CN116355509A - Anti-aging low-adhesion composite coating with sea wear applicability, preparation method and application - Google Patents

Anti-aging low-adhesion composite coating with sea wear applicability, preparation method and application Download PDF

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CN116355509A
CN116355509A CN202310242690.0A CN202310242690A CN116355509A CN 116355509 A CN116355509 A CN 116355509A CN 202310242690 A CN202310242690 A CN 202310242690A CN 116355509 A CN116355509 A CN 116355509A
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modified
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marine
composite coating
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王楠
吉锦程
唐玲玲
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Jiangsu University
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Jiangsu University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02—Polyureas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2506/00—Halogenated polymers
    • B05D2506/10—Fluorinated polymers
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05D2601/00—Inorganic fillers
    • B05D2601/20—Inorganic fillers used for non-pigmentation effect
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05D2601/00—Inorganic fillers
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    • B05D2601/24—Titanium dioxide, e.g. rutile
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    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract

The invention discloses an anti-aging low-adhesion composite coating with sea wear applicability, a preparation method and application thereof, and belongs to the technical field of surface coatings of coastal devices; the adhesive force of the polyurea coating to the matrix is improved by modifying the isocyanate, so that the impact resistance of the coating is improved; the modified carbon nanofiber and the modified graphene oxide are added, so that the shock resistance of the polyurea coating is improved, and the coating has marine corrosion resistance; the ultraviolet light absorber and the light stabilizer are added, so that the coating has high weather resistance, the polyaspartic acid resin with carboxymethyl cellulose is added, the corrosion resistance of the coating is improved, and the anti-icing performance of the coating is improved by spraying nano hexagonal boron nitride modified perfluoropolyether lubricating grease.

Description

Anti-aging low-adhesion composite coating with sea wear applicability, preparation method and application
Technical Field
The invention relates to the field of marine coating, in particular to an anti-aging low-adhesion composite coating with marine applicability, a preparation method and application thereof.
Background
The total yield of the marine industry in China is about 9% of the total yield in China, and the marine industry is vigorously developed. However, in the process of ocean foundation construction and construction, ultraviolet rays and sea wind bring about serious potential safety hazards and cause serious property loss, and according to statistics, the corrosion of the ocean industry in China accounts for about 1/3 of the corrosion in China, and in a cold environment, ice coating on the surface of the ocean can also cause energy loss and cause potential safety hazards. Therefore, the development of a protection technology with low cost, marine pollution resistance, ultraviolet aging resistance and ice coating resistance is particularly important. The current technology for preventing marine corrosion is mainly divided into the following steps: 1. electrochemical protection, when a metal-electrolyte dissolution corrosion system is subjected to cathodic polarization, the potential is shifted negatively, the overpotential of metal anodic oxidation reaction is reduced, and the reaction speed is reduced, so that the metal corrosion speed is reduced. However, a non-conductive shell is easily formed outside the anode, which affects the corrosion resistance. 2. The anti-corrosion material and the anti-corrosion metal material are adopted, so that the reaction rate of electrochemical corrosion is retarded. However, this method can only delay the corrosion rate and still causes serious loss over a long period of time. 3. Compared with the two methods, the coating protection method has the advantages of low cost, environmental protection, energy saving and high performance. Compared with manual deicing, the automatic deicing cost is greatly reduced, and the safety is correspondingly improved.
The polyurea is an elastomer spraying material formed by reacting isocyanate components and amino compounds, has the advantages of low cost, environmental protection, energy conservation and the like, and has the characteristics of good impact strength, corrosion resistance, water resistance and high flexibility. However, the existing polyurea coating has poor ultraviolet aging resistance and a higher friction coefficient on the surface, can not promote ocean pollution to fall off from the surface, can not promote liquid drops to roll off, can not delay the crystallization process and reduce the adhesive force of ice to a matrix after crystallization, and therefore has no anti-icing function.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the anti-aging low-adhesion composite coating with sea wear applicability, which has higher adhesive force performance on a marine device, can resist ultraviolet aging and prevent ice coating, and can not only improve the service life of the coating, but also reduce the adhesive force of the crystallized ice on a matrix and the corrosion of marine pollution, and improve the working efficiency and the service life of the marine device.
The present invention achieves the above technical object by the following means.
The sea wear-resistant anti-aging low-adhesion composite coating is prepared by spraying polyaspartic acid polyurea on the surface of a substrate, and then coating a layer of modified perfluoropolyether lubricating grease, wherein the modified perfluoropolyether lubricating grease is obtained by adding nano hexagonal boron nitride into the perfluoropolyether lubricating grease for modification;
wherein the polyaspartic acid polyurea consists of a component A and a component B; the mass ratio of the component A to the component B is 1:1.2 to 1.5;
the raw materials for preparing the component A comprise, by weight, 35-50 parts of modified isocyanate, 15-30 parts of modified graphene oxide and 1-10 parts of diluent;
the raw materials for preparing the component B comprise, by weight, 30-50 parts of polyaspartic acid resin, 2-5 parts of a dispersing agent, 1-3 parts of an ultraviolet light absorber, 2-5 parts of a light stabilizer, 1-10 parts of a diluent, 3-10 parts of modified nano titanium dioxide and 10-20 parts of an auxiliary agent.
In the scheme, the modified isocyanate is prepared from isocyanate and biuret according to the following weight ratio of 1:1, and then adding the modified carbon nano-fiber into the mixture for mixing. In the above scheme, the preparation method of the modified carbon nanofiber comprises the following steps: and (3) modifying the carbon nanofiber CNF-OH with the hydroxyl on the surface by using methyltrimethoxysilane to obtain the modified carbon nanofiber.
In the above scheme, the preparation method of the modified graphene oxide comprises the following steps: and modifying the graphene oxide by using an L-tryptophan solution to obtain modified graphene oxide.
In the scheme, the polyaspartic acid resin is polyaspartic acid ester, modified polysuccinimide and carboxymethyl cellulose according to the proportion of 8:1:1, and then modifying in NaOH solution.
In the scheme, the modified polysuccinimide is obtained by modifying polysuccinimide in N, N' -Dimethylformamide (DMF) solution.
In the scheme, the modified nano titanium dioxide is prepared by mixing liquid-phase titanium dioxide with sodium aluminate aqueous solution for modification.
In the above scheme, the diluents in component a and component B independently comprise propylene carbonate or n-butyl acetate; the auxiliary agent comprises 7-10 parts of ethyl acetate, 2-3 parts of flatting agent, 1-2 parts of defoaming agent and 2-5 parts of silane coupling agent according to parts by weight.
The preparation method of the marine anti-aging low-adhesion composite coating comprises the steps of mixing the component A with the component B at the temperature of 60-80 ℃, spraying, curing, and spraying modified perfluoropolyether lubricating ester on the surface of the cured coating to obtain the marine anti-aging low-adhesion composite coating.
The application of the anti-aging low-adhesion composite coating with sea wear applicability is that the prepared anti-aging low-adhesion composite coating with sea wear applicability is applied to the surface of a sea device.
The beneficial effects are that:
the adhesive force of the polyurea coating to the matrix is improved through the modified isocyanate, so that the impact resistance of the coating is improved, and the construction performance and the service life of the coating are improved; the modified graphene oxide is added, so that the coating has marine corrosion resistance; the ageing resistance of the coating is improved by adding the modified nano titanium dioxide; through adding ultraviolet light absorber and light stabilizer for the coating has high weatherability, through adding the polyaspartic acid resin that has carboxymethyl cellulose, promote the corrosion resistance of coating, through the coefficient of friction of modified perfluoropolyether lubricating grease greatly reduced polyurea coating surface, further reduce the adhesive force of ice to the polyurea coating after crystallization, reach the functionality of preventing icing.
Detailed Description
The invention provides an anti-aging low-adhesion composite coating with sea wear applicability, which is formed by spraying polyaspartic acid polyurea on the surface of a base member and then spraying modified perfluoropolyether lubricating grease; the polyaspartic polyurea is formed by curing a component A and a component B; the mass ratio of the component A to the component B is 1:1.2-1.5;
the raw materials for preparing the component A comprise, by weight, 35-50 parts of modified isocyanate, 15-30 parts of modified graphene oxide and 1-10 parts of diluent;
the modified isocyanate is prepared by mixing isocyanate and biuret according to the weight ratio of 1:1, and then adding the modified carbon nano-fiber into the mixture for mixing. The method comprises the steps of carrying out a first treatment on the surface of the The preparation method of the modified carbon nanofiber comprises the following steps: modifying the carbon nanofiber CNF-OH with the surface having the hydroxyl group by using methyltrimethoxysilane to obtain a modified carbon nanofiber;
the modified graphene oxide is L-tryptophan modified graphene oxide dispersion liquid prepared by graphene oxide in NaOH solution;
the raw materials for preparing the component B comprise, by weight, 30-50 parts of polyaspartic acid resin, 2-5 parts of a dispersing agent, 1-3 parts of a defoaming agent, 1-3 parts of an ultraviolet light absorber, 2-5 parts of a light stabilizer, 3-7 parts of a diluent, 3-10 parts of modified nano titanium dioxide and 10-20 parts of an auxiliary agent.
The preparation method of the polyaspartic acid resin comprises the steps of using polyaspartic acid ester, modified polysuccinimide and carboxymethyl cellulose according to the proportion of 8:1:1, and then modifying in NaOH solution.
The preparation method of the modified polysuccinimide comprises the step of modifying the polysuccinimide in N, N' -Dimethylformamide (DMF) solution to obtain the modified polysuccinimide.
The preparation method of the modified nano titanium dioxide comprises the step of mixing silicon dioxide dissolved in water with sodium aluminate aqueous solution for modification to obtain the modified nano titanium dioxide.
In the invention, the polyaspartic acid polyurea coating is formed by curing a component A and a component B; the mass ratio of the component A to the component B is 1:1.2-1.5, preferably 1:1.4-1.5. The invention controls the mass ratio of the component A to the component B in the range, which is beneficial to the solidification of the component A and the component B, thereby obtaining the multifunctional polyurea coating.
The raw materials for preparing the component A comprise 30-55 parts by weight of modified isocyanate, preferably 38-50 parts by weight, and more preferably 47-50 parts by weight. In the present invention, the modified isocyanate is an isocyanate and biuret in a ratio of 1:1, and then adding the modified carbon nano-fiber after the mass fraction is compounded and used. The adhesive force of the coating is improved through the chemical bond action of the hydroxyl group and the surface of the matrix, so that the impact resistance of the coating is improved.
In the present invention, the isocyanate in the modified isocyanate preferably includes one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl polyisocyanate and isophorone diisocyanate, more preferably one or more of diphenylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate. The source of the isocyanate is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the preparation method of the modified isocyanate preferably comprises: under nitrogen, the isocyanate and biuret were mixed at a ratio of 1:1, adding the modified carbon nano fiber to mix after the mass fraction is compounded and used, and obtaining the modified isocyanate. In the present invention, the mass ratio of isocyanate to biuret is preferably 1: (0.8 to 1), more preferably 1:1. In the present invention, the mixing is preferably stirring after ultrasonic treatment. In the present invention, the power of the ultrasonic treatment is preferably 20 to 40kHz, more preferably 30 to 40kHz; the time of the ultrasonic treatment is preferably 40 to 60 minutes, more preferably 50 to 60 minutes. In the present invention, the stirring rate is preferably 1500 to 2500r/min, more preferably 2000 to 2500r/min; the stirring time is preferably 4 to 6 hours, more preferably 6 hours.
In the present invention, the preparation method of the carbon nanofiber CNF-OH with hydroxyl groups on the surface preferably comprises the following steps: mixing the carbon nanofiber with concentrated nitric acid, and sequentially performing first ultrasonic treatment and first heating reflux to obtain an acidified carbon nanofiber CNF-COOH; mixing the acidified carbon nanofiber CNF-COOH with thionyl chloride, and sequentially performing second ultrasonic treatment and second heating reflux to obtain an acylated carbon nanofiber CNF-COCl; and mixing the acylated carbon nanofiber CNF-COCl with ethylene glycol, and then sequentially carrying out third ultrasonic treatment and hydroxylation reaction to obtain the carbon nanofiber CNF-OH with the surface having hydroxyl. The invention preferably mixes the carbon nanofiber with concentrated nitric acid, and then sequentially carries out first ultrasonic treatment and first heating reflux to obtain the acidified carbon nanofiber CNF-COOH. In the present invention, the diameter of the carbon nanofiber is preferably 120 to 130nm; the length of the carbon nanofibers is preferably 10 to 20 μm. In the present invention, the volume ratio of the mass of the carbon nanofibers to the concentrated nitric acid is preferably (5 to 6) g: (80-100) mL. In the present invention, the mass concentration of the concentrated nitric acid is preferably 75 to 78%.
In the present invention, the frequency of the first ultrasonic treatment is preferably 25 to 30kHz; the time of the first ultrasonic treatment is preferably 10 to 20 minutes.
In the invention, the temperature of the first heating reflux is preferably 120-130 ℃; the time of the first heating reflux is preferably 2-3 hours.
After the first heating reflux is finished, the invention preferably sequentially dilutes, pumps, washes and dries the product of the first heating reflux to obtain the acidified carbon nanofiber CNF-COOH. The operations of dilution, suction filtration, washing and drying are not particularly limited, and the technical schemes of dilution, suction filtration, washing and drying, which are well known to those skilled in the art, can be adopted. In the present invention, the diluent used for the dilution is preferably deionized water; the deionized water is preferably used in an amount of 1000mL. In the invention, the filter membrane used for suction filtration is preferably a phi 0.22 μm mixed fiber microporous filter membrane. In the present invention, the detergent used for the washing is preferably deionized water. In the present invention, the drying temperature is preferably 80 to 90 ℃; the drying time is preferably 24-25 hours; the drying mode is preferably vacuum drying. After the acidified carbon nanofiber CNF-COOH is obtained, the invention preferably mixes the acidified carbon nanofiber CNF-COOH with thionyl chloride, and then sequentially carries out second ultrasonic treatment and second heating reflux to obtain the acylated carbon nanofiber CNF-COCl.
In the present invention, the mass ratio of the acylated carbon nanofiber CNF-COOH to thionyl chloride is preferably (2-3) g: (80-90) mL. In the present invention, the frequency of the second ultrasonic treatment is preferably 25 to 30kHz; the time of the second ultrasonic treatment is preferably 10 to 20 minutes. In the invention, the temperature of the second heating reflux is preferably 75-85 ℃; the second heating reflux time is preferably 24 to 25 hours. After the second heating reflux is finished, the product of the second heating reflux is preferably subjected to reduced pressure distillation to obtain the acylated carbon nanofiber CNF-COCl. The invention removes excessive thionyl chloride by reduced pressure distillation, which is beneficial to obtaining pure acylated carbon nanofiber CNF-COCl. The operation of the reduced pressure distillation is not particularly limited, and the reduced pressure distillation method known to those skilled in the art may be employed.
After the acylated carbon nanofiber CNF-COCl is obtained, the acylated carbon nanofiber CNF-COCl is preferably mixed with ethylene glycol, and then third ultrasonic treatment and hydroxylation reaction are sequentially carried out, so that the carbon nanofiber CNF-OH with the hydroxyl on the surface is obtained. In the present invention, the mass ratio of the acylated carbon nanofiber CNF-COCl to the ethylene glycol is preferably (1.5-2) g: (80-90) mL. In the present invention, the frequency of the third ultrasonic treatment is preferably 25 to 30kHz; the time of the third ultrasonic treatment is preferably 10 to 20 minutes. In the present invention, the temperature of the hydroxylation reaction is preferably 120 to 130 ℃; the hydroxylation reaction time is preferably 48 to 50 hours.
After the hydroxylation reaction is completed, the product of the hydroxylation reaction is preferably subjected to dilution, suction filtration, washing and drying in sequence to obtain the carbon nanofiber CNF-OH with the surface having the hydroxyl. The operations of dilution, suction filtration, washing and drying are not particularly limited, and the technical schemes of dilution, suction filtration, washing and drying, which are well known to those skilled in the art, can be adopted. In the present invention, the diluent used for the dilution is preferably deionized water; the deionized water is preferably used in an amount of 1000mL. In the invention, the filter membrane used for suction filtration is preferably a phi 0.22 μm mixed fiber microporous filter membrane. In the present invention, the detergent used for the washing is preferably deionized water. In the present invention, the drying temperature is preferably 80 to 90 ℃; the drying time is preferably 24-25 hours; the drying mode is preferably vacuum drying.
The raw materials for preparing the component A comprise 15-30 parts, preferably 17-30 parts, more preferably 22-30 parts, of modified graphene oxide based on 30-55 parts of modified isocyanate by weight. The modified graphene oxide is derived from an L-tryptophan modified graphene oxide dispersion liquid in the invention.
The preparation method of the L-tryptophan modified graphene oxide dispersion liquid comprises the following raw materials in percentage by weight:
graphene oxide slurry (40% aqueous): 1-10%, L-tryptophan: 0.5-6%, deionized water: 80-95%, sodium hydroxide: 0.1-2%; and the sum of the weight percentages of the components is 100 percent;
preparation of L-tryptophan solution: mixing L-tryptophan with deionized water to prepare a solution, adding granular sodium hydroxide, and starting a magnetic stirrer to disperse for 0.5-2 h to obtain a pale yellow transparent L-tryptophan solution;
preparing graphene oxide aqueous dispersion liquid: dissolving graphene oxide slurry into the L-tryptophan solution obtained in the step (1.2), magnetically stirring for 0.5-2 h, and performing ultrasonic water bath for 0.5-2 h to initially obtain uniformly dispersed dark brown graphene oxide aqueous dispersion;
preparing an L-tryptophan modified graphene oxide dispersion liquid: and (3) magnetically stirring the graphene oxide aqueous dispersion liquid obtained in the step (1.3), and reacting for 24 hours at room temperature. The graphene oxide slurry can be rapidly dissolved in an L-tryptophan solution due to high water content, and is subjected to grafting reaction with the L-tryptophan, so that the graphene oxide is slightly reduced, the dispersion liquid is changed from dark brown to black brown, and a uniform sol state is presented, and the L-tryptophan modified graphene oxide dispersion liquid is obtained;
the raw materials for preparing the component A comprise 3 to 10 parts of diluent, preferably 5 to 10 parts, more preferably 8 to 10 parts, based on 30 to 55 parts of modified isocyanate by weight. In the present invention, the diluent is used to adjust the NCO value and viscosity of component A. In the present invention, the diluent preferably includes propylene carbonate or n-butyl acetate, more preferably propylene carbonate. The source of the diluent is not particularly limited, and commercially available products known to those skilled in the art may be used.
In the present invention, the preparation method of the component A preferably comprises: isocyanate, biuret and modified carbon nanofiber react for 3-4 hours at 60-90 ℃, then modified graphene oxide and a diluent are sequentially added, and stirring is carried out for 4-5 hours, so that the component A is obtained.
The invention preferably makes the carbon nano fiber with hydroxyl on the surface react with isocyanate and biuret for 3-4 hours in nitrogen atmosphere at 60-90 ℃ to obtain the polymer. The invention takes isocyanate and biuret as raw materials to carry out polymerization reaction to prepare the polymer. In the present invention, the temperature of the reaction is preferably 60 to 70 ℃; the reaction time is preferably 3 hours. After the polymer is obtained, the modified graphene oxide and the diluent are preferably added in sequence, and the mixture is stirred for 4 to 5 hours to obtain the component A. According to the invention, the ocean corrosion resistance and the aging resistance of the polymer are improved by adding the modified graphene oxide into the polymer, and the NCO value and the viscosity of the polymer are adjusted by adding the diluent. In the present invention, the NCO value of component A is preferably 12 to 15%; the viscosity of the component A is preferably 700 to 800 mPas. In the invention, the stirring speed is preferably 1500-2000 r/min; the stirring time is preferably 4 hours.
The raw materials for preparing the component B comprise 30 to 50 parts of polyaspartic acid resin, more preferably 33 to 45 parts, and even more preferably 35 to 45 parts by weight of modified isocyanate, wherein the polyaspartic acid resin is modified polyaspartic acid/polyacrylic acid/carboxymethyl cellulose ternary composite super absorbent resin
According to the invention, 1g of polysuccinimide is placed in a beaker containing 10mLN, N' -dimethylformamide, fully dissolved for 2 hours in a water bath at 35 ℃, then 40 mu L of KH-550 silane coupling agent is added, the temperature is raised to 50 ℃, the reaction is carried out for 3 hours under constant temperature stirring (the rotating speed is 100 r/min), 10mL of absolute ethyl alcohol is used for precipitation after the reaction, and the reaction is repeatedly washed for 3 times, thus obtaining powdery modified polysuccinimide. 1g of modified polysuccinimide is taken to be dispersed in a beaker containing 10mL of deionized water, 2mol/L NaOH solution is added dropwise in a water bath at 35 ℃, and the pH value of the solution is maintained to be 9-10 and no change occurs. Then, a certain amount of carboxymethyl cellulose is weighed and stirred (the rotating speed is 100 r/min) in the reaction liquid for gelatinization for 30min, 0.5% (based on acrylic acid) of KPS is sequentially added, a certain amount of acrylic acid with the neutralization degree of 70% is added, 0.1% (based on acrylic acid) of N, N' -methylene bisacrylamide is introduced, stirring (the rotating speed is 100 r/min) is stopped for 10min, standing and reacting for 3h at 70 ℃, the product is placed in an oven for drying for 24h at 70 ℃, and the solid powder modified polyaspartic acid/polyacrylic acid/carboxymethyl cellulose ternary composite super absorbent resin is obtained after crushing.
The raw material for preparing the component B comprises 1 to 10 parts of ultraviolet light absorber, preferably 5 to 10 parts, more preferably 8 to 10 parts, based on 30 to 55 parts of modified isocyanate by weight. According to the invention, the ultraviolet light absorber is added to improve the weather resistance of the paint, so that the corrosion resistance of the paint to marine corrosion environment is improved.
In the present invention, the ultraviolet light absorber preferably includes one or more of phenyl o-hydroxybenzoate, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, resorcinol monobenzoate, more preferably one or more of phenyl o-hydroxybenzoate, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole. The source of the ultraviolet light absorber is not particularly limited, and commercially available products known to those skilled in the art may be used.
The raw material for preparing the component B comprises 1 to 10 parts of light stabilizer, preferably 5 to 10 parts, more preferably 8 to 10 parts, based on 30 to 55 parts by weight of modified isocyanate. According to the invention, the ultraviolet light absorber and the light hindered amine stabilizer are compounded for use by adding the light stabilizer, so that the polyurea coating has excellent weather resistance. In the present invention, the source of the light stabilizer is not particularly limited, and commercially available products known to those skilled in the art may be used.
The raw materials for preparing the component B comprise 12-20 parts of auxiliary agents according to the weight of 10-28 parts of chain extender. In the invention, the auxiliary agent preferably comprises 7-10 parts by weight of ethyl acetate, 2-3 parts by weight of flatting agent, 1-2 parts by weight of defoaming agent and 2-5 parts by weight of silane coupling agent. In the present invention, the leveling agent is preferably AKN to 3600; the defoamer is preferably DU-964; the silane coupling agent is preferably KH550.
The raw materials for preparing the component B comprise 10-28 parts by weight of chain extender, preferably 20-28 parts by weight, and more preferably 25-28 parts by weight. In the present invention, the chain extender preferably includes one or more of diethyltoluenediamine, dimethylthiotoluenediamine and N, N '-dialkylmethyldiamine, more preferably diethyltoluenediamine and N, N' -dialkylmethyldiamine. The source of the chain extender is not particularly limited, and commercially available products known to those skilled in the art may be used.
The raw materials for preparing the component B comprise 5 to 15 parts of diluent, preferably 7 to 10 parts, more preferably 9 to 10 parts, based on 10 to 28 parts by weight of the chain extender. In the present invention, the diluent preferably includes propylene carbonate or n-butyl acetate, more preferably n-butyl acetate. The source of the diluent is not particularly limited, and commercially available products known to those skilled in the art may be used.
The raw materials for preparing the component B comprise 3-10 parts of nano titanium dioxide and the preparation method of the modified nano titanium dioxide with hydrophobic and ultraviolet aging resistance according to the weight of 10-28 parts of the chain extender. (1) 1000g of nano titanium dioxide aqueous dispersion with the mass percent of 10 percent is measured and placed in a 3000mL three-neck flask, and a stirring device is started to disperse the nano titanium dioxideThe temperature of the solution is regulated to 40 ℃,4 percent by mass of sodium aluminate aqueous solution and 5 percent by mass of phosphoric acid aqueous solution are respectively added into the nano titanium dioxide aqueous dispersion, and the pH value of the system is maintained to be 8.0. Sodium aluminate in an amount to form AlPO 4 Accounting for 4 percent of the mass of the nano titanium dioxide. After the addition of the sodium aluminate aqueous solution was completed, the mixture was further stirred and aged at 40℃for 10 minutes. The temperature of the nano titanium dioxide aqueous dispersion is raised to 95 ℃, 10 mass percent sodium silicate aqueous solution and 5 mass percent nitric acid aqueous solution are respectively added into the nano titanium dioxide aqueous dispersion, and the pH value of the system is maintained to be 10.5. The amount of sodium silicate to form SiO 2 Accounting for 8 percent of the mass of the nano titanium dioxide. After the addition of the aqueous sodium silicate solution was completed, the mixture was further stirred and aged at 95℃for 60 minutes. The temperature of the nano titanium dioxide aqueous dispersion is regulated to 50 ℃, and the nano titanium dioxide 4% sodium aluminate aqueous solution and the 5% nitric acid aqueous solution are respectively added, and the pH value of the system is maintained to be 8.0. The amount of sodium aluminate to form Al 2 O 3 Accounting for 10 percent of the mass of the nano titanium dioxide. After the addition of the sodium aluminate aqueous solution was completed, the mixture was continuously stirred and aged at 50℃for 30 minutes. The pH value of the system is adjusted to 5.0 by 5% nitric acid aqueous solution, the temperature of the nano titanium dioxide aqueous dispersion is adjusted to 85 ℃, and the aqueous solution dissolved with 20g of sodium stearate is added into the nano titanium dioxide aqueous dispersion, and the stirring and curing are continued for 300 minutes. The nano titanium dioxide slurry is filtered by suction and washed by deionized water until the conductivity of the filtrate is less than 500 mu S/cm. Drying and crushing to obtain the hydrophobic nano titanium dioxide powder.
The raw materials for preparing the component B comprise 1 to 10 parts of foaming agent, preferably 1 to 5 parts, more preferably 1 to 3 parts, based on 10 to 28 parts by weight of the chain extender. The invention can reduce the use of polyurea coating by adding the foaming agent, simultaneously achieve the purposes of reducing the load of sea wear, saving cost and protecting environment, and does not influence the shock resistance of the polyurea coating
In the present invention, the foaming agent preferably includes azobisisobutyronitrile or N, N '-dimethyl-N, N' -dinitroso terephthalamide, more preferably azobisisobutyronitrile. The source of the foaming agent is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the preparation method of the component B preferably includes: mixing the raw materials except the auxiliary agent, heating at 90-102 ℃ for 3-4 hours, adding the auxiliary agent, and stirring for 20-30 minutes to obtain the component B.
In the present invention, the raw materials other than the auxiliary agent are preferably mixed to obtain a mixture. In the present invention, the mixing of the raw materials other than the auxiliary agent is preferably performed under stirring. In the invention, the stirring speed is preferably 1500-2000 r/min; the stirring time is preferably 30 to 50 minutes.
After the mixture is obtained, the invention preferably heats the mixture at 90-102 ℃ for 3-4 hours to obtain the amino polymer. In the present invention, the temperature of the heating is preferably 90 ℃; the heating time is preferably 3 hours.
After the amino polymer is obtained, the invention preferably adds an auxiliary agent to the amino polymer and stirs for 20-30 min to obtain the component B. In the invention, the stirring speed is preferably 2000-2500 r/min; the stirring time is preferably 20min.
The preparation method of the modified perfluoropolyether grease comprises the steps of taking the perfluoropolyether grease as a reference, mixing and stirring 95-98 wt% of base oil and 2-5 wt% of nano hexagonal boron nitride at 40-60 ℃ for 30-40 min. In the invention, the stirring speed is preferably 1500-2000 r/min; the stirring time is preferably 35min.
And (3) spraying modified perfluoropolyether grease on the surface of the A, B component after the component is combined and cured.
According to the invention, the adhesive force of the polyaspartic acid polyurea coating to the matrix is improved by adding the modified isocyanate, so that the construction performance of the coating is improved; the corrosion resistance of the coating is further improved through the modified graphene oxide; by adding the ternary composite polyaspartic acid resin, the marine corrosion resistance of the coating is improved and the service life is prolonged; the sea pollution resistance and the ice coating resistance of the coating are improved by spraying nano hexagonal boron nitride modified perfluoropolyether lubricating grease on the surface of the polyaspartic acid polyurea coating.
The invention also provides a preparation method of the marine applicability anti-aging low-adhesion composite coating, which comprises the following steps: mixing the component A and the component B at 60-80 ℃, spraying, combining A, B components, curing, and spraying modified perfluoropolyether grease on the surface of the components to obtain the marine applicability anti-aging low-adhesion composite coating.
The invention makes the component A and the component B react at 60-80 ℃ to generate the polyurea coating, and then the polyurea coating is sprayed to obtain the multifunctional polyurea coating. In the present invention, the apparatus for spraying is preferably a high pressure coater.
According to the invention, the component A and the component B are mixed and then sprayed, and after solidification, the modified perfluoropolyether grease is sprayed to obtain the marine applicability anti-aging low-adhesion composite coating. The preparation method of the marine applicability anti-aging low-adhesion composite coating provided by the invention is simple to operate, and ensures the performance of the coating.
The invention also provides an application of the marine applicability anti-aging low-adhesion composite coating or the multifunctional coating for the marine equipment prepared by the preparation method in the marine device. In the invention, the multifunctional polyurea coating is coated on the surface of the marine device, and plays a role in protecting the marine device.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the invention, the following components are added:
the polyaspartic polyurea consists of a component A and a component B; the mass ratio of the component A to the component B is 1:1.2 to 1.5;
the raw materials for preparing the component A comprise, by weight, 35-50 parts of modified isocyanate, 15-30 parts of modified graphene oxide and 1-10 parts of diluent;
the raw materials for preparing the component B comprise, by weight, 30-50 parts of polyaspartic acid resin, 2-5 parts of a dispersing agent, 1-3 parts of an ultraviolet light absorber, 2-5 parts of a light stabilizer, 1-10 parts of a diluent, 3-10 parts of modified nano titanium dioxide and 10-20 parts of an auxiliary agent;
the modified isocyanate is prepared from isocyanate and biuret according to the following weight ratio of 1:1, adding the modified carbon nano fiber after mixing the mass fractions; the preparation method of the modified carbon nanofiber comprises the following steps: and (3) modifying the carbon nanofiber CNF-OH with the hydroxyl on the surface by using methyltrimethoxysilane to obtain the modified carbon nanofiber.
Example 1
The mass ratio of the component A to the component B is as follows: 1:1.2;
the raw materials of the component A (weight parts):
50 parts of modified diphenylmethane diisocyanate, 30 parts of modified graphene oxide and 8 parts of propylene carbonate DBGA.
Preparation of carbon nanofiber CNF-OH with hydroxyl on surface: putting 5g of carbon nanofiber (with the diameter of 120nm and the length of 10 mu m) and 80mL of 75wt% concentrated nitric acid into a 300mL single-neck round-bottom beaker provided with a magnetic rotor, carrying out ultrasonic treatment for 10min at 25kHz, installing a spherical condensation pipe and a tail gas absorption pipe, heating to 120 ℃, stirring and refluxing for reaction for 2h, diluting with 1000mL of deionized water after the reaction is finished, carrying out suction filtration with a phi 0.22 mu m mixed fiber microporous filter membrane, repeatedly washing with deionized water for multiple times to be neutral, and carrying out vacuum drying at 80 ℃ for 24h to obtain acidified carbon nanofiber CNF-COOH;
putting 2g of acidified carbon nanofiber CNF-COOH and 80mL of thionyl chloride into a 300mL single-neck round-bottom beaker provided with a magnetic rotor, performing ultrasonic treatment for 10min at 25kHz, heating to 75 ℃, stirring and refluxing for reaction for 24h, and performing reduced pressure distillation to remove excess thionyl chloride to obtain acylated carbon nanofiber CNF-COCl;
putting 1.5g of acylated carbon nanofiber CNF-COCl and 80mL of ethylene glycol into a 300mL single-neck round-bottom beaker provided with a magnetic rotor, carrying out ultrasonic treatment at 25kHz for 10min, then reacting at 120 ℃ for 48h, diluting with 1000mL of deionized water after the reaction is finished, filtering out excessive ethylene glycol and byproducts by using a phi 0.22 mu m mixed fiber microporous filter membrane, washing by using deionized water repeatedly, and carrying out vacuum drying at 80 ℃ to obtain carbon nanofiber CNF-OH with hydroxyl groups on the surface;
preparation of modified carbon nanofibers: taking 3g of carbon nanofiber CNF-OH with hydroxyl on the surface, 1mL of methyltrimethoxysilane MTMS and 3mL of H 2 Placing O in a closed reaction vessel, reacting for 10min at 25 ℃, and then drying for 8h in a dryer at-20 ℃ to obtain modified carbon nanofiber;
the modified isocyanate is prepared from isocyanate and biuret according to the following weight ratio of 1:1, adding the modified carbon nano fiber after mixing the mass fractions; the preparation method of the modified carbon nanofiber comprises the following steps: and (3) modifying the carbon nanofiber CNF-OH with the hydroxyl on the surface by using methyltrimethoxysilane to obtain the modified carbon nanofiber.
Preparation of modified diphenylmethane diisocyanate: in a three-neck flask protected by nitrogen, mixing 100g of diphenylmethane diisocyanate with 100g of biuret, adding 1g of carbon nanofiber CNF-OH with hydroxyl on the surface into the mixture after ultrasonic treatment for 10min at 20kHz, ultrasonic treatment for 20min at 25kHz, and stirring for 5h at a rate of 2000r/min to obtain modified diphenylmethane diisocyanate;
preparation of modified graphene oxide: graphene oxide slurry (40% aqueous): 1-10%, L-tryptophan: 0.5-6%, deionized water: 80-95%, sodium hydroxide: 0.1-2%; and the sum of the weight percentages of the components is 100 percent; mixing L-tryptophan with deionized water to prepare a solution, adding granular sodium hydroxide, starting a magnetic stirrer for dispersion, and stirring for 0.5-2 h at a speed of 2500r/min to obtain a pale yellow transparent L-tryptophan solution; dissolving graphene oxide slurry into an L-tryptophan solution, stirring at a speed of 3000r/min for 0.5-2 h, and performing ultrasonic water bath for 0.5-2 h to initially obtain a uniformly dispersed dark brown graphene oxide aqueous dispersion; stirring at a speed of 3000r/min for 24 hours at room temperature to obtain the L-tryptophan modified graphene oxide dispersion.
Preparation of a component A: adding the modified diphenylmethane diisocyanate into a reaction kettle, reacting for 3 hours at the temperature of 60 ℃ in a nitrogen atmosphere, sequentially adding DBGA and modified graphene, and stirring for 4 hours at the speed of 2500r/min to obtain a component A, wherein the NCO value is 12%, and the viscosity is 750 mPa.s.
The raw materials of the component B (weight portions): the raw materials of the component B comprise 35 parts of polyaspartic acid resin, 1 part of ultraviolet light absorber, 2 parts of light stabilizer, 1 part of azodiisobutyronitrile AIBN, 3-10 parts of nano titanium dioxide, AKN-3600 parts of fluorocarbon modified acrylate leveling agent, 2 parts of defoamer DU-964 parts and 550 parts of silane coupling agent KH;
preparation of polyaspartic acid resin: 1g of polysuccinimide is placed in a beaker containing 10mLN, N' -dimethylformamide, fully dissolved for 2 hours in a water bath at 35 ℃, 40 mu L of KH-550 silane coupling agent is added, the temperature is raised to 50 ℃, the reaction is carried out for 3 hours under constant temperature stirring (rotating speed 100 r/min), 10mL of absolute ethyl alcohol is used for precipitation after the reaction, and the powder modified polysuccinimide is obtained after repeated washing for 3 times. 1g of modified polysuccinimide is taken to be dispersed in a beaker containing 10mL of deionized water, 2mol/L NaOH solution is added dropwise in a water bath at 35 ℃, and the pH value of the solution is maintained to be 9-10 and no change occurs. Then, a certain amount of carboxymethyl cellulose is weighed and stirred (the rotating speed is 100 r/min) in the reaction liquid for gelatinization for 30min, 0.5% (based on acrylic acid) of KPS is sequentially added, a certain amount of acrylic acid with the neutralization degree of 70% is added, 0.1% (based on acrylic acid) of N, N' -methylene bisacrylamide is introduced, stirring (the rotating speed is 100 r/min) is stopped for 10min, standing and reacting for 3h at 70 ℃, the product is placed in an oven for drying for 24h at 70 ℃, and the solid powder modified polyaspartic acid/polyacrylic acid/carboxymethyl cellulose ternary composite super absorbent resin is obtained after crushing.
Preparation of component B: adding the raw materials except the auxiliary agent into a reaction kettle, stirring for 30min at the speed of 2000r/min, heating to 90 ℃ and heating for 3h, sequentially adding ethyl acetate, a leveling agent AKN-3600, a defoaming agent DU-964 and a silane coupling agent KH550, and stirring for 20min at the speed of 2000r/min to obtain a component B.
Preparing a polyaspartic acid polyurea coating: and (3) uniformly mixing the component A and the component B in a dynamic mixing chamber at 60 ℃, spraying by adopting a high-pressure spraying machine, and after curing, spraying the modified perfluoropolyether lubricating grease on the surface of the component A and the component B by adopting the high-pressure spraying machine to obtain the ageing-resistant low-adhesion polyurea coating for the sea. The polyurea coatings were subjected to performance testing after being left for 7 days according to the conditions specified by the state adjustment of the GB9278-08-T coating sample and the temperature and humidity of the test, and the test results are shown in Table 1.
Example 2
The mass ratio of the component A to the component B is as follows: 1:1.3;
raw material of component A (parts by weight)
50 parts of modified isophorone diisocyanate, 50 parts of biuret, 28 parts of modified graphene oxide, 9 parts of modified carbon nanofiber and 10 parts of n-butyl acetate.
Preparing modified isophorone diisocyanate: in a three-neck flask protected by nitrogen, adding 2g of carbon nanofiber CNF-OH with hydroxyl on the surface, prepared in example 1, into 200g of isophorone diisocyanate, carrying out ultrasonic treatment at 30kHz for 20min, and stirring at a rate of 2000r/min for 6h to obtain modified isophorone diisocyanate; preparation of modified isophorone diisocyanate: in a three-neck flask protected by nitrogen, mixing 100g of isophorone diisocyanate with 100g of biuret, carrying out ultrasonic treatment at 25kHz for 10min, adding 2g of carbon nanofiber CNF-OH with hydroxyl on the surface, prepared in example 1, carrying out ultrasonic treatment at 25kHz for 20min, and stirring at 2000r/min for 6h to obtain modified isophorone diisocyanate;
preparation of component A: adding modified isophorone diisocyanate into a reaction kettle, reacting for 3 hours at 60 ℃ in nitrogen atmosphere, sequentially adding modified carbon nanofibers and n-butyl acetate, and stirring for 4 hours at a speed of 2500r/min to obtain a component A, wherein the NCO value is 11%, and the viscosity is 730 mPa.s.
The raw materials of the component B (weight portions):
preparation of component B: adding the raw materials except the auxiliary agent into a reaction kettle, stirring for 30min at the speed of 2000r/min, heating to 90 ℃ and heating for 3h, sequentially adding ethyl acetate, a leveling agent AKN-3600, a defoaming agent DU-964 and a silane coupling agent KH550, and stirring for 20min at the speed of 2000r/min to obtain a component B.
Preparing a polyaspartic acid polyurea coating: and (3) uniformly mixing the component A and the component B in a dynamic mixing chamber at 70 ℃, spraying by adopting a high-pressure spraying machine, curing, and then spraying modified perfluoropolyether lubricating grease to obtain the sea-wear-resistant ageing-resistant low-adhesion-characteristic polyurea coating. The polyurea coatings were subjected to performance testing after being left for 7 days according to the conditions specified by the state adjustment of the GB9278-08-T coating sample and the temperature and humidity of the test, and the test results are shown in Table 1.
Example 3
The mass ratio of the component A to the component B is as follows: 1:1.5;
the raw materials of the component A (weight parts):
50 parts of modified hexamethylene diisocyanate, 25 parts of modified graphene oxide and 9 parts of n-butyl acetate.
Preparation of modified hexamethylene diisocyanate: in a three-neck flask protected by nitrogen, 100g of hexamethylene diisocyanate and 100g of biuret are mixed, after ultrasonic treatment is carried out for 10min at 25kHz, 2g of carbon nanofiber CNF-OH with hydroxyl on the surface and prepared in example 1 is added, ultrasonic treatment is carried out for 20min at 25kHz, and then stirring is carried out for 6h at a speed of 2000r/min, so as to obtain modified hexamethylene diisocyanate;
preparation of component A: adding the modified hexamethylene diisocyanate and biuret into a reaction kettle, reacting for 3 hours at 60 ℃ in a nitrogen atmosphere, adding n-butyl acetate, and stirring for 4 hours at a speed of 2000r/min to obtain a component A, wherein the NCO value is 11%, and the viscosity is 740 mPa.s.
The raw materials of the component B (weight portions):
the raw materials of the component B comprise 45 parts of polyaspartic acid resin, 2 parts of ultraviolet light absorber, 5 parts of light stabilizer, 1 part of azodiisobutyronitrile AIBN, 8 parts of modified nano titanium dioxide, AKN-3600 parts of acrylate leveling agent, 3 parts of defoamer DU-964 parts and 550 parts of silane coupling agent KH;
preparation of component B: adding the raw materials except the auxiliary agent into a reaction kettle, stirring for 30min at the speed of 2000r/min, heating to 90 ℃ and heating for 3h, sequentially adding ethyl acetate, a leveling agent AKN-3600, a defoaming agent DU-964 and a silane coupling agent KH550, and stirring for 20min at the speed of 2000r/min to obtain a component B.
Preparation of polyaspartic acid polyurea: and (3) uniformly mixing the component A and the component B in a dynamic mixing chamber at 80 ℃, spraying by adopting a high-pressure spraying machine, curing, and then spraying modified perfluoropolyether lubricating grease to obtain the sea-wear-resistant ageing-resistant low-adhesion-characteristic polyurea coating. The polyurea coatings were subjected to performance testing after being left for 7 days according to the conditions specified by the state adjustment of the GB9278-08-T coating sample and the temperature and humidity of the test, and the test results are shown in Table 1.
TABLE 1 results of Performance test of polyurea coatings prepared in examples 1-3
Example 1 Example 2 Example 3
Tensile Strength (MPa) 40 38 35
Artificial accelerated aging 1500 1500 1500
Resistance to 5% NaOH (23+ -2) DEG C (h) 168 156 150
Salt spray resistance (h) 2000 2000 2000
Resistant to 5% H2SO4 (23+ -2) DEG C (h) 168 156 150
Adhesive force, 45 steel (MPa) 16.57 18.67 17.56
Contact angle (°) 153 150 155
Adhesion of coating to ice (KPa) 15 10 12
As can be seen from the above examples, the marine applicability anti-aging low-adhesion composite coating provided by the invention has strong anti-aging, corrosion resistance, ice coating resistance, tensile strength of 40MPa, manual accelerated aging of 1500h, 5% NaOH168H resistance and 5%H resistance 2 SO 4 168h, contact angle 153 degrees, adhesion force with 45 steel 16.57MPa, salt spray resistance 2000h, and adhesion force with ice 10KPa.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations may be made in the above embodiments by those skilled in the art without departing from the spirit and principles of the invention.

Claims (10)

1. The marine-suitability anti-aging low-adhesion composite coating is characterized in that polyaspartic acid polyurea is sprayed on the surface of a substrate, and then a layer of modified perfluoropolyether grease is covered, wherein the modified perfluoropolyether grease is obtained by adding nano hexagonal boron nitride into the perfluoropolyether grease for modification;
wherein the polyaspartic acid polyurea consists of a component A and a component B; the mass ratio of the component A to the component B is 1:1.2 to 1.5;
the raw materials for preparing the component A comprise, by weight, 35-50 parts of modified isocyanate, 15-30 parts of modified graphene oxide and 1-10 parts of diluent;
the raw materials for preparing the component B comprise, by weight, 30-50 parts of polyaspartic acid resin, 2-5 parts of a dispersing agent, 1-3 parts of an ultraviolet light absorber, 2-5 parts of a light stabilizer, 1-10 parts of a diluent, 3-10 parts of modified nano titanium dioxide and 10-20 parts of an auxiliary agent.
2. The marine compatible anti-aging low adhesion composite coating of claim 1, wherein the modified isocyanate is prepared from isocyanate and biuret in a ratio of 1:1, and then adding the modified carbon nano-fiber into the mixture for mixing.
3. The marine applicability anti-aging low-adhesion composite coating according to claim 2, wherein the preparation method of the modified carbon nanofiber is as follows: and (3) modifying the carbon nanofiber CNF-OH with the hydroxyl on the surface by using methyltrimethoxysilane to obtain the modified carbon nanofiber.
4. The marine applicability anti-aging low-adhesion composite coating according to claim 1, wherein the preparation method of the modified graphene oxide is as follows: and modifying the graphene oxide by using an L-tryptophan solution to obtain modified graphene oxide.
5. The marine compatible anti-aging low adhesion composite coating of claim 1, wherein the polyaspartic resin is polyaspartate, modified polysuccinimide, and carboxymethyl cellulose in an amount of 8:1:1, and then modifying in NaOH solution.
6. The marine compatibility anti-aging low adhesion composite coating of claim 1, wherein the modified polysuccinimide is a modified polysuccinimide obtained by modifying polysuccinimide in an N, N' -Dimethylformamide (DMF) solution.
7. The marine compatibility anti-aging low-adhesion composite coating according to claim 1, wherein the modified nano titanium dioxide is prepared by mixing liquid phase titanium dioxide with sodium aluminate aqueous solution for modification.
8. The marine compatible anti-aging low adhesion composite coating of claim 1, wherein the diluents in component a and component B independently comprise propylene carbonate or n-butyl acetate; the auxiliary agent comprises 7-10 parts of ethyl acetate, 2-3 parts of flatting agent, 1-2 parts of defoaming agent and 2-5 parts of silane coupling agent according to parts by weight.
9. The method for preparing the marine-suitability anti-aging low-adhesion composite coating according to any one of claims 1 to 8, wherein the marine-suitability anti-aging low-adhesion composite coating is prepared by mixing the component A and the component B at 60-80 ℃, spraying, curing, and spraying the modified perfluoropolyether lubricating ester on the surface of the mixture.
10. The use of a marine compatible anti-aging low adhesion composite coating according to claim 9, wherein the marine compatible anti-aging low adhesion composite coating is prepared for use on a marine device surface.
CN202310242690.0A 2023-03-14 2023-03-14 Anti-aging low-adhesion composite coating with sea wear applicability, preparation method and application Pending CN116355509A (en)

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CN103031180A (en) * 2011-09-30 2013-04-10 无锡市美城合成材料科技有限公司 Grease
CN107793901A (en) * 2017-10-20 2018-03-13 安徽快来防水防腐有限公司 A kind of production method for the poly-aspartate polyurea water-proof corrosion-inhibiting coating that graphene is modified
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