Preparation method of environment-friendly adhesive agent for aluminum alloy

Abstract

The invention relates to the technical field of adherence promoters, and discloses a preparation method of an environment-friendly adherence promoter 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 adherence promoter, sulfosuccinate and sodium isooctanol sulfate into a reaction kettle, uniformly stirring, adding a catalyst, and uniformly stirring to obtain the environment-friendly adherence promoter for aluminum alloy. The environment-friendly adherence promoter for the aluminum alloy is obtained. 8-hydroxyquinoline groups contained in the 8-hydroxyquinoline polycarboxylic acid adherence promoter and the surface of the aluminum alloy or tinplate can generate interaction such as coordination, and carboxyl contained in the polycarboxylic acid adherence promoter and groups such as carboxyl in the water-based acrylic resin emulsion generate interaction such as hydrogen bonds; therefore, the polycarboxylic acid adhesive agent plays a role in bridging groups such as aluminum alloy and the like with an acrylic resin paint film, the adhesive force and the adhesive property between the acrylic resin paint film and a base material are enhanced, and a better adhesive force grade and higher T peel strength are shown.

Description

Technical Field

[0001] The invention relates to the technical field of adhesives, and in particular to a method for preparing an environmentally friendly adhesive for aluminum alloys. Background Art

[0002] In the past industrial production, the application of aluminum alloys has become increasingly widespread. Due to the poor combination of acrylic resin and metal substrates such as aluminum alloys, many problems have been caused. For example, in the metal processing process, coating shedding and weak bonding are prone to occur, which not only affects the appearance quality of the product, but also reduces its service life and stability. In the field of surface treatment, insufficient adhesion also greatly reduces the protective effect and increases the risk of metal corrosion and damage. In some industrial production links that have high requirements for bonding strength, such as automobile manufacturing, aerospace, etc., this performance defect has seriously restricted the progress of the process and the quality of the product. Therefore, in order to solve these long-standing and thorny problems, a preparation method of this environmentally friendly adhesive for aluminum alloys has been developed. Summary of the invention

[0003] (I) Technical problems to be solved: In view of the deficiencies in the prior art, the present invention provides a method for preparing an environmentally friendly adhesive for aluminum alloy, which can improve the adhesion and bonding between acrylic resin and metal materials such as aluminum alloy.

[0004] (II) Technical solution: (1) Add water to a reaction vessel in a molar ratio of (0.05-0.06) 1:(0.08-0.14):(0.07-0.08) allyl polyoxyethylene ether, methacrylic acid, 5-(2-methylallyloxymethylene)-8-quinolinol hydrochloride, and ammonium persulfate, heat to 75-85°C in a N2 atmosphere, stir and react for 4-6 hours, dry and remove water after the reaction, wash with ethanol, and obtain 8-hydroxyquinoline polycarboxylic acid adhesive.

[0005] (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 into a reaction kettle, heat to 40-60° C., stir evenly, cool and discharge the material, and obtain an environmentally friendly adhesive for aluminum alloy.

[0006] Preferably, 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).

[0007] Preferably, the preparation method of 5-(2-methylallyloxymethylene)-8-quinolinol hydrochloride is: add 1,4-dioxane, 2-methylallyl alcohol, sodium acetate, water, and 5-(chloromethyl)-8-quinolinol hydrochloride into a reaction vessel, heat to 80-95° C. in a N2 atmosphere, react for 3-5 hours, concentrate under reduced pressure, filter, wash with water, and dry to obtain 5-(2-methylallyloxymethylene)-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 invention utilizes 5-(chloromethyl)-8-quinolinol hydrochloride and 2-methylallyl alcohol to generate 5-(2-methylallyloxymethylene)-8-quinolinol hydrochloride under the condition of sodium acetate as a catalyst, and then polymerizes with allyl polyoxyethylene ether and methacrylic acid to obtain 8-hydroxyquinoline polycarboxylic acid adhesive, and finally compounded with water, sodium gluconate, anhydrous tripotassium phosphate, polyether DF-20, sulfosuccinate, sodium isooctyl sulfate, etc. to obtain an environmentally friendly adhesive for aluminum alloy.

[0010] The environmentally friendly adhesive of the present invention contains an 8-hydroxyquinoline polycarboxylic acid adhesive, and the 8-hydroxyquinoline group contained in the adhesive can interact with the surface of aluminum alloy or tinplate by coordination, and at the same time, the carboxyl group contained in the polycarboxylic acid adhesive can interact with the carboxyl group and other groups in the water-based acrylic resin emulsion by hydrogen bonding, so that the polycarboxylic acid adhesive plays a role in bridging the aluminum alloy and other groups and the acrylic resin paint film, thereby enhancing the adhesion and bonding performance between the acrylic resin paint film and the substrate, and showing a better adhesion grade and a greater T peel strength. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 This is the reaction formula for preparing 5-(2-methylallyloxymethylene)-8-quinolinol hydrochloride. DETAILED DESCRIPTION

[0012] Example 1

[0013] (1) Add 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 to a reaction container, heat to 85° C. in a N2 atmosphere, react for 4 h, concentrate under reduced pressure, filter, wash with water, and dry to obtain 5-(2-methylallyloxymethylene)-8-quinolinol hydrochloride.

[0014] (2) Add water, 0.15 mmol of allyl polyoxyethylene ether, 3 mmol of methacrylic acid, and 0.3 mmol of 5-(2-methylallyloxymethylene)-8-quinolinol hydrochloride to a reaction container, heat to 80° C. in a N2 atmosphere, add 0.24 mmol of ammonium persulfate, stir and react for 6 hours, dry and remove water after the reaction, wash with ethanol, and obtain an 8-hydroxyquinoline polycarboxylic acid adhesive.

[0015] (3) Add 32 g of water, 17 g of potassium hydroxide, 0.9 g of sodium chloride, 6 g of sodium gluconate, 13 g of anhydrous tripotassium phosphate, 12 g of polyether DF-20, 6 g of 8-hydroxyquinoline polycarboxylic acid adhesive, 4 g of sulfosuccinate, and 1.5 g of sodium isooctyl sulfate to a reaction kettle, heat to 45 ° C, stir evenly, cool and discharge, and obtain an environmentally friendly adhesive for aluminum alloy.

[0016] Example 2

[0017] (1) Add 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 to a reaction container, heat to 95° C. in a N2 atmosphere, react for 3 h, concentrate under reduced pressure, filter, wash with water, and dry to obtain 5-(2-methylallyloxymethylene)-8-quinolinol hydrochloride.

[0018] (2) Add water, 0.18 mmol of allyl polyoxyethylene ether, 3 mmol of methacrylic acid, and 0.42 mmol of 5-(2-methylallyloxymethylene)-8-quinolinol hydrochloride to a reaction container, heat to 85° C. in a N2 atmosphere, then add 0.21 mmol of ammonium persulfate, stir and react for 4 hours, dry and remove water after the reaction, wash with ethanol, and obtain an 8-hydroxyquinoline polycarboxylic acid adhesive.

[0019] (3) Add 28 g of water, 17 g of potassium hydroxide, 0.7 g of sodium chloride, 5 g of sodium gluconate, 15 g of anhydrous tripotassium phosphate, 10 g of polyether DF-20, 7 g of 8-hydroxyquinoline polycarboxylic acid adhesive, 5 g of sulfosuccinate, and 2.2 g of sodium isooctyl sulfate to a reactor, heat to 40° C., stir evenly, cool and discharge, and obtain an environmentally friendly adhesive for aluminum alloy.

[0020] Example 3

[0021] (1) Add 10 mL of 1,4-dioxane, 10.2 mmol of 2-methylallyl alcohol, 3 mmol of sodium acetate, 10 mL of water, and 3 mmol of 5-(chloromethyl)-8-quinolinol hydrochloride to a reaction container, heat to 80° C. in a N2 atmosphere, react for 5 h, concentrate under reduced pressure, filter, wash with water, and dry to obtain 5-(2-methylallyloxymethylene)-8-quinolinol hydrochloride.

[0022] (2) Add water, 0.17 mmol of allyl polyoxyethylene ether, 3 mmol of methacrylic acid, and 0.24 mmol of 5-(2-methylallyloxymethylene)-8-quinolinol hydrochloride to a reaction container, heat to 75° C. in a N2 atmosphere, then add 0.24 mmol of ammonium persulfate, stir and react for 5 hours, dry and remove water after the reaction, wash with ethanol, and obtain an 8-hydroxyquinoline polycarboxylic acid adhesive.

[0023] (3) Add 30 g of water, 18 g of potassium hydroxide, 1.1 g of sodium chloride, 4 g of sodium gluconate, 18 g of anhydrous tripotassium phosphate, 13 g of polyether DF-20, 8.5 g of 8-hydroxyquinoline polycarboxylic acid adhesive, 6 g of sulfosuccinate, and 2 g of sodium isooctyl sulfate to a reactor, heat to 55 ° C, stir evenly, cool and discharge, and obtain an environmentally friendly adhesive for aluminum alloy.

[0024] Example 4

[0025] (1) Add 10 mL of 1,4-dioxane, 9 mmol of 2-methylallyl alcohol, 3.1 mmol of sodium acetate, 10 mL of water, and 3 mmol of 5-(chloromethyl)-8-quinolinol hydrochloride to a reaction container, heat to 85° C. in a N2 atmosphere, react for 4 h, concentrate under reduced pressure, filter, wash with water, and dry to obtain 5-(2-methylallyloxymethylene)-8-quinolinol hydrochloride.

[0026] (2) Add water, 0.18 mmol of allyl polyoxyethylene ether, 3 mmol of methacrylic acid, and 0.36 mmol of 5-(2-methylallyloxymethylene)-8-quinolinol hydrochloride to a reaction container, heat to 75° C. in a N2 atmosphere, then add 0.23 mmol of ammonium persulfate, stir and react for 4 hours, dry and remove water after the reaction, wash with ethanol, and obtain an 8-hydroxyquinoline polycarboxylic acid adhesive.

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

[0028] Comparative Example 1

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

[0030] Comparative Example 2

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

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

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

[0034] Refer to the method of GB / T9286-2021 to test the adhesion level between the paint film and the substrate.

[0035] Refer to the method of GB / T2791-1995 to test the T peel strength between the paint film and the substrate.

[0036] Table 1

[0037]

[0038]

[0039] Table 2

[0040]

[0041] As shown in Table 1 and Table 2, the adhesion grade of Examples 1-4 of the present invention is good and the T peeling strength is large. The reason is that the environmentally friendly adhesive for aluminum alloy in the examples contains 8-hydroxyquinoline polycarboxylic acid adhesive, and the 8-hydroxyquinoline group contained in the adhesive can interact with the surface of aluminum alloy or tinplate by coordination, and at the same time, the carboxyl group contained in the polycarboxylic acid adhesive can interact with the carboxyl group and other groups in the water-based acrylic resin emulsion by hydrogen bonding, so that the polycarboxylic acid adhesive plays a role in bridging the aluminum alloy and other groups and the acrylic resin paint film, enhancing the adhesion and bonding performance between the acrylic resin paint film and the substrate, showing a better adhesion grade and a greater T peeling strength.

[0042] Compared with Example 1, Comparative Example 1 does not add 8-hydroxyquinoline polycarboxylic acid adhesive, the adhesive has a relatively low adhesion level with metal materials such as aluminum alloy, and the peel strength is relatively small.

[0043] Compared with Example 1, Comparative Example 2 is different in that a polycarboxylic acid adhesive is used instead of the 8-hydroxyquinoline polycarboxylic acid adhesive. The polycarboxylic acid adhesive lacks an 8-hydroxyquinoline group, and the interaction force between the aluminum alloy and other substrates and the adhesive is low. The adhesion and bonding properties between the acrylic resin paint film and the substrate are poor, resulting in a poor adhesion grade and a low T-peel strength.

Claims

1. A method for preparing an environmentally friendly adhesive for aluminum alloy, characterized in that: The preparation method comprises: (1) adding water, allyl polyoxyethylene ether, methacrylic acid, and 5-(2-methylallyloxymethylene)-8-quinolinol hydrochloride to a reaction container in a N2 atmosphere, heating to a reaction temperature, then adding ammonium persulfate, stirring for reaction, drying to remove water after the reaction, and washing with ethanol to obtain an 8-hydroxyquinoline 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 into a reaction kettle, heat to 40-60° C., stir evenly, cool and discharge the material, and obtain an environmentally friendly adhesive for aluminum alloy.

2. The method for preparing an environmentally friendly adhesive for aluminum alloy according to claim 1, characterized in that: In the 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).

3. The method for preparing an environmentally friendly adhesive for aluminum alloy according to claim 1, characterized in that: In the step (1), the reaction temperature is 75-85° C. and the reaction time is 4-6 hours.

4. The method for preparing an environmentally friendly adhesive for aluminum alloy according to claim 1, characterized in that: In the step (2), the mass ratios of water, potassium hydroxide, sodium chloride, sodium gluconate, anhydrous tripotassium phosphate, polyether DF-20, 8-hydroxyquinoline polycarboxylic acid adhesive, sulfosuccinate, and sodium isooctyl sulfate are (26-32):(17-20):(0.7-1.3):(4-6):(13-18):(10-14):(6-10):(4-7):(1.5-2.2).

5. The method for preparing an environmentally friendly adhesive for aluminum alloy according to claim 1, characterized in that: 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 into a reaction container, reacted in a N2 atmosphere, concentrated under reduced pressure, filtered, washed with water, and dried to obtain 5-(2-methylallyloxymethylene)-8-quinolinol hydrochloride.

6. The method for preparing an environmentally friendly adhesive for aluminum alloy according to claim 5, characterized in that: The molar ratio of the 2-methylallyl alcohol, 5-(chloromethyl)-8-quinolinol hydrochloride and sodium acetate is (2.5-3.4):1:(1-1.1).

7. The method for preparing an environmentally friendly adhesive for aluminum alloy according to claim 5, characterized in that: The reaction temperature is 80-95°C and the reaction time is 3-5h.

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