CN116162408B - Organosilicon solvent-free waterproof anticorrosive paint and preparation method and application thereof - Google Patents
Organosilicon solvent-free waterproof anticorrosive paint and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation of anti-corrosion paint, and in particular relates to an organosilicon solvent-free waterproof anti-corrosion paint, and a preparation method and application thereof, wherein the organosilicon solvent-free waterproof anti-corrosion paint comprises the following raw materials in parts by mass: 100 parts of modified cage-shaped dendritic organic silicon resin, 35-45 parts of vinyl fluorosilicone oil, 0.5-1 part of photoinitiator, 3-5 parts of vinyl triacetoxy silane and 15-25 parts of nano filler; the modified cage-shaped dendritic organic silicon resin is formed by graft copolymerization of vinyl polysiloxane, octavinyl POSS and 1-hydroxymethyl pyrazole-3-carboxylic acid; the organic silicon solvent-free waterproof anticorrosive paint is applied to marine ship anticorrosive treatment. The modified cage-shaped dendritic organic silicon resin, vinyl fluorosilicone oil, vinyl triacetoxy silane and other compound organic silicon solvent-free waterproof anticorrosive paint are adopted, so that a special structure of an inner and an outer double films can be formed on the surface of ship steel, and the waterproof anticorrosive paint has a good antibacterial and sterilizing effect on sulfate reducing bacteria, and effectively improves waterproof anticorrosive performance.
Description
Technical Field
The invention belongs to the technical field of preparation of anti-corrosion paint, and particularly relates to an organosilicon solvent-free waterproof anti-corrosion paint, and a preparation method and application thereof.
Background
The organic silicon solvent-free coating is a novel solvent-free coating based on organic silicon resin, is formed by mixing organic silicon resin and other auxiliary agents, has excellent waterproof performance, chemical corrosion resistance, sun-proof performance, weather resistance and the like, and is widely applied to the fields of buildings, bridges, tunnels, hydraulic engineering, roof waterproof engineering, underground engineering, chemical plants and the like. After the organosilicon solvent-free coating is crosslinked and cured, a layer of compact siloxane polymer waterproof film can be formed on the surface of a substrate, and the organosilicon solvent-free coating can be applied to the anti-corrosion treatment of steel, for example, the invention patent with publication number CN111471395B discloses an organosilicon solvent-free anti-corrosion coating which is prepared from a component A and a component B according to a mass ratio of 10:1-1.1; wherein, the raw materials of the component A comprise: two low-viscosity organic silicon resins with reactive groups, an auxiliary agent and a filler; the raw materials of the component B comprise special reinforced resin, a reaction inhibitor and a catalyst; the component A comprises the following raw materials in parts by weight: vinyl polysiloxane resin: 80-100 parts of organic silicon dispersing agent: 0.5-2.0 parts of titanium dioxide: 5-15 parts of nano zinc oxide: 1.0 to 3.0 parts of precipitated silica: 3.0-5.0 parts of antirust filler: 10-20 parts of a coloring pigment: 2-10 parts of methyl hydrogen-containing polysiloxane: 1.0-5.0 parts of adhesion promoter: 1.0-2.0 parts; the raw materials of the component B comprise the following components in parts by weight: vinyl polysiloxane resin: 10-30 parts of MQ resin: 5-20 parts of a catalyst: 0.01 to 0.1 part of diallyl maleate: 0.03-0.10 part of vinyl silicone oil: 1.0-5.0 parts of an organosilicon leveling agent: 0.5-1.5 parts; wherein the MQ resin is powdery vinyl MQ resin; the anticorrosive paint is formed by catalyzing the polyaddition reaction of methyl hydrogen-containing polysiloxane and vinyl reactants (vinyl polysiloxane resin, vinyl silicone oil, powdery vinyl MQ resin and diallyl maleate) to be solidified into a film by using chloroplatinic acid complex.
However, the corrosion resistance of the existing organosilicon solvent-free coating is mainly based on the waterproof performance of the coating, when the coating is applied to the surface treatment of ship steel, the coating needs to be used for a long time in a seawater environment with high salt content and high sulfate reducing bacteria content, and moreover, the coating on the surface of the ship is extremely easily damaged due to the existence of a submerged reef in the ocean, and the rapid corrosion of the surface of the steel is caused under the combined action of sulfate, sulfate reducing bacteria and moisture.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an organosilicon solvent-free waterproof anticorrosive paint, and a preparation method and application thereof.
The technical scheme of the invention is summarized as follows:
on one hand, the invention provides an organosilicon solvent-free waterproof anticorrosive paint, which comprises the following raw materials in parts by mass: 100 parts of modified cage-shaped dendritic organic silicon resin, 35-45 parts of vinyl fluorosilicone oil, 0.5-1 part of photoinitiator, 3-5 parts of vinyl triacetoxy silane and 15-25 parts of nano filler;
the modified cage-shaped dendritic organic silicon resin is 1-hydroxymethyl pyrazole-3-carboxylic acid grafting cage-shaped organic silicon resin and is formed by grafting copolymerization of vinyl polysiloxane, octavinyl POSS and 1-hydroxymethyl pyrazole-3-carboxylic acid.
Further, the preparation method of the modified cage-shaped dendritic organic silicon resin comprises the following steps:
A. the preparation method comprises the following steps of: 5-8 parts of 1-hydroxymethyl pyrazole-3-carboxylic acid, 20-30 parts of ethanol-tetrahydrofuran solvent, 25-30 parts of vinyl triethoxysilane, 180-250 parts of acetone solvent, 8-10 parts of HCl solution, 75-85 parts of vinyl polysiloxane and 1-1.5 parts of methyl ethyl ketone peroxide;
B. adding 1-hydroxymethyl pyrazole-3-carboxylic acid into ethanol-tetrahydrofuran solvent, stirring at 30-60 ℃ for dissolution to obtain 1-hydroxymethyl pyrazole-3-carboxylic acid solution;
C. adding vinyltriethoxysilane into an acetone solvent, dropwise adding an HCl solution, and stirring at 40-50 ℃ for reacting for 18-24 hours to obtain an octavinyl POSS solution;
D. uniformly mixing vinyl polysiloxane and octavinyl POSS solution, adding methyl ethyl ketone peroxide, stirring at 50-55 ℃ for reaction for 4-8 hours, then dripping 1-hydroxymethyl pyrazole-3-carboxylic acid solution, stirring at 60-70 ℃ for reaction for 2-3 hours, and removing the solvent by rotary evaporation to obtain the modified cage-shaped dendritic organic silicon resin.
Further, the ethanol-tetrahydrofuran solvent is formed by mixing absolute ethanol and tetrahydrofuran according to a mass ratio of 1:1.
Further, the mass concentration of the HCl solution is 15-20%.
Further, the photoinitiator comprises one or two of 2-hydroxy-2-methyl-1-phenylpropion and 1-hydroxycyclohexyl phenyl ketone.
Further, the nanofiller comprises one or more of nano silicon oxide, nano silicon carbide and nano silicon nitride.
On the other hand, the invention further provides a preparation method of the organic silicon solvent-free waterproof anticorrosive paint, which comprises the following steps:
s1: dripping vinyl triacetoxy silane into the nano filler, stirring for 30-60min, adding vinyl fluorosilicone oil and photoinitiator, stirring and dispersing to obtain mixed auxiliary materials;
s2: adding the mixed auxiliary materials into the modified cage-shaped dendritic organic silicon resin, and performing ultrasonic dispersion to obtain the organic silicon solvent-free waterproof anticorrosive paint.
On the other hand, the invention further provides application of the organic silicon solvent-free waterproof anticorrosive paint in marine ship corrosion prevention.
Further, the organic silicon solvent-free waterproof anticorrosive paint is uniformly coated on the surface of the ship steel plate, and the coating amount is controlled to be 50-100g/m 2 And adopts the strength of 180-250mJ/cm 2 After 3-5s of ultraviolet radiation treatment, the mixture is naturally solidified for 7-10d.
The invention has the beneficial effects that:
the modified cage-shaped dendritic organic silicon resin, vinyl fluorosilicone oil, vinyl triacetoxy silane and other compound organic silicon solvent-free waterproof anticorrosive paint are adopted, so that a special structure of an inner and an outer double films can be formed on the surface of ship steel, and the special structure has a good antibacterial and sterilizing effect on sulfate reducing bacteria, and the waterproof and anticorrosive performance is effectively improved; wherein the modified cage-shaped dendritic organic silicon resin is 1-hydroxymethyl pyrazole-3-carboxylic acid grafted cage-shaped organic silicon resin, the grafted and dispersed 1-hydroxymethyl pyrazole-3-carboxylic acid contains carboxylic acid anion groups with negative charges, the carboxylic acid anion groups are adsorbed by the basal plane of positively charged steel through electrostatic attraction, and simultaneously, the carboxylic acid groups, the nitrogen heterocyclic groups and Fe with empty orbitals on the surface of the steel 3+ 、Fe 2+ 、Mn 2+ 、Ni 2+ The coordination reaction of the plasma metal ions is carried out, and the structure is further constructedThe chelate crystal inner film and the outer compact hydrophobic organic fluorine-silicon outer film form double protection, so that the waterproof and anti-corrosion effects are obviously improved, and the service life of the ship steel plate is prolonged.
Meanwhile, when the organosilicon solvent-free waterproof anticorrosive paint is applied to steel, the growth and propagation of sulfate reducing bacteria can be effectively inhibited, the key effect on the improvement of the corrosion resistance of steel for ships and ocean engineering is realized, the corrosion resistance, durability and service life of the steel for ships and ocean engineering can be obviously improved, and the multi-core complex is generated by the reaction of 1-hydroxymethyl pyrazole-3-carboxylic acid in the modified cage-shaped dendritic organic resin structure and metal ions on the surface of the steel.
Drawings
FIG. 1 is a flow chart of a preparation method of the organic silicon solvent-free waterproof anticorrosive paint.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same and to refer to the description.
The invention provides an organosilicon solvent-free waterproof anticorrosive paint, which comprises the following raw materials in parts by mass: 100 parts of modified cage-shaped dendritic organic silicon resin, 35-45 parts of vinyl fluorosilicone oil, 0.5-1 part of photoinitiator, 3-5 parts of vinyl triacetoxy silane and 15-25 parts of nano filler;
the modified cage-shaped dendritic organic silicon resin is 1-hydroxymethyl pyrazole-3-carboxylic acid grafted cage-shaped organic silicon resin, is formed by graft copolymerization of vinyl polysiloxane and octavinyl POSS, and 1-hydroxymethyl pyrazole-3-carboxylic acid, and the preparation method specifically comprises the following steps:
A. the preparation method comprises the following steps of: 5-8 parts of 1-hydroxymethyl pyrazole-3-carboxylic acid, 20-30 parts of ethanol-tetrahydrofuran solvent, 25-30 parts of vinyl triethoxysilane, 180-250 parts of acetone solvent, 8-10 parts of 15-20wt% HCl solution, 75-85 parts of vinyl polysiloxane and 1-1.5 parts of methyl ethyl ketone peroxide; the ethanol-tetrahydrofuran solvent is formed by mixing absolute ethanol and tetrahydrofuran according to a mass ratio of 1:1;
B. adding 1-hydroxymethyl pyrazole-3-carboxylic acid into ethanol-tetrahydrofuran solvent, stirring at 30-60 ℃ for dissolution to obtain 1-hydroxymethyl pyrazole-3-carboxylic acid solution;
C. adding vinyltriethoxysilane into an acetone solvent, dropwise adding an HCl solution, and stirring at 40-50 ℃ for reacting for 18-24 hours to obtain an octavinyl POSS solution;
D. uniformly mixing vinyl polysiloxane and octavinyl POSS solution, adding methyl ethyl ketone peroxide, stirring at 50-55 ℃ for reaction for 4-8 hours, then dripping 1-hydroxymethyl pyrazole-3-carboxylic acid solution, stirring at 60-70 ℃ for reaction for 2-3 hours, and removing solvent by rotary evaporation to obtain modified cage-shaped dendritic organic silicon resin;
specifically, the photoinitiator comprises one or two of 2-hydroxy-2-methyl-1-phenylpropion and 1-hydroxycyclohexyl phenyl ketone;
specifically, the nanofiller comprises one or more of nano silicon oxide, nano silicon carbide and nano silicon nitride.
The preparation method of the organic silicon solvent-free waterproof anticorrosive paint comprises the following steps:
s1: dripping vinyl triacetoxy silane into the nano filler, stirring for 30-60min, adding vinyl fluorosilicone oil and photoinitiator, stirring and dispersing to obtain mixed auxiliary materials;
s2: adding the mixed auxiliary materials into the modified cage-shaped dendritic organic silicon resin, and performing ultrasonic dispersion to obtain the organic silicon solvent-free waterproof anticorrosive paint.
The application of the organic silicon solvent-free waterproof anticorrosive paint in marine vessel corrosion prevention is specifically that the organic silicon solvent-free waterproof anticorrosive paint is uniformly coated on the surface of a steel plate of a vessel, and the coating amount is controlled to be 50-100g/m 2 And adopts the strength of 180-250mJ/cm 2 After 3-5s of ultraviolet radiation treatment, the mixture is naturally solidified for 7-10d.
Example 1:
a preparation method of an organosilicon solvent-free waterproof anticorrosive paint comprises the following steps:
s1: preparing modified cage-shaped dendritic organic silicon resin;
s101: adding 5kg of 1-hydroxymethyl pyrazole-3-carboxylic acid into 20kg ethanol-tetrahydrofuran solvent, stirring and dissolving at 30 ℃ to obtain 1-hydroxymethyl pyrazole-3-carboxylic acid solution; the ethanol-tetrahydrofuran solvent is formed by mixing absolute ethanol and tetrahydrofuran according to a mass ratio of 1:1;
s102: 25kg vinyl triethoxysilane is added into 180 kg acetone solvent, then 8 kg of 15wt% HCl solution is added dropwise, and the mixture is stirred at 40 ℃ for reaction for 18 hours to obtain octavinyl POSS solution;
s103: uniformly mixing 75kg vinyl polysiloxane and the octavinyl POSS solution obtained in the step S102, adding 1kg of methyl ethyl ketone peroxide, stirring at 50 ℃ for reaction for 4 hours, then dropwise adding the 1-hydroxymethyl pyrazole-3-carboxylic acid solution obtained in the step S101, stirring at 60 ℃ for reaction for 2 hours, and removing the solvent by rotary evaporation to obtain the modified cage-shaped dendritic organic silicon resin;
s2: 3kg of vinyl triacetoxy silane is dropwise added into 15kg of nano silicon oxide, after stirring treatment is carried out for 30min, 35kg of vinyl fluorosilicone oil and 0.5kg of 2-hydroxy-2-methyl-1-phenylpropion are added, and after stirring and dispersing, mixed auxiliary materials are obtained;
s3: and (3) adding the mixed auxiliary material obtained in the step (S2) into 100kg of modified cage-shaped dendritic organic silicon resin, and performing ultrasonic dispersion to obtain the organic silicon solvent-free waterproof anticorrosive paint.
Example 2:
a preparation method of an organosilicon solvent-free waterproof anticorrosive paint comprises the following steps:
s1: preparing modified cage-shaped dendritic organic silicon resin;
s101: adding 6.5kg of 1-hydroxymethyl pyrazole-3-carboxylic acid into 25kg of ethanol-tetrahydrofuran solvent, stirring and dissolving at 45 ℃ to obtain 1-hydroxymethyl pyrazole-3-carboxylic acid solution; the ethanol-tetrahydrofuran solvent is formed by mixing absolute ethanol and tetrahydrofuran according to a mass ratio of 1:1;
s102: 27.5kg of vinyltriethoxysilane is added into 220 kg acetone solvent, 9kg of 17.5wt% HCl solution is added dropwise, and the mixture is stirred at 45 ℃ for reaction for 21 hours to obtain octavinyl POSS solution;
s103: uniformly mixing 80 kg vinyl polysiloxane and octavinyl POSS solution obtained in the step S102, adding 1.5 kg methyl ethyl ketone peroxide, stirring at 55 ℃ for reaction for 6 hours, then dropwise adding 1-hydroxymethyl pyrazole-3-carboxylic acid solution obtained in the step S101, stirring at 65 ℃ for reaction for 2.5 hours, and removing the solvent by rotary evaporation to obtain the modified cage-shaped dendritic organic silicon resin;
s2: dripping 4kg of vinyl triacetoxy silane into 20kg of nano silicon carbide, stirring for 45min, adding 40kg of vinyl fluorosilicone oil and 0.75kg of 2-hydroxy-2-methyl-1-phenylpropionic acid, stirring and dispersing to obtain mixed auxiliary materials;
s3: and (3) adding the mixed auxiliary material obtained in the step (S2) into 100kg of modified cage-shaped dendritic organic silicon resin, and performing ultrasonic dispersion to obtain the organic silicon solvent-free waterproof anticorrosive paint.
Example 3:
a preparation method of an organosilicon solvent-free waterproof anticorrosive paint comprises the following steps:
s1: preparing modified cage-shaped dendritic organic silicon resin;
s101: adding 8 kg of 1-hydroxymethyl pyrazole-3-carboxylic acid into 30 kg ethanol-tetrahydrofuran solvent, stirring and dissolving at 60 ℃ to obtain 1-hydroxymethyl pyrazole-3-carboxylic acid solution; the ethanol-tetrahydrofuran solvent is formed by mixing absolute ethanol and tetrahydrofuran according to a mass ratio of 1:1;
s102: 30 kg vinyl triethoxysilane is added into 250 kg acetone solvent, and then 10 kg of 20wt% HCl solution is added dropwise, and the mixture is stirred at 50 ℃ for reaction for 24 hours to obtain octavinyl POSS solution;
s103: uniformly mixing 85 kg vinyl polysiloxane and octavinyl POSS solution obtained in the step S102, adding 1.5 kg methyl ethyl ketone peroxide, stirring at 55 ℃ for reaction for 8 hours, then dropwise adding 1-hydroxymethyl pyrazole-3-carboxylic acid solution obtained in the step S101, stirring at 70 ℃ for reaction for 3 hours, and removing the solvent by rotary evaporation to obtain the modified cage-type dendritic organic silicon resin;
s2: dropwise adding 5kg of vinyl triacetoxy silane into 25kg of nano silicon nitride, stirring for 60min, adding 45kg of vinyl fluorosilicone oil and 1kg of 1-hydroxycyclohexyl phenyl ketone, and stirring and dispersing to obtain mixed auxiliary materials;
s3: and (3) adding the mixed auxiliary material obtained in the step (S2) into 100kg of modified cage-shaped dendritic organic silicon resin, and performing ultrasonic dispersion to obtain the organic silicon solvent-free waterproof anticorrosive paint.
Comparative example 1 is the same as example 1, except that: in the step of S1 preparing the modified cage-shaped dendritic organic silicon resin, 1-hydroxymethyl pyrazole-3-carboxylic acid is not added, and the method specifically comprises the following steps:
s101: adding 25-kg vinyl triethoxysilane into 180-kg acetone solvent, dropwise adding 8-10 kg of 15wt% HCl solution, and stirring at 40 ℃ for reaction for 18h to obtain octavinyl POSS solution;
s102: and (3) uniformly mixing 75kg vinyl polysiloxane and the octavinyl POSS solution obtained in the step (S101), adding 1kg of methyl ethyl ketone peroxide, stirring at 50 ℃ for reaction for 4 hours, then dropwise adding 20kg ethanol-tetrahydrofuran solvent (prepared by mixing absolute ethanol and tetrahydrofuran according to the mass ratio of 1:1), stirring at 60 ℃ for reaction for 2 hours, and removing the solvent by rotary evaporation to obtain the modified cage-type dendritic organic silicon resin.
Comparative example 2 is the same as example 1, except that: in the step of S1 preparing the modified cage-type dendritic organic silicon resin, an octavinyl POSS solution is not added, and the method specifically comprises the following steps:
s101: adding 5kg of 1-hydroxymethyl pyrazole-3-carboxylic acid into 20kg ethanol-tetrahydrofuran solvent, stirring and dissolving at 30 ℃ to obtain 1-hydroxymethyl pyrazole-3-carboxylic acid solution; the ethanol-tetrahydrofuran solvent is formed by mixing absolute ethanol and tetrahydrofuran according to a mass ratio of 1:1;
s102: after 75kg of vinyl polysiloxane and 1kg methyl ethyl ketone peroxide are uniformly mixed, 1-hydroxymethyl pyrazole-3-carboxylic acid solution obtained by S101 is dropwise added, and the mixture is stirred at 60 ℃ for reaction for 6 hours, and the solvent is removed by rotary evaporation, so that the modified cage-shaped dendritic organic silicon resin is obtained.
Comparative example 3 is the same as example 1, except that: the modified cage-type dendritic silicone resin in example 1 was replaced with vinyl polysiloxane, and there was no step of preparing the modified cage-type dendritic silicone resin by S1.
Test one:
the organosilicon solvent-free waterproof anticorrosive paint prepared in examples 1-3 and comparative examples 1-3 was constructed according to JG/T224-2007, wherein the construction test board is a tinplate, the curing period is 7d, the physicochemical properties of the cured paint film are measured, and the test results are shown in Table 1:
table 1: physical and chemical properties of the paint films after curing of the waterproof and anticorrosive paint prepared in examples 1 to 3 and comparative examples 1 to 3
As is clear from Table 1, compared with comparative examples 1-3, the overall performance of the organosilicon solvent-free waterproof anticorrosive paint prepared in examples 1-3 is improved, and the reason is that the organosilicon solvent-free waterproof anticorrosive paint prepared in examples 1-3 can form a special structure of an inner film and an outer film on the surface of a tinplate, the modified cage-shaped dendritic organosilicon resin in the paint is grafted with 1-hydroxymethyl pyrazole-3-carboxylic acid, the grafted monomer contains a negatively charged carboxylic acid anionic group and is adsorbed by the basal plane of the positively charged tinplate through electrostatic attraction, and meanwhile, the carboxylic acid group and the nitrogen heterocyclic group are subjected to coordination reaction with iron ions with empty tracks on the surface of the tinplate, so that a chelate crystal anticorrosive inner film taking iron as a central ion is constructed, and the chelate crystal anticorrosive inner film and the outer film are tightly hydrophobic, so that double protection is formed, the waterproof anticorrosive effect is obviously improved, and the service life of the metal plate is prolonged. The overall performance of the organic silicon solvent-free waterproof anticorrosive paint prepared in comparative example 1 is better than that of comparative example 3, and the analysis reasons are probably that the introduction of octavinyl POSS leads the paint system to have a more complex branched structure, after curing, a three-dimensional interpenetrating network structure with higher crosslinking density and higher compactness is formed, so that the waterproof anticorrosive performance is improved, and the inventor finds that the introduction of octavinyl POSS in comparative example 1 plays a key role in improving the bending resistance of a paint film compared with comparative examples 2-3, and the reason is that the introduction of octavinyl POSS leads the organic silicon resin to have a cage-type branched structure, so that compared with a linear polymer, the octavinyl POSS has smaller steric hindrance, and has higher flexibility and higher degree of freedom of a molecular chain, thereby further representing more excellent bending resistance. The organosilicon solvent-free waterproof anticorrosive paint prepared in the comparative example 2 is superior to the comparative example 1 in terms of water resistance and corrosion resistance, and the fact that the chelate crystal inner film is formed by grafting 1-hydroxymethyl pyrazole-3-carboxylic acid on the organosilicon resin has more important influence on the improvement of the waterproof anticorrosive performance of the paint.
And (2) testing II:
test piece one: the specification of the AH36 steel plate for the ship is 1cm x 20cm, and the chemical components and the mass percentages of the AH36 steel plate for the ship are shown in table 2:
table 2: chemical components and mass percent of AH36 marine steel plate
Test piece II: acrylic plate, specification is 1cm x 20cm.
The organic silicon solvent-free waterproof anticorrosive paint prepared in the examples 1-3 and the comparative example 1 are respectively and evenly coated on the surfaces of an AH36 marine steel plate and an acrylic plate, and the coating amount is controlled to be 50g/m 2 And adopts the strength of 200mJ/cm 2 After 3s of ultraviolet radiation treatment, the material is naturally cured for 7d.
Antibacterial property measurement was performed on the test pieces after surface treatment of examples 1 to 3 and comparative example 1 according to "antibacterial paint" HG-T3950-2007:
the test strains comprise staphylococcus aureus and sulfate reducing bacteria, wherein the formula of a broth culture medium (NB) of the sulfate reducing bacteria is as follows: beef extract 5.0g, peptone 10.0g, sodium chloride 2.5g, sodium sulfate 5.0g, distilled water 1000ml, pH=7.0, wherein the culture solution is broth (NB)/physiological saline solution, and the concentration of the culture solution is 1/100.
The antibacterial property results are shown in table 3:
table 3: antibacterial Properties of the waterproof anticorrosive paint prepared in examples 1 to 3 and comparative example 1
As shown in Table 3, the inventors have unexpectedly found that the organic silicon solvent-free waterproof anticorrosive paint of examples 1 to 3 has excellent antibacterial performance when applied to steel, which has a key effect on improving the corrosion resistance of steel for ships and ocean engineering, and can significantly improve the corrosion resistance, durability and service life of steel for ships and ocean engineering, because the modified cage-shaped dendritic organic silicon resin structure of examples 1 to 3 reacts with metal ions on the surface of steel to produce a polynuclear complex, which can significantly improve the antibacterial and bacteriostatic effects and has high sterilization activity.
And (3) test III:
the organic silicon solvent-free waterproof anticorrosive paint prepared in the example 1 and the organic silicon solvent-free waterproof anticorrosive paint prepared in the comparative example 1 are respectively and uniformly coated on the surface of an AH36 marine steel plate, and the coating amount is controlled to be 50g/m 2 And adopts the strength of 200mJ/cm 2 After 3s of ultraviolet radiation treatment, the material is naturally cured for 7d.
The AH36 marine steel plates after the surface treatments of the coatings of example 1 and comparative example 1 were immersed in sulfate-reducing bacteria at a content of 5.0X10, respectively 4 Per mL, na 2 SO 4 In simulated seawater with the content of 5000mg/L, the consumption of the simulated seawater is 2L, standing is carried out for 60 days at 35 ℃, an AH36 ship steel plate which is not subjected to surface treatment is used as a blank control group, the weight of a sample before and after a test is compared, the uniform corrosion rate is calculated, the spot corrosion rate is calculated by carrying out section analysis on a spot corrosion pit, and the test result is shown in Table 4:
table 4: corrosion rate of AH36 marine steel plate treated with different surfaces
As can be seen from Table 4, the salt and corrosion resistance of example 1 is significantly better than that of comparative example 1. On the one hand, the modified cage-like dendritic silicone resin of example 1 was adsorbed by the positively charged basal plane of the steel sheet for boat by electrostatic attraction, and at the same time, the carboxylic acid group and the aza ring group were together with Fe having empty orbitals on the surface of the steel sheet for boat 3+ 、Fe 2+ 、Mn 2+ 、Ni 2+ 、Cu 2+ The coordination reaction of the plasma metal ions is carried outThe anti-corrosion chelate crystal inner film is constructed to form double protection with the external compact hydrophobic organic fluorine silicon outer film, so that the waterproof and anti-corrosion effects are obviously improved, and the service life of the ship steel plate is prolonged; on the other hand, the grafting monomer 1-hydroxymethyl pyrazole-3-carboxylic acid reacts with metal ions on the surface of the marine steel plate to generate a polynuclear complex, the complex also has obvious inhibition effect on sulfate reducing bacteria, has high sterilization activity, and skillfully overcomes the difficulty of long-term use of the marine steel in a seawater environment with high sulfate content and high sulfate reducing bacteria content.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (8)
1. The organic silicon solvent-free waterproof anticorrosive paint is characterized by comprising the following raw materials in parts by mass: 100 parts of modified cage-shaped dendritic organic silicon resin, 35-45 parts of vinyl fluorosilicone oil, 0.5-1 part of photoinitiator, 3-5 parts of vinyl triacetoxy silane and 15-25 parts of nano filler;
the modified cage-shaped dendritic organic silicon resin is 1-hydroxymethyl pyrazole-3-carboxylic acid grafted cage-shaped organic silicon resin and is formed by graft copolymerization of vinyl polysiloxane, octavinyl POSS and 1-hydroxymethyl pyrazole-3-carboxylic acid;
the preparation method of the modified cage-shaped dendritic organic silicon resin comprises the following steps:
A. the preparation method comprises the following steps of: 5-8 parts of 1-hydroxymethyl pyrazole-3-carboxylic acid, 20-30 parts of ethanol-tetrahydrofuran solvent, 25-30 parts of vinyl triethoxysilane, 180-250 parts of acetone solvent, 8-10 parts of HCl solution, 75-85 parts of vinyl polysiloxane and 1-1.5 parts of methyl ethyl ketone peroxide;
B. adding 1-hydroxymethyl pyrazole-3-carboxylic acid into ethanol-tetrahydrofuran solvent, stirring at 30-60 ℃ for dissolution to obtain 1-hydroxymethyl pyrazole-3-carboxylic acid solution;
C. adding vinyltriethoxysilane into an acetone solvent, dropwise adding an HCl solution, and stirring at 40-50 ℃ for reacting for 18-24 hours to obtain an octavinyl POSS solution;
D. uniformly mixing vinyl polysiloxane and octavinyl POSS solution, adding methyl ethyl ketone peroxide, stirring at 50-55 ℃ for reaction for 4-8 hours, then dripping 1-hydroxymethyl pyrazole-3-carboxylic acid solution, stirring at 60-70 ℃ for reaction for 2-3 hours, and removing the solvent by rotary evaporation to obtain the modified cage-shaped dendritic organic silicon resin.
2. The organic silicon solvent-free waterproof anticorrosive paint according to claim 1, wherein the ethanol-tetrahydrofuran solvent is prepared by mixing absolute ethanol and tetrahydrofuran according to a mass ratio of 1:1.
3. The organic silicon solvent-free waterproof anticorrosive paint according to claim 1, wherein the mass concentration of the HCl solution is 15-20%.
4. The organic silicon solvent-free waterproof anticorrosive paint according to claim 1, wherein the photoinitiator comprises one or two of 2-hydroxy-2-methyl-1-phenyl acetone and 1-hydroxycyclohexyl phenyl ketone.
5. The organic silicon solvent-free waterproof anticorrosive paint according to claim 1, wherein the nano filler comprises one or more of nano silicon oxide, nano silicon carbide and nano silicon nitride.
6. A method for preparing the organic silicon solvent-free waterproof anticorrosive paint according to any one of claims 1 to 5, comprising the following steps:
s1: dripping vinyl triacetoxy silane into the nano filler, stirring for 30-60min, adding vinyl fluorosilicone oil and photoinitiator, stirring and dispersing to obtain mixed auxiliary materials;
s2: adding the mixed auxiliary materials into the modified cage-shaped dendritic organic silicon resin, and performing ultrasonic dispersion to obtain the organic silicon solvent-free waterproof anticorrosive paint.
7. Use of the silicone solvent-free waterproof anticorrosive paint according to any one of claims 1 to 5 for marine vessel corrosion protection.
8. The use according to claim 7, characterized in that: uniformly coating the organosilicon solvent-free waterproof anticorrosive paint on the surface of the ship steel plate, and controlling the coating amount to be 50-100g/m 2 And adopts the strength of 180-250mJ/cm 2 After 3-5s of ultraviolet radiation treatment, the mixture is naturally solidified for 7-10d.
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| CN105131835B (en) * | 2015-08-04 | 2017-05-10 | 天津大学 | A UV-curable POSS fluorine-containing acrylate block copolymer coating and its preparation and application |
| CN113372816A (en) * | 2021-05-21 | 2021-09-10 | 无锡时生高分子科技有限公司 | Solvent-free UV (ultraviolet) curing type organic silicon three-proofing adhesive |
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