Preparation process of an antibacterial impregnated paper

By forming the antibacterial structure of polyacrylate chains and chitosan quaternary ammonium salts on the surface of the paper, the problem of loss of antibacterial components is solved, and the long-lasting antibacterial effect of antibacterial impregnated paper is achieved.

CN117904898BActive Publication Date: 2025-07-29寿光市鲁丽木业股份有限公司
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Patent Information

Application Number
CN202410199480.2
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Priority Date
2024-01-03
Filing Date
2024-02-23
Publication Date
2025-07-29
Estimated Expiration
2044-02-23

AI Technical Summary

Technical Problem

The existing antibacterial impregnation paper process cannot keep the antibacterial ingredients on the paper surface for a long time, resulting in a significant reduction in the antibacterial effect over time.

Method used

By dispersing modified chitosan, acrylic acid and ethyl acrylate in water, polymerization with pretreated pulp, polyacrylate chains are formed on the paper surface, combining the antibacterial mechanism of chitosan and quaternary ammonium salts to form a lasting antibacterial structure.

Benefits of technology

The long-lasting antibacterial effect of antibacterial impregnated paper is achieved. Chitosan interacts with bacterial enzymes and proteins, and the adsorption of quaternary ammonium salts with anion charges on the surface of the cell, destroying bacterial metabolism and cell structure, achieving the effect of killing bacteria.

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Abstract

The present invention discloses a preparation process of an antibacterial impregnated paper, which is prepared by dispersing modified chitosan, acrylic acid and ethyl acrylate in water, soaking the pretreated paper therein, adding potassium persulfate to initiate polymerization, and forming polyacrylate chains on the surface of the pretreated paper. The surface of the antibacterial impregnated paper contains polyacrylate chains. Through polymerization grafting of antibacterial structures, the antibacterial effect of the antibacterial impregnated paper is more persistent. The chitosan and quaternary ammonium salt on the surface have good antibacterial effects. Chitosan can interact with enzymes and proteins inside bacteria, resulting in a decrease in the activity of enzymes and proteins, making it impossible for bacteria to carry out normal metabolic processes, thereby causing bacteria to die. Quaternary ammonium cations can generate charge adsorption with anions carried on the cell surface. The electrostatic effect not only disrupts the normal metabolism of live bacteria but also damages the surface structure of cells, achieving the effect of killing bacteria.
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Description

Technical Field

[0001] The present invention relates to the technical field of antibacterial impregnated paper preparation, and particularly relates to a preparation process of antibacterial impregnated paper. Background Art

[0002] With the development of society and the progress of technology, humans have been pursuing a good sanitary environment and paying more and more attention to health problems caused by infectious bacteria, which has promoted the development of various antibacterial materials. As a daily consumable, consumers have higher and higher requirements for the quality and function of paper. Foreign scholars have made great breakthroughs in the research and development of antibacterial paper, combining experimental theories with practical applications and paying attention to the research of antibacterial mechanisms, the research and development and application of antibacterial agents. At present, the application scope of products is very wide, covering all aspects of real life. Such products include disinfected paper, medical paper, food preservation paper, and napkins. The principle of antibacterial impregnated paper to achieve antibacterial effect is that when bacteria come into contact with the antibacterial active components on the paper surface, their growth and reproduction can be quickly inhibited or killed. However, the existing process cannot keep the antibacterial components on the paper surface for a long time, resulting in a significant reduction in antibacterial effect after storage for a period of time, which affects the normal use of antibacterial impregnated paper. Summary of the Invention

[0003] The purpose of the present invention is to provide a preparation process of antibacterial impregnated paper, which solves the problem that the antibacterial effect of impregnated paper is general at the present stage.

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

[0005] A preparation process of antibacterial impregnated paper specifically includes the following steps:

[0006] Step A1: Immerse the original pulp board in deionized water. After soaking for 10 - 12 h, perform beating treatment to obtain a pulp suspension. Add 2,2,6,6 - tetramethylpiperidine - 1 - oxyl radical and sodium bromide to the pulp suspension. Under the conditions of a rotation speed of 600 - 800 r / min, a temperature of 20 - 25 °C, and a pH value of 10 - 11, add sodium hypochlorite and react for 3 - 5 h. Then add ethanol to stop the reaction, centrifuge to remove the supernatant, and wash the substrate to neutral to obtain pretreated pulp.

[0007] Step A2: Disperse the pretreated pulp in DMF, add allyl alcohol and dibutyltin dilaurate, and introduce nitrogen for protection. Under the conditions of a rotation speed of 300 - 500 r / min and a temperature of 80 - 85 °C, react for 20 - 25 h. Then filter to remove the filtrate, disperse the substrate in deionized water, pour it into a paper sample making machine for paper making, and then press and form to obtain pretreated paper.

[0008] Step A3: Mix modified chitosan, acrylic acid, ethyl acrylate and deionized water, soak the pretreated paper in it, introduce nitrogen for protection, under the conditions of a frequency of 20 - 30 kHz and a temperature of 55 - 60 °C, perform ultrasonic treatment and add potassium persulfate. After ultrasonic treatment for 3 - 5 h, take it out and dry it to obtain the antibacterial impregnated paper.

[0009] Furthermore, the dosage ratio of the original pulp board, 2,2,6,6 - tetramethylpiperidine - 1 - oxyl radical, sodium bromide and sodium hypochlorite described in Step A1 is 100 g: 29.7 mg: 318 mg: 35 mg.

[0010] Furthermore, the mass ratio of the pretreated pulp, allyl alcohol and dibutyltin dilaurate described in Step A2 is 1 g: 3 g: 0.2 mL.

[0011] Furthermore, the dosage ratio of the modified chitosan, acrylic acid, ethyl acrylate and deionized water described in Step A3 is 1 g: 12.5 g: 6.32 g: 100 mL, and the dosage of potassium persulfate is 0.3 - 0.5% of the sum of the masses of the modified chitosan, acrylic acid and ethyl acrylate.

[0012] Furthermore, the modified chitosan is prepared by the following steps:

[0013] Step B1: Disperse chitosan in a sodium hydroxide solution, keep it at a temperature of - 20 °C for 10 - 15 h, then raise the temperature to 20 - 25 °C, add isopropanol, stir and add chloroacetic acid under the condition of a rotation speed of 150 - 200 r / min, and react for 2 - 3 h to obtain carboxymethyl chitosan. Mix 2,3 - dimercaptopropanol, dimethylaminoethyl methacrylate and methanol evenly, and react for 3 - 5 h under the conditions of a rotation speed of 200 - 300 r / min and 365 nm ultraviolet light irradiation to obtain Intermediate 1;

[0014] Step B2: Mix Intermediate 1, decyl bromide and acetonitrile evenly, and react for 10 - 15 h under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 40 - 45 °C to obtain Intermediate 2. Mix Intermediate 2, epichlorohydrin, benzyltrimethylammonium bromide and DMF evenly, and react for 3 - 5 h under the conditions of a rotation speed of 150 - 200 r / min and a temperature of 100 - 110 °C, then cool down to 70 - 75 °C, add sodium hydroxide, and continue to react for 5 - 7 h to obtain Intermediate 3;

[0015] Step B3: Dissolve carboxymethyl chitosan in deionized water. Under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 80 - 85 °C, stir and add sodium hydroxide until the pH value reaches 9 - 10. Then add Intermediate 3 and react for 7 - 8 h to obtain pretreated chitosan. Mix the pretreated chitosan, allyl alcohol, p-toluenesulfonic acid, and toluene evenly, and react under the conditions of a rotation speed of 120 - 150 r / min and a temperature of 100 - 110 °C for 6 - 8 h to obtain modified chitosan.

[0016] Further, the dosage ratio of the chitosan, sodium hydroxide solution, isopropanol, and chloroacetic acid described in Step B1 is 5 g: 6 mL: 60 mL: 6 g. The mass fraction of the sodium hydroxide solution is 50%, and the molar ratio of 2,3-dimercapto-1-propanol to dimethylaminoethyl methacrylate is 1:2.

[0017] Further, the molar ratio of Intermediate 1 to 1-bromodecane described in Step B2 is 1:2, the molar ratio of Intermediate 2 to epichlorohydrin is 1:2. The dosage of sodium hydroxide is 10% of the mass of Intermediate 2, and the dosage of benzyltrimethylammonium bromide is 2% of the mass of Intermediate 2.

[0018] Further, the mass ratio of the carboxymethyl chitosan to Intermediate 3 described in Step B3 is 5:12. The molar ratio of the carboxyl group on the pretreated chitosan to allyl alcohol is 1:1, and the dosage of p-toluenesulfonic acid is 3 - 5% of the mass of allyl alcohol.

[0019] Advantages of the present invention: The present invention discloses an antibacterial impregnated paper. The original pulp board is soaked and beaten to obtain a pulp suspension. The pulp suspension is treated with 2,2,6,6-tetramethylpiperidine-1-oxyl radical and sodium hypochlorite to convert the hydroxyl groups on cellulose into carboxyl groups, thus obtaining a pretreated pulp. The pretreated pulp is reacted with acrylic acid, so that the carboxyl groups on the pretreated pulp react with the hydroxyl groups on allyl alcohol, and double bonds are grafted onto cellulose, thus obtaining a pretreated paper. Modified chitosan, acrylic acid and ethyl acrylate are dispersed in water, and the pretreated paper is soaked therein. Potassium persulfate is added to initiate polymerization, and polyacrylate chains are formed on the surface of the pretreated paper. Modified chitosan uses chitosan as a raw material. After chitosan is treated with sodium hydroxide and then reacted with chloroacetic acid, carboxymethyl chitosan is obtained. 2,3-Dimercapto-1-propanol and dimethylaminoethyl methacrylate are reacted under ultraviolet irradiation conditions, so that the mercapto groups on 2,3-dimercapto-1-propanol react with the double bonds on dimethylaminoethyl methacrylate, thus obtaining intermediate 1. Intermediate 1 is reacted with decyl bromide, so that the dimethylaminoethyl group on intermediate 1 reacts with the bromine atom on decyl bromide to form a quaternary ammonium salt, thus obtaining intermediate 2. Epichlorohydrin is reacted with intermediate 2, so that the epoxy group on epichlorohydrin is ring-opened and reacts with the hydroxyl group on intermediate 2, and then is closed-loop under alkaline conditions, thus obtaining intermediate 3. Intermediate 3 and carboxymethyl chitosan are reacted under alkaline conditions, so that the epoxy group on intermediate 3 reacts with the amino group on carboxymethyl chitosan, thus obtaining a pretreated chitosan. The pretreated chitosan and allyl alcohol are reacted under the action of p-toluenesulfonic acid, so that the carboxyl group on the pretreated chitosan is esterified with the alcohol hydroxyl group on allyl alcohol, thus obtaining modified chitosan. The surface of the antibacterial impregnated paper contains polyacrylate chains. Through polymerization grafting of antibacterial structures, the antibacterial effect of the antibacterial impregnated paper is more lasting. The chitosan and quaternary ammonium salt on the surface have good antibacterial effects. Chitosan can interact with enzymes and proteins inside bacteria, resulting in a decrease in the activity of enzymes and proteins, making bacteria unable to carry out normal metabolic processes, thus causing bacteria to die. The quaternary ammonium salt cations can produce charge adsorption with the anions carried on the cell surface. The electrostatic action not only destroys the normal metabolism of live bacteria but also damages the surface structure of cells, achieving the effect of killing bacteria. Specific embodiments

[0020] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention. Example 1

[0021] A preparation process of an antibacterial impregnated paper specifically includes the following steps:

[0022] Step A1: Immerse the original pulp board in deionized water. After soaking for 10 h, perform beating treatment to obtain a pulp suspension. Add 2,2,6,6 - tetramethylpiperidine - 1 - oxyl radical and sodium bromide to the pulp suspension. Under the conditions of a rotation speed of 600 r / min, a temperature of 20 °C, and a pH value of 10, add sodium hypochlorite and react for 3 h. Then add ethanol to stop the reaction, centrifuge to remove the supernatant, and wash the substrate until it is neutral to obtain the pretreated pulp.

[0023] Step A2: Disperse the pretreated pulp in DMF, add allyl alcohol and dibutyltin dilaurate, and introduce nitrogen for protection. Under the conditions of a rotation speed of 300 r / min and a temperature of 80 °C, react for 20 h. Then filter to remove the filtrate, disperse the substrate in deionized water, pour it into a paper sample sheet - making machine to make a sheet, and then press - form it to obtain the pretreated paper.

[0024] Step A3: Mix modified chitosan, acrylic acid, ethyl acrylate, and deionized water, immerse the pretreated paper in it, introduce nitrogen for protection. Under the conditions of a frequency of 20 kHz and a temperature of 55 °C, perform ultrasonic treatment and add potassium persulfate. After ultrasonic treatment for 3 h, take it out and dry it to obtain the antibacterial impregnated paper.

[0025] The dosage ratio of the original pulp board, 2,2,6,6 - tetramethylpiperidine - 1 - oxyl radical, sodium bromide, and sodium hypochlorite described in Step A1 is 100 g:29.7 mg:318 mg:35 mg.

[0026] The mass ratio of the pretreated pulp, allyl alcohol, and dibutyltin dilaurate described in Step A2 is 1 g:3 g:0.2 mL.

[0027] The dosage ratio of the modified chitosan, acrylic acid, ethyl acrylate, and deionized water described in Step A3 is 1 g:12.5 g:6.32 g:100 mL, and the dosage of potassium persulfate is 0.3% of the sum of the masses of the modified chitosan, acrylic acid, and ethyl acrylate.

[0028] The modified chitosan is prepared by the following steps:

[0029] Step B1: Disperse chitosan in a sodium hydroxide solution. Under the condition of a temperature of - 20 °C, keep it warm for 10 h, then raise the temperature to 20 °C, add isopropyl alcohol, and under the condition of a rotation speed of 150 r / min, stir and add chloroacetic acid and react for 2 h to obtain carboxymethyl chitosan. Mix 2,3 - dimercaptopropanol, dimethylaminoethyl methacrylate, and methanol evenly. Under the conditions of a rotation speed of 200 r / min and ultraviolet light irradiation at 365 nm, react for 3 h to obtain Intermediate 1.

[0030] Step B2: Mix intermediate 1, decyl bromide, and acetonitrile evenly. React for 10 h under the conditions of a rotation speed of 200 r / min and a temperature of 40 °C to obtain intermediate 2. Mix intermediate 2, epichlorohydrin, benzyltrimethylammonium bromide, and DMF evenly. React for 3 h under the conditions of a rotation speed of 150 r / min and a temperature of 100 °C. Cool down to 70 °C, add sodium hydroxide, and continue to react for 5 h to obtain intermediate 3;

[0031] Step B3: Dissolve carboxymethyl chitosan in deionized water. Stir and add sodium hydroxide to a pH value of 9 under the conditions of a rotation speed of 200 r / min and a temperature of 80 °C. Add intermediate 3 and react for 7 h to obtain pretreated chitosan. Mix pretreated chitosan, allyl alcohol, p-toluenesulfonic acid, and toluene evenly. React for 6 h under the conditions of a rotation speed of 120 r / min and a temperature of 100 °C to obtain modified chitosan.

[0032] The dosage ratio of chitosan, sodium hydroxide solution, isopropanol, and chloroacetic acid described in Step B1 is 5 g: 6 mL: 60 mL: 6 g. The mass fraction of the sodium hydroxide solution is 50%. The molar ratio of 2,3-dimercapto-1-propanol and dimethylaminoethyl methacrylate is 1:2.

[0033] The molar ratio of intermediate 1 and decyl bromide described in Step B2 is 1:2. The molar ratio of intermediate 2 and epichlorohydrin is 1:2. The dosage of sodium hydroxide is 10% of the mass of intermediate 2. The dosage of benzyltrimethylammonium bromide is 2% of the mass of intermediate 2.

[0034] The mass ratio of carboxymethyl chitosan and intermediate 3 described in Step B3 is 5:12. The molar ratio of the carboxyl group on pretreated chitosan and allyl alcohol is 1:1. The dosage of p-toluenesulfonic acid is 3% of the mass of allyl alcohol. Example 2

[0035] A preparation process of an antibacterial impregnated paper specifically includes the following steps:

[0036] Step A1: Immerse the original pulp board in deionized water. After soaking for 11 h, perform beating treatment to obtain a pulp suspension. Add 2,2,6,6-tetramethylpiperidine-1-oxyl radical and sodium bromide to the pulp suspension. Add sodium hypochlorite under the conditions of a rotation speed of 600 r / min, a temperature of 23 °C, and a pH value of 10. After reacting for 4 h, add ethanol to stop the reaction. Centrifuge to remove the supernatant, and wash the substrate to neutral to obtain pretreated pulp;

[0037] Step A2: Disperse the pretreated pulp in DMF, add allyl alcohol and dibutyltin dilaurate, protect with nitrogen, react at a rotation speed of 300 r / min and a temperature of 83 °C for 23 h, then filter to remove the filtrate. Disperse the substrate in deionized water, pour it into a paper sheet forming machine to form a sheet, and then press it into shape to obtain the pretreated paper;

[0038] Step A3: Mix modified chitosan, acrylic acid, ethyl acrylate and deionized water, soak the pretreated paper in it, protect with nitrogen, ultrasonically treat it at a frequency of 25 kHz and a temperature of 58 °C, add potassium persulfate, and after ultrasonically treating for 4 h, take it out and dry it to obtain the antibacterial impregnated paper.

[0039] The dosage ratio of the original pulp board, 2,2,6,6-tetramethylpiperidine-1-oxyl, sodium bromide and sodium hypochlorite described in Step A1 is 100 g: 29.7 mg: 318 mg: 35 mg.

[0040] The mass ratio of the pretreated pulp, allyl alcohol and dibutyltin dilaurate described in Step A2 is 1 g: 3 g: 0.2 mL.

[0041] The dosage ratio of the modified chitosan, acrylic acid, ethyl acrylate and deionized water described in Step A3 is 1 g: 12.5 g: 6.32 g: 100 mL, and the dosage of potassium persulfate is 0.4% of the sum of the masses of the modified chitosan, acrylic acid and ethyl acrylate.

[0042] The modified chitosan is prepared by the following steps:

[0043] Step B1: Disperse chitosan in a sodium hydroxide solution, keep it at a temperature of -20 °C for 13 h, then raise the temperature to 23 °C, add isopropanol, stir and add chloroacetic acid at a rotation speed of 180 r / min, react for 2.5 h to obtain carboxymethyl chitosan. Mix 2,3-dimercapto-1-propanol, dimethylaminoethyl methacrylate and methanol evenly, and react at a rotation speed of 200 r / min under 365 nm ultraviolet light irradiation for 4 h to obtain Intermediate 1;

[0044] Step B2: Mix Intermediate 1, decyl bromide and acetonitrile evenly, and react at a rotation speed of 200 r / min and a temperature of 43 °C for 13 h to obtain Intermediate 2. Mix Intermediate 2, epichlorohydrin, benzyltrimethylammonium bromide and DMF evenly, and react at a rotation speed of 150 r / min and a temperature of 105 °C for 4 h, cool down to 73 °C, add sodium hydroxide, and continue to react for 6 h to obtain Intermediate 3;

[0045] Step B3: Dissolve carboxymethyl chitosan in deionized water. Under the conditions of a rotation speed of 200 r / min and a temperature of 85 °C, stir and add sodium hydroxide until the pH value reaches 10. Add intermediate 3 and react for 7.5 h to obtain pretreated chitosan. Mix the pretreated chitosan, allyl alcohol, p-toluenesulfonic acid, and toluene evenly, and react under the conditions of a rotation speed of 120 r / min and a temperature of 105 °C for 7 h to obtain modified chitosan.

[0046] The dosage ratio of the chitosan, sodium hydroxide solution, isopropanol, and chloroacetic acid described in Step B1 is 5 g: 6 mL: 60 mL: 6 g. The mass fraction of the sodium hydroxide solution is 50%, and the molar ratio of 2,3-dimercaptopropanol and dimethylaminoethyl methacrylate is 1:2.

[0047] The molar ratio of intermediate 1 and decyl bromide described in Step B2 is 1:2. The molar ratio of intermediate 2 and epichlorohydrin is 1:2. The dosage of sodium hydroxide is 10% of the mass of intermediate 2, and the dosage of benzyltrimethylammonium bromide is 2% of the mass of intermediate 2.

[0048] The mass ratio of the carboxymethyl chitosan and intermediate 3 described in Step B3 is 5:12. The molar ratio of the carboxyl group on the pretreated chitosan and allyl alcohol is 1:1. The dosage of p-toluenesulfonic acid is 4% of the mass of allyl alcohol. Example 3

[0049] A preparation process of an antibacterial impregnated paper specifically includes the following steps:

[0050] Step A1: Immerse the original pulp board in deionized water. After soaking for 12 h, perform beating treatment to obtain a pulp suspension. Add 2,2,6,6-tetramethylpiperidine-1-oxyl radical and sodium bromide to the pulp suspension. Under the conditions of a rotation speed of 800 r / min, a temperature of 25 °C, and a pH value of 11, add sodium hypochlorite and react for 5 h. Then add ethanol to stop the reaction, centrifuge to remove the supernatant, and wash the substrate to neutrality to obtain pretreated pulp.

[0051] Step A2: Disperse the pretreated pulp in DMF, add allyl alcohol and dibutyltin dilaurate, and introduce nitrogen for protection. React under the conditions of a rotation speed of 500 r / min and a temperature of 85 °C for 25 h. Then filter to remove the filtrate, disperse the substrate in deionized water, pour it into a paper sample sheet former to form a sheet, and then press and mold it to obtain pretreated paper.

[0052] Step A3: Mix modified chitosan, acrylic acid, ethyl acrylate, and deionized water, immerse the pretreated paper in it, introduce nitrogen for protection, and under the conditions of a frequency of 30 kHz and a temperature of 60 °C, perform ultrasonic treatment and add potassium persulfate. After ultrasonic treatment for 5 h, take it out and dry it to obtain the antibacterial impregnated paper.

[0053] The dosage ratio of the original pulp board, 2,2,6,6-tetramethylpiperidine-1-oxyl radical, sodium bromide, and sodium hypochlorite described in step A1 is 100 g: 29.7 mg: 318 mg: 35 mg.

[0054] The mass ratio of the pretreated pulp, allyl alcohol, and dibutyltin dilaurate described in step A2 is 1 g: 3 g: 0.2 mL.

[0055] The dosage ratio of the modified chitosan, acrylic acid, ethyl acrylate, and deionized water described in step A3 is 1 g: 12.5 g: 6.32 g: 100 mL, and the dosage of potassium persulfate is 0.5% of the sum of the masses of the modified chitosan, acrylic acid, and ethyl acrylate.

[0056] The modified chitosan is prepared by the following steps:

[0057] Step B1: Disperse chitosan in a sodium hydroxide solution, keep it at -20 °C for 15 h, then raise the temperature to 25 °C, add isopropanol, stir and add chloroacetic acid at a rotation speed of 200 r / min, and react for 3 h to obtain carboxymethyl chitosan. Mix 2,3-dimercapto-1-propanol, dimethylaminoethyl methacrylate, and methanol evenly, and react for 5 h under the conditions of a rotation speed of 300 r / min and 365 nm ultraviolet light irradiation to obtain intermediate 1;

[0058] Step B2: Mix intermediate 1, decyl bromide, and acetonitrile evenly, and react for 15 h under the conditions of a rotation speed of 200 - 300 r / min and a temperature of 45 °C to obtain intermediate 2. Mix intermediate 2, epichlorohydrin, benzyltrimethylammonium bromide, and DMF evenly, and react for 5 h under the conditions of a rotation speed of 200 r / min and a temperature of 110 °C. Cool down to 75 °C, add sodium hydroxide, and continue to react for 7 h to obtain intermediate 3;

[0059] Step B3: Dissolve carboxymethyl chitosan in deionized water, stir and add sodium hydroxide to a pH value of 10 at a rotation speed of 300 r / min and a temperature of 85 °C, add intermediate 3, and react for 8 h to obtain pretreated chitosan. Mix pretreated chitosan, allyl alcohol, p-toluenesulfonic acid, and toluene evenly, and react for 8 h under the conditions of a rotation speed of 150 r / min and a temperature of 110 °C to obtain modified chitosan.

[0060] The dosage ratio of the chitosan, sodium hydroxide solution, isopropanol, and chloroacetic acid described in step B1 is 5 g: 6 mL: 60 mL: 6 g, the mass fraction of the sodium hydroxide solution is 50%, and the molar ratio of 2,3-dimercapto-1-propanol and dimethylaminoethyl methacrylate is 1:2.

[0061] The molar ratio of intermediate 1 to decyl bromide described in step B2 is 1:2, the molar ratio of intermediate 2 to epichlorohydrin is 1:2, the dosage of sodium hydroxide is 10% of the mass of intermediate 2, and the dosage of benzyltrimethylammonium bromide is 2% of the mass of intermediate 2.

[0062] The mass ratio of carboxymethyl chitosan to intermediate 3 described in step B3 is 5:12, the molar ratio of carboxyl groups on the pretreated chitosan to allyl alcohol is 1:1, and the dosage of p-toluenesulfonic acid is 5% of the mass of allyl alcohol.

[0063] Comparative Example 1

[0064] In this comparative example, compared with Example 1, acryloyloxyethyl trimethyl ammonium chloride is used instead of the modified chitosan, and the remaining steps are the same.

[0065] Comparative Example 2

[0066] In this comparative example, compared with Example 1, the product obtained by uniformly mixing carboxymethyl chitosan, allyl alcohol, p-toluenesulfonic acid and toluene and reacting for 6 h under the conditions of a rotation speed of 120 r / min and a temperature of 100 °C is used instead of the modified chitosan.

[0067] Escherichia coli and Staphylococcus aureus were respectively diluted with phosphate buffer into bacterial suspensions of 10 6 cfu / mL. 100 μL of the bacterial suspension was poured into a petri dish, and 15 mL of bacterial culture medium was added. The components of the bacterial culture medium were 1% peptone, 0.5% beef extract, 0.5% sodium chloride and 2% agar, with a pH value of 7.2. After mixing evenly and solidifying, the antibacterial impregnated papers with a diameter of 8 mm prepared in Examples 1-3 and Comparative Examples 1-2 were respectively placed on the culture medium, and incubated at 37 °C for 24 h to observe the antibacterial effect. The results are shown in the following table.

[0068]

[0069] As can be seen from the above table, the antibacterial impregnated papers prepared in Examples 1-3 have good antibacterial effects.

[0070] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the described specific embodiments or use similar methods for substitution, as long as they do not deviate from the concept of the invention or exceed the scope defined by the claims of the present invention, they should fall within the protection scope of the present invention.

Claims

1. A preparation process of an antibacterial impregnated paper, characterized in that: Specifically, it includes the following steps: Step A1: Immerse the original pulp board in deionized water. After immersion treatment, perform beating treatment to obtain a pulp suspension. Add 2,2,6,6-tetramethylpiperidine-1-oxyl radical and sodium bromide to the pulp suspension, then add sodium hypochlorite. After reaction, add ethanol to stop the reaction, centrifuge to remove the supernatant, and wash the substrate to neutrality to obtain the pretreated pulp. Step A2: Disperse the pretreated pulp in DMF, add allyl alcohol and dibutyltin dilaurate, and pass nitrogen for protection. After reaction, filter to remove the filtrate. Disperse the substrate in deionized water, pour it into a paper sample making machine for sampling, and then press and mold to obtain the pretreated paper. Step A3: Mix modified chitosan, acrylic acid, ethyl acrylate, and deionized water, immerse the pretreated paper in it, pass nitrogen for protection, perform ultrasonic treatment and add potassium persulfate. After ultrasonic treatment, take it out and dry to obtain the antibacterial impregnated paper. The modified chitosan is prepared by the following steps: Step B1: Disperse chitosan in a sodium hydroxide solution, add isopropanol, stir and add chloroacetic acid for reaction to obtain carboxymethyl chitosan. Mix 2,3-dimercapto-1-propanol, dimethylaminoethyl methacrylate, and methanol for ultraviolet irradiation reaction to obtain Intermediate 1. Step B2: Mix Intermediate 1, decyl bromide, and acetonitrile for reaction to obtain Intermediate 2. Mix Intermediate 2, epichlorohydrin, benzyltrimethylammonium bromide, and DMF for reaction, then cool down and add sodium hydroxide, and continue the reaction to obtain Intermediate 3. Step B3: Dissolve carboxymethyl chitosan in deionized water, stir and add sodium hydroxide, add Intermediate 3 for reaction to obtain the pretreated chitosan. Mix the pretreated chitosan, allyl alcohol, p-toluenesulfonic acid, and toluene for reaction to obtain the modified chitosan.

2. The preparation process of an antibacterial impregnated paper according to claim 1, characterized in that: The dosage ratio of the original pulp board, 2,2, June 6, 6-tetramethylpiperidine-1-oxyl radical, sodium bromide, and sodium hypochlorite in Step A1 is 100g:29.7mg:318mg:35mg.

3. The preparation process of an antibacterial impregnated paper according to claim 1, characterized in that: The mass ratio of the pretreated pulp, allyl alcohol, and dibutyltin dilaurate in Step A2 is 1g:3g:0.2mL.

4. The preparation process of an antibacterial impregnated paper according to claim 1, characterized in that: The dosage ratio of the modified chitosan, acrylic acid, ethyl acrylate, and deionized water in Step A3 is 1g:12.5g:6.32g:100mL, and the dosage of potassium persulfate is 0.3 - 0.5% of the sum of the masses of the modified chitosan, acrylic acid, and ethyl acrylate.

5. The preparation process of an antibacterial impregnated paper according to claim 1, characterized in that: The dosage ratio of chitosan, sodium hydroxide solution, isopropanol, and chloroacetic acid in Step B1 is 5g:6mL:60mL:6g, the mass fraction of the sodium hydroxide solution is 50%, and the molar ratio of 2,3-dimercapto-1-propanol and dimethylaminoethyl methacrylate is 1:

2.

6. The preparation process of an antibacterial impregnated paper according to claim 1, characterized in that: The molar ratio of Intermediate 1 and decyl bromide in Step B2 is 1:2, the molar ratio of Intermediate 2 and epichlorohydrin is 1:2, the dosage of sodium hydroxide is 10% of the mass of Intermediate 2, and the dosage of benzyltrimethylammonium bromide is 2% of the mass of Intermediate 2.

7. The preparation process of an antibacterial impregnated paper according to claim 1, characterized in that: The mass ratio of the carboxymethyl chitosan and intermediate 3 described in step B3 is 5:12, the molar ratio of the carboxyl group on the pretreated chitosan to allyl alcohol is 1:1, and the dosage of p-toluenesulfonic acid is 3-5% of the mass of allyl alcohol.

Citation Information

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