 rpm to obtain solution A, which was then transferred to a 500 ml three-necked flask.

2) Prepare solution B and prepare solution C

44.76 wt % of glycidyl methacrylate, 23.52 wt % of ethylene glycol dimethacrylate, 20.41 wt % of deionized water, 0.41 wt % of azobisisobutyronitrile, 2.70 wt % of n-octanol, and 8.2 wt % of 2-octanone were measured and stirred at 300 rpm to obtain a solution B.

Solution C was obtained by dissolving 1.50 wt % polyvinyl pyrrolidone in 98.50 wt % deionized water.

3) Preparation of porous polymers

Place a three-necked flask containing 18g of solution A in an oil bath, start stirring and heat to 75°C. After 2 hours of reaction, slowly add 90g of solution B to the flask, and after 30 minutes, add 450g of solution C. Repeat this cycle until all solutions B and C have been added. Continue the reaction for 6 hours.

Then the reaction was closed, and the reactants were washed three times with ethanol and deionized water, and then dried under vacuum at 70° C. The results of the porous polymer (12 μm cross-linked porous poly(glycidyl methacrylate-ethylene glycol methacrylate) microspheres prepared in this example are shown in FIG2 , and the average pore size is 12 nm.

Comparative Example 1

The difference from Example 1 is that solution B does not contain porogens toluene and dibutyl phthalate, and the rest is the same as Example 1.

In this comparative example, since the porogens toluene and dibutyl phthalate were not added during the microsphere deposition growth stage, a solid non-porous polymer of 8 μm was finally prepared. The results are shown in FIG3 .

Comparative Example 2

The difference from Example 1 is that the porogen is added in excess in Solution B, and the amount of the porogen is 36.85 wt % (specifically, the amount of toluene added is 11.85%, and the amount of dibutyl phthalate added is 25%), and the rest is the same as Example 1.

In this comparative example, excessive porogen was added during the microsphere deposition growth stage, which resulted in the product being broken and unable to form particles. The results are shown in FIG4 .

Comparative Example 3

The difference from Example 1 is that solution C is not added during the reaction process. The rest is the same as Example 1.

In this comparative example, since no stabilizer was added during the polymer deposition growth stage, the product polymer particle size was uneven and the monodispersity was poor. The results are shown in FIG5 .

Application Example 1

The surface of the 8 μm porous polymer prepared in Example 1 was modified with carboxyl groups and loaded into a 1 ml chromatography prepacked column for dynamic loading capacity test. The results are shown in FIG6 .

Application Example 2

The surface of the 8 μm non-porous polymer prepared in Comparative Example 1 was modified with carboxyl groups and loaded into a 1 ml chromatography prepacked column for a dynamic loading capacity test. The results are shown in FIG7 .

In the dynamic loading test result graph, the UV-280 curve represents the absorbance of the buffer to ultraviolet light, and the UV-280 curve can reflect the content of the target; the conductivity curve refers to the conductivity of the buffer, which can reflect the ionic strength of the buffer; the pH curve can reflect the pH of the buffer. Among them, the "normal mark" at the front end of the graph is the sign of starting the injection, and the front end "control mark" and the back end "control mark" are the signs for adaptive adjustment of system parameters.

As shown in FIG6 , when the porous polymer prepared in Example 1 is used as a chromatographic filler, its dynamic loading capacity can reach 160 mg/ml.

As shown in FIG. 7 , when the solid polymer prepared in Comparative Example 1 is used as a chromatographic filler, its dynamic loading capacity can only reach 65 mg/ml.

It can be seen from Examples 1 to 2 and Comparative Examples 2 to 3 that the porous polymer obtained by the technical solution of the present application has good dispersion and uniform particle size, and its particle size and pore size can be adjusted according to production needs.

The dynamic loading capacity of chromatographic packing often indicates the packing's ability to adsorb and separate sample components in the chromatographic column. A high dynamic loading capacity of a chromatographic packing indicates that the chromatographic packing has better adsorption and separation capabilities, while a low dynamic loading capacity of a chromatographic packing indicates that the chromatographic packing has poor adsorption and separation capabilities.

It can be seen from Application Examples 1 and 2 that the porous polymer prepared in Example 1 has a high dynamic loading capacity of 160 mg/ml when used as a chromatographic filler, while the polymer prepared in Comparative Example 1 has a low dynamic loading capacity of only 65 mg/ml when used as a chromatographic filler. This shows that the porous polymer obtained by the technical solution of the present invention has excellent performance when used as a chromatographic filler and can provide better separation potential in subsequent separation applications.

Among them, the specific method of dynamic load test is:

The polymer microspheres prepared in Example 1 and Comparative Example 1 of the present application were loaded into chromatography columns, and their dynamic loadings were tested using a chromatograph.

The sample was 1 mg/ml lysozyme (0.05M PB buffer pH 6.0), the equilibration solution used was 0.05M PB buffer (PH 6.0), the eluent was 0.05M PB, 1M Nacl buffer (PH 6.0), and the flow rate of the chromatograph was set to 2.5 ml/min. The experimental results were recorded to obtain the dynamic loading.

The test method for porous polymer particle size is:

The cleaned porous polymer microspheres were dispersed in water and ultrasonicated for 5 minutes, and then the particle size was measured using a laser particle size analyzer.

The test method for the pore size of porous polymers is:

Weigh an appropriate amount of washed and dried porous polymer microspheres into a sample tube and degas at 120°C for 120 min. Use a specific surface area analyzer to automatically perform pore size testing.

In summary, the technical solution provided by the present invention can produce a porous polymer with good dispersibility, uniform particle size, and adjustable particle size and pore size. At the same time, when the porous polymer is used as a chromatographic filler, it has a high dynamic loading capacity and good adsorption and separation capabilities for samples, and can meet the subsequent application requirements in chromatographic separation. In addition, the technical solution is simple to operate, has a simple process, is environmentally friendly, and can reduce the amount of reagents used, thereby reducing waste and reducing costs.

The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical ideas disclosed by the present invention shall still be covered by the claims of the present invention.

Claims (10)

1. A method for preparing a porous polymer as a chromatographic filler, characterized in that it comprises the following steps: Providing solution A, solution B and solution C; in-situ polymerizing and first crosslinking solution A under the protection of inert gas; then alternately adding solution B and solution C to perform in-situ deposition and second crosslinking to obtain the porous polymer; Solution A includes 2 wt% to 40 wt% of a first monomer, 0.5 wt% to 35 wt% of a second monomer, 0.2wt% to 5wt% initiator, 0.2wt% to 15wt% stabilizer, and the balance is solvent; Solution B includes 5wt% to 45wt% of the third monomer, 1wt% to 30wt% of the fourth monomer, 0.2wt% to 5wt% of the initiator, 8wt% to 20wt% of the porogen, and the balance is a solvent; Solution C includes 0.2 wt% to 15 wt% of a stabilizer, and the remainder is a solvent. 2. The preparation method according to claim 1, characterized in that the first monomer is selected from one or more of styrene, glycidyl methacrylate, methyl methacrylate, butyl methacrylate and hydroxyethyl methacrylate; and/or, the second monomer is selected from one or both of divinylbenzene and ethylene glycol dimethacrylate; And/or, the third monomer is selected from one or more of styrene, glycidyl methacrylate, methyl methacrylate, butyl methacrylate and hydroxyethyl methacrylate; And/or, the fourth monomer is selected from one or both of divinylbenzene and ethylene glycol dimethacrylate. 3. The preparation method according to claim 1, characterized in that the initiator is selected from one or more of benzoyl peroxide, diisobutyronitrile peroxide, azobisisobutyronitrile, dimethyl azobisisobutyrate, tert-butyl benzoyl peroxide, potassium persulfate, sodium persulfate and ammonium persulfate; And/or, the stabilizer is selected from one or more of polyvinyl alcohol, polyethylene glycol, sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecylbenzene sulfonate, polyvinyl pyrrolidone, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, β-cyclodextrin, gelatin, lignin, tween and span; and/or, the porogen is selected from one or more of alkanes, alcohols, esters without carbon-carbon double bonds, and alkyl ketones; And/or, the solvent is selected from deionized water. 4. The preparation method according to claim 3, characterized in that the porogen comprises one or more of toluene, isooctane, n-heptane, n-octanol, cyclohexanol, dibutyl phthalate and 2-octanone; And/or, the mass ratio of solution A to solution B is (1-3):(1-55); And/or, the mass ratio of solution B to solution C is (1-6):(1-20). 5. The preparation method according to claim 1, characterized in that solution B and solution C are added dropwise into solution A; And/or, the in-situ polymerization method includes one of photoin-situ polymerization and thermal in-situ polymerization; and/or, the in-situ polymerization temperature and the first cross-linking temperature are 65 to 95° C.; and/or, the temperature of the in-situ deposition and the second cross-linking is 65 to 95° C.; and/or, solution A is polymerized in situ for 1 to 4 hours before solution B is added; and/or, adding solution C at least 30 minutes after the addition of solution B is completed; And/or, the second cross-linking further includes a post-treatment step, and the post-treatment step includes washing and drying. 6. The preparation method according to claim 5, characterized in that ethanol and water are used for the washing; And/or, the drying is vacuum drying; And/or, the drying temperature is 60-80°C. 7. A porous polymer obtained by the preparation method according to any one of claims 1 to 6. 8. The porous polymer according to claim 7, characterized in that the particle size of the porous polymer is 3 μm to 80 μm; And/or, the pore size of the porous polymer is 5 nm to 200 nm. 9. Use of the porous polymer according to any one of claims 7 to 8 as a chromatographic filler for separating macromolecular substances. 10. The use according to claim 9, characterized in that the porous polymer is also used as a stationary phase to separate and purify macromolecular substances in the field of biological detection and analysis.