Heat-insulating antibacterial coating for aluminum profile and preparation method of heat-insulating antibacterial coating

Abstract

The invention relates to the technical field of coatings, and discloses a heat-insulating antibacterial coating for an aluminum profile and a preparation method of the heat-insulating antibacterial coating for the aluminum profile, and the heat-insulating antibacterial coating for the aluminum profile comprises the following raw materials in parts by weight: 100 parts of vinyl silicone oil, 10-25 parts of methyl vinyl polysiloxane, 6-12 parts of hydrogen-containing silicone oil, 2-6 parts of acrylamide triazole quaternary ammonium salt and the like. Alkenyl of acrylamide triazole quaternary ammonium salt and hydrogen-containing silicone oil are subjected to a hydrosilylation reaction, and a triazole structure is introduced into molecular chains of vinyl silicone oil and polysiloxane, so that the interfacial acting force between the molecular chains of a polysiloxane polymer and the aluminum alloy is enhanced, and the adhesive force of a polysiloxane coating and the aluminum alloy is improved. The acrylamide triazole quaternary ammonium salt contains biquaternary ammonium salt groups, an organosilicon quaternary ammonium salt antibacterial structure is formed, and the antibacterial performance of the coating and the aluminum alloy is remarkably improved.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, and specifically to a heat-insulating and antibacterial coating for aluminum profiles and a preparation method thereof. Background Art

[0002] Aluminum alloy profiles have the advantages of light weight, high strength, electrical and thermal conductivity, etc., and are widely used in building engineering fields such as door and window frames, automotive industry fields such as brake discs, and biological tissue engineering fields such as orthotics.

[0003] In order to improve the corrosion resistance, mechanical strength, aesthetic degree and other properties of aluminum alloy profiles, it is necessary to spray a resin coating on the surface of aluminum profiles. Common coatings for aluminum profiles include epoxy resins, polyurethanes, polysiloxanes, etc. Among them, polysiloxane coatings have good waterproof and anti-corrosion properties, high temperature resistance, and high wear resistance, and are widely used.

[0004] The patent with the publication number CN115651530B discloses a preparation method of an aluminum alloy nano-easy-to-clean film and an easy-to-clean aluminum alloy plate. Using fluorinated polyester polysiloxane, methyltriethoxysilane, octamethylcyclotetrasiloxane, toluene diisocyanate, etc. as raw materials, the coating prepared for the aluminum alloy plate has good hydrophobic and oleophobic, weather resistance, friction resistance and other properties. However, the polysiloxane coating has a low adhesion to aluminum alloy, resulting in problems such as easy peeling of the coating, and the antibacterial performance of the polysiloxane coating is not high, which limits its practical application. Summary of the Invention

[0005] The present invention provides a heat-insulating and antibacterial coating for aluminum profiles and a preparation method thereof, which solves the problem of low adhesion between the silicone coating and the aluminum alloy surface, and at the same time reflects the good antibacterial performance of the aluminum alloy.

[0006] Technical Solution: A heat-insulating and antibacterial coating for aluminum profiles, the raw materials include 100 parts by weight of vinyl silicone oil, 10 - 25 parts by weight of methyl vinyl polysiloxane, 6 - 12 parts by weight of hydrogen-containing silicone oil, 2 - 6 parts by weight of acrylamide triazole quaternary ammonium salt, and 0.008 - 0.013 parts by weight of platinum catalyst.

[0007] Preferably, the preparation method of the heat-insulating and antibacterial coating for aluminum profiles is: stir and mix vinyl silicone oil, methyl vinyl polysiloxane, hydrogen-containing silicone oil, and acrylamide triazole quaternary ammonium salt, then add platinum catalyst, stir and coat it on the surface of aluminum alloy profiles, and thermally cure to obtain the heat-insulating and antibacterial coating for aluminum profiles.

[0008] Preferably, the temperature of thermal curing is 100 - 125 °C, and the time is 15 - 60 min.

[0009] Preferably, the preparation method of acrylamide triazole quaternary ammonium salt includes: (1) In an ice bath, 4-amino-1,2,4-triazole, acryloyl chloride, and triethylamine were added to a solvent, and then the reaction was carried out at 15 - 25 °C for 12 - 18 h. After filtration, the filtrate was rotary evaporated, and the product was recrystallized and purified in ethanol to obtain 4-acrylamide-1,2,4-triazole. The reaction formula is as follows: .

[0010] (2) 4-Acrylamide-1,2,4-triazole and a dibromo compound were added to a solvent, heated to 75 - 85 °C, and refluxed for 6 - 18 h. After rotary evaporation and washing with ethanol, the product was recrystallized and purified in a mixed solution of ethanol and water to obtain an acrylamide triazole quaternary ammonium salt. The reaction formula is: .

[0011] Preferably, the solvent in (1) is dichloromethane or tetrahydrofuran.

[0012] Preferably, the ratio of 4-amino-1,2,4-triazole, acryloyl chloride, and triethylamine in (1) is 1 mol : (0.8 - 1.4) mol : (1 - 1.4) mol.

[0013] Preferably, the solvent in (2) is isopropanol or acetonitrile.

[0014] Preferably, the ratio of 4-acrylamide-1,2,4-triazole and the dibromo compound in (2) is (2 - 2.2) mol : 1 mol.

[0015] Preferably, the structural formula of the dibromo compound in (2) is Br-(CH2) n Br, where n is 2 - 8.

[0016] Beneficial technical effects: In the present invention, vinyl silicone oil, methyl vinyl polysiloxane, and hydrogen-containing silicone oil are used as the main agents of the polysiloxane coating, and an acrylamide triazole quaternary ammonium salt is added at the same time. During the thermal curing process, the alkenyl group of the acrylamide triazole quaternary ammonium salt undergoes a hydrosilylation reaction with the hydrogen-containing silicone oil, thereby introducing the triazole structure into the molecular chains of vinyl silicone oil and polysiloxane. The triazole structure can form a strong coordination interaction with the aluminum alloy surface, thereby enhancing the interfacial force between the polysiloxane polymer molecular chain and the aluminum alloy, improving the adhesion of the polysiloxane coating to the aluminum alloy, and making the coating not easily peel off.

[0017] The acrylamide triazole quaternary ammonium salt of the present invention contains a bis-quaternary ammonium salt group, which is grafted onto the polysiloxane polymer molecular chain to form an organosilicon quaternary ammonium salt antibacterial structure and is uniformly dispersed in the coating matrix through chemical bonding, having more bactericidal sites and significantly improving the antibacterial properties of the coating and the aluminum alloy.

[0018] Aluminum alloy itself has a very high thermal conductivity, while the thermal conductivity of the polysiloxane coating is relatively low. Coating on the surface of aluminum alloy profiles is beneficial to reducing the heat conduction effect and improving the heat insulation performance of aluminum alloy profiles. Specific Embodiments

[0019] The present invention will be further described below in conjunction with specific embodiments. The raw materials and reagents used in the following examples and comparative examples are all commercially available products. The hydrogen-containing silicone oil product number is ZX-P05, the vinyl silicone oil model is ZX-P04, and the platinum catalyst product number is ZX-BJ01, all of which are purchased from Dongguan Zhongxin Organosilicon Materials Co., Ltd. The content of methyl vinyl polysiloxane is 99%, which is purchased from Hubei Zhonglong Kangsheng Fine Chemical Co., Ltd.

[0020] Example 1 (1) In an ice bath, 30 mmol of 4-amino-1,2,4-triazole, 42 mmol of acryloyl chloride, and 42 mmol of triethylamine were added to 150 mL of dichloromethane, and then reacted at 15 °C for 18 h. After filtration, the filtrate was rotary evaporated, and the product was recrystallized and purified in ethanol to obtain 4-acrylamide-1,2,4-triazole.

[0021] (2) 40 mmol of 4-acrylamide-1,2,4-triazole and 20 mmol of 1,2-dibromoethane were added to 25 mL of acetonitrile, heated to 80 °C, and refluxed for 8 h. After rotary evaporation and washing with ethanol, the product was recrystallized and purified in a mixed solution of ethanol and water with a volume ratio of 2:8 to obtain acrylamide triazole quaternary ammonium salt.

[0022] (3) 100 g of vinyl silicone oil, 21 g of methyl vinyl polysiloxane, 10.6 g of hydrogen-containing silicone oil, and 2 g of acrylamide triazole quaternary ammonium salt were stirred and mixed, and then 0.012 g of platinum catalyst was added. After stirring, it was coated on the surface of aluminum alloy profiles and heat-cured at 110 °C for 40 min to obtain a heat-insulating and antibacterial coating for aluminum profiles.

[0023] Example 2 (1) In an ice bath, 30 mmol of 4-amino-1,2,4-triazole, 24 mmol of acryloyl chloride, and 30 mmol of triethylamine were added to 200 mL of tetrahydrofuran, and then reacted at 25 °C for 12 h. After filtration, the filtrate was rotary evaporated, and the product was recrystallized and purified in ethanol to obtain 4-acrylamide-1,2,4-triazole.

[0024] (2) 40 mmol of 4-acrylamide-1,2,4-triazole and 20 mmol of 1,4-dibromobutane were added to 35 mL of isopropanol, heated to 85 °C, and refluxed for 6 h. After rotary evaporation and washing with ethanol, the product was recrystallized and purified in a mixed solution of ethanol and water with a volume ratio of 2:8 to obtain acrylamide triazole quaternary ammonium salt.

[0025] (3) Stir and mix 100 g of vinyl silicone oil, 25 g of methyl vinyl polysiloxane, 12 g of hydrogen-containing silicone oil, and 3 g of acrylamide triazole quaternary ammonium salt, then add 0.013 g of platinum catalyst. After stirring, coat it on the surface of the aluminum alloy profile and thermally cure it at 100 °C for 60 min to obtain a heat-insulating and antibacterial coating for aluminum profiles.

[0026] Example 3 (1) Add 44 mmol of 4-acrylamide-1,2,4-triazole (prepared in the same way as in Example 1) and 20 mmol of 1,8-dibromooctane to 30 mL of acetonitrile, heat to 75 °C, and carry out a condensation reflux reaction for 18 h. Rotate and evaporate, wash with ethanol, and then recrystallize and purify the product in a mixed solution of ethanol and water with a volume ratio of 3:7 to obtain acrylamide triazole quaternary ammonium salt.

[0027] (2) Stir and mix 100 g of vinyl silicone oil, 10 g of methyl vinyl polysiloxane, 6 g of hydrogen-containing silicone oil, and 4.5 g of acrylamide triazole quaternary ammonium salt, then add 0.008 g of platinum catalyst. After stirring, coat it on the surface of the aluminum alloy profile and thermally cure it at 125 °C for 15 min to obtain a heat-insulating and antibacterial coating for aluminum profiles.

[0028] Example 4 (1) Add 42 mmol of 4-acrylamide-1,2,4-triazole (prepared in the same way as in Example 1) and 20 mmol of 1,6-dibromohexane to 30 mL of acetonitrile, heat to 80 °C, and carry out a condensation reflux reaction for 8 h. Rotate and evaporate, wash with ethanol, and then recrystallize and purify the product in a mixed solution of ethanol and water with a volume ratio of 3:7 to obtain acrylamide triazole quaternary ammonium salt.

[0029] (2) Stir and mix 100 g of vinyl silicone oil, 16 g of methyl vinyl polysiloxane, 8 g of hydrogen-containing silicone oil, and 6 g of acrylamide triazole quaternary ammonium salt, then add 0.01 g of platinum catalyst. After stirring, coat it on the surface of the aluminum alloy profile and thermally cure it at 120 °C for 30 min to obtain a heat-insulating and antibacterial coating for aluminum profiles.

[0030] Comparative Example 1 (1) Stir and mix 100 g of vinyl silicone oil, 21 g of methyl vinyl polysiloxane, and 10.6 g of hydrogen-containing silicone oil, then add 0.012 g of platinum catalyst. After stirring, coat it on the surface of the aluminum alloy profile and thermally cure it at 110 °C for 40 min to obtain a heat-insulating and antibacterial coating for aluminum profiles.

[0031] Comparative Example 2 (1) Stir and mix 100 g of vinyl silicone oil, 21 g of methyl vinyl polysiloxane, 10.6 g of hydrogen-containing silicone oil, and 2 g of 4-acrylamido-1,2,4-triazole (prepared in the same way as in Example 1), then add 0.012 g of platinum catalyst. After stirring, coat it on the surface of the aluminum alloy profile and cure it thermally at 110 °C for 40 min to obtain a heat-insulating and antibacterial coating for aluminum profiles.

[0032] Comparative Example 3 (1) Add 20 mmol of 4-amino-1,2,4-triazole and 10 mmol of 1,2-dibromoethane to 10 mL of acetonitrile, heat to 80 °C, carry out a condensation reflux reaction for 4 h, rotary evaporate, wash with acetonitrile, and dry to obtain a triazole quaternary ammonium salt with the structural formula .

[0033] (2) Stir and mix 100 g of vinyl silicone oil, 21 g of methyl vinyl polysiloxane, 10.6 g of hydrogen-containing silicone oil, and 2 g of triazole quaternary ammonium salt, then add 0.012 g of platinum catalyst. After stirring, coat it on the surface of the aluminum alloy profile and cure it thermally at 110 °C for 40 min to obtain a heat-insulating and antibacterial coating for aluminum profiles.

[0034] The adhesion grade of the coating to the aluminum alloy was tested according to the standard of GB / T 9286-2021.

[0035] The antibacterial performance of the coating was tested according to the standard of GB / T 21866-2008. Antibacterial rate = (B - C) / B × 100%. B is the average number of recovered bacteria (cfu / sheet) after 24 h of the antibacterial coating sample. C is the average number of recovered bacteria (cfu / sheet) after 24 h of the blank control sample (the antibacterial coating of Comparative Example 1).

[0036] Table 1 Performance Test of Heat-Insulating and Antibacterial Coatings for Aluminum Profiles Compared with Comparative Example 1, the adhesion of the polysiloxane coatings of Examples 1-4 to the aluminum alloy surface reached level 0-1. The main reason is that acrylamido triazole quaternary ammonium salt was added to the polysiloxane coating. It contains alkenyl groups and can undergo a hydrosilylation reaction with the hydrogen-containing silicone oil, thereby introducing the triazole structure into the molecular chains of vinyl silicone oil and polysiloxane. The triazole structure can form a strong coordination interaction with the aluminum alloy surface, thus enhancing the interfacial force between the polysiloxane polymer molecular chain and the aluminum alloy and improving the adhesion of the polysiloxane coating to the aluminum alloy. And acrylamido triazole quaternary ammonium salt contains double quaternary ammonium salt groups, which are grafted into the polysiloxane polymer molecular chain to form an organosilicon quaternary ammonium salt antibacterial structure and are uniformly dispersed in the coating matrix through chemical bonding. It has more bactericidal sites, significantly improves the antibacterial rate of the coating against Escherichia coli and Staphylococcus aureus, and has strong antibacterial performance.

[0037] 4-acrylamide-1,2,4-triazole was added to the polysiloxane coating of Comparative Example 2. It does not contain a bisquaternary ammonium salt group and cannot form an organosilicon quaternary ammonium salt antibacterial structure, so the antibacterial performance of the coating is poor. The triazole quaternary ammonium salt added in Comparative Example 3 does not contain an alkenyl group and cannot undergo a hydrosilylation reaction with vinyl silicone oil, hydrogen-containing silicone oil, etc. It is difficult to introduce the triazole structure into the molecular chain of the polysiloxane polymer, and it is difficult to effectively improve the interfacial force between the polysiloxane polymer molecular chain and the aluminum alloy. As a result, the adhesion between the polysiloxane coating and the aluminum alloy is only Grade 2. Moreover, the triazole quaternary ammonium salt cannot be uniformly dispersed in the coating matrix through chemical bonding, resulting in fewer bactericidal sites in the coating and an antibacterial rate lower than that of each example.

[0038] The above content is only an example and illustration of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the described specific embodiments or use similar methods for substitution. As long as they do not deviate from the invention or exceed the scope defined by this claims, they should all fall within the protection scope of the present invention.

Claims

1. A heat-insulating and antibacterial coating for aluminum profiles, characterized in that, The raw materials of the coating include 100 parts by weight of vinyl silicone oil, 10 - 25 parts by weight of methyl vinyl polysiloxane, 6 - 12 parts by weight of hydrogen-containing silicone oil, 2 - 6 parts by weight of acrylamide triazole quaternary ammonium salt, and 0.008 - 0.013 parts by weight of platinum catalyst; The structural general formula of the acrylamide triazole quaternary ammonium salt is as follows: , where n is from 2 to 8.

2. The heat-insulating and antibacterial coating for aluminum profiles according to claim 1, wherein The preparation method of the acrylamide triazole quaternary ammonium salt includes: (1) In an ice bath, add 4-amino-1,2,4-triazole, acryloyl chloride, and triethylamine to a solvent, then react at 15 - 25 °C for 12 - 18 h. After filtration, rotary evaporate the filtrate, and purify the product by recrystallization to obtain 4-acrylamide-1,2,4-triazole; (2) Add 4-acrylamide-1,2,4-triazole and dibromo compound to a solvent, heat to 75 - 85 °C, and carry out reflux condensation reaction for 6 - 18 h. Rotary evaporate, wash, and then purify the product by recrystallization to obtain acrylamide triazole quaternary ammonium salt.

3. The heat-insulating and antibacterial coating for aluminum profiles according to claim 2, wherein, The solvent in (1) is dichloromethane or tetrahydrofuran.

4. The heat-insulating and antibacterial coating for aluminum profiles according to claim 2, characterized in that, The ratio of 4-amino-1,2,4-triazole, acryloyl chloride, and triethylamine in (1) is 1 mol : (0.8 - 1.4) mol : (1 - 1.4) mol.

5. The heat-insulating and antibacterial coating for aluminum profiles according to claim 2, characterized in that, The solvent in (2) is isopropanol or acetonitrile.

6. The heat-insulating and antibacterial coating for aluminum profiles according to claim 2, wherein The ratio of 4-acrylamide-1,2,4-triazole and dibromo compound in (2) is (2 - 2.2) mol : 1 mol.

7. The heat-insulating and antibacterial coating for aluminum profiles according to claim 6, characterized in that, The structural formula of the dibromo compound is Br-(CH2) n Br, where n is 2 - 8.

8. A method for preparing a heat-insulating and antibacterial coating for aluminum profiles according to any one of claims 1-7, characterized in that, The preparation method includes: Stir and mix vinyl silicone oil, methyl vinyl polysiloxane, hydrogen-containing silicone oil, and acrylamide triazole quaternary ammonium salt, then add platinum catalyst, stir and coat on the surface of aluminum alloy profiles, and thermally cure to obtain a heat-insulating and antibacterial coating for aluminum profiles.

9. The preparation method of the heat-insulating and antibacterial coating for aluminum profiles according to claim 8, characterized in that, The temperature of the thermal curing is 100 - 125 °C, and the time is 15 - 60 min.

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