CN116196222A - Caries preventing additive, caries preventing material, dental diaphragm and invisible appliance - Google Patents
Caries preventing additive, caries preventing material, dental diaphragm and invisible appliance Download PDFInfo
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- CN116196222A CN116196222A CN202310176448.8A CN202310176448A CN116196222A CN 116196222 A CN116196222 A CN 116196222A CN 202310176448 A CN202310176448 A CN 202310176448A CN 116196222 A CN116196222 A CN 116196222A
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- caries
- prepared
- carbonate
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- 208000002925 dental caries Diseases 0.000 title claims abstract description 157
- 230000003405 preventing effect Effects 0.000 title claims abstract description 155
- 239000000654 additive Substances 0.000 title claims abstract description 98
- 230000000996 additive effect Effects 0.000 title claims abstract description 98
- 239000000463 material Substances 0.000 title claims abstract description 60
- 150000001875 compounds Chemical class 0.000 claims abstract description 64
- 238000001035 drying Methods 0.000 claims abstract description 56
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 55
- 238000010438 heat treatment Methods 0.000 claims abstract description 53
- 238000003756 stirring Methods 0.000 claims abstract description 40
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 37
- 238000009830 intercalation Methods 0.000 claims abstract description 36
- 230000002687 intercalation Effects 0.000 claims abstract description 36
- 239000007864 aqueous solution Substances 0.000 claims abstract description 27
- 238000001914 filtration Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 27
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 18
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 17
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 17
- 239000011261 inert gas Substances 0.000 claims abstract description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 83
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 72
- 239000011347 resin Substances 0.000 claims description 51
- 229920005989 resin Polymers 0.000 claims description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- -1 iron ion Chemical class 0.000 claims description 42
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 40
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 36
- 239000012266 salt solution Substances 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 30
- 239000003513 alkali Substances 0.000 claims description 28
- 239000000725 suspension Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- 239000011775 sodium fluoride Substances 0.000 claims description 20
- 235000013024 sodium fluoride Nutrition 0.000 claims description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 13
- 230000003179 granulation Effects 0.000 claims description 13
- 238000005469 granulation Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 8
- 230000000675 anti-caries Effects 0.000 claims description 6
- 239000011698 potassium fluoride Substances 0.000 claims description 6
- 235000003270 potassium fluoride Nutrition 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001422 barium ion Inorganic materials 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000002265 prevention Effects 0.000 claims 1
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 30
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 27
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 27
- 239000011777 magnesium Substances 0.000 description 18
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 8
- 229960001545 hydrotalcite Drugs 0.000 description 8
- 229910001701 hydrotalcite Inorganic materials 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 3
- ICXVJVVYSULERR-UHFFFAOYSA-L dichlorozinc hexahydrate Chemical compound O.O.O.O.O.O.Cl[Zn]Cl ICXVJVVYSULERR-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 3
- 229910052586 apatite Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 208000025157 Oral disease Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001013 cariogenic effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005115 demineralization Methods 0.000 description 1
- 230000002328 demineralizing effect Effects 0.000 description 1
- 208000019786 dental pulp disease Diseases 0.000 description 1
- WSUTUEIGSOWBJO-UHFFFAOYSA-N dizinc oxygen(2-) Chemical compound [O-2].[O-2].[Zn+2].[Zn+2] WSUTUEIGSOWBJO-UHFFFAOYSA-N 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 208000030194 mouth disease Diseases 0.000 description 1
- 208000028169 periodontal disease Diseases 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C7/00—Orthodontics, i.e. obtaining or maintaining the desired position of teeth, e.g. by straightening, evening, regulating, separating, or by correcting malocclusions
- A61C7/08—Mouthpiece-type retainers or positioners, e.g. for both the lower and upper arch
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/50—Preparations specially adapted for dental root treatment
- A61K6/52—Cleaning; Disinfecting
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
- A61K6/69—Medicaments
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- A61K6/893—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
Landscapes
- Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Cosmetics (AREA)
Abstract
The invention provides a caries preventing additive, a caries preventing material, a dental diaphragm and an invisible appliance, wherein the caries preventing additive is prepared by the following method: step 1, preparing a compound with a structural general formula [ M ] II (1‑x) M III x (OH) 2 ] x+ (CO 3 2‑ ) x/2 ·mH 2 O carbonate intercalation hydrotalcite-like compound of 0.2<x<0.33，M II Represents divalent metal ions, M III Represents trivalent metal ions; step 2, calcining the hydrotalcite-like compound intercalated by carbonate to obtain double goldA metal hydroxide; and step 3, adding the double metal hydroxide into the fluoride aqueous solution, heating and stirring under the protection of inert gas, and filtering, washing, drying and crushing after the reaction is finished to obtain the fluoride ion intercalated hydrotalcite-like compound.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a caries preventing additive, a caries preventing material, a dental diaphragm and an invisible appliance.
Background
The invisible appliance is gradually replacing the traditional bracket appliance, and the invisible appliance is mainly made of PET, PETG, TPU and the like. The change in the appliance diaphragm material can provide a longer lasting appliance force and more comfort. However, wearing the invisible appliance still has a certain influence on the oral environment, and oral diseases such as carious teeth, periodontal disease, dental pulp disease and the like are easily caused. Currently, the existing invisible appliances on the market have little effect of preventing and treating dental caries.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a caries preventing additive, caries preventing material, dental film and invisible appliance having a stable and durable caries preventing effect.
The invention provides an anti-caries additive, which is characterized in that the anti-caries additive is prepared by the following method:
step 1, preparing a compound with a structural general formula [ M ] II (1-x) M III x (OH) 2 ] x+ (CO 3 2- ) x/2 ·mH 2 O carbonate intercalation hydrotalcite-like compound of 0.2<x<0.33，M II Represents divalent metal ions, M III The preparation method of hydrotalcite-like compound representing trivalent metal ions and carbonate intercalation comprises the following steps:
step 1-1, dissolving divalent metal ion salt and trivalent metal ion salt in water to form clear and transparent mixed salt solution,
step 1-2, dissolving carbonate and hydroxide in water to form clear and transparent mixed alkali solution,
step 1-3, dropwise adding the mixed salt solution prepared in the step 1-1 into the mixed alkali solution prepared in the step 1-2, continuously stirring in the dropwise adding process to obtain a suspension, heating the suspension, performing hydrothermal reaction at a constant temperature, filtering, washing, drying and crushing after the reaction is completed to obtain the carbonate intercalation hydrotalcite-like compound,
wherein the added substances of divalent metal ion salt, trivalent metal ion salt, carbonate and hydroxide are M in the structural general formula of hydrotalcite-like compound intercalated by carbonate II 、M III 、OH - And CO 3 2- Atomic number ratio (1-x): x:2: x/2 addition;
step 2, calcining the carbonate intercalation hydrotalcite-like compound prepared in the step 1 to obtain a double metal hydroxide;
and 3, adding the double metal hydroxide prepared in the step 2 into the fluoride aqueous solution, heating and stirring under the protection of inert gas, and filtering, washing, drying and crushing after the reaction is finished to obtain the fluoride ion intercalated hydrotalcite-like compound.
Further, in the caries preventing additive provided by the present invention, it may also have such a feature that: the carbonate is sodium carbonate or potassium carbonate;
the hydroxide is sodium hydroxide or potassium hydroxide;
the divalent metal ion is any one of magnesium ion, calcium ion, barium ion, copper ion, zinc ion and ferrous ion;
the trivalent metal ion is any one of iron ion, aluminum ion, cobalt ion and cerium ion;
the fluoride is any one of sodium fluoride, potassium fluoride and ammonium fluoride.
Further, in the caries preventing additive provided by the present invention, it may also have such a feature that: in the step 1-3, the temperature of the mixed salt solution is 20-60 ℃ when the mixed salt solution is dripped into the mixed alkali solution, the suspension is heated to 100-160 ℃ for hydrothermal reaction, and the time of the hydrothermal reaction is 6-48 h.
Further, in the caries preventing additive provided by the present invention, it may also have such a feature that: the calcination temperature in step 2 is 400-700 ℃.
Further, in the caries preventing additive provided by the present invention, it may also have such a feature that: the reaction temperature in the step 3 is 50-100 ℃, the reaction time is 12-24h, and the ratio of the molar mass of fluoride in the aqueous solution of fluoride to the molar mass of carbonate in the step 1-2 is (2+/-0.2): 1. the fluoride concentration is not limited as long as it is a clear and transparent solution.
The invention also provides a caries preventing material, which is characterized in that: the caries preventing material is prepared from TPU and the caries preventing additive.
Further, in the caries preventing material provided by the present invention, it may also have such a feature that: the preparation method of the caries preventing material comprises the following steps:
step 1, putting TPU resin into an oven, heating to 70-90 ℃, and drying for 4-8 hours to obtain dried TPU resin;
step 2, placing the caries preventing additive according to claim 6 into an oven, heating to 180-250 ℃, and drying for 12-24 hours to obtain a dried caries preventing additive;
and 3, adding the dried TPU resin and the dried caries preventing additive into a stirrer, uniformly stirring, discharging, adding into a double-screw extruder, and performing melt extrusion granulation to obtain the caries preventing material. Specifically, the TPU resin and the caries preventing additive are set according to the required fluorine ion content.
The invention also provides a dental diaphragm, which is characterized in that: the dental diaphragm is prepared from the caries preventing material.
The invention also provides an invisible appliance, which is characterized in that: the tooth invisible appliance is prepared from the dental diaphragm.
The invention has the following advantages:
the caries preventing material of the present invention makes the TPU film possess certain caries preventing effect through introducing fluoride ion intercalated hydrotalcite. Because the fluoride ion intercalated hydrotalcite is unstable, the hydrotalcite is easy to exchange with other ions in the environment and replace, so that a certain amount of fluoride ions are released. A small amount of fluoride can accelerate the formation of apatite in the hard tissue of the tooth body, and the stability of the apatite is improved; fluorine can reduce the solubility of enamel, promote remineralization of enamel, enable demineralization areas to form sediment, and promote caries repair and reconstruction; fluorine can inhibit the fermentation acidogenesis of cariogenic bacteria and reduce the corrosion to dental tissues, thereby preventing dental caries, and in addition, the content of fluorine in the caries preventing material is easy to grasp by adjusting the content of fluorine ion intercalated hydrotalcite in the caries preventing material due to the slow release property of the hydrotalcite for releasing fluorine ions, so that the health and safety of human bodies can be ensured.
The dental diaphragm is prepared from the caries preventing material, so that the dental diaphragm has stable and durable caries preventing effect.
The invisible appliance is prepared by adopting the dental film, so that the invisible appliance has stable and durable caries preventing effect.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement of the purposes and the effects achieved by the present invention easy to understand, the following examples illustrate the caries preventing additive, caries preventing material, dental film and invisible appliance of the present invention.
Example 1
The caries preventing additive is prepared by the following method:
step 1, preparing a structural formula Mg 0.8 Al 0.2 (OH) 2 (CO 3 ) 0.1 Hydrotalcite-like compounds intercalated with carbonates. Magnesium chloride hexahydrate, aluminum nitrate nonahydrate, potassium carbonate and potassium hydroxide are mixed according to the mole ratio of magnesium ions in magnesium chloride hexahydrate, aluminum ions in aluminum nitrate nonahydrate, carbonate ions in potassium carbonate and hydroxide ions in potassium hydroxide of Mg 2+ ：Al 3+ ：OH - ：CO 3 2- Feed was performed=0.8:0.2:2:0.1.
And step 1-1, dissolving magnesium chloride hexahydrate and aluminum nitrate nonahydrate in water to form a clear and transparent mixed salt solution.
And step 1-2, dissolving potassium carbonate and potassium hydroxide in water to form a clear and transparent mixed alkali solution.
And step 1-3, dropwise adding the mixed salt solution prepared in the step 1-1 into the mixed alkali solution prepared in the step 1-2 at the temperature of 30 ℃, continuously stirring in the dropwise adding process to obtain a suspension, heating the suspension to 120 ℃, performing hydrothermal reaction at the constant temperature, reacting for 12 hours, and filtering, washing, drying and crushing to obtain the carbonate intercalation hydrotalcite-like compound.
Step 2, calcining the carbonate intercalation hydrotalcite-like compound prepared in the step 1 at the temperature of 500 ℃ to obtain a double metal hydroxide;
and 3, adding the bimetal hydroxide prepared in the step 2 into a proper amount of sodium fluoride aqueous solution with the mass fraction of 2%, wherein the molar mass of fluoride ions in the sodium fluoride aqueous solution is equal to twice that of potassium carbonate in the step 1-2, heating to 80 ℃ under the protection of inert gas, stirring, reacting for 20 hours, and then filtering, washing, drying and crushing to obtain the fluoride ion intercalated hydrotalcite-like compound, and the product is denoted as a1.
Caries preventing material with caries preventing additive of 20% is prepared. The preparation process is as follows:
step 1, putting TPU resin into an oven, heating to 70 ℃, and drying for 4 hours to obtain dried TPU resin;
step 2, putting the caries preventing additive into a baking oven, wherein the adding amount of the caries preventing additive is one fourth of the adding amount of the TPU resin in the step 1, heating to 200 ℃, and drying for 12 hours to obtain a dried caries preventing additive;
and 3, adding the dried TPU resin and the dried caries preventing additive into a stirrer, uniformly stirring, discharging, adding into a double-screw extruder, and performing melt extrusion granulation to obtain the caries preventing material.
The caries preventing material is prepared into dental film.
The invisible appliance is prepared by adopting the dental diaphragm.
Example 2
The caries preventing additive is prepared by the following method:
step 1, preparing a structural formula Mg 0.75 Al 0.25 (OH) 2 (CO 3 ) 0.125 Hydrotalcite-like compounds intercalated with carbonates. Magnesium chloride hexahydrate, aluminum nitrate nonahydrate, potassium carbonate and potassium hydroxide are mixed according to the mole ratio of magnesium ions in magnesium chloride hexahydrate, aluminum ions in aluminum nitrate nonahydrate, carbonate ions in potassium carbonate and hydroxide ions in potassium hydroxide of Mg 2+ ：Al 3+ ：OH - ：CO 3 2- Feed was performed=0.75:0.25:2:0.125.
And step 1-1, dissolving magnesium chloride hexahydrate and aluminum nitrate nonahydrate in water to form a clear and transparent mixed salt solution.
And step 1-2, dissolving potassium carbonate and potassium hydroxide in water to form a clear and transparent mixed alkali solution.
And step 1-3, dropwise adding the mixed salt solution prepared in the step 1-1 into the mixed alkali solution prepared in the step 1-2 at the temperature of 30 ℃, continuously stirring in the dropwise adding process to obtain a suspension, heating the suspension to 120 ℃, performing hydrothermal reaction at the constant temperature, reacting for 12 hours, and filtering, washing, drying and crushing to obtain the carbonate intercalation hydrotalcite-like compound.
Step 2, calcining the carbonate intercalation hydrotalcite-like compound prepared in the step 1 at the temperature of 500 ℃ to obtain a double metal hydroxide;
and 3, adding the bimetal hydroxide prepared in the step 2 into a proper amount of sodium fluoride aqueous solution with the mass fraction of 2%, wherein the molar mass of fluoride ions in the sodium fluoride aqueous solution is equal to twice that of potassium carbonate in the step 1-2, heating to 80 ℃ under the protection of inert gas, stirring, reacting for 20 hours, and then filtering, washing, drying and crushing to obtain the fluoride ion intercalated hydrotalcite-like compound, and the product is denoted as a2.
Caries preventing material with caries preventing additive of 20% is prepared. The preparation process is as follows:
step 1, putting TPU resin into an oven, heating to 70 ℃, and drying for 4 hours to obtain dried TPU resin;
step 2, putting the caries preventing additive into a baking oven, wherein the adding amount of the caries preventing additive is one fourth of the adding amount of the TPU resin in the step 1, heating to 200 ℃, and drying for 12 hours to obtain a dried caries preventing additive;
and 3, adding the dried TPU resin and the dried caries preventing additive into a stirrer, uniformly stirring, discharging, adding into a double-screw extruder, and performing melt extrusion granulation to obtain the caries preventing material.
The caries preventing material is prepared into dental film.
The invisible appliance is prepared by adopting the dental diaphragm.
Example 3
The caries preventing additive is prepared by the following method:
step 1, preparing a structural formula Mg 0.67 Al 0.33 (OH) 2 (CO 3 ) 0.165 Hydrotalcite-like compounds intercalated with carbonates. Magnesium chloride hexahydrate, aluminum nitrate nonahydrate, potassium carbonate and potassium hydroxide are mixed according to the mole ratio of magnesium ions in magnesium chloride hexahydrate, aluminum ions in aluminum nitrate nonahydrate, carbonate ions in potassium carbonate and hydroxide ions in potassium hydroxide of Mg 2+ ：Al 3+ ：OH - ：CO 3 2- Feed was performed=0.67:0.33:2:0.165.
And step 1-1, dissolving magnesium chloride hexahydrate and aluminum nitrate nonahydrate in water to form a clear and transparent mixed salt solution.
And step 1-2, dissolving potassium carbonate and potassium hydroxide in water to form a clear and transparent mixed alkali solution.
And step 1-3, dropwise adding the mixed salt solution prepared in the step 1-1 into the mixed alkali solution prepared in the step 1-2 at the temperature of 30 ℃, continuously stirring in the dropwise adding process to obtain a suspension, heating the suspension to 120 ℃, performing hydrothermal reaction at the constant temperature, reacting for 12 hours, and filtering, washing, drying and crushing to obtain the carbonate intercalation hydrotalcite-like compound.
Step 2, calcining the carbonate intercalation hydrotalcite-like compound prepared in the step 1 at the temperature of 500 ℃ to obtain a double metal hydroxide;
and 3, adding the bimetal hydroxide prepared in the step 2 into a proper amount of sodium fluoride aqueous solution with the mass fraction of 2%, wherein the molar mass of fluoride ions in the sodium fluoride aqueous solution is equal to twice that of potassium carbonate in the step 1-2, heating to 80 ℃ under the protection of inert gas, stirring, reacting for 20 hours, filtering, washing, drying and crushing to obtain the hydrotalcite-like compound with the fluoride ion intercalation, and the product is denoted as a3.
Caries preventing material with caries preventing additive of 20% is prepared. The preparation process is as follows:
step 1, putting TPU resin into an oven, heating to 70 ℃, and drying for 4 hours to obtain dried TPU resin;
step 2, putting the caries preventing additive into a baking oven, wherein the adding amount of the caries preventing additive is one fourth of the adding amount of the TPU resin in the step 1, heating to 200 ℃, and drying for 12 hours to obtain a dried caries preventing additive;
and 3, adding the dried TPU resin and the dried caries preventing additive into a stirrer, uniformly stirring, discharging, adding into a double-screw extruder, and performing melt extrusion granulation to obtain the caries preventing material.
The caries preventing material is prepared into dental film.
The invisible appliance is prepared by adopting the dental diaphragm.
Example 4
The caries preventing additive is prepared by the following method:
step 1, preparing a structural formula Mg 0.7 Al 0.3 (OH) 2 (CO 3 ) 0.15 Hydrotalcite-like compounds intercalated with carbonates. Magnesium chloride hexahydrate, aluminum nitrate nonahydrate, potassium carbonate and sodium hydroxide are mixed according to the molar ratio of magnesium ions in magnesium chloride hexahydrate, aluminum ions in aluminum nitrate nonahydrate, carbonate ions in potassium carbonate and hydroxide ions in potassium hydroxide of Mg 2+ ：Al 3+ ：OH - ：CO 3 2- Feed was performed=0.7:0.3:2:0.15.
And step 1-1, dissolving magnesium chloride hexahydrate and aluminum nitrate nonahydrate in water to form a clear and transparent mixed salt solution.
And step 1-2, dissolving sodium carbonate and sodium hydroxide in water to form a clear and transparent mixed alkali solution.
And step 1-3, dropwise adding the mixed salt solution prepared in the step 1-1 into the mixed alkali solution prepared in the step 1-2 at the temperature of 30 ℃, continuously stirring in the dropwise adding process to obtain a suspension, heating the suspension to 150 ℃, performing hydrothermal reaction at the constant temperature, reacting for 24 hours, and filtering, washing, drying and crushing to obtain the carbonate intercalation hydrotalcite-like compound.
Step 2, calcining the carbonate intercalation hydrotalcite-like compound prepared in the step 1 at the temperature of 600 ℃ to obtain a double metal hydroxide;
and 3, adding the bimetal hydroxide prepared in the step 2 into a proper amount of sodium fluoride aqueous solution with the mass fraction of 2%, wherein the molar mass of fluoride ions in the sodium fluoride aqueous solution is equal to twice that of sodium carbonate in the step 1-2, heating to 80 ℃ under the protection of inert gas, stirring, reacting for 20 hours, filtering, washing, drying and crushing to obtain the hydrotalcite-like compound with the fluoride ion intercalation, and the product is denoted as a4.
Caries preventing material with caries preventing additive of 20% is prepared. The preparation process is as follows:
step 1, putting TPU resin into an oven, heating to 90 ℃, and drying for 4 hours to obtain dried TPU resin;
step 2, putting the caries preventing additive into a baking oven, wherein the adding amount of the caries preventing additive is one fourth of the adding amount of the TPU resin in the step 1, heating to 200 ℃, and drying for 12 hours to obtain a dried caries preventing additive;
and 3, adding the dried TPU resin and the dried caries preventing additive into a stirrer, uniformly stirring, discharging, adding into a double-screw extruder, and performing melt extrusion granulation to obtain the caries preventing material.
The caries preventing material is prepared into dental film.
The invisible appliance is prepared by adopting the dental diaphragm.
Example 5
The caries preventing additive is prepared by the following method:
step 1, preparing a structural formula Mg 0.7 Al 0.3 (OH) 2 (CO 3 ) 0.15 Hydrotalcite-like compounds intercalated with carbonates. Magnesium chloride hexahydrate, aluminum nitrate nonahydrate, potassium carbonate and sodium hydroxide are mixed according to the molar ratio of magnesium ions in magnesium chloride hexahydrate, chloride ions in aluminum nitrate nonahydrate, carbonate ions in potassium carbonate and hydroxide ions in potassium hydroxide of Mg 2+ ：Al 3+ ：OH - ：CO 3 2- Feed was performed=0.7:0.3:2:0.15.
And step 1-1, dissolving magnesium chloride hexahydrate and aluminum nitrate nonahydrate in water to form a clear and transparent mixed salt solution.
And step 1-2, dissolving sodium carbonate and sodium hydroxide in water to form a clear and transparent mixed alkali solution.
And step 1-3, dropwise adding the mixed salt solution prepared in the step 1-1 into the mixed alkali solution prepared in the step 1-2 at the temperature of 20 ℃, continuously stirring in the dropwise adding process to obtain a suspension, heating the suspension to 100 ℃, performing hydrothermal reaction at the constant temperature, reacting for 24 hours, and filtering, washing, drying and crushing to obtain the carbonate intercalation hydrotalcite-like compound.
Step 2, calcining the carbonate intercalation hydrotalcite-like compound prepared in the step 1 at the temperature of 700 ℃ to obtain a double metal hydroxide;
and 3, adding the bimetal hydroxide prepared in the step 2 into a proper amount of potassium fluoride aqueous solution with the mass fraction of 2%, wherein the molar mass of fluoride ions in the potassium fluoride aqueous solution is equal to twice that of sodium carbonate in the step 1-2, heating to 80 ℃ under the protection of inert gas, stirring, reacting for 20 hours, filtering, washing, drying and crushing to obtain the fluoride ion intercalated hydrotalcite-like compound, and the product is denoted as a5.
Caries preventing material with caries preventing additive of 20% is prepared. The preparation process is as follows:
step 1, putting TPU resin into an oven, heating to 90 ℃, and drying for 6 hours to obtain dried TPU resin;
step 2, putting the caries preventing additive into a baking oven, wherein the adding amount of the caries preventing additive is one fourth of the adding amount of the TPU resin in the step 1, heating to 220 ℃, and drying for 18 hours to obtain a dried caries preventing additive;
and 3, adding the dried TPU resin and the dried caries preventing additive into a stirrer, uniformly stirring, discharging, adding into a double-screw extruder, and performing melt extrusion granulation to obtain the caries preventing material.
The caries preventing material is prepared into dental film.
The invisible appliance is prepared by adopting the dental diaphragm.
Example 6
The caries preventing additive is prepared by the following method:
step 1, preparing Zn with the structural formula 0.7 Al 0.3 (OH) 2 (CO 3 ) 0.15 Hydrotalcite-like compounds intercalated with carbonates. Zinc chloride hexahydrate, aluminum nitrate nonahydrate, potassium carbonate and sodium hydroxide are used for preparing the zinc oxide-zinc oxide composite material according to the mole ratio of zinc ions in zinc chloride hexahydrate, aluminum ions in aluminum nitrate nonahydrate, carbonate ions in potassium carbonate and hydroxide ions in sodium hydroxide 2+ ：Al 3+ ：OH - ：CO 3 2- Feed was performed=0.7:0.3:2:0.15.
And step 1-1, dissolving zinc chloride hexahydrate and aluminum nitrate nonahydrate in water to form clear and transparent mixed salt solution.
And step 1-2, dissolving sodium carbonate and sodium hydroxide in water to form a clear and transparent mixed alkali solution.
And step 1-3, dropwise adding the mixed salt solution prepared in the step 1-1 into the mixed alkali solution prepared in the step 1-2 at the temperature of 60 ℃, continuously stirring in the dropwise adding process to obtain a suspension, heating the suspension to 100 ℃, performing hydrothermal reaction at the constant temperature, reacting for 24 hours, and filtering, washing, drying and crushing to obtain the carbonate intercalation hydrotalcite-like compound.
Step 2, calcining the carbonate intercalation hydrotalcite-like compound prepared in the step 1 at the temperature of 700 ℃ to obtain a double metal hydroxide;
and 3, adding the bimetal hydroxide prepared in the step 2 into a proper amount of potassium fluoride aqueous solution with the mass fraction of 2%, wherein the molar mass of fluoride ions in the potassium fluoride aqueous solution is equal to twice that of sodium carbonate in the step 1-2, heating to 50 ℃ under the protection of inert gas, stirring, reacting for 24 hours, filtering, washing, drying and crushing to obtain the fluoride ion intercalated hydrotalcite-like compound, and the product is denoted as a6.
Caries preventing material with caries preventing additive of 20% is prepared. The preparation process is as follows:
step 1, putting TPU resin into an oven, heating to 80 ℃, and drying for 6 hours to obtain dried TPU resin;
step 2, putting the caries preventing additive into a baking oven, wherein the adding amount of the caries preventing additive is one fourth of the adding amount of the TPU resin in the step 1, heating to 180 ℃, and drying for 24 hours to obtain a dried caries preventing additive;
and 3, adding the dried TPU resin and the dried caries preventing additive into a stirrer, uniformly stirring, discharging, adding into a double-screw extruder, and performing melt extrusion granulation to obtain the caries preventing material.
The caries preventing material is prepared into dental film.
The invisible appliance is prepared by adopting the dental diaphragm.
Example 7
The caries preventing additive is prepared by the following method:
step 1, preparing Cu in structural formula 0.7 Fe 0.3 (OH) 2 (CO 3 ) 0.15 Hydrotalcite-like compounds intercalated with carbonates. Copper chloride dihydrate, ferric nitrate nonahydrate, potassium carbonate and sodium hydroxide are mixed according to the mole ratio of copper ions in the copper chloride dihydrate, iron ions in the ferric nitrate nonahydrate, carbonate ions in the potassium carbonate and hydroxide ions in the sodium hydroxide of Cu 2+ ：Fe 3+ ：OH - ：CO 3 2- Feed was performed=0.7:0.3:2:0.15.
And step 1-1, dissolving copper chloride dihydrate and ferric nitrate nonahydrate in water to form a clear and transparent mixed salt solution.
And step 1-2, dissolving sodium carbonate and sodium hydroxide in water to form a clear and transparent mixed alkali solution.
And step 1-3, dropwise adding the mixed salt solution prepared in the step 1-1 into the mixed alkali solution prepared in the step 1-2 at the temperature of 30 ℃, continuously stirring in the dropwise adding process to obtain a suspension, heating the suspension to 100 ℃, performing hydrothermal reaction at the constant temperature, reacting for 24 hours, and filtering, washing, drying and crushing to obtain the carbonate intercalation hydrotalcite-like compound.
Step 2, calcining the carbonate intercalation hydrotalcite-like compound prepared in the step 1 at the temperature of 700 ℃ to obtain a double metal hydroxide;
and 3, adding the bimetal hydroxide prepared in the step 2 into a proper amount of sodium fluoride aqueous solution with the mass fraction of 2%, wherein the molar mass of fluoride ions in the sodium fluoride aqueous solution is equal to twice that of sodium carbonate in the step 1-2, heating to 100 ℃ under the protection of inert gas, stirring, reacting for 12 hours, filtering, washing, drying and crushing to obtain the hydrotalcite-like compound with the fluoride ion intercalation, and the product is denoted as a7.
Caries preventing material with caries preventing additive of 20% is prepared. The preparation process is as follows:
step 1, putting TPU resin into an oven, heating to 70 ℃, and drying for 8 hours to obtain dried TPU resin;
step 2, putting the caries preventing additive into a baking oven, wherein the adding amount of the caries preventing additive is one fourth of the adding amount of the TPU resin in the step 1, heating to 250 ℃, and drying for 12 hours to obtain a dried caries preventing additive;
and 3, adding the dried TPU resin and the dried caries preventing additive into a stirrer, uniformly stirring, discharging, adding into a double-screw extruder, and performing melt extrusion granulation to obtain the caries preventing material.
The caries preventing material is prepared into dental film.
The invisible appliance is prepared by adopting the dental diaphragm.
Comparative example 1
The caries preventing additive is prepared by the following method:
step 1, preparing a structural formula Mg 0.8 Al 0.2 (OH) 2 (CO 3 ) 0.1 Hydrotalcite-like compounds intercalated with carbonates. Magnesium chloride hexahydrate, aluminum nitrate nonahydrate, potassium carbonate and potassium hydroxide are mixed according to the mole ratio of magnesium ions in magnesium chloride hexahydrate, aluminum ions in aluminum nitrate nonahydrate, carbonate ions in potassium carbonate and hydroxide ions in potassium hydroxide of Mg 2+ ：Al 3+ ：OH - ：CO 3 2- Feed was performed=0.8:0.2:2:0.1.
And step 1-1, dissolving magnesium chloride hexahydrate and aluminum nitrate nonahydrate in water to form a clear and transparent mixed salt solution.
And step 1-2, dissolving potassium carbonate and potassium hydroxide in water to form a clear and transparent mixed alkali solution.
And step 1-3, dropwise adding the mixed salt solution prepared in the step 1-1 into the mixed alkali solution prepared in the step 1-2 at the temperature of 30 ℃, continuously stirring in the dropwise adding process to obtain a suspension, heating the suspension to 120 ℃, performing hydrothermal reaction at the constant temperature, reacting for 12 hours, and filtering, washing, drying and crushing to obtain the carbonate intercalation hydrotalcite-like compound.
Step 2, calcining the carbonate intercalation hydrotalcite-like compound prepared in the step 1 at the temperature of 400 ℃ to obtain a double metal hydroxide;
and 3, adding the bimetal hydroxide prepared in the step 2 into a proper amount of sodium fluoride aqueous solution with the mass fraction of 2%, wherein the molar mass of fluoride ions in the sodium fluoride aqueous solution is equal to twice that of potassium carbonate in the step 1-2, heating to 80 ℃ under the protection of inert gas, stirring, reacting for 20 hours, filtering, washing, drying and crushing to obtain the hydrotalcite-like compound with the fluoride ion intercalation, and the product is denoted as a8.
Caries preventing material with caries preventing additive of 20% is prepared. The preparation process is as follows:
step 1, putting TPU resin into an oven, heating to 70 ℃, and drying for 4 hours to obtain dried TPU resin;
step 2, putting the caries preventing additive into a baking oven, wherein the adding amount of the caries preventing additive is one fourth of the adding amount of the TPU resin in the step 1, heating to 200 ℃, and drying for 12 hours to obtain a dried caries preventing additive;
and 3, adding the dried TPU resin and the dried caries preventing additive into a stirrer, uniformly stirring, discharging, adding into a double-screw extruder, and performing melt extrusion granulation to obtain the caries preventing material.
The caries preventing material is prepared into dental film.
The invisible appliance is prepared by adopting the dental diaphragm.
Comparative example 2
The caries preventing additive is prepared by the following method:
step 1, preparing a structural formula Mg 0.75 Al 0.25 (OH) 2 (CO 3 ) 0.125 Hydrotalcite-like compounds intercalated with carbonates. Magnesium chloride hexahydrate, aluminum nitrate nonahydrate, potassium carbonate and potassium hydroxide are mixed according to the mole ratio of magnesium ions in magnesium chloride hexahydrate, aluminum ions in aluminum nitrate nonahydrate, carbonate ions in potassium carbonate and hydroxide ions in potassium hydroxide of Mg 2+ ：Al 3+ ：OH - ：CO 3 2- Feed was performed=0.75:0.25:2:0.125.
And step 1-1, dissolving magnesium chloride hexahydrate and aluminum nitrate nonahydrate in water to form a clear and transparent mixed salt solution.
And step 1-2, dissolving potassium carbonate and potassium hydroxide in water to form a clear and transparent mixed alkali solution.
And step 1-3, dropwise adding the mixed salt solution prepared in the step 1-1 into the mixed alkali solution prepared in the step 1-2 at the temperature of 30 ℃, continuously stirring in the dropwise adding process to obtain a suspension, heating the suspension to 120 ℃, performing hydrothermal reaction at the constant temperature, reacting for 12 hours, and filtering, washing, drying and crushing to obtain the carbonate intercalation hydrotalcite-like compound.
Step 2, calcining the carbonate intercalation hydrotalcite-like compound prepared in the step 1 at the temperature of 800 ℃ to obtain a double metal hydroxide;
and 3, adding the bimetal hydroxide prepared in the step 2 into a proper amount of sodium fluoride aqueous solution with the mass fraction of 2%, wherein the molar mass of fluoride ions in the sodium fluoride aqueous solution is equal to twice that of potassium carbonate in the step 1-2, heating to 80 ℃ under the protection of inert gas, stirring, reacting for 20 hours, filtering, washing, drying and crushing to obtain the fluoride ion intercalated hydrotalcite-like compound, and the product is denoted as a9.
Caries preventing material with caries preventing additive of 20% is prepared. The preparation process is as follows:
step 1, putting TPU resin into an oven, heating to 70 ℃, and drying for 4 hours to obtain dried TPU resin;
step 2, putting the caries preventing additive into a baking oven, wherein the adding amount of the caries preventing additive is one fourth of the adding amount of the TPU resin in the step 1, heating to 200 ℃, and drying for 12 hours to obtain a dried caries preventing additive;
and 3, adding the dried TPU resin and the dried caries preventing additive into a stirrer, uniformly stirring, discharging, adding into a double-screw extruder, and performing melt extrusion granulation to obtain the caries preventing material.
The caries preventing material is prepared into dental film.
The invisible appliance is prepared by adopting the dental diaphragm.
Comparative example 3
The caries preventing additive is prepared by the following method:
step 1, preparing a structural formula Mg 0.67 Al 0.33 (OH) 2 (CO 3 ) 0.165 Hydrotalcite-like compounds intercalated with carbonates. Magnesium chloride hexahydrate, aluminum nitrate nonahydrate, potassium carbonate and potassium hydroxide according to magnesium ions in magnesium chloride hexahydrate, aluminum ions in aluminum nitrate nonahydrate, carbonate ions in potassium carbonate and potassium hydroxideThe molar ratio of hydroxyl ions in the catalyst is Mg 2+ ：Al 3+ ：OH - ：CO 3 2- Feed was performed=0.67:0.33:2:0.165.
And step 1-1, dissolving magnesium chloride hexahydrate and aluminum nitrate nonahydrate in water to form a clear and transparent mixed salt solution.
And step 1-2, dissolving potassium carbonate and potassium hydroxide in water to form a clear and transparent mixed alkali solution.
And step 1-3, dropwise adding the mixed salt solution prepared in the step 1-1 into the mixed alkali solution prepared in the step 1-2 at the temperature of 30 ℃, continuously stirring in the dropwise adding process to obtain a suspension, heating the suspension to 120 ℃, performing hydrothermal reaction at the constant temperature, reacting for 12 hours, and filtering, washing, drying and crushing to obtain the carbonate intercalation hydrotalcite-like compound.
Step 2, calcining the carbonate intercalation hydrotalcite-like compound prepared in the step 1 at the temperature of 500 ℃ to obtain a double metal hydroxide;
and 3, adding the bimetal hydroxide prepared in the step 2 into a proper amount of sodium fluoride aqueous solution with the mass fraction of 2%, wherein the molar mass of fluoride ions in the sodium fluoride aqueous solution is equal to twice that of potassium carbonate in the step 1-2, heating to 80 ℃ under the protection of inert gas, stirring, reacting for 20 hours, and then filtering, washing, drying and crushing to obtain the fluoride ion intercalated hydrotalcite-like compound, and the product is denoted as a10.
Caries preventing material with caries preventing additive of 20% is prepared. The preparation process is as follows:
step 1, putting TPU resin into an oven, heating to 70 ℃, and drying for 4 hours to obtain dried TPU resin;
step 2, putting the caries preventing additive into a baking oven, wherein the adding amount of the caries preventing additive is one fourth of the adding amount of the TPU resin in the step 1, heating to 150 ℃, and drying for 12 hours to obtain a dried caries preventing additive;
and 3, adding the dried TPU resin and the dried caries preventing additive into a stirrer, uniformly stirring, discharging, adding into a double-screw extruder, and performing melt extrusion granulation to obtain the caries preventing material.
The caries preventing material is prepared into dental film.
The invisible appliance is prepared by adopting the dental diaphragm.
Comparative example 4
The caries preventing additive is prepared by the following method:
step 1, preparing a structural formula Mg 0.7 Al 0.3 (OH) 2 (CO 3 ) 0.15 Hydrotalcite-like compounds intercalated with carbonates. Magnesium chloride hexahydrate, aluminum nitrate nonahydrate, potassium carbonate and sodium hydroxide are mixed according to the molar ratio of magnesium ions in magnesium chloride hexahydrate, aluminum ions in aluminum nitrate nonahydrate, carbonate ions in potassium carbonate and hydroxide ions in sodium hydroxide of Mg 2+ ：Al 3+ ：OH - ：CO 3 2- Feed was performed=0.7:0.3:2:0.15.
And step 1-1, dissolving magnesium chloride hexahydrate and aluminum nitrate nonahydrate in water to form a clear and transparent mixed salt solution.
And step 1-2, dissolving sodium carbonate and sodium hydroxide in water to form a clear and transparent mixed alkali solution.
And step 1-3, dropwise adding the mixed salt solution prepared in the step 1-1 into the mixed alkali solution prepared in the step 1-2 at the temperature of 30 ℃, continuously stirring in the dropwise adding process to obtain a suspension, heating the suspension to 150 ℃, performing hydrothermal reaction at the constant temperature, reacting for 24 hours, and filtering, washing, drying and crushing to obtain the carbonate intercalation hydrotalcite-like compound.
Step 2, calcining the carbonate intercalation hydrotalcite-like compound prepared in the step 1 at the temperature of 600 ℃ to obtain a double metal hydroxide;
and 3, adding the bimetal hydroxide prepared in the step 2 into a proper amount of sodium fluoride aqueous solution with the mass fraction of 2%, wherein the molar mass of fluoride ions in the sodium fluoride aqueous solution is equal to twice that of sodium carbonate in the step 1-2, heating to 80 ℃ under the protection of inert gas, stirring, reacting for 20 hours, filtering, washing, drying and crushing to obtain the hydrotalcite-like compound with the fluoride ion intercalation, and the product is denoted as a4.
Caries preventing material with caries preventing additive of 20% is prepared. The preparation process is as follows:
step 1, putting TPU resin into an oven, heating to 90 ℃, and drying for 4 hours to obtain dried TPU resin;
step 2, putting the caries preventing additive into a baking oven, wherein the adding amount of the caries preventing additive is one fourth of the adding amount of the TPU resin in the step 1, heating to d300 ℃, and drying for 12 hours to obtain a dried caries preventing additive;
and 3, adding the dried TPU resin and the dried caries preventing additive into a stirrer, uniformly stirring, discharging, adding into a double-screw extruder, and performing melt extrusion granulation to obtain the caries preventing material.
The caries preventing material is prepared into dental film.
The invisible appliance is prepared by adopting the dental diaphragm.
Taking 1g of each of the dental films in examples 1-7 and comparative examples 1-4, respectively soaking the dental films in a 1L oral simulated liquid environment, standing for one week, taking a proper amount of liquid, and testing the change of the fluoride ion concentration in the released environment by using an ion chromatography method. The state of the membrane and the fluoride ion concentration in each example are shown in table 1.
TABLE 1
From examples 1 to 7, comparative example 1 and comparative example 2 in Table 1, it is understood that the calcination temperature has a large influence on the release effect of the caries preventing additive: as is clear from comparative examples 1 and 2, the fluorine ion concentration is greatly reduced when the calcination temperature is 400 ℃, and the recombination of the fluorine ion intercalated hydrotalcite is not favored because the carbonate is not completely escaped due to the too low temperature; when the calcining temperature is 800 ℃, the concentration of fluoride ions is greatly reduced, and the bimetallic oxide is sintered, so that the recombination of fluoride ion intercalated hydrotalcite is not facilitated, and the optimal calcining temperature is 400-700 ℃ according to the required fluoride ion concentration. As can be seen from examples 1 to 3The structure of the hydrotalcite-like compound intercalated by carbonate has a certain influence on the release of fluoride ions, and the hydrotalcite-like compound has a structural general formula [ M II (1-x) M III x (OH) 2 ] x+ (CO 3 2- ) x/2 ·mH 2 O(0.2<x<0.33 Under otherwise identical conditions, the fluoride ion release concentration decreases as the value of x increases. In preparing caries preventing materials, as is known from comparative example 3, when the drying temperature of caries preventing additive is too low, the processed dental film has bubbles; from example 4 and comparative example 4, it is known that too high a drying temperature for the caries preventing additive also affects the fluoride ion concentration, and therefore, in preparing the caries preventing material, a proper drying temperature is required to dry crystal water in hydrotalcite, which may affect film processing.
The caries preventing additive, caries preventing material, dental film and concealed appliance according to the present invention are not limited in scope to the specific embodiments. The above is merely a basic description of the present invention, and any equivalent transformation according to the technical solution of the present invention shall fall within the protection scope of the present invention.
Claims (9)
1. The caries preventing additive is characterized in that the caries preventing additive is prepared by the following method:
step 1, preparing a compound with a structural general formula [ M ] II (1-x) M III x (OH) 2 ] x+ (CO 3 2- ) x/2 ·mH 2 O carbonate intercalation hydrotalcite-like compound of 0.2<x<0.33，M II Represents divalent metal ions, M III The preparation method of hydrotalcite-like compound representing trivalent metal ions and carbonate intercalation comprises the following steps:
step 1-1, dissolving divalent metal ion salt and trivalent metal ion salt in water to form clear and transparent mixed salt solution,
step 1-2, dissolving carbonate and hydroxide in water to form clear and transparent mixed alkali solution,
step 1-3, dropwise adding the mixed salt solution prepared in the step 1-1 into the mixed alkali solution prepared in the step 1-2, continuously stirring in the dropwise adding process to obtain a suspension, heating the suspension, performing hydrothermal reaction at a constant temperature, filtering, washing, drying and crushing after the reaction is completed to obtain the carbonate intercalation hydrotalcite-like compound,
wherein the added substances of divalent metal ion salt, trivalent metal ion salt, carbonate and hydroxide are M in the structural general formula of hydrotalcite-like compound intercalated by carbonate II 、M III 、OH - And CO 3 2- Atomic number ratio (1-x): x:2: x/2 addition;
step 2, calcining the carbonate intercalation hydrotalcite-like compound prepared in the step 1 to obtain a double metal hydroxide;
and 3, adding the double metal hydroxide prepared in the step 2 into the fluoride aqueous solution, heating and stirring under the protection of inert gas, and filtering, washing, drying and crushing after the reaction is finished to obtain the fluoride ion intercalated hydrotalcite-like compound.
2. An anti-caries additive as claimed in claim 1 wherein:
the carbonate is sodium carbonate or potassium carbonate;
the hydroxide is sodium hydroxide or potassium hydroxide;
the divalent metal ion is any one of magnesium ion, calcium ion, barium ion, copper ion, zinc ion and ferrous ion;
the trivalent metal ion is any one of iron ion, aluminum ion, cobalt ion and cerium ion;
the fluoride is any one of sodium fluoride, potassium fluoride and ammonium fluoride.
3. An anti-caries additive as claimed in claim 1 wherein:
in the step 1-3, the temperature of the mixed salt solution is 20-60 ℃ when the mixed salt solution is dripped into the mixed alkali solution, the suspension is heated to 100-160 ℃ for hydrothermal reaction, and the time of the hydrothermal reaction is 6-48 h.
4. An anti-caries additive as claimed in claim 1 wherein:
the calcination temperature in step 2 is 400-700 ℃.
5. An anti-caries additive as claimed in claim 1 wherein:
the reaction temperature in the step 3 is 50-100 ℃, the reaction time is 12-24h, and the ratio of the molar mass of fluoride in the aqueous solution of fluoride to the molar mass of carbonate in the step 1-2 is (2+/-0.2): 1.
6. a caries preventing material characterized by: the caries preventing material is prepared from TPU and the caries preventing additive according to any one of claims 1-5.
7. A caries prevention material as defined in claim 6 wherein: the preparation method of the caries preventing material comprises the following steps:
step 1, putting TPU resin into a baking oven, heating to 70-90 ℃, and drying for 4-8 hours to obtain dried TPU resin;
step 2, placing the caries preventing additive according to claim 6 into an oven, heating to 180-250 ℃, and drying for 12-24 hours to obtain a dried caries preventing additive;
and 3, adding the dried TPU resin and the dried caries preventing additive into a stirrer, uniformly stirring, discharging, adding into a double-screw extruder, and performing melt extrusion granulation to obtain the caries preventing material.
8. A dental diaphragm, characterized in that: the dental film is prepared from the caries preventing material according to claim 6.
9. An invisible appliance, characterized in that: the tooth invisible appliance is prepared by adopting the dental film sheet of claim 8.
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| CN108128797A (en) * | 2017-12-29 | 2018-06-08 | 王崇 | A kind of intercalated houghite and preparation method thereof and tooth whitening gel |
| CN108554373A (en) * | 2018-05-25 | 2018-09-21 | 黄智慧 | A kind of preparation method of hydrotalcite de-fluoridation adsorbent |
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| CN111282583A (en) * | 2020-02-19 | 2020-06-16 | 天津大学 | Fluorine-doped hydrotalcite material loaded metal-based catalyst, preparation method and application |
| CN111348666A (en) * | 2020-03-26 | 2020-06-30 | 中国船舶重工集团公司第七二五研究所 | Preparation method of corrosion inhibitor composite anion intercalation hydrotalcite |
| CN111744017A (en) * | 2020-07-09 | 2020-10-09 | 湖北民族大学 | Ibuprofen intercalation magnalium hydrotalcite sustained-release material and preparation method thereof |
| CN113929492A (en) * | 2021-10-15 | 2022-01-14 | 成都工业学院 | Preparation method of hydrotalcite-like composite material for phosphorus recovery, and product and application thereof |
| CN115554334A (en) * | 2022-09-23 | 2023-01-03 | 拜斯特药业(广州)有限公司 | Caries preventing coating agent capable of being applied to teeth and having relieving effect and preparation method thereof |
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