CN111440519A - A kind of preparation method of long-term stable amphiphilic antifouling coating based on mussel biomimetic - Google Patents

Abstract

The invention relates to a preparation method of a mussel bionic long-term stable amphiphilic antifouling coating. The method comprises the following steps: mixing dopamine hydrochloride, sodium borate, sodium carbonate and deionized water, dropwise adding a methacrylic anhydride solution, mixing the obtained dopamine methacrylamide with mercapto polydimethylsiloxane, polyethylene glycol diacrylate, a photoinitiator and a solvent, coating the mixture on a base material, and curing under the irradiation of ultraviolet light. The method has simple process synthesis conditions, cleanness and environmental protection, and has rapid and good effect of ultraviolet light initiated crosslinking reaction; the prepared coating has good mechanical property and stability, has small swelling degree in a seawater environment, has an excellent seaweed adhesion resistant effect, and has potential application in the aspect of marine antifouling materials.

Description

A kind of preparation method of long-term stable amphiphilic antifouling coating based on mussel biomimetic

technical field

The invention belongs to the field of preparation of antifouling coatings, in particular to a preparation method of a long-term stable amphiphilic antifouling coating based on mussel bionics.

Background technique

The ocean contains a variety of rich resources. In order to make full and effective use of various resources in the ocean, human beings have built a large number of marine facilities for the development and utilization of marine resources. Such as offshore artificial drilling platforms, offshore signal devices, offshore oil gathering and transportation equipment, and marine fishery equipment. At the same time, the globalization of economic and trade has also driven the rapid development of shipping, and maritime trade has become the most important transaction method in global trade. However, there are a large number of microorganisms, plants and animals in seawater, these organisms will adhere to ships, ships and various marine equipment to cause surface pollution and reduce their service life. In fact, the surface of any facility immersed in the ocean will be covered with a layer of marine life, which includes not only various bacteria, planktonic microorganisms, animals, but also various types of algae that exist in the ocean. This phenomenon of surface attachment by marine organisms is called marine biofouling.

At present, there are more than 4,000 marine fouling organisms, mainly including marine bacteria, algae, polyps, sea anemones, sponges, tube-dwelling polychaetes, bivalve mollusks, cirriped crustaceans, bryozoans, sea squirts, etc. Among them, the main fouling organisms are barnacles, oysters, mussels, coil worms and other species. Marine biofouling has caused huge economic losses to humans, especially in shipping. When the ship is attached by marine organisms, it will increase the friction with the sea water, thereby increasing the fuel consumption of sailing and further producing more greenhouse gases. This can increase the fuel consumption during sailing to 40% or even a maximum of 77%. At the same time, marine biological pollution also creates conditions for metal corrosion, resulting in the destruction of the overall structure of the hull. According to preliminary statistics, damages related to marine biocorrosion alone account for US$30-50 billion in losses worldwide each year. Moreover, marine biofouling may further lead to the "invasion" of alien species, which is a huge and potential danger to local marine life caused by marine organisms attaching to the bottom of ships and entering non-native areas.

Marine biological pollution has not only caused huge troubles to human beings, but also caused high economic losses. Therefore, solving this worldwide problem is of great significance to the development of the marine economy, and at the same time, it also solves the hidden safety hazards for coastal defense. Among them, the method of using antifouling coatings to inhibit marine biological pollution has been widely promoted.

The most studied marine antifouling coatings currently include low surface energy antifouling coatings, surface microstructure bionic coatings, conductive antifouling coatings, silicate antifouling coatings, antifouling agent antifouling coatings and some new The marine antifouling coatings include polymer polymer brush antifouling coatings and amphiphilic antifouling coatings with microphase separation structures. Low surface energy antifouling is based on the physical action of the material surface for antifouling, that is, the fouling organisms are not easy to adhere to the low surface energy surface or the adhesion is not strong, and it is easy to fall off under the action of sailing water currents or other external forces. The usual low-surface anti-fouling coating is composed of materials with low surface energy such as silicon and fluorine; the conductive anti-fouling coating uses the conductivity of its coating to electrolyze seawater to produce certain anti-fouling properties; The antifouling coating of fouling agent uses the small molecule antifouling agent encapsulated in the coating to kill some marine organisms and play an anti-biofouling effect.

The amphiphilic polymer coating is generally a polymer composed of a low surface energy hydrophobic component (usually a fluorosilicon material) and a hydrophilic block. Due to the incompatibility between the segments, phase separation tends to occur in the solvent, forming a special surface chemistry of a certain phase domain. The hydration layer formed on the surface of the hydrophilic component inhibits the attachment of proteins and the non-polarity and low surface energy characteristics of the hydrophobic segment work together to achieve the purpose of antifouling. And the study found that the micro-nano structure formed by micro-phase separation also plays an irreplaceable role in anti-bioadhesion.

However, the amphiphilic polymer coating has weak adhesion to the substrate due to its amphiphilic properties, which limits its use in marine antifouling coatings. It is a multifunctional coating with anti-fouling performance and excellent comprehensive anti-fouling performance. In the current urgent need for environmentally friendly anti-fouling coatings to replace traditional organic tin and cuprous oxide marine anti-fouling coatings, amphiphilic polymers can be solved. The disadvantage of weak adhesion of the coating to the substrate is worthy of attention and research.

Dopa (DOPA) is the main component existing in a variety of marine biological adhesive proteins. Due to the chemical versatility and affinity diversity of the catechol functional group in its structure, DOPA has unique chemical properties. . Among them, the study found that the catechol structure is the key to the strong viscosity. Therefore, the researchers prepared a variety of polymer coatings containing catechol structures, including traditional hydrophilic block PEO, hyperbranched polyglycerol, heparin, and hydrophobic fluorohydrocarbons, when they contained catechol structures. Both show the advantage of their long-term stability. The catechol structure provides a strong anchoring effect to firmly fix the coating on the substrate. This non-toxic biomimetic coating shows an excellent desorption effect on microorganisms in the ocean. For example, Zhang et al. (Coating morphology and surface composition of acrylicterpolymers with pendant catechol, OEG and perfluoroalkyl groups in varyingratio and the effect on protein adsorption [J]. Colloids and Surfaces B: Biointerfaces, 2016, 140: 254-261) by free radicals The triblock amphiphilic copolymer with catechol structure as a pendant was prepared by copolymerization. By controlling the ratio of catechol structure, a variety of anti-fouling coatings with resistance to salt, acid and alkali, soaking and protein adsorption were prepared. .

Click chemistry is a concept of organic synthesis proposed by Shapless, a Nobel Prize winner in chemistry in 2001. It refers to the use of readily available chemical raw materials through fast, efficient, efficient and selective modular chemical reactions. to achieve the connection between carbon and heteroatoms. Typical reaction types are copper-catalyzed azide-alkynyl Husigen cycloaddition reactions and mercapto-ene/alkyne click reactions. In particular, the green click reaction of ene/alkyne based on thiol copper-free catalysis has the advantages of simple reaction conditions, rapidity, strong stereoselectivity, product insensitivity to water and oxygen, low shrinkage stress, and high yield. Modifications, nano-network structured materials, and polymer functionalization have been extensively studied. LiQun Xu et al. (Poly(dopamine acrylamide)-co-poly(propargyl acrylamide)-modifiedtitanium surfaces for'click'functionalization[J].Polymer Chemistry,2012,3(4):920-927) have used click chemistry to The group was introduced onto the catechol-modified substrate to prepare an antifouling coating, which achieved good antifouling effect on various substrates.

SUMMARY OF THE INVENTION

The technical problem to be solved by the present invention is to provide a preparation method of a long-term stable amphiphilic antifouling coating based on mussel bionics, so as to overcome the amphiphilic polymer coating in the prior art. Defects such as weak adhesion of the material.

The present invention provides an amphiphilic antifouling coating based on mussel bionics. The initiator and solvent are mixed and coated on the substrate, and cured under ultraviolet light.

The photoinitiator is at least one of benzoin ethers and benzophenones, preferably benzoin dimethyl ether (DMPA).

The base material is at least one of stainless steel, aluminum alloy, and glass.

The present invention also provides a preparation method of the amphiphilic antifouling coating based on mussel bionics, comprising:

(1) Mixing dopamine hydrochloride, sodium borate, sodium carbonate and deionized water, adding methacrylic anhydride solution dropwise, adjusting the pH value to more than 8, nucleophilic reaction, and purifying to obtain dopamine methacrylamide, wherein dopamine hydrochloride, sodium borate , the weight ratio of sodium carbonate, deionized water and methacrylic anhydride is 3:10～20:2:1～10;

(2) in the step (1), dopamine methacrylamide, mercapto polydimethylsiloxane, polyethylene glycol diacrylate (hydrophilic prepolymer), photoinitiator and solvent in a weight ratio of 1～ 9: 10: 8-30: 0.5-5: 100-200 mixed, coated on a substrate, and cured under ultraviolet light irradiation to obtain an amphiphilic antifouling coating based on mussel bionics.

In the step (1), the weight ratio of dopamine hydrochloride, sodium borate, sodium carbonate, deionized water and methacrylic anhydride is 3:10-17:2:3-9.

The solvent of the methacrylic anhydride solution in the step (1) is tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone. at least one.

In the step (1), the pH value of 8 or more is adjusted by adding at least one of 0.1-3.0 mol/L sodium hydroxide solution and potassium hydroxide solution.

In the step (1), the nucleophilic reaction temperature is 25°C to 65°C (preferably, 28 to 40°C), and the nucleophilic reaction time is 6 to 36 hours.

The purification in the step (1) includes pH adjustment and extraction with an extractant.

The adjustment of the pH value is as follows: using a hydrochloric acid solution to adjust the pH value to within 2.

The extraction agent is at least one of ethyl acetate and n-hexane, preferably a mixture of n-hexane and ethyl acetate with a volume ratio of 0.25-0.65.

In the step (2), the mercapto polydimethylsiloxane is a polydimethylsiloxane containing a mercapto functional group.

In the step (2), the molecular weight of polyethylene glycol diacrylate is 200-2000 Da, preferably 600-1800 Da.

In the step (2), the solvent is one or more of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone.

In the step (2), the weight ratio of dopamine methacrylamide, mercapto polydimethylsiloxane, polyethylene glycol diacrylate, photoinitiator and solvent is 3-6:10:15-25:0.5 ~5:100~150.

The process parameters for curing under ultraviolet light irradiation in the step (2) are as follows: the wavelength of the ultraviolet light is 365 nm, the power is 4W, the light intensity is 0.48-2.0W/cm ² (preferably 0.8-1.6W/cm ² ), and the curing time is It is 60s～300s (preferably 80～300s).

In the step (2), the mussel bionic-based amphiphilic antifouling coating layer is soaked in deionized water for two hours to remove residual solvent and dried.

The structure of the amphiphilic antifouling coating based on mussel biomimetic in the step (2) is:

Among them, m is a positive integer from 20 to 100, n is a positive integer from 10 to 100, z is a positive integer from 5 to 135, and n, m, and z respectively represent the number of repeating units of each segment in the entire molecule.

The invention also provides an application of the mussel bionic amphiphilic antifouling coating in marine antifouling materials.

beneficial effect

The invention successfully solves the problem of weak adhesion between the low surface energy PDMS-based coating and the substrate, introduces a bionic dopamine structure and a macromolecular segment of polyethylene glycol, and is obtained by simple ultraviolet light-induced thiol-ene click chemical cross-linking. Amphiphilic copolymer network with phase-separated structure, in which polyethylene glycol molecular segments and dopamine structure are beneficial to resist protein contamination, and PDMS is beneficial to realize the desorption of large fouling organisms, thereby realizing bifunctional anti-fouling. effect.

The process of the invention has simple synthesis conditions, is clean and environment-friendly, and has good effect of rapid cross-linking reaction induced by ultraviolet light. The prepared amphiphilic antifouling coating has the following advantages: good substrate adhesion, small swelling degree in seawater environment and excellent anti-protein adsorption and seaweed adhesion effect, antifouling in marine environment There are potential uses in terms of materials.

The adhesive strength of the amphiphilic antifouling coating obtained by the invention to the substrate is 1.0 MPa to 6.5 MPa, the swelling degree in water is 0.10% to 4.80%, the sol content is not higher than 5%, and the coating is resistant to bovine serum. Compared with pure polydimethylsiloxane (PDMS), the adsorption amount of protein can be reduced by 35% to 95%, and the anti-adhesion effect on Phaeodactylum tricornutum is comparable to that of pure polydimethylsiloxane (PDMS). The ratio can be reduced by 50% to 95%. (Pure PDMS here refers to components containing only polydimethylsiloxane, unmodified, not specifically PDMS containing only mercapto groups)

Description of drawings

Fig. 1 is the nuclear magnetic resonance spectrum of the first step product methacrylic dopamine in the embodiment of the present invention (the solvent is DMSO-d ₆ ).

FIG. 2 is an infrared characterization diagram of the first step product, methacrylic dopamine, in the embodiment of the present invention.

3 is an infrared spectrum diagram of the second-step product of the amphiphilic polymer cross-linked network coating in the embodiment of the present invention.

Figure 4 is the fluorescence adsorption image of bovine serum albumin and its quantitative adsorption histogram of PDMS and amphiphilic polymer network in Example 3 ((a) is PDMS, (b) polymer amphiphilic coating).

5 is a fluorescence microscope image of PDMS (A) and amphiphilic polymer network (B) obtained in Example 9 immersed in Phaeodactylum tricornutum solution and quantitative data obtained by a hemocytometer.

FIG. 6 is a schematic diagram of a photocrosslinking curing process in an embodiment of the present invention.

Detailed ways

The present invention will be further described below in conjunction with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

The present invention relates to the addition amount, content and concentration of various substances, wherein the “part” refers to “part by weight” unless otherwise specified; the percentage content refers to mass unless otherwise specified. percent content.

1. Test methods and standards:

Sol content test: Wipe the surface of the sample after cross-linking film formation and weigh it to obtain the initial mass m ₀ , and then soak the sample in DMF for 24 hours. Until all unreacted sol in the sample is washed out. After wiping with test paper and drying, weighed to obtain mass m _t . The sol content Sol% is calculated as follows:

Swelling ratio (swelling degree) _Sw test: Weigh the dried film sample to obtain the initial mass m ₀ , and then soak it in artificial seawater (the main components are sodium chloride, magnesium sulfate, and potassium chloride in a ratio of 3:2:1 (weight ratio) mixture plus trace elements). Weigh the sample after 160h, wipe it with test paper, dry it and weigh to obtain the mass m _t until the sample mass does not change. The following formula is the calculation formula of swelling ratio (swelling degree) S _w %:

Coating and substrate adhesion test: The coating was applied to the substrate, and the pull-off strength of the coating on the substrate was tested by a pull-off adhesion tester (DeFelskoPosiTest AT-M) to characterize the coating pair. The adhesion of the substrate.

Protein adsorption test: the preparation method of the FITC-labeled bovine serum albumin BSA solution is as follows: the bovine serum albumin is dissolved in an alkaline solution of pH=9 to prepare a solution with a concentration of 1 mg/ml. At the same time, FITC was dissolved in dimethyl sulfoxide to prepare a 1 mg/ml solution. The protein solution and the FITC solution were added dropwise at a ratio of 1:150 (weight ratio), placed in a dark place, and reacted at 4°C for 8 hours. Then, 5 mol/L NH ₄ Cl was added to the final concentration of 50 mmol/L, and the reaction was terminated at 4° C. for 2 h. The solution after the termination of the reaction was dialyzed in PBS buffer solution for more than four times until the solution was clear and translucent.

Preparation method of phosphate buffered saline (PBS): potassium dihydrogen phosphate, dodecahydrate, disodium hydrogen phosphate, sodium chloride (NaCl, potassium chloride (KCl) are added in a weight ratio of 1.38:18:40:1 into deionized water, phosphate buffered saline (PBS), pH 7.4.

Prepare fluorescein isothiocyanate FITC-labeled bovine serum albumin BSA solution (both concentrations are 0.01 mol/L, pH=7.4) and pH 7.4 phosphate buffered saline (PBS), and then soak the membrane samples in them for 24 hours. Take it out, wash the surface of the membrane with deionized water for several times, and then wipe off the residual liquid on the surface with test paper, and observe the qualitative adsorption of protein on the membrane surface with a fluorescence microscope (BX-51, Japan Olympus). The protein solution was subjected to standard curve determination, and then the samples were soaked in PBS buffer solution to fully swell and equilibrate, and then incubated with bovine serum albumin solution. 96) Carry out absorbance measurement.

Desorption experiment of seaweed marine fouling organisms: after drying the prepared samples, they are placed in seaweed solution containing seaweed and f/2 nutrients (the seaweed is Phaeodactylum tricornutum, the mass concentration is 1%), and placed in an incubator Culture was performed under certain conditions (temperature 16±0.5°C, 8 hours light, 16 hours dark conditions, light intensity 3500 lux) for 7 days. After the test, use a hemocytometer (Marienfeld, Germany, FD16-065001) to count and compare its antifouling performance.

2. Experimental materials:

Mercaptopolymethylsiloxane, the manufacturer is GELEST Company of the United States, polyethylene glycol diacrylate (200-2000Da), purchased from Shanghai Sigma Co., Ltd. All other reagents were of analytical grade and were purchased from China Pharmaceutical (Group) Shanghai Chemical Reagent Company.

Example 1

(1) Take 10 parts of sodium borate (specific weight is 10g), and dissolve 2 parts of sodium carbonate in 100 parts of deionized water, and remove the air therein. Take 3 parts of dopamine hydrochloride, dissolve it in 15 parts of deionized water, dissolve 3 parts of methacrylic anhydride in 4.5 parts of tetrahydrofuran, add it dropwise to the reaction solution, and then add 0.1mol/L sodium hydroxide solution to adjust the pH value to 8.5, react at 25°C for 36 hours. The reaction mixture was dissolved in 50 parts of ethyl acetate, and the solution was filtered to adjust the pH of the filtrate to 2.0. Extract three times with ethyl acetate, add 2 parts of anhydrous magnesium sulfate to the extracted mixture, concentrate the mixture after removing water for 12 hours, and quickly pour into 20 parts of a mixture of n-hexane and ethyl acetate (volume ratio 0.25) , freeze crystallization to obtain a white crystalline powder, which is dried in a vacuum oven and stored in a vacuum to obtain dopamine methacrylamide.

(2) 1 part of dopamine methacrylamide (specific weight is 0.5g), 10 parts of mercaptopolydimethylsiloxane, 30 parts of polyethylene glycol diacrylate (molecular weight is 200Da), photoinitiator benzoin dimethyl 0.5 part of ether was dissolved in 100 parts of N,N-dimethylformamide. The pre-crosslinking solution is coated on the aluminum alloy substrate, and the crosslinking is induced by ultraviolet light irradiation. The wavelength of the ultraviolet light is 365nm, the power is 4W, the intensity is 0.48W/cm ² , and the curing time is 300s to obtain amphiphilic properties. Polymer cross-linked network coating.

(3) Soak the prepared amphiphilic polymer cross-linked network coating in deionized water for 12 h to remove residual organic solvent. The coating was tested according to the test method described above, and the obtained amphiphilic cross-linked network coating had an adhesion of 1.0 MPa to an aluminum alloy substrate, a swelling rate of 4.8% in water, and a sol content of Sol=4.8%. Compared with pure PDMS, the adsorption amount of bovine serum albumin was reduced by 75%, and the adhesion amount to Phaeodactylum tricornutum was reduced by 85%.

Example 2

(1) Take 15 parts of sodium borate (specific weight is 15g), and 2 parts of sodium carbonate are dissolved in 100 parts of deionized water, and the air therein is excluded. Take 3 parts of dopamine hydrochloride, dissolve it in 15 parts of deionized water, dissolve 4 parts of methacrylic anhydride in 6 parts of tetrahydrofuran, add it dropwise to the reaction solution, and add 1.5mol/L sodium hydroxide solution to adjust the pH value to 8.5, react at 30°C for 24 hours. The reaction mixture was dissolved in 50 parts of ethyl acetate, then the solution was filtered off, and the pH of the filtrate was adjusted to 2.0. After extraction with ethyl acetate three times, 2 parts of anhydrous magnesium sulfate was added to the extracted mixture, and water was removed for 12 hours. The mixed solution was then concentrated, quickly poured into 25 parts of a mixed solution of n-hexane and ethyl acetate (volume ratio 0.3), and frozen and crystallized to obtain a white crystal powder, which was dried in a vacuum oven, stored in a vacuum, and dopamine methyl propylene amide.

(2) 2 parts of dopamine methacrylamide (specific weight is 1 g), 10 parts of mercaptopolydimethylsiloxane, 25 parts of polyethylene glycol diacrylate (molecular weight is 400Da), photoinitiator benzoin dimethyl ether 1 part is dissolved in 100 parts of N,N dimethylacetamide, the pre-crosslinking solution is applied to the stainless steel substrate, and the crosslinking is initiated by ultraviolet light irradiation. The wavelength of the ultraviolet light is 365nm, the power is 4W, and the intensity is 1.0 W/cm ² , the curing time is 260s, and the amphiphilic polymer cross-linked network coating is obtained.

(3) Soak the prepared amphiphilic polymer cross-linked network coating in deionized water for 12 h to remove residual organic solvent. The coating was tested according to the test methods described above, and the resulting amphiphilic cross-linked network coating had an adhesion to the substrate of 2.8 MPa and a swelling rate of 3.6% in water. The sol content Sol=3.8%, the adsorption amount to bovine serum albumin was reduced by 83% compared with pure PDMS, and the adhesion amount to Phaeodactylum tricornutum was reduced by 90%.

Example 3

(1) Get 12 parts of sodium borate (specific weight is 12g), and 2 parts of sodium carbonate are dissolved in 100 parts of deionized water in a three-necked flask, and remove the air therein. Take 3 parts of dopamine hydrochloride, dissolve it in 15 parts of deionized water, dissolve 5 parts of methacrylic anhydride in 7.5 parts of tetrahydrofuran, add it dropwise to the reaction solution, and then add 2.0mol/L potassium hydroxide solution to keep the whole reaction The pH of the system was 8.5, and the reaction was carried out at 32°C for 22 hours. The reaction mixture was dissolved in 20 parts of ethyl acetate, and the solution was filtered to adjust the pH of the filtrate to 2.0. After extraction with ethyl acetate three times, 2 parts of anhydrous magnesium sulfate was added to the extracted mixture, and water was removed for 12 hours. After removing water, the mixed solution was concentrated, and the obtained hot concentrated solution was quickly poured into 15 parts of a mixed solution of n-hexane and ethyl acetate (volume ratio 0.25) to obtain a white crystalline powder. Dry it in a vacuum oven, save it under vacuum, dopamine methacrylamide

(2) 3 parts of dopamine methacrylamide (specific weight is 1.5g), 10 parts of mercaptopolydimethylsiloxane, 8 parts of polyethylene glycol diacrylate (molecular weight is 500Da), photoinitiator benzoin dimethyl 2.0 parts of ether was dissolved in 150 parts of dimethylformamide, the pre-crosslinking solution was coated on the glass substrate, and crosslinking was initiated by ultraviolet light irradiation. The wavelength of the ultraviolet light was 365nm, the power was 4W, and the intensity was 1.6W /cm ² , the curing time is 60 s, and an amphiphilic polymer network coating is obtained.

(3) Soak the prepared amphiphilic polymer cross-linked network coating in deionized water for 12 h to remove residual organic solvent. The coating was tested according to the test methods described above, and the resulting amphiphilic crosslinked network coating had an adhesion to the substrate of 5.5 MPa and a swelling rate of 0.20% in water. The sol content Sol=0.8%, the adsorption amount to bovine serum albumin was reduced by 50% compared with pure PDMS, and the adhesion amount to Phaeodactylum tricornutum was reduced by 50%.

Example 4

(1) Get 15 parts of sodium borate (specific weight is 15g), and 2 parts of sodium carbonate are dissolved in 100 parts of deionized water in a three-necked flask, and remove the air therein. Take 3 parts of dopamine hydrochloride, dissolve it in 15 parts of deionized water, dissolve 9 parts of methacrylic anhydride in 13.5 parts of dimethylacetamide, add it dropwise to the reaction solution, and then add 2.5mol/L sodium hydroxide solution , adjust the pH of the whole reaction system at 8.5, and react at 30 °C for 24 hours. The reaction mixture was dissolved in 35 parts of ethyl acetate, and the solution was filtered, and the pH of the filtrate was adjusted to 2.0. After extraction with ethyl acetate three times, 2 parts of anhydrous magnesium sulfate was added to the extracted mixture, and water was removed for 12 hours. After removing water, the mixed solution was concentrated and poured into 20 parts of a mixed solution of n-hexane and ethyl acetate (volume ratio 0.5) quickly to obtain a white crystalline powder. It was dried in a vacuum oven, dopamine methacrylamide.

(2) 3 parts of dopamine methacrylamide (specific weight is 1.5g), 10 parts of mercapto polydimethylsiloxane, 18 parts of polyethylene glycol diacrylate (molecular weight is 1000Da), photoinitiator benzoin dimethyl Dissolve 2.5 parts of ether in 200 parts of dimethylformamide, apply the pre-crosslinking solution to the stainless steel substrate, and initiate crosslinking by ultraviolet light irradiation. The wavelength of the ultraviolet light is 365nm, the power is 4W, and the intensity is 1.8W /cm ² , the curing time is 120s, and the amphiphilic polymer cross-linked network coating is obtained.

(3) Soak the prepared amphiphilic polymer cross-linked network coating in deionized water for 12 h to remove residual organic solvent. The coating was tested according to the test methods described above, and the resulting amphiphilic cross-linked network coating had a surface adhesion of 3.5 MPa to a stainless steel substrate and a swelling rate of 4.8% in water. The sol content Sol=3.6%, the adsorption amount to bovine serum albumin was reduced by 95% compared with pure PDMS, and the adhesion amount to Phaeodactylum tricornutum was reduced by 85%.

Example 5

(1) Get 17 parts of sodium borate (specific weight is 17g), and 2 parts of sodium carbonate are dissolved in 120 parts of deionized water in a three-necked flask, and remove the air therein. Take 3 parts of dopamine hydrochloride, dissolve it in 15 parts of deionized water, dissolve 8 parts of methacrylic anhydride in 12 parts of tetrahydrofuran, add it dropwise to the reaction solution, and then add 1.8mol/L sodium hydroxide solution to adjust the whole reaction The pH of the system was 8.5, and the reaction was carried out at 35°C for 8 hours. The reaction mixture was dissolved in 35 parts of ethyl acetate, and the solution was filtered to adjust the pH of the filtrate to 2.0. After three extractions with ethyl acetate, 2 parts of anhydrous magnesium sulfate was added, and water was removed for 12 hours. After removing water, the mixed solution was concentrated and poured into a mixed solution of 20 parts of n-hexane and ethyl acetate (volume ratio 0.5), and a white crystalline powder was obtained by freezing and crystallization, which was dried in a vacuum oven, and dopamine methyl propylene amide.

(2) 2 parts of dopamine methacrylamide (specific weight is 1g), 10 parts of mercaptopolydimethylsiloxane, 12 parts of polyethylene glycol diacrylate (molecular weight is 1600Da), photoinitiator benzoin dimethyl ether 1.8 parts were dissolved in 180 parts of tetrahydrofuran, the pre-crosslinking was applied to the stainless steel substrate, and the crosslinking was initiated by ultraviolet light irradiation. The wavelength of the ultraviolet light was 365nm, the power was 4W, the intensity was 1.5W/cm ² , and the curing time was For 150 s, an amphiphilic polymer network coating was obtained.

(3) Soak the prepared amphiphilic polymer cross-linked network coating in deionized water for 12 h to remove residual organic solvent. The coating was tested according to the test method described above, and the resulting amphiphilic cross-linked network coating had an adhesion of 3.8 MPa to a stainless steel substrate and a swelling rate of 2.3% in water. The sol content Sol=1.1%, the adsorption amount to bovine serum albumin was reduced by 73% compared with pure PDMS, and the adhesion amount to Phaeodactylum tricornutum was reduced by 65%.

Example 6

(1) Get 20 parts of sodium borate (specific weight is 20g), and 5 parts of sodium carbonate are dissolved in 120 parts of deionized water in a three-necked flask, and the air therein is excluded. Take 3 parts of dopamine hydrochloride, dissolve it in 15 parts of deionized water, dissolve 7.5 parts of methacrylic anhydride in 10 parts of dimethyl sulfoxide, add it dropwise to the reaction solution, and then add 2.8mol/L sodium hydroxide solution , adjust the pH value of the whole reaction system at 8.5, and react at 40 °C for 12 hours. The reaction mixture was dissolved in 25 parts of ethyl acetate, and the solution was filtered to adjust the pH of the filtrate to 2.0. After three extractions with ethyl acetate, 2 parts of anhydrous magnesium sulfate was added, and water was removed for 12 hours. After removing water, the mixed solution was concentrated, the obtained hot concentrated solution was quickly poured into a mixture of 15 ml of n-hexane and ethyl acetate (volume ratio 0.5), and a white crystal powder was obtained by freezing and crystallization, which was dried in a vacuum oven to obtain Dopamine Methacrylamide.

(2) 7.5 parts of dopamine methacrylamide (specific weight is 3.75g), 10 parts of mercaptopolydimethylsiloxane, 8 parts of polyethylene glycol diacrylate (molecular weight is 300Da), photoinitiator benzoin dimethyl 5 parts of ether was dissolved in 150 parts of methylpyrrolidone, the pre-crosslinking solution was applied to the glass substrate, and crosslinking was initiated by ultraviolet light irradiation. The wavelength of the ultraviolet light was 365nm, the power was 4W, and the intensity was 2.0W/cm ² , the curing time is 60s, and the amphiphilic polymer network coating is obtained.

(3) Soak the prepared amphiphilic polymer cross-linked network coating in deionized water for 12 h to remove residual organic solvent. The coating was tested according to the test methods described above, and the resulting amphiphilic cross-linked network coating had an adhesion of 6.5 MPa to a glass substrate and a swelling rate of 0.1% in water. The sol content Sol=0.9%, the adsorption amount to bovine serum albumin was reduced by 35% compared with pure PDMS, and the adhesion amount to Phaeodactylum tricornutum was reduced by 50%.

Example 7

(1) Get 15 parts of sodium borate (specific weight is 15g), and 2 parts of sodium carbonate are dissolved in 100 parts of deionized water in a three-necked flask, and remove the air therein. Take 3 parts of dopamine hydrochloride, dissolve it in 15 parts of deionized water, dissolve 5.5 parts of methacrylic anhydride in 9 parts of tetrahydrofuran, add it dropwise to the reaction solution, and then add 3.0mol/L potassium hydroxide solution to adjust the whole reaction The pH of the system was 8.5, and the reaction was carried out at 50°C for 10 hours. The reaction mixture was dissolved in 50 parts of ethyl acetate, then the solution was filtered off, and the pH of the filtrate was adjusted to 2.0. After three extractions with ethyl acetate, 2 parts of anhydrous magnesium sulfate was added, and water was removed for 12 hours. After dewatering, the mixed solution was concentrated, the obtained hot concentrated solution was quickly poured into 30 parts of a mixed solution of n-hexane and ethyl acetate (volume ratio 0.45), and a white crystal powder was obtained by freezing and crystallization, which was dried in a vacuum oven , Dopamine Methacrylamide.

(2) 5 parts of dopamine methacrylamide (specific weight is 2.5g), 10 parts of mercaptopolydimethylsiloxane, 20 parts of polyethylene glycol diacrylate (molecular weight is 1400Da), photoinitiator benzoin dimethyl 5 parts of ether was dissolved in 120 parts of tetrahydrofuran, the pre-crosslinking solution was dropped on the aluminum alloy substrate, and the crosslinking was induced by ultraviolet light irradiation. The wavelength of the ultraviolet light was 365nm, the power was 4W, and the intensity was 1.0W/cm ² . The curing time was 125 s, resulting in an amphiphilic polymer network coating.

(3) Soak the prepared amphiphilic polymer cross-linked network coating in deionized water for 12 h to remove residual organic solvent. The coating was tested according to the test methods described above, and the resulting amphiphilic cross-linked network coating had an adhesion to the substrate of 4.0 MPa and a swelling rate of 3.7% in water. The sol content Sol=1.8%, the adsorption amount to bovine serum albumin was reduced by 91% compared with pure PDMS, and the adhesion amount to Phaeodactylum tricornutum was reduced by 95%.

Example 8

(1) Get 17 parts of sodium borate (specific weight is 17g), and 2 parts of sodium carbonate are dissolved in 120 parts of deionized water in a three-necked flask, and remove the air therein. Take 3 parts of dopamine hydrochloride, dissolve it in 15 parts of deionized water, dissolve 1.0 part of methacrylic anhydride in 2 parts of tetrahydrofuran, add it dropwise to the reaction solution, and then add 3.0mol/L sodium hydroxide solution to adjust the whole reaction The pH of the system was 8.5, and the reaction was carried out at 65°C for 6 hours. The reaction mixture was dissolved in 20 parts of ethyl acetate, and the solution was filtered to adjust the pH of the filtrate to 2.0. After three extractions with ethyl acetate, 2 parts of anhydrous magnesium sulfate was added, and water was removed for 12 hours. Concentrate the dewatered mixed solution and pour it into 20 parts of a mixture of n-hexane and ethyl acetate (volume ratio 0.5), freeze and crystallize to obtain a white crystalline powder, and dry it in a vacuum oven with dopamine methyl propylene amide.

(2) 9 parts of dopamine methacrylamide (specific weight is 4.5g), 10 parts of mercaptopolydimethylsiloxane, 30 parts of polyethylene glycol diacrylate (molecular weight is 700Da), photoinitiator diphenylmethane Mix 4 parts of ketone in a mixture of 70 parts of dimethylformamide and 40 parts of dimethyl sulfoxide, apply the pre-crosslinking solution to the glass substrate, and initiate crosslinking by ultraviolet light irradiation, the wavelength of ultraviolet light It is 365nm, the power is 4W, the strength is 1.45W/cm ² , and the curing time is 75s to obtain an amphiphilic polymer network coating.

(3) Soak the prepared amphiphilic polymer cross-linked network coating in deionized water for 12 h to remove residual organic solvent. The coating was tested according to the test methods described above, and the resulting amphiphilic cross-linked network coating had an adhesion of 5.5 MPa to a glass substrate and a swelling rate of 2.6% in water. The sol content Sol=1.4%, the adsorption amount to bovine serum albumin was reduced by 66% compared with pure PDMS, and the adhesion amount to Phaeodactylum tricornutum was reduced by 68%.

Example 9

(1) Get 16 parts of sodium borate (specific weight is 16g), and 2 parts of sodium carbonate are dissolved in 120 parts of deionized water in a three-necked flask, and remove the air therein. Take 3 parts of dopamine hydrochloride, dissolve it in 15 parts of deionized water, dissolve 4.5 parts of methacrylic anhydride in 8 parts of tetrahydrofuran, add it dropwise to the reaction solution, and then add 0.6mol/L sodium hydroxide solution to adjust the whole reaction The pH of the system was 8.5, and the reaction was carried out at 55°C for 9 hours. The reaction mixture was dissolved in 50 parts of ethyl acetate, and the solution was filtered to adjust the pH of the filtrate to 2.0. Anhydrous magnesium sulfate was added to the mixture after three extractions with ethyl acetate, and water was removed for 12 hours. The mixed solution was then concentrated, quickly poured into 20 parts of a mixed solution of n-hexane and ethyl acetate (volume ratio 0.3), freeze-crystallized to obtain a white crystal powder, which was dried in a vacuum oven to obtain dopamine methacrylamide.

(2) 3 parts of dopamine methacrylamide (specific weight is 1.5g), 10 parts of mercaptopolydimethylsiloxane, 10 parts of polyethylene glycol diacrylate (molecular weight is 2000Da), photoinitiator benzoin dimethyl 1.3 parts of ether was dissolved in a mixed solution of 85 parts of tetrahydrofuran and 60 parts of dimethylformamide, the pre-crosslinking solution was coated on the stainless steel substrate, and cross-linking was initiated by ultraviolet light irradiation. The wavelength of the ultraviolet light was 365nm, the power is 4W, the strength is 0.8W/cm ² , the curing time is 200s, and the amphiphilic polymer network coating is obtained.

(3) Soak the prepared amphiphilic polymer cross-linked network coating in deionized water for 12 h to remove residual organic solvent. The coating was tested according to the test method described above, and the resulting amphiphilic cross-linked network coating had an adhesion of 1.8 MPa to a stainless steel substrate and a swelling rate of 2.6% in water. The sol content Sol=1.4%, the adsorption amount to bovine serum albumin was reduced by 72% compared with pure PDMS, and the adhesion amount to Phaeodactylum tricornutum was reduced by 80%.

Example 10

(1) Take 11 parts of sodium borate (specific weight is 11g), and 2 parts of sodium carbonate are dissolved in 100 parts of deionized water in a three-necked flask, and the air therein is excluded. Take 3 parts of dopamine hydrochloride, dissolve it in 15 parts of deionized water, dissolve 2 parts of methacrylic anhydride in 3 parts of N-methylpyrrolidone, add it dropwise to the reaction solution, and then add 2.4mol/L potassium hydroxide solution , adjust the pH value of the whole reaction system at 8.5, and react at 45 °C for 10 hours. The reaction mixture was dissolved in 50 parts of ethyl acetate, and the solution was filtered to adjust the pH of the filtrate to 2.0. The mixed solution extracted with ethyl acetate three times was added with 2 parts of anhydrous magnesium sulfate, and water was removed for 12 hours. Afterwards, the mixed solution was concentrated by a rotary evaporator, poured into 30 parts of a mixed solution of n-hexane and ethyl acetate (volume ratio 0.25), and frozen and crystallized to obtain a white crystal powder, which was dried in a vacuum oven, and the dopamine methyl base acrylamide.

(2) 4.5 parts of dopamine methacrylamide (specific weight is 2.25g), 10 parts of mercaptopolydimethylsiloxane, 8 parts of polyethylene glycol diacrylate (molecular weight is 1800Da), photoinitiator benzoin dimethyl 2.5 parts of ether was mixed in a mixed solution of 80 parts of N-methylpyrrolidone and 40 parts of tetrahydrofuran, the pre-crosslinking solution was coated on the stainless steel substrate, and the crosslinking was induced by ultraviolet light irradiation. The wavelength of the ultraviolet light was 365nm, the power is 4W, the strength is 1.8W/cm ² , the curing time is 80s, and the amphiphilic polymer network coating is obtained.

(3) Soak the prepared amphiphilic polymer cross-linked network coating in deionized water for 12 h to remove residual organic solvent. The coating was tested according to the test methods described above, and the resulting amphiphilic cross-linked network coating had an adhesion of 4.9 MPa to stainless steel and a swelling rate of 1.7% in water. The sol content Sol=1.4%, the adsorption amount to bovine serum albumin was reduced by 86% compared with pure PDMS, and the adhesion amount to Phaeodactylum tricornutum was reduced by 76%.

Example 11

(1) Get 10 parts of sodium borate (specific weight is 10g), and 2 parts of sodium carbonate are dissolved in 100 parts of deionized water in a three-necked flask, and the air therein is excluded. Take 3 parts of dopamine hydrochloride, dissolve it in 15 parts of deionized water, dissolve 7 parts of methacrylic anhydride in 12 parts of tetrahydrofuran, add it dropwise to the reaction solution, and then add 1.5mol/L potassium hydroxide solution to adjust the whole reaction The pH of the system was 8.5, and the reaction was carried out at 60°C for 12 hours. The reaction mixture was dissolved in 30 parts of ethyl acetate, and the solution was filtered to adjust the pH of the filtrate to 2.0. The mixed solution extracted with ethyl acetate three times was added with 2 parts of anhydrous magnesium sulfate, and water was removed for 12 hours. The mixed solution was then concentrated, quickly poured into 50 parts of a mixed solution of n-hexane and ethyl acetate (volume ratio 0.3), freeze-crystallized to obtain a white crystal powder, which was dried in a vacuum oven to obtain dopamine methacrylamide.

(2) 6.5 parts of dopamine methacrylamide (specific weight is 3.25g), 10 parts of mercaptopolydimethylsiloxane, 23 parts of polyethylene glycol diacrylate (molecular weight is 100Da), photoinitiator benzoin dimethyl 3 parts of ether was dissolved in a mixed solution of 50 parts of tetrahydrofuran and 50 parts of dimethyl sulfoxide, the pre-crosslinking solution was coated on the glass substrate, and cross-linking was induced by ultraviolet light irradiation. The wavelength of the ultraviolet light was 365nm, the power is 4W, the strength is 1.2W/cm ² , the curing time is 95s, and the amphiphilic polymer network coating is obtained.

(3) Soak the prepared amphiphilic polymer cross-linked network coating in deionized water for 12 h to remove residual organic solvent. The coating was tested according to the test method described above, and the resulting amphiphilic crosslinked network coating had an adhesion to the substrate of 4.5 MPa and a swelling rate of 2.6% in water. The sol content Sol=2.3%, the adsorption amount to bovine serum albumin was reduced by 79% compared with pure PDMS, and the adhesion amount to Phaeodactylum tricornutum was reduced by 92%.

Example 12

(1) Get 12 parts of sodium borate (specific weight is 12g), and 2 parts of sodium carbonate are dissolved in 100 parts of deionized water in a three-necked flask, and remove the air therein. Take 3 parts of dopamine hydrochloride, dissolve it in 15 parts of deionized water, dissolve 6 parts of methacrylic anhydride in a mixture of 9 parts of tetrahydrofuran and dimethylformamide, add it dropwise to the reaction solution, and then add 1.8mol/L potassium hydroxide solution, adjust the pH of the whole reaction system at 8.5, and react at 37 °C for 14 hours. The reaction mixture was dissolved in 30 parts of ethyl acetate, and the solution was filtered to adjust the pH of the filtrate to 2.0. The mixed solution extracted with ethyl acetate three times was added with 2 parts of anhydrous magnesium sulfate, and water was removed for 12 hours. Then, the mixed solution was concentrated, quickly poured into a mixed solution of n-hexane and ethyl acetate (volume ratio 0.5), and a white crystal powder was obtained by freezing and crystallization, which was dried in a vacuum oven to obtain dopamine methacrylamide.

(2) 6.5 parts of dopamine methacrylamide (specific weight is 3.25g), 10 parts of mercaptopolydimethylsiloxane, 25 parts of polyethylene glycol diacrylate (molecular weight is 800Da), photoinitiator benzoin dimethyl 3.5 parts of ether was dissolved in a mixed solution of 100 parts of tetrahydrofuran and 20 parts of dimethylacetamide, the pre-crosslinking solution was coated on the aluminum alloy substrate, and the crosslinking was induced by ultraviolet light irradiation. The wavelength of the ultraviolet light was 365nm, The power was 4W, the strength was 1.2W/cm ² , and the curing time was 100s to obtain an amphiphilic polymer network coating.

(3) Soak the prepared amphiphilic polymer cross-linked network coating in deionized water for 12 h to remove residual organic solvent. The coating was tested according to the test method described above, and the resulting amphiphilic cross-linked network coating had an adhesion force to the aluminum alloy of 5.0 MPa and a swelling rate of 2.8% in water. The sol content Sol=2.3%, the adsorption amount to bovine serum albumin was reduced by 73% compared with pure PDMS, and the adhesion amount to Phaeodactylum tricornutum was reduced by 87%.

Example 13

(1) Get 10 parts of sodium borate (specific weight is 10g), and 2 parts of sodium carbonate are dissolved in 100 parts of deionized water in a three-necked flask, and the air therein is excluded. Take 3 parts of dopamine hydrochloride, dissolve in 15 parts of deionized water, dissolve 2 parts of methacrylic anhydride in 3 parts of dimethylformamide, add dropwise to the reaction solution, and then add 2.0mol/L potassium hydroxide solution , adjust the pH value of the whole reaction system at 8.5, and react at 45 °C for 16 hours. The reaction mixture was dissolved in 30 parts of ethyl acetate, and the solution was filtered to adjust the pH of the filtrate to 2.0. The mixed solution extracted with ethyl acetate three times was added with 2 parts of anhydrous magnesium sulfate, and water was removed for 12 hours. Then, the mixed solution was concentrated, quickly poured into 10 parts of a mixed solution of n-hexane and ethyl acetate (volume ratio 0.65), frozen and crystallized to obtain a white crystal powder, which was dried in a vacuum oven to obtain dopamine methacrylamide.

(2) 6.5 parts of dopamine methacrylamide (specific weight is 3.25g), 10 parts of mercaptopolydimethylsiloxane, 15 parts of polyethylene glycol diacrylate (molecular weight is 2400Da), photoinitiator diphenylmethane Mix 3 parts of ketone with 110 parts of a mixture of tetrahydrofuran and dimethylacetamide, apply the pre-crosslinking solution to the stainless steel substrate, and initiate crosslinking by ultraviolet light irradiation. The wavelength of the ultraviolet light is 365nm and the power is 4W. , the strength is 0.9W/cm ² , the curing time is 195s, and the amphiphilic polymer network coating is obtained.

(3) Soak the prepared amphiphilic polymer cross-linked network coating in deionized water for 12 h to remove residual organic solvent. The coating was tested according to the test method described above, and the resulting amphiphilic cross-linked network coating had an adhesion to stainless steel of 6.0 MPa and a swelling rate of 2.6% in water. The sol content Sol=2.3%, the adsorption amount to bovine serum albumin was reduced by 58% compared with pure PDMS, and the adhesion amount to Phaeodactylum tricornutum was reduced by 62%.

Example 14

(1) Get 16 parts of sodium borate (specific weight is 16g), and 2 parts of sodium carbonate are dissolved in 120 parts of deionized water in a three-necked flask, and remove the air therein. Take 3 parts of dopamine hydrochloride, dissolve it in 15 parts of deionized water, dissolve 4.5 parts of methacrylic anhydride in 7 parts of tetrahydrofuran, add it dropwise to the reaction solution, and then add 2.8mol/L potassium hydroxide solution to adjust the whole reaction The pH of the system was 8.5, and the reaction was carried out at 62°C for 8 hours. The reaction mixture was dissolved in 50 parts of ethyl acetate, and the solution was filtered to adjust the pH of the filtrate to 2.0. The mixed solution extracted with ethyl acetate three times was added with 2 parts of anhydrous magnesium sulfate, and water was removed for 12 hours. The mixed solution was then concentrated, quickly poured into 30 parts of a mixed solution of n-hexane and ethyl acetate (volume ratio 0.5), freeze-crystallized to obtain a white crystal powder, which was dried in a vacuum oven to obtain dopamine methacrylamide.

(2) 4 parts of dopamine methacrylamide (specific weight is 2g), 10 parts of mercaptopolydimethylsiloxane, 10 parts of polyethylene glycol diacrylate (molecular weight is 3600Da), photoinitiator benzoin dimethyl ether 2 parts were dissolved in a mixed solution of 60 parts of tetrahydrofuran and 40 parts of N-methylpyrrolidone, the pre-crosslinking solution was coated on the stainless steel substrate, and cross-linking was induced by ultraviolet light irradiation. The wavelength of the ultraviolet light was 365 nm, The power was 4W, the strength was 1.8W/cm ² , and the curing time was 90s to obtain an amphiphilic polymer network coating.

(3) Soak the prepared amphiphilic polymer cross-linked network coating in deionized water for 12 h to remove residual organic solvent. The coating was tested according to the test methods described above, and the resulting amphiphilic cross-linked network coating had an adhesion to stainless steel of 2.5 MPa and a swelling rate of 2.6% in water. The sol content Sol=1.4%, the adsorption amount to bovine serum albumin was reduced by 70% compared with pure PDMS, and the adhesion amount to Phaeodactylum tricornutum was reduced by 72%.

Example 15

(1) Get 13 parts of sodium borate (specific weight is 13g), and 2 parts of sodium carbonate are dissolved in 100 parts of ionized water in a three-necked flask, and the air therein is excluded. Take 3 parts of dopamine hydrochloride, dissolve it in 15 parts of deionized water, dissolve 4.5 parts of methacrylic anhydride in a mixture of 8 parts of N-methylpyrrolidone and dimethyl sulfoxide, add dropwise through a constant pressure dropping funnel In the reaction solution, 0.5 mol/L potassium hydroxide solution was added, the pH value of the whole reaction system was adjusted to 8.5, and the reaction was carried out at 57° C. for 6 hours. The reaction mixture was dissolved in 50 parts of ethyl acetate, and the solution was filtered to adjust the pH of the filtrate to 2.0. The mixed solution extracted with ethyl acetate three times was added with 2 parts of anhydrous magnesium sulfate, and water was removed for 12 hours. Afterwards, the mixed solution was concentrated by a rotary evaporator, poured into 25 parts of a mixed solution of n-hexane and ethyl acetate (volume ratio 0.5), and freeze-crystallized to obtain a white crystal powder, which was dried in a vacuum oven, and the dopamine methyl base acrylamide.

(2) 2 parts of dopamine methacrylamide (specific weight is 1g), 10 parts of mercaptopolydimethylsiloxane, 10 parts of polyethylene glycol diacrylate (molecular weight is 4000Da), photoinitiator benzoin dimethyl ether 3 parts were dissolved in a mixed solution of 100 parts of methylpyrrolidone and 50 parts of dimethyl sulfoxide, and the pre-crosslinking solution was coated on the glass substrate, and cross-linking was initiated by ultraviolet light irradiation. The wavelength of the ultraviolet light was 365 nm, The power was 4W, the strength was 0.6W/cm ² , and the curing time was 260s to obtain an amphiphilic polymer network coating.

(3) Soak the prepared amphiphilic polymer cross-linked network coating in deionized water for 12 h to remove residual organic solvent. The coating was tested according to the test methods described above, and the resulting amphiphilic cross-linked network coating had an adhesion of 1.8 MPa to a glass substrate and a swelling rate of 4.6% in water. The sol content Sol=3.4%, the adsorption amount to bovine serum albumin was reduced by 82% compared with pure PDMS, and the adhesion amount to Phaeodactylum tricornutum was reduced by 80%.

Example 16

(1) Get 15 parts of sodium borate (specific weight is 15g), and 2 parts of sodium carbonate are dissolved in 120 parts of deionized water in a three-necked flask, and remove the air therein. Take 3 parts of dopamine hydrochloride, dissolve it in 15 parts of deionized water, dissolve 5 parts of methacrylic anhydride into a mixture of 8 parts of N-methylpyrrolidone and dimethylformamide, add dropwise through a constant pressure dropping funnel In the reaction solution, 1.0 mol/L potassium hydroxide solution was added, and the pH value of the entire reaction system was adjusted at 8.5, and the reaction was carried out at 26° C. for 16 hours. The reaction mixture was dissolved in 50 parts of ethyl acetate, and the solution was filtered to adjust the pH of the filtrate to 2.0. The mixed solution extracted with ethyl acetate three times was added with 2 parts of anhydrous magnesium sulfate, and water was removed for 12 hours. Then, the mixed solution was concentrated, quickly poured into 30 parts of a mixed solution of n-hexane and ethyl acetate (volume ratio 0.45), frozen and crystallized to obtain a white crystal powder, which was dried in a vacuum oven to obtain dopamine methacrylamide.

(2) 2 parts of dopamine methacrylamide (specific weight is 1g), 6 parts of mercaptopolydimethylsiloxane, 10 parts of polyethylene glycol diacrylate (molecular weight is 3000Da), photoinitiator benzophenone 2 parts were dissolved in a mixture of 45 parts of methylpyrrolidone and 75 parts of tetrahydrofuran, and the pre-crosslinking solution was coated on the stainless steel substrate, and cross-linking was initiated by ultraviolet light irradiation. The wavelength of the ultraviolet light was 365nm, the power was 4W, and the intensity is 0.7W/cm ² , the curing time is 220s, and the amphiphilic polymer network coating is obtained.

(3) Soak the prepared amphiphilic polymer cross-linked network coating in deionized water for 12 h to remove residual organic solvent. The coating was tested according to the test methods described above, and the resulting amphiphilic cross-linked network coating had an adhesion to stainless steel of 2.3 MPa and a swelling rate of 3.5% in water. The sol content Sol=3.2%, the adsorption amount to bovine serum albumin was reduced by 86% compared with pure PDMS, and the adhesion amount to Phaeodactylum tricornutum was reduced by 78%.

Example 17

(1) Get 12 parts of sodium borate (specific weight is 12g), and 2 parts of sodium carbonate are dissolved in 100 parts of deionized water in a three-necked flask, and remove the air therein. Take 3 parts of dopamine hydrochloride, dissolve it in 15 parts of deionized water, dissolve 6 parts of methacrylic anhydride into a mixture of 9 parts of N-methylpyrrolidone, tetrahydrofuran and dimethylacetamide, add it dropwise to the reaction solution, Then add 0.1 mol/L sodium hydroxide solution, adjust the pH value of the whole reaction system to 8.5, and react at 35° C. for 20 hours. The reaction mixture was dissolved in 50 parts of ethyl acetate, and the solution was filtered to adjust the pH of the filtrate to 2.0. The mixed solution extracted with ethyl acetate three times was added with 2 parts of anhydrous magnesium sulfate, and water was removed for 12 hours. The mixed solution was then concentrated, quickly poured into 30 parts of a mixed solution of n-hexane and ethyl acetate (volume ratio 0.25), freeze-crystallized to obtain a white crystal powder, which was dried in a vacuum oven to obtain dopamine methacrylamide.

(2) 4 parts of dopamine methacrylamide (specific weight is 2g), 10 parts of mercaptopolydimethylsiloxane, 10 parts of polyethylene glycol diacrylate (molecular weight is 6000Da), photoinitiator benzoin dimethyl ether 3 parts were dissolved in a mixture of 45 parts of methylpyrrolidone, 40 parts of dimethyl sulfoxide, and 40 parts of tetrahydrofuran, and the pre-crosslinking solution was coated on the aluminum alloy substrate, and the crosslinking was initiated by ultraviolet light irradiation. The wavelength is 365nm, the power is 4W, the intensity is 1.6W/cm ² , and the curing time is 160s to obtain an amphiphilic polymer network coating.

(3) Soak the prepared amphiphilic polymer cross-linked network coating in deionized water for 12 h to remove residual organic solvent. The coating was tested according to the test method described above, and the resulting amphiphilic cross-linked network coating had an adhesion to the aluminum alloy of 2.7 MPa and a swelling rate of 1.5% in water. The sol content Sol=3.4%, the adsorption amount to bovine serum albumin was reduced by 77% compared with pure PDMS, and the adhesion amount to Phaeodactylum tricornutum was reduced by 63%.

Example 18

(1) Get 14 parts of sodium borate (specific weight is 14g), and 2 parts of sodium carbonate are dissolved in 100 parts of deionized water in a three-necked flask, and remove the air therein. Take 3 parts of dopamine hydrochloride, dissolve it in 15 parts of deionized water, dissolve 10 parts of methacrylic anhydride in 15 parts of a mixture of dimethylformamide, dimethylacetamide and tetrahydrofuran, add dropwise to the reaction solution, Then add 3 mol/L potassium hydroxide solution, adjust the pH value of the whole reaction system to 8.5, and react at 45° C. for 13 hours. The reaction mixture was dissolved in 30 parts of ethyl acetate, and the solution was filtered to adjust the pH of the filtrate to 2.0. The mixed solution extracted with ethyl acetate three times was added with 2 parts of anhydrous magnesium sulfate, and water was removed for 12 hours. Then, the mixed solution was concentrated, quickly poured into 50 parts of a mixed solution of n-hexane and ethyl acetate (volume ratio 0.5), and a white crystal powder was obtained by freezing and crystallization, which was dried in a vacuum oven to obtain dopamine methacrylamide.

(2) 4 parts of dopamine methacrylamide (specific weight is 2g), 10 parts of mercaptopolydimethylsiloxane, 10 parts of polyethylene glycol diacrylate (molecular weight is 5000Da), photoinitiator benzophenone 2 parts were dissolved in a mixture of 20 parts of dimethylformamide, 30 parts of dimethylacetamide and 50 parts of tetrahydrofuran, and the pre-crosslinking solution was applied to the stainless steel substrate, and the crosslinking was initiated by ultraviolet light irradiation. The wavelength of light is 365 nm, the power is 4 W, the intensity is 1.6 W/cm ² , and the curing time is 90 s to obtain an amphiphilic polymer network coating.

(3) Soak the prepared amphiphilic polymer cross-linked network coating in deionized water for 12 h to remove residual organic solvent. The coating was tested according to the test methods described above, and the resulting amphiphilic cross-linked network coating had an adhesion to stainless steel of 2.5 MPa and a swelling rate of 4.3% in water. The sol content Sol=1.4%, the adsorption amount to bovine serum albumin was reduced by 83% compared with pure PDMS, and the adhesion amount to Phaeodactylum tricornutum was reduced by 80%.

Figure 1 shows that when deuterated dimethyl sulfoxide is used as the solvent, the hydrogen on the amino group is shifted by 7.99 ppm and the phenolic hydroxyl peaks are shifted by 8.79 ppm and 8.65 ppm, indicating that the material was successfully synthesized.

Figure 2 shows that the absorption peaks at 3365cm ^-1 and 3200cm ^-1 are the infrared stretching vibrations of methyl and methylene, respectively, and the stretching vibration peaks at 1550cm ^-1 and 1649cm ^-1 are NH and C=O, respectively The absorption peak of 1459cm ^-1 is generated by C=C. The absorption peaks located at 1358 cm ^-1 , 1193 cm ^-1 , and 1270 cm ^-1 are due to the stretching vibration generated by the benzene ring and the phenolic hydroxyl group. The characterization results of infrared images further verified the successful synthesis of this product.

Figure 3 shows that the absorption peak (-SH) at 2560 cm ^-1 and the absorption peak at 1638 cm ^-1 (C=C) disappeared after photo-crosslinking, indicating that the cross-linking was completed and a cross-linked network was formed.

The upper picture in Figure 4 shows that the fluorescence images of bovine serum albumin on PDMS are brighter, indicating that the amount of protein adsorption is large, while the fluorescence images of the cross-linked network introduced with PEG and DMA are all dark, indicating that the amount of protein adsorption is significantly less. The introduction of PEG and DMA hydrophilic segments effectively improved their anti-protein adsorption properties. In addition, the histogram in the figure below shows the quantitative analysis of the BCA kit, and the adsorption of the modified coating protein is reduced by 50%.

Figure 5 shows that the microscopic analysis and quantitative analysis showed that the amphiphilic polymer network significantly improved the colonization and adsorption of Phaeodactylum tricornutum, indicating that the introduction of PEG and DMA effectively improved its anti-seaweed adsorption performance.

Comparative Example 1

2 parts of hydroxyethyl methacrylate, 10 parts of mercaptopolydimethylsiloxane, 25 parts of polyethylene glycol diacrylate (molecular weight 400Da), 1 part of photoinitiator benzoin dimethyl ether dissolved in 100 parts of N, In N-dimethylacetamide, the pre-crosslinking solution is applied to the stainless steel substrate, and the crosslinking is initiated by ultraviolet light irradiation. The wavelength of the ultraviolet light is 365 nm, the power is 4W, the intensity is 1.0W/cm ² , and the curing time is 260s, the amphiphilic polymer cross-linked network coating was obtained.

The prepared amphiphilic polymer cross-linked network coating was soaked in deionized water for 12 h to remove residual organic solvent. The coating was tested according to the test methods described above, and the resulting amphiphilic cross-linked network coating had an adhesion to the substrate of 0.75 MPa and a swelling rate of 4.8% in water. The sol content Sol=3.7%, the adsorption amount to bovine serum albumin was reduced by 13% compared with pure PDMS, and the adhesion amount to Phaeodactylum tricornutum was reduced by 30%.

After replacing the dopamine methacrylamide in the system with an equal amount of hydroxyethyl methacrylate, the prepared amphiphilic coating has a significantly reduced adhesion to the stainless steel substrate, and is resistant to protein adsorption and algae adhesion. There is also a downward trend in the effect.

Claims (9)

1. a kind of amphiphilic antifouling coating based on mussel bionic, it is characterized in that, dopamine hydrochloride and methacrylic anhydride are carried out nucleophilic reaction, then with mercapto polydimethylsiloxane, polyethylene glycol diacrylic acid The ester, photoinitiator and solvent are mixed and coated on the substrate, and cured under ultraviolet light. 2 . The coating according to claim 1 , wherein the photoinitiator is at least one of benzoin ethers and benzophenones; the base material is at least one of stainless steel, aluminum alloy, and glass. 3 . 3. A preparation method of an amphiphilic antifouling coating based on mussel bionics, comprising: (1) Mixing dopamine hydrochloride, sodium borate, sodium carbonate and deionized water, adding methacrylic anhydride solution dropwise, adjusting the pH value to more than 8, nucleophilic reaction, and purifying to obtain dopamine methacrylamide, wherein dopamine hydrochloride, sodium borate , the weight ratio of sodium carbonate, deionized water and methacrylic anhydride is 3:10～20:2:1～10; (2) in the step (1), dopamine methacrylamide, mercapto polydimethylsiloxane, polyethylene glycol diacrylate, photoinitiator and solvent in a weight ratio of 1～9:10:8～30: 0.5-5:100-200 mixed, coated on a substrate, and cured under ultraviolet light irradiation to obtain an amphiphilic antifouling coating based on mussel bionics. 4. method according to claim 3 is characterized in that, in described step (1), adjusting pH value more than 8 is by adding at least one in the sodium hydroxide solution of 0.1～3.0mol/L, potassium hydroxide solution Make adjustments. 5 . The method according to claim 3 , wherein in the step (1), the temperature of the nucleophilic reaction is 25° C. to 65° C., and the time of the nucleophilic reaction is 6 to 36 h. 6 . 6 . The method according to claim 3 , wherein the molecular weight of the polyethylene glycol diacrylate in the step (2) is 200-2000 Da. 7 . 7. method according to claim 3, is characterized in that, in described step (2), solvent is tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide , one or more of N-methylpyrrolidone. 8. method according to claim 3, is characterized in that, in described step (2), the technological parameter of curing under ultraviolet light irradiation is: ultraviolet light wavelength is 365nm, power is 4W, light intensity is 0.48～2.0W/cm ² , the curing time is 60s ~ 300s. 9. An application of the coating of claim 1 in marine antifouling materials.

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