CN109943227B - Low-density anti-fouling coating for surface of solid buoyancy material substrate - Google Patents
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Abstract
The invention relates to the technical field of anti-fouling coatings, and discloses a low-density anti-fouling coating for the surface of a solid buoyancy material substrate, which comprises the following raw materials in parts by weight: 30.2-39.4 parts of an anti-fouling component, 10.7 parts of a filling component and 12-14 parts of a bonding component; the antifouling component comprises the following raw materials in parts by weight: 20-30 parts of octamethylcyclotetrasiloxane; the filling component comprises the following raw materials in parts by weight: 4 parts of methacrylonitrile, 4 parts of methacrylic acid; the bonding component comprises the following raw materials in parts by weight: 3-5 parts of E03 brand bisphenol A type epoxy resin and 1-2 parts of isophorone diamine. The invention solves the technical problem that the antifouling paint for the surface of the solid buoyancy material substrate in the prior art can not effectively reduce the self weight of marine organisms while effectively preventing the marine organisms from attaching to the surface of equipment.
Description
Technical Field
The invention relates to the technical field of anti-fouling coatings, in particular to a low-density anti-fouling coating for the surface of a solid buoyancy material substrate.
Background
The solid buoyancy material is widely applied to ocean development equipment such as ocean buoys, oil production marine risers and underwater operation submergence vehicles. However, in the course of long-term use of the conventional solid buoyant material, marine growth gradually adheres to the surface of equipment such as a marine buoy and an oil production riser, and the weight of the material gradually increases, thereby losing its buoyancy.
In order to prevent marine fouling, it is common practice to coat the surface of the equipment with a marine fouling resistant coating, for example, ZL patent No. 99816367.8 discloses a marine fouling resistant composition and/or coating which contains not only hydrolytic enzymes, microorganisms or a mixture of hydrolytic enzymes and microorganisms, but also inorganic salts (NaCl, CaCl) for enhancing the catalytic hydrolysis of hydrolytic enzymes2、MgSO4) Although the composition and/or coating can achieve the technical effect of effectively preventing marine organisms from attaching to the surface of equipment, the composition and/or coating is added with a relatively high-density inorganic salt component, the relatively high-density inorganic salt component enables the weight of the composition and/or coating to be remarkably increased, and if the composition and/or coating is coated on the surface of the equipment for marine development made of a buoyancy material, the buoyancy of the equipment is remarkably weakened.
The invention provides a low-density anti-fouling coating for the surface of a solid buoyancy material matrix, and aims to solve the technical problem that the anti-fouling coating for the surface of the solid buoyancy material matrix in the prior art can not effectively reduce the self weight of marine organisms while effectively preventing the marine organisms from attaching to the surface of equipment.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a low-density anti-fouling coating for the surface of a solid buoyancy material substrate, which solves the technical problem that the self weight of marine organisms cannot be effectively reduced while the marine organisms are effectively prevented from being attached to the surface of equipment in the prior art.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme:
a low-density anti-fouling coating for the surface of a solid buoyancy material matrix comprises the following raw materials in parts by weight: 30.2-39.4 parts of an anti-fouling component, 10.7 parts of a filling component and 12-14 parts of a bonding component;
the antifouling component comprises the following raw materials in parts by weight: 20-30 parts of octamethylcyclotetrasiloxane; the filling component comprises the following raw materials in parts by weight: 4 parts of methacrylonitrile, 4 parts of methacrylic acid; the bonding component comprises the following raw materials in parts by weight: 3-5 parts of E03 brand bisphenol A type epoxy resin and 1-2 parts of isophorone diamine.
Preferably, the anti-fouling component comprises the following raw materials in parts by weight: 20g octamethylcyclotetrasiloxane, 0.1g sodium hydroxide, 1mL LN, N-dimethylformamide, 1mL hexamethyldisiloxane, 4mL gamma-aminopropyltriethoxysilane, 2mL propionic acid, 3mL butyl acetate.
Preferably, the filling component comprises the following raw materials in parts by weight: 5mL of methacrylonitrile, 4mL of methacrylic acid, 0.1g of dibenzoyl peroxide, 2mL of isobutanol, 1mL of allyl methacrylate.
Preferably, the bonding component comprises the following raw materials in parts by weight: 3g of bisphenol A epoxy resin, No. 03, 10mL of butanone, and 1mL of isophorone diamine.
Preferably, the preparation method of the anti-fouling coating comprises the following steps:
s1, preparing an anti-fouling component by using octamethylcyclotetrasiloxane as a main raw material;
s2, preparing a filling component by using methacrylonitrile and methacrylic acid as main raw materials;
s3, uniformly mixing the anti-fouling component in the step S1 with the filling component in the step S2, injecting the mixture into a sealed mold, placing the mold in a water bath at 50-70 ℃, carrying out constant-temperature polymerization reaction for 24 hours, then demolding, placing the copolymer in a foaming reaction at 180-230 ℃ for 1 hour, and then cooling to prepare the anti-fouling agent;
s4, preparing an adhesive component by using E03-grade bisphenol A epoxy resin, butanone and isophorone diamine as raw materials;
s5, adding the anti-fouling agent in the step S3 into the bonding component in the step S4, uniformly stirring, and placing in a vacuum drying oven to remove air bubbles in vacuum for 30min to prepare the anti-fouling coating.
Preferably, in the step S3, after the polymer foaming reaction, the temperature is reduced to 120-150 ℃ and the reaction is carried out for 3h at 120-150 ℃.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the anti-fouling coating prepared by the invention is coated on the surface of a solid buoyancy material to prepare an anti-fouling coating, the maintenance is carried out for 7 days, the contact angle of the anti-fouling coating after being stabilized in water is 102.4-110.3 degrees, the contact angle after being stabilized in diiodomethane is 98.4-105.8 degrees, and the density of the anti-fouling coating is 0.22-0.28g/cm3；
Contact angle of 91.5 ° after stabilization in water, 69.2 ° after stabilization in diiodomethane, and density of 0.68g/cm with the antifouling coating in the comparative example3Compared with the prior art, the contact angle of the anti-fouling coating in water and diiodomethane is remarkably improved, and the density of the anti-fouling coating is remarkably reduced, so that the marine organisms are effectively prevented from attaching to the surface of equipment, and the technical effect of effectively reducing the weight of the marine organisms is achieved.
Detailed Description
The first embodiment is as follows:
the low-density anti-fouling coating comprises the following raw materials: 30.2g of an anti-fouling component, 10.7g of a filling component, 12g of a binding component;
the antifouling component comprises the following raw materials: 20g of octamethylcyclotetrasiloxane, 0.1g of sodium hydroxide, 1mL of N, N-dimethylformamide (. rho.0.945 g/cm)3) 1mL of hexamethyldisiloxane (. rho.0.762 g/cm)3) 4mL of gamma-aminopropyltriethoxysilane (p 0.942 g/cm)3) 2mL of propionic acid (. rho.0.99 g/cm)3) 3mL of butyl acetate (. rho.0.88 g/cm)3)；
The filling component comprises the following raw materials: 5mL of methacrylonitrile (. rho.0.8 g/cm)3) 4mL of methacrylic acid (p: 1.015 g/cm)3) 0.1g of dibenzoyl peroxide, 2mL of isobutanol (. rho.0.802g/cm3) 1mL of allyl methacrylate (. rho.0.94 g/cm)3)；
The bonding component comprises the following raw materials: 3gE03 brand bisphenol A type epoxy resin, 10mL butanone (rho 0.805 g/cm)3) 1mL of isophoronediamine (. rho.0.924 g/cm)3)；
The preparation method of the anti-fouling coating comprises the following steps:
s1, stirring 20g of octamethylcyclotetrasiloxane, 0.1g of sodium hydroxide, 1mLN, N-dimethylformamide, 1mL of hexamethyldisiloxane and 4mL of gamma-aminopropyltriethoxysilane at 100 ℃ for reaction for 10 hours, adding 2mL of propionic acid, reacting for 1 hour, heating to 130 ℃ for reaction for 3 hours, and finally adding 3mL of butyl acetate to prepare an anti-fouling component;
s2, preparing 5mL of methacrylonitrile, 4mL of methacrylic acid, 0.1g of dibenzoyl peroxide, 2mL of isobutanol and 1mL of allyl methacrylate to obtain a filling component;
s3, uniformly mixing the anti-fouling component in the step S1 with the filling component in the step S2, injecting the mixture into a sealed mold, placing the mold in a water bath at 60 ℃, carrying out constant-temperature polymerization for 24 hours, then demolding, placing the copolymer in an oven with the preheating temperature of 100 ℃, heating to 180 ℃ at the heating rate of 4 ℃/min, carrying out foaming reaction for 1 hour at 180 ℃, then cooling to 120 ℃, carrying out reaction for 3 hours at 120 ℃, and cooling to room temperature to prepare the anti-fouling agent;
s4, dissolving 3g of E03-grade bisphenol A epoxy resin in 10mL of butanone, adding 1mL of isophorone diamine, and uniformly stirring to prepare a bonding component;
s5, adding the anti-fouling agent in the step S3 into the bonding component in the step S4, uniformly stirring, and placing in a vacuum drying oven for vacuum bubble removal for 30min to prepare the anti-fouling coating;
s6, coating the anti-fouling paint in the step S5 on the surface of the solid buoyancy material to prepare a coating, maintaining for 7 days, wherein the contact angles of the coating after the coating is stabilized in water and diiodomethane are respectively 102.4 degrees and 98.9 degrees, and the density of the coating is 0.23g/cm3。
Example two:
the low-density anti-fouling coating comprises the following raw materials: 39.4g of an anti-fouling component, 10.7g of a filler component, 12.9g of a binding component;
the antifouling component comprises the following raw materials: 30g octamethylcyclotetrasiloxane, 0.2g sodium hydroxide, 1mL LN, N-dimethylformamide, 1mL hexamethyldisiloxane, 3mL gamma-aminopropyltriethoxysilane, 2mL propionic acid, 3mL butyl acetate;
the filling component comprises the following raw materials: 5mL of methacrylonitrile, 4mL of methacrylic acid, 0.1g of dibenzoyl peroxide, 2mL of isobutanol, and 1mL of allyl methacrylate;
the bonding component comprises the following raw materials: 3g of E03 brand bisphenol A epoxy resin, 10mL of butanone and 2mL of isophorone diamine;
the preparation method of the anti-fouling coating comprises the following steps:
s1, stirring 30g of octamethylcyclotetrasiloxane, 0.2g of sodium hydroxide, 1mLN, N-dimethylformamide, 1mL of hexamethyldisiloxane and 3mL of gamma-aminopropyltriethoxysilane at 100 ℃ for reaction for 10 hours, adding 2mL of propionic acid, reacting for 1 hour, heating to 100 ℃ for reaction for 3 hours, and finally adding 3mL of butyl acetate to prepare an anti-fouling component;
s2, preparing 5mL of methacrylonitrile, 4mL of methacrylic acid, 0.1g of dibenzoyl peroxide, 2mL of isobutanol and 1mL of allyl methacrylate to obtain a filling component;
s3, uniformly mixing the anti-fouling component in the step S1 with the filling component in the step S2, injecting the mixture into a sealed mold, placing the mold in a water bath at 50 ℃, carrying out constant-temperature polymerization for 24 hours, then demolding, placing the copolymer in an oven with the preheating temperature of 100 ℃, heating to 230 ℃ at the heating rate of 4 ℃/min, carrying out foaming reaction for 1 hour at 230 ℃, then cooling to 150 ℃, carrying out reaction for 3 hours at 150 ℃, and cooling to room temperature to prepare the anti-fouling agent;
s4, dissolving 3g of E03-grade bisphenol A epoxy resin in 10mL of butanone, adding 2mL of isophorone diamine, and uniformly stirring to prepare a bonding component;
s5, adding the anti-fouling agent in the step S3 into the bonding component in the step S4, uniformly stirring, and placing in a vacuum drying oven for vacuum bubble removal for 30min to prepare the anti-fouling coating;
s6, coating the anti-fouling paint in the step S5 on the surface of the solid buoyancy material to prepare a coating, maintaining for 7 days, wherein the contact angles of the coating after the coating is stabilized in water and diiodomethane are 110.3 degrees and 105.8 degrees respectively, and the density of the coating is 0.22g/cm3。
Example three:
the low-density anti-fouling coating comprises the following raw materials: 33.2g of an anti-fouling component, 10.7g of a filler component, 14g of a binding component;
the antifouling component comprises the following raw materials: 23g octamethylcyclotetrasiloxane, 0.1g sodium hydroxide, 1mL LN, N-dimethylformamide, 1mL hexamethyldisiloxane, 4mL gamma-aminopropyltriethoxysilane, 2mL propionic acid, 3mL butyl acetate;
the filling component comprises the following raw materials: 5mL of methacrylonitrile, 4mL of methacrylic acid, 0.1g of dibenzoyl peroxide, 2mL of isobutanol, and 1mL of allyl methacrylate;
the bonding component comprises the following raw materials: 5g of E03 brand bisphenol A epoxy resin, 10mL of butanone and 1mL of isophorone diamine;
the preparation method of the anti-fouling coating comprises the following steps:
s1, stirring 23g of octamethylcyclotetrasiloxane, 0.1g of sodium hydroxide, 1mLN, N-dimethylformamide, 1mL of hexamethyldisiloxane and 4mL of gamma-aminopropyltriethoxysilane at 120 ℃ for reaction for 8 hours, adding 2mL of propionic acid, reacting for 1 hour, heating to 150 ℃ for reaction for 3 hours, and finally adding 3mL of butyl acetate to prepare an anti-fouling component;
s2, preparing 5mL of methacrylonitrile, 4mL of methacrylic acid, 0.1g of dibenzoyl peroxide, 2mL of isobutanol and 1mL of allyl methacrylate to obtain a filling component;
s3, uniformly mixing the anti-fouling component in the step S1 with the filling component in the step S2, injecting the mixture into a sealed mold, placing the mold in a water bath at 70 ℃, carrying out constant-temperature polymerization for 24 hours, then demolding, placing the copolymer in an oven with a preheating temperature of 100 ℃, heating to 200 ℃ at a heating rate of 4 ℃/min, carrying out foaming reaction for 1 hour at 200 ℃, then cooling to 130 ℃, carrying out reaction for 3 hours at 130 ℃, and cooling to room temperature to prepare the anti-fouling agent;
s4, dissolving 5g of E03-grade bisphenol A epoxy resin in 10mL of butanone, adding 1mL of isophorone diamine, and uniformly stirring to prepare a bonding component;
s5, adding the anti-fouling agent in the step S3 into the bonding component in the step S4, uniformly stirring, and placing in a vacuum drying oven for vacuum bubble removal for 30min to prepare the anti-fouling coating;
s6, coating the anti-fouling paint in the step S5 on the surface of the solid buoyancy material to prepare a coating, maintaining for 7 days, wherein the contact angles of the coating after the coating is stabilized in water and diiodomethane are respectively 108.4 degrees and 98.4.6 degrees, and the density of the coating is 0.28g/cm3。
Comparative example:
the low-density anti-fouling coating comprises the following raw materials: 30.2g of an anti-fouling component, 12g of a binding component;
the antifouling component comprises the following raw materials: 20g octamethylcyclotetrasiloxane, 0.1g sodium hydroxide, 1mL LN, N-dimethylformamide, 1mL hexamethyldisiloxane, 4mL gamma-aminopropyltriethoxysilane, 2mL propionic acid, 3mL butyl acetate;
the bonding component comprises the following raw materials: 3g of E03 brand bisphenol A epoxy resin, 10mL of butanone and 1mL of isophorone diamine;
the preparation method of the anti-fouling coating comprises the following steps:
s1, stirring 20g of octamethylcyclotetrasiloxane, 0.1g of sodium hydroxide, 1mLN, N-dimethylformamide, 1mL of hexamethyldisiloxane and 4mL of gamma-aminopropyltriethoxysilane at 100 ℃ for reaction for 10 hours, adding 2mL of propionic acid, reacting for 1 hour, heating to 130 ℃ for reaction for 3 hours, and finally adding 3mL of butyl acetate to prepare an anti-fouling component;
s2, injecting the anti-fouling component in the step S1 into a sealed mold, placing the mold in a water bath at 60 ℃, carrying out constant-temperature polymerization reaction for 24 hours, then demolding, placing the copolymer in a drying oven with a preheating temperature of 100 ℃, heating to 180 ℃ at a heating rate of 4 ℃/min, carrying out foaming reaction for 1 hour at 180 ℃, then cooling to 120 ℃, carrying out reaction for 3 hours at 120 ℃, and cooling to room temperature to prepare the anti-fouling agent;
s3, dissolving 3g of E03-grade bisphenol A epoxy resin in 10mL of butanone, adding 1mL of isophorone diamine, and uniformly stirring to prepare a bonding component;
s4, adding the anti-fouling agent in the step S2 into the bonding component in the step S3, uniformly stirring, and placing in a vacuum drying oven for vacuum bubble removal for 30min to prepare the anti-fouling coating;
s5, coating the anti-fouling paint in the step S4 on the surface of the solid buoyancy material to prepare a coating, maintaining for 7 days, wherein the contact angles of the coating after the coating is stabilized in water and diiodomethane are respectively 91.5 degrees and 69.2 degrees, and the density of the coating is 0.68g/cm3。
Claims (1)
1. The low-density anti-fouling coating for the surface of the solid buoyancy material matrix is characterized by comprising the following raw materials: an anti-fouling component, a filling component, a bonding component;
wherein, the anti-fouling component comprises the following raw materials: 20g octamethylcyclotetrasiloxane, 0.1g sodium hydroxide, 1mL LN, N-dimethylformamide, 1mL hexamethyldisiloxane, 4mL gamma-aminopropyltriethoxysilane, 2mL propionic acid, 3mL butyl acetate; the filling component comprises the following raw materials in parts by weight: 5mL of methacrylonitrile, 4mL of methacrylic acid, 0.1g of dibenzoyl peroxide, 2mL of isobutanol, and 1mL of allyl methacrylate; the adhesive component comprises the following raw materials in parts by weight: 3g of E03 brand bisphenol A epoxy resin, 10mL of butanone and 1mL of isophorone diamine; the preparation method of the anti-fouling coating comprises the following steps:
s1, preparing an anti-fouling component by using octamethylcyclotetrasiloxane as a main raw material;
s2, preparing a filling component by using methacrylonitrile and methacrylic acid as main raw materials;
s3, uniformly mixing the anti-fouling component in the step S1 with the filling component in the step S2, injecting the mixture into a sealed mold, placing the mold in a water bath at 50-70 ℃, carrying out constant-temperature polymerization reaction for 24 hours, then demolding, placing the copolymer in a foaming reaction at 180-230 ℃ for 1 hour, and then cooling to prepare the anti-fouling agent;
s4, preparing an adhesive component by using E03-grade bisphenol A epoxy resin, butanone and isophorone diamine as raw materials;
s5, adding the anti-fouling agent in the step S3 into the bonding component in the step S4, uniformly stirring, and placing in a vacuum drying oven for vacuum bubble removal for 30min to prepare the anti-fouling coating; in the step S3, after the polymer foaming reaction, the temperature is reduced to 150 ℃ below 120 ℃ and the reaction is carried out for 3 hours at 150 ℃ below 120 ℃.
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