Functional polymers for reducing biofouling on material surfaces, their preparation methods, and methods for preparing functional polymer coatings.

Abstract

This application discloses a functional polymer for reducing biofouling on material surfaces, its preparation method, and a method for preparing a functional polymer coating. In the structural formula of the functional polymer, the degree of polymerization n ranges from 5 to 200, m ranges from 2 to 120, z ranges from 2 to 20, and k ranges from 1 to 12. The functional polymer provided in this application can form a smooth functional polymer coating on the substrate surface. The functional polymer coating surface is hydrophilic and has good anti-protein adsorption capacity. By adjusting the degree of polymerization of the PEG side chains, the anti-protein adsorption capacity can be further improved.

Description

Technical Field

[0001] This application relates to the field of polymer technology, and in particular to a functional polymer for reducing biocontamination on material surfaces, a method for preparing the same, and a method for preparing a functional polymer coating. Background Technology

[0002] Biofouling is a common problem faced by materials in practical applications in fields such as biomedicine, separation membranes, and marine antifouling. The non-specific adsorption of contaminants such as proteins and bacteria on material surfaces not only affects the interfacial properties of the materials but may also reduce their stability during use. Therefore, improving the biofouling resistance of material surfaces is an urgent problem to be solved. Summary of the Invention

[0003] Based on this, this application provides a functional polymer that can reduce biocontamination on the surface of materials. The functional polymer forms a monomolecular coating on the surface of the substrate, reducing the non-specific adsorption of pollutants such as proteins and bacteria on the surface of the material and increasing the stability of the material in use.

[0004] A functional polymer for reducing biofouling on material surfaces, the structural formula of which is shown below:

[0005] Among them, the degree of polymerization n ranges from 5 to 200, m ranges from 2 to 120, z ranges from 2 to 20, and k ranges from 1 to 12.

[0006] The functional polymer provided in this application has amine groups as anchoring groups, which stably bond the functional polymer to the substrate through electrostatic interactions. The thickness of the functional polymer coating can be controlled by adjusting the value of k.

[0007] Multiple PEG side chains on the functional polymer form a bristle-like structure. The grafting density of the PEG side chains can be adjusted by changing the value of m. PEG, or polyethylene glycol, possesses excellent hydrophilicity, biocompatibility, and anti-protein adsorption capabilities. Combined with the special topological structure of the functional polymer, high-density PEG side chains exhibit excellent anti-protein adsorption capacity. By adjusting the value of z, the chain length of PEG can be adjusted. Increasing the chain length of PEG can further improve its hydrophilicity and anti-protein adsorption capabilities.

[0008] Several alternative methods are provided below, but they are not intended as additional limitations on the overall solution above. They are merely further additions or optimizations. Provided there are no technical or logical contradictions, each alternative method can be combined individually with respect to the overall solution above, or multiple alternative methods can be combined with each other.

[0009] Optionally, the degree of polymerization n ranges from 10 to 100, m ranges from 40 to 120, z ranges from 6 to 20, and k ranges from 6 to 12.

[0010] This application also provides a method for preparing the functional polymer that reduces biofouling on material surfaces, comprising the following steps: (1) A functional monomer was prepared, and the structural formula of the functional monomer is shown below: ; (2) The functional monomer reacts with the RAFT chain transfer agent to obtain a macromolecular initiator, the structural formula of which is shown below: ; (3) The macromolecular initiator reacts with polyethylene glycol acrylate monomer to obtain molecular brush polymer, and the molecular brush polymer is post-treated to obtain the functional polymer that reduces biocontamination on the material surface.

[0011] In step (1), the functional monomer contains Boc protected amino groups and ATRP initiation sites. In step (2), a macromolecular initiator was prepared by RAFT polymerization. Subsequently, PPEGA side chains were introduced into the functional polymer by ATRP reaction. After post-treatment, the Boc protecting groups were removed to obtain the functional polymer that reduces biofouling on the material surface.

[0012] The reaction equation for step (2) is as follows:

[0013]

[0014] The RAFT chain transfer agent in step (2) is 2-[dodecylthio(thiocarbonyl)thio]-2-methylpropionic acid; the initiator in step (2) is azobisisobutyronitrile, and the reaction is carried out under anhydrous and oxygen-free conditions. Step (2) is carried out in tetrahydrofuran solvent, and the ratio of the functional monomer to tetrahydrofuran is 1 mmol: 0.2~0.3 mL.

[0015] The reaction equation for step (3) is as follows:

[0016]

[0017] Step (3) uses CuBr as a catalyst and tris[2-(dimethylamino)ethyl]amine as a ligand. The molar ratio of CuBr to tris[2-(dimethylamino)ethyl]amine is 1:1. Tetrahydrofuran is used as a solvent. The ratio of macromolecular initiator, CuBr and tetrahydrofuran is 1 mmol: 2~3 mmol: 25~35 mL.

[0018] Step (3) 10-20 min before the end of the reaction, add 2,2,6,6-tetramethylpiperidine nitride to remove the Br at the end of the side chain and continue stirring the reaction.

[0019] In step (3), the post-treatment of the molecular brush polymer involves using trifluoroacetic acid to deprotect the NH-Boc groups in the polymer, thereby removing the Boc protecting groups and exposing the amino structure. The reaction equation for the post-treatment is as follows:

[0020]

[0021] The post-treatment reaction conditions were room temperature, and the post-treatment time was no less than 8 hours. The solvent for post-treatment was dichloromethane (DCM), and the ratio of molecular brush polymer, solvent, and trifluoroacetic acid was 1 g : 80~120 mL : 40~60 mL.

[0022] Optionally, the molar ratio of the functional monomer to the RAFT chain transfer agent is 60-70:1.

[0023] RAFT polymerization is a living, controllable radical polymerization. The molar ratio of the functional monomer to the RAFT chain transfer agent affects the degree of polymerization n. For example, if the molar ratio of the functional monomer to the RAFT chain transfer agent is 60:1, theoretically the degree of polymerization n is approximately 60.

[0024] Optionally, the molar ratio of the macromolecular initiator to the polyethylene glycol acrylate monomer is 1:50~600. More preferably, the molar ratio of the macromolecular initiator to the polyethylene glycol acrylate monomer is 1:300~600.

[0025] ATRP polymerization is a type of reactive and controllable free radical polymer, and the molar ratio of macromolecular initiator to polyethylene glycol acrylate monomer affects the value of m.

[0026] The number average molecular weight range of polyethylene glycol acrylate monomers is 160 to 700.

[0027] Optionally, the reaction conditions for step (2) are: temperature 60~80℃, reaction time 15~20 hours.

[0028] Optionally, the reaction conditions for step (3) are: temperature 30~50℃, reaction time 5~10 hours.

[0029] Optionally, the method for preparing the functional monomer includes the following steps: (a) Acryloyl chloride reacts with tert-butyl N-(6-hydroxyhexyl)carbamate to give the first monomer, the structural formula of which is as follows: ; (b) The first monomer reacts with paraformaldehyde to obtain the second monomer, the structural formula of which is as follows: ; (c) The second monomer reacts with 2-bromopropionyl bromide to obtain the functional monomer.

[0030] The reaction equation for step (a) is as follows:

[0031] In step (a), the molar ratio of N-(6-hydroxyhexyl)carbamate tert-butyl ester to acryloyl chloride is 1:1 to 1.5. Step (a) is carried out in triethylamine and dichloromethane (DCM), with an acrylamide, triethylamine, and dichloromethane molar ratio of 1 mol: 1 to 1.2 mol: 70 to 80 mL. The reaction conditions for step (a) are room temperature and a reaction time of at least 8 hours.

[0032] The reaction equation for step (b) is as follows:

[0033] In step (b), the reaction is carried out in an aqueous solution of trimethylamine, with a molar ratio of trimethylamine to the first monomer of 0.5 to 0.7:1.

[0034] The reaction temperature in step (b) is 50~70℃ and the reaction time is 65~80 hours.

[0035] The reaction equation for step (c) is as follows:

[0036] Step (c) involves the reaction in triethylamine and dichloromethane (DCM), with the ratio of the second monomer, triethylamine, and dichloromethane being 1 mol: 1.5~2 mol: 800~1200 mL.

[0037] The reaction temperature in step (b) is room temperature, and the reaction time is at least 8 hours.

[0038] Optionally, in step (b), the molar ratio of the first monomer to paraformaldehyde is 1.5 to 2.5:1; In step (c), the molar ratio of the second monomer to 2-bromopropionyl bromide is 1:1~2.

[0039] This application also provides a method for preparing a functional polymer coating, comprising the following steps: (1) The functional polymer for reducing biofouling on the material surface is dissolved in N,N-dimethylformamide to prepare a first solution; (2) The first solution was mixed with HEPES buffer solution at pH 7.4 at a volume ratio of 1:1~2 to obtain the second solution; (3) Immerse the substrate in the second solution for at least 12 hours, clean the immersed substrate with ethanol, and form the functional polymer coating on the surface of the substrate.

[0040] The functional polymer provided in this application can form a smooth functional polymer coating on the surface of a substrate (e.g., a silicon wafer). The surface of the functional polymer coating is hydrophilic and has good anti-protein adsorption ability. By adjusting the degree of polymerization of the PEG side chains, the anti-protein adsorption ability can be further improved. Attached Figure Description

[0041] Figure 1 It is the first monomer in Embodiment 1 of this application. 1 HNMR spectrum; Figure 2 It is the second monomer in Embodiment 1 of this application. 1 HNMR spectrum; Figure 3 It is the functional monomer Br-acrylate-NHBoc in Example 1 of this application. 1 HNMR spectrum; Figure 4 It is the poly(Br-acrylate-Boc) in Example 1 of this application. 1 HNMR spectrum; Figure 5 It is PAboc-g-PPEGA-1 in Example 1 of this application. 1 HNMR spectrum; Figure 6 It is PA-g-PPEGA-1 in Example 1 of this application. 1 HNMR spectrum; Figure 7 These are the GPC curves of PAboc-g-PPEGA in Examples 1 to 3 of this application, wherein poly(Br-acrylate-Boc) corresponds to the macromolecular initiator in Example 1, PAboc-g-PPEGA-1 corresponds to Example 1, PAboc-g-PPEGA-2 corresponds to Example 2, and PAboc-g-PPEGA-3 corresponds to Example 3. Figure 8 The AFM diagrams for the functional polymer coatings of Examples 1-3 are shown from left to right: (a) Functional polymer coating of Example 1; (b) Functional polymer coating of Example 2; (c) Functional polymer coating of Example 3. Figure 9Figure (a) shows the water contact angles, where (a) is the statistical result; (b) is the water contact angle image of SiO2; (c) is the water contact angle image of the macromolecular initiator poly(Br-acrylate-Boc); (d) is the water contact angle image of PA-g-PPEGA-1; (e) is the water contact angle image of PA-g-PPEGA-2; and (f) is the water contact angle image of PA-g-PPEGA-3. The column heights from left to right in Figure (a) correspond to the contact angles in (b) to (f).

[0042] Figure 10 The QCM-D curves of the functional polymer coatings prepared in Application Examples 1-3 are shown, where blank SiO2 is the silicon wafer treated in step (1) of Application Example 1, and PA- g -PPEGA-1 corresponds to the functional polymer coating in Application Example 1, PA- g -PPEGA-2 corresponds to the functional polymer coating in Application Example 2, PA- g -PPEGA-3 corresponds to the functional polymer coating in Application Example 3. Detailed Implementation

[0043] The technical solution of this application will be described in detail below with reference to specific embodiments.

[0044] Example 1 A method for preparing a functional polymer that reduces biofouling on material surfaces includes the following steps: 1. Synthesis of the functional monomer Br-acrylate-NHBoc (1) Under a nitrogen atmosphere, tert-butyl N-(6-hydroxyhexyl)carbamate (20.00 g, 0.092 mol), triethylamine (Et3N, 18 mL, 0.13 mol), and ultra-dry dichloromethane (DCM, 75 mL) were added to a three-necked flask. After stirring in an ice-water bath, acryloyl chloride (10.86 g, 0.12 mol) was added dropwise, and the reaction was allowed to proceed overnight at room temperature. The reaction solution was diluted with DCM, filtered, washed with saturated brine, extracted with DCM, dried over anhydrous MgSO4, concentrated by rotary evaporation, and purified by silica gel column chromatography (hexane (Hex): ethyl acetate (EA) = 10:1) to obtain product 1, i.e., the first monomer. The reaction equation is as follows:

[0045] For the NMR characterization of the first monomer, see [link to NMR characterization]. Figure 1 As shown in the figure. δ The signals appearing at 6.41 ppm, 6.12 ppm and 5.82 ppm are attributed to proton peaks on the carbon-carbon double bonds in the acrylate structure; δ The triplet at 4.14 ppm corresponds to the methylene proton attached to the ester group; δ The signal at 3.10 ppm is attributed to the methylene proton linked to NH-Boc. Furthermore, δ The singlet at 1.43 ppm is a characteristic peak of the tert-butyl methyl proton in the Boc protecting group. This characteristic peak matches the target structure, indicating that the first monomer was successfully synthesized. Its 1H NMR data are as follows: 1 ¹H NMR (400 MHz, CDCl₃, ppm): δ =1.31-1.75 (m, 8H, -C H 2C H 2C H 2C H 2-), 1.43 (s, 9H, -C(C H 3)3), 3.10 (t, 2H, -C H 2-NH), 4.14 (t, 2H, -OC H 2-), 5.82, 6.41 (dd, 2H, C H 2=), 6.12 (dd, 1H, -C H =) (2) Product 1 (19.00 g, 0.07 mmol), paraformaldehyde (1.05 g, 0.035 mmol), and trimethylamine aqueous solution (NMe3, 11.7 mL, 0.042 mmol) were added to a round-bottom flask and reacted at 60 °C for 72 h. The reaction solution was allowed to stand and separate into layers. The organic phase was collected, extracted with anhydrous diethyl ether, dried over anhydrous MgSO4, concentrated by rotary evaporation, and purified by silica gel column chromatography (Hex:EA = 6:1) to obtain colorless liquid product 2, which is the second monomer. The reaction equation is as follows:

[0046] For the NMR characterization of the second monomer, see [link to NMR characterization]. Figure 2 As shown. Compared to the first monomer, the second monomer... δ A new singlet appeared at 4.34 ppm, which can be attributed to the proton signal of the newly introduced -CH2OH group in the hydroxymethyl group. Meanwhile, δ The proton peaks of the carbon-carbon double bond are still observed at 6.25 ppm and 5.83 ppm, indicating that the double bond in the monomer structure is still preserved after the reaction. The appearance of the characteristic peak of hydroxymethyl indicates that the Baylis-Hillman reaction proceeded smoothly and the hydroxyl group was successfully introduced into the monomer structure. The 1H NMR data of the second monomer are as follows: 1 ¹H NMR (400 MHz, CDCl₃, ppm): δ = 1.31-1.75 (m, 8H, -C H 2C H2C H 2C H 2-), 1.43 (s, 9H, -C(C H 3)3), 3.10 (t, 2H, -C H 2-NH), 4.18 (t, 2H, -OC H 2-), 4.34 (s, 2H, C H 2OH), 5.83, 6.25 (dd, 2H, C H 2=C).

[0047] (3) Under a nitrogen atmosphere, product 2 (9 g, 0.03 mol), triethylamine (6.25 mL, 0.045 mol), and ultra-dry DCM (50 mL) were added to a three-necked flask. After stirring in an ice-water bath, bromopropionyl bromide (9.025 g, 0.042 mol) was added dropwise, and the reaction was allowed to proceed overnight at room temperature. The reaction solution was diluted with DCM, filtered, washed with saturated brine, extracted with DCM, dried overnight with anhydrous MgSO4, concentrated by rotary evaporation, and purified by silica gel column chromatography (Hex:EA = 10:1) to obtain 6.5 g of product 3, which is the functional monomer Br-acrylate-NHBoc. The reaction equation is as follows:

[0048] For NMR characterization of functional monomers, see [link to NMR description]. Figure 3 As shown. Compared to the second monomer, the one originally located δ The methylene proton peak at 4.34 ppm, linked to the hydroxyl group, shifted to [a later position] after the reaction. δ The concentration of approximately 4.92 ppm indicates a significant change in the surrounding chemical environment after the acylation reaction of the hydroxyl group. Meanwhile, δ The methyl proton signal appearing at 1.85 ppm, and δ The methylene proton peak at 4.40 ppm, corresponding to -CH-Br, is a characteristic signal of the 2-bromopropionyl group. The appearance of these new peaks indicates that the 2-bromopropionyl group has been successfully incorporated into the monomer structure, and the functional monomer Br-acrylate-Boc has been successfully synthesized. The 1H NMR data of the functional monomer are as follows: 1 ¹H NMR (400 MHz, CDCl₃, ppm): δ = 1.25-1.83 (m, 8H, -C H 2C H 2C H 2C H 2-), 1.43 (s, 9H, -C(C H 3)3), 3.10 (t, 2H, -C H2-NH), 4.18 (t, 2H, -OC H 2-), 4.40 (q, 1H, -C H -Br), 4.92 (q, 2H, -C H 2O), 5.91, 6.39 (dd, 2H, C H 2=C).

[0049] 2. Synthesis of Functional Polymers (1) After anhydrous and oxygen-free treatment, azobisisobutyronitrile (AIBN, 0.82 mg, 0.005 mmol) and 2-[dodecylthio(thiocarbonyl)thio]-2-methylpropionic acid (CDSA, 6 mg, 0.015 mmol) were added to a 10 mL Schlenk flask, followed by monomer 3 (400 mg, 0.966 mmol) and ultra-dry tetrahydrofuran (THF, 0.25 mL). After three cycles of liquid nitrogen freezing-vacuuming-nitrogen purging, the reaction was carried out in an oil bath at 70 °C for 17 h, and then quenched with liquid nitrogen. The reaction solution was diluted with THF, centrifuged three times in an ice-cold mixed solvent with a volume ratio of diethyl ether:n-hexane = 1:1, and dried in an oven to obtain the macromolecular initiator poly(Br-acrylate-Boc). The reaction equation is as follows:

[0050] See NMR spectrum of macromolecular initiator Figure 4 As shown, compared with the 1H NMR spectrum of the monomer Br-acrylate-Boc, the spectrum originally located at... δ The proton peaks of the carbon-carbon double bond at δ=5.91ppm and 6.39ppm essentially disappeared in the polymer spectrum, indicating that the double bonds in the monomer had participated in the polymerization reaction. Simultaneously, the sharp characteristic peaks in the original monomer spectrum transformed into broader peaks after polymerization, which is consistent with the typical characteristics of polymer NMR spectra, indicating that poly(Br-acrylate-Boc) had been successfully formed. Furthermore, the proton signal related to the methylene group near the amide at δ=3.10ppm, and the proton peak of the tert-butylmethyl group in the Boc protecting group, still existed, indicating that the Boc protecting group was not significantly damaged during RAFT polymerization, and the functional groups in the monomer were well preserved. The degree of polymerization n was calculated to be 20 from the NMR spectrum.

[0051] (2) After the 50 mL Schlenk flask was treated to be anhydrous and oxygen-free, CuBr (29.60 mg, 0.206 mmol) was added, followed by the injection of the macromolecular initiator (30 mg, 0.069 mmol), polyethylene glycol acrylate monomer (Mn = 480 g / mol, 10 g, 20.64 mmol), and ultra-dry THF (2 mL) prepared in step (1). After two freezing-vacuuming-nitrogen purging cycles, tris[2-(dimethylamino)ethyl]amine (HMTETA, 53.2 μL, 0. After a second freezing-vacuuming-nitrogen purging, the mixture was reacted in an oil bath at 40°C for 6 hours. 15 minutes before the end of the reaction, 2,2,6,6-tetramethylpiperidine nitride oxide (TEMPO, 11 mg, 0.07 mmol) was added to remove the Br at the end of the side chain, and stirring was continued. After quenching the reaction solution, it was diluted with THF, passed through a neutral alumina column, concentrated by rotary evaporation, and centrifuged three times in an ice-cold mixed solvent with a volume ratio of ether:n-hexane = 1:1. The precipitate was then dried in an oven to obtain the molecular brush polymer PAboc-g-PPEGA-1.

[0052] NMR spectra of the molecular brush polymer PAboc-g-PPEGA-1 are shown below. Figure 5 As shown, a characteristic peak of PEG terminal methyl protons appeared at δ=3.37ppm, and a characteristic peak of methylene protons in the PEG repeating unit appeared at δ=3.64ppm, indicating that the PPEGA side chains were successfully introduced into the polymer structure. Compared with the macromolecular initiator poly(Br-acrylate-Boc), the appearance of PEG segment-related characteristic peaks indicates that the ATRP graft polymerization proceeded smoothly.

[0053] (3) Take a Schlenk flask with a pre-placed stir bar, add 0.1g of the molecular brush polymer prepared in step (2), add 10mL of ultra-dry DCM under a nitrogen atmosphere, and stir continuously for 30min to allow the polymer to dissolve completely. Place the reaction flask in an ice-water bath to cool, and then add 5mL of trifluoroacetic acid (TFA) to the flask under a nitrogen atmosphere using a syringe. After stirring in the ice-water bath for 30min, remove the ice-water bath and place the reaction system at room temperature to continue the reaction overnight.

[0054] After the reaction was completed, the system was concentrated by rotary evaporation. An appropriate amount of THF was added to the concentrate to dissolve it. The product was treated with n-hexane as a settling agent, and the resulting product was dried in a vacuum oven to constant weight to obtain the functional polymer PA-g-PPEGA-1, which reduces biofouling on material surfaces. The functional polymer was stored in a glove box under nitrogen atmosphere at room temperature.

[0055] In this step, trifluoroacetic acid (TFA) is used to treat the molecular brush polymer PAboc- gThe NH-Boc groups in PPEGA undergo deprotection treatment, removing the Boc protecting group and exposing the amino structure. Compared to the molecular brush polymer before deprotection, δ The characteristic peak at 1.41 ppm, attributed to the tert-butyl methyl proton in the Boc protecting group, essentially disappeared after the reaction, indicating that the Boc group was effectively removed. Simultaneously, the positions of the characteristic peaks related to the polymer backbone and PPEGA side chains did not change significantly, indicating that the deprotection process did not significantly affect the polymer's main structure. These results demonstrate that PPEGA- g The NH-Boc group in -PPEGA was successfully converted to an amino group, providing a basis for subsequent functionalization reactions, revealing the NH group under acidic conditions. 3+ The positive charge.

[0056] Example 2 The only difference from Example 1 is that the amount of polyethylene glycol acrylate monomer used is 15g, 30.96mmol. All other conditions are the same as in Example 1. In this example, m was calculated to be 80 using NMR spectroscopy, and the resulting functional polymer was PA-g-PPEGA-2.

[0057] Example 3 The only difference from Example 1 is that the amount of polyethylene glycol acrylate monomer used is 20g, 41.28mmol. All other conditions are the same as in Example 1. In this example, m was calculated to be 120 using NMR spectroscopy, and the resulting functional polymer was PA-g-PPEGA-3.

[0058] Application Example 1 A method for preparing a functional polymer coating includes the following steps: (1) The silicon wafer was cleaned with piranha solution and treated with plasma; (2) The functional polymer PA-g-PPEGA-1 prepared in Example 1 was dissolved in N,N-dimethylformamide to prepare a first solution of 0.1 mg / mL; (3) The first solution was mixed with HEPES buffer at pH 7.4 to obtain the second solution, and the volume ratio of the first solution to the HEPES buffer was 2:3; (4) Soak the silicon wafer from step (1) in the second solution overnight, and clean it with a large amount of ethanol to obtain a monomolecular functional polymer coating on the surface of the silicon wafer.

[0059] Application Example 2 The functional polymer PA-g-PPEGA-2 prepared in Example 2 was used to prepare a functional polymer coating using the method in Application Example 1.

[0060] Application Example 3 The functional polymer PA-g-PPEGA-3 prepared in Example 3 was used to prepare a functional polymer coating using the method in Application Example 1.

[0061] Performance Characterization The AFM morphology of the functional polymer coatings prepared in Examples 1-3 is shown in [reference]. Figure 8 As shown. The surfaces of the three functional polymer coatings are generally continuous, with no obvious large-scale agglomeration or phase separation observed, indicating that the polymers can cover the substrate surface relatively uniformly. Further analysis of surface roughness shows that PA- g -PPEGA-1, PA- g -PPEGA-2 and PA- g The RMS roughness of the PPEGA-3 modified surfaces were 0.32 μm, 0.31 μm, and 0.22 μm, respectively. The roughness of the three samples was at a low level, indicating that the obtained polymer-modified layers were generally smooth.

[0062] Comparing the surfaces modified by the three functional polymers, it can be found that as the degree of polymerization of PPEGA side chains increases, the surface morphology is not significantly damaged, indicating that the change in the degree of polymerization of side chains does not lead to severe agglomeration or uneven coverage of the film.

[0063] See Figure 9 As shown, the water contact angle gradually decreases from (b) to (c), indicating that the surface modified with the functional polymer has good wetting properties.

[0064] The QCM-D frequency variation curves of the different functional polymer coatings prepared in Examples 1-3 in 30 mg / mL BSA (bovine serum albumin) solution are shown in the figure. Figure 10 As shown, the frequency of BSA adsorption on the blank silica substrate decreased significantly after adsorption, indicating that BSA readily undergoes non-specific adsorption on the unmodified silicon wafer surface. In contrast, the frequency of BSA adsorption on the PA-... g The surface frequency variation amplitude was significantly reduced after modification with PPEGA functional polymer, indicating that the functional polymer coating can effectively reduce the direct contact between BSA and the substrate, thereby reducing protein adsorption.

[0065] It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. Therefore, the scope of protection of this patent application shall be determined by the appended claims.

Claims

1. A functional polymer for reducing biofouling on material surfaces, characterized in that, The structural formula of the functional polymer is shown below: Among them, the degree of polymerization n ranges from 5 to 200, m ranges from 2 to 120, z ranges from 2 to 20, and k ranges from 1 to 12.

2. The functional polymer for reducing biofouling on material surfaces according to claim 1, characterized in that, The degree of polymerization n ranges from 10 to 100, m ranges from 40 to 120, z ranges from 6 to 20, and k ranges from 6 to 12.

3. A method for preparing a functional polymer for reducing biofouling on material surfaces as described in claim 1 or 2, characterized in that, Includes the following steps: (1) A functional monomer was prepared, and the structural formula of the functional monomer is shown below: ； (2) The functional monomer reacts with the RAFT chain transfer agent to obtain a macromolecular initiator, the structural formula of which is shown below: ； (3) The macromolecular initiator reacts with polyethylene glycol acrylate monomer to obtain molecular brush polymer, and the molecular brush polymer is post-treated to obtain the functional polymer that reduces biocontamination on the material surface.

4. The method for preparing the functional polymer for reducing biofouling on material surfaces as described in claim 3, characterized in that, The molar ratio of the functional monomer to the RAFT chain transfer agent is 60-70:

1.

5. The method for preparing the functional polymer for reducing biofouling on material surfaces as described in claim 3, characterized in that, The molar ratio of the macromolecular initiator to the polyethylene glycol acrylate monomer is 1:50~600.

6. The method for preparing the functional polymer for reducing biofouling on material surfaces as described in claim 3, characterized in that, The reaction conditions for step (2) are: temperature 60~80℃, reaction time 15~20 hours.

7. The method for preparing the functional polymer for reducing biofouling on material surfaces as described in claim 3, characterized in that, The reaction conditions for step (3) are: temperature 30~50℃, reaction time 5~10 hours.

8. The method for preparing the functional polymer for reducing biofouling on material surfaces as described in claim 3, characterized in that, The method for preparing the functional monomer includes the following steps: (a) Acryloyl chloride reacts with tert-butyl N-(6-hydroxyhexyl)carbamate to give the first monomer, the structural formula of which is as follows: ； (b) The first monomer reacts with paraformaldehyde to obtain the second monomer, the structural formula of which is as follows: ； (c) The second monomer reacts with 2-bromopropionyl bromide to obtain the functional monomer.

9. The method for preparing the functional polymer for reducing biofouling on material surfaces as described in claim 8, characterized in that, In step (b), the molar ratio of the first monomer to paraformaldehyde is 1.5 to 2.5:1; In step (c), the molar ratio of the second monomer to 2-bromopropionyl bromide is 1:1~2.

10. A method for preparing a functional polymer coating, characterized in that, Includes the following steps: (1) The functional polymer for reducing biofouling on material surfaces as described in claim 1 or 2 is dissolved in N,N-dimethylformamide to prepare a first solution; (2) The first solution was mixed with HEPES buffer solution at pH 7.4 at a volume ratio of 1:1~2 to obtain the second solution; (3) Immerse the substrate in the second solution for at least 12 hours, clean the immersed substrate with ethanol, and form the functional polymer coating on the surface of the substrate.

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