阅读说明：本技术 一种底面合一型无溶剂聚天门冬氨酸酯重防腐涂料、制备方法及其应用 (Bottom-surface integrated solvent-free polyaspartic acid ester heavy-duty anticorrosive paint, and preparation method and application thereof ) 是由 冯刚 于 2021-08-25 设计创作，主要内容包括：本发明提供了一种底面合一型无溶剂聚天门冬氨酸酯重防腐涂料、制备方法及其应用。所述底面合一型无溶剂聚天门冬氨酸酯重防腐涂料包含A和B组份,按重量份数,所述A组分包含：超支化改性天门冬氨酸树脂20-40、天冬氨酸树脂10-30、磷酸锌5.2、助剂0.1-15、改性填料1-30,所述B组分包含：异氰酸酯70-80、二异氰酸酯预聚物20-30、消泡剂3-5、流平剂2-3。所述A和B组分的体积比是1：1,可用于石油化工领域储罐、管道和设备内外壁防腐以及钢结构防腐的涂料。本发明通过对天门冬氨酸树脂进行特定的超支化改性,使其具有更多的温和的反应活性点,极大改善涂料的耐温性、耐磨性、耐腐蚀性和耐候性；填料更好的参与固化反应,最终使涂料各项性能指标更为优异,综合性能好。(The invention provides a primer-topcoat integrated solvent-free polyaspartic acid ester heavy-duty anticorrosive paint, and a preparation method and application thereof. The bottom-surface integrated solvent-free polyaspartic acid ester heavy-duty anticorrosive paint comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 20-40 parts of hyperbranched modified aspartic acid resin, 10-30 parts of aspartic acid resin, 5.2 parts of zinc phosphate, 0.1-15 parts of auxiliary agent and 1-30 parts of modified filler, wherein the component B comprises: 70-80 parts of isocyanate, 20-30 parts of diisocyanate prepolymer, 3-5 parts of defoaming agent and 2-3 parts of leveling agent. The volume ratio of the A component to the B component is 1:1, can be used for the anticorrosion of the inner and outer walls of storage tanks, pipelines and equipment in the field of petrochemical industry and the anticorrosion of steel structures. According to the invention, specific hyperbranched modification is carried out on the aspartic acid resin, so that the aspartic acid resin has more mild reaction active points, and the temperature resistance, wear resistance, corrosion resistance and weather resistance of the coating are greatly improved; the filler can better participate in the curing reaction, so that various performance indexes of the coating are more excellent and the comprehensive performance is good.)

1. The bottom-surface integrated solvent-free polyaspartic acid ester heavy-duty anticorrosive paint comprises a component A and a component B, and is characterized in that the component A comprises the following components in parts by weight:

the component B comprises:

。

2. the primer-topcoat solvent-free polyaspartic acid ester heavy-duty anticorrosive coating as claimed in claim 1, wherein the modified filler is one or a combination of barium sulfate, titanium dioxide, calcium carbonate and white carbon black; the isocyanate is one or the combination of more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and HDI tripolymer; the diisocyanate prepolymer is one of HDI trimer, TDI trimer and IPDI trimer.

3. The primer-topcoat solvent-free polyaspartate heavy-duty coating as claimed in claim 1, wherein the auxiliary agent comprises one or a combination of a dispersant, a defoamer, an anti-settling agent, a water scavenger, a leveling agent and a silane coupling agent.

4. The primer-topcoat solvent-free polyaspartate heavy-duty anticorrosive coating as claimed in claim 1, wherein the preparation method of the modified filler comprises the following steps: (1) dissolving a silane coupling agent in absolute ethyl alcohol to prepare a solution with the mass concentration of 30-50%; (2) and spraying the solution on the filler in a high-speed stirrer, uniformly stirring at a high speed, drying for 2-5h at the temperature of 105 ℃ in a forced air drying box, and naturally cooling to obtain the modified filler.

5. The primer-topcoat solvent-free polyaspartate heavy-duty coating as claimed in claim 3 or 4, wherein the silane coupling agent is one or a combination of γ -aminopropyltrimethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane, N- β - (aminoethyl) - γ -aminopropyltriethoxysilane, and phenylaminomethyltrimethoxysilane.

6. The primer-topcoat solvent-free polyaspartic acid ester heavy-duty anticorrosive paint of claim 1, wherein the preparation method of the hyperbranched modified aspartic acid resin comprises the following steps: (1) adding a trichlorosilane ethanol solution with the mass concentration of 10-30% into a reaction kettle protected by inert gas, dropwise adding deionized water under the stirring state, wherein the molar ratio of the deionized water to the trichlorosilane is 1:3, reacting for 0.5-1 hour at the temperature of 75-85 ℃, adding diisocyanate, and continuously reacting for 0.5-1 hour to obtain a pre-reaction solution; (2) controlling the temperature of the reaction kettle within the range of 15-20 ℃ by water cooling, and dropwise adding aliphatic primary diamine terminated end into the pre-reaction liquid under a stirring state to obtain silicon block branched modified organic diamine reaction liquid; (3) and slowly dropwise adding dialkyl maleate into the silicon block branched modified organic diamine reaction liquid by using a titration funnel, after dropwise adding, heating to 90-100 ℃, reacting at a constant temperature for 10-15h, and then removing and recovering the solvent to finally obtain the hyperbranched modified aspartic acid resin.

7. The primer-topcoat-type solvent-free polyaspartic acid ester heavy-duty anticorrosive paint of claim 4, wherein the degree of reaction of the hyperbranched modified aspartic acid resin is determined by a thiol-iodine titration analysis method.

8. The primer-topcoat solvent-free polyaspartate heavy-duty coating of claim 4, wherein the diisocyanate is one or a combination of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, and xylylene diisocyanate; the aliphatic primary diamine is one or a combination of hexamethylene diamine, butanediamine, hexamethylene diamine, 2, 4-trimethyl-1, 6-butanediamine, 4' -diaminodicyclohexyl methane and 3, 3-dimethyl-4, 4-diaminodicyclohexyl methane; the dialkyl maleate is one or more of dimethyl maleate, diethyl maleate, diisobutyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate and dibutyl fumarate.

9. The method for preparing a primer-topcoat type solvent-free polyaspartate heavy-duty paint according to any one of claims 1 to 8, comprising the steps of: (1) weighing hyperbranched modified aspartic acid resin, zinc phosphate, modified filler and an auxiliary agent according to the parts by weight to obtain a mixed material; (2) the mixed materials are put in a high-speed stirrer, the temperature is controlled to be 40-50 ℃, the rotating speed is 2500-; (2) weighing the materials of isocyanate, diisocyanate prepolymer, defoaming agent and flatting agent according to the weight proportion, and uniformly mixing to obtain the component B.

10. The primer-topcoat solvent-free polyaspartate heavy duty coating of any one of claims 1-8, wherein the volume ratio of the A and B components is 1:1, can be used for the anticorrosion of the inner and outer walls of storage tanks, pipelines and equipment in the field of petrochemical industry and the anticorrosion of steel structures.

Technical Field

The invention relates to a paint technology for corrosion prevention of inner and outer walls of a storage tank, a pipeline and equipment and corrosion prevention of a steel structure in the field of petrochemical industry, in particular to a solvent-free polyaspartic acid ester heavy-duty paint for corrosion prevention of inner and outer walls of a crude oil storage tank and a pipeline, and more particularly relates to a bottom-surface-integrated solvent-free polyaspartic acid ester heavy-duty paint, a preparation method and application thereof.

Background

With the increase of the requirement of national environmental protection, the limitation of the GB30981-2020 on the VOC requirement of the coating is more and more strict. In order to reduce VOC emissions, the main solutions for coatings are mastic products, solventless products and water-borne coating products. However, for most petrochemical fields, the corrosion environment is classified according to ISO12944-2-2017, and is classified as C5 (very high) or CX (extreme) corrosion environment, and particularly, the medium corrosion environment is worse. For the water-based paint, the problems cannot be solved by the water-based raw materials and the technical research and development level, and particularly the requirements on construction and maintenance conditions of the water-based paint are higher, so that the final protective performance of the water-based paint is greatly changed, the corrosion prevention requirement in the field of petrochemical industry cannot be met, and the application of the water-based paint is also limited. The solvent-free type coating does not contain solvent, has relatively excellent performance, can meet the anticorrosion requirement in the field of petrochemical industry on the product performance, and is the focus of foreign technologies on the research and development of the petrochemical industry. The key point of the solvent-free type coating is that the research and development technical requirement of the product is high, the requirement of construction equipment is high, and the solvent-free epoxy coating is mature at present. The solvent-free epoxy coating has poor weather resistance and cannot meet the working condition with weather resistance requirement. The solvent-free polyaspartic acid ester coating researched by the invention is a primer-topcoat integrated heavy-duty anticorrosive coating, has excellent corrosion resistance, long-acting weather resistance, color retention and gloss retention, and can achieve the long-acting protection effect of C5 and CX once as a single coating system. In the current stage, most of the solvent-free polyaspartic acid ester coating and the solvent-free polyurethane coating are used as finish paint and matched with corresponding anticorrosive primer for matched use. Therefore, the solvent-free polyaspartic acid ester heavy-duty anticorrosive coating needs at least two times of construction on construction, increases construction cost, increases uncontrollable construction, and has very high parking and maintenance cost under some working conditions.

Disclosure of Invention

The invention relates to a coating technology for corrosion prevention of inner and outer walls of a storage tank, a pipeline and equipment and corrosion prevention of a steel structure in the field of petrochemical industry, in particular to solvent-free polyaspartic acid ester heavy-duty coating for corrosion prevention of the inner and outer walls of a crude oil storage tank, corrosion prevention of outer walls of an intermediate product tank, a sewage tank, a sump oil tank and the like and corrosion prevention of partial inner walls. For buried or overhead pipelines and equipment, the solvent-free polyurethane coating is used for external corrosion prevention under the working condition of the temperature of-25-120 ℃, and for the internal wall corrosion prevention of the pipelines and the equipment under partial working conditions. Meanwhile, the corrosion resistance of the steel structure can be solved by a single coating. In order to realize the use purpose, the aspartic acid resin is subjected to specific hyperbranched modification, so that the aspartic acid resin has more mild reaction active points, is more balanced in curing reaction, uniform in curing reaction, generates smaller curing stress, and has stronger binding power, and the existence of silicon in a molecular midblock greatly improves the temperature resistance, wear resistance, corrosion resistance and weather resistance of the coating; the filler can better participate in the curing reaction, so that various performance indexes of the coating are more excellent and the comprehensive performance is good.

Based on the above, in a first aspect, the invention provides a primer-topcoat type solvent-free polyaspartic acid ester heavy-duty anticorrosive paint, which comprises a component A and a component B, wherein the component A comprises the following components in parts by weight:

the component B comprises:

optionally, the modified filler is one or a combination of barium sulfate, titanium dioxide, calcium carbonate and white carbon black; the isocyanate is one or the combination of more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and HDI tripolymer; the diisocyanate prepolymer is one of HDI trimer, TDI trimer and IPDI trimer.

Optionally, the auxiliary agent comprises one or a combination of a dispersing agent, a defoaming agent, an anti-settling agent, a water removing agent, a leveling agent and a silane coupling agent.

Optionally, the preparation method of the modified filler comprises the following steps: (1) dissolving a silane coupling agent in absolute ethyl alcohol to prepare a solution with the mass concentration of 30-50%; (2) and spraying the solution on the filler in a high-speed stirrer, uniformly stirring at a high speed, drying for 2-5h at the temperature of 105 ℃ in a forced air drying box, and naturally cooling to obtain the modified filler.

Optionally, the silane coupling agent is one or a combination of gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltriethoxysilane and phenylaminomethyltrimethoxysilane.

Optionally, the preparation method of the hyperbranched modified aspartic acid resin comprises the following steps: (1) adding a trichlorosilane ethanol solution with the mass concentration of 10-30% into a reaction kettle protected by inert gas, dropwise adding deionized water under the stirring state, wherein the molar ratio of the deionized water to the trichlorosilane is 1:3, reacting for 0.5-1 hour at the temperature of 75-85 ℃, adding diisocyanate, and continuously reacting for 0.5-1 hour to obtain a pre-reaction solution; (2) controlling the temperature of the reaction kettle within the range of 15-20 ℃ by water cooling, and dropwise adding aliphatic primary diamine terminated end into the pre-reaction liquid under a stirring state to obtain silicon block branched modified organic diamine reaction liquid; (3) and slowly dropwise adding dialkyl maleate into the silicon block branched modified organic diamine reaction liquid by using a titration funnel, after dropwise adding, heating to 90-100 ℃, reacting at a constant temperature for 10-15h, and then removing and recovering the solvent to finally obtain the hyperbranched modified aspartic acid resin.

Optionally, the reaction degree of the hyperbranched modified aspartic acid resin is determined by a mercaptan-iodine titration analysis method.

Optionally, the diisocyanate is one or a combination of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate and xylylene diisocyanate; the aliphatic primary diamine is one or a combination of hexamethylene diamine, butanediamine, hexamethylene diamine, 2, 4-trimethyl-1, 6-butanediamine, 4' -diaminodicyclohexyl methane and 3, 3-dimethyl-4, 4-diaminodicyclohexyl methane; the dialkyl maleate is one or more of dimethyl maleate, diethyl maleate, diisobutyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate and dibutyl fumarate;

in a second aspect, the invention provides a preparation method of a primer-topcoat type solvent-free polyaspartic acid ester heavy-duty anticorrosive paint, which comprises the following steps: (1) weighing hyperbranched modified aspartic acid resin, zinc phosphate, modified filler and an auxiliary agent according to the parts by weight to obtain a mixed material; (2) the mixed materials are put in a high-speed stirrer, the temperature is controlled to be 40-50 ℃, the rotating speed is 2500-; (2) weighing the materials of isocyanate, diisocyanate prepolymer, defoaming agent and flatting agent according to the weight proportion, and uniformly mixing to obtain the component B.

In a third aspect, the primer-topcoat type solvent-free polyaspartic acid ester heavy-duty anticorrosive coating disclosed by the invention is characterized in that the volume ratio of the component A to the component B is 1:1, can be used for the anticorrosion of the inner and outer walls of storage tanks, pipelines and equipment in the field of petrochemical industry and the anticorrosion of steel structures.

The invention has the following beneficial effects:

1. the invention generates trihydroxy silane (SiH (OH) by the hydrolysis of trichlorosilane in ethanol solution₃)，SiH(OH)₃Reaction with diisocyanate (OCN-R-NCO) to form SiH (O-CONH-R-NCO)₃Then reacts with aliphatic primary diamine to generate SiH (O-CONH-R-NHCO-NH-R' -NH)₂)₃And finally the primary amino group (-NH) therein₂) And carrying out Michael addition reaction with the double bond of dialkyl maleate to obtain the hyperbranched modified aspartic acid resin containing a plurality of secondary amino groups (-NH-). The hyperbranched modified aspartic acid resin has more mild reactive sites, is more balanced in participating in curing reaction, is uniform in curing reaction, generates smaller curing stress and has stronger binding power. In addition, the existence of silicon in a molecular midblock greatly improves the temperature resistance, the wear resistance and the corrosion resistance of the coatingCorrosion resistance and weather resistance.

2. The modification of the amino-containing silane coupling agent on the surface of the filler enables the filler to better participate in the curing reaction, and finally, various performance indexes of the coating are more excellent.

3. The product of the invention is a bi-component, wherein the volume ratio of A, B components is 1:1, the operation of the spraying equipment is more stable, the spraying proportion of the coating is more stable, the abrasion to the equipment is reduced, and the final protective performance of the coating is also ensured. The primer-topcoat integrated coating has the advantages that the thickness of a single construction dry film can reach 1700 micrometers, the curing rate is high, the surface is dried within 5min, the hoisting can be carried out within 15min, and the construction efficiency is improved by 75%.

4. The curing principle of the product of the invention has the advantages of reducing the sensitivity to moisture and improving the applicability of the product.

5. The product of the invention has excellent corrosion resistance and aging resistance, high adhesive force, high collision resistance and high friction resistance, can play an excellent protection effect except being used as an external anticorrosive coating in a strong corrosion environment, and also can play an excellent role in protecting the outer wall of a buried pipeline, the inner wall of a transmission pipeline with friction and corrosion and the inner wall of a storage tank, and has wider application range.

6. The VOC content of the product is 0, zero emission is realized, the construction environment and the health of constructors are protected, and the coating is a green low-carbon environment-friendly heavy-duty anticorrosive coating.

Detailed Description

The present invention will be described in detail with reference to the following embodiments in order to make the aforementioned objects, features and advantages of the invention more comprehensible.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.

The primer-topcoat type solvent-free polyaspartic acid ester heavy-duty anticorrosive coating comprises a component A and a component B, wherein the component A comprises the following components in parts by weight:

the component B comprises:

in an embodiment according to the present invention, the modified filler is one or a combination of barium sulfate, titanium dioxide, calcium carbonate and white carbon black; the isocyanate is one or the combination of more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and HDI tripolymer; the diisocyanate prepolymer is one of HDI trimer, TDI trimer and IPDI trimer.

In an embodiment according to the present invention, the assistant includes one or a combination of a dispersant, an antifoaming agent, an anti-settling agent, a water removing agent, a leveling agent, and a silane coupling agent.

In one embodiment of the present invention, the preparation method of the modified filler comprises the following steps: (1) dissolving a silane coupling agent in absolute ethyl alcohol to prepare a solution with the mass concentration of 30-50%; (2) and spraying the solution on the filler in a high-speed stirrer, uniformly stirring at a high speed, drying for 2-5h at the temperature of 105 ℃ in a forced air drying box, and naturally cooling to obtain the modified filler.

In one embodiment according to the present invention, the silane coupling agent is one or a combination of γ -aminopropyltrimethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane, N- β - (aminoethyl) - γ -aminopropyltriethoxysilane, and phenylaminomethyltrimethoxysilane.

In an embodiment of the present invention, the preparation method of the hyperbranched modified aspartic acid resin comprises the following steps: (1) adding a trichlorosilane ethanol solution with the mass concentration of 10-30% into a reaction kettle protected by inert gas, dropwise adding deionized water under the stirring state, wherein the molar ratio of the deionized water to the trichlorosilane is 1:3, reacting for 0.5-1 hour at the temperature of 75-85 ℃, adding diisocyanate, and continuously reacting for 0.5-1 hour to obtain a pre-reaction solution; (2) controlling the temperature of the reaction kettle within the range of 15-20 ℃ by water cooling, and dropwise adding aliphatic primary diamine terminated end into the pre-reaction liquid under a stirring state to obtain silicon block branched modified organic diamine reaction liquid; (3) and slowly dropwise adding dialkyl maleate into the silicon block branched modified organic diamine reaction liquid by using a titration funnel, after dropwise adding, heating to 90-100 ℃, reacting at a constant temperature for 10-15h, and then removing and recovering the solvent to finally obtain the hyperbranched modified aspartic acid resin.

In one embodiment of the present invention, the degree of reaction of the hyperbranched modified aspartic acid resin is determined by thiol-iodine titration analysis.

In an embodiment according to the present invention, the diisocyanate is one or a combination of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, and xylylene diisocyanate; the aliphatic primary diamine is one or a combination of hexamethylene diamine, butanediamine, hexamethylene diamine, 2, 4-trimethyl-1, 6-butanediamine, 4' -diaminodicyclohexyl methane and 3, 3-dimethyl-4, 4-diaminodicyclohexyl methane; the dialkyl maleate is one or more of dimethyl maleate, diethyl maleate, diisobutyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate and dibutyl fumarate;

the preparation method of the primer-topcoat solvent-free polyaspartic acid ester heavy-duty anticorrosive paint according to the second aspect of the invention comprises the following steps: (1) weighing hyperbranched modified aspartic acid resin, zinc phosphate, modified filler and an auxiliary agent according to the parts by weight to obtain a mixed material; (2) the mixed materials are put in a high-speed stirrer, the temperature is controlled to be 40-50 ℃, the rotating speed is 2500-; (2) weighing the materials of isocyanate, diisocyanate prepolymer, defoaming agent and flatting agent according to the weight proportion, and uniformly mixing to obtain the component B.

In the primer-topcoat type solvent-free polyaspartic acid ester heavy-duty anticorrosive coating, the volume ratio of the component A to the component B is 1:1, can be used for the anticorrosion of the inner and outer walls of storage tanks, pipelines and equipment in the field of petrochemical industry and the anticorrosion of steel structures.

Next, the preparation method of the present invention will be explained, and the preparation method of the present invention specifically includes the steps of:

preparing hyperbranched modified aspartic acid resin:

(1) adding a trichlorosilane ethanol solution with the mass concentration of 10-30% into a reaction kettle protected by inert gas, dropwise adding deionized water under the stirring state, wherein the molar ratio of the deionized water to the trichlorosilane is 1:3, reacting for 0.5-1 hour at the temperature of 75-85 ℃, adding diisocyanate, and continuously reacting for 0.5-1 hour to obtain a pre-reaction solution; (2) controlling the temperature of the reaction kettle within the range of 15-20 ℃ by water cooling, and dropwise adding aliphatic primary diamine terminated end into the pre-reaction liquid under a stirring state to obtain silicon block branched modified organic diamine reaction liquid; (3) and (2) slowly dropwise adding dialkyl maleate into the silicon block branched modified organic diamine reaction liquid by using a titration funnel, after dropwise adding, heating to 90-100 ℃, reacting for 10-15h at constant temperature, then removing and recovering the solvent, and determining the reaction degree by using a mercaptan-iodine titration analysis method to finally obtain the hyperbranched modified aspartic acid resin.

(II) filler modification:

(1) dissolving a silane cross-linking agent in absolute ethyl alcohol to prepare a solution with the mass concentration of 30-50%; (2) and spraying the solution on the filler in a high-speed stirrer, uniformly stirring at a high speed, drying for 2-5h at the temperature of 105 ℃ in a forced air drying box, and naturally cooling to obtain the modified filler.

(III) preparing an anticorrosive paint:

(1) weighing hyperbranched modified aspartic acid resin, zinc phosphate, modified filler and auxiliary agent according to the parts by weight to obtain the mixed material. (2) The mixed materials are put in a high-speed stirrer, the temperature is controlled to be 40-50 ℃, the rotating speed is 2500-; transferring the mixture into a ball mill, and grinding and dispersing to obtain a component A; the component A comprises the following components: 20-40 parts of hyperbranched modified aspartic acid resin, 10-30 parts of aspartic acid resin, 5.2 parts of zinc phosphate, 0.1-15 parts of auxiliary agent and 1-30 parts of modified filler;

(2) weighing the materials of isocyanate, diisocyanate prepolymer, defoaming agent and flatting agent according to the weight ratio, and uniformly mixing to obtain a component B; the component B comprises the following components: 70-80 parts of isocyanate, 20-30 parts of diisocyanate prepolymer, 3-5 parts of defoaming agent and 2-3 parts of flatting agent.

The polyaspartic acid ester heavy-duty anticorrosive paint and the preparation method thereof according to the present invention will be specifically described with reference to specific examples.

The main raw materials and equipment used are as follows: unless otherwise specified, the raw materials and equipment of each example and comparative example were the same; materials with specific types or kinds are not specified, such as a dispersing agent, a defoaming agent, an anti-settling agent, a water removing agent and a leveling agent, are from the same common type purchased in the market, and are not particularly limited.

Example 1

Preparing hyperbranched modified aspartic acid resin:

(1) adding a trichlorosilane ethanol solution with the mass concentration of 10-30% into a nitrogen-protected reaction kettle, dropwise adding deionized water under the stirring state, wherein the molar ratio of the deionized water to the trichlorosilane is 1:3, reacting at the temperature of 75 ℃ for 0.5 hour, adding hexamethylene diisocyanate, and continuing to react for 0.5 hour to obtain a pre-reaction solution; (2) controlling the temperature of the reaction kettle within 15 ℃ by water cooling, and dropwise adding hexamethylene diamine for end capping into the pre-reaction liquid under a stirring state to obtain a silicon block branched modified organic diamine reaction liquid; (3) slowly dripping dimethyl maleate into the silicon block branched modified organic diamine reaction liquid by using a titration funnel, heating to 90 ℃ after dripping is finished, reacting for 10 hours at constant temperature, then removing and recovering the solvent, and measuring the reaction degree by using a mercaptan-iodine titration analysis method to finally obtain the hyperbranched modified aspartic acid resin.

(II) filler modification:

(1) dissolving gamma-aminopropyltrimethoxysilane in absolute ethyl alcohol to prepare a solution with the mass concentration of 30%; (2) and spraying the solution on barium sulfate in a high-speed stirrer, uniformly stirring at a high speed, drying for 2 hours at 100 ℃ in a forced air drying oven, and naturally cooling to obtain the modified filler.

(III) preparing an anticorrosive paint:

(1) weighing hyperbranched modified aspartic acid resin, zinc phosphate, modified filler and auxiliary agent according to the parts by weight to obtain the mixed material. (2) The mixed materials are put in a high-speed stirrer, the temperature is controlled at 40 ℃, the rotating speed is 2500 rpm, and the materials are uniformly mixed; transferring the mixture into a ball mill, and grinding and dispersing to obtain a component A; the component A comprises the following components: 20 parts of hyperbranched modified aspartic acid resin, 10 parts of aspartic acid resin, 5.2 parts of zinc phosphate, 0.1 part of an auxiliary agent and 1 part of modified filler; the auxiliary agent comprises a dispersing agent, a defoaming agent, an anti-settling agent, a water removing agent and a flatting agent in a mass ratio of 1:1:1:1: 1.

(2) Weighing 70 parts of toluene diisocyanate, 20 parts of HDI trimer, 3 parts of defoaming agent and 2 parts of flatting agent according to the weight proportion, and uniformly mixing to obtain the component B.

Example 2

Preparing hyperbranched modified aspartic acid resin:

(1) adding a trichlorosilane ethanol solution with the mass concentration of 30% into a reaction kettle protected by nitrogen, dropwise adding deionized water under the stirring state, wherein the molar ratio of the deionized water to the trichlorosilane is 1:3, reacting for 1 hour at the temperature of 85 ℃, adding isophorone diisocyanate, and continuing to react for 1 hour to obtain a pre-reaction solution; (2) controlling the temperature of the reaction kettle within the range of 15-20 ℃ by water cooling, and dropwise adding 2,2, 4-trimethyl-1, 6-butanediamine terminated end into the pre-reaction liquid under a stirring state to obtain silicon block branched modified organic diamine reaction liquid; (3) and slowly dripping diethyl maleate into the silicon block branched modified organic diamine reaction liquid by using a titration funnel, heating to 100 ℃ after dripping is finished, reacting for 15 hours at constant temperature, removing and recovering the solvent, and measuring the reaction degree by using a mercaptan-iodine titration analysis method to finally obtain the hyperbranched modified aspartic acid resin.

(II) filler modification:

(1) dissolving N-beta- (aminoethyl) -gamma-aminopropyltriethoxysilane in absolute ethanol to prepare a solution with the mass concentration of 50%; (2) and spraying the solution on titanium dioxide in a high-speed stirrer, uniformly stirring at a high speed, drying for 5 hours at 105 ℃ in a forced air drying oven, and naturally cooling to obtain the modified filler.

(III) preparing an anticorrosive paint:

(1) weighing hyperbranched modified aspartic acid resin, zinc phosphate, modified filler and auxiliary agent according to the parts by weight to obtain the mixed material. (2) The mixed materials are put in a high-speed stirrer, the temperature is controlled at 50 ℃, the rotating speed is 3500 rpm, and the materials are uniformly mixed; transferring the mixture into a ball mill, and grinding and dispersing to obtain a component A; the component A comprises the following components: 40 parts of hyperbranched modified aspartic acid resin, 30 parts of aspartic acid resin, 5.2 parts of zinc phosphate, 15 parts of an auxiliary agent and 30 parts of modified filler; the auxiliary agent comprises a dispersing agent, a defoaming agent, an anti-settling agent, a water removing agent and a flatting agent in a mass ratio of 1:1:1:1: 1.

(2) Weighing 80 parts of hexamethylene diisocyanate, 30 parts of TDI trimer, 5 parts of defoaming agent and 3 parts of flatting agent according to the weight proportion, and uniformly mixing to obtain the component B.

Example 3

Preparing hyperbranched modified aspartic acid resin:

(1) adding a trichlorosilane ethanol solution with the mass concentration of 20% into a reaction kettle protected by argon, dropwise adding deionized water under the stirring state, wherein the molar ratio of the deionized water to the trichlorosilane is 1:3, reacting at the temperature of 80 ℃ for 0.8 hour, adding xylylene diisocyanate, and continuing to react for 0.5-1 hour to obtain a pre-reaction solution; (2) controlling the temperature of the reaction kettle within the range of 15-20 ℃ by water cooling, and dropwise adding 4, 4' -diaminodicyclohexylmethane into the pre-reaction liquid under a stirring state to terminate to obtain a silicon block branched modified organic diamine reaction liquid; (3) slowly dripping diisobutyl maleate into the silicon block branched modified organic diamine reaction liquid by using a titration funnel, heating to 95 ℃ after dripping is finished, reacting for 12 hours at constant temperature, then removing and recovering the solvent, and determining the reaction degree by using a mercaptan-iodine titration analysis method to finally obtain the hyperbranched modified aspartic acid resin.

(II) filler modification:

(1) dissolving a silane cross-linking agent in absolute ethyl alcohol to prepare a solution with the mass concentration of 40%; (2) and spraying the solution on a filler in a high-speed stirrer, uniformly stirring at a high speed, drying at 102 ℃ in a forced air drying oven for 3.5 hours, and naturally cooling to obtain the modified filler.

(III) preparing an anticorrosive paint:

(1) weighing hyperbranched modified aspartic acid resin, zinc phosphate, modified filler and auxiliary agent according to the parts by weight to obtain the mixed material. (2) The mixed materials are put in a high-plasticity mixer, the temperature is controlled at 45 ℃, the rotating speed is 3000 r/min, and the materials are uniformly mixed; transferring the mixture into a ball mill, and grinding and dispersing to obtain a component A; the component A comprises the following components: 30 parts of hyperbranched modified aspartic acid resin, 20 parts of aspartic acid resin, 5.2 parts of zinc phosphate, 8 parts of an auxiliary agent and 15 parts of modified filler;

(2) weighing 75 parts of 4, 4' -dicyclohexylmethane diisocyanate, 25 parts of IPDI trimer, 4 antifoaming agent and 2.5 parts of flatting agent according to the weight proportion, and uniformly mixing to obtain the component B.

Comparative example 1

The procedure was as in example 3 except that the aspartic acid resin was not modified.

Comparative example 2

The procedure was as in example 3, except that the aspartic acid resin was not modified and the modifier of the filler was KH570 containing no amino group.

Performance testing

The coatings obtained in example 3 and the comparative examples were subjected to performance tests with reference to the corresponding national and industrial standards, and the test results are shown in the following table:

therefore, the solvent-free polyaspartic acid ester heavy-duty anticorrosive coating with the integrated bottom surface, which is prepared by the invention, has more mild reaction active points by carrying out specific hyperbranched modification on aspartic acid resin, is more balanced in participating in a curing reaction, is uniform in curing reaction, generates smaller curing stress and stronger in binding power, and greatly improves the temperature resistance, wear resistance, corrosion resistance and weather resistance of the coating due to the existence of silicon in a molecular midblock; in addition, the modification of the amino-containing silane coupling agent on the surface of the filler enables the filler to better participate in the curing reaction, and finally, various performance indexes of the coating are more excellent and the comprehensive performance is good. Moreover, the film forming property of a product system is improved, the thickness of a dry film of more than 1700 micrometers can be achieved by one-time spraying, the construction efficiency is improved by 75%, and the construction cost is reduced by 50%.

Although some specific embodiments of the present invention have been described in detail by way of illustration, it should be understood by those skilled in the art that the above illustration is only for the purpose of illustration and is not intended to limit the scope of the invention. It will be appreciated by those skilled in the art that modifications may be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.