CN113583538B - Solvent-free nontoxic anticorrosive paint for marine culture cabin - Google Patents
Solvent-free nontoxic anticorrosive paint for marine culture cabin Download PDFInfo
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- CN113583538B CN113583538B CN202110800652.3A CN202110800652A CN113583538B CN 113583538 B CN113583538 B CN 113583538B CN 202110800652 A CN202110800652 A CN 202110800652A CN 113583538 B CN113583538 B CN 113583538B
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
- C08G59/5013—Amines aliphatic containing more than seven carbon atoms, e.g. fatty amines
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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Abstract
The invention relates to a solvent-free nontoxic anticorrosive paint for a marine culture cabin, which is prepared by mixing raw materials including a component A and a component B; the component A comprises epoxy resin, a reactive diluent, pigment and filler, a thixotropic agent and an auxiliary agent; the component B comprises a curing agent and a curing accelerator. According to the invention, the curing agent is modified, so that the water absorption of the coating is reduced, the medium resistance of the coating is enhanced, and then the modified aliphatic amine curing agent and other components are reasonably compounded, so that the solvent-free and non-toxic coating for the marine culture tank, which meets the environmental protection requirement, is prepared. The solvent-free nontoxic coating prepared by the invention meets the national fishery water quality standard requirement, passes the acute toxicity test and meets the use requirement of marine culture.
Description
Technical Field
The invention relates to the technical field of coatings, and further relates to a solvent-free nontoxic anticorrosive coating for a ship culture cabin.
Background
The Qingdao intelligent fishery large-scale aquaculture industrial ship project-10-kiloton large-scale aquaculture industrial ship which is already built is 2-3 million yuan per year, the industrial ship integrates multiple functions of aquaculture, processing, scientific investigation, marine logistics supply and the like, and a 'culturing-capturing-adding' integrated intelligent fishery comprehensive platform is innovatively constructed.
According to the ship, the culture cabin is innovatively arranged in the ship body, the combination of new technologies such as ship design and construction, intelligent fishery culture and Internet of things is realized, and deep and distant sea industrial ship culture of main culture varieties such as large yellow croakers and Atlantic salmon is carried out in domestic sea areas by carrying various culture equipment.
The core part in the cultivation worker ship is a cultivation cabin, and the coating is particularly important for the anticorrosion protection in the cultivation cabin. The coating formed by the coating has long-acting corrosion resistance, no harmful substances are separated out after the coating is soaked in seawater, and the coating cannot generate adverse effect on live fish in the cabin; in addition, seawater is discharged from the culture cabin every day, the cabin wall is cleaned regularly, and the coating has enough toughness to meet the requirements of water flow impact during water discharge and high-pressure water impact during cleaning. At present, no coating which can meet the requirement of marine culture of a cabin exists in the domestic coating market for a while. Therefore, according to the urgent need of the breeding ships, a solvent-free and non-toxic coating meeting the environmental protection requirement for the ship breeding cabin needs to be developed.
The invention develops a solvent-free nontoxic coating for a marine culture tank, which meets the environmental protection requirement.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a solvent-free non-toxic anticorrosive paint for a marine culture cabin. According to the invention, the curing agent is modified, so that the water absorption of the coating is reduced, the medium resistance of the coating is enhanced, and then the modified aliphatic amine curing agent and other components are reasonably compounded, so that the solvent-free and non-toxic coating for the marine culture tank, which meets the environmental protection requirement, is prepared. The solvent-free nontoxic coating prepared by the invention meets the national fishery water quality standard requirement, passes the acute toxicity test, and meets the use requirement of marine culture.
One of the purposes of the invention is to provide a solvent-free nontoxic anticorrosive paint for a marine culture cabin, which is prepared by mixing raw materials including a component A and a component B;
the component A comprises:
the components are counted by weight part, and the weight percentage is,
the component B comprises:
the components are calculated according to the parts by weight,
100 parts by weight of curing agent
0 to 30 parts by weight of a curing accelerator
The weight ratio of the component A to the component B is 4-5: 1.
In a preferred embodiment of the method of the invention,
the component A comprises:
the components are calculated according to the parts by weight,
the component B comprises:
the components are calculated according to the parts by weight,
100 parts by weight of curing agent
10-20 parts by weight of a curing accelerator.
In a preferred embodiment of the method of the invention,
the epoxy value of the epoxy resin is 0.51-0.54; bisphenol a type epoxy resins are preferred.
The resin has low viscosity and is very suitable for preparing solvent-free paint. Preferably, the epoxy resin 0164 (a new blue star chemical material) and the epoxy resin 128 (south Asia) are selected.
Preferably, the first and second liquid crystal materials are,
the structural formula of the reactive diluent is shown in the specification
The reactive diluent is preferably selected from the group consisting of cadela NC-513; the cadlely NC-513 has an active epoxy functional group so that the epoxy group and the amine group can react and enter the epoxy system coating. The flexibility and the viscosity are improved while the performance of the coating is maintained, and the compatibility of the resin and the curing agent is improved.
Preferably, the first and second liquid crystal materials are,
the pigment and filler is selected from one or a combination of titanium dioxide, black iron oxide, medical precipitated barium sulfate or medical talcum powder; the pigment and the filler can affect the physical and mechanical properties of the coating film; and/or the presence of a gas in the atmosphere,
the thixotropic agent is fumed silica, and as the viscosity of the solvent-free paint is greatly influenced by the temperature, the thixotropic effect of the paint is adjusted by adding the fumed silica, and meanwhile, the anti-settling and anti-sagging effects of the paint can be improved.
In a preferred embodiment of the method of the invention,
the auxiliary agent comprises a defoaming agent, a wetting dispersant and a flatting agent;
the defoamer is selected from a combination of a silicone defoamer and a silicone-free polymeric defoamer.
Because the solvent-free coating of the invention has high viscosity, bubbles are easily generated during stirring and are not easy to eliminate, and a proper defoaming agent is required to be added to eliminate the bubbles generated by a paint film. Preferentially selecting BYK-055 and a D.modest 6800 to be matched for use, wherein the weight ratio of BYK-055 to D.modest 6800 is 1: 0.9-1; the best defoaming effect can be obtained.
According to the characteristics that the solvent-free coating is difficult to disperse and not easy to level, BYK-204 is selected as the wetting dispersant, and BYK-378 is selected as the leveling agent.
Preferably, the first and second liquid crystal materials are,
the molecular formula of the curing agent is as follows:
the value range of n is 1-10.
Preferably, the first and second liquid crystal materials are,
the curing accelerator is 2,4, 6-tri (dimethylaminomethyl) phenol.
The curing agent accelerator is preferably selected from DMP-30, DMP-30 is a commercial product, the product is prepared by adding a proper amount of low molecular weight epoxy resin into diaminodiphenylmethane (DDM) for modification, free amine is basically not separated out, and no harm is caused to human bodies.
The solvent-free nontoxic anticorrosive paint can also be added with conventional components in the field according to the use requirement.
Preferably, the first and second liquid crystal materials are,
the curing agent is prepared by reacting polypropylene glycol diglycidyl ether, isopropoxy tri (dioctyl phosphate) titanate and tetraethylene pentamine.
Preferably, the first and second liquid crystal materials are,
the preparation method of the curing agent comprises the following steps:
(1) uniformly mixing polypropylene glycol diglycidyl ether and isopropoxy tri (dioctyl phosphate) titanate to prepare a mixed solution;
(2) under the condition of stirring, dropwise adding the mixed liquid into tetraethylenepentamine for reaction to obtain a curing agent;
the weight ratio of the polypropylene glycol diglycidyl ether to the isopropoxy tri (dioctyl phosphate) titanate to the tetraethylenepentamine is (38-42) to 2 (55-60);
the reaction temperature is 65-75 ℃;
the reaction time is 2-10 hours.
Has the beneficial effects that:
1. compared with the existing aliphatic amine curing agent, the modified curing agent modified by the invention has the advantages that the water absorption point amino (amino is hydrophilic, the water absorption of the compound with more amino is increased) is reduced, the water absorption of the coating is reduced, and the medium resistance of the coating is enhanced; the molecular chain of the modified curing agent is lengthened, so that the flexibility of the epoxy coating is further improved, and the coating can better resist the impact of water flow, thereby keeping the integrity of the coating for a long time and meeting the use requirement of the marine culture cabin.
2. Compared with the existing aliphatic amine curing agent, the modified curing agent modified by the invention contains a large number of hydroxyl groups in the molecular structure, has stronger binding force with the surface of a metal substrate, and can effectively improve the adhesive force of a coating.
3. The solvent-free low-viscosity film-forming resin system selected by the invention has the advantages that the coating after curing and crosslinking is actually nontoxic, the cultured fish is not influenced, and the coating has good corrosion resistance under the condition of oxygen enrichment in mariculture.
4. The solvent-free nontoxic anticorrosive paint formula comprehensively considers the safety performance, anticorrosive performance, adhesive force and toughness of the coating, has a very good using effect on the marine culture tank, and does not have a paint suitable for the marine culture tank in the market at present. The solvent-free nontoxic anticorrosive paint of the invention is well applied to the cultivation ships.
5. In the preparation process of the modified curing agent, the catalyst isopropoxy trititanate is added, so that the obtained modified curing agent product has high hydroxyl content, high polarity and high adhesion to a metal substrate, and the corrosion resistance of a coating can be effectively improved.
Detailed Description
While the present invention will be described in conjunction with specific embodiments thereof, it is to be understood that the following embodiments are presented by way of illustration only and not by way of limitation, and that numerous insubstantial modifications and adaptations of the invention may be made by those skilled in the art in light of the teachings herein.
The raw material sources are as follows:
the reagents used in the present invention are commercially available products except for the self-synthesis of the curing agent.
The test method of the coating of the invention is as follows:
1. adhesion (GB/T5210-2006 paint and varnish adhesion test by pulling method)
2. Salt spray resistance (paint film thickness about 300 um) 3000 hours of good paint film (GB/T1771-2007 determination of neutral salt spray resistance of colored paint and varnish)
3. The paint film is good after 24 cycles of cold resistance and heat resistance alternation (minus 55-80 ℃, 2 hours and 1 cycle). (GJB GJB 150.5-1986 temperature shock test)
4. Sea water resistance (GB/T9274-1988 determination of liquid-resistant Medium of colored paint and varnish)
5. Flexibility (GB/T1731-1993 paint film flexibility determination method)
6. And (3) testing the toxicity of the coating:
the paint prepared by the invention is detected by fishery machinery instrument research institute of Chinese aquatic science research institute, and the test result of the paint on the acute toxicity damage of zebra fish shows whether the paint can be applied to fish culture in a culture cabin, and the detection items are as follows:
whether the heavy metal substances generated by the coating soaking solution are lower than the national fishery water quality standard (the content of Pb (ug/L) is less than or equal to 50 or not; cd (ug/L) is less than or equal to 5; cr (ug/L) is less than or equal to 100; cu (ug/L) is less than or equal to 10; ni (ug/L) is less than or equal to 50; hg (ug/L) is less than or equal to 0.5, is a nontoxic substance for zebra fish, and meets the national fishery water quality standard.
And (3) detecting the formaldehyde content of the coating soaking solution with 0 to 140 times of the normal coating amount of the cabin by using a liquid chromatography instrument, and finding whether the coating soaking solution contains formaldehyde or not by referring to a phloroglucinol method qualitative detection formaldehyde principle.
Whether or not the benzene series content is in LC 50 >10000mg/L or more.
7. Impact strength: 50cm according to GB/T1732 & 1993 test for impact resistance of paint films.
Example 1
Preparation of modified fatty amine curing agent:
mixing polypropylene glycol diglycidyl ether and isopropoxy tri (dioctyl phosphate) titanate uniformly according to the proportion to prepare a mixed solution; adding tetraethylenepentamine into a reaction kettle, heating to 70 ℃, slowly dripping the mixed solution at a dripping speed of 10mL/min while stirring, and reacting for 3 hours while stirring at the temperature of 70 ℃ to obtain the colorless transparent liquid modified fatty amine curing agent.
The structural formula of the modified fatty amine curing agent prepared by the method is as follows:
the value range of n is 1-10.
Example 2
Preparation of modified fatty amine curing agent:
the polypropylene glycol diglycidyl ether and the isopropoxy tri (dioctyl phosphate) titanate are uniformly mixed according to the proportion to prepare a mixed solution. And adding tetraethylenepentamine into the reaction kettle, heating to 75 ℃, slowly dripping the mixed solution at a dripping speed of 10mL/min while stirring, and reacting for 2 hours while stirring at the temperature of 75 ℃ to obtain the colorless transparent liquid modified fatty amine curing agent.
The structural formula of the modified fatty amine curing agent prepared by the method is as follows:
the value range of n is 1-10.
Example 3
Preparation of modified fatty amine curing agent:
the polypropylene glycol diglycidyl ether and the isopropoxy tri (dioctyl phosphate) titanate are uniformly mixed according to the proportion to prepare a mixed solution. And adding tetraethylenepentamine into the reaction kettle, heating to 65 ℃, slowly dripping the mixed solution at the dripping speed of 10mL/min while stirring, and reacting for 10 hours while stirring at the temperature of 65 ℃ to obtain the colorless transparent liquid modified fatty amine curing agent.
The structural formula of the modified fatty amine curing agent prepared by the method is as follows:
the value range of n is 1-10.
Example 4
The preparation of the solvent-free nontoxic anticorrosive paint comprises the following steps:
0164100 parts of epoxy resin by weight and NC-51325 parts of reactive diluent by weight are weighed and put into a stainless steel tank to be stirred by a high-speed stirrer, 1.3 parts of antifoaming agent (BYK-055 and Demodex 6800, the weight ratio of which is 6:7), 1.1 parts of wetting dispersant (BYK-204) and 0.6 part of flatting agent (BYK-378) are added into the stainless steel tank to be stirred uniformly with the resin, 45 parts of titanium pigment by weight, 50 parts of medical talcum powder and 2 parts of thixotropic agent fumed silica by weight are added into the stainless steel tank to be stirred uniformly, and then the mixture is ground by a sand mill or a three-roll mill to the standard fineness to obtain the component A of the coating after being filtered and barreled.
100 parts by weight of the modified aliphatic amine curing agent prepared in the example 1 and 0 part by weight of the curing accelerator are weighed, further stirred uniformly, filtered and barreled to form the component B of the coating.
When in use, A, B is prepared by mixing the following two components in a weight ratio of 5:1, and mechanically stirring uniformly to prepare the solvent-free nontoxic anticorrosive paint.
The performance test result of a coating film (paint film) formed by spraying the solvent-free nontoxic anticorrosive paint is as follows:
1. the adhesive force is 20.2 MPa;
2. the salt spray resistance (the thickness of the paint film is about 300 um) is 3000 hours, and the paint film is intact;
3. the paint film is good after 12 cycles of cold resistance and heat resistance alternation (minus 55-80 ℃, 2 hours and 1 cycle).
4. Under the condition of normal temperature, the paint film is unchanged after being soaked in seawater for 3000 hours.
5. Flexibility is 1 mm.
6. Paint toxicity test results:
heavy metal substances generated by the coating soaking solution are all lower than the national fishery water quality standard (the content of Pb (ug/L) is less than or equal to 50; cd (ug/L) is less than or equal to 5; cr (ug/L) is less than or equal to 100; cu (ug/L) is less than or equal to 10; ni (ug/L) is less than or equal to 50; hg (ug/L) is less than or equal to 0.5, is a nontoxic substance for zebra fish, and meets the national fishery water quality standard.
And (3) detecting the formaldehyde content of the coating soaking solution which is 0 to 140 times of the normal coating amount of the cabin by using a liquid chromatography instrument, and qualitatively detecting the formaldehyde principle by referring to a phloroglucinol method, wherein the formaldehyde is not found to exist in the coating soaking solution.
Content of benzene series in LC 50 >10000mg/L above, in a safe concentration range, and can greatly reduce the content of volatile benzene series in the paint after aeration and cabin soaking for 15 days before use.
Example 5
128100 parts of south Asia epoxy resin and NC-51367 parts of reactive diluent are added into a stainless steel tank and stirred by a high-speed stirrer, 0.6 part of defoamer (BYK-055 and Demodex 6800, the weight ratio of the BYK-055 to the Demodex 6800 is 6:7), 0.8 part of wetting dispersant (BYK-204) and 0.6 part of flatting agent (BYK-378) are added into the stainless steel tank and stirred uniformly with the epoxy resin, 60 parts of titanium pigment, 57 parts of medical precipitated barium sulfate and 17 parts of thixotropic agent fumed silica are added into the stainless steel tank and stirred uniformly, and then the mixture is ground by a sand mill or a three-roll grinder to standard fineness and filtered and barreled into the component A of the coating.
100 parts by weight of the modified aliphatic amine curing agent prepared in example 1 and 30 parts by weight of the curing accelerator were uniformly stirred by a high-speed dispersion machine, and the mixture was filtered and barreled to form a component B of the coating.
When in use, A, B is mixed according to the weight ratio of 4:1, and mechanically stirring uniformly to prepare the solvent-free nontoxic anticorrosive paint.
The performance test result of a coating film (paint film) formed by spraying the solvent-free nontoxic anticorrosive paint is as follows:
1. the adhesive force is 20.1 MPa;
2. salt spray resistance (the thickness of the paint film is about 300 mu m) is good after 3000 hours;
3. the paint film is good after 24 cycles of cold and heat resistance alternation (at the temperature of between 55 and 80 ℃ and 2 hours and 1 cycle).
4. Under the condition of normal temperature, the paint film does not change after being soaked in seawater for 3000 hours.
5. The flexibility is 1 mm;
6. paint toxicity test results:
heavy metal substances generated by the coating soaking solution are all lower than the national fishery water quality standard (the content of Pb (ug/L) is less than or equal to 50; cd (ug/L) is less than or equal to 5; cr (ug/L) is less than or equal to 100; cu (ug/L) is less than or equal to 10; ni (ug/L) is less than or equal to 50; hg (ug/L) is less than or equal to 0.5, is a nontoxic substance for zebra fish, and meets the national fishery water quality standard.
And (3) detecting the formaldehyde content of the coating soaking solution which is 0 to 140 times of the normal coating amount of the cabin by using a liquid chromatography instrument, and qualitatively detecting the formaldehyde principle by referring to a phloroglucinol method, wherein the formaldehyde is not found to exist in the coating soaking solution.
Content of benzene series in LC 50 >More than 10000mg/L, in a safe concentration range, and can greatly reduce the content of volatile benzene series in the coating after aeration and cabin soaking for 15 days before use.
Example 6
128100 parts of south Asia epoxy resin and NC-51333 parts of active diluent are added into a stainless steel tank and stirred by a high-speed stirrer, 2 parts of defoaming agent (BYK-055 and a moderate 6800, the weight ratio of the BYK-055 to the moderate 6800 is 1:1), 3 parts of wetting dispersant (BYK-204) and 1 part of flatting agent (BYK-378) are added into the stainless steel tank and stirred uniformly with the epoxy resin, 34 parts of titanium pigment, 39 parts of medical precipitated barium sulfate and 5 parts of thixotropic agent fumed silica are added into the stainless steel tank and stirred uniformly, the mixture is ground to standard fineness by a sand mill or a three-roll grinder and filtered and barreled to form the component A of the coating.
100 parts by weight of the modified aliphatic amine curing agent prepared in example 1 and 10 parts by weight of the curing accelerator were uniformly stirred by a high-speed dispersion machine, and the mixture was filtered and barreled to form a component B of the coating.
When in use, A, B is mixed according to the weight ratio of 4:1, and mechanically stirring uniformly to prepare the solvent-free nontoxic anticorrosive paint.
The performance test result of a coating film (paint film) formed by spraying the solvent-free nontoxic anticorrosive paint is as follows:
1. the adhesive force is 20 MPa;
2. salt spray resistance (the thickness of the paint film is about 300 mu m) is good after 3000 hours;
3. the paint film is good after 24 cycles of cold and heat resistance alternation (at the temperature of between 55 and 80 ℃ and 2 hours and 1 cycle).
4. Under the condition of normal temperature, the paint film is unchanged after being soaked in seawater for 3000 hours.
5. The flexibility is 1 mm;
6. paint toxicity test results:
heavy metal substances generated by the coating soaking solution are all lower than the national fishery water quality standard (the content of Pb (ug/L) is less than or equal to 50; cd (ug/L) is less than or equal to 5; cr (ug/L) is less than or equal to 100; cu (ug/L) is less than or equal to 10; ni (ug/L) is less than or equal to 50; hg (ug/L) is less than or equal to 0.5 percent, is a nontoxic substance for zebra fish, and meets the national fishery water quality standard.
And (3) detecting the formaldehyde content of the coating soaking solution which is 0 to 140 times of the normal coating amount of the cabin by using a liquid chromatography instrument, and qualitatively detecting the formaldehyde principle by referring to a phloroglucinol method, wherein the formaldehyde is not found to exist in the coating soaking solution.
Content of benzene series in LC 50 >More than 10000mg/L, in a safe concentration range, and can greatly reduce the content of volatile benzene series in the coating after aeration and cabin soaking for 15 days before use.
Example 7
128100 parts of south Asia epoxy resin and NC-51350 parts of reactive diluent are added into a stainless steel tank and stirred by a high-speed stirrer, 4 parts of defoaming agent (BYK-055 and Demodex 6800, the weight ratio of the BYK-055 to the Demodex 6800 is 6:7), 5 parts of wetting dispersant (BYK-204) and 4 parts of flatting agent (BYK-378) are added into the stainless steel tank and stirred uniformly with the epoxy resin, 50 parts of titanium pigment, 42 parts of medical precipitated barium sulfate and 15 parts of thixotropic agent fumed silica are added into the stainless steel tank and stirred uniformly, then the mixture is ground to standard fineness by a sand mill or a three-roll grinder and filtered and barreled to form the component A of the coating.
100 parts by weight of the modified aliphatic amine curing agent prepared in example 1 and 20 parts by weight of the curing accelerator were uniformly stirred by a high-speed dispersion machine, and the mixture was filtered and barreled to form a component B of the coating.
When in use, A, B is prepared by mixing the following two components in a weight ratio of 4:1, and mechanically stirring uniformly to prepare the solvent-free nontoxic anticorrosive paint.
The performance test result of a coating film (paint film) formed by spraying the solvent-free nontoxic anticorrosive paint is as follows:
1. the adhesive force is 20.2 MPa;
2. salt spray resistance (the thickness of the paint film is about 300 mu m) is good after 3000 hours;
3. the paint film is good after 24 cycles of cold resistance and heat resistance alternation (minus 55-80 ℃, 2 hours and 1 cycle).
4. Under the condition of normal temperature, the paint film does not change after being soaked in seawater for 3000 hours.
5. The flexibility is 1 mm;
6. paint toxicity test results:
7. heavy metal substances generated by the coating soaking solution are all lower than the national fishery water quality standard (the content of Pb (ug/L) is less than or equal to 50); cd (ug/L) is less than or equal to 5; cr (ug/L) is less than or equal to 100; cu (ug/L) is less than or equal to 10; ni (ug/L) is less than or equal to 50; hg (ug/L) is less than or equal to 0.5 percent, is a nontoxic substance for zebra fish, and meets the national fishery water quality standard.
And (3) detecting the formaldehyde content of the coating soaking solution which is 0 to 140 times of the normal coating amount of the cabin by using a liquid chromatography instrument, and qualitatively detecting the formaldehyde principle by referring to a phloroglucinol method, wherein the formaldehyde is not found to exist in the coating soaking solution.
Content of benzene series in LC 50 >10000mg/L above, in a safe concentration range, and can greatly reduce the content of volatile benzene series in the paint after aeration and cabin soaking for 15 days before use.
Comparative example 1
Comparative example 1 a solventless coating was prepared according to the method of example 2 disclosed in patent CN 103059695A.
And (3) testing: weighing 30 parts by weight of DER331 epoxy resin, adopting NC-51315 parts by weight of toughened resin, putting into a stainless steel tank, stirring by using a high-speed stirrer, adding 1.5 parts by weight of defoaming agent (AFCONA2723 and 2020), 1.5 parts by weight of wetting dispersant (BYK-P104S) and 1.5 parts by weight of flatting agent (AFCONA3700), stirring uniformly with resin, adding 10 parts by weight of titanium dioxide, 40 parts by weight of talcum powder and 0.5 part by weight of thixotropic agent, further stirring uniformly, grinding to a standard fineness by using a sand mill or a three-roll mill, filtering and barreling to obtain the component A of the coating.
15 parts by weight of the modified aromatic amine curing agent prepared in CN103059695A in example 1 and 10 parts by weight of the adhesion promoter are weighed, further stirred uniformly, filtered and barreled to form a component B of the coating.
When in use, A, B is prepared by mixing the following two components in a weight ratio of 4:1, mechanically stirring uniformly, and spraying to form a coating film.
Comparative example 1 compares the performance of the solventless coating materials prepared in examples 4, 5 and 6 of the present invention, and the specific results are shown in table 1.
TABLE 1
As can be seen from Table 1, the adhesion and the salt spray resistance of the paint film prepared in comparative example 1 are substantially the same as those of the paint films prepared in examples 4, 5 and 6 of the invention, but the flexibility, the impact strength and the cold and heat exchange resistance of the paint film are poorer than those of the paint films prepared in examples 4, 5 and 6 of the invention, so that the paint film can not meet the use requirements in the cultivation cabin. Through a large number of experiments, the invention develops a solvent-free nontoxic system suitable for the industrial and marine culture environment, and successfully solves the problems.
Example 8
The application of the coating prepared by the invention in the marine culture cabin is as follows:
the sand blasting type artificial breeding cabin is used in a typical breeding cabin part of a certain breeding base in south jiao Nan of Qingdao, and the surface of the cabin wall of the breeding cabin is subjected to sand blasting until Sa2.5 is achieved during construction. The coating prepared in example 4 is prepared by weighing A, B components according to the weight ratio of A to B to 5 to 1, uniformly stirring, spraying twice by using special high-pressure airless spraying equipment, detecting the thickness, curing the coating at normal temperature (25 ℃) for seven days after the thickness is qualified, and cleaning with water for use. The obtained coating is flat and has a bright surface, seawater is poured into the coating after washing, large yellow croaker is placed into a typical part for culture test, the seawater quality in the typical part is periodically detected, and after 6 months of culture test, a paint film has no problem.
Example 9
The application of the coating prepared by the invention in the marine culture cabin is as follows:
the method is applied to three culture cabins of a pilot ship for Chinese letter culture in a maple shipyard in Taizhou, Zhejiang, and sand blasting is performed on the surface of the cabin wall of the culture cabin to Sa2.5 during construction. The coating prepared in example 4 is prepared by weighing A, B two components in parts by weight of A: B: 5:1, uniformly stirring, spraying by using special high-pressure airless spraying equipment, curing the coating at normal temperature (25 ℃) for seven days, cleaning the whole cabin by using seawater, and storing for at least 48 hours. The obtained coating is flat and has a bright surface, and the coating is intact after the coating is used for 12 months.
Example 10
The application of the coating prepared by the invention in the marine culture cabin is as follows:
the paint prepared in example 5 is applied to the inner wall of a cement culture pond of a certain hippocampus of Qingdao. The inner wall surface of the cement pit is cleaned and has no impurities, A, B two components are mixed and roll-coated according to the weight ratio of A: B to 4:1, the dry film thickness is about 300um, the mixture is solidified for seven days at normal temperature (25 ℃), and the mixture is repeatedly washed with clean water for three times for use. The obtained coating has the advantages of smooth appearance, bright surface and better permeability resistance. The sea horse is cultured in the sea horse pool for 8 months, has no adverse effect on sea horses, and has good use effect.
Claims (9)
1. A solvent-free nontoxic anticorrosive paint for a marine culture cabin is characterized in that: the coating is prepared by mixing raw materials including a component A and a component B;
the component A comprises:
the components are counted by weight part, and the weight percentage is,
the component B comprises:
the components are counted by weight part, and the weight percentage is,
100 parts by weight of curing agent
0-30 parts by weight of curing accelerator
The weight ratio of the component A to the component B is 4-5: 1;
the molecular formula of the curing agent is as follows:
the value range of n is 1-10;
the curing agent is prepared by reacting polypropylene glycol diglycidyl ether, isopropoxy tri (dioctyl phosphate) titanate and tetraethylene pentamine.
2. The solvent-free non-toxic anticorrosive coating for marine culture tanks according to claim 1, characterized in that:
the component A comprises:
the components are counted by weight part, and the weight percentage is,
the component B comprises:
the components are counted by weight part, and the weight percentage is,
100 parts by weight of curing agent
10-20 parts by weight of a curing accelerator.
3. The solvent-free non-toxic anticorrosive coating for marine culture tanks according to claim 1, characterized in that: the epoxy value of the epoxy resin is 0.51-0.54.
4. The solvent-free non-toxic anticorrosive coating for marine culture tanks according to claim 3, characterized in that: the epoxy resin is bisphenol A type epoxy resin.
5. The solvent-free non-toxic anticorrosive coating for marine culture tanks according to claim 1, characterized in that: the structural formula of the active diluent is
6. The solvent-free non-toxic anticorrosive coating for marine culture tanks according to claim 1, characterized in that: the pigment and filler is selected from one or a combination of titanium dioxide, black iron oxide, medical precipitated barium sulfate or medical talcum powder; and/or the presence of a gas in the atmosphere,
the thixotropic agent is fumed silica.
7. The solvent-free non-toxic anticorrosive coating for marine culture tanks according to claim 1, characterized in that: the auxiliary agent comprises a defoaming agent, a wetting dispersant and a flatting agent;
the defoamer is selected from the group consisting of a silicone defoamer and a silicone-free polymeric defoamer.
8. The solvent-free non-toxic anticorrosive coating for marine culture tanks according to claim 1, characterized in that: the curing accelerator is 2,4, 6-tri (dimethylaminomethyl) phenol.
9. The solvent-free non-toxic anticorrosive coating for marine culture tanks according to claim 1, characterized in that:
the preparation method of the curing agent comprises the following steps:
(1) uniformly mixing polypropylene glycol diglycidyl ether and isopropoxy tri (dioctyl phosphate) titanate to prepare a mixed solution;
(2) under the condition of stirring, dropwise adding the mixed liquid into tetraethylenepentamine for reaction to obtain a curing agent;
the weight ratio of the polypropylene glycol diglycidyl ether to the isopropoxy tri (dioctyl phosphate) titanate to the tetraethylenepentamine is (38-42) to 2 (55-60);
the reaction temperature is 65-75 ℃;
the reaction time is 2-10 hours.
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