CN107987274B - Polyaspartic acid ester resin, preparation method thereof, anticorrosive paint and preparation method thereof - Google Patents
Polyaspartic acid ester resin, preparation method thereof, anticorrosive paint and preparation method thereof Download PDFInfo
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/60—Polyamides or polyester-amides
- C08G18/603—Polyamides
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
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- 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 resin is mainly prepared from the following raw materials: 2-5 parts of aminosilane modified graphene oxide, 10-30 parts of primary diamine, 0.1-0.3 part of alkaline catalyst and 25-45 parts of maleic acid ester. The preparation method comprises the steps of stirring aminosilane modified graphene oxide, primary diamine and an alkaline catalyst, heating, dropwise adding maleic acid ester, heating, keeping the temperature for reaction, and cooling. The anticorrosive coating is formed by mixing a component A and a component B; the component A comprises aliphatic isocyanate and an elastic curing agent; the component B comprises the polyaspartic acid ester resin, an anti-settling agent, a pigment, a filler, a molecular sieve, a defoaming agent, a leveling agent, a dispersing agent, hydroxyl acrylic resin and an organic solvent. Also discloses a preparation method of the anticorrosive paint. The resin has good dispersibility; the anticorrosive coating has high solid content and good coating elasticity, impact resistance and corrosion resistance.
Description
Technical Field
The invention relates to an acid ester resin, a preparation method, an anticorrosive coating and a preparation method, in particular to a polyaspartic acid ester resin, a preparation method, an anticorrosive coating and a preparation method.
Background
Polyaspartate polyureas are low activity, slow reacting aliphatic polyureas that occur subsequent to aromatic polyureas and conventional aliphatic polyureas. Compared with the traditional polyurea, the polyurea coating is simpler and more convenient in construction operation, has relatively low requirement on equipment, greatly improves the coating performance and the like, and solves the problems of complex coating forming, performance reduction, poor adhesion and the like caused by overhigh reaction speed of the traditional polyurea.
CN105440272A discloses a preparation method of polyaspartic acid ester resin, which comprises the steps of firstly carrying out chemical reaction on polyetheramine and maleate, and then adding cyclic carbonate for chemical reaction; CN101817924A discloses a preparation method of a slow reaction type polyurea coating component, which comprises the steps of carrying out catalytic reaction on dicarboxylic ester and primary amine to generate a Michael adduct, then adding epoxy resin, and carrying out reaction to obtain polyaspartic acid ester resin; CN104130390A discloses a preparation method of polyether polyaspartic acid ester, which is to react dicarboxylic ester with diamine to obtain diamine terminated by dicarboxylic ester at two ends, diamine terminated by dicarboxylic ester at one end, or a mixture of diamine terminated by dicarboxylic ester at two ends and diamine terminated by dicarboxylic ester at one end; mixing and heating a polyether polyol, a carbonic acid diester and a catalyst to obtain a polyether terminated with a carbonate; mixing and heating a carboxylic acid terminated diamine and a carbonate terminated polyether to obtain a polyether polyaspartic acid ester. Although the reaction of the polyaspartic acid ester obtained by the above method with polyisocyanate can prolong the gel time of the polyurea coating. However, the polyaspartic acid ester polyurea is easy to absorb moisture, poor in hydrophobicity, thermal property and mechanical property due to the introduction of hydrophilic groups in the preparation process. Therefore, modification treatment must be performed to use the polyaspartate polyurea for the preparation of anticorrosive coatings.
The graphene oxide has excellent performances such as unique two-dimensional structure, ultrahigh strength, excellent electric and thermal conductivity and the like, and can greatly improve the antistatic property and the corrosion resistance of the coating. However, if graphene oxide is directly added to the polyurea coating prepared from the polyaspartic acid resin obtained by the method, the polyaspartic acid ester is only directly coated on the surface of the graphene oxide, so that the dispersibility and the compatibility are poor, flocculation is easy to occur, and the corrosion resistance of the coating is directly influenced.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing the polyaspartic acid ester resin which has strong stability, is not easy to flocculate and has excellent corrosion resistance.
The invention further aims to solve the technical problem of overcoming the defects in the prior art and provide a preparation method of polyaspartic ester resin, which has simple process flow and low cost and is suitable for industrial production.
The invention further aims to solve the technical problem of overcoming the defects in the prior art and provide the anticorrosive coating with good dispersibility, compatibility and stability, and strong mechanical property, ageing resistance and corrosion resistance of a coating.
The invention further aims to solve the technical problem of overcoming the defects in the prior art and provide a preparation method of the anticorrosive paint, which has simple process flow and low cost and is suitable for industrial production.
The technical scheme adopted by the invention for solving the technical problems is as follows: a polyaspartic acid ester resin is mainly prepared from the following raw materials in parts by weight: 2-5 parts (preferably 2.5-4.0 parts) of aminosilane modified graphene oxide, 10-30 parts (preferably 12-22 parts) of primary diamine, 0.1-0.3 part of alkaline catalyst and 25-45 parts of maleic acid ester. If the dosage of the aminosilane-modified graphene oxide is too large, the grafting reaction is affected, and if the dosage of the aminosilane-modified graphene oxide is too small, the corrosion resistance of the acid ester resin is affected.
Preferably, the preparation method of the aminosilane-modified graphene oxide comprises the following steps: adding graphene oxide into an alcohol aqueous solution, heating, fully stirring, adding an amino silane coupling agent alcohol solution, heating, preserving heat, refluxing, cooling to normal temperature, standing, performing centrifugal separation, taking a precipitate, washing, and drying to obtain the graphene oxide nano-particles. And reacting ethoxy on the aminosilane coupling agent with hydroxyl on the surface of the graphene oxide to obtain the aminosilane modified graphene oxide. The alcohol in the alcohol aqueous solution or the amino silane coupling agent alcohol solution is one or more of methanol, ethanol or propanol.
Preferably, the mass ratio of the graphene oxide to the alcohol aqueous solution is 1: 100-450 (more preferably 1: 200-400). In the proportion, the hydroxylation of the graphene oxide is promoted more favorably.
Preferably, the mass ratio of the alcohol to the water in the alcohol aqueous solution is 1: 10-30 (more preferably 1: 15-26).
Preferably, after the graphene oxide is added, the temperature is raised to 50-70 ℃, and the stirring time is 20-40 min. In the proportion, the hydroxylation of the graphene oxide is promoted more favorably.
Preferably, in the amino silane coupling agent alcoholic solution, the mass ratio of the amino silane coupling agent to the alcohol is 1: 80-120 (more preferably 1: 85-110). At the ratio, the dissolving of the aminosilane coupling agent in the alcohol solution is more favorably promoted.
Preferably, the mass ratio of the aminosilane coupling agent to the graphene oxide is 3-30: 1 (more preferably 5-15: 1). And (3) adding excessive aminosilane coupling agent to promote chemical modification reaction of the aminosilane coupling agent on the graphene oxide.
Preferably, after the amino silane coupling agent alcohol solution is added, the temperature is raised to 75-85 ℃, and the time of heat preservation and reflux is 10-15 h. Under the temperature and time, the chemical modification effect of the amino silane coupling agent on the graphene oxide is facilitated.
Preferably, the washing mode is that after the washing with ethanol is more than or equal to 1 time, the washing with acetone is more than or equal to 2 times.
Preferably, the drying temperature is 50-70 ℃, and the drying time is 8-12 h. More preferably, the drying mode is vacuum drying.
Preferably, the aminosilane coupling agent is KH550 and/or KH 602.
Preferably, the graphene oxide is multilayer graphene oxide powder produced by Nanjing Xiapong nanomaterial Co.
Preferably, the primary diamine is one or more of 1, 6-hexanediamine, 4-diaminocyclohexylmethane or 3, 3-dimethyl-4, 4-diaminocyclohexylmethane.
Preferably, the basic catalyst is proline or sodium ethoxide, etc. The proline is preferably L-proline.
Preferably, the maleic acid ester is one or more of diethyl maleate, dipropyl maleate or dibutyl maleate.
The technical scheme adopted for further solving the technical problems is as follows: a preparation method of polyaspartic acid ester resin comprises the steps of mixing and stirring aminosilane modified graphene oxide, primary diamine and an alkaline catalyst, heating, dropwise adding maleic acid ester, continuously heating and keeping the temperature for reaction, stopping heating, and cooling to normal temperature. And reacting the aminosilane modified graphene oxide, primary diamine and maleic acid ester under the action of a catalyst to obtain the graphene oxide modified polyaspartic acid ester resin. The aminosilane modified graphene oxide is grafted to the resin through a grafting reaction, so that the dispersion performance of the graphene oxide in the coating is greatly improved, the stability of Si-O bonds is good, the hardness, the wear resistance and the weather resistance of the coating can be improved, and the graphene oxide is favorable for improving the antistatic and anticorrosive performances of a coating film, so that the corrosion resistance of the coating is improved.
Preferably, the maleic acid ester is added dropwise within 25-35 min. The crystallization of the ester monomer is prevented by controlling the dropping rate.
Preferably, the temperature is raised to 55-65 ℃ before the maleic ester is dripped, and the temperature is raised to 95-105 ℃ after the maleic ester is dripped. Before the maleic acid ester is dropwise added, diamine is fully dissolved at low temperature, and after the maleic acid ester is dropwise added, the temperature is raised to the reaction temperature for Michael addition reaction.
Preferably, the heat preservation reaction time is 8-12 h, and the heat preservation reaction is carried out until the primary amine conversion rate is more than or equal to 95%. Conversion was calculated by measuring the amine number.
The technical scheme adopted by the invention for further solving the technical problems is as follows: an anticorrosive coating is prepared by mixing a component A and a component B according to the mass ratio of 1: 1.5-3.5 (more preferably 1: 2-3); the component A comprises aliphatic isocyanate and an elastic curing agent; the component B comprises the polyaspartic acid ester resin, an anti-settling agent, a pigment, a filler, a molecular sieve, a defoaming agent, a leveling agent, a dispersing agent, hydroxyl acrylic resin and an organic solvent. The anticorrosive paint of the present invention is a two-component paint, and A, B components react after being mixed at room temperature to form a film after curing, so that the anticorrosive paint must be stored separately during storage and mixed during use. The component A is a component containing-NCO groups, the component B is a component containing-NH and-OH groups, at room temperature, the-NCO groups react with the-NH and-OH groups to generate polyurea or polyurethane, and the polyurea or polyurethane is cured to form a film. A. After the component B is mixed, in the component B, because the aminosilane modified graphene oxide is grafted on the polyaspartic acid ester resin, the chain extension effect is realized, and the special steric hindrance effect is formed, so that the reactivity of the secondary amino group is reduced, and the construction time of the coating is prolonged; meanwhile, in the component B, in the aminosilane modified graphene oxide of the polyaspartic acid ester resin, the crosslinking density of the coating is improved when the hydroxyl on the aminosilane coupling agent and the isocyanate of the component A are subjected to curing reaction, so that the mechanical property and the chemical resistance of the coating are improved. The graphene oxide serving as an excellent anticorrosive material is easy to flocculate and poor in dispersity and compatibility in a mixed system if directly added into a coating, and the aminosilane modified graphene oxide is grafted onto the polyaspartic acid ester resin by a chemical grafting method, so that the defects are overcome, and the advantages of the graphene oxide can be well played.
Preferably, in the component A, the weight parts of the raw materials are as follows: 10-30 parts of aliphatic isocyanate and 10-30 parts of elastic curing agent. The aliphatic isocyanate and the elastic curing agent both provide-NCO groups to participate in the reaction, wherein the aliphatic isocyanate has better hardness, and the elastic curing agent has better flexibility and elasticity.
Preferably, in the component B, the weight parts of the raw materials are as follows: 30-50 parts (preferably 38-48 parts) of polyaspartic acid ester resin, 0.2-0.8 part of anti-settling agent, 25-35 parts of pigment, 5-15 parts of filler, 2-10 parts of molecular sieve, 0.2-0.8 part of defoaming agent, 0.2-0.8 part of flatting agent, 0.2-0.8 part of dispersing agent, 5-20 parts of hydroxy acrylic resin and 3-10 parts of organic solvent.
Preferably, in the component A, the aliphatic isocyanate is one or more of polymethylene polyphenyl diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate. More preferably, the aliphatic isocyanate is hexamethylene diisocyanate trimer or hexamethylene diisocyanate biuret. Still more preferably, the aliphatic isocyanate is an aliphatic isocyanate N-3390 or N-75 curing agent manufactured by Bayer, Germany.
Preferably, in the component A, the elastic curing agent is GB905-85 curing agent and/or GB805A-100 curing agent produced by the Zhuhai Feiyang chemical industry.
Preferably, in the component B, the anti-settling agent is one or more of fumed silica, polyethylene wax or organic bentonite anti-settling agents and the like. More preferably, the anti-settling agent is fumed silica R975 white carbon black.
Preferably, in the component B, the pigment is one or more of titanium dioxide, iron yellow or iron red and the like. More preferably, the titanium dioxide is rutile type titanium dioxide. More preferably, the titanium dioxide is R930 rutile type titanium dioxide produced by Mitsubishi corporation of Japan.
Preferably, in the component B, the filler is one or more of sericite, calcium carbonate, kaolin, aluminum tripolyphosphate and the like. More preferably, the filler is sericite produced by Asahi mineral products.
Preferably, in the component B, the molecular sieve is a 3A molecular sieve. More preferably, the molecular sieve is a 3A molecular sieve produced by molecular sieves in shanghai brocade.
Preferably, in the component B, the defoaming agent is one or more of mineral oil, polyorganosiloxane, organosilicon or polyether defoaming agent and the like. More preferably, the defoamer is a BYK306 silicone defoamer from the germany BYK company and/or a polyorganosiloxane defoamer from the netherlands EFKA 2038.
Preferably, in the component B, the leveling agent is one or more of an organic silicon type leveling agent, an acrylate type leveling agent or a fluorocarbon polymer type leveling agent. More preferably, the leveling agent is a fluorocarbon polymer type EFKA3600 leveling agent of Dutch EFKA company and/or an organic silicon type BYK300 leveling agent of Germany BYK company.
Preferably, in the component B, the dispersant is one or more of polyurethane acrylic, polycarboxylate or active polymer dispersants. More preferably, the dispersant is a German BYK163 polyurethane acrylic dispersant and/or a Netherlands EFKA4010 reactive polymeric dispersant.
Preferably, in the component B, the hydroxy acrylic resin is SM515 hydroxy acrylic resin produced by Cyanorthe corporation.
Preferably, in the component B, the organic solvent is one or more of butyl acetate, xylene or high-boiling point mixed ester. More preferably, the high-boiling mixed ester is methyl nylon carboxylate, and still more preferably, the methyl nylon carboxylate is DBE methyl nylon carboxylate produced by dupont, usa.
The invention further solves the technical problems by adopting the following technical scheme: a preparation method of an anticorrosive paint comprises the following steps:
(1) preparation of component A: stirring and dispersing aliphatic isocyanate and an elastic curing agent to obtain a component A;
(2) preparation of the component B: mixing, stirring and dispersing the polyaspartic ester resin and the anti-settling agent until the solution is transparent, adding the pigment, the filler, the molecular sieve, the defoaming agent, the leveling agent and the dispersing agent, stirring and dispersing, grinding, then adding the hydroxyl acrylic resin and the organic solvent, stirring and dispersing to obtain a component B;
(3) preparing an anticorrosive coating: when the adhesive is used, the component A obtained in the step (1) and the component B obtained in the step (2) are mixed according to the mass ratio of 1: 1.5-3.0, and the mixture is uniformly stirred, so that the adhesive is obtained.
Preferably, in the step (1), the stirring and dispersing speed is 400-600 r/min, and the time is 15-25 min.
Preferably, in the step (2), the mixing, stirring and dispersing speed of the polyaspartic acid ester resin and the anti-settling agent is 600-800 r/min, and the time is 25-35 min.
Preferably, in the step (2), after the pigment, the filler, the molecular sieve, the defoaming agent, the leveling agent and the dispersing agent are added, stirring and dispersing are carried out at a speed of 600-800 r/min for 50-70 min.
Preferably, in step (2), the fineness after grinding is less than or equal to 30 μm.
Preferably, in the step (2), after the hydroxy acrylic resin and the organic solvent are added, the stirring and dispersing speed is 400-600 r/min, and the time is 50-70 min.
The invention has the following beneficial effects:
(1) according to the polyaspartic acid ester resin, the graphene oxide is directly grafted on the polyaspartic acid ester resin, so that the problem that the graphene oxide is difficult to disperse in a coating and is easy to flocculate is solved, the dispersibility of the graphene oxide in the coating is improved, the storage stability of the coating is ensured, the resin is centrifuged at a high speed of 4000r/min for 30min, no black precipitate is separated out, and the anti-corrosion performance of the coating is improved;
(2) the anticorrosive coating has the solid content of more than 85 percent, can be directly sprayed, can form a film of 200-300 mu m once, has high coating film elasticity, good impact resistance, good salt mist resistance and aging resistance, and is particularly used for the surface of steel and iron to have good anticorrosive performance;
(3) the method has simple process flow and low cost, and is suitable for industrial production.
Detailed Description
The present invention will be further described with reference to the following examples.
The names, specifications/models and manufacturers of the chemical reagents used in the examples of the present invention are as follows.
The chemical reagents used in the examples of the present invention, unless otherwise specified, are commercially available in a conventional manner.
Preparation method of aminosilane-modified graphene oxide reference example 1
Adding 1.5 parts by weight of graphene oxide into 500 parts by weight of ethanol aqueous solution (30 parts by weight of deionized water and 470 parts by weight of absolute ethanol are mixed), heating to 60 ℃, fully stirring for 30min, adding 1300 parts by weight of aminosilane coupling agent ethanol solution (14 parts by weight of aminosilane coupling agent KH550 are dispersed in 1286 parts by weight of absolute ethanol), heating to 78 ℃, carrying out heat preservation and reflux for 12h, cooling to normal temperature, standing, carrying out centrifugal separation, taking precipitate, washing 1 time by using absolute ethanol, washing 2 times by using acetone, and finally carrying out vacuum drying for 10h at 50 ℃ to obtain the product.
Preparation method of aminosilane-modified graphene oxide reference example 2
Adding 1.5 parts by weight of graphene oxide into 600 parts by weight of methanol aqueous solution (30 parts by weight of deionized water and 570 parts by weight of anhydrous methanol are mixed), heating to 70 ℃, fully stirring for 20min, adding 1600 parts by weight of aminosilane coupling agent methanol solution (15 parts by weight of aminosilane coupling agent KH550 are dispersed in 1585 parts by weight of anhydrous methanol), heating to 75 ℃, carrying out heat preservation and reflux for 10h, cooling to normal temperature, standing, carrying out centrifugal separation, taking precipitate, washing with anhydrous ethanol for 2 times, washing with acetone for 3 times, and finally carrying out vacuum drying for 10h at 55 ℃ to obtain the graphene oxide.
Preparation method of aminosilane-modified graphene oxide reference example 3
Adding 1.4 parts by weight of graphene oxide into 400 parts by weight of ethanol aqueous solution (15 parts by weight of deionized water and 385 parts by weight of absolute ethanol are mixed), heating to 50 ℃, fully stirring for 40min, adding 1400 parts by weight of aminosilane coupling agent ethanol solution (16 parts by weight of aminosilane coupling agent KH602 are dispersed in 1384 parts by weight of absolute ethanol), heating to 82 ℃, carrying out heat preservation and reflux for 14h, cooling to normal temperature, standing, carrying out centrifugal separation, taking precipitate, washing 1 time by using absolute ethanol, washing 2 times by using acetone, and finally carrying out vacuum drying for 8h at 60 ℃ to obtain the product.
Examples 1 to 3 of polyaspartic acid ester resin
The components and the proportions of the raw materials of the polyaspartic acid ester resin in the embodiments 1-3 are shown in Table 1:
TABLE 1 polyaspartic acid ester resin examples 1-3 raw material components and compounding ratio Table
Note: in the table, "-" indicates no addition.
Preparation of polyaspartic acid ester resin method example 1
According to the raw material components and the proportion in the example 1 in the table 1, aminosilane modified graphene oxide, primary diamine and a basic catalyst are mixed and stirred, maleic ester is dropwise added after the temperature is raised to 60 ℃, the temperature is continuously raised to 100 ℃ after the dropwise addition is finished for 30min, the reaction is kept for 11h, the amine value conversion rate is measured to be 97.00% by adopting a JIS K7327 method, the heating is stopped, and the reaction is cooled to the normal temperature, so that the polyaspartic ester resin 1 is obtained.
Through detection, the polyaspartic acid ester resin 1 is centrifuged at a high speed of 4000r/min for 30min, and no black precipitate is separated out.
Preparation of polyaspartic acid ester resin method example 2
According to the raw material components and the proportion in the example 2 in the table 1, aminosilane modified graphene oxide, primary diamine and an alkaline catalyst are mixed and stirred, maleic ester is dropwise added after the temperature is raised to 65 ℃, the temperature is continuously raised to 105 ℃ after 25min of dropwise addition is finished, the temperature is kept for reaction for 13h, the amine value conversion rate is measured to be 96.73% by adopting a JIS K7327 method, heating is stopped, and the mixture is cooled to the normal temperature, so that the polyaspartic ester resin 2 is obtained.
Through detection, the obtained polyaspartic ester resin 2 is centrifuged at a high speed of 4000r/min for 30min, and no black precipitate is separated out.
Preparation of polyaspartic acid ester resin method example 3
According to the raw material components and the proportion in the example 3 in the table 1, aminosilane modified graphene oxide, primary diamine and a basic catalyst are mixed and stirred, maleic ester is dropwise added after the temperature is raised to 55 ℃, the temperature is continuously raised to 95 ℃ after the dropwise addition is finished for 35min, the reaction is kept for 12 hours, the amine value conversion rate is measured to be 97.73% by adopting a JIS K7327 method, the heating is stopped, and the reaction is cooled to the normal temperature, so that the polyaspartic ester resin 3 is obtained.
Through detection, the polyaspartic acid ester resin 3 is centrifuged at a high speed of 4000r/min for 30min, and no black precipitate is separated out.
Preparation method of polyaspartic acid ester resin comparative example 1
According to the raw material components and the proportion in the table 1 and the comparative example 1, the primary diamine and the alkaline catalyst are mixed and stirred, after the temperature is raised to 60 ℃, the maleic acid ester is dripped, after the dripping is finished for 30min, the temperature is continuously raised to 100 ℃, the heat preservation reaction is carried out for 11h, the amine value conversion rate is measured to be 96.8 percent by adopting the method of JISK7327, the heating is stopped, and the mixture is cooled to the normal temperature, thus obtaining the polyaspartic acid ester resin 4.
Examples 1 to 3 of anticorrosive coating
The raw material components and the mixture ratio of the anticorrosive paint in the embodiment 1-3 are shown in the following table 2:
table 2 raw material components and proportioning table of anticorrosive paint examples 1-3
Note: in the table, "-" indicates no addition.
Preparation of anticorrosive coatings example 1
(1) Preparation of component A: according to the raw material components and the proportion in the example 1 in the table 2, adding aliphatic isocyanate and an elastic curing agent into a size mixing tank, stirring and dispersing for 20min by a high-speed dispersion machine at the stirring speed of 500r/min, and immediately sealing and packaging to obtain a component A;
(2) preparation of the component B: according to the raw material components and the proportion in the example 1 in the table 2, the polyaspartic acid ester resin 1 and the anti-settling agent are added into a dispersion tank, the mixture is stirred and dispersed for 30min by a high-speed dispersion machine at the stirring speed of 700r/min until the solution is transparent, then the pigment, the filler, the molecular sieve, the antifoaming agent, the leveling agent and the dispersing agent are added into the dispersion tank, the mixture is stirred and dispersed for 60min by the high-speed dispersion machine at the stirring speed of 700r/min, the material in the dispersion tank is ground by a sand mill until the fineness is less than or equal to 30 mu m, then the hydroxyl acrylic resin and the organic solvent are added, and the mixture is stirred and dispersed for 60min by the high-speed dispersion machine at the stirring speed of 500r/min to obtain a component B;
(3) preparing an anticorrosive coating: when in use, the component A obtained in the step (1) and the component B obtained in the step (2) are mixed according to the mass ratio of 1:3, and the mixture is stirred uniformly to obtain the high-performance anti-static anti.
Preparation method of anticorrosive paint example 2
(1) Preparation of component A: according to the raw material components and the proportion in the example 2 in the table 2, adding aliphatic isocyanate and an elastic curing agent into a size mixing tank, stirring and dispersing for 25min by a high-speed dispersion machine at the stirring speed of 400r/min, and immediately sealing and packaging to obtain a component A;
(2) preparation of the component B: according to the raw material components and the proportion in the example 2 in the table 2, the polyaspartic acid ester resin 2 and the anti-settling agent are added into a dispersion tank, the mixture is stirred and dispersed for 25min by a high-speed dispersion machine at the stirring speed of 800r/min until the solution is transparent, then the pigment, the filler, the molecular sieve, the antifoaming agent, the leveling agent and the dispersing agent are added into the dispersion tank, the mixture is stirred and dispersed for 50min by the high-speed dispersion machine at the stirring speed of 800r/min, the material in the dispersion tank is ground by a sand mill until the fineness is less than or equal to 25 mu m, then the hydroxyl acrylic resin and the organic solvent are added, and the mixture is stirred and dispersed for 50min by the high-speed dispersion machine at the stirring speed of 600r/min to obtain a component B;
(3) preparing an anticorrosive coating: and (3) mixing the component A obtained in the step (1) and the component B obtained in the step (2) according to the mass ratio of 1:2.75, and uniformly stirring to obtain the adhesive.
Preparation of anticorrosive coatings example 3
(1) Preparation of component A: according to the raw material components and the proportion in the example 3 in the table 2, adding aliphatic isocyanate and an elastic curing agent into a size mixing tank, stirring and dispersing for 15min by a high-speed dispersion machine at the stirring speed of 600r/min, and immediately sealing and packaging to obtain a component A;
(2) preparation of the component B: according to the raw material components and the proportion in the example 3 in the table 2, the polyaspartic acid ester resin 3 and the anti-settling agent are added into a dispersion tank, the mixture is stirred and dispersed for 35min by a high-speed dispersion machine at the stirring speed of 600r/min until the solution is transparent, then the pigment, the filler, the molecular sieve, the antifoaming agent, the leveling agent and the dispersing agent are added into the dispersion tank, the mixture is stirred and dispersed for 70min by the high-speed dispersion machine at the stirring speed of 600r/min, the material in the dispersion tank is ground by a sand mill until the fineness is less than or equal to 30 mu m, then the hydroxyl acrylic resin and the organic solvent are added, and the mixture is stirred and dispersed for 70min by the high-speed dispersion machine at the stirring speed of 400r/min to obtain a component;
(3) preparing an anticorrosive coating: when in use, the component A obtained in the step (1) and the component B obtained in the step (2) are mixed according to the mass ratio of 1:2.5, and are stirred uniformly to obtain the high-performance anti-static.
Comparative example 1
(1) Preparation of component A: according to the raw material components and the proportion in the comparative example 1 in the table 2, adding aliphatic isocyanate and an elastic curing agent into a size mixing tank, stirring and dispersing for 20min by a high-speed dispersion machine at a stirring speed of 500r/min, and immediately sealing and packaging to obtain a component A;
(2) preparation of the component B: according to the raw material components and the proportion in the comparative example 1 in the table 2, the polyaspartic acid ester resin 4, the graphene oxide and the anti-settling agent are added into a dispersion tank, the mixture is stirred and dispersed for 30min by a high-speed dispersion machine at the stirring speed of 700r/min until the solution is transparent, then the pigment, the filler, the molecular sieve, the defoaming agent, the flatting agent and the dispersing agent are added into the dispersion tank, the mixture is stirred and dispersed for 60min by the high-speed dispersion machine at the stirring speed of 700r/min, the material in the dispersion tank is ground to the fineness of less than or equal to 30 mu m by a sand mill, then the hydroxyl acrylic resin and the organic solvent are added, and the mixture is stirred and dispersed for 60min by the high-speed dispersion machine at the stirring speed of 500r/min to;
(3) preparing an anticorrosive coating: when in use, the component A obtained in the step (1) and the component B obtained in the step (2) are mixed according to the mass ratio of 1:3, and the mixture is stirred uniformly to obtain the high-performance anti-static anti.
Through detection, the solid contents of the anticorrosive coatings of examples 1-3 and comparative example 1 are 86.5%, 89.10%, 85.80% and 87.10% in sequence.
Adopting air spraying, spraying the anticorrosive coatings of examples 1-3 and comparative example 1 on the pretreated steel plate, drying for 7 days at room temperature, and detecting according to national standard: adhesion (cross-hatch method, 2mm, GB/T9286-1998), pencil hardness (scratch, GB/T6739-2006), impact resistance (positive impact, recoil, GB/T20624.2-2006), abrasion resistance (750 g, 500r, GB/T1768-2006), aging resistance (QUV-340, 1000h, GB/T1865-2009), salt spray resistance (1000 h, GB/T1771-2007), moisture-resistant cold-heat cycles (5 times, GB/T0004-2012), and the test results are shown in Table 3.
TABLE 3 comparison table of the performance test results of the anticorrosive coatings of examples 1-3 and comparative example 1
As shown in Table 3, comparing examples 1 to 3 with comparative example 1, examples 1 to 3 are superior to comparative example 1 in salt spray resistance and humidity-resistant cold and heat cycle resistance, and the coating film has more excellent corrosion resistance, and the component B of the coating in examples 1 to 3 has better storage stability and does not flocculate after long-term storage.
Claims (11)
1. The polyaspartic acid ester resin is characterized by being mainly prepared from the following raw materials in parts by weight: 2-5 parts of aminosilane modified graphene oxide, 10-30 parts of primary diamine, 0.1-0.3 part of alkaline catalyst and 25-45 parts of maleic acid ester;
the primary diamine is 1, 6-hexanediamine or 4,4，Diaminocyclohexylmethane or 3,3，-dimethyl-4, 4，-one or more of diaminocyclohexylmethane.
2. The polyaspartate resin of claim 1, wherein: the preparation method of the aminosilane modified graphene oxide comprises the following steps: adding graphene oxide into an alcohol aqueous solution, heating, fully stirring, adding an amino silane coupling agent alcohol solution, heating, preserving heat, refluxing, cooling to normal temperature, standing, performing centrifugal separation, taking a precipitate, washing, and drying to obtain the graphene oxide nano-particles.
3. The polyaspartate resin of claim 2, wherein: the mass ratio of the graphene oxide to the alcohol-water solution is 1: 100-450; the mass ratio of alcohol to water in the alcohol-water solution is 1: 10-30; after adding graphene oxide, heating to 50-70 ℃, wherein the stirring time is 20-40 min; in the amino silane coupling agent alcoholic solution, the mass ratio of the amino silane coupling agent to the alcohol is 1: 80-120; the mass ratio of the aminosilane coupling agent to the graphene oxide is 3-30: 1; adding an amino silane coupling agent alcohol solution, heating to 75-85 ℃, and keeping the temperature for refluxing for 10-15 h; the washing mode is that after the washing with ethanol is more than or equal to 1 time, the washing with acetone is more than or equal to 2 times; the drying temperature is 50-70 ℃, and the drying time is 8-12 h.
4. A polyaspartic acid ester resin according to any one of claims 1 to 3, wherein: the alkaline catalyst is proline or sodium ethoxide; the maleic acid ester is one or more of diethyl maleate, dipropyl maleate or dibutyl maleate.
5. A method for producing a polyaspartic acid ester resin according to any one of claims 1 to 4, comprising: and mixing and stirring the aminosilane modified graphene oxide, the primary diamine and the alkaline catalyst, heating, dropwise adding maleic acid ester, continuously heating, keeping the temperature for reaction, stopping heating, and cooling to the normal temperature to obtain the catalyst.
6. The method for producing a polyaspartic acid ester resin according to claim 5, wherein: the maleic acid ester is dropwise added within 25-35 min; heating to 55-65 ℃ before dripping the maleic ester, and heating to 95-105 ℃ after dripping the maleic ester; the time of the heat preservation reaction is 8-12 h, and the heat preservation reaction is carried out until the conversion rate of primary amine is more than or equal to 95%.
7. An anticorrosive paint is characterized in that: the adhesive is prepared by mixing a component A and a component B according to the mass ratio of 1: 1.5-3.5; the component A comprises aliphatic isocyanate and an elastic curing agent; the component B comprises the polyaspartic ester resin as described in any one of claims 1 to 4, an anti-settling agent, a pigment, a filler, a molecular sieve, a defoaming agent, a leveling agent, a dispersing agent, a hydroxy acrylic resin and an organic solvent.
8. The anticorrosive paint according to claim 7, characterized in that: in the component A, the weight parts of the raw materials are as follows: 10-30 parts of aliphatic isocyanate and 10-30 parts of an elastic curing agent; in the component B, the weight parts of the raw materials are as follows: 30 to 50 parts of polyaspartic acid ester resin, 0.2 to 0.8 part of anti-settling agent, 25 to 35 parts of pigment, 5 to 15 parts of filler, 2 to 10 parts of molecular sieve, 0.2 to 0.8 part of defoaming agent, 0.2 to 0.8 part of leveling agent, 0.2 to 0.8 part of dispersing agent, 5 to 20 parts of hydroxy acrylic resin and 3 to 10 parts of organic solvent according to claims 1 to 4; in the component A, the aliphatic isocyanate is one or more of polymethylene polyphenyl diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate; in the component B, the anti-settling agent is one or more of fumed silica, polyethylene wax or organic bentonite anti-settling agents; the pigment is one or more of titanium dioxide, iron oxide yellow or iron oxide red, and the titanium dioxide is rutile type titanium dioxide; the filler is one or more of sericite, calcium carbonate, kaolin or aluminum tripolyphosphate; the molecular sieve is a 3A molecular sieve; the defoaming agent is one or more of mineral oil, organic silicon or polyether defoaming agent; the flatting agent is one or more of organic silicon type, acrylate type or fluorocarbon polymer type flatting agents; the dispersant is one or more of polyurethane acrylic acid, polycarboxylate or active polymer dispersant; the organic solvent is one or more of butyl acetate, dimethylbenzene or high-boiling-point mixed ester.
9. The anticorrosive paint according to claim 8, characterized in that: the silicone is a polyorganosiloxane.
10. A method for preparing the anticorrosive paint according to claim 7 or 8, characterized by comprising the steps of:
(1) preparation of component A: stirring and dispersing aliphatic isocyanate and an elastic curing agent to obtain a component A;
(2) preparation of the component B: mixing, stirring and dispersing the polyaspartic ester resin and the anti-settling agent according to any one of claims 1 to 4 until the solution is transparent, adding the pigment, the filler, the molecular sieve, the defoaming agent, the leveling agent and the dispersing agent, stirring and dispersing, grinding, then adding the hydroxyl acrylic resin and the organic solvent, and stirring and dispersing to obtain a component B;
(3) preparing an anticorrosive coating: when the adhesive is used, the component A obtained in the step (1) and the component B obtained in the step (2) are mixed according to the mass ratio of 1: 1.5-3.0, and the mixture is uniformly stirred, so that the adhesive is obtained.
11. The method for preparing the anticorrosive paint according to claim 10, characterized in that: in the step (1), the stirring and dispersing speed is 400-600 r/min, and the time is 15-25 min; in the step (2), the mixing, stirring and dispersing speed of the polyaspartic acid ester resin and the anti-settling agent is 600-800 r/min, and the time is 25-35 min; in the step (2), after the pigment, the filler, the molecular sieve, the defoaming agent, the leveling agent and the dispersing agent are added, stirring and dispersing are carried out at the speed of 600-800 r/min for 50-70 min; in the step (2), the fineness after grinding is less than or equal to 30 mu m; in the step (2), after the hydroxyl acrylic resin and the organic solvent are added, stirring and dispersing are carried out at a speed of 400-600 r/min for 50-70 min.
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