CN103214655B - Modified epoxy resin and high-solid anticorrosive coating prepared therewith - Google Patents

Abstract

The invention discloses a modified epoxy resin and a high solid anticorrosion paint prepared by using the modified epoxy resin. The modified epoxy resin is prepared by reacting E-44 epoxy resin, fluoroacrylic acid mixed monomer and styrene, wherein the fluoroacrylic acid mixed monomer is made of methacrylic acid, butyl acrylate and hexafluorobutyl methacrylate Raw material preparation. In the present invention, by adopting new components and proportioning, the prepared modified epoxy resin reaches the following technical indicators: light yellow transparent viscous liquid, acid value 4.6mgKOH/g, epoxy value 0.03 equivalent/l00g, viscosity (25 °C) is 0.245 Pa·s, and has excellent performance in water resistance, acid and alkali resistance, high and low temperature resistance, anti-corrosion performance and adhesion. The present invention adopts the above-mentioned modified epoxy resin and the high-solid anticorrosion coating made by the new proportion. The test results show that it has superior performance in water resistance, acid and alkali resistance, high and low temperature resistance, anti-corrosion performance and adhesion. It is suitable for different low-altitude aircraft substrates such as aluminum alloy, titanium alloy, magnesium alloy and composite materials.

Description

Modified epoxy resin and high solid content anti-corrosion coating prepared by it

technical field

The invention relates to a modified epoxy resin and a high solid content anticorrosion coating prepared by the modified epoxy resin.

Background technique

Epoxy resin is widely used. Due to its own structural characteristics, its corrosion resistance and thermal stability are limited, so it is necessary to modify the epoxy resin. There have been some reports on the modification of epoxy resin by polyester, such as Chinese invention patents CN101864236 and CN101885831; there are also some reports on the use of acrylic monomers to modify epoxy resin, such as Li Weili et al. published in "Paint Industry" 2012 "Preparation and Performance Research of Anti-corrosion Iron Red Primer Based on Acrylic Grafted Epoxy Resin", Volume 42, Issue 6, pp. 1-5. Existing anticorrosion coatings for low-altitude aircraft substrates have the defect that they cannot be applied to different low-altitude aircraft substrates.

Contents of the invention

The object of the present invention is to provide a modified epoxy resin and a high-solid anticorrosion coating prepared by using the modified epoxy resin. The modified epoxy resin prepared by the present invention has excellent performance in water resistance, high and low temperature resistance, anti-corrosion performance and adhesion; the present invention utilizes the above-mentioned modified epoxy resin to prepare high solid content anti-corrosion coatings suitable for different low-altitude aircraft substrates. The coating overcomes the defect that existing anticorrosion coatings for low-altitude aircraft substrates cannot be applied to different low-altitude aircraft substrates.

Technical solution of the present invention: modified epoxy resin, the weight ratio of raw material components is as follows, and the consumption is parts by weight;

Epoxy resin 60-75 parts, fluoroacrylic acid mixed monomer 18-25 parts,

Styrene 12-20 parts;

The fluoroacrylic acid mixed monomer comprises the following components in mass fraction:

Methacrylic acid 25～40%, Butyl acrylate 25～40%,

Hexafluorobutyl methacrylate 25-40%.

In the aforementioned modified epoxy resin, the weight ratio of raw material components is as follows:

65-70 parts of epoxy resin, 20-22 parts of fluoroacrylic acid mixed monomer,

Styrene 15-18 parts;

The fluoroacrylic acid mixed monomer comprises the following components in mass fraction:

Methacrylic acid 30～36%, Butyl acrylate 30～36%,

Hexafluorobutyl methacrylate 30-36%.

In the aforementioned modified epoxy resin, the epoxy resin is E-44 epoxy resin; the fluoroacrylic acid mixed monomer is composed of methacrylic acid, butyl acrylate and methacrylic acid with a mass ratio of 1:1:1 Composition of hexafluorobutyl ester.

The method for preparing the aforementioned modified epoxy resin is as follows: heating E-44 epoxy resin to 105-115°C, adding fluoroacrylic acid mixed monomer dropwise under stirring, and measuring the acid value after the heat preservation reaction for 3-4 hours. When the acid value is less than 5mgKOH/g, cool down to about 70°C, add styrene to dilute, stir evenly, cool down and discharge the material to obtain the modified epoxy resin.

A high-solids anti-corrosion coating prepared with the above-mentioned modified epoxy resin, which is composed of A component and B component, and the mass ratio of A component and B component is 100:20-40;

A component is prepared according to the following weight ratio raw materials:

Modified epoxy resin 16-20 parts, 601-75 epoxy resin 10-13 parts,

Pigment 24~30 parts, anti-settling agent 0.1~0.3 parts,

Leveling agent 0.05~0.15 parts, filler 8~10 parts,

Matting agent 3~4 parts, Rust inhibitor 4~6 parts,

Defoamer 0.1~0.2 parts, Ethylene glycol butyl ether 1~1.5 parts,

3-4 parts of toluene, 18-21 parts of xylene;

B component is prepared according to the raw materials of the following weight ratio:

Curing agent 60-66 parts, toluene 19-22 parts,

4-6 parts of n-butanol, 0.5-1.5 parts of ethylene glycol butyl ether,

4-6 parts of xylene, 2-4 parts of drier.

In the aforementioned high-solid content anti-corrosion coating, the mass ratio of component A and component B is 100:25-35.

In the above-mentioned high solid content anti-corrosion coating, the mass ratio of A component and B component is 100:33.

In the aforementioned high-solid anticorrosion coating, the pigment is made of titanium dioxide; the anti-settling agent is bentonite; the filler is made of talcum powder and barium sulfate; and the matting agent is matting powder.

In the aforementioned high-solid anticorrosion coating, the pigment is composed of titanium dioxide TR-33 and R902+titanium dioxide in a mass ratio of 1:0.8 to 1.2; the anti-settling agent is bentonite 938; the leveling agent is MAA flow leveling agent; the filler is composed of superfine talcum powder CMS-666 and barium sulfate in a mass ratio of 1:0.8 to 1.2; the matting agent is C906 matting powder; the rust inhibitor is zinc phosphochromate; The foaming agent is 5400 defoamer; the curing agent is curing agent 2015; the drier is drier T-30.

The method for preparing aforementioned high solid anticorrosion coating is characterized in that it comprises the following three steps:

a. First mix modified epoxy resin, 601-75 epoxy resin and xylene, slowly add anti-settling agent under stirring, disperse at high speed for about 5 minutes until uniform, add pigment and defoamer under stirring, stir for 15 minutes, Then add filler and stir for 15 minutes, then add matting agent, leveling agent, rust inhibitor, ethylene glycol butyl ether and toluene under stirring, stir for 20 minutes, disperse evenly, grind to a fineness of less than 40 μm with a sand mill, filter to remove the grinding Sand, filtered and packaged to obtain A component;

b. Mix curing agent, toluene, n-butanol, ethylene glycol butyl ether, xylene and drier, stir for 20 minutes, disperse evenly, filter and package to obtain component B;

c. Mix component A and component B and stir evenly to obtain a high solid content anti-corrosion coating.

Compared with the prior art, the modified epoxy resin prepared by the present invention achieves the following technical indicators by adopting new components and proportions: light yellow transparent viscous liquid, acid value 4.6mgKOH/g, epoxy value 0.03 Equivalent/l00g, viscosity (at 25°C) is 0.245Pa·s, and has superior performance in water resistance, acid and alkali resistance, high and low temperature resistance, anti-corrosion performance and adhesion. The present invention adopts the above-mentioned modified epoxy resin and the high-solid anticorrosion coating made by the new proportion. The test results show that it has superior performance in water resistance, acid and alkali resistance, high and low temperature resistance, anti-corrosion performance and adhesion. It is suitable for different low-altitude aircraft substrates such as aluminum alloy, titanium alloy, magnesium alloy and composite materials.

Detailed ways

The present invention will be further described below in conjunction with the examples, but not as a basis for limiting the present invention.

Example.

Prepare modified epoxy resin according to the following steps:

a. Mix methacrylic acid, butyl acrylate and hexafluorobutyl methacrylate in a mass ratio of 1:1:1 to prepare fluoroacrylic acid mixed monomers.

b. Take 67.65 parts of E-44 epoxy resin, heat it up to 110°C, add 21.18 parts of fluoroacrylic acid mixed monomer dropwise under stirring, and measure the acid value after 4 hours of heat preservation reaction. When the acid value is less than 5mgKOH/g, lower the temperature To 70°C, add 16.47 parts of styrene to dilute, stir well, then cool down and discharge to prepare modified epoxy resin.

The performance index of the prepared modified epoxy resin is as follows: the appearance is light yellow transparent viscous liquid, the acid value is 4.6mgKOH/g, the epoxy value is 0.03 equivalent/l00g, and the viscosity (under the situation of 25 ℃) is 0.245 Pa·s.

Prepare high solids anti-corrosion coatings according to the following steps:

a. First take 18.2 parts of modified epoxy resin, 11.29 parts of 601-75 epoxy resin and 19.45 parts of xylene. After mixing, slowly add 0.2 parts of bentonite 938 under stirring, and disperse at a high speed for about 5 minutes to uniformity. Add 14.88 parts of TR-33 titanium dioxide, 14.88 parts of R902 ⁺ titanium dioxide and 0.13 parts of 5400 defoamer, stir for 15 minutes, then add 4.92 parts of talcum powder 666 and 4.99 parts of barium sulfate, stir for 15 minutes, then add 3.46 parts of C906 under stirring Matting powder, 0.09 parts of MAA leveling agent, 4.99 parts of zinc phosphochromate, 1.32 parts of ethylene glycol butyl ether and 3.29 parts of toluene, stirred for 20 minutes, dispersed evenly, and ground with sand mill until the fineness is less than 40 μm, filtered to remove the grinding sand, Filter the package to obtain A component.

b. Take 64.09 parts of curing agent 2015, 21.12 parts of toluene, 5.92 parts of n-butanol, 0.99 parts of ethylene glycol butyl ether, 4.93 parts of xylene and 2.96 parts of drying agent T-30. After mixing, stir for 20 minutes to disperse evenly. Filter the package to get the B component.

c. Take component A and component B with a mass ratio of 100:33, mix them, and stir evenly to prepare a high-solid anti-corrosion coating.

The above-mentioned 601-75 epoxy resin and E-44 epoxy resin are produced by Jiangsu Sanmu Group Co., Ltd.

The above-mentioned titanium dioxide TR-33 is produced by Dongguan Shuangli Titanium Dioxide Co., Ltd.

The above-mentioned R902+ titanium dioxide is produced by Shanghai Xiangtai Chemical Co., Ltd.

The above-mentioned bentonite 938 is produced by Xiamen Aikema Chemical Raw Materials Co., Ltd.

The above-mentioned MAA leveling agent is produced by Xintike Chemical (China).

The above-mentioned superfine talcum powder CMS-666 is produced by Heshan Chemical (Liaoning) Co., Ltd.

The above-mentioned barium sulfate was produced by Shanghai Yuejiang Titanium White Chemical Products Co., Ltd.

The above C906 matting powder is produced by Shanghai Xinxin Industrial Co., Ltd.

The zinc phosphochromate mentioned above is produced by Lanxi Xinrong Metal Chemical Co., Ltd.

The above-mentioned 5400 defoamer is produced by Shanghai Beida Packaging Materials Co., Ltd.

The above-mentioned 2015 curing agent is produced by Shanghai Yaoshan Chemical Co., Ltd.

The above-mentioned drier T-30 was produced by Shanghai Baiyin Chemical Co., Ltd.

The high solid anticorrosion coating prepared above was tested on aluminum alloys, titanium alloys, magnesium alloys and composite materials. The coating properties are shown in the table below.

The above test data shows that the high solid content anti-corrosion coating prepared by the present invention has superior performance in water resistance, high and low temperature resistance, anti-corrosion performance and adhesion, and can be used for different low-altitude aircraft substrates.

The above general description of the invention involved in this application and the description of its specific implementation should not be understood as limiting the technical solution of the invention. Based on the disclosure of this application, those skilled in the art can add or subtract the disclosed technical features in the above general description or/and specific implementation methods (including examples) without violating the constituent elements of the invention involved. Or in combination to form other technical solutions belonging to the invention.

Claims (9)

1. High-solid anti-corrosion coating prepared by modified epoxy resin, characterized in that it is composed of component A and component B, and the mass ratio of component A and component B is 100:20-40; A component is prepared according to the following weight ratio raw materials: B component is prepared according to the raw materials of the following weight ratio: 60-66 parts of curing agent, 19-22 parts of toluene, 4-6 parts of n-butanol, 0.5-1.5 parts of ethylene glycol butyl ether, 4-6 parts of xylene, 2-4 parts of drier; The weight ratio of the raw material components of the modified epoxy resin is as follows, and the consumption is parts by weight; 60-75 parts of epoxy resin, 18-25 parts of fluoroacrylic acid mixed monomer, Styrene 12-20 parts; The fluoroacrylic acid mixed monomer comprises the following components in mass fraction: Methacrylic acid 25-40%, butyl acrylate 25-40%, Hexafluorobutyl methacrylate 25-40%. 2. the high solid anticorrosion paint prepared by modified epoxy resin according to claim 1, is characterized in that, the weight ratio of the raw material component of described modified epoxy resin is as follows: 65-70 parts of epoxy resin, 20-22 parts of fluoroacrylic acid mixed monomer, Styrene 15-18 parts; The fluoroacrylic acid mixed monomer comprises the following components in mass fraction: Methacrylic acid 30-36%, butyl acrylate 30-36%, Hexafluorobutyl methacrylate 30-36%. 3. according to the high solid content anticorrosion paint prepared by the described modified epoxy resin of claim 1 or 2, it is characterized in that: the epoxy resin is E-44 epoxy resin; Composition of methacrylic acid, butyl acrylate and hexafluorobutyl methacrylate in a ratio of 1:1:1. 4. prepare the high solid anticorrosion coating prepared by the modified epoxy resin described in claim 1, 2 or 3, it is characterized in that, the method for described modified epoxy resin is: heating epoxy resin to 105～115 ℃, add fluorinated acrylic acid mixed monomer dropwise under stirring, after 3-4 hours of heat preservation reaction, measure the acid value, when the acid value is less than 5mgKOH/g, cool down to about 70 ℃, add styrene to dilute, stir well and cool down material to obtain modified epoxy resin. 5. The high solid content anti-corrosion coating according to claim 1, characterized in that: the mass ratio of component A and component B is 100:25-35. 6. The high solid content anti-corrosion coating according to claim 5, characterized in that: the mass ratio of component A and component B is 100:33. 7. The high-solid anticorrosion coating according to claim 1, 5 or 6, characterized in that: the pigment is made of titanium dioxide; the anti-sedimentation agent is bentonite; the filler is made of talcum powder and barium sulfate into; the matting agent is matting powder. 8. The high-solid anti-corrosion coating according to claim 7, characterized in that: the pigment is composed of titanium dioxide TR-33 and R902+titanium dioxide in a mass ratio of 1:0.8-1.2; the anti-sedimentation agent is bentonite 938; the leveling agent is MAA leveling agent; the filler is composed of ultrafine talc powder CMS-666 and barium sulfate in a mass ratio of 1:0.8 to 1.2; the matting agent is C906 matting powder; the rust The agent is zinc phosphochromate; the defoamer is 5400 defoamer; the curing agent is curing agent 2015; the drier is drier T-30. 9. prepare the method for high solid anticorrosion coating as claimed in claim 7, is characterized in that, it comprises following three steps: a. First mix modified epoxy resin, 601-75 epoxy resin and xylene, slowly add anti-settling agent under stirring, disperse at high speed for 5 minutes until uniform, add pigment and defoamer under stirring, stir for 15 minutes, then Add filler, stir for 15 minutes, then add matting agent, leveling agent, rust inhibitor, ethylene glycol butyl ether and toluene under stirring, stir for 20 minutes, disperse evenly, grind with sand until the fineness is less than 40 μm, filter to remove the grinding sand , filter and package to obtain A component; b. Mix curing agent, toluene, n-butanol, butyl glycol ether, xylene and drier, stir for 20 minutes, disperse evenly, filter and package to obtain component B; c. Mix component A and component B and stir evenly to obtain a high solid content anti-corrosion coating.