Modified graphite oxide allyl acid resin and preparation method and application thereof
阅读说明：本技术 一种改性氧化石墨烯丙烯酸树脂及其制备方法和应用 (Modified graphite oxide allyl acid resin and preparation method and application thereof ) 是由 李茹民 沙建昂 陈蓉蓉 刘琦 刘婧媛 于静 朱佳慧 孙高辉 张宏森 刘培礼 王君 于 2021-10-26 设计创作，主要内容包括：本发明属于涂料技术领域。本发明提供了一种改性氧化石墨烯丙烯酸树脂。本发明在氧化石墨烯的表面修饰硅烷偶联剂引入碳碳双键；然后使用甲基丙烯酸二甲氨基乙酯进行自由基聚合,由于链段的正电排斥作用在水中会发生去质子化自发形成环状构象,转变为两性离子,从而在聚合物链中形成两亲性的水化层,使得水中的小分子有机物在水化层的作用下不易黏附于表面；通过卤代烷将甲基丙烯酸二甲氨基乙酯中的叔胺转化为季铵,得到改性氧化石墨烯；对丙烯酸单体采用自由基聚合法得到丙烯酸硅烷酯。本发明将改性氧化石墨烯和丙烯酸硅烷酯按照质量比为1：0.001～0.015的比例进行超声得到改性氧化石墨烯丙烯酸树脂,具有很好的抗污效果。(The invention belongs to the technical field of coatings. The invention provides a modified graphite oxide allyl acid resin. According to the invention, a carbon-carbon double bond is introduced into the surface modification silane coupling agent of graphene oxide; then, dimethylaminoethyl methacrylate is used for free radical polymerization, and due to the positive electric repulsion action of the chain segment, deprotonation can occur in water to spontaneously form a ring conformation and be converted into zwitterions, so that an amphiphilic hydration layer is formed in the polymer chain, and micromolecular organic matters in water are not easy to adhere to the surface under the action of the hydration layer; converting tertiary amine in dimethylaminoethyl methacrylate into quaternary ammonium through alkyl halide to obtain modified graphene oxide; and (3) carrying out a free radical polymerization method on the acrylic monomer to obtain the acrylic silane ester. According to the invention, modified graphene oxide and acrylic silane ester are mixed according to a mass ratio of 1: the modified graphite oxide allyl acid resin is obtained by carrying out ultrasonic treatment at a ratio of 0.001-0.015, and has a good anti-fouling effect.)
1. A modified graphene oxide allyl acid resin, which is characterized by comprising modified graphene oxide and silane acrylate;
the mass ratio of the acrylic silane ester to the modified graphene oxide is 1: 0.001 to 0.015.
2. The resin according to claim 1, wherein the method for preparing the modified graphene oxide comprises the following steps:
(1) mixing a graphene oxide enol solution and a silane coupling agent alcoholic solution, and carrying out polymerization reaction to obtain silane graphene oxide;
(2) under the protective atmosphere, mixing a silane oxidized graphene alcohol solution and a dimethylaminoethyl methacrylate monomer, and carrying out free radical polymerization reaction under the action of azobisisobutyronitrile to obtain modified graphene oxide;
(3) and mixing the halogenated alkanol solution and the modified graphene oxide, and carrying out quaternization reaction to obtain the modified graphene oxide.
3. The resin of claim 2, wherein the graphene oxide alcohol solution and the silane coupling agent alcohol solution in step (1) are independently an ethanol solution;
the dosage ratio of the graphene oxide to the ethanol in the graphene oxide enol solution is 280-320 mg: 240-260 mL;
the dosage ratio of the silane coupling agent to the ethanol in the silane coupling agent alcoholic solution is 1-2 g: 50-70 mL;
the silane coupling agent is KH570, A-171, A-172 or A151;
the mass ratio of the graphene oxide to the silane coupling agent is 0.3: 1.2 to 1.8;
the temperature of the polymerization reaction in the step (1) is 50-70 ℃, the time of the polymerization reaction in the step (1) is 22-26 h, the polymerization reaction in the step (1) is carried out in a stirring state, and the stirring rotating speed is 350-450 rpm.
4. The resin according to claim 2 or 3, wherein the gas of the protective atmosphere in the step (2) is nitrogen, argon or helium, and the flow rate of the protective atmosphere is 0.07 to 0.08m3/h；
The silicon alkoxide graphene alcohol solution in the step (2) is an ethanol solution;
the dosage ratio of the silane graphene oxide to the ethanol is 280-320 mg: 240-260 mL;
the dosage ratio of the silane graphene oxide to the dimethylaminoethyl methacrylate monomer is 280-320 mg: 280-320 mmol;
the dosage ratio of the silane graphene oxide to the azodiisobutyronitrile is 280-320 mg: 4-8 mmol;
the temperature of the free radical polymerization reaction in the step (2) is 60-80 ℃, and the time of the free radical polymerization reaction is 22-26 h.
5. The resin according to claim 4, wherein the halogenated alkanol solution in the step (3) is an ethanol solution, the mass fraction of the halogenated alkanol solution is 40-60%, and the halogenated alkane is n-butyl bromide, n-butyl chloride, propyl bromide, ethane bromide, n-pentane bromide or dodecane bromide;
the dosage ratio of the modified graphene oxide to the halogenated alkanol solution is 0.3 g: 25-35 mL;
the temperature of the quaternization reaction in the step (3) is 40-60 ℃, the quaternization reaction time is 22-26 h, the quaternization reaction is carried out in a stirring state, and the stirring rotating speed is 500-700 rpm.
6. The resin of claim 1 or 5, wherein the method for preparing the silane acrylate comprises the steps of:
(a) mixing an acrylic monomer, azodiisobutyronitrile and N, N-dimethylformamide to obtain a mixed solution;
(b) mixing the mixed solution with N, N-dimethylformamide under a protective atmosphere to obtain a mixed system;
(c) under the protective atmosphere, mixing the benzoyl peroxide solution with the mixed system to perform polymerization reaction, thereby obtaining the acrylic silane ester;
the acrylic monomers in the step (a) comprise methyl methacrylate, butyl methacrylate, methoxyethyl methacrylate, hexafluorobutyl methacrylate and triisopropylsilyl acrylate;
the mass ratio of the methyl methacrylate to the butyl methacrylate to the methoxyethyl methacrylate to the hexafluorobutyl methacrylate to the triisopropylsilyl acrylate is 150-160: 80-90: 6-7: 25-35: 45-55.
7. The resin according to claim 6, wherein the mass ratio of the acrylic monomer to the azobisisobutyronitrile in the step (a) is 300 to 350: 4-5;
the mass ratio of the acrylic acid monomer to the N, N-dimethylformamide in the step (a) is 300-350: 300 to 350 parts by weight;
the protective atmosphere in the step (b) is nitrogen, argon or helium;
the mass ratio of the N, N-dimethylformamide to the mixed solution in the step (b) is 1: 1.8-2.0;
the mixing in the step (b) is to drop the mixed solution into N, N-dimethylformamide at a dropping rate of 210-230 g/h;
the temperature of mixing in the step (b) is 80-100 ℃.
8. The resin of claim 7, wherein the protective atmosphere in step (c) is nitrogen, argon or helium;
the solvent of the benzoyl peroxide solution in the step (c) is N, N-dimethylformamide, and the mass ratio of the benzoyl peroxide to the N, N-dimethylformamide is 1: 18 to 22;
the mass ratio of the benzoyl peroxide to the azobisisobutyronitrile in the step (a) is 1: 4-5;
in the mixing step (c), the benzoyl peroxide solution is dripped into a mixing system, and the dripping speed is 40-45 g/h;
the temperature of the polymerization reaction in the step (c) is 80-100 ℃, and the time of the polymerization reaction is 1.5-2.5 h.
9. The method for preparing the resin according to any one of claims 1 to 8, wherein the modified graphene oxide is mixed with the silane acrylate to obtain the modified graphene oxide allyl acid resin;
the mixing mode is ultrasonic, the temperature of the ultrasonic is 5-15 ℃, the frequency of the ultrasonic is 20-30 KHz, and the time of the ultrasonic is 90-180 min.
10. Use of the modified graphene oxide acrylic resin according to any one of claims 1 to 8 in a coating.
Technical Field
The invention relates to the technical field of coatings, and particularly relates to a modified graphite oxide allyl acid resin and a preparation method and application thereof.
Background
The marine fouling problem brings great inconvenience to the development of marine resources and the marine military activities. The most convenient and economic method for preventing marine biological pollution is the antifouling paint. Among them, antifouling paints based on self-polishing copolymers (SPC), commonly known as side group hydrolysable acrylate copolymers, including silicon-based, copper-based or zinc-based acrylate copolymers, are most commonly used because of their good performance, convenient construction process and good economy. Tributyltin-based SPC has been used for decades. However, they were banned in 2008 due to their serious ecological impact. At present, tin-free self-polishing antifouling coatings containing silicon-based, copper-based or zinc-based acrylate copolymers occupy a major position in the market. However, most SPCs have antifouling properties mainly determined by the shear force of seawater flow, and have poor antifouling properties in static seawater. In addition, high concentrations of heavy metals can also be harmful to marine life.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a modified graphite oxide allyl acid resin and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a modified graphene oxide allyl acid resin, which comprises modified graphene oxide and silane acrylate;
the mass ratio of the acrylic silane ester to the modified graphene oxide is 1: 0.001 to 0.015.
Preferably, the preparation method of the modified graphene oxide comprises the following steps:
(1) mixing a graphene oxide enol solution and a silane coupling agent alcoholic solution, and carrying out polymerization reaction to obtain silane graphene oxide;
(2) under the protective atmosphere, mixing a silane oxidized graphene alcohol solution and a dimethylaminoethyl methacrylate monomer, and carrying out free radical polymerization reaction under the action of azobisisobutyronitrile to obtain modified graphene oxide;
(3) and mixing the halogenated alkanol solution and the modified graphene oxide, and carrying out quaternization reaction to obtain the modified graphene oxide.
Preferably, the graphene oxide alcohol solution and the silane coupling agent alcohol solution in the step (1) are ethanol solutions independently;
the dosage ratio of the graphene oxide to the ethanol in the graphene oxide enol solution is 280-320 mg: 240-260 mL;
the dosage ratio of the silane coupling agent to the ethanol in the silane coupling agent alcoholic solution is 1-2 g: 50-70 mL;
the silane coupling agent is KH570, A-171, A-172 or A151;
the mass ratio of the graphene oxide to the silane coupling agent is 0.3: 1.2 to 1.8;
the temperature of the polymerization reaction in the step (1) is 50-70 ℃, the time of the polymerization reaction in the step (1) is 22-26 h, the polymerization reaction in the step (1) is carried out in a stirring state, and the stirring rotating speed is 350-450 rpm.
Preferably, the gas of the protective atmosphere in the step (2) is nitrogen, argon or helium, and the flow rate of the protective atmosphere is 0.07-0.08 m3/h；
The silicon alkoxide graphene alcohol solution in the step (2) is an ethanol solution;
the dosage ratio of the silane graphene oxide to the ethanol is 280-320 mg: 240-260 mL;
the dosage ratio of the silane graphene oxide to the dimethylaminoethyl methacrylate monomer is 280-320 mg: 280-320 mmol;
the dosage ratio of the silane graphene oxide to the azodiisobutyronitrile is 280-320 mg: 4-8 mmol;
the temperature of the free radical polymerization reaction in the step (2) is 60-80 ℃, and the time of the free radical polymerization reaction is 22-26 h.
Preferably, the halogenated alkanol solution in the step (3) is an ethanol solution, the mass fraction of the halogenated alkanol solution is 40-60%, and the halogenated alkane is n-butyl bromide, n-butyl chloride, propyl bromide, ethyl bromide, n-pentane bromide or dodecane bromide;
the dosage ratio of the modified graphene oxide to the halogenated alkanol solution is 0.3 g: 25-35 mL;
the temperature of the quaternization reaction in the step (3) is 40-60 ℃, the quaternization reaction time is 22-26 h, the quaternization reaction is carried out in a stirring state, and the stirring rotating speed is 500-700 rpm.
Preferably, the preparation method of the acrylic silane ester comprises the following steps:
(a) mixing an acrylic monomer, azodiisobutyronitrile and N, N-dimethylformamide to obtain a mixed solution;
(b) mixing the mixed solution with N, N-dimethylformamide under a protective atmosphere to obtain a mixed system;
(c) under the protective atmosphere, mixing the benzoyl peroxide solution with the mixed system to perform polymerization reaction, thereby obtaining the acrylic silane ester;
the acrylic monomers in the step (a) comprise methyl methacrylate, butyl methacrylate, methoxyethyl methacrylate, hexafluorobutyl methacrylate and triisopropylsilyl acrylate;
the mass ratio of the methyl methacrylate to the butyl methacrylate to the methoxyethyl methacrylate to the hexafluorobutyl methacrylate to the triisopropylsilyl acrylate is 150-160: 80-90: 6-7: 25-35: 45-55.
Preferably, the mass ratio of the acrylic monomer to the azobisisobutyronitrile in the step (a) is 300-350: 4-5;
the mass ratio of the acrylic acid monomer to the N, N-dimethylformamide in the step (a) is 300-350: 300 to 350 parts by weight;
the protective atmosphere in the step (b) is nitrogen, argon or helium;
the mass ratio of the N, N-dimethylformamide to the mixed solution in the step (b) is 1: 1.8-2.0;
the mixing in the step (b) is to drop the mixed solution into N, N-dimethylformamide at a dropping rate of 210-230 g/h;
the temperature of mixing in the step (b) is 80-100 ℃.
Preferably, the protective atmosphere in step (c) is nitrogen, argon or helium;
the solvent of the benzoyl peroxide solution in the step (c) is N, N-dimethylformamide, and the mass ratio of the benzoyl peroxide to the N, N-dimethylformamide is 1: 18 to 22;
the mass ratio of the benzoyl peroxide to the azobisisobutyronitrile in the step (a) is 1: 4-5;
in the mixing step (c), the benzoyl peroxide solution is dripped into a mixing system, and the dripping speed is 40-45 g/h;
the temperature of the polymerization reaction in the step (c) is 80-100 ℃, and the time of the polymerization reaction is 1.5-2.5 h.
The invention also provides a preparation method of the resin, which comprises the steps of mixing the modified graphene oxide and the silane acrylate to obtain the modified graphene oxide allyl acid resin;
the mixing mode is ultrasonic, the temperature of the ultrasonic is 5-15 ℃, the frequency of the ultrasonic is 20-30 KHz, and the time of the ultrasonic is 90-180 min.
The invention also provides application of the modified graphite oxide allyl acid resin in a coating.
The invention provides a modified graphene oxide allyl acid resin which is prepared from modified graphene oxide and silane acrylate under an ultrasonic condition. According to the invention, a carbon-carbon double bond is introduced into the surface modification silane coupling agent of graphene oxide; then, dimethyl aminoethyl methacrylate is used for free radical polymerization, and due to the positive electric repulsion action of the chain segment, deprotonation can be carried out in water, a ring conformation is spontaneously formed and is converted into zwitterion, so that an amphiphilic hydration layer is formed in a polymer chain, and micromolecular organic matters in water are not easy to adhere to the surface under the action of the hydration layer; converting tertiary amine in dimethylaminoethyl methacrylate into quaternary ammonium through alkyl halide to obtain modified graphene oxide; adopting a free radical polymerization method for an acrylic monomer to obtain acrylic silane ester; the modified graphene oxide and the acrylic silane ester are mixed, so that the static antifouling effect is obvious when the content is 0.1%, and the industrial application prospect is achieved.
Drawings
FIG. 1 is a Fourier infrared spectrum of GO, GO-KH570, GO-PDMAEMA, GO-PQDMAEMA of example 1;
FIG. 2 is the X-ray photoelectron energy spectra of GO, GO-KH570, GO-PDMAEMA and GO-PQDMAEMA in example 1;
FIG. 3 is a graph of the peak separation of GO-PDMAEMA and GO-PQDMAEMAX in example 1;
in fig. 3: (a) n1s, (b) C1 s, and (C) O1 s are X-ray photoelectron energy spectrograms of GO-PDMAEMA; (d) n1s, (e) C1 s, and (f) O1 s are X-ray photoelectron energy spectrograms of GO-PQDMAEMA;
FIG. 4 is a Fourier infrared spectrum of the silane acrylate of example 1;
FIG. 5 is a schematic view showing the antifouling principle of the modified graphene oxide acrylic resin;
FIG. 6 is a graph of the weight loss of the coating of example 1;
FIG. 7 is a graph showing the change in contact angle of the coating in example 1;
FIG. 8 is a scanning electron micrograph of the coating of example 1 after drying;
in fig. 8: (a) GQF-0; (b) GQF-0.1; (c) GQF-0.25; (d) GQF-0.5; (e) GQF-1; (f) GQF-1.5;
FIG. 9 is a scanning electron micrograph of the coating of example 1 after immersion in seawater for 14 days;
in fig. 9: (a) GQF-0; (b) GQF-0.1; (c) GQF-0.25; (d) GQF-0.5; (e) GQF-1; (f) GQF-1.5;
FIG. 10 is a fluorescent microscope photograph of the coating of example 1 immersed in algae solution for 72 hours;
FIG. 11 is a graph of the rate of anti-diatom adhesion of the coatings of example 1;
FIG. 12 is a graph of the culture of E.coli and S.aureus for the coating of example 1;
FIG. 13 is a graph of the antibacterial efficiency of the coating of example 1 against E.coli and S.aureus.
Detailed Description
The invention provides a modified graphene oxide allyl acid resin, which comprises modified graphene oxide and silane acrylate;
the mass ratio of the acrylic silane ester to the modified graphene oxide is 1: 0.001 to 0.015.
In the invention, the mass ratio of the acrylic silane ester to the modified graphene oxide is 1: 0.001 to 0.015, preferably 1: 0.004-0.011, more preferably 1: 0.007-0.008.
In the invention, the preparation method of the modified graphene oxide comprises the following steps:
(1) mixing a graphene oxide enol solution and a silane coupling agent alcoholic solution, and carrying out polymerization reaction to obtain silane graphene oxide;
(2) under the protective atmosphere, mixing a silane oxidized graphene alcohol solution and a dimethylaminoethyl methacrylate monomer, and carrying out free radical polymerization reaction under the action of azobisisobutyronitrile to obtain modified graphene oxide;
(3) and mixing the halogenated alkanol solution and the modified graphene oxide, and carrying out quaternization reaction to obtain the modified graphene oxide.
In the invention, the graphene oxide is prepared by a hummers method.
In the present invention, the graphene oxide alcohol solution and the silane coupling agent alcohol solution in the step (1) are independently preferably ethanol solutions.
In the invention, the dosage ratio of the graphene oxide to the ethanol in the graphene oxide enol solution is preferably 280-320 mg: 240-260 mL, more preferably 290-310 mg: 245-255 mL, more preferably 295-305 mg: 248-252 mL.
In the invention, graphene oxide and ethanol are mixed and then dispersed under ultrasound, wherein the ultrasound temperature is preferably 5-15 ℃, more preferably 6-14 ℃, and more preferably 8-12 ℃; the frequency of the ultrasonic wave is preferably 20-30 KHz, more preferably 22-28 KHz, and even more preferably 24-26 KHz; the ultrasonic time is preferably 1-1.5 h, more preferably 1.1-1.4 h, and even more preferably 1.2-1.3 h. And obtaining an ethanol solution of the graphene oxide after the ultrasonic treatment is finished.
In the invention, the dosage ratio of the silane coupling agent to the ethanol in the silane coupling agent alcoholic solution is preferably 1-2 g: 50 to 70mL, more preferably 1.2 to 1.8 g: 54-66 mL, more preferably 1.4-1.6 g: 58-62 mL.
In the present invention, the silane coupling agent is preferably KH570, A-171, A-172 or A151.
In the invention, the concentration of ethanol in the ethanol solution of the silane coupling agent is preferably 94-96%, more preferably 94.4-95.6%, and more preferably 94.8-95.2%.
In the invention, after a silane coupling agent is dissolved in ethanol, the pH value is adjusted, and the pH value of the pH value is preferably 3.5-4, more preferably 3.6-3.9, and more preferably 3.7-3.8; the reagent for adjusting the pH value is preferably hydrochloric acid; after the pH value is adjusted to a target value, standing the mixed system for prehydrolysis, wherein the standing time is preferably 1-1.5 h, more preferably 1.1-1.4 h, and even more preferably 1.2-1.3 h; and standing to obtain the silane coupling agent alcoholic solution.
In the present invention, the mass ratio of the graphene oxide to the silane coupling agent is preferably 0.3: 1.2 to 1.8, and more preferably 0.3: 1.3 to 1.6, more preferably 0.3: 1.4 to 1.5.
In the invention, after the graphene oxide alcohol solution and the silane coupling agent alcohol solution are mixed, protective atmosphere is introduced into the mixed system; the gas of the protective atmosphere is preferably nitrogen, argon or helium, and the flow of the protective atmosphere is preferably 0.07-0.08 m3More preferably 0.072-0.078 m3More preferably 0.074 to 0.076m3H; the introducing time of the protective atmosphere is preferably 15-20 min, more preferably 16-19 min, and even more preferably 17-18 min. After the end of the introduction of the protective atmosphere, the next polymerization reaction was carried out.
In the invention, the temperature of the polymerization reaction in the step (1) is preferably 50-70 ℃, more preferably 54-66 ℃, and more preferably 58-62 ℃; the time of the polymerization reaction in the step (1) is preferably 22-26 h, more preferably 23-25 h, and even more preferably 23.5-24.5 h; the polymerization reaction in the step (1) is preferably carried out in a stirring state, and the rotation speed of the stirring is preferably 350 to 450rpm, more preferably 360 to 440rpm, and even more preferably 380 to 420 rpm.
In the present invention, centrifugation is performed after the polymerization reaction in the step (1) is completed, the rotation speed of the centrifugation is preferably 8500rpm or more, more preferably 9000rpm or more, and more preferably 9500rpm or more, and the time of the centrifugation is preferably 20min or more, more preferably 25min or more, and more preferably 30min or more; and (3) carrying out next washing after the centrifugation is finished, wherein the reagent for washing is preferably ethanol, and the dosage ratio of the ethanol to the graphene oxide is preferably 40-60 mL: 280-320 mg, more preferably 45-55 mL: 290-310 mg, more preferably 48-52 mL: 295-305 mg; the number of washing is preferably 5 or more, more preferably 6 or more, and still more preferably 7 or more.
In the invention, a carbon-carbon double bond is introduced on the surface of the graphene oxide through modification of a silane coupling agent, so that the next step of free radical polymerization is facilitated.
In the invention, the gas of the protective atmosphere in the step (2) is preferably nitrogen, argon or helium, and the flow rate of the protective atmosphere is preferably 0.07-0.08 m3More preferably 0.072-0.078 m3More preferably 0.074 to 0.076m3/h。
In the present invention, the solution of silicon alkoxide graphene alcohol in the step (2) is preferably an ethanol solution.
In the invention, the preferable dosage ratio of the silane graphene oxide to the ethanol is 280-320 mg: 240-260 mL, more preferably 290-310 mg: 245-255 mL, more preferably 295-305 mg: 248-252 mL.
In the invention, before mixing the silane graphene oxide and the ethanol, introducing a protective atmosphere into the ethanol; the gas of the protective atmosphere is preferably nitrogen, argon or helium, and the flow of the protective atmosphere is preferably 0.07-0.08 m3More preferably 0.072-0.078 m3More preferably 0.074 to 0.076m3H; the introducing time of the protective atmosphere is preferably 15-20 min, more preferably 16-19 min, and even more preferably 17-18 min. And mixing the silane graphene oxide with ethanol after the protective atmosphere is introduced.
In the invention, the mixing mode of the silane graphene oxide and the ethanol is ultrasonic, and the ultrasonic temperature is preferably 5-15 ℃, more preferably 6-14 ℃, and more preferably 8-12 ℃; the frequency of the ultrasonic wave is preferably 20-30 KHz, more preferably 22-28 KHz, and even more preferably 24-26 KHz; the ultrasonic time is preferably 1-1.5 h, more preferably 1.1-1.4 h, and even more preferably 1.2-1.3 h.
In the invention, the preferable dosage ratio of the silane graphene oxide to the dimethylaminoethyl methacrylate monomer is 280-320 mg: 280 to 320mmol, more preferably 290 to 310 mg: 290 to 310mmol, more preferably 295 to 305 mg: 295 to 305 mmol.
In the invention, the preferable dosage ratio of the silane graphene oxide to the azobisisobutyronitrile is 280-320 mg: 4-8 mmol, more preferably 290-310 mg: 5-7 mmol, more preferably 295-305 mg: 5.5 to 6.5 mmol.
In the invention, the temperature of the free radical polymerization reaction in the step (2) is preferably 60-80 ℃, more preferably 65-75 ℃, and more preferably 68-72 ℃; the time of the free radical polymerization reaction is preferably 22-26 hours, more preferably 23-25 hours, and even more preferably 23.5-24.5 hours.
In the invention, after the free radical polymerization reaction in the step (2) is finished, centrifuging the system, wherein the rotating speed of the centrifugation is preferably 8500-9500 rpm, more preferably 8600-9400 rpm, more preferably 8800-9200 rpm, and the time of the centrifugation is preferably 15-20 min, more preferably 16-19 min, more preferably 17-18 min; after the centrifugation is finished, the next step of washing is carried out, wherein the washing is preferably ethanol washing and acetone washing which are carried out sequentially; the preferable dosage ratio of ethanol to graphene oxide in ethanol washing is 40-60 mL: 280-320 mg, more preferably 45-55 mL: 290-310 mg, more preferably 48-52 mL: 295-305 mg; the number of washing with ethanol is preferably not less than 3, more preferably not less than 4, and still more preferably not less than 5; the preferable dosage ratio of acetone to graphene oxide in acetone washing is 40-60 mL: 280-320 mg, more preferably 45-55 mL: 290-310 mg, more preferably 48-52 mL: 295-305 mg; the number of acetone washes is preferably not less than 3, more preferably not less than 4, and still more preferably not less than 5; drying is carried out after the washing is finished.
In the invention, the drying temperature is preferably 60-70 ℃, more preferably 62-68 ℃, and more preferably 64-66 ℃; the drying time is preferably 2-2.5 h, more preferably 2.1-2.4 h, and even more preferably 2.2-2.3 h. And obtaining the modified graphene oxide after drying.
In the invention, the graphene oxide grafted poly (dimethylamino ethyl methacrylate) (GO-PDMAEMA) is prepared by polymerizing dimethyl aminoethyl methacrylate on the surface of graphene oxide through free radical polymerization; the incompletely quaternized dimethylaminoethyl methacrylate moiety will undergo deprotonation in water due to the positive electrical repulsion of the segment, spontaneously forming a cyclic conformation, which is converted to a zwitterion. Thus, an amphiphilic hydration layer is formed in a polymer chain, so that small molecular organic matters in water are not easy to adhere to the surface under the action of the hydration layer, namely the modified graphene oxide.
In the invention, the halogenated alkanol solution in the step (3) is preferably an ethanol solution, and the mass fraction of the halogenated alkanol solution is preferably 40-60%, more preferably 45-55%, and more preferably 48-52%; the alkyl halide is preferably n-butyl bromide, n-butyl chloride, propyl bromide, ethyl bromide, n-pentyl bromide or dodecyl bromide.
In the present invention, the ratio of the amount of the modified graphene oxide to the amount of the haloalkanol solution is preferably 0.3 g: 25 to 35mL, more preferably 0.3 g: 26-34 mL, more preferably 0.3 g: 28-32 mL.
In the invention, the temperature of the quaternization reaction in the step (3) is preferably 40-60 ℃, more preferably 45-55 ℃, and more preferably 48-52 ℃; the time of the quaternization reaction is preferably 22-26 h, more preferably 23-25 h, and even more preferably 23.5-24.5 h; the quaternization reaction is preferably carried out under a stirring state, and the stirring rotating speed is preferably 500-700 rpm, more preferably 550-650 rpm, and even more preferably 580-620 rpm.
In the invention, after the quaternization reaction in the step (3) is finished, ethanol washing and acetone washing are sequentially carried out; the preferable dosage ratio of ethanol to graphene oxide in ethanol washing is 40-60 mL: 280-320 mg, more preferably 45-55 mL: 290-310 mg, more preferably 48-52 mL: 295-305 mg; the number of washing with ethanol is preferably not less than 3, more preferably not less than 4, and still more preferably not less than 5; the preferable dosage ratio of acetone to graphene oxide in acetone washing is 40-60 mL: 280-320 mg, more preferably 45-55 mL: 290-310 mg, more preferably 48-52 mL: 295-305 mg; the number of acetone washes is preferably not less than 3, more preferably not less than 4, and still more preferably not less than 5; drying is carried out after the washing is finished. The drying temperature is preferably 70-90 ℃, more preferably 75-85 ℃, and more preferably 78-82 ℃, and the modified graphene oxide is obtained after drying to constant weight.
In the invention, alkyl halide is adopted to convert tertiary amine in dimethylaminoethyl methacrylate into quaternary ammonium, so that graphene oxide-quaternized dimethylaminoethyl methacrylate (GO-PQDMAEMA) is synthesized, namely modified graphene oxide.
In the present invention, the method for preparing the silane acrylate preferably comprises the steps of:
(a) mixing an acrylic monomer, azodiisobutyronitrile and N, N-dimethylformamide to obtain a mixed solution;
(b) mixing the mixed solution with N, N-dimethylformamide under a protective atmosphere to obtain a mixed system;
(c) under the protective atmosphere, mixing the benzoyl peroxide solution with the mixed system to perform polymerization reaction, thereby obtaining the acrylic silane ester;
in the present invention, the acrylic monomer in the step (a) preferably comprises methyl methacrylate, butyl methacrylate, methoxyethyl methacrylate, hexafluorobutyl methacrylate and triisopropylsilyl acrylate.
In the present invention, the mass ratio of methyl methacrylate, butyl methacrylate, methoxyethyl methacrylate, hexafluorobutyl methacrylate and triisopropylsilyl acrylate is preferably 150 to 160: 80-90: 6-7: 25-35: 45-55, more preferably 152-158: 82-88: 6.2-6.8: 27-33: 47 to 53, more preferably 154 to 156: 84-86: 6.4-6.6: 29-31: 49 to 51.
In the present invention, the mass ratio of the acrylic monomer to the azobisisobutyronitrile in the step (a) is preferably 300 to 350: 4-5, more preferably 310-340: 4.2 to 4.8, more preferably 320 to 330: 4.4 to 4.6.
In the present invention, the mass ratio of the acrylic monomer to the N, N-dimethylformamide in the step (a) is preferably 300 to 350: 300 to 350, more preferably 310 to 340: 310 to 340, more preferably 320 to 330: 320-330.
In the present invention, the protective atmosphere in the step (b) is preferably nitrogen, argon or helium.
In the present invention, the mass ratio of N, N-dimethylformamide to the mixed solution in the step (b) is preferably 1: 1.8 to 2.0, and more preferably 1: 1.84-1.96, more preferably 1: 1.88 to 1.92.
In the invention, the mixing in the step (b) is preferably to add the mixed liquid into the N, N-dimethylformamide dropwise, and the dropwise adding rate is preferably 210-230 g/h, more preferably 215-225 g/h, and more preferably 218-222 g/h.
In the invention, the mixing temperature in the step (b) is preferably 80-100 ℃, more preferably 85-95 ℃, and even more preferably 88-92 ℃.
In the present invention, the protective atmosphere in the step (c) is preferably nitrogen, argon or helium.
In the present invention, the solvent of the benzoyl peroxide solution in the step (c) is preferably N, N-dimethylformamide, and the mass ratio of the benzoyl peroxide to the N, N-dimethylformamide is preferably 1: 18 to 22, and more preferably 1: 19-21, more preferably 1: 19.5 to 20.5.
In the present invention, the mass ratio of the benzoyl peroxide to the azobisisobutyronitrile in step (a) is preferably 1: 4-5, and more preferably 1: 4.2-4.8, more preferably 1: 4.4 to 4.6.
In the invention, the mixing in the step (c) is preferably to drop the benzoyl peroxide solution into the mixing system, and the dropping rate is preferably 40-45 g/h, more preferably 41-44 g/h, and even more preferably 42-43 g/h.
In the invention, the polymerization reaction temperature in the step (c) is preferably 80-100 ℃, more preferably 85-95 ℃, and even more preferably 88-92 ℃; the time of the polymerization reaction is preferably 1.5 to 2.5 hours, more preferably 1.6 to 2.4 hours, and even more preferably 1.8 to 2.2 hours.
In the present invention, after the polymerization reaction in the step (c) is completed, the reaction system is exposed to air to terminate the reaction, and is naturally cooled to room temperature to obtain the silyl acrylate.
The invention also provides a preparation method of the resin, and the modified graphene oxide allyl acid resin is obtained by mixing the modified graphene oxide and the silane acrylate.
In the invention, the mixing mode is ultrasonic, and the ultrasonic temperature is 5-15 ℃, preferably 6-14 ℃, and more preferably 8-12 ℃; the frequency of the ultrasonic is 20-30 KHz, preferably 22-28 KHz, and more preferably 24-26 KHz; the ultrasonic treatment time is preferably 90-180 min, more preferably 100-170 min, and even more preferably 120-150 min.
The invention also provides application of the modified graphite oxide allyl acid resin in a coating.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
In the present invention, the ethanol used is anhydrous ethanol unless otherwise specified.
Example 1
Preparing modified graphene oxide:
carrying out ultrasonic treatment on 300mg of graphene oxide and 250mL of ethanol for 1h at 10 ℃ under the condition of 20KHz to obtain an ethanol solution of the graphene oxide; dissolving 1.5gKH570 in 60mL 95% ethanol, adjusting pH to 3.5 with hydrochloric acid, and adding ethanol to obtain solutionThen standing for 1h for prehydrolysis to obtain an ethanol solution of the silane coupling agent; mixing the silane coupling agent ethanol solution and the graphene oxide ethanol solution, and controlling the nitrogen flow to be 0.075m3Introducing nitrogen for 15 min; after the nitrogen is introduced, heating to 60 ℃, controlling the rotating speed to be 400rpm, and stirring for 24 hours to perform polymerization reaction; after the reaction is finished, the obtained reaction system is centrifuged for 20min at 9000rpm, and then 50mL of ethanol is used for single washing, and silane graphene oxide is obtained after 5 times of washing and is recorded as GO-KH 570.
The control flow is 0.075m3Continuously introducing nitrogen into ethanol, adding 300mg of silane oxidized graphene into 250mL of ethanol treated by nitrogen after 15min, and carrying out ultrasonic treatment for 1.5h under the conditions of 10 ℃, 25KHz and nitrogen to obtain a silane oxidized graphene ethanol solution; then adding 300mmol of dimethylaminoethyl methacrylate monomer and 6mmol of azobisisobutyronitrile, uniformly mixing, then reacting for 24h at 70 ℃ in a nitrogen atmosphere to obtain a reaction system, centrifuging the obtained reaction system for 20min at 9000rpm, then washing with 50mL of ethanol for a single time, washing with 5 times of ethanol and then with 50mL of acetone for a single time, washing with 5 times of acetone and drying at 65 ℃ for 2.5h to obtain modified graphene oxide, which is recorded as GO-PDMAEMA.
Dissolving n-butyl bromide in ethanol to obtain an n-butyl bromide ethanol solution with the mass fraction of 50%; mixing 0.3g of modified graphene oxide and 30mL of n-butyl bromide ethanol solution at 50 ℃ and stirring at 600rpm for 24h to complete quaternization, then washing with 50mL of ethanol for a single time, washing with 5 times of ethanol, then washing with 50mL of acetone for a single time, washing with 5 times of acetone, and drying at 80 ℃ to constant weight to obtain modified graphene oxide, which is marked as GO-PQDMAEMA.
The results of Fourier infrared tests on Graphene Oxide (GO), silane graphene oxide (GO-KH570), modified graphene oxide (GO-PDMAEMA) and modified graphene oxide (GO-PQDMAEMA) are shown in FIG. 1. As can be seen from FIG. 1, GO-KH570 has stretching vibration peak (v) of methyl and methyleneC-HAt 2978cm-1And 2892cm-1)There are Si-O-Si bonds and a stretching vibration peak (v) of Si-O-CSi-OAt 1063cm-1)，(vC-OAt 1190cm-1) KH570 proved to be successfully decorated on the GO surface. For GO-PDMAEMA, at 2820cm-1And 2871cm-1Is N- (CH)3)2Peak of key stretching vibration at 1726cm-1And 1381cm-1The peak is the stretching vibration peak of the C ═ O and C-O-C bonds, which indicates the successful synthesis of GO-PDMAEMA; for GO-PQDMAEMA, at 2868cm-1Nearby absorption peaks due to CH2(CH3)2-N+Stretching and contraction of the bond indicates successful quaternization. The method is characterized in that Graphene Oxide (GO), silane graphene oxide (GO-KH570), modified graphene oxide (GO-PDMAEMA) and modified graphene oxide (GO-PQDMAEMA) are subjected to X-ray photoelectron spectroscopy (xps) tests by using an Al-Kalpha X-ray source of PHI 5700ESCA, and the results are shown in FIG. 2, wherein GO-KH570 is more than Si elements in GO, GO-PDMAEMA is more than N elements in GO-KH570, GO-PQDMAEMA is more than Br elements in GO-PDMAEMA, and the successful preparation of GO-KH570, GO-PDMAEMA and GO-PQDMAEMA is assisted.
The xps results for GO-PDMAEMA and GO-PQDMAEMA were peaked and are shown in FIG. 3. The peak value of N1s of GO-PQDMAEMA shows that a nitrogen peak appears at 399.65 and 402.29eV, which are respectively assigned to tertiary ammonium (non-quaternized) and quaternary ammonium, and further confirms that the quaternization of GO-PDMAEMA is successful.
The valence state distribution of the elements of the x-ray photoelectron spectrum of GO-PDMAEMA is shown in Table 1, and the valence state distribution of the elements of the x-ray photoelectron spectrum of GO-PQDMAEMA is shown in Table 2; the shift of the C-N peak is seen in tables 1 and 2, further demonstrating the success of quaternization.
TABLE 1
Name
PeakBE
Atomic％
C1s C-C
284.8
28.23
C1s C-N
285.65
20.08
C1s C-O
286.65
13.17
C1s C＝O
288.79
7.33
N1s C-N
399.36
4.1
N1s C-N+
401.73
1.19
O1s C-O
533.35
8.03
O1s C＝O
531.97
13.28
O1s Si-O
530.77
2.77
Si2p Si-O-C
102.32
1.8
TABLE 2
Name
PeakBE
Atomic％
C1s C-C
284.8
29.09
C1s C-N
285.63
12.52
C1s C-O
286.63
25.87
C1s C＝O
288.89
6.38
N1s C-N
399.65
0.75
N1s C-N+
402.29
3.92
O1s C-O
533.61
7.5
O1s C＝O
532.3
11.91
O1s Si-O
530.75
1.09
Si2p Si-O-C
102.07
0.95
The Zeta potentials of GO, GO-KH570, GO-PDMAEMA and GO-PQDMAEMA were tested in water at pH 7 (equilibration time 3 minutes, 3 scans per sample) and the results are shown in Table 3. The surface pure GO shows negative electricity in water with the pH value of 7, GO-PDMAEMA shows positive electricity, and the positive electricity of GO-PQDMAEMA is stronger than that of GO-PDMAEMA. This is because the protonation ability of the quaternized polymer is stronger and the success of quaternization is evidenced by the test results.
TABLE 3
Samples
Zeta(mV)
GO
-33.5
GO-KH570
0.12
GO-PDMAEMA
11.0
GO-PQDMAEMA
36.6
Preparation of acrylic silane ester:
a mixed solution was prepared by dissolving 156g of methyl methacrylate, 84.5g of butyl methacrylate, 6.5g of methoxyethyl methacrylate, 29.25g of hexafluorobutyl methacrylate, 48.75g of triisopropylsilyl acrylate and 4.5g of azobisisobutyronitrile in 325g N, N-dimethylformamide; controlling the temperature to be 90 ℃, and dropwise adding the mixed solution into 350g of N, N-dimethylformamide at a speed of 220g/h under the protection of nitrogen to obtain a mixed system; dissolving 1g of benzoyl peroxide in 20g of N, N-dimethylformamide to obtain a benzoyl peroxide solution, dropwise adding the benzoyl peroxide solution into a mixed system at the speed of 45g/h under the protection of nitrogen, starting polymerization reaction at a certain time after the dropwise adding is finished, reacting for 2h at 90 ℃, then exposing the mixed system in the air to terminate the reaction, and naturally cooling to room temperature to obtain the acrylic silane ester.
The prepared acrylic silane ester is subjected to Fourier infrared test by a VATAR 360 infrared tester, and the result is shown in figure 4, wherein 3000-2850cm-1Tensile vibration peak at C-H in methyl and methylene, 1734cm-1Is the stretching vibration peak of carbonyl group in methyl methacrylate, 1265cm-1Is the peak of C-F stretching vibration. 1610cm-1No peak appears nearby, which proves that no carbon-carbon double bond exists, thus the acrylic monomer is completely reacted, and the preparation of the acrylic silane ester is successfully proved.
Carrying out ultrasonic treatment on the prepared acrylic silane ester and the modified graphene oxide at the temperature of 10 ℃ and the frequency of 25KHz for 120min to obtain modified graphene oxide acrylic resin, which is recorded as GQF; the antifouling principle schematic diagram of the prepared modified graphene oxide allyl acid resin is shown in fig. 5, and it can be seen from the diagram that GQF has obvious antibacterial and anti-algae adhesion performances after GO-PQDMAEMA is added. Hydrophilic GO-PQDMAEMA increases hydrolysis of the matrix resin, forming a static antifouling dynamic surface. Further analysis found that GO-PQDMAEMA had both cationically charged tertiary amine groups as "spears" and the zwitterionic ring conformation of the DMAEMA monomer as a "shield" due to incomplete conversion by quaternization. The zwitterions in the ring conformation combine firmly with water to form a hydrated layer, which becomes the "shield" of the GO surface, while the quaternary ammonium zwitterions become the "spear" of the GO surface. The "contradictory" mechanism enhances the antifouling properties of the GO surface.
Marking a coating prepared from the resin without modified graphene oxide as GQF-0;
the mass ratio of the modified graphene oxide to the acrylic silane ester is 0.001: the coating prepared by the resin obtained in 1 is recorded as GQF-0.1;
the mass ratio of the modified graphene oxide to the acrylic silane ester is 0.0025: the coating prepared by the resin obtained in 1 is recorded as GQF-0.25;
the mass ratio of the modified graphene oxide to the acrylic silane ester is 0.005: the coating prepared by the resin obtained in 1 is recorded as GQF-0.5;
the mass ratio of the modified graphene oxide to the acrylic silane ester is 0.01: the coating prepared by the resin obtained in 1 is recorded as GQF-1;
the mass ratio of the modified graphene oxide to the acrylic silane ester is 0.015: the coating obtained at 1 was recorded as GQF-1.5.
GQF-0, GQF-0.1, GQF-0.25, GQF-0.5, GQF-1 and GQF-1.5 are soaked in simulated seawater, the curve of the weight loss of the coating along with time is shown in figure 6, and it can be seen that the weight loss of the modified graphene oxide allyl acid resin is increased along with the increase of the content of the modified graphene oxide.
GQF-0, GQF-0.1, GQF-0.25, GQF-0.5, GQF-1 and GQF-1.5 are soaked in simulated seawater, the change of the contact angle after 14 days is shown in figure 7, and the contact angles of GQF-0.1 before and after soaking are 94.7 degrees and 87.8 degrees respectively; GQF-0.25 has contact angles of 91.6 degrees and 87.8 degrees before and after soaking respectively; GQF-0.5, the contact angles before and after soaking are 87.5 degrees and 76.6 degrees respectively; GQF-1 has contact angles of 84.4 degrees and 75.9 degrees before and after soaking; GQF-1.5 the contact angles before and after soaking were 83.0 ° and 74.3 °, respectively.
Drying GQF-0, GQF-0.1, GQF-0.25, GQF-0.5, GQF-1 and GQF-1.5 coatings, and observing by using an electron microscope, wherein figure 8 is a scanning electron microscope image after drying; soaking the coating in simulated seawater for 14 days, and observing by using an electron microscope, wherein FIG. 9 is a scanning electron microscope image after soaking; as can be seen from the figure, the graphene oxide is gradually exposed to the coating surface as the coating is polished in water.
Diatom adhesion tests using Nitzschia clostridium (n.closterium), Phaeodactylum tricornutum (p.tricornutum) and Halamphora were performed, and the coating was immersed in algae broth for 72 hours and photographed using BX53 fluorescence microscope of OLYMPUS, and the obtained photograph is shown in fig. 10, from which it can be seen that the diatom adhesion rate was significantly decreased as the content of modified graphene oxide was increased.
The results of calculation of diatom attachment resistance using GQF-0 as a blank are shown in FIG. 11, where it can be seen that GQF-0.1 algae resistance against N.clausium, P.tricornutum and Halamphora was 83.7%, 52.4% and 65.8%, respectively; GQF-0.25 has anti-diatom rates of 92.1%, 60.32% and 71.1%, respectively; GQF-0.5 has anti-diatom ratio of 94.4%, 66.7% and 76.3%, respectively; GQF-1 has anti-diatom rates of 96.6%, 82.5% and 89.5%, respectively; GQF-1.5 have anti-diatom rates of 96.8%, 84.1% and 90.7%, respectively. With the increase of the content of the modified graphene oxide, the diatom resistance rate of the coating is also increased.
The antibacterial properties of the copolymers were evaluated with cells of escherichia coli (e.coli) and staphylococcus aureus (s.aureus). The prepared sample was soaked in PBS buffer solution for 24 hours and then sterilized with ultraviolet lamp (20W, 253.7nm) for 30 minutes, and the treated sample was placed in a petri dish containing 10ml of luria bertani (lb) liquid medium and predetermined concentrations of escherichia coli or staphylococcus aureus cells calculated using standard serial dilution. The liquid medium was cultured at 37 ℃ for 12 hours, and then a sample was taken out, and escherichia coli and staphylococcus aureus were separated from the sample using 10mL of LB medium and diluted to 0.1% of the original concentration. Then, 10. mu.L of a diluted liquid medium sample was uniformly scraped onto LB solid medium and cultured at 37 ℃ for 24 hours. The photograph of the medium is shown in FIG. 12. It can be seen from the figure that the number of escherichia coli and staphylococcus aureus is obviously reduced with the increase of the content of the modified graphene oxide. The number of colonies on the surface of each medium was counted by plate counting using GQF-0 coating as a blank and the antibacterial ratio was calculated, and the result calculated using GQF-0 coating as a blank is shown in FIG. 13. GQF-0.1 has 78.6% and 59.7% antibacterial rate to Escherichia coli and Staphylococcus aureus; GQF-0.25, the antibacterial rate is 82.4% and 62.5% respectively; GQF-0.5, the antibacterial rate is 88.6% and 67.2% respectively; GQF-1 has antibacterial rate of 90.4% and 88.4% respectively; GQF-1.5, the antibacterial rates are respectively 92.0% and 89.1%, and it can be seen that the modified graphene oxide allyl acid resin provided by the embodiment has good antibacterial effect.
Example 2
Preparing modified graphene oxide:
carrying out ultrasonic treatment on 320mg of graphene oxide and 240mL of ethanol for 1.5h at 5 ℃ under the condition of 25KHz to obtain an ethanol solution of the graphene oxide; dissolving 1gA-171 in 50mL of 94% ethanol, adjusting the pH value to 4 by using hydrochloric acid, and standing for 1.3h for prehydrolysis to obtain an ethanol solution of a silane coupling agent; mixing the silane coupling agent ethanol solution and the graphene oxide ethanol solution, and controlling the nitrogen flow to be 0.076m3Introducing nitrogen for 20 min; after the nitrogen is introduced, heating to 50 ℃, controlling the rotating speed to be 350rpm, stirring for 22h, and carrying out polymerization reaction; after the reaction is finished, the obtained reaction system is centrifuged for 20min at 8500rpm, and then 60mL of ethanol is used for single washing, and silane graphene oxide is obtained after 6 times of washing.
The control flow is 0.08m3Continuously introducing nitrogen into ethanol, adding 280mg of silane oxidized graphene into 240mL of ethanol treated by nitrogen after 20min, and performing ultrasonic treatment for 1.2h under the conditions of 5 ℃, 20KHz and nitrogen to obtain a silane oxidized graphene ethanol solution; then 280mmol of methacrylic acid dimethyl are addedUniformly mixing an aminoethyl ester monomer and 4mmol of azobisisobutyronitrile, reacting for 22h at 60 ℃ in a nitrogen atmosphere to obtain a reaction system, centrifuging the obtained reaction system for 15min at 8500rpm, washing with 50mL of ethanol for a single time, washing with ethanol for 5 times, washing with 40mL of acetone for a single time, washing with acetone for 5 times, and drying at 60 ℃ for 2h to obtain the modified graphene oxide.
Dissolving n-butyl chloride in ethanol to obtain a 40% n-butyl chloride ethanol solution; 0.3g of modified graphene oxide and 25mL of chloro-n-butane ethanol solution are mixed and stirred at the rotating speed of 500rpm at 40 ℃ for 22h to complete quaternization, then 40mL of ethanol is used for single washing, 40mL of acetone is used for single washing after 5 times of ethanol washing, and the mixture is dried at 70 ℃ to constant weight after 5 times of acetone washing to obtain the modified graphene oxide.
Preparation of acrylic silane ester:
dissolving 150g of methyl methacrylate, 80g of butyl methacrylate, 6g of methoxyethyl methacrylate, 25g of hexafluorobutyl methacrylate, 45g of triisopropylsilyl acrylate and 4g of azobisisobutyronitrile in 300g of N, N-dimethylformamide to obtain a mixed solution; controlling the temperature to be 80 ℃, and dropwise adding the mixed solution into 320gN, N-dimethylformamide at the speed of 210g/h under the protection of nitrogen to obtain a mixed system; dissolving 1g of benzoyl peroxide in 18g of N, N-dimethylformamide to obtain a benzoyl peroxide solution, dropwise adding the benzoyl peroxide solution into a mixed system at the rate of 40g/h under the protection of nitrogen, starting polymerization reaction at a certain time after the dropwise adding is finished, reacting at 80 ℃ for 1.5h, then exposing the mixed system in the air to terminate the reaction, and naturally cooling to room temperature to obtain the acrylic silane ester.
Preparing the obtained acrylic silane ester and the modified graphene oxide according to the ratio of 1: 0.005, at 5 ℃, and carrying out ultrasonic treatment for 180min at the frequency of 20KHz to obtain the modified graphite oxide allyl acid resin.
The coating obtained from the modified graphene oxide acrylic resin prepared in this example was subjected to the diatom attachment test according to the procedure in example 1, and the anti-algae rates for n.closed, p.tricornutum and Halamphora were 94.3%, 66.9% and 76.4%, respectively; the antibacterial rates of the escherichia coli and the staphylococcus aureus are 88.4% and 67.3%, respectively.
Example 3
Preparing modified graphene oxide:
carrying out ultrasonic treatment on 280mg of graphene oxide and 260mL of ethanol for 1.2h at the temperature of 15 ℃ and under the condition of 30KHz to obtain an ethanol solution of the graphene oxide; dissolving 2gA151 in 70mL of 96% ethanol, adjusting the pH value to 3.9 by using hydrochloric acid, and standing for 1.5h for prehydrolysis to obtain an ethanol solution of a silane coupling agent; mixing the silane coupling agent ethanol solution and the graphene oxide ethanol solution, and controlling the nitrogen flow to be 0.08m3Introducing nitrogen for 15 min; heating to 70 ℃ after the nitrogen gas is introduced, controlling the rotating speed to be 450rpm, stirring for 26h, and carrying out polymerization reaction; after the reaction is finished, the obtained reaction system is centrifuged for 30min at 9500rpm, and then single washing is carried out by using 40mL of ethanol, and silane graphene oxide is obtained after 7 times of washing.
The control flow is 0.07m3Continuously introducing helium into ethanol, adding 320mg of silane oxidized graphene into 260mL of ethanol treated by helium after 15min, and performing ultrasonic treatment for 1.5h under the conditions of 15 ℃, 30KHz and helium to obtain a silane oxidized graphene ethanol solution; then, 320mmol of dimethylaminoethyl methacrylate monomer and 8mmol of azobisisobutyronitrile are added and uniformly mixed, then the mixture reacts for 26h in a helium atmosphere at 80 ℃ to obtain a reaction system, the obtained reaction system is centrifuged for 20min at 9500rpm, then 60mL of ethanol is used for single washing, 60mL of acetone is used for single washing after ethanol is used for 4 times, and the mixture is dried for 2.5h at 70 ℃ after acetone is used for 4 times to obtain the modified graphene oxide.
Dissolving bromododecane in ethanol to obtain a chlorinated n-butane ethanol solution with the mass fraction of 60%; 0.3g of modified graphene oxide and 35mL of bromododecane ethanol solution are mixed and stirred at the rotating speed of 700rpm at 60 ℃ for 26 hours to complete quaternization, then 60mL of ethanol is used for single washing, 60mL of acetone is used for single washing after 3 times of ethanol washing, and the mixture is dried at 90 ℃ to constant weight after 3 times of acetone washing to obtain the modified graphene oxide.
Preparation of acrylic silane ester:
160g of methyl methacrylate, 90g of butyl methacrylate, 7g of methoxyethyl methacrylate, 35g of hexafluorobutyl methacrylate, 55g of triisopropylsilyl acrylate and 5g of azobisisobutyronitrile were dissolved in 350g of N, N-dimethylformamide to obtain a mixed solution; controlling the temperature to be 100 ℃, and dropwise adding the mixed solution into 360gN, N-dimethylformamide at a speed of 230g/h under the protection of nitrogen to obtain a mixed system; dissolving 1g of benzoyl peroxide in 22g of N, N-dimethylformamide to obtain a benzoyl peroxide solution, dropwise adding the benzoyl peroxide solution into a mixed system at the speed of 45g/h under the protection of nitrogen, starting polymerization reaction at a certain time after the dropwise adding is finished, reacting for 2.5h at 100 ℃, then exposing the mixed system in the air to terminate the reaction, and naturally cooling to room temperature to obtain the acrylic silane ester.
Preparing the obtained acrylic silane ester and the modified graphene oxide according to the ratio of 1: 0.014, at 15 ℃, and carrying out ultrasonic treatment for 90min at the frequency of 30KHz to obtain the modified graphene oxide allyl acid resin.
The coating obtained by using the modified graphene oxide allyl acid resin prepared in the embodiment was subjected to a diatom adhesion test according to the procedure in example 1, and the anti-algae rates of n.closed, p.tricornutum and Halamphora were 96.4%, 83.6% and 90.1%, respectively; the antibacterial rates of the escherichia coli and the staphylococcus aureus are 91.6% and 88.9%, respectively.
From the above examples, the present invention provides a modified graphene oxide allyl acid resin, which is obtained by subjecting modified graphene oxide and silane acrylate to ultrasonic conditions. According to the invention, a carbon-carbon double bond is introduced into the surface modification silane coupling agent of graphene oxide; then, carrying out free radical polymerization by using dimethylaminoethyl methacrylate, and converting tertiary amine in the dimethylaminoethyl methacrylate into quaternary ammonium by alkyl halide to obtain modified graphene oxide; adopting a free radical polymerization method to acrylic monomers to obtain acrylic silane ester; and (3) obtaining the resin by using the modified graphene oxide and the acrylic silane ester under the ultrasonic condition. The modified resin provided by the invention has a good inhibiting effect on diatom and bacteria, can effectively prevent the invasion of bacterial microorganisms to machinery in a seawater environment, and effectively solves the antifouling problem of the machinery surface on the sea level.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
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