Preparation method and application of marine antifouling functionalized graphene-polyurethane composite coating

Abstract

The invention relates to the technical field of new materials, in particular to a marine antifouling functionalized graphene-polyurethane composite coating, poly (dimethylaminoethyl methacrylate) enables a weak polyelectrolyte to show protein adsorption resistance under high solution pH and ionic strength, and under a marine high-salinity environment, the composite coating has good anti-fouling performance. The poly (dimethylaminoethyl methacrylate) introduced to the side chain of a polyurethane molecule is electrically neutral like zwitterions, the electrostatic interaction force is eliminated, the hydrophilic property of polyurethane can be improved by the poly (dimethylaminoethyl methacrylate) side group, and the good antibacterial property can be achieved, so that effective protein adsorption resistance can be achieved, and the antibacterial property of the polyurethane is improved. The graphene is introduced into the polyurethane matrix in a covalent grafting manner, so that the graphene can be well dispersed in the polyurethane matrix, and the well dispersed graphene can effectively enhance the mechanical property of the polyurethane due to the nano lamellar structure and excellent mechanical property.

Description

Technical Field

[0001] The present invention relates to the technical field of new materials, and in particular to a preparation method and application of a marine antifouling functionalized graphene-polyurethane composite coating. Background Art

[0002] Marine biofouling refers to the biological aggregation and scaling formed on marine facilities such as ship hulls, marine mining equipment, aquaculture facilities, etc. in the seawater environment. Since the spores, eggs and larvae of some smaller marine organisms will flow into the marine facility system with seawater and grow and reproduce, thus affecting the normal operation of the equipment and facilities or affecting the maintenance cost and service life of the equipment and facilities, marine biofouling can easily cause serious economic losses. Therefore, it is necessary to effectively prevent marine facilities from operating normally to ensure the normal operation of marine equipment and facilities. The main anti-fouling method at present is to apply anti-fouling coatings that are not easy for marine organisms to attach. Anti-fouling coatings are usually able to prevent the formation of a base film on the surface of the equipment that can inhibit the adhesion of marine organisms, thereby achieving an anti-fouling effect.

[0003] One of the components of the base membrane of protein, so using coatings to resist protein adhesion can effectively improve the antifouling performance of the coating. In Chinese patent CN107936831B "A hydrophilic modified fouling-releasing marine antifouling coating and its preparation method", a hydrophilic polyurethane coating obtained by introducing zwitterions prepared with triethanolamine and 1,3-propanesulfonic acid lactone as antifouling factors is disclosed, which can effectively resist protein adhesion and have a good antifouling effect. The marine environment is complex. In addition to having a good antifouling effect, it also requires better mechanical properties to play a good protective effect. Therefore, the introduction of dimethylaminoethyl methacrylate side chain with good anti-protein adhesion performance and the addition of excellent nano-reinforcement material graphene is a very good solution, but simple addition has the problem of poor agglomeration and dispersibility, and the introduction of graphene by grafting can solve these problems well. Summary of the invention

[0004] 1. Technical issues to be resolved In view of the shortcomings of the prior art, the present invention provides a method for preparing and applying a marine antifouling functionalized graphene-polyurethane composite coating, which solves the problems that polyurethane does not have antifouling properties and that directly adding graphene causes poor agglomeration and dispersion in the polyurethane matrix.

[0005] (II) Technical solution To achieve the above object, the present invention provides the following technical solution: A method for preparing a marine antifouling functionalized graphene-polyurethane composite coating comprises the following steps: (1) Add polyester diol and isophorone diisocyanate to dimethylformamide solvent, then add dibutyltin dilaurate, then add butanediol, dihydroxypropionic acid and a molecule of formula C 10 H 18 O4 2,2-bis(hydroxymethyl)butyl methacrylate, heated to 70-80°C in a nitrogen atmosphere, reacted for 3-6 hours, after the reaction was completed, precipitated with deionized water, washed, and dried to obtain olefin-modified polyurethane; (2) Add olefin-modified polyurethane to deionized water, stir and disperse, then add potassium persulfide and dimethylaminoethyl methacrylate, heat to 70-90°C and stir to react for 1-2h to form a seed emulsion, then add the remaining potassium persulfide and dimethylaminoethyl methacrylate to react for 4-8h, wait for the reaction to be completed, precipitate, wash, and vacuum dry to obtain dimethylaminoethyl ester-modified polyurethane; (3) Add dimethylaminoethyl ester modified polyurethane to dimethylformamide solvent, then add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and stir to dissolve, then add amino graphene and stir to disperse, inject triethylamine under nitrogen atmosphere and stir to react, after the reaction is completed, precipitate with hydrochloric acid solution, wash and dry to obtain a marine antifouling functionalized graphene-polyurethane composite coating.

[0006] Preferably, in step (1), the mass ratio of polyester diol, isophorone diisocyanate, dibutyltin dilaurate, dimethylformamide, butanediol, dihydroxypropionic acid and 2,2-bis(hydroxymethyl)butyl methacrylate is 100:60-80:0.5-1.2:3500-6000:18-45:2-4:9-20.

[0007] Preferably, in step (2), the mass ratio of olefin-modified polyurethane, deionized water, potassium persulfide and dimethylaminoethyl methacrylate is 100:5000-9000:0.1-0.2:10-17.

[0008] Preferably, in step (3), the mass ratio of dimethylaminoethyl ester modified polyurethane, dimethylformamide, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, amino graphene and triethylamine is 100:3500-6000:2-5:0.5-1.2:1-3.

[0009] Preferably, the reaction temperature in step (3) is 20-40° C., and the reaction time is 12-24 h.

[0010] 3. Beneficial technical effects Compared with the prior art, the present invention has the following experimental principles and beneficial technical effects: The marine antifouling functionalized graphene-polyurethane composite coating obtains a modified polyurethane having two functional groups, namely, alkenyl and carboxyl, in a chain extension process by using 2,2-bis(hydroxymethyl)butyl methacrylate, an alkenyl functional group chain extender having a dihydroxy structure, and dihydroxypropionic acid, a carboxyl functional group chain extender. Then, potassium sulfide is used to initiate the graft polymerization of dimethylaminoethyl methacrylate on the polyurethane side chain, thereby introducing the polymethylaminoethyl methacrylate group with good protein adhesion resistance into the polyurethane side chain, thereby obtaining the dimethylaminoethyl ester modified polyurethane. Then, in the system of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and triethylamine, the carboxyl group of the polyurethane side chain undergoes an amidation reaction with the amino group on the amino graphene, thereby causing the dispersed graphene to be grafted on the polyurethane molecular chain, thereby obtaining the marine antifouling functionalized graphene-polyurethane composite coating.

[0011] The invention discloses a marine antifouling functionalized graphene-polyurethane composite coating, wherein poly(dimethylaminoethyl methacrylate) is a weak polyelectrolyte, which can exhibit anti-protein adsorption performance under higher solution pH and ionic strength, and the marine environment has high ionic strength. In the marine high-salinity environment, the poly(dimethylaminoethyl methacrylate) introduced on the side chain of the polyurethane molecule is electrically neutral like zwitterions, thereby eliminating electrostatic interaction forces, and the side groups of poly(dimethylaminoethyl methacrylate) can increase the hydrophilicity of the polyurethane, and can also play a good antibacterial role, thereby playing an effective role in resisting protein adsorption, thereby giving the polyurethane coating excellent antifouling performance.

[0012] The marine antifouling functionalized graphene-polyurethane composite coating introduces graphene into a polyurethane matrix in a covalently grafted manner through an amidation reaction. The polyurethane molecular chain can increase the compatibility between the graphene and the polyurethane matrix, so that the graphene can be well dispersed in the polyurethane matrix, and the graphene sheets and the polyurethane have a stronger interaction. The well-dispersed graphene can effectively enhance the mechanical properties of the polyurethane due to its nanosheet structure and excellent mechanical properties, and play a role in strengthening and toughening, giving the antifouling polyurethane coating excellent mechanical properties. The graphene also has good antibacterial properties and can play a synergistic antifouling effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 It is the structural formula of 2,2-bis(hydroxymethyl)butyl methacrylate. DETAILED DESCRIPTION

[0014] To achieve the above object, the present invention provides the following technical solution: The preparation method of the marine antifouling functionalized graphene-polyurethane composite coating is as follows: Antifouling performance test: QCM-I dissipative quartz crystal microbalance was used to test the protein adsorption behavior of polyurethane coatings. The sample coating was loaded into the QCM-I dissipative quartz crystal microbalance for testing. The solution was an artificial seawater solution of bovine serum albumin, the pH was adjusted to 8.2, the temperature was set to 25°C, and the solution flow rate was 150μL / min.

[0015] Mechanical properties test: The prepared polyurethane coating film was cut into standard tensile specimens and the tensile strength was tested using a CMT-5 electronic universal testing machine. The test standard was GB / T 528-2009.

[0016] Example 1

[0017] (1) Add 20g of polyester diol and 12g of isophorone diisocyanate to 700g of dimethylformamide solvent, then add 0.01g of dibutyltin dilaurate, then add 3.6g of butanediol, 0.4g of dihydroxypropionic acid and 1.8g of C 10 H 18 O4 2,2-bis(hydroxymethyl)butyl methacrylate, heated to 70°C in a nitrogen atmosphere, reacted for 3 hours, after the reaction was completed, precipitated with deionized water, washed, and dried to obtain olefin-modified polyurethane; (2) Add 3 g of olefin-modified polyurethane to 150 g of deionized water, stir and disperse, then add 0.005 g of potassium persulfide and 0.05 g of dimethylaminoethyl methacrylate, heat to 70 °C and stir to react for 1 h to form a seed emulsion, then add 0.025 g of potassium persulfide and 0.25 g of dimethylaminoethyl methacrylate to react for 4 h, wait for the reaction to be completed, precipitate, wash, and vacuum dry to obtain dimethylaminoethyl ester-modified polyurethane; (3) 100 g of dimethylaminoethyl ester modified polyurethane was added to 3500 g of dimethylformamide solvent, followed by adding 2 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and stirring to dissolve, and then adding 0.5 g of amino graphene and stirring to disperse. In a nitrogen atmosphere, 1 g of triethylamine was injected and stirred at 20 ° C for 12 h. After the reaction was completed, hydrochloric acid solution was used for precipitation, washing, and drying to obtain a marine antifouling functionalized graphene-polyurethane composite coating, and the mass of bovine serum protein adsorbed was 2.1 ng / mm 2 , the tensile strength is 48.7Mpa.

[0018] Example 2

[0019] (1) Add 20g of polyester diol and 13g of isophorone diisocyanate to 800g of dimethylformamide solvent, then add 0.14g of dibutyltin dilaurate, then add 4.2g of butanediol, 0.5g of dihydroxypropionic acid and 2.2g of C 10 H 18O4 2,2-bis(hydroxymethyl)butyl methacrylate, heated to 75°C in a nitrogen atmosphere, reacted for 4 hours, after the reaction was completed, precipitated with deionized water, washed, and dried to obtain olefin-modified polyurethane; (2) Add 3 g of olefin-modified polyurethane to 170 g of deionized water, stir and disperse, then add 0.005 g of potassium persulfide and 0.065 g of dimethylaminoethyl methacrylate, heat to 70 °C and stir to react for 1 h to form a seed emulsion, then add 0.03 g of potassium persulfide and 0.29 g of dimethylaminoethyl methacrylate to react for 5 h, wait for the reaction to be completed, precipitate, wash, and vacuum dry to obtain dimethylaminoethyl ester-modified polyurethane; (3) 100 g of dimethylaminoethyl ester modified polyurethane was added to 3600 g of dimethylformamide solvent, followed by adding 3 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and stirring to dissolve, and then adding 0.7 g of amino graphene and stirring to disperse. 2 g of triethylamine was injected under nitrogen atmosphere, and the mixture was stirred and reacted at 25 °C for 18 h. After the reaction was completed, hydrochloric acid solution was used for precipitation, washing, and drying to obtain a marine antifouling functionalized graphene-polyurethane composite coating, and the mass of bovine serum protein adsorbed was 1.6 ng / mm 2 , the tensile strength is 54.9Mpa.

[0020] Example 3

[0021] (1) Add 20g of polyester diol and 14g of isophorone diisocyanate to 1000g of dimethylformamide solvent, then add 0.16g of dibutyltin dilaurate, then add 5g of butanediol, 0.6g of dihydroxypropionic acid and 3g of C 10 H 18 O4 2,2-bis(hydroxymethyl)butyl methacrylate, heated to 75°C in a nitrogen atmosphere, reacted for 5 hours, after the reaction was completed, precipitated with deionized water, washed, and dried to obtain olefin-modified polyurethane; (2) Add 3 g of olefin-modified polyurethane to 200 g of deionized water, stir and disperse, then add 0.008 g of potassium persulfide and 0.07 g of dimethylaminoethyl methacrylate, heat to 80 °C and stir to react for 1.5 h to form a seed emulsion, then add 0.03 g of potassium persulfide and 0.32 g of dimethylaminoethyl methacrylate to react for 6 h, wait for the reaction to be completed, precipitate, wash, and vacuum dry to obtain dimethylaminoethyl ester-modified polyurethane; (3) 100 g of dimethylaminoethyl ester modified polyurethane was added to 4200 g of dimethylformamide solvent, followed by adding 3 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and stirring to dissolve, and then adding 0.9 g of amino graphene and stirring to disperse. 2 g of triethylamine was injected under nitrogen atmosphere, and the mixture was stirred and reacted at 30 ° C for 16 h. After the reaction was completed, hydrochloric acid solution was used for precipitation, washing, and drying to obtain a marine antifouling functionalized graphene-polyurethane composite coating, and the mass of bovine serum protein adsorbed was 1.2 ng / mm 2 , the tensile strength is 57.4Mpa.

[0022] Example 4

[0023] (1) Add 20g of polyester diol and 15g of isophorone diisocyanate to 1100g of dimethylformamide solvent, then add 0.20g of dibutyltin dilaurate, then add 8g of butanediol, 0.4-0.8g of dihydroxypropionic acid and 3.4g of C 10 H 18 O4 2,2-bis(hydroxymethyl)butyl methacrylate, heated to 75°C in a nitrogen atmosphere, reacted for 5 hours, after the reaction was completed, precipitated with deionized water, washed, and dried to obtain olefin-modified polyurethane; (2) Add 3 g of olefin-modified polyurethane to 250 g of deionized water, stir and disperse, then add 0.008 g of potassium persulfide and 0.079 g of dimethylaminoethyl methacrylate, heat to 80 °C and stir to react for 2 h to form a seed emulsion, then add 0.04 g of potassium persulfide and 0.4 g of dimethylaminoethyl methacrylate to react for 7 h, wait for the reaction to be completed, precipitate, wash, and vacuum dry to obtain dimethylaminoethyl ester-modified polyurethane; (3) 100 g of dimethylaminoethyl ester modified polyurethane was added to 5000 g of dimethylformamide solvent, followed by adding 4 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and stirring to dissolve, and then adding 1 g of amino graphene and stirring to disperse. 2 g of triethylamine was injected under nitrogen atmosphere, and the mixture was stirred and reacted at 40 °C for 24 h. After the reaction was completed, hydrochloric acid solution was used for precipitation, washing, and drying to obtain a marine antifouling functionalized graphene-polyurethane composite coating, and the mass of bovine serum protein adsorbed was 0.2 ng / mm 2 , the tensile strength is 51.7Mpa.

[0024] Example 5

[0025] (1) Add 20g of polyester diol and 16g of isophorone diisocyanate to 1200g of dimethylformamide solvent, then add 0.24g of dibutyltin dilaurate, then add 9g of butanediol, 0.8g of dihydroxypropionic acid and 4g of C 10 H 18O4 2,2-bis(hydroxymethyl)butyl methacrylate, heated to 80°C in a nitrogen atmosphere, reacted for 6 hours, after the reaction was completed, precipitated with deionized water, washed, and dried to obtain olefin-modified polyurethane; (2) Add 3 g of olefin-modified polyurethane to 270 g of deionized water, stir and disperse, then add 0.01 g of potassium persulfide and 0.085 g of dimethylaminoethyl methacrylate, heat to 90 °C and stir to react for 2 h to form a seed emulsion, then add 0.05 g of potassium persulfide and 0.425 g of dimethylaminoethyl methacrylate to react for 8 h, wait for the reaction to be completed, precipitate, wash, and vacuum dry to obtain dimethylaminoethyl ester-modified polyurethane; (3) 100 g of dimethylaminoethyl ester modified polyurethane was added to 6000 g of dimethylformamide solvent, followed by adding 5 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and stirring to dissolve, and then adding 1.2 g of amino graphene and stirring to disperse. 3 g of triethylamine was injected under nitrogen atmosphere, and the mixture was stirred and reacted at 40 °C for 24 h. After the reaction was completed, hydrochloric acid solution was used for precipitation, washing, and drying to obtain a marine antifouling functionalized graphene-polyurethane composite coating, and the mass of bovine serum protein adsorbed was 0.6 ng / mm 2 , the tensile strength is 49.7Mpa.

[0026] Comparative Example 1 (1) 100 g of polyurethane was added to 3500 g of dimethylformamide solvent, followed by adding 2 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and stirring to dissolve, and then adding 0.5 g of amino graphene and stirring to disperse. In a nitrogen atmosphere, 1 g of triethylamine was injected and stirred at 20 °C for 12 h. After the reaction was completed, hydrochloric acid solution was used for precipitation, washing, and drying to obtain a graphene-polyurethane composite coating. The mass of bovine serum protein adsorbed was 3.4 ng / mm 2 , the tensile strength is 46.6Mpa.

Claims

1. A marine antifouling functionalized graphene-polyurethane composite coating, characterized in that: The method for preparing a marine antifouling functionalized graphene-polyurethane composite coating comprises the following steps: (1) Add polyester diol and isophorone diisocyanate to dimethylformamide solvent, then add dibutyltin dilaurate, then add butanediol, dihydroxypropionic acid and a molecule of formula C 10 H 18 O4 2,2-bis(hydroxymethyl)butyl methacrylate, heated to 70-80°C in a nitrogen atmosphere, reacted for 3-6 hours, after the reaction was completed, precipitated with deionized water, washed, and dried to obtain olefin-modified polyurethane; (2) Add olefin-modified polyurethane to deionized water, stir and disperse, then add potassium persulfide and dimethylaminoethyl methacrylate, heat to 70-90°C and stir to react for 1-2h to form a seed emulsion, then add the remaining potassium persulfide and dimethylaminoethyl methacrylate to react for 4-8h, wait for the reaction to be completed, precipitate, wash, and vacuum dry to obtain dimethylaminoethyl ester-modified polyurethane; (3) Add dimethylaminoethyl ester modified polyurethane to dimethylformamide solvent, then add 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and stir to dissolve, then add amino graphene and stir to disperse, inject triethylamine under nitrogen atmosphere and stir to react, after the reaction is completed, precipitate with hydrochloric acid solution, wash and dry to obtain a marine antifouling functionalized graphene-polyurethane composite coating.

2. The marine antifouling functionalized graphene-polyurethane composite coating according to claim 1, characterized in that: In the step (1), the mass ratio of polyester diol, isophorone diisocyanate, dibutyltin dilaurate, dimethylformamide, butanediol, dihydroxypropionic acid and 2,2-bis(hydroxymethyl)butyl methacrylate is 100:60-80:0.5-1.2:3500-6000:18-45:2-4:9-20.

3. The marine antifouling functionalized graphene-polyurethane composite coating according to claim 1, characterized in that: In the step (2), the mass ratio of olefin-modified polyurethane, deionized water, potassium persulfide and dimethylaminoethyl methacrylate is 100:5000-9000:0.1-0.2:10-17.

4. The marine antifouling functionalized graphene-polyurethane composite coating according to claim 1, characterized in that: In the step (3), the mass ratio of dimethylaminoethyl modified polyurethane, dimethylformamide, 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, amino graphene and triethylamine is 100:3500-6000:2-5:0.5-1.2:1-3.

5. The marine antifouling functionalized graphene-polyurethane composite coating according to claim 1, characterized in that: The reaction temperature in step (3) is 20-40° C. and the reaction time is 12-24 h.

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