Toothpaste containing nano material and preparation method thereof

Abstract

The invention relates to the technical field of toothpaste, and discloses toothpaste containing a nanometer material and a preparation method thereof.The preparation method comprises the steps that vitamin C, carrageenan, polyethylene glycol, a xylitol sweetening agent, peppermint essence, a sodium phytate tooth whitening agent, sorbitol, quaternized silicone oil, quaternized chitosan, nanometer silicon dioxide and deionized water are added into a stirrer to be stirred, and the mixture is stirred to be uniform; and degassing in vacuum to obtain the toothpaste containing the nano material. Quaternized silicone oil and quaternary ammonium salt groups in quaternized chitosan in the toothpaste containing the nano material can inhibit growth of various bacteria, a good antibacterial effect is achieved, a chain of the quaternized silicone oil is long, and the quaternized silicone oil can be better adsorbed on the surfaces of teeth; silicone oil in quaternized silicone oil has a good lubricating effect, and nano silicon dioxide can provide a better attractive effect and has a grinding aiding effect in the toothpaste, so that teeth are whiter and brighter.

Description

Technical Field

[0001] The invention relates to the technical field of toothpaste, in particular to a toothpaste containing nano materials and a preparation method thereof. Background Art

[0002] Toothpaste is a must for people's daily oral care. It is generally in a gel state and is generally applied to a toothbrush. It is applied to the surface of human teeth in a frictional manner to play a role in cleaning and care, and to purify and refresh the oral cavity. Therefore, to make teeth beautiful, protect gum health and prevent bad breath, tooth cleaning is the most important. For example, patent CN113332183B discloses a desensitizing toothpaste and a preparation method thereof. The desensitizing toothpaste prepared by the invention not only has a therapeutic effect on oral diseases such as tooth sensitivity, periodontal disease, and caries, but also can effectively inhibit the growth of oral bacteria, strengthen root teeth, and further improve the anti-sensitivity ability of teeth, but its antibacterial and whitening effects need to be further improved. Summary of the invention

[0003] 1. Technical issues to be resolved In view of the deficiencies in the prior art, the present invention provides a toothpaste containing nanomaterials and a preparation method thereof, which has good anti-oxidation and whitening effects and provides better protection for teeth.

[0004] (II) Technical solution To achieve the above-mentioned purpose, the present invention provides the following technical scheme: a toothpaste containing nano materials, comprising the following components by weight: 3-5 parts by weight of vitamin C, 1-2 parts by weight of carrageenan, 0.8-1 parts by weight of polyethylene glycol, 2-3 parts by weight of xylitol sweetener, 0.4-0.6 parts by weight of mint flavor, 3-5 parts by weight of sodium phytate tooth whitening agent, 1-3 parts by weight of sorbitol, 5-12 parts by weight of quaternized silicone oil, 3-6 parts by weight of quaternized chitosan, 0.01-0.04 parts by weight of nano silicon dioxide, and 100-200 parts by weight of deionized water.

[0005] Preferably, the preparation method of the quaternary ammonium silicone oil is: (1) Under nitrogen atmosphere, 1,2-hexanediol and ε-caprolactone are added into a reactor, stirred evenly, and then dibutyltin diosilicate catalyst is added, and the mixture is reacted at 95-120°C for 6-8 hours. After the reaction is completed, the mixture is precipitated with anhydrous ether and dried to obtain ε-caprolactone-modified 1,2-hexanediol; (2) Add di(dimethylamino)methylvinylsilane and hydrogenated silicone oil to acetonitrile solvent, stir for 2-4 min, continue to add chloroplatinic acid catalyst, raise the temperature to 40-65°C and react for 7-10 h. After the reaction is completed, perform rotary distillation, wash, and dry to obtain intermediate 1; (3) Add 5-10 parts by weight of intermediate 1 and 8-12 parts by weight of chloroacetic acid to N,N-dimethylformamide solvent, stir evenly, carry out quaternization reaction, heat to 55-70° C. and react for 5-8 hours, and then perform vacuum distillation after reaction, wash with acetone, and obtain carboxylated silane; (4) Add carboxylated silane and ε-caprolactone-modified 1,2-hexanediol into N,N-dimethylformamide solvent, stir and mix, then add p-toluenesulfonic acid catalyst, react at 65-80°C for 7-9h, distill, filter and wash after reaction to obtain quaternary ammonium silicone oil.

[0006] Preferably, the mass ratio of 1,2-hexanediol, ε-caprolactone and dibutyltin diosilicate catalyst in (1) is 1:1.2-1.5:0.01-0.03.

[0007] Preferably, the mass ratio of di(dimethylamino)methylvinylsilane, hydrogenated silicone oil and chloroplatinic acid catalyst in (2) is 0.8-1.2:1:0.02-0.03.

[0008] Preferably, the mass ratio of carboxylated silane, ε-caprolactone-modified 1,2-hexanediol, and p-toluenesulfonic acid catalyst in (4) is 1.1-1.4:1:0.02-0.04.

[0009] Preferably, the preparation method of the quaternized chitosan is: adding 5-14 parts by weight of chitosan to an acetic acid solvent for dissolution, heating in a water bath at 60-90° C., adding 7-15 parts by weight of 2,3-epoxypropyltrimethylammonium chloride at a constant pressure for reaction, washing with anhydrous ethanol after the reaction, drying, dialyzing, and concentrating to obtain quaternized chitosan.

[0010] Preferably, the reaction time is 5-8h.

[0011] Preferably, the preparation method of the toothpaste containing nano materials comprises the following steps: adding vitamin C, carrageenan, polyethylene glycol, xylitol sweetener, mint flavor, sodium phytate tooth whitening agent, sorbitol, quaternary ammonium silicone oil, quaternary ammonium chitosan, nano silicon dioxide, and deionized water into a stirrer, stirring for 10-15 minutes, and vacuum degassing to obtain the toothpaste containing nano materials.

[0012] 3. Beneficial technical effects The invention comprises the following steps: adding vitamin C, carrageenan, polyethylene glycol, xylitol sweetener, mint essence, sodium phytate tooth whitening agent, sorbitol, quaternary ammonium silicone oil, quaternary ammonium chitosan, nano silicon dioxide and deionized water into a stirrer, stirring and vacuum degassing to obtain a toothpaste containing nano materials.

[0013] The quaternary ammonium salt groups in the quaternary ammonium silicone oil and quaternary ammonium chitosan in the toothpaste containing nanomaterials can inhibit the growth of many kinds of bacteria. The reaction of carboxylated silane and ε-caprolactone modified 1,2-hexanediol increases the degree of substitution of the quaternary ammonium salt, which helps to prevent the formation and accumulation of dental plaque and has a good antibacterial effect. The chain of quaternary ammonium silicone oil is also longer and can be better adsorbed on the tooth surface. The silicone oil in the quaternary ammonium silicone oil has a good lubricating effect, and nano-silicon dioxide can provide better aesthetic effects and play a grinding aid role in toothpaste, making teeth whiter and brighter. The chitosan in the quaternary chitosan has certain antibacterial properties. Its application in toothpaste helps to inhibit the growth of bacteria in the oral cavity, thereby reducing the risk of caries and periodontal disease. DETAILED DESCRIPTION

[0014] Example 1 (1) Under a nitrogen atmosphere, 1,2-hexanediol and ε-caprolactone were added into a reactor, stirred evenly, and then dibutyltin diosilicate catalyst was added, wherein the mass ratio of 1,2-hexanediol, ε-caprolactone and dibutyltin diosilicate catalyst was 1:1.2:0.01, and the mixture was reacted at 95°C for 6 hours. After the reaction, the mixture was precipitated with anhydrous ether and dried to obtain ε-caprolactone-modified 1,2-hexanediol; (2) Add di(dimethylamino)methylvinylsilane and hydrogenated silicone oil to acetonitrile solvent, stir for 2 min, continue to add chloroplatinic acid catalyst, wherein the mass ratio of di(dimethylamino)methylvinylsilane, hydrogenated silicone oil and chloroplatinic acid catalyst is 0.8:1:0.02, heat to 40°C and react for 7 h. After the reaction is completed, rotary distillation, washing and drying are performed to obtain intermediate 1; (3) Add 5 parts by weight of intermediate 1 and 8 parts by weight of chloroacetic acid to N,N-dimethylformamide solvent, stir evenly, carry out quaternization reaction, heat to 55° C. and react for 5 h, then perform vacuum distillation and wash with acetone to obtain carboxylated silane; (4) Add carboxylated silane and ε-caprolactone-modified 1,2-hexanediol to N,N-dimethylformamide solvent, stir and mix, then add p-toluenesulfonic acid catalyst, wherein the mass ratio of carboxylated silane, ε-caprolactone-modified 1,2-hexanediol and p-toluenesulfonic acid catalyst is 1.1:1:0.02, react at 65°C for 7h, distill after reaction, filter and wash to obtain quaternary ammonium silicone oil.

[0015] (5) adding 5 parts by weight of chitosan to an acetic acid solvent to dissolve it, heating it in a water bath at 60° C., adding 7 parts by weight of 2,3-epoxypropyltrimethylammonium chloride at a constant pressure, reacting it for 5 hours, washing it with anhydrous ethanol after the reaction, drying it, dialyzing it, and concentrating it to obtain quaternized chitosan; (6) Add 3 parts by weight of vitamin C, 1 part by weight of carrageenan, 0.8 parts by weight of polyethylene glycol, 2 parts by weight of xylitol sweetener, 0.4 parts by weight of mint flavor, 3 parts by weight of sodium phytate tooth whitening agent, 1 part by weight of sorbitol, 5 parts by weight of quaternary ammonium silicone oil, 3 parts by weight of quaternary ammonium chitosan, 0.01 parts by weight of nano-silicon dioxide, and 100 parts by weight of deionized water into a blender, stir for 10 minutes, and vacuum degas. After the degassing, a toothpaste containing nano-materials is obtained.

[0016] Example 2 (1) Under a nitrogen atmosphere, 1,2-hexanediol and ε-caprolactone were added into a reactor, stirred evenly, and then dibutyltin diisocyanate catalyst was added, wherein the mass ratio of 1,2-hexanediol, ε-caprolactone and dibutyltin diisocyanate catalyst was 1:1.5:0.03, and the mixture was reacted at 20°C for 8 hours. After the reaction, the mixture was precipitated with anhydrous ether and dried to obtain ε-caprolactone-modified 1,2-hexanediol; (2) Add di(dimethylamino)methylvinylsilane and hydrogenated silicone oil to acetonitrile solvent, stir for 4 min, continue to add chloroplatinic acid catalyst, wherein the mass ratio of di(dimethylamino)methylvinylsilane, hydrogenated silicone oil and chloroplatinic acid catalyst is 1.2:1:0.03, heat to 65°C and react for 10 h. After the reaction is completed, rotary distillation, washing and drying are performed to obtain intermediate 1; (3) Add 10 parts by weight of intermediate 1 and 12 parts by weight of chloroacetic acid to N,N-dimethylformamide solvent, stir evenly, carry out quaternization reaction, heat to 70° C. and react for 8 h, then perform vacuum distillation and wash with acetone to obtain carboxylated silane; (4) Carboxylated silane and ε-caprolactone-modified 1,2-hexanediol are added to N,N-dimethylformamide solvent, stirred and mixed, and then p-toluenesulfonic acid catalyst is added, wherein the mass ratio of carboxylated silane, ε-caprolactone-modified 1,2-hexanediol and p-toluenesulfonic acid catalyst is 1.4:1:0.04, and the reaction is carried out at 80°C for 9 hours. After the reaction, distillation, suction filtration and washing are carried out to obtain quaternary ammonium silicone oil.

[0017] (5) adding 14 parts by weight of chitosan to an acetic acid solvent to dissolve it, heating it in a water bath at 90° C., adding 15 parts by weight of 2,3-epoxypropyltrimethylammonium chloride at a constant pressure, reacting it for 8 hours, washing it with anhydrous ethanol after the reaction, drying it, dialyzing it, and concentrating it to obtain quaternized chitosan; (6) Add 5 parts by weight of vitamin C, 2 parts by weight of carrageenan, 1 part by weight of polyethylene glycol, 3 parts by weight of xylitol sweetener, 0.6 parts by weight of mint flavor, 5 parts by weight of sodium phytate tooth whitening agent, 3 parts by weight of sorbitol, 12 parts by weight of quaternary ammonium silicone oil, 6 parts by weight of quaternary ammonium chitosan, 0.04 parts by weight of nano silicon dioxide, and 200 parts by weight of deionized water into a blender, stir for 15 minutes, and vacuum degas. After the degassing, a toothpaste containing nanomaterials is obtained.

[0018] Example 3 (1) Under a nitrogen atmosphere, 1,2-hexanediol and ε-caprolactone were added into a reactor, stirred evenly, and then dibutyltin diosilicate catalyst was added, wherein the mass ratio of 1,2-hexanediol, ε-caprolactone and dibutyltin diosilicate catalyst was 1:1.35:0.02, and the mixture was reacted at 107°C for 7 hours. After the reaction, the mixture was precipitated with anhydrous ether and dried to obtain ε-caprolactone-modified 1,2-hexanediol; (2) Add di(dimethylamino)methylvinylsilane and hydrogenated silicone oil to acetonitrile solvent, stir for 3 min, continue to add chloroplatinic acid catalyst, wherein the mass ratio of di(dimethylamino)methylvinylsilane, hydrogenated silicone oil and chloroplatinic acid catalyst is 1.0:1:0.025, heat to 52°C and react for 8.5 h. After the reaction is completed, rotary distillation, washing and drying are performed to obtain intermediate 1; (3) Add 7.5 parts by weight of intermediate 1 and 10 parts by weight of chloroacetic acid to N,N-dimethylformamide solvent, stir evenly, carry out quaternization reaction, heat to 62° C. and react for 6.5 hours, and then distill under reduced pressure and wash with acetone to obtain carboxylated silane; (4) Add carboxylated silane and ε-caprolactone-modified 1,2-hexanediol to N,N-dimethylformamide solvent, stir and mix, then add p-toluenesulfonic acid catalyst, wherein the mass ratio of carboxylated silane, ε-caprolactone-modified 1,2-hexanediol and p-toluenesulfonic acid catalyst is 1.25:1:0.03, react at 70°C for 8h, distill after reaction, filter and wash to obtain quaternary ammonium silicone oil.

[0019] (5) adding 8 parts by weight of chitosan to acetic acid solvent to dissolve it, heating it in a water bath at 75° C., adding 12 parts by weight of 2,3-epoxypropyltrimethylammonium chloride at constant pressure, reacting it for 6.5 hours, washing it with anhydrous ethanol after the reaction, drying it, dialyzing it, and concentrating it to obtain quaternized chitosan; (6) 4 parts by weight of vitamin C, 1.5 parts by weight of carrageenan, 0.9 parts by weight of polyethylene glycol, 2.5 parts by weight of xylitol sweetener, 0.5 parts by weight of mint flavor, 4 parts by weight of sodium phytate tooth whitening agent, 2 parts by weight of sorbitol, 8.5 parts by weight of quaternary ammonium silicone oil, 4.5 parts by weight of quaternary ammonium chitosan, 0.025 parts by weight of nano-silicon dioxide, and 150 parts by weight of deionized water are added into a blender, stirred for 12.5 minutes, and vacuum degassed to obtain a toothpaste containing nanomaterials.

[0020] Comparative Example 1 This comparative example is compared with Example 3, except that no quaternary ammonium silicone oil is added.

[0021] Comparative Example 2 The difference between this comparative example and Example 3 is that no quaternary ammonium chitosan is added.

[0022] The toothpastes prepared in Examples 1-5 and Comparative Example 1 were subjected to an accelerated test. They were placed in an electric constant temperature drying oven at 50°C for 3 months and then taken out and compared with the samples stored at room temperature. The changes in the appearance and aroma of the high temperature samples were observed to infer the antioxidant effect of the toothpaste within the 3-year shelf life. The test results are shown in Table 2.

[0023] Table 2: Toothpaste antioxidant test.

[0024]

[0025] It can be seen from Table 1 that Examples 1-3 of the present invention have better antioxidant effects than Comparative Examples 1-2.

[0026] 100 volunteers with yellow teeth were divided into 5 groups, with 20 people in each group using the toothpaste of the embodiment of the present invention and the comparative example. The conditions of the teeth were recorded on the 1st day and the 30th day respectively. The test results are shown in Table 2.

[0027] Table 2: Teeth whitening tests.

[0028]

[0029] It can be seen from Table 2 that Examples 1-3 of the present invention have better whitening effects than Comparative Examples 1-2.

[0030] The Oxford cup double-layer plate method was adopted, and Actinomycetemcomitans, Streptococcus mutans, and Fusobacterium nucleatum suspensions were used respectively. 100 μL of the prepared toothpaste was aspirated and added to the Oxford cup holes. The culture dishes were cultured at 37°C for 48 hours and then the diameter of the inhibition zone was measured. The results are shown in Table 3.

[0031] Table 3: Antibacterial test.

[0032]

[0033] It can be seen from Table 3 that Examples 1-3 of the present invention have better antibacterial effects than Comparative Examples 1-2.

[0034] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A toothpaste containing nanomaterials, characterized in that: The invention comprises the following components by weight: 3-5 parts by weight of vitamin C, 1-2 parts by weight of carrageenan, 0.8-1 parts by weight of polyethylene glycol, 2-3 parts by weight of xylitol sweetener, 0.4-0.6 parts by weight of mint flavor, 3-5 parts by weight of sodium phytate tooth whitening agent, 1-3 parts by weight of sorbitol, 5-12 parts by weight of quaternized silicone oil, 3-6 parts by weight of quaternized chitosan, 0.01-0.04 parts by weight of nano silicon dioxide and 100-200 parts by weight of deionized water.

2. The nanomaterial-containing toothpaste according to claim 1, characterized in that: The preparation method of the quaternary ammonium silicone oil is: (1) Under nitrogen atmosphere, 1,2-hexanediol and ε-caprolactone are added into a reactor, stirred evenly, and then dibutyltin diosilicate catalyst is added, and the mixture is reacted at 95-120°C for 6-8 hours. After the reaction is completed, the mixture is precipitated with anhydrous ether and dried to obtain ε-caprolactone-modified 1,2-hexanediol; (2) Add di(dimethylamino)methylvinylsilane and hydrogenated silicone oil to acetonitrile solvent, stir for 2-4 min, continue to add chloroplatinic acid catalyst, raise the temperature to 40-65°C and react for 7-10 h. After the reaction is completed, perform rotary distillation, wash, and dry to obtain intermediate 1; (3) Add 5-10 parts by weight of intermediate 1 and 8-12 parts by weight of chloroacetic acid to N,N-dimethylformamide solvent, stir evenly, carry out quaternization reaction, heat to 55-70° C. and react for 5-8 hours, and then perform vacuum distillation after reaction, wash with acetone, and obtain carboxylated silane; (4) Add carboxylated silane and ε-caprolactone-modified 1,2-hexanediol into N,N-dimethylformamide solvent, stir and mix, then add p-toluenesulfonic acid catalyst, react at 65-80°C for 7-9h, distill, filter and wash after reaction to obtain quaternary ammonium silicone oil.

3. The nanomaterial-containing toothpaste according to claim 2, characterized in that: The mass ratio of 1,2-hexanediol, ε-caprolactone and dibutyltin diosilicate catalyst in (1) is 1:1.2-1.5:0.01-0.

03.

4. The toothpaste containing nanomaterials according to claim 2, characterized in that: The mass ratio of di(dimethylamino)methylvinylsilane, hydrogenated silicone oil and chloroplatinic acid catalyst in (2) is 0.8-1.2:1:0.02-0.

03.

5. The toothpaste containing nanomaterials according to claim 2, characterized in that: The mass ratio of carboxylated silane, ε-caprolactone modified 1,2-hexanediol and p-toluenesulfonic acid catalyst in (4) is 1.1-1.4:1:0.02-0.

04.

6. The toothpaste containing nanomaterials according to claim 1, characterized in that: The preparation method of the quaternized chitosan comprises: adding 5-14 parts by weight of chitosan to an acetic acid solvent for dissolving, heating in a water bath at 60-90° C., adding 7-15 parts by weight of 2,3-epoxypropyltrimethylammonium chloride at a constant pressure for reaction, washing with anhydrous ethanol after the reaction, drying, dialyzing and concentrating to obtain the quaternized chitosan.

7. The toothpaste containing nanomaterials according to claim 6, characterized in that: The reaction time is 5-8h.

8. A method for preparing a toothpaste containing nanomaterials according to any one of claims 1 to 7, characterized in that: The preparation method of the toothpaste containing nano materials comprises the following steps: adding vitamin C, carrageenan, polyethylene glycol, xylitol sweetener, mint flavor, sodium phytate tooth whitening agent, sorbitol, quaternary ammonium silicone oil, quaternary ammonium chitosan, nano silicon dioxide and deionized water into a stirrer, stirring for 10-15 minutes, vacuum degassing, and obtaining the toothpaste containing nano materials after completion.

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