Preparation method of bacteriostatic and deodorant plastic

Abstract

The application discloses a preparation method of bacteriostatic and deodorant plastic and relates to the technical field of plastics. The self-prepared antibacterial agent is prepared by using triethoxysilane butyraldehyde, 4-chloro-1-butylamine and (R)-2-(dimethylamino) propionamide, the Schiff base structure and the quaternary ammonium structure in the molecular chain of the self-prepared antibacterial agent interact, bacterial growth is effectively inhibited, and then the antibacterial and deodorant properties of the plastic are improved; then porous calcium silicate and porous calcium carbonate are used as deodorant fillers of the plastic, the self-prepared antibacterial agent is used as a crosslinking agent, the fillers and the urea-formaldehyde resin are combined with each other, the uniform dispersion of the fillers is facilitated, meanwhile, a crosslinked network structure is formed in the plastic, and the mechanical properties of the plastic are greatly improved.

Description

Technical Field

[0001] This invention relates to the field of plastics technology, specifically to a method for preparing antibacterial and deodorizing plastics. Background Technology

[0002] The problem of stench from rotting garbage is particularly prominent at urban waste collection points and transfer stations. Without deodorization, the odor can reach level 4. Odor is one of the world's seven major public health hazards, often leading to bacterial growth and viral spread. Odor pollution can easily harm humans; severe stench can even affect the endocrine system, causing endocrine disorders and reducing metabolic activity. Furthermore, with industrial development, plastic products have become increasingly widely used. Currently, plastic products are typically single-function, leading to an increasing demand for multi-functional composite plastics. Summary of the Invention

[0003] The purpose of this invention is to provide an antibacterial and deodorizing plastic and its preparation method, so as to solve the problems existing in the prior art.

[0004] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a method for preparing antibacterial and odor-resistant plastic, wherein the antibacterial and odor-resistant plastic is made from porous calcium carbonate, porous calcium silicate, self-made antibacterial agent, urea-formaldehyde resin, plasticizer, and ordinary starch.

[0005] Furthermore, the self-made antibacterial agent is prepared from triethoxysilylbutyraldehyde, 4-chloro-1-butamine, 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 self-made antibacterial agent are mixed and reacted at room temperature for 3-4 hours. Then, the mixture is dried at 80°C under a vacuum of -0.08 MPa until the solid content is 60-70%. The mixture is then fed into a kneader, and urea-formaldehyde resin with a mass of 25-38 times that of porous calcium carbonate is added. After reacting at 50-65°C for 1 hour, the mixture is fed into a dryer, and plasticizer with a mass of 0.8-1 times that of porous calcium carbonate and ordinary starch with a mass of 0.5-1.2 times that of porous calcium carbonate are added. The mixture is dried at 80-95°C until the moisture content is 1-3%. The mixture is then extruded and granulated in a twin-screw extruder. After the granules are fully dried, they are injection molded into standard samples to obtain the antibacterial and deodorizing plastic.

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

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

[0009] Furthermore, the preparation method of the self-made antibacterial agent is as follows: Schiff base compound, diethyl ether, and (R)-2-(dimethylamino)propionamide are mixed, stirred at 50-60℃ and 100rpm for 4-6 hours, filtered, washed with deionized water 4-6 times, and dried at 60℃ for 24 hours to obtain the self-made 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 Schiff base compound is prepared by mixing 4-chloro-1-butanamine, triethoxysilylbutanal, and methanol, stirring for 4-6 hours, filtering, washing three times with methanol and distilled water respectively, and drying at 60°C for 8 hours to obtain the Schiff base compound.

[0012] Furthermore, the mass ratio of 4-chloro-1-butamine, 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] This invention utilizes porous calcium silicate and porous calcium carbonate as plastic fillers, whose surface pores provide odor adsorption points. Then, a self-made antibacterial agent is used as a crosslinking agent to combine the filler and urea-formaldehyde resin. While the filler is uniformly dispersed, a crosslinked network structure is formed inside the plastic, which greatly improves the mechanical properties of the plastic.

[0016] This invention utilizes the reaction between the aldehyde group of triethoxysilylbutyraldehyde and the amino group of 4-chloro-1-butamine to form a Schiff base structure. Introducing the Schiff base functional group creates chelating binding sites, enhancing the adsorption of porous calcium silicate and porous calcium carbonate. Subsequently, 4-chloro-1-butamine reacts with the dimethylamino group of (R)-2-(dimethylamino)propionamide to form a quaternary ammonium structure, effectively inhibiting bacterial growth. Simultaneously, the interaction between the Schiff base and the quaternary ammonium structure enhances the antibacterial properties of the plastic. Furthermore, the introduction of amide groups allows for further binding with calcium silicate and calcium carbonate. The porous structure of calcium silicate and calcium carbonate works together to adsorb odors, achieving a deodorizing effect in the plastic. In addition, triethoxysilylbutyraldehyde, 4-chloro-1-butamine, and (R)-2-(dimethylamino)propionamide cross-link with each other on the surfaces of calcium silicate and calcium carbonate. Simultaneously, some silanol groups bind with the hydroxyl groups of the urea-formaldehyde resin polymer, ensuring uniform dispersion of the filler while allowing it to bind with the base material, thus improving the mechanical properties of the plastic. Detailed Implementation

[0017] 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.

[0018] To more clearly illustrate the method provided by the present invention, the following embodiments are provided in detail. The test methods for various indicators of the antibacterial and odor-resistant plastics produced in the following embodiments are as follows:

[0019] Antibacterial: The plastic samples from the examples and comparative examples were cut into circular specimens with a radius of 0.5 cm, and then a concentration of 10 was applied. 7 A CFU / mL *E. coli* suspension was added to phosphate buffer solution, followed by a sample disc. The mixture was shaken at room temperature for 3 hours, and 2 mL of the resulting solution was used as the experimental group. The *E. coli* suspension was then added to phosphate buffer solution, shaken thoroughly, and 2 mL of this solution was used as the blank group. Both the experimental and blank *E. coli* solutions were inoculated into Petri dishes using the agar pour method and incubated at 37°C for 24 hours. The experiment was repeated three times. Viable cell counts were performed after incubation, and the average value was taken.

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

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

[0022] Deodorization: Take the example or comparative example and place it in a sealed box. Then, introduce 100ppm ammonia gas into the sealed box and let it stand for 10 minutes. Use a TVOC detector to detect the residual gas concentration in each flask after a specified time from the time after standing. Calculate the deodorization rate after the specified time.

[0023] Example 1

[0024] (1) Mix 4-chloro-1-butamine, triethoxysilylbutyraldehyde and methanol, stir for 4 hours, filter, wash with methanol and distilled water 3 times respectively, and dry at 60°C for 8 hours to obtain Schiff base compound; the mass ratio of 4-chloro-1-butamine, triethoxysilylbutyraldehyde and methanol is 1:1:10.

[0025] (2) Mix Schiff base compound, diethyl ether, and (R)-2-(dimethylamino)propionamide, stir at 50°C and 100 rpm for 4 h, filter, wash with deionized water 4 times, and dry at 60°C for 24 h to obtain the self-made antibacterial agent; the mass ratio of Schiff base compound, diethyl ether, and (R)-2-(dimethylamino)propionamide is 1:10:0.5;

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

[0027] Example 2

[0028] (1) Mix 4-chloro-1-butamine, triethoxysilylbutyraldehyde and methanol, stir for 5 hours, filter, wash with methanol and distilled water 3 times respectively, and dry at 60°C for 8 hours to obtain Schiff base compound; the mass ratio of 4-chloro-1-butamine, triethoxysilylbutyraldehyde and methanol is 1:2:15.

[0029] (2) Mix Schiff base compound, diethyl ether, and (R)-2-(dimethylamino)propionamide, stir at 55°C and 100 rpm for 5 h, filter, wash with deionized water 5 times, and dry at 60°C for 24 h to obtain the self-made antibacterial agent; the mass ratio of Schiff base compound, diethyl ether, and (R)-2-(dimethylamino)propionamide is 1:15:1;

[0030] (3) Porous calcium carbonate, porous calcium silicate, and self-made antibacterial agent solution are mixed in a ratio of 2g:2g:30mL. After reacting at room temperature for 3.5h, the mixture is dried at 80℃ under a vacuum of -0.08MPa until the solid content is 65%. The mixture is then fed into a kneader, and urea-formaldehyde resin with a mass of 30 times that of porous calcium carbonate is added. After reacting at 57℃ for 1h, the mixture is fed into a dryer, and plasticizer with a mass of 0.9 times that of porous calcium carbonate and ordinary starch with a mass of 0.8 times that of porous calcium carbonate are added. The mixture is dried at 86℃ until the water content is 2%. The mixture is then extruded and granulated in a twin-screw extruder. After the granules are fully dried, they are injection molded into standard samples to obtain antibacterial and deodorizing plastic. The mass ratio of the self-made antibacterial agent, xylene, and ethanol in the self-made antibacterial agent solution is 1:20:40. The plasticizer is a mixture of glycerol and tributyl citrate with a mass ratio of 1:3.

[0031] Example 3

[0032] (1) Mix 4-chloro-1-butamine, triethoxysilylbutyraldehyde and methanol, stir for 6 hours, filter, wash with methanol and distilled water 3 times respectively, and dry at 60°C for 8 hours to obtain Schiff base compound; the mass ratio of 4-chloro-1-butamine, triethoxysilylbutyraldehyde and methanol is 1:3:20.

[0033] (2) Mix Schiff base compound, diethyl ether, and (R)-2-(dimethylamino)propionamide, stir at 60°C and 100 rpm for 6 h, filter, wash with deionized water 6 times, and dry at 60°C for 24 h to obtain the self-made antibacterial agent; the mass ratio of Schiff base compound, diethyl ether, and (R)-2-(dimethylamino)propionamide is 1:20:1.5;

[0034] (3) Porous calcium carbonate, porous calcium silicate, and self-made antibacterial agent solution are mixed in a ratio of 3g:3g:30mL. After reacting at room temperature for 4 hours, the mixture is dried at 80°C under a vacuum of -0.08MPa until the solid content is 70%. The mixture is then fed into a kneader, and urea-formaldehyde resin with a mass of 38 times that of porous calcium carbonate is added. After reacting at 65°C for 1 hour, the mixture is fed into a dryer, and plasticizer with a mass of 1 times that of porous calcium carbonate and ordinary starch with a mass of 1.2 times that of porous calcium carbonate are added. The mixture is dried at 95°C until the water content is 3%. The mixture is then extruded and granulated in a twin-screw extruder. After the granules are fully dried, they are injection molded into standard samples to obtain antibacterial and deodorizing plastic. The mass ratio of the self-made antibacterial agent solution, xylene, and ethanol in the self-made antibacterial agent solution is 1:20:40. The plasticizer is a mixture of glycerol and tributyl citrate with a mass ratio of 1:3.

[0035] Comparative Example 1

[0036] (1) Mix 4-chloro-1-butamine, diethyl ether, and (R)-2-(dimethylamino)propionamide, stir at 55°C and 100 rpm for 5 h, filter, wash with deionized water 5 times, and dry at 60°C for 24 h to obtain the self-made antibacterial agent; the mass ratio of the Schiff base compound, diethyl ether, and (R)-2-(dimethylamino)propionamide is 1:15:1;

[0037] (2) Porous calcium carbonate, porous calcium silicate, and self-made antibacterial agent solution are mixed in a ratio of 2g:2g:30mL. After reacting at room temperature for 3.5h, the mixture is dried at 80℃ under a vacuum of -0.08MPa until the solid content is 65%. The mixture is then fed into a kneader, and urea-formaldehyde resin with a mass of 30 times that of porous calcium carbonate is added. After reacting at 57℃ for 1h, the mixture is fed into a dryer, and plasticizer with a mass of 0.9 times that of porous calcium carbonate and ordinary starch with a mass of 0.8 times that of porous calcium carbonate are added. The mixture is dried at 86℃ until the water content is 2%. The mixture is then extruded and granulated in a twin-screw extruder. After the granules are fully dried, they are injection molded into standard samples to obtain antibacterial and deodorizing plastic. The mass ratio of the self-made antibacterial agent, xylene, and ethanol in the self-made antibacterial agent solution is 1:20:40. The plasticizer is a mixture of glycerol and tributyl citrate with a mass ratio of 1:3.

[0038] Comparative Example 2

[0039] (1) Mix 4-chloro-1-butamine, triethoxysilylbutyraldehyde and methanol, stir for 5 hours, filter, wash with methanol and distilled water 3 times respectively, and dry at 60°C for 8 hours to obtain the self-made antibacterial agent; the mass ratio of 4-chloro-1-butamine, triethoxysilylbutyraldehyde and methanol is 1:2:15.

[0040] (2) Porous calcium carbonate, porous calcium silicate, and self-made antibacterial agent solution are mixed in a ratio of 2g:2g:30mL. After reacting at room temperature for 3.5h, the mixture is dried at 80℃ under a vacuum of -0.08MPa until the solid content is 65%. The mixture is then fed into a kneader, and urea-formaldehyde resin with a mass of 30 times that of porous calcium carbonate is added. After reacting at 57℃ for 1h, the mixture is fed into a dryer, and plasticizer with a mass of 0.9 times that of porous calcium carbonate and ordinary starch with a mass of 0.8 times that of porous calcium carbonate are added. The mixture is dried at 86℃ until the water content is 2%. The mixture is then extruded and granulated in a twin-screw extruder. After the granules are fully dried, they are injection molded into standard samples to obtain antibacterial and deodorizing plastic. The mass ratio of the self-made antibacterial agent, xylene, and ethanol in the self-made antibacterial agent solution is 1:20:40. The plasticizer is a mixture of glycerol and tributyl citrate with a mass ratio of 1:3.

[0041] Comparative Example 3

[0042] (1) Mix 4-chloro-1-butamine, triethoxysilylbutyraldehyde and methanol, stir for 5 hours, filter, wash with methanol and distilled water 3 times respectively, and dry at 60°C for 8 hours to obtain Schiff base compound; the mass ratio of 4-chloro-1-butamine, triethoxysilylbutyraldehyde and methanol is 1:2:15.

[0043] (2) Mix Schiff base compound, diethyl ether, and (R)-2-(dimethylamino)propionamide, stir at 55°C and 100 rpm for 5 h, filter, wash with deionized water 5 times, and dry at 60°C for 24 h to obtain the self-made antibacterial agent; the mass ratio of Schiff base compound, diethyl ether, and (R)-2-(dimethylamino)propionamide is 1:15:1;

[0044] (3) Mix the self-made antibacterial agent, urea-formaldehyde resin with a mass of 30 times that of the self-made antibacterial agent, plasticizer with a mass of 0.9 times that of the self-made antibacterial agent, and ordinary starch with a mass of 0.8 times that of the self-made antibacterial agent, and extrude and granulate the mixture in a twin-screw extruder. After the granules are fully dried, they are injection molded into standard samples by an injection molding machine to obtain 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) Mix 4-chloro-1-butamine, triethoxysilylbutyraldehyde and methanol, stir for 5 hours, filter, wash with methanol and distilled water 3 times respectively, and dry at 60°C for 8 hours to obtain Schiff base compound; the mass ratio of 4-chloro-1-butamine, triethoxysilylbutyraldehyde and methanol is 1:2:15.

[0047] (2) Mix Schiff base compound, diethyl ether, and (R)-2-(dimethylamino)propionamide, stir at 55°C and 100 rpm for 5 h, filter, wash with deionized water 5 times, and dry at 60°C for 24 h to obtain the self-made antibacterial agent; the mass ratio of Schiff base compound, diethyl ether, and (R)-2-(dimethylamino)propionamide is 1:15:1;

[0048] (3) Porous calcium carbonate, porous calcium silicate, self-made antibacterial agent, urea-formaldehyde resin, plasticizer, and ordinary starch are mixed in a mass ratio of 1:1:2.5:30:0.9:0.8 and extruded into granules in a twin-screw extruder. After the granules are fully dried, they are injection molded into standard samples to obtain antibacterial and deodorizing plastics. The plasticizer is a mixture of glycerol and tributyl citrate in a mass ratio of 1:3.

[0049] Example of effect

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

[0051] Table 1

[0052]

[0053] This invention utilizes porous calcium silicate and porous calcium carbonate as plastic fillers, whose surface pores provide odor adsorption points. Then, a self-made antibacterial agent is used as a crosslinking agent to combine the filler and urea-formaldehyde resin. While the filler is uniformly dispersed, a crosslinked network structure is formed inside the plastic, which greatly improves the mechanical properties of the plastic. The aldehyde group of triethoxysilylbutyraldehyde reacts with the amino group of 4-chloro-1-butamine to form a Schiff base structure. Introducing the Schiff base functional group creates chelating binding sites, enhancing the adsorption of porous calcium silicate and porous calcium carbonate. Subsequently, 4-chloro-1-butamine reacts with the dimethylamino group of (R)-2-(dimethylamino)propionamide to form a quaternary ammonium structure, effectively inhibiting bacterial growth. Simultaneously, the interaction between the Schiff base and the quaternary ammonium structure enhances the antibacterial properties of the plastic. The introduction of amide groups further allows for binding with calcium silicate and calcium carbonate. Utilizing the porous structure of calcium silicate and calcium carbonate, they work together to adsorb odors, achieving a deodorizing effect in the plastic. Furthermore, triethoxysilylbutyraldehyde, 4-chloro-1-butamine, and (R)-2-(dimethylamino)propionamide react and crosslink on the surfaces of calcium silicate and calcium carbonate. Simultaneously, some silanol groups bind with the hydroxyl groups of urea-formaldehyde resin polymers, ensuring uniform dispersion of the filler while allowing it to bind with the base material, thus improving the mechanical properties of the plastic.

[0054] It will be apparent to those skilled in the art that the present 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 its spirit or essential characteristics. 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. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.

Claims

1. A process for the preparation of bacteriostatic odor control plastic, characterized in that: The method mainly comprises the following steps: (1) mixing 4-chloro-1-butylamine, triethoxysilyl butyraldehyde and methanol, stirring for 5 hours, filtering, washing with methanol and distilled water for 3 times respectively, and drying at 60 DEG C for 8 hours to obtain a Schiff base compound; the mass ratio of 4-chloro-1-butylamine, triethoxysilyl butyraldehyde and methanol is 1:2:15; (2) mixing the Schiff base compound, ether and (R)-2-(dimethylamino) propionamide, stirring at 55 DEG C and 100 rpm for 5 hours, filtering, washing with deionized water for 5 times, and drying at 60 DEG C for 24 hours to obtain a self-made antibacterial agent; the mass ratio of the Schiff base compound, ether and (R)-2-(dimethylamino) propionamide is 1:15:1; (3) mixing porous calcium carbonate, porous calcium silicate and the self-made antibacterial agent solution according to the proportion of 2g:2g:30mL, reacting at room temperature for 3.5 hours, drying at a vacuum degree of-0.08 MPa and 80 DEG C until the solid content is 65%, feeding into a kneader, adding urea-formaldehyde resin with a mass of 30 times of the porous calcium carbonate, reacting at 57 DEG C for 1 hour, feeding into a dryer, adding plasticizer with a mass of 0.9 times of the porous calcium carbonate and common starch with a mass of 0.8 times of the porous calcium carbonate, drying at 86 DEG C until the water content is 2%, extruding and granulating in a double-screw extruder, sufficiently drying the granules, and injecting the granules into a standard sample by an injection molding machine to obtain antibacterial and deodorant plastics; the mass ratio of the self-made antibacterial agent, dimethylbenzene and ethanol in the self-made antibacterial agent solution is 1:20:40; the plasticizer is a mixture of glycerol and tributyl citrate with a mass ratio of 1:3.

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