Antibacterial plastic and production process thereof

By reacting with zinc organic frames and modified additives in antibacterial plastics, an antibacterial filler with composite structures is solved, and the antibacterial effect of existing antibacterial plastics is generally and the effect is reduced after long-term use, achieving high-efficiency, long-acting and broad-spectrum antibacterial effects.

CN119286106BActive Publication Date: 2025-04-29DONGGUAN XINLUN PLASTIC TECH CO LTD
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Patent Information

Application Number
CN202411315661.3
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2024-09-20
Publication Date
2025-04-29
Estimated Expiration
2044-09-20

AI Technical Summary

Technical Problem

At this stage, the antibacterial effect of antibacterial plastics is average, and the antibacterial effect decreases after long-term use.

Method used

By hydrothermal reaction of raw materials such as 4-aminoimidazole, polyvinylpyrrolidone and zinc nitrate hexahydrate under specific conditions, an organic zinc frame is prepared, and reacted with modified additives, dicyandiamide, etc., an antibacterial filler with composite structure is formed, and antibacterial plastic is prepared by melt-extruding linear low-density polyethylene.

Benefits of technology

The antibacterial plastic maintains an efficient antibacterial effect during long-term use. The antibacterial components are organic and inorganic composite structures, which avoid precipitation problems. Through electrostatic adsorption and the release of metal cations, a broad-spectrum and long-term antibacterial effect is achieved.

✦ Generated by Eureka AI based on patent content.

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Abstract

The invention discloses an antibacterial plastic and a production process thereof. The antibacterial plastic comprises the following raw materials in parts by weight: 100-120 parts of linear low-density polyethylene and 10-15 parts of antibacterial filler. The antibacterial component in the antibacterial plastic is an organic-inorganic composite structure, and the problem of precipitation will not occur during long-term use. Meanwhile, the antibacterial filler contains a composite structure of quaternary ammonium salt and quaternary phosphonium salt. The composite structure enables the antibacterial filler to have a positive charge and can be adsorbed on the surface of negatively charged bacterial cells through electrostatic adsorption. The guanidine structure can further adsorb bacteria, thereby interfering with the normal physiological function of the bacteria, and changing the permeability of the cell membrane, resulting in the destruction of the cell membrane structure, causing the leakage of cell contents, and the zinc organic framework can release zinc cations, thereby causing the metal cations to be adsorbed on the cell membrane, thereby accelerating the leakage of nutrients in the bacteria.
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Description

Technical Field

[0001] The invention relates to the technical field of antibacterial plastic preparation, in particular to an antibacterial plastic and a production process thereof. Background Art

[0002] As a widely used general-purpose plastic, polyethylene is highly praised for its good mechanical properties, chemical corrosion resistance and low cost. However, ordinary polyethylene is easily contaminated by microorganisms, which limits its use in medical devices, food packaging and other fields. Therefore, people are constantly seeking to develop polyethylene materials with antibacterial properties to improve their safety and application range. At present, antibacterial materials mainly include two categories: inorganic antibacterial materials and organic antibacterial materials. Inorganic materials include silver, zinc-zeolite, silver, zinc-zirconium phosphate, silver, zinc-glass, etc., and organic materials include quaternary ammonium salts, quaternary phosphonium salts, imidazoles, pyridines, organic metals, etc. The advantage of organic antibacterial materials is that they have a fast sterilization effect, but since most of them are small molecular compounds, they have poor heat resistance, are easy to fail after aging, and are easy to precipitate from the plastic surface after long-term placement, affecting the appearance of the product. Due to its advantages of high safety and good heat resistance, the market share of inorganic antibacterial materials has increased year by year, but the antibacterial plastics obtained by directly adding such antibacterial materials on the market do not have high-efficiency, long-term and broad-spectrum antibacterial effects. Summary of the invention

[0003] The purpose of the present invention is to provide a production process of antibacterial plastics, which solves the problem that the antibacterial effect is mediocre at present and the antibacterial effect decreases after long-term use.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A production process of antibacterial plastics specifically comprises the following steps:

[0006] Step A1: 4-aminoimidazole, polyvinyl pyrrolidone and deionized water are mixed evenly, stirred for 10-15 minutes at a speed of 800-1000 r / min and a temperature of 25-30° C., zinc nitrate hexahydrate is added, the temperature is raised to 130-140° C., and a hydrothermal reaction is performed for 3-5 hours to obtain a zinc organic framework;

[0007] Step A2: Mix the zinc organic framework, the modified additive, dicyclohexylcarbodiimide and DMF, and react for 4-6 hours at a speed of 120-150 r / min and a temperature of 20-25° C. to obtain a modified framework; mix dicyandiamide, 4-trifluoromethylaniline and isopropanol evenly, stir and add hydrochloric acid solution at a speed of 60-80 r / min and a temperature of 100-105° C., and react for 6-8 hours; adjust the pH value to neutral to obtain a synergist;

[0008] Step A3: Mix the synergist and N,N-dimethylacetamide evenly, introduce nitrogen protection, stir and add the modified framework at a speed of 120-150r / min and a temperature of 150-155°C, react for 20-25h, filter and remove the filtrate to obtain an antibacterial filler, weigh the following raw materials in parts by weight: 100-120 parts of linear low-density polyethylene and 10-15 parts of antibacterial filler, melt and extrude the raw materials to obtain an antibacterial plastic.

[0009] Furthermore, the usage ratio of 4-aminoimidazole, polyvinyl pyrrolidone, deionized water and zinc nitrate hexahydrate described in step A1 is 7 mmol:20 mg:2 mL:1 mmol.

[0010] Furthermore, the molar ratio of the amino group on the zinc organic framework, the carboxyl group on the modified additive and the dicyclohexylcarbodiimide described in step A2 is 4:1:1.1, the dosage ratio of dicyandiamide, 4-trifluoromethylaniline, isopropanol and hydrochloric acid solution is 80mmol:80mmol:100mL:7mL, and the mass fraction of the hydrochloric acid solution is 36%.

[0011] Furthermore, the dosage ratio of the synergist, N,N-dimethylacetamide and modified framework described in step A3 is 5g:15mL:1g.

[0012] Further, the modified additive is prepared by the following steps:

[0013] Step B1: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and dimethyl sulfoxide are uniformly mixed, nitrogen is introduced for protection, and the reaction is carried out for 3-5 hours at a speed of 120-150 r / min and a temperature of 90-95° C. to obtain a diamine-terminated polysiloxane;

[0014] Step B2: Dimethylaminoethanol, epichlorohydrin, boron trifluoride etherate and DMF are mixed evenly, reacted at a speed of 120-150 r / min and a temperature of 65-70° C. for 2-3 hours, and then sodium hydroxide solution is added, the temperature is raised to 75-80° C., and the reaction is carried out for 3-5 hours to obtain intermediate 1. Diamine-terminated polysiloxane, intermediate 1 and DMF are mixed evenly, and reacted at a speed of 150-200 r / min, a temperature of 60-70° C. and a pH value of 11-12 for 6-8 hours to obtain intermediate 2;

[0015] Step B3: The intermediate 2, 1,6-dibromohexane, potassium carbonate and DMF are mixed evenly, and the reaction is carried out at a speed of 120-150 r / min and a temperature of 50-60° C. for 10-15 hours, and then tributylphosphine is added, the temperature is raised to 82-85° C., and the reaction is continued for 20-25 hours to obtain a modifier. The modifier, acrylic acid, chloroplatinic acid and DMF are mixed, and nitrogen is introduced for protection, and the reaction is carried out at a speed of 200-300 r / min and a temperature of 70-80° C. for 8-10 hours to obtain a modified additive.

[0016] Furthermore, the molar ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane in step B1 is 2:0.4:3:2.

[0017] Furthermore, the dosage ratio of dimethylaminoethanol, epichlorohydrin, boron trifluoride etherate and sodium hydroxide solution in step B2 is 10mmol:10mmol:0.9g:20mL, the mass fraction of sodium hydroxide solution is 20%, and the molar ratio of diamine-terminated polysiloxane to intermediate 1 is 1:4.

[0018] Furthermore, the molar ratio of the intermediate 2, 1,6-dibromohexane, potassium carbonate and tributylphosphine described in step B3 is 1:8:8.2:8, the molar ratio of the Si-H bond on the modifier and acrylic acid is 1:1, and the amount of chloroplatinic acid used is 1‰ of the mass of acrylic acid.

[0019] The beneficial effects of the present invention are as follows: an antibacterial plastic prepared by the present invention comprises the following raw materials: linear low-density polyethylene and an antibacterial filler, the antibacterial filler is made of 4-aminoimidazole and zinc nitrate hexahydrate as raw materials to prepare a zinc organic framework, the zinc organic framework is reacted with a modified additive so that the carboxyl group on the zinc organic framework and part of the amino groups on the modified additive are dehydrated and condensed to prepare a modified framework, dicyandiamide is reacted with 4-trifluoromethylaniline so that the cyano group on the dicyandiamide and the amino group on the 4-trifluoromethylaniline react, and then under the action of a hydrochloric acid solution, biguanamine hydrochloride is formed to prepare a synergist, the synergist is reacted with the modified framework so that the biguanamine hydrochloride on the synergist reacts with the amino groups on the modified framework to prepare the antibacterial filler.

[0020] The modified additive is prepared by ring-opening octamethylcyclotetrasiloxane and tetramethylcyclotetrasiloxane, and then reacting with 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to obtain diamine-terminated polysiloxane. Dimethylaminoethanol and epichlorohydrin are reacted to make the hydroxyl group on dimethylaminoethanol react with the epoxy group on epichlorohydrin, and then the ring is closed under the action of sodium hydroxide solution to form a new epoxy group to obtain intermediate 1. Intermediate 1 is reacted with diamine-terminated polysiloxane to make the epoxy group on intermediate 1 react with diamine-terminated polysiloxane. The amino group on the oxane is reacted to obtain intermediate 2, and intermediate 2 is reacted with 1,6-dibromohexane so that the dimethylamino group on intermediate 2 reacts with the bromine atom site on 1,6-dibromohexane to form a quaternary ammonium salt structure, and the hydroxyl group also reacts with the bromine atom site on 1,6-dibromohexane, and finally tributylphosphine is added to react with the remaining bromine atom sites to form a quaternary phosphonium salt to obtain a modifier, and the modifier and acrylic acid are reacted in the presence of chloroplatinic acid so that the Si-H bond on the modifier and the double bond on the chloroplatinic acid are grafted to obtain a modified additive.

[0021] The antibacterial component in the antibacterial plastic is an organic-inorganic composite structure, and there will be no precipitation problem during long-term use. At the same time, the antibacterial filler contains a quaternary ammonium salt and a quaternary phosphonium salt composite structure. The composite structure makes the antibacterial filler have a positive charge and can be adsorbed on the surface of negatively charged bacterial cells through electrostatic adsorption. The guanidine structure can further adsorb bacteria, thereby interfering with the normal physiological function of the bacteria and changing the permeability of the cell membrane, causing the structural destruction of the cell membrane and causing the leakage of cell contents. The zinc organic framework can release zinc cations, which in turn causes the metal cations to be adsorbed on the cell membrane, accelerating the leakage of nutrients in the bacteria. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. 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. Example

[0023] A production process of antibacterial plastics specifically comprises the following steps:

[0024] Step A1: 4-aminoimidazole, polyvinyl pyrrolidone and deionized water were mixed evenly, stirred for 10 min at a speed of 800 r / min and a temperature of 25° C., zinc nitrate hexahydrate was added, the temperature was raised to 130° C., and a hydrothermal reaction was performed for 3 h to obtain a zinc organic framework;

[0025] Step A2: Mix the zinc organic framework, the modified additive, dicyclohexylcarbodiimide and DMF, and react for 4 hours at a speed of 120 r / min and a temperature of 20° C. to obtain a modified framework; mix dicyandiamide, 4-trifluoromethylaniline and isopropanol evenly, stir and add hydrochloric acid solution at a speed of 60 r / min and a temperature of 100° C., and react for 6 hours; adjust the pH value to neutral to obtain a synergist;

[0026] Step A3: Mix the enhancer and N,N-dimethylacetamide evenly, introduce nitrogen protection, stir and add the modified framework at a speed of 120r / min and a temperature of 150°C, react for 20 hours, filter and remove the filtrate to obtain an antibacterial filler, weigh the following raw materials by weight: 100 parts of linear low-density polyethylene and 10 parts of antibacterial filler, melt and extrude the raw materials to obtain an antibacterial plastic.

[0027] The amount ratio of 4-aminoimidazole, polyvinyl pyrrolidone, deionized water and zinc nitrate hexahydrate described in step A1 is 7mmol:20mg:2mL:1mmol, and the Mw of polyvinyl pyrrolidone is 55k.

[0028] The molar ratio of the amino group on the zinc organic framework, the carboxyl group on the modified additive and dicyclohexylcarbodiimide described in step A2 is 4:1:1.1, the amount ratio of dicyandiamide, 4-trifluoromethylaniline, isopropanol and hydrochloric acid solution is 80mmol:80mmol:100mL:7mL, and the mass fraction of the hydrochloric acid solution is 36%.

[0029] The dosage ratio of the synergist, N,N-dimethylacetamide and modified framework described in step A3 is 5 g:15 mL:1 g, and the density of the linear low-density polyethylene is 0.923 g·cm -3 , melt index 2g·(10min) -1 .

[0030] The modified additive is prepared by the following steps:

[0031] Step B1: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and dimethyl sulfoxide are uniformly mixed, nitrogen is introduced for protection, and the reaction is carried out at a speed of 120 r / min and a temperature of 90° C. for 3 hours to obtain a diamine-terminated polysiloxane;

[0032] Step B2: Dimethylaminoethanol, epichlorohydrin, boron trifluoride etherate and DMF were mixed evenly, reacted at a speed of 120 r / min and a temperature of 65° C. for 2 h, and then sodium hydroxide solution was added, the temperature was raised to 75° C., and the reaction was carried out for 3 h to obtain intermediate 1. Diamine-terminated polysiloxane, intermediate 1 and DMF were mixed evenly, and reacted at a speed of 150 r / min, a temperature of 60° C. and a pH value of 11 for 6 h to obtain intermediate 2;

[0033] Step B3: The intermediate 2, 1,6-dibromohexane, potassium carbonate and DMF are mixed evenly, and the reaction is carried out at a speed of 120 r / min and a temperature of 50°C for 10 hours. Then, tributylphosphine is added, the temperature is raised to 82°C, and the reaction is continued for 20 hours to obtain a modifier. The modifier, acrylic acid, chloroplatinic acid and DMF are mixed, nitrogen is introduced for protection, and the reaction is carried out at a speed of 200 r / min and a temperature of 70°C for 8 hours to obtain a modified additive.

[0034] The molar ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane in step B1 is 2:0.4:3:2.

[0035] The amount ratio of dimethylaminoethanol, epichlorohydrin, boron trifluoride etherate and sodium hydroxide solution described in step B2 is 10mmol:10mmol:0.9g:20mL, the mass fraction of sodium hydroxide solution is 20%, and the molar ratio of diamine-terminated polysiloxane to intermediate 1 is 1:4.

[0036] The molar ratio of the intermediate 2, 1,6-dibromohexane, potassium carbonate and tributylphosphine described in step B3 is 1:8:8.2:8, the molar ratio of the Si-H bond on the modifier and acrylic acid is 1:1, and the amount of chloroplatinic acid used is 1‰ of the mass of acrylic acid. Example

[0037] A production process of antibacterial plastics specifically comprises the following steps:

[0038] Step A1: 4-aminoimidazole, polyvinyl pyrrolidone and deionized water were mixed evenly, stirred for 15 minutes at a speed of 800 r / min and a temperature of 30° C., zinc nitrate hexahydrate was added, the temperature was raised to 135° C., and a hydrothermal reaction was performed for 4 hours to obtain a zinc organic framework;

[0039] Step A2: Mix the zinc organic framework, the modified additive, dicyclohexylcarbodiimide and DMF, and react for 5 hours at a speed of 50 r / min and a temperature of 20° C. to obtain a modified framework; mix dicyandiamide, 4-trifluoromethylaniline and isopropanol evenly, stir and add hydrochloric acid solution at a speed of 60 r / min and a temperature of 105° C., and react for 7 hours; adjust the pH value to neutral to obtain a synergist;

[0040] Step A3: Mix the enhancer and N,N-dimethylacetamide evenly, introduce nitrogen protection, stir and add the modified framework at a speed of 120r / min and a temperature of 155°C, react for 25 hours, filter and remove the filtrate to obtain an antibacterial filler, weigh the following raw materials by weight: 110 parts of linear low-density polyethylene and 13 parts of antibacterial filler, melt and extrude the raw materials to obtain an antibacterial plastic.

[0041] The amount ratio of 4-aminoimidazole, polyvinyl pyrrolidone, deionized water and zinc nitrate hexahydrate described in step A1 is 7mmol:20mg:2mL:1mmol, and the Mw of polyvinyl pyrrolidone is 55k.

[0042] The molar ratio of the amino group on the zinc organic framework, the carboxyl group on the modified additive and dicyclohexylcarbodiimide described in step A2 is 4:1:1.1, the amount ratio of dicyandiamide, 4-trifluoromethylaniline, isopropanol and hydrochloric acid solution is 80mmol:80mmol:100mL:7mL, and the mass fraction of the hydrochloric acid solution is 36%.

[0043] The dosage ratio of the synergist, N,N-dimethylacetamide and modified framework described in step A3 is 5 g:15 mL:1 g, and the density of the linear low-density polyethylene is 0.923 g·cm -3 , melt index 2g·(10min) -1 .

[0044] The modified additive is prepared by the following steps:

[0045] Step B1: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and dimethyl sulfoxide are uniformly mixed, nitrogen is introduced for protection, and the reaction is carried out at a speed of 120 r / min and a temperature of 95° C. for 4 hours to obtain a diamine-terminated polysiloxane;

[0046] Step B2: Dimethylaminoethanol, epichlorohydrin, boron trifluoride etherate and DMF were mixed evenly, reacted at a speed of 120 r / min and a temperature of 70°C for 2 hours, and then sodium hydroxide solution was added, the temperature was raised to 80°C, and the reaction was carried out for 4 hours to obtain intermediate 1. Diamine-terminated polysiloxane, intermediate 1 and DMF were mixed evenly, and reacted at a speed of 150 r / min, a temperature of 65°C and a pH value of 12 for 7 hours to obtain intermediate 2;

[0047] Step B3: The intermediate 2, 1,6-dibromohexane, potassium carbonate and DMF are mixed evenly, and the reaction is carried out at a speed of 120 r / min and a temperature of 55°C for 15 hours. Then, tributylphosphine is added, the temperature is raised to 82°C, and the reaction is continued for 25 hours to obtain a modifier. The modifier, acrylic acid, chloroplatinic acid and DMF are mixed, nitrogen is introduced for protection, and the reaction is carried out at a speed of 200 r / min and a temperature of 75°C for 9 hours to obtain a modified additive.

[0048] The molar ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane in step B1 is 2:0.4:3:2.

[0049] The amount ratio of dimethylaminoethanol, epichlorohydrin, boron trifluoride etherate and sodium hydroxide solution described in step B2 is 10mmol:10mmol:0.9g:20mL, the mass fraction of sodium hydroxide solution is 20%, and the molar ratio of diamine-terminated polysiloxane to intermediate 1 is 1:4.

[0050] The molar ratio of the intermediate 2, 1,6-dibromohexane, potassium carbonate and tributylphosphine described in step B3 is 1:8:8.2:8, the molar ratio of the Si-H bond on the modifier and acrylic acid is 1:1, and the amount of chloroplatinic acid used is 1‰ of the mass of acrylic acid. Example

[0051] A production process of antibacterial plastics specifically comprises the following steps:

[0052] Step A1: 4-aminoimidazole, polyvinyl pyrrolidone and deionized water are mixed evenly, stirred for 10-15 minutes at a speed of 800-1000 r / min and a temperature of 25-30° C., zinc nitrate hexahydrate is added, the temperature is raised to 130-140° C., and a hydrothermal reaction is performed for 3-5 hours to obtain a zinc organic framework;

[0053] Step A2: Mix the zinc organic framework, the modified additive, dicyclohexylcarbodiimide and DMF, and react for 6 hours at a speed of 150 r / min and a temperature of 25° C. to obtain a modified framework; mix dicyandiamide, 4-trifluoromethylaniline and isopropanol evenly, stir and add hydrochloric acid solution at a speed of 80 r / min and a temperature of 105° C., and react for 8 hours; adjust the pH value to neutral to obtain a synergist;

[0054] Step A3: Mix the enhancer and N,N-dimethylacetamide evenly, introduce nitrogen protection, stir and add the modified framework at a speed of 150r / min and a temperature of 155°C, react for 25 hours, filter and remove the filtrate to obtain an antibacterial filler, weigh the following raw materials by weight: 120 parts of linear low-density polyethylene and 15 parts of antibacterial filler, melt and extrude the raw materials to obtain an antibacterial plastic.

[0055] The amount ratio of 4-aminoimidazole, polyvinyl pyrrolidone, deionized water and zinc nitrate hexahydrate described in step A1 is 7mmol:20mg:2mL:1mmol, and the Mw of polyvinyl pyrrolidone is 55k.

[0056] The molar ratio of the amino group on the zinc organic framework, the carboxyl group on the modified additive and dicyclohexylcarbodiimide described in step A2 is 4:1:1.1, the amount ratio of dicyandiamide, 4-trifluoromethylaniline, isopropanol and hydrochloric acid solution is 80mmol:80mmol:100mL:7mL, and the mass fraction of the hydrochloric acid solution is 36%.

[0057] The dosage ratio of the synergist, N,N-dimethylacetamide and modified framework described in step A3 is 5 g:15 mL:1 g, and the density of the linear low-density polyethylene is 0.923 g·cm -3 , melt index 2g·(10min) -1 .

[0058] The modified additive is prepared by the following steps:

[0059] Step B1: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and dimethyl sulfoxide are uniformly mixed, nitrogen is introduced for protection, and the reaction is carried out at a speed of 150 r / min and a temperature of 95° C. for 5 hours to obtain a diamine-terminated polysiloxane;

[0060] Step B2: Dimethylaminoethanol, epichlorohydrin, boron trifluoride etherate and DMF were mixed evenly, reacted at a speed of 150 r / min and a temperature of 70°C for 3 hours, and then sodium hydroxide solution was added, the temperature was raised to 80°C, and the reaction was carried out for 5 hours to obtain intermediate 1. Diamine-terminated polysiloxane, intermediate 1 and DMF were mixed evenly, and reacted at a speed of 200 r / min, a temperature of 70°C and a pH value of 12 for 8 hours to obtain intermediate 2;

[0061] Step B3: The intermediate 2, 1,6-dibromohexane, potassium carbonate and DMF are mixed evenly, and the reaction is carried out at a speed of 150 r / min and a temperature of 60°C for 15 hours. Then, tributylphosphine is added, the temperature is raised to 85°C, and the reaction is continued for 25 hours to obtain a modifier. The modifier, acrylic acid, chloroplatinic acid and DMF are mixed, nitrogen is introduced for protection, and the reaction is carried out at a speed of 300 r / min and a temperature of 80°C for 10 hours to obtain a modified additive.

[0062] The molar ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane in step B1 is 2:0.4:3:2.

[0063] The amount ratio of dimethylaminoethanol, epichlorohydrin, boron trifluoride etherate and sodium hydroxide solution described in step B2 is 10mmol:10mmol:0.9g:20mL, the mass fraction of sodium hydroxide solution is 20%, and the molar ratio of diamine-terminated polysiloxane to intermediate 1 is 1:4.

[0064] The molar ratio of the intermediate 2, 1,6-dibromohexane, potassium carbonate and tributylphosphine described in step B3 is 1:8:8.2:8, the molar ratio of the Si-H bond on the modifier and acrylic acid is 1:1, and the amount of chloroplatinic acid used is 1‰ of the mass of acrylic acid.

[0065] Comparative Example 1

[0066] Compared with Example 1, this comparative example uses a modified additive to replace the antibacterial filler, and the remaining steps are the same.

[0067] Comparative Example 2

[0068] Compared with Example 1, this comparative example uses a zinc organic framework instead of a modified framework, and the remaining steps are the same.

[0069] Comparative Example 3

[0070] Compared with Example 1, in this comparative example, intermediate 2, bromohexane, potassium carbonate and DMF were uniformly mixed, and the reaction was carried out at a speed of 120 r / min and a temperature of 50° C. for 10 hours. The obtained product replaced the modifier, and the remaining steps were the same.

[0071] The antibacterial plastics prepared in Examples 1-3 and Comparative Examples 1-3 were tested for their sterilization rates against Staphylococcus aureus and Escherichia coli according to the standard of QB / T2591-2003A. The antibacterial plastics were placed at a temperature of 50°C for 30 days, and the sterilization rates against Staphylococcus aureus and Escherichia coli were tested. The test results are shown in the following table.

[0072]

[0073] It can be seen from the above table that the present application has a very good and lasting antibacterial effect.

[0074] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field 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 concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A production process for antibacterial plastics, characterized in that: The specific steps include: Step A1: 4-aminoimidazole, polyvinyl pyrrolidone and deionized water are mixed and stirred, zinc nitrate hexahydrate is added, and the temperature is increased for hydrothermal reaction to prepare a zinc organic framework; Step A2: mixing a zinc organic framework, a modification additive, dicyclohexylcarbodiimide and DMF, reacting to obtain a modified framework, mixing dicyandiamide, 4-trifluoromethylaniline and isopropanol, stirring and adding a hydrochloric acid solution, reacting, and adjusting the pH value to be neutral to obtain a synergist; Step A3: uniformly mix the synergist and N,N-dimethylacetamide, introduce nitrogen protection, stir and add the modified framework, react, filter and remove the filtrate, and prepare the antibacterial filler. Weigh the following raw materials in parts by weight: 100-120 parts of linear low-density polyethylene and 10-15 parts of antibacterial filler, melt and extrude the raw materials to prepare the antibacterial plastic; The modified additive is prepared by the following steps: Step B1: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide, 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane and dimethyl sulfoxide are uniformly mixed, nitrogen is introduced for protection, and the mixture is reacted to obtain a diamine-terminated polysiloxane; Step B2: After dimethylaminoethanol, epichlorohydrin, boron trifluoride etherate and DMF are mixed for reaction, sodium hydroxide solution is added, and the temperature is raised to react to obtain intermediate 1, and diamine-terminated polysiloxane, intermediate 1 and DMF are mixed for reaction to obtain intermediate 2; Step B3: After the intermediate 2, 1,6-dibromohexane, potassium carbonate and DMF are mixed for reaction, tributylphosphine is added, the temperature is raised to continue the reaction to obtain a modifier, the modifier, acrylic acid, chloroplatinic acid and DMF are mixed, nitrogen is introduced for protection, and the reaction is carried out to obtain a modified additive.

2. The production process of an antibacterial plastic according to claim 1, characterized in that: The usage ratio of 4-aminoimidazole, polyvinyl pyrrolidone, deionized water and zinc nitrate hexahydrate described in step A1 is 7mmol:20mg:2mL:1mmol.

3. The production process of an antibacterial plastic according to claim 1, characterized in that: The molar ratio of the amino group on the zinc organic framework, the carboxyl group on the modified additive and dicyclohexylcarbodiimide described in step A2 is 4:1:1.1, and the amount ratio of dicyandiamide, 4-trifluoromethylaniline, isopropanol and hydrochloric acid solution is 80mmol:80mmol:100mL:7mL.

4. The production process of an antibacterial plastic according to claim 1, characterized in that: The dosage ratio of the synergist, N,N-dimethylacetamide and modified framework described in step A3 is 5g:15mL:1g.

5. The production process of an antibacterial plastic according to claim 1, characterized in that: The molar ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane in step B1 is 2:0.4:3:

2.

6. The production process of an antibacterial plastic according to claim 1, characterized in that: The amount ratio of dimethylaminoethanol, epichlorohydrin, boron trifluoride etherate and sodium hydroxide solution in step B2 is 10mmol:10mmol:0.9g:20mL, and the molar ratio of diamine-terminated polysiloxane to intermediate 1 is 1:

4.

7. The production process of an antibacterial plastic according to claim 1, characterized in that: The molar ratio of the intermediate 2, 1,6-dibromohexane, potassium carbonate and tributylphosphine described in step B3 is 1:8:8.2:8, and the molar ratio of the Si-H bond on the modifier and acrylic acid is 1:

1.

8. An antibacterial plastic, characterized in that: Produced according to any one of the production processes described in claims 1-7.

Citation Information

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