Antibacterial and deodorizing plastic and preparation method thereof

Abstract

The invention discloses an antibacterial and deodorizing plastic and a preparation method thereof, and relates to the technical field of plastics. The invention uses triethoxysilyl butyraldehyde, 4-chloro-1-butylamine, and (R)-2-(dimethylamino) propionamide to prepare a homemade antibacterial agent, and the Schiff base structure and the quaternary ammonium structure in the molecular chain interact with each other, effectively inhibiting bacterial growth, thereby improving the antibacterial and deodorizing properties of the plastic; then porous calcium silicate and porous calcium carbonate are used as deodorizing fillers for the plastic, and the homemade antibacterial agent is used as a cross-linking agent, so that the filler and urea-formaldehyde resin are combined with each other, which is conducive to uniform dispersion of the filler, and a cross-linked network structure is formed inside the plastic, which greatly improves the mechanical properties of the plastic.

Description

Technical Field

[0001] The invention relates to the technical field of plastics, in particular to an antibacterial and anti-odor plastic and a preparation method thereof. Background Art

[0002] In urban domestic waste collection points and waste transfer stations, the problem of garbage rot is particularly prominent. If it is not deodorized, the odor can reach level 4. Odor is one of the seven major public hazards in the world, often leading to the growth of bacteria and the spread of viruses. Odor pollution is easy to cause harm to humans, and even severe stench can affect the human endocrine system, causing endocrine system disorders and reducing metabolic activities. With the development of industry, plastic products have been used more and more widely. At present, plastic products usually have a single function, and the demand for multifunctional composite plastics has also increased. Summary of the invention

[0003] The purpose of the present invention is to provide an antibacterial and anti-odor plastic and a preparation method thereof, so as to solve the problems existing in the prior art.

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions: a method for preparing an antibacterial and deodorizing plastic, wherein the antibacterial and deodorizing plastic is made of porous calcium carbonate, porous calcium silicate, a homemade antibacterial agent, urea-formaldehyde resin, a plasticizer, and common starch.

[0005] Furthermore, the self-made antibacterial agent is prepared from triethoxysilylbutyraldehyde, 4-chloro-1-butylamine, and (R)-2-(dimethylamino)propionamide.

[0006] Furthermore, the preparation method of the antibacterial and deodorizing plastic is as follows: porous calcium carbonate, porous calcium silicate, and a homemade antibacterial agent are mixed, reacted at room temperature for 3 to 4 hours, dried at a vacuum degree of -0.08MPa and 80°C to a solid content of 60 to 70%, sent to a kneader, 25 to 38 times the mass of the porous calcium carbonate urea-formaldehyde resin is added, reacted at 50 to 65°C for 1 hour, sent to a dryer, 0.8 to 1 times the mass of the porous calcium carbonate plasticizer and 0.5 to 1.2 times the mass of the porous calcium carbonate ordinary starch are added, dried at 80 to 95°C to a moisture content of 1 to 3%, extruded into granules in a twin-screw extruder, and the granules are fully dried and injection molded into standard specimens by an injection molding machine to obtain an antibacterial and deodorizing plastic.

[0007] Furthermore, the ratio of the porous calcium carbonate, porous calcium silicate and homemade antibacterial agent solution is 1-3 g: 1-3 g: 30 mL.

[0008] Furthermore, the mass ratio of the homemade antibacterial agent, xylene and ethanol in the homemade antibacterial agent solution is 1:20:40.

[0009] Furthermore, the preparation method of the homemade antibacterial agent is: mix the Schiff base compound, ether, and (R)-2-(dimethylamino)propionamide, stir at 50-60°C and 100 rpm for 4-6 hours, filter, wash with deionized water 4-6 times, and dry at 60°C for 24 hours to obtain the homemade antibacterial agent.

[0010] Furthermore, the mass ratio of the Schiff base compound, diethyl ether, and (R)-2-(dimethylamino)propionamide is 1:10:0.5 to 1:20:1.5.

[0011] Furthermore, the preparation method of the Schiff base compound is: 4-chloro-1-butylamine, triethoxysilylbutyraldehyde and methanol are mixed, stirred for 4 to 6 hours, filtered, washed with methanol and distilled water for 3 times respectively, and dried at 60° C. for 8 hours to obtain the Schiff base compound.

[0012] Furthermore, the mass ratio of the 4-chloro-1-butylamine, triethoxysilylbutyraldehyde and methanol is 1:1:10 to 1:3:20.

[0013] Furthermore, the plasticizer is a mixture of glycerol and tributyl citrate in a mass ratio of 1:3.

[0014] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0015] The present invention utilizes porous calcium silicate and porous calcium carbonate as plastic fillers, the surface holes of which provide odor adsorption points, and then utilizes a homemade antibacterial agent as a cross-linking agent to combine the filler and urea-formaldehyde resin with each other. While the filler is evenly dispersed, a cross-linked network structure is formed inside the plastic, thereby greatly improving the mechanical properties of the plastic.

[0016] The invention utilizes the aldehyde group of triethoxysilyl butyraldehyde to react with the amino group of 4-chloro-1-butylamine to form a Schiff base structure. After the Schiff base functional group is introduced, a binding site with a chelating effect can be generated, and the adsorption of porous calcium silicate and porous calcium carbonate can be improved. Then, 4-chloro-1-butylamine reacts with the dimethylamino group of (R)-2-(dimethylamino) propionamide to form a quaternary ammonium structure, which effectively inhibits bacterial growth. At the same time, the Schiff base interacts with the quaternary ammonium structure to enhance the antibacterial property of the plastic. An amide group is introduced to further combine with calcium silicate and calcium carbonate. The porous structure of calcium silicate and calcium carbonate is utilized to jointly adsorb odor, so that the plastic achieves a deodorizing effect. In addition, triethoxysilyl butyraldehyde, 4-chloro-1-butylamine and (R)-2-(dimethylamino) propionamide react and crosslink with each other on the surface of calcium silicate and calcium carbonate. At the same time, part of the silicon hydroxyl groups are combined with the hydroxyl groups of the urea-formaldehyde resin polymer, so that the filler can be evenly dispersed and combined with the base material, thereby improving the mechanical properties of the plastic. DETAILED DESCRIPTION

[0017] 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 making creative work are within the scope of protection of the present invention.

[0018] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the test methods of various indicators of the antibacterial and deodorizing plastics prepared in the following examples are as follows:

[0019] Antibacterial: The plastics of the examples and comparative examples were cut into disc samples with a radius of 0.5 cm, and then the concentration of 10 7 The E. coli suspension of 100 CFU / mL was added to the phosphate buffer solution, and the disc sample was added, and the mixture was shaken at room temperature for 3 hours, and 2 mL of the solution was taken as the experimental group solution. The E. coli suspension was added to the phosphate buffer solution, and after shaking evenly, 2 mL of the solution was taken as the blank group solution. The E. coli experimental group solution and the blank group solution were inoculated in a plate by the agar pouring method, and cultured at 37°C for 24 hours. The experiment was repeated 3 times, and the live bacteria culture counts were performed after culture, and the average value was taken.

[0020] Inhibition rate = (number of colonies in the blank group - colony efficiency in the experimental group) / number of colonies in the blank group × 100%.

[0021] Strength: Tested in accordance with GB / T1040-2018 standard, with a tensile loading rate of 5 mm / min.

[0022] Deodorization: Place the examples or comparative examples in a sealed box, then introduce ammonia gas with a concentration of 100 ppm into the sealed box, and then let it stand for 10 minutes. Use a TVOC detection instrument to detect the residual gas concentration in each flask after a specified time has passed since the standing time, and calculate the deodorization rate after the specified time has passed.

[0023] Example 1

[0024] (1) 4-chloro-1-butylamine, triethoxysilylbutyraldehyde and methanol were mixed, stirred for 4 hours, filtered, washed with methanol and distilled water for 3 times, respectively, and dried at 60° C. for 8 hours to obtain a Schiff base compound; the mass ratio of 4-chloro-1-butylamine, triethoxysilylbutyraldehyde and methanol was 1:1:10;

[0025] (2) Mixing a Schiff base compound, ether, and (R)-2-(dimethylamino)propionamide, stirring at 50° C. and 100 rpm for 4 h, filtering, washing with deionized water 4 times, and drying at 60° C. for 24 h to obtain a homemade antibacterial agent; the mass ratio of the Schiff base compound, ether, and (R)-2-(dimethylamino)propionamide is 1:10:0.5;

[0026] (3) Porous calcium carbonate, porous calcium silicate, and a homemade antibacterial agent solution are mixed in a ratio of 1g:1g:30mL, reacted at room temperature for 3h, dried at 80°C with a vacuum degree of -0.08MPa to a solid content of 60%, sent to a kneader, and urea-formaldehyde resin 25 times the mass of the porous calcium carbonate is added. After reacting at 50°C for 1h, sent to a dryer, and a plasticizer 0.8 times the mass of the porous calcium carbonate and ordinary starch 0.5 times the mass of the porous calcium carbonate are added. The mixture is dried at 80°C to a moisture content of 3%, extruded into granules in a twin-screw extruder, and the granules are fully dried and then injection molded into standard specimens by an injection molding machine to obtain an antibacterial and deodorizing plastic. The mass ratio of the homemade antibacterial agent, xylene, and ethanol in the homemade antibacterial agent solution is 1:20:40; the plasticizer is a mixture of glycerol and tributyl citrate in a mass ratio of 1:3.

[0027] Example 2

[0028] (1) 4-chloro-1-butylamine, triethoxysilylbutyraldehyde and methanol were mixed, stirred for 5 hours, filtered, washed with methanol and distilled water for 3 times respectively, and dried at 60° C. for 8 hours to obtain a Schiff base compound; the mass ratio of 4-chloro-1-butylamine, triethoxysilylbutyraldehyde and methanol was 1:2:15;

[0029] (2) Mixing a Schiff base compound, ether, and (R)-2-(dimethylamino)propionamide, stirring at 55° C. and 100 rpm for 5 h, filtering, washing with deionized water 5 times, and drying at 60° C. for 24 h to obtain a homemade antibacterial agent; the mass ratio of the Schiff base compound, ether, and (R)-2-(dimethylamino)propionamide is 1:15:1;

[0030] (3) Porous calcium carbonate, porous calcium silicate and a homemade antibacterial agent solution are mixed in a ratio of 2g:2g:30mL, reacted at room temperature for 3.5h, dried at 80°C with a vacuum degree of -0.08MPa to a solid content of 65%, sent to a kneader, 30 times the mass of urea-formaldehyde resin of the porous calcium carbonate are added, reacted at 57°C for 1h, sent to a dryer, 0.9 times the mass of the porous calcium carbonate and 0.8 times the mass of the porous calcium carbonate Common starch is added, dried at 86°C to a moisture content of 2%, extruded and granulated in a twin-screw extruder, and the granules were fully dried and injection molded into standard specimens by an injection molding machine to obtain an antibacterial and deodorizing plastic; the mass ratio of the homemade antibacterial agent, xylene and ethanol in the homemade antibacterial agent solution is 1:20:40; the plasticizer is a mixture of glycerol and tributyl citrate in a mass ratio of 1:3.

[0031] Example 3

[0032] (1) 4-chloro-1-butylamine, triethoxysilylbutyraldehyde and methanol were mixed, stirred for 6 hours, filtered, washed with methanol and distilled water for 3 times respectively, and dried at 60° C. for 8 hours to obtain a Schiff base compound; the mass ratio of 4-chloro-1-butylamine, triethoxysilylbutyraldehyde and methanol was 1:3:20;

[0033] (2) Mixing a Schiff base compound, ether, and (R)-2-(dimethylamino)propionamide, stirring at 60° C. and 100 rpm for 6 hours, filtering, washing with deionized water for 6 times, and drying at 60° C. for 24 hours to obtain a homemade antibacterial agent; the mass ratio of the Schiff base compound, ether, and (R)-2-(dimethylamino)propionamide is 1:20:1.5;

[0034] (3) Porous calcium carbonate, porous calcium silicate and a homemade antibacterial solution are mixed in a ratio of 3 g:3 g:30 mL, reacted at room temperature for 4 h, dried at 80°C with a vacuum degree of -0.08 MPa to a solid content of 70%, sent to a kneader, and 38 times the mass of urea-formaldehyde resin of the porous calcium carbonate are added. After reacting at 65°C for 1 h, sent to a dryer, and a plasticizer of 1 times the mass of the porous calcium carbonate and ordinary starch of 1.2 times the mass of the porous calcium carbonate are added. The mixture is dried at 95°C to a moisture content of 3%, extruded into granules in a twin-screw extruder, and the granules are fully dried and then injection-molded into standard specimens by an injection molding machine to obtain an antibacterial and deodorizing plastic. The mass ratio of the homemade antibacterial solution, xylene and ethanol in the homemade antibacterial solution is 1:20:40. The plasticizer is a mixture of glycerol and tributyl citrate in a mass ratio of 1:3.

[0035] Comparative Example 1

[0036] (1) 4-chloro-1-butylamine, ether, and (R)-2-(dimethylamino)propionamide were mixed, stirred at 55° C. and 100 rpm for 5 h, filtered, washed with deionized water 5 times, and dried at 60° C. for 24 h to obtain a homemade antibacterial agent; the mass ratio of the Schiff base compound, ether, and (R)-2-(dimethylamino)propionamide was 1:15:1;

[0037] (2) Porous calcium carbonate, porous calcium silicate, and a homemade antibacterial agent solution are mixed in a ratio of 2g:2g:30mL, reacted at room temperature for 3.5h, dried at 80°C with a vacuum degree of -0.08MPa to a solid content of 65%, sent to a kneader, and 30 times the mass of urea-formaldehyde resin of the porous calcium carbonate are added. After reacting at 57°C for 1h, sent to a dryer, and 0.9 times the mass of the porous calcium carbonate and 0.8 times the mass of the porous calcium carbonate. Ordinary starch is added, dried at 86°C to a moisture content of 2%, extruded and granulated in a twin-screw extruder, and the granules are fully dried and then injection-molded into standard specimens by an injection molding machine to obtain an antibacterial and deodorizing plastic; the mass ratio of the homemade antibacterial agent, xylene, and ethanol in the homemade antibacterial agent solution is 1:20:40; the plasticizer is a mixture of glycerol and tributyl citrate in a mass ratio of 1:3.

[0038] Comparative Example 2

[0039] (1) 4-chloro-1-butylamine, triethoxysilylbutyraldehyde and methanol were mixed, stirred for 5 hours, filtered, washed with methanol and distilled water for 3 times respectively, and dried at 60° C. for 8 hours to obtain a homemade antibacterial agent; the mass ratio of 4-chloro-1-butylamine, triethoxysilylbutyraldehyde and methanol was 1:2:15;

[0040] (2) Porous calcium carbonate, porous calcium silicate, and a homemade antibacterial agent solution are mixed in a ratio of 2g:2g:30mL, reacted at room temperature for 3.5h, dried at 80°C with a vacuum degree of -0.08MPa to a solid content of 65%, sent to a kneader, and 30 times the mass of urea-formaldehyde resin of the porous calcium carbonate are added. After reacting at 57°C for 1h, sent to a dryer, and 0.9 times the mass of the porous calcium carbonate and 0.8 times the mass of the porous calcium carbonate. Ordinary starch is added, dried at 86°C to a moisture content of 2%, extruded and granulated in a twin-screw extruder, and the granules are fully dried and then injection-molded into standard specimens by an injection molding machine to obtain an antibacterial and deodorizing plastic; the mass ratio of the homemade antibacterial agent, xylene, and ethanol in the homemade antibacterial agent solution is 1:20:40; the plasticizer is a mixture of glycerol and tributyl citrate in a mass ratio of 1:3.

[0041] Comparative Example 3

[0042] (1) 4-chloro-1-butylamine, triethoxysilylbutyraldehyde and methanol were mixed, stirred for 5 hours, filtered, washed with methanol and distilled water for 3 times respectively, and dried at 60° C. for 8 hours to obtain a Schiff base compound; the mass ratio of 4-chloro-1-butylamine, triethoxysilylbutyraldehyde and methanol was 1:2:15;

[0043] (2) Mixing a Schiff base compound, ether, and (R)-2-(dimethylamino)propionamide, stirring at 55° C. and 100 rpm for 5 h, filtering, washing with deionized water 5 times, and drying at 60° C. for 24 h to obtain a homemade antibacterial agent; the mass ratio of the Schiff base compound, ether, and (R)-2-(dimethylamino)propionamide is 1:15:1;

[0044] (3) A homemade antibacterial agent, urea-formaldehyde resin with a mass of 30 times that of the homemade antibacterial agent, a plasticizer with a mass of 0.9 times that of the homemade antibacterial agent, and common starch with a mass of 0.8 times that of the homemade antibacterial agent are mixed, extruded into granules in a twin-screw extruder, and the granules are fully dried and injection-molded into standard specimens through an injection molding machine to obtain an antibacterial and deodorizing plastic; the plasticizer is a mixture of glycerol and tributyl citrate in a mass ratio of 1:3.

[0045] Comparative Example 4

[0046] (1) 4-chloro-1-butylamine, triethoxysilylbutyraldehyde and methanol were mixed, stirred for 5 hours, filtered, washed with methanol and distilled water for 3 times respectively, and dried at 60° C. for 8 hours to obtain a Schiff base compound; the mass ratio of 4-chloro-1-butylamine, triethoxysilylbutyraldehyde and methanol was 1:2:15;

[0047] (2) Mixing a Schiff base compound, ether, and (R)-2-(dimethylamino)propionamide, stirring at 55° C. and 100 rpm for 5 h, filtering, washing with deionized water 5 times, and drying at 60° C. for 24 h to obtain a homemade antibacterial agent; the mass ratio of the Schiff base compound, ether, and (R)-2-(dimethylamino)propionamide is 1:15:1;

[0048] (3) Porous calcium carbonate, porous calcium silicate, a homemade antibacterial agent, urea-formaldehyde resin, a plasticizer, and ordinary starch are mixed in a mass ratio of 1:1:2.5:30:0.9:0.8, extruded into granules in a twin-screw extruder, and the granules are fully dried and then injection-molded into standard specimens using an injection molding machine to obtain an antibacterial and deodorizing plastic; the plasticizer is a mixture of glycerol and tributyl citrate in a mass ratio of 1:3.

[0049] Effect example

[0050] Table 1 below shows the performance analysis results of the antibacterial and deodorizing plastics of Examples 1 to 3 of the present invention and Comparative Examples 1 to 4.

[0051] Table 1

[0052]

[0053]

[0054] The present invention utilizes porous calcium silicate and porous calcium carbonate as plastic fillers, the surface holes of which provide odor adsorption points, and then utilizes a homemade antibacterial agent as a cross-linking agent to combine the filler and urea-formaldehyde resin with each other. While the filler is evenly dispersed, a cross-linked network structure is formed inside the plastic, thereby greatly improving the mechanical properties of the plastic. The aldehyde group of triethoxysilyl butyraldehyde reacts with the amino group of 4-chloro-1-butylamine to form a Schiff base structure. After the Schiff base functional group is introduced, a binding site with a chelating effect can be generated, which can improve the adsorption of porous calcium silicate and porous calcium carbonate. Then, 4-chloro-1-butylamine reacts with the dimethylamino group of (R)-2-(dimethylamino) propionamide to form a quaternary ammonium structure, which effectively inhibits bacterial growth. At the same time, the Schiff base interacts with the quaternary ammonium structure to enhance the antibacterial property of the plastic. An amide group is also introduced to further combine with calcium silicate and calcium carbonate. The porous structure of calcium silicate and calcium carbonate is used to jointly adsorb odor, so that the plastic achieves a deodorizing effect. In addition, triethoxysilyl butyraldehyde, 4-chloro-1-butylamine, and (R)-2-(dimethylamino) propionamide react and cross-link on the surface of calcium silicate and calcium carbonate. At the same time, part of the silicon hydroxyl group combines with the hydroxyl group of the urea-formaldehyde resin polymer, so that the filler is evenly dispersed and can be combined with the base material to improve the mechanical properties of the plastic.

[0055] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A method for preparing an antibacterial and deodorizing plastic, characterized in that: The antibacterial and deodorizing plastic is made of porous calcium carbonate, porous calcium silicate, a homemade antibacterial agent, urea-formaldehyde resin, a plasticizer, and common starch; The preparation method of the antibacterial and deodorizing plastic is as follows: porous calcium carbonate, porous calcium silicate and a self-made antibacterial agent solution are mixed, reacted at room temperature for 3-4 hours, dried at 80° C. with a vacuum degree of -0.08 MPa to a solid content of 60-70%, sent to a kneader, urea-formaldehyde resin of 25-38 times the mass of the porous calcium carbonate is added, reacted at 50-65° C. for 1 hour, sent to a dryer, a plasticizer of 0.8-1 times the mass of the porous calcium carbonate and common starch of 0.5-1.2 times the mass of the porous calcium carbonate are added, dried at 80-95° C. to a water content of 1-3%, extruded and granulated in a twin-screw extruder, and the granules are fully dried and then injection-molded into standard samples by an injection molding machine to obtain the antibacterial and deodorizing plastic; The mass ratio of the homemade antibacterial agent, xylene and ethanol in the homemade antibacterial agent solution is 1:20:40; The preparation method of the self-made antibacterial agent is as follows: a Schiff base compound, ether and (R)-2-(dimethylamino)propionamide are mixed, stirred at 50-60° C. and 100 rpm for 4-6 hours, filtered, washed with deionized water for 4-6 times, and dried at 60° C. for 24 hours to obtain the self-made antibacterial agent; The preparation method of the Schiff base compound is as follows: 4-chloro-1-butylamine, triethoxysilylbutyraldehyde and methanol are mixed, stirred for 4-6 hours, filtered, washed with methanol and distilled water for 3 times respectively, and dried at 60° C. for 8 hours to obtain the Schiff base compound.

2. The method for preparing an antibacterial and deodorizing plastic according to claim 1, characterized in that: The ratio of the porous calcium carbonate, porous calcium silicate and the homemade antibacterial agent solution is 1-3 g: 1-3 g: 30 mL.

3. The method for preparing an antibacterial and deodorizing plastic according to claim 1, characterized in that: The mass ratio of the Schiff base compound, ether and (R)-2-(dimethylamino)propionamide is 1:10:0.5 to 1:20:1.

5.

4. The method for preparing an antibacterial and deodorizing plastic according to claim 1, characterized in that: The mass ratio of the 4-chloro-1-butylamine, triethoxysilylbutyraldehyde and methanol is 1:1:10-1:3:

20.

5. The method for preparing an antibacterial and deodorizing plastic according to claim 1, characterized in that: The plasticizer is a mixture of glycerol and tributyl citrate in a mass ratio of 1:3.

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