A wear-resistant and anti-scaling silicone-modified acrylic resin heavy-duty anticorrosive coating and preparation method thereof

Abstract

The present invention discloses a wear-resistant and anti-scaling organosilicon-modified acrylic resin heavy-duty anticorrosion coating and a preparation method thereof, wherein the heavy-duty anticorrosion coating comprises modified epoxy resin, organosilicon-modified acrylic resin, dispersant, curing agent and butyl acetate; the organosilicon-modified acrylic resin is prepared by copolymerizing acrylic acid, methyl methacrylate and organofluorine silicon monomer; the organofluorine silicon monomer has a structure as shown in the following formula A. The heavy-duty anticorrosion coating of the present invention is prepared by organosilicon-fluorine modification of acrylic resin and effectively compounding modified epoxy resin, dispersant and curing agent, so that the coating prepared by the heavy-duty anticorrosion coating has excellent adhesion, strong wear resistance and anti-scaling ability, and can be used in the field of coatings in a long-lasting and stable manner.

Description

Technical Field

[0001] The invention relates to the technical field of heavy-duty anti-corrosion coatings, and in particular to a wear-resistant and anti-scaling organosilicon-modified acrylic resin heavy-duty anti-corrosion coating and a preparation method thereof. Background Art

[0002] Corrosion is the process of damage and breakage of metal, concrete, wood and other substrates under physical, chemical or electrochemical effects. Every year, the economic losses caused by corrosion are huge, and it also poses a safety hazard to its future use. Therefore, anti-corrosion research has received more and more attention. Among the many anti-corrosion methods, anti-corrosion coatings are recognized as the most economical, convenient and safest method. As the public's requirements for environmental protection become more and more urgent and stringent, the development of low-energy, low-pollution, high-performance heavy-duty anti-corrosion coatings has become one of the current research hotspots.

[0003] The concept of heavy-duty anti-corrosion coatings originated in Japan in the 1960s. It refers to coatings with long service life that are used in harsh corrosive environments. The so-called harsh corrosive environment refers to a highly corrosive environment. According to the definition of ISO12944-2, it refers to an atmospheric environment of C4 (high), C5-I (very high industrial), C5-M (very high marine) and an environment of 1m2 immersed in seawater or saline water. There is no exact definition of the so-called long service life. It is generally believed that it should be more than 5 years of service life, that is, the medium or high coating service life specified in ISO12944-5.

[0004] The currently available heavy-duty anti-corrosion coatings have the following characteristics: high film thickness, good surface treatment performance, the application of new resins and pigments and fillers, etc.

[0005] Acrylic resin has the characteristics of light color, high transparency, full gloss, tough coating, strong adhesion and corrosion resistance, and is widely used as coating material in industrial and civil construction fields. However, the presence of a large number of hydrophilic ester groups in acrylic resin coatings makes the shielding, water resistance and solvent resistance of the coating less than ideal, limiting its application in complex environments, especially marine environments. The fluorine-containing functional groups and siloxane chains in organic fluorosilicone materials can give the materials excellent surface properties, weather resistance, solvent resistance and high and low temperature resistance. Organic fluorosilicone synergistic modification of acrylic resin can give play to the complementary advantages of each functional group, which is an important development direction for the preparation and development of highly weather-resistant and corrosion-resistant acrylic resin coatings.

[0006] However, the adhesion ability of the organic fluorine-silicon modified acrylic resin in the prior art still needs to be improved, and the wear resistance and anti-fouling ability of the formed coating are poor, which limits the application of acrylic resin anti-corrosion coatings.

[0007] Therefore, there is an urgent need for a silicone-modified acrylic resin heavy-duty anti-corrosion coating with excellent adhesion, wear resistance and anti-fouling ability. Summary of the invention

[0008] Purpose of the invention: In view of the defects of the prior art, the purpose of the present invention is to provide a silicone-modified acrylic resin heavy-duty anti-corrosion coating with excellent adhesion, wear resistance and anti-fouling ability and a preparation method thereof.

[0009] Technical solution:

[0010] A wear-resistant and anti-scaling organosilicon-modified acrylic resin heavy-duty anticorrosive coating, comprising modified epoxy resin, organosilicon-modified acrylic resin, dispersant, curing agent and butyl acetate;

[0011] The organosilicon-modified acrylic resin is prepared by copolymerizing acrylic acid, methyl methacrylate and organofluorine silicon monomers;

[0012] The organic fluorine silicon monomer has a structure as shown in the following formula A:

[0013]

[0014] The organosilicon-modified acrylic resin prepared by copolymerization of acrylic acid, methyl methacrylate and organofluorine silicon monomer in the present invention can effectively make the anti-corrosion coating into an anti-corrosion coating based on the excellent film-forming ability and anti-corrosion ability of acrylic resin, and has excellent anti-corrosion ability.

[0015] Furthermore, the modified epoxy resin is prepared by the following steps: in a reactor, bisphenol F epoxy resin, phenolic resin and catalyst are added, heated to 110-120° C. for reaction for 30-60 minutes, organic siloxane monomer is added with stirring, the temperature is raised to 140-150° C. for reaction for 1-2 hours, and then cooled and filtered to obtain the modified epoxy resin.

[0016] The modified epoxy resin prepared by the present invention is prepared by epoxy resin, phenolic resin and organosiloxane monomer, which not only has good compatibility with organosilicon-modified acrylic resin and can be effectively compounded with it, but also its epoxy resin structure can effectively improve the adhesion of the prepared coating and increase the service life.

[0017] Furthermore, the mass ratio of the bisphenol F epoxy resin, the phenolic resin and the organosiloxane monomer is (1.2-1.5):(0.8-1):(0.3-0.5); the organosiloxane monomer is selected from one of vinyl triisopropoxy silane, octavinyl cyclotetrasiloxane or octamethyl cyclotetrasiloxane; and the catalyst is selected from one of triethylamine, tetraethylammonium bromide or triphenylphosphine.

[0018] Furthermore, the organic fluorine silicon monomer is prepared by the following steps: adding an organic solvent, 1,3-bis(3-hydroxyisobutyl)tetramethyldisiloxane and a base catalyst into a reactor, heating to 60-70°C and stirring to dissolve, slowly dropping 4-bromo-3,3,4,4-tetrafluorobutene, and after the addition is completed, keeping the reaction warm for 30-50 minutes, cooling, filtering, washing and drying to obtain the organic fluorine silicon monomer.

[0019] The organic fluorine monomer of the present invention contains a large number of carbon-fluorine bonds, silicon-oxygen bonds, carbon-silicon bonds and unsaturated bonds, which can not only be effectively polymerized with acrylic acid and methyl methacrylate to prepare modified acrylic resin, but also can significantly improve the anti-scaling ability of acrylic resin.

[0020] Furthermore, the molar ratio of the 1,3-bis(3-hydroxyisobutyl)tetramethyldisiloxane to 4-bromo-3,3,4,4-tetrafluorobutene is 1:2.5-3; and the base catalyst is selected from one of potassium carbonate, potassium phosphate or sodium carbonate.

[0021] Furthermore, the organosilicon-modified acrylic resin is prepared by the following steps: adding acrylic acid, methyl methacrylate, organic fluorosilicone monomer, initiator and organic solvent into a reactor, heating to 60-80° C., stirring and reacting for 12-18 hours, cooling, filtering and drying to obtain the organosilicon-modified acrylic resin.

[0022] The present invention modifies acrylic resin by using organic fluorine silicon monomers. On the one hand, by introducing a large number of carbon-fluorine bonds with high stability and low surface energy into the acrylic resin, the weather resistance and hydrophobicity of the formed coating can be effectively improved, thereby avoiding the deposition of scale substances on the surface of the coating, and improving the anti-scaling ability of the coating; on the other hand, the silane structure therein can form a dense film structure on the surface of the coating, greatly reducing the number and area of ​​pores in the coating, which can not only effectively reduce the deposition ability of scale components such as calcium magnesium scale and barium strontium scale on the surface of the coating, further improving the anti-scaling ability of the coating, but also its dense structure and stability can significantly improve the wear resistance of the coating.

[0023] Furthermore, the initiator is selected from one of azobisisobutyronitrile and ammonium persulfate; the molar ratio of acrylic acid, methyl methacrylate and organic fluorine silicon monomer is (15-20): (10-15): (5-8).

[0024] Furthermore, the dispersant is selected from one of sodium dodecylbenzene sulfonate, sodium lignin sulfonate or hexadecyltrimethylammonium bromide; and the curing agent is selected from one of methyl ethyl ketone peroxide, m-phenylenediamine or diaminodiphenyl sulfone.

[0025] Furthermore, based on the total mass fraction being 100%, the mass percentage of each component is:

[0026]

[0027] The preparation method of any of the above-mentioned wear-resistant and anti-scaling silicone-modified acrylic resin heavy-duty anti-corrosion coatings comprises the following steps: weighing modified epoxy resin, silicone-modified acrylic resin, dispersant, curing agent and butyl acetate in proportion, mixing and dispersing them evenly to obtain the wear-resistant and anti-scaling silicone-modified acrylic resin heavy-duty anti-corrosion coating.

[0028] Beneficial effects:

[0029] (1) The wear-resistant and anti-fouling silicone-modified acrylic resin heavy-duty anti-corrosion coating provided by the present invention is obtained by modifying acrylic resin with silicone fluorine and effectively compounding modified epoxy resin, dispersant and curing agent. The coating made of the heavy-duty anti-corrosion coating has excellent adhesion ability, strong wear resistance and anti-fouling ability, and can be used in the field of coatings in a long-term and stable manner.

[0030] (2) In the wear-resistant and anti-fouling organosilicon-modified acrylic resin heavy-duty anti-corrosion coating provided by the present invention, the organosilicon-modified acrylic resin prepared by copolymerization of acrylic acid, methyl methacrylate and organic fluorosilicone monomers can effectively make the anti-corrosion coating into an anti-corrosion coating based on the excellent film-forming ability and anti-corrosion ability of acrylic resin, and has excellent anti-corrosion ability.

[0031] (3) In the wear-resistant and anti-fouling organosilicon-modified acrylic resin heavy-duty anti-corrosion coating provided by the present invention, the organic fluorine monomer contains a large amount of carbon-fluorine bonds, silicon-oxygen bonds, carbon-silicon bonds and unsaturated bonds, which can not only be effectively polymerized with acrylic acid and methyl methacrylate to form modified acrylic resin, but also can significantly improve the anti-fouling ability of acrylic resin.

[0032] (4) In the wear-resistant and anti-fouling organosilicon-modified acrylic resin heavy-duty anti-corrosion coating provided by the present invention, the acrylic resin is modified by an organic fluorosilicone monomer. On the one hand, by introducing a large number of carbon-fluorine bonds with high stability and low surface energy into the acrylic resin, the weather resistance and hydrophobicity of the formed coating can be effectively improved, thereby avoiding the deposition of scale substances on the coating surface and improving the anti-fouling ability of the coating; on the other hand, the silane structure therein can form a dense film structure on the surface of the coating, greatly reducing the number and area of ​​pores in the coating, which can not only effectively reduce the deposition ability of scale components such as calcium-magnesium scale and barium-strontium scale on the coating surface, further improving the anti-fouling ability of the coating, but also its dense structure and stability can significantly improve the wear resistance of the coating.

[0033] (5) The wear-resistant and anti-fouling organosilicon-modified acrylic resin heavy-duty anti-corrosion coating provided by the present invention is prepared by using epoxy resin, phenolic resin and organosiloxane monomers to form a modified epoxy resin. It not only has good compatibility with organosilicon-modified acrylic resin and can be effectively compounded with it, but also the structure of the epoxy resin can effectively improve the adhesion ability of the prepared coating and increase the service life. DETAILED DESCRIPTION

[0034] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0035] The commercially available heavy-duty anti-corrosion coating is epoxy anti-corrosion coating HC104 purchased from Tianjin Ren'ai Technology Development Co., Ltd.; the commercially available epoxy resin is epoxy resin E51 purchased from Wanqing Chemical Technology Co., Ltd.; the commercially available acrylic resin is 518 acrylic resin purchased from Shandong Lingsai Coatings Co., Ltd.; the remaining reagents and equipment are conventional reagents and equipment in this technical field.

[0036] Preparation of modified epoxy resin

[0037] The modified epoxy resin was prepared by the following steps:

[0038] In a reactor, 3 g of bisphenol F epoxy resin, 1.8 g of phenolic resin and 0.1 g of triethylamine were added, and the mixture was heated to 115° C. and reacted for 50 minutes. Then, 0.8 g of vinyl triisopropoxy silane was added with stirring, and the mixture was heated to 145° C. and reacted for 1 hour. After that, the mixture was cooled and filtered to obtain the modified epoxy resin.

[0039] Preparation of organic fluorine silicon monomer-1

[0040] The organic fluorine silicon monomer-1 was prepared by the following steps:

[0041] In a reactor, 50 mL of N,N-dimethylformamide, 0.02 mol of 1,3-bis(3-hydroxyisobutyl)tetramethyldisiloxane and 0.3 g of potassium carbonate were added, heated to 70° C. and stirred to dissolve, 0.05 mol of 4-bromo-3,3,4,4-tetrafluorobutene was slowly added dropwise, and after the addition was completed, the reaction was kept warm for 30 minutes, and then cooled, filtered, washed and dried to obtain the organic fluorine silicon monomer-1;

[0042] Mass spectrum data of organic fluorine silicon monomer-1: The product was analyzed by LC-MS, and the m / z of the product was 530.19 (100.0%), 531.21 (32.8%), 532.20 (11.8%), and 533.21 (2.4%).

[0043] Preparation of organic fluorine silicon monomer-2

[0044] The preparation method is basically the same as that of organic fluorine silicon monomer-1, except that 1,3-bis(3-hydroxyisobutyl)tetramethyldisiloxane is replaced by an equal amount of hydroxybutyltrimethylsilane.

[0045] Preparation of silicone modified acrylic resin-1

[0046] The silicone-modified acrylic resin-1 was prepared by the following steps:

[0047] In the reactor, 0.15 mol of acrylic acid, 0.1 mol of methyl methacrylate, 0.05 mol of organic fluorine silicon monomer-1, 0.5 g of azobisisobutyronitrile and 100 mL of N,N-dimethylformamide were added, heated to 70° C. and stirred for reaction for 16 hours, then cooled, filtered and dried to obtain the organic silicon modified acrylic resin-1.

[0048] Preparation of silicone modified acrylic resin-2

[0049] The preparation method is basically the same as that of organosilicon-modified acrylic resin-1, except that the organofluorine silicon monomer-1 is replaced by an equal amount of organofluorine silicon monomer-2.

[0050] Example 1

[0051] The wear-resistant and anti-fouling silicone-modified acrylic resin heavy-duty anticorrosive coating was prepared by the following steps:

[0052] Modified epoxy resin, organosilicon-modified acrylic resin-1, sodium dodecylbenzene sulfonate, methyl ethyl ketone peroxide and butyl acetate are weighed in proportion, mixed and dispersed evenly to obtain the wear-resistant and anti-scaling organosilicon-modified acrylic resin heavy-duty anticorrosive coating;

[0053] Taking the total mass fraction as 100%, the mass percentage of each component is:

[0054]

[0055] Example 2

[0056] Basically the same as Example 1, except that, based on the total mass fraction being 100%, the components and their mass percentages are:

[0057]

[0058] Example 3

[0059] Basically the same as Example 1, except that, based on the total mass fraction being 100%, the components and their mass percentages are:

[0060]

[0061] Comparative Example 1

[0062] Commercially available heavy duty anti-corrosion coating.

[0063] Comparative Example 2

[0064] The method is basically the same as Example 1, except that the modified epoxy resin is replaced by an equal amount of commercially available epoxy resin.

[0065] Comparative Example 3

[0066] The process is basically the same as Example 1, except that the organosilicon-modified acrylic resin-1 is replaced by an equal amount of commercially available acrylic resin.

[0067] Comparative Example 4

[0068] The method is basically the same as Example 1, except that the organosilicon-modified acrylic resin-1 is replaced by an equal amount of organosilicon-modified acrylic resin-2.

[0069] Performance Testing

[0070] The Q235 steel plate was cut into substrates of 50 mm × 70 mm in size. The substrates were degreased with acetone and anhydrous ethanol, and then polished smooth with 120#, 240# and 600# sandpapers in turn. Then, they were cleaned with anhydrous ethanol, blown dry and sealed with tape. The products of Examples 1-3 and Comparative Examples 1-4 were evenly scraped and coated on the cleaned Q235 steel plate substrates. After natural drying for 24 hours, they were placed in an oven at 80°C and dried for 8 hours. The coating thickness was 100 μm.

[0071] Adhesion ability test: According to the test standard of GB / T9286-1998 "Scratch test for paint and varnish films", the adhesion of the coating films made of the above-mentioned examples 1-3 and comparative examples 1-4 products on Q235 steel plate substrates was tested.

[0072] Wear resistance test: According to the test standard of GB / T1768-2006 "Determination of wear resistance of paint films", the wear quality of the coating films made of the above-mentioned examples 1-3 and comparative examples 1-4 products on Q235 steel plate substrates was tested under the condition of 750g / 500r.

[0073] Anti-scaling ability test: The Q235 steel plate substrate coated with the products of the above-mentioned Examples 1-3 and Comparative Examples 1-4 was placed in a heat exchanger simulation experimental device, and the simulated crude oil production liquid was heated to 60°C with heat transfer oil. After 14 days, it was taken out and the mass of scale attached to the steel plate substrate was calculated.

[0074] Adhesion grade Wear mass (mg) <![CDATA[Adherent fouling mass (g / m 2 )]]> Example 1 0 6.9 0.74 Example 2 0 7.1 0.75 Example 3 0 6.8 0.74 Comparative Example 1 2 19.4 3.62 Comparative Example 2 1 8.4 0.81 Comparative Example 3 0-1 15.9 2.21 Comparative Example 4 0 12.6 1.38

[0075] According to the comparison of the test results of Examples 1-3 with those of Comparative Example 1, the wear-resistant and anti-fouling silicone-modified acrylic resin heavy-duty anti-corrosion coating provided by the present invention has better adhesion and wear resistance than the heavy-duty anti-corrosion coating in the prior art, and can improve the anti-fouling ability of the coating film, thereby expanding its application range and service life.

[0076] According to the comparison of the test results of Examples 1-3 and Comparative Example 2, it can be seen that in the wear-resistant and anti-fouling silicone-modified acrylic resin heavy-duty anti-corrosion coating provided by the present invention, the adhesion ability of the coating film can be effectively improved by adding modified epoxy resin, and its overall performance can be further improved.

[0077] According to the comparison of the test results of Examples 1-3 and Comparative Examples 3-4, it can be seen that in the wear-resistant and anti-fouling organosilicon-modified acrylic resin heavy-duty anti-corrosion coating provided by the present invention, the organosilicon-modified acrylic resin prepared by modifying the acrylic resin by adding organic fluorosilicone monomers can significantly improve the wear resistance and anti-fouling ability of the prepared coating.

[0078] The above implementation modes are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A wear-resistant and anti-scaling silicone-modified acrylic resin heavy-duty anti-corrosion coating, characterized in that: Contains modified epoxy resin, silicone modified acrylic resin, dispersant, curing agent and butyl acetate; The organosilicon-modified acrylic resin is prepared by copolymerizing acrylic acid, methyl methacrylate and organofluorine silicon monomers; The organic fluorine silicon monomer has a structure as shown in the following formula A: 。 2. The wear-resistant and anti-scaling silicone-modified acrylic resin heavy-duty anti-corrosion coating according to claim 1, characterized in that: The modified epoxy resin is prepared by the following steps: adding bisphenol F epoxy resin, phenolic resin and catalyst into a reactor, heating to 110-120° C. for reaction for 30-60 minutes, adding organic siloxane monomer with stirring, heating to 140-150° C. for reaction for 1-2 hours, cooling and filtering to obtain the modified epoxy resin.

3. The wear-resistant and anti-scaling silicone-modified acrylic resin heavy-duty anti-corrosion coating according to claim 2, characterized in that: The mass ratio of the bisphenol F epoxy resin, the phenolic resin and the organosiloxane monomer is (1.2-1.5): (0.8-1): (0.3-0.5); the organosiloxane monomer is selected from one of vinyl triisopropoxy silane, octavinyl cyclotetrasiloxane or octamethyl cyclotetrasiloxane; and the catalyst is selected from one of triethylamine, tetraethylammonium bromide or triphenylphosphine.

4. The wear-resistant and anti-scaling silicone-modified acrylic resin heavy-duty anti-corrosion coating according to claim 1, characterized in that: The organic fluorine silicon monomer is prepared by the following steps: adding an organic solvent, 1,3-bis(3-hydroxyisobutyl)tetramethyldisiloxane and a base catalyst into a reactor, heating to 60-70° C. and stirring to dissolve, slowly dropping 4-bromo-3,3,4,4-tetrafluorobutene, and keeping the temperature for reaction for 30-50 minutes after the dropping is completed, cooling, filtering, washing and drying to obtain the organic fluorine silicon monomer.

5. The wear-resistant and anti-scaling silicone-modified acrylic resin heavy-duty anti-corrosion coating according to claim 4, characterized in that: The molar ratio of the 1,3-bis(3-hydroxyisobutyl)tetramethyldisiloxane to 4-bromo-3,3,4,4-tetrafluorobutene is 1:2.5-3; and the base catalyst is selected from potassium carbonate, potassium phosphate or sodium carbonate.

6. The wear-resistant and anti-scaling silicone-modified acrylic resin heavy-duty anti-corrosion coating according to claim 1, characterized in that: The organosilicon-modified acrylic resin is prepared by the following steps: adding acrylic acid, methyl methacrylate, organic fluorine silicon monomer, initiator and organic solvent into a reactor, heating to 60-80° C., stirring and reacting for 12-18 hours, cooling, filtering and drying to obtain the organosilicon-modified acrylic resin.

7. The wear-resistant and anti-scaling silicone-modified acrylic resin heavy-duty anticorrosive coating according to claim 6, characterized in that: The initiator is selected from azobisisobutyronitrile or ammonium persulfate; the molar ratio of acrylic acid, methyl methacrylate and organic fluorine silicon monomer is (15-20): (10-15): (5-8).

8. The wear-resistant and anti-scaling silicone-modified acrylic resin heavy-duty anti-corrosion coating according to claim 1, characterized in that: The dispersant is selected from one of sodium dodecylbenzene sulfonate, sodium lignin sulfonate or hexadecyltrimethylammonium bromide; the curing agent is selected from one of methyl ethyl ketone peroxide, m-phenylenediamine or diaminodiphenyl sulfone.

9. The wear-resistant and anti-scaling silicone-modified acrylic resin heavy-duty anti-corrosion coating according to claim 1, characterized in that: Taking the total mass fraction as 100%, the mass percentage of each component is: Modified epoxy resin 5-10% Silicone modified acrylic resin 55-65% Dispersant 3-5% Curing agent 3-5% The balance was butyl acetate.

10. The method for preparing the wear-resistant and anti-scaling silicone-modified acrylic resin heavy-duty anticorrosive coating according to any one of claims 1 to 9, characterized in that: The following steps are involved: The modified epoxy resin, the organosilicon-modified acrylic resin, the dispersant, the curing agent and butyl acetate are weighed in proportion, mixed and dispersed uniformly to obtain the wear-resistant and anti-scaling organosilicon-modified acrylic resin heavy-duty anticorrosive coating.

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