Environmentally friendly and non-toxic toothbrush cleaner and preparation process thereof

Abstract

The present invention relates to the field of oral care, specifically a kind of environmentally friendly nontoxic toothbrush cleaning agent and its preparation process. The present invention first prepares a chitosan-based surfactant, uses alkali solution to swell chitosan, and the swollen chitosan is reacted with propylene oxide under the action of catalyst tetramethylammonium hydroxide to obtain O-hydroxypropyl chitosan; O-hydroxypropyl chitosan and citral are used as raw materials to react, chitosan citral Schiff base is generated, octadecane bromide and phase transfer catalyst tetrabutylammonium bromide are added, long chains are grafted onto chitosan, hydrophobic segments are formed, and chitosan-based surfactants are obtained. Chitosan-based surfactants, purified water, hydrogenated castor oil polyether 40, ethanol, sodium bicarbonate, sodium octadecyl sulfate are mixed to obtain environmentally friendly nontoxic toothbrush cleaning agents. The toothbrush cleaning agent prepared by the present invention has good antibacterial effect and strong decontamination performance.

Description

Technical Field

[0001] The invention relates to the field of oral care, in particular to an environmentally friendly and non-toxic toothbrush cleaner and a preparation process thereof. Background Art

[0002] Toothbrush cleaner is a product specially designed for cleaning and disinfecting toothbrushes. Its main function is to remove bacteria, viruses, mold and other contaminants growing on the surface of toothbrushes, thereby ensuring oral hygiene and health. Such cleaners usually contain a variety of ingredients, among which antibacterial agents, bleaches, surfactants, natural antibacterial ingredients and disinfectants are common. Among them, antibacterial agents such as sodium chloride and chlorhexidine are added to cleaners to inhibit the growth of microorganisms on toothbrushes; bleaches such as hydrogen peroxide help remove stains on toothbrushes and provide a cleaning effect; surfactants can effectively remove food residues, dirt and grease, enhancing the cleaning effect.

[0003] As people's health concepts continue to penetrate, pure natural and non-toxic natural antibacterial ingredients are favored and used to prepare toothbrush cleaners, such as tea tree oil or peppermint oil, which are not only naturally antibacterial but also can freshen breath. In addition, some products may contain disinfectants, such as alcohol, to ensure that potential bacteria or viruses are killed. In view of consumer preferences and market demand, it is very necessary to invent environmentally friendly and non-toxic toothbrush cleaners. Summary of the invention

[0004] The purpose of the present invention is to provide an environmentally friendly and non-toxic toothbrush cleaner and a preparation process thereof, so as to solve the problems raised in the above background technology.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions: an environmentally friendly and non-toxic toothbrush cleaner and a preparation process thereof, comprising the following steps:

[0006] Step 1:

[0007] S11: weigh chitosan and add it to isopropanol, mix and stir for 30 to 60 minutes; add an aqueous solution of NaOH, seal and freeze overnight after swelling;

[0008] S12: After thawing the chitosan swollen with the alkaline solution, add isopropanol, propylene oxide and catalyst tetramethylammonium hydroxide, stir at 25-35° C. for 1-2 hours, and heat with a microwave at 200-300W for 40-70 minutes, with the reaction temperature being 50-60° C.; cool, let stand and precipitate, remove the supernatant, and filter; wash the filter cake with isopropanol and dry it to obtain O-hydroxypropyl chitosan;

[0009] S13: Mix O-hydroxypropyl chitosan and citral and add them to methanol, stir and react at a constant temperature of 30-40° C. for 2-4 hours to obtain chitosan citral Schiff base; continue to add octadecane bromide and phase transfer catalyst tetrabutylammonium bromide, heat to 70-80° C., react for 1-2 hours, cool and stir, add dilute hydrochloric acid to neutralize; precipitate with ethanol, filter, and wash the filter cake with ethanol, and dry to obtain a chitosan-based surfactant;

[0010] Step 2:

[0011] Purified water, hydrogenated castor oil polyether 40, ethanol, sodium bicarbonate, sodium octadecyl sulfate and chitosan-based surfactant are mixed to obtain an environmentally friendly and non-toxic toothbrush cleaning agent.

[0012] Furthermore, in S11, the mass ratio of chitosan to isopropanol is (3-5):100.

[0013] Furthermore, in S11, sodium hydroxide is used to adjust the pH value to 9-10.

[0014] Furthermore, in S11, the swelling temperature is 25-35°C, the swelling time is 2-3h, and the freezing temperature is 1-5°C.

[0015] Furthermore, in S12, the amounts of the components used, by weight, are 20 to 35 parts of chitosan swollen with an alkaline solution, 120 to 150 parts of isopropanol, 13 to 18 parts of propylene oxide, and 0.3 to 0.5 parts of catalyst tetramethylammonium hydroxide.

[0016] Furthermore, in S13, the molar ratio of chitosan amino, citral and octadecane bromide is (4-5):(1-2):1.

[0017] Further, in S13, dilute hydrochloric acid is neutralized to a pH value of 7 to 8.

[0018] Furthermore, in step 2, the content of each component in the toothbrush cleaner is calculated by weight percentage: 0.3-1% hydrogenated castor oil polyether 40, 1-2% ethanol, 1-2% sodium bicarbonate, 1-2% sodium octadecyl sulfate, 2-3% chitosan-based surfactant, and the remainder is purified water.

[0019] Compared with the prior art, the invention has the following beneficial effects: the invention first prepares a chitosan-based surfactant, first performs an alkali solution swelling treatment on the chitosan, and then reacts the alkali-swollen chitosan with propylene oxide under the action of a catalyst, tetramethylammonium hydroxide, to obtain O-hydroxypropyl chitosan. O-hydroxypropyl chitosan has good antibacterial effect like chitosan, but has better solubility.

[0020] In order to further improve the antibacterial effect of chitosan, citral and the amino groups on O-hydroxypropyl chitosan were reacted to generate chitosan citral Schiff base, followed by the addition of octadecane bromide and phase transfer catalyst tetrabutylammonium bromide to graft the long chain onto chitosan to form a hydrophobic segment. Since chitosan itself has hydrophilic properties, the chitosan-based surfactant obtained after modification has amphiphilic properties.

[0021] In the present invention, because citral itself has antibacterial properties, citral is used to assist in the modification of chitosan, so as to further improve the antibacterial effect of chitosan. In addition, citral itself has hydrophobicity, so the hydrophobicity of chitosan after citral modification is also enhanced, and synergistic effect can be produced with octadecyl bromide, and emulsifying power is improved together. It should be additionally explained that citral and octadecyl bromide should be used sequentially to modify chitosan, and the reaction sequence of the two cannot be changed. If octadecyl bromide is reacted with chitosan first, the long-chain group introduced has a larger steric hindrance, which will hinder the subsequent citral and chitosan reactions.

[0022] The toothbrush cleaning agent prepared by the invention has good sterilization and decontamination effects, can effectively clean toothbrush stains, and realizes the cleaning effect on the oral cavity. DETAILED DESCRIPTION

[0023] 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.

[0024] Materials used in the present invention and their sources: chitosan comes from Yihaihua Biotechnology Co., Ltd., food grade; hydrogenated castor oil polyether 40 comes from BASF, model Eumulgin CO 40; ethanol comes from Xunye Chemical Reagent, 95% medical alcohol.

[0025] Embodiment 1: An environmentally friendly and non-toxic toothbrush cleaner and a preparation process thereof, comprising the following steps:

[0026] Step 1:

[0027] S11: Weigh 3 g of chitosan, add it to 100 g of isopropanol and stir for 30 min; add 40% by mass NaOH aqueous solution, adjust the pH value to 9, and swell at 25°C for 2 h, seal it and freeze it at 1°C overnight;

[0028] S12: After thawing 20 g of chitosan swollen with an alkaline solution, 120 g of isopropanol, 18 g of propylene oxide and 0.5 g of tetramethylammonium hydroxide catalyst were added, stirred at 25°C for 1 h, and heated with a 200 W microwave for 40 min at a reaction temperature of 50°C; cooled, allowed to stand and precipitate, the supernatant was removed, and filtered; the filter cake was washed with isopropanol and dried to obtain O-hydroxypropyl chitosan;

[0029] S13: Mix O-hydroxypropyl chitosan and citral and add them to methanol, stir and react at a constant temperature of 30°C for 2 hours to obtain chitosan citral Schiff base; continue to add octadecane bromide and phase transfer catalyst tetrabutylammonium bromide, heat to 70°C, react for 1 hour, cool and stir, add dilute hydrochloric acid to neutralize to pH=7; precipitate with ethanol, filter, and wash the filter cake with ethanol, and dry to obtain a chitosan-based surfactant; wherein the molar ratio of chitosan amino, citral and octadecane bromide is 5:1:1;

[0030] Step 2:

[0031] By weight percentage, 96.2% purified water, 0.3% hydrogenated castor oil polyether 40, 1% ethanol, 1% sodium bicarbonate, 0.5% sodium octadecyl sulfate, and 1% chitosan-based surfactant are mixed to obtain an environmentally friendly and non-toxic toothbrush cleaning agent.

[0032] Embodiment 2: An environmentally friendly and non-toxic toothbrush cleaner and a preparation process thereof, comprising the following steps:

[0033] Step 1:

[0034] S11: Weigh 3 g of chitosan, add it to 100 g of isopropanol and stir for 45 min; add 40% by mass NaOH aqueous solution, adjust the pH value to 9.5, and swell at 30°C for 2.5 h, seal it and freeze it at 3°C ​​overnight;

[0035] S12: After thawing 20 g of chitosan swollen with an alkaline solution, 120 g of isopropanol, 18 g of propylene oxide and 0.5 g of tetramethylammonium hydroxide catalyst were added, stirred at 30° C. for 1.5 h, and subjected to microwave heating at 240 W for 50 min at a reaction temperature of 55° C.; cooled, allowed to stand for precipitation, the supernatant liquid was removed, and filtered; the filter cake was washed with isopropanol and dried to obtain O-hydroxypropyl chitosan;

[0036] S13: Mix O-hydroxypropyl chitosan and citral and add them to methanol, stir and react at a constant temperature of 35°C for 3 hours to obtain chitosan citral Schiff base; continue to add octadecane bromide and phase transfer catalyst tetrabutylammonium bromide, heat to 75°C, react for 1.5 hours, cool and stir, add dilute hydrochloric acid to neutralize to pH=7; precipitate with ethanol, filter, and wash the filter cake with ethanol, and dry to obtain a chitosan-based surfactant; wherein the molar ratio of chitosan amino, citral and octadecane bromide is 5:1:1;

[0037] Step 2:

[0038] By weight percentage, 96.2% purified water, 0.3% hydrogenated castor oil polyether 40, 1% ethanol, 1% sodium bicarbonate, 0.5% sodium octadecyl sulfate, and 1% chitosan-based surfactant are mixed to obtain an environmentally friendly and non-toxic toothbrush cleaning agent.

[0039] Embodiment 3: An environmentally friendly and non-toxic toothbrush cleaner and a preparation process thereof, comprising the following steps:

[0040] Step 1:

[0041] S11: Weigh 3 g of chitosan, add it to 100 g of isopropanol and stir for 60 min; add 40% by mass NaOH aqueous solution, adjust the pH value to 10, and swell at 35°C for 3 h, seal it and freeze it at 5°C overnight;

[0042] S12: After thawing 20 g of chitosan swollen with an alkaline solution, 120 g of isopropanol, 18 g of propylene oxide and 0.5 g of tetramethylammonium hydroxide catalyst were added, stirred at 35°C for 2 h, and heated with a 300 W microwave for 70 min at a reaction temperature of 60°C; cooled, allowed to stand and precipitate, the supernatant was removed, and filtered; the filter cake was washed with isopropanol and dried to obtain O-hydroxypropyl chitosan;

[0043] S13: Mix O-hydroxypropyl chitosan and citral and add them to methanol, stir and react at a constant temperature of 40°C for 4 hours to obtain chitosan citral Schiff base; continue to add octadecane bromide and phase transfer catalyst tetrabutylammonium bromide, heat to 80°C, react for 2 hours, cool and stir, add dilute hydrochloric acid to neutralize to pH=7; precipitate with ethanol, filter, and wash the filter cake with ethanol, and dry to obtain a chitosan-based surfactant; wherein the molar ratio of chitosan amino, citral and octadecane bromide is 5:1:1;

[0044] Step 2:

[0045] By weight percentage, 96.2% purified water, 0.3% hydrogenated castor oil polyether 40, 1% ethanol, 1% sodium bicarbonate, 0.5% sodium octadecyl sulfate, and 1% chitosan-based surfactant are mixed to obtain an environmentally friendly and non-toxic toothbrush cleaning agent.

[0046] Embodiment 4: An environmentally friendly and non-toxic toothbrush cleaner and a preparation process thereof, comprising the following steps:

[0047] Step 1:

[0048] S11: Weigh 3 g of chitosan, add it to 100 g of isopropanol and stir for 30 min; add 40% by mass NaOH aqueous solution, adjust the pH value to 9, and swell at 25°C for 2 h, seal it and freeze it at 1°C overnight;

[0049] S12: After thawing 20 g of chitosan swollen with an alkaline solution, 120 g of isopropanol, 18 g of propylene oxide and 0.5 g of tetramethylammonium hydroxide catalyst were added, stirred at 25°C for 1 h, and subjected to microwave heating at 280 W for 45 min, with the reaction temperature being 50°C; cooled, allowed to stand for precipitation, the supernatant liquid was removed, and suction filtered; the filter cake was washed with isopropanol and then dried to obtain O-hydroxypropyl chitosan;

[0050] S13: Mix O-hydroxypropyl chitosan and citral and add them to methanol, stir and react at a constant temperature of 30°C for 2 hours to obtain chitosan citral Schiff base; continue to add octadecane bromide and phase transfer catalyst tetrabutylammonium bromide, heat to 70°C, react for 1 hour, cool and stir, add dilute hydrochloric acid to neutralize to pH=7; precipitate with ethanol, filter, and wash the filter cake with ethanol, and dry to obtain a chitosan-based surfactant; wherein the molar ratio of chitosan amino, citral and octadecane bromide is 5:1:1;

[0051] Step 2:

[0052] By weight percentage, 95.2% purified water, 0.3% hydrogenated castor oil polyether 40, 1% ethanol, 1% sodium bicarbonate, 0.5% sodium octadecyl sulfate, and 2% chitosan-based surfactant are mixed to obtain an environmentally friendly and non-toxic toothbrush cleaning agent.

[0053] Embodiment 5: An environmentally friendly and non-toxic toothbrush cleaner and a preparation process thereof, comprising the following steps:

[0054] Step 1:

[0055] S11: Weigh 3 g of chitosan, add it to 100 g of isopropanol and stir for 50 min; add 40% by mass NaOH aqueous solution, adjust the pH value to 9.5, and swell at 30°C for 2 h, seal it and freeze it at 2°C overnight;

[0056] S12: After thawing 20 g of chitosan swollen with an alkaline solution, 120 g of isopropanol, 18 g of propylene oxide and 0.5 g of tetramethylammonium hydroxide catalyst were added, stirred at 30°C for 1 h, and subjected to microwave heating at 280 W for 60 min, with the reaction temperature at 55°C; cooled, allowed to stand and precipitate, the supernatant was removed, and filtered; the filter cake was washed with isopropanol and dried to obtain O-hydroxypropyl chitosan;

[0057] S13: Mix O-hydroxypropyl chitosan and citral and add them to methanol, stir and react at a constant temperature of 35°C for 3 hours to obtain chitosan citral Schiff base; continue to add octadecane bromide and phase transfer catalyst tetrabutylammonium bromide, heat to 75°C, react for 1 hour, cool and stir, add dilute hydrochloric acid to neutralize to pH=7; precipitate with ethanol, filter, and wash the filter cake with ethanol, and dry to obtain a chitosan-based surfactant; wherein the molar ratio of chitosan amino, citral and octadecane bromide is 5:1:1;

[0058] Step 2:

[0059] By weight percentage, 94.7% purified water, 0.3% hydrogenated castor oil polyether 40, 1% ethanol, 1% sodium bicarbonate, 0.5% sodium octadecyl sulfate, and 2.5% chitosan-based surfactant are mixed to obtain an environmentally friendly and non-toxic toothbrush cleaning agent.

[0060] Embodiment 6: An environmentally friendly and non-toxic toothbrush cleaner and a preparation process thereof, comprising the following steps:

[0061] Step 1:

[0062] S11: Weigh 3 g of chitosan, add it to 100 g of isopropanol and stir for 60 min; add 40% by mass NaOH aqueous solution, adjust the pH value to 10, and swell at 35°C for 3 h, seal it and freeze it at 5°C overnight;

[0063] S12: After thawing 20 g of chitosan swollen with an alkaline solution, 120 g of isopropanol, 18 g of propylene oxide and 0.5 g of tetramethylammonium hydroxide catalyst were added, stirred at 35°C for 2 h, and heated with a 300 W microwave for 70 min at a reaction temperature of 60°C; cooled, allowed to stand and precipitate, the supernatant was removed, and filtered; the filter cake was washed with isopropanol and dried to obtain O-hydroxypropyl chitosan;

[0064] S13: Mix O-hydroxypropyl chitosan and citral and add them to methanol, stir and react at a constant temperature of 40°C for 4 hours to obtain chitosan citral Schiff base; continue to add octadecane bromide and phase transfer catalyst tetrabutylammonium bromide, heat to 80°C, react for 2 hours, cool and stir, add dilute hydrochloric acid to neutralize to pH=7; precipitate with ethanol, filter, and wash the filter cake with ethanol, and dry to obtain a chitosan-based surfactant; wherein the molar ratio of chitosan amino, citral and octadecane bromide is 5:1:1;

[0065] Step 2:

[0066] By weight percentage, 94.2% purified water, 0.3% hydrogenated castor oil polyether 40, 1% ethanol, 1% sodium bicarbonate, 0.5% sodium octadecyl sulfate, and 3% chitosan-based surfactant are mixed to obtain an environmentally friendly and non-toxic toothbrush cleaning agent.

[0067] Comparative Example 1: No chitosan-based surfactant was added, and other parameters were the same as those in Example 1.

[0068] By weight percentage, 97.2% purified water, 0.3% hydrogenated castor oil polyether 40, 1% ethanol, 1% sodium bicarbonate, and 0.5% sodium octadecyl sulfate are mixed to obtain an environmentally friendly and non-toxic toothbrush cleaning agent.

[0069] Comparative Example 2: No octadecane bromide was added to S13, and the remaining parameters were the same as those in Example 2.

[0070] Step 1:

[0071] S11: Weigh 3 g of chitosan, add it to 100 g of isopropanol and stir for 45 min; add 40% by mass NaOH aqueous solution, adjust the pH value to 9.5, and swell at 30°C for 2.5 h, seal it and freeze it at 3°C ​​overnight;

[0072] S12: After thawing 20 g of chitosan swollen with an alkaline solution, 120 g of isopropanol, 18 g of propylene oxide and 0.5 g of tetramethylammonium hydroxide catalyst were added, stirred at 30° C. for 1.5 h, and subjected to microwave heating at 240 W for 50 min at a reaction temperature of 55° C.; cooled, allowed to stand for precipitation, the supernatant liquid was removed, and filtered; the filter cake was washed with isopropanol and dried to obtain O-hydroxypropyl chitosan;

[0073] S13: mixing O-hydroxypropyl chitosan and citral into methanol, stirring and reacting at a constant temperature of 35° C. for 3 hours to obtain chitosan citral Schiff base; drying to obtain a chitosan-based surfactant; wherein the molar ratio of chitosan amino group to citral is 5:1;

[0074] Step 2:

[0075] By weight percentage, 96.2% purified water, 0.3% hydrogenated castor oil polyether 40, 1% ethanol, 1% sodium bicarbonate, 0.5% sodium octadecyl sulfate, and 1% chitosan-based surfactant are mixed to obtain an environmentally friendly and non-toxic toothbrush cleaning agent.

[0076] Comparative Example 3: Citral was not added to S13, and the remaining parameters were the same as those in Example 3.

[0077] Step 1:

[0078] S11: Weigh 3 g of chitosan, add it to 100 g of isopropanol and stir for 45 min; add 40% by mass NaOH aqueous solution, adjust the pH value to 9.5, and swell at 30°C for 2.5 h, seal it and freeze it at 3°C ​​overnight;

[0079] S12: After thawing 20 g of chitosan swollen with an alkaline solution, 120 g of isopropanol, 18 g of propylene oxide and 0.5 g of tetramethylammonium hydroxide catalyst were added, stirred at 30° C. for 1.5 h, and subjected to microwave heating at 240 W for 50 min at a reaction temperature of 55° C.; cooled, allowed to stand for precipitation, the supernatant liquid was removed, and filtered; the filter cake was washed with isopropanol and dried to obtain O-hydroxypropyl chitosan;

[0080] S13: O-hydroxypropyl chitosan, octadecane bromide and phase transfer catalyst tetrabutylammonium bromide are mixed, heated to 75°C, reacted for 1.5 hours, cooled and stirred, and diluted hydrochloric acid is added to neutralize to pH=7; ethanol is used for precipitation, suction filtration, and the filter cake is fully washed with ethanol, and then dried to obtain a chitosan-based surfactant; wherein the molar ratio of chitosan amino group to octadecane bromide is 5:1;

[0081] Step 2:

[0082] By weight percentage, 96.2% purified water, 0.3% hydrogenated castor oil polyether 40, 1% ethanol, 1% sodium bicarbonate, 0.5% sodium octadecyl sulfate, and 1% chitosan-based surfactant are mixed to obtain an environmentally friendly and non-toxic toothbrush cleaning agent.

[0083] Comparative Example 4: The reaction order of citral and octadecyl bromide was adjusted, and the other parameters were the same as those in Example 4.

[0084] Step 1:

[0085] S11: Weigh 3 g of chitosan, add it to 100 g of isopropanol and stir for 30 min; add 40% by mass NaOH aqueous solution, adjust the pH value to 9, and swell at 25°C for 2 h, seal it and freeze it at 1°C overnight;

[0086] S12: After thawing 20 g of chitosan swollen with an alkaline solution, 120 g of isopropanol, 18 g of propylene oxide and 0.5 g of tetramethylammonium hydroxide catalyst were added, stirred at 25°C for 1 h, and subjected to microwave heating at 280 W for 45 min, with the reaction temperature being 50°C; cooled, allowed to stand for precipitation, the supernatant liquid was removed, and suction filtered; the filter cake was washed with isopropanol and then dried to obtain O-hydroxypropyl chitosan;

[0087] S13: O-hydroxypropyl chitosan, octadecane bromide and phase transfer catalyst tetrabutylammonium bromide are mixed, heated to 70°C, reacted for 1 hour, cooled and stirred, and diluted hydrochloric acid is added to neutralize to pH=7, precipitated with ethanol, filtered, and the filter cake is fully washed with ethanol, dried and mixed with citral, added to methanol, and reacted at a constant temperature of 30°C with stirring for 2 hours to obtain a chitosan-based surfactant; wherein the molar ratio of chitosan amino, citral and octadecane bromide is 5:1:1;

[0088] Step 2:

[0089] By weight percentage, 95.2% purified water, 0.3% hydrogenated castor oil polyether 40, 1% ethanol, 1% sodium bicarbonate, 0.5% sodium octadecyl sulfate, and 2% chitosan-based surfactant are mixed to obtain an environmentally friendly and non-toxic toothbrush cleaning agent.

[0090] experiment:

[0091] Examples 1 to 6 and Comparative Examples 1 to 4 were tested, and the experimental results are shown in the following table.

[0092] Antibacterial performance test of toothbrush cleaner: Escherichia coli was selected as the test strain, 0.5g of toothbrush cleaner sample was added to 10mL of Escherichia coli strain solution, and placed at a constant temperature of 37℃ for 24h to test the bacterial inhibition rate;

[0093] Emulsifying power test of chitosan-based surfactant: weigh 2.5 g of chitosan-based surfactant sample, add a small amount of distilled water to dissolve it, and then make up the volume in a 100 ml volumetric flask; use a pipette to measure 20 ml of the sample, place it in a 100 ml stoppered measuring cylinder, then add 20 ml of liquid paraffin, cover the stopper, keep warm in a 34°C water bath for 5 min, shake vigorously 10 times, put it back in the water bath and let it stand for 1 min, repeat this operation 5 times, start the stopwatch, and record the time when the water layer is separated to the 10 ml scale.

[0094] project Antibacterial rate / % Emulsification time / s Example 1 97.2 329 Example 2 97.3 325 Example 3 97.1 324 Example 4 98.2 324 Example 5 98.4 326 Example 6 98.8 327 Comparative Example 1 92.2 / Comparative Example 2 97.2 468 Comparative Example 3 95.4 339 Comparative Example 4 96.6 334

[0095] Conclusion: The data of Examples 1 to 6 show that the toothbrush cleaner prepared by the present invention has a good antibacterial effect, and the antibacterial rate reaches more than 97%. The data of Example 1 and Comparative Example 1 show that the chitosan-based surfactant prepared by the present invention can effectively improve the antibacterial rate, and at the same time has a good emulsifying effect, which can effectively improve the decontamination performance. The data of Example 2 and Comparative Example 2 show that after grafting octadecane bromide, the hydrophobic long chain improves the emulsifying power of the chitosan-based surfactant. The data of Example 3 and Comparative Example 3 show that citral has a good antibacterial effect, and the antibacterial rate can be improved after grafting reaction with chitosan. The data of Example 4 and Comparative Example 4 show that when octadecane bromide is grafted first, the long chain has a large steric hindrance, which affects the grafting of citral, and therefore the antibacterial efficiency is poor.

[0096] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A preparation process of an environmentally friendly and non-toxic toothbrush cleaner, characterized in that: The following steps are involved: Purified water, hydrogenated castor oil polyether 40, ethanol, sodium bicarbonate, sodium octadecyl sulfate, and chitosan-based surfactant are mixed to obtain an environmentally friendly and non-toxic toothbrush cleaning agent; by weight percentage, 0.3-1% hydrogenated castor oil polyether 40, 1-2% ethanol, 1-2% sodium bicarbonate, 1-2% sodium octadecyl sulfate, 2-3% chitosan-based surfactant, and the remainder is purified water; The preparation method of the chitosan-based surfactant comprises the following steps: S11: weigh chitosan and add it to isopropanol, mix and stir for 30 to 60 minutes; add an aqueous solution of NaOH, swell at 25 to 35° C. for 2 to 3 hours, seal it, and store it at 1 to 5° C. overnight; S12: After thawing the chitosan swollen with alkaline solution, add isopropanol, propylene oxide and catalyst tetramethylammonium hydroxide, stir at 25-35°C for 1-2h, and heat with 200-300W microwave for 40-70min, with the reaction temperature being 50-60°C; cool, let stand and settle, remove the supernatant, and filter; wash the filter cake with isopropanol and dry to obtain O-hydroxypropyl chitosan; the amount of each component, by weight, is 20-35 parts of chitosan swollen with alkaline solution, 120-150 parts of isopropanol, 13-18 parts of propylene oxide, and 0.3-0.5 parts of catalyst tetramethylammonium hydroxide; S13: Mix O-hydroxypropyl chitosan and citral and add them to methanol, stir and react at a constant temperature of 30-40°C for 2-4 hours to obtain chitosan citral Schiff base; continue to add octadecane bromide and phase transfer catalyst tetrabutylammonium bromide, heat to 70-80°C, react for 1-2 hours, cool and stir, add dilute hydrochloric acid to neutralize; precipitate with ethanol, filter, and wash the filter cake with ethanol, and obtain chitosan-based surfactant after drying.

2. The preparation process of an environmentally friendly and non-toxic toothbrush cleaner according to claim 1, characterized in that: In S11, the mass ratio of chitosan to isopropanol is (3-5):

100.

3. The preparation process of an environmentally friendly and non-toxic toothbrush cleaner according to claim 1, characterized in that: In S11, sodium hydroxide is used to adjust the pH value to 9-10.

4. The preparation process of an environmentally friendly and non-toxic toothbrush cleaner according to claim 1, characterized in that: In S13, the molar ratio of chitosan amino, citral and octadecane bromide is (4-5):(1-2):

1.

5. The preparation process of an environmentally friendly and non-toxic toothbrush cleaner according to claim 1, characterized in that: In S13, the pH value is neutralized to 7-8 with dilute hydrochloric acid.

6. A toothbrush cleaner prepared by the preparation process of an environmentally friendly and non-toxic toothbrush cleaner according to any one of claims 1 to 5.