CN107804865B

CN107804865B - Preparation of vaterite microsphere and application of vaterite microsphere in daily chemical field

Info

Publication number: CN107804865B
Application number: CN201610812185.5A
Authority: CN
Inventors: 丁观军
Original assignee: Individual
Current assignee: Individual
Priority date: 2016-09-09
Filing date: 2016-09-09
Publication date: 2020-04-28
Anticipated expiration: 2036-09-09
Also published as: CN107804865A

Abstract

The invention discloses a vaterite microsphere, which is prepared by mixing an aqueous solution containing water-soluble calcium salt with a carbonate aqueous solution containing a stabilizer, adjusting the pH value of the solution to 7.0-11.0, and stirring at the reaction temperature of 5-40 ℃; the stabilizer is phytate, adenosine diphosphate, adenosine triphosphate or a mixture of any of the phytate, the adenosine diphosphate and the adenosine triphosphate; the mass proportion of calcium ions in the total solution is more than 0.3 wt%; the molar ratio of the calcium ions to the carbonate ions is 1: 5-5: 1. Research shows that the prepared vaterite microsphere can obviously promote the mineralization and repair of demineralized enamel and dentin, and can also be cooperated with fluorine to effectively avoid the generation of decayed teeth.

Description

Preparation of vaterite microsphere and application of vaterite microsphere in daily chemical field

Technical Field

The invention belongs to the technical field of daily chemicals, and particularly relates to a calcium carbonate microsphere and application thereof in the field of daily chemicals.

Background

In China, due to the high sugar intake, the mouth materials and the surfaces of the mouth materials of the masses can go deep into the inner holes. Calcium carbonate materials have good biocompatibility and the hard tissue of the biological cavity is often eroded by acidic substances, the enamel of the tooth surface is lost, and the exposed fragile tooth activity is widely applied to toothpaste formulas to promote the restoration of dentin and enamel. In an aqueous solution or paste, the vaterite type calcium carbonate microspheres are in a metastable crystal form, so that in practical application, the vaterite type calcium carbonate microspheres can be favorably adsorbed in the oral cavity, the pH value is adjusted, calcium ions are released, and the mineralization and repair of teeth are promoted.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a vaterite microsphere and a method thereof, which is characterized by comprising the following steps: mixing an aqueous solution containing water-soluble calcium salt with a carbonate aqueous solution containing a stabilizer, adjusting the pH value of the solution to 7.0-11.0, and stirring at the reaction temperature of 5-40 ℃; the stabilizer is phytate, adenosine diphosphate, adenosine triphosphate or a mixture of any of the phytate, the adenosine diphosphate and the adenosine triphosphate; the mass proportion of calcium ions in the total solution is more than 0.3 wt%; the molar ratio of the calcium ions to the carbonate ions is 1: 5-5: 1.

The method for preparing the vaterite microsphere is characterized in that the calcium salt of the aqueous solution is calcium chloride, calcium nitrate, calcium acetate or the mixture of any of the calcium chloride, the calcium nitrate and the calcium acetate; the carbonate is sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate or a mixture of any of the above.

The method for preparing the vaterite microsphere is characterized in that the stabilizer is adenosine disodium triphosphate; the molar ratio of the adenosine disodium triphosphate to the calcium ions is 3/250-1/3.

The method for preparing the vaterite microsphere is characterized in that the calcium salt in the aqueous solution is calcium chloride; the carbonate is sodium carbonate; the pH regulator is NaOH aqueous solution or HCl aqueous solution; the molar ratio of the adenosine disodium triphosphate to the calcium ions is 3/250-1/5; the molar ratio of calcium ions to carbonate ions was 1/1.

The method for preparing the vaterite microsphere is characterized in that the mass proportion of calcium chloride is 1.110wt%, and the molar ratio of adenosine disodium triphosphate to calcium ions is 2/25; the reaction was carried out at room temperature for 24 hours.

A method for stabilizing the phase of the prepared vaterite microsphere in an aqueous solution, dispersion or paste, characterized in that a water-soluble stabilizer, disodium adenosine triphosphate, is added, the concentration of disodium adenosine triphosphate being more than 0.22% by weight.

A vaterite microsphere characterized by a diameter size of less than 3 microns using the method for making vaterite as described above.

A method for preparing hollow calcite microspheres, which is characterized in that the vaterite microspheres prepared by the method are put into an aqueous solution containing adenosine disodium triphosphate, and are subjected to standing reaction at room temperature for 3 months; the concentration of the adenosine disodium triphosphate is 0.22 wt%.

The application of the vaterite microsphere prepared by the method in toothpaste products is characterized in that the content of the calcium carbonate microsphere is 1-35%, and the concentration of adenosine disodium triphosphate additionally added in the products is more than or equal to 0.22 wt%.

The toothpaste is characterized by comprising the following components in percentage by mass: 3-35 wt% of vaterite microspheres, 2-40 wt% of abrasive, 0.02-8 wt% of thickening agent, 1-50 wt% of humectant, 0.001-0.1 wt% of sweetening agent, 0.004-0.1 wt% of bacteriostatic agent, 0.1-5 wt% of foaming agent, 0-2 wt% of fluoride, 0.6-3 wt% of essence and 0-0.01 wt% of pigment.

Compared with the prior art, the technical scheme of the invention has the following advantages

1. The invention discloses a vaterite microsphere and a preparation method thereof. The vaterite microsphere is stabilized by adenosine disodium triphosphate; in the method, the adopted calcium ion concentration is high, so that the method is suitable for large-scale production; in the method, the stabilizer adenosine triphosphate exists in an effective concentration range.

2 adding stabilizer with more than or equal to 0.22wt% into the prepared vaterite-containing formula solution or paste has super strong effect on the phase stability of the vaterite microspheres.

3, the vaterite microsphere is added into the toothpaste formula, can obviously promote the mineralization and repair of demineralized enamel and dentin, and can also be cooperated with fluorine to effectively avoid the occurrence of dental caries.

Drawings

FIG. 1X-ray diffraction patterns of products a, b, c, d, e, f, g and h;

FIG. 2 scanning electron micrograph of product a;

FIG. 3 scanning electron micrograph of product b;

FIG. 4 scanning electron micrograph of product c;

FIG. 5 scanning electron micrograph of product d;

FIG. 6 scanning electron micrograph of product e;

FIG. 7 scanning electron micrograph of product f;

FIG. 8 scanning electron micrograph of product g;

FIG. 9 scanning electron micrograph of product h;

FIG. 10X-ray diffraction patterns of products i, j and k;

FIG. 11 scanning electron micrograph of product i;

FIG. 12 scanning electron micrograph of product j;

FIG. 13 scanning electron micrograph of product k;

FIG. 14 scanning electron micrographs of dentin after acid etching;

FIG. 15 scanning electron micrographs of demineralized dentin after 8 SOF treatments;

FIG. 16 scanning electron micrographs of demineralized dentin after 8 treatments with toothpaste 1;

FIG. 17 scanning electron micrographs of demineralized dentin after 8 treatments with toothpaste 2;

Detailed Description

The present invention will be described in further detail with reference to specific examples, and specific embodiments will be given below. The target of the X-ray diffractometer was Co, and the wavelength was 1.54056 angstroms. Adetphos molecular weight 550.

Preparation of calcium carbonate product example 1

The preparation method of the calcium carbonate microspheres is characterized in that 80g of aqueous solution containing 2.220 g of calcium chloride and 100g of aqueous solution containing 0.220g of adenosine disodium triphosphate and 2.120g of sodium carbonate are mixed and stirred, then the pH value is adjusted to 9.5 by using 4M NaOH aqueous solution, deionized water is added to 200 g, the mixture is reacted for 24 hours at room temperature, and the product a is obtained after centrifugal filtration, cleaning and 60-degree drying, and the product a is shown in figure 1 and figure 2. In the X-ray diffraction spectrum of the product a, diffraction peaks at approximately 20.7, 24.7, 26.9, 32.7, 43.7 and 49.8 degrees are characteristic peaks of vaterite. Product a is vaterite microspheres, mostly a few microns in diameter.

Example 2

The preparation method of the calcium carbonate microspheres is characterized in that 80g of aqueous solution containing 2.220 g of calcium chloride and 100g of aqueous solution containing 0.0660 g of adenosine disodium triphosphate and 2.120g of sodium carbonate are mixed and stirred, then 4M NaOH aqueous solution is used for adjusting the pH value to 9.5, deionized water is added to 200 g, reaction is carried out at room temperature for 24 hours, centrifugal filtration and washing are carried out, and then drying is carried out at 60 ℃ to obtain a product b, wherein the product b is shown in figure 1 and figure 3. In the X-ray diffraction spectrum of the product b, diffraction peaks at the positions of approximately 20.7 degrees, 24.7 degrees, 26.9 degrees, 32.7 degrees, 43.7 degrees and 49.8 degrees are characteristic peaks of the vaterite; the diffraction peak at nearly 29.1 degrees can be a calcite characteristic peak. The product b is vaterite microspheres of a few microns in diameter, with a small amount of vaterite having a tendency to transform towards the calcite phase.

Example 3

The preparation method of the calcium carbonate microspheres is characterized in that 80g of aqueous solution containing 2.220 g of calcium chloride and 100g of aqueous solution containing 2.120g of sodium carbonate are mixed and stirred, then the pH value is adjusted to 9.5 by using 4M NaOH aqueous solution, deionized water is added to 200 g, the mixture reacts at room temperature for 24 hours, and the product a is obtained after centrifugal filtration, cleaning and drying at 60 ℃, and is shown in figure 1 and figure 4. In the X-ray diffraction spectrum of the product c, diffraction peaks at about 23.1, 29.1, 31.4, 35.8, 39.3, 43.1, 47.5 and 48.4 degrees are characteristic peaks of calcite. The product c is calcite bulk particles of a few microns in size.

Example 4

The preparation method of the calcium carbonate microspheres is characterized in that 80g of aqueous solution containing 2.220 g of calcium chloride is mixed with 100g of aqueous solution containing 0.0550 g of adenosine disodium triphosphate and 2.120g of sodium carbonate, the mixture is stirred, then the pH value is adjusted to 9.5 by using 4M NaOH aqueous solution, deionized water is added to 200 g, the mixture is reacted for 24 hours at room temperature, and the product d is obtained after centrifugal filtration, cleaning and 60-degree drying, and the figure 1 and the figure 5 show that. In the X-ray diffraction spectrum of the product d, there were diffraction peaks at approximately 20.7, 24.7, 26.9, 32.7, 43.7 and 49.8 degrees, which are characteristic peaks of vaterite. The product d is vaterite microspheres with a diameter of a few microns.

Example 5

The preparation method of the calcium carbonate microspheres is characterized in that 80g of aqueous solution containing 2.220 g of calcium chloride and 100g of aqueous solution containing 0.440 g of adenosine disodium triphosphate and 2.120g of sodium carbonate are mixed and stirred, then the pH value is adjusted to 9.5 by using 4M NaOH aqueous solution, deionized water is added to 200 g, the mixture is reacted for 24 hours at room temperature, and the product e is obtained after centrifugal filtration, cleaning and 60-degree drying, and the product e is shown in figure 1 and figure 6. In the X-ray diffraction spectrum of the product e, diffraction peaks at approximately 20.7, 24.7, 26.9, 32.7, 43.7 and 49.8 degrees were found, which are characteristic peaks of vaterite. The product e is vaterite microspheres with a diameter of a few microns.

Example 6

The preparation method of the calcium carbonate microspheres is characterized in that 80g of aqueous solution containing 2.220 g of calcium chloride and 100g of aqueous solution containing 0.660 g of adenosine disodium triphosphate and 2.120g of sodium carbonate are mixed and stirred, then the pH value is adjusted to 9.5 by using 4M NaOH aqueous solution, deionized water is added to 200 g, the mixture is reacted for 24 hours at room temperature, and the product f is obtained after centrifugal filtration, cleaning and 60-degree drying, and the figure 1 and the figure 7 show that the product f is obtained. In the X-ray diffraction spectrum of the product f, there were diffraction peaks at approximately 20.7, 24.7, 26.9, 32.7, 43.7 and 49.8 degrees, which are characteristic peaks of vaterite. The product f is a vaterite mass of dimensions of some tens of microns.

Example 7

The preparation method of the calcium carbonate microspheres is characterized in that 80g of aqueous solution containing 2.220 g of calcium chloride and 100g of aqueous solution containing 1.100 g of adenosine disodium triphosphate and 2.120g of sodium carbonate are mixed and stirred, then the pH value is adjusted to 9.5 by using 4M NaOH aqueous solution, deionized water is added to 200 g, the mixture is reacted for 24 hours at room temperature, and the product g is obtained after centrifugal filtration, cleaning and 60-degree drying, and the figure 1 and the figure 8 show that. In the X-ray diffraction spectrum of the product g, there were diffraction peaks at approximately 20.7, 24.7, 26.9, 32.7, 43.7 and 49.8 degrees, which are characteristic peaks of vaterite. The product g is a vaterite mass of size some tens of microns.

Example 8

The preparation method of the calcium carbonate microspheres is characterized in that 80g of aqueous solution containing 2.220 g of calcium chloride and 100g of aqueous solution containing 2.200 g of adenosine disodium triphosphate and 2.120g of sodium carbonate are mixed and stirred, then 4M NaOH aqueous solution is used for adjusting the pH value to 9.5, deionized water is added to 200 g, reaction is carried out at room temperature for 24 h, centrifugal filtration and washing are carried out, and then drying is carried out at 60 ℃ to obtain a product h, wherein the product h is shown in figure 1 and figure 9. In the X-ray diffraction spectrum of the product h, diffraction peaks were observed at approximately 11.5, 20.7, 29.1, 30.3 and 34.0 degrees, and the phase was difficult to confirm. The reason for this is that the addition of adenosine triphosphate is excessive, resulting in amorphous calcium phosphate, inhibiting the formation of vaterite and other phases, with possible inclusion of disodium adenosine triphosphate in the middle. The product h is a mass of several tens of microns in size.

And (4) conclusion: product c had distinct calcite crystals compared to the other products, indicating that the stabilizer adenosine triphosphate helps to stabilize the crystal formation or phase transition of calcium carbonate. The products a and e are vaterite microspheres; the products b and d have a calcite phase in some degree in the vaterite microspheres; products f, g and h were free of vaterite microspheres. This shows that in the method for preparing the vaterite microsphere, the molar ratio of the adenosine disodium triphosphate to the calcium ions is 3/500-3/50, and the optimal molar ratio is 1/50-1/25. Finally, in the preparation method, the mass proportion of calcium ions is more than or equal to 1.11wt%

Stability of vaterite microspheres

50 g of an aqueous dispersion containing 0.500 g of product d was placed in a closed container and placed in a 50-degree oven for 1 month, and after centrifugal filtration and washing, 60-degree drying was carried out to obtain product i, as shown in FIG. 10 and FIG. 11. In the X-ray diffraction spectrum of the product i, diffraction peaks at about 23.1, 29.1, 31.4, 35.8, 39.3, 43.1, 47.5 and 48.4 degrees are characteristic peaks of calcite. The product i is a microsphere assembled by calcite blocks with the size of a few micrometers.

50 g of an aqueous dispersion containing 0.500 g of the product d and 0.0030 g of disodium adenosine triphosphate was put into a closed container, and placed in a 50-degree oven to stand for 1 month, and dried at 60 degrees after centrifugal filtration and washing to obtain a product j, as shown in FIG. 10 and FIG. 12. In the X-ray diffraction spectrum of product j, there were diffraction peaks at approximately 23.1, 29.1, 31.4, 35.8, 39.3, 43.1, 47.5, and 48.4 degrees, which are characteristic peaks of calcite. The product j is in the shape of easily broken calcite hollow microspheres.

50 g of an aqueous dispersion containing 0.500 g of the product c and 0.0080 g of disodium adenosine triphosphate was put into a closed container, and was left to stand in an oven at 50 degrees for 1 month, and was dried at 60 degrees after centrifugal filtration and washing to obtain a product k, as shown in FIG. 10 and FIG. 13. The position and the intensity of the diffraction peak of the product k are approximately consistent with those of the diffraction peak of the product c; the morphology of product k is also arbitrarily micron-sized microspheres.

And (4) conclusion: in the stability test, the d-phase of the vaterite microspheres in the aqueous solution or dispersion changed to the calcite phase without the addition of a stabilizer; when the concentration of the extra added adenosine disodium triphosphate is 0.0060wt%, the product is calcite hollow microspheres; when the concentration of the additional added adenosine disodium triphosphate is 0.0160wt%, the phase and the shape of the vaterite microsphere d are unchanged, and the vaterite microsphere d has strong crystalline phase stability.

Oral care product

Simulating oral Saliva (SOF), which comprises the following components：137.35 mM NaCl、4.17 mM NaHCO₃、3.01 mMKCl、7.17 mM K₂HPO₄•3H₂O、1.53 mM MgCl₂•6H₂O、20.00 mM HCl、0.90 mM CaCl₂、0.51 mMNa₂SO4 and Tris adjusted the pH to 7.0.

Example toothpaste 1 this example provides a toothpaste 1 containing vaterite microspheres, product e, consisting of the following raw materials, in mass percent: 12wt% of calcium hydrogen phosphate dihydrate, 2wt% of carrageenan, 28 wt% of glycerol, 0.1wt% of sucralose, 0.05wt% of zinc citrate, 2wt% of sodium dodecyl sulfate, 0.76 wt% of sodium monofluorophosphate, 1.25 wt% of mint essence, 0.005 wt% of lemon yellow pigment, 10wt% of hydrated silicon dioxide, 6 wt% of vaterite microsphere and the balance of deionized water. The preparation method of the toothpaste comprises the following steps: s1, placing the components in a stirrer and stirring for 40min at 800 rpm; and S2, degassing in vacuum to form paste.

Example toothpaste 2 this example provides a toothpaste 2 containing vaterite microspheres, product e, consisting of the following raw materials, in mass percent: 12wt% of calcium hydrogen phosphate dihydrate, 2wt% of carrageenan, 28 wt% of glycerol, 0.1wt% of sucralose, 0.05wt% of zinc citrate, 2wt% of sodium dodecyl sulfate, 0.76 wt% of sodium monofluorophosphate, 1.25 wt% of mint essence, 0.005 wt% of lemon yellow pigment, 10wt% of hydrated silicon dioxide, 12wt% of vaterite microspheres, and the balance of deionized water. The preparation method of the toothpaste comprises the following steps: s1, placing the components in a stirrer and stirring for 40min at 800 rpm; and S2, degassing in vacuum to form paste.

In vitro restoration experiment of demineralized dentin

Healthy third molars pulled out by orthodontics (informed consent of the patient) were collected in the oral hospital, washed thoroughly and placed in 0.5 wt% thymol aqueous solution. Preparing dentine slices with the thickness of 2 mm by using a low-speed diamond cutting machine (SYJ-160 low-speed diamond cutting machine), and polishing and grinding the dentine slices by using silicon carbide water sand paper of 200 meshes, 400 meshes, 1000 meshes, 2000 meshes and 4000 meshes until the surfaces are bright and flat; and finally, polishing the mixture smoothly by using 3M polishing paper (3 microns), and ultrasonically cleaning the mixture for 3 min in deionized water for later use.

Before use, each dentin tablet was demineralized in a 36 wt% aqueous phosphoric acid solution for 2 min, followed by rinsing with deionized water for 3 min, 3 dentin tablets were removed for pre-toothpaste treatment samples for characterization, and the remainder was randomly divided into 3 groups of 3 tablets each. The dentin sheet is fixed in the oral elastomer material (Shanghai Pigeon brand) with dentin facing upward. The specific steps of processing the dentin sample by the toothpaste are as follows: weighing 5.0 g SOF, experimental group toothpastes 1 and 2, respectively adding 10.0 g deionized water, stirring to obtain water solution or toothpaste slurry, pouring onto 3 groups of elastomer materials embedded with dentin sample, manually brushing with soft hair toothbrush for 1min, and standing for 1 min; then, washing with 20 mL of deionized water for 3 times, and soaking in 20 mL of simulated oral saliva; subsequently, the container containing the simulated buccal saliva and dentin disks was placed in a 37 ℃ constant speed 150 rpm thermostatic shaker (THZ-98A) for 4 h. Dentin samples were treated 3 times per day and after the third treatment, overnight in 37 degrees simulated oral saliva. When the number of the samples is 8, taking out 3 dentin samples, drying, storing, and performing characterization analysis on dentin surface deposition and dentin tubule diameter change conditions by a scanning electron microscope SEM (Hitachi S-3400N) (before characterization, vacuum gold plating is performed on the dentin sample surface). According to the SEM picture of the sample, the diameter of the dentinal tubule is measured (diameter of the dentinal tubule measuring method: the shortest distance from the center of the dentinal tubule to both sides of the tubule, and the number of measurements is more than 120, and the average value of 3 dentinal tubules is taken).

In the electron micrograph, the acid-eroded dentin surface was smooth, the surface tubules were fully exposed, and the average pore diameter was 3.63. + -. 0.70. mu.m (FIG. 14). Different treatments bring about various changes to the demineralized dentin: after 8 SOF treatments, the dentinal surface was still smooth, but the tubule pore size was reduced to 3.21. + -. 0.52 μm (FIG. 15); after 8 times of treatment of the toothpaste 1, a certain amount of deposits are formed on the surface of dentin, and the aperture of the tubules is also reduced to be 2.72 +/-0.62 mu m respectively (figure 16); after 8 times of treatment with toothpaste 2, there were deposits on the dentinal surface, some of the tubules were blocked, and the tubule diameters were significantly smaller, respectively, 2.3 ± 0.34 μm (fig. 17). The demineralization dentin restoration effect showed significant difference in 3 groups of samples, from large to small, of toothpaste 2, toothpaste 1 and SOF, respectively, and toothpaste 2 was significantly different from toothpaste 1.

In the actual treatment process, the reduction of the tooth tubule pore size on the surface of the demineralized dentin is the result of biomineralization, and is the result that the vaterite microspheres in the toothpaste provide calcium ions, increase the pH value, and under the action of fluoride ions, the vaterite microspheres and phosphate ions in the SOF help to form hydroxyapatite phase substances. Wherein the higher the vaterite content, the better the dentin repair effect.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.

Claims

1. A method for preparing hollow calcite microspheres is characterized in that prepared vaterite microspheres are put into an aqueous solution containing adenosine disodium triphosphate, and the mixture is kept stand at room temperature for reaction for 3 months; the concentration of the adenosine disodium triphosphate is 0.0060 wt%; the preparation method of the vaterite microsphere in advance comprises the following steps: mixing an aqueous solution containing water-soluble calcium salt with a carbonate aqueous solution containing a stabilizer, adjusting the pH value of the solution to 7.0-11.0, and stirring at the reaction temperature of 5-40 ℃; the mass proportion of calcium ions in the total solution is more than 0.3 wt%; the stabilizer is adenosine disodium triphosphate; the aqueous calcium salt is calcium chloride; the carbonate is sodium carbonate; the pH regulator is NaOH aqueous solution or HCl aqueous solution; the molar ratio of the adenosine disodium triphosphate to the calcium ions is 1/50-1/25; the molar ratio of calcium ions to carbonate ions was 1/1.