Preparation method of environment-friendly adhesion agent for aluminum alloy

Abstract

The application relates to the technical field of adhesion agents, and discloses a preparation method of an environment-friendly adhesion agent for aluminum alloy, which comprises the following steps: adding water, potassium hydroxide, sodium chloride, sodium gluconate, anhydrous tripotassium phosphate, polyether DF-20, 8-hydroxyquinolyl polycarboxylic acid adhesion agent, sulfosuccinate and sodium isooctyl alcohol sulfate into a reaction kettle and stirring uniformly to obtain the environment-friendly adhesion agent for aluminum alloy. The 8-hydroxyquinolyl group contained in the 8-hydroxyquinolyl polycarboxylic acid adhesion agent can interact with the surface of the aluminum alloy or the tinplate through coordination, and meanwhile, the carboxyl contained in the polycarboxylic acid adhesion agent can interact with the carboxyl and other groups in the water-based acrylic resin emulsion through hydrogen bonding, so that the polycarboxylic acid adhesion agent plays a bridging role between the aluminum alloy and the acrylic resin paint film, the adhesion and the bonding performance between the acrylic resin paint film and the base material are enhanced, and better adhesion grade and greater T-peeling strength are achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of adhesion agents, and particularly to a preparation method of an environmentally-friendly adhesion agent for aluminum alloy. BACKGROUND

[0002] In the past industrial production, the application of aluminum alloy is increasingly widespread. Due to the poor combination of acrylic resin and aluminum alloy and other metal substrates, many problems are caused. For example, in the metal processing process, the coating is easy to fall off, and the adhesion is not firm, which not only affects the appearance quality of the product, but also reduces the service life and stability. In the surface treatment field, the insufficient adhesion also greatly reduces the protection effect, increasing the risk of metal corrosion and damage. In some industrial production processes with high requirements for adhesion strength, such as automobile manufacturing, aerospace, etc., this performance defect seriously restricts the progress of the process and the quality of the product. Therefore, in order to solve these long-standing problems, the preparation method of the environmentally-friendly adhesion agent for aluminum alloy is developed. SUMMARY

[0003] (I) The technical problem solved by the present application is to provide a preparation method of an environmentally-friendly adhesion agent for aluminum alloy, which can improve the adhesion and adhesion between acrylic resin and aluminum alloy and other metal materials.

[0004] (II) Technical solution: (1) water, molar ratio of (0.05-0.06) 1:(0.08-0.14):(0.07-0.08) allyl polyoxyethylene ether, methacrylic acid, 5-(2-methylallyloxy methylene)-8-quinolinol hydrochloride, ammonium persulfate are added to the reaction container, heated to 75-85℃ under N2 atmosphere, stirred for 4-6h, dried after reaction, washed with ethanol, and 8-hydroxyquinolinyl polycarboxylic acid adhesion agent is obtained.

[0005] (2) water, potassium hydroxide, sodium chloride, sodium gluconate, anhydrous potassium phosphate, polyether DF-20, 8-hydroxyquinolinyl polycarboxylic acid adhesion agent, sulfosuccinate, isooctanol sodium sulfate are added to the reaction kettle, heated to 40-60℃, stirred uniformly, cooled and discharged, and an environmentally-friendly adhesion agent for aluminum alloy is obtained.

[0006] Preferably, in step (2), the mass ratio of water, potassium hydroxide, sodium chloride, sodium gluconate, anhydrous potassium phosphate, polyether DF-20, 8-hydroxyquinolinyl polycarboxylic acid adhesion agent, sulfosuccinate, isooctanol sodium sulfate is (26-32):(17-20):(0.7-1.3):(4-6):(13-18):(10-14):(6-10):(4-7):(1.5-2.2).

[0007] Preferably, the preparation method of 5-(2-methylallyloxy methylene)-8-quinolinol hydrochloride is as follows: 1,4-dioxane, 2-methylallyl alcohol, sodium acetate, water, 5-(chloromethyl)-8-quinolinol hydrochloride are added into a reaction container, heated to 80-95 DEG C under N2 atmosphere, and reacted for 3-5 h, concentrated under reduced pressure, filtered, washed with water, and dried to obtain 5-(2-methylallyloxy methylene)-8-quinolinol hydrochloride.

[0008] Preferably, the molar ratio of 2-methylallyl alcohol, 5-(chloromethyl)-8-quinolinol hydrochloride, and sodium acetate is (2.5-3.4):1:(1-1.1).

[0009] (III) Beneficial technical effects: the present application utilizes 5-(chloromethyl)-8-quinolinol hydrochloride and 2-methylallyl alcohol to generate 5-(2-methylallyloxy methylene)-8-quinolinol hydrochloride under the condition of sodium acetate as a catalyst, then performs polymerization reaction with allyl polyoxyethylene ether and methacrylic acid to obtain 8-hydroxyquinolyl polycarboxylic acid adhesion agent, and finally performs compounding with water, sodium gluconate, anhydrous potassium phosphate, polyether DF-20, sulfosuccinate, isooctanol sodium sulfate, etc. to obtain environment-friendly adhesion agent for aluminum alloy.

[0010] The environment-friendly adhesion agent of the present application contains 8-hydroxyquinolyl polycarboxylic acid adhesion agent, the 8-hydroxyquinolyl group contained in the adhesion agent can interact with the surface of aluminum alloy or tinplate through coordination, etc., and the carboxyl group contained in the polycarboxylic acid adhesion agent can interact with the carboxyl group in the water-based acrylic resin emulsion through hydrogen bond, etc., so that the polycarboxylic acid adhesion agent plays a role of bridging the aluminum alloy group and the acrylic resin film, enhances the adhesion and bonding performance between the acrylic resin film and the substrate, and exhibits better adhesion grade and greater T-peeling strength. BRIEF DESCRIPTION OF DRAWINGS

[0011] Figure 1 is the preparation reaction formula of 5-(2-methylallyloxy methylene)-8-quinolinol hydrochloride. DETAILED DESCRIPTION

[0012] Example 1

[0013] (1) 10 mL of 1,4-dioxane, 7.5 mmol of 2-methylallyl alcohol, 3.1 mmol of sodium acetate, 10 mL of water, and 3 mmol of 5-(chloromethyl)-8-quinolinol hydrochloride are added into a reaction container, heated to 85 DEG C under N2 atmosphere, and reacted for 4 h, concentrated under reduced pressure, filtered, washed with water, and dried to obtain 5-(2-methylallyloxy methylene)-8-quinolinol hydrochloride.

[0014] (2) To the reaction vessel, water was added, 0.15 mmol of allyl polyoxyethylene ether, 3 mmol of methacrylic acid, 0.3 mmol of 5-(2-methylallyloxy methylene)-8-quinolinol hydrochloride, heated to 80°C under N2 atmosphere, 0.24 mmol of ammonium persulfate was added, and the reaction was stirred for 6 h. After the reaction, water was removed by drying, and ethanol was washed to obtain 8-hydroxyquinolinyl polycarboxylic acid adhesion agent.

[0015] (3) To the reaction vessel, 32 g of water, 17 g of potassium hydroxide, 0.9 g of sodium chloride, 6 g of sodium gluconate, 13 g of anhydrous potassium phosphate tribasic, 12 g of polyether DF-20, 6 g of 8-hydroxyquinolinyl polycarboxylic acid adhesion agent, 4 g of sulfosuccinate, and 1.5 g of sodium isooctanol sulfate were added, heated to 45°C, and stirred uniformly. After cooling, the product was discharged to obtain an environmentally friendly adhesion agent for aluminum alloy.

[0016] Example 2

[0017] (1) To the reaction vessel, 10 mL of 1,4-dioxane, 8 mmol of 2-methylallyl alcohol, 3.3 mmol of sodium acetate, 10 mL of water, and 3 mmol of 5-(chloromethyl)-8-quinolinol hydrochloride were added, heated to 95°C under N2 atmosphere, and the reaction was performed for 3 h. After concentration under reduced pressure, the product was filtered, washed with water, and dried to obtain 5-(2-methylallyloxy methylene)-8-quinolinol hydrochloride.

[0018] (2) To the reaction vessel, water was added, 0.18 mmol of allyl polyoxyethylene ether, 3 mmol of methacrylic acid, 0.42 mmol of 5-(2-methylallyloxy methylene)-8-quinolinol hydrochloride, heated to 85°C under N2 atmosphere, 0.21 mmol of ammonium persulfate was added, and the reaction was stirred for 4 h. After the reaction, water was removed by drying, and ethanol was washed to obtain 8-hydroxyquinolinyl polycarboxylic acid adhesion agent.

[0019] (3) To the reaction vessel, 28 g of water, 17 g of potassium hydroxide, 0.7 g of sodium chloride, 5 g of sodium gluconate, 15 g of anhydrous potassium phosphate tribasic, 10 g of polyether DF-20, 7 g of 8-hydroxyquinolinyl polycarboxylic acid adhesion agent, 5 g of sulfosuccinate, and 2.2 g of sodium isooctanol sulfate were added, heated to 40°C, and stirred uniformly. After cooling, the product was discharged to obtain an environmentally friendly adhesion agent for aluminum alloy.

[0020] Example 3

[0021] (1) To the reaction vessel, 10 mL of 1,4-dioxane, 9 mmol of 2-methylallyl alcohol, 3.1 mmol of sodium acetate, 10 mL of water, 3 mmol of 5-(chloromethyl)-8-quinolinol hydrochloride were added, heated to 85°C under N2 atmosphere, and reacted for 4 h. After concentration under reduced pressure, the product was filtered, washed with water, and dried to obtain 5-(2-methylallyloxy-methyl)-8-quinolinol hydrochloride.

[0022] (2) To the reaction vessel, water was added, and 0.18 mmol of allyl polyoxyethylene ether, 3 mmol of methacrylic acid, and 0.36 mmol of 5-(2-methylallyloxy-methyl)-8-quinolinol hydrochloride were added. The mixture was heated to 75°C under N2 atmosphere, and 0.23 mmol of ammonium persulfate was further added. The mixture was stirred for 4 h. After drying, the product was washed with ethanol to obtain 8-hydroxyquinolinyl polycarboxylic acid adhesion agent.

[0023] (3) To the reaction vessel, 30 g of water, 18 g of potassium hydroxide, 1.1 g of sodium chloride, 4 g of sodium gluconate, 18 g of anhydrous potassium phosphate, 13 g of polyether DF-20, 8.5 g of 8-hydroxyquinolinyl polycarboxylic acid adhesion agent, 6 g of sulfosuccinate, and 2 g of sodium isooctanol sulfate were added, and the mixture was stirred and uniformly mixed while being heated to 55°C. The mixture was cooled and discharged to obtain an environmentally friendly adhesion agent for aluminum alloy.

[0024] Example 4

[0025] (1) To the reaction vessel, 10 mL of 1,4-dioxane, 9 mmol of 2-methylallyl alcohol, 3.1 mmol of sodium acetate, 10 mL of water, 3 mmol of 5-(chloromethyl)-8-quinolinol hydrochloride were added, heated to 85°C under N2 atmosphere, and reacted for 4 h. After concentration under reduced pressure, the product was filtered, washed with water, and dried to obtain 5-(2-methylallyloxy-methyl)-8-quinolinol hydrochloride.

[0026] (2) To the reaction vessel, water was added, and 0.18 mmol of allyl polyoxyethylene ether, 3 mmol of methacrylic acid, and 0.36 mmol of 5-(2-methylallyloxy-methyl)-8-quinolinol hydrochloride were added. The mixture was heated to 75°C under N2 atmosphere, and 0.23 mmol of ammonium persulfate was further added. The mixture was stirred for 4 h. After drying, the product was washed with ethanol to obtain 8-hydroxyquinolinyl polycarboxylic acid adhesion agent.

[0027] (3) Add 26g of water, 20g of potassium hydroxide, 1.3g of sodium chloride, 6g of sodium gluconate, 18g of anhydrous tripotassium phosphate, 14g of polyether DF-20, 10g of 8-hydroxyquinoline polycarboxylic acid adhesive, 7g of sulfosuccinate, and 1.5g of sodium isooctyl sulfate to the reaction vessel. Heat to 60°C, stir evenly, cool and discharge to obtain an environmentally friendly adhesive for aluminum alloys.

[0028] Comparative Example 1

[0029] (1) Add 32g of water, 17g of potassium hydroxide, 0.9g of sodium chloride, 6g of sodium gluconate, 13g of anhydrous tripotassium phosphate, 12g of polyether DF-20, 4g of sulfosuccinate, and 1.5g of sodium isooctyl sulfate to the reaction vessel, heat to 45°C, stir evenly, cool and discharge to obtain an environmentally friendly adhesive for aluminum alloys.

[0030] Comparative Example 2

[0031] (1) Add water to the reaction vessel, add 0.15 mmol of allyl polyoxyethylene ether and 3 mmol of methacrylic acid, heat to 80°C in N2 atmosphere, add 0.24 mmol of ammonium persulfate, stir and react for 6 h, dry to remove water after reaction, wash with ethanol to obtain polycarboxylic acid adhesive.

[0032] (2) Add 32g of water, 17g of potassium hydroxide, 0.9g of sodium chloride, 6g of sodium gluconate, 13g of anhydrous tripotassium phosphate, 12g of polyether DF-20, 6g of polycarboxylic acid adhesive, 4g of sulfosuccinate, and 1.5g of sodium isooctanol sulfate to the reaction vessel. Heat to 45°C, stir evenly, cool and discharge to obtain an environmentally friendly adhesive for aluminum alloys.

[0033] Weigh 3g of environmentally friendly aluminum alloy adhesive and add it to 100mL of water-based acrylic resin emulsion. After stirring, spray the emulsion onto the surface of the aluminum alloy plate or tinplate substrate and dry it at 120℃ to form a paint film.

[0034] The adhesion level between the paint film and the substrate was tested according to the method in GB / T9286-2021.

[0035] The T-peel strength between the paint film and the substrate was tested according to the method in GB / T2791-1995.

[0036] Table 1

[0037]

[0038]

[0039] Table 2

[0040]

[0041] As shown in Tables 1 and 2, Examples 1-4 of the present invention exhibit good adhesion grades and high T-peel strength. This is because the environmentally friendly adhesive for aluminum alloys in these examples contains an 8-hydroxyquinoline polycarboxylate adhesive. The 8-hydroxyquinoline groups in the adhesive can interact with the aluminum alloy or tinplate surface through coordination, while the carboxyl groups in the polycarboxylate adhesive form hydrogen bonds with the carboxyl groups in the water-based acrylic resin emulsion. This allows the polycarboxylate adhesive to bridge the gap between the aluminum alloy groups and the acrylic resin coating, enhancing the adhesion and bonding performance between the acrylic resin coating and the substrate, resulting in a better adhesion grade and higher T-peel strength.

[0042] Compared with Example 1, Comparative Example 1 did not include 8-hydroxyquinoline polycarboxylic acid adhesive, resulting in a lower adhesion level and peel strength between the adhesive and metal materials such as aluminum alloys.

[0043] Compared with Example 1, Comparative Example 2 differs in that a polycarboxylic acid adhesive is used instead of an 8-hydroxyquinoline polycarboxylic acid adhesive. Since the polycarboxylic acid adhesive lacks an 8-hydroxyquinoline group, the interaction force between the substrate such as aluminum alloy and the adhesive is low, resulting in poor adhesion and bonding performance between the acrylic resin paint film and the substrate, leading to poor adhesion grade and low T-peel strength.

Claims

1. A method for preparing an environmentally friendly adhesive for aluminum alloys, characterized in that, The preparation method includes: (1) Add water, allyl polyoxyethylene ether, methacrylic acid, and 5-(2-methylallyloxymethylene)-8-quinolinol hydrochloride to the reaction vessel. Heat to the reaction temperature in a N2 atmosphere, then add ammonium persulfate and stir to react. After the reaction, dry to remove water and wash with ethanol to obtain 8-hydroxyquinolinyl polycarboxylic acid adhesive. (2) Add water, potassium hydroxide, sodium chloride, sodium gluconate, anhydrous tripotassium phosphate, polyether DF-20, 8-hydroxyquinoline polycarboxylic acid adhesive, sulfosuccinate, and sodium isooctyl sulfate to the reaction vessel, heat to 40-60℃, stir evenly, cool and discharge to obtain an environmentally friendly adhesive for aluminum alloys. In step (1), the molar ratio of allyl polyoxyethylene ether, methacrylic acid, 5-(2-methylallyloxymethylene)-8-quinolinol hydrochloride, and ammonium persulfate is (0.05-0.06):1:(0.08-0.14):(0.07-0.08). In step (2), the mass ratio of water, potassium hydroxide, sodium chloride, sodium gluconate, anhydrous tripotassium phosphate, polyether DF-20, 8-hydroxyquinoline polycarboxylic acid adhesive, sulfosuccinate, and sodium isooctyl sulfate is (26-32):(17-20):(0.7-1.3):(4-6):(13-18):(10-14):(6-10):(4-7):(1.5-2.2). The preparation method of the 5-(2-methylallyloxymethylene)-8-quinolinol hydrochloride is as follows: 1,4-dioxane, 2-methylallyl alcohol, sodium acetate, water, and 5-(chloromethyl)-8-quinolinol hydrochloride are added to a reaction vessel, and the reaction is carried out in a N2 atmosphere. The mixture is concentrated under reduced pressure, filtered, washed with water, and dried to obtain 5-(2-methylallyloxymethylene)-8-quinolinol hydrochloride. The molar ratio of 2-methylallyl alcohol, 5-(chloromethyl)-8-quinolinol hydrochloride, and sodium acetate is (2.5-3.4):1:(1-1.1).

2. The method for preparing the environmentally friendly adhesive for aluminum alloys according to claim 1, characterized in that, In step (1), the reaction temperature is 75-85℃ and the reaction time is 4-6h.

3. The method for preparing the environmentally friendly adhesive for aluminum alloys according to claim 1, characterized in that, In the preparation method of the 5-(2-methylallyloxymethylene)-8-quinolinol hydrochloride, the reaction temperature is 80-95℃ and the reaction time is 3-5h.

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