Antibacterial weather-resistant ASA composite material and preparation method thereof

Abstract

The invention relates to an antibacterial weather-resistant ASA composite material and a preparation method thereof, and belongs to the technical field of ASA composite material preparation. The composite material comprises the following raw materials in parts by weight: 100 parts of ASA resin, 30-50 parts of an antibacterial agent and 1-5 parts of an auxiliary agent, the antibacterial agent is a compound with an inorganic filler as a core and quaternary ammonium salt polyester as a shell. The antibacterial agent is formed by inorganic filler through two steps of surface grafting and surface condensation reaction, the core is a rigid core, the layer is a polyester elastic layer (the polyester layer contains a flexible chain of a polysiloxane chain), and the antibacterial agent can exert the synergistic toughness enhancing effect of rigid particles and the flexible chain while exerting the antibacterial performance of quaternary ammonium salt, so that the antibacterial property of the quaternary ammonium salt is greatly improved. The toughness performance of the ASA resin is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of ASA composite material preparation, and specifically relates to an antibacterial and weather-resistant ASA composite material and a preparation method thereof. Background Art

[0002] ASA resin is a ternary polymer composed of acrylonitrile (Acrylate), styrene (Styrene) and acrylic rubber (Acrylate). Similar to ABS resin, it has good mechanical properties, processing properties, electrical insulation and chemical resistance. In addition, because the raw material of ASA resin replaces butadiene rubber with acrylic rubber, its weather resistance is stronger than that of ABS. This excellent weather resistance makes it widely used in outdoor products and automotive fields. However, when it is promoted to outdoor products or automotive products, as people pursue the antibacterial properties of the products, antibacterial properties are also required for the performance of ASA composite materials. Summary of the invention

[0003] The object of the present invention is to provide an antibacterial and weather-resistant ASA composite material and a preparation method thereof, so as to solve the problem that the existing ASA composite material cannot meet the antibacterial requirements of the product.

[0004] The first object of the present invention can be achieved by the following technical solutions:

[0005] An antibacterial and weather-resistant ASA composite material comprises the following raw materials in parts by weight: 100 parts of ASA resin and 30-50 parts of antibacterial agent;

[0006] The antibacterial agent is a composite material with an inorganic filler as a core and quaternary ammonium salt polyester as a shell.

[0007] Furthermore, the antibacterial agent is obtained by:

[0008] Ultra-dispersing an inorganic filler in a mixed solution of water and ethanol, adjusting the pH of the mixed solution to 5-6, stirring and heating to a first temperature, adding ethanol containing antibacterial siloxane under stirring, keeping the temperature and stirring for 2-6 hours, stopping the reaction, and post-treating to obtain a surface-grafted inorganic filler;

[0009] The surface quaternary ammonium salt grafted inorganic filler is ultra-dispersed in a mixed solution of a first organic solvent and dihydroxy-terminated polydimethylsiloxane, heated to a second temperature under stirring, an esterification reaction catalyst and citric acid are added, the reaction is stirred and kept warm for 12-24 hours, the reaction is stopped, and an antibacterial agent is obtained through post-treatment.

[0010] Furthermore, the first temperature is 50-60° C., and the mass ratio of the inorganic filler to the antibacterial silicone is 10:2-4.

[0011] Furthermore, the second temperature is 80-95° C., the molar ratio of the antibacterial siloxane, citric acid, and dihydroxy-terminated polydimethylsiloxane is 1:4-6:1-2, and the first organic solvent is one of benzene, toluene, and N,N-dimethylformamide.

[0012] Furthermore, the antibacterial silicone is obtained by:

[0013] The amino-protected 4-aminopyridine reacts with γ-chloropropyltriethoxysilane to obtain the amino-protected quaternary ammonium salt 4-aminopyridine;

[0014] Deprotecting the amino-protected quaternary ammonium salt 4-aminopyridine to obtain quaternary ammonium salt 4-aminopyridine;

[0015] Quaternary ammonium salt of 4-aminopyridine reacts with 2,2-dihydroxymethylpropionic acid to obtain antibacterial siloxane.

[0016] Furthermore, the molecular structure of the antibacterial siloxane is as follows:

[0017]

[0018] Furthermore, the amino-protected 4-aminopyridine is formed by reacting 4-aminopyridine and 2-nitrotoluenesulfonyl chloride.

[0019] Preferably, the reaction for obtaining the amino-protected 4-aminopyridine comprises:

[0020] The 4-aminopyridine, the 2-nitrotoluenesulfonyl chloride and triethylamine are added to carbon dichloride in a molar ratio of 1:1-1.5:1-2 and stirred evenly, and then stirred for reaction at 20-23° C. for 1-4 hours, and the reaction is stopped, and the reaction is performed by rotary evaporation, washing and drying to obtain amino-protected 4-aminopyridine.

[0021] Furthermore, in the reaction of the amino-protected 4-aminopyridine and γ-chloropropyltriethoxysilane, the reaction solvent is one of benzene, toluene, and N,N-dimethylformamide, the reaction temperature is 65-85°C, the reaction time is 6-18h, and the molar ratio of the amino-protected 4-aminopyridine to the γ-chloropropyltriethoxysilane is 1:1-1.5.

[0022] Further, the amino-protected quaternary ammonium salt 4-aminopyridine is deprotected, comprising:

[0023] After the amino-protected quaternary ammonium salt 4-aminopyridine, thioacetic acid, lithium hydroxide and N,N-dimethylformamide are uniformly mixed, stirred at 20-30°C for 2-4 hours, cooled, and rotary evaporated, the product is washed with 0.1M NaOH solution, washed with water, and dried to obtain quaternary ammonium salt 4-aminopyridine.

[0024] Furthermore, in the reaction of the quaternized 4-aminopyridine and 2,2-dihydroxymethylpropionic acid, the reaction solvent is one of N,N-dimethylformamide and N,N-dimethylacetamide, the reaction temperature is 80-95°C, the reaction time is 5-12h, and the molar ratio of the quaternized 4-aminopyridine to 2,2-dihydroxymethylpropionic acid is 1:1-1.5.

[0025] Furthermore, the condensation reagent is a mixture of EDCI (carbodiimide hydrochloride) and HOBT (1-hydroxybenzotriazole).

[0026] Furthermore, the inorganic filler is one of silicon dioxide, graphene, carbon fiber and montmorillonite.

[0027] Preferably, the inorganic filler is silicon dioxide.

[0028] Furthermore, the particle size of the inorganic filler is 5-20 μm.

[0029] Furthermore, the auxiliary agent is a mixture of a lubricant and an antioxidant well known in the art; wherein the types of the lubricant and the antioxidant are not specifically limited in the present invention.

[0030] The second object of the present invention can be achieved by the following technical solutions:

[0031] A method for preparing an antibacterial and weather-resistant ASA composite material, comprising:

[0032] The ASA resin, the antibacterial agent and the auxiliary agent are mixed, melt-blended, extruded and granulated to obtain a composite material.

[0033] Beneficial effects of the present invention:

[0034] The antibacterial and weather-resistant ASA composite material and the preparation method thereof of the present invention endow the composite material with excellent antibacterial properties by introducing an antibacterial agent;

[0035] What is outstanding is that the antibacterial agent is a composite material with an inorganic filler as a core and a quaternary ammonium polyester as a shell, and is formed by two steps of surface grafting of the inorganic filler (surface grafting of a molecular chain containing a quaternary ammonium salt structure) and surface condensation reaction (esterification reaction between hydroxyl and dihydroxy-terminated polydimethylsiloxane of a molecular chain containing a quaternary ammonium salt structure and citric acid to form a quaternary ammonium polyester shell layer), the core is a rigid core, and the layer is a polyester elastic layer (the polyester layer contains a flexible chain of a polysiloxane chain), which can exert the antibacterial properties of the quaternary ammonium salt while also exerting the synergistic toughness enhancement effect of the rigid particles and the flexible chain to improve the toughness properties of the ASA resin. DETAILED DESCRIPTION

[0036] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0037] Example 1

[0038] Preparation of antimicrobial agents:

[0039] A1. Add 0.1 mol 4-aminopyridine, 0.13 mol 2-nitrotoluenesulfonyl chloride and 0.15 mol triethylamine into 100 mL carbon dichloride and stir evenly. Stir and react at 20°C for 2 h. Stop the reaction, rotary evaporate, wash and dry to obtain amino-protected 4-aminopyridine.

[0040] A2, after 0.1 mol of amino-protected 4-aminopyridine, 0.1 mol of γ-chloropropyltriethoxysilane and 100 mL of benzene are uniformly mixed, the mixture is heated to 70° C., the mixture is stirred and reacted for 8 h at the temperature, the reaction is stopped, the mixture is cooled, the mixture is rotary evaporated, the mixture is washed, and the mixture is dried to obtain amino-protected quaternary ammonium salt 4-aminopyridine;

[0041] A3, after 0.1mol of amino-protected quaternary ammonium salt 4-aminopyridine, 0.13mol of thioacetic acid, 0.01mol of lithium hydroxide and 100mL of N,N-dimethylformamide were mixed evenly, stirred at 25°C for 2h, cooled, quenched with water, washed with 0.1M NaOH solution, washed with water, and dried to obtain quaternary ammonium salt 4-aminopyridine;

[0042] A4, react 0.1mol of quaternary ammonium salt 4-aminopyridine and 0.1mol of 2,2-dihydroxymethylpropionic acid, mix well with 100mL of N,N-dimethylformamide, heat to 75°C, add 0.15mol of EDCI, stir for 0.5h, add 0.01mol of HOBT, heat to 85°C, continue stirring and react for 8h, cool, rotary evaporate, wash with water, wash with 0.1M, wash with water, and dry to obtain antibacterial siloxane;

[0043] A5. Disperse 100 g of silica with a particle size of 10-20 μm in 500 mL of a mixed solution of water and ethanol (the volume ratio of water to ethanol is 1:9), adjust the pH of the mixed solution to 5-6, heat to 50° C. with stirring, add 100 mL of ethanol containing 20 g of antibacterial siloxane under stirring, keep the mixture warm and stir for 4 h, stop the reaction, cool, age, filter, wash, and dry to obtain a surface-grafted inorganic filler;

[0044] A6. Disperse 4.0 g of surface quaternized grafted inorganic filler in a mixed solution of 200 mL of benzene and 25 g of dihydroxy-terminated polydimethylsiloxane (average molecular weight of 1500-2000), heat to 85°C while stirring, add 1.1 g of p-toluenesulfonic acid and 7 g of citric acid, keep stirring and react for 24 hours, cool, and recover benzene by rotary evaporation. Add the resulting product into a large amount of water, stir, age, filter, wash repeatedly, filter with suction, and dry to obtain an antibacterial agent.

[0045] Example 2

[0046] Preparation of antimicrobial agents:

[0047] A1. Add 0.1 mol 4-aminopyridine, 0.0.15 mol 2-nitrotoluenesulfonyl chloride and 0.15 mol triethylamine into 100 mL carbon dichloride and stir evenly. Stir and react at 23°C for 1 hour. Stop the reaction, rotary evaporate, wash and dry to obtain amino-protected 4-aminopyridine.

[0048] A2, after 0.1 mol of amino-protected 4-aminopyridine, 0.1 mol of γ-chloropropyltriethoxysilane and 100 mL of benzene are uniformly mixed, the mixture is heated to 85° C., the mixture is stirred and reacted for 6 h at the temperature, the reaction is stopped, the mixture is cooled, the mixture is rotary evaporated, the mixture is washed, and the mixture is dried to obtain amino-protected quaternary ammonium salt 4-aminopyridine;

[0049] A3, after 0.1mol of amino-protected quaternary ammonium salt 4-aminopyridine, 0.13mol of thioacetic acid, 0.01mol of lithium hydroxide and 100mL of N,N-dimethylformamide were mixed evenly, stirred at 30°C for 2h, cooled, quenched with water, washed with 0.1M NaOH solution, washed with water, and dried to obtain quaternary ammonium salt 4-aminopyridine;

[0050] A4, react 0.1mol of quaternary ammonium salt 4-aminopyridine and 0.1mol of 2,2-dihydroxymethylpropionic acid, mix well with 100mL of N,N-dimethylformamide, heat to 85°C, add 0.15mol of EDCI, stir for 0.5h, add 0.01mol of HOBT, heat to 95°C, continue stirring and reacting for 5h, cool, rotary evaporate, wash with water, wash with 0.1M, wash with water, and dry to obtain antibacterial siloxane;

[0051] A5. Disperse 100 g of silica with a particle size of 10-20 μm in 500 mL of a mixed solution of water and ethanol (the volume ratio of water to ethanol is 1:9), adjust the pH of the mixed solution to 5-6, heat to 60° C. with stirring, add 100 mL of ethanol containing 40 g of antibacterial siloxane under stirring, keep the mixture warm and stir for 6 h, stop the reaction, cool, age, filter, wash, and dry to obtain a surface-grafted inorganic filler;

[0052] A6. Disperse 4.5 g of surface quaternized grafted inorganic filler in a mixed solution of 200 mL of benzene and 25 g of dihydroxy-terminated polydimethylsiloxane (average molecular weight of 1500-2000), heat to 95°C while stirring, add 1.2 g of p-toluenesulfonic acid and 8 g of citric acid, keep stirring and react for 12 hours, cool, and recover benzene by rotary evaporation. Add the resulting product into a large amount of water, stir, age, filter, wash repeatedly, filter with suction, and dry to obtain an antibacterial agent.

[0053] Example 3

[0054] Preparation of composite materials:

[0055] The first step is to prepare the following raw materials in parts by weight: 100 parts of ASA resin, 30 parts of antibacterial agent, 10101.5 parts of antioxidant, and 0.5 parts of calcium stearate;

[0056] In the second step, the ASA resin, the antibacterial agent and the auxiliary agent are mixed, melt-blended, extruded and granulated to obtain a composite material.

[0057] Example 4

[0058] Preparation of composite materials:

[0059] The first step is to prepare the following raw materials in parts by weight: 100 parts of ASA resin, 40 parts of antibacterial agent, 1 part of antioxidant 1010, and 1 part of calcium stearate;

[0060] In the second step, the ASA resin, the antibacterial agent and the auxiliary agent are mixed, melt-blended, extruded and granulated to obtain a composite material.

[0061] Example 5

[0062] Preparation of composite materials:

[0063] The first step is to prepare the following raw materials in parts by weight: 100 parts of ASA resin, 50 parts of antibacterial agent, 1 part of antioxidant 1010, and 1 part of calcium stearate;

[0064] In the second step, the ASA resin, the antibacterial agent and the auxiliary agent are mixed, melt-blended, extruded and granulated to obtain a composite material.

[0065] Comparative Example 1

[0066] Preparation of composite materials:

[0067] Compared with Example 3, the antibacterial agent in the raw material is deleted, and the rest is the same.

[0068] Comparative Example 2

[0069] Preparation of composite materials:

[0070] Compared with Example 3, the antibacterial agent in the raw material is replaced with 10-20 μm silicon dioxide, and the rest is the same.

[0071] The composite materials obtained in Examples 3-5 and Comparative Examples 1-2 were subjected to physical property tests, and the test results are shown in Table 1. Inhibition rate test method: the antibacterial test was conducted using a thin film adhesion method, the antibacterial test piece had a size of 60 mm×30 mm×2 mm, and the test strain was Escherichia coli ATCC 25922.

[0072] Table 1

[0073]

[0074]

[0075] From the data in Table 1, it can be seen that the composite materials of Examples 3-5 of the present invention have excellent toughness and antibacterial properties.

[0076] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0077] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. An antibacterial and weather-resistant ASA composite material, characterized in that: The method comprises the following raw materials in parts by weight: 100 parts of ASA resin, 30-50 parts of antibacterial agent, and 1-5 parts of auxiliary agent; The antibacterial agent is a composite material with an inorganic filler as a core and quaternary ammonium salt polyester as a shell.

2. The antibacterial and weather-resistant ASA composite material according to claim 1, characterized in that: The antibacterial agent is obtained, comprising: Ultra-dispersing an inorganic filler in a mixed solution of water and ethanol, adjusting the pH of the mixed solution to 5-6, stirring and heating to a first temperature, adding ethanol containing antibacterial siloxane under stirring, keeping the temperature and stirring for 2-6 hours, stopping the reaction, and post-treating to obtain a surface-grafted inorganic filler; The surface quaternary ammonium salt grafted inorganic filler is ultra-dispersed in a mixed solution of a first organic solvent and dihydroxy-terminated polydimethylsiloxane, heated to a second temperature under stirring, an esterification reaction catalyst and citric acid are added, the reaction is stirred and kept warm for 12-24 hours, the reaction is stopped, and an antibacterial agent is obtained through post-treatment.

3. The antibacterial and weather-resistant ASA composite material according to claim 2, characterized in that: The first temperature is 50-60° C., and the mass ratio of the inorganic filler to the antibacterial siloxane is 10:2-4; The second temperature is 80-95° C., and the molar ratio of the antibacterial siloxane, citric acid, and dihydroxy-terminated polydimethylsiloxane is 1:4-6:1-2.

4. The antibacterial and weather-resistant ASA composite material according to claim 2, characterized in that: The antibacterial silicone is obtained by: The amino-protected 4-aminopyridine reacts with γ-chloropropyltriethoxysilane to obtain the amino-protected quaternary ammonium salt 4-aminopyridine; Deprotecting the amino-protected quaternary ammonium salt 4-aminopyridine to obtain quaternary ammonium salt 4-aminopyridine; Quaternary ammonium salt of 4-aminopyridine reacts with 2,2-dihydroxymethylpropionic acid to obtain antibacterial siloxane.

5. The antibacterial and weather-resistant ASA composite material according to claim 4, characterized in that: The amino-protected 4-aminopyridine is formed by reacting 4-aminopyridine with 2-nitrotoluenesulfonyl chloride.

6. The antibacterial and weather-resistant ASA composite material according to claim 4, characterized in that: In the reaction of the amino-protected 4-aminopyridine and γ-chloropropyltriethoxysilane, the reaction solvent is one of benzene, toluene, and N,N-dimethylformamide, the reaction temperature is 65-85° C., the reaction time is 6-18 hours, and the molar ratio of the amino-protected 4-aminopyridine and the γ-chloropropyltriethoxysilane is 1:1-1.

5.

7. The antibacterial and weather-resistant ASA composite material according to claim 4, characterized in that: In the reaction of the quaternized 4-aminopyridine and 2,2-dimethylolpropionic acid, the reaction solvent is one of N,N-dimethylformamide and N,N-dimethylacetamide, the reaction occurs in the presence of a condensation agent, the reaction temperature is 80-95° C., the reaction time is 5-12 hours, and the molar ratio of the quaternized 4-aminopyridine to 2,2-dimethylolpropionic acid is 1:1-1.

5.

8. The antibacterial and weather-resistant ASA composite material according to claim 7, characterized in that: The condensation reagent is a mixture of EDCI and HOBT.

9. The antibacterial and weather-resistant ASA composite material according to claim 1, characterized in that: The inorganic filler is one of silicon dioxide, graphene, carbon fiber and montmorillonite.

10. The method for preparing an antibacterial and weather-resistant ASA composite material according to claim 1, characterized in that: include: The ASA resin, the antibacterial agent and the auxiliary agent are mixed, melt-blended, extruded and granulated to obtain a composite material.

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