Antibacterial weatherable ASA composite and method for preparing the same
By introducing an antibacterial agent with an inorganic filler core and a quaternary ammonium salt polyester shell into ASA composite materials, the problem of insufficient antibacterial properties of ASA composite materials was solved, and the antibacterial properties and toughness of the materials were improved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SHENZHEN FUHENG PLASTICS PIGMENT
- Filing Date
- 2024-12-25
- Publication Date
- 2026-06-02
AI Technical Summary
Existing ASA composite materials cannot meet the antibacterial performance requirements of the product.
By introducing an antibacterial agent with an inorganic filler core and a quaternary ammonium salt polyester shell, a complex is formed through surface grafting and esterification reactions, thereby endowing the ASA composite material with antibacterial properties. The antibacterial and weather-resistant ASA composite material is then prepared by melt blending extrusion.
The excellent antibacterial properties of ASA composite materials were achieved, while their toughness was enhanced and the mechanical properties of ASA resin were improved.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of ASA composite material preparation technology, specifically, it relates to an antibacterial and weather-resistant ASA composite material and its preparation method. Background Technology
[0002] ASA resin is a ternary polymer composed of acrylonitrile, styrene, and acrylic rubber. Similar to ABS resin, it possesses excellent mechanical properties, processability, electrical insulation, and chemical resistance. Furthermore, because acrylic rubber replaces butadiene rubber in its raw materials, its weather resistance is superior to that of ABS. This excellent weather resistance makes it widely used in outdoor products and the automotive industry. However, with the increasing demand for antibacterial properties in outdoor and automotive products, antibacterial performance requirements have also been placed on ASA composite materials. Summary of the Invention
[0003] The purpose of this invention is to provide an antibacterial and weather-resistant ASA composite material and its preparation method, so as to solve the problem that existing ASA composite materials cannot meet the antibacterial requirements of products.
[0004] The first objective of this invention can be achieved through the following technical solution:
[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 core and a quaternary ammonium salt-treated polyester shell.
[0007] Furthermore, obtaining the antibacterial agent includes:
[0008] Inorganic fillers were ultradispersed in a mixed solution of water and ethanol. The pH of the mixed solution was adjusted to 5-6. The mixture was stirred and heated to the first temperature. Ethanol containing antibacterial siloxane was added while stirring. The mixture was kept warm and stirred for 2-6 hours. The reaction was stopped. After post-treatment, the surface-grafted inorganic fillers were obtained.
[0009] The surface quaternary ammonium salt grafted inorganic filler was ultradispersed in a mixed solution of a first organic solvent and a dihydroxyl-terminated polydimethylsiloxane. The mixture was heated to a second temperature with stirring, and an esterification reaction catalyst and citric acid were added. The mixture was kept at this temperature and stirred for 12-24 hours. The reaction was then stopped, and the product was post-treated to obtain an antibacterial agent.
[0010] Furthermore, the first temperature is 50-60℃, and the mass ratio of the inorganic filler to the antibacterial siloxane is 10:2-4.
[0011] Further, the second temperature is 80-95℃, 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 acquisition of the antibacterial siloxane includes:
[0013] The amino-protected 4-aminopyridine reacts with γ-chloropropyltriethoxysilane to give amino-protected quaternary ammonium salted 4-aminopyridine.
[0014] The amino-protected quaternized 4-aminopyridine is deprotected to give quaternized 4-aminopyridine.
[0015] Quaternized 4-aminopyridine reacts with 2,2-dimethylolpropionic acid to yield antibacterial siloxanes.
[0016] Furthermore, the molecular structural formula of the antibacterial siloxane is shown below:
[0017]
[0018] Furthermore, the amino-protected 4-aminopyridine is formed by reacting 4-aminopyridine with 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 were added to carbon dichloride in a molar ratio of 1:1-1.5:1-2 and stirred until homogeneous. The mixture was then stirred at 20-23°C for 1-4 hours. The reaction was stopped, and the mixture was rotary evaporated, washed, and dried 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℃, 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 deprotection of the amino-protected quaternary ammonium salt of 4-aminopyridine includes:
[0023] Amino-protected quaternized 4-aminopyridine, thioacetic acid, lithium hydroxide, and N,N-dimethylformamide were mixed evenly and stirred at 20-30℃ for 2-4 hours. After cooling, the mixture was rotary evaporated, and the product was washed with 0.1M NaOH solution, washed with water, and dried to obtain quaternized 4-aminopyridine.
[0024] Furthermore, in the reaction of quaternized 4-aminopyridine with 2,2-dimethylolpropionic acid, the reaction solvent is one of N,N-dimethylformamide and N,N-dimethylacetamide, the reaction temperature is 80-95℃, the reaction time is 5-12h, and the molar ratio of quaternized 4-aminopyridine to 2,2-dimethylolpropionic 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 silica, 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 lubricants and antioxidants well known in the art; wherein, the types of lubricants and antioxidants are not specifically limited in this invention.
[0030] The second objective of this invention can be achieved through the following technical solution:
[0031] A method for preparing an antibacterial and weather-resistant ASA composite material, comprising:
[0032] ASA resin, antibacterial agent and auxiliary agent are mixed, and then melt-blended and extruded, and granulated to obtain composite material.
[0033] The beneficial effects of this invention are:
[0034] The present invention provides an antibacterial and weather-resistant ASA composite material and its preparation method, which endows the composite material with excellent antibacterial properties by introducing an antibacterial agent;
[0035] Notably, the antibacterial agent is a composite with an inorganic filler core and a quaternized polyester shell. It is formed by two steps: surface grafting (surface grafting of molecular chains containing quaternary ammonium salt structures) and surface condensation reaction (formation of a quaternized polyester shell by esterification reaction between hydroxyl groups of molecular chains containing quaternary ammonium salt structures, dihydroxyl-terminated polydimethylsiloxane, and citric acid). The core is rigid, and the layer is a polyester elastic layer (the polyester layer contains flexible chains of polysiloxane chains). While exerting the antibacterial properties of quaternary ammonium salts, it can also exert the toughness-enhancing effect of the synergistic effect of rigid particles and flexible chains, thereby improving the toughness properties of ASA resin. Detailed Implementation
[0036] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0037] Example 1
[0038] Preparation of antibacterial agents:
[0039] A1. 0.1 mol 4-aminopyridine, 0.13 mol 2-nitrotoluenesulfonyl chloride, and 0.15 mol triethylamine were added to 100 mL of carbon dichloride and stirred until homogeneous. The mixture was stirred at 20 °C for 2 h, and then the reaction was stopped. The mixture was then rotary evaporated, washed, and dried to obtain amino-protected 4-aminopyridine.
[0040] A2. Mix 0.1 mol of amino-protected 4-aminopyridine, 0.1 mol of γ-chloropropyltriethoxysilane and 100 mL of benzene evenly, heat to 70 °C, stir and keep warm for 8 h, stop the reaction, cool, rotary evaporate, wash and dry to obtain amino-protected quaternary ammonium salted 4-aminopyridine.
[0041] A3. Mix 0.1 mol of amino-protected quaternized 4-aminopyridine, 0.13 mol of thioacetic acid, 0.01 mol of lithium hydroxide and 100 mL of N,N-dimethylformamide evenly, stir at 25 °C for 2 h, cool, quench with water, wash with 0.1 M NaOH solution, wash with water again, and dry to obtain quaternized 4-aminopyridine.
[0042] A4. 0.1 mol of quaternized 4-aminopyridine and 0.1 mol of 2,2-dimethylolpropionic acid were reacted and mixed with 100 mL of N,N-dimethylformamide. The mixture was heated to 75 °C, 0.15 mol of EDCI was added, and the mixture was stirred for 0.5 h. 0.01 mol of HOBT was added, and the mixture was heated to 85 °C. The mixture was stirred for another 8 h, cooled, rotary evaporated, washed with water, washed with 0.1 M solution, washed with water, and dried to obtain antibacterial siloxane.
[0043] A5. 100g of silica with a particle size of 10-20μm was ultradispersed in a 500mL mixed solution of water and ethanol (volume ratio of water to ethanol is 1:9). The pH of the mixed solution was adjusted to 5-6. The mixture was stirred and heated to 50℃. 100mL of ethanol containing 20g of antibacterial siloxane was added while stirring. The mixture was kept warm and stirred for 4h. The reaction was stopped, cooled, aged, filtered, washed, and dried to obtain the surface-grafted inorganic filler.
[0044] A6. 4.0 g of surface quaternary ammonium salt grafted inorganic filler was ultradispersed in a mixed solution of 200 mL benzene and 25 g of dihydroxyl-terminated polydimethylsiloxane (average molecular weight 1500-2000). The mixture was heated to 85 °C with stirring, and 1.1 g of p-toluenesulfonic acid and 7 g of citric acid were added. The mixture was kept warm and stirred for 24 h. After cooling, benzene was recovered by rotary evaporation. The obtained product was added to a large amount of water and stirred, aged, filtered, repeatedly washed, filtered again, and dried to obtain an antibacterial agent.
[0045] Example 2
[0046] Preparation of antibacterial agents:
[0047] A1. 0.1 mol 4-aminopyridine, 0.015 mol 2-nitrotoluenesulfonyl chloride, and 0.15 mol triethylamine were added to 100 mL of carbon dichloride and stirred until homogeneous. The mixture was stirred at 23 °C for 1 h, and then the reaction was stopped. The mixture was then rotary evaporated, washed, and dried to obtain amino-protected 4-aminopyridine.
[0048] A2. Mix 0.1 mol of amino-protected 4-aminopyridine, 0.1 mol of γ-chloropropyltriethoxysilane and 100 mL of benzene evenly, heat to 85°C, stir and keep warm for 6 h, stop the reaction, cool, rotary evaporate, wash and dry to obtain amino-protected quaternary ammonium salted 4-aminopyridine.
[0049] A3. Mix 0.1 mol of amino-protected quaternized 4-aminopyridine, 0.13 mol of thioacetic acid, 0.01 mol of lithium hydroxide and 100 mL of N,N-dimethylformamide evenly, stir at 30 °C for 2 h, cool, quench with water, wash with 0.1 M NaOH solution, wash with water again, and dry to obtain quaternized 4-aminopyridine.
[0050] A4. 0.1 mol of quaternized 4-aminopyridine and 0.1 mol of 2,2-dimethylolpropionic acid were reacted and mixed with 100 mL of N,N-dimethylformamide. The mixture was heated to 85 °C, 0.15 mol of EDCI was added, and the mixture was stirred for 0.5 h. 0.01 mol of HOBT was added, and the mixture was heated to 95 °C. The mixture was stirred for another 5 h, cooled, rotary evaporated, washed with water, washed with 0.1 M solution, washed with water, and dried to obtain antibacterial siloxane.
[0051] A5. 100g of silica with a particle size of 10-20μm was ultradispersed in a 500mL mixed solution of water and ethanol (volume ratio of water to ethanol is 1:9). The pH of the mixed solution was adjusted to 5-6. The mixture was stirred and heated to 60℃. 100mL of ethanol containing 40g of antibacterial siloxane was added while stirring. The mixture was kept warm and stirred for 6h. The reaction was stopped, cooled, aged, filtered, washed, and dried to obtain the surface-grafted inorganic filler.
[0052] A6. 4.5g of surface quaternary ammonium salt grafted inorganic filler was ultradispersed in a mixed solution of 200mL benzene and 25g of dihydroxyl-terminated polydimethylsiloxane (average molecular weight 1500-2000). The mixture was heated to 95℃ with stirring, and 1.2g of p-toluenesulfonic acid and 8g of citric acid were added. The mixture was kept warm and stirred for 12h. After cooling, benzene was recovered by rotary evaporation. The obtained product was added to a large amount of water and stirred, aged, filtered, repeatedly washed, filtered again, and dried to obtain an antibacterial agent.
[0053] Example 3
[0054] Preparation of composite materials:
[0055] Step 1: Prepare the following raw materials by weight: 100 parts ASA resin, 30 parts antibacterial agent, 1.5 parts antioxidant, and 0.5 parts calcium stearate;
[0056] The second step involves mixing ASA resin, antibacterial agent, and auxiliary agents, followed by melt blending and extrusion, and granulation to obtain the composite material.
[0057] Example 4
[0058] Preparation of composite materials:
[0059] Step 1: Prepare the following raw materials by weight: 100 parts ASA resin, 40 parts antibacterial agent, 1 part antioxidant 1010, and 1 part calcium stearate;
[0060] The second step involves mixing ASA resin, antibacterial agent, and auxiliary agents, followed by melt blending and extrusion, and granulation to obtain the composite material.
[0061] Example 5
[0062] Preparation of composite materials:
[0063] Step 1: Prepare the following raw materials by weight: 100 parts ASA resin, 50 parts antibacterial agent, 1 part antioxidant 1010, and 1 part calcium stearate;
[0064] The second step involves mixing ASA resin, antibacterial agent, and auxiliary agents, followed by melt blending and extrusion, and granulation to obtain the composite material.
[0065] Comparative Example 1
[0066] Preparation of composite materials:
[0067] Compared to Example 3, the antibacterial agent in the raw materials was removed, but the rest were the same.
[0068] Comparative Example 2
[0069] Preparation of composite materials:
[0070] Compared with Example 3, the antibacterial agent in the raw materials was replaced with an equal amount of 10-20μm silica, and the rest were 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. The antibacterial rate was tested using the film adhesion method. The antibacterial test specimen was 60mm × 30mm × 2mm in size, and the test bacteria was Escherichia coli ATCC 25922.
[0072] Table 1
[0073]
[0074]
[0075] As can be seen from the data in Table 1, the composite materials of Examples 3-5 of the present invention have excellent toughness and antibacterial properties.
[0076] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.
[0077] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.
Claims
1. An antibacterial and weather-resistant ASA composite material, characterized in that, The raw materials include the following parts by weight: 100 parts ASA resin, 30-50 parts antibacterial agent, and 1-5 parts auxiliary agent; The antibacterial agent is a composite with an inorganic filler core and a quaternary ammonium salt-treated polyester shell; Obtaining the antibacterial agent includes: Inorganic filler was dispersed in a mixed solution of water and ethanol. The pH of the mixed solution was adjusted to 5-6. The mixture was stirred and heated to the first temperature. Ethanol containing antibacterial siloxane was added while stirring. The mixture was kept warm and stirred for 2-6 hours. The reaction was stopped. After post-treatment, the surface-grafted inorganic filler was obtained. The surface-grafted inorganic filler was dispersed in a mixed solution of a first organic solvent and a dihydroxyl-terminated polydimethylsiloxane. The mixture was heated to a second temperature with stirring, and an esterification reaction catalyst and citric acid were added. The mixture was kept at the temperature and stirred for 12-24 hours. The reaction was then stopped, and the product was post-treated to obtain an antibacterial agent. Obtaining the antibacterial siloxane includes: The amino-protected 4-aminopyridine reacts with γ-chloropropyltriethoxysilane to give amino-protected quaternary ammonium salted 4-aminopyridine. The amino-protected quaternized 4-aminopyridine is deprotected to give quaternized 4-aminopyridine. The quaternized 4-aminopyridine reacts with 2,2-dimethylolpropionic acid to yield an antibacterial siloxane; The amino-protected 4-aminopyridine is formed by reacting 4-aminopyridine with 2-nitrotoluenesulfonyl chloride.
2. The antibacterial and weather-resistant ASA composite material according to claim 1, characterized in that, The first temperature is 50-60℃, and the mass ratio of the inorganic filler to the antibacterial siloxane is 10:2-4; The second temperature is 80-95℃, and the molar ratio of the antibacterial siloxane, citric acid, and dihydroxy-terminated polydimethylsiloxane is 1:4-6:1-2.
3. The antibacterial and weather-resistant ASA composite material according to claim 1, characterized in that, In the reaction of 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℃, the reaction time is 6-18h, and the molar ratio of amino-protected 4-aminopyridine to γ-chloropropyltriethoxysilane is 1:1-1.
5.
4. The antibacterial and weather-resistant ASA composite material according to claim 1, characterized in that, In the reaction of quaternized 4-aminopyridine with 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 condensing agent, the reaction temperature is 80-95℃, the reaction time is 5-12h, and the molar ratio of quaternized 4-aminopyridine to 2,2-dimethylolpropionic acid is 1:1-1.
5.
5. The antibacterial and weather-resistant ASA composite material according to claim 4, characterized in that, The condensation reagent is a mixture of EDCI and HOBT.
6. The antibacterial and weather-resistant ASA composite material according to claim 1, characterized in that, The inorganic filler is one of silica, graphene, carbon fiber, and montmorillonite.
7. The method for preparing an antibacterial and weather-resistant ASA composite material according to claim 1, characterized in that, include: ASA resin, antibacterial agent and auxiliary agent are mixed, and then melt-blended and extruded, and granulated to obtain composite material.