CN113499767A - Visible light catalytic modified titanium dioxide and preparation method and application thereof - Google Patents
Visible light catalytic modified titanium dioxide and preparation method and application thereof Download PDFInfo
- Publication number
- CN113499767A CN113499767A CN202110684501.6A CN202110684501A CN113499767A CN 113499767 A CN113499767 A CN 113499767A CN 202110684501 A CN202110684501 A CN 202110684501A CN 113499767 A CN113499767 A CN 113499767A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- tooth whitening
- visible light
- gel
- modified titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 230000002087 whitening effect Effects 0.000 claims abstract description 83
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 44
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 7
- 238000003837 high-temperature calcination Methods 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003381 stabilizer Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- RJHSCCZVRVXSEF-UHFFFAOYSA-N (2-hydroxyphenyl) benzoate Chemical group OC1=CC=CC=C1OC(=O)C1=CC=CC=C1 RJHSCCZVRVXSEF-UHFFFAOYSA-N 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- -1 5-tertiary butyl-4-hydroxyphenyl Chemical group 0.000 claims description 5
- 229940090898 Desensitizer Drugs 0.000 claims description 5
- 230000002745 absorbent Effects 0.000 claims description 5
- 239000002250 absorbent Substances 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 229960001631 carbomer Drugs 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical group [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 3
- 239000003349 gelling agent Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 claims description 3
- 229910001637 strontium fluoride Inorganic materials 0.000 claims description 3
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims description 2
- XGRSAFKZAGGXJV-UHFFFAOYSA-N 3-azaniumyl-3-cyclohexylpropanoate Chemical compound OC(=O)CC(N)C1CCCCC1 XGRSAFKZAGGXJV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- 239000003975 dentin desensitizing agent Substances 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229960004711 sodium monofluorophosphate Drugs 0.000 claims description 2
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract description 3
- 239000000499 gel Substances 0.000 description 58
- 238000003860 storage Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 208000024891 symptom Diseases 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 208000030533 eye disease Diseases 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/042—Gels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/22—Peroxides; Oxygen; Ozone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
- A61K8/347—Phenols
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
- A61K8/375—Esters of carboxylic acids the alcohol moiety containing more than one hydroxy group
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/413—Nanosized, i.e. having sizes below 100 nm
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
- A61K2800/81—Preparation or application process involves irradiation
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Cosmetics (AREA)
Abstract
The invention relates to a tooth whitening technology, in particular to visible light catalytic modified titanium dioxide and a preparation method and application thereof. Butyl titanate and bismuth nitrate are subjected to sol-gel reaction in a low-boiling-point organic solvent, and then the bismuth-doped titanium dioxide with a spherical structure is obtained by high-temperature calcination. The nano-modified titanium dioxide is applied to a tooth whitening gel. The tooth whitening gel prepared by the invention utilizes the photocatalytic activity of the nano modified titanium dioxide, generates strong-oxidative electron holes by assisting the illumination of visible light, and the electron holes can also be used for synergistically catalyzing and decomposing hydrogen peroxide to generate hydroxyl radicals (OH), so that the catalytic activity of the hydrogen peroxide is improved, and the electron holes and the OH can obviously improve the tooth whitening effect.
Description
Technical Field
The invention relates to a tooth whitening technology, in particular to visible light catalytic modified titanium dioxide and a preparation method and application thereof.
Background
The whitening gel is a tooth whitening technology popular in Europe and America, high-intensity blue light with the wavelength of 480-520 nm is irradiated on hydrogen peroxide gel, hydrogen peroxide is decomposed to generate oxidation species with strong oxidation activity, such as hydroxyl free radical (OH), the oxidation potential of OH is as high as 2.8V, yellow pigment and melanin deposited on teeth can be oxidized, and the whitening effect is achieved. Although whitening gel technology is well established, there are still some problems with the currently marketed cold light tooth whitening products. Firstly, the oxidation efficiency of the whitening gel is not high, and good whitening effect can be obtained only by prolonging the illumination time; secondly, when high-energy blue light is used as an excitation light source, eye splash and dazzling can be caused, and even the probability of eye diseases is increased; meanwhile, the whitening gel has the defects of short storage period, and during storage and production, visible light can accelerate the decomposition of hydrogen peroxide, so that the storage time of the whitening gel is shortened.
Therefore, it is an urgent problem to develop a tooth whitening gel which can catalyze oxidation by mild light, for example, light, and generate OH in cooperation with decomposition of hydrogen peroxide, and to prolong the storage time of the whitening gel, thereby improving the safety and reliability of the tooth whitening technology.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide modified titanium dioxide containing visible light catalytic activity.
The invention also aims to provide a preparation process of the nano modified titanium dioxide with visible light catalytic activity and a preparation process of the light absorbent.
The invention also aims to provide the application of the nano modified titanium dioxide with the photocatalytic activity in preparing the luminescent tooth whitening gel.
In order to achieve the purpose, the invention adopts the technical scheme that:
a visible light catalytic modified titanium dioxide is prepared by performing sol-gel reaction on butyl titanate and bismuth nitrate in a low-boiling-point organic solvent, and then calcining at high temperature to obtain the bismuth-doped titanium dioxide with a spherical structure.
The molar ratio of the butyl titanate to the bismuth nitrate is 1: 3-1: 10 (preferably 1:5), and the organic solvent is any one or more of acetone, methyl ethyl ketone, absolute ethyl alcohol and cyclohexanone.
A preparation method of visible light photocatalytic modified titanium dioxide comprises the steps of dropwise adding butyl titanate into a mixed solution of a low-boiling-point organic solvent and bismuth nitrate to perform sol-gel reaction for 5-10 hours (preferably 8 hours), then performing vacuum drying, and calcining for 1-2 hours (preferably 1.5 hours) at 500 ℃ -700 ℃ (preferably 600 ℃) to obtain the spherical structure bismuth-doped titanium dioxide.
A preparation method of visible light catalytic modified titanium dioxide, and application of the visible light catalytic modified titanium dioxide in preparing tooth whitening gel.
A tooth whitening gel comprises the following components in parts by weight: the visible light catalytic modified titanium dioxide as claimed in claim 1, wherein the visible light catalytic modified titanium dioxide comprises 1-5 parts, 0.01-0.5 part, 1-3 parts of a gelling agent, 20-35 parts of 30% hydrogen peroxide, 0.1-2 parts of a desensitizer, 0.1-0.5 part of an auxiliary agent, 10-30 parts of an alkali solution and 80-300 parts of deionized water.
Further, the composition comprises the following components in parts by weight: the visible light catalytic modified titanium dioxide as claimed in claim 1, wherein the visible light catalytic modified titanium dioxide comprises 1.5 parts, 0.30 part of stabilizer, 1.4 parts of gelling agent, 25 parts of 30% hydrogen peroxide, 0.5 part of desensitizer, 1.0 part of auxiliary agent, 10 parts of alkaline solution and 85 parts of deionized water.
The stabilizer is prepared from an antioxidant and a light absorbent in a mass ratio of 1: 5-1: 10 (preferably 1:7), wherein the antioxidant is 2, 6-tertiary butyl-4-methylphenol and/or bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether, and the light absorber is catechol monobenzoate.
The catechol monobenzoate is prepared from benzoyl chloride and catechol serving as raw materials through an esterification reaction, wherein the molar ratio of the benzoyl chloride to the catechol is 1: 1-3: 1; the pH value of the reaction system is 6.5-8.5; the reaction temperature is 25-35 ℃; the reaction time is 1.5-3 h.
The gel is carbomer and/or carboxymethyl cellulose; desensitizing agent is calcium fluoride, sodium monofluorophosphate, strontium fluoride or strontium acetate; the alkali solution is sodium hydroxide and/or triethanolamine; the auxiliary agent is disodium ethylene diamine tetraacetate, glycerol or polyethylene glycol.
The preparation method of the tooth whitening gel comprises the following steps:
1) adding the gel into deionized water according to the proportion, soaking, adding an auxiliary agent, and performing ultrasonic dispersion to obtain a mixture A;
2) adding a stabilizer into the mixture A, uniformly stirring, adding the nano modified titanium dioxide, and uniformly mixing to obtain a mixture B;
3) adding 30% hydrogen peroxide into the mixture B, mixing uniformly, adding desensitizer and stabilizer, and adjusting pH with alkali solution to obtain mixture C, i.e. tooth whitening gel.
The tooth whitening gel is smeared on teeth, is irradiated by LED visible light, and generates oxidized electron holes through the illumination of nano modified titanium dioxide, the electron holes can catalyze hydrogen peroxide to generate hydroxyl free radicals (OH) with strong oxidizing property, and the electron holes and the OH realize the tooth whitening through the cooperation; the wavelength of the LED visible light is 400-800 nm, and the irradiation time is 30-60 min.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the technical progress that:
1. the bismuth-doped nano titanium dioxide prepared by the method can be excited by visible light to generate an electron hole with strong oxidizing property, and the electron hole can realize the oxidation and whitening effects on pigments on the surface of teeth.
2. The modified nano titanium dioxide is used as a main component in the tooth whitening gel, so that electron holes generated by visible light irradiation can be used for catalytically decomposing hydrogen peroxide to generate OH with strong oxidizing property (the oxidizing potential of OH is as high as 2.8V), the catalytic oxidation activity of hydrogen peroxide on teeth is improved, and the tooth whitening effect is enhanced.
3. A small amount of antioxidant and light absorbent are added into the tooth whitening gel as stabilizers, so that decomposition of hydrogen peroxide in the production and storage processes of the whitening gel can be effectively reduced on the premise that whitening is realized, and the storage time of the whitening gel is effectively prolonged.
4. The invention adopts the LED visible light when realizing tooth whitening, and compared with blue light and ultraviolet light, the visible light energy is small and milder, and the irritation to eyes and skin is small, so the use is safer.
5. The preparation and application process method is simple and safe, convenient to operate, low in equipment requirement and suitable for industrial production.
Drawings
FIG. 1 is an XPS spectrum of nano-modified titanium dioxide prepared in example 1 of the present invention.
FIG. 2 is a TEM photograph of nano-modified titanium dioxide prepared in example 1 of the present invention.
Fig. 3 is a change curve of hydrogen peroxide in a whitening gel provided by an embodiment of the present invention when illuminated by LED visible light, wherein a is the whitening gel prepared in embodiment 1, b: whitening gel prepared in example 2.
Fig. 4 is a change curve of hydroxyl radical (& OH) of the whitening gel provided by the embodiment of the invention when the gel is irradiated by LED visible light, wherein, a is the whitening gel prepared in the embodiment 1, b: whitening gel prepared in example 2.
Fig. 5 is a photograph of a filled tooth whitening gel according to an embodiment of the present invention.
Fig. 6 is a photograph showing the variation of the whitening gel applied to the teeth according to the embodiment of the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples, which are to be construed as merely illustrative, and not limitative of the remainder of the disclosure.
Example 1 Cold light tooth whitening gel, preparation method and application
Preparation of nano modified titanium dioxide and light absorbent
Slowly and dropwise adding 9mL of butyl titanate into a mixed solution of 200mL of absolute ethyl alcohol and 5g of bismuth nitrate, putting the mixed solution into a water bath kettle at 85 ℃ after dripping, mechanically stirring the mixed solution for 6 hours to evaporate the solvent, then drying the mixed solution in vacuum at 80 ℃, putting the dried mixed solution into a crucible with a cover after grinding, and burning the dried mixed solution for 2 hours at 600 ℃ to obtain Bi modified nano titanium dioxide powder (the XPS picture of the Bi modified nano titanium dioxide powder is shown in figure 1, and the TEM picture of an electron projection electron microscope is shown in figure 2).
As can be seen from FIG. 1, the Bi element has been successfully doped into the nano titanium dioxide by the sol-gel method. Bi can reduce the forbidden bandwidth of the titanium dioxide and improve the visible light catalytic activity of the titanium dioxide. Fig. 2 is a TEM photograph of the Bi-modified nano titania, which shows that the prepared Bi-modified nano titania has a spherical structure, the spherical structure has a higher specific surface area, a larger contact area with visible light, and a stronger photocatalytic activity.
Adding 25g of catechol and 200g of water into a three-neck flask with a dropping funnel, a condenser and a thermometer, stirring to dissolve, then simultaneously adding 10g of benzoyl chloride and 0.1g of NaOH into the flask, controlling the reaction temperature to be 30 ℃, the pH value to be 8.0, reacting for 2h, performing suction filtration after the reaction is finished, washing for 3 times with water, and drying to obtain the light absorbing agent catechol monobenzoate.
② tooth whitening gel and preparation method thereof
1) Adding 0.5kg of carbomer and 0.2kg of carboxymethyl cellulose into 32kg of deionized water, soaking and completely swelling, adding 0.5kg of glycerol and 0.1kg of disodium ethylene diamine tetraacetate, and uniformly stirring to obtain a mixture A1;
2) adding 0.5kg of the Bi modified nano titanium dioxide powder into the mixture A1 under the condition of keeping stirring, and uniformly stirring to obtain a mixture B1;
3) adding 15kg of 30% hydrogen peroxide into the mixture B1, then sequentially adding 0.1kg of strontium fluoride, 0.05kg of bis (3, 5-tertiary butyl-4-hydroxyphenyl) sulfide and 0.1kg of the catechol monobenzoate prepared above, stirring at room temperature of 200r/min for 4h, uniformly mixing, adding 6kg of 10% triethanolamine aqueous solution, detecting the pH value, adjusting the pH value to 7.0, and completely thickening carbomer to obtain a mixture C1, thus obtaining the tooth whitening gel; the visible light tooth whitening gel prepared above was irradiated with LED visible light, and the change of hydrogen peroxide and. OH in the visible light was detected, and the change results are shown in fig. 3 and 4.
Filling the tooth whitening gel into a PVC tube, and packaging to obtain a commercially available visible light tooth whitening gel, and storing in dark (see figure 5).
Use of cold light tooth whitening gel
100 subjects were selected and randomly divided into two groups, one group was coated with the tooth whitening gel prepared in example 1, and the other group was coated with a commercially available cold light tooth whitening gel;
a1) the tooth whitening gel prepared in example 1 was applied to the teeth of 50 subjects, respectively, at a thickness of 0.5mm, and irradiated with LED visible light for 35min, so that the tooth whitening was accomplished once a day for ten consecutive days. Significant whitening effect was achieved compared to untreated teeth, and no discomfort symptoms appeared. Wherein a typical tooth whitening effect trend is shown in fig. 6.
a2) The conventional cold light tooth whitening gel (purchased from Novashine) was applied to the teeth of another 50 subjects at a thickness of 0.5mm, and irradiated with LED visible light for 35min, and thus applied once a day for ten consecutive days to complete tooth whitening. Compared with the untreated product, 28 persons have remarkable whitening effect, and 22 persons have no tooth whitening effect, wherein 2 persons have tooth bleeding and pain symptoms, and 1 person has eye flower and dazzling symptoms.
Example 2
The tooth whitening gel, the preparation method and the application are substantially the same as those of the example 1, except that the calcination temperature is 500 ℃ when the modified nano titanium dioxide powder is prepared, the visible light tooth whitening gel prepared above is irradiated by the LED visible light, the change of hydrogen peroxide and OH in the visible light tooth whitening gel is detected, and the change result is shown in fig. 3 and 4. Meanwhile, the application process of the embodiment 2 is the same as that of the embodiment 1, and the trial results are detailed in table 1.
As can be seen from fig. 3 and 4, in the process of preparing the nano modified titanium dioxide, the calcination temperature is different, and the detected concentrations of hydrogen peroxide and OH are different in the process of irradiating the whitening gel. Wherein, when the calcining temperature is 600 ℃, the concentration of hydrogen peroxide and OH is higher, and the whitening effect on teeth is better.
Example 3
The tooth whitening gel, the preparation method and the application are basically the same as those of the tooth whitening gel in the example 1, except that the addition amount of triethanolamine in the preparation process of the whitening gel is 0.5kg, the application process of the example 3 is the same as that of the example 1, and the test results are detailed in the table 1.
Comparative examples 1-2 tooth whitening gel, preparation method and application
Comparative examples 1-2 the process for preparing the tooth whitening gel is shown in example 1, but the difference is only in the difference of the preparation process parameters of the whitening gel, wherein the nano modified titanium dioxide is not added in the comparative example 1, the stabilizing agent is not added in the comparative example 2, the application process of the nano modified titanium dioxide and the stabilizing agent is the same as that of the example 1, and the trial results are shown in table 1.
Table 1 shows the results of different tooth whitening gels
The results show that the whitening gel product provided by the invention can generate an oxidation cavity through visible light excitation, the oxidation cavity can catalyze hydrogen peroxide to generate hydroxyl free radical OH, the oxidation cavity and the OH can synergistically enhance the whitening effect of the gel on teeth, the gel storage time can last for more than 18 months, the gel is in a gel state before and after storage, and the product is green and environment-friendly; the comparative example has no obvious tooth whitening effect, poor storage stability and water dissolving phenomenon; the commercial product has uncomfortable symptoms, has no obvious tooth whitening effect on the tested person, and only has the tooth whitening effect on 28 tested persons.
It should be noted that the above-mentioned embodiments are only for illustrating the technical concept and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and to implement the same, and any person skilled in the art may use the above-mentioned technical concept as a teaching to make changes or modifications to the equivalent embodiments, but all simple modifications, equivalents and modifications made to the above-mentioned embodiments do not depart from the technical spirit of the present invention, and still fall within the scope of the present invention claimed.
Claims (10)
1. A visible light catalytic modified titanium dioxide is characterized in that: butyl titanate and bismuth nitrate are subjected to sol-gel reaction in a low-boiling-point organic solvent, and then the bismuth-doped titanium dioxide with a spherical structure is obtained by high-temperature calcination.
2. The visible-light-catalytically modified titanium dioxide as claimed in claim 1, wherein: the molar ratio of the butyl titanate to the bismuth nitrate is 1: 3-1: 10, and the organic solvent is any one or more of acetone, methyl ethyl ketone, absolute ethyl alcohol and cyclohexanone.
3. A method for preparing the visible light catalytic modified titanium dioxide according to claim 1, which is characterized in that: dropwise adding butyl titanate into a mixed solution of a low-boiling-point organic solvent and bismuth nitrate to perform sol-gel reaction for 5-10 h, then performing vacuum drying, and calcining at 500-700 ℃ for 1-2h to obtain the bismuth-doped titanium dioxide with the spherical structure.
4. A method for preparing the visible light catalytic modified titanium dioxide according to claim 1, which is characterized in that: the visible light catalytic modified titanium dioxide is applied to preparing the tooth whitening gel.
5. A tooth whitening gel characterized by: the composition comprises the following components in parts by weight: the visible light catalytic modified titanium dioxide as claimed in claim 1, wherein the visible light catalytic modified titanium dioxide comprises 1-5 parts, 0.01-0.1 part, 2-3 parts of a gelling agent, 25-35 parts of 30% hydrogen peroxide, 0.1-2 parts of a desensitizer, 0.1-0.5 part of an auxiliary agent, 20-30 parts of an alkali solution and 80-300 parts of deionized water.
6. The tooth whitening gel of claim 5, wherein: the stabilizer is prepared from an antioxidant and a light absorbent in a mass ratio of 1: 5-1: 10, wherein the antioxidant is 2, 6-tertiary butyl-4-methylphenol and/or bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether, and the light absorber is catechol monobenzoate.
7. The tooth whitening gel of claim 6, wherein: the catechol monobenzoate is prepared from benzoyl chloride and catechol serving as raw materials through an esterification reaction, wherein the molar ratio of the benzoyl chloride to the catechol is 1: 1-3: 1; the pH value of the reaction system is 6.5-8.5; the reaction temperature is 25-35 ℃; the reaction time is 1.5-3 h.
8. The tooth whitening gel of claim 5, wherein: the gel is carbomer and/or carboxymethyl cellulose; desensitizing agent is calcium fluoride, sodium monofluorophosphate, strontium fluoride or strontium acetate; the alkali solution is sodium hydroxide and/or triethanolamine; the auxiliary agent is disodium ethylene diamine tetraacetate, glycerol or polyethylene glycol.
9. The method of preparing a tooth whitening gel according to claim 5, characterized in that:
1) adding the gel into deionized water according to the proportion, soaking, adding an auxiliary agent, and performing ultrasonic dispersion to obtain a mixture A;
2) adding a stabilizer into the mixture A, uniformly stirring, adding the nano modified titanium dioxide, and uniformly mixing to obtain a mixture B;
3) adding 30% hydrogen peroxide into the mixture B, mixing uniformly, adding desensitizer and stabilizer, and adjusting pH with alkali solution to obtain mixture C, i.e. tooth whitening gel.
10. A method of preparing a tooth whitening gel according to claim 9, characterized in that: the tooth whitening gel is smeared on teeth and is irradiated by LED visible light to whiten the teeth; the wavelength of the LED visible light is 400-800 nm, and the irradiation time is 30-60 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110684501.6A CN113499767B (en) | 2021-06-21 | 2021-06-21 | Visible light catalytic modified titanium dioxide and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110684501.6A CN113499767B (en) | 2021-06-21 | 2021-06-21 | Visible light catalytic modified titanium dioxide and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113499767A true CN113499767A (en) | 2021-10-15 |
| CN113499767B CN113499767B (en) | 2024-03-15 |
Family
ID=78010358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110684501.6A Active CN113499767B (en) | 2021-06-21 | 2021-06-21 | Visible light catalytic modified titanium dioxide and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113499767B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114983849A (en) * | 2022-01-10 | 2022-09-02 | 宁波楚月新材料科技有限公司 | Single-component visible light catalysis tooth whitening gel with low hydrogen peroxide concentration as well as preparation and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101653725A (en) * | 2009-09-17 | 2010-02-24 | 三峡大学 | Bismuth-doped nano titanium dioxide catalyst and preparation method thereof |
| KR20140142886A (en) * | 2013-06-05 | 2014-12-15 | 주식회사 비에스앤코 | Bleaching Composition of teeth which is used with visible light |
| CN109998933A (en) * | 2019-03-04 | 2019-07-12 | 西安蓝极医疗电子科技有限公司 | A kind of tooth whitening gel and preparation method thereof, application method |
| CN111494230A (en) * | 2020-04-30 | 2020-08-07 | 江西师范大学 | Cold light tooth whitening gel, preparation method and application |
| CN112402266A (en) * | 2020-11-06 | 2021-02-26 | 陈宇 | Dissolvable oral whitening biological film tooth paste |
-
2021
- 2021-06-21 CN CN202110684501.6A patent/CN113499767B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101653725A (en) * | 2009-09-17 | 2010-02-24 | 三峡大学 | Bismuth-doped nano titanium dioxide catalyst and preparation method thereof |
| KR20140142886A (en) * | 2013-06-05 | 2014-12-15 | 주식회사 비에스앤코 | Bleaching Composition of teeth which is used with visible light |
| CN109998933A (en) * | 2019-03-04 | 2019-07-12 | 西安蓝极医疗电子科技有限公司 | A kind of tooth whitening gel and preparation method thereof, application method |
| CN111494230A (en) * | 2020-04-30 | 2020-08-07 | 江西师范大学 | Cold light tooth whitening gel, preparation method and application |
| CN112402266A (en) * | 2020-11-06 | 2021-02-26 | 陈宇 | Dissolvable oral whitening biological film tooth paste |
Non-Patent Citations (4)
| Title |
|---|
| 《合成材料助剂手册》编写组编: "《合成材料助剂手册》", vol. 2, 石油化学工业出版社, pages: 504 - 505 * |
| 丁欣宇等: "铋掺杂纳米TiO2的制备及其光电催化性能", vol. 9, no. 6, pages 1 * |
| 桑换新等: "Bi掺杂纳米TiO2光催化甘油水溶液制氢性能研究", 《无机材料学报》, vol. 27, no. 12, pages 1 * |
| 邹浩等: "Bi2O3/TiO2复合光催化剂对甲基橙的光催化作用", vol. 36, no. 9 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114983849A (en) * | 2022-01-10 | 2022-09-02 | 宁波楚月新材料科技有限公司 | Single-component visible light catalysis tooth whitening gel with low hydrogen peroxide concentration as well as preparation and application thereof |
| WO2023130629A1 (en) * | 2022-01-10 | 2023-07-13 | 宁波楚月新材料科技有限公司 | Single-component visible-light-catalyzed teeth whitening gel having low hydrogen peroxide concentration, and preparation and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113499767B (en) | 2024-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5032178A (en) | Dental composition system and method for bleaching teeth | |
| RU2694936C1 (en) | Core-shell type silicon dioxide particles and uses thereof as antibacterial agent | |
| US7326055B2 (en) | Method for bleaching teeth and bleaching agent for teeth | |
| CN111494230B (en) | Cold light tooth whitening gel, preparation method and application | |
| CN111759751B (en) | Whitening toothpaste excited by blue light LED and preparation method thereof | |
| CA2261741A1 (en) | Chlorine dioxide tooth whitening compositions | |
| CN113499767B (en) | Visible light catalytic modified titanium dioxide and preparation method and application thereof | |
| CN106726648A (en) | A kind of nano photo-catalytic tooth whitening gel | |
| JP2016507584A (en) | Tooth whitening composition | |
| EP1669059B1 (en) | Photocatalytic bleaching agent for teeth based on bismuth vanadate and bleaching method | |
| EP1824445A1 (en) | Teeth whitening agents | |
| DE102009032410A1 (en) | Producing a discolored solution of sodium aluminate comprises heat treating a suspension comprising solid magnesium oxide and sodium aluminate solution, and a suspension comprising solid magnesium oxide at a specific temperature | |
| CN113350211A (en) | Fenton composition, preparation method and application in preparation of tooth whitening products | |
| KR101735564B1 (en) | Whitening Agent Composition and Method for Preparing the Same | |
| US20080246000A1 (en) | Bleaching Composition | |
| EP3050553A1 (en) | Composition for dental whitening | |
| KR102508774B1 (en) | Non-aqueous gel composition for water treatment with improved oxidation stability of vitamin C | |
| CN114983849B (en) | Single-component low-hydrogen-peroxide-concentration visible light catalytic tooth whitening gel and preparation and application thereof | |
| WO2009133525A2 (en) | Composition for dental bleaching | |
| MX2014000326A (en) | Indicator for oxygen generation. | |
| KR101735566B1 (en) | Dental Bleaching Composition and Method for Preparing the Same | |
| CN114671463B (en) | Mesoporous Kong Zhaidai-gap titanium oxide nanosphere and preparation method and application thereof | |
| CN115363049B (en) | Preparation method of nanocomposite and product thereof | |
| JP6376748B2 (en) | Teeth bleaching material composition and tooth bleaching method | |
| JP2002326910A (en) | Bleaching composition and method for bleaching tooth |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |