WO2023241033A1 - Polymerization method mediated and initiated by oxygen-resistant and biocompatible metallic tin and use thereof - Google Patents

Abstract

Disclosed in the present application are a polymerization method mediated and initiated by oxygen-resistant and biocompatible metallic tin and the use thereof. The polymerization method comprises: subjecting a pre-reaction mixed solution comprising a free radical polymerization monomer, a coordination agent and a solvent to a polymerization reaction confined between metallic tin and a substrate deposited with an initiator, thereby preparing a biocompatible polymer brush thin film. The polymerization method provided in the present application uses a metallic tin sheet/foil to mediate a surface initiated polymerization reaction, is simple, convenient and efficient, has high polymerization efficiency, requires no addition of any metal salt, requires no complex deoxygenization operation or inert environment, and can achieve large-scale preparation. Moreover, the method avoids the use of a copper catalyst, overcomes the defects of a high price, high toxicity, etc., caused by the use of metal copper and a copper salt as catalysts in existing atom transfer radical polymerization systems, and has huge application potential in the field of biomedicine.

Description

An oxygen-resistant and biocompatible metallic tin-mediated polymerization method and its application

This application is based on and claims priority to the Chinese patent application with application number 202210672339.0 and the invention title "An oxygen-resistant and biocompatible metal tin-mediated polymerization method and application" submitted on June 14, 2022 .

Technical field

This application belongs to the field of polymer synthesis technology, and specifically relates to an oxygen-resistant and biocompatible metal tin-mediated polymerization method and its application.

Background technique

Biomimetic polymer brushes refer to grafting polymers of a certain chain length onto the surface of a substrate to form an aggregate of polymer chains with a high grafting density. Through steric hindrance and inter-molecular chain repulsion, the grafted polymer chains usually It will be perpendicular to the surface of the substrate, with one end fixed and the other end extending outward to form a brush-like configuration, so it is called a polymer brush. Due to their rich and diverse structures and functions, biomimetic polymer molecular brushes have potential application value in marine antifouling, surface lubrication, tissue engineering, biosensing and other fields. Surface-initiated polymerization is an important method for preparing polymer brushes. Common surface-initiated polymerization methods include nitroxide radical polymerization (NMP), reversible addition-fragmentation chain transfer radical polymerization (RAFT) and atom transfer radical polymerization (ATRP). wait. Among these methods, atom transfer radical polymerization is the most common route to prepare polymer brushes.

The classic ATRP reaction system uses alkyl halide (RX) as the initiator, a complex formed by a low-valence transition metal halide (commonly used CuBr) combined with a ligand (commonly used 2,2-bipyridyl) as the catalyst, and the active species A reversible atom transfer balance is established between the polymer and the dormancy clock, thereby ensuring that the concentration of free radicals is low enough to inhibit termination caused by binding between free radicals, thus enabling living polymerization to be achieved. However, transition metal Cu(I) is widely used as a catalyst in traditional SI-ATRP, and the reaction is biologically toxic, which seriously restricts the wide application of polymer molecular brushes in biomedicine and other fields. Therefore, the development of new biocompatible polymer brush film preparation methods is an urgent problem to be solved.

Contents of the invention

The main purpose of this application is to provide an oxygen-resistant and biocompatible metal tin-mediated polymerization method and application to overcome the shortcomings of the existing technology.

In order to achieve the foregoing invention objectives, the technical solutions adopted in this application include:

The embodiments of the present application provide an oxygen-resistant and biocompatible metal tin-mediated polymerization method, which includes: confining a pre-reaction mixture containing free radical polymerization monomers, complexing agents and solvents to metal tin A polymerization reaction occurs with the substrate on which the initiator is deposited, thereby producing a biocompatible polymer brush film.

The embodiments of the present application also provide the use of the aforementioned polymerization method in the fields of marine antifouling, surface lubrication, tissue engineering or biosensing.

Compared with the existing technology, the beneficial effects of this application are:

(1) This application uses metal tin sheets/foils to mediate surface-initiated polymerization. This polymerization method does not require the addition of metal salts, complex oxygen removal operations or inert environments. The monomers are allowed to undergo surface-initiated polymerization reactions through the catalytic effect of metal elemental tin. , prepare polymer brush films with controllable structure;

(2) The polymerization method provided by this application uses metal tin sheets/foils as catalysts for surface-initiated polymerization reactions. The preparation method is simple and efficient, has high polymerization efficiency, and can be prepared in large areas; at the same time, this method avoids the use of copper catalysts and overcomes the existing problems. It has the disadvantages of using metallic copper and copper salts as catalysts in atom transfer radical polymerization systems such as high price and high toxicity. It has excellent biocompatibility and has huge potential in the fields of tissue engineering, intelligent drug delivery and biomedicine. application potential.

Description of the drawings

In order to explain the embodiments of the present application or the technical solutions in the prior art more clearly, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings in the following description are only These are some embodiments recorded in this application. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without exerting creative efforts.

Figure 1 is a schematic diagram of the metal tin sheet/foil mediated surface initiated polymerization device and preparation in a typical embodiment of the present application;

Figures 2a-2b are atomic force microscope test images of the polymer molecular brush prepared in Example 1 of the present application;

Figure 3 is a polymerization kinetics curve diagram of the polymerization system in Examples 2 and 7 of the present application;

Figure 4 is a diagram of the thickness and water contact angle of different types of monomers after polymerization for 1 hour in Example 4 of the present application;

Figures 5a-5b are fluorescence microscopy photos of the polymer brush film prepared in Example 5 of the present application and cells co-cultured for 24 hours;

Figures 6a-6c are test charts of the thickness and roughness of the wafer-level polymer brush film obtained in Example 6 of the present application.

Detailed ways

In view of the shortcomings of the prior art, the inventor of the present case was able to propose the technical solution of the present application after long-term research and extensive practice. The technical solution of the present application will be clearly and completely described below. Obviously, the described embodiments are part of the present application. Examples, not all examples. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without making creative efforts fall within the scope of protection of this application.

Specifically, as an aspect of the technical solution of the present application, it involves an oxygen-resistant and biocompatible metal tin-mediated initiated polymerization method including: making a pre-formed polymer containing a free radical polymerization monomer, a complexing agent and a solvent. The reaction mixture is confined to a polymerization reaction between the metallic tin and the substrate on which the initiator is deposited, thereby producing a biocompatible polymer brush film.

In some preferred embodiments, the polymerization method includes:

In an atmospheric environment, the free radical polymerization monomer, the complexing agent and the solvent are uniformly mixed at room temperature to form the pre-reaction mixture;

And, the pre-reaction mixed liquid is placed between the metal tin and the substrate on which the initiator is deposited, so that at least the metal tin, the pre-reaction mixed liquid and the substrate on which the initiator is deposited form a sandwich structure, and in 15 to 60 ℃ reaction time is not less than 15 minutes, thereby producing the biocompatible polymer brush film.

In some preferred embodiments, the schematic diagram of the device and preparation of the metal tin sheet/foil-mediated surface-initiated polymerization of the biocompatible polymer brush film in the present application is shown in Figure 1 .

In some preferred embodiments, the free radical polymerizable monomers include acrylates, methacrylates, styrene, 4-vinylpyridine, 3-vinylaniline, acrylamide, methacrylamide, 1 - Any one or a combination of two or more vinylimidazole salts, but not limited thereto.

Further, the acrylates include any one or a combination of two or more of methyl acrylate, ethyl acrylate, and tert-butyl acrylate, and are not limited thereto.

Further, the methacrylates include methyl methacrylate and/or butyl methacrylate, but are not limited thereto.

Further, the acrylamide includes N-isopropylacrylamide and/or N-tert-butylacrylamide, and is not limited thereto.

Further, the methacrylamide includes N-isopropyl methacrylamide and/or N-tert-butyl methacrylamide, and is not limited thereto.

Further, the 1-vinylimidazole salts include 1-vinylimidazole bromide and/or 1-vinylimidazole tetrafluoroborate, and are not limited thereto.

In some preferred embodiments, the complexing agent includes N,N,N′,N″,N″-pentamethyldiethylenetriamine, tris(2-pyridyl)methylamine, 1,1, Any one of 4,7,10,10-hexamethyltriethylenetetramine, tris-(N,N-dimethylaminoethyl)amine, 2,2-bipyridine, and hexamethylenetetramine Or a combination of two or more, but not limited to this.

In some preferred embodiments, the initiator includes ethyl 2-bromophenylacetate, ethyl 2-bromoisobutyrate, methyl 2-bromoisobutyrate, ethyl 2-bromopropionate, ethyl 2-bromoisobutyrate Any one or a combination of two or more of ethylbenzene, α-chlorophenylethane, 2-chloropropionitrile and 2-bromopropionitrile, and is not limited thereto.

In some preferred embodiments, the solvent includes water and/or a mixed solution of water and methanol, but is not limited thereto.

Further, the ratio of methanol to water in the mixed solution formed by water and methanol does not exceed 1/2.

In some preferred embodiments, the metallic tin includes tin sheets and/or tin foils, but is not limited thereto.

In some preferred embodiments, the substrate includes any one or a combination of two or more of monocrystalline silicon, silica, glass, plastic, stainless steel, alumina, and fiber, but is not limited thereto.

In some preferred embodiments, the volume ratio of the free radical polymerization monomer to the complexing agent is 20:1 to 100:1.

In some preferred embodiments, the volume ratio of the free radical polymerizable monomer to the solvent is 1:15 to 2:3.

In some preferred embodiments, the distance between the metallic tin and the substrate on which the initiator is deposited is 0.01 to 0.15 mm.

In some preferred embodiments, the polymerization method further includes: first pretreating the surface of the metallic tin.

Further, the pretreatment specifically includes: using sandpaper to smooth the surface of the metal tin, and then performing oil and rust removal activation treatment in a pickling solution, followed by ultrasonic cleaning with acetone, alcohol, deionized water, and N ₂ Blow dry.

Furthermore, the time of the rust removal activation treatment is 2 to 10 minutes.

Furthermore, the pickling liquid is a mixed solution of hydrochloric acid and methanol.

In some preferred embodiments, the polymerization method also includes: ultrasonic cleaning of the substrate with acetone, alcohol, and deionized water, and N ₂ blow-drying treatment; and then depositing a large amount of initiator on the surface of the obtained substrate at 30-80°C. for 30 minutes to form an initiator monolayer on the surface of the substrate.

In some more specific embodiments, the oxygen-resistant and biocompatible metallic tin-mediated initiated polymerization method includes:

(1) Metal tin surface pre-treatment: Pre-treat the surface of the tin sheet or tin foil, first polish it with sandpaper, and carry out oil and rust removal activation treatment in pickling solution, and then in acetone, alcohol, deionized water Clean ultrasonically for 10 minutes respectively, then blow dry with _N2 after taking out.

(2) Preparation of surface initiator layer: Ultrasonically clean the substrate with acetone, alcohol, and deionized water for 10 minutes, blow dry with _N2 , and place it in a plasma cleaning machine for 10 minutes. The cleaned substrate is then placed in a vacuum drying oven, and the initiator is deposited on the surface of the substrate at a certain temperature for a certain period of time.

(3) Preparation of pre-reaction mixed liquid: At room temperature, mix the free radical polymerized monomer, complexing agent and solvent evenly to form a pre-reacted mixed liquid; wherein, the volume ratio of the free radical polymerized monomer to the complexing agent The ratio is 20:1 to 100:1; the volume ratio of the free radical polymerization monomer to the solvent is 1:15 to 2:3.

(4) Place the pre-reaction mixture of step (3) between the surface-treated metal tin sheet/foil and the substrate deposited with the initiator, control a certain distance to form a sandwich structure, and the free radical polymerization of the monomer begins. Surface-initiated polymerization is performed to produce polymer brush films with controllable thickness.

Further, the rust removal activation time is 2-10 minutes, and the pickling solution is a mixed solution of 3M hydrochloric acid and methanol (v:v=1:1~3).

In this application, tin (Sn) is an environmentally friendly, inexpensive metal element that has been widely used as food containers dating back to 3000 BC, and is still widely used as packaging materials. In addition, as an essential trace element for the human body, tin has excellent intrinsic biocompatibility, can be used as a reinforcing phase in medical implants, and has no rejection effect on tissues and organs of living organisms.

Another aspect of the embodiments of the present application also provides a biocompatible polymer brush film prepared by the aforementioned polymerization method.

Another aspect of the embodiments of the present application also provides the use of the aforementioned polymerization method in the fields of marine antifouling, surface lubrication, tissue engineering or biosensing.

The technical solution of the present application will be further described in detail below in conjunction with several preferred embodiments and drawings. This embodiment is implemented based on the technical solution of the invention and provides detailed implementation modes and specific operating processes. However, the technical solution of the present application is The scope of protection is not limited to the following examples.

The experimental materials used in the following examples can be purchased from conventional biochemical reagent companies unless otherwise specified.

Example 1

(1) Metal tin surface pretreatment: Pretreat the surface of tin foil with a size of 2×2cm and a thickness of 0.2mm. First, polish it smooth with sandpaper, and add it in a mixed solution of 3M hydrochloric acid and methanol (v:v=1:1). Clean in medium for 5 minutes, then ultrasonic clean in acetone, alcohol, and deionized water for 10 minutes respectively, and blow dry with _N2 after taking out.

(2) Preparation of surface initiator layer: Ultrasonically clean the silicon wafer coated with _SiO2 layer with acetone, alcohol and deionized water for 10 minutes respectively, then blow dry with _N2 , place it in a plasma cleaning machine for 10 minutes, and then clean it The substrate was placed in a vacuum drying oven, and 2-bromoisobutyric acid ethyl ester was deposited on the surface of the substrate at 60°C for 3 hours.

(3) Preparation of pre-reaction mixture: At room temperature, combine methyl methacrylate (0.25 mL), tris-(N, N-dimethylaminoethyl)amine (25 μL) and deionized water (1.5 mL). Mix evenly to form a pre-reaction mixture.

(4) Place the pre-reaction mixture of step (3) between the surface-treated metal tin foil and the substrate, and control the distance to 0.01 mm to form a sandwich structure (Figure 1 shows the metal tin sheet/foil mediated surface initiated polymerization device and Preparation diagram), a polymer brush film is generated after 1 hour of polymerization reaction. Figures 2a-2b are atomic force microscope images of the prepared polymer brush film, and its thickness was measured to be 110±4nm.

Example 2

(1) Metal tin surface pretreatment: Pretreat the surface of tin foil with a size of 2×2cm and a thickness of 0.1mm. First, polish it smooth with sandpaper, and add it in a mixed solution of 3M hydrochloric acid and methanol (v:v=1:1). Clean in medium for 3 minutes, then ultrasonic clean in acetone, alcohol, and deionized water for 10 minutes respectively, and blow dry with _N2 after taking out.

(2) Preparation of surface initiator layer: Ultrasonically clean the stainless steel sheet with acetone, alcohol, and deionized water for 10 minutes, then blow dry with _N2 , and place it in a plasma cleaning machine for 10 minutes. Then the cleaned substrate was placed in a vacuum drying oven, and 2-bromoisobutyric acid ethyl ester was deposited on the surface of the substrate at 70°C for 3 hours.

(3) Preparation of pre-reaction mixture: Mix poly(ethylene glycol) methacrylate (1 mL), tris(2-pyridyl)methylamine (25 μL) and deionized water (1.5 mL) at room temperature. The pre-reaction mixture is uniformly formed.

(4) Place the pre-reaction mixture in step (3) between the surface-treated metal tin foil and the substrate, controlling the distance to 0.01mm to form a sandwich structure, and generate a polymer brush film after a certain period of polymerization reaction. Figure 3 shows the change curve of the thickness of the polymer brush film as a function of polymerization time, indicating that the polymerization reaction under this condition has good controllability.

Example 3

(1) Metal tin surface pretreatment: Pretreat the surface of tin foil with a size of 2×2cm and a thickness of 0.2mm. First, polish it smooth with sandpaper, and add it in a mixed solution of 3M hydrochloric acid and methanol (v:v=1:1). Clean in medium for 5 minutes, then ultrasonic clean in acetone, alcohol, and deionized water for 10 minutes respectively, and blow dry with _N2 after taking out.

(2) Preparation of surface initiator layer: Ultrasonically clean the alumina template with acetone, alcohol, and deionized water for 10 minutes, blow dry with _N2 , and place it in a plasma cleaning machine for 10 minutes. Then the cleaned substrate was placed in a vacuum drying oven, and ethyl 2-bromophenyl acetate was deposited on the surface of the substrate at 80°C for 3 hours.

(3) Preparation of pre-reaction mixture: At room temperature, combine 3-sulfonate propyl methacrylate potassium salt (1 mL), tris-(N, N-dimethylaminoethyl)amine (25 μL) and deionized Mix the water and methanol mixed solution (v:v=2:1, 1.5mL) evenly to form a pre-reaction mixed solution.

(4) Place the pre-reaction mixture in step (3) between the surface-treated metal tin foil and the substrate, and control the distance to 0.01mm to form a sandwich structure. After 1 hour of polymerization reaction, a polymer brush film is obtained on the surface of the alumina. .

Example 4

(1) Metal tin surface pretreatment: Pretreat the surface of tin foil with a size of 2×2cm and a thickness of 0.2mm. First, polish it smooth with sandpaper, and add it in a mixed solution of 3M hydrochloric acid and methanol (v:v=1:1). Clean in medium for 3 minutes, then ultrasonic clean in acetone, alcohol, and deionized water for 10 minutes respectively, and blow dry with _N2 after taking out.

(2) Preparation of surface initiator layer: Ultrasonically clean the silicon wafer coated with SiO ₂ layer with acetone, alcohol and deionized water for 10 minutes respectively, then blow dry with N ₂ and place it in a plasma cleaning machine for 10 minutes. Then the cleaned substrate was placed in a vacuum drying oven, and 2-bromoisobutyric acid ethyl ester was deposited on the substrate surface at 60°C for 3 hours.

(3) Preparation of pre-reaction mixture: At room temperature, combine N-isopropylacrylamide (NIPAM, 0.5g), hydroxyethyl methacrylate (HEMA, 1mL), poly(ethylene glycol) methacrylate Ester (OEGMA, 1 mL), 3-sulfonate propyl methacrylate potassium salt (SPMA, 0.5 g), dimethylaminoethyl methacrylate (DMAEMA, 1 mL), methacryloyloxyethyltrimethyl chloride Ammonium chloride (METAC, 1 mL) was mixed with tris(2-pyridyl)methylamine (25 μL) and deionized water (1.5 mL) to form a pre-reaction mixture.

(4) Place the pre-reaction mixture in step (3) between the surface-treated metal tin foil and the substrate, controlling the distance to 0.01mm to form a sandwich structure, and generate a polymer brush film after 1 hour of polymerization reaction. Figure 4 shows the thickness of the film after polymerization of different monomers, indicating that this polymerization method is suitable for a large number of different types of monomers.

Example 5

(1) Metal tin surface pretreatment: Pretreat the surface of tin foil with a size of 2×2cm and a thickness of 0.2mm. First, polish it smooth with sandpaper, and add it in a mixed solution of 3M hydrochloric acid and methanol (v:v=1:1). Clean in medium for 5 minutes, then ultrasonic clean in acetone, alcohol, and deionized water for 10 minutes respectively, and blow dry with _N2 after taking out.

(2) Preparation of surface initiator layer: Ultrasonically clean the silicon wafer coated with SiO ₂ layer with acetone, alcohol and deionized water for 10 minutes respectively, then blow dry with N ₂ and place it in a plasma cleaning machine for 10 minutes. The cleaned substrate was then placed in a vacuum drying oven, and ethyl 2-bromophenyl acetate was deposited on the surface of the substrate at 60°C for 3 hours.

(3) Preparation of pre-reaction mixture: At room temperature, combine 1-vinylimidazole tetrafluoroborate (1mL), tris-(N,N-dimethylaminoethyl)amine (25μL) and deionized water. Mix evenly with methanol mixed solution (v:v=2:1, 1.5mL) to form a pre-reaction mixed solution.

(4) Place the pre-reaction mixture in step (3) between the surface-treated metal tin foil and the substrate, controlling the distance to 0.01mm to form a sandwich structure. After 1 hour of polymerization reaction, a polymer brush film is obtained on the surface of the silicon wafer. . Figures 5a-5b are fluorescence microscope photos of the prepared polymer brush film and cells co-cultured for 24 hours, indicating that the obtained polymer brush has good biocompatibility.

Example 6

(1) Metal tin surface pretreatment: Pretreat the surface of the tin foil disc with a diameter of 10cm and a thickness of 0.2mm. First, polish it smooth with sandpaper, and add it in a mixed solution of 3M hydrochloric acid and methanol (v:v=1:1). Clean in medium for 8 minutes, then ultrasonic clean in acetone, alcohol, and deionized water for 10 minutes respectively, and blow dry with _N2 after taking out.

(2) Surface initiator layer preparation: Silicon wafers coated with _SiO2 layer at the wafer level are ultrasonically cleaned with acetone, alcohol, and deionized water for 10 minutes respectively, then blown dry with _N2 , and placed in a plasma cleaning machine for 10 minutes. Then the cleaned substrate was placed in a vacuum drying oven, and 2-bromoisobutyric acid ethyl ester was deposited on the substrate surface at 60°C for 3 hours.

(3) Preparation of pre-reaction mixture: At room temperature, combine methacryloyloxyethyltrimethylammonium chloride (1mL), N, N, N′, N″, N″-pentamethyldioxide Mix ethyltriamine (18 μL) and a mixed solution of deionized water and methanol (v:v=2:1, 1.5mL) evenly to form a pre-reaction mixture.

(4) Place the pre-reaction mixture in step (3) between the surface-treated metal tin foil and the substrate, controlling the distance to 0.01 mm to form a sandwich structure, and generate a wafer-level polymer brush film after 30 minutes of polymerization reaction. Figures 6a-6c show that the average thickness measured by ellipsometer is 81±6nm and the roughness is 3±0.6nm.

Example 7

(1) Metal tin surface pretreatment: Pretreat the surface of tin foil with a size of 5×5cm and a thickness of 0.2mm. First, polish it smooth with sandpaper, and add it in a mixed solution of 3M hydrochloric acid and methanol (v:v=1:1). Clean in medium for 5 minutes, then ultrasonic clean in acetone, alcohol, and deionized water for 10 minutes respectively, and blow dry with _N2 after taking out.

(2) Preparation of surface initiator layer: Ultrasonically clean the PVA plastic with acetone, alcohol, and deionized water for 10 minutes, then blow dry with _N2 , and place it in a plasma cleaning machine for 10 minutes. Then the cleaned substrate was placed in a vacuum drying oven, and 2-bromoethylbenzene was deposited on the surface of the substrate at 60°C for 3 hours.

(3) Preparation of pre-reaction mixture: At room temperature, add styrene (1mL), tris-(N,N-dimethylaminoethyl)amine (30μL) and a mixed solution of deionized water and methanol (v:v =2:1, 1.5mL) and mix evenly to form a pre-reaction mixture.

(4) Place the pre-reaction mixture in step (3) between the surface-treated metal tin foil and the substrate, controlling the distance to 0.01mm to form a sandwich structure, and generate a polymer brush film after 1 hour of polymerization reaction. Figure 3 shows the change curve of the thickness of the polymer brush film as a function of polymerization time, indicating that the polymerization reaction under this condition has good controllability.

In addition, the inventor of the present case also conducted experiments with other raw materials, process operations, and process conditions mentioned in this specification with reference to the aforementioned embodiments, and achieved relatively ideal results.

It should be understood that the technical solution of the present application is not limited to the above-mentioned specific implementation cases. All technical modifications made based on the technical solution of the present application will fall within the scope of the present application without departing from the purpose of the present application and the scope protected by the claims. within the scope of protection applied for.

Claims (10)

An oxygen-resistant and biocompatible metal tin-mediated initiated polymerization method, characterized by comprising: confining a pre-reaction mixture containing free radical polymerization monomers, complexing agents and solvents to metal tin and deposition triggers A polymerization reaction occurs between the agent and the substrate, thereby producing a biocompatible polymer brush film. The polymerization method according to claim 1, characterized in that it includes: In an atmospheric environment, the free radical polymerization monomer, the complexing agent and the solvent are uniformly mixed at room temperature to form the pre-reaction mixture; And, the pre-reaction mixed liquid is placed between the metal tin and the substrate on which the initiator is deposited, so that at least the metal tin, the pre-reaction mixed liquid and the substrate on which the initiator is deposited form a sandwich structure, and in 15 to 60 ℃ reaction time is not less than 15 minutes, thereby producing the biocompatible polymer brush film. The polymerization method according to claim 1, characterized in that: the free radical polymerization monomers include acrylates, methacrylates, styrene, 4-vinylpyridine, 3-vinylaniline, acrylamide, Any one or a combination of two or more of methacrylamides and 1-vinylimidazole salts; preferably, the acrylates include any one of methyl acrylate, ethyl acrylate, and tert-butyl acrylate. One or a combination of two or more; preferably, the methacrylates include methyl methacrylate and/or butyl methacrylate; preferably, the acrylamide includes N-isopropylacrylamide and/or N-tert-butyl acrylamide; preferably, the methacrylamides include N-isopropyl methacrylamide and/or N-tert-butyl methacrylamide; preferably, the 1-ethylene Base imidazole salts include 1-vinylimidazole bromide and/or 1-vinylimidazole tetrafluoroborate; And/or, the complexing agent includes N, N, N′, N″, N″-pentamethyldiethylenetriamine, tris(2-pyridyl)methylamine, 1,1,4,7 , any one or two of 10,10-hexamethyltriethylenetetramine, tris-(N,N-dimethylaminoethyl)amine, 2,2-bipyridine, and hexamethylenetetramine A combination of the above; And/or, the initiator includes ethyl 2-bromophenylacetate, ethyl 2-bromoisobutyrate, methyl 2-bromoisobutyrate, ethyl 2-bromopropionate, 2-bromoethylbenzene , any one or a combination of two or more of α-chlorophenylethane, 2-chloropropionitrile and 2-bromopropionitrile; And/or, the solvent includes water and/or a mixed solution of water and methanol. The polymerization method according to claim 1, characterized in that: the metal tin includes tin sheets and/or tin foil; And/or, the substrate includes any one of single crystal silicon, silicon dioxide, glass, plastic, stainless steel, alumina, and fiber. The polymerization method according to claim 1, characterized in that: the volume ratio of the free radical polymerization monomer to the complexing agent is 20:1 to 100:1; And/or, the volume ratio of the free radical polymerization monomer to the solvent is 1:15 to 2:3. The polymerization method according to claim 1, wherein the distance between the metal tin and the substrate on which the initiator is deposited is 0.01 to 0.15 mm. The polymerization method according to claim 1, further comprising: first pre-treating the surface of the metallic tin. The polymerization method according to claim 7, wherein the pretreatment specifically includes: polishing the surface of the metal tin with sandpaper, and then performing degreasing and rust removal activation treatment in a pickling solution, and then using acetone. , ultrasonic cleaning with alcohol and deionized water, and N ₂ blow-drying treatment; preferably, the time of the rust removal activation treatment is 2 to 10 minutes; preferably, the pickling solution is a mixed solution of hydrochloric acid and methanol. The polymerization method according to claim 1, further comprising: ultrasonic cleaning of the substrate with acetone, alcohol, and deionized water, and _N2 blow-drying treatment; and then depositing an initiator on the surface of the obtained substrate at 30 to 80°C. No less than 30 minutes to form a monolayer of initiator on the surface of the substrate. Use of the polymerization method according to any one of claims 1 to 9 in the fields of marine antifouling, surface lubrication, tissue engineering or biosensing.

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