阅读说明：本技术 一种防腐耐酸碱丙烯酸涂料及其制备方法 (Anticorrosive acid-alkali-resistant acrylic coating and preparation method thereof ) 是由 高建明 李瑞海 黄桐 于 2021-06-28 设计创作，主要内容包括：本发明公开了一种防腐耐酸碱丙烯酸涂料及其制备方法,所述丙烯酸涂料包括以下原料：丁醇70-80质量份、醋酸丁酯50-60质量份、丙烯酸丁酯20-30质量份、丙烯酸20-30质量份、丙烯酸羟乙酯20-30质量份、甲基丙烯酸甲酯20-30质量份、偶氮二异丁腈0.1-0.3质量份、甲基丙烯酸六氟丁酯0-14质量份、环氧树脂10-12质量份、交联剂10-12质量份、催化剂0.1-0.4份。本发明的丙烯酸涂料防腐耐酸碱性能优异、工艺简便、无毒无害,具有极好的经济价值。(The invention discloses an anticorrosive acid and alkali resistant acrylic coating and a preparation method thereof, wherein the acrylic coating comprises the following raw materials: 70-80 parts of butanol, 50-60 parts of butyl acetate, 20-30 parts of butyl acrylate, 20-30 parts of acrylic acid, 20-30 parts of hydroxyethyl acrylate, 20-30 parts of methyl methacrylate, 0.1-0.3 part of azobisisobutyronitrile, 0-14 parts of hexafluorobutyl methacrylate, 10-12 parts of epoxy resin, 10-12 parts of a cross-linking agent and 0.1-0.4 part of a catalyst. The acrylic coating disclosed by the invention is excellent in corrosion resistance, acid and alkali resistance, simple in process, non-toxic and harmless, and has extremely high economic value.)

1. The corrosion-resistant acid-alkali-resistant acrylic coating is characterized by comprising the following components in parts by weight: the preparation method comprises the following raw materials: 70-80 parts of butanol, 50-60 parts of butyl acetate, 20-30 parts of butyl acrylate, 20-30 parts of acrylic acid, 20-30 parts of hydroxyethyl acrylate, 20-30 parts of methyl methacrylate, 0.1-0.3 part of azobisisobutyronitrile, 0-14 parts of hexafluorobutyl methacrylate, 10-12 parts of epoxy resin, 10-12 parts of a cross-linking agent and 0.1-0.4 part of a catalyst.

2. The acrylic coating according to claim 1, characterized in that: the preparation method comprises the following raw materials: 80 parts by mass of butanol, 50 parts by mass of butyl acetate, 25 parts by mass of butyl acrylate, 25 parts by mass of acrylic acid, 25 parts by mass of hydroxyethyl acrylate, 25 parts by mass of methyl methacrylate, 0.2 part by mass of azobisisobutyronitrile, 5 parts by mass of hexafluorobutyl methacrylate, 10 parts by mass of epoxy resin, 10 parts by mass of a crosslinking agent, and 0.1 part by mass of a catalyst.

3. The acrylic coating according to claim 1 or 2, characterized in that: the epoxy resin is selected from epoxy resins with an epoxy value of 0.41-0.47.

4. The acrylic coating according to claim 1 or 2, characterized in that: the cross-linking agent is selected from methylated amino resin and/or ethylenediamine.

5. The acrylic coating according to claim 1 or 2, characterized in that: the catalyst is selected from p-toluenesulfonic acid.

6. The method for producing an acrylic coating material as set forth in any one of claims 1 to 5, characterized in that: the method comprises the following steps:

(1) reacting a part of the butanol, the butyl acetate, the azobisisobutyronitrile, the butyl acrylate, the acrylic acid, the hydroxyethyl acrylate, the methyl methacrylate and the hexafluorobutyl methacrylate for 1-4 hours to obtain a basic reaction system;

(2) adding the rest hexafluorobutyl methacrylate into the basic reaction system, and reacting for 0.5-1.5 hours to obtain fluorine-containing acrylic resin;

(3) and adding the cross-linking agent, the epoxy resin, the butanol and the catalyst into the fluorine-containing acrylic resin, fully mixing and discharging to obtain the anticorrosive acid-alkali-resistant acrylic coating.

7. The method of claim 6, wherein: the reaction in the step (1) is carried out at a constant temperature of 80-90 ℃.

8. The method of claim 6, wherein: the step (1) comprises the following steps: firstly, 10-30% of the total amount of the butanol, the butyl acetate, the azobisisobutyronitrile, the butyl acrylate, the acrylic acid, the hydroxyethyl acrylate, the methyl methacrylate and the part of hexafluorobutyl methacrylate are added, and then the rest part is dripped under the constant temperature condition of 80-90 ℃ to carry out the reaction.

9. The production method according to claim 7 or 8, characterized in that: the reaction was carried out at a stirring rate of 150 ℃ and 250 r/min.

10. The method of claim 6, wherein: and (2) adding only one part of the azobisisobutyronitrile in the step (1), and adding the other part of the azobisisobutyronitrile after adding the hexafluorobutyl methacrylate in the step (2).

Technical Field

The invention relates to the technical field of acrylic coatings.

Background

The stainless steel material is a basic building material for developing economy in China, is widely used in various fields and plays an increasingly important role. In the practical application process, the application effect of the stainless steel is related to the surface treatment process and the coating protection technology which are carried out by the stainless steel in many times. In the actual production living environment, the surface of the stainless steel can generate various aging and corrosion under the continuous erosion action of various acid, alkali and humid conditions. The potential safety hazard and even the serious accidents caused by the corrosion cause endless, and even the stainless steel materials are replaced after the stainless steel is corroded, the great resource waste is caused. Therefore, the stainless steel material can be reasonably protected, the service time of the stainless steel is prolonged, and the method has very important significance for the healthy and sustainable development of national economy.

In order to achieve a good anticorrosion effect, the acrylic coating in the prior art uses benzene compounds, such as the technical scheme of the Chinese patent application CN202010221552.0, which has high toxicity, is not beneficial to safe production and pollutes the environment.

Disclosure of Invention

The invention aims to provide an anticorrosive acid-alkali-resistant acrylic coating which has good anticorrosive and weather-resistant properties, excellent hydrophobic and oleophobic properties, acid-alkali resistance and no toxicity and harm, and a specific preparation method of the coating.

The invention firstly provides the following technical scheme:

an anticorrosive acid and alkali resistant acrylic coating comprises the following raw materials: 70-80 parts of butanol, 50-60 parts of butyl acetate, 20-30 parts of butyl acrylate, 20-30 parts of acrylic acid, 20-30 parts of hydroxyethyl acrylate, 20-30 parts of methyl methacrylate, 0.1-0.3 part of azobisisobutyronitrile, 0-14 parts of hexafluorobutyl methacrylate, 10-12 parts of epoxy resin, 10-12 parts of a cross-linking agent and 0.1-0.4 part of a catalyst.

According to some preferred embodiments of the present invention, the acrylic coating comprises the following raw materials: 80 parts by mass of butanol, 50 parts by mass of butyl acetate, 25 parts by mass of butyl acrylate, 25 parts by mass of acrylic acid, 25 parts by mass of hydroxyethyl acrylate, 25 parts by mass of methyl methacrylate, 0.2 part by mass of azobisisobutyronitrile, 5 parts by mass of hexafluorobutyl methacrylate, 10 parts by mass of epoxy resin, 10 parts by mass of a crosslinking agent, and 0.1 part by mass of a catalyst.

According to some preferred embodiments of the present invention, the epoxy resin is selected from epoxy resins having an epoxy value of 0.41 to 0.47.

According to some preferred embodiments of the invention, the cross-linking agent is selected from a methylated amino resin and/or ethylenediamine.

According to some preferred embodiments of the invention, the catalyst is selected from p-toluenesulfonic acid.

The invention further provides a preparation method of the acrylic coating, which is characterized by comprising the following steps: the method comprises the following steps:

reacting a part of the butanol, the butyl acetate, the azobisisobutyronitrile, the butyl acrylate, the acrylic acid, the hydroxyethyl acrylate, the methyl methacrylate and the hexafluorobutyl methacrylate for 1-4 hours to obtain a basic reaction system;

adding the rest hexafluorobutyl methacrylate into the basic reaction system, and reacting for 0.5-1.5 hours to obtain fluorine-containing acrylic resin;

and adding the cross-linking agent, the epoxy resin, the butanol and the catalyst into the fluorine-containing acrylic resin, fully mixing and discharging to obtain the anticorrosive acid-alkali-resistant acrylic coating.

According to some preferred embodiments of the invention, the reaction in step (1) is carried out at a constant temperature of between 80 and 90 ℃.

According to some preferred embodiments of the present invention, step (1) comprises: firstly, 10-30% of the total amount of the butanol, the butyl acetate, the azobisisobutyronitrile, the butyl acrylate, the acrylic acid, the hydroxyethyl acrylate, the methyl methacrylate and the part of hexafluorobutyl methacrylate are added, and then the rest part is dripped under the constant temperature condition of 80-90 ℃ to carry out the reaction.

According to some preferred embodiments of the present invention, the reaction of step (1) is carried out at a stirring rate of 150-250 r/min.

According to some preferred embodiments of the present invention, in the preparation method, the azobisisobutyronitrile is added in only one part in the step (1), and the hexafluorobutyl methacrylate is added in the other part in the step (2).

According to the invention, hexafluorobutyl methacrylate (HFMA) is added to modify the coating, the C-F bond has large energy and short bond length, and the electronegativity of the F element is strongest in all elements, so that the modified acrylic coating with better chemical stability and weather resistance is obtained, and in addition, the high-polarity C-F bond also enables the acrylic coating to have good hydrophobic and oleophobic properties and higher acid and alkali resistance.

The acrylic monomers selected by the invention comprise; under the condition of keeping the weather resistance of the acrylic resin, the methyl methacrylate, the hydroxyethyl acrylate, the acrylic acid, the butyl acrylate and the hexafluorobutyl methacrylate can also synergistically enhance the chemical corrosion resistance, the acid and alkali resistance and the like of the resin, wherein fluorine elements in the fluorine-containing monomer can be arranged on the surface of a coating based on the electronegativity of the fluorine-containing monomer, so that the surface properties of the coating are enhanced, and the corrosion resistance and the chemical damage resistance of the coating are further enhanced.

The preparation method has the advantages of simple process, wide raw materials, low cost, no toxicity and harm, excellent corrosion resistance, acid and alkali resistance and great application value.

Detailed Description

The present invention is described in detail with reference to the following examples, but it should be understood that the examples are only for illustrative purposes and are not intended to limit the scope of the present invention. All reasonable variations and combinations that fall within the spirit of the invention are intended to be within the scope of the invention.

According to the technical scheme of the invention, a specific implementation mode of the preparation method comprises the following steps:

(1) adding 50-60 parts by mass of butanol, 50-60 parts by mass of butyl acetate and 0.1-0.3 part by mass of Azobisisobutyronitrile (AIBN) into a flask, then adding 20-30 parts by mass of Butyl Acrylate (BA), 20-30 parts by mass of Acrylic Acid (AA), 20-30 parts by mass of hydroxyethyl acrylate (HEA), 20-30 parts by mass of Methyl Methacrylate (MMA) and 0-14 parts by mass of hexafluorobutyl methacrylate (HFMA), and fully reacting for 3 hours;

(2) adding 0-14 parts by mass of hexafluorobutyl methacrylate (HFMA) into the reaction system after the step (1) is completed, and reacting for one hour to obtain the fluorine-containing acrylic resin;

(3) taking 50 parts by mass of the prepared resin, adding 10-12 parts by mass of a cross-linking agent, 10-12 parts by mass of epoxy resin, 20-30 parts by mass of butanol and 0.1-0.4 part by mass of a catalyst, fully mixing and discharging to obtain the anticorrosive acid and alkali resistant acrylic coating;

wherein:

further, the epoxy resin can be selected from E-44 type epoxy resin, and the cross-linking agent can be correspondingly selected from a cross-linking agent for cross-linking the E-44 type epoxy resin and the acrylic resin, such as ethylenediamine;

further, the catalyst may be selected from p-toluenesulfonic acid, such as catalyst 4040(CYCAT 4040);

further, in the step (1), the addition manner of BA, AA, HEA, MMA and HFMA is preferably that 20% of the total amount is added at one time, and the rest 80% is added within 3 hours;

further, after 20% of the raw materials are added at one time, the reaction is preferably carried out at a constant temperature of 85 ℃, and mechanical stirring is preferably carried out simultaneously in the constant temperature process at a speed of 200 rad/min;

further, it is preferable to add 0.1 part by mass of AIBN after the addition of HFMA in step (2), that is, 0 to 0.2 part by mass of Azobisisobutyronitrile (AIBN) in step (1) and 0.1 part by mass of Azobisisobutyronitrile (AIBN) in step (3) are added.

Further, after AIBN is added in the step (2), the rotating speed is adjusted to 120 rad/min.

The invention further provides the following examples (in which parts are parts by mass) and the resulting products were tested as follows:

coating of the paint on the stainless steel plate: coating fluorine-containing acrylic acid coating on the surface of a stainless steel plate by GB 1727-; naturally leveling for l-2 min after roller coating by using a steel roller, placing the stainless steel plate in an oven for thermosetting molding, setting the temperature in the oven to be 180 ℃, and baking for 10-12min to finally obtain the stainless steel plate with a smooth and transparent coating.

And (3) acid and alkali corrosion resistance testing: according to the GB 1763-79 standard, NaOH (the normal temperature concentration is 0.01mol/L) or citric acid (the mass fraction is 1%) is used for soaking the coating-coated non-induced steel plate in the solution for 24 hours, then the non-induced steel plate is taken out, naturally washed and dried by water, and the acid and alkali resistance degree is judged according to the mass residual quantity.

Corrosion resistance test (salt spray test): the corrosion resistance of the surface coating of the stainless steel plate is tested according to relevant test regulations of GB 1771-91, and the test conditions are that the internal temperature of a salt spray tester is set to be 40 ℃, the salt water concentration is 3.5 percent, and the test time is 300 hours. After the test is finished, the corrosion degree of the steel plate is judged according to the mass residual quantity after the steel plate is naturally cleaned and dried by water.

Example 1

The raw material ratio is as follows: 80 parts of butanol, 50 parts of butyl acetate, 25 parts of Butyl Acrylate (BA), 25 parts of Acrylic Acid (AA), 25 parts of hydroxyethyl acrylate (HEA), 25 parts of Methyl Methacrylate (MMA), 0.2 part of Azobisisobutyronitrile (AIBN), 5 parts of hexafluorobutyl methacrylate (HFMA), 10 parts of ethylenediamine, 10 parts of epoxy resin E-4410 parts and 40400.1 parts of catalyst.

The preparation process comprises the following steps:

(1) adding 50 parts of butanol, 50 parts of butyl acetate and 0.1 part of AIBN into a flask, adding weighed BA, AA, HEA, MMA and HFMA, and fully reacting for 3 hours;

(2) adding 5 parts of hexafluorobutyl methacrylate (HFMA) into the reaction system after the step (1) is finished, and reacting for one hour to obtain the fluorine-containing acrylic resin;

(3) taking 50 parts of the prepared resin, adding 10 parts of cross-linking agent ethylenediamine, 10 parts of E-4410 parts of butanol and 40400.1 parts of cross-linking agent ethylenediamine, fully mixing and discharging.

Example 2

The raw material ratio is as follows: 80 parts of butanol, 50 parts of butyl acetate, 25 parts of Butyl Acrylate (BA), 25 parts of Acrylic Acid (AA), 25 parts of hydroxyethyl acrylate (HEA), 25 parts of Methyl Methacrylate (MMA), 0.2 part of Azobisisobutyronitrile (AIBN), 5 parts of hexafluorobutyl methacrylate (HFMA), 10 parts of ethylenediamine, 10 parts of epoxy resin E-4410 parts and 40400.1 parts of catalyst.

The preparation process comprises the following steps:

(1) adding 50 parts of butanol, 50 parts of butyl acetate and 0.1 part of AIBN into a flask, adding weighed BA, AA, HEA, MMA and HFMA, and fully reacting for 3 hours;

(2) adding 10 parts of hexafluorobutyl methacrylate (HFMA) into the reaction system after the step (1) is finished, and reacting for one hour to obtain the fluorine-containing acrylic resin;

(3) taking 50 parts of the prepared resin, adding 10 parts of cross-linking agent, E-4410 parts, 30 parts of butanol and 40400.1 parts, fully mixing and discharging.

Example 3

The raw material ratio is as follows: 80 parts of butanol, 50 parts of butyl acetate, 25 parts of Butyl Acrylate (BA), 25 parts of Acrylic Acid (AA), 25 parts of hydroxyethyl acrylate (HEA), 25 parts of Methyl Methacrylate (MMA), 0.3 part of Azobisisobutyronitrile (AIBN), 5 parts of hexafluorobutyl methacrylate (HFMA), 10 parts of ethylenediamine, 10 parts of epoxy resin E-4410 parts and 40400.1 parts of catalyst.

The preparation process comprises the following steps:

(1) adding 50 parts of butanol, 50 parts of butyl acetate and 0.2 part of AIBN into a flask, adding weighed BA, AA, HEA, MMA and HFMA, and fully reacting for 3 hours;

(2) adding 10 parts of hexafluorobutyl methacrylate (HFMA) into the reaction system after the step (1) is finished, and reacting for one hour to obtain the fluorine-containing acrylic resin;

(3) taking 50 parts of the prepared resin, adding 10 parts of cross-linking agent, E-4410 parts, 30 parts of butanol and 40400.1 parts, fully mixing and discharging.

Example 4

The raw material ratio is as follows: 80 parts of butanol, 50 parts of butyl acetate, 25 parts of Butyl Acrylate (BA), 25 parts of Acrylic Acid (AA), 25 parts of hydroxyethyl acrylate (HEA), 25 parts of Methyl Methacrylate (MMA), 0.3 part of Azobisisobutyronitrile (AIBN), 5 parts of hexafluorobutyl methacrylate (HFMA), 10 parts of ethylenediamine, 10 parts of epoxy resin E-4410 parts and 40400.1 parts of catalyst.

The preparation process comprises the following steps:

(1) adding 50 parts of butanol, 50 parts of butyl acetate and 0.2 part of AIBN into a flask, adding weighed BA, AA, HEA, MMA and HFMA, and fully reacting for 3 hours;

(2) adding 10 parts of hexafluorobutyl methacrylate (HFMA) into the reaction system after the step (1) is finished, and reacting for one hour to obtain the fluorine-containing acrylic resin;

(3) and taking 50 parts of the prepared resin, adding 12 parts of cross-linking agent, E-4410 parts, 30 parts of butanol and 40400.1 parts, fully mixing and discharging.

Example 5

The raw material ratio is as follows: 80 parts of butanol, 50 parts of butyl acetate, 25 parts of Butyl Acrylate (BA), 25 parts of Acrylic Acid (AA), 25 parts of hydroxyethyl acrylate (HEA), 25 parts of Methyl Methacrylate (MMA), 0.3 part of Azobisisobutyronitrile (AIBN), 5 parts of hexafluorobutyl methacrylate (HFMA), 10 parts of ethylenediamine, 10 parts of epoxy resin E-4410 parts and 40400.1 parts of catalyst.

The preparation process comprises the following steps:

(4) adding 50 parts of butanol, 50 parts of butyl acetate and 0.2 part of AIBN into a flask, adding weighed BA, AA, HEA, MMA and HFMA, and fully reacting for 3 hours;

(5) adding 12 parts of hexafluorobutyl methacrylate (HFMA) into the reaction system after the step (1) is finished, and reacting for one hour to obtain the fluorine-containing acrylic resin;

(6) and taking 50 parts of the prepared resin, adding 12 parts of cross-linking agent, E-4410 parts, 30 parts of butanol and 40400.1 parts, fully mixing and discharging.

Comparative example 1

The raw material ratio is as follows: 80 parts of butanol, 50 parts of butyl acetate, 25 parts of Butyl Acrylate (BA), 25 parts of Acrylic Acid (AA), 25 parts of hydroxyethyl acrylate (HEA), 25 parts of Methyl Methacrylate (MMA), 0.2 part of Azobisisobutyronitrile (AIBN), 0 part of hexafluorobutyl methacrylate (HFMA), 10 parts of ethylenediamine, 10 parts of epoxy resin E-4410 parts and 40400.1 parts of catalyst.

The preparation process comprises the following steps:

(1) adding 50 parts of butanol, 50 parts of butyl acetate and 0.1 part of AIBN into a flask, adding weighed BA, AA, HEA, MMA and HFMA, and fully reacting for 3 hours;

(2) and (2) taking 50 parts of the resin prepared in the step (1), adding 10 parts of ethylenediamine, E-4410 parts, 30 parts of butanol and 40400.1 parts, fully mixing and discharging.

The products and intermediates of examples 1-4 and comparative example 1 were tested and the results are as follows:

TABLE test data for various examples

	NaOH resistant (%)	Citric acid resistant (%)	Salt spray test (%)
				Comparative example 1	90.3	89.2	85.2
Example 1	95.6	94.2	90.7
				Example 2	97.5	96.1	92.1
Example 3	98.5	97.9	94.2
				Example 4	99.3	98.5	96.2
Example 5	98.1	97.1	93.2

Comparing example 1 with comparative example 1, it can be seen that the corrosion resistance and acid and alkali resistance of the acrylic coating are obviously improved after HFMA is added.

Comparing example 1 with example 2, it can be seen that the amount of HFMA is increased, and the corrosion resistance and acid and alkali resistance of the acrylic coating are further enhanced.

Comparing example 2 with example 3, it can be seen that the amount of the initiator is increased and the corrosion resistance and acid and alkali resistance are enhanced.

Comparing example 3 with example 4, it can be seen that the amount of the cross-linking agent is increased, and the corrosion resistance and acid and alkali resistance are further improved.

Comparing example 3 with example 4, it can be seen that the amount of HFMA is further increased, and the corrosion resistance and acid and alkali resistance are reduced.

The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.